Simultaneous and single-step syntheses of the random-graft copolymers formed using various vinyl monomers and lactones together with N-[tris(hydroxymethyl)methyl]acrylamide

Simultaneous and single-step syntheses of the random-graft copolymers formed using various vinyl monomers and lactones together with N-[tris(hydroxymethyl)methyl]acrylamide | 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 Research Article Simultaneous and single-step syntheses of the random-graft copolymers formed using various vinyl monomers and lactones together with N-[tris(hydroxymethyl)methyl]acrylamide Ergül Meyvacı, Temel Öztürk This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6369274/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 10 Dec, 2025 Read the published version in Polymer Bulletin → Version 1 posted 9 You are reading this latest preprint version Abstract Poly(methyl methacrylate-ra- N -[tris(hydroxymethyl)methyl]acrylamide-g-ε-caprorolactone) random-graft copolymer was obtained by simultaneous reaction in a single step using free-radical polymerization and ring-opening polymerization techniques. In the presence of 2,2'-azobisisobutyronitrile, N -[tris(hydroxymethyl)methyl]acrylamide and four different vinyl monomers (acrylamide, butyl methacrylate, methyl methacrylate, and styrene) were separately incorporated, and ε-caprolactone (or β-butyrolactone) was simultaneously grafted to the hydroxyl groups of the copolymer. The dependence of eight different graft copolymers on the monomer type was investigated by applying identical experimental parameters. The effects of the monomer type on the molecular weights and dispersity values were examined. The spectroscopic properties of the obtained products were determined using Fourier-transform infrared and proton-nuclear magnetic resonance spectroscopies, and their thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry techniques. The average molecular weights were defined using gel permeation chromatography. The morphological properties were examined with scanning electron microscope. Simultaneous and single-step polymerization random-graft copolymer N-[tris(hydroxymethyl)methyl]acrylamide free-radical polymerization ring-opening polymerization Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction Polylactones formed by the polymerization of cyclic esters have attracted attention due to their physical compatibility, biodegradability, biocompatibility, and miscibility with other polymers. [ 1 – 4 ] They have areas of use such as biomedical applications, tissue engineering, and drug delivery systems. Lactones such as ε-caprolactone (CL), β-butyrolactone (BL), and δ-valerolactone are important cyclic monomers. The most preferred method for the polymerization of these cyclic monomers is the ring-opening polymerization (ROP) method based on the release of monomer ring strain. [ 5 ] This process is a single-step polymerization catalyzed by metal complexes. [ 6 – 8 ] ROP is used in the polymerization of different types of cyclic monomers such as ethers, olefins, thioethers, lactones, thiolactones, amines, lactams, carbonates, disulfides, anhydrides, silicones, phosphonites, and phosphazenes. High molecular weight polymers with unique properties are formed. [ 9 ] In addition, the free-radical polymerization (FRP) method is an important classical method used in the formation of these high-property polymers. [ 10 , 11 ] Many polymers synthesized by these methods have been reported in the literature. [ 12 – 18 ] ROP follows anionic and cationic mechanisms. There are also methods such as metathesis, uncatalyzed ring-opening, and radical ring-opening. Polymerization of CL monomer occurs in the presence of tin(II) 2-ethylhexanoate (Sn(Oct) 2 ) catalyst. The complex makes a nucleophilic attack on carbon by reacting the R'OH compound containing a hydroxyl group with the lactone/Sn+(Oct) 2 complex, and thus the polymerization starts. After the coordination complex is formed, a new coordination type containing CL is formed again. Here, R' is the growing polymer chain. The catalyst is not attached to the end of the growing chain. [ 19 – 21 ] Poly(ε-caprolactone) (PCL) and poly(β-butyrolactone) (PBL) are polymers with superior properties obtained by ROP. In the literature, poly(CL-co-BL) polyurethane-based polymers have been synthesized and their mechanical and biodegradable properties have been investigated. [ 22 ] In this study, poly( N -[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-g-poly(ε-caprolactone) [P(TrisNHMAm-MMA)-PCL] and poly( N -[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-g-poly(β-butyrolactone) [P(TrisNHMAm-MMA)-PBL] random-graft copolymers were prepared by simultaneous reaction in a single-step using FRP and ROP techniques. 2. Experimental 2.1. Materials N -[tris(hydroxymethyl)methyl]acrylamide (TrisNHMAm) (Sigma-Aldrich, 93%), CL (AlfaAesar, 99%), BL (Sigma-Aldrich, 98%), 2,2' - azobisisobutyronitrile (AIBN) (Sigma-Aldrich, 98%), Sn(Oct) 2 (Sigma-Aldrich, 92.5–100.0%), titanium(IV) isopropoxide (Ti(OR) 4 ) (Sigma-Aldrich, 97%), acrylamide (AAm), butyl methacrylate (BMA) (Sigma-Aldrich, 99%), methyl methacrylate (MMA) (Sigma-Aldrich, 99%), styrene (S) (Sigma-Aldrich, 99%), diethyl ether (Merck), dimethyl sulfoxide (DMSO) (Merck), and other chemicals were used as purchased. An alumina column was used to exclude the inhibitors from BMA, S, and MMA vinyl monomers. 2.2. Instrumentation Proton-nuclear magnetic resonance ( 1 H-NMR) spectra were recorded using a Bruker Ultra Shield Plus, ultra-long hold time 400 MHz NMR spectrometer in chloroform-d. Fourier-transform infrared-attenuated total reflectance (FTIR-ATR) spectra were detected using a Jasco FT/IR 6600 FTIR spectrometer. Thermogravimetric analysis (TGA) was conducted using a Seiko II Exstar 6000 model instrument. The samples were heated at 10°C/min from 25°C to 600°C under nitrogen. Differential scanning analysis (DSC) was obtained using the Mettler Toledo TGA/DSC2 Star system. Scanning electron microscopy (SEM) images were taken on a Carl Zeiss Sigma 300 Field Emission electron microscope. The random-graft copolymer was covered by a thin gold plate. The average molecular weights and their dispersity were examined with Malvern VISCOTEK GPCmax; TGuard + 2xT6000M column model gel permeation chromatography (GPC) instrument with tetrahydrofuran mobile phase as the solvent at a rate of 1 mL/min using Viscotek VE3580 RI Detector. Mw values of polystyrene standards were 44800000, 1970000, 950000, 410000, 171000, 104401, 78200, 30100, 13700, 6220, 2630, and 1241 g/mol. 2.3. Synthesis of poly( N -[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-graft-poly(β-butyrolactone) [P(TrisNHMAm-MMA)-PBL] random-graft copolymer P(TrisNHMAm-MMA)-PBL random-graft copolymer was obtained by simultaneous reaction in a single step using FRP and ROP techniques. For this purpose, 15 mL of DMSO solvent and a magnetic stir bar were placed in a 250 mL glass flask. A trace amount of AIBN, 0.4525 gram of TrisNHMAm, 1 mL of MMA (or AAm or BMA or S), 5 mL of BL, and 2 drops of Ti(OR) 4 as the catalyst were added to this glass flask at the tip of a spatula to ensure dissolution of the flask content. The content of the flask was passed through nitrogen gas to provide an inert environment. Thermally, the mixture was provided at 100 ºC on a magnetic stirrer at 160 rpm for 10 hours. After this period, the flask was removed from the magnetic stirrer. The excess solvent in the flask was removed from the solution utilizing a rotary evaporator. The mixture was placed in a beaker, and then diethyl ether was added. In the meantime, it was mixed. It was covered with aluminum foil. It was kept in the refrigerator for 1 day, and the substance was allowed to precipitate. Then, after decanting, it was dried in an oven at 40 o C for 4 days. The synthesized product, P(TrisNHMAm-MMA)-PBL random-graft copolymer, was weighed. The yield was calculated. The reaction steps and synthesis parameters are shown in Scheme 1 and Table 1 , respectively. 