Borinane Boosted Bifunctional Organocatalysts for Ultrafast Ring-Opening Polymerization of Cyclic Ethers

Borinane Boosted Bifunctional Organocatalysts for Ultrafast Ring-Opening Polymerization of Cyclic Ethers | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Borinane Boosted Bifunctional Organocatalysts for Ultrafast Ring-Opening Polymerization of Cyclic Ethers Chao Chen, Yves Gnanou, xiaoshuang feng This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1807966/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The design of reactive species that can either serve to initiate the ring-opening polymerization (ROP) of epoxides for the synthesis of high molar mass polyethers or be alternatively used to catalyze the synthesis of polyether telechelics in the presence of chain transfer agents (CTAs) has long been an elusive goal. Here we report the synthesis of a series of bifunctional borinane-based catalysts that enable the living ROP of epoxides with unprecedented activity (TOF ≥ 1.8×10 5 h − 1 ) and molar mass up to 10 6 g/mol under mild conditions. When used along with CTAs to generate low M n telechelics, the same borinane-based catalysts exhibit ultrahigh productivity even for loading amounts as low as 50 ppb for ethylene oxide polymerization. These newly designed catalysts also afford the polymerization of oxetane with record TOF values and molar masses. DFT computation provides a full understanding of how these bifunctional catalysts operate when used in the ROP of epoxides. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction Aliphatic polyethers, namely poly(propylene oxide) (PPO), poly(ethylene oxide) (PEO) and their copolymers are industrially produced in megaton scale with molar masses ranging from a few hundreds g/mol to ultrahigh millions g/mol. These polyethers have found applications in a variety of situations such as nonionic surfactants, biomedical materials, polyelectrolytes, elastomers 1 , 2 , 3 , 4 , 5 , 6 , 7 or as precursors for polyurethane. 8 , 9 The synthesis of high molar mass PPO is a challenge because of the occurrence of transfer reactions which prevent the formation of well-defined PPO beyond 10 kg/mol. Aluminum-based Vandenberg’s catalyst 10 which implies monomer coordination before insertion affords high molar mass PPO but the polymerization is not well controlled. Even zinc/cobalt double metal cyanide (DMC) 11 , 12 , 13 , 14 , 15 catalyst which is employed for PPO production in industry is not without drawbacks such as long induction time, specific equipment to meet harsh polymerization conditions (high temperature and pressure build-up during polymerization), high molar mass impurities (100–400 kg/mol), necessity of specific chain transfer agents (CTAs), and unsuitability for ROP of EO. Other outstanding metallic catalysts have been specially designed for the synthesis of PPO by Coates 16 , 17 , 18 , 19 and Deffieux, 20 , 21 , 22 , 23 respectively. The Coates group synthesized perfectly isotactic PPO with molar masses up to 290 kg/mol using monometallic Co(III) complex fitted with a salicylidine ligand. 16 , 17 Deffieux and Carlotti et al. on the other hand resorted to the formation of an “ate complex” between trialkylaluminum and the growing oxyanion to obtain high molar mass PPO free of chain transfer reactions. In order to broaden the applications of polyethers and avoid the presence of metal residues resulting from the use of metal complexes, several efforts have been made to prepare polyethers under metal-free conditions. Organocatalysts such as phosphazene base, 24 N-heterocyclic carbenes (NHC), 25 , 26 , 27 N-heterocyclic olefins (NHO) 7 , 28 , 29 , triethylborane (TEB) 30 , 31 , 32 , and 9-borabicyclo[3.3.1]nonane (9-BBN) based catalysts 33 have been utilized for ROP of epoxides. The TEB system enables the synthesis of well-defined polyethers, but is not suitable for the preparation of low molar mass polyols. In contrast, NHO does provide an efficient route to ultrahigh molar mass polyethers but it lacks control as the molar masses eventually obtained generally deviate from the expected values. Overall, rare are organocatalysts that are capable to produce ultrahigh molar mass polyethers without entailing long reaction time, harsh conditions, and low turnover numbers (TON). As a consequence, there is a dearth of articles reporting the organocatalyzed synthesis of telechelic polyether diols carried out in the presence of transfer agents yet the use of CTA is beneficial as it allows the generation of numerous chains from a very limited number of catalyst centers; it also allows the control of polymer molar mass and of its architecture. The development of very reactive organocatalysts that enable the synthesis of polyethers with a high reactivity, productivity, ultrahigh molar mass, broad monomer scope, and that can be simultaneously compatible with CTAs for the synthesis of telechelic polyether diols is a long-standing goal that this work aims to address. From the examples of highly active metallic catalysts that have been utilized along with transfer agents, 34 , 35 , 36 we reasoned that organoboron catalysts can serve the same purpose provided their activity is dramatically boosted. On the other hand, our experience in alkylborane mediated polymerization showed us that the steric hindrance around boron centers is an important factor affecting the polymerization of epoxides. By covalently attaching 2, 3 and 4 borinane moieties to ammonium salts (Scheme 1 ), we wanted to ease steric hindrance around the boron centers of these catalysts. As a result, this novel generation of borinane-based catalysts exhibited outstanding performance when directly used in the ROP of epoxides and oxetane; in the presence of CTAs they could catalyze in minute amounts the synthesis of low molar mass telechelic polyether diols. Results And Discussion Synthesis of borinane based bifunctional catalysts The six-membered cyclic borinane (shown in Scheme S1 ) was synthesized by cyclization of 1,4-pentadiene with borane. 37 Pure borinane was finally obtained with a total yield of 95% as a white solid. Once enough borinane was isolated it was used as seeds: as shown in Scheme S1 , 2 moles of borinane could indeed afford up to 3 moles of borinane through direct hydroboration of 1,4-pentadiene using borinane followed by treatment with borane. The obtained borinane was fully characterized by 1 H, 13 C and 11 B NMR spectroscopy ( Figure S1-S3 ), confirming its high purity without contamination of 9-BBN and other boranes. The subsequent hydroboration of allyl-containing ammonium salts carrying different numbers of terminal double bonds was carried out after quaternization of the initial tertiary amine using a stoichiometric amount of 5-bromo-1-pentene (SI Experimental, Scheme S2 , S3 and Figure S4 - S9 ). Upon hydroboration of terminal double bonds carried by the above obtained ammonium chloride, bifunctional catalysts possessing one ammonium cation and 2, 3, 4 borinane moieties named B2 , B3 , and B4 could be easily prepared in quantitative yield, the structure of obtained catalysts were determined by 1 H NMR, 13 C NMR and 11 B NMR spectroscopy ( Scheme 1 , Figure S10 - S18 ). In all cases, the signals in 1 H or 13 C NMR spectra corresponding to double bonds completely vanished after hydroboration; instead, a broad peak at 85.5 ppm in 11 B NMR spectra was clearly detected, indicating the successful synthesis of bifunctional catalysts B2 , B3 , and B4 . Table 1 . Comparison of catalysts B2 , B3 , and B4 with other catalyst system for the ROP of PO. a Entry Catalysts Monomer M:Cat T ( ℃ ) Time (h) Conv. (%) b TOF (h -1 ) c M n,GPC d (kg/ mol ) Ð e 1 B2 PO 10000:1 25 10 min 100 6000 0 465 1.12 2 B4 PO 30000:1 0 10 min 100 18 0000 1539 1.18 3 B3 PO 30000:1 0 10 min 68 122400 957 1.23 4 B2 PO 30000:1 0 10 min 21 37800 278 1.25 5 B4 BO 30000:1 0 1 100 30000 1441 1.23 6 B4 AGE 30000:1 25 1 100 30000 1174 1.26 7 B4 EO 30000:1 25 1 min 97 1.7×10 6 538 1.28 8 f B4 EO 30000:1 25 1 100 30000 811 1.12 9 g, 27 I i Pr / TiBAl PO 1500:1 25 0.7 84 1800 62.1 1.56 10 h, 22 P4/TiBAl PO 2586:1 20 3 100 862 12.4 1.15 11 i, 23 TBACl/TiBAl PO 350:1 0 0.5 100 700 13.8 1.77 12 j, 19 (salen)Co PO 2000:1 0 0.25 34 2720 26.4 1.8 13 k, 18 (salen)Cr PO 32000:1 23 24 61.5 1333 104 2.68 14 l, 29 NHO PO 1000:1 r.t. 5 min 100 12000 61 1.47 15 m, 38 Co-Ni-DMC PO 2530:1 70 1 78 1990 188 2.3 16 n, 26 I i Pr /TEB PO 1000:1 25 4 89 223 49.9 1.13 17 o, 30 P2/TEB PO 250:1 0 2 min 100 7500 18.9 1.06 18 p, 33 N + [(9-BBN) 2 ] PO 10000:1 25 1 23.7 2370 80.7 1.33 a Polymerizations were performed in neat condition unless otherwise mentioned. b Conversion was determined by 1 H NMR. c Turnover frequency (TOF) = TON/ time (h). d,e Determined by GPC in THF using multidetectors corrected by the dn/dc values of PPO, PBO and PAGE. f EO was polymerized in THF with [EO]= 10 M, the molar mass was determined by GPC calibrated by PEO linear standards.. g 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene (I i Pr): triisobutylaluminum (TiBAl) = 1: 3, in 2-Methyltetrahydrofuran with [PO]= 10 M. h Phosphazene base (P4): TiBAl= 1:3 in toluene with [PO]= 2 M. i Tetrabutylammonium chloride (TBACl): TiBAl= 1:3 in toluene with [PO]= 4 M. j Catalyst (salen)Co: bis(triphenylphosphine)iminium acetate ( PPNOAc )= 1:2 in toluene with [PO]= 2 M, produced highly isotactic PPO. k (salen)Cr: bis(triphenylphosphine)iminium chloride ( PPNCl): 1,6-hexanediol = 1:2:15 in dimethoxyethane with [PO]= 27.6 M, produced highly isotactic PPO. l NHO: magnesium bis(hexamethyldisilazide) (Mg(HMDS) 2 )= 1:5 with [PO]= 5 M in pentane. m Double metal cyanide catalyst ( Co-Ni-DMC ) with [PO]= 7.1 M in toluene. n I i Pr: TEB: benzyl alcohol= 1:3:1.5 in neat PO . o Phosphazene base (P2):TEB=1:3 in neat PO. p Ammonium bromide carrying two 9-borabicyclo (3.3.1) nonane (9-BBN) moieties, polymerization was run in neat PO. ROP of epoxides for ultrahigh molar mass polyethers and the comparison of catalytic performance of bifunctional catalysts with reported ones As mentioned in the introduction, the access to high molar mass polyethers is challenging especially for substituted epoxides due to potential transfer reactions. The efficiencies of bifunctional borinane-bearing ammonium salts B2 , B3 and B4 carrying 2, 3 and 4 borinane moieties were respectively evaluated through the ROP of PO carried out in bulk under a feeding molar ratio of [PO]/[ B2 ] or [PO]/[ B3 ] or [PO]/[ B4 ] of 30,000. After 10 mins of reaction aliquots were sampled out: with B4 100% conversion of PO was reached, whereas with B3 and B2 conversion reached 68% and 21%, respectively. Higher the number of borinane moieties carried by these three ammonium salts, higher the corresponding rate of polymerization of PO. In fact, the TOF value measured in the case of entry 2 was 1.8 × 10 5 h -1 with B4 , which is 5 times higher than that measured in the case of entry 4 with B2 as catalyst (37800 h -1 ), and also significantly higher than for entry 3 involving B3 as catalyst (122400 h -1 ). Remarkable synergistic effects were thus observed when borinane moieties carried by this family of ammonium salts were increased from 2 to 3 and then from 3 to 4. As summarized in Table 1 , all these catalysts showed unprecedented activity in comparison to any other reported catalysts. Importantly, comparison with recently described bifunctional catalysts carrying two 9-BBN moieties (TOF 2370 h -1 , entry 18, Table 1 ) shows that B2 exhibits an activity that is at least one order of magnitude higher (60,000 h -1 , entry 1, Table 1 ) under the same polymerization conditions. Actually, both types of bifunctional catalysts benefit from the reduced entropy due to the proximity of the anionic growing centers with the boron-based monomer activating centers. Because boron centers carried by 9-BBN are more hindered than those carried by borinane, monomer activation is more efficient in the latter case resulting in turn in a significant enhancement of the catalyst activity. With the borinane family of bifunctional ammonium salts the molar masses of obtained PPO samples reach up to 1.5 ×10 6 g/mol with monomodal and narrow molar mass distributions ( 10 6 g/mol ( Ð > 1.2), 29, 33 but with B4 as catalyst the synthesis of a sample of 1.5 ×10 6 g/mol could be obtained in milder conditions. As seen from the 1 H NMR spectrum, no vinyl group could be detected ( Figure S19 ), confirming the living character of the polymerization carried out in the presence of borinane-based bifunctional catalysts. Indeed, the molar masses drawn from by MALLS are close to their theoretical values calculated based on monomer conversion. Overall, B4 represents the first example of catalyst that allowed the synthesis of ultrahigh molar mass polyether with a very high rate of polymerization. Notably, the difference is striking between the PPO sample of 0.46 ×10 6 g/mol which is a viscous liquid ( Figure 1A , entry 1, Table 1 ) and the PPO sample of 1.5 ×10 6 g/mol molar mass which is a soft solid ( Figure 1B , entry 2, Table 1 ). The efficiency of borinane-based bifunctional catalysts at bringing about the ROP of other epoxides was tested with EO, BO and AGE. Being the most active catalyst for PO B4 was chosen for this screening. As seen in T able 1 , EO, BO and a functional epoxide such as AGE could be efficiently initiated by B4 and polymerized with TOF values up to 30,000 h -1 ; in all these cases, the obtained polyethers exhibited monomodal and narrow distribution of molar masses (~1.20, Figure 1C ), whose values could easily reach around 10 6 g/mol level. In the case of EO, supposedly the most reactive monomer among epoxides, its polymerization had to be carried out in the presence of a solvent rather than in bulk due to its tendency to crystallize in order to obtain PEO samples with a narrow