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Two series of polyurethane acrylate grafted acrylic resins (Acr-g-TPU-PETA and Acr-gPPU-PETA) self-emulsifying systems are obtained by grafting -NCO group modified polyurethane acrylates with acrylic copolymer prepared from n-butyl acrylate, styrene,βhydroxyethyl methacrylate and acrylic acid The self-emulsifying systems showed Newtonian fluidity with viscosity closed to that of water, the solid contents were around 30% The T〓 of 15~4℃ for dried film before photocuring favored film formation at room temperature DSC and DMA results showed that PU-PETA is compatible with acrylic resin in the grafted resin The TG and dTG curves for Acr-g-PU-PETA samples were substantially different from the corresponding blends, and the brodened dTG peaks for photocured grafted resin suggest that there might be multiple interactions among chain segments The photocued film of the grafted resins self-emulsifying system exhibited good overall properties with polyurethane acrylate grafts ranging from 30% to 50%, and Acr-g-TPU-PETA series showed better properties than Acr-gPPU-PETA series The adhesion of the photocured film was 1~2 grade, impact strength was 50kg-cm and flexibility was 1mm The Shore hardness and the adhesion of the film decreased markedly if PETA was replaced by HEMA as photoactive group due to the lower C=C double bond content in the grafted resin The polyhydroxy amine-linked thioxanthones photoinitiators can be evenly dispersed in self-emulsifying system without color spot appearing in the dried film The films photocured with IV〓~IV〓 generally exhibited higher Shore hardness, gloss and solventresistance than that cured with Irgacure 2959 and did not induce the rusting of the iron substrate Pigmenting with titanium oxide had no effect on the photocuring The polyhydroxy amine-linked thioxanthone IV〓 and IV〓 can be new candidates for the formulation of titanium oxide pigmented photocurable water-borne coatings for their pale-yellow appearance and slight interference with the color of the coatings WB 4759 with high water-solubility coalesced and separated from the dried resin film, and even induced the rusting of iron substrate.
以丙烯酸丁酯,甲基丙烯酸-β-羟乙酯,丙烯酸及苯乙烯合成厂丙烯酸共聚树脂,并与含-NCO端基的聚氨酯丙烯酸酯接枝反应,经水性化后,得到两个系列(Acr-g-TPU-PETA和Acr-g-PPU-PETA)各5个不同配比的丙烯酸树脂接枝聚氨酯丙烯酸酯自乳化体系,粘度与水相近,为牛顿流体,固含量30%左右。光固化前干燥涂膜的玻璃化转变温度在-15℃~4℃之间,有利于室温下成膜。DSC及DMA谱表明两种树脂基本相容。Acr-g-PU-PETA的热失重行为明显不同于共混材料,接枝样dTG峰明显宽化,表明接枝样中链段之间的相互作刚有多重性,丙烯酸树脂与聚氨酯之间有一定的相容性。接枝树脂自乳化体系光固化涂层的综合性能以聚氨酯丙烯酸酯成分为50%~30%者相对较好,且以Acr-g-TPU-PETA系列更理想。光固化膜的附着力为1~2级,冲击强度为50kg·cm,柔软性多为1mm。以HEMA代替PETA作为接枝树脂的活性基团,碳—碳双键密度太低,光固化膜交联点太少,硬度和附着力均较差。多羟基胺连硫杂蒽酮光引发剂能均匀分散于树脂自乳化体系和接枝树脂干膜中,不出现色斑,光固化膜肖氏硬度一般高于以Irgacure 2959为光引发剂的光固化膜,光泽度及耐丁酮溶剂性能均有所提高,不会诱导铁基生锈,钛白着色对光固化结果几乎没有影响。本论文所合成的多羟基胺连硫杂蒽酮光引发剂IV〓与IV〓为浅黄色,对光固化涂层的颜色干扰较小,为配制钛白着色光固化水性涂料提供了新的光引发剂。水溶性太强的WB 4759在干膜中易聚结析出,且对所附着的铁基有诱导锈蚀作用。