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Abstract The copolymerization system of styrene (ST) and citraconic (α-methymaleic) anhydride (CA) was found to form semi-alternating copolymers when polymerized with a total monomer concentration of 4 mol/L in CCl4 at 50°C, with alternating copolymers being formed only when the CA mole fraction in feed was greater than 0.9. More than 50% of the linkage configurations at the cyclic CA units in the copolymers were found to be in cis configuration. This, together with the following observations, is consistent with a participation of the electron donor-acceptor (EDA) complex formed between ST and CA: (a) the complex participation model fits best, although only marginally, to the experimental triad mole fraction of alternating sequences; (b) the alternating monomer unit sequences and the cis linkage configuration at the cyclic CA units are more efficiently formed in non polar CCl4 solutions than in polar methy ethyl ketone. The equilibrium constant for the EDA complexation of ST and CA in CCl4 at 23°C is determined to be 0.142 ± 0.015 L/mol. 相似文献
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《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):253-261
The title copolymers have been prepared by the free-radical-initiated copolymerization of 2-chlorostyrene (2-ClSt), 4-chlorostyrene (4-ClSt) and 2,6-dichlorostyrene (2,6-DClSt) with maleic anhydride (MAn) in toluene at 65°C. Copolymers of chlorinated styrenes with MAn prepared under different monomer-to-monomer ratios in the feed have alternating composition. In all cases, the mixture of comonomers forms charge-transfer complex monomers (CTC). The initial rate of copolymerization increases with the increase of electron donors in the comonomer feed, and the highest rates were at the equimolar ratios of comonomers in the feed. The thermal stability of the polymers was measured by thermogravimetric analysis in nitrogen. Homopolymers decompose by a one-step mechanism, while copolymers are more thermostable and decompose by a two-step mechanism. Glass transition temperatures (Tgs) of homopolymers are lower than Tgs of copolymers. The number and weight average molecular weights of chlorinated copolymers are higher than those of the corresponding homopolymers. 相似文献
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CONTROLLED RADICAL COPOLYMERIZATION OF STYRENE AND MALEIC ANHYDRIDE UNDER GAMMA RADIATION IN THE PRESENCE OF BENZYL DITHIOBENZOATE 总被引:1,自引:0,他引:1
De-cheng Wu Ying-fang Zou Cai-yuan Pan Department of Polymer Science Engineering University of Science Technology of China Hefei China 《高分子科学》2002,(6):525-530
The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature inthe presence of benzyl dithiobenzoate (BDTB) was found to display "living" nature evidenced by constant concentration ofchain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecularweight distribution (M_w/M_n = 1.23-1.35). The compositional analysis and the sequence structural information of thecopolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that thecopolymers obtained also possess strictly alternating structure. 相似文献
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《Computational and Theoretical Polymer Science》1999,9(1):11-17
Fifteen copolymers of maleic anhydride (MA or 0) and styrene (ST or 1) were prepared in a wide range of MA mole fraction in feed of f0=0.01–0.90. ST (1) centred triad mole fractions (F010, F(011+110), F111) were determined from quaternary 13C NMR spectra of aromatic “next to chain” carbon of ST units. Non-linear least squares (NLLS) curve fitting was used to fit the theoretical equations of the (1) terminal-, (2) penultimate unit effect-, (3) complex participation-, (4) complex dissociation- and (5) comppen-model to the experimental data of the triad mole fractions and the copolymer composition (Scheme. 1)>. The sum of squares (SS) and the reactivity ratios were calculated from these fitting processes. The smallest SS value of F010 data, the test functions a and b and the “order grade matrix” consistently show that the (3) complex participation model is the most applicable model; while the (2) penultimate model is closely indicated for this copolymerisation. The (5) comppen model, unexpectedly, is the third best fit model. It can be explained by the small number of the meaningful experimental data (which is 10 for copolymer samples of f0=0.01–0.40) compared to the number of variable parameters (p) of the comppen model (which is seven). It is suggested when the number of the meaningful experimental data (i.e. the triad fractions vary widely from 0 to 1) is much greater than the number of variable parameters (p) of the comppen model, the comppen model will be proved by the SS value to be the best fitted model in describing this MA–ST copolymerisation. 相似文献
