Effect of para-substituent on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative

Effect of para-substituent on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative | 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 Effect of para-substituent on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative Changlei Yang, Yanping Wang, Yufei Liu, Jun Qin, Min He, Shuhao Qin, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3602005/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 18 Mar, 2024 Read the published version in Journal of Polymer Research → Version 1 posted 5 You are reading this latest preprint version Abstract The investigation of the polymerization kinetics and thermal degradation kinetics of maleic anhydride copolymers is of significant reference value for the synthesis of multifunctional and high-performance maleic anhydride-based copolymers and their applications in different fields. In this study, anhydride (MAH) derived styrene copolymers, namely Poly( N -phenylmaleimide-alt-styrene) (PNS), Poly( N -(4-carboxyphenyl) maleimide-alt-styrene) (PCS), and poly (N-fluorine- phenylmaleimide- alt-styrene) (PFS), were prepared using a solution copolymerization method. The copolymerization kinetics and thermal degradation kinetics of MAH derived styrene copolymers were investigated using nuclear magnetic resonance (NMR) and thermogravimetric analysis (TGA), as well as the Arrhenius equation and Kim-Park method. The study revealed that the incorporation of carboxyl and fluorine groups had varying degrees of influence on maleic anhydride-styrene copolymers. The copolymerization rate constant ( K value) followed the order PNS > PCS > PFS, while the copolymerization activation energy ( E a ) followed the order PNS < PFS < PCS. Moreover, the thermal degradation activation energy ( E a ′ ) followed the order PNS < PNS < PFS, indicating that PFS exhibited easier polymerization and the fluorine group significantly enhanced the thermal stability of the maleic anhydride-styrene copolymers. maleic anhydride derivative styrene copolymer polymerization kinetics thermal degradation kinetics activating energy Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Introduction Maleic anhydride copolymers and their derivatives possess excellent structure and properties, such as good rigidity, mechanical strength, thermal stability, amphiphilicity, etc. The reactive points provided by the active anhydride groups on the main chain allow for facile functionalization and modification through reactions with alcohols, amines, and other reagents. The flexible styrene monomers can also undergo reversible addition reactions with maleic anhydride. The structure of maleic anhydride enables the synthesis of various derivatives of maleic anhydride copolymers [ 1 – 5 ] . Maleic anhydride copolymers and their derivatives have been widely applied in fluorescent materials, medical drug carriers and linkers, pollution-removing filter membranes, recyclable aerogels, heat-resistant agents, surfactants, dispersants, and other additives to improve the properties of polymer matrix materials [ 6 – 11 ] . Styrene-maleic anhydride copolymer is one of the earliest systems studied in maleic anhydride radical copolymerization. The copolymerization of styrene-maleic anhydride exhibits a strong alternation trend. There are two main viewpoints regarding the copolymerization mechanism of styrene-maleic anhydride: one involves the formation of charge transfer complexes between the electron-rich monomer styrene and the electron-deficient monomer maleic anhydride to explain the formation of alternating sequences in the polymer; the other is the penultimate unit model to describe the copolymerization process [ 12 – 14 ] . The degree of alternation and molecular weight of copolymers have a significant impact on their physical properties. Traditional free radical polymerization has difficulty in controlling monomer composition, resulting in complex copolymer composition distributions. Therefore, the development of living/controlled free radical polymerization (FRP) techniques such as reversible addition-fragmentation chain transfer polymerization (RAFT) and nitroxide-mediated polymerization (NMP) has been continuously advancing in maleic anhydride copolymerization [ 15 – 17 ] . The successful synthesis of well-defined maleic anhydride copolymers has been achieved through controlled free radical polymerization, utilizing the appropriate monomer properties and free radical addition kinetics to design and regulate the microstructure and desired properties of copolymers, leading to the preparation of nearly perfect styrene-maleic anhydride alternating copolymers and their derivatives [ 18 , 19 ] . The study of the kinetics of maleic anhydride copolymerization is of great reference value for the preparation of well-defined novel structured macromolecules. The main factors studied in polymerization kinetics include monomer concentration, initiator concentration, reaction rate, temperature, and their quantitative relationships. These factors often influence the sequence structure of polymers, monomer composition in the polymer, rate constants, activation energy, etc. In copolymer systems, larger molecular weight styrene monomers result in higher reaction activation energy. Increasing the feed ratio of monomers relative to maleic anhydride accelerates the reaction rate, leading to an increase in the reaction rate constant. Increasing the concentration of maleic anhydride monomer promotes copolymerization rate and improves the molecular weight. Higher initiator content can enhance monomer conversion rate. Increasing the reaction temperature is conducive to increasing the reaction rate and monomer conversion rate [ 20 – 24 ] . The choice of solvent also affects the reaction rate due to chain transfer to the solvent [ 25 ] . By studying the polymerization kinetics parameters and constructing mathematical models or modifying existing models, it is possible to describe the polymerization process, control the sequence structure of polymers, and predict useful information such as copolymer molecular weight, molecular weight distribution, conversion, and properties [ 26 – 29 ] . The molecular weight and molecular structure have an impact on the thermal stability of maleic anhydride copolymers. The apparent thermal stability of copolymers decreases with the sequence of alternating, random, and block structures [ 30 , 31 ] . Many researchers have studied the thermal stability and decomposition mechanisms of copolymers using techniques such as thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). They have further utilized the Ozawa equation and Kissinger equation to calculate the thermal degradation activation energy, which characterizes the thermal degradation kinetics of copolymers [ 32 – 36 ] . This paper aims to study effect of para-substituent (F-group and carboxyl group) on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative. In this study, the effects of different para-substituents on maleic anhydride-derived styrene copolymers on the copolymerization and thermal degradation kinetics were investigated using nuclear magnetic resonance (NMR) and thermal gravimetric analysis (TGA). The activation energy for copolymerization and thermal degradation kinetics of the copolymers was calculated using the Arrhenius equation and Kim-Park method. By studying the polymerization kinetics and thermal degradation kinetics of Poly(N-phenylmaleimide-alt-styrene) (PNS), ploy(N-(4-carboxyphenyl)maleimide-alt-styrene) (PCS), and ploy(N-fluorine-phenylmaleimide-alt-styrene) (PFS), the polymerization behavior and thermal stability of styrene copolymers composed with maleic anhydride derivative were thoroughly studied. To optimize experimental conditions and regulate good experimental parameters, design and prepare styrene copolymers composed with maleic anhydride derivative with special structures and high thermal stability for reference and guidance. Experimental section 2.1. Materials Styrene (Sinopharm chemical reagent co. LTD), benzoyl peroxide (BPO) from Shanghai Aladdin biochemical technology co. LTD, N-Phenylmaleimide (NPMI) from our lab, N-(4-Carboxyphenyl) maleimide (CPMI) from our lab, N-(4-F-Phenylmaleimide) (FPMI) from our lab, Cyclohexanone (Chengdu kelong chemical reagent plant) [ 37 ] . 2.2. Methods 2.2.1. Synthesis of copolymers The maleic anhydride derivatives obtained according to our previous work were used to copolymerize with styrene monomers through solution free radical copolymerization. The synthesis process of the monomer derived from maleic anhydride is illustrated in Figure S1. The melting points of NPMI, CPMI, and FPMI are determined as 89.5°C, 240.3°C, and 154.1°C, respectively, as depicted in Figures S2 to S4. The chemical structure of NPMI, CPMI, and FPMI was characterized by 1 H NMR, and 13 C NMR as shown in Fig. S5 to S10. For the copolymerization dissolved gases in cyclohexanone were removed by nitrogen gas flow for about 40 min, in an oil bath at 75°C. Next, styrene monomers (9.8 g, 0.1mol), maleic anhydride derivatives and BPO in a molar ratio 100:100:0.5 were added to the dried three-necked flask with 40mL cyclohexanone. The three-necked flask was then heated for 2 h at 80, 90, 100, and 110°C. During this period, samples are taken every 2 minutes for characterization purposes. 2.2.2 Characterization of the copolymer Nuclear magnetic resonance spectroscopy (NMR): 1 H NMR and 13 C NMR spectra were determined by NMR spectroscopy (Bruker Ascend400) 400MHz (600MHz) with CDCl 3 or acetone-d6 as solvents and tetramethylsilane (TMS) as the internal reference at ambient Deuterated chlorine mimics or deuterated DMSO. The coupling constant (J, Hz) and the peak shape are as follows: s is single peak, d is double peak, t is triple peak, q is quadruple peak, and m is multiple peak. The abscissa is chemical shift (8.ppm), and the ordinate is intensity. Thermogravimetric analysis(DTG): Dry the sample in vacuum, weigh 8mg and put it in the sample tray: under the protection of nitrogen (the flow rate of balanced gas is 20 mL/min, and the protective gas is 50 ml/min), raise the temperature from room temperature to 800°C at the rates of 5, 10, 15 and 20°C/min. 2.3 Theoretical background 2.3.1 Copolymerization kinetics The copolymer depends on the equilibrium constant of polymerization temperature, K(c). When K(c) > 0.1 L/mol, styrene (St) and maleic anhydride (Mah) easily undergo free radical copolymerization, resulting in strictly alternating SMA copolymers at low temperatures. [ 37 ] . In the case of free radical polymerization at low concentration, the initiator efficiency is not related to the monomer concentration, and the equation is as follows: $$\text{ln}\left(\frac{{\left[M\right]}_{0}}{\left[M\right]}\right)={k}_{app}t$$ 1 Where, [M] 0 is the concentration of the monomer before the initial reaction, [M] is the concentration of the corresponding monomer at time t , and k app is the rate constant of the radical reaction at this temperature. Generally, the higher the temperature is, the faster the decomposition rate of the initiator will be, to improve the rate of radical polymerization. Therefore, we can calculate the activation energy of radical reaction according to the polymerization rate constant ( k app ) and Arrhenius equation. $$k={k}_{0}{\text{e}\text{x}\text{p}}^{\left(-E/\left(RT\right)\right)}$$ 2 Where, k 0 is the initial polymerization rate constant, E is the activation energy of the polymerization reaction, R is the gas constant, and T is the reaction temperature (international unit). If you take the logarithm of both sides, you can get: $$\text{l}\text{n}k=\text{l}\text{n}{k}_{0}-\frac{E}{RT}$$ 3 So, with the natural log of k as the y-coordinate, -1/ RT as the x-coordinate, we can figure out the slope of E and the intercept of natural log of k 0 [ 38 ] . 