distribution of molar masses. As anticipated, the presence of B4 enabled the ROP of EO with a record TOF value up to 1.7×10 6 h -1 , in other words one gram of B4 could produce 117.5 kg PEO per hour. The scope of CTAs and their effect on polymerization One of the very important applications of polyethers is their use as precursors for the synthesis of polyurethanes that require telechelic samples with very well defined terminal functionality, generally hydroxyl functions, and molar masses below 10,000 g/mol. Unlike the preparation of polymers of large molar mass, the synthesis of low molar mass telechelics would require large amounts of borinane-based catalysts. One way to reduce the amount of borinane-based catalyst load is to use them in catalytic quantity and to resort to CTAs to precisely control the molar mass of the telechelics formed. In other words, after demonstrating that borinane-based ammonium salts are remarkable catalysts for ROP of epoxides we wanted next to investigate their potential in the presence of protic transfer agents when the ROP of cyclic ethers involve exchange reactions between minute concentration of active oxyanions and a large amount of dormant hydroxyls. First, various CTAs with different structures and functionalities, including water, monofunctional species and tetrafunctional star-shaped PEOs were screened for ROP of PO ( B4 : CTA: PO=1:1000:20000) at room temperature using B4 as catalyst ( Table S1 , Figure S20 - 29 ). We were delighted to see that the borinane-based bifunctional catalysts were tolerant of the various protic functional groups carried by CTAs, including water. Among all the protic CTAs tested, the highest activity was observed for benzyl alcohols (BnOH and DBnOH) and propagyl alcohol (PA) with super-conjugated structure, with around 90% of PO conversion within 10 minutes, which is almost 10 times faster than the activity measured for other aliphatic alcohols, thiol and water. In comparison, the ROP of PO carried out in the presence of the binary system composed of TEB and tetrabutylammonium chloride (TBACl) (4:1) that we reported previously afforded only 5% of conversion in ( Table S1 , entry 1) which is 18 times lower than that catalyzed by B4 ( Table S1 , entry 4), confirming the synergistic effect of bifunctional catalysts where ammonium cation and chloride anion stand in a close proximity with monomer-activating boron centers. Similar catalytic activities to that measured for B4 ( Table S1 , entry 2-4,) were also observed in the cases of B2 and B3 ( Table S1 , entry 2 and 3) when used to prepare PPO telechelics. Logically B4 with its 4 boron centers and B3 with 3 boron centers exhibited higher activities than B2 . In summary, borinane-based bifunctional ammonium salts present broad tolerance to various protic functional transfer agents including water, vinyl, alkynyl, fluorine moieties allowing the synthesis of α-vinyl, ω-OH PPO macromonomers, α-, ω- diOH PPO telechelics and even hydroxyl-ended 4-arm PPO stars. Molar mass control by CTA The four boron centers carried by the ammonium salt ( B4 ) induce such a synergistic effect that its catalytic performance is unrivalled compared to any other catalysts used for the ROP of epoxides. To demonstrate the unmatched advantages of B4 , we further investigated its catalytic performance and efficiency for the ROP of PO carried out in the presence of a CTA: various [PO] to [CTA] (BnOH) ratios for a same [PO] to [ B4 ] ratio (detailed data was shown in Table S2 ) and various [CTA] to [ B4 ] ratios for a same [PO] to [CTA] ratio were applied. As shown in Figure 2A , the molar mass of resulting PPO samples could be controlled independently of the [PO] ratio to [ B4 ] ratio. As expected, increasing the amount of CTA resulted in a decreased molar mass. On the other hand, an excellent control of molar mass could also be achieved for all samples prepared with a same [PO] to [CTA] ratio but varying loading of B4 ( Figure 2B ). Notably, decreasing the B4 loading had no obvious effect on the resulting molar mass of the samples obtained. Moreover, the GPC traces for all PPO samples exhibited symmetrical and narrow molar mass distributions ( Ð < 1.10, Figure S30 ); the characterized molar masses were found very close to the expected values which were calculated upon taking into account the monomer conversion and the ratio of PO to the amount of BnOH and B4 used. The above results revealed the remarkable advantages provided by the bifunctional ammonium salt B4 for the preparation of polyols, allowing one to perfectly control the molar mass of the polyether samples synthesized using B4 as a catalyst at ultralow loading. Compared to the industrial scale production of PPO diols relying on the use of DMC as catalyst, and necessitating oligomers or noncomplexing alcohols 39 as CTAs which tend to generate higher molar mass chains, 40, 41 the process catalyzed by B4 not only affords sample free of any high molar mass contaminant, but it can also be carried out under much milder conditions, using standard protic CTAs to generate well-defined PPO diols. Ultra low catalysts loading for polyols preparation with broad monomer scope After demonstrating that borinane-based ammonium salts are excellent catalysts for the ROP of various epoxides carried out in the presence of CTAs and for the preparation of ω-functional low molar mass samples, we wanted to explore the catalytic limit of B4 . Hence, the catalyst loading was thus decreased to 2 ppm to polymerize PO ( Table 2 , entry 3): yet a high reactivity characterized by a TOF value of 18,125 was observed with DBnOH as CTA. More interestingly, B4 still showed a remarkable activity with a catalyst loading as low as 2 ppm ( Table 2 , entry 4) in the case of water as CTA and PO as monomer. In the latter case, the rate of polymerization was found to be slower in comparison with that measured using DBnOH as CTA but the TOF value was only divided by a factor of 2. With a view of exploring the catalytic limits of B4 for the ROP of EO, the catalyst loading was further decreased to ppb level ( Table 2 , entry 6): in EO case TON and TOF values of 9×10 6 and 1.9×10 5 h -1 were respectively measured, positioning B4 as the most efficient catalyst ever synthesized for the synthesis of PEO telechelics. In other words, one gram of B4 can produce no less than 606 kg PEO in 48h in the presence of CTA, which is an unrivalled value reached by any other catalyst. NMR spectra confirm the successful incorporation of CTA motifs into PEO diols ( Figure S31 - S33 ). Next, we evaluated the catalytic performance of B4 with a broad range of epoxide monomers in the presence of water as CTA. In the case of epoxides substituted by long chains, namely butylene oxide (BO, Figure S34 ) and octene oxide (OO, Figure S35 ), negligible differences were observed between their rates of polymerization and that of PO. In contrast, the polymerization rate of allyl glycidyl ether (AGE, Figure S36 ) and phenyl glycidyl ether (PGE, Figure S37 ) were slower compared to that of PO likely because of the interaction of the extra oxygen atom carried by PGE and the double bond carried by AGE with the boron centers of B4 . Nevertheless, the molar mass of all the diols obtained showed excellent agreement with the expected values; a narrow distribution of molar mass and no high molar mass impurities were observed ( Figure S3A ). Table 2 . B4 catalyzed ROP of epoxides for polyols in the presence of CTA. a Entry monomer CTA M:Cat:CTA T ( ℃ ) Time (h) Conv. (%) b TON c TOF (h -1 ) d M n,thero. e (kg/ mol ) M n,GPC f (kg/ mol ) Ð f 1 PO H 2 O 20000:1:250 25 4 95 19000 4750 4.4 4.8 1.03 2 PO PEG4OH 20000:1:250 25 3 89 17800 5933 4.9 5.7 1.05 3 PO DBnOH 5×10 5 :1:25000 60 24 87 435000 18125 1.1 1.1 1.04 4 PO H 2 O 5×10 5 :1:25000 60 48 81 405000 8438 0.9 1.3 1.04 5 PO PEG4OH 5×10 5 :1:25000 60 48 96 480000 10000 1.9 2.3 1.03 6 EO DBnOH 1×10 7 :1:25000 40 48 90 9×10 6 187500 1.7 1.8 1.03 7 EO DBnOH 2×10 7 :1:250000 40 48 9 1.8×10 6 37500 0.3 0.5 1.08 8 EO H 2 O 1×10 7 :1:250000 40 48 47 4.7×10 6 97917 0.8 0.8 1.06 9 EO PEG4OH 1×10 7 :1:250000 40 48 77 7.7×10 6 160417 2.2 2.4 1.05 10 BO H 2 O 5×10 5 :1:25000 60 48 65 325000 6771 0.9 1.2 1.05 11 PGE H 2 O 5×10 5 :1:25000 60 48 31 155000 3229 0.9 1.4 1.04 12 AGE H 2 O 5×10 5 :1:25000 60 48 26 130000 2708 0.6 0.7 1.06 13 OO H 2 O 5×10 5 :1:25000 60 48 52 260000 5417 1.3 1.5 1.05 a Polymerizations were run in neat condition. b Conversion was determined by 1 H NMR. c Turnover number (TON) = moles of PO consumed/ moles of catalysts. d Turnover frequency (TOF) = TON/ time (h). e Determined by 1 H NMR. f Determined by GPC in THF using standard PEO as calibration. Effective ROP of oxetane The anionic ROP of oxetane has seldom been reported and the highest molar mass of polyoxetane ever obtained was limited to 19 kg/mol. 42, 43 . On the other hand, Amass and coworkers 44 reported a controlled/“living” cationic ROP of oxetane carried out in 1,4-dioxane using a specially synthesized initiator 3-phenoxypropyl1-oxonia-4-oxacyclohexane hexafluoroantimonate (3-PPOA): polyoxetane with molar mass up to 160 kg/mol, containing 10 % of cyclic oligomers and incorporating dioxane units were obtained. Due to its high basicity and low ring strain, the ROP of oxetane through either cationic or anionic mechanism and thus the synthesis of high molar mass polyoxetane are still a challenge. As shown in Table S3 entry 3, B4 catalyzed polymerization of oxetane (TMO) shows a TOF value 1000 times higher than that of last reported value obtained by anionic means 45 in 2018 (entry 5). Moreover, the polyoxetane sample obtained by the use of B4 exhibited an unprecedented molar mass value of 600 kg/mol ( Figure 3B ). The experimental molar mass showed an excellent agreement with the expected value, indicating that the polymerization of oxetane is living when initiated by B4 . Chain end group fidelity Chain end group fidelity was confirmed by matrix-assisted laser desorption/ ionization time-of-flight (MALDI-TOF) mass spectrometry. The mass spectra of PPO ( Figure S38 ) and PTMO ( Figure S39 ) showed a single population indicating that chloride solely initiated polymerization in absence of CTA. Furthermore, in the presence of water as CTA only one single population ( Figure 3C ) is observed that appears to be in excellent agreement with the experimental mass obtained by GPC. The repeating intervals of 58 is in agreement with the molar mass of PO. Owing to the high ratio of CTA (water) to B4 , the chloride initiated population was undetectable in spite of the single initiation nature by B4 . Importantly, α-allyloxy,ω-OH PPO was not observed in MALDI-TOF, indicating the absence of any chain transfer reaction to monomer in B4 -catalyzed polymerization. Additionally, the absence of any hydrogen abstraction side reaction was also supported by 1 H NMR since no allyl group was observed ( Figure S19 ). Finally, B4 effectively produced α-,ω-diOH PPO and its molar mass was precisely controlled by the ratio of CTA: B4 . The high fidelity of two primary hydroxyl ended PPO make this kind of diol precursors particularly valuable for high quality polyurethane preparation. Mechanism investigation Boron centers in organoboron catalysts play a double role when used in the ROP of epoxides: 1) activate the latter monomers; 2) form growing “ate complexes” through their interaction with oxyanions. In such “ate complexes” the nucleophilicity of oxyanions is decreased which helps to prevent side reactions. Because boron centers in borinane are more accessible to monomers than with any other bulky boron, the overall activity of such catalysts is enhanced by at least one order of magnitude compared to the best-known catalysts. In addition, the ring opening of PO in the presence of these borinane-based bifunctional ammonium salts strictly happened at the methylene C‒O bond to produces regio-regular PPO as confirmed by the regioselective polymerization of chiral S -PO ( Figure S40 ). In the presence of CTA, no inhibition period is observed in the ROP of epoxides in the presence of borinane-based catalysts unlike other systems. In contrast, the binary system (TBACl/TEB) is inoperative when used for the ROP of epoxides in the presence of CTAs because of a low rate constant of initiation (k 1 )/propagation (k 3 ) compared to the rate of exchange (k 2 ). On the other hand, the synergistic effect in borinane-based bifunctional catalysts likely results in a slightly higher value of k 1 compared to k 2 ( Figure 4 ) which enabled initiation. In addition, the k 3 certainly lower than k 2 which allows a precise control of molar masses through fast exchange between dormant and active species (boron-based ate complex, Figure S41 ), thus affording polyols with a narrow dispersity. The above features indicate that borinane-based ammonium salts behave as excellent catalysts for the ROP of epoxides carried out in the presence of CTAs. To gain a deeper insight into the mechanism of bifunctional catalysts mediated ROP, DFT computation was performed ( Figure 5 , Figure S42 ). The energy barrier of the initiation step (25.11 kcal/mol), INT1-TS1, is lower than that of exchange (28.15 kcal/mol, INT2-TS2) which indicates a slightly higher value of k 1 compared to that of k 2 , confirming the above proposed mechanism. Furthermore, the increased energy barrier observed between INT3 and TS3 (35.43 kcal/mol) provides sufficient room for exchange between active chains and dormant chains which resulted in well-defined polyols. This DFT study thus provides perfect understanding of the mechanism in borinane-based bifunctional catalysts mediated ROP. Conclusion In this contribution, we described the rational design of a series of borinane-based bifunctional ammonium salts that proved to be excellent catalysts for the ROP of