Macromolecular Chain Structure Regulation of AN–MA–IA Aqueous Copolymerization with a Water-Soluble Azo Initiator AIBA
Macromolecular Chain Structure Regulation of AN–MA–IA Aqueous Copolymerization with a Water-Soluble Azo Initiator AIBA
复制标题
水溶性偶氮引发剂AIBA对AN-MA-IA水相共聚的大分子链结构调控
DOI：
10.1021/acs.iecr.1c00997
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发表时间：
2021-06
影响因子：
4.2
通讯作者：
Wei-Kang Yuan
中科院分区：
文献类型：
--
作者：
Tong Qin;Xun Pan;Zhenhao Xi;Ling Zhao;Wei-Kang Yuan
丙烯腈（AN）-丙烯酸甲酯（MA）-衣康酸（IA）三元共聚物的性能与其序列结构的均匀性密切相关。在这项工作中，通过基于密度泛函理论（DFT）的计算，研究了IA的解离行为和酸性反应性的变化。不同解离形式的能垒、动力学、SOMO-LUMO能隙和静电排斥的结果表明，IA与AN增长自由基之间的反应性遵循IA > IA-> IA 2-的顺序，尽管IA-和AN表现出相似的反应性。此外，考虑到竞聚率的结果，IA单体的反应性和解离状态之间的关系被澄清。建立了一种利用IA解离态在稳定pH控制下调控聚丙烯腈（PAN）三元共聚物序列结构的策略。采用水溶性偶氮引发剂2，2 ′-偶氮二（2-甲基丙脒）二盐酸盐（AIBA），其引发过程与pH无关，将AIBA应用于水相聚合过程，得到了链分布相对均匀的PAN微球。结果表明，当pH值控制在4.7时，IA大部分以第一步解离形式存在，其反应活性与单体AN相当。此外，聚丙烯腈纤维的组成为：AN 94.96-95.07%，MA 3.11-3.36%，IA 1.68-1.82%，原料比为95：3.2：1.8，表明存在具有均匀链分布的PAN纤维。
The performance of acrylonitrile (AN)–methyl acrylate (MA)–itaconic acid (IA) terpolymer is closely related to the uniformity of the sequence structure. In this work, the changes in the dissociative behavior and reactivity of the IA with acidity were examined through calculations based on the density functional theory (DFT). The results of the energy barrier, kinetics, SOMO–LUMO energy gap, and electrostatic repulsion of different dissociated forms demonstrated that the corresponding reactivity between the IA with the AN propagation radical follows the order IA > IA–> IA2–, although the IA–and AN exhibit a similar reactivity. Furthermore, the relationship between the reactivity and dissociated state of the IA monomer was clarified considering the results of the reactivity ratios. A strategy of controlling the sequence structure of polyacrylonitrile (PAN) terpolymers at a stable pH control with the IA-dissociated state was established. Notably, a water-soluble azo initiator, 2,2′-azobis (2-methylpropionamidine) dihydrochloride (AIBA), was adopted because its initiation process is not related to the pH. AIBA was applied in the aqueous polymerization process to obtain a PAN terpolymer with a relatively uniform chain distribution. The results demonstrated that when the pH value is controlled at 4.7, most of the IA exists in the first-step dissociated form, and its reactivity is comparable to that of monomer AN. In addition, the composition of terpolymer is as follows: 94.96–95.07% of AN, 3.11–3.36% of MA, and 1.68–1.82% of IA, with the raw material ratios being 95:3.2:1.8, indicating the presence of a PAN terpolymer with a uniform chain distribution.
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使用氧化还原引发剂系统进行丙烯酸丁酯种子乳液聚合：动力学和机理
DOI：
10.1021/ie901359z
发表时间：
2010-07
期刊：
Industrial & Engineering Chemistry Research
影响因子：
--
作者：
Liu, Zhen-guo;Han, Ye;Zhou, Chao;Zhang, Ming-yao;Li, Wei-ming;Zhang, Hui-xuan;Liu, Feng-qi;Liu, Wan-Jun
通讯作者：
Liu, Wan-Jun
影响因子：
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作者：
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通讯作者：
Dilek Suadiye Can;H. Baskan;Selin Gumrukcu;A. Sarac
影响因子：
5.9
作者：
E. Ismar;M. Mičušík;Ilknur Gergin;M. Omastová;A. Sarac
通讯作者：
E. Ismar;M. Mičušík;Ilknur Gergin;M. Omastová;A. Sarac
影响因子：
4.6
作者：
Rintoul, I;Wandrey, C
通讯作者：
Wandrey, C
影响因子：
4.4
作者：
Eyring, H
通讯作者：
Eyring, H