2.3.2 Thermal degradation kinetics According to the nonisothermal dynamics theory and Arrhenius experience equation, the dynamic equation for degradation of materials is as the following: $$\frac{\text{d}{\alpha }}{\text{d}\text{t}}=\text{A}{(1-{\alpha })}^{\text{n}}{\text{e}}^{(-\frac{{\text{E}}_{\text{a}}{\prime }}{\text{R}\text{T}})}$$ 4 When the heating rate of sample is constant, due to β = d T /d t , the above equation can change into as the following: $$\frac{\text{d}{\alpha }}{\text{d}\text{T}}=\frac{\text{A}}{{\beta }}{(1-{\alpha })}^{\text{n}}{\text{e}}^{(-\frac{{\text{E}}_{\text{a}}{\prime }}{\text{R}\text{T}})}$$ 5 Here, A is the Pre-exponential factor, E a ′ is the activation energy and R is the gas constant. α , β , n and T are the weight loss rate or conversion rate, heating rate, reaction order and absolute temperature, respectively. According to the Eq. ( 2 ), using different mathematical processing method, we can get different thermal degradation dynamics calculation method. Kim-Park method [ 39 ] The thermal degradation kinetics equation formulated by Kim-Park is as follows: $$\text{ln}{\beta }=\text{l}\text{n}\text{A}+\text{ln}\left(\frac{{\text{E}}_{\text{a}}{\prime }}{\text{R}}\right)+\text{ln}\left[1-\text{n}+\frac{\text{n}}{0.9444}\right]-5.3305-1.0516\left(\frac{{\text{E}}_{\text{a}}{\prime }}{\text{R}{\text{T}}_{\text{m}\text{d}}}\right)$$ 6 Where n = ((1- α m )/[( RT md 2 ) (d α /d t )]. Where T md is the largest weight loss temperature, α m is the conversion of weight loss at that time. E a ′ can be obtained from the slope of ln β vs. 1/ T md and ln A can be calculated from the intercept value. Results and discussions 3.1 Copolymerization kinetics of styrene copolymers composed with maleic anhydride derivative In order to characterize the reaction degree of styrene and maleic anhydride derivatives at different temperature and time points, the concentration of styrene monomer was quantitatively calculated by 1 H NMR. Figure. 1 shows the attribution of H atoms of styrene and CPMI. Figure 1 depicts the 1 H NMR spectrum of the reaction system consisting of the monomer CPMI and St before undergoing any temperature elevation. The peaks at 5.8 ppm and 5.2 ppm correspond to the chemical shifts of two hydrogen atoms on tertiary carbons involved in the reaction with St double bonds [40] .During the early stage of the reaction, under the initiation of free radicals, CPMI and St monomers first form alternating copolymer blocks, such as St-CPMI or CPMI-St, until one of the monomers is depleted [41] . The progress of the reaction system was monitored in situ through 1 H NMR, with the consumption of monomers characterized by the consumption of St at different reaction times. Figure 2 illustrates the reaction system of CPMI and styrene at 80-110°C. As the reaction time increases, the monomers are gradually consumed, leading to a decrease in the intensity of the absorption peaks in the 1 H NMR spectrum. With the progression of the reaction, the molecular weight of PCS gradually increases, resulting in the appearance of new peaks. The peaks corresponding to the benzene ring transform from distinct and sharp to broadened, exhibiting the typical peak shape of large molecular weight compounds in nuclear magnetic resonance spectroscopy.As the reaction time increases, the two peaks of St (δ= The strength of 5.8 and 5.2 is decreasing, indicating that as the reaction progresses, the St monomer is continuously consumed, and finally the copolymer PCS is synthesized. Figure 3 presents the linear fitting plot of the monomer conversion of St in the CPMI-St reaction system at different reaction temperatures. Initially, the conversion rate achieves a relatively high level, followed by a slow increase with prolonged reaction time. Under conditions of constant initiator concentration, an increase in reaction temperature leads to an enhancement in the conversion rate. Temperature exhibits a significant influence on the monomer conversion rate within the range of 90°C to 100°C, conforming to the principles of free radical copolymerization. The plot in Figure 4 displays the linear fitting relationship between ln( [M] 0 /[M] ) and reaction time during the copolymerization of PCS at different temperatures. The slope of the fitted line, which represents the value of K , was obtained using Equation (1). The calculated K values at different temperatures were 8.41×10 -5 , 1.64×10 -4 , 2.76×10 -4 , and 3.45×10 -4 , respectively. The high fitting variances (above 0.98) indicate a strong agreement between the experimental data and the theoretical model. The polymerization temperature exerts an influence on intermolecular motion and energy propagation, with elevated temperatures being conducive to enhanced mass and heat transfer between materials [42] .It can be observed from Figure 4 that as the temperature increases, the K value also increases, indicating an accelerated reaction rate. This can be attributed to the enhanced decomposition rate of the initiator and the increased participation of monomers in the reaction. Figure 5 presents the relationship between ln( [M] 0 /[M] ) and reaction time for PNS, PCS, and PFS. The slope of PNS is greater than that of PCS, which is greater than that of PFS. This suggests that the K value of PNS is higher than that of PCS, which is higher than that of PFS. Therefore, in copolymerization reactions, PNS exhibits a faster reaction rate compared to PCS, and PCS shows a faster reaction rate compared to PFS. To determine the activation energy of the copolymerization of St and CPMI, Figure 6 demonstrates the linear fitting of ln( k ) versus -1/( RT ) values at different temperatures, based on Equation (3). The obtained slope yields an E a value of 22.6 kJ/mol with a fitting degree of 0.996. The K values and polymerization activation energies of PNS and PFS are similarly obtained using the same method and are presented in Table 1. The fitting variances for all the data are above 0.95. Table. 1. Kinetic parameters for polymerization of PNS, PCS, and PFS. Simple T （℃） a k b R 1 c E a （kJ/mol） d R 2 e PNS 80 3.13×10 -4 0.9898 22.6 0.996 90 4.35×10 -4 0.9896 100 4.71×10 -4 0.9868 110 5.32×10 -4 0.9869 PCS 80 8.41×10 -5 0.9701 59.5 0.982 90 1.67×10 -4 0.9868 100 2.76×10 -4 0.9985 110 3.45×10 -4 0.9976 PFS 80 6.64×10 -5 0.9527 54.8 0.997 90 1.11×10 -4 0.9915 100 1.76×10 -4 0.9641 110 2.45×10 -4 0.9899 As shown in Table 1, the K value of PNS is higher than that of PCS, which is higher than that of PFS. Furthermore, the required activation energy for the synthesis of PFS is higher than that for PNS but lower than that for PCS. Therefore, the introduction of carboxyl and fluorine groups has varying effects on the polymerization process of maleic anhydride-styrene copolymers. The study of polymerization kinetics provides a theoretical foundation for the synthesis of such copolymers, considering the influence of functional groups on monomer reactivity. The electron-withdrawing ability of electron-withdrawing groups is attenuated, resulting in a more challenging reaction process. 3.2 Thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative. Table. 2. Thermal degradation kinetic parameters of PNS, PCS, and PFS. Samples β (°C/min) T o ( o C) T max ( o C) R md (%/min) E a ′(KJ/mol) R PNS 5 350.6 410.5 -6.79 129.7 0.9851 10 369.2 423.8 -13.43 15 376.0 430.9 -19.76 20 386.4 434.4 -28.06 PCS 5 360.4 416.7 -9.16 161.3 0.98434 10 373.3 425.6 -18.49 15 384.4 438.0 -30.02 20 387.7 440.7 -34.33 PFS 5 374.2 414.0 -11.03 209.8 0.98967 10 383.9 430.0 -20.47 15 392.5 437.1 -30.44 20 396.3 442.0 -40.21 Thermogravimetric analysis (TGA) is commonly used to investigate the thermal decomposition behavior of polymers and analyze their thermal stability. Figure 7 shows the TG and DTG curves of maleic anhydride-derived styrene copolymers at heating rates of 5°C/min, 10°C/min, 15°C/min, and 20°C/min. The thermal degradation kinetics parameters obtained from TGA testing and calculated using theoretical formula (6) are listed in Table 2. The main degradation process of maleic anhydride-derived styrene copolymers occurs in only one stage, with a single maximum weight loss peak rate. The degradation temperature range is between 350°C and 470°C, and the maximum degradation rate is between 410°C and 440°C, indicating good thermal stability of the maleic anhydride-derived styrene copolymers, which is suitable for most polymer processing conditions. From the Figure 7, it can be observed that the TG and DTG curves are influenced by the heating rate. With increasing heating rate, the TG and DTG curves shift towards higher temperatures, and the decomposition temperature and maximum decomposition rate increase. This can be attributed to the lag effect in the heat transfer process. As the heating rate increases, the time required for the sample to reach the specified temperature is shortened, resulting in faster reaction times. Temperature differences within the sample may lead to an increase in peak values [43,44] . With increasing heating rate, the degradation temperature of the maleic anhydride-derived styrene copolymers also increases. According to the equilibrium theory, at lower heating rates, it is easier to reach equilibrium at any point as the temperature increases. At faster heating rates, heat diffusion is slower, making it difficult to reach equilibrium, resulting in a shift of the curve towards higher temperatures and an increase in decomposition temperature [45-47] . Figure 8a shows the linear fitting of ln β and 1/ T values for PNS, PCS, and PFS at different heating rates based on theoretical formula (6), and the fitting slopes correspond to the thermal activation energy Ea ′. Figure 8b is a bar figure showing the thermal activation energy of PNS, PCS, and PFS. The thermal activation energy of PNS, PCS, and PFS is 129.7 KJ/mol, 161.3 KJ/mol, and 209.8 KJ/mol, respectively, with a fitting degree above 0.98. The thermal activation energies of PCS and PFS, which introduce carboxyl and fluorine groups, are higher than that of PNS, indicating that the introduction of carboxyl and fluorine groups is beneficial for enhancing the thermal stability of maleic anhydride-derived styrene copolymers. However, the thermal activation energy of PFS is higher than that of PCS, suggesting that the influence of the fluorine group on the thermal stability of maleic anhydride-derived styrene copolymers is greater, resulting in a more significant enhancement of thermal stability. This may be attributed to the large electronegativity and small size of the fluorine atom, as well as the strong polarity of the fluorine atom, which can generate strong intermolecular interactions and higher strength between C-F bonds [48] . The aromatic C-F bonds have high bond energy, strong electron-withdrawing effects, and the small size of the F group, which favors the formation of a dense linear structure and contributes to the good thermal stability of maleic anhydride-derived styrene copolymers with fluorine groups [49] . Conclusion In summary, carboxyl and fluorine groups were introduced into the maleic anhydride-styrene copolymer PNS through solution polymerization, resulting in the synthesis of maleic anhydride derivatives, namely polystyrene-carboxyl copolymer (PCS) and polystyrene-fluorine copolymer (PFS). The copolymerization kinetics and thermal degradation kinetics of PNS, PCS, and PFS were studied using the Arrhenius equation and the Kim-Park method. The results indicate that the incorporation of carboxyl and fluorine groups has varying effects on the maleic anhydride-styrene copolymer. The addition of carboxyl and fluorine groups reduces the polymerization activity of maleic anhydride styrene copolymer, resulting in a decrease in K value and an increase in polymerization activation energy. The K value of PNS is higher than that of PCS, which in turn is higher than PFS. During copolymerization, the reaction rate of PCS is higher than that of PFS. The co-polymerization activation energy of PNS is higher than that of PFS, which is higher than that of PCS. Therefore, PFS is more prone to copolymerization compared to PCS. The decomposition temperature and decomposition activation energy E a ′ of PCS and PFS are higher than that of PNS, indicating that the addition of carboxyl and fluorine groups improves