CN116731288A - 一种含动态酯键环氧类玻璃高分子、玻璃纤维布层压板及其制备方法和应用 - Google Patents
一种含动态酯键环氧类玻璃高分子、玻璃纤维布层压板及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域，具体涉及一种含动态酯键环氧类玻璃高分子、玻璃纤维布层压板及其制备方法和应用。以环氧树脂、环氧活性稀释剂、甲基四氢苯酐为单体，在酯交换催化剂作用下合成含动态酯键环氧类玻璃高分子。本发明提供的一种含动态酯键环氧类玻璃高分子，在高温下具有自修复、焊接和可再加工的特性。将本发明的含动态酯键环氧类玻璃高分子涂覆浸润在玻璃纤维布上，其玻璃纤维布层压板也具有可再工性能。制备玻璃纤维布层压板的方法简单，由两层及以上玻璃纤维布预浸料经热压工艺制成，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上即可，制备的玻璃纤维布层压板可应用于制备风力叶片。
Description
技术领域
本发明属于高分子材料技术领域，具体涉及一种含动态酯键环氧类玻璃高分子、玻璃纤维布层压板及其制备方法和应用。
背景技术
风力叶片通常由连续玻璃纤维增强聚合物（如环氧树脂，聚酯或乙烯基酯）复合材料制成。环氧树脂是一类重要的热固性塑料，与其他传统热固性塑料类似，不溶不熔、具有不可逆的共价网络，阻止了环氧树脂的再加工、回收和重塑。因此，对大多数老化、损坏和丢弃的环氧树脂基玻璃纤维风力叶片的回收和再加工具有挑战性。近年来，通过将可逆共价键引入环氧树脂交联网络来制备环氧类玻璃高分子，从而使环氧树脂结合了热固性塑料的优异机械性能和热塑性塑料的再加工性，赋予了环氧类玻璃高分子优异的再加工、自愈、焊接、重塑和回收性能。经检索，并未有将环氧类玻璃高分子用来制备风力叶片的文献。
发明内容
本发明的目的在于克服现有技术的缺点，提供一种含动态酯键环氧类玻璃高分子、玻璃纤维布层压板及其制备方法和应用。
本发明的目的通过以下技术方案来实现：
一种含动态酯键环氧类玻璃高分子的制备方法，以环氧树脂、环氧活性稀释剂、甲基四氢苯酐为单体，在酯交换催化剂作用下合成含动态酯键环氧类玻璃高分子。
进一步地，所述的环氧树脂包含双酚A型环氧树脂或双酚F型环氧树脂中的任意一种。
进一步地，所述环氧活性稀释剂为苄基缩水甘油醚或1,4-丁二醇二缩水甘油醚中的至少一种。
进一步地，所述酯交换催化剂为乙酰丙酮锌或1 ,5 ,7-三氮杂二环[4 ,4 ,0]癸-5-烯中的至少一种。
进一步地，所述环氧树脂与环氧活性稀释剂的质量比为2～9:1，甲基四氢苯酐与环氧基的物质的量比为0.5～0.8:1，酯交换催化剂与环氧基的物质的量比为1:5～15。所述环氧基为环氧树脂和环氧活性稀释剂中环氧基的总和。
进一步地，将环氧树脂与环氧活性稀释剂混合搅拌均匀，随后在85～95℃的温度下将酯交换催化剂加入混合树脂中，搅拌混合25～35 min，待冷却至室温后加入甲基四氢苯酐继续搅拌混合均匀。
上述的方法制备的含动态酯键环氧类玻璃高分子。
一种玻璃纤维布层压板，由两层及以上玻璃纤维布预浸料经热压工艺制成，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上的树脂组合物组成，所述树脂组合物为上述的含动态酯键环氧类玻璃高分子。
进一步地，所述热压工艺为： 85～95℃固化1.5～2.5 h、115～125℃固化1.5～2.5 h，控制压力为1～5MPa，热压结束后取出冷却至室温。
上述的含动态酯键环氧类玻璃高分子，上述的玻璃纤维布层压板在制备风力叶片中的应用。
本发明具有以下优点：本发明提供的一种含动态酯键环氧类玻璃高分子，在高温下具有自修复、焊接和可再加工的特性。将本发明的含动态酯键环氧类玻璃高分子涂覆浸润在玻璃纤维布上，其玻璃纤维布层压板也具有可再工性能。制备玻璃纤维布层压板的方法简单，由两层及以上玻璃纤维布预浸料经热压工艺制成，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上即可，制备的玻璃纤维布层压板可应用于制备风力叶片。