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Penultimate effects in the copolymerization of maleic anhydride with electron‐rich styrene derivatives 下载免费PDF全文
Niels ten Brummelhuis Marvin Björn Stutz 《Journal of polymer science. Part A, Polymer chemistry》2016,54(18):2932-2939
The (controlled) free‐radical copolymerization of maleic anhydride and styrene or derivatives thereof is often thought to provide nearly perfect alternating copolymers. Here, the RAFT copolymerization of electron‐rich styrene derivatives with maleic anhydride is reported. This copolymerization shows distinct penultimate effects, resulting in polymers with increased incorporation of styrene monomers, that is, where a tendency toward periodic (S‐S‐MA) copolymers exists. This work could be a first step towards periodic copolymers based on maleic anhydride and styrene derivatives. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2932–2939 相似文献
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Paul G. Brown Kiyohisa Fujimori 《Journal of polymer science. Part A, Polymer chemistry》1994,32(15):2971-2978
The Comppen model for the mechanism of free-radical copolymerization has been developed to account for both penultimate effects and the participation of 1:1 electron donor-acceptor complexes during chain propagation. This was achieved by incorporating penultimate effects into the existing complex participation model of Cais, Farmer, Hill, and O'Donnell, using probability theory to derive new copolymer composition and sequence distribution equations that are solely functions of the reactivity ratios, the composition of the comonomer feed, and the equilibrium constant for 1:1 electron donor-acceptor complex formation. The model was applied to experimental data from styrene/maleic anhydride copolymers prepared in methyl ethyl ketone at 50°C over a wide range of comonomer feed compositions, using nonlinear least-squares curve fitting techniques to determine best estimates of the reactivity ratios. Copolymer compositions and sequence distributions for copolymers in this comonomer system were then predicted using the Comppen model and compared to those determined experimentally via 13C-NMR spectroscopy. © 1994 John Wiley & Sons, Inc. 相似文献
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《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):1087-1097
The 13C NMR technique of distortionless enhancement by polarization transfer and quaternary 13C NMR are used to quantitatively determine the proportion of alternating triad and the proportion of cis/trans linkage configurations at the cyclic N-phenylmaleimide (PMI) monomer units in the copolymers of PMI and 2-chloroethyl vinyl ether (CEVE), which are prepared by a radical initiator in chloroform solvent at 50°C. The amount of the cis linkage configuration at PMI units is found to be proportional to the amount of alternating CEVE-PMI-CEVE triads in the copolymers; i.e., a relation, (% of cis linkages at PMI units) = (48 ± 5.0%) (mol fraction of CEVE-PMI-CEVE triads), is found in the PMI-CEVE copolymers. It is concluded that the cis linkage configuration is formed predominantly in the process of the formation of the alternating CEVE-PMI-CEVE triads in this copolymerization, and that, according to the Olson-Butler mechanism of a complex participation, 48 ± 5.0% of all the reactions which give CEVE-PMI-CEVE triads is the attack by growing CEVE radicals on the PMI component of an electron donor-acceptor (EDA) complex of the comonomers from the syn direction relative to the CEVE component of the complex. The equilibrium constant K of the 1:1 EDA complexation in chloroform at 25°C is determined to be 0.260 L mol?1 by 1H NMR spectroscopy. 相似文献
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Loc Quach Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1981,19(10):2405-2418