the thermal stability of the maleic anhydride-styrene copolymer. Due to the unique properties of fluorine atoms, PFS exhibits a higher decomposition temperature and degradation activation energy E a ′, resulting in a more significant enhancement in thermal stability. Declarations Acknowledgements This work was supported by the Natural Science Foundation of China [grant number 51663006, 52163009], Guizhou Provincial Science and Technology Program Project (Qiankehe Support [2023] General 084) and the Special Research Fund of Guizhou University (GZU Special Position Contract No 2021(44)). Conflicts of interest: The authors have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References Jing Huang, Turner S-Richard. Recent advances in alternating copolymers: The synthesis, modification, and applications of precision polymers[J]. Polymer, 2017, 116572–586. Weiwei Liu, Li Qian, Zhang Yin, et al. Continuous-flow RAFT copolymerization of styrene and maleic anhydride: acceleration of reaction and effect of polymerization conditions on reaction kinetics[J]. Journal of Flow Chemistry, 2021, 11(4): 867–875. Yong-guang Jia, Liu Ling-yan, Lei Bin, et al. Crown Ether Cavity-Containing Copolymers via Controlled Alternating Cyclocopolymerization[J]. Macromolecules, 2011, 44(16): 6311–6317. Guijing Chen, Yang Yuanyuan, Kang Dongdong, et al. Enhanced performances of chlorinated polyvinyl chloride (CPVC) ultrafiltration membranes by styrene-maleic anhydride copolymer[J]. Separation and Purification Technology, 2021, 258118043. Hongyun Duan, Qiu Teng, Guo Longhai, et al. The aminolysis of styrene–maleic anhydride copolymers for a new modifier used in urea-formaldehyde resins[J]. International Journal of Adhesion and Adhesives, 2016, 66138–146. Hossein Mahdavi, Ardeshiri Fatemeh. An efficient nanofiltration membrane based on blending of polyethersulfone with modified (styrene/maleic anhydride) copolymer[J]. Journal of the Iranian Chemical Society, 2016, 13(5): 873–880. S-Duygu Sütekin, Atıcı Ayşe-Bakar, Güven Olgun, et al. Controlling of free radical copolymerization of styrene and maleic anhydride via RAFT process for the preparation of acetaminophen drug conjugates[J]. Radiation Physics and Chemistry, 2018, 1485-12. Sara Shaghaghi, Mahdavian Ali-Reza. Flame-Retardancy Improvement of Novel Styrene–Maleic Anhydride Based Copolymers[J]. Journal of Polymer Research, 2006, 13(5): 413–419. Yuan Yao, Zhang Xiaohong, Guo Zhaoyan, et al. Preparation and application of recyclable polymer aerogels from styrene-maleic anhydride alternating copolymers[J]. Chemical Engineering Journal, 2023, 455140363. Tao Qian, Zhong Yi, Mao Zhiping, et al. The comb-like modified styrene-maleic anhydride copolymer dispersant for disperse dyes[J]. Journal of Applied Polymer Science, 2019, 136(16): 47330. Chen Li, Pan Xingang, Hua Chunfan, et al. Synthesis of novel copoly(styrene–maleic anhydride) materials and their luminescent properties[J]. European Polymer Journal, 2003, 39(6): 1091–1097. Bert Klumperman. Mechanistic considerations on styrene–maleic anhydride copolymerization reactions[J]. Polymer Chemistry, 2010, 1(5): 558. Niels Ten Brummelhuis, Stutz Marvin-Björn. Penultimate effects in the copolymerization of maleic anhydride with electron-rich styrene derivatives[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2016, 54(18): 2932–2939. Kun Liu, Xiong Qiaoqiao, Gu Zhuowei, et al. Highly efficient one-pot synthesis of anhydride-riched terpolymers from radical dual-alternating strategy[J]. Journal of Polymer Research, 2023, 30(6). Sagar Bag, Ghosh Soumyadeep, Paul Soumya, et al. Styrene-Maleimide/Maleic Anhydride Alternating Copolymers: Recent Advances and Future Perspectives[J]. Macromolecular Rapid Communications, 2021, 42(23): 2100501. Gustaaf Schoukens, Samyn Pieter. Thermo-analytical study on transitions in styrene–maleic anhydride copolymers with low- and high-molecular weights[J]. Thermochimica Acta, 2014, 58028–37. Shihui Li, Cai Ling, Cui Dongmei. Lewis Acids Activated Spontaneous Alternating Copolymerization of Maleic Anhydride and Styrene Derivatives[J]. Chemistry – An Asian Journal, 2023, 18(4). Guillaume-Gody-Matthias-Hartlieb Guillaume Moriceau. Functional multisite copolymer by one-pot sequential RAFT copolymerization of styrene and maleic anhydride[J]. Polymer Chemistry, 2017, 84116–4152. Mingqiang-Ding-Mengting-Chen Shaogan Niu, Zhenping Cheng Xiulin-Zhu. Synthesis of Well-Defined Copolymer of Acrylonitrile and Maleic Anhydride via RAFT Polymerization[J]. 2013, 51(24): 5263–5269. Kun-Cao-Yuan-Huang He-Yang Liu. Kinetics and Simulation of the Imidization of Poly(styrene-co-maleic anhydride) with Amines[J]. 2006, 100(4): 2744–2749. G Ahmetli, Yazicigil Z, Kocak A, et al. Effects of different molecular weights of polystyrene on the acylation reaction and on the reaction kinetics[J]. Journal of Applied Polymer Science, 2005, 96(1): 253–259. Polina-Terpugova-Chuong-Bui Elena Chernikova. Effect of comonomer composition on the controlled free-radical copolymerization of styrene and maleic anhydride by reversible addition–fragmentation chain transfer (RAFT)[J]. 2003, 44(15): 4101–4107. MAL-NAM-KIM-IK-MO-LEE EUN-SOO PARK. Living Radical Copolymerization of Styrene/Maleic Anhydride[J]. Polymer Chemistry, 2000, 28(12): 2239–2244. Yitao Yu, Zhan Xiaoli, Zhang Qinghua, et al. Synthesis of triblock copolymer having alternating structures and kinetics study on RAFT-mediated bulk, miniemulsion and seed miniemulsion polymerizations[J]. Polymer Engineering & Science, 2011, 51(6): 1041–1050. Wafaa-M Sayed. Preparation of modified polystyrene with maleic anhydride in the presence of different solvents[J]. Journal of Applied Polymer Science, 2008, 109(6): 4099–4104. Tomás Romero Pietrafesa, Brandolin Adriana, Sarmoria Claudia, et al. A Comprehensive Monte Carlo Model of the Grafting of Maleic Anhydride onto Polypropylene with Experimental Validation[J]. Macromolecular Theory and Simulations, 2023. Carla-V Luciani, Choi Kyu-Yong. Mathematical Modeling of Free Radical Solution Terpolymerization Reactions in a Batch and Continuous Flow Stirred Tank Reactors[J]. Macromolecular Theory and Simulations, 2021, 30(3): 2000094. Bert Klumperman, Heuts Johan-P-A. The solution copolymerization of styrene and maleic anhydride in a continuous stirred tank reactor and its theoretical modelling[J]. Polymer, 2020, 202122730. Xiaoyu Zou, Zhao Qian, Zhan Yikai, et al. Polymerization kinetics analysis of a thermostable, sequence-controllable polyamide polymer[J]. Journal of Molecular Structure, 2022, 1264133286. Gustaaf Schoukens, Samyn Pieter. Thermo-analytical study on transitions in styrene–maleic anhydride copolymers with low- and high-molecular weights[J]. Thermochimica Acta, 2014, 58028–37. C-N Cascaval, Chitanu G, Carpov A. On the thermal decomposition of copolymers of maleic anhydride with styrene[J]. Thermochimica acta, 1996, 275(2): 225–233. Linghan Xiao, Li Zhenguang, Dong Jinglong, et al. Fabrication of poly (methyl methacrylate-co-maleic anhydride) copolymers and their kinetic analysis of the thermal degradation[J]. Colloid and Polymer Science, 2015, 293(10): 2807–2813. Güzin Pıhtılı, Biryan Fatih. Electrical investigation on Eu + 3- doped copolymer composite system and conventional kinetic analysis[J]. Journal of Molecular Structure, 2021, 1230129638. Yong-Zhong-Yao-Li-Li Jun Zhang. Thermooxidative Aging and Kinetics of the Thermooxidative Degradation of Ethylene – Propylene – Diene Terpolymer-graft-Maleic Anhydride/Calcium Carbonate Composites[J]. Journal of Applied Polymer Science, 2006, 103(4): 2575–2767. Pi-Pi-hui-Wen-Xiu-fang Wang Zhai-min. Analysis of Most Probable Mechanism Functions and Thermal Degradation Kinetics of N-phenylmaleimide-styrene-maleic Copolymers[J]. Polymers and Polymer Composite, 2006, 15(5): 343–414. Güzin Pıhtılı, Biryan Fatih. Electrical investigation on Eu + 3- doped copolymer composite system and conventional kinetic analysis[J]. Journal of Molecular Structure, 2021, 1230129638. Juxiang Luo, Cheng Deshu, Li Mingchun, et al. RAFT Copolymerization of Styrene and Maleic Anhydride with Addition of Ascorbic Acid at Ambient Temperature[J]. Advances in Polymer Technology, 2020, 20201–8. Özlen Altun, Koçer Melike-Özge. Spectral, kinetic and thermodynamic studies of Pd (II) with Schiff base derived from L-asparagine and furfuraldehyde in the presence of 8-hydroxyquinoline[J]. Journal of Molecular Structure, 2021, 1224129242. Mostafizur-Rahaman-Dipak-Khastgir Lalatendu Nayak. Thermal Decomposition Behavior and Durability Evaluation of Thermotropic Liquid Crystalline Polymers[J]. Journal of Applied Polymer Science, 2017, 135(7): 1–9. Xuwen Li, Han Li, Zhang Ruixue, et al. Regulation from gradient to near periodic sequence during anionic copolymerization of styrene and dimethyl-[4-(1-phenyl-vinyl)phenyl]silane (DPE-SiH)[J]. Polymer, 2022, 244124663. José Bonilla-Cruz, Guerrero-Sánchez Carlos, Schubert Ulrich-S, et al. Controlled “Grafting-from” of poly[styrene-co-maleic anhydride] onto polydienes using nitroxide chemistry[J]. European Polymer Journal, 2010, 46(2): 298–312. Weiwei Liu, Li Qian, Zhang Yin, et al. Continuous-flow RAFT copolymerization of styrene and maleic anhydride: acceleration of reaction and effect of polymerization conditions on reaction kinetics[J]. Journal of Flow Chemistry, 2021, 11(4): 867–875. Chihan Meng, Liu Xiucai. Study on thermal degradation kinetics of bio-based semi-aromatic high-temperature polyamide PA5T/56 and the effect of benzene ring[J]. Iranian Polymer Journal, 2022, 31(5): 641–650. Yichen-Wang-Meiyun-Chai Yingkai Li. Pyrolysis kinetics and thermodynamic parameters of bamboo residues and its three main components using thermogravimetric analysis[J]. Biomass and Bioenergy, 2023, 170106705. Pradip Paik, Kar Kamal-K. Thermal degradation kinetics and estimation of lifetime of polyethylene particles: Effects of particle size[J]. Materials Chemistry and Physics, 2009, 113(2–3): 953–961. Haonan Chen, Zhu Sheng, Zhou Rongfan, et al. Thermal Degradation Behavior of Thiol-ene Composites Loaded with a Novel Silicone Flame Retardant[J]. Polymers, 2022, 14(20): 4335. Wei Tang, Li Xin-Gui, Yan Deyue. Thermal decomposition kinetics of thermotropic copolyesters made from trans-p-hydroxycinnamic acid and p-hydroxybenzoic acid[J]. Journal of applied polymer science, 2004, 91(1): 445–454. Ion Sava, Damaceanu Mariana-Dana, Constantin Catalin-Paul, et al. Structure – promoted high performance properties of triphenylmethane - containing polyimides and copolyimides[J]. European Polymer Journal, 2018, 108554–569. Wei-Feng Peng, Lei Huan-Yu, Zhang Xin-Xin, et al. Fluorine Substitution Effect on the Material Properties in Transparent Aromatic Polyimides[J]. Chinese Journal of Polymer Science, 2022, 40(7): 781–788. Supplementary Files SupportingMaterial.docx Cite Share Download PDF Status: Published Journal Publication published 18 Mar, 2024 Read the published version in Journal of Polymer Research → Version 1 posted Reviewers agreed at journal 25 Nov, 2023 Reviewers invited by journal 25 Nov, 2023 Editor invited by journal 17 Nov, 2023 Editor assigned by journal 13 Nov, 2023 First submitted to journal 11 Nov, 2023 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-3602005","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":253233263,"identity":"9f30808e-c6db-4f45-9fa0-732b73d4f3ad","order_by":0,"name":"Changlei Yang","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Changlei","middleName":"","lastName":"Yang","suffix":""},{"id":253233264,"identity":"f2d7b4aa-8821-4771-872d-fc4debbc6451","order_by":1,"name":"Yanping Wang","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Yanping","middleName":"","lastName":"Wang","suffix":""},{"id":253233265,"identity":"d67c9db9-9bea-4a71-b43b-46826aee6038","order_by":2,"name":"Yufei Liu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAt0lEQVRIiWNgGAWjYBACPmYgUVEB4UgQpYUNpOXMGZK0gIizbSRpYecxkzg4r9be4ADzwds8DHZ5RDgMpGXbcWaDA2zJ1jwMycVEaZH+uO0Ym8EBIIOH4UBiA3G2zDnGY3CA/xspWhpqJIC2sBGrha3Y4sCxAwaSh9mMLecYJBPWws9/eOONAzV19nzHmx/eeFNhR1gLELAAo+MwAwMoThkMiFAPBMwfGBjqiFM6CkbBKBgFIxMAAMXRM1OS8FYRAAAAAElFTkSuQmCC","orcid":"","institution":"Guizhou