乳酸—脯氨酸共聚物的制备与表征
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摘要
聚乳酸(PLA)来源于可再生资源,具有优异的生物降解性,良好的生物相容性及生物可吸收性,广泛应用在生物医学、工业、农业等领域。然而,PLA均聚物存在着亲水性差、结晶度高、降解周期难以控制等一系列缺陷,极大地限制了PLA的实际应用。目前,通过与氨基酸共聚是改善PLA性能的有效方法之一。乳酸-氨基酸共聚物既可以保留PLA生物降解性,生物相容性和生物可吸收性的特点,又可以改善PLA诸多性能,因而是近年研究的热点之一。
关于合成乳酸-氨基酸交替共聚物的报道主要集中于吗啉-2,5-二酮及其衍生物的均聚。由于吗啉-2,5-二酮衍生物制备繁琐,开环困难,给乳酸-氨基酸交替共聚物的合成带来了难度。此外,通过脯氨酸改性PLA也少见报道。针对这两问题,本论文以脯氨酸和乳酸为原料制备乳酸-脯氨酸线型二聚体(PL),将其作为单体通过直接熔融共聚合成乳酸-脯氨酸交替共聚物(PLAP);将其与乳酸共聚合成乳酸-脯氨酸无规共聚物(PLAPL)、本论文的主要内容包括：
①通过脯氨酸的甲酯化、乳酸的乙酰化、脯氨酸甲酯与乙酰乳酸的酰胺反应、乙酰乳酸-脯氨酸甲酯的水解制备PL。在制备PL的过程中,得到了部分乳酸-脯氨酸环状二聚体(POL)。通过红外光谱(FTIR)、核磁共振谱(1H-NMR)对PL和POL的结构进行确证。
②以PL为原料,氯化亚锡为催化剂,通过熔融共聚合成PLAP,产率为20%。经凝胶色谱法(GPC)测定,PLAP的Mn=3700, PDI=1.08。差示扫描热分析(DSC)表明PLAP的玻璃化转变温度(约64℃)高于相近分子量PLA,呈非晶态；热分解温度与PLA相近。尝试POL开环聚合,但产率<10%。
③将LA分别与PL和POL为原料通过直接熔融共聚合成了一系列分子量不同的PLAPL。采用FTIR、1H-NMR、DS、GPC等手段对PLAPL的结构和热性能进行了研究。结果表明随着PL及POL投料量的增加,共聚物的产率和分子量均在下降；PLAPL的玻璃化温度随着PL投料量的增加在逐渐升高,而熔融峰则逐渐消失。
In recent years, PLA[ply(lactic acid)], a typical biodegradable polymer produced from renewable agricultural resources, has been extensively applied in the biomedical, industrial and agricultural fields due to its outstanding properties, such as good biodegradability, excellent biocompatibility and bioabsorbability. However, for specific applications, PLA homopolymer has some disadvantages, such as high crystallinity, slow and uncontrolled degradation speed, poor hydrophilicity, which limits the application scope of PLA. Currently, copolymerization of amino acid(AA) and lactic acid(LA) is a well-known method to modify the properties of PLA. Poly(LA-AA) could change properties of PLA, such as hydrophilicity, crystallinity or biodegradation rate, while keep the good biodegradability, excellent biocompatibility and bioabsorbability.
However, the synthesis of poly(LA-alt-AA) has rarely been focused on ring-opening homopolymerization of morpholine-2,5-dione derivatives. Unfortunately, the synthesis of morpholine-2,5-dione derivatives was very complicated and the reactivity of the monomers was low. Moreover, few people have considered to introduce proline into PLA to modify PLA. In order to solve the two problems, poly(lactic acid-alt-proline)(PLAP) and poly(lactic acid-co-proline)(PLAPL) was prepared by homopolymerization of line dimer of lactic acid-proline(PL) and copolymerization of PL and LA. This thesis mainly includes:
①The PL was prepared by methyl esterification of proline, acetylation of lactic acid, amidation and hydrolysis. At the same time, cyclic dimer of lactic acid-proline(POL) was obtained. PL and POL were characterized by FTIR、1-NMR.
②The PLAP was synthetized by direct melt polycondensation, starting from the PL. The yield of PLAP is about20%and Mn=3700, PDI=1.08. The glass transition temperature of PLAP(64.2℃) is higher than PLA and the thermal degradation temperature is similar with PLA, whereas the neat PLAP exhibited almost amorphous state corresponding to no apparent crystallization peak. We tried the ring-opening polymerization of POL, but the yield was<10%.