2.4. Synthesis of poly( N -[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-graft-poly(ε-caprolactone) [ P(TrisNHMAm-MMA)-PCL ] random-graft copolymer P(TrisNHMAm-MMA)-PCL random-graft copolymer was obtained by simultaneous reaction in a single step using FRP and ROP techniques. For this purpose, 15 mL of DMSO solvent and a magnetic stir bar were placed in a 250 mL glass flask as shown in Table 1 . In this glass flask, a trace amount of AIBN, 0.4895 gram of TrisNHMAm, 1 mL of MMA (or AAm or BMA or S), 5 mL of CL, and 2 drops of Sn(Oct) 2 as a catalyst were added to the spatula tip, and the contents of the flask were dissolved. The following procedure was applied as in the synthesis of P(TrisNHMAm-MMA)-PBL random-graft copolymer. The copolymerization steps and synthesis parameters are shown in Scheme 2 and Table 2 , respectively. Table 1 Synthesis parameters of the random-graft copolymer including β-butyrolactone. Code TrisNHMAm (g) BL (mL) Monomer (1 mL) Product(g) Yield (wt. %) Mn,GPC (g/mol) Mw/Mn Poly 1 P(TrisNHMAm-AAm)-PBL 0.4196 5 AAm 4.7739 74.36 - - Poly 2 P(TrisNHMAm-BMA)-PBL 0.4674 5 BMA 4.1225 63.74 9627 3.06 Poly 3 P(TrisNHMAm-MMA)-PBL 0.4525 5 MMA 3.7965 58.83 6747 2.72 Poly 4 P(TrisNHMAm-S)-PBL 0.4748 5 S 1.2176 18.80 5928 2.92 Polymerization temperature: 100°C, polymerization time: 10 hours, DMSO: 15 mL, Ti(OR) 4 : 2 drops, a trace amount of AIBN. Table 2 Synthesis parameters of the random-graft copolymer including ε-caprolactone. Code TrisNHMAm (g) CL (mL) Monomer (1 mL) Product(g) Yield (wt. %) Mn,GPC (g/mol) Mw/Mn Poly 5 P(TrisNHMAm-AAm)-PCL 0.4341 5 AAm 4.8625 75.57 24461 1.78 Poly 6 P(TrisNHMAm-BMA)-PCL 0.4054 5 BMA 5.0073 78.17 12217 2.64 Poly 7 P(TrisNHMAm-MMA)-PCL 0.4895 5 MMA 3.9123 60.28 9819 1.90 Poly 8 P(TrisNHMAm-S)-PCL 0.4438 5 S 3.4519 53.56 8874 2.57 Polymerization temperature: 100°C, polymerization time: 10 hours, DMSO: 15 mL, Sn(Oct) 2 : 2 drops, a trace amount of AIBN. 3. Results and Discussion 3.1. Simultaneous and single-step synthesis of the random-graft copolymers The 1 H-NMR spectrum of P(TrisNHMAm-MMA)-PBL random-graft copolymer in Fig. 1 displayed signals at; (δ, ppm): 8.2 (-N H of poly( N -[tris(hydroxymethyl)methyl]acrylamide) [P(TrisNHMAm)] trace), 5.2 (-C H of PBL trace), 3.6 (-C H 2 of P(TrisNHMAm) trace), 3.4 (-OC H 3 of poly(methyl methacrylate) (PMMA) unit), 2.4 (-C H of P(TrisNHMAm) trace), 2.1–2.2 (-C H 2 of PBL trace), 1.8 (-OC H 2 of PMMA unit), 1.1 (-C H 2 of P(TrisNHMAm) trace and -C H 3 of PBL trace) and, 0.7–0.9 (-C H 3 of PMMA unit). 1 H-NMR of P(TrisNHMAm-AAM)-PBL coded in Table 1 1 H NMR (400 MHz, DMSO) δ 8.19 (s, 3H), 7.51 (d, J = 513.4 Hz, 7H), 12.91–5.83 (m, 13H), 12.91–5.12 (m, 22H), 4.30 (dd, J = 264.4, 7.3 Hz, 28H), 3.97 (d, J = 5.9 Hz, 3H), 3.90 (dt, J = 510.7, 172.4 Hz, 136H), 4.74–2.42 (m, 196H), 4.74–2.30 (m, 201H), 4.74–2.08 (m, 208H), 4.74–1.46 (m, 215H), 4.74–1.86 (m, 211H), 4.74–0.71 (m, 233H). 1 H-NMR of P(TrisNHMAm-BMA)-PBL coded in Table 1 1 H NMR (400 MHz, DMSO) δ 5.27–5.11 (m, 9H), 4.63 (dt, J = 11.4, 7.7 Hz, 4H), 4.18–3.93 (m, 12H), 2.77–2.63 (m, 7H), 3.93–1.77 (m, 188H), 2.59–2.14 (m, 100H), 2.98–1.77 (m, 127H), 1.86 (dd, J = 18.4, 6.9 Hz, 2H), 2.13 – -2.47 (m, 64H), 1.93 – -2.47 (m, 57H), 1.47–1.20 (m, 10H), 1.24 (dd, J = 16.4, 8.5 Hz, 6H), 1.29–0.92 (m, 33H), 0.84 (d, J = 56.3 Hz, 6H), 0.59 – -2.81 (m, 4H). 1 H-NMR of P(TrisNHMAm-S)-PBL coded in Table 1 1 H NMR (400 MHz, DMSO) δ 8.60–7.61 (m, 1H), 7.52–6.77 (m, 12H), 6.58 (s, 5H), 5.40–4.87 (m, 4H), 4.80–4.41 (m, 2H), 4.41–3.84 (m, 3H), 3.50 (d, J = 96.1 Hz, 5H), 2.83–2.47 (m, 9H), 2.44–2.35 (m, 2H), 2.27–2.10 (m, 5H), 1.99 (d, J = 61.5 Hz, 3H), 1.83 (s, 3H), 1.53–1.33 (m, 3H), 1.55–0.88 (m, 12H). 1 H-NMR of P(TrisNHMAm-AAm)-PCL coded in Table 2 1 H NMR (400 MHz, DMSO) δ 8.07–6.02 (m, 3H), 4.18 (s, 10H), 3.66 (d, J = 238.8 Hz, 57H), 3.36–3.21 (m, 2H), 2.96 (d, J = 8.8 Hz, 3H), 3.36–2.63 (m, 4H), 2.55 (s, 34H), 2.55 (s, 58H), 1.67 (d, J = 10.6 Hz, 8H), 3.36–0.28 (m, 131H), 3.21–0.28 (m, 129H), 3.36–0.48 (m, 131H), 1.57 (d, J = 9.1 Hz, 4H), 1.56 (s, 2H), 1.51 (s, 21H), 2.07–0.48 (m, 59H), 1.58–0.77 (m, 45H). 1 H-NMR of P(TrisNHMAm-BMA)-PCL coded in Table 2 1 H NMR (400 MHz, DMSO) δ 4.50–4.15 (m, 3H), 4.25–4.15 (m, 2H), 4.19 (dd, J = 23.0, 18.4 Hz, 2H), 3.98 (d, J = 5.8 Hz, 2H), 3.90 (s, 1H), 3.40 (s, 69H), 2.72–2.43 (m, 46H), 2.24–1.09 (m, 35H), 2.40–0.50 (m, 47H), 1.51 (tddd, J = 52.8, 46.7, 38.3, 30.6 Hz, 31H), 2.25–0.50 (m, 43H), 1.90–0.65 (m, 39H), 1.24–0.65 (m, 10H), 1.24–0.50 (m, 10H). 1 H-NMR of P(TrisNHMAm-MMA)-PCL coded in Table 2 1 H NMR (400 MHz, DMSO) δ 4.85 (s, 6H), 4.35 (d, J = 27.0 Hz, 37H), 3.95 (t, J = 110.5 Hz, 114H), 3.62 (s, 16H), 3.47 (d, J = 57.3 Hz, 575H), 2.46 (t, J = 44.5 Hz, 150H), 2.33–1.47 (m, 388H), 1.53 (s, 176H), 1.53 (s, 141H), 1.41 (s, 41H), 1.29 (s, 51H), 1.14 (d, J = 17.3 Hz, 25H), 0.94–0.71 (m, 131H), 0.71–0.14 (m, 40H). 1 H-NMR of P(TrisNHMAm-S)-PCL coded in Table 2 1 H NMR (400 MHz, DMSO) δ 7.94 (d, J = 101.6 Hz, 4H), 7.82 (t, J = 92.5 Hz, 7H), 7.73 (dd, J = 157.0, 72.5 Hz, 9H), 8.32–5.80 (m, 132H), 6.00–4.68 (m, 9H), 5.42 (ddd, J = 122.8, 109.9, 27.0 Hz, 5H), 4.91 (s, 4H), 4.48 (dd, J = 135.5, 114.1 Hz, 18H), 4.28–3.70 (m, 37H), 3.70–3.57 (m, 5H), 3.49 (d, J = 83.9 Hz, 50H), 3.63–2.85 (m, 62H), 3.63–2.74 (m, 65H), 3.63–2.40 (m, 138H), 3.63–2.23 (m, 159H), 3.63–2.16 (m, 167H), 3.63–1.65 (m, 243H), 1.60 (s, 26H), 1.52 (s, 33H), 1.47–1.39 (m, 23H), 1.12 (d, J = 135.2 Hz, 43H), 0.85 (d, J = 4.4 Hz, 16H). The FT-IR spectra of the random-graft copolymers synthesized in Table 1 are shown in Fig. 2 . In the FT-IR spectrum of P(TrisNHMAm-AAm)-PBL (Poly 1), peaks of N-H at 3333 cm − 1 , asymmetric aliphatic C-H at 2932 cm − 1 , amide C = O at 1659 cm − 1 , and etheric O-C groups at 1188 cm − 1 are observed. In the FT-IR spectrum of P(TrisNHMAm-BMA)-PBL (Poly 2), peaks of asymmetric aliphatic C-H at 2955 cm − 1 , ester C = O at 1721 cm − 1 , and etheric O-C groups at 1150 cm − 1 are observed. In the FT-IR spectrum of P(TrisNHMAm-MMA)-PBL (Poly 3), asymmetric aliphatic C-H at 2924 cm − 1 , ester C = O at 1728 cm − 1 , etheric O-C groups peaks at 1150 cm − 1 are observed. In the FT-IR spectrum of P(TrisNHMAm-S)-PBL (Poly 4), asymmetric aliphatic C-H at 2924 cm − 1 , ester C = O at 1736 cm − 1 , etheric O-C at 1165 cm − 1 , and aromatic C-H groups peaks at 756 cm − 1 are observed. The FT-IR spectra of the random-graft copolymers synthesized in Table 2 are shown in Fig. 3 . In the FT-IR spectrum of P(TrisNHMAm-AAm)-PCL (Poly 5), N-H peaks are observed at 3379 cm − 1 , asymmetric aliphatic C-H at 2932 cm − 1 , ester C = O at 1721 cm − 1 , amide C = O at 1667 cm − 1 , and ethereal O-C groups peaks are observed at 1165 cm − 1 . In the FT-IR spectrum of P(TrisNHMAm-BMA)-PCL (Poly 6), N-H peaks are observed at 3372 cm − 1 , asymmetric aliphatic C-H at 2940 cm − 1 , ester C = O at 1721 cm − 1 , amide C = O at 1667 cm − 1 , and ethereal O-C groups peaks are observed at 1157 cm − 1 . In the FT-IR spectrum of P(TrisNHMAm-MMA)-PCL (Poly 7), peaks of N-H at 3372 cm − 1 , asymmetric aliphatic C-H at 2940 cm − 1 , ester C = O at 1721 cm − 1 , and ethereal O-C groups at 1159 cm − 1 are observed. In the FT-IR spectrum of P(TrisNHMAm-S)-PCL (Poly 8), peaks of asymmetric aliphatic C-H at 2932 cm − 1 , ester C = O at 1728 cm − 1 , ethereal O-C at 1165 cm − 1 , and aromatic C-H groups at 756 cm − 1 are observed. The GPC curves of the random-graft copolymers are shown in Fig. 4 . In the reactions performed in Tables 1 and 2 , it was seen that the highest Mn value (Mn = 24461 g/mol) was the reaction performed with AAm monomer. The lowest dispersity value (1.78) was obtained in the experiment performed with AAm monomer. The use of TrisNHMAm and AAm monomers together can be shown to provide more stable results. TGA thermograms of P(TrisNHMAm-MMA)-PBL and P(TrisNHMAm-MMA)-PCL random-graft copolymers are given in Fig. 5 . Derivative thermograms show that the thermal decompositions of the random-graft copolymers occur in multiple steps. It is known that PMMA undergoes maximum decomposition at 405°C, [ 23 ] PBL at 191°C, and PCL at 389°C. [ 24 ] The first mass loss can be related to the evaporation of the solvents in the sample. In Fig. 5 (a), the mass loss of the P(TrisNHMAm-MMA)-PBL sample can be divided into three main parts. The first demonstrated continuous weight loss from about 77°C to nearly 230°C with maxima at 169°C with 40.5% weight loss (decomposition of PBL units). The second demonstrated a continuous slight weight loss from about 230°C to nearly 274°C with maxima at 248°C with 7.0% weight loss (degradation of PTrisNHMAm units). Thirdly, continuous weight loss was demonstrated, from about 274°C to nearly 455°C, with maxima at 380°C and 42.4% weight loss (degradation of PMMA units). In Fig. 5 (b), the mass loss of the P(TrisNHMAm-MMA)-PCL sample can also be divided into three main parts. The first demonstrated continuous slight weight loss from about 208°C to nearly 248°C with maxima at 230°C with 6.0% weight loss (degradation of PTrisNHMAm units). The second demonstrated a continuous weight loss from about 248°C to nearly 330°C with maxima at 303°C with 23.4% weight loss (decomposition of PBL units). Thirdly, continuous weight loss was demonstrated, from about 330°C to nearly 447°C, with maxima at 378°C and 44.2% (wt.) weight loss (decomposition of PMMA units). A small additional weight loss of PTrisNHMAm units is to be expected. These TGA thermograms show that P(TrisNHMAm-MMA)-PBL has lower thermal stability than P(TrisNHMAm-MMA)-PCL. DSC thermogram of P(TrisNHMAm-MMA)-PCL random-graft copolymer is given in Fig. 6 . The glass transition temperature (Tg) of the random-graft copolymer was obtained as 7 o C. The Tg value of PMMA is 100 o C [ 10 , 25 ] and that of PCL is -60 o C. [ 26 ] The fact that the Tg value of the copolymer is between the Tg values ​​of the blocks that form it can be interpreted as the compatibility of these blocks with each other. SEM photos of the random-graft copolymers were taken to examine their surface morphologies and are given in Figs. 7 and 8 . The copolymers obtained using different monomers exhibited significantly different morphologies in terms of surface shape. However, all copolymers were relatively in a homogeneous phase. The surface of the P(TrisNHMAm-AAm)-PBL (A) random-graft copolymer has an aggregated cauliflower structure. [ 27 – 29 ] In Fig. 8 , it was observed that the random-graft copolymers coded with P(TrisNHMAm-AAm)-PCL (E) and P(TrisNHMAm-MMA)-PCL (G) formed a curved flat surface, creating a continuous phase. The surfaces of the polymers coded P(TrisNHMAm-BMA)-PBL (B), P(TrisNHMAm-MMA)-PBL (C), P(TrisNHMAm-S)-PBL 2000 X (D), P(TrisNHMAm-BMA)-PCL (F) and P(TrisNHMAm-S)-PCL (H) exhibited a curved surface forming a continuous phase. [ 30 ] 4. Conclusions The random-graft copolymers formed using TrisNHMAm, various vinyl monomers, and lactones were successfully synthesized simultaneously and in a single step using FRP and ROP techniques. In these simultaneous reactions, varying parameters were investigated using different monomers. Significant changes were observed in values ​​such as yield, morphological properties, molecular weights, and decomposition temperatures. The most stable results were determined to be the random-graft copolymer formed with AAm monomer. It is thought that the presence of biodegradable PCL and PBL units, compatible with many materials in the structure of the random-graft copolymer, increases the advantages of the synthesized polymers. Declarations Conflict of Interest None. Author Contribution Temel Öztürk and Ergül Meyvacı wrote the main manuscript text. Ergül Meyvacı prepared all figures, schemes and tables. All authors reviewed the manuscript. Acknowledgement This work was supported by the Giresun University Scientific Research Projects Coordination Unit (project number: FEN-BAP-A-290224-44) References Fortelny, I., Ujcic, A., Fambri, L., Slouf, M. (2019). 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Ovidius University Annals of Chemistry , 33 (1), 17-22. Meyvacı, E., Öztürk, T., Savaş, B. (2021). Syntheses and characterizations of poly (ε-caprolactone-b-ethylene glycol methyl ether) block copolymers via ring-opening polymerization and "click" chemistry. Journal of the Institute of Science and Technology , 11 (2), 1329-1340. Çatıker, E., Öztürk, T., Atakay, M., Salih, B. (2020). Synthesis and characterization of the ABA-type poly (ester-ether-ester) block copolymers. Journal of Macromolecular Science, Part A , 57 (8), 600-609. Penczek, S., Kubisa, P., Matyjaszewski, K. (Eds.). (1985). Cationic Ring-Opening Polymerization: 2. Synthetic Applications . Berlin, Heidelberg: Springer Berlin Heidelberg. Penczek, S., Slomkowski, S. (1987). Progress in anionic ring-opening polymerization. In Recent Advances in Anionic Polymerization: Proceedings of the International Symposium on Recent Advances in Anionic Polymerization, April 13–18, 1986 at the American Chemical Society Meeting in New York, New York, USA , Springer, Netherlands, pp. 275-295. Nakayama, A., Kawasaki, N., Arvanitoyannis, I., Aiba, S., Yamamoto, N. (1996). Synthesis and biodegradation of poly (γ-butyrolactone-co-L-lactide). Journal of environmental polymer degradation , 4 , 205-211. Hong, J. H., Jeon, H. J., Yoo, J. H., Yu, W. R., Youk, J. H. (2007). Synthesis and characterization of biodegradable poly (ɛ-caprolactone-co-β-butyrolactone)-based polyurethane. Polymer Degradation and Stability , 92 (7), 1186-1192. Balci, Z., Akbulut, U., Toppare, L., Alkan, S., Bakir, U., Yagci, Y. (2002). Immobilization of yeast cells in several conducting polymer matrices. Journal of Macromolecular Science, Part A , 39 (3), 183-197. Monsalve, M., Contreras, J. M., Laredo, E., López-Carrasquero, F. (2010). Ring-opening copolymerization of (R, S)-β-butyrolactone and ε-caprolactone using sodium hydride as initiator. Express Polym. Lett , 4 (7), 431-441. Brandrup, J., Immergut, E. H. (1975) Polymer handbook, 2nd edn. New York, Wiley. Munsch, M. (2017) Laser additive manufacturing of customized prosthetics and implants for biomedical applications. Ed: Brandt, M., In: Woodhead Publishing Series in Electronic and Optical Materials, Laser Additive Manufacturing , Woodhead Publishing, pp 399-420. Bozkurt, A., Ercelebi, C., Toppare, L. (1997). Electronic properties of polypyrrole/polyindene composite/metal junctions. Synthetic Metals , 87 (3), 219-223. Kizilyar, N., Toppare, L., Önen, A., Yağci, Y. (1999). Synthesis of conducting PPy/pTHF copolymers. Journal of Applied Polymer Science , 71 (5), 713-720. Goel, S., Mazumdar, N. A., Gupta, A. (2010). Synthesis and characterization of poly (indene‐co‐pyrrole) nanofibers. Polymers for Advanced Technologies , 21 (12), 888-895. Engin, M. S., Sayın, S., Çay, S. (2021). Yeni kaliks[4] aren-içeren polimerik membranların hazırlanması, karakterizasyonu ve uygulamaları. Karadeniz Fen Bilimleri Dergisi , 11 (2), 533-543. Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 10 Dec, 2025 Read the published version in Polymer Bulletin → Version 1 posted Editorial decision: Revision requested 28 Jul, 2025 Reviews received at journal 10 Jul, 2025 Reviews received at journal 24 Jun, 2025 Reviewers agreed at journal 13 Jun, 2025 Reviewers agreed at journal 11 Jun, 2025 Reviewers invited by journal 10 Jun, 2025 Editor assigned by journal 11 Apr, 2025 Submission checks completed at journal 03 Apr, 2025 First submitted to journal 03 Apr, 2025 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. 