University","correspondingAuthor":true,"prefix":"","firstName":"Yufei","middleName":"","lastName":"Liu","suffix":""},{"id":253233266,"identity":"47394ca3-89b1-4796-9f61-2e69137f6418","order_by":3,"name":"Jun Qin","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Jun","middleName":"","lastName":"Qin","suffix":""},{"id":253233267,"identity":"5892da78-3747-4461-82c5-8f8c587ab117","order_by":4,"name":"Min He","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Min","middleName":"","lastName":"He","suffix":""},{"id":253233268,"identity":"78cbeec1-7dbf-45f1-bb71-2e631d768e0a","order_by":5,"name":"Shuhao Qin","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Shuhao","middleName":"","lastName":"Qin","suffix":""},{"id":253233269,"identity":"c5b1599d-9fa1-4323-8d8f-29b4bfa9d93c","order_by":6,"name":"Jie Yu","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Jie","middleName":"","lastName":"Yu","suffix":""}],"badges":[],"createdAt":"2023-11-12 23:04:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3602005/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3602005/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10965-024-03945-1","type":"published","date":"2024-03-18T08:12:49+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":47313753,"identity":"ff3e8f48-6361-4b8e-a3cb-8b7651877dd9","added_by":"auto","created_at":"2023-11-29 17:01:00","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":118487,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectrum of St and CPMI\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/e089626a9850afe858183b4b.png"},{"id":47313755,"identity":"38edfeff-ec8e-4dc1-a6a4-e91a411c750c","added_by":"auto","created_at":"2023-11-29 17:01:00","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":646635,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectra of the reaction system between St and CPMI at the different temperature: (a)80 °C, (b)90 °C, (c)100 °C, (d)110 °C.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/eaaeb5f2ed58d01c5628aaae.png"},{"id":47312525,"identity":"13c0fd1e-f91f-4558-9d1b-6ad2cb485453","added_by":"auto","created_at":"2023-11-29 16:53:00","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":165906,"visible":true,"origin":"","legend":"\u003cp\u003eConversion of St over time at different temperatures.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/f0c03a47d7657efbec91e62c.png"},{"id":47312528,"identity":"8da6917c-91aa-4c72-93a9-9d1a470bb571","added_by":"auto","created_at":"2023-11-29 16:53:00","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":66800,"visible":true,"origin":"","legend":"\u003cp\u003eThe relationship between ln(\u003cem\u003e[M]\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e/[M]\u003c/em\u003e) of PCS and reaction time.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/a875e9049f9d256aa278ac09.png"},{"id":47312522,"identity":"eabf7088-9758-42c3-ac54-3215b7a7198b","added_by":"auto","created_at":"2023-11-29 16:53:00","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":90584,"visible":true,"origin":"","legend":"\u003cp\u003eThe relationship between ln(\u003cem\u003e[M]\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e/[M]\u003c/em\u003e) of PCS and reaction. time.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/e0fda6ac4cd355b7e6fd505a.png"},{"id":47313754,"identity":"07299430-0f87-4193-a4d5-644de25bac00","added_by":"auto","created_at":"2023-11-29 17:01:00","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":11674,"visible":true,"origin":"","legend":"\u003cp\u003eThe relationship between ln(\u003cem\u003ek\u003c/em\u003e) and -1/\u003cem\u003eRT\u003c/em\u003e of PCS.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/3faf422f909a9fd7d1770950.png"},{"id":47312530,"identity":"361e67ae-9691-41b4-8697-e351999fbbc0","added_by":"auto","created_at":"2023-11-29 16:53:00","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":186229,"visible":true,"origin":"","legend":"\u003cp\u003eTG and DTG of maleic anhydride derivative styrene copolymer. (a) TG, (b) DTG.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/98cad35fca2bbf7bf8c47122.png"},{"id":47312524,"identity":"b980bcd5-c5dc-4632-9d0e-caaf01a0c7ab","added_by":"auto","created_at":"2023-11-29 16:53:00","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":59466,"visible":true,"origin":"","legend":"\u003cp\u003eColumn chart of the relationship between ln\u003cem\u003eβ\u003c/em\u003e and 1/\u003cem\u003eT\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e for PNS, PCS, and PFS, and (a) ln\u003cem\u003eβ\u003c/em\u003e vs. 1/\u003cem\u003eT\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e, (b) activation energy column chart.\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/6d26d5e95031c972196c9ffa.png"},{"id":53149477,"identity":"871df8bc-0883-47de-94de-0c9e49e71830","added_by":"auto","created_at":"2024-03-21 08:12:55","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1569055,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/6465f477-d114-4b49-9253-91d7693e892b.pdf"},{"id":47313756,"identity":"5be4b153-1215-49d5-b10e-a06622604d46","added_by":"auto","created_at":"2023-11-29 17:01:00","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1370530,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-3602005/v1/bfad3351358119ac5997d38c.docx"}],"financialInterests":"","formattedTitle":"Effect of para-substituent on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative","fulltext":[{"header":"Introduction","content":"\u003cp\u003eMaleic anhydride copolymers and their derivatives possess excellent structure and properties, such as good rigidity, mechanical strength, thermal stability, amphiphilicity, etc. The reactive points provided by the active anhydride groups on the main chain allow for facile functionalization and modification through reactions with alcohols, amines, and other reagents. The flexible styrene monomers can also undergo reversible addition reactions with maleic anhydride. The structure of maleic anhydride enables the synthesis of various derivatives of maleic anhydride copolymers\u003csup\u003e[\u003cspan additionalcitationids=\"CR2 CR3 CR4\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]\u003c/sup\u003e. Maleic anhydride copolymers and their derivatives have been widely applied in fluorescent materials, medical drug carriers and linkers, pollution-removing filter membranes, recyclable aerogels, heat-resistant agents, surfactants, dispersants, and other additives to improve the properties of polymer matrix materials\u003csup\u003e[\u003cspan additionalcitationids=\"CR7 CR8 CR9 CR10\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]\u003c/sup\u003e. Styrene-maleic anhydride copolymer is one of the earliest systems studied in maleic anhydride radical copolymerization. The copolymerization of styrene-maleic anhydride exhibits a strong alternation trend. There are two main viewpoints regarding the copolymerization mechanism of styrene-maleic anhydride: one involves the formation of charge transfer complexes between the electron-rich monomer styrene and the electron-deficient monomer maleic anhydride to explain the formation of alternating sequences in the polymer; the other is the penultimate unit model to describe the copolymerization process\u003csup\u003e[\u003cspan additionalcitationids=\"CR13\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]\u003c/sup\u003e. The degree of alternation and molecular weight of copolymers have a significant impact on their physical properties. Traditional free radical polymerization has difficulty in controlling monomer composition, resulting in complex copolymer composition distributions. Therefore, the development of living/controlled free radical polymerization (FRP) techniques such as reversible addition-fragmentation chain transfer polymerization (RAFT) and nitroxide-mediated polymerization (NMP) has been continuously advancing in maleic anhydride copolymerization\u003csup\u003e[\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e. The successful synthesis of well-defined maleic anhydride copolymers has been achieved through controlled free radical polymerization, utilizing the appropriate monomer properties and free radical addition kinetics to design and regulate the microstructure and desired properties of copolymers, leading to the preparation of nearly perfect styrene-maleic anhydride alternating copolymers and their derivatives\u003csup\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]\u003c/sup\u003e. The study of the kinetics of maleic anhydride copolymerization is of great reference value for the preparation of well-defined novel structured macromolecules. The main factors studied in polymerization kinetics include monomer concentration, initiator concentration, reaction rate, temperature, and their quantitative relationships. These factors often influence the sequence structure of polymers, monomer composition in the polymer, rate constants, activation energy, etc. In copolymer systems, larger molecular weight styrene monomers result in higher reaction activation energy. Increasing the feed ratio of monomers relative to maleic anhydride accelerates the reaction rate, leading to an increase in the reaction rate constant. Increasing the concentration of maleic anhydride monomer promotes copolymerization rate and improves the molecular weight. Higher initiator content can enhance monomer conversion rate. Increasing the reaction temperature is conducive to increasing the reaction rate and monomer conversion rate\u003csup\u003e[\u003cspan additionalcitationids=\"CR21 CR22 CR23\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e. The choice of solvent also affects the reaction rate due to chain transfer to the solvent\u003csup\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e. By studying the polymerization kinetics parameters and constructing mathematical models or modifying existing models, it is possible to describe the polymerization process, control the sequence structure of polymers, and predict useful information such as copolymer molecular weight, molecular weight distribution, conversion, and properties\u003csup\u003e[\u003cspan additionalcitationids=\"CR27 CR28\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]\u003c/sup\u003e. The molecular weight and molecular structure have an impact on the thermal stability of maleic anhydride copolymers. The apparent thermal stability of copolymers decreases with the sequence of alternating, random, and block structures\u003csup\u003e[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]\u003c/sup\u003e. Many researchers have studied the thermal stability and decomposition mechanisms of copolymers using techniques such as thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). They have further utilized the Ozawa equation and Kissinger equation to calculate the thermal degradation activation energy, which characterizes the thermal degradation kinetics of copolymers\u003csup\u003e[\u003cspan additionalcitationids=\"CR33 CR34 CR35\" citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThis paper aims to study effect of para-substituent (F-group and carboxyl group) on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative. In this study, the effects of different para-substituents on maleic anhydride-derived styrene copolymers on the copolymerization and thermal degradation kinetics were investigated using nuclear magnetic resonance (NMR) and thermal gravimetric analysis (TGA). The activation energy for copolymerization and thermal degradation kinetics of the copolymers was calculated using the Arrhenius equation and Kim-Park method. By studying the polymerization kinetics and thermal degradation kinetics of Poly(N-phenylmaleimide-alt-styrene) (PNS), ploy(N-(4-carboxyphenyl)maleimide-alt-styrene) (PCS), and ploy(N-fluorine-phenylmaleimide-alt-styrene) (PFS), the polymerization behavior and thermal stability of styrene copolymers composed with maleic anhydride derivative were thoroughly studied. To optimize experimental conditions and regulate good experimental parameters, design and prepare styrene copolymers composed with maleic anhydride derivative with special structures and high thermal stability for reference and guidance.