③The PLAPL was prepared via the direct melt polycondensation starting from the PL and LA or POL and LA with different molar feed. PLAPL was characterized by FTIR、1-NMR、DSC etc. The results show that with the increase of the molar feed ratio of PL or POL in the copolymerization, not only molecular weight decreased gradually, but also conversion had the trend of gradual decrease. The glass transition temperature of PLAPL increased gradually and PLAPL changed from crystalline to amorphous cuvres as the PL in the reaction mixture was increased.
关于合成乳酸-氨基酸交替共聚物的报道主要集中于吗啉-2,5-二酮及其衍生物的均聚。由于吗啉-2,5-二酮衍生物制备繁琐,开环困难,给乳酸-氨基酸交替共聚物的合成带来了难度。此外,通过脯氨酸改性PLA也少见报道。针对这两问题,本论文以脯氨酸和乳酸为原料制备乳酸-脯氨酸线型二聚体(PL),将其作为单体通过直接熔融共聚合成乳酸-脯氨酸交替共聚物(PLAP);将其与乳酸共聚合成乳酸-脯氨酸无规共聚物(PLAPL)、本论文的主要内容包括：
①通过脯氨酸的甲酯化、乳酸的乙酰化、脯氨酸甲酯与乙酰乳酸的酰胺反应、乙酰乳酸-脯氨酸甲酯的水解制备PL。在制备PL的过程中,得到了部分乳酸-脯氨酸环状二聚体(POL)。通过红外光谱(FTIR)、核磁共振谱(1H-NMR)对PL和POL的结构进行确证。
②以PL为原料,氯化亚锡为催化剂,通过熔融共聚合成PLAP,产率为20%。经凝胶色谱法(GPC)测定,PLAP的Mn=3700, PDI=1.08。差示扫描热分析(DSC)表明PLAP的玻璃化转变温度(约64℃)高于相近分子量PLA,呈非晶态；热分解温度与PLA相近。尝试POL开环聚合,但产率<10%。
③将LA分别与PL和POL为原料通过直接熔融共聚合成了一系列分子量不同的PLAPL。采用FTIR、1H-NMR、DS、GPC等手段对PLAPL的结构和热性能进行了研究。结果表明随着PL及POL投料量的增加,共聚物的产率和分子量均在下降；PLAPL的玻璃化温度随着PL投料量的增加在逐渐升高,而熔融峰则逐渐消失。
In recent years, PLA[ply(lactic acid)], a typical biodegradable polymer produced from renewable agricultural resources, has been extensively applied in the biomedical, industrial and agricultural fields due to its outstanding properties, such as good biodegradability, excellent biocompatibility and bioabsorbability. However, for specific applications, PLA homopolymer has some disadvantages, such as high crystallinity, slow and uncontrolled degradation speed, poor hydrophilicity, which limits the application scope of PLA. Currently, copolymerization of amino acid(AA) and lactic acid(LA) is a well-known method to modify the properties of PLA. Poly(LA-AA) could change properties of PLA, such as hydrophilicity, crystallinity or biodegradation rate, while keep the good biodegradability, excellent biocompatibility and bioabsorbability.
However, the synthesis of poly(LA-alt-AA) has rarely been focused on ring-opening homopolymerization of morpholine-2,5-dione derivatives. Unfortunately, the synthesis of morpholine-2,5-dione derivatives was very complicated and the reactivity of the monomers was low. Moreover, few people have considered to introduce proline into PLA to modify PLA. In order to solve the two problems, poly(lactic acid-alt-proline)(PLAP) and poly(lactic acid-co-proline)(PLAPL) was prepared by homopolymerization of line dimer of lactic acid-proline(PL) and copolymerization of PL and LA. This thesis mainly includes:
①The PL was prepared by methyl esterification of proline, acetylation of lactic acid, amidation and hydrolysis. At the same time, cyclic dimer of lactic acid-proline(POL) was obtained. PL and POL were characterized by FTIR、1-NMR.
②The PLAP was synthetized by direct melt polycondensation, starting from the PL. The yield of PLAP is about20%and Mn=3700, PDI=1.08. The glass transition temperature of PLAP(64.2℃) is higher than PLA and the thermal degradation temperature is similar with PLA, whereas the neat PLAP exhibited almost amorphous state corresponding to no apparent crystallization peak. We tried the ring-opening polymerization of POL, but the yield was<10%.
③The PLAPL was prepared via the direct melt polycondensation starting from the PL and LA or POL and LA with different molar feed. PLAPL was characterized by FTIR、1-NMR、DSC etc. The results show that with the increase of the molar feed ratio of PL or POL in the copolymerization, not only molecular weight decreased gradually, but also conversion had the trend of gradual decrease. The glass transition temperature of PLAPL increased gradually and PLAPL changed from crystalline to amorphous cuvres as the PL in the reaction mixture was increased.
引文
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