Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)3/Al(<italic style="font-style: italic">i</italic>-Bu)2H/AlEt3/EASC Catalyst

Wen-jie Zheng; Ji-fu Bi; Ri-xin Cong; Feng Wang; Heng Liu; Yan-ming Hu; Xue-quan Zhang

doi:10.11777/j.issn1000-3304.2020.20287

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Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)₃/Al(i-Bu)₂H/AlEt₃/EASC Catalyst

Research Article | 更新时间：2021-05-07

- Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)₃/Al(i-Bu)₂H/AlEt₃/EASC Catalyst
- Acta Polymerica Sinica Vol. 52, Issue 5, Pages: 541-548(2021)
- 作者机构：
  
  1.沈阳理工大学材料科学与工程学院　沈阳 110159
  2.中国科学院长春应用化学研究所　长春 130022
  3.中国石油天然气股份有限公司石油化工研究院兰州化工研究中心　兰州 730060
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20287
  CLC：
- Published：3 May 2021，
  
  Published Online：15 March 2021，
  
  Received：28 December 2020，
  
  Revised：20 January 2021，
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Wen-jie Zheng, Ji-fu Bi, Ri-xin Cong, Feng Wang, Heng Liu, Yan-ming Hu, Xue-quan Zhang. Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)₃/Al(i-Bu)₂H/AlEt₃/EASC Catalyst. [J]. Acta Polymerica Sinica 52(5):541-548(2021)
DOI：

Wen-jie Zheng, Ji-fu Bi, Ri-xin Cong, Feng Wang, Heng Liu, Yan-ming Hu, Xue-quan Zhang. Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)₃/Al(i-Bu)₂H/AlEt₃/EASC Catalyst. [J]. Acta Polymerica Sinica 52(5):541-548(2021) DOI： 10.11777/j.issn1000-3304.2020.20287.

摘要

采用新癸酸钕(Nd(vers)

)/氢化二异丁基铝(Al(

-Bu)

H)/三乙基铝(AlEt

)/乙基倍半氯化铝(EASC)体系催化丁二烯(Bd)/异戊二烯(Ip)及Bd/Ip/月桂烯(My)共聚合. 所得丁戊共聚物组成与催化剂用量无关，单体的投料量与共聚物中此单体的含量几乎呈线性关系；用示差扫描量热仪(DSC)测得共聚物只有一个玻璃化转变，共聚物中Ip含量与其玻璃化转变温度(

)呈良好的线性关系. 采用Fineman-Ross方法计算竞聚率得到

=1.04，

=1.18，Kelen-Tüdos法计算竞聚率得到

=1.33，

=1.59；

，

均接近于1，说明在此催化体系下反应可以得到无规的丁戊共聚物. 利用核磁碳谱对共聚物的序列结构进行了分析和归属，采用Bernoulli模型和一级Markov模型验证共聚物的序列结构，通过比较数均序列长度，一级Markov模型计算得到的序列长度与核磁计算的实际值更接近. Bd/Ip/My三元共聚合时，所得共聚物中My单元含量随着投料比的增加而增加，其DSC曲线上只有一个玻璃化转变，

值随着My含量的增加而稍增加.

Abstract

Copolymerization of butadiene (Bd)/isoprene (Ip) and Bd/Ip/myrcene (My) was carried out with Nd(vers)

/Al(

-Bu)

H/AlEt

/EASC catalyst system. For the BD and Ip copolymerization

the catalyst content has rare effect on the copolymer composition and the unit content in copolymer was almost proportional to the monomer feed; only one glass transition temperature (

) was detected by DSC and it increased linearly with the increasing Ip unit content in copolymers

which indicated the random structure of copolymers. The reactivity ratios of butadiene (

) to isoprene (

) were calculated with both Fineman-Ross and Kelen-Tüdos method.

and

were close to 1

suggesting random copolymerization of Bd and Ip with the present catalyst system. The structure and distribution of copolymer sequences were analyzed and assigned with

C-NMR. The number average sequence lengths calculated by

C-NMR and Bernoullian/Markov model

respectively

were compared

and the result showed that Markov model was more suitable for simulating the copolymer sequence distribution. Ternary copolymerization of Bd

Ip and My catalyzed by the catalyst system showed that the My unit content in the copolymer increased with the monomer feed

only one glass transition was detected and the value slowly increased with the increasing My unit content in copolymers. The reactivity ratios calculated by Kelen-Tüdos method were

=1.03

=1.69

=1.11

=3.62

=0.80

=4.67.

关键词

丁戊共聚物钕系催化剂月桂烯竞聚率序列分布

Keywords

Butadiene-isoprene copolymerNeodymium-based catalystMyrceneReactivity rateSequence distribution

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State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology

School of Materials Science and Engineering, Beijing Institute of Technology

National Engineering Research Center for Synthesis of Novel Rubber and Plastic Materials, Yanshan Branch, Beijing Research Institute of Chemical Industry, SINOPEC

Faculty of Materials Science and Chemical Engineering, Ningbo University

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Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)3/Al(i-Bu)2H/AlEt3/EASC Catalyst

DOI：10.11777/j.issn1000-3304.2020.20287

摘要

Abstract

关键词

Keywords

references

Copolymerization of Butadiene/Isoprene and Butadiene/Isoprene/Myrcene with Nd(vers)₃/Al(i-Bu)₂H/AlEt₃/EASC Catalyst