\u003c/p\u003e"},{"header":"Experimental section","content":"\u003cp\u003e2.1. Materials\u003c/p\u003e \u003cp\u003eStyrene (Sinopharm chemical reagent co. LTD), benzoyl peroxide (BPO) from Shanghai Aladdin biochemical technology co. LTD, N-Phenylmaleimide (NPMI) from our lab, N-(4-Carboxyphenyl) maleimide (CPMI) from our lab, N-(4-F-Phenylmaleimide) (FPMI) from our lab, Cyclohexanone (Chengdu kelong chemical reagent plant)\u003csup\u003e[\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e2.2. Methods\u003c/p\u003e \u003cp\u003e2.2.1. Synthesis of copolymers\u003c/p\u003e \u003cp\u003eThe maleic anhydride derivatives obtained according to our previous work were used to copolymerize with styrene monomers through solution free radical copolymerization. The synthesis process of the monomer derived from maleic anhydride is illustrated in Figure S1. The melting points of NPMI, CPMI, and FPMI are determined as 89.5\u0026deg;C, 240.3\u0026deg;C, and 154.1\u0026deg;C, respectively, as depicted in Figures S2 to S4. The chemical structure of NPMI, CPMI, and FPMI was characterized by \u003csup\u003e1\u003c/sup\u003eH NMR, and \u003csup\u003e13\u003c/sup\u003eC NMR as shown in Fig. S5 to S10. For the copolymerization dissolved gases in cyclohexanone were removed by nitrogen gas flow for about 40 min, in an oil bath at 75\u0026deg;C. Next, styrene monomers (9.8 g, 0.1mol), maleic anhydride derivatives and BPO in a molar ratio 100:100:0.5 were added to the dried three-necked flask with 40mL cyclohexanone. The three-necked flask was then heated for 2 h at 80, 90, 100, and 110\u0026deg;C. During this period, samples are taken every 2 minutes for characterization purposes.\u003c/p\u003e \u003cp\u003e2.2.2 Characterization of the copolymer\u003c/p\u003e \u003cp\u003eNuclear magnetic resonance spectroscopy (NMR):\u003c/p\u003e \u003cp\u003e \u003csup\u003e1\u003c/sup\u003eH NMR and \u003csup\u003e13\u003c/sup\u003eC NMR spectra were determined by NMR spectroscopy (Bruker Ascend400) 400MHz (600MHz) with CDCl\u003csub\u003e3\u003c/sub\u003e or acetone-d6 as solvents and tetramethylsilane (TMS) as the internal reference at ambient Deuterated chlorine mimics or deuterated DMSO. The coupling constant (J, Hz) and the peak shape are as follows: s is single peak, d is double peak, t is triple peak, q is quadruple peak, and m is multiple peak. The abscissa is chemical shift (8.ppm), and the ordinate is intensity.\u003c/p\u003e \u003cp\u003eThermogravimetric analysis(DTG):\u003c/p\u003e \u003cp\u003eDry the sample in vacuum, weigh 8mg and put it in the sample tray: under the protection of nitrogen (the flow rate of balanced gas is 20 mL/min, and the protective gas is 50 ml/min), raise the temperature from room temperature to 800\u0026deg;C at the rates of 5, 10, 15 and 20\u0026deg;C/min.\u003c/p\u003e \u003cp\u003e2.3 Theoretical background\u003c/p\u003e\u003cp\u003e2.3.1 Copolymerization kinetics\u003c/p\u003e\u003cp\u003eThe copolymer depends on the equilibrium constant of polymerization temperature, K(c). When K(c)\u0026thinsp;\u0026gt;\u0026thinsp;0.1 L/mol, styrene (St) and maleic anhydride (Mah) easily undergo free radical copolymerization, resulting in strictly alternating SMA copolymers at low temperatures.\u003csup\u003e[\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]\u003c/sup\u003e. In the case of free radical polymerization at low concentration, the initiator efficiency is not related to the monomer concentration, and the equation is as follows:\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\text{ln}\\left(\\frac{{\\left[M\\right]}_{0}}{\\left[M\\right]}\\right)={k}_{app}t$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere, \u003cem\u003e[M]\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e is the concentration of the monomer before the initial reaction, \u003cem\u003e[M]\u003c/em\u003e is the concentration of the corresponding monomer at time \u003cem\u003et\u003c/em\u003e, and \u003cem\u003ek\u003c/em\u003e\u003csub\u003eapp\u003c/sub\u003e is the rate constant of the radical reaction at this temperature.\u003c/p\u003e \u003cp\u003eGenerally, the higher the temperature is, the faster the decomposition rate of the initiator will be, to improve the rate of radical polymerization. Therefore, we can calculate the activation energy of radical reaction according to the polymerization rate constant (\u003cem\u003ek\u003c/em\u003e\u003csub\u003e\u003cem\u003eapp\u003c/em\u003e\u003c/sub\u003e) and Arrhenius equation.\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$k={k}_{0}{\\text{e}\\text{x}\\text{p}}^{\\left(-E/\\left(RT\\right)\\right)}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere, \u003cem\u003ek\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e is the initial polymerization rate constant, \u003cem\u003eE\u003c/em\u003e is the activation energy of the polymerization reaction, \u003cem\u003eR\u003c/em\u003e is the gas constant, and \u003cem\u003eT\u003c/em\u003e is the reaction temperature (international unit).\u003c/p\u003e \u003cp\u003eIf you take the logarithm of both sides, you can get:\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e\n$$\\text{l}\\text{n}k=\\text{l}\\text{n}{k}_{0}-\\frac{E}{RT}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eSo, with the natural log of \u003cem\u003ek\u003c/em\u003e as the y-coordinate, -1/\u003cem\u003eRT\u003c/em\u003e as the x-coordinate, we can figure out the slope of \u003cem\u003eE\u003c/em\u003e and the intercept of natural log of \u003cem\u003ek\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e\u003csup\u003e[\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e2.3.2 Thermal degradation kinetics\u003c/p\u003e \u003cp\u003eAccording to the nonisothermal dynamics theory and Arrhenius experience equation, the dynamic equation for degradation of materials is as the following:\u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e\n$$\\frac{\\text{d}{\\alpha }}{\\text{d}\\text{t}}=\\text{A}{(1-{\\alpha })}^{\\text{n}}{\\text{e}}^{(-\\frac{{\\text{E}}_{\\text{a}}{\\prime }}{\\text{R}\\text{T}})}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhen the heating rate of sample is constant, due to \u003cem\u003eβ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;d\u003cem\u003eT\u003c/em\u003e/d\u003cem\u003et\u003c/em\u003e, the above equation can change into as the following:\u003cdiv id=\"Equ5\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ5\" name=\"EquationSource\"\u003e\n$$\\frac{\\text{d}{\\alpha }}{\\text{d}\\text{T}}=\\frac{\\text{A}}{{\\beta }}{(1-{\\alpha })}^{\\text{n}}{\\text{e}}^{(-\\frac{{\\text{E}}_{\\text{a}}{\\prime }}{\\text{R}\\text{T}})}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eHere, \u003cem\u003eA\u003c/em\u003e is the Pre-exponential factor, \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e\u0026prime; is the activation energy and \u003cem\u003eR\u003c/em\u003e is the gas constant. \u003cem\u003eα\u003c/em\u003e, \u003cem\u003eβ\u003c/em\u003e, \u003cem\u003en\u003c/em\u003e and \u003cem\u003eT\u003c/em\u003e are the weight loss rate or conversion rate, heating rate, reaction order and absolute temperature, respectively.\u003c/p\u003e \u003cp\u003eAccording to the Eq.\u0026nbsp;(\u003cspan refid=\"Equ2\" class=\"InternalRef\"\u003e2\u003c/span\u003e), using different mathematical processing method, we can get different thermal degradation dynamics calculation method.\u003c/p\u003e \u003cp\u003e \u003cb\u003eKim-Park method\u003c/b\u003e \u003csup\u003e[\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]\u003c/sup\u003e \u003c/p\u003e \u003cp\u003eThe thermal degradation kinetics equation formulated by Kim-Park is as follows:\u003cdiv id=\"Equ6\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ6\" name=\"EquationSource\"\u003e\n$$\\text{ln}{\\beta }=\\text{l}\\text{n}\\text{A}+\\text{ln}\\left(\\frac{{\\text{E}}_{\\text{a}}{\\prime }}{\\text{R}}\\right)+\\text{ln}\\left[1-\\text{n}+\\frac{\\text{n}}{0.9444}\\right]-5.3305-1.0516\\left(\\frac{{\\text{E}}_{\\text{a}}{\\prime }}{\\text{R}{\\text{T}}_{\\text{m}\\text{d}}}\\right)$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere \u003cem\u003en\u003c/em\u003e = ((1-\u003cem\u003eα\u003c/em\u003e\u003csup\u003em\u003c/sup\u003e)/[(\u003cem\u003eRT\u003c/em\u003e\u003csub\u003emd\u003c/sub\u003e\u003csup\u003e2\u003c/sup\u003e) (d\u003cem\u003eα\u003c/em\u003e/d\u003cem\u003et\u003c/em\u003e)].\u003c/p\u003e \u003cp\u003eWhere \u003cem\u003eT\u003c/em\u003e\u003csub\u003emd\u003c/sub\u003e is the largest weight loss temperature, \u003cem\u003eα\u003c/em\u003e\u003csup\u003em\u003c/sup\u003e is the conversion of weight loss at that time. \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e\u0026prime; can be obtained from the slope of ln\u003cem\u003eβ\u003c/em\u003e vs. 1/\u003cem\u003eT\u003c/em\u003e\u003csub\u003emd\u003c/sub\u003e and ln\u003cem\u003eA\u003c/em\u003e can be calculated from the intercept value.\u003c/p\u003e"},{"header":"Results and discussions","content":"\u003cp\u003e\u003cstrong\u003e3.1 Copolymerization kinetics of styrene copolymers composed with maleic anhydride derivative\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn order to characterize the reaction degree of styrene and maleic anhydride derivatives at different temperature and time points, the concentration of styrene monomer was quantitatively calculated by \u003csup\u003e1\u003c/sup\u003eH NMR. Figure. 1 shows the attribution of H atoms of styrene and CPMI.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFigure 1 depicts the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of the reaction system consisting of the monomer CPMI and St before undergoing any temperature elevation. The peaks at 5.8 ppm and 5.2 ppm correspond to the chemical shifts of two hydrogen atoms on tertiary carbons involved in the reaction with St double bonds\u003csup\u003e[40]\u003c/sup\u003e.During the early stage of the reaction, under the initiation of free radicals, CPMI and St monomers first form alternating copolymer blocks, such as St-CPMI or CPMI-St, until one of the monomers is depleted\u003csup\u003e[41]\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eThe progress of the reaction system was monitored in situ through \u003csup\u003e1\u003c/sup\u003eH NMR, with the consumption of monomers characterized by the consumption of St at different reaction times. Figure 2 illustrates the reaction system of CPMI and styrene at 80-110\u0026deg;C. As the reaction time increases, the monomers are gradually consumed, leading to a decrease in the intensity of the absorption peaks in the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum. With the progression of the reaction, the molecular weight of PCS gradually increases, resulting in the appearance of new peaks. The peaks corresponding to the benzene ring transform from distinct and sharp to broadened, exhibiting the typical peak shape of large molecular weight compounds in nuclear magnetic resonance spectroscopy.As the reaction time increases, the two peaks of St (\u0026delta;= The strength of 5.8 and 5.2 is decreasing, indicating that as the reaction progresses, the St monomer is continuously consumed, and finally the copolymer PCS is synthesized.\u003c/p\u003e\n\u003cp\u003eFigure 3 presents the linear fitting plot of the monomer conversion of St in the CPMI-St reaction system at different reaction temperatures. Initially, the conversion rate achieves a relatively high level, followed by a slow increase with prolonged reaction time. Under conditions of constant initiator concentration, an increase in reaction temperature leads to an enhancement in the conversion rate. Temperature exhibits a significant influence on the monomer conversion rate within the range of 90\u0026deg;C to 100\u0026deg;C, conforming to the principles of free radical copolymerization.