CN113801318A - 双羟基低分子量聚苯醚烷基磷酸酯及其热固性树脂组合物和应用 - Google Patents
双羟基低分子量聚苯醚烷基磷酸酯及其热固性树脂组合物和应用 Download PDFInfo
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Abstract
本发明的提供了一种双羟基低分子量聚苯醚烷基磷酸酯及其热固性树脂组合物和应用,本发明的双羟基低分子量聚苯醚烷基磷酸酯,在聚苯醚中引入磷酸酯基团,既能作为环氧树脂的固化剂,又引入了具有阻燃作用的磷酸酯基团,同时消除了环氧树脂产生大量的羟基基团,提升了材料的耐老化性能;本发明利用双羟基低分子量聚苯醚烷基磷酸酯作为树脂组合物中的固化剂、阻燃剂,可以显著提高该树脂组合物制作的预浸料、及印制电路用层压板的玻璃化温度和耐热性,并使其具有优异的介电性能、低吸水率、耐湿热性及良好的工艺加工性能;固化后的层压板可以实现无卤阻燃,达到UL94V‑0。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及双羟基低分子量聚苯醚烷基磷酸酯及其热固性树脂组合物和应用。
背景技术
随着通讯产品走向高速化及高频化,高玻璃化温度、低介电常数与低介电损耗、低吸湿率和良好的加工型等综合性能优良的基板材料越来越受到国内外厂商的青睐。近几年5G板材的应用,聚苯醚PPO 材料受到极大的关注,尤其是低分子量PPO商业化产品的推出,使得应用更加广泛。但是环氧树脂体系原料易得、价格便宜及具有好的加工型,因此在数量上和技术上,都大量采用环氧树脂制成的FR-4 板为主。因此,目前将PPO引入到环氧树脂体系中,即PPO改性环氧树脂是较为常用的。该解决方案可以改善环氧树脂的韧性,也可以提高其耐热性和介电性能。但聚苯醚是一种热塑性树脂,与环氧树脂在化学结构和性能上有很大的差异,二者很难相容。容易造成聚苯醚 PPO改性环氧时发生相分离的现象。
目前,最常用的方法是对聚苯醚PPO/PPE进行改性,增加反应性基团。例如可以引入氨基、羧基及环氧基团,但是氨基引入通常比较困难,而引入羧基后,羧基的热稳定性通常不会太高。因此,通常引入较多的是环氧基团。例如通过与环氧氯丙烷或环氧溴丙烷发生反应,可以得到末端为环氧基的可交联热固性PPE树脂。初期人们多通过在溶剂中加入过氧化物的方法降低PPE的分子量,近些年,SABIC公司等也推出了双端羟基的低分子量PPO材料,以适应对低分子量PPE 的需要。例如FRX公司报道了利用SA90与环氧树脂结合制备的线路板材料的Tg在153-175度之间。但是酚羟基化合物与环氧树脂发生固化反应时,会生成极性较大的羟基,导致固化物的介电性能较差,且对Tg有影响。
发明内容
为了解决现有技术中存在的上述问题,本发明的目的在于提供一种双羟基低分子量聚苯醚烷基磷酸酯,在聚苯醚中引入磷酸酯基团,既能作为环氧树脂的固化剂,又引入了具有阻燃作用的磷酸酯基团,同时消除了环氧树脂产生大量的羟基基团,提升了材料的耐老化性能。
本发明采用的技术方案是:一种双羟基低分子量聚苯醚烷基磷酸酯,其结构式如下:
其中,Y为:
其中,m+n为2-35,m,n均为整数;
其中,R1=-C2H5、-C6H5中的一种,R2=-C2H5、-C6H5中的一种。
优选的,所述的双羟基低分子量聚苯醚烷基磷酸酯作为环氧树脂固化剂的应用。
优选的,所述的双羟基低分子量聚苯醚烷基磷酸酯作为添加型阻燃剂的应用。
本发明将PPO羟基磷酸酯化得到磷酸酯化的PPO材料,将其用作环氧树脂的固化剂,当其与环氧树脂反应时发生如下反应:
该化合物与环氧体系固化后的体系介电性能较好,同时磷酸酯基团的转移反应使固化体系具有无卤阻燃的功效,可以少量添加或无需添加其他阻燃剂就可以使板材达到UL94 V-0无卤阻燃效果。同时,在固化前,该双羟基低分子量聚苯醚烷基磷酸酯可以以添加型阻燃剂形式进入到预浸料,不会发生预固化带来的粘度升高。
基于此,本发明的另一目的在于提供一种热固性树脂组合物,其包括环氧树脂以及上述固化剂,其中,固化剂至少包含一种双羟基低分子量聚苯醚烷基磷酸酯。
