双固化聚氨酯的制备及其性能研究
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摘要
紫外光固化是一种环保技术,具有环境友好、效率高、经济和节约能源等优点,在日益苛刻的环保要求下,该项技术获得了前所未有的发展,已被广泛用于电子材料封装、塑料制件表面保护、木地板上光、汽车小面积修补等行业中。然而对于一些形状比较复杂的基材,其应用受到了限制,为此国内外研究者开发了光/暗双重固化体系。本研究以传统光固化技术为基础,制备线形和超支化丙烯酸酯/硅氧烷双固化树脂,研究两种体系的固化行为、涂层性能及形貌等,并最终将超支化双固化树脂用于制备有机/无机杂化体系。具体研究内容如下：
线形双固化聚氨酯体系的研究
制备具有丙烯酸酯端基和三乙氧基硅烷侧链的线形光/潮气双固化聚氨酯树脂,以其为预聚物,调节配方,制备一系列的双固化涂料,研究了这些体系的固化工艺、涂层性能及热性能。结果表明：体系发生了明显的潮气固化,且潮气固化后涂层硬度、附着力及热性能等均有明显提升。
超支化双固化聚氨酯体系的研究
通过"AA'+CB2"一步法合成羟端基的超支化聚氨酯,并对其改性制备了一系列具有不同端基比的丙烯酸酯/三甲氧基硅烷的超支化聚氨酯树脂,以其为光/潮气双固化预聚物,研究双固化体系的潮气固化机理,结果表明：涂层的潮气固化过程是硅氧烷水解缩合的过程,形成一种均相体系,并没有明显无机纳米颗粒形成。通过对双固化涂层的表面形貌、动态力学性能、热性能和基本性能的研究,结果表明：超支化双固化涂层经过潮气固化后,涂层表面的粗糙度随着树脂中三甲氧基硅烷端基含量的增加先下降后上升；这些涂层具有良好的阻尼性能(较高的阻尼因子和较宽的温度范围)；超支化双固化涂层的基本性能和热稳定性都随着树脂中三甲氧基硅烷端基含量的增加而提升。
光固化超支化有机无机杂化体系的研究
以双固化超支化聚氨酯体系为基础,通过溶胶-凝胶,原位聚合分别制备SiO2和TiO2光固化有机无机杂化体系,研究了杂化体系的结晶性能、表面形貌、动态力学性能和热性能,结果表明：制备的有机无机杂化体系,无机相是以非晶型形式存在；有机无机杂化体系制备的光固化涂层,其表面粗糙度随着无机物质的含量增加而增加；动态力学性能表明杂化涂层的玻璃化温度随着无机物质的增加先下降后上升；热性能研究表明杂化涂层中的无机物质,降低了低温热稳定性,提高了高温热稳定性。
UV curing technology is one technology with advantages such as environmental-friend, efficiency, economy and energy saving. Due to even strict environmental protection policy, this new technology has gained a very rapidly development in the past few years and therefore being widely used in electronic packaging, surface protection of plastic device, flooring and small pitch car refinish. But it is restricted in the complicated shapes. In order to solve the problems, researchers invent the UV/dark dual curable systems. In this study, linear and hyperbranched acrylate siloxane dual curable resins were synthesized. The curable behaviors, the properties and the surface topographies of coatings were studied. At last the hyperbranched dual curable resins were applied to prepare the UV curable organic and inorganic hybrid systems. The detailed research contents and results are summarized as follows:
Linear dual curable polyurethane systems
Linear UV/moisture dual curable polyurethane resin was synthesized with acrylate end group and triethoxysilane side chain, which was used as oligomer to prepare varieties of the dual curable coatings. The UV/moisture curing process, the coating properties and the thermal properties were studied. The results indicated that the systems appeared the obvious moisture curing process; and the coating properties and thermal properties of the dual curable coatings were great improved by moisture curing.
Hyperbranched dual curable polyurethane systems
Hyperbranched polyurethane was synthesized with terminal hydroxyls by " AA' +CB2" one step way. The polyurethane was further modified to prepare a series of hyperbranched dual curable polyurethane resins with different end group ratio of acrylate and trimethoxysilane, which were used as oligomers for UV/moisture dual curable coatings and the moisture curing theory of these oligomers were studied. The results indicated that the moisture curing was mainly due to the hydrolysis and condensation of trimethoxysilane and the coatings presented homogeneous system without obvious inorganic particle forming. The surface topographies, dynamic mechanical properties, thermal properties and coating properties of the dual curable coatings were also measured, which indicated that the superficial degree of roughness decreased firstly and then increased with the increasing content of trimethoxysilane end groups; Coatings showed a good damping property with high damping factor and wide temperature range. Moreover the coating properties and thermal properties were improved with the increasing content of trimethoxysilane end groups.
The UV curable hyperbranched organic and inorganic hybrid systems
A series of UV curable hyperbranched SiO2 and TiO2 organic and inorganic collosols are synthesized by sol-gel and situ method according to hyperbranched dual curable polyurethane systems. The crystalline behaviors, dynamic mechanical properties and thermal properties were studied. The results indicated that the inorganic phase existed with an amorphous form, and the superficial degree of roughness enlarged with increasing inorganic component contents. The dynamic mechanical results indicated that the glass temperature of the hybrid coatings increased firstly and then decreased with increasing inorganic component contents. The thermal properties indicated that the thermal stabilities of the hybrid coatings decreased at low temperature with inorganic component contents, whereas the high temperature thermal stabilities were improved.