Alternating head-to-head (h-h) copolymers of methyl or n-butyl acrylates with the corresponding methacrylates were synthesized by alternating copolymerization of ethylene with citraconic anhydride, followed by esterification and Characterization. The respective equimolar (1:) head-to-tail (h-t) copolymers were also prepared by conventional radical copolymerization as comparison. The alternating, relatively low molecular weight h-h copolymers obtained showed softening, glass transition, and degradation temperatures somewhat higher than those displayed by the 1:1 h-t copolymers. After pyrolysis the main decomposition products from both h-h and h-t copolymers were alcohols, acrylates, and methacrylates. Furthermore, the ratios of alcohols to acrylates were larger for the h-h than for the h-t copolymers and smaller for the methyl than for the n-butyl esters. 相似文献
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Hidefumi Hirai Tsuneaki Tanabe Hideomi Koinuma 《Journal of polymer science. Part A, Polymer chemistry》1980,18(1):203-222
Triad cotacticities of alternating copolymers of methyl methacrylate with styrene prepared in the presence of zinc chloride, ethylaluminium sesquichloride, and ethylboron dichloride are investigated from the mechanistic point of view by means of 1H- and 13C-NMR. The cotacticities from 1H-NMR spectra are obtained accurately by using α-d-styrene in the place of styrene and by measuring the spectra on the copolymer in o-dichlorobenzene at 170°C. The relative intensities of three peaks of the splitting signal for the methoxy protons in the nonalternating copolymers obtained by the use of benzoyl peroxide in the absence of metal halides agree well with the cotacticity distribution calculated theoretically by the Lewis-Mayo mechanism with the stereoregulation following Bernoullian statistics. The splitting signals in the 1H- and 13C-NMR spectra of the alternating copolymers prepared in the presence of metal halides cannot be explained by the same mechanism. The relative intensities of three peaks of the splitting signals for the methoxy protons and for the carbonyl carbon in the methyl methacrylate unit (the contents of cotactic triads centered by the methyl methacrylate unit) are not equal to those for the aromatic C1 carbon in the styrene unit (the contents of cotactic triads centered by styrene unit). The value of f2Y - 4fxfz is not equal to zero, where fx, fy, and fz are the cosyndiotactic, coheterotactic, and coisotactic triad contents, respectively, in the alternating copolymer. Copolymers obtained in the presence of zinc chloride are not exactly equimolar alternating but always contain a methyl methacrylate unit in excess, and the relative intensities of the three peaks for the aromatic C1 carbon change with the copolymer composition. These results are explained by a proposed mechanism: the alternating copolymerization proceeds through the homopolymerization of a ternary molecular complex composed of a metal halide, methyl methacrylate, and styrene, accompanied with the stereoregulation following first-order Markovian statistics; the increase of methyl methacrylate content in the copolymer prepared in the presence of zinc chloride is caused by the participation of the binary molecular complex composed of a metal halide and methyl methacrylate in addition to the ternary molecular complex. 相似文献
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Yi Li 《European Polymer Journal》2010,46(4):821-828
Stilbene-maleic anhydride is a well-known donor-acceptor comonomer pair which undergoes free radical copolymerization to form an alternating copolymer. A series of methyl substituted stilbenes were synthesized and copolymerized with maleic anhydride. A conversion versus time study was undertaken to understand the methyl substituent effect on copolymerization rates. Methyl substituents on the phenyl ring of stilbene can change the reactivity of stilbene by changing the resonance stability of the propagating radical and steric hindrance in the propagation step and thereby change the copolymerization rate. Methyl substituted stilbene-maleic anhydride copolymers were determined by quantitative 13C 1D NMR to be alternating copolymers. Size exclusion chromatography (SEC) measurements showed that the weight-average molecular weights of these copolymers varied from 3000 to over 1,000,000 g/mol. Interchain aggregation was observed in poly((E)-4-methylstilbene-alt-maleic anhydride) by dynamic light scattering (DLS). The SEC trace for poly((E)-4-methylstilbene-alt-maleic anhydride) exhibited bimodal peaks. No glass transition temperature or crystalline melting temperature was observed between 0 °C and 250 °C by differential scanning calorimetry (DSC). Thermogravimetric analysis (TGA) showed that these polymers have 5% weight loss around 290 °C. 相似文献
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Jun Ma Chong Cheng Guorong Sun Karen L. Wooley 《Journal of polymer science. Part A, Polymer chemistry》2008,46(11):3488-3498
