Well-Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

被引：48

作者：

Kwon, Wonsang ^{[1
,2
]}

Rho, Yecheol ^{[1
,2
]}

Kamoshida, Kensuke ^{[3
]}

Kwon, Kyung Ho ^{[1
,2
]}

Jeong, Youn Cheol ^{[1
,2
]}

Kim, Jonghyun ^{[1
,2
,4
]}

Misaka, Hideki ^{[3
]}

Shin, Tae Joo ^{[4
]}

Kim, Jehan

Kim, Kwang-Woo ^{[4
]}

Jin, Kyeong Sik ^{[4
]}

Chang, Taihyun ^{[1
,2
]}

Kim, Heesoo ^{[5
,6
]}

Satoh, Toshifumi ^{[3
]}

Kakuchi, Toyoji ^{[3
]}

Ree, Moonhor ^{[1
,2
]}

机构：

[1] Pohang Univ Sci & Technol, Polymer Res Inst, Ctr Electrophoto Behav Adv, Dept Chem,Div Adv Mat Sci,Pohang Accelerator Lab, Pohang 790784, South Korea

[2] Pohang Univ Sci & Technol, BK Sch Mol Sci, Pohang 790784, South Korea

[3] Hokkaido Univ, Fac Engn, Div Biotechnol & Macromol Chem, Polymer Chem Lab, Sapporo, Hokkaido 0608628, Japan

[4] Pohang Univ Sci & Technol, Pohang Accelerator Lab, PLS 2, SAXS Grp,Beamline Div, Pohang 790784, South Korea

[5] Dongguk Univ, Coll Med, Gyeongju 780714, South Korea

[6] Dongguk Med Inst, Gyeongju 780714, South Korea

来源：

ADVANCED FUNCTIONAL MATERIALS | 2012年 / 22卷 / 24期

基金：

新加坡国家研究基金会;

关键词：

anionic ring-opening polymerization; glycidol derivatives; phosphazene base catalyst; linear aliphatic homopolyethers; linear aliphatic diblock copolyethers; deprotection; phase-separated nanostructures; RING-OPENING POLYMERIZATION; X-RAY-SCATTERING; ORGANOSILICATE DIELECTRIC FILMS; HIGH-MOLECULAR-WEIGHT; THIN-FILMS; MEMORY CHARACTERISTICS; BLOCK-COPOLYMERS; BRUSH POLYMERS; OXIDE; POLYGLYCIDOL;

D O I：

10.1002/adfm.201201101

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Low-temperature anionic ring-opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal-free catalyst system, 3-phenyl-1-propanol (PPA) (an initiator) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris-(dimethylamino)phosphoranylidenamino]-2?5,4?5-catenadi(phosphazene) (t-Bu-P4) (a promoter) in order to obtain well-defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring-opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well-defined linear AGE-homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE-homopolymer in a unimodal narrow molecular-weight distribution. In this case, however, a side reaction (i.e., chain-transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well-defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post-modification products are examined. Overall, this study demonstrates that a low-temperature metal-free anionic ROP using the PPA/t-Bu-P4 catalyst system is suitable for the production of well-defined linear AGE-homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post-modifications, nanostructures, and their applications.

引用

页码：5194 / 5208

页数：15

共 46 条

[31] Ultralow-k nanoporous organosilicate dielectric films imprinted with dendritic spheres [J].