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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-6369274","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":469962712,"identity":"48b3867b-6b68-4492-939e-bba2f79e6829","order_by":0,"name":"Ergül Meyvacı","email":"","orcid":"","institution":"Giresun University","correspondingAuthor":false,"prefix":"","firstName":"Ergül","middleName":"","lastName":"Meyvacı","suffix":""},{"id":469962717,"identity":"b0b938e7-a215-4c20-b94e-f00c7875adf9","order_by":1,"name":"Temel Öztürk","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAy0lEQVRIiWNgGAWjYLCCB2CSjfEBUap5QEQCA4MEUAuzAcla2CSI0mLP3p34IKGirs7g9rG0qht/7jDwt3cn4LeF5+xmg4QzbBIG59KO3c5te8YgcebsBvxaJHK3SSS28UgYnGFvu53bcJjBQCKXgBb5t9t/JLZJgLUU5/whRosE7zaGxDYDoBa2Y8w5bMRoOZO7WSLhTILkzDNsydK5bYd5CPqFvf3sxg8fKur4+c6wGX4GOkyOv70XvxZMa0lTPgpGwSgYBaMAKwAA9lZE7CLksXIAAAAASUVORK5CYII=","orcid":"","institution":"Giresun University","correspondingAuthor":true,"prefix":"","firstName":"Temel","middleName":"","lastName":"Öztürk","suffix":""}],"badges":[],"createdAt":"2025-04-03 12:23:24","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6369274/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6369274/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00289-025-06177-5","type":"published","date":"2025-12-10T15:57:59+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":84481572,"identity":"85df4fab-998c-4383-a5bd-04f8db96bbcf","added_by":"auto","created_at":"2025-06-12 12:40:52","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":97652,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR spectrum of P(TrisNHMAm-MMA)-PBL coded in Table 1.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/60eec893f745ffc8932e09f1.png"},{"id":84482029,"identity":"7632ff2d-57a9-4c69-8d75-ecea5652a308","added_by":"auto","created_at":"2025-06-12 12:48:52","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":178740,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of (Poly 1) P(TrisNHMAm-AAm)-PBL coded in Table 1; (Poly 2) P(TrisNHMAm-BMA)-PBL coded in Table 1; (Poly 3) P(TrisNHMAm-MMA)-PBL coded in Table 1; (Poly 4) P(TrisNHMAm-S)-PBL coded in Table 1.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/9821c5eb5642e82a4c2d22f8.png"},{"id":84481573,"identity":"9d1f0cbb-baf5-4be3-9cd0-d42d0e024caa","added_by":"auto","created_at":"2025-06-12 12:40:52","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":158352,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of (Poly 5) P(TrisNHMAm-AAm)-PCL coded in Table 2; (Poly 6) P(TrisNHMAm-BMA)-PCL coded in Table 2; (Poly 7) P(TrisNHMAm-MMA)-PCL coded in Table 2; (Poly 8) P(TrisNHMAm-S)-PCL coded in Table 2.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/ee677fa6ab927a836bdb46b5.png"},{"id":84481579,"identity":"b04a6c7f-ba7f-4f3b-a6e0-53f662043b19","added_by":"auto","created_at":"2025-06-12 12:40:53","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":121727,"visible":true,"origin":"","legend":"\u003cp\u003eGPC curves of (a) P(TrisNHMAm-BMA)-PBL, (b) P(TrisNHMAm-MMA)-PBL, and (c) P(TrisNHMAm-S)-PBL in Table 1.\u003cstrong\u003e \u003c/strong\u003eGPC curve of (d) P(TrisNHMAm-AAm)-PCL in Table 2.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/3e302ab4050dc89bae691e9f.png"},{"id":84481583,"identity":"9e11e376-a316-4e45-b027-fd4e63ef9946","added_by":"auto","created_at":"2025-06-12 12:40:53","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":111450,"visible":true,"origin":"","legend":"\u003cp\u003eTGA curves of the (a) P(TrisNHMAm-MMA)-PBL in Table 1; (b) P(TrisNHMAm-MMA)-PCL in Table 2.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/c1db82889351acd4cbb43b00.png"},{"id":84483021,"identity":"4b70b2a4-3c95-4780-beb1-97ee955c522e","added_by":"auto","created_at":"2025-06-12 12:56:53","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":39268,"visible":true,"origin":"","legend":"\u003cp\u003eDSC thermogram of the P(TrisNHMAm-MMA)-PCL in Table 2.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/be8fe688e9be6ba6460f3d94.png"},{"id":84481589,"identity":"07b5e0bf-6fca-4325-bf2d-09890d64e7fd","added_by":"auto","created_at":"2025-06-12 12:40:53","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":1214798,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of P(TrisNHMAm-AAm)-PBL 2000X (A), P(TrisNHMAm-BMA)-PBL 100X (B), P(TrisNHMAm-MMA)-PBL 500X (C), P(TrisNHMAm-S)-PBL 2000X (D) coded in Table 1.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/ec47144876d3f981d0a9a502.png"},{"id":84482035,"identity":"9178312e-67e1-49de-8626-cd110814bd76","added_by":"auto","created_at":"2025-06-12 12:48:53","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":950565,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of P(TrisNHMAm-AAm)-PCL 1000X (E), P(TrisNHMAm-BMA)-PCL 500X (F), P(TrisNHMAm-MMA)-PCL 500X (G), P(TrisNHMAm-S)-PCL 200X (H) coded in Table 2.\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/bb43abc9b6cbcc9dac09586b.png"},{"id":98243712,"identity":"abb10565-fd43-4ead-bc23-35ef26a7a044","added_by":"auto","created_at":"2025-12-15 16:10:05","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3596828,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6369274/v1/719cbbc1-7c2c-4c0d-956c-849811563ca7.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Simultaneous and single-step syntheses of the random-graft copolymers formed using various vinyl monomers and lactones together with N-[tris(hydroxymethyl)methyl]acrylamide","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ePolylactones formed by the polymerization of cyclic esters have attracted attention due to their physical compatibility, biodegradability, biocompatibility, and miscibility with other polymers.\u003csup\u003e[\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]\u003c/sup\u003e They have areas of use such as biomedical applications, tissue engineering, and drug delivery systems. Lactones such as ε-caprolactone (CL), β-butyrolactone (BL), and δ-valerolactone are important cyclic monomers. The most preferred method for the polymerization of these cyclic monomers is the ring-opening polymerization (ROP) method based on the release of monomer ring strain.\u003csup\u003e[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]\u003c/sup\u003e This process is a single-step polymerization catalyzed by metal complexes.\u003csup\u003e[\u003cspan additionalcitationids=\"CR7\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]\u003c/sup\u003e ROP is used in the polymerization of different types of cyclic monomers such as ethers, olefins, thioethers, lactones, thiolactones, amines, lactams, carbonates, disulfides, anhydrides, silicones, phosphonites, and phosphazenes. High molecular weight polymers with unique properties are formed.\u003csup\u003e[\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]\u003c/sup\u003e In addition, the free-radical polymerization (FRP) method is an important classical method used in the formation of these high-property polymers.\u003csup\u003e[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]\u003c/sup\u003e Many polymers synthesized by these methods have been reported in the literature.\u003csup\u003e[\u003cspan additionalcitationids=\"CR13 CR14 CR15 CR16 CR17\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]\u003c/sup\u003e ROP follows anionic and cationic mechanisms. There are also methods such as metathesis, uncatalyzed ring-opening, and radical ring-opening. Polymerization of CL monomer occurs in the presence of tin(II) 2-ethylhexanoate (Sn(Oct)\u003csub\u003e2\u003c/sub\u003e) catalyst. The complex makes a nucleophilic attack on carbon by reacting the R'OH compound containing a hydroxyl group with the lactone/Sn+(Oct)\u003csub\u003e2\u003c/sub\u003e complex, and thus the polymerization starts. After the coordination complex is formed, a new coordination type containing CL is formed again. Here, R' is the growing polymer chain. The catalyst is not attached to the end of the growing chain.