附图说明
图1为实例1制备的含动态酯键环氧类玻璃高分子的FTIR图。
图2为实例1制备的含动态酯键环氧类玻璃高分子的DSC图。
图3为实例1制备的含动态酯键环氧类玻璃高分子的储能模量和损耗角正切图。
图4为实例1制备的含动态酯键环氧类玻璃高分子的自修复图。
图5为实例1制备的含动态酯键环氧类玻璃高分子的焊接和再加工图。
图6为实例2制备的含动态酯键环氧类玻璃高分子玻璃纤维布层压板可再加工图。
具体实施方式
下面结合附图及实施例对本发明做进一步的描述，本发明的保护范围不局限于以下所述：
实施例1：一种含动态酯键环氧类玻璃高分子的制备方法，将环氧树脂与环氧活性稀释剂混合搅拌均匀，随后在85℃的温度下将酯交换催化剂加入混合树脂中，搅拌混合25min，待冷却至室温后加入甲基四氢苯酐继续搅拌混合均匀，合成含动态酯键环氧类玻璃高分子。
其中，所述环氧树脂与环氧活性稀释剂的质量比为2:1，甲基四氢苯酐与环氧基的物质的量比为0.5:1；酯交换催化剂与环氧基的物质的量比为1:5；所述的环氧树脂为双酚A型环氧树脂；所述环氧活性稀释剂为苄基缩水甘油醚；所述酯交换催化剂为乙酰丙酮锌。
实施例2：一种含动态酯键环氧类玻璃高分子的制备方法，将环氧树脂与环氧活性稀释剂混合搅拌均匀，随后在95℃的温度下将酯交换催化剂加入混合树脂中，搅拌混合35min，待冷却至室温后加入甲基四氢苯酐继续搅拌混合均匀，合成含动态酯键环氧类玻璃高分子。
其中，所述环氧树脂与环氧活性稀释剂的质量比为9:1，甲基四氢苯酐与环氧基的物质的量比为0.8:1，酯交换催化剂与环氧基的物质的量比为1:15；所述的环氧树脂为双酚F型环氧；所述环氧活性稀释剂为1,4-丁二醇二缩水甘油醚；所述酯交换催化剂为1 ,5 ,7-三氮杂二环[4 ,4 ,0]癸-5-烯。
实施例3：一种含动态酯键环氧类玻璃高分子的制备方法，将环氧树脂与环氧活性稀释剂混合搅拌均匀，随后在90℃的温度下将酯交换催化剂加入混合树脂中，搅拌混合30min，待冷却至室温后加入甲基四氢苯酐继续搅拌混合均匀，合成含动态酯键环氧类玻璃高分子。
其中，所述环氧树脂与环氧活性稀释剂的质量比为5:1，甲基四氢苯酐与环氧基的物质的量比为0.6:1，酯交换催化剂与环氧基的物质的量比为1:10；所述的环氧树脂包含双酚A型环氧树脂；所述环氧活性稀释剂为苄基缩水甘油醚和1,4-丁二醇二缩水甘油醚的混合物，其体积比为1:2；所述酯交换催化剂为乙酰丙酮锌和1 ,5 ,7-三氮杂二环[4 ,4 ,0]癸-5-烯的混合物，重量比为1:1。
实施例4：一种玻璃纤维布层压板，由两层玻璃纤维布预浸料经热压工艺制成，所述热压工艺为：85℃固化1.5 h、115℃固化1.5 h，控制压力为1 MPa，热压结束后取出冷却至室温，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上的树脂组合物组成，所述树脂组合物为实施例1制备的含动态酯键环氧类玻璃高分子。
实施例5：一种玻璃纤维布层压板，由三层玻璃纤维布预浸料经热压工艺制成，所述热压工艺为： 95℃固化2.5 h、125℃固化2.5 h，控制压力为5 MPa，热压结束后取出冷却至室温，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上的树脂组合物组成，所述树脂组合物为实施例2制备的含动态酯键环氧类玻璃高分子。
实施例6：一种玻璃纤维布层压板，由三层玻璃纤维布预浸料经热压工艺制成，所述热压工艺为： 90℃固化2 h、120℃固化2 h，控制压力为3 MPa，热压结束后取出冷却至室温，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上的树脂组合物组成，所述树脂组合物为实施例3制备的含动态酯键环氧类玻璃高分子。
以下通过实验说明本发明的有益效果：
实例1：
