CN110627999B - 一种环氧树脂抗紫外阻燃固化剂及其制备 - Google Patents
一种环氧树脂抗紫外阻燃固化剂及其制备 Download PDFInfo
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Abstract
本发明属于环氧树脂材料技术领域，具体涉及一种抗紫外阻燃型环氧树脂固化剂及其制备，本发明提供的抗紫外阻燃型环氧树脂固化剂，结构如式(I)所示，所述固化剂含有的紫外吸收活性基团和阻燃活性基团参与环氧树脂的固化反应，均匀地将紫外吸收元素和阻燃元素引入环氧树脂链中，大大地提高了环氧树脂的使用性能，
Description
技术领域
本发明属于环氧树脂材料技术领域，具体涉及一种环氧树脂抗紫外阻燃固化剂及其制备。
技术背景
环氧树脂是一种重要的热固性树脂，以优异的力学性能，电性能和粘结性能著称，广泛的应用于电子电器、化工防腐、航空航天、玻璃钢复合材料制备等领域，并越来越受到人们的重视。但是，环氧树脂光环境下易老化、易燃性等缺点也成为了限制其广泛应用的主要瓶颈。因此，提高环氧树脂的抗紫外性能、阻燃性能具有十分重要的意义。
发明内容
本发明的一个目的是提供一种环氧树脂抗紫外阻燃固化剂，所述固化剂含有的紫外吸收活性基团和阻燃活性基团，参与环氧树脂的固化反应，均匀地将紫外吸收元素和阻燃元素引入环氧树脂链中，大大地提高了环氧树脂的使用性能。
本发明的另一个目的是提供上述环氧树脂抗紫外阻燃固化剂的制备方法。
为实现上述发明目的，本发明提供以下技术方案：
一方面，本发明提供一种环氧树脂抗紫外阻燃固化剂，结构如式(I)所示：
第二方面，本发明提供式(I)化合物的制备方法，包括以下步骤：
步骤(1)：乙烯基二甲基氯硅烷与2-氨基-5-硝基苯甲酸甲酯反应制得式a的化合物；
步骤(2)：式a的化合物与DOPO反应制得式b的化合物；
步骤(3)：式b的化合物水解制得式c的化合物；
步骤(4)：式c的化合物与2,4-二羟基二苯甲酮反应制得式d的化合物；
步骤(5)：式d的化合物还原制得式I的化合物，反应方程式如下：
本发明提供的环氧树脂抗紫外阻燃型固化剂，不仅能在环氧树脂固化过程中，通过化学键均匀、牢固地引入紫外吸收活性基团邻羟基二苯甲酮，同时将阻燃元素氮、磷、硅三种元素引入环氧树脂链中进行改性，氮、磷、硅三种元素协同阻燃，大大提高环氧树脂材料的阻燃性能，同时具备优良的抗紫外性能。
具体实施方式
实施例1式a化合物的制备
称取2-氨基-5-硝基苯甲酸甲酯11.30g于反应瓶中，加入四氢呋喃60mL、三乙胺30mL溶解后，室温下滴加10mL溶解有12.05g乙烯基二甲基氯硅烷的四氢呋喃溶液，滴毕，45℃搅拌过夜，反应结束后，冷却至室温，加水80mL，二氯甲烷萃取(3*50mL)，合并二氯甲烷层，无水硫酸钠干燥，过滤，减压蒸除溶剂即得，无需纯化，直接用于下一步。
ES：M/Z 281[M+H]+。
实施例2：式b化合物的制备
称取5gDOPO于反应瓶中，加入7.2g实施例1所得物式a化合物，80ml二氧六环，氮气保护下回流反应10h，反应结束后，冷却至室温，减压蒸除溶剂，柱层析纯化得式b化合物。
ES：M/Z 497[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):8.36～8.34(m,1H),8.24～8.22(m,1H),7.98～7.96(m,1H),7.80～7.79(m,1H),7.67～7.65(m,1H),7.55～7.53(m,1H),7.42～7.40(m,1H),7.25～7.24(m,1H),7.09～7.07(m,1H),7.01～7.00(m,2H),4.05(s,1H),3.90(s,3H),1.85～1.83(m,2H),1.05～1.04(m,2H),0.09(s,6H)。
实施例3:式c化合物的制备
称取4.2g实施例2所得物式b的化合物于反应瓶中，加入40％的氢氧化钠水溶液20mL，70℃搅拌2h，反应结束后，冷却至室温，1M的盐酸调节pH至7左右，加入二氯甲烷萃取(3*20mL)，合并有几层，无水硫酸钠干燥，过滤，减压蒸除溶剂，残渣用甲醇重结晶制得式c的化合物。
