[1]黄文艳,宋肄业,柴晨琼,等.膦腈碱催化己内酯开环聚合制备线型/支化聚己内酯[J].常州大学学报(自然科学版),2020,32(01):36-43.[doi:10.3969/j.issn.2095-0411.2020.01.006]
　HUANG Wenyan,SONG Yiye,CHAI Chenqiong,et al.Preparation of Linear/Branched Polycaprolactone by Phosphazene- Catalyzed Ring-Opening Polymerization of Caprolactone[J].Journal of Changzhou University(Natural Science Edition),2020,32(01):36-43.[doi:10.3969/j.issn.2095-0411.2020.01.006]
点击复制

膦腈碱催化己内酯开环聚合制备线型/支化聚己内酯()
分享到：

常州大学学报(自然科学版)[ISSN:2095-0411/CN:32-1822/N]

卷:
第32卷
期数:
2020年01期
页码:
36-43
栏目:
材料科学与工程
出版日期:
2020-01-28

文章信息/Info

Title:
Preparation of Linear/Branched Polycaprolactone by Phosphazene- Catalyzed Ring-Opening Polymerization of Caprolactone
文章编号:
2095-0411(2020)01-0036-08
作者:
黄文艳1; 宋肄业2; 柴晨琼1; 韩 彪1; 蒋其民1; 薛小强1; 杨宏军1; 蒋必彪1; 2
(1.常州大学 材料科学与工程学院,江苏 常州 213164; 2.常州大学 怀德学院,江苏 靖江 214500)
Author(s):
HUANG Wenyan1;  SONG Yiye2;  CHAI Chenqiong1;  HAN Biao1;  JIANG Qimin1;  XUE Xiaoqiang1;  YANG Hongjun1;  JIANG Bibiao1; 2
(1. School of Materials Science and Engineering, Changzhou University, Changzhou 213164, China; 2. Huaide College, Changzhou University, Jingjiang 214500, China)
关键词:
聚己内酯;  膦腈碱;  开环聚合
Keywords:
poly(δ-caprolactone);  phosphazene base;  ring opening polymerization
分类号:
TQ 316.334
DOI:
10.3969/j.issn.2095-0411.2020.01.006
文献标志码:
A
摘要:
以膦腈碱t-BuP4为催化剂分别催化乙酸乙酯(EAc)和甲基丙烯酸乙酰氧基乙酯(AcEMA)引发己内酯(CL)的开环聚合反应,制备了线型和支化聚己内酯。利用核磁共振氢谱(1H NMR)、三检测体积排阻色谱仪(TD-SEC)和差示扫描量热仪(DSC)对共聚物进行了表征。结果表明,t-BuP4催化EAc引发CL的开环聚合反应时,随n(CL):n(EAc)的增加,聚合物的分子质量增加。t-BuP4催化AcEMA引发CL的开环聚合反应可成功制备支化PCL。当n(AcEMA):n(t-BuP4)为10:2时,CL的转化率接近100%。所得聚合物的Mark-Houwink参数α值为0.36,结晶度仅有39.68%。
Abstract:
Organic phosphazene superbase t-BuP4 was employed to catalyze ethyl acetate(EAc)and acetoxyethyl methacrylate(AcEMA)to initiate the ring opening polymerization of δ-caprolactone(CL). The structures of resulting polymers were characterized in detail by nuclear magnetic resonance spectroscopy(1H NMR), triple detection size exclusion chromatography(TD-SEC), and differential scanning calorimetry(DSC). The results showed that t-BuP4 could catalyze EAc to initiate the ring opening polymerization of CL resulting a linear poly(δ-caprolactone)(l-PCL). The molecular weight of the l-PCL increased with the increasing of n(CL):n(EAc)ratios. By using AcEMA as an initiator, branched poly(δ-caprolactone)(b-PCL)were obtained. When the molar ratio of n(AcEMA):n(t-BuP4)was 10:2, the conversion of CL was close to 100%. The mark-houwink constant(α)and the degree of crystallinity of the corresponding b-PCL was 0.36 and 39.68%, respectively.

参考文献/References:

