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Synthesis of Poly(Tetramethylene Ether) Glycol Containing Ester Linkages Derived from Castor Oil and Properties of Recyclable Polyurethanes Prepared Therefrom

含蓖麻油酯键聚四亚甲基醚二醇的合成及其制备的可回收聚氨酯的性能

基本信息

批准号：
23656568
负责人：
HASHIMOTO Tamotsu
金额：
$ 2.08万
依托单位：
University of Fukui
依托单位国家：
日本
项目类别：
Grant-in-Aid for Challenging Exploratory Research
财政年份：
2011
资助国家：
日本
起止时间：
2011 至 2012
项目状态：
已结题

项目摘要

Ricinoleic acid derived from castor oil was utilized for the preparation of ester linkages-containing poly(tetramethylene ether) [or poly(tetrahydrofuran)] glycol {HO-CH[(CH2)5CH3]CH2CH=CH(CH2)7-C(=O)O-[(CH2)4O]n-1-(CH2)4-OC(=O)-(CH2)7-CH=CH-CH2CH[(CH2)5CH3]-OH; PTHF-RA-OH}. This polyol was reacted with two-fold amount of 4,4’-diphenylmethane diisocyanate followed by the chain-extension reaction with1,4-butanediol to give a new polyurethane with degradable ester moieties. The obtained polyurethane (PTHF-RA-BD-PU) exhibited similar thermal and mechanical properties to those of the polyurethane (PTHF-BD-PU) prepared from poly(tetramethylene ether) [or poly(tetrahydrofuran)] glycol (PTHF-OH). The treatment of PTHF-RA-BD-PU with potassium hydroxide in tetrahydrofuran/ethanol (9/1 v/v) solvent in the presence of a small amount of water caused hydrolysis reaction of the recinolate ester linkages to give the mixture of PTHF-OH and the urethane oligomers capped with recinoleic acid moieties.The extraction of PTHF-OH with methylene chloride from the mixture resulted in the recovery of PTHF-OH in over 90% yield based on the poly(tetrahydrofuran) segments of PTHF-RA-BD-PU. Enzymatic degradation of PTHF-RA-BD-PU was carried out with lipase as a catalyst. Both of the heterogeneous reaction with film specimens in water using phosphate buffer solution (pH 7.4) at 37 oC and the homogeneous reaction in N,N-dimethylformamide at 45 oC caused the decrease in the molecular weight of PTHF-RA-BD-PU. This is probably due to the lipase-catalyzed hydrolysis of the recinolate ester groups of PTHF-RA-BD-PU.

以蓖麻油为原料合成了含酯键的聚四亚甲基醚[或聚四氢呋喃]二醇{HO-CH[（CH 2）5CH 3] CH 2 CH =CH（CH 2）7-C（=O）O-[（CH 2）4 O]n-1-（CH 2）4-OC（=O）-（CH 2）7-CH= CH-CH 2 CH [（CH 2）5CH 3]-OH; PTHF-RA-OH}。该多元醇与2倍量的4，4 ′-二苯基甲烷二异氰酸酯反应，再与1，4-丁二醇扩链，得到了一种含可降解酯基的新型聚氨酯。所得聚氨酯（PTHF-RA-BD-PU）的热性能和力学性能与由聚四氢呋喃二醇（PTHF-OH）或聚四氢呋喃二醇（PTHF-OH）制备的聚氨酯（PTHF-BD-PU）相似。PTHF-RA-BD-PU在四氢呋喃/乙醇（9/1 v/v）溶剂中，在少量水存在下，用氢氧化钾处理，使蓖麻油酸酯键发生水解反应，得到PTHF-OH和蓖麻油酸封端的聚氨酯低聚物的混合物，用二氯甲烷萃取，PTHF-OH的回收率在90%以上产率基于PTHF-RA-BD-PU的聚（四氢呋喃）链段。以脂肪酶为催化剂，对PTHF-RA-BD-PU进行酶降解。PTHF-RA-BD-PU在37 ℃的磷酸盐缓冲溶液（pH7.4）中与薄膜样品的非均相反应和在45 ℃的N，N-二甲基甲酰胺中的均相反应均导致PTHF-RA-BD-PU的分子量降低。这可能是由于PTHF-RA-BD-PU的蓖麻油酸酯基团的脂肪酶催化水解。