高硅含量硅—丙核/壳乳液的低温合成与表征
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摘要
性能互补的聚丙烯酸酯与聚硅氧烷复合具有重要的应用价值,但聚丙烯酸酯和聚硅氧烷相容性差,常规聚合技术很难使二者有机融合在一起。本文详细介绍了聚丙烯酸酯和聚硅氧烷的复合手段,阐述了核/壳乳液聚合技术的合成方法,并剖析了其聚合机理;通过概述国内外研究现状及进展,指出核/壳型硅.丙乳液具有广阔的应用前景。
以八甲基环四硅氧烷(D4)、四甲基四乙烯基环四硅氧烷(Vi-D4)为有机硅单体,以阴离子乳化剂和非离子乳化剂为复合乳化剂,以十二烷基苯磺酸为催化剂进行了环状有机硅的阴离子开环聚合。采用预乳化一次性投料法,增加了有机硅在体系中的反应时间,提高了转化率。
以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主要共聚单体,丙烯酸羟丙酯(HPA)、丙烯酸(AA)等为亲水功能性单体,以烯丙基聚醚类反应性乳化剂(M-1、M-2)为复合乳化剂,采用氧化.还原(K2S2O8-.NaHSO3)和水溶性偶氮(VA-044)复合引发体系,通过种子乳液聚合技术在低温下合成了高硅含量(15%)的、凝聚物生成量少的硅.丙核/壳乳液。
系统探讨了乳化剂的种类及用量、引发剂用量、活性物含量、有机硅用量、反应温度、:MMA与BA的比例、HPA用量、Vi-D4用量等因素对单体的转化率、接枝率、乳胶膜吸水率、乳胶粒形貌及粒径分布的影响。通过正交试验法确定了最佳合成条件为:乳化剂用量0.66g,引发剂用量2000mg·Kg-1,活性物含量30%,有机硅用量15%,反应温度50℃。
借助于红外光谱、透射电镜(TEM)、激光粒度分布等手段,对所制备的共聚物乳液产品微观特征进行了表征,证明所得产品是硅氧烷和丙烯酸酯的共聚物,且具有核/壳结构;同时,采用Zeta电位测定、热失重分析、差示扫描量热分析,拉伸性能测试等手段对乳液产品的稳定性和乳胶膜应用性能进行了测试,研究有机硅的加入对乳胶膜的耐热性能和力学性能的影响。
Composite materials of polyacrylate and polysiloxane have an important application on many fields, but the compatibility of polyacrylate and polysiloxane is poor, and the conventional polymeric technology is hard to make the both combining completely. In this paper, the compound means of polyacrylate and polysiloxane was described in details. Meanwhile, the technology of the seed-emulsion polymerization was introduced, and the polymerization mechanism was analyzed. Moreover, with discussing the status and development of the core/shell silicon-acrylate emulsion, it could be concluded that the core/shell silicon-acrylate emulsion products had a broad application prospects.
Anion ring-open polymerization was carried out with ocatmethyl cylcotetra-siloxane (D4) and tetra-methyl tetravinylcylcotetra- siloxane (Vi-D4) as the organic-silicon raw materials, allyl-polyoxyethylene ether (M-l) and octyl phenol ethoxylate-10 (OP-10) as the composite emulsifiers, dodecyl benzene sulfonic acid(DBSA) as the catalyst. Ring-open emulsion with high conversion was sythesized using the way of pre-emulsification batch addition which can increase the reactive time of ring- organicsilicon in the system.
With the methyl methacrylate(MMA), butylacrylate (BA) and 2-hydroxypropyl acrylate (HPA) as the main monomers, the allyl-polyoxyethylene ether (M-1&M-2 ) as the composite emulsifiers, and the potassium-persulphate (KPS), sodium formaldehyde sulfoxylate (SFS) and 2,2'-Azobis (2-(2-imidazolin-2-yl) propane) dihydrochloride (VA-044) as the composite initiators, the stable silicon-acrylate core/shell emulsion of high silicon content (15%) was prepared by the seed-emulsion polymerization technology at low-temperature.
The influence of the kind and dosage of emulsifiers, dosage of initiators, monomers content, dosage of organic silicon, the reaction temperature, the ratios of MM A and BA, dosage of HPA and Vi-D4 on conversion and grafting rate of monomer, water absorption ratio of film, particle morphology and size distribution were studied comprehensively. By orthogonal test method to determine the optimum conditions: dosage of emulsifier was 0.66g (100g system), dosage of the initiator was 2000 mg·Kg-1. mononer content was 30%, dosage of silicone was 15%, reaction temperature was50°C.
