聚乳酸/纳米二氧化硅原位复合材料的制备和性能
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摘要
本文采用原位聚合法,在催化剂作用下,使丙交酯单体在改性的纳米二氧化硅表面开环聚合,改善了聚乳酸的性能,简化了制备工艺,直接制得聚乳酸/纳米二氧化硅复合材料。
首先以D, L-乳酸为原料,在催化剂氧化锌作用下通过脱水环化制备出了D, L-丙交酯,研究了减压脱水时间和解聚温度对丙交酯产率的影响,得出合理的制备工艺条件为:先常压脱水至液体温度为145℃,然后加入用量为1.5wt%的催化剂,在150℃下脱水反应2h;裂解温度范围为170℃~250℃,丙交酯粗产率能达到85%左右。选用无水乙醇为丙交酯重结晶溶剂,通过加热套加热,缩短了重结晶时间,并将纯丙交酯的收率提高到70%左右。经三次重结晶,丙交酯的熔程为125.2~126.3℃。
然后用硅烷偶联剂γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)改性纳米二氧化硅粉体,讨论了偶联剂的用量对改性效果的影响,得出了较合理的偶联剂用量为纳米二氧化硅用量的10wt%。
最后讨论了聚乳酸/纳米二氧化硅复合材料的制备方法。分析了复合材料制备过程中各种单因素(催化剂的种类和用量、反应温度、反应时间以及改性纳米二氧化硅用量)对聚合物质均分子量的影响,通过正交实验得出了最优制备工艺为:以辛酸亚锡为催化剂,其用量为丙交酯的0.25 wt%,聚合反应时间为72h,反应温度为140℃,改性纳米二氧化硅的用量为丙交酯的5wt%。按此最佳条件进行复合材料的制备,最终得到聚合物的质均分子量( M w)为1.5091×105。通过复合材料的红外光谱和扫描电镜分析,表明纳米二氧化硅与聚乳酸发生了化学结合,并且均匀的分散于聚乳酸基体中。热失重分析结果表明,随着纳米二氧化硅含量的增加,聚乳酸纳米二氧化硅复合材料的热稳定性提高。通过力学性能分析,可以看出无机纳米粒子的加入提高了材料的拉伸强度。通过材料的吸水性分析,表明纳米二氧化硅的加入明显地改善了聚乳酸的亲水性,这可以加快聚乳酸的降解速率,增强相容性。用紫外-可见光分光光度仪分析聚乳酸/纳米二氧化硅复合材料的透光性,结果表明复合材料膜的透光率与纯聚乳酸膜的透光率相当,纳米二氧化硅粒子对透光率没有影响。
In this thesis, in situ melt polymerization of D, L-lactide (DLLA) and modified nano-silica in the presence of catalyst has been proposed as a novel approach to prepare PLA/nano-silica composites. The preparation process was simplified and the properties were improved.
Firstly, D, L-lactide was prepared from D, L-lactic acid with zinc oxide as catalyst. Effects of dehydration time of lactic acid and pyrolytic temperature on crude yield of DLLA were studied. The results showed that the optimal conditions were as follows: liquid temperature was heated to 145.0℃under atmospheric dehydrated condition, then added zinc oxide amount of which was 1.5wt%, vacuum dehydration temperature was 150.0℃for 2 hours, the range of depolymerizing temperature was 170℃~250℃,crude yield of DLLA was 85%. Ethanol was used as solvent for recrystallization of DLLA. Time for recrystallization was shortened because of using heating jacket. The total yield of purified lactide increased to 70% after three recrystallizations.
Then, nano-silica was modified by coupling agentγ-glycidoxypropyl trimethoxysilane (KH-560). Influences of mass ratio of nano-SiO2/KH-560 were investigated. The optimal content of KH-560 was 10wt%.
Preparation methods of PLA/nano-silica were discussed. The influences of catalyst species and quantity, reaction temperature and time, content of nano-silica on the weight average molecular weight ( M w) of composites were discussed. The resules of orthogonal tests showed that the optimal reaction conditions were as follows:tin octoate was used as catalyst; W(SnOct2)/W(DLLA) and W(nano-SiO2)/W(DLLA) was 1:400 and 1:20, respectively; the reaction temperature was 140℃and the reaction time was 72h. Under this conditions, composites with M w of 1.5091×105 was obtained. The results of FTIR and SEM showed that nano-silica and polylactide were connected with covalent bonds, and inorganic phases were dispersed in polylactide homogeneously. The results of TG indicated that thermal decomposition temperature was increased with the increasing of silica content. The tensile strength of composites was enhanced because of adding nano-inorganic particles into polylactide. The water absorption results showed that water absorption property of PLA was improved by adding modified nano-silica which could accelerate degradation of PLA and enhance compatibility. The results of ultraviolet spectro-photometric analysis of composites indicated that light transmittance of composites was similar to that of pure PLA. The existence of nano-silica had non clear influence on the light transmittance of composites.
