CN115417862A - 一种可降解脂环族环氧树脂及其制备方法 - Google Patents
一种可降解脂环族环氧树脂及其制备方法 Download PDFInfo
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Abstract
本发明属于环氧树脂制备技术,具体涉及一种可降解脂环族环氧树脂及其制备方法。在对甲苯磺酸催化下,以环己烯甲醛与双羟基化合物为原料,回流反应3~10小时,得到中间体;然后室温下利用过氧乙酸将中间体环氧化,得到所述可降解脂环族环氧树脂,将其与ERL‑4221进行复配,有效降低了ERL‑4221的粘度,同时能有效提高ERL‑4221固化后的附着力,尤其是提升固化速度。同时还具备了一般环氧树脂不具备的许多优点,如常温为液态易于加工、不含有芳环等发色基团而耐紫外辐射、不含游离氯和金属离子而具有良好的电绝缘性能等,使其在很多领域尤其电子封装领域广泛应用。
Description
技术领域
本发明属于环氧树脂制备技术,具体涉及一种可降解脂环族环氧树脂及其制备方法。
背景技术
ERL-4221作为一种性能优异的树脂具有固化后良好的热稳定性、机械性能、耐化学药品等性能被广泛使用。但是脂环族环氧树脂固化交联后以一种不溶不熔的热固性树脂形式存在,在电子封装应用过程中,封装过程中难免有操作失误、不良电子元件从基板上拆除、整个原件使用完对于贵重元件的回收等需要,但是不溶不熔的树脂明显使得这些操作可望而不可及,因此,对于可控降解脂环族环氧树脂的研究是有必要的。
发明内容
本发明设计了可降解型脂环族环氧树脂,将其与ERL-4221进行复配,有效降低了ERL-4221的粘度,同时能有效提高ERL-4221固化后的附着力。同时还具备了一般环氧树脂不具备的许多优点,如常温为液态易于加工、不含有芳环等发色基团而耐紫外辐射、不含游离氯和金属离子而具有良好的电绝缘性能等,使其在很多领域尤其电子封装领域广泛应用。
本发明采用如下技术方案:
一种可降解脂环族环氧树脂,其化学结构式如下:
R1、R2独立的选自烷基或者氢、烷氧基。
本发明公开了上述可降解脂环族环氧树脂的制备方法,以环己烯甲醛与双羟基化合物为原料,得到中间体;然后将中间体环氧化,得到所述可降解脂环族环氧树脂。
本发明中,双羟基化合物的化学结构式如下:
R1、R2独立的选自烷基或者氢、烷氧基。
中间体的化学结构式:
R1、R2独立的选自烷基或者氢、烷氧基。
本发明中,在对甲苯磺酸催化下,以环己烯甲醛与双羟基化合物为原料,回流反应3~10小时,得到中间体;然后利用过氧乙酸将中间体环氧化,得到所述可降解脂环族环氧树脂。优选的,环氧化在碳酸钠存在进行。对甲苯磺酸用量为环己烯甲醛与双羟基化合物质量和的0.1~0.5%。
本发明中,环己烯甲醛、双羟基化合物、过氧乙酸、碳酸钠的摩尔比为1∶(1~1.5)∶(1.5~1.9)∶(0.2~0.5)。
本发明中,环氧化的温度为室温,时间为5~10小时。
本发明公开了一种环氧组合物,由上述可降解脂环族环氧树脂与其他脂环族环氧树脂组成;优选的,其他指环族环氧树脂包括ERL-4221;本发明可降解脂环族环氧树脂占ERL-4221质量的15~25%。
本发明公开了一种光固化环氧体系,由上述可降解脂环族环氧树脂与其他脂环族环氧树脂、光固化环氧树脂、助剂组成;优选的,其他指环族环氧树脂包括ERL-4221;本发明可降解脂环族环氧树脂占ERL-4221质量的15~25%。
本发明设计了可降解型脂环族环氧树脂,将其与ERL-4221进行复配,有效降低了ERL-4221的粘度,同时能有效提高ERL-4221固化后的附着力。同时还具备了一般环氧树脂不具备的许多优点,如常温为液态易于加工、不含有芳环等发色基团而耐紫外辐射、不含游离氯和金属离子而具有良好的电绝缘性能等,使其在很多领域尤其电子封装领域广泛应用。
附图说明
图1为3-(4-乙基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷的核磁图。
图2为3-(4,5-二甲基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷的核磁图。
