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纸质出版日期:2009-1-20,
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刘迎, 魏荣卿, 刘晓宁. 乳酸-3-苯甲基-2,5-吗啉二酮共聚物的合成及共聚物组分分析[J]. 高分子学报, 2009,(1):66-71.
LIU Ying, WEI Rongqing, LIU Xiaoning. SYNTHESIS AND COMPOSITIONAL ANALYSIS OF POLY(LACTIC ACID-co-3-PHENYLMETHYL-2,5-MORPHOLINEDIONE)[J]. Acta Polymerica Sinica, 2009,(1):66-71.
刘迎, 魏荣卿, 刘晓宁. 乳酸-3-苯甲基-2,5-吗啉二酮共聚物的合成及共聚物组分分析[J]. 高分子学报, 2009,(1):66-71. DOI: 10.3724/SP.J.1105.2009.00066.
LIU Ying, WEI Rongqing, LIU Xiaoning. SYNTHESIS AND COMPOSITIONAL ANALYSIS OF POLY(LACTIC ACID-co-3-PHENYLMETHYL-2,5-MORPHOLINEDIONE)[J]. Acta Polymerica Sinica, 2009,(1):66-71. DOI: 10.3724/SP.J.1105.2009.00066.
以苯丙氨酸为原料合成3-苯甲基-2
5-吗啉二酮(PMD),以辛酸亚锡为催化剂,研究PMD与丙交酯(LA)开环共聚得到乳酸-3-苯甲基-2
5-吗啉二酮共聚物,用IR、1H-NMR、DSC对共聚物进行分析表征,表明可得到含有苯丙氨酸的聚乳酸共聚物.利用红外定量分析法替代1H-NMR法测定共聚物中PMD的组分含量,以1671.53 cm-1和870.82 cm-1两波数处特征峰的吸光度比值,作标准工作曲线Y=0.05567X+0.1091,r=0.9993.比较了催化剂浓度、反应时间、温度对共聚物组分含量、共聚物特性黏数[η]的影响.结果表明,低催化剂浓度条件下(0.025 mol%与0.1 mol%),产物特性黏数[η]随反应时间的延长先增加然后下降;而在高催化剂浓度(0.2 mol%)的条件下,因主链中形成了更多更稳定的酰胺键,产物特性黏数[η]10 h内维持不变;随PMD加入量的增多,进入共聚物中的PMD组分也相应地呈线性增加,但因PMD的开环活性低于丙交酯,所以苯丙氨酸引入聚乳酸链段中比较困难,但在低投料比条件下(20 mol%),升高反应温度有利于PMD含量的增加;同样也因为PMD在共聚物中组分含量的增多,苯环的稳定性使共聚物[η]受催化剂浓度及温度的影响逐渐减弱.
In the first step
3-phenylmethyl-2
5-morpholinedione (PMD) was synthesized by using phenylalanine as the raw material.In the second step
poly(lactic acid-co-3-phenylmethyl-2
5-morpholinedione) was prepared by ring-opening copolymerization of PMD and lactide (LA).Stannous octanoate was used as catalyst in the reaction of second step.The structure of copolymers was analyzed by IR
1H-NMRand DSC.The contents of copolymers were detected by infrared spectroscopy instead of 1H-NMR. Two characteristic peaks at 1671.53 cm-1 and 870.82 cm-1-were selected for PMD and PLA in IR.A standard working curve was established:Y=0.05567X+0.1091(r=0.9993)
where X was the reciprocal of PMD monomer molar concentration
and Y was the absorbance ratio of PLA to PMD at their characteristic peaks.Effects of catalyst content
reaction time and temperature on the concentration of PMD and [η] in copolymers were studied.It was found that
with prolonging of reaction time
the [η] was first increased then decreased under the condition of low catalyst concentration.Furthermore
under the condition of high catalyst concentration
the [η] suspended during 10 h because of the formation of amide linkage products which are more stable.The concentration of PMD in resulting copolymers increases linerly with the increase of PMD in feed.The PMD was less ring-opening reactive than LA
so it was difficult to incorporate the phenyls into the copolymer.However
under the condition of low feed ratio
the contents of PMD can increase when the temperature becomes higher.Moreover
with increasing the concentration of PMD in copolymer
the influence of catalyst content and temperature on copolymer decreased by the stability of phenyl.
丙交酯3-苯甲基-25-吗啉二酮乳酸-3-苯甲基-25-吗啉二酮共聚物红外定量共聚物组成分析
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