\u003csup\u003e[\u003cspan additionalcitationids=\"CR20\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/sup\u003e Poly(ε-caprolactone) (PCL) and poly(β-butyrolactone) (PBL) are polymers with superior properties obtained by ROP. In the literature, poly(CL-co-BL) polyurethane-based polymers have been synthesized and their mechanical and biodegradable properties have been investigated.\u003csup\u003e[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eIn this study, poly(\u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-g-poly(ε-caprolactone) [P(TrisNHMAm-MMA)-PCL] and poly(\u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-g-poly(β-butyrolactone) [P(TrisNHMAm-MMA)-PBL] random-graft copolymers were prepared by simultaneous reaction in a single-step using FRP and ROP techniques.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials\u003c/h2\u003e \u003cp\u003e \u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide (TrisNHMAm) (Sigma-Aldrich, 93%), CL (AlfaAesar, 99%), BL (Sigma-Aldrich, 98%), 2,2'\u003cb\u003e-\u003c/b\u003eazobisisobutyronitrile (AIBN) (Sigma-Aldrich, 98%), Sn(Oct)\u003csub\u003e2\u003c/sub\u003e (Sigma-Aldrich, 92.5\u0026ndash;100.0%), titanium(IV) isopropoxide (Ti(OR)\u003csub\u003e4\u003c/sub\u003e) (Sigma-Aldrich, 97%), acrylamide (AAm), butyl methacrylate (BMA) (Sigma-Aldrich, 99%), methyl methacrylate (MMA) (Sigma-Aldrich, 99%), styrene (S) (Sigma-Aldrich, 99%), diethyl ether (Merck), dimethyl sulfoxide (DMSO) (Merck), and other chemicals were used as purchased. An alumina column was used to exclude the inhibitors from BMA, S, and MMA vinyl monomers.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Instrumentation\u003c/h2\u003e \u003cp\u003eProton-nuclear magnetic resonance (\u003csup\u003e1\u003c/sup\u003eH-NMR) spectra were recorded using a Bruker Ultra Shield Plus, ultra-long hold time 400 MHz NMR spectrometer in chloroform-d. Fourier-transform infrared-attenuated total reflectance (FTIR-ATR) spectra were detected using a Jasco FT/IR 6600 FTIR spectrometer. Thermogravimetric analysis (TGA) was conducted using a Seiko II Exstar 6000 model instrument. The samples were heated at 10\u0026deg;C/min from 25\u0026deg;C to 600\u0026deg;C under nitrogen. Differential scanning analysis (DSC) was obtained using the Mettler Toledo TGA/DSC2 Star system. Scanning electron microscopy (SEM) images were taken on a Carl Zeiss Sigma 300 Field Emission electron microscope. The random-graft copolymer was covered by a thin gold plate. The average molecular weights and their dispersity were examined with Malvern VISCOTEK GPCmax; TGuard\u0026thinsp;+\u0026thinsp;2xT6000M column model gel permeation chromatography (GPC) instrument with tetrahydrofuran mobile phase as the solvent at a rate of 1 mL/min using Viscotek VE3580 RI Detector. Mw values of polystyrene standards were 44800000, 1970000, 950000, 410000, 171000, 104401, 78200, 30100, 13700, 6220, 2630, and 1241 g/mol.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Synthesis of poly(\u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-graft-poly(β-butyrolactone) [P(TrisNHMAm-MMA)-PBL] random-graft copolymer\u003c/h2\u003e \u003cp\u003eP(TrisNHMAm-MMA)-PBL random-graft copolymer was obtained by simultaneous reaction in a single step using FRP and ROP techniques. For this purpose, 15 mL of DMSO solvent and a magnetic stir bar were placed in a 250 mL glass flask. A trace amount of AIBN, 0.4525 gram of TrisNHMAm, 1 mL of MMA (or AAm or BMA or S), 5 mL of BL, and 2 drops of Ti(OR)\u003csub\u003e4\u003c/sub\u003e as the catalyst were added to this glass flask at the tip of a spatula to ensure dissolution of the flask content. The content of the flask was passed through nitrogen gas to provide an inert environment. Thermally, the mixture was provided at 100 \u0026ordm;C on a magnetic stirrer at 160 rpm for 10 hours. After this period, the flask was removed from the magnetic stirrer. The excess solvent in the flask was removed from the solution utilizing a rotary evaporator. The mixture was placed in a beaker, and then diethyl ether was added. In the meantime, it was mixed. It was covered with aluminum foil. It was kept in the refrigerator for 1 day, and the substance was allowed to precipitate. Then, after decanting, it was dried in an oven at 40 \u003csup\u003eo\u003c/sup\u003eC for 4 days. The synthesized product, P(TrisNHMAm-MMA)-PBL random-graft copolymer, was weighed. The yield was calculated. The reaction steps and synthesis parameters are shown in Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e\u003cb\u003e2.4. Synthesis of poly(\u003c/b\u003e\u003cb\u003eN\u003c/b\u003e\u003cb\u003e-[tris(hydroxymethyl)methyl]acrylamide-ra-methyl methacrylate)-graft-poly(ε-caprolactone)\u003c/b\u003e [\u003cb\u003eP(TrisNHMAm-MMA)-PCL\u003c/b\u003e] \u003cb\u003erandom-graft copolymer\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eP(TrisNHMAm-MMA)-PCL random-graft copolymer was obtained by simultaneous reaction in a single step using FRP and ROP techniques. For this purpose, 15 mL of DMSO solvent and a magnetic stir bar were placed in a 250 mL glass flask as shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. In this glass flask, a trace amount of AIBN, 0.4895 gram of TrisNHMAm, 1 mL of MMA (or AAm or BMA or S), 5 mL of CL, and 2 drops of Sn(Oct)\u003csub\u003e2\u003c/sub\u003e as a catalyst were added to the spatula tip, and the contents of the flask were dissolved. The following procedure was applied as in the synthesis of P(TrisNHMAm-MMA)-PBL random-graft copolymer. The copolymerization steps and synthesis parameters are shown in Scheme \u003cspan refid=\"Sch2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSynthesis parameters of the random-graft copolymer including β-butyrolactone.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"9\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCode\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTrisNHMAm\u003c/p\u003e \u003cp\u003e(g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eBL\u003c/p\u003e \u003cp\u003e(mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMonomer\u003c/p\u003e \u003cp\u003e(1 mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eProduct(g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eYield (wt. %)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eMn,GPC\u003c/p\u003e \u003cp\u003e(g/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003eMw/Mn\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 1\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-AAm)-PBL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4196\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eAAm\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e4.7739\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e74.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-BMA)-PBL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4674\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eBMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e4.1225\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e63.74\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e9627\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e3.06\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-MMA)-PBL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4525\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e3.7965\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e58.