epoxides under mild conditions. Such bifunctional catalysts were synthesized by simple hydroboration of alkene ammonium salts using borinane in quantative yield. In the presence of these bifunctional catalysts the ROP of epoxides is living, no side reaction and in particular no transfer to monomer could be detected; these catalysts afford a highly regioselective ring-opening of epoxides producing stereoregular polyethers. Ultrahigh molar mass polyether of > 10 6 g/mol could be obtained with narrow distribution upon using these bifunctional catalysts. Record TOF values were reached for PO (1.8×10 5 h − 1 ) and EO (1.7×10 6 h − 1 ), respectively. Significantly, the borinane-based bifunctional catalysts exhibit remarkable tolerance against various CTAs thus enabling the synthesis of polyols with precisely controlled molar mass and high end group fidelity using ppm level catalyst loading for PO and ppb level loading for EO. Moreover, an unprecedented productivity of 606 kg PEO/g B4 catalyst in 48 h in the presence of CTA was achieved with polymers of well-defined structure. In the presence of B4 , record values of TOF and of molar mass were reached for the ROP of oxetane. Finally, DFT computation gives a deep insight into the ROP of epoxides in the presence of these bifunctional catalysts and CTAs. Overall, such outstanding performance of these borinane-based bifunctional catalysts exhibit a great potential for an industrial preparation of polyols and can inspire the design of new generation of catalysts for effective ROP. Methods Materials All the reagents were purchased from Sigma-Aldrich and used as received unless otherwise stated. Triethylborane (TEB, 1 M in THF), 9-Borabicyclo[3.3.1]nonane (9-BBN, 0.4 M in Hexane), borane dimethyl sulfide complex (BMS), boron trifluoride diethyl etherate and 1,4-Pentadiene was used as received. Tetrabutylammonium chloride (TBAC) were purified by recrystallization from cold n-hexane three times and followed by drying under vacuum to remove the solvents. The traces of water in the above ammonium salt were removed by drying under vacuum in the presence of P 2 O 5 for 2 days. Tributyl amine and 5-bromo-1-pentene were purified by distillation. Propylene oxide (PO), oxetane, 1-butylene oxide (BO), 1-ocene oxide (OO), allyl glycidyl ether (AGE) and phenyl glycidyl ether (PGE) were purified by distilling firstly over CaH 2 and then over n-butyl lithium for two times using standard Schlenk technique. Ethylene oxide (EO) were purified by distilling over sodium. The purified monomers were stored in Schlenk flasks and kept in glovebox. Benzyl alcohol (BzOH), trifluoroethanol (TFE), propargyl alcohol (PA), 2-Hydroxyethyl acrylate (HEA), propylene glycol (PG), deionized water (H2O) and pentaerythritol ethoxylate (PEG4OH, average Mn ~797) were degassed via three times of freeze-pump-thaw procedure. 1,4-Benzenedimethanol (DBnOH) and 1,4-Benzenedimethanethiol (DBnSH) were used as received. 1,4-diazabicyclo[2.2.2]octane (DABCO) was purified by two times of sublimation and stored in glove box. Characterization Nuclear magnetic resonance (NMR): 1 H, 11 B, 19 Fand 13 C NMR spectra were recorded on a Bruker AVANCE III-400 Hz instrument in CDCl 3 . Gel permeation chromatography (GPC): GPC traces were acquired on a VISCOTEK VE2001 system equipped with the Styragel HR2 THF and Styragel HR4 THF using THF (1 mL/min) as the eluent. The relative molar masses and distributions were obtained at 35 ℃ using a RID detector and against linear polystyrene standards. The matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra were collected on an Autoflex (Bruker) mass spectrometer. The trans-2-[3-(4-t-butyl-phenyl)-2-methyl2-propenylidene] malononitrile (DCTB) was used as the matrix with a loading of 2:1 to sodium acetate which used as the ionizing agent. Synthesis of borinane . The six-membered cyclic borinane was synthesized as reported method. 46 A flame dried round bottom flask equipped with magnetic stir bar was cooled under vacuum and transferred to glove box. The flask was charged with 48.5 mL 9-BBN and 1 mL 1,4 pentadiene (9.7 mmol). The flask was stirred at room temperature in glove box overnight before adding 0.92 mL BMS. The reaction continued at room temperature for 24 h before anhydrous DABCO (0.54 g) THF solution was added to the above borane mixture solution. Borinane was immediately form complex with DABCO and precipitated. However, 9-BBN has no complexation with DABCO. In this case, pure borinane was separated with 9-BBN by filtration. And 9-BBN could be recycled for further reaction. The free borinane could be generated from the DABCO complex by reacting with boron trifluoride. The above solution was concentrated by distillation to yield pure borinane as white solid (0.76 g, 95% yield). Once the pure borinane was obtained, three moles of borinane could be easily generated from two moles of borinane ( Scheme S1 ) without further separation or purification procedure. Synthesis of catalysts As shown in Scheme 1 , all the bifunctional catalysts were synthesized via the direct hydroboration of borinane with vinyl groups. All the solvents utilized in this reaction were carefully dried to afford high yield and eliminate side reaction. B4 mediated RD-ROP of PO The obtained bifunctional borinane catalyst ( B4 ) was dissolved in THF to obtain a 1 M solution. And the solution was further diluted 100 times to afford a 0.01 M THF solution. A typical polymerization procedure which corresponding to Table 2 , entry 3 was described as follows: A flame dried Schlenk tube was transferred to glovebox. Then the tube was charged with 1 eq. B4 (50 µL, 0.5 µmmol), 100 eq DBnOH (6.9 mg, 0.05 mmol) and 20000 eq. PO (0.7 mL, 10 mmol). The tube was stirred at room temperature for 30 min. The crude polymer was dried in vacuo at 50 °C to yield a vicious oil (0.58 g, 100% yield). References Wilms D, Stiriba S-E, Frey H. Hyperbranched Polyglycerols: From the Controlled Synthesis of Biocompatible Polyether Polyols to Multipurpose Applications. Acc Chem Res 43 , 129–141 (2010). Dimitrov I, Tsvetanov CB. 4.21 - High-Molecular-Weight Poly(ethylene oxide). In: Polymer Science: A Comprehensive Reference (eds Matyjaszewski K, Möller M). Elsevier (2012). Brocas A-L, Mantzaridis C, Tunc D, Carlotti S. Polyether synthesis: From activated or metal-free anionic ring-opening polymerization of epoxides to functionalization. Prog Polym Sci 38 , 845–873 (2013). Pohlit H, Bellinghausen I, Schomer M, Heydenreich B, Saloga J, Frey H. Biodegradable pH-Sensitive Poly(ethylene glycol) Nanocarriers for Allergen Encapsulation and Controlled Release. Biomacromolecules 16 , 3103–3111 (2015). Klein R, Wurm FR. Aliphatic Polyethers: Classical Polymers for the 21st Century. 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Gerhard Wegener MB, Lothar Duda, J¨org Hofmann, Bert Klesczewski, Daniel Koch, Robert-Joseph Kumpf, Holger Orzesek, Hans-Georg Pirkl, Christian Six, Christian Steinlein, Markus Weisbeck. Trends in industrial catalysis in the polyurethane industry. Appl Catal, A 221 , 303–335 (2001). Huang Y-J, Zhang X-H, Hua Z-J, Chen S-L, Qi G-R. Ring-Opening Polymerization of Propylene Oxide Catalyzed by a Calcium-Chloride-Modified Zinc-Cobalt Double Metal-Cyanide Complex. Macromol Chem Phys 211 , 1229–1237 (2010). Mohr R, Wagner M, Zarbakhsh S, Frey H. The Unique Versatility of the Double Metal Cyanide (DMC) Catalyst: Introducing Siloxane Segments to Polypropylene Oxide by Ring-Opening Copolymerization. Macromol Rapid Commun 42 , e2000542 (2021). Matthes R, Bapp C, Wagner M, Zarbakhsh S, Frey H. Unexpected Random Copolymerization of Propylene Oxide with Glycidyl Methyl Ether via Double Metal Cyanide Catalysis: Introducing Polarity in Polypropylene Oxide. Macromolecules, (2021). Peretti KL, Ajiro H, Cohen CT, Lobkovsky EB, Coates GW. A Highly Active, Isospecific Cobalt Catalyst for Propylene Oxide Polymerization. J Am Chem Soc 127 , 11566–11567 (2005). Hirahata W, Thomas RM, Lobkovsky EB, Coates GW. Enantioselective polymerization of epoxides: A highly active and selective catalyst for the preparation of stereoregular polyethers and enantiopure epoxides. J Am Chem Soc 130 , 17658–17659 (2008). Lipinski BM, Morris LS, Silberstein MN, Coates GW. Isotactic Poly(propylene oxide): A Photodegradable Polymer with Strain Hardening Properties. J Am Chem Soc 142 , 6800–6806 (2020). Wataru Hirahata RMT, Emil B. Lobkovsky, and Geoffrey W. Coates. Enantioselective Polymerization of Epoxides: A Highly Active and Selective Catalyst for the Preparation of Stereoregular Polyethers and Enantiopure Epoxides. J Am Chem Soc 130 , 17658–17659 (2008). Carlotti S, Billouard C, Gautriaud E, Desbois P, Deffieux A. Activation Mechanisms of Trialkylaluminum in Alkali Metal Alkoxides or Tetraalkylammonium Salts / Propylene Oxide Controlled Anionic Polymerization. Macromol Symp 226 , 61–68 (2005). Cyrille Billouard SpC, Philippe Desbois, and Alain Deffieux. “Controlled” High-Speed Anionic Polymerization of Propylene Oxide Initiated by Alkali Metal Alkoxide/Trialkylaluminum Systems. Macromolecules 37 , 4038–4043 (2004). Brocas A-L, Deffieux A, Le Malicot N, Carlotti S. Combination of phosphazene base and triisobutylaluminum for the rapid synthesis of polyhydroxy telechelic poly(propylene oxide). Polym Chem 3 , 1189–1195 (2012). Labbé A, Carlotti S, Billouard C, Desbois P, Deffieux A. Controlled High-Speed Anionic Polymerization of Propylene Oxide Initiated by Onium Salts in the Presence of Triisobutylaluminum. Macromolecules 40 , 7842–7847 (2007). Zhao J, Pahovnik D, Gnanou Y, Hadjichristidis N. A “Catalyst Switch” Strategy for the Sequential Metal-Free Polymerization of Epoxides and Cyclic Esters/Carbonate. Macromolecules 47 , 3814–3822 (2014). Raynaud J, Ottou WN, Gnanou Y, Taton D. Metal-free and solvent-free access to alpha,omega-heterodifunctionalized poly(propylene oxide)s by N-heterocyclic carbene-induced ring opening polymerization. Chem Commun (Camb) 46 , 3203–3205 (2010). Song Q, Zhao J, Zhang G, Taton D, Peruch F, Carlotti S. N-Heterocyclic carbene/Lewis acid-mediated ring-opening polymerization of propylene oxide. Part 2: Toward dihydroxytelechelic polyethers using triethylborane. Eur Polym J 134 , 109839 (2020). Song Q, Zhao J, Zhang G, Taton D, Peruch F, Carlotti S. N-Heterocyclic carbene/Lewis acid-mediated ring-opening polymerization of propylene oxide. Part 1: Triisobutylaluminum as an efficient controlling agent. Eur Polym J 134 , 109819 (2020). Naumann S, Thomas AW, Dove AP. N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide). Angew Chem Int Ed 54 , 9550–9554 (2015). Walther P, Krauss A, Naumann S. Lewis Pair Polymerization of Epoxides via Zwitterionic Species as a Route to High-Molar-Mass Polyethers. Angew Chem Int Ed 58 , 10737–10741 (2019). Zhang CJ, Duan HY, Hu LF, Zhang CH, Zhang XH. Metal-Free Route to Precise Synthesis of Poly(propylene oxide) and Its Blocks with High Activity. ChemSusChem 11 , 4209–4213 (2018). Chen Y, Shen J, Liu S, Zhao J, Wang Y, Zhang G. High Efficiency Organic Lewis Pair Catalyst for Ring-Opening Polymerization of Epoxides with Chemoselectivity. Macromolecules 51 , 8286–8297 (2018). Boopathi SK, Hadjichristidis N, Gnanou Y, Feng X. Direct access to poly(glycidyl azide) and its copolymers through anionic (co-)polymerization of glycidyl azide. Nat Commun 10 , 293 (2019). Yang GW, Zhang YY, Xie R, Wu GP. High-Activity Organocatalysts for Polyether Synthesis via Intramolecular Ammonium Cation Assisted SN 2 Ring-Opening Polymerization. Angew Chem, Int Ed 59 , 16910–16917 (2020). Deacy AC, Moreby E, Phanopoulos A, Williams CK. Co(III)/Alkali-Metal(I) Heterodinuclear Catalysts for the Ring-Opening Copolymerization of CO2 and Propylene Oxide. J Am Chem Soc 142 , 19150–19160 (2020). Lidston CAL, Abel BA, Coates GW. Bifunctional Catalysis Prevents Inhibition in Reversible-Deactivation Ring-Opening Copolymerizations of Epoxides and Cyclic Anhydrides. J Am Chem Soc 142 , 20161–20169 (2020). Cyriac A, Lee SH, Varghese JK, Park ES, Park JH, Lee BY. Immortal CO2/Propylene Oxide Copolymerization: Precise Control of Molecular Weight and Architecture of Various Block Copolymers. Macromolecules 43 , 7398–7401 (2010). Brown HC, Pai GG. Organoboranes: XXVIII. Convenient procedures for the synthesis of borinane. J Organomet Chem 250 , 13–22 (1983). Robertson NJ, Qin Z, Dallinger GC, Lobkovsky EB, Lee S, Coates GW. Two-dimensional double metal cyanide complexes: highly active catalysts for the homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide. Dalton Trans, 5390–5395 (2006). Huang Y-J, Qi G-R, Wang Y-H. Controlled ring-opening polymerization of propylene oxide catalyzed by double metal-cyanide complex. J Polym Sci, Part A: Polym Chem 40 , 1142–1150 (2002). Almora-Barrios N, et al. Structure, Activity, and Deactivation Mechanisms in Double Metal Cyanide Catalysts for the Production of Polyols. ChemCatChem 7 , 928–935 (2015). Zhao J, Li B-G, Fan H. Molecular Weight Distribution in Ring-Opening Polymerization of Propylene Oxide Catalyzed by Double Metal Complex: A Model Simulation. Macromol Theory Simul 30 , 2000101 (2021). Daisuke Takeuchi YW, Takuzo Aida, and Shohei Inoue. Lewis Acid-Promoted Anionic Polymerization of a Monomer with High Cationic Polymerizability. Synthesis of Narrow Molecular Weight Distribution Polyoxetane and Polyoxetane-Poly(methyl methacrylate) Block Copolymer with Aluminum Porphyrin Initiators. Macromolecules 28 , 651–652 (1995). Aida DTaT. Controlled Coordinate Anionic Polymerization of Oxetane by Novel Initiating Systems: Onium Salts/Bulky Organoaluminum Diphenolates. Macromolecules 29 , 8096–8100 (1996). Bouchékif H, Philbin MI, Colclough E, Amass AJ. Cationic ring-opening polymerization of oxetane via a non-steady-state controlled polymerization process: A comparison of Initiators yielding living and nonliving polymers. Macromolecules 41 , 1989–1995 (2008). Gervais M, Forens A, Ibarboure E, Carlotti S. Anionic polymerization of activated oxetane and its copolymerization with ethylene oxide for the synthesis of amphiphilic block copolymers. Polym Chem 9 , 2660–2668 (2018). Brown HCaP, G.G. Organoboranes: XXVIII. Convenient procedures for the synthesis of borinane. J Organomet Chem 250 , 13–22 (1983). Declarations Acknowledgements This research work is supported by KAUST under baseline funding (BAS/1/1374-01-01). Author contributions Y.G. and X.F. directed the investigations, and revised the manuscript. C.C. carried out all experiments and analyses, and wrote the draft. All the authors participated in the discussions and revised the manuscript. Additional information Supporting Information . Details for synthesis of catalysts, and DFT computation. 