限制几何构型三价钛金属配合物介导的可控自由基聚合

秦宇飞; 景帅然; 刘波

doi:10.11777/j.issn1000-3304.2024.24057

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限制几何构型三价钛金属配合物介导的可控自由基聚合

研究论文 | 更新时间：2024-11-26

- 限制几何构型三价钛金属配合物介导的可控自由基聚合
- Controlled Radical Polymerization Mediated by Constrained Geometry Construction Trivalent Titanium Complex
- 高分子学报 2024年55卷第9期页码：1200-1206
- 作者机构：
  
  1.中国科学院长春应用化学研究所高分子物理与化学国家重点实验室长春 130022
  2.中国科学技术大学应用化学与工程学院合肥 230026
  3.北京化工大学化学学院北京 102202
- 作者简介：
  
  E-mail: liubo@ciac.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号 22171256)
- DOI：10.11777/j.issn1000-3304.2024.24057
  中图分类号：
- 纸质出版日期：2024-09-20，
  
  网络出版日期：2024-06-26，
  
  收稿日期：2024-02-26，
  
  录用日期：2024-04-30
- 稿件说明：
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秦宇飞, 景帅然, 刘波. 限制几何构型三价钛金属配合物介导的可控自由基聚合. 高分子学报, 2024, 55(9), 1200-1206

Qin, Y. F.; Jing, S. R.;Liu, B. Controlled radical polymerization mediated by constrained geometry construction trivalent titanium complex. Acta Polymerica Sinica, 2024, 55(9), 1200-1206
秦宇飞, 景帅然, 刘波. 限制几何构型三价钛金属配合物介导的可控自由基聚合. 高分子学报, 2024, 55(9), 1200-1206 DOI： 10.11777/j.issn1000-3304.2024.24057.

Qin, Y. F.; Jing, S. R.;Liu, B. Controlled radical polymerization mediated by constrained geometry construction trivalent titanium complex. Acta Polymerica Sinica, 2024, 55(9), 1200-1206 DOI： 10.11777/j.issn1000-3304.2024.24057.

摘要

三价钛金属配合介导的自由基聚合因其可控性好、所得聚合物无需进一步纯化而受到广泛关注. 本工作利用限制几何构型三价钛金属配合物

作为控制剂，分别与1-溴-1-苯乙烷(

)、

-二甲基苄溴(

)、1-碘-1-苯乙烷(

)构成引发体系，引发甲基丙烯酸甲酯自由基聚合，研究了引发剂种类对聚合活性及所得聚合物的分子量及分子量分布的影响，进一步以

和

构成的二元引发体系为模型，研究了聚合动力学，同时对单体与引发剂比例以及聚合温度对单体转化率、所得聚合物分子量及分布的影响进行了研究，结合核磁技术和顺磁共振技术对

和

反应的跟踪，对聚合机理进行了推测.

Abstract

Controlled radical polymerization has aroused considerable attentions during the past decades due to its ability to adjust the polymer chain structure such as molecular weight

molecular weight distribution

composition

and topology. Transition metals compounds such as copper

iron

ruthenium

nickel

etc

have been extensively explored. While the effect of the auxiliary ligands on the polymerization behaviour was rarely investigated. Especially for titanium complexes

only metallocene titanium chloride Cp

TiCl

was examined under the reduction by Zinc. Herein

the binary systems composed by constrain geometry construction trivalent titanium complex (

) and 1-bromo-1-phenylethane (

)

(2-bromo-2-propanyl)benzene (

) and 1-iodo-1-phenylethane (

)

respectively

were employed to catalyzed radical polymerization of methyl methacrylate (MMA). The influence of initiators on the molecular weight and molecular weight distribution was assayed. The kinetic study of MMA polymerization initiated by

indicated linear relationship between MMA conversion and polymerization time

suggesting zero order dependent on MMA concentration. While with the increase of monomer conversion

the molecular weights of the afforded polymers have no obvious change. In addition

with the increase of the ratio of MMA to

while keeping the MMA concentration as constant

the molecular weight of the corresponding polymer increased despite the MMA conversion decreased. Meanwhile

with the decrease of the polymerization temperature

the molecular weight of the afforded polymer increased. These results suggested that the polymerization performed in slow initiation

fast propagation. This is consistent with the typical radical polymerization mechanism

but different from those of at

om transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP) which are mediated by organometallic complexes. The above results indicated that the auxiliary ligand has a significantly effect on a radical polymerization process.bromo-2-propanyl)benzene (

) and 1-iodo-1-phenylethane (

)

respectively

was employed to catalyze radical polymerization of methyl methacrylate. The influence of initiator on the molecular weight and molecular weight distribution was assayed. The kinetic study of MMA polymerization initiated by

was carried out. The influence of reaction conditions

such as the ratio of MMA to

temperature

was also investigated. Combined with the results of monitoring the reaction between

and

by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR)

the mechanism was proposed.

关键词

自由基聚合三价钛配合物甲基丙烯酸甲酯

Keywords

Radical polymerizationTrivalent titanium complexMethyl methacrylate

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