改性水性聚氨酯接枝氯乙烯复合树脂的制备与性能研究
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摘要
以预聚体分散法为主,结合丙酮法,以异佛尔酮二异氰酸酯(IPDI)、聚醚(PPG-1000)和二羟甲基丙酸(DMPA)为主要原料,以NaOH为中和剂合成了阴离子水性聚氨酯(PU),并以此为种子制备了聚氨酯/聚丙烯酸酯(PUA-Ⅰ)复合乳液;以IPDI、聚乙二醇单甲醚(MPEG)和甲基丙烯酸β-羟乙酯(HEMA)为原料首先合成了含双键的混合单体,与丙烯酸丁酯(BA)共聚制备了聚氨酯/聚丙烯酸酯(PUA-Ⅱ)复合乳液。接着在高压釜中分别采用PU、PUA-Ⅰ和PUA-Ⅱ作为种子进行氯乙烯原位接枝共聚,制备了聚氨酯/聚氯乙烯(PU/PVC)、聚氨酯/聚丙烯酸酯/聚氯乙烯(PUA-Ⅰ/PVC)和聚氨酯/聚丙烯酸酯/聚氯乙烯(PUA-Ⅱ/PVC)复合乳液树脂。
通过动态激光粒度分析仪考察了PU/PVC及PUA-Ⅱ/PVC复合粒子的粒径大小及其分布,说明大量的VC单体在PU和PUA-Ⅱ种子上聚合增长。通过透射电镜(TEM)观察了PUA-Ⅱ/PVC复合粒子的微观结构,粒子呈现典型的核壳结构。对复合树脂的力学性能进行了研究。对于PU/PVC,在研究范围内,DMPA含量为6wt%时,PU含量为9wt%时,材料的冲击强度最高,选择1,4-丁二醇为扩链剂对于材料力学性能的提高效果最好。对于PUA-Ⅰ/PVC,PA含量的升高有利于复合树脂冲击强度的提高。随着PUA-Ⅱ含量的增加,PUA-Ⅱ/PVC复合树脂的冲击强度逐渐下降。
通过动态力学分析仪(DMA)、TA-2000热分析仪、扫描电子显微镜(SEM)和毛细管流变仪等手段对复合树脂及材料的动态力学性能、耐热稳定性、材料的断面形貌和流变性能进行了测试表征。DMA研究表明,预聚时扩链所得到的聚氨酯与PVC的相容性较好;BA的引入降低了PUA-Ⅰ、PUA-Ⅱ的玻璃化转变温度。SEM显示:材料缺口断面为韧性断裂。PU和PUA橡胶相的加入,使复合树脂的耐热稳定性略有降低,使复合树脂的流动性提高。
Anionic waterborne polyurethane emulsion was prepared with isophorone diisocyanate (IPDI), polypropylene glycol (PPG)and dimethylol propionic acid (DMPA), following a self-emulsification process. Polyurethane/polyacrylate (PUA-Ⅰ) hybrid emulsion was prepared using PU dispersion as seeds. Mixmonomer was prepared with IPDI, polyethylene glycol monomethylether (MPEG) and hydroxyl ethyl methacrylate (HEMA). Then it was copolymerized with butyl acrylate to prepare polyurethane-acrylate (PUA-Ⅱ) composite latex. In the presence of PU, PUA-Ⅰand PUA-Ⅱhybrid emulsions, PU/PVC, PUA-Ⅰ/PVC and PUA-Ⅱ/PVC composite emulsion resins were obtained by in-situ emulsion copolymerization in autoclave.
The particle sizes and distributions of the PU/PVC and PUA-Ⅱ/PVC composite latices were characterized via a laser particle size analyzer. The increasing particle sizes of the PU/PVC and PUA-Ⅱ/PVC latices obviously indicated that a large number of VC monomer was polymerized around PU and PUA-Ⅱrubbery phase. The morphology of the PUA-Ⅱ/PVC composite latex particles was observed via transmission electron microscopy (TEM). The result showed that PUA-Ⅱ/PVC composite latex has the typical core/shell structure.
The mechanical properties of the modified PVC resins were investigated in details. When DMPA content was 6wt% and the PU content was 9wt%, among the range of researches, the notched impact strength of the PU/PVC composite resins was biggest. It was shown that the mechanical properties of composite resins was better when 1, 4-butanediol was used as chain-extended agent of PU. The notched impact strength of the PUA-Ⅰ/PVC composite resins increased with increasing PA content. The notched impact strength of the PUA-Ⅱ/PVC composite resins decreased with increasing PUA-Ⅱcontent.