1 H, 13 C, 19 F and 11 B NMR spectra and GPC Characterization data shown in Scheme S1 - S3 , Table S1-S2 , Figure S1-S43 . Corresponding Author * E-mail: [email protected] * E-mail: [email protected] Competing interests The authors declare no competing financial interests. Schemes Scheme 1 is available in the supplementary files section. Additional Declarations There is NO Competing Interest. Supplementary Files SIUltrafastRingOpeningPolymerizationofCyclicEthersNC.docx floatimage7.jpeg TOC Scheme.docx Scheme 1 Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-1807966","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":122206641,"identity":"64840e92-fd22-48d5-84b0-d8d871e67033","order_by":0,"name":"Chao Chen","email":"","orcid":"","institution":"Kaust","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Chao","middleName":"","lastName":"Chen","suffix":""},{"id":122206642,"identity":"b842b9d3-99ce-4856-839c-d2470cd497b4","order_by":1,"name":"Yves Gnanou","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABCUlEQVRIiWNgGAWjYJADxocNUJYEsVqYDUFaeEjRwiZJlBaDG8mHPzD8uiNvzt5jVjmj5rC9PQPzwds8DHXyuLWkpUkw9j0z3NlzxuzmhmOHE3sY2JKteRgOg12JVcuZM2YMjD2HGTfcyDG7+YDtcAIPA4+ZNA/DAUbcWs5//gDUYg/SUvjg32F7Hgb+b0AtdfY4tRzvAXr2x+FEkBbGjW2HGXsYeNiAWpgTcWmRPN5mJpHYcDh5w5ljxZIz+9ITew6zGVvOMTicjEsL32Hmxx8+/Dlsu+F488aPPd+s7dnbmx/eeFNRZ4tLi8IBIJHYhizEDHYwDvVAIA826w9uBaNgFIyCUTAKGADcqlvTRWfW8gAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0001-6253-7856","institution":"Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Yves","middleName":"","lastName":"Gnanou","suffix":""},{"id":122206643,"identity":"16a45d96-e462-4da3-9db7-d2b0f3f002d6","order_by":2,"name":"xiaoshuang feng","email":"","orcid":"https://orcid.org/0000-0001-7473-1728","institution":"","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"xiaoshuang","middleName":"","lastName":"feng","suffix":""}],"badges":[],"createdAt":"2022-06-29 13:11:30","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1807966/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1807966/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":24047005,"identity":"cd805cd2-174a-4419-ad97-e03f56606f44","added_by":"auto","created_at":"2022-07-19 16:25:31","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":152515,"visible":true,"origin":"","legend":"\u003cp\u003eDigital photographs of (A) low (\u003cstrong\u003eTable 1\u003c/strong\u003e, entry 1) and (B) ultrahigh (\u003cstrong\u003eTable 1\u003c/strong\u003e, entry 2) \u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e PPO, (C) SEC traces of ultrahigh \u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e polyethers.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/ed926cba9e9df4be87b56619.png"},{"id":24047002,"identity":"6160bfae-e6e3-445a-b087-ebf7a4e5e8b5","added_by":"auto","created_at":"2022-07-19 16:25:31","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":37977,"visible":true,"origin":"","legend":"\u003cp\u003eThe effect of CTA (BnOH) on the polymerization of PO using bifunctional borinane-bearing ammonium salt \u003cstrong\u003eB4\u003c/strong\u003e. (A) Keeping the ratio of PO to \u003cstrong\u003eB4\u003c/strong\u003e constant and increasing the ratio of BnOH to \u003cstrong\u003eB4\u003c/strong\u003e. (B) Keeping the initiating species constant, varying the ratio of BnOH to \u003cstrong\u003eB4\u003c/strong\u003e. Detailed data are shown in \u003cstrong\u003eTable S2\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/ff2fc76fe91bfadd3bcae8b6.png"},{"id":24047003,"identity":"eea9bea0-90fc-4489-89f1-877b9a97296d","added_by":"auto","created_at":"2022-07-19 16:25:31","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":78442,"visible":true,"origin":"","legend":"\u003cp\u003e(A) SEC traces of polyethers with low \u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e (\u003cstrong\u003eTable 2\u003c/strong\u003e). (B) Comparison of catalysts \u003cstrong\u003eB4\u003c/strong\u003e with other catalyst system for the ROP of oxetane and (C) MALDI-TOF spectra of PPO obtained using H\u003csub\u003e2\u003c/sub\u003eO as CTA refer to \u003cstrong\u003eTable 2\u003c/strong\u003e, entry 1.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/d5bbc1b16ead21e3fc82a19b.png"},{"id":24047007,"identity":"2b5baccb-b570-451c-b48b-6ffa9d172b17","added_by":"auto","created_at":"2022-07-19 16:25:31","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":40688,"visible":true,"origin":"","legend":"\u003cp\u003eProposed mechanism of \u003cstrong\u003eB2\u003c/strong\u003e mediated ROP of PO in the presence of CTA.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/5b0250ec813c4227233cf5e9.png"},{"id":24047006,"identity":"96562765-3571-4ab4-92fb-bf049832bd65","added_by":"auto","created_at":"2022-07-19 16:25:31","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":48670,"visible":true,"origin":"","legend":"\u003cp\u003eGibbs free energy profile comprise intermediates (INT1-INT4) and transition states (TS1-TS3) for ROP of PO in the presence of BnOH as CTA.\u0026nbsp;\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/b49d4e1877f0a843abad7da0.png"},{"id":25604464,"identity":"2bd815a5-86f2-4fd5-b6ba-b41fba8a32f3","added_by":"auto","created_at":"2022-08-24 14:13:06","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":903736,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/9fbd648c-3f0d-4293-98c3-97141eb2f45f.pdf"},{"id":24047743,"identity":"1cacce2b-e351-4c7a-9ce5-4211e2f43c4f","added_by":"auto","created_at":"2022-07-19 16:30:31","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4371987,"visible":true,"origin":"","legend":"","description":"","filename":"SIUltrafastRingOpeningPolymerizationofCyclicEthersNC.docx","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/f4a6fe4cbe066205eade53cd.docx"},{"id":24047009,"identity":"3f1b02ef-2497-4b81-a8ce-f7264ebd5292","added_by":"auto","created_at":"2022-07-19 16:25:31","extension":"jpeg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":310015,"visible":true,"origin":"","legend":"\u003cp\u003eTOC\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/cc4b0bfc2483cd74009c61dc.jpeg"},{"id":24047742,"identity":"a699263f-0a79-4ecd-a8e7-cec68a6a5cb4","added_by":"auto","created_at":"2022-07-19 16:30:31","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":98535,"visible":true,"origin":"","legend":"\u003cp\u003eScheme 1\u003c/p\u003e","description":"","filename":"Scheme.docx","url":"https://assets-eu.researchsquare.com/files/rs-1807966/v1/06fc78724dd1e82b0ae67792.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Borinane Boosted Bifunctional Organocatalysts for Ultrafast Ring-Opening Polymerization of Cyclic Ethers","fulltext":[{"header":"Introduction","content":"\u003cp\u003eAliphatic polyethers, namely poly(propylene oxide) (PPO), poly(ethylene oxide) (PEO) and their copolymers are industrially produced in megaton scale with molar masses ranging from a few hundreds g/mol to ultrahigh millions g/mol. These polyethers have found applications in a variety of situations such as nonionic surfactants, biomedical materials, polyelectrolytes, elastomers\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e or as precursors for polyurethane.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e The synthesis of high molar mass PPO is a challenge because of the occurrence of transfer reactions which prevent the formation of well-defined PPO beyond 10 kg/mol. Aluminum-based Vandenberg\u0026rsquo;s catalyst\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e which implies monomer coordination before insertion affords high molar mass PPO but the polymerization is not well controlled. Even zinc/cobalt double metal cyanide (DMC)\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e catalyst which is employed for PPO production in industry is not without drawbacks such as long induction time, specific equipment to meet harsh polymerization conditions (high temperature and pressure build-up during polymerization), high molar mass impurities (100\u0026ndash;400 kg/mol), necessity of specific chain transfer agents (CTAs), and unsuitability for ROP of EO. Other outstanding metallic catalysts have been specially designed for the synthesis of PPO by Coates\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e and Deffieux,\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e respectively. The Coates group synthesized perfectly isotactic PPO with molar masses up to 290 kg/mol using monometallic Co(III) complex fitted with a salicylidine ligand.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e Deffieux and Carlotti et al. on the other hand resorted to the formation of an \u0026ldquo;ate complex\u0026rdquo; between trialkylaluminum and the growing oxyanion to obtain high molar mass PPO free of chain transfer reactions.\u003c/p\u003e \u003cp\u003eIn order to broaden the applications of polyethers and avoid the presence of metal residues resulting from the use of metal complexes, several efforts have been made to prepare polyethers under metal-free conditions. Organocatalysts such as phosphazene base,\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e N-heterocyclic carbenes (NHC),\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e N-heterocyclic olefins (NHO)\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e, triethylborane (TEB) \u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e, \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e, and 9-borabicyclo[3.3.1]nonane (9-BBN) based catalysts\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e have been utilized for ROP of epoxides. The TEB system enables the synthesis of well-defined polyethers, but is not suitable for the preparation of low molar mass polyols. In contrast, NHO does provide an efficient route to ultrahigh molar mass polyethers but it lacks control as the molar masses eventually obtained generally deviate from the expected values. Overall, rare are organocatalysts that are capable to produce ultrahigh molar mass polyethers without entailing long reaction time, harsh conditions, and low turnover numbers (TON). As a consequence, there is a dearth of articles reporting the organocatalyzed synthesis of telechelic polyether diols carried out in the presence of transfer agents yet the use of CTA is beneficial as it allows the generation of numerous chains from a very limited number of catalyst centers; it also allows the control of polymer molar mass and of its architecture. The development of very reactive organocatalysts that enable the synthesis of polyethers with a high reactivity, productivity, ultrahigh molar mass, broad monomer scope, and that can be simultaneously compatible with CTAs for the synthesis of telechelic polyether diols is a long-standing goal that this work aims to address.\u003c/p\u003e \u003cp\u003eFrom the examples of highly active metallic catalysts that have been utilized along with transfer agents,\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e we reasoned that organoboron catalysts can serve the same purpose provided their activity is dramatically boosted. On the other hand, our experience in alkylborane mediated polymerization showed us that the steric hindrance around boron centers is an important factor affecting the polymerization of epoxides. By covalently attaching 2, 3 and 4 borinane moieties to ammonium salts (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), we wanted to ease steric hindrance around the boron centers of these catalysts. As a result, this novel generation of borinane-based catalysts exhibited outstanding performance when directly used in the ROP of epoxides and oxetane; in the presence of CTAs they could catalyze in minute amounts the synthesis of low molar mass telechelic polyether diols.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results And Discussion","content":"\u003cp\u003e\u003cstrong\u003eSynthesis of borinane based bifunctional catalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe six-membered cyclic borinane (shown in \u003cstrong\u003eScheme S1\u003c/strong\u003e) was synthesized by cyclization of 1,4-pentadiene with borane.\u003csup\u003e37\u003c/sup\u003e\u0026nbsp; Pure borinane was finally obtained with a total yield of 95% as a white solid. Once enough borinane was isolated it was used as seeds: as shown in \u003cstrong\u003eScheme S1\u003c/strong\u003e, 2 moles of borinane could indeed afford up to 3 moles of borinane through direct hydroboration of 1,4-pentadiene using borinane followed by treatment with borane. The obtained borinane was fully characterized by \u003csup\u003e1\u003c/sup\u003eH, \u003csup\u003e13\u003c/sup\u003eC and \u003csup\u003e11\u003c/sup\u003eB NMR spectroscopy (\u003cstrong\u003eFigure S1-S3\u003c/strong\u003e), confirming its high purity without contamination of 9-BBN and other boranes.