Synthesis of amphiphilic copolymer PEO-b-PtBA with narrow molecular weight distribution and its hydrolysis

doi:10.3969/j.issn.1000-5641.2015.03.014

Abstract

Abstract: A group of amphiphilic diblock copolymers PEO₄₅-b-PtBAx(x=28, 35, 53) were synthesized by ATRP using PEO-Br as macroinitiator. Samples were characterized by SEC, 1H NMR, FTIR and TEM. The influence of feed ratio to the control of the structure, molecular weight and molecular weight distributions were discussed. The results showed that, the conversion of tBA was high and the 1H NMR results confirmed the targeted products were synthesized successfully. All three copolymers had a narrow molecular weight distributions (Mw/Mn≤1.07). When the feed ratio of tBA to PEOBr was low, the structures of copolymers could be controlled accurately. The increase of feed ratio of tBA to PEOBr caused broadening of molecular weight distributions and the decreasing of initiating efficiency. The hydrolysis of PEO₄₅-b-PtBA₃₅ to PEO₄₅-b-PAA₃₅ was performed successfully. PEO₄₅-b-PAA₃₅was selfassembled into well dispersed spherical micelles in neutral aqueous solution.

Key words: amphiphilic copolymer, ATRP, PEO-PtBA, hydrolysis

CLC Number:

TQ314.2

KAYIRBEK Gulsum,ANAS Hudrat,MUSLIM Arzugul. Synthesis of amphiphilic copolymer PEO-b-PtBA with narrow molecular weight distribution and its hydrolysis[J]. Journal of East China Normal University(Natural Sc, 2015, 2015(3): 116-123.

References

［1］秦江雷,陈永明.由嵌段共聚物制备有形状的核壳结构聚合物纳米颗粒［J］.高分子学报,2011(6)：572585.

［2］WYMAN I W, LIU G J. Micellar structures of linear triblock terpolymers: Three blocks but many possiblities ［J］. Polymer, 2013, 54(8):19501978.

［3］BARTELS J W, CAUET S I, BILLINGS P L, et al. Evaluation of isoprene chain extension from PEO macromolecular chain transfer agents for the preparation of dual, invertible block copolymer nanoassemblies［J］. Macromolecules, 2010, 43: 71287138.

［4］栗志广,马晓燕,常海,等. 含聚乙二醇的嵌段共聚物的合成及自组装研究进展［J］.化工进展, 2013, 32(2):381387, 413.

［5］李光华, 杨苹苹, 赵治巨, 等. 自由基调聚法合成聚丙烯酸叔丁酯调聚物［J］.化工学报, 2011, 62(7):20612066.

［6］MORI H, MULLER A H E. New polymeric architectures with (meth)acrylicacid segments［J］. Prog Polym Sci, 2003, 28: 14031439.

［7］XING Y H, LIN S L, LIN J P. Synthesis, selfassembly and responsive properties of PEGbPDMAEMAbPMMAzo triblockcopolymers［J］. Chinese Journal of Polymer Science, 2013, 31(5): 833840.

［8］董建华. 高分子科学前沿与进展［M］北京：科学出版社, 2006.

［9］LONG Y Z, LI M M, GU C Z, et al. Recent advances in synthesis, physical properties and applicantions of conducting polymer nanotubes and nanofibers［J］. Prog Polym Sci , 2011,36: 14151442.

［10］PARK M, HARRISON C, CHAIKIN P M, et al. Block copolymer lithography: Periodic arrays of ~1011 holes in 1 square centimeter［J］. Science, 1997, 276: 14011404.

［11］KRISHNAMOORTHY S, HINDERLING C, HEINZELMANN H. Nanoscale patterning with blockcopolymers［J］. Materials Today, 2006, 9(9): 4047.

［12］唐新德, 范星河, 陈小芳, 等. 基于ATRP技术的多嵌段共聚物研究进展［J］.高分子通报,2006(6): 3643.

［13］罗婕, 义建军, 胡杰, 等. 嵌段共聚物合成方法研究进展［J］.化工新型材料,2010,38(4): 1012,19.

