自稳定沉淀聚合制备单分散苯乙烯/马来酸酐共聚物微球增长方式的研究
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摘要
自稳定沉淀聚合是近些年发现的一种制备单分散聚合物微球的方法。与传统乳液聚合、分散聚合、种子聚合、沉聚聚合等制备单分散微球的方法相比,自稳定沉淀聚合法的优点是：不需要加任何稳定剂和表面活性剂,制备微球表面洁净,后处理方便；不需要搅拌,反应体系简单；单体浓度最高可达到反应物重量分数的40%、反应时间短,聚合效率高。本文主要对自稳定沉淀聚合制备单分散苯乙烯／马来酸酐微球增长方式进行了研究。
以偶氮二异丁氰(AIBN)为引发剂,丁酸乙酯为溶剂,80℃通过自稳定沉淀聚合制备了单分散苯乙烯／马来酸酐共聚物微球,通过对反应过程中不同反应时间单体转化率、共聚物分子量、微球形貌及粒径的研究,提出了自稳定沉淀聚合体系AIBN引发制备单分散苯乙烯／马来酸酐共聚物微球增长机理。
以异丙基硫杂葸酮(ITX)和对二甲氨基苯甲酸乙酯(EDAB)为光引发剂和助引发剂,通过光引发合成出含有ITXH基团碎片的大分子引发剂,通过一系列的平行试验得出了合成大分子引发剂的最佳条件。用大分子引发剂通过自稳定沉淀聚合制备了单分散的苯乙烯／马来酸酐共聚物微球,证实了大分子引发剂再引发聚合是个“假活性”过程。总结了自稳定沉淀聚合体系下大分子引发剂引发制备单分散St/MAH共聚物微球主要增长方式。
用RAFT调控,通过自稳定沉淀聚合法制备了苯乙烯／马来酸酐共聚物微球。通过对成核后加RAFT试剂、起始加RAFT试剂、成核后加RAFT试剂制备的微球种子沉淀聚合、起始加RAFT试剂制备的微球种子沉淀聚合四个体系的研究,证实了自稳定沉淀聚合体系下RAFT调控制备苯乙烯／马来酸酐共聚物微球增长方式和大分子引发剂体系是一致的。
Self-stable precipitation polymerization, as one of methods of preparation of mono-disperse polymer microspheres, has been discovered recently. Comparing with the existing methods of preparation of mono-disperse polymer microspheres, such as emulsion polymerization, dispersion polymerization, seeded polymerization and precipitation polymerization, the advantages of self-stable precipitation polymerization include no need to add any stabililizer or surfactant, neatness in microsphere surface, convenience to deal with production after experiment, no need to agitate, high concentration of monomer reaching as much as 40% of the weight of reactant and short polymerization time. This paper mainly researched on the growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) in self-stable precipitation polymerization.
Mono-disperse microspheres of poly(styrene-co-maleic anhydride) were prepared by self-stable precipitation polymerization in 80℃, with AIBN as initiator and ethyl butyrate as solvent. The growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) initiated by AIBN in self-stable precipitation polymerization was proposed by researching on the conversion of monomer, the molecular of poly(styrene-co-maleic anhydride), the morphology and size of microspheres in different polymerization time.
The macroinitiator containing ITXH moiety was synthesized by photo reaction with 4-isopropylthioxanthone (ITX) as photoinitiator and ethyl 4-dimethylaminobenzoate (EDAB) as coinitiator. The optimum conditions were attainted by series of parallel experiments. Mono-disperse microspheres of poly(styrene-co-maleic anhydride) was prepared by self-stable precipitation polymerization with marcoinitiator as initiator. The reinitiation of macroinitiator is living. The growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) initiated by macroinitiator by self-stable precipitation polymerization was proposed.
Mono-disperse microspheres of poly(styrene-co-maleic anhydride) was prepared by self-stable precipitation polymerization by RAFT. The polymerization of adding RAFT after and before particle formation, seeded polymerization of microspheresⅠandⅡwere investigated. The growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) in self-stable precipitation polymerization by RAFT, which is similar with the system of initiation of macroinitiator, was proposed.
以偶氮二异丁氰(AIBN)为引发剂,丁酸乙酯为溶剂,80℃通过自稳定沉淀聚合制备了单分散苯乙烯／马来酸酐共聚物微球,通过对反应过程中不同反应时间单体转化率、共聚物分子量、微球形貌及粒径的研究,提出了自稳定沉淀聚合体系AIBN引发制备单分散苯乙烯／马来酸酐共聚物微球增长机理。
以异丙基硫杂葸酮(ITX)和对二甲氨基苯甲酸乙酯(EDAB)为光引发剂和助引发剂,通过光引发合成出含有ITXH基团碎片的大分子引发剂,通过一系列的平行试验得出了合成大分子引发剂的最佳条件。用大分子引发剂通过自稳定沉淀聚合制备了单分散的苯乙烯／马来酸酐共聚物微球,证实了大分子引发剂再引发聚合是个“假活性”过程。总结了自稳定沉淀聚合体系下大分子引发剂引发制备单分散St/MAH共聚物微球主要增长方式。
用RAFT调控,通过自稳定沉淀聚合法制备了苯乙烯／马来酸酐共聚物微球。通过对成核后加RAFT试剂、起始加RAFT试剂、成核后加RAFT试剂制备的微球种子沉淀聚合、起始加RAFT试剂制备的微球种子沉淀聚合四个体系的研究,证实了自稳定沉淀聚合体系下RAFT调控制备苯乙烯／马来酸酐共聚物微球增长方式和大分子引发剂体系是一致的。
Self-stable precipitation polymerization, as one of methods of preparation of mono-disperse polymer microspheres, has been discovered recently. Comparing with the existing methods of preparation of mono-disperse polymer microspheres, such as emulsion polymerization, dispersion polymerization, seeded polymerization and precipitation polymerization, the advantages of self-stable precipitation polymerization include no need to add any stabililizer or surfactant, neatness in microsphere surface, convenience to deal with production after experiment, no need to agitate, high concentration of monomer reaching as much as 40% of the weight of reactant and short polymerization time. This paper mainly researched on the growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) in self-stable precipitation polymerization.
Mono-disperse microspheres of poly(styrene-co-maleic anhydride) were prepared by self-stable precipitation polymerization in 80℃, with AIBN as initiator and ethyl butyrate as solvent. The growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) initiated by AIBN in self-stable precipitation polymerization was proposed by researching on the conversion of monomer, the molecular of poly(styrene-co-maleic anhydride), the morphology and size of microspheres in different polymerization time.
The macroinitiator containing ITXH moiety was synthesized by photo reaction with 4-isopropylthioxanthone (ITX) as photoinitiator and ethyl 4-dimethylaminobenzoate (EDAB) as coinitiator. The optimum conditions were attainted by series of parallel experiments. Mono-disperse microspheres of poly(styrene-co-maleic anhydride) was prepared by self-stable precipitation polymerization with marcoinitiator as initiator. The reinitiation of macroinitiator is living. The growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) initiated by macroinitiator by self-stable precipitation polymerization was proposed.
Mono-disperse microspheres of poly(styrene-co-maleic anhydride) was prepared by self-stable precipitation polymerization by RAFT. The polymerization of adding RAFT after and before particle formation, seeded polymerization of microspheresⅠandⅡwere investigated. The growth mechanism of mono-disperse microspheres of poly(styrene-co-maleic anhydride) in self-stable precipitation polymerization by RAFT, which is similar with the system of initiation of macroinitiator, was proposed.
引文
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