\u003c/p\u003e\n\u003cp\u003eThe subsequent hydroboration of allyl-containing ammonium salts carrying different numbers of terminal double bonds was carried out after quaternization of the initial tertiary amine using a stoichiometric amount of 5-bromo-1-pentene (SI Experimental, \u003cstrong\u003eScheme S2\u003c/strong\u003e, \u003cstrong\u003eS3\u003c/strong\u003e and \u003cstrong\u003eFigure S4\u003c/strong\u003e-\u003cstrong\u003eS9\u003c/strong\u003e). Upon hydroboration of terminal double bonds carried by the above obtained ammonium chloride, bifunctional catalysts possessing one ammonium cation and 2, 3, 4 borinane moieties named \u003cstrong\u003eB2\u003c/strong\u003e, \u003cstrong\u003eB3\u003c/strong\u003e, and \u003cstrong\u003eB4\u003c/strong\u003e could be easily prepared in quantitative yield, the structure of obtained catalysts were determined by \u003csup\u003e1\u003c/sup\u003eH NMR, \u003csup\u003e13\u003c/sup\u003eC NMR and \u003csup\u003e11\u003c/sup\u003eB NMR spectroscopy (\u003cstrong\u003eScheme 1\u003c/strong\u003e, \u003cstrong\u003eFigure S10\u003c/strong\u003e-\u003cstrong\u003eS18\u003c/strong\u003e). In all cases, the signals in \u003csup\u003e1\u003c/sup\u003eH or \u003csup\u003e13\u003c/sup\u003eC NMR spectra corresponding to double bonds completely vanished after hydroboration; instead, a broad peak at 85.5 ppm in \u003csup\u003e11\u003c/sup\u003eB NMR spectra was clearly detected, indicating the successful synthesis of bifunctional catalysts\u003cstrong\u003e\u0026nbsp;B2\u003c/strong\u003e, \u003cstrong\u003eB3\u003c/strong\u003e, and \u003cstrong\u003eB4\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp style='margin-top:0in;margin-right:0in;margin-bottom:8.0pt;margin-left:0in;line-height:200%;font-size:16px;font-family:\"Times New Roman\",serif;text-align:justify;'\u003e\u003cstrong\u003e\u003cspan style=\"line-height:200%;\"\u003eTable 1\u003c/span\u003e\u003c/strong\u003e\u003cspan style=\"line-height:200%;\"\u003e. Comparison of catalysts \u003cstrong\u003eB2\u003c/strong\u003e\u003c/span\u003e\u003cspan style=\"line-height:200%;\"\u003e,\u0026nbsp;\u003cstrong\u003eB3\u003c/strong\u003e, and \u003cstrong\u003eB4\u003c/strong\u003e with other catalyst system for the ROP of PO.\u003csup\u003ea\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n\u003cdiv align=\"center\" style='margin-top:0in;margin-right:0in;margin-bottom:8.0pt;margin-left:0in;line-height:107%;font-size:16px;font-family:\"Times New Roman\",serif;'\u003e\n \u003ctable style=\"width: 4.8e+2pt;border: none;border-collapse:collapse;\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 49.65pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eEntry\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85.05pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eCatalysts\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 28.35pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eMonomer\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.5pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eM:Cat\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.45pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eT (\u003c/span\u003e℃\u003cspan style=\"color:black;\"\u003e)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eTime (h)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eConv. (%)\u003csup\u003eb\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 53.9pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eTOF\u0026nbsp;\u003c/span\u003e\u003c/p\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e(h\u003csup\u003e-1\u003c/sup\u003e)\u003csup\u003ec\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59.45pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cem\u003e\u003cspan style=\"color:black;\"\u003eM\u003c/span\u003e\u003c/em\u003e\u003csub\u003e\u003cspan style=\"color:black;\"\u003en,GPC\u003c/span\u003e\u003c/sub\u003e\u003csup\u003e\u003cspan style=\"color:black;\"\u003ed\u003c/span\u003e\u003c/sup\u003e\u003cspan style=\"color:black;\"\u003e\u0026nbsp;\u003c/span\u003e\u003c/p\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e(kg/\u003c/span\u003emol\u003cspan style=\"color:black;\"\u003e)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.4pt;border-color: black currentcolor;border-style: solid none;border-width: 1.5pt medium;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cem\u003e\u003cspan style=\"color:black;\"\u003e\u0026ETH;\u003c/span\u003e\u003c/em\u003e\u003csup\u003e\u003cspan style=\"color:black;\"\u003ee\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 49.65pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85.05pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cstrong\u003eB2\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 28.35pt;border: medium none;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.5pt;border: medium none;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e10000:1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.45pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e25\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e10 min\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e100\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 53.9pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e6000\u003c/span\u003e\u003cspan style=\"color:black;\"\u003e0\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59.45pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e465\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.4pt;border: medium none;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.12\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 49.65pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e2\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85.05pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cstrong\u003eB4\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 28.35pt;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.5pt;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e30000:1\u003c/span\u003e\u003c/p\u003e\n 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1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.18\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 49.65pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e3\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85.05pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e0\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e10 min\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e68\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.5pt;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e30000:1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.45pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e0\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e5\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 85.05pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cstrong\u003eB4\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 28.35pt;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eBO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1441\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.4pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.23\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width: 49.65pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e0\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e0.25\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e34\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e23\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e24\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e61.5\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003er.t.\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e5 min\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e100\u003c/span\u003e\u003c/p\u003e\n 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e70\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e78\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e25\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e4\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e89\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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style=\"color:black;\"\u003eP2/TEB\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 28.35pt;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.5pt;padding: 0in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e250:1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.45pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e0\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e2 min\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;padding: 0.05in 0.1in;height: 1pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e100\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n 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0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003eN\u003csup\u003e+\u003c/sup\u003e[(9-BBN)\u003csub\u003e2\u003c/sub\u003e]\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 28.35pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.5pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e10000:1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.45pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e25\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 49.6pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 42.6pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e23.7\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 53.9pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e2370\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 59.45pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e80.7\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width: 35.4pt;border-color: currentcolor currentcolor black;border-style: none none solid;border-width: medium medium 1.5pt;border-image: none 100% / 1 / 0 stretch;padding: 0.05in 0.1in;height: 9pt;vertical-align: top;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.33\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp style='margin-top:0in;margin-right:0in;margin-bottom:8.0pt;margin-left:0in;line-height:200%;font-size:16px;font-family:\"Times New Roman\",serif;text-align:justify;'\u003e\u003csup\u003e\u003cspan style=\"line-height:200%;\"\u003ea\u003c/span\u003e\u003c/sup\u003e\u003cspan style=\"line-height:200%;\"\u003e\u0026nbsp;Polymerizations were performed in neat condition unless otherwise mentioned. \u003csup\u003eb\u003c/sup\u003e Conversion was determined by \u003csup\u003e1\u003c/sup\u003eH NMR. \u003csup\u003ec\u003c/sup\u003e Turnover frequency (TOF) = TON/ time (h). \u003csup\u003ed,e\u003c/sup\u003e Determined by GPC in THF using multidetectors corrected by the dn/dc values of PPO, PBO and PAGE.\u0026nbsp;\u003c/span\u003e\u003csup\u003ef\u003c/sup\u003e EO was polymerized in THF with [EO]= 10 M, the molar mass was determined by GPC calibrated by PEO linear standards.. \u003csup\u003eg\u003c/sup\u003e 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene (I\u003csup\u003ei\u003c/sup\u003ePr): triisobutylaluminum (TiBAl) = 1: 3, in 2-Methyltetrahydrofuran with [PO]= 10 M. \u003csup\u003eh\u003c/sup\u003e Phosphazene base (P4): TiBAl= 1:3 in toluene with [PO]= 2 M. \u003csup\u003ei\u003c/sup\u003e Tetrabutylammonium chloride (TBACl): TiBAl= 1:3 in toluene with [PO]= 4 M. \u003csup\u003ej\u003c/sup\u003e Catalyst (salen)Co: bis(triphenylphosphine)iminium acetate (\u003cspan style=\"line-height:200%;color:black;\"\u003ePPNOAc\u003c/span\u003e)= 1:2 in toluene with [PO]= 2 M, produced highly isotactic PPO. \u003csup\u003ek\u003c/sup\u003e \u003cspan style=\"line-height:200%;color:black;\"\u003e(salen)Cr:\u003c/span\u003e bis(triphenylphosphine)iminium chloride (\u003cspan style=\"line-height:200%;color:black;\"\u003ePPNCl): 1,6-hexanediol = 1:2:15 in dimethoxyethane\u003c/span\u003e with [PO]= 27.6 M, produced highly isotactic PPO. \u003csup\u003el\u003c/sup\u003e \u003cspan style=\"line-height:200%;color:black;\"\u003eNHO: magnesium bis(hexamethyldisilazide) (Mg(HMDS)\u003csub\u003e2\u003c/sub\u003e)= 1:5 with\u0026nbsp;\u003c/span\u003e[PO]= 5 M in pentane. \u003csup\u003em\u003c/sup\u003e Double metal cyanide catalyst (\u003cspan style=\"line-height:200%;color:black;\"\u003eCo-Ni-DMC\u003c/span\u003e) with [PO]= 7.1 M in toluene. \u003csup\u003en\u003c/sup\u003e I\u003csup\u003ei\u003c/sup\u003ePr: TEB: benzyl alcohol= 1:3:1.5 \u003cspan style=\"line-height:200%;color:black;\"\u003ein neat PO\u003c/span\u003e. \u003csup\u003eo\u003c/sup\u003e Phosphazene base (P2):TEB=1:3 in neat PO. \u003csup\u003ep\u003c/sup\u003e Ammonium bromide carrying two 9-borabicyclo (3.3.1) nonane (9-BBN) moieties, polymerization was run in neat PO.