Synthesis of Hydroxyl-functionalized 3,4-Poly(2-aryl-1,3-butadiene)s

Li-xian Huang; Li-peng Sang; Gao-pan Su; Xiang Guo; Shi-hui Li

doi:10.11777/j.issn1000-3304.2023.23185

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Synthesis of Hydroxyl-functionalized 3,4-Poly(2-aryl-1,3-butadiene)s

Research Article | 更新时间：2024-01-19

- Synthesis of Hydroxyl-functionalized 3,4-Poly(2-aryl-1,3-butadiene)s
  增强出版
- Acta Polymerica Sinica Vol. 55, Issue 2, Pages: 153-160(2024)
- 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.湖北航天化学技术研究所航天化学动力技术重点实验室襄阳 441003
- 作者简介：
  
  Xiang Guo, E-mail: 13308672368@189.com
  Shi-hui Li, E-mail: shihui-li@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23185
  CLC：
- Published：20 February 2024，
  
  Published Online：02 November 2023，
  
  Received：12 July 2023，
  
  Accepted：29 August 2023
- 稿件说明：
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黄立贤, 桑丽鹏, 苏高攀, 郭翔, 李世辉. 羟基功能化3,4-聚2-芳基-1,3-丁二烯的合成. 高分子学报, 2024, 55(2), 153-160

Huang, L. X.; Sang, L. P.; Su, G. P.; Guo, X.; Li, S. H. Synthesis of hydroxyl-functionalized 3,4-poly(2-aryl-1,3-butadiene)s. Acta Polymerica Sinica, 2024, 55(2), 153-160
黄立贤, 桑丽鹏, 苏高攀, 郭翔, 李世辉. 羟基功能化3,4-聚2-芳基-1,3-丁二烯的合成. 高分子学报, 2024, 55(2), 153-160 DOI： 10.11777/j.issn1000-3304.2023.23185.

Huang, L. X.; Sang, L. P.; Su, G. P.; Guo, X.; Li, S. H. Synthesis of hydroxyl-functionalized 3,4-poly(2-aryl-1,3-butadiene)s. Acta Polymerica Sinica, 2024, 55(2), 153-160 DOI： 10.11777/j.issn1000-3304.2023.23185.

摘要

采用(C

(NCHCCHN)C

-2

6)Lu(CH

SiMe

)

(

)、Ph

P(=NDip)(NDip)Lu(CH

SiMe

)

(THF) (Dip = C

-2

；

)、Ph

P(=NDip)(NC

-2-Et)Lu(CH

SiMe

)

(THF) (

)和Ph

P(=NDip) (NC

-2-Et)Sc(CH

SiMe

)

(THF) (

) 4种稀土催化剂，催化2-对甲基苯基-1

3-丁二烯(2-MPBD)均聚合. 通过核磁共振(NMR)、凝胶渗透色谱(GPC)和示差扫描量热法(DSC)等对聚合物的微观结构和热性能进行了表征. 催化剂

对2-MPBD聚合活性低，3

4-选择性低(65.2%)；催化剂

几乎无催化活性；催化剂

和

表现出非常高的催化活性(2 min转化率达100%)和3

4-选择性(分别为98.1%和

99%). 催化剂

对催化2-MPBD聚合具有活性聚合特征，产生的3

4-聚2-MPBD分子量随单体投入量呈线性增加，分子量分布介于1.12~1.25之间. 对于苯基、间甲基苯基、4-戊基苯基、4-氟苯基和4-氯苯基取代的1

3-丁二烯单体，催化剂

也表现出较高的催化活性和3

4-选择性. 3

4-聚芳基1

3-丁二烯侧链双键与硼烷、双氧水和氢氧化钠反应之后，转变为醇羟基功能化的3

4-聚芳基1

3-丁二烯.

Abstract

The polymerization of 2-(4-methylphenyl)-1

3-butadiene (2-MPBD) is performed using [C

(NCHCCHN)C

-2

‍4

‍6]Lu(CH

SiMe

)

(

)

P(=NDip)‍(NDip)Lu(CH

Si-Me

)

(THF) (Dip=C

-2

;

)

P(=NDip)(NC

-2-Et)Lu(CH

SiMe

)

(THF) (

) and Ph

P(=NDip)(NC

-2-Et)Sc(CH

SiMe

)

(THF) (

). The microstructures and thermal properties of resultant polymers are characterized by nuclear magnetic resonance spectroscopy (

H-NMR

C-NMR)

gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Complex

activated by [Ph

C][B(C

)

] and Al

shows low catalytic activity and 3

4-selectivity (65.2%) for 2-MPBD polymerization. Under the same conditions

complex

is nearly inert. In contrast

complexes

and

demonstrate high 3

4-selectivity (98.1% and

99%

respectively) and enable 100% conversion of 200 equivalents of 2-MPBD into polymers at 20 ℃ with 2 min. The resultant molecular weights increase with monomer-to-catalyst ratios varying from 200:1 to 600:1 with narrow molecular weight distributions of 1.12-1.25. Furthermore

complex

also shows high catalytic activity and high 3

‍4-selectivity for the polymerizations of 2-phenyl-1

3-butadiene

2-(3-methylphenyl)-1

‍3-butadiene

2-(4-pentylphenyl)-1

3-butadiene

2-(4-fluorophenyl)-1

3-butadiene and 2-‍(4-chlorophenyl)-1

‍3-butadiene. The resultant 3

‍4-poly(2-aryl-1

‍3-butadiene)s are readily transformed into hydroxyl functionalized polymers by the treatment of BH

and H

关键词

稀土催化剂功能化聚烯烃34-选择性共轭双烯反应性功能化法

Keywords

Rare-earth metal catalystFunctional polyolefin3‍4-SelectivityConjugated dieneReactive polyolefin intermediate

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