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e6747\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2.72\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-S)-PBL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4748\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1.2176\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e18.80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5928\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e2.92\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003ePolymerization temperature: 100\u0026deg;C, polymerization time: 10 hours, DMSO: 15 mL, Ti(OR)\u003csub\u003e4\u003c/sub\u003e: 2 drops, a trace amount of AIBN.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSynthesis parameters of the random-graft copolymer including ε-caprolactone.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"9\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCode\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTrisNHMAm\u003c/p\u003e \u003cp\u003e(g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCL\u003c/p\u003e \u003cp\u003e(mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMonomer\u003c/p\u003e \u003cp\u003e(1 mL)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eProduct(g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eYield (wt. %)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eMn,GPC\u003c/p\u003e \u003cp\u003e(g/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003eMw/Mn\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-AAm)-PCL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4341\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eAAm\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e4.8625\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e75.57\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e24461\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e1.78\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 6\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-BMA)-PCL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4054\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eBMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e5.0073\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e78.17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e12217\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.64\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 7\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-MMA)-PCL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4895\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eMMA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e3.9123\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e60.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e9819\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e1.90\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePoly 8\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP(TrisNHMAm-S)-PCL\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4438\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e3.4519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e53.56\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e8874\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.57\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003ePolymerization temperature: 100\u0026deg;C, polymerization time: 10 hours, DMSO: 15 mL, Sn(Oct)\u003csub\u003e2\u003c/sub\u003e: 2 drops, a trace amount of AIBN.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Simultaneous and single-step synthesis of the random-graft copolymers\u003c/h2\u003e \u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH-NMR spectrum of P(TrisNHMAm-MMA)-PBL random-graft copolymer in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e displayed signals at; (δ, ppm): 8.2 (-N\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e of poly(\u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide) [P(TrisNHMAm)] trace), 5.2 (-C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e of PBL trace), 3.6 (-C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e of P(TrisNHMAm) trace), 3.4 (-OC\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e3\u003c/sub\u003e of poly(methyl methacrylate) (PMMA) unit), 2.4 (-C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e of P(TrisNHMAm) trace), 2.1\u0026ndash;2.2 (-C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e of PBL trace), 1.8 (-OC\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e of PMMA unit), 1.1 (-C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e2\u003c/sub\u003e of P(TrisNHMAm) trace and -C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e3\u003c/sub\u003e of PBL trace) and, 0.7\u0026ndash;0.9 (-C\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003eH\u003c/span\u003e\u003csub\u003e3\u003c/sub\u003e of PMMA unit).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-AAM)-PBL coded in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 8.19 (s, 3H), 7.51 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;513.4 Hz, 7H), 12.91\u0026ndash;5.83 (m, 13H), 12.91\u0026ndash;5.12 (m, 22H), 4.30 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;264.4, 7.3 Hz, 28H), 3.97 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;5.9 Hz, 3H), 3.90 (dt, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;510.7, 172.4 Hz, 136H), 4.74\u0026ndash;2.42 (m, 196H), 4.74\u0026ndash;2.30 (m, 201H), 4.74\u0026ndash;2.08 (m, 208H), 4.74\u0026ndash;1.46 (m, 215H), 4.74\u0026ndash;1.86 (m, 211H), 4.74\u0026ndash;0.71 (m, 233H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-BMA)-PBL coded in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 5.27\u0026ndash;5.11 (m, 9H), 4.63 (dt, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;11.4, 7.7 Hz, 4H), 4.18\u0026ndash;3.93 (m, 12H), 2.77\u0026ndash;2.63 (m, 7H), 3.93\u0026ndash;1.77 (m, 188H), 2.59\u0026ndash;2.14 (m, 100H), 2.98\u0026ndash;1.77 (m, 127H), 1.86 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;18.4, 6.9 Hz, 2H), 2.13 \u0026ndash; -2.47 (m, 64H), 1.93 \u0026ndash; -2.47 (m, 57H), 1.47\u0026ndash;1.20 (m, 10H), 1.24 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;16.4, 8.5 Hz, 6H), 1.29\u0026ndash;0.92 (m, 33H), 0.84 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;56.3 Hz, 6H), 0.59 \u0026ndash; -2.81 (m, 4H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-S)-PBL coded in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 8.60\u0026ndash;7.61 (m, 1H), 7.52\u0026ndash;6.77 (m, 12H), 6.58 (s, 5H), 5.40\u0026ndash;4.87 (m, 4H), 4.80\u0026ndash;4.41 (m, 2H), 4.41\u0026ndash;3.84 (m, 3H), 3.50 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;96.1 Hz, 5H), 2.83\u0026ndash;2.47 (m, 9H), 2.44\u0026ndash;2.35 (m, 2H), 2.27\u0026ndash;2.10 (m, 5H), 1.99 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;61.5 Hz, 3H), 1.83 (s, 3H), 1.53\u0026ndash;1.33 (m, 3H), 1.55\u0026ndash;0.88 (m, 12H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-AAm)-PCL coded in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 8.07\u0026ndash;6.02 (m, 3H), 4.18 (s, 10H), 3.66 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;238.8 Hz, 57H), 3.36\u0026ndash;3.21 (m, 2H), 2.96 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;8.8 Hz, 3H), 3.36\u0026ndash;2.63 (m, 4H), 2.55 (s, 34H), 2.55 (s, 58H), 1.67 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;10.6 Hz, 8H), 3.36\u0026ndash;0.28 (m, 131H), 3.21\u0026ndash;0.28 (m, 129H), 3.36\u0026ndash;0.48 (m, 131H), 1.57 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;9.1 Hz, 4H), 1.56 (s, 2H), 1.51 (s, 21H), 2.07\u0026ndash;0.48 (m, 59H), 1.58\u0026ndash;0.77 (m, 45H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-BMA)-PCL coded in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 4.50\u0026ndash;4.15 (m, 3H), 4.25\u0026ndash;4.15 (m, 2H), 4.19 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;23.0, 18.4 Hz, 2H), 3.98 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;5.8 