A new synthetic methodology for the preparation of copolymers having high incorporation of 1‐alkene together with multifunctionalities has been developed by polarity‐activated reversible addition‐fragmentation chain transfer (RAFT) copolymerization. This approach provides well‐defined alternating poly(1‐decene‐alt‐maleic anhydride), expanding the monomer types for living copolymerizations. Although neither 1‐decene (DE) nor maleic anhydride (MAn) has significant reactivity in RAFT homopolymerization, their copolymers have been synthesized by RAFT copolymerizations. The controlled characteristics of DE‐MAn copolymerizations were verified by increased copolymer molecular weights during the copolymerization process. Ternary copolymers of DE and MAn, with high conversion of DE, could be obtained by using additive amounts (5 mol %) of vinyl acetate or styrene (ST), demonstrating further enhanced monomer reactivities and complex chain structures. When ST was selected as the third monomer, copolymers with block structures were obtained, because of fast consumption of ST in the copolymerization. Moreover, a wide variety of well‐defined multifunctional copolymers were prepared by RAFT copolymerizations of various functional 1‐alkenes with MAn. For each copolymerization, gel permeation chromatography analysis showed that the resulting copolymer had well‐controlled Mn values and fairly low polydispersities (PDI = 1.3–1.4), and 1H and 13C NMR spectroscopies indicated strong alternating tendency during copolymerization with high incorporation of 1‐alkene units, up to 50 mol %. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3488–3498, 2008 相似文献
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The copolymerization of styrene (St) with maleic anhydride (MAh) performed at 22 °C in the presence of dibenzyl trithiocarbonate exhibits controlled nature evidenced by: narrow molecular weight distribution, controlled molecular weight and first-order polymerization kinetics. The composition analysis of the copolymers obtained by 13C NMR spectra shows the molar fraction of St in obtained copolymers is almost equal to 0.5 throughout the copolymerization. The sequence structure of the copolymer was obtained from DEPT experiments by recording the spectra at π/4 and 3π/4, and then combining them together, the results showed that the copolymers obtained possessed well-defined alternating structure. The experiment shows that charge-transfer-complex formed from St and MAh participates in both initiation and chain growth throughout the copolymerization. 相似文献
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马来酸酐和苯乙烯是被广为研究的一对电荷转移复合物 (Chargetransfercomplex,简称CTC) ,而且能通过通常的自由基聚合发生交替共聚[1] .所得的聚合物由于酸酐基团的存在 ,很易进行大分子改性得到具有某些特殊功能的高分子 .不过 ,所得共聚物的分子量难以控制且分子量分布也较宽 .近年来发展起来的“活性” 可控自由基聚合越来越为人们所关注 ,因为采用这种方法不仅可对聚合物的分子量进行设计 ,同时分子量分布也较窄 ,也不需要活性离子型聚合那样严格的聚合条件 .关于烯类单体的活性自由基聚合迄今主要有氮氧自由基… 相似文献
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The mechanism of copolymerization of vinyl chloride (V) with sulfur dioxide (S) to form a variable composition polysulfone with average V:S molar ratio n ≥ 1 is examined. The copolymerization deviates from Lewis-Mayo behavior above -78°C. Alternative models for propagation involving (1) penultimate and pen-penultimate unit effects, (2) complex participation, and (3) depropagation are considered quantitatively by comparison of calculated and experimental copolymer/comonomer composition relationships and comonomer sequence distributions. Our theoretical modeling of the copolymerization shows that it is difficult to discriminate convincingly between alternative mechanisms. The penultimate and pen-penultimate effect models can account for the copolymer compositions, but not for the dilution effects which were observed provided the diluent is truly inert. The complex participation model can account for experimental behavior from -78 to -18°C by the assumption of addition of SV complexes, but it becomes rapidly less satisfactory at higher temperatures. Depropagation is the only model which can account for the compositions and dilution effects above 0°C. Progressive depropagation, with increasing temperature, of chains ending in the triad sequences ~SVS?, ~VVS?, and ~VSV? can explain the observed behavior over the entire comonomer composition and temperature range, but involvement of comonomer complexes in the propagation reactions is highly likely below 0°C. 相似文献
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