Various properties of the composite resin and resulted materials, such as dynamic mechanical properties, thermal properties, broken profiles of the materials and rheological behaviors, were determined and characterized with the aid of DMA, TA-2000 type thermal analyzer, SEM and capillary rheometer, respectively. DMA results revealed that the compatibility between PU and PVC was better by chain-extending before dispersion. And Tg of the PUA composite latices decreased because of incorporating BA composition. SEM showed that the fractured surface of the notched sample has toughness. The stability of heat-resistance of the composite resins decreased a little with the adding of PU or PUA rubbery phase. Because of adding PU or PUA rubbery phase, the mobility of the composite resin became better than that of pure emulsion PVC.
通过动态激光粒度分析仪考察了PU/PVC及PUA-Ⅱ/PVC复合粒子的粒径大小及其分布,说明大量的VC单体在PU和PUA-Ⅱ种子上聚合增长。通过透射电镜(TEM)观察了PUA-Ⅱ/PVC复合粒子的微观结构,粒子呈现典型的核壳结构。对复合树脂的力学性能进行了研究。对于PU/PVC,在研究范围内,DMPA含量为6wt%时,PU含量为9wt%时,材料的冲击强度最高,选择1,4-丁二醇为扩链剂对于材料力学性能的提高效果最好。对于PUA-Ⅰ/PVC,PA含量的升高有利于复合树脂冲击强度的提高。随着PUA-Ⅱ含量的增加,PUA-Ⅱ/PVC复合树脂的冲击强度逐渐下降。
通过动态力学分析仪(DMA)、TA-2000热分析仪、扫描电子显微镜(SEM)和毛细管流变仪等手段对复合树脂及材料的动态力学性能、耐热稳定性、材料的断面形貌和流变性能进行了测试表征。DMA研究表明,预聚时扩链所得到的聚氨酯与PVC的相容性较好;BA的引入降低了PUA-Ⅰ、PUA-Ⅱ的玻璃化转变温度。SEM显示:材料缺口断面为韧性断裂。PU和PUA橡胶相的加入,使复合树脂的耐热稳定性略有降低,使复合树脂的流动性提高。
Anionic waterborne polyurethane emulsion was prepared with isophorone diisocyanate (IPDI), polypropylene glycol (PPG)and dimethylol propionic acid (DMPA), following a self-emulsification process. Polyurethane/polyacrylate (PUA-Ⅰ) hybrid emulsion was prepared using PU dispersion as seeds. Mixmonomer was prepared with IPDI, polyethylene glycol monomethylether (MPEG) and hydroxyl ethyl methacrylate (HEMA). Then it was copolymerized with butyl acrylate to prepare polyurethane-acrylate (PUA-Ⅱ) composite latex. In the presence of PU, PUA-Ⅰand PUA-Ⅱhybrid emulsions, PU/PVC, PUA-Ⅰ/PVC and PUA-Ⅱ/PVC composite emulsion resins were obtained by in-situ emulsion copolymerization in autoclave.
The particle sizes and distributions of the PU/PVC and PUA-Ⅱ/PVC composite latices were characterized via a laser particle size analyzer. The increasing particle sizes of the PU/PVC and PUA-Ⅱ/PVC latices obviously indicated that a large number of VC monomer was polymerized around PU and PUA-Ⅱrubbery phase. The morphology of the PUA-Ⅱ/PVC composite latex particles was observed via transmission electron microscopy (TEM). The result showed that PUA-Ⅱ/PVC composite latex has the typical core/shell structure.
The mechanical properties of the modified PVC resins were investigated in details. When DMPA content was 6wt% and the PU content was 9wt%, among the range of researches, the notched impact strength of the PU/PVC composite resins was biggest. It was shown that the mechanical properties of composite resins was better when 1, 4-butanediol was used as chain-extended agent of PU. The notched impact strength of the PUA-Ⅰ/PVC composite resins increased with increasing PA content. The notched impact strength of the PUA-Ⅱ/PVC composite resins decreased with increasing PUA-Ⅱcontent.
Various properties of the composite resin and resulted materials, such as dynamic mechanical properties, thermal properties, broken profiles of the materials and rheological behaviors, were determined and characterized with the aid of DMA, TA-2000 type thermal analyzer, SEM and capillary rheometer, respectively. DMA results revealed that the compatibility between PU and PVC was better by chain-extending before dispersion. And Tg of the PUA composite latices decreased because of incorporating BA composition. SEM showed that the fractured surface of the notched sample has toughness. The stability of heat-resistance of the composite resins decreased a little with the adding of PU or PUA rubbery phase. Because of adding PU or PUA rubbery phase, the mobility of the composite resin became better than that of pure emulsion PVC.
引文
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