图3为3-(4-丙基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷的核磁图。
图4为3-(4-丁基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷的核磁图。
具体实施方式
本发明可降解脂环族环氧树脂,其化学结构式如下:
R1、R2独立的选自烷基或者氢、烷氧基。
优选为以下化学结构式:
本发明采用的原料都是市售产品,具体制备操作以及测试方法都为常规技术。
实施例一3-(4-乙基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷
500mL反应瓶中加入环己烯甲醛110.1g(1.0mol)和1,2-丁二醇117.1g(1.3mol),搅拌下加入二氯乙烷250g(2.52mol),再加入对甲苯磺酸(TsOH)0.7g(0.3%wt),90℃回流分水,反应6h后,冷却至室温,待投下一步反应。
将上述反应液转移至1000mL反应瓶中,加入500mL二氯乙烷,保持温度在10-15℃,搅拌下滴加过氧乙酸120g(1.76mol),碳酸钠17.17g(0.31mol),保持反应体系温度为25℃,反应7h后,静置分水,有机相用水和碱分别洗涤2次,无水硫酸钠干燥,浓缩脱溶,粗品经130℃,0.22mmHg蒸馏提纯,得无色透明液体171.4g(0.86mol),收率86.45%,纯度97.17%,环氧当量214.6。1H NMR(400MHz,CDCl3):δ4.92–4.47(m,1H),4.11–3.78(m,2H),3.55–3.30(m,1H),3.29–2.90(m,2H),2.25–1.97(m,2H),1.90–1.32(m,6H),1.35–0.66(m,4H)。
实施例二3-(4,5-二甲基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷
500mL反应瓶中加入环己烯甲醛110.1g(1.0mol)和2,3-丁二醇117.1g(1.3mol),搅拌下加入二氯乙烷250g(2.52mol),再加入对甲苯磺酸(TsOH)0.6g(0.3%wt),90℃回流分水,反应6h后,冷却至室温,待投下一步反应。
将上述反应液转移至1000mL反应瓶中,加入500mL二氯乙烷,保持温度在10-15℃,滴加过氧乙酸120g(1.76mol),碳酸钠17.17g(0.31mol),保持反应体系温度为25℃,反应7h后,静置分水,有机相用水和碱分别洗涤2次,无水硫酸钠干燥,浓缩脱溶,粗品经130℃,0.22mmHg蒸馏提纯,得无色透明液体171.4g(0.86mol),收率86.45%,纯度97.17%,环氧当量214.6。1H NMR(400MHz,CDCl3)δ4.94–4.49(m,1H),4.25–3.44(m,2H),3.16(m,,2H),2.29–1.94(m,2H),1.93–1.33(m,4H),1.34–0.77(m,7H).
实施例三3-(4-丙基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷
500mL反应瓶中加入环己烯甲醛110.1g(1.0mol)和1,2-戊二醇135.4g(1.3mol),搅拌下加入二氯乙烷250g(2.52mol),再加入对甲苯磺酸(TsOH)0.7g(0.3%wt),90℃回流分水,反应6h后,冷却至室温,待投下一步反应。
将上述反应液转移至1000mL反应瓶中,加入500mL二氯乙烷,保持温度在10-15℃,滴加过氧乙酸120g(1.76mol),碳酸钠17.17g(0.31mol),保持反应体系温度为25℃,反应7h后,静置分水,有机相用水和碱分别洗涤2次,无水硫酸钠干燥,浓缩脱溶,粗品经130℃,0.22mmHg蒸馏提纯,得无色透明液体193.2g(0.91mol),收率91.07%,纯度99.03%,环氧当量227.56。1H NMR(400MHz,CDCl3)δ:4.78–4.44(m,1H),4.13–3.74(m,2H),3.40(m,1H),3.25–3.01(m,2H),2.27–1.91(m,2H),1.93–0.96(m,10H),0.98–0.65(m,3H).