\u003c/p\u003e\n\u003cp\u003eThe plot in Figure 4 displays the linear fitting relationship between ln(\u003cem\u003e[M]\u003csub\u003e0\u003c/sub\u003e/[M]\u003c/em\u003e) and reaction time during the copolymerization of PCS at different temperatures. The slope of the fitted line, which represents the value of \u003cem\u003eK\u003c/em\u003e, was obtained using Equation (1). The calculated \u003cem\u003eK\u003c/em\u003e values at different temperatures were 8.41\u0026times;10\u003csup\u003e-5\u003c/sup\u003e, 1.64\u0026times;10\u003csup\u003e-4\u003c/sup\u003e, 2.76\u0026times;10\u003csup\u003e-4\u003c/sup\u003e, and 3.45\u0026times;10\u003csup\u003e-4\u003c/sup\u003e, respectively. The high fitting variances (above 0.98) indicate a strong agreement between the experimental data and the theoretical model. The polymerization temperature exerts an influence on intermolecular motion and energy propagation, with elevated temperatures being conducive to enhanced mass and heat transfer between materials\u003csup\u003e[42]\u003c/sup\u003e.It can be observed from Figure 4 that as the temperature increases, the \u003cem\u003eK\u003c/em\u003e value also increases, indicating an accelerated reaction rate. This can be attributed to the enhanced decomposition rate of the initiator and the increased participation of monomers in the reaction.\u003c/p\u003e\n\u003cp\u003eFigure 5 presents the relationship between ln(\u003cem\u003e[M]\u003csub\u003e0\u003c/sub\u003e/[M]\u003c/em\u003e) and reaction time for PNS, PCS, and PFS. The slope of PNS is greater than that of PCS, which is greater than that of PFS. This suggests that the \u003cem\u003eK\u003c/em\u003e value of PNS is higher than that of PCS, which is higher than that of PFS. Therefore, in copolymerization reactions, PNS exhibits a faster reaction rate compared to PCS, and PCS shows a faster reaction rate compared to PFS.\u003c/p\u003e\n\u003cp\u003eTo determine the activation energy of the copolymerization of St and CPMI, Figure 6 demonstrates the linear fitting of ln(\u003cem\u003ek\u003c/em\u003e) versus -1/(\u003cem\u003eRT\u003c/em\u003e) values at different temperatures, based on Equation (3). The obtained slope yields an \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e value of 22.6 kJ/mol with a fitting degree of 0.996. The \u003cem\u003eK\u003c/em\u003e values and polymerization activation energies of PNS and PFS are similarly obtained using the same method and are presented in Table 1. The fitting variances for all the data are above 0.95.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTable. 1. Kinetic parameters for polymerization of PNS, PCS, and PFS.\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" width=\"100%\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"13.26530612244898%\" valign=\"top\"\u003e\n \u003cp\u003eSimple\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.367346938775512%\"\u003e\n \u003cp\u003e\u003cem\u003eT\u003c/em\u003e（℃） \u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.346938775510203%\"\u003e\n \u003cp\u003e\u003cem\u003ek\u003c/em\u003e\u003csup\u003e\u0026nbsp;b\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.26530612244898%\"\u003e\n \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e1\u003c/sub\u003e\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.53061224489796%\"\u003e\n \u003cp\u003e\u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e（kJ/mol） \u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.224489795918368%\"\u003e\n \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026nbsp;e\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"13.26530612244898%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003ePNS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.367346938775512%\"\u003e\n \u003cp\u003e80\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.346938775510203%\"\u003e\n \u003cp\u003e3.13\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.26530612244898%\"\u003e\n \u003cp\u003e0.9898\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.53061224489796%\" rowspan=\"4\"\u003e\n \u003cp\u003e22.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.224489795918368%\" rowspan=\"4\"\u003e\n \u003cp\u003e0.996\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e4.35\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9896\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e100\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e4.71\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9868\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e5.32\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9869\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"13.26530612244898%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003ePCS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.367346938775512%\"\u003e\n \u003cp\u003e80\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.346938775510203%\"\u003e\n \u003cp\u003e8.41\u0026times;10\u003csup\u003e-5\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.26530612244898%\"\u003e\n \u003cp\u003e0.9701\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.53061224489796%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003e59.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.224489795918368%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003e0.982\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e1.67\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9868\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e100\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e2.76\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9985\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e3.45\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9976\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"13.26530612244898%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003ePFS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.367346938775512%\"\u003e\n \u003cp\u003e80\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"17.346938775510203%\"\u003e\n \u003cp\u003e6.64\u0026times;10\u003csup\u003e-5\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.26530612244898%\"\u003e\n \u003cp\u003e0.9527\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.53061224489796%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003e54.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"11.224489795918368%\" rowspan=\"4\" valign=\"top\"\u003e\n \u003cp\u003e0.997\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e1.11\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9915\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e100\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e1.76\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9641\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"37.5%\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"35.416666666666664%\"\u003e\n \u003cp\u003e2.45\u0026times;10\u003csup\u003e-4\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"27.083333333333332%\"\u003e\n \u003cp\u003e0.9899\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eAs shown in Table 1, the \u003cem\u003eK\u003c/em\u003e value of PNS is higher than that of PCS, which is higher than that of PFS. Furthermore, the required activation energy for the synthesis of PFS is higher than that for PNS but lower than that for PCS. Therefore, the introduction of carboxyl and fluorine groups has varying effects on the polymerization process of maleic anhydride-styrene copolymers. The study of polymerization kinetics provides a theoretical foundation for the synthesis of such copolymers, considering the influence of functional groups on monomer reactivity. The electron-withdrawing ability of electron-withdrawing groups is attenuated, resulting in a more challenging reaction process.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.2 Thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTable. 2. Thermal degradation kinetic parameters of PNS, PCS, and PFS.\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" width=\"100%\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd width=\"11.458333333333334%\"\u003e\n \u003cp\u003eSamples\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.541666666666666%\"\u003e\n \u003cp\u003e\u003cem\u003e\u0026beta;\u003c/em\u003e (\u0026deg;C/min)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"10.416666666666666%\"\u003e\n \u003cp\u003e\u003cem\u003eT\u003csub\u003eo\u003c/sub\u003e\u003c/em\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003e(\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"14.583333333333334%\"\u003e\n \u003cp\u003e\u003cem\u003eT\u003csub\u003emax\u0026nbsp;\u003c/sub\u003e\u003c/em\u003e(\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\"\u003e\n \u003cp\u003e\u003cem\u003eR\u003csub\u003emd\u0026nbsp;\u003c/sub\u003e\u003c/em\u003e(%/min)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eE\u003csub\u003ea\u003c/sub\u003e\u003c/em\u003e\u0026prime;(KJ/mol)\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"11.458333333333334%\" rowspan=\"4\"\u003e\n \u003cp\u003ePNS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.541666666666666%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"10.416666666666666%\"\u003e\n \u003cp\u003e350.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"14.583333333333334%\"\u003e\n \u003cp\u003e410.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\"\u003e\n \u003cp\u003e-6.79\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" rowspan=\"4\"\u003e\n \u003cp\u003e129.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" rowspan=\"4\"\u003e\n \u003cp\u003e0.9851\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e369.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e423.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-13.43\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e376.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e430.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-19.76\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e386.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e434.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-28.06\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"11.458333333333334%\" rowspan=\"4\"\u003e\n \u003cp\u003ePCS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.541666666666666%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"10.416666666666666%\"\u003e\n \u003cp\u003e360.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"14.583333333333334%\"\u003e\n \u003cp\u003e416.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\"\u003e\n \u003cp\u003e-9.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" rowspan=\"4\"\u003e\n \u003cp\u003e161.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" rowspan=\"4\"\u003e\n \u003cp\u003e0.98434\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e373.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e425.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-18.49\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e384.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e438.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-30.02\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e387.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e440.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-34.33\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"11.458333333333334%\" rowspan=\"4\"\u003e\n \u003cp\u003ePFS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"13.541666666666666%\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"10.416666666666666%\"\u003e\n \u003cp\u003e374.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"14.583333333333334%\"\u003e\n \u003cp\u003e414.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\"\u003e\n \u003cp\u003e-11.03\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" rowspan=\"4\"\u003e\n \u003cp\u003e209.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"16.666666666666668%\" rowspan=\"4\"\u003e\n \u003cp\u003e0.98967\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e383.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e430.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-20.47\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e392.