微波辐照合成多孔高分子微球及机理研究
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摘要
本论文讨论了在微波辐照条件下，采用间歇无皂种子乳液聚合合成出以聚苯乙烯为骨架的聚（苯乙烯-甲基丙烯酸甲酯-丙烯酸）[P(St-MMA-AA)]、聚（苯乙烯-甲基丙烯酸甲酯-甲基丙烯酸）[P(St-MMA-MAA)]、聚（苯乙烯-丙烯酸甲酯-丙烯酸）[P(St-MA-AA)]、聚（苯乙烯-丙烯酸乙酯-丙烯酸）[P(St-EA-AA)]和聚（苯乙烯-丙烯酸丁酯-甲基丙烯酸）[P(St-BA-MAA)]三元共聚乳液，将所得复合胶乳进行碱/酸分段处理或碱/冷却处理，得到多孔高分子微球。用蒸干称重法测量聚合反应的转化率，聚合物粒子用TEM、IR、GPC、DTA等方法进行了表征。通过对种子乳液聚合中种子用量、不饱和酸含量、单体滴加速度和引发剂加入方式等因素的控制得到基本不产生新胶粒的种子共聚乳胶粒子。研究了碱处理初始pH值、碱处理时间、酸处理初始pH值、酸处理时间、温度等因素对粒子大小、孔径的影响，探讨了制备粒径、孔径可控的多孔乳胶粒子的最佳条件。
通过分析各种因素对形成多孔乳胶粒子的影响，探讨了碱/酸分段处理和碱/冷却处理法合成多孔乳胶粒子的机理，认为碱处理过程中粒子溶胀，分子链段运动，内部存在许多小水区是形成多孔粒子的关键。酸处理或冷却过程使分子链段固定、小水区逐渐团聚形成更大的水区，形成多孔结构。整个处理过程与聚合物和水之间的表面张力密切相关。
Multihollow macromolecule microspheres were synthesized by seeded emulsion polymerization and subsequently alkali/acid or alkali/cooling treatment under microwave irradiation. These multihollow particles were poly(styrene-methylmeth- acrylate-acrylic acid), poly (styrene-methylmethacrylate-methacrylic acid), poly (styrene-methylacrylate-acrylic acid)，poly(styrene-ethylacrylate-acrylic acid) and poly(styrene-butylacrylate-methacrylic acid). The polymer conversion was deter- mined by gravimetrically analytical method and the particles were characterized using TEM, IR, GPC and DTA. The copolymer which was prepared by seeded emulsion polymerization almost containing no new particles was gained by the control of the seed concentration, amount of unsaturated monomer, monomer addition velocity and initiator addition method, etc. The suitable conditions for the preparation of multihollow particles with controllable diameter and hollow size were investigated by changing the factors such as initial alkali treatment pH value, alkali treatment time, initial acid treatment pH value, acid treatment time and temperature.
The multihollow particle formation mechanism was discussed. It was considered the swelling of the particles, the movement of molecule segment and small water pool existed in the alkali treatment process were crucial step for the formation of multihollow particle. Subsequently, these small water pools would form larger water pool by coagulation through acid treatment or cooling process, which resulted in multihollow structure. The whole treatment process was connected with the interfacial free energy of polymer and water.
通过分析各种因素对形成多孔乳胶粒子的影响，探讨了碱/酸分段处理和碱/冷却处理法合成多孔乳胶粒子的机理，认为碱处理过程中粒子溶胀，分子链段运动，内部存在许多小水区是形成多孔粒子的关键。酸处理或冷却过程使分子链段固定、小水区逐渐团聚形成更大的水区，形成多孔结构。整个处理过程与聚合物和水之间的表面张力密切相关。
Multihollow macromolecule microspheres were synthesized by seeded emulsion polymerization and subsequently alkali/acid or alkali/cooling treatment under microwave irradiation. These multihollow particles were poly(styrene-methylmeth- acrylate-acrylic acid), poly (styrene-methylmethacrylate-methacrylic acid), poly (styrene-methylacrylate-acrylic acid)，poly(styrene-ethylacrylate-acrylic acid) and poly(styrene-butylacrylate-methacrylic acid). The polymer conversion was deter- mined by gravimetrically analytical method and the particles were characterized using TEM, IR, GPC and DTA. The copolymer which was prepared by seeded emulsion polymerization almost containing no new particles was gained by the control of the seed concentration, amount of unsaturated monomer, monomer addition velocity and initiator addition method, etc. The suitable conditions for the preparation of multihollow particles with controllable diameter and hollow size were investigated by changing the factors such as initial alkali treatment pH value, alkali treatment time, initial acid treatment pH value, acid treatment time and temperature.
The multihollow particle formation mechanism was discussed. It was considered the swelling of the particles, the movement of molecule segment and small water pool existed in the alkali treatment process were crucial step for the formation of multihollow particle. Subsequently, these small water pools would form larger water pool by coagulation through acid treatment or cooling process, which resulted in multihollow structure. The whole treatment process was connected with the interfacial free energy of polymer and water.
引文
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