［14］蔡远利, 卢礼灿, 姜稳定, 等. 环境友好的可控自由基聚合［J］.化学进展, 2010, 22(7): 14901498.

［15］曹健. 原子转移自由基聚合基本原理及最新进展［J］. 长春理工大学学报, 2005, 28(3): 9299.

［16］唐燕春, 艾长军, 张莉, 等. 聚丙烯酸叔丁酯b聚(N异丙基丙烯酰胺)嵌段共聚物的制备及其自组装［J］. 功能高分子学报, 2007, 1920(1): 6064.

［17］胡亮, 张超灿, 陈艳军, 等. 原子转移自由聚合的研究新进展［J］. 材料导报A:综述篇, 2011, 25(5): 6872.

［18］DU J Z, CHEN Y M. Atomtransfer radical polymerization of a reactive monomer: 3(trimethoxysilyl)propyl methacrylate ［J］. Macromolecules, 2004, 37: 63226328.

［19］章莉娟, 陈锐毫, 蓝荣肇, 等. ATRP 法合成两亲性聚乙二醇聚丙烯酸叔丁酯嵌段共聚物［J］. 高校化学工程学报, 2011, 25(5): 781786.

［20］JEFFREY R L, JEIRAN J , GREGORY T C, et al. Toward a universal method to pattern metals on a polymer［J］. Chem Mater, 2008, 20: 65836585.

［21］秦江雷. 基于嵌段共聚物本体自组装制备可分散纳米颗粒和层间距可变的多孔纳米材料［D］. 北京：中国科学院北京化学研究所, 2011.

［22］陈磊山,胡利强,郭晓伟,等. 梳状聚合物 PAALigPEO的合成与表征［J］. 化学试剂, 2013, 35(3): 285288.

［23］QIN J L, CHEN Y M, YAN D D, et al. Dispersible shaped nanoobjects from bulk microphase separation of high Tg block copolymers without chemical crosslinking［J］. Macromolecules, 2010, 43: 1065210658.

［24］QIN J L, JIANG X B, GAO L, et al. Functional polymeric nanoobjects by crosslinking bulk selfassemblies of poly(tertbutyl acrylate)blockpoly(glycidyl methacrylate)［J］. Macromolecules, 2010, 43: 80948100.

［25］孙春会,曹霞, 付鹏, 等. 聚(ε己内酯)b聚丙烯酸嵌段聚合物的合成［J］. 高分子材料科学与工程, 2012, 28(1): 4144.

［26］朱蕙, 刘世勇, 潘全名, 等. 窄分布两亲性嵌段共聚物的合成及其胶束化行为研究［J］. 高等学校化学学报, 2002, 23(1): 138142.

［27］岳玲, 张晓宏, 吴世康.两亲性嵌段共聚物PSbPAA合成及其在溶液中的形态和纳米聚集结构形成［J］.高分子学报, 2004(2): 236239.

［28］华曼, 杨伟, 薛乔, 等. 两亲性嵌段共聚物PSbPAA合成与胶束化行为研究［J］. 化学学报, 2005, 63(7): 631636.

［29］杨婷婷, 徐莹莹, 姚丽, 等. ATRP法合成两亲的含氟柱状刷PBIEMg(PAAbPFA)［J］. 高分子学报, 2009(11): 11461152.

［30］张二琴, 柴云, 张普玉. 两亲性嵌段共聚物的合成及其自组装行为［J］. 广州化工, 2010, 38(4): 125126,157.

［31］朱寅, 史明辉, 奚骏, 等. PSbPAA 嵌段共聚物修饰的智能表面的制备及其响应行为的研究［J］. 化学学报, 2007, 65(15): 14871492.

［32］陈鹏宇, 曹亚. RAFT聚合合成聚丙烯酸b聚(N异丙基丙烯酰胺)嵌段共聚物的自组装行为［J］.高分子材料科学与工程, 2011, 27(9): 2832.

［33］YOO S I, SOHN B H, ZIN W C, et al. Localized synthesis of polypyrrole in the nanopattern of monolayer fil ms of diblock copolymer micelles［J］. Langmuir,2004,20:1073410736.