CN107760016A - 一种电路板专用阻燃防水聚氨酯复合材料 - Google Patents
一种电路板专用阻燃防水聚氨酯复合材料 Download PDFInfo
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Abstract
本发明公开了一种电路板专用阻燃防水聚氨酯复合材料,其原料包括:二甲基联苯二异氰酸酯、L‑赖氨酸二异氰酸酯、聚四亚甲基醚二醇、环氧树脂、氯丁橡胶、甲基乙烯基苯基硅橡胶、二甲硫基甲苯二胺、1,2‑二甲基咪唑、山梨醇、己二酸二辛酯、1H,1H,8H,8H‑十二氟‑1,8‑辛二醇、硫磺、六氟双酚A、复合填料;复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成。本发明提出的电路板专用阻燃防水聚氨酯复合材料,其具有优异的耐热性和阻燃性,且防水防潮性好,能满足电路板材料的使用要求。
Description
技术领域
本发明涉及电路板材料技术领域,尤其涉及一种电路板专用阻燃防水聚氨酯复合材料。
背景技术
聚氨酯是主链上含有重复氨基甲酸酯基团的大分子化合物的统称,与传统的不饱和树脂以及乙烯基酯树脂体系相比,聚氨酯具有优异的耐疲劳性和耐化学腐蚀性,良好的冲击韧性,不含有苯乙烯,低收缩率等特点,是发展最快、用途最广的一种新材料,目前已被应用在了电路板中。
目前,电子产品正朝着小型化、轻便化、多功能化方向发展,对所用材料的品质提出了更严格的要求,但是现有的聚氨酯材料极易燃烧,且耐水性欠佳,在电路板长期使用的过程中存在隐患,大大限制了聚氨酯材料在电路板中的应用。
发明内容
基于背景技术存在的技术问题,本发明提出了一种电路板专用阻燃防水聚氨酯复合材料,其具有优异的耐热性和阻燃性,且防水防潮性好,能满足电路板材料的使用要求。
本发明提出的一种电路板专用阻燃防水聚氨酯复合材料,其原料按重量份包括:二甲基联苯二异氰酸酯20-50份、L-赖氨酸二异氰酸酯5-22份、聚四亚甲基醚二醇35-55份、环氧树脂2-8份、氯丁橡胶1-5份、甲基乙烯基苯基硅橡胶2-10份、二甲硫基甲苯二胺5-23份、1,2-二甲基咪唑0.1-1份、山梨醇2-10份、己二酸二辛酯2-8份、1H,1H,8H,8H-十二氟-1,8-辛二醇0.5-2份、硫磺0.1-0.8份、六氟双酚A 2-5份、复合填料3-12份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成。
优选地,所述复合填料中,改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝的重量比为3-10:1-5:2-6:3-12:3-10:2-6。
优选地,所述改性氧化石墨烯按照以下工艺进行制备:将6-羟基-2-萘甲醛和无水碳酸钾加入四氢呋喃中,搅拌均匀后加入六氯环三磷腈,在35-50℃下反应30-50min,升温后回流反应10-18h,反应结束将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料A;将物料A加入丙酮中,搅拌均匀后加入γ-氨乙基氨丙基三甲氧基硅烷,在45-55℃下反应2-5h,反应结束后将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料B;将物料B和氧化石墨烯加入乙醇中,调节pH值为2-3后升温至45-60℃,搅拌反应60-150min,反应结束后经洗涤、过滤、干燥得到所述改性氧化石墨烯。
优选地,在改性氧化石墨烯的制备过程中,6-羟基-2-萘甲醛、六氯环三磷腈的重量比为110-135:17-34。
优选地,在改性氧化石墨烯的制备过程中,物料A、γ-氨乙基氨丙基三甲氧基硅烷的重量比为2-3:20-30。
优选地,在改性氧化石墨烯的制备过程中,物料B、氧化石墨烯的重量比为3-10:20-48。
优选地,其原料按重量份包括:二甲基联苯二异氰酸酯38份、L-赖氨酸二异氰酸酯20份、聚四亚甲基醚二醇42份、环氧树脂6份、氯丁橡胶3份、甲基乙烯基苯基硅橡胶6份、二甲硫基甲苯二胺17份、1,2-二甲基咪唑0.4份、山梨醇6份、己二酸二辛酯5份、1H,1H,8H,8H-十二氟-1,8-辛二醇1份、硫磺0.6份、六氟双酚A 3份、复合填料10份。
优选地,所述环氧树脂的环氧值为0.3-0.47。