进一步的,所述固化剂占热固性树脂组合物的比例为5-30%。
进一步的,所述环氧树脂占热固性树脂组合物的比例为32-70%。
优选的,所述环氧树脂为无卤环氧树脂,是在一个分子中具有两个或两个以上环氧基团的环氧树脂,选自缩水甘油醚类、缩水甘油酯类,脂环族环氧树脂、环氧化烯烃类、酰亚胺环氧树脂中的一种或至少两种的混合物。
优选的,所述缩水甘油醚类包括双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物。
进一步的,所述热固性树脂组合物,还包括阻燃剂。
优选的,所述阻燃剂选自三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、聚膦酸酯或膦酸酯-碳酸酯共聚物中的任意一种或至少两种的混合物。
优选的,所述热固性树脂组合物中无卤阻燃剂的含量为10-40%。
进一步的,所述热固性树脂组合物还包含促进剂。
优选的,所述固化促进剂包括有机金属盐和选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、吡啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物。
优选的,所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、 2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
进一步的,本发明所述的热固性树脂组合物在印制电路用层压板中的应用。
本发明的再一目的在于提供一种利用双羟基低分子量聚苯醚烷基磷酸酯与环氧树脂结合制备热固性树脂组合物,应用在线路板材料中。
一种预浸料,包括如上所述的热固性树脂组合物。
一种层压板,其包括如上所述的预浸料。
一种印制电路板,其包括如上所述的预浸料。
本发明使用该树脂制作的印制电路板用层压板,具有高玻璃化转变温度、优异的介电性能、高耐热性和耐湿性、良好的工艺加工性,并能实现无卤阻燃。
与现有技术相比,本发明的有益效果在于:
本发明通过在在聚苯醚中引入磷酸酯基团,既能作为环氧树脂的固化剂,又引入了具有阻燃作用的磷酸酯基团,同时消除了环氧树脂产生大量的羟基基团,提升了材料的耐老化性能。本发明利用双羟基低分子量聚苯醚烷基磷酸酯作为树脂组合物中的固化剂、阻燃剂,可以显著提高该树脂组合物制作的预浸料、及印制电路用层压板的玻璃化温度和耐热性,并使其具有优异的介电性能、低吸水率、耐湿热性及良好的工艺加工性能;固化后的层压板可以实现无卤阻燃,达到 UL94 V-0。
附图说明
图1.SA-90的凝胶色谱图;市售双羟基聚苯醚树脂分子量分布情况;
图2.SA-90P1的凝胶色谱图;
图3.SA-90P1的1H NMR图。
具体实施方式
下面将结合本发明实施例、及附图,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本实用发明的范围。
原材料:
阻燃剂:美国FRX公司OL3001;
交联剂:沙比克SA-90,自制的交联剂SA90-P1、SA90-P2;
环氧树脂:NC-3000-H三菱化学;简称:EPOXY 1
环氧树脂:HP-6000,DIC株式会社;简称:EPOXY 2
催化剂1(固化促进剂):2-乙基-4甲基咪唑;
催化剂2(固化促进剂):DBU。
1.双羟基低分子量聚苯醚烷基磷酸酯SA90-P1的制备方法:
将SA-90溶解于甲苯中,然后加入三乙胺,分散均匀后,保持温度在0-15℃,慢慢滴加二乙基次膦酰氯,保温反应3h,滤除三乙胺盐酸盐。水洗,饱和食盐水洗涤后,加入无水硫酸钠干燥,过滤,蒸除溶剂和三乙胺,得到淡黄褐色SA90-P1;
产物SA90-P1的结构式如下:
2.双羟基低分子量聚苯醚烷基磷酸酯SA90-P2的制备方法:
