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Amphiphilic random and random block terpolymers with PEG, octadecyl, and oleyl pendants for controlled crystallization and microphase separation
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-12-8 , DOI: 10.1039/d0py01505a
Sahori Imai 1, 2, 3, 4, 5 , Yasuyuki Ommura 1, 2, 3, 4, 5 , Yuki Watanabe 3, 5, 6, 7 , Hiroki Ogawa 3, 5, 6, 7, 8 , Mikihito Takenaka 3, 5, 6, 7, 8 , Makoto Ouchi 1, 2, 3, 4, 5 , Takaya Terashima 1, 2, 3, 4, 5
Affiliation  

Controlled crystallization and microphase separation of multi-component copolymers are one possibility to construct precise nanostructures in functional polymer materials. In this paper, we report the crystallization and sub-10 nm microphase separation of amphiphilic random and random block terpolymers in the solid state. By using living radical copolymerization, we designed A/B/C random terpolymers and A/C–B/C random block terpolymers, into which a hydrophobic and crystalline octadecyl group (A), a hydrophobic and amorphous oleyl group (B), and hydrophilic poly(ethylene glycol) (C) were randomly and/or site-selectively introduced as side chains. The crystallization and melting temperatures of A/B/C random terpolymers gradually decreased with increasing content of amorphous oleyl units. The random terpolymers with a relatively small amount of oleyl units induced microphase separation of the side chains to form lamellae with hydrophilic and hydrophobic alternating layers in a domain spacing of about 6 nm, while the lamellar structure was gradually disordered by increasing oleyl groups. In contrast, A/C–B/C random block terpolymers efficiently induced crystallization of the octadecyl groups even in the presence of random copolymer segments with amorphous oleyl units. The random block copolymers opened the possibility of controlling microphase separation from the side chains of the random copolymers and the main chains of the block copolymers.

中文翻译:

具有PEG,十八烷基和油基侧基的两亲无规和无规嵌段三元共聚物,可控制结晶和微相分离

多组分共聚物的受控结晶和微相分离是在功能聚合物材料中构建精确纳米结构的一种可能性。在本文中,我们报告了固态两亲无规和无规嵌段三元共聚物的结晶和亚10纳米微相分离。通过使用活性自由基共聚,我们设计了A / B / C无规三元共聚物和A / C-B / C无规嵌段三元共聚物,其中疏水和结晶的十八烷基(A),疏水和无定形的油基(B)以及亲水性聚乙二醇(C)作为侧链无规和/或定点引入。随着无定形油基单元含量的增加,A / B / C无规三元共聚物的结晶和熔融温度逐渐降低。具有相对少量油基单元的无规三元共聚物引起侧链的微相分离,以形成具有亲水性和疏水性交替层的薄层,其亲水性和疏水性交替层的畴间距为约6nm,而层状结构通过增加油基而逐渐无序。相反,即使存在具有无定形油基单元的无规共聚物链段,A / C–B / C无规嵌段三元共聚物也能有效地诱导十八烷基的结晶。无规嵌段共聚物打开了控制从无规共聚物的侧链和嵌段共聚物的主链进行微相分离的可能性。而层状结构逐渐被油基的增加所扰乱。相反,即使存在具有无定形油基单元的无规共聚物链段,A / C–B / C无规嵌段三元共聚物也能有效地诱导十八烷基的结晶。无规嵌段共聚物为控制从无规共聚物的侧链和嵌段共聚物的主链的微相分离提供了可能性。而层状结构逐渐被油基的增加所扰乱。相反,即使存在具有无定形油基单元的无规共聚物链段,A / C–B / C无规嵌段三元共聚物也能有效地诱导十八烷基的结晶。无规嵌段共聚物为控制从无规共聚物的侧链和嵌段共聚物的主链的微相分离提供了可能性。
更新日期:2020-12-17
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