本发明所述电路板专用阻燃防水聚氨酯复合材料,其原料中,加入了环氧树脂、氯丁橡胶和甲基乙烯基苯基硅橡胶,使三者与聚氨酯的性能协同促进,显著提高了复合材料的粘结性能、韧性和耐热性,并赋予复合材料一定的阻燃性;以二甲硫基甲苯二胺为固化剂,与1,2-二甲基咪唑和山梨醇配合,提高了复合材料的固化速度和固化率;优选方式中,在改性氧化石墨烯的制备过程中,首先以6-羟基-2-萘甲醛与六氯环三磷腈为原料,使6-羟基-2-萘甲醛中的羟基与六氯环三磷腈中的氯发生了反应,得到了物料A,将物料A与γ-氨乙基氨丙基三甲氧基硅烷混合,使物料A中的醛基与γ-氨乙基氨丙基三甲氧基硅烷中的氨基发生了反应得到了物料B,将物料B与氧化石墨烯配合后,物料B与氧化石墨烯表面的羟基进行了作用,从而将6-羟基-2-萘甲醛、六氯环三磷腈、γ-氨乙基氨丙基三甲氧基硅烷和氧化石墨烯结合为一体,得到了同时含有N、P、Si原子以及萘环的改性氧化石墨烯,将其加入体系中,在体系中分散均匀,且与基体的界面强度高,与复合填料配合赋予复合材料优异的耐热性和阻燃性;1H,1H,8H,8H-十二氟-1,8-辛二醇、六氟双酚A加入体系中,性能协同,赋予复合材料优异的防水性。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种电路板专用阻燃防水聚氨酯复合材料,其原料按重量份包括:二甲基联苯二异氰酸酯50份、L-赖氨酸二异氰酸酯5份、聚四亚甲基醚二醇55份、环氧树脂2份、氯丁橡胶5份、甲基乙烯基苯基硅橡胶2份、二甲硫基甲苯二胺23份、1,2-二甲基咪唑0.1份、山梨醇10份、己二酸二辛酯2份、1H,1H,8H,8H-十二氟-1,8-辛二醇2份、硫磺0.1份、六氟双酚A 5份、复合填料12份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成。
实施例2
本发明提出的一种电路板专用阻燃防水聚氨酯复合材料,其原料按重量份包括:二甲基联苯二异氰酸酯20份、L-赖氨酸二异氰酸酯22份、聚四亚甲基醚二醇35份、环氧树脂8份、氯丁橡胶1份、甲基乙烯基苯基硅橡胶10份、二甲硫基甲苯二胺5份、1,2-二甲基咪唑1份、山梨醇2份、己二酸二辛酯8份、1H,1H,8H,8H-十二氟-1,8-辛二醇0.5份、硫磺0.8份、六氟双酚A 2份、复合填料3份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成。
实施例3
本发明提出的一种电路板专用阻燃防水聚氨酯复合材料,其原料按重量份包括:二甲基联苯二异氰酸酯27份、L-赖氨酸二异氰酸酯20份、聚四亚甲基醚二醇39份、环氧树脂7份、氯丁橡胶2份、甲基乙烯基苯基硅橡胶9份、二甲硫基甲苯二胺10份、1,2-二甲基咪唑0.9份、山梨醇4份、己二酸二辛酯7份、1H,1H,8H,8H-十二氟-1,8-辛二醇1份、硫磺0.7份、六氟双酚A 3份、复合填料10份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成,且改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝的重量比为3:5:2:12:3:6;
所述改性氧化石墨烯按照以下工艺进行制备:将6-羟基-2-萘甲醛和无水碳酸钾加入四氢呋喃中,搅拌均匀后加入六氯环三磷腈,在50℃下反应30min,升温后回流反应18h,反应结束将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料A;将物料A加入丙酮中,搅拌均匀后加入γ-氨乙基氨丙基三甲氧基硅烷,在45℃下反应5h,反应结束后将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料B;将物料B和氧化石墨烯加入乙醇中,调节pH值为2后升温至60℃,搅拌反应60min,反应结束后经洗涤、过滤、干燥得到所述改性氧化石墨烯;
在改性氧化石墨烯的制备过程中,6-羟基-2-萘甲醛、六氯环三磷腈的重量比为135:17;物料A、γ-氨乙基氨丙基三甲氧基硅烷的重量比为3:20;物料B、氧化石墨烯的重量比为10:20;
所述环氧树脂的环氧值为0.3。
实施例4
本发明提出的一种电路板专用阻燃防水聚氨酯复合材料,其原料按重量份包括:二甲基联苯二异氰酸酯43份、L-赖氨酸二异氰酸酯8份、聚四亚甲基醚二醇50份、环氧树脂4份、氯丁橡胶4.3份、甲基乙烯基苯基硅橡胶5份、二甲硫基甲苯二胺21份、1,2-二甲基咪唑0.4份、山梨醇9份、己二酸二辛酯3份、1H,1H,8H,8H-十二氟-1,8-辛二醇1.8份、硫磺0.2份、六氟双酚A 4.2份、复合填料6份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成,且改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝的重量比为10:1:6:3:10:2;
所述改性氧化石墨烯按照以下工艺进行制备:将6-羟基-2-萘甲醛和无水碳酸钾加入四氢呋喃中,搅拌均匀后加入六氯环三磷腈,在35℃下反应50min,升温后回流反应10h,反应结束将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料A;将物料A加入丙酮中,搅拌均匀后加入γ-氨乙基氨丙基三甲氧基硅烷,在55℃下反应2h,反应结束后将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料B;将物料B和氧化石墨烯加入乙醇中,调节pH值为3后升温至45℃,搅拌反应150min,反应结束后经洗涤、过滤、干燥得到所述改性氧化石墨烯;