Hz, 2H), 3.90 (s, 1H), 3.40 (s, 69H), 2.72\u0026ndash;2.43 (m, 46H), 2.24\u0026ndash;1.09 (m, 35H), 2.40\u0026ndash;0.50 (m, 47H), 1.51 (tddd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;52.8, 46.7, 38.3, 30.6 Hz, 31H), 2.25\u0026ndash;0.50 (m, 43H), 1.90\u0026ndash;0.65 (m, 39H), 1.24\u0026ndash;0.65 (m, 10H), 1.24\u0026ndash;0.50 (m, 10H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-MMA)-PCL coded in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 4.85 (s, 6H), 4.35 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;27.0 Hz, 37H), 3.95 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;110.5 Hz, 114H), 3.62 (s, 16H), 3.47 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;57.3 Hz, 575H), 2.46 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;44.5 Hz, 150H), 2.33\u0026ndash;1.47 (m, 388H), 1.53 (s, 176H), 1.53 (s, 141H), 1.41 (s, 41H), 1.29 (s, 51H), 1.14 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;17.3 Hz, 25H), 0.94\u0026ndash;0.71 (m, 131H), 0.71\u0026ndash;0.14 (m, 40H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003e \u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH-NMR of P(TrisNHMAm-S)-PCL coded in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003c/strong\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, DMSO) δ 7.94 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;101.6 Hz, 4H), 7.82 (t, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;92.5 Hz, 7H), 7.73 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;157.0, 72.5 Hz, 9H), 8.32\u0026ndash;5.80 (m, 132H), 6.00\u0026ndash;4.68 (m, 9H), 5.42 (ddd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;122.8, 109.9, 27.0 Hz, 5H), 4.91 (s, 4H), 4.48 (dd, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;135.5, 114.1 Hz, 18H), 4.28\u0026ndash;3.70 (m, 37H), 3.70\u0026ndash;3.57 (m, 5H), 3.49 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;83.9 Hz, 50H), 3.63\u0026ndash;2.85 (m, 62H), 3.63\u0026ndash;2.74 (m, 65H), 3.63\u0026ndash;2.40 (m, 138H), 3.63\u0026ndash;2.23 (m, 159H), 3.63\u0026ndash;2.16 (m, 167H), 3.63\u0026ndash;1.65 (m, 243H), 1.60 (s, 26H), 1.52 (s, 33H), 1.47\u0026ndash;1.39 (m, 23H), 1.12 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;135.2 Hz, 43H), 0.85 (d, \u003cem\u003eJ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;4.4 Hz, 16H).\u003c/p\u003e \u003c/p\u003e \u003cp\u003eThe FT-IR spectra of the random-graft copolymers synthesized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. In the FT-IR spectrum of P(TrisNHMAm-AAm)-PBL (Poly 1), peaks of N-H at 3333 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, asymmetric aliphatic C-H at 2932 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, amide C\u0026thinsp;=\u0026thinsp;O at 1659 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and etheric O-C groups at 1188 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are observed. In the FT-IR spectrum of P(TrisNHMAm-BMA)-PBL (Poly 2), peaks of asymmetric aliphatic C-H at 2955 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1721 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and etheric O-C groups at 1150 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are observed. In the FT-IR spectrum of P(TrisNHMAm-MMA)-PBL (Poly 3), asymmetric aliphatic C-H at 2924 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1728 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, etheric O-C groups peaks at 1150 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are observed. In the FT-IR spectrum of P(TrisNHMAm-S)-PBL (Poly 4), asymmetric aliphatic C-H at 2924 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1736 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, etheric O-C at 1165 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and aromatic C-H groups peaks at 756 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are observed.\u003c/p\u003e \u003cp\u003eThe FT-IR spectra of the random-graft copolymers synthesized in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. In the FT-IR spectrum of P(TrisNHMAm-AAm)-PCL (Poly 5), N-H peaks are observed at 3379 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, asymmetric aliphatic C-H at 2932 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1721 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, amide C\u0026thinsp;=\u0026thinsp;O at 1667 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and ethereal O-C groups peaks are observed at 1165 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. In the FT-IR spectrum of P(TrisNHMAm-BMA)-PCL (Poly 6), N-H peaks are observed at 3372 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, asymmetric aliphatic C-H at 2940 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1721 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, amide C\u0026thinsp;=\u0026thinsp;O at 1667 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and ethereal O-C groups peaks are observed at 1157 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. In the FT-IR spectrum of P(TrisNHMAm-MMA)-PCL (Poly 7), peaks of N-H at 3372 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, asymmetric aliphatic C-H at 2940 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1721 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and ethereal O-C groups at 1159 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are observed. In the FT-IR spectrum of P(TrisNHMAm-S)-PCL (Poly 8), peaks of asymmetric aliphatic C-H at 2932 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ester C\u0026thinsp;=\u0026thinsp;O at 1728 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, ethereal O-C at 1165 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and aromatic C-H groups at 756 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are observed.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe GPC curves of the random-graft copolymers are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. In the reactions performed in Tables\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, it was seen that the highest Mn value (Mn\u0026thinsp;=\u0026thinsp;24461 g/mol) was the reaction performed with AAm monomer. The lowest dispersity value (1.78) was obtained in the experiment performed with AAm monomer. The use of TrisNHMAm and AAm monomers together can be shown to provide more stable results.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTGA thermograms of P(TrisNHMAm-MMA)-PBL and P(TrisNHMAm-MMA)-PCL random-graft copolymers are given in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. Derivative thermograms show that the thermal decompositions of the random-graft copolymers occur in multiple steps. It is known that PMMA undergoes maximum decomposition at 405\u0026deg;C,\u003csup\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/sup\u003e PBL at 191\u0026deg;C, and PCL at 389\u0026deg;C.