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中文摘要: 先使用偶联剂γ-巯丙基三甲氧基硅烷(MPMS) 对微米级硅胶微粒进行了表面改性，然后使改性微粒表面的巯基与溶液中的偶氮二异丁腈(AIBN)构成巯基-AIBN引发体系，引发油溶性单体甲基丙烯酸缩水甘油酯(GMA)在硅胶微粒表面发生接枝聚合，制得了高接枝度(23 g/100 g)的接枝微粒PGMA SiO2。对影响GMA接枝聚合的主要因素进行了考察，对表面引发接枝聚合的机理进行了研究。以对氨基苯磺酸钠为试剂,通过环氧基团的开环反应,对PGMA-SiO2接枝微粒进行了功能化改性，将阴离子基团苯磺酸钠(BSNa)键合于接枝大分子PGMA侧链，制得功能接枝微粒BSNa PGMA SiO2，并初步研究了其功能性。 研究表明，受溶液中的AIBN分解反应的诱导，改性硅胶微粒表面的巯基会发生氢原子转移，在硅胶微粒表面产生硫自由基，使GMA可在硅胶微粒表面有效地发生接枝聚合。接枝聚合适宜的温度为55 ℃，适宜的AIBN用量为单体质量的0.8%。功能接枝微粒BSNa PGMA-SiO2表面携带有高密度的负电荷，对苦参碱和金雀花碱等生物碱分子具有强吸附作用。
中文关键词: 表面引发接枝 甲基丙烯酸缩水甘油酯 硅胶 巯基 氢原子转移
Abstract:Abstract:Micro sized silica gel particles were first surface modified with coupling agent γ-mercaptopro pyltrimethoxysilane (MPMS), obtaining the modified particles MPMS-SiO2, on which thiol groups were chemically attached. Subsequently, a surface initiating system was constituted with the thiol groups on the surfaces of MPMS-SiO2 particles and 2,2′-azobis(2-methylpropionitrile) (AIBN) in the organic solvent, namely the thiol AIBN initiating system was formed. The “surface initiated graft polymerization” of glycidyl methacrylate (GMA) was carried out, preparing the grafted particles PGMA-SiO2 with a high grafting degree of 23 g/100 g. The effects of the main factors on the graft polymerization of GMA were examined, and the mechanism of the surface initiated graft polymerization was explored.The functional modification of the grafted particles was conducted using sodium 4 aminobenzenesulfonate as reagent via the ring opening reaction of the epoxy groups of the grafted PGMA, obtaining the functional particles BSNa-PGMA-SiO2 on which sodium benzenesulfonate (BSNa) groups were bonded, and their functionality was preliminarily investigated. Results show that by inducing the decomposition reaction of AIBN, the thiol groups on the surfaces of the particles MPMS SiO2 will produce a hydrogen atom transfer process from thiol groups to the free radicals that were the product of the decomposition reaction of AIBN. As a result, a great deal of sulfur free radicals will produce on the surfaces of silica gel particles, and they will effectively initiate the monomer GMA to be graft polymerized onto silica gel particles. For the graft polymerization system, 55 ℃ should be selected as a suitable reaction temperature, and an amount of AIBN with 0.8% of the monomer mass should be selected as an appropriate used amount of AIBN in the solution. The functional particles BSNa-PGMA-SiO2 carry negative charge with a high density because of the presence of anionic polyelectrolyte on their surfaces. By right of strong electrostatic interaction, the functional particles BSNa-PGMA-SiO2 possess strong adsorption ability towards alkaloids such as for matrine and cytisine.
keywords: surface initiated graft polymerization glycidyl methacrylate silica gel thiol hydrogen atom transfer
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基金项目:山西省青年科学基金资助项目(20110210215)
| 作者 | 单位 | |
| 曹林交 | 中北大学化工系 | 705683412@qq.com |
| 高保娇 | 中北大学化工系 | |
| 胡伟民 | 中北大学化工系 | gaobaojiao@126.com |
引用本文：
曹林交,高保娇,胡伟民.构建巯基-AIBN表面引发体系制备接枝微粒PGMA-SiO2及其功能性转变的研究[J].功能高分子学报,2013,26(3):.
CAO Lin jiao,GAO Bao jiao,HU Wei min.Constructing New Surface Initiating System to Prepare Grafted ParticlesPGMA-SiO2 and Realizing Their Functional Transform[J].Journal of Functional Polymers,2013,26(3):.
曹林交,高保娇,胡伟民.构建巯基-AIBN表面引发体系制备接枝微粒PGMA-SiO2及其功能性转变的研究[J].功能高分子学报,2013,26(3):.
CAO Lin jiao,GAO Bao jiao,HU Wei min.Constructing New Surface Initiating System to Prepare Grafted ParticlesPGMA-SiO2 and Realizing Their Functional Transform[J].Journal of Functional Polymers,2013,26(3):.
