基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相：链伸展行为的研究

刘宣伯; 许佳儒; 赵永峰; 杨爽; 范星河; 陈尔强

doi:10.11777/j.issn1000-3304.2017.17145

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基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相：链伸展行为的研究

研究论文 | 更新时间：2021-01-26

- 基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相：链伸展行为的研究
- Lamellar Phase of Rod-Coil Diblock Copolymer Based on Mesogen-jacketed Liquid Crystalline Polymer: A Study of Chain Stretching
- 高分子学报 2017年第10期页码：1668-1678
- 作者机构：
  
  1.北京大学化学学院高分子化学与物理教育部重点实验室北京 100871
  2.中石化北京化工研究院材料科学研究所北京 100013
- 作者简介：
  
  陈尔强, E-mail: eqchen@pku.edu.cn Er-qiang Chen, E-mail: eqchen@pku.edu.cn
- 基金信息：
  
  国家自然科学基金(20990232);国家自然科学基金(21634001)
- DOI：10.11777/j.issn1000-3304.2017.17145
  中图分类号：
- 纸质出版日期：2017-10-20，
  
  收稿日期：2017-5-31，
  
  修回日期：2017-7-27，
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刘宣伯, 许佳儒, 赵永峰, 杨爽, 范星河, 陈尔强. 基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相：链伸展行为的研究[J]. 高分子学报, 2017,(10):1668-1678.

Liu Xuan-bo, Xu Jia-ru, Zhao Yong-feng, Yang Shuang, Fan Xing-he, Chen Er-qiang. Lamellar Phase of Rod-Coil Diblock Copolymer Based on Mesogen-jacketed Liquid Crystalline Polymer: A Study of Chain Stretching[J]. Acta Polymerica Sinica, 2017,(10):1668-1678.
刘宣伯, 许佳儒, 赵永峰, 杨爽, 范星河, 陈尔强. 基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相：链伸展行为的研究[J]. 高分子学报, 2017,(10):1668-1678. DOI： 10.11777/j.issn1000-3304.2017.17145.

Liu Xuan-bo, Xu Jia-ru, Zhao Yong-feng, Yang Shuang, Fan Xing-he, Chen Er-qiang. Lamellar Phase of Rod-Coil Diblock Copolymer Based on Mesogen-jacketed Liquid Crystalline Polymer: A Study of Chain Stretching[J]. Acta Polymerica Sinica, 2017,(10):1668-1678. DOI： 10.11777/j.issn1000-3304.2017.17145.

摘要

研究了一系列以聚己内酯（PCL）为柔性链段、甲壳型液晶高分子聚{2，5-二[（4-甲氧基苯基）氧羰基]苯乙烯}（PMPCS）为刚性链段的刚-柔型二嵌段共聚物（PCL-

-PMPCS）的微相分离结构.小角X射线散射（SAXS）和广角X射线衍射（WAXD）实验结果表明，当PMPCS为无定形态时，PCL-

-PMPCS的微相分离行为与柔-柔型二嵌段共聚物相似，其相形态主要取决于两段的体积分数.随温度升高，PMPCS链段采取伸展的棒状构象，形成六方柱状向列相（

），会诱导体系的微相分离结构出现“有序-有序”或“无序-有序”转变，使得在很宽的PMPCS体积分数（

PMPCS

：40%~80%）内样品均呈现层状微相分离结构.我们对在200℃得到的层状相SAXS数据进行了一维相关函数分析，详细考察了层状相中PMPCS及PCL相区的厚度（

PMPCS

、

PCL

）与相应链段聚合度（

PMPCS

、

PCL

）的关系.对PMPCS相区，发现

PMPCS

=0.2

PMPCS

（nm）.因棒状PMPCS链段与层的法线方向平行，该线性关系表明PCL-

-PMPCS的层状相为“单层近晶A相”结构，

PMPCS

即为棒状PMPCS链段的长度，可通过控制PMPCS的聚合度予以精确控制.对PCL相区，则

PCL

与

PCL

近似有标度关系

PCL

0.85

，说明处于熔融态的PCL链段受迫强烈伸展.进一步分析WAXD实验数据并计算每根PMPCS链段在层状相中的界面面积（

）可知，随

PMPS

增大，PMPCS链段的液晶度从~20%增至~55%，

则从~2.4 nm

增至~2.7 nm

.与此相应，PCL链段的伸展程度会略有降低，说明

PCL

有较弱的

PMPCS

依赖性.另一方面，

PCL

与

的乘积与

PCL

满足线性关系

PCL

（

）=0.21

PCL

（nm

），斜率即为PCL重复单元的体积.

Abstract

We have studied the microphase phase separation behavior of a series of rod-coil diblock copolymers withpoly(2

5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PMPCS) as the rod and poly(

-caprolactone) (PCL) as the coil. PMPCS is a typical mesogen-jacketed liquid crystalline polymer

of which the hexatic columnar nematic (

) phase can develop from the amorphous state upon heating irreversibly once the chain conformation becomes extended. It is found that the PCL-

-PMPCS samples with amorphous PMPCS behave similar to the coil-coil diblock copolymer

with the microphase separated morphology mainly determined by the volume fraction of PMPCS (

PMPCS

). At the temperature above the glass transition temperature of PMPCS (~116 ℃)

the transition from amorphous phase to

phase of PMPCS blocks occurs. This induces the “order-order” and/or “disorder-order” transition of the phase morphology

resulting in the lamellar morphology existing in a wide range of

PMPCS

from 40% to 80%. In this case

PCL-

-PMPCS presents the typical feature of rod-coil diblock copolymer. Using one-dimensional correlation function to analyze the small-angle X-ray scattering data measured at 200 ℃

we obtained the thicknesse of PMPCS and PCL domain (

PMPCS

and

PCL

) in the lamellar structures. A linear relationship is identified

PMPCS

= 0.2

PMPCS

(nm)

with

PMPCS

as the degree of polymerization of PMPCS block. As the chain axis of PMPCS block is parallel to the normal of the lamellae

we conclude that the diblocks form a “single-layer smectic A” lamellar phase

and more importantly

PMPCS

is the extended chain length of PMPCS block

which can be well controlled by polymerization. For PCL block

a scaling of

PCL

0.85

(

PCL

is the degree of polymerization of PCL block) is observed

indicating that the molten PCL block is highly stretched. We further estimated the interfacial area per rod-like PMPCS (

) in the lamellar phase

which is always smaller than the cross section area of PMPCS rod in the

phase. Combining with the liquid crystallinity of samples measured by wide-angle X-ray diffraction

we consider that the variation of

reflects that

near the PMPCS/PCL interface

the PMPCS segments are not packed in

phase. This is mainly due to the strong segregation between the molten PCL and the liquid crystalline PMPCS which can cause the PMPCS blocks to be further stretched. For a fixed

PCL

the smaller

the larger

PCL

is. However

a linear relationship of

PCL

(

) = 0.21

PCL

(nm

) can be realized

wherein the value of slope is the volume of PCL repeating unit.

关键词

甲壳型液晶高分子刚-柔型二嵌段共聚物层状微相分离分子量依赖性

Keywords

Mesogen-jacketed liquid crystalline polymerRod-coil diblock copolymerMicrophase separated lamellar phaseMolecular weight dependence

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