\u003csup\u003e[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e The first mass loss can be related to the evaporation of the solvents in the sample. In Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(a), the mass loss of the P(TrisNHMAm-MMA)-PBL sample can be divided into three main parts. The first demonstrated continuous weight loss from about 77\u0026deg;C to nearly 230\u0026deg;C with maxima at 169\u0026deg;C with 40.5% weight loss (decomposition of PBL units). The second demonstrated a continuous slight weight loss from about 230\u0026deg;C to nearly 274\u0026deg;C with maxima at 248\u0026deg;C with 7.0% weight loss (degradation of PTrisNHMAm units). Thirdly, continuous weight loss was demonstrated, from about 274\u0026deg;C to nearly 455\u0026deg;C, with maxima at 380\u0026deg;C and 42.4% weight loss (degradation of PMMA units). In Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(b), the mass loss of the P(TrisNHMAm-MMA)-PCL sample can also be divided into three main parts. The first demonstrated continuous slight weight loss from about 208\u0026deg;C to nearly 248\u0026deg;C with maxima at 230\u0026deg;C with 6.0% weight loss (degradation of PTrisNHMAm units). The second demonstrated a continuous weight loss from about 248\u0026deg;C to nearly 330\u0026deg;C with maxima at 303\u0026deg;C with 23.4% weight loss (decomposition of PBL units). Thirdly, continuous weight loss was demonstrated, from about 330\u0026deg;C to nearly 447\u0026deg;C, with maxima at 378\u0026deg;C and 44.2% (wt.) weight loss (decomposition of PMMA units). A small additional weight loss of PTrisNHMAm units is to be expected. These TGA thermograms show that P(TrisNHMAm-MMA)-PBL has lower thermal stability than P(TrisNHMAm-MMA)-PCL. DSC thermogram of P(TrisNHMAm-MMA)-PCL random-graft copolymer is given in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. The glass transition temperature (Tg) of the random-graft copolymer was obtained as 7 \u003csup\u003eo\u003c/sup\u003eC. The Tg value of PMMA is 100 \u003csup\u003eo\u003c/sup\u003eC\u003csup\u003e[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e and that of PCL is -60 \u003csup\u003eo\u003c/sup\u003eC.\u003csup\u003e[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]\u003c/sup\u003e The fact that the Tg value of the copolymer is between the Tg values ​​of the blocks that form it can be interpreted as the compatibility of these blocks with each other.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eSEM photos of the random-graft copolymers were taken to examine their surface morphologies and are given in Figs.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e and \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. The copolymers obtained using different monomers exhibited significantly different morphologies in terms of surface shape. However, all copolymers were relatively in a homogeneous phase. The surface of the P(TrisNHMAm-AAm)-PBL (A) random-graft copolymer has an aggregated cauliflower structure.\u003csup\u003e[\u003cspan additionalcitationids=\"CR28\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]\u003c/sup\u003e In Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e, it was observed that the random-graft copolymers coded with P(TrisNHMAm-AAm)-PCL (E) and P(TrisNHMAm-MMA)-PCL (G) formed a curved flat surface, creating a continuous phase. The surfaces of the polymers coded P(TrisNHMAm-BMA)-PBL (B), P(TrisNHMAm-MMA)-PBL (C), P(TrisNHMAm-S)-PBL 2000 X (D), P(TrisNHMAm-BMA)-PCL (F) and P(TrisNHMAm-S)-PCL (H) exhibited a curved surface forming a continuous phase.\u003csup\u003e[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eThe random-graft copolymers formed using TrisNHMAm, various vinyl monomers, and lactones were successfully synthesized simultaneously and in a single step using FRP and ROP techniques. In these simultaneous reactions, varying parameters were investigated using different monomers. Significant changes were observed in values ​​such as yield, morphological properties, molecular weights, and decomposition temperatures. The most stable results were determined to be the random-graft copolymer formed with AAm monomer. It is thought that the presence of biodegradable PCL and PBL units, compatible with many materials in the structure of the random-graft copolymer, increases the advantages of the synthesized polymers.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eConflict of Interest\u003c/h2\u003e \u003cp\u003eNone.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eTemel \u0026Ouml;zt\u0026uuml;rk and Erg\u0026uuml;l Meyvacı wrote the main manuscript text. Erg\u0026uuml;l Meyvacı prepared all figures, schemes and tables. All authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThis work was supported by the Giresun University Scientific Research Projects Coordination Unit (project number: FEN-BAP-A-290224-44)\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eFortelny, I., Ujcic, A., Fambri, L., Slouf, M. (2019). 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Yeni kaliks[4] aren-i\u0026ccedil;eren polimerik membranların hazırlanması, karakterizasyonu ve uygulamaları. \u003cem\u003eKaradeniz Fen Bilimleri Dergisi\u003c/em\u003e, \u003cem\u003e11\u003c/em\u003e(2), 533-543.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Simultaneous and single-step polymerization, random-graft copolymer, N-[tris(hydroxymethyl)methyl]acrylamide, free-radical polymerization, ring-opening polymerization","lastPublishedDoi":"10.21203/rs.3.rs-6369274/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6369274/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePoly(methyl methacrylate-ra-\u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide-g-ε-caprorolactone) random-graft copolymer was obtained by simultaneous reaction in a single step using free-radical polymerization and ring-opening polymerization techniques. In the presence of 2,2'-azobisisobutyronitrile, \u003cem\u003eN\u003c/em\u003e-[tris(hydroxymethyl)methyl]acrylamide and four different vinyl monomers (acrylamide, butyl methacrylate, methyl methacrylate, and styrene) were separately incorporated, and ε-caprolactone (or β-butyrolactone) was simultaneously grafted to the hydroxyl groups of the copolymer. The dependence of eight different graft copolymers on the monomer type was investigated by applying identical experimental parameters. The effects of the monomer type on the molecular weights and dispersity values were examined. The spectroscopic properties of the obtained products were determined using Fourier-transform infrared and proton-nuclear magnetic resonance spectroscopies, and their thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry techniques. The average molecular weights were defined using gel permeation chromatography. The morphological properties were examined with scanning electron microscope.\u003c/p\u003e","manuscriptTitle":"Simultaneous and single-step syntheses of the random-graft copolymers formed using various vinyl monomers and lactones together with N-[tris(hydroxymethyl)methyl]acrylamide","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-12 12:40:48","doi":"10.21203/rs.3.rs-6369274/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-07-28T18:15:44+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-07-10T21:57:52+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-24T13:25:24+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"82057837855863863504105194975327693053","date":"2025-06-13T19:49:25+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"293495992411054630416145370692541783318","date":"2025-06-11T12:38:25+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-06-10T20:57:42+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-04-11T11:28:08+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-04-04T03:13:47+00:00","index":"","fulltext":""},{"type":"submitted","content":"Polymer Bulletin","date":"2025-04-03T12:21:42+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"538789d7-0d62-439e-8b69-e3a13c533190","owner":[],"postedDate":"June 12th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-12-15T16:02:24+00:00","versionOfRecord":{"articleIdentity":"rs-6369274","link":"https://doi.org/10.1007/s00289-025-06177-5","journal":{"identity":"polymer-bulletin","isVorOnly":false,"title":"Polymer Bulletin"},"publishedOn":"2025-12-10 15:57:59","publishedOnDateReadable":"December 10th, 2025"},"versionCreatedAt":"2025-06-12 12:40:48","video":"","vorDoi":"10.1007/s00289-025-06177-5","vorDoiUrl":"https://doi.org/10.1007/s00289-025-06177-5","workflowStages":[]},"version":"v1","identity":"rs-6369274","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6369274","identity":"rs-6369274","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}