\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eROP of epoxides for ultrahigh molar mass polyethers and the comparison of catalytic performance of bifunctional catalysts with reported ones\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAs mentioned in the introduction, the access to high molar mass polyethers is challenging especially for substituted epoxides due to potential transfer reactions. The efficiencies of bifunctional borinane-bearing ammonium salts \u003cstrong\u003eB2\u003c/strong\u003e, \u003cstrong\u003eB3\u003c/strong\u003e and \u003cstrong\u003eB4\u0026nbsp;\u003c/strong\u003ecarrying 2, 3 and 4 borinane moieties were respectively evaluated through the ROP of PO carried out in bulk under a feeding molar ratio of [PO]/[\u003cstrong\u003eB2\u003c/strong\u003e] or [PO]/[\u003cstrong\u003eB3\u003c/strong\u003e] or [PO]/[\u003cstrong\u003eB4\u003c/strong\u003e] of 30,000. After 10 mins of reaction aliquots were sampled out: with \u003cstrong\u003eB4\u003c/strong\u003e 100% conversion of PO was reached, whereas with \u003cstrong\u003eB3\u003c/strong\u003e and \u003cstrong\u003eB2\u003c/strong\u003e conversion reached 68% and 21%, respectively. Higher the number of borinane moieties carried by these three ammonium salts, higher the corresponding rate of polymerization of PO. In fact, the TOF value measured in the case of entry 2 was 1.8 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e h\u003csup\u003e-1\u003c/sup\u003e with \u003cstrong\u003eB4\u003c/strong\u003e, which is 5 times higher than that measured in the case of entry 4 with \u003cstrong\u003eB2\u003c/strong\u003e as catalyst (37800 h\u003csup\u003e-1\u003c/sup\u003e), and also significantly higher than for entry 3 involving \u003cstrong\u003eB3\u003c/strong\u003e as catalyst (122400 h\u003csup\u003e-1\u003c/sup\u003e). Remarkable synergistic effects were thus observed when borinane moieties carried by this family of ammonium salts were increased from 2 to 3 and then from 3 to 4. As summarized in \u003cstrong\u003eTable 1\u003c/strong\u003e, all these catalysts showed unprecedented activity in comparison to any other reported catalysts. Importantly, comparison with recently described bifunctional catalysts carrying two 9-BBN moieties (TOF 2370 h\u003csup\u003e-1\u003c/sup\u003e, entry 18, \u003cstrong\u003eTable 1\u003c/strong\u003e) shows that \u003cstrong\u003eB2\u003c/strong\u003e exhibits an activity that is at least one order of magnitude higher (60,000 h\u003csup\u003e-1\u003c/sup\u003e, entry 1, \u003cstrong\u003eTable 1\u003c/strong\u003e) under the same polymerization conditions. Actually, both types of bifunctional catalysts benefit from the reduced entropy due to the proximity of the anionic growing centers with the boron-based monomer activating centers. Because boron centers carried by 9-BBN are more hindered than those carried by borinane, monomer activation is more efficient in the latter case resulting in turn in a significant enhancement of the catalyst activity. With the borinane family of bifunctional ammonium salts the molar masses of obtained PPO samples reach up to 1.5 \u0026times;10\u003csup\u003e6\u003c/sup\u003e g/mol with monomodal and narrow molar mass distributions (\u0026lt; 1.2). To the best of our knowledge, only two examples of PPO were reported with \u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e \u0026gt; 10\u003csup\u003e6\u003c/sup\u003e g/mol (\u003cem\u003e\u0026ETH;\u003c/em\u003e\u0026gt; 1.2),\u003csup\u003e29, 33\u003c/sup\u003e but with \u003cstrong\u003eB4\u003c/strong\u003e as catalyst the synthesis of a sample of 1.5 \u0026times;10\u003csup\u003e6\u003c/sup\u003e g/mol could be obtained in milder conditions. As seen from the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum, no vinyl group could be detected (\u003cstrong\u003eFigure S19\u003c/strong\u003e), confirming the living character of the polymerization carried out in the presence of borinane-based bifunctional catalysts. Indeed, the molar masses drawn from by MALLS are close to their theoretical values calculated based on monomer conversion. Overall, \u003cstrong\u003eB4\u003c/strong\u003e represents the first example of catalyst that allowed the synthesis of ultrahigh molar mass polyether with a very high rate of polymerization. Notably, the difference is striking between the PPO sample of 0.46 \u0026times;10\u003csup\u003e6\u003c/sup\u003e g/mol which is a viscous liquid (\u003cstrong\u003eFigure 1A\u003c/strong\u003e, entry 1, \u003cstrong\u003eTable 1\u003c/strong\u003e) and the PPO sample of \u0026nbsp;1.5 \u0026times;10\u003csup\u003e6\u003c/sup\u003e g/mol molar mass which is a soft solid (\u003cstrong\u003eFigure 1B\u003c/strong\u003e, entry 2,\u003cstrong\u003eTable 1\u003c/strong\u003e).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe efficiency of borinane-based bifunctional catalysts at bringing about the ROP of other epoxides was tested with EO, BO and AGE. Being the most active catalyst for PO \u003cstrong\u003eB4\u003c/strong\u003e was chosen for this screening. As seen in \u0026nbsp;\u003cstrong\u003eT\u003c/strong\u003e\u003cstrong\u003eable 1\u003c/strong\u003e, EO, BO and a functional epoxide such as AGE could be efficiently initiated by \u003cstrong\u003eB4\u0026nbsp;\u003c/strong\u003eand polymerized with TOF values up to 30,000 h\u003csup\u003e-1\u003c/sup\u003e; in all these cases, the obtained polyethers exhibited monomodal and narrow distribution of molar masses (~1.20, \u003cstrong\u003eFigure 1C\u003c/strong\u003e), whose values could easily reach around 10\u003csup\u003e6\u003c/sup\u003e g/mol level. In the case of EO, supposedly the most reactive monomer among epoxides, its polymerization had to be carried out in the presence of a solvent rather than in bulk due to its tendency to crystallize in order to obtain PEO samples with a narrow distribution of molar masses. As anticipated, the presence of \u003cstrong\u003eB4\u003c/strong\u003e enabled the ROP of EO with a record TOF value up to 1.7\u0026times;10\u003csup\u003e6\u003c/sup\u003e h\u003csup\u003e-1\u003c/sup\u003e, in other words one gram of \u003cstrong\u003eB4\u003c/strong\u003e could produce 117.5 kg PEO per hour.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eThe scope of CTAs and their effect on polymerization\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eOne of the very important applications of polyethers is their use as precursors for the synthesis of polyurethanes that require telechelic samples with very well defined terminal functionality, generally hydroxyl functions, and molar masses below 10,000 g/mol. Unlike the preparation of polymers of large molar mass, the synthesis of low molar mass telechelics would require large amounts of borinane-based catalysts. One way to reduce the amount of borinane-based catalyst load is to use them in catalytic quantity and to resort to CTAs to precisely control the molar mass of the telechelics formed. In other words, after demonstrating that borinane-based ammonium salts are remarkable catalysts for ROP of epoxides we wanted next to investigate their potential in the presence of protic transfer agents when the ROP of cyclic ethers involve exchange reactions between minute concentration of active oxyanions and a large amount of dormant hydroxyls. First, various CTAs with different structures and functionalities, including water, monofunctional species and tetrafunctional star-shaped PEOs were screened for ROP of PO (\u003cstrong\u003eB4\u003c/strong\u003e: CTA: PO=1:1000:20000) at room temperature using \u003cstrong\u003eB4\u003c/strong\u003e as catalyst (\u003cstrong\u003eTable S1\u003c/strong\u003e, \u003cstrong\u003eFigure S20\u003c/strong\u003e-\u003cstrong\u003e29\u003c/strong\u003e). We were delighted to see that the borinane-based bifunctional catalysts were tolerant of the various protic functional groups carried by CTAs, including water. Among all the protic CTAs tested, the highest activity was observed for benzyl alcohols (BnOH and DBnOH) and propagyl alcohol (PA) with super-conjugated structure, with around 90% of PO conversion within 10 minutes, which is almost 10 times faster than the activity measured for other aliphatic alcohols, thiol and water. In comparison, the ROP of PO carried out in the presence of the binary system composed of TEB and tetrabutylammonium chloride (TBACl) (4:1) that we reported previously afforded only 5% of conversion in (\u003cstrong\u003eTable\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eS1\u003c/strong\u003e, entry 1) which is 18 times lower than that catalyzed by \u003cstrong\u003eB4\u003c/strong\u003e (\u003cstrong\u003eTable S1\u003c/strong\u003e, entry 4), confirming the synergistic effect of bifunctional catalysts where ammonium cation and chloride anion stand in a close proximity with monomer-activating boron centers. Similar catalytic activities to that measured for \u003cstrong\u003eB4\u003c/strong\u003e (\u003cstrong\u003eTable S1\u003c/strong\u003e, entry 2-4,) were also observed in the cases of \u003cstrong\u003eB2\u003c/strong\u003e and \u003cstrong\u003eB3\u003c/strong\u003e (\u003cstrong\u003eTable S1\u003c/strong\u003e, entry 2 and 3) when used to prepare PPO telechelics. \u0026nbsp;Logically \u003cstrong\u003eB4\u0026nbsp;\u003c/strong\u003ewith its 4 boron centers and \u003cstrong\u003eB3\u0026nbsp;\u003c/strong\u003ewith 3 boron centers exhibited higher activities than \u003cstrong\u003eB2\u003c/strong\u003e.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eIn summary, borinane-based bifunctional ammonium salts present broad tolerance to various protic functional transfer agents including water, vinyl, alkynyl, fluorine moieties allowing the synthesis of \u0026alpha;-vinyl, \u0026omega;-OH PPO macromonomers, \u0026alpha;-, \u0026omega;- diOH PPO telechelics and even hydroxyl-ended 4-arm PPO stars.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMolar mass control by CTA\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe four boron centers carried by the ammonium salt (\u003cstrong\u003eB4\u003c/strong\u003e) induce such a synergistic effect that its catalytic performance is unrivalled compared to any other catalysts used for the ROP of epoxides. To demonstrate the unmatched advantages of \u003cstrong\u003eB4\u003c/strong\u003e, we further investigated its catalytic performance and efficiency for the ROP of PO carried out in the presence of a CTA: various [PO] to [CTA] (BnOH) ratios for a same [PO] to [\u003cstrong\u003eB4\u003c/strong\u003e] ratio (detailed data was shown in \u003cstrong\u003eTable S2\u003c/strong\u003e) and various [CTA] to [\u003cstrong\u003eB4\u003c/strong\u003e] ratios for a same [PO] to [CTA] ratio were applied. As shown in \u003cstrong\u003eFigure 2A\u003c/strong\u003e, the molar mass of resulting PPO samples could be controlled independently of the [PO] ratio to [\u003cstrong\u003eB4\u003c/strong\u003e] ratio. As expected, increasing the amount of CTA resulted in a decreased molar mass. On the other hand, an excellent control of molar mass could also be achieved for all samples prepared with a same [PO] to [CTA] ratio but varying loading of \u003cstrong\u003eB4\u003c/strong\u003e (\u003cstrong\u003eFigure 2B\u003c/strong\u003e). Notably, decreasing the \u003cstrong\u003eB4\u003c/strong\u003e loading had no obvious effect on the resulting molar mass of the samples obtained. Moreover, the GPC traces for all PPO samples exhibited symmetrical and narrow molar mass distributions (\u003cem\u003e\u0026ETH;\u003c/em\u003e\u0026lt; 1.10, \u003cstrong\u003eFigure S30\u003c/strong\u003e); the characterized molar masses were found very close to the expected values which were calculated upon taking into account the monomer conversion and the ratio of PO to the amount of BnOH and \u003cstrong\u003eB4\u003c/strong\u003e used. The above results revealed the remarkable advantages provided by the bifunctional ammonium salt \u003cstrong\u003eB4\u003c/strong\u003e for the preparation of polyols, allowing one to perfectly control the molar mass of the polyether samples synthesized using \u003cstrong\u003eB4\u003c/strong\u003e as a catalyst at ultralow loading. Compared to the industrial scale production of PPO diols relying on the use of DMC as catalyst, and necessitating oligomers or noncomplexing alcohols\u003csup\u003e39\u003c/sup\u003e as CTAs which tend to generate higher molar mass chains,\u003csup\u003e40, 41\u003c/sup\u003e the process catalyzed by \u003cstrong\u003eB4\u003c/strong\u003e not only affords sample free of any high molar mass contaminant, but it can also be carried out under much milder conditions, using standard protic CTAs to generate well-defined PPO diols.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eUltra low catalysts loading for polyols preparation with broad monomer scope\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAfter demonstrating that borinane-based ammonium salts are excellent catalysts for the ROP of various epoxides carried out in the presence of CTAs and for the preparation of \u0026omega;-functional low molar mass samples, we wanted to explore the catalytic limit of \u003cstrong\u003eB4\u003c/strong\u003e. Hence, the catalyst loading was thus decreased to 2 ppm to polymerize PO (\u003cstrong\u003eTable 2\u003c/strong\u003e, entry 3): yet a high reactivity characterized by a TOF value of 18,125 was observed with DBnOH as CTA. More interestingly, \u003cstrong\u003eB4\u003c/strong\u003e still showed a remarkable activity with a catalyst loading as low as 2 ppm (\u003cstrong\u003eTable 2\u003c/strong\u003e, entry 4) in the case of water as CTA and PO as monomer. In the latter case, the rate of polymerization was found to be slower in comparison with that measured using DBnOH as CTA but the TOF value was only divided by a factor of 2. With a view of exploring the catalytic limits of \u003cstrong\u003eB4\u003c/strong\u003e for the ROP of EO, the catalyst loading was further decreased to ppb level (\u003cstrong\u003eTable 2\u003c/strong\u003e, entry 6): in EO case TON and TOF values of 9\u0026times;10\u003csup\u003e6\u003c/sup\u003e and 1.9\u0026times;10\u003csup\u003e5\u003c/sup\u003e h\u003csup\u003e-1\u003c/sup\u003e were respectively measured, positioning \u003cstrong\u003eB4\u003c/strong\u003e as the most efficient catalyst ever synthesized for the synthesis of PEO telechelics. In other words, one gram of \u003cstrong\u003eB4\u003c/strong\u003e can produce no less than 606 kg PEO in 48h in the presence of CTA, which is an unrivalled value reached by any other catalyst. NMR spectra confirm the successful incorporation of CTA motifs into PEO diols (\u003cstrong\u003eFigure S31\u003c/strong\u003e-\u003cstrong\u003eS33\u003c/strong\u003e). Next, we evaluated the catalytic performance of \u003cstrong\u003eB4\u003c/strong\u003e with a broad range of epoxide monomers in the presence of water as CTA. In the case of epoxides substituted by long chains, namely butylene oxide (BO, \u003cstrong\u003eFigure S34\u003c/strong\u003e) and octene oxide (OO, \u003cstrong\u003eFigure S35\u003c/strong\u003e), negligible differences were observed between their rates of polymerization and that of PO. In contrast, the polymerization rate of allyl glycidyl ether (AGE, \u003cstrong\u003eFigure S36\u003c/strong\u003e) and phenyl glycidyl ether (PGE, \u003cstrong\u003eFigure S37\u003c/strong\u003e) were slower compared to that of PO likely because of the interaction of the extra oxygen atom carried by PGE and the double bond carried by AGE with the boron centers of \u003cstrong\u003eB4\u003c/strong\u003e. Nevertheless, the molar mass of all the diols obtained showed excellent agreement with the expected values; a narrow distribution of molar mass and no high molar mass impurities were observed (\u003cstrong\u003eFigure S3A\u003c/strong\u003e). \u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp style='margin-top:0in;margin-right:0in;margin-bottom:8.0pt;margin-left:0in;line-height:200%;font-size:16px;font-family:\"Times New Roman\",serif;text-align:justify;'\u003e\u003cstrong\u003e\u003cspan style=\"line-height:200%;\"\u003eTable 2\u003c/span\u003e\u003c/strong\u003e\u003cspan style=\"line-height:200%;\"\u003e. \u003cstrong\u003eB4\u003c/strong\u003e catalyzed ROP of epoxides for polyols in the presence of CTA.