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e437.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-30.44\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd width=\"24.528301886792452%\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"18.867924528301888%\"\u003e\n \u003cp\u003e396.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"26.41509433962264%\"\u003e\n \u003cp\u003e442.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd width=\"30.18867924528302%\"\u003e\n \u003cp\u003e-40.21\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eThermogravimetric analysis (TGA) is commonly used to investigate the thermal decomposition behavior of polymers and analyze their thermal stability. Figure 7 shows the TG and DTG curves of maleic anhydride-derived styrene copolymers at heating rates of 5\u0026deg;C/min, 10\u0026deg;C/min, 15\u0026deg;C/min, and 20\u0026deg;C/min. The thermal degradation kinetics parameters obtained from TGA testing and calculated using theoretical formula (6) are listed in Table 2. The main degradation process of maleic anhydride-derived styrene copolymers occurs in only one stage, with a single maximum weight loss peak rate. The degradation temperature range is between 350\u0026deg;C and 470\u0026deg;C, and the maximum degradation rate is between 410\u0026deg;C and 440\u0026deg;C, indicating good thermal stability of the maleic anhydride-derived styrene copolymers, which is suitable for most polymer processing conditions.\u003c/p\u003e\n\u003cp\u003eFrom the Figure 7, it can be observed that the TG and DTG curves are influenced by the heating rate. With increasing heating rate, the TG and DTG curves shift towards higher temperatures, and the decomposition temperature and maximum decomposition rate increase. This can be attributed to the lag effect in the heat transfer process. As the heating rate increases, the time required for the sample to reach the specified temperature is shortened, resulting in faster reaction times. Temperature differences within the sample may lead to an increase in peak values\u003csup\u003e[43,44]\u003c/sup\u003e .\u003c/p\u003e\n\u003cp\u003eWith increasing heating rate, the degradation temperature of the maleic anhydride-derived styrene copolymers also increases. According to the equilibrium theory, at lower heating rates, it is easier to reach equilibrium at any point as the temperature increases. At faster heating rates, heat diffusion is slower, making it difficult to reach equilibrium, resulting in a shift of the curve towards higher temperatures and an increase in decomposition temperature \u003csup\u003e[45-47]\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eFigure 8a shows the linear fitting of ln\u003cem\u003e\u0026beta;\u003c/em\u003e and 1/\u003cem\u003eT\u003c/em\u003e values for PNS, PCS, and PFS at different heating rates based on theoretical formula (6), and the fitting slopes correspond to the thermal activation energy \u003cem\u003eEa\u003c/em\u003e\u0026prime;. Figure 8b is a bar figure showing the thermal activation energy of PNS, PCS, and PFS. The thermal activation energy of PNS, PCS, and PFS is 129.7 KJ/mol, 161.3 KJ/mol, and 209.8 KJ/mol, respectively, with a fitting degree above 0.98. The thermal activation energies of PCS and PFS, which introduce carboxyl and fluorine groups, are higher than that of PNS, indicating that the introduction of carboxyl and fluorine groups is beneficial for enhancing the thermal stability of maleic anhydride-derived styrene copolymers. However, the thermal activation energy of PFS is higher than that of PCS, suggesting that the influence of the fluorine group on the thermal stability of maleic anhydride-derived styrene copolymers is greater, resulting in a more significant enhancement of thermal stability. This may be attributed to the large electronegativity and small size of the fluorine atom, as well as the strong polarity of the fluorine atom, which can generate strong intermolecular interactions and higher strength between C-F bonds\u003csup\u003e[48]\u003c/sup\u003e . The aromatic C-F bonds have high bond energy, strong electron-withdrawing effects, and the small size of the F group, which favors the formation of a dense linear structure and contributes to the good thermal stability of maleic anhydride-derived styrene copolymers with fluorine groups\u003csup\u003e[49]\u003c/sup\u003e .\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, carboxyl and fluorine groups were introduced into the maleic anhydride-styrene copolymer PNS through solution polymerization, resulting in the synthesis of maleic anhydride derivatives, namely polystyrene-carboxyl copolymer (PCS) and polystyrene-fluorine copolymer (PFS). The copolymerization kinetics and thermal degradation kinetics of PNS, PCS, and PFS were studied using the Arrhenius equation and the Kim-Park method. The results indicate that the incorporation of carboxyl and fluorine groups has varying effects on the maleic anhydride-styrene copolymer. The addition of carboxyl and fluorine groups reduces the polymerization activity of maleic anhydride styrene copolymer, resulting in a decrease in K value and an increase in polymerization activation energy. The \u003cem\u003eK\u003c/em\u003e value of PNS is higher than that of PCS, which in turn is higher than PFS. During copolymerization, the reaction rate of PCS is higher than that of PFS. The co-polymerization activation energy of PNS is higher than that of PFS, which is higher than that of PCS. Therefore, PFS is more prone to copolymerization compared to PCS. The decomposition temperature and decomposition activation energy \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e\u0026prime; of PCS and PFS are higher than that of PNS, indicating that the addition of carboxyl and fluorine groups improves the thermal stability of the maleic anhydride-styrene copolymer. Due to the unique properties of fluorine atoms, PFS exhibits a higher decomposition temperature and degradation activation energy \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e\u0026prime;, resulting in a more significant enhancement in thermal stability.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the Natural Science Foundation of China [grant number 51663006, 52163009], Guizhou Provincial Science and Technology Program Project (Qiankehe Support [2023] General 084) and the Special Research Fund of Guizhou University (GZU Special Position Contract No 2021(44)).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflicts of interest:\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe authors have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eJing Huang, Turner S-Richard. Recent advances in alternating copolymers: The synthesis, modification, and applications of precision polymers[J]. Polymer, 2017, 116572\u0026ndash;586.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWeiwei Liu, Li Qian, Zhang Yin, et al. Continuous-flow RAFT copolymerization of styrene and maleic anhydride: acceleration of reaction and effect of polymerization conditions on reaction kinetics[J]. Journal of Flow Chemistry, 2021, 11(4): 867\u0026ndash;875.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYong-guang Jia, Liu Ling-yan, Lei Bin, et al. Crown Ether Cavity-Containing Copolymers via Controlled Alternating Cyclocopolymerization[J]. Macromolecules, 2011, 44(16): 6311\u0026ndash;6317.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGuijing Chen, Yang Yuanyuan, Kang Dongdong, et al. Enhanced performances of chlorinated polyvinyl chloride (CPVC) ultrafiltration membranes by styrene-maleic anhydride copolymer[J]. Separation and Purification Technology, 2021, 258118043.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHongyun Duan, Qiu Teng, Guo Longhai, et al. The aminolysis of styrene\u0026ndash;maleic anhydride copolymers for a new modifier used in urea-formaldehyde resins[J]. International Journal of Adhesion and Adhesives, 2016, 66138\u0026ndash;146.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHossein Mahdavi, Ardeshiri Fatemeh. An efficient nanofiltration membrane based on blending of polyethersulfone with modified (styrene/maleic anhydride) copolymer[J]. Journal of the Iranian Chemical Society, 2016, 13(5): 873\u0026ndash;880.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eS-Duygu S\u0026uuml;tekin, Atıcı Ayşe-Bakar, G\u0026uuml;ven Olgun, et al. Controlling of free radical copolymerization of styrene and maleic anhydride via RAFT process for the preparation of acetaminophen drug conjugates[J]. Radiation Physics and Chemistry, 2018, 1485-12.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSara Shaghaghi, Mahdavian Ali-Reza. Flame-Retardancy Improvement of Novel Styrene\u0026ndash;Maleic Anhydride Based Copolymers[J]. Journal of Polymer Research, 2006, 13(5): 413\u0026ndash;419.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYuan Yao, Zhang Xiaohong, Guo Zhaoyan, et al. Preparation and application of recyclable polymer aerogels from styrene-maleic anhydride alternating copolymers[J]. Chemical Engineering Journal, 2023, 455140363.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTao Qian, Zhong Yi, Mao Zhiping, et al. The comb-like modified styrene-maleic anhydride copolymer dispersant for disperse dyes[J]. Journal of Applied Polymer Science, 2019, 136(16): 47330.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChen Li, Pan Xingang, Hua Chunfan, et al. Synthesis of novel copoly(styrene\u0026ndash;maleic anhydride) materials and their luminescent properties[J]. European Polymer Journal, 2003, 39(6): 1091\u0026ndash;1097.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBert Klumperman. Mechanistic considerations on styrene\u0026ndash;maleic anhydride copolymerization reactions[J]. Polymer Chemistry, 2010, 1(5): 558.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNiels Ten Brummelhuis, Stutz Marvin-Bj\u0026ouml;rn. Penultimate effects in the copolymerization of maleic anhydride with electron-rich styrene derivatives[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2016, 54(18): 2932\u0026ndash;2939.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKun Liu, Xiong Qiaoqiao, Gu Zhuowei, et al. Highly efficient one-pot synthesis of anhydride-riched terpolymers from radical dual-alternating strategy[J]. Journal of Polymer Research, 2023, 30(6).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSagar Bag, Ghosh Soumyadeep, Paul Soumya, et al. Styrene-Maleimide/Maleic Anhydride Alternating Copolymers: Recent Advances and Future Perspectives[J]. Macromolecular Rapid Communications, 2021, 42(23): 2100501.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGustaaf Schoukens, Samyn Pieter. Thermo-analytical study on transitions in styrene\u0026ndash;maleic anhydride copolymers with low- and high-molecular weights[J]. Thermochimica Acta, 2014, 58028\u0026ndash;37.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eShihui Li, Cai Ling, Cui Dongmei. Lewis Acids Activated Spontaneous Alternating Copolymerization of Maleic Anhydride and Styrene Derivatives[J]. Chemistry \u0026ndash; An Asian Journal, 2023, 18(4).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGuillaume-Gody-Matthias-Hartlieb Guillaume Moriceau. Functional multisite copolymer by one-pot sequential RAFT copolymerization of styrene and maleic anhydride[J]. Polymer Chemistry, 2017, 84116\u0026ndash;4152.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMingqiang-Ding-Mengting-Chen Shaogan Niu, Zhenping Cheng Xiulin-Zhu. Synthesis of Well-Defined Copolymer of Acrylonitrile and Maleic Anhydride via RAFT Polymerization[J]. 2013, 51(24): 5263\u0026ndash;5269.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKun-Cao-Yuan-Huang He-Yang Liu. Kinetics and Simulation of the Imidization of Poly(styrene-co-maleic anhydride) with Amines[J]. 2006, 100(4): 2744\u0026ndash;2749.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG Ahmetli, Yazicigil Z, Kocak A, et al. Effects of different molecular weights of polystyrene on the acylation reaction and on the reaction kinetics[J]. Journal of Applied Polymer Science, 2005, 96(1): 253\u0026ndash;259.