线形双固化聚氨酯体系的研究
制备具有丙烯酸酯端基和三乙氧基硅烷侧链的线形光/潮气双固化聚氨酯树脂,以其为预聚物,调节配方,制备一系列的双固化涂料,研究了这些体系的固化工艺、涂层性能及热性能。结果表明：体系发生了明显的潮气固化,且潮气固化后涂层硬度、附着力及热性能等均有明显提升。
超支化双固化聚氨酯体系的研究
通过"AA'+CB2"一步法合成羟端基的超支化聚氨酯,并对其改性制备了一系列具有不同端基比的丙烯酸酯/三甲氧基硅烷的超支化聚氨酯树脂,以其为光/潮气双固化预聚物,研究双固化体系的潮气固化机理,结果表明：涂层的潮气固化过程是硅氧烷水解缩合的过程,形成一种均相体系,并没有明显无机纳米颗粒形成。通过对双固化涂层的表面形貌、动态力学性能、热性能和基本性能的研究,结果表明：超支化双固化涂层经过潮气固化后,涂层表面的粗糙度随着树脂中三甲氧基硅烷端基含量的增加先下降后上升；这些涂层具有良好的阻尼性能(较高的阻尼因子和较宽的温度范围)；超支化双固化涂层的基本性能和热稳定性都随着树脂中三甲氧基硅烷端基含量的增加而提升。
光固化超支化有机无机杂化体系的研究
以双固化超支化聚氨酯体系为基础,通过溶胶-凝胶,原位聚合分别制备SiO2和TiO2光固化有机无机杂化体系,研究了杂化体系的结晶性能、表面形貌、动态力学性能和热性能,结果表明：制备的有机无机杂化体系,无机相是以非晶型形式存在；有机无机杂化体系制备的光固化涂层,其表面粗糙度随着无机物质的含量增加而增加；动态力学性能表明杂化涂层的玻璃化温度随着无机物质的增加先下降后上升；热性能研究表明杂化涂层中的无机物质,降低了低温热稳定性,提高了高温热稳定性。
UV curing technology is one technology with advantages such as environmental-friend, efficiency, economy and energy saving. Due to even strict environmental protection policy, this new technology has gained a very rapidly development in the past few years and therefore being widely used in electronic packaging, surface protection of plastic device, flooring and small pitch car refinish. But it is restricted in the complicated shapes. In order to solve the problems, researchers invent the UV/dark dual curable systems. In this study, linear and hyperbranched acrylate siloxane dual curable resins were synthesized. The curable behaviors, the properties and the surface topographies of coatings were studied. At last the hyperbranched dual curable resins were applied to prepare the UV curable organic and inorganic hybrid systems. The detailed research contents and results are summarized as follows:
Linear dual curable polyurethane systems
Linear UV/moisture dual curable polyurethane resin was synthesized with acrylate end group and triethoxysilane side chain, which was used as oligomer to prepare varieties of the dual curable coatings. The UV/moisture curing process, the coating properties and the thermal properties were studied. The results indicated that the systems appeared the obvious moisture curing process; and the coating properties and thermal properties of the dual curable coatings were great improved by moisture curing.
Hyperbranched dual curable polyurethane systems
Hyperbranched polyurethane was synthesized with terminal hydroxyls by " AA' +CB2" one step way. The polyurethane was further modified to prepare a series of hyperbranched dual curable polyurethane resins with different end group ratio of acrylate and trimethoxysilane, which were used as oligomers for UV/moisture dual curable coatings and the moisture curing theory of these oligomers were studied. The results indicated that the moisture curing was mainly due to the hydrolysis and condensation of trimethoxysilane and the coatings presented homogeneous system without obvious inorganic particle forming. The surface topographies, dynamic mechanical properties, thermal properties and coating properties of the dual curable coatings were also measured, which indicated that the superficial degree of roughness decreased firstly and then increased with the increasing content of trimethoxysilane end groups; Coatings showed a good damping property with high damping factor and wide temperature range. Moreover the coating properties and thermal properties were improved with the increasing content of trimethoxysilane end groups.
The UV curable hyperbranched organic and inorganic hybrid systems
A series of UV curable hyperbranched SiO2 and TiO2 organic and inorganic collosols are synthesized by sol-gel and situ method according to hyperbranched dual curable polyurethane systems. The crystalline behaviors, dynamic mechanical properties and thermal properties were studied. The results indicated that the inorganic phase existed with an amorphous form, and the superficial degree of roughness enlarged with increasing inorganic component contents. The dynamic mechanical results indicated that the glass temperature of the hybrid coatings increased firstly and then decreased with increasing inorganic component contents. The thermal properties indicated that the thermal stabilities of the hybrid coatings decreased at low temperature with inorganic component contents, whereas the high temperature thermal stabilities were improved.
引文
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