Paint & Coatings Industry ›› 2013, Vol. 43 ›› Issue (3): 5-11.

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Study on Synthesis of Block Copolymer of ε-Caprolactone/Glycolide and Its Hydrolysis Behaviors

Deng Bingfeng1,Huang zhixiong1, Huang Congshu 2,3, Ren Runtao 2,3, Wang Jingjing 2,3, Jiang Xuezhi 2,3   

  1. 1. Key Laboratory of Advanced Technology for Specially Functional Materials, Ministry of Education, Wuhan University of Technology, Whan 430070, China; 2. Xiamen Branch of Luoyang Ship MaterialResearch Instinte, Xiamen, Fuian 361101, China; 3. Science and Technology on Marine Corrosion and Protection Laboratory, Qingdao, Shandong 266101,China
  • Online:2013-03-31 Published:2019-05-31

己内酯 /乙交酯嵌段共聚物的合成及水解行为研究

邓冰锋1,黄志雄1,黄从树2,3,任润桃2,3,王晶晶2,3,江学志2,3   

  1. 1、武汉理工大学特种功能材料技术教育部重点实验室,武汉 430070; 2、中国船舶重工集团公司第七二五研究所厦门分部,福建厦门 361101; 3、海洋腐蚀与防护重点实验室,中国船舶重工集团公司第七二五研究所,山东青岛 266101
  • 基金资助:
    国家重点基础研究发展计划(973计划)(613109)

Abstract: With stannous octoate as a catalyst, caprolactone prepolymers( PCL) was synthesized, which was then melten copolymerized with glycolide( GA)to prepare the block copolymer of caprolactone glycolide (PCL/GA). The structure of the PCL/GA were characterized by GPC, FT-IR, 1 H-NMR and 13 C- NMR, confirming the block structure of the copolymer. The crystallization state and thermal properties of the PCL/GA was tested by XRD and DSC. It was found that all the prepared copolymers were crystalline polymers and the crystallization behavior was related with monomer composition. The hydrolysis behavior of the PCL/GA( 80/20)in seawater was investigated by use of QCM-D. It was found that the hydrolysis rate of the polyester fluctuated in the first three hours, which was inferred due to the simultaneous absorbent and hydrolysis of the polyerter at initial stage. With the completion of the water absorption, the hydrolysis rate of the block polyester was maintained at about ng/(cm2.h)stably. Crystallinity and the morphology changes of the film in the hydrolysis process was characterizationed by POM and SEM.

Key words: caprolactone, glycolide, block copolymers, hydrolysis, QCM-D

摘要: 以辛酸亚锡为催化剂,合成了己内酯预聚物(PCL),再与乙交酯(GA)熔融共聚,制备了嵌段型己内酯乙交酯共聚物(PCL/GA)。利用GPC、FT-IR、1H-NMR和13C-NMR等对PCL/GA的结构进行了表征,确认合成的共聚物为嵌段型聚酯共聚物。利用XRD和DSC测试了PCL/GA的结晶状态和热学性能,测试发现合成的共聚物均为结晶型聚合物,且结晶情况与单体组成有关,利用石英微晶天平考察了PCL/GA(80/20)在海水中的水解行为,发现前3h聚酯降解速率波动较大,推断是由于初期嵌段聚酯吸水与降解作用同时进行所致,随着吸水作用的完成,后期嵌段聚酯的降解速率维持在80ng/(cm2·h)左右,降解速率稳定。利用POM、SEM观察了水解过程中薄膜结晶及形貌变化。

关键词: 己内酯, 乙交酯, 嵌段共聚物, 水解, 石英微晶天平