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePolina-Terpugova-Chuong-Bui Elena Chernikova. Effect of comonomer composition on the controlled free-radical copolymerization of styrene and maleic anhydride by reversible addition\u0026ndash;fragmentation chain transfer (RAFT)[J]. 2003, 44(15): 4101\u0026ndash;4107.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMAL-NAM-KIM-IK-MO-LEE EUN-SOO PARK. Living Radical Copolymerization of Styrene/Maleic Anhydride[J]. Polymer Chemistry, 2000, 28(12): 2239\u0026ndash;2244.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYitao Yu, Zhan Xiaoli, Zhang Qinghua, et al. Synthesis of triblock copolymer having alternating structures and kinetics study on RAFT-mediated bulk, miniemulsion and seed miniemulsion polymerizations[J]. Polymer Engineering \u0026amp; Science, 2011, 51(6): 1041\u0026ndash;1050.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWafaa-M Sayed. Preparation of modified polystyrene with maleic anhydride in the presence of different solvents[J]. Journal of Applied Polymer Science, 2008, 109(6): 4099\u0026ndash;4104.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTom\u0026aacute;s Romero Pietrafesa, Brandolin Adriana, Sarmoria Claudia, et al. A Comprehensive Monte Carlo Model of the Grafting of Maleic Anhydride onto Polypropylene with Experimental Validation[J]. Macromolecular Theory and Simulations, 2023.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCarla-V Luciani, Choi Kyu-Yong. Mathematical Modeling of Free Radical Solution Terpolymerization Reactions in a Batch and Continuous Flow Stirred Tank Reactors[J]. Macromolecular Theory and Simulations, 2021, 30(3): 2000094.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBert Klumperman, Heuts Johan-P-A. The solution copolymerization of styrene and maleic anhydride in a continuous stirred tank reactor and its theoretical modelling[J]. Polymer, 2020, 202122730.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXiaoyu Zou, Zhao Qian, Zhan Yikai, et al. Polymerization kinetics analysis of a thermostable, sequence-controllable polyamide polymer[J]. Journal of Molecular Structure, 2022, 1264133286.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGustaaf Schoukens, Samyn Pieter. Thermo-analytical study on transitions in styrene\u0026ndash;maleic anhydride copolymers with low- and high-molecular weights[J]. Thermochimica Acta, 2014, 58028\u0026ndash;37.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eC-N Cascaval, Chitanu G, Carpov A. On the thermal decomposition of copolymers of maleic anhydride with styrene[J]. Thermochimica acta, 1996, 275(2): 225\u0026ndash;233.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLinghan Xiao, Li Zhenguang, Dong Jinglong, et al. Fabrication of poly (methyl methacrylate-co-maleic anhydride) copolymers and their kinetic analysis of the thermal degradation[J]. Colloid and Polymer Science, 2015, 293(10): 2807\u0026ndash;2813.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG\u0026uuml;zin Pıhtılı, Biryan Fatih. Electrical investigation on Eu + 3- doped copolymer composite system and conventional kinetic analysis[J]. Journal of Molecular Structure, 2021, 1230129638.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYong-Zhong-Yao-Li-Li Jun Zhang. Thermooxidative Aging and Kinetics of the Thermooxidative Degradation of Ethylene \u0026ndash; Propylene \u0026ndash; Diene Terpolymer-graft-Maleic Anhydride/Calcium Carbonate Composites[J]. Journal of Applied Polymer Science, 2006, 103(4): 2575\u0026ndash;2767.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePi-Pi-hui-Wen-Xiu-fang Wang Zhai-min. Analysis of Most Probable Mechanism Functions and Thermal Degradation Kinetics of N-phenylmaleimide-styrene-maleic Copolymers[J]. Polymers and Polymer Composite, 2006, 15(5): 343\u0026ndash;414.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eG\u0026uuml;zin Pıhtılı, Biryan Fatih. Electrical investigation on Eu + 3- doped copolymer composite system and conventional kinetic analysis[J]. Journal of Molecular Structure, 2021, 1230129638.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJuxiang Luo, Cheng Deshu, Li Mingchun, et al. RAFT Copolymerization of Styrene and Maleic Anhydride with Addition of Ascorbic Acid at Ambient Temperature[J]. Advances in Polymer Technology, 2020, 20201\u0026ndash;8.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003e\u0026Ouml;zlen Altun, Ko\u0026ccedil;er Melike-\u0026Ouml;zge. Spectral, kinetic and thermodynamic studies of Pd (II) with Schiff base derived from L-asparagine and furfuraldehyde in the presence of 8-hydroxyquinoline[J]. Journal of Molecular Structure, 2021, 1224129242.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMostafizur-Rahaman-Dipak-Khastgir Lalatendu Nayak. Thermal Decomposition Behavior and Durability Evaluation of Thermotropic Liquid Crystalline Polymers[J]. Journal of Applied Polymer Science, 2017, 135(7): 1\u0026ndash;9.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXuwen Li, Han Li, Zhang Ruixue, et al. Regulation from gradient to near periodic sequence during anionic copolymerization of styrene and dimethyl-[4-(1-phenyl-vinyl)phenyl]silane (DPE-SiH)[J]. Polymer, 2022, 244124663.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJos\u0026eacute; Bonilla-Cruz, Guerrero-S\u0026aacute;nchez Carlos, Schubert Ulrich-S, et al. Controlled \u0026ldquo;Grafting-from\u0026rdquo; of poly[styrene-co-maleic anhydride] onto polydienes using nitroxide chemistry[J]. European Polymer Journal, 2010, 46(2): 298\u0026ndash;312.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWeiwei Liu, Li Qian, Zhang Yin, et al. Continuous-flow RAFT copolymerization of styrene and maleic anhydride: acceleration of reaction and effect of polymerization conditions on reaction kinetics[J]. Journal of Flow Chemistry, 2021, 11(4): 867\u0026ndash;875.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChihan Meng, Liu Xiucai. Study on thermal degradation kinetics of bio-based semi-aromatic high-temperature polyamide PA5T/56 and the effect of benzene ring[J]. Iranian Polymer Journal, 2022, 31(5): 641\u0026ndash;650.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYichen-Wang-Meiyun-Chai Yingkai Li. Pyrolysis kinetics and thermodynamic parameters of bamboo residues and its three main components using thermogravimetric analysis[J]. Biomass and Bioenergy, 2023, 170106705.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePradip Paik, Kar Kamal-K. Thermal degradation kinetics and estimation of lifetime of polyethylene particles: Effects of particle size[J]. Materials Chemistry and Physics, 2009, 113(2\u0026ndash;3): 953\u0026ndash;961.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHaonan Chen, Zhu Sheng, Zhou Rongfan, et al. Thermal Degradation Behavior of Thiol-ene Composites Loaded with a Novel Silicone Flame Retardant[J]. Polymers, 2022, 14(20): 4335.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWei Tang, Li Xin-Gui, Yan Deyue. Thermal decomposition kinetics of thermotropic copolyesters made from trans-p-hydroxycinnamic acid and p-hydroxybenzoic acid[J]. Journal of applied polymer science, 2004, 91(1): 445\u0026ndash;454.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eIon Sava, Damaceanu Mariana-Dana, Constantin Catalin-Paul, et al. Structure \u0026ndash; promoted high performance properties of triphenylmethane - containing polyimides and copolyimides[J]. European Polymer Journal, 2018, 108554\u0026ndash;569.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWei-Feng Peng, Lei Huan-Yu, Zhang Xin-Xin, et al. Fluorine Substitution Effect on the Material Properties in Transparent Aromatic Polyimides[J]. Chinese Journal of Polymer Science, 2022, 40(7): 781\u0026ndash;788.\u003c/span\u003e\u003c/li\u003e\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":"journal-of-polymer-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jpol","sideBox":"Learn more about [Journal of Polymer Research](https://www.springer.com/journal/10965)","snPcode":"10965","submissionUrl":"https://www.editorialmanager.com/jpol/","title":"Journal of Polymer Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"maleic anhydride derivative, styrene, copolymer, polymerization kinetics, thermal degradation kinetics, activating energy","lastPublishedDoi":"10.21203/rs.3.rs-3602005/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3602005/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe investigation of the polymerization kinetics and thermal degradation kinetics of maleic anhydride copolymers is of significant reference value for the synthesis of multifunctional and high-performance maleic anhydride-based copolymers and their applications in different fields. In this study, anhydride (MAH) derived styrene copolymers, namely Poly(\u003cem\u003eN\u003c/em\u003e-phenylmaleimide-alt-styrene) (PNS), Poly(\u003cem\u003eN\u003c/em\u003e-(4-carboxyphenyl) maleimide-alt-styrene) (PCS), and poly (N-fluorine- phenylmaleimide- alt-styrene) (PFS), were prepared using a solution copolymerization method. The copolymerization kinetics and thermal degradation kinetics of MAH derived styrene copolymers were investigated using nuclear magnetic resonance (NMR) and thermogravimetric analysis (TGA), as well as the Arrhenius equation and Kim-Park method. The study revealed that the incorporation of carboxyl and fluorine groups had varying degrees of influence on maleic anhydride-styrene copolymers. The copolymerization rate constant (\u003cem\u003eK\u003c/em\u003e value) followed the order PNS\u0026thinsp;\u0026gt;\u0026thinsp;PCS\u0026thinsp;\u0026gt;\u0026thinsp;PFS, while the copolymerization activation energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e) followed the order PNS\u0026thinsp;\u0026lt;\u0026thinsp;PFS\u0026thinsp;\u0026lt;\u0026thinsp;PCS. Moreover, the thermal degradation activation energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u0026prime;\u003c/em\u003e) followed the order PNS\u0026thinsp;\u0026lt;\u0026thinsp;PNS\u0026thinsp;\u0026lt;\u0026thinsp;PFS, indicating that PFS exhibited easier polymerization and the fluorine group significantly enhanced the thermal stability of the maleic anhydride-styrene copolymers.\u003c/p\u003e","manuscriptTitle":"Effect of para-substituent on copolymerization and thermal degradation kinetics of styrene copolymers composed with maleic anhydride derivative","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-11-29 16:52:56","doi":"10.21203/rs.3.rs-3602005/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2023-11-25T10:04:23+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2023-11-25T09:51:58+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Journal of Polymer Research","date":"2023-11-17T17:29:05+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2023-11-13T07:26:36+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Polymer Research","date":"2023-11-11T23:13:36+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-polymer-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jpol","sideBox":"Learn more about [Journal of Polymer Research](https://www.springer.com/journal/10965)","snPcode":"10965","submissionUrl":"https://www.editorialmanager.com/jpol/","title":"Journal of Polymer Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"8e8d1dfd-3afd-4cf4-aee1-c88722fd8e4b","owner":[],"postedDate":"November 29th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-03-21T08:12:49+00:00","versionOfRecord":{"articleIdentity":"rs-3602005","link":"https://doi.org/10.1007/s10965-024-03945-1","journal":{"identity":"journal-of-polymer-research","isVorOnly":false,"title":"Journal of Polymer Research"},"publishedOn":"2024-03-18 08:12:49","publishedOnDateReadable":"March 18th, 2024"},"versionCreatedAt":"2023-11-29 16:52:56","video":"","vorDoi":"10.1007/s10965-024-03945-1","vorDoiUrl":"https://doi.org/10.1007/s10965-024-03945-1","workflowStages":[]},"version":"v1","identity":"rs-3602005","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3602005","identity":"rs-3602005","version":["v1"]},"buildId":"_2-kVJe1T_tPrBINL-cwx","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}