Transformation of the Counterion of Active Species and Anionic Block Copolymerization of PBMA-b-PMMA

Min-ze Shu; Bo Chen; Bin Zou; Fei-yan Chen; An-na Zheng; Yong Guan

doi:10.11777/j.issn1000-3304.2015.14427

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Transformation of the Counterion of Active Species and Anionic Block Copolymerization of PBMA-b-PMMA

Research Article | 更新时间：2021-03-19

- Transformation of the Counterion of Active Species and Anionic Block Copolymerization of PBMA-b-PMMA
- Acta Polymerica Sinica Issue 7, Pages: 835-844(2015)
- 作者机构：
  
  华东理工大学材料科学与工程学院上海市先进聚合物材料重点实验室超细材料制备与应用教育部重点实验室,上海,200237
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2015.14427
  CLC：
- Published：20 July 2015，
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Min-ze Shu, Bo Chen, Bin Zou, Fei-yan Chen, An-na Zheng, Yong Guan. Transformation of the Counterion of Active Species and Anionic Block Copolymerization of PBMA-b-PMMA. [J]. Acta Polymerica Sinica (7):835-844(2015)
DOI：

Min-ze Shu, Bo Chen, Bin Zou, Fei-yan Chen, An-na Zheng, Yong Guan. Transformation of the Counterion of Active Species and Anionic Block Copolymerization of PBMA-b-PMMA. [J]. Acta Polymerica Sinica (7):835-844(2015) DOI： 10.11777/j.issn1000-3304.2015.14427.

摘要

采用7Li-NMR对正丁基锂(n-BuLi)与不同摩尔比叔丁醇钾(t-BuOK)的混合物在四氢呋喃与环己烷溶液中的体系进行了分析.继而以1

1-二苯基己基锂作为引发剂

分别采用苯酚锂、叔丁醇钠以及t-BuOK作为副反应抑制剂

进行了甲基丙烯酸正丁酯(BMA)和甲基丙烯酸甲酯(MMA)的负离子嵌段共聚合

并用GPC、1H-NMR对聚合物的结构进行了表征.结果发现n-BuLi 与t-BuOK会产生Li与K交换的反应

形成不具备引发活性的t-BuOLi

以及以K为反离子的活性种.其对MMA类极性单体嵌段聚合的副反应有着极为有效的抑制作用.过量的t-BuOK

将进一步提高对副反应的抑制作用.在体系中nt-BuOK/nn-BuL20后

即便聚合温度升高至40 ℃

BMA与MMA极性单体嵌段聚合的总产率也可达到100%

且分子量分布仅为1.40

呈单峰分布.实测的Mn与设定的Mn非常接近;采用1H-NMR实测的nMMA/nBMA也与原料十分接近.从而为MMA类极性单体嵌段聚合的工业化奠定了基础.

Abstract

7Li-NMR was used to characterize the mixed system of n-butyl lithium (n-BuLi) and potassium t-butoxide (t-BuOk) with different molar ratios in THF and cyclohexane.The anionic block-copolymerization of butyl methacrylate (BMA) and methyl methacrylate (MMA) was initiated by 1

1-diphenyl hexyl lithium and using phenol lithium

sodium t-butoxide and t-BuOk as the side reaction inhibitors.GPC and1H-NMR were used to characterize the structure of the block copolymers.It was found that the exchange reaction of Li in n-BuLi and K in t-BuOK could be generated

in which the inactive lithium t-butoxide and active species with K as the counterion formed.The new species had admirable impact on inhibiting the side reaction in the anionic polymerization of the polar monomers

such as MMA.The surplus t-BuOK in the system could further promote the inhibition effect.When the mole ratio of nt-BuOK/nn-BuLi was not lower than 20

the total yield of the block copolymerization of BMA and MMA could reach up to 100% and the molecular weight distribution was only 1.40 with unimodal distribution even when the copolymerization temperature was up to 40 ℃.Mn determined by GPC well coincided with the calculated theoretically data.The value of nMMA/nBMA in copolymer determined by 1H-NMR was also well close to that of raw material.The results could lay an industrial foundation for the block copolymerization of polar monomers

such as MMA.

关键词

叔丁醇钾反离子交换副反应抑制甲基丙烯酸正丁酯甲基丙烯酸甲酯

Keywords

Potassium t-ButoxideCounterion exchangeSide reaction inhibitionButyl methacryladeMethyl methacrylate

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State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology

State Key Laboratory of Chemical Engineering(Zhejiang University), College of Chemical Engineering and Biochemical Engineering, Zhejiang University

School of Chemistry and Chemical Engineering, Hefei University of Technology

Key Laboratory of Advanced Functional Materials and Devices

The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University

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