将SA-90溶解于甲苯中,然后加入三乙胺,分散均匀后,保持温度在0-15℃,慢慢滴加乙基苯基次膦酰氯,保温反应3h,滤除三乙胺盐酸盐。水洗,饱和食盐水洗涤后,加入无水硫酸钠干燥,过滤,蒸除溶剂和三乙胺,得到淡黄褐色SA90-P2;
产物SA90-P2的结构式如下:
3.一种热固性树脂组合物制备流程
一种热固性树脂组合物制备流程:按重量份计:包含如表1所示配比的环氧树脂、阻燃剂、交联剂(SA-90或SA90-P1)和固化促进剂 2-乙基-4-甲基咪唑,溶解在MEK中形成60%的分散体;将分散体与 10cm*10cm7628玻纤片进行浸渍,然后干燥过夜,取4-5片叠压在 200℃,固化90min,即得层压板。按照标准方法测试阻燃性能,评价其UL-94阻燃等级,如表1所示;
表1.各实施例和比较例的配方组成及性能测试
从表1中可以看出与对比例比较,可以看出,利用双羟基低分子量聚苯醚烷基磷酸酯作为固化剂,可以明显提升环氧树脂固化片的玻璃化转变温度,阻燃性能也有较大的改善。
Claims (19)
2.如权利要求1所述的双羟基低分子量聚苯醚烷基磷酸酯作为环氧树脂固化剂的应用。
4.如权利要求1所述的双羟基低分子量聚苯醚烷基磷酸酯作为添加型阻燃剂的应用。
5.一种热固性树脂组合物,其特征在于,包括环氧树脂以及权利要求1所述的固化剂,其中,固化剂至少包含一种双羟基低分子量聚苯醚烷基磷酸酯。
6.如权利要求5所述的热固性树脂组合物,其特征在于,所述固化剂占热固性树脂组合物的比例为5-30%。
7.如权利要求5或6所述的热固性树脂组合物,其特征在于,所述环氧树脂占热固性树脂组合物的比例为32-70%。
8.如权利要求7所述的热固性树脂组合物,其特征在于,所述环氧树脂为无卤环氧树脂,是在一个分子中具有两个或两个以上环氧基团的环氧树脂,选自缩水甘油醚类、缩水甘油酯类,脂环族环氧树脂、环氧化烯烃类、酰亚胺环氧树脂中的一种或至少两种的混合物。
9.如权利要求8所述的热固性树脂组合物,其特征在于,所述缩水甘油醚类包括双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物。
10.如权利要求5-9任一项所述的热固性树脂组合物,其特征在于,还包括阻燃剂。
11.如权利要求10所述的热固性树脂组合物,其特征在于,所述阻燃剂选自三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、聚膦酸酯或膦酸酯-碳酸酯共聚物中的任意一种或至少两种的混合物。
12.如权利要求11所述的热固性树脂组合物,其特征在于,所述热固性树脂组合物中无卤阻燃剂的含量为10-40%。
13.如权利要求5、6、8、9、11或12所述的热固性树脂组合物,其特征在于,还包括固化促进剂。
14.如权利要求13所述的热固性树脂组合物,其特征在于,所述固化促进剂包括有机金属盐和选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、吡啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物。
15.如权利要求14所述的热固性树脂组合物,其特征在于,所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
16.如权利要求5、6、8、9、11、12、14或15所述的热固性树脂组合物在印制电路用层压板中的应用。
17.一种预浸料,包括如权利要求5、6、8、9、11、12、14或15所述的热固性树脂组合物。
18.一种层压板,其包括如权利要求17所述的预浸料。
19.一种印制电路板,其包括如权利要求17所述的预浸料。
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CN115873403A (zh) * | 2022-12-30 | 2023-03-31 | 江苏蔚观新材料科技有限公司 | 一种高gwit无卤阻燃玻璃纤维增强尼龙 |
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