首先以D, L-乳酸为原料,在催化剂氧化锌作用下通过脱水环化制备出了D, L-丙交酯,研究了减压脱水时间和解聚温度对丙交酯产率的影响,得出合理的制备工艺条件为:先常压脱水至液体温度为145℃,然后加入用量为1.5wt%的催化剂,在150℃下脱水反应2h;裂解温度范围为170℃~250℃,丙交酯粗产率能达到85%左右。选用无水乙醇为丙交酯重结晶溶剂,通过加热套加热,缩短了重结晶时间,并将纯丙交酯的收率提高到70%左右。经三次重结晶,丙交酯的熔程为125.2~126.3℃。
然后用硅烷偶联剂γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)改性纳米二氧化硅粉体,讨论了偶联剂的用量对改性效果的影响,得出了较合理的偶联剂用量为纳米二氧化硅用量的10wt%。
最后讨论了聚乳酸/纳米二氧化硅复合材料的制备方法。分析了复合材料制备过程中各种单因素(催化剂的种类和用量、反应温度、反应时间以及改性纳米二氧化硅用量)对聚合物质均分子量的影响,通过正交实验得出了最优制备工艺为:以辛酸亚锡为催化剂,其用量为丙交酯的0.25 wt%,聚合反应时间为72h,反应温度为140℃,改性纳米二氧化硅的用量为丙交酯的5wt%。按此最佳条件进行复合材料的制备,最终得到聚合物的质均分子量( M w)为1.5091×105。通过复合材料的红外光谱和扫描电镜分析,表明纳米二氧化硅与聚乳酸发生了化学结合,并且均匀的分散于聚乳酸基体中。热失重分析结果表明,随着纳米二氧化硅含量的增加,聚乳酸纳米二氧化硅复合材料的热稳定性提高。通过力学性能分析,可以看出无机纳米粒子的加入提高了材料的拉伸强度。通过材料的吸水性分析,表明纳米二氧化硅的加入明显地改善了聚乳酸的亲水性,这可以加快聚乳酸的降解速率,增强相容性。用紫外-可见光分光光度仪分析聚乳酸/纳米二氧化硅复合材料的透光性,结果表明复合材料膜的透光率与纯聚乳酸膜的透光率相当,纳米二氧化硅粒子对透光率没有影响。
In this thesis, in situ melt polymerization of D, L-lactide (DLLA) and modified nano-silica in the presence of catalyst has been proposed as a novel approach to prepare PLA/nano-silica composites. The preparation process was simplified and the properties were improved.
Firstly, D, L-lactide was prepared from D, L-lactic acid with zinc oxide as catalyst. Effects of dehydration time of lactic acid and pyrolytic temperature on crude yield of DLLA were studied. The results showed that the optimal conditions were as follows: liquid temperature was heated to 145.0℃under atmospheric dehydrated condition, then added zinc oxide amount of which was 1.5wt%, vacuum dehydration temperature was 150.0℃for 2 hours, the range of depolymerizing temperature was 170℃~250℃,crude yield of DLLA was 85%. Ethanol was used as solvent for recrystallization of DLLA. Time for recrystallization was shortened because of using heating jacket. The total yield of purified lactide increased to 70% after three recrystallizations.
Then, nano-silica was modified by coupling agentγ-glycidoxypropyl trimethoxysilane (KH-560). Influences of mass ratio of nano-SiO2/KH-560 were investigated. The optimal content of KH-560 was 10wt%.
Preparation methods of PLA/nano-silica were discussed. The influences of catalyst species and quantity, reaction temperature and time, content of nano-silica on the weight average molecular weight ( M w) of composites were discussed. The resules of orthogonal tests showed that the optimal reaction conditions were as follows:tin octoate was used as catalyst; W(SnOct2)/W(DLLA) and W(nano-SiO2)/W(DLLA) was 1:400 and 1:20, respectively; the reaction temperature was 140℃and the reaction time was 72h. Under this conditions, composites with M w of 1.5091×105 was obtained. The results of FTIR and SEM showed that nano-silica and polylactide were connected with covalent bonds, and inorganic phases were dispersed in polylactide homogeneously. The results of TG indicated that thermal decomposition temperature was increased with the increasing of silica content. The tensile strength of composites was enhanced because of adding nano-inorganic particles into polylactide. The water absorption results showed that water absorption property of PLA was improved by adding modified nano-silica which could accelerate degradation of PLA and enhance compatibility. The results of ultraviolet spectro-photometric analysis of composites indicated that light transmittance of composites was similar to that of pure PLA. The existence of nano-silica had non clear influence on the light transmittance of composites.
引文
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[2]钟伟,戈进杰,马敬红,等.聚乳酸的直接缩合制备及其异氰酸酯扩链探索[J].复旦学报:自然科学版, 1999, 38(6): 705-708.
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