含酯键环氧类玻璃高分子的制备：称取8 g牌号为BPF-170的双酚F环氧树脂和2 g苄基缩水甘油醚混合搅拌均匀得到稀释后的混合环氧树脂；随后在混合环氧树脂中加入0.73 g乙酰丙酮锌，在90℃下混合磁力搅拌半小时，待冷却至室温后再加入4.6 g甲基四氢苯酐混合搅拌均匀，然后将混合物倒入聚四氟乙烯模具中，90℃固化2h+120℃2h，待固化程序结束后取出样品得到含酯键环氧类玻璃高分子。
通过红外测试，如图1可以看出环氧树脂在915 cm-1处环氧基吸收峰消失，说明环氧树脂完全固化；通过DSC测试，如图2测得含酯键环氧类玻璃高分子玻璃化转变温度约为67℃；通过动态热机械分析，如图3测得含酯键环氧类玻璃高分子玻璃化转变温度约为64℃，玻璃态储能模量约为5.6 GPa；如图4，含酯键环氧类玻璃高分子在160℃下热修复80min后，划痕能明显减小；如图5，含酯键环氧类玻璃高分子在100℃下可以进行再加工，同时外力作用下，具有可焊接性能。
实例2：
玻璃纤维布层压板的制备：称取24 g牌号为BPF-170的双酚F环氧树脂和6 g苄基缩水甘油醚混合搅拌均匀得到稀释后的混合环氧树脂；随后在混合环氧树脂中加入2.19 g乙酰丙酮锌，在90℃下混合磁力搅拌半小时，待冷却至室温后再加入13.8 g甲基四氢苯酐混合搅拌均匀放置备用；
将上述树脂混合物手动浸涂在玻璃纤维布上制作预浸料，然后将三层预浸料叠铺在两块钢板间，钢板与预浸料间用一层聚四氟乙烯薄膜隔开，放入热压机中，热压工艺条件为：90℃热压固化2h、120℃热压固化2h，控制压力为5MPa，热压结束后取出冷却至室温，即制得玻璃纤维布层压板。如图5所示，制的层压板具有可再加工性能。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都涵盖在本发明的保护范围之内。
Claims (10)
1.一种含动态酯键环氧类玻璃高分子的制备方法，其特征在于，以环氧树脂、环氧活性稀释剂、甲基四氢苯酐为单体，在酯交换催化剂作用下合成含动态酯键环氧类玻璃高分子。
2.根据权利要求1所述的一种含动态酯键环氧类玻璃高分子的制备方法，其特征在于，所述的环氧树脂包含双酚A型环氧树脂或双酚F型环氧树脂中的任意一种。
3.根据权利要求1所述的一种含动态酯键环氧类玻璃高分子的制备方法，其特征在于，所述环氧活性稀释剂为苄基缩水甘油醚或1,4-丁二醇二缩水甘油醚中的至少一种。
4.根据权利要求1所述的一种含动态酯键环氧类玻璃高分子的制备方法，其特征在于，所述酯交换催化剂为乙酰丙酮锌或1 ,5 ,7-三氮杂二环[4 ,4 ,0]癸-5-烯中的至少一种。
5.根据权利要求1所述的一种含动态酯键环氧类玻璃高分子制备方法，其特征在于，所述环氧树脂与环氧活性稀释剂的质量比为2～9:1，甲基四氢苯酐与环氧基的物质的量比为0.5～0.8:1，酯交换催化剂与环氧基的物质的量比为1:5～15。
6.根据权利要求1所述的一种含动态酯键环氧类玻璃高分子的制备方法，其特征在于，将环氧树脂与环氧活性稀释剂混合搅拌均匀，随后在85～95℃的温度下将酯交换催化剂加入混合树脂中，搅拌混合25～35 min，待冷却至室温后加入甲基四氢苯酐继续搅拌混合均匀。
7.根据权利要求1-6中任一项所述的方法制备的含动态酯键环氧类玻璃高分子。
8.一种玻璃纤维布层压板，其特征在于，由两层及以上玻璃纤维布预浸料经热压工艺制成，各层玻璃纤维布预浸料均由一层玻璃纤维布和涂覆浸润在玻璃纤维布两面上的树脂组合物组成，所述树脂组合物为权利要求7所述的含动态酯键环氧类玻璃高分子。
9.根据权利要求1所述的一种玻璃纤维布层压板，其特征在于，所述热压工艺为： 85～95℃固化1.5～2.5 h、115～125℃固化1.5～2.5 h，控制压力为1～5MPa，热压结束后取出冷却至室温。
10.权利要求7所述的含动态酯键环氧类玻璃高分子，权利要求8或9所述的玻璃纤维布层压板在制备风力叶片中的应用。
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