[1]LUCKACHAN G E,PILLAI C K S. Biodegradable polymers-a review on recent trends and emerging perspectives[J]. Journal of Polymers and the Environment,2011,19(3):637-676.
[2]ISHIDA K,WANG Y,INOUE Y. Comonomer unit composition and thermal properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)s biosynthesized by ralstonia eutropha[J]. Biomacromolecules,2001,2(4):1285-1293.
[3]KASPERCZYK J. NMR investigation of biodegradable polyesters for medical applications[J]. Macromolecular Symposium,2001,175(1):19-32.
[4]WANG Y,GOU M, GONG C,et al. Pharmacokinetics and disposition of nanomedicine using biodegradable PEG/PCL polymers as drug carriers[J]. Current Drug Metabolism,2012,13(4):338-353.
[5]GUO B,GLAVAS L,ALBERTSSON A C. Biodegradable and electrically conducting polymers for biomedical applications[J]. Progress in Polymer Science,2013,38(9):1263-1286.
[6]杨宏军,钱小磊,黄文艳,等. 膦腈碱催化甲基丙烯酸烯丙酯与甲基丙烯酸甲酯的负离子共聚反应[J]. 高分子学报, 2015(5):550-555.
[7]张敏,徐科,李成涛,等. 不同成膜工艺对PCL结晶及微生物降解性能的影响[J]. 高分子材料科学与工程,2012,28(1):113-116.
[8]RUTLEDGE B,HUYETTE D,DAY D,et al. Treatment of osteomyelitis with local antibiotics delivered via bioabsorbable polymer[J]. Clinical Orthopaedics & Related Research,2003(411):280-287.
[9]苏健裕,陈玲,杨连生,等. 聚己内酯/淀粉共混材料的非等温结晶动力学[J]. 华南理工大学学报(自然科学版),2008,36(11):79-84.
[10]FUKUZAKI H,YOSHIDA M,ASANO M,et al. Synthesis of low-molecular-weight copoly(l-lactic acid/-caprolactone)by direct copolycondensation in the absence of catalysts,and enzymatic degradation of the polymers[J]. Polymer,1990, 31(10):2006-2014.
[11]杨宏军,钱小磊,柏涛,等. 己内酯与N-苯基马来酰亚胺的杂化共聚[J]. 高分子学报,2014(3):356-360.
[12]宋肄业, 李静, 柏涛,等. 主链含酯键的基于聚甲基丙烯酸二甲氨基乙酯的共聚物合成与表征[J]. 高分子学报,2016(6):769-774.
[13]HU S,ZHAO J,ZHANG G. Noncopolymerization approach to copolymers via concurrent transesterification and ring-opening reactions[J]. ACS Macro Letters,2015,5(1):40-44.
[14]LIU M,VLADIMIROV N,FRÉCHET J M J. A new approach to hyperbranched polymers by ring-opening polymerization of an AB monomer:4-(2-Hydroxyethyl)-ε-caprolactone[J]. Macromolecules,1999,32(20):6881-6884.
[15]MIKAEL T,BJÖRN A,HANS C,et al. Hyperbranched poly(ε-caprolactone)s[J]. Macromolecules,1998,31(11):3439-3445.
[16]MIKAEL T,HEDRICK J L. Hyperbranched poly(ε-caprolactone)derived from intrinsically branched AB2[J]. Macromolecules,1998,31(13):4390-4395.
[17]MAGNUSSON H,MALMSTRÖM E,HULT A. Synthesis of hyperbranched aliphatic polyethers via cationic ring-opening polymerization of 3-ethyl-3-(hydroxymethyl)oxetane[J]. Macromolecular Rapid Communications, 1999,20(8):453-457.
[18]DAVID M,MIKAEL T,HEDRICK J L. ABC BCD polymerization: a self-condensing vinyl and cyclic ester polymerization by combination free-radical and ring-opening techniques[J]. Macromolecules,1999,32(26):8753-8759.
[19]杨宏军,柏涛,刘荣兴,等. 含悬垂双键的可降解支化聚合物的合成与表征[J]. 高分子学报,2016(3):330-336.
[20]杨宏军,孙爱斌,柴晨琼,等. 膦腈碱催化甲基丙烯酸烯丙酯的基团转移聚合反应[J]. 常州大学学报(自然科学版),2018, 30(4):1-6.
[21]杨宏军,柏涛,薛小强,等. 含悬垂双键超支化聚合物的一步法合成[J]. 常州大学学报(自然科学版),2016, 28(2):14-19.
[22]PIETZONKA T,SEEBACH D. The P4 phosphazene base as part of a new metal-free initiator system for the anionic polymerization of methyl methacrylate[J]. Angewandte Chemie International Edition,1993,32(5):716-717.
[23]PHILLIPS P J,RENSCH G J,TAYLOR K D. Crystallization studies of poly(ε-caprolactone). I. Morphology and kinetics[J]. Journal of Polymer Science Part B: Polymer Physics,1987,25(8):1725-1740.
[24]HARRISON K L,JENKINS D M J. The effect of crystallinity and water absorption on the dynamic mechanical relaxation behaviour of polycaprolactone[J]. Polymer International,2004,53(9):1298-1304.
[25]杨宏军,常贺,宋肄业,等. 自缩合可逆络合聚合制备支化聚甲基丙烯酸甲酯[J]. 高校化学工程学报,2019, 33(2):388-393.

相似文献/References:

[1]杨宏军,孙爱斌,柴晨琼,等.膦腈碱催化甲基丙烯酸烯丙酯的基团转移聚合反应[J].常州大学学报(自然科学版),2018,30(04):1.[doi:10.3969/j.issn.2095-0411.2018.04.001]
　YANG Hongjun,SUN Aibin,CHAI Chenqiong,et al.Phosphazene Bases Catalyzed Group Transfer Polymerization of Allyl Methacrylate[J].Journal of Changzhou University(Natural Science Edition),2018,30(01):1.[doi:10.3969/j.issn.2095-0411.2018.04.001]

备注/Memo

备注/Memo:
收稿日期:2019-06-30。
基金项目:国家自然科学青年基金资助项目(21304010); 江苏省自然科学优秀青年基金资助项目(BK20170056); 江苏高校优势学科建设工程资助项目(PAPD)。
作者简介:黄文艳(1975—),女,江苏常熟人,博士,副教授。通信联系人:杨宏军(1983—),E-mail:hjyang0519@cczu.edu.cn
更新日期/Last Update: 2020-01-13