\u003csup\u003ea\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n\u003cdiv align=\"center\" style='margin-top:0in;margin-right:0in;margin-bottom:8.0pt;margin-left:0in;line-height:107%;font-size:16px;font-family:\"Times New Roman\",serif;'\u003e\n \u003ctable style=\"width: 5.2e+2pt;border: none;border-collapse:collapse;\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd style=\"width:21.3pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eEntry\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:35.45pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003emonomer\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:48.55pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:0in 0in 0in 0in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eCTA\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:1.25in;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eM:Cat:CTA\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:31.5pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eT (\u003c/span\u003e℃\u003cspan style=\"color:black;\"\u003e)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;border-top:solid black 1.5pt;border-left:none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eTime (h)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;border-top:solid black 1.5pt;border-left:none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eConv. (%)\u003csup\u003eb\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:45.0pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eTON\u003csup\u003ec\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:45.0pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eTOF\u003c/span\u003e\u003c/p\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e(h\u003csup\u003e-1\u003c/sup\u003e)\u003csup\u003ed\u003c/sup\u003e\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:50.65pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cem\u003e\u003cspan style=\"color:black;\"\u003eM\u003c/span\u003e\u003c/em\u003e\u003csub\u003e\u003cspan style=\"color:black;\"\u003en,thero.\u003c/span\u003e\u003c/sub\u003e\u003csup\u003e\u003cspan style=\"color:black;\"\u003ee\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e(kg/\u003c/span\u003emol\u003cspan style=\"color:black;\"\u003e)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:49.6pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cem\u003e\u003cspan style=\"color:black;\"\u003eM\u003c/span\u003e\u003c/em\u003e\u003csub\u003e\u003cspan style=\"color:black;\"\u003en,GPC\u003c/span\u003e\u003c/sub\u003e\u003csup\u003e\u003cspan style=\"color:black;\"\u003ef\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e(kg/\u003c/span\u003emol\u003cspan style=\"color:black;\"\u003e)\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:28.35pt;border-top:solid black 1.5pt;border-left: none;border-bottom:solid black 1.5pt;border-right:none;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cem\u003e\u003cspan style=\"color:black;\"\u003e\u0026ETH;\u003c/span\u003e\u003c/em\u003e\u003csup\u003e\u003cspan style=\"color:black;\"\u003ef\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width:21.3pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:35.45pt;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:48.55pt;padding:0in 0in 0in 0in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:1.25in;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e20000:1:250\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:31.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e25\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e4\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e95\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:45.0pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e19000\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:45.0pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e4750\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:50.65pt;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e4.4\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:49.6pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e4.8\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:28.35pt;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.03\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd style=\"width:21.3pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e2\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:35.45pt;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:48.55pt;padding:0in 0in 0in 0in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003ePEG4OH\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:1.25in;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e20000:1:250\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:31.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e25\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e3\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan 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style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e4.9\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:49.6pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e5.7\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:28.35pt;padding:.05in .05in .05in .05in;height: 1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.05\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n 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1.5pt;padding:0in 0in 0in 0in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:1.25in;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e5\u0026times;10\u003csup\u003e5\u003c/sup\u003e:1:25000\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:31.5pt;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e60\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e48\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:.5in;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e52\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:45.0pt;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e260000\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:45.0pt;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e5417\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:50.65pt;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.3\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:49.6pt;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.5\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd style=\"width:28.35pt;border:none;border-bottom:solid black 1.5pt;padding:.05in .05in .05in .05in;height:1.0pt;\"\u003e\n \u003cp style='margin-top:0in;margin-right:0in;margin-bottom:0in;margin-left:0in;line-height:normal;font-size:16px;font-family:\"Times New Roman\",serif;text-align:center;'\u003e\u003cspan style=\"color:black;\"\u003e1.05\u003c/span\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp style='margin-top:0in;margin-right:0in;margin-bottom:8.0pt;margin-left:0in;line-height:200%;font-size:16px;font-family:\"Times New Roman\",serif;text-align:justify;'\u003e\u003csup\u003e\u003cspan style=\"line-height:200%;\"\u003ea\u003c/span\u003e\u003c/sup\u003e\u003cspan style=\"line-height:200%;\"\u003e\u0026nbsp;Polymerizations were run in neat condition. \u003csup\u003eb\u003c/sup\u003e Conversion was determined by \u003csup\u003e1\u003c/sup\u003eH NMR. \u003csup\u003ec\u003c/sup\u003e Turnover number (TON) = moles of PO consumed/ moles of catalysts. \u003csup\u003ed\u003c/sup\u003e Turnover frequency (TOF) = TON/ time (h). \u003csup\u003ee\u003c/sup\u003e Determined by \u003csup\u003e1\u003c/sup\u003eH NMR. \u003csup\u003ef\u003c/sup\u003e Determined by GPC in THF using standard PEO as calibration.\u003c/span\u003e\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEffective ROP of oxetane\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe anionic ROP of oxetane has seldom been reported and the highest molar mass of polyoxetane ever obtained was limited to 19 kg/mol.\u003csup\u003e42, 43\u003c/sup\u003e. On the other hand, Amass and coworkers\u003csup\u003e44\u003c/sup\u003e reported a controlled/\u0026ldquo;living\u0026rdquo; cationic ROP of oxetane carried out in 1,4-dioxane using a specially synthesized initiator 3-phenoxypropyl1-oxonia-4-oxacyclohexane hexafluoroantimonate (3-PPOA): polyoxetane with molar mass up to 160 kg/mol, containing 10 % of cyclic oligomers and incorporating dioxane units were obtained. Due to its high basicity and low ring strain, the ROP of oxetane through either cationic or anionic mechanism and thus the synthesis of high molar mass polyoxetane are still a challenge. As shown in \u003cstrong\u003eTable S3\u003c/strong\u003e entry 3, \u003cstrong\u003eB4\u003c/strong\u003e catalyzed polymerization of oxetane (TMO) shows a TOF value 1000 times higher than that of last reported value obtained by anionic means\u003csup\u003e45\u003c/sup\u003e in 2018 (entry 5). Moreover, the polyoxetane sample obtained by the use of \u003cstrong\u003eB4\u003c/strong\u003e exhibited an unprecedented molar mass value of 600\u0026nbsp;kg/mol (\u003cstrong\u003eFigure 3B\u003c/strong\u003e). The experimental molar mass showed an excellent agreement with the expected value, indicating that the polymerization of oxetane is living when initiated by \u003cstrong\u003eB4\u003c/strong\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eChain end group fidelity\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eChain end group fidelity was confirmed by matrix-assisted laser desorption/ ionization time-of-flight (MALDI-TOF) mass spectrometry. The mass spectra of PPO (\u003cstrong\u003eFigure S38\u003c/strong\u003e) and PTMO (\u003cstrong\u003eFigure S39\u003c/strong\u003e) showed a single population indicating that chloride solely initiated polymerization in absence of CTA. Furthermore, in the presence of water as CTA only one single population (\u003cstrong\u003eFigure 3C\u003c/strong\u003e) is observed that appears to be in excellent agreement with the experimental mass obtained by GPC. The repeating intervals of 58 is in agreement with the molar mass of PO. Owing to the high ratio of CTA (water) to \u003cstrong\u003eB4\u003c/strong\u003e, the chloride initiated population was undetectable in spite of the single initiation nature by \u003cstrong\u003eB4\u003c/strong\u003e. Importantly, \u0026alpha;-allyloxy,\u0026omega;-OH PPO was not observed in MALDI-TOF, \u0026nbsp;indicating the absence of any chain transfer reaction to monomer in \u003cstrong\u003eB4\u003c/strong\u003e-catalyzed polymerization. Additionally, the absence of any hydrogen abstraction side reaction was also supported by \u003csup\u003e1\u003c/sup\u003eH NMR since no allyl group was observed (\u003cstrong\u003eFigure S19\u003c/strong\u003e). Finally, \u003cstrong\u003eB4\u003c/strong\u003e effectively produced \u0026alpha;-,\u0026omega;-diOH PPO and its molar mass was precisely controlled by the ratio of CTA: \u003cstrong\u003eB4\u003c/strong\u003e. The high fidelity of two primary hydroxyl ended PPO make this kind of diol precursors particularly valuable for high quality polyurethane preparation.