苯乙烯和马来酸酐共聚物的13C NMR谱解析和分子链结构表征

波谱学杂志

苯乙烯和马来酸酐共聚物的¹³C NMR谱解析和分子链结构表征

杜定准, 吴德成, 潘才元

中国科学技术大学高分子科学与工程系，安徽合肥 230026

出版日期:2003-12-05 发布日期:2003-12-05
作者简介:杜定准(1945-)，河南人，副教授，长期从事仪器分析谱学、高分子波谱学和材料研究方法等课程的教学工作,E-mail:dzdu@ustc.edu.cn,电话：(0551)3601703
基金资助:
国家自然科学基金资助项目(50173025).

MICROSTRUCTURE OF STYRENE-MALEIC ANHYDRIDE COPOLYMERS STUDIED BY ¹³C NMR

DU Ding-zhun, WU De-cheng, PAN Cai-yuan

Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China

Online:2003-12-05 Published:2003-12-05
Supported by:
国家自然科学基金资助项目(50173025).

摘要/Abstract

摘要：

通过比较高温110 ℃下特定苯乙烯-马来酸酐共聚物H10和常温紫外辐照特定共聚合的苯乙烯-马来酸酐共聚物UV4的¹³C质子去偶谱和DEPT135谱，总结给出共聚
物链中马来酸酐环中酸酐基的取代效应参数（α=13.5、β=2.5、γ=-2）及引用苯基取代参数：α=16、β=6、γ=-2，对共聚物主链碳的化学位移进行了经验计算，对所有碳，尤其是主链碳在三单元组或四单元组水平上进行了链序列结构归属. 在进行峰面积积分的基础上，对共聚物分子链两种组份摩尔比或摩尔含量、交替度、链嵌段长度、马来酸酐环残基中顺反异构体比和共聚物数均分子量等进行了表征. 共聚物UV4比H10的交替度高许多，表明聚合温度对苯乙烯和马来酸酐共聚合交替链结构的形成有重要影响.

关键词: 核磁共振, 苯乙烯-马来酸酐共聚物, 碳化学位移计算, 交替度, 数均序列长度

Abstract:

Two styrene/maleic anhydride copolymers (St/MAh), H10 and UV4, were prepared by controlled polymerization at 110 ℃, using 1-(ethoxycarbonyl)-prop-1-yl dithiobenzoate (EPDTB) as a chain transfer agent and AIBN as an initiator, and by copolymerization in THF with EPDTB as an initiator under UV irradiation at
room temperature respectively. Normal ¹³C NMR spectra and DEPT135 spectra were measured for both copolymers. All carbon chemical shifts in St/MAh copolymers were assigned. As a comparison, chemical shifts of the main chain carbons were calculated based on the substitution constants for phenyl group of St unit: α=16, β=6, γ=-2, and for anhydride group of MAh: α=13.5, β=2.5, γ=-2. The molar ratio of St to MAh, (F_S/F_M), alternation degree, number-average sequence length of St block, molar ratio of cis- to trans-configuration of MAh ring and numberaverage molecular weight for the samples H10 and UV4 were calculated using integral values of the corresponding peaks. The copolymer UV4 had much higher alternating degree than that of H10, indicating a big influence of polymerization temperature on the formation of alternating structure in the copolymerization of St and MAh.

Key words: ¹³C NMR, styrene/maleic anhydride copolymers, NMR chemical shift, degree of alternation, number-average sequence length

中图分类号:

O641.13

杜定准, 吴德成, 潘才元. 苯乙烯和马来酸酐共聚物的¹³C NMR谱解析和分子链结构表征[J]. 波谱学杂志.

DU Ding-zhun, WU De-cheng, PAN Cai-yuan. MICROSTRUCTURE OF STYRENE-MALEIC ANHYDRIDE COPOLYMERS STUDIED BY ¹³C NMR[J]. Chinese Journal of Magnetic Resonance.

参考文献

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苯乙烯和马来酸酐共聚物的¹³C NMR谱解析和分子链结构表征

MICROSTRUCTURE OF STYRENE-MALEIC ANHYDRIDE COPOLYMERS STUDIED BY ¹³C NMR

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