左永康¹,宋肄业²,杨宏军¹,黄文艳¹,薛小强¹,蒋其民¹,江力¹,蒋必彪^1,2

• 1:江苏省绿色环保重点实验室 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

摘要(Abstract)：

聚己内酯因其良好的生物相容性而备受关注，但其较慢的降解速率限制了其应用和发展。为此，研究以ε-己内酯（CL）、乙醇胺（MEA）和二丙烯酸新戊二醇酯（NPGDA）为原料一锅法合成了以CL为主要结构单元且具有优异降解性能的支化聚酯醚。通过核磁共振（NMR）、三检测凝胶渗透色谱（TD-GPC）和差示扫描量热仪（DSC）对聚合反应过程及聚合物进行了分析和表征。对聚合反应过程研究表明，MEA上的-NH₂和-OH都可参与CL的开环聚合和与NPGDA双键的氧迈克尔加成反应，最终生成具有支化结构的聚酯醚。NPGDA和CL的转化率可均接近100%，所得聚合物组成与投料比接近。对聚合物结构研究表明，较线型聚己内酯，所制备支化聚合物具有更小的结晶度、更低的结晶温度和更快的降解速率。

关键词(KeyWords)： 支化聚合物;聚酯醚;迈克尔加成反应;开环聚合

Abstract:

Keywords:

基金项目(Foundation): 江苏省自然科学优秀青年基金（BK20170056）；江苏高校优势学科建设工程（PADA）。

作者(Author): 左永康¹,宋肄业²,杨宏军¹,黄文艳¹,薛小强¹,蒋其民¹,江力¹,蒋必彪^1,2

DOI: 10.3969/j.issn.1003-9015.2020.03.028

参考文献(References)：

• [1] VERT M, LI S M, SPENLEHAUER G, et al. Bioresorbability and biocompatibility of aliphatic polyesters[J]. Journal of Materials Science:Materials in Medicine, 1992, 3(6):432-446.
  [2] SOUSA B, ARIANE D J, CERQUEIRA C, et al. Polycaprolactone antimony nanoparticles as drug delivery system for leishmaniasis[J]. American Journal of Therapeutics, 2019, 26(1):12-17.
  [3] ENGELBERG I, KOHN J. Physico-mechanical properties of degradable polymers used in medical applications:A comparative study[J]. Biomaterials, 1991, 12(3):292-304.
  [4] LANGER R. New methods of drug delivery[J]. Science, 1990, 249(4976):1527-1533.
  [5] DAVIES M. Biodegradable polymers as drug delivery systems[J]. Biomaterials, 1993, 14(4):284-284.
  [6] BEDNAREK M. Branched aliphatic polyesters by ring-opening (co)polymerization[J]. Progress in Polymer Science, 2016, 58(2):27-58.
  [7] IANNACE S, LUCA N D, NICOLAIS L, et al. Physical characterization of incompatible blends of polymethylmethacrylate and polycaprolactone[J]. Journal of Applied Polymer Science, 1990, 41(11):2691-2704.
  [8] YANG H J, SUN A B. Synthesis and post-functionalization of a degradable aliphatic polyester containing allyl pendent groups[J]. Polymer, 2017, 121(6):256-261.
  [9] LU F, LEI L, SHEN Y Y, et al. Effects of amphiphilic PCL-PEG-PCL copolymer addition on 5-fluorouracil release from biodegradable PCL films for stent application[J]. International Journal of Pharmaceutics, 2011, 419(1-2):77-84.
  [10] GONG C Y, SHI S, DONG P W, et al. Synthesis and characterization of PEG-PCL-PEG thermosensitive hydrogel[J]. International Journal of Pharmaceutics, 2009, 365(1):89-99.
  [11] GONG C, SHI S, WU L, et al. Biodegradable in situ gel-forming controlled drug delivery system based on thermosensitive PCL-PEG-PCL hydrogel. Part 2:Sol-gel-sol transition and drug delivery behavior[J]. Acta Biomaterialia, 2009, 5(9):3358-3370.
  [12] AHMED F, DISCHER D E. Self-porating polymersomes of PEG-PLA and PEG-PCL:Hydrolysis-triggered controlled release vesicles[J]. Journal of Controlled Release, 2004, 96(1):37-53.
  [13] HOQUE M E, HUTMACHER D W, FENG W, et al. Fabrication using a rapid prototyping system and in vitro characterization of PEG-PCL-PLA scaffolds for tissue engineering[J]. Journal of Biomaterials Science, Polymer Edition, 2005, 16(12):1595-1610.
  [14] SUN M, KINGHAM P J, REID A J, et al. In vitro and in vivotesting of novel ultrathin PCL and PCL/PLA blend films as peripheral nerve conduit[J]. Journal of Biomedical Materials Research Part A, 2010, 93(4):1470-1481.
  [15] HUSKIC M, PULKO I. The synthesis and characterization of multiarm star-shaped graft copolymers of polycaprolactone and hyperbranched polyester[J]. European Polymer Journal, 2015, 70(7):384-391.

  
  [16] XU P, HUANG X, PAN X, et al. Hyperbranched polycaprolactone through RAFT polymerization of 2-methylene-1,3-dioxepane[J]. Polymers, 2019, 11(2):318-331.

  
  [17] 宋肄业, 孙爱斌, 黄文艳, 等. 可降解功能性聚合物多孔材料的制备与表征[J]. 高分子材料科学与工程, 2018, 34(3):7-11. SONG Y Y, SUN A B, HUANG W Y, et al. Preparation and characterization of degradable functional polymer porous materials[J]. Polymer Materials Science and Engineering, 2018, 34(3):7-11.
  [18] YANG H J, ZUO Y K, ZHANG J D, et al. Phosphazene-catalyzed oxa-Michael addition click polymerization[J]. Polymer Chemistry, 2018, 9(38):4716-4723.
  [19] YANG H J, ZHANG J D, ZUO Y K, et al. Anionic hybrid copolymerization via concurrent oxa-Michael addition and ring-opening polymerizations[J]. Macromolecular Chemistry and Physics, 2019, 220(13), 1900147.
  [20] YANG H J, BAI T, XUE X, et al. A simple route to vinyl-functionalized hyperbranched polymers:Self-condensing anionic copolymerization of allyl methacrylate and hydroxyethyl methacrylate[J]. Polymer, 2015, 72(6):63-68.
  [21] 黄文艳, 张俊, 张东亮, 等. 乳液聚合合成高分子量支化聚苯乙烯[J]. 高校化学工程学报, 2015, 29(1):247-251. HUANG W Y, ZHANG J, ZHANG D L, et al. Synthesis of high molecular weight branched polystyrene by emulsion polymerization[J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(1):247-251.
  [22] MORI H, MÜLLER A H E, SIMON P F W. Linear versus (hyper)branched polymers[M]. Weinheim:Wiley-VCH Verlag GmbH & Co. KGaA, 2011.
  [23] YANG H J, XU J B, PISPAS S, et al. One-step synthesis of hyperbranched biodegradable polymer[J]. RSC Advances, 2013, 3(19):6853-6858.