ES：M/Z 483[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):11.88(br,1H),8.59～8.57(m,1H),8.38～8.37(m,1H),7.97～7.96(m,1H),7.83～7.81(m,1H),7.66～7.65(m,1H),7.55～7.53(m,1H),7.42～7.40(m,1H),7.25～7.24(m,1H),7.09～7.07(m,1H),7.01～7.00(m,2H),4.05(s,1H),1.88～1.86(m,2H),1.10～1.09(m,2H),0.09(s,6H)。
实施例4:式d化合物的制备
称取2g实施3所得物式c化合物于反应瓶中，加入二氯亚砜30mL，DMF 2mL，升温回流2h，减压蒸除溶剂备用；称取2,4-二羟基二苯甲酮3.5g于反应瓶中，加入三乙胺3mL，四氢呋喃20mL，0-5℃下缓慢滴加15mL溶解有上步所得酰氯的四氢呋喃溶液，滴毕，0-10℃下继续搅拌4h，反应结束后，加入水30mL，二氯甲烷萃取(3*50mL)，无水硫酸钠干燥，柱层析纯化即得式d化合物。
ES：M/Z 679[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):8.53～8.52(m,1H),8.28～8.26(m,1H),7.98～7.97(m,1H),7.80～7.78(m,1H),7.70～7.68(m,2H),7.65～7.63(m,1H),7.58～7.56(m,2H),7.52～7.50(m,3H),7.40～7.38(m,1H),7.24～7.22(m,1H),7.08～7.03(m,5H),5.36(s,1H),4.10(s,1H),1.84～1.82(m,2H),1.05～1.04(m,2H),0.09(s,6H)。
实施例5:式I化合物的制备
称取1.0g实施例4所得物式d的化合物于反应瓶中，加入乙醇50ml，还原铁粉0.5g，盐酸5ml，回流反应2h，反应结束后，冷却至室温，将反应液倒入冰水中，加碳酸氢钠调节pH至中性，抽滤，滤液用二氯甲烷萃取(30ml*3)，无水硫酸钠干燥，过滤，柱层析纯化得标准化合物。
ES：M/Z 649[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):7.96～7.95(m,1H),7.83～7.81(m,1H),7.78～7.77(m,2H),7.68～7.67(m,1H),7.64～7.62(m,2H),7.59～7.57(m,3H),7.40～7.39(m,1H),7.24～7.22(m,1H),7.08～7.03(m,51H),6.68～6.66(m,1H),6.55～6.54(m,1H),6.27(br,2H),5.35(s,1H),4.10(s,1H),1.84～1.82(m,2H),1.05～1.04(m,2H),0.09(s,6H)。
实验例1阻燃性能测试
将双酚A型环氧树脂、表1中的固化剂混合后，在100-110℃下搅拌均匀后将所得组合物浇注到模具中，按80℃/2小时预固化，120℃/5小时固化，140℃/2小时,160℃/2h固化工艺成型，得到改性环氧树脂,依据UL94《设备和器具部件材料的可燃性能试验》中的垂直燃烧试验方法测定阻燃性能，结果见表1。
表1
实验例2抗紫外性能测定
将双酚A型环氧树脂20g、实施例5化合物4g混合后，在100-110℃下搅拌均匀后将所得组合物浇注到模具中，按80℃/2小时预固化，120℃/5小时固化，140℃/2小时,160℃/2h固化工艺成型，得到改性环氧树脂，作为实验组；将双酚A型环氧树脂20g、4,4’-二氨基二苯甲烷混合后，同法制得环氧树脂，作为对照组。参照标准HG/T3689-2001，将样品条(1mm×10mm×50mm)置于340nm的UV灯箱内60℃连续照射7天，以标准GB250-2008用ISO105九级变色灰卡测定黄变程度，其色牢固级别可达8级以上，耐黄变性能良好。
Claims (2)
1.一种环氧树脂抗紫外阻燃固化剂，结构如式(I)所示：
2.权利要求1所述环氧树脂抗紫外阻燃固化剂的制备方法，包括如下步骤：
步骤(1)：乙烯基二甲基氯硅烷与2-氨基-5-硝基苯甲酸甲酯反应制得式a的化合物；
步骤(2)：式a的化合物与DOPO反应制得式b的化合物；
步骤(3)：式b的化合物水解制得式c的化合物；
步骤(4)：式c的化合物与2,4-二羟基二苯甲酮反应制得式d的化合物；
步骤(5)：式d的化合物还原制得式I的化合物，反应方程式如下：
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