The microcosmic characteristics of silicone-acrylate copolymer products were characterized by infrared spectroscopy, transmission electron microscopy (TEM) and laser particle size distribution. The product is proven and Silicone acrylate copolymer, which has core/shell structure. Meanwhile, The stablility of emulsion and application performance of latex film were tested by the Zeta potential, the thermal gravimetric analysis(TG), the differential scanning calorimetry(DSC) and the tensile properties testing, and the influences of adding organic-silicon on heat-resistance and mechanical properties of the film were studied.
以八甲基环四硅氧烷(D4)、四甲基四乙烯基环四硅氧烷(Vi-D4)为有机硅单体,以阴离子乳化剂和非离子乳化剂为复合乳化剂,以十二烷基苯磺酸为催化剂进行了环状有机硅的阴离子开环聚合。采用预乳化一次性投料法,增加了有机硅在体系中的反应时间,提高了转化率。
以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主要共聚单体,丙烯酸羟丙酯(HPA)、丙烯酸(AA)等为亲水功能性单体,以烯丙基聚醚类反应性乳化剂(M-1、M-2)为复合乳化剂,采用氧化.还原(K2S2O8-.NaHSO3)和水溶性偶氮(VA-044)复合引发体系,通过种子乳液聚合技术在低温下合成了高硅含量(15%)的、凝聚物生成量少的硅.丙核/壳乳液。
系统探讨了乳化剂的种类及用量、引发剂用量、活性物含量、有机硅用量、反应温度、:MMA与BA的比例、HPA用量、Vi-D4用量等因素对单体的转化率、接枝率、乳胶膜吸水率、乳胶粒形貌及粒径分布的影响。通过正交试验法确定了最佳合成条件为:乳化剂用量0.66g,引发剂用量2000mg·Kg-1,活性物含量30%,有机硅用量15%,反应温度50℃。
借助于红外光谱、透射电镜(TEM)、激光粒度分布等手段,对所制备的共聚物乳液产品微观特征进行了表征,证明所得产品是硅氧烷和丙烯酸酯的共聚物,且具有核/壳结构;同时,采用Zeta电位测定、热失重分析、差示扫描量热分析,拉伸性能测试等手段对乳液产品的稳定性和乳胶膜应用性能进行了测试,研究有机硅的加入对乳胶膜的耐热性能和力学性能的影响。
Composite materials of polyacrylate and polysiloxane have an important application on many fields, but the compatibility of polyacrylate and polysiloxane is poor, and the conventional polymeric technology is hard to make the both combining completely. In this paper, the compound means of polyacrylate and polysiloxane was described in details. Meanwhile, the technology of the seed-emulsion polymerization was introduced, and the polymerization mechanism was analyzed. Moreover, with discussing the status and development of the core/shell silicon-acrylate emulsion, it could be concluded that the core/shell silicon-acrylate emulsion products had a broad application prospects.
Anion ring-open polymerization was carried out with ocatmethyl cylcotetra-siloxane (D4) and tetra-methyl tetravinylcylcotetra- siloxane (Vi-D4) as the organic-silicon raw materials, allyl-polyoxyethylene ether (M-l) and octyl phenol ethoxylate-10 (OP-10) as the composite emulsifiers, dodecyl benzene sulfonic acid(DBSA) as the catalyst. Ring-open emulsion with high conversion was sythesized using the way of pre-emulsification batch addition which can increase the reactive time of ring- organicsilicon in the system.
With the methyl methacrylate(MMA), butylacrylate (BA) and 2-hydroxypropyl acrylate (HPA) as the main monomers, the allyl-polyoxyethylene ether (M-1&M-2 ) as the composite emulsifiers, and the potassium-persulphate (KPS), sodium formaldehyde sulfoxylate (SFS) and 2,2'-Azobis (2-(2-imidazolin-2-yl) propane) dihydrochloride (VA-044) as the composite initiators, the stable silicon-acrylate core/shell emulsion of high silicon content (15%) was prepared by the seed-emulsion polymerization technology at low-temperature.
The influence of the kind and dosage of emulsifiers, dosage of initiators, monomers content, dosage of organic silicon, the reaction temperature, the ratios of MM A and BA, dosage of HPA and Vi-D4 on conversion and grafting rate of monomer, water absorption ratio of film, particle morphology and size distribution were studied comprehensively. By orthogonal test method to determine the optimum conditions: dosage of emulsifier was 0.66g (100g system), dosage of the initiator was 2000 mg·Kg-1. mononer content was 30%, dosage of silicone was 15%, reaction temperature was50°C.
The microcosmic characteristics of silicone-acrylate copolymer products were characterized by infrared spectroscopy, transmission electron microscopy (TEM) and laser particle size distribution. The product is proven and Silicone acrylate copolymer, which has core/shell structure. Meanwhile, The stablility of emulsion and application performance of latex film were tested by the Zeta potential, the thermal gravimetric analysis(TG), the differential scanning calorimetry(DSC) and the tensile properties testing, and the influences of adding organic-silicon on heat-resistance and mechanical properties of the film were studied.
引文
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