实施例四3-(4-丁基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷
500mL反应瓶中加入环己烯甲醛110.1g(1.0mol)和1,2-己二醇153.6g(1.3mol),搅拌下加入二氯乙烷250g(2.52mol),再加入对甲苯磺酸(TsOH)0.8g(0.3%wt),90℃回流分水,反应6h后,冷却至室温,待投下一步反应。
将上述反应液转移至1000mL反应瓶中,加入500mL二氯乙烷,保持温度在10-15℃,滴加过氧乙酸120g(1.76mol),碳酸钠17.17g(0.31mol),保持反应体系温度为25℃,反应7h后,静置分水,有机相用水和碱分别洗涤2次,无水硫酸钠干燥,浓缩脱溶,粗品经140℃,0.22mmHg蒸馏提纯,得无色透明液体198.8g(0.87mol),收率87.84%,纯度98.11%,环氧当量240.39。1H NMR(400MHz,CDCl3)δ4.78–4.51(m,1H),3.99(m,2H),3.41(m,1H),3.15(m,2H),2.12(m,2H),1.93–0.99(m,12H),0.98–0.66(m,3H).
实施例五
将表1、表2的原料常规混合,然后涂覆在基材上固化,再测试。
表1光固化环氧体系,原料用量单位为千克
表2不同缩醛添加浓度对整体产品性能的影响,原料用量单位为千克
ERL-4221:江苏泰特尔新材料科技股份有限公司;TTA UV692:江苏泰特尔新材料科技股份有限公司;BYK-333:毕克助剂(上海)有限公司。
测试条件:相对湿度:60%;基材:玻璃、马口铁;涂层厚度:20μm;固化条件:UV汞灯,75mw/cm2,H=150mm,10s(除特殊提及);表层固化:在紫外线照射后立即用棉球轻轻接触涂层来判断表面固化程度,如果纤维不黏附,则认为涂层表面已固化,表1中以固化速度表示;铅笔硬度:TQC铅笔硬度计,按ISO15184-2012执行;附着力:评判标准,0级最优,5级最差,按ISO 2409-2013执行。3-(4-丁基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷固化时间变长,不能很好的应用于UV光固化条件下,且成本价格高。
3-(4,5-二甲基-1,3-二氧戊环-2-基)-7-氧杂双环[4.1.0]庚烷为10千克时,体系对印铁的附着力测试结果为5级爆边;缩醛固化的很慢,汞灯光照3分钟,表面仍粘毛,指压有指纹;缩醛的加入,意外的提高附着力,尤其是20%的添加量,不仅提升了固化速度,而且明显提升附着力,这是紫外固化体系迫切需要的性能;缩醛的加入量超过30%,对固化速率影响非常明显,对铅笔硬度也有明显影响。
Claims (10)
2.权利要求1所述可降解脂环族环氧树脂的制备方法,以环己烯甲醛与双羟基化合物为原料,得到中间体;然后将中间体环氧化,得到所述可降解脂环族环氧树脂。
4.根据权利要求1所述可降解脂环族环氧树脂的制备方法,其特征在于,在对甲苯磺酸催化下,以环己烯甲醛与双羟基化合物为原料,回流反应3~10小时,得到中间体;然后室温下利用过氧乙酸将中间体环氧化,得到所述可降解脂环族环氧树脂。
5.根据权利要求1所述可降解脂环族环氧树脂的制备方法,其特征在于,环氧化在碳酸钠存在进行;对甲苯磺酸用量为环己烯甲醛与双羟基化合物质量和的0.1~0.5%;环己烯甲醛、双羟基化合物、过氧乙酸、碳酸钠的摩尔比为1∶(1~1.5)∶(1.5~1.9)∶(0.2~0.5)。
6.权利要求1所述可降解脂环族环氧树脂在制备可降解环氧树脂材料中的应用。
7.一种环氧组合物,由权利要求1所述可降解脂环族环氧树脂与其他脂环族环氧树脂组成。
8.根据权利要求7所述环氧组合物,其特征在于,所述可降解脂环族环氧树脂占其他脂环族环氧树脂质量的15~25%。
9.一种光固化环氧体系,由权利要求1所述可降解脂环族环氧树脂与其他脂环族环氧树脂、光固化环氧树脂、助剂组成。
10.根据权利要求9所述光固化环氧体系,其特征在于,其他指环族环氧树脂包括ERL-4221。
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PET\'KO, I. P.等: "Catalytic curing of aliphatic-alicyclic oxides by phenol-formaldehyde oligomers", ZHURNAL PRIKLADNOI KHIMII, vol. 62, no. 3, 31 December 1989 (1989-12-31), pages 642 - 646 * |
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