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMechanism investigation\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eBoron centers in organoboron catalysts play a double role when used in the ROP of epoxides: 1) activate the latter monomers; 2) form growing \u0026ldquo;ate complexes\u0026rdquo; through their interaction with oxyanions. In such \u0026ldquo;ate complexes\u0026rdquo; the nucleophilicity of oxyanions is decreased which helps to prevent side reactions. Because boron centers in borinane are more accessible to monomers than with any other bulky boron, the overall activity of such catalysts is enhanced by at least one order of magnitude compared to the best-known catalysts. In addition, the ring opening of PO in the presence of these borinane-based bifunctional ammonium salts strictly happened at the methylene C‒O bond to produces regio-regular PPO as confirmed by the regioselective polymerization of chiral \u003cem\u003eS\u003c/em\u003e-PO (\u003cstrong\u003eFigure S40\u003c/strong\u003e). In the presence of CTA, no inhibition period is observed in the ROP of epoxides in the presence of borinane-based catalysts unlike other systems. In contrast, the binary system (TBACl/TEB) is inoperative when used for the ROP of epoxides in the presence of CTAs because of a low rate constant of initiation (k\u003csub\u003e1\u003c/sub\u003e)/propagation (k\u003csub\u003e3\u003c/sub\u003e) compared to the rate of exchange (k\u003csub\u003e2\u003c/sub\u003e). On the other hand, the synergistic effect in borinane-based bifunctional catalysts likely results in a slightly higher value of k\u003csub\u003e1\u003c/sub\u003e compared to k\u003csub\u003e2\u003c/sub\u003e (\u003cstrong\u003eFigure 4\u003c/strong\u003e) which enabled initiation. In addition, the k\u003csub\u003e3\u003c/sub\u003e certainly lower than k\u003csub\u003e2\u003c/sub\u003e which allows a precise control of molar masses through fast exchange between dormant and active species (boron-based ate complex, \u003cstrong\u003eFigure S41\u003c/strong\u003e), thus affording polyols with a narrow dispersity. The above features indicate that borinane-based ammonium salts behave as excellent catalysts for the ROP of epoxides carried out in the presence of CTAs. To gain a deeper insight into the mechanism of bifunctional catalysts mediated ROP, DFT computation was performed (\u003cstrong\u003eFigure 5\u003c/strong\u003e, \u003cstrong\u003eFigure S42\u003c/strong\u003e). The energy barrier of the initiation step (25.11 kcal/mol), INT1-TS1, is lower than that of exchange (28.15 kcal/mol, INT2-TS2) which indicates a slightly higher value of k\u003csub\u003e1\u003c/sub\u003e compared to that of k\u003csub\u003e2\u003c/sub\u003e, confirming the above proposed mechanism. Furthermore, the increased energy barrier observed between INT3 and TS3 (35.43 kcal/mol) provides sufficient room for exchange between active chains and dormant chains which resulted in well-defined polyols. This DFT study thus provides perfect understanding of the mechanism in borinane-based bifunctional catalysts mediated ROP.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this contribution, we described the rational design of a series of borinane-based bifunctional ammonium salts that proved to be excellent catalysts for the ROP of epoxides under mild conditions. Such bifunctional catalysts were synthesized by simple hydroboration of alkene ammonium salts using borinane in quantative yield. In the presence of these bifunctional catalysts the ROP of epoxides is living, no side reaction and in particular no transfer to monomer could be detected; these catalysts afford a highly regioselective ring-opening of epoxides producing stereoregular polyethers. Ultrahigh molar mass polyether of \u0026gt;\u0026thinsp;10\u003csup\u003e6\u003c/sup\u003e g/mol could be obtained with narrow distribution upon using these bifunctional catalysts. Record TOF values were reached for PO (1.8\u0026times;10\u003csup\u003e5\u003c/sup\u003e h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and EO (1.7\u0026times;10\u003csup\u003e6\u003c/sup\u003e h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), respectively. Significantly, the borinane-based bifunctional catalysts exhibit remarkable tolerance against various CTAs thus enabling the synthesis of polyols with precisely controlled molar mass and high end group fidelity using ppm level catalyst loading for PO and ppb level loading for EO. Moreover, an unprecedented productivity of 606 kg PEO/g \u003cb\u003eB4\u003c/b\u003e catalyst in 48 h in the presence of CTA was achieved with polymers of well-defined structure. In the presence of \u003cb\u003eB4\u003c/b\u003e, record values of TOF and of molar mass were reached for the ROP of oxetane. Finally, DFT computation gives a deep insight into the ROP of epoxides in the presence of these bifunctional catalysts and CTAs. Overall, such outstanding performance of these borinane-based bifunctional catalysts exhibit a great potential for an industrial preparation of polyols and can inspire the design of new generation of catalysts for effective ROP.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003eMaterials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll the reagents were purchased from Sigma-Aldrich and used as received unless otherwise stated. Triethylborane (TEB, 1 M in THF), 9-Borabicyclo[3.3.1]nonane (9-BBN, 0.4 M in Hexane), borane dimethyl sulfide complex (BMS), boron trifluoride diethyl etherate and 1,4-Pentadiene was used as received. Tetrabutylammonium chloride (TBAC) were purified by recrystallization from cold n-hexane three times and followed by drying under vacuum to remove the solvents. \u0026nbsp;The traces of water in the above ammonium salt were removed by drying under vacuum in the presence of P\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e for 2 days. Tributyl amine and 5-bromo-1-pentene were purified by distillation. Propylene oxide (PO), oxetane, 1-butylene oxide (BO), 1-ocene oxide (OO), allyl glycidyl ether (AGE) and \u0026nbsp;phenyl glycidyl ether (PGE) were purified by distilling firstly over CaH\u003csub\u003e2\u003c/sub\u003e and then over n-butyl lithium for two times using standard Schlenk technique. Ethylene oxide (EO) were purified by distilling over sodium. The purified monomers were stored in Schlenk flasks and kept in glovebox. Benzyl alcohol (BzOH), trifluoroethanol (TFE), propargyl alcohol (PA), 2-Hydroxyethyl acrylate (HEA), propylene glycol (PG), deionized water (H2O) and pentaerythritol ethoxylate (PEG4OH, average Mn ~797) were degassed via three times of freeze-pump-thaw procedure. 1,4-Benzenedimethanol (DBnOH) and 1,4-Benzenedimethanethiol (DBnSH) were used as received. 1,4-diazabicyclo[2.2.2]octane (DABCO) was purified by two times of sublimation and stored in glove box.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCharacterization\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNuclear magnetic resonance (NMR): \u003csup\u003e1\u003c/sup\u003eH, \u003csup\u003e11\u003c/sup\u003eB, \u003csup\u003e19\u003c/sup\u003eFand \u003csup\u003e13\u003c/sup\u003eC NMR spectra were recorded on a Bruker AVANCE III-400 Hz instrument in CDCl\u003csub\u003e3\u003c/sub\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eGel permeation chromatography (GPC): GPC traces were acquired on a VISCOTEK VE2001 system equipped with the Styragel HR2 THF and Styragel HR4 THF using THF (1 mL/min) as the eluent. The relative molar masses and distributions were obtained at 35\u0026nbsp;℃\u0026nbsp;using a RID detector and against linear polystyrene standards.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectra were \u0026nbsp;collected \u0026nbsp;on \u0026nbsp;an \u0026nbsp;Autoflex (Bruker) \u0026nbsp;mass \u0026nbsp;spectrometer. \u0026nbsp;The trans-2-[3-(4-t-butyl-phenyl)-2-methyl2-propenylidene] malononitrile (DCTB) was used as the matrix with a loading of 2:1 to sodium acetate which used as the ionizing agent.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of borinane\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003eThe six-membered cyclic borinane was synthesized as reported method.\u003csup\u003e46\u003c/sup\u003e A flame dried round bottom flask equipped with magnetic stir bar was cooled under vacuum and transferred to glove box. The flask was charged with 48.5 mL 9-BBN and 1 mL 1,4 pentadiene (9.7 mmol). The flask was stirred at room temperature in glove box overnight before adding 0.92 mL BMS. The reaction continued at room temperature for 24 h before anhydrous DABCO (0.54 g) THF solution was added to the above borane mixture solution. Borinane was immediately form complex with DABCO and precipitated. However, 9-BBN has no complexation with DABCO. In this case, pure borinane was separated with 9-BBN by filtration. And 9-BBN could be recycled for further reaction. The free borinane could be generated from the DABCO complex by reacting with boron trifluoride. The above solution was concentrated by distillation to yield pure borinane as white solid (0.76 g, 95% yield). Once the pure borinane was obtained, three moles of borinane could be easily generated from two moles of borinane (\u003cstrong\u003eScheme\u003c/strong\u003e \u003cstrong\u003eS1\u003c/strong\u003e) without further separation or purification procedure.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSynthesis of catalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAs shown in \u003cstrong\u003eScheme 1\u003c/strong\u003e, all the bifunctional catalysts were synthesized via the direct hydroboration of borinane with vinyl groups. All the solvents utilized in this reaction were carefully dried to afford high yield and eliminate side reaction.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eB4 mediated RD-ROP of PO\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe obtained bifunctional borinane catalyst (\u003cstrong\u003eB4\u003c/strong\u003e) was dissolved in THF to obtain a 1 M solution. And the solution was further diluted 100 times to afford a 0.01 M THF solution. A typical polymerization procedure which corresponding to \u003cstrong\u003eTable 2\u003c/strong\u003e, entry 3 was described as follows: \u0026nbsp;A flame dried Schlenk tube was transferred to glovebox. Then the tube was charged with 1 eq. \u003cstrong\u003eB4\u003c/strong\u003e (50 \u0026micro;L, 0.5 \u0026micro;mmol), 100 eq DBnOH (6.9 mg, 0.05 mmol) and 20000 eq. PO (0.7 mL, 10 mmol). The tube was stirred at room temperature for 30 min. The crude polymer was dried in vacuo at 50 \u0026deg;C to yield a vicious oil (0.58 g, 100% yield).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eWilms D, Stiriba S-E, Frey H. Hyperbranched Polyglycerols: From the Controlled Synthesis of Biocompatible Polyether Polyols to Multipurpose Applications. Acc Chem Res \u003cb\u003e43\u003c/b\u003e, 129\u0026ndash;141 (2010).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDimitrov I, Tsvetanov CB. 4.21 - High-Molecular-Weight Poly(ethylene oxide). In: \u003cem\u003ePolymer Science: A Comprehensive Reference\u003c/em\u003e (eds Matyjaszewski K, M\u0026ouml;ller M). Elsevier (2012).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBrocas A-L, Mantzaridis C, Tunc D, Carlotti S. Polyether synthesis: From activated or metal-free anionic ring-opening polymerization of epoxides to functionalization. Prog Polym Sci \u003cb\u003e38\u003c/b\u003e, 845\u0026ndash;873 (2013).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePohlit H, Bellinghausen I, Schomer M, Heydenreich B, Saloga J, Frey H. Biodegradable pH-Sensitive Poly(ethylene glycol) Nanocarriers for Allergen Encapsulation and Controlled Release. 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J Organomet Chem \u003cb\u003e250\u003c/b\u003e, 13\u0026ndash;22 (1983).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research work is supported by KAUST under baseline funding (BAS/1/1374-01-01).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eY.G. and X.F. directed the investigations, and revised the manuscript. C.C. carried out all experiments and analyses, and wrote the draft. All the authors participated in the discussions and revised the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupporting Information\u003c/strong\u003e. Details for synthesis of catalysts, and DFT computation. \u003csup\u003e1\u003c/sup\u003eH, \u003csup\u003e13\u003c/sup\u003eC, \u003csup\u003e19\u003c/sup\u003eF and \u003csup\u003e11\u003c/sup\u003eB NMR spectra and GPC Characterization data shown in \u003cstrong\u003eScheme S1\u003c/strong\u003e-\u003cstrong\u003eS3\u003c/strong\u003e, \u003cstrong\u003eTable S1-S2\u003c/strong\u003e, \u003cstrong\u003eFigure S1-S43\u003c/strong\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorresponding Author\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e* E-mail:\u0026nbsp;\u003ca href=\"mailto:[email protected]\"\[email protected]\u003c/a\u003e * E-mail: [email protected]\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003cbr\u003e\u0026nbsp;\u003c/strong\u003eThe authors declare no competing financial interests.\u003c/p\u003e"},{"header":"Schemes","content":"Scheme 1 is available in the supplementary files section."}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-1807966/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-1807966/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe design of reactive species that can either serve to initiate the ring-opening polymerization (ROP) of epoxides for the synthesis of high molar mass polyethers or be alternatively used to catalyze the synthesis of polyether telechelics in the presence of chain transfer agents (CTAs) has long been an elusive goal. Here we report the synthesis of a series of bifunctional borinane-based catalysts that enable the living ROP of epoxides with unprecedented activity (TOF\u0026thinsp;\u0026ge;\u0026thinsp;1.8\u0026times;10\u003csup\u003e5\u003c/sup\u003e h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and molar mass up to 10\u003csup\u003e6\u003c/sup\u003e g/mol under mild conditions. When used along with CTAs to generate low \u003cem\u003eM\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e telechelics, the same borinane-based catalysts exhibit ultrahigh productivity even for loading amounts as low as 50 ppb for ethylene oxide polymerization. These newly designed catalysts also afford the polymerization of oxetane with record TOF values and molar masses. DFT computation provides a full understanding of how these bifunctional catalysts operate when used in the ROP of epoxides.\u003c/p\u003e","manuscriptTitle":"Borinane Boosted Bifunctional Organocatalysts for Ultrafast Ring-Opening Polymerization of Cyclic Ethers","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2022-07-19 16:25:29","doi":"10.21203/rs.3.rs-1807966/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"6db57e7e-0f08-4d80-be1d-f661e235a145","owner":[],"postedDate":"July 19th, 2022","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2022-08-24T14:13:01+00:00","versionOfRecord":[],"versionCreatedAt":"2022-07-19 16:25:29","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-1807966","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1807966","identity":"rs-1807966","version":["v1"]},"buildId":"rHA-KDH7Qsr4HCuvH75dn","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}