在改性氧化石墨烯的制备过程中,6-羟基-2-萘甲醛、六氯环三磷腈的重量比为110:34;物料A、γ-氨乙基氨丙基三甲氧基硅烷的重量比为2:30;物料B、氧化石墨烯的重量比为3:48;
所述环氧树脂的环氧值为0.47。
实施例5
本发明提出的一种电路板专用阻燃防水聚氨酯复合材料,其原料按重量份包括:二甲基联苯二异氰酸酯38份、L-赖氨酸二异氰酸酯20份、聚四亚甲基醚二醇42份、环氧树脂6份、氯丁橡胶3份、甲基乙烯基苯基硅橡胶6份、二甲硫基甲苯二胺17份、1,2-二甲基咪唑0.4份、山梨醇6份、己二酸二辛酯5份、1H,1H,8H,8H-十二氟-1,8-辛二醇1份、硫磺0.6份、六氟双酚A 3份、复合填料10份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成,且改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝的重量比为7:3:4:10:7:5;
所述改性氧化石墨烯按照以下工艺进行制备:将6-羟基-2-萘甲醛和无水碳酸钾加入四氢呋喃中,搅拌均匀后加入六氯环三磷腈,在45℃下反应40min,升温后回流反应13h,反应结束将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料A;将物料A加入丙酮中,搅拌均匀后加入γ-氨乙基氨丙基三甲氧基硅烷,在50℃下反应4h,反应结束后将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料B;将物料B和氧化石墨烯加入乙醇中,调节pH值为2后升温至53℃,搅拌反应120min,反应结束后经洗涤、过滤、干燥得到所述改性氧化石墨烯;
在改性氧化石墨烯的制备过程中,6-羟基-2-萘甲醛、六氯环三磷腈的重量比为120:21;物料A、γ-氨乙基氨丙基三甲氧基硅烷的重量比为2.6:27;物料B、氧化石墨烯的重量比为7:38;
所述环氧树脂的环氧值为0.45。
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,都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种电路板专用阻燃防水聚氨酯复合材料,其特征在于,其原料按重量份包括:二甲基联苯二异氰酸酯20-50份、L-赖氨酸二异氰酸酯5-22份、聚四亚甲基醚二醇35-55份、环氧树脂2-8份、氯丁橡胶1-5份、甲基乙烯基苯基硅橡胶2-10份、二甲硫基甲苯二胺5-23份、1,2-二甲基咪唑0.1-1份、山梨醇2-10份、己二酸二辛酯2-8份、1H,1H,8H,8H-十二氟-1,8-辛二醇0.5-2份、硫磺0.1-0.8份、六氟双酚A 2-5份、复合填料3-12份;
其中,所述复合填料由改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝混合而成。
2.根据权利要求1所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,所述复合填料中,改性氧化石墨烯、玄武岩纤维、纳米碳酸钙、凹凸棒土、硫酸钙晶须、氮化铝的重量比为3-10:1-5:2-6:3-12:3-10:2-6。
3.根据权利要求1或2所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,所述改性氧化石墨烯按照以下工艺进行制备:将6-羟基-2-萘甲醛和无水碳酸钾加入四氢呋喃中,搅拌均匀后加入六氯环三磷腈,在35-50℃下反应30-50min,升温后回流反应10-18h,反应结束将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料A;将物料A加入丙酮中,搅拌均匀后加入γ-氨乙基氨丙基三甲氧基硅烷,在45-55℃下反应2-5h,反应结束后将反应产物浓缩后加入水中,搅拌后过滤、洗涤、干燥得到物料B;将物料B和氧化石墨烯加入乙醇中,调节pH值为2-3后升温至45-60℃,搅拌反应60-150min,反应结束后经洗涤、过滤、干燥得到所述改性氧化石墨烯。
4.根据权利要求3所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,在改性氧化石墨烯的制备过程中,6-羟基-2-萘甲醛、六氯环三磷腈的重量比为110-135:17-34。
5.根据权利要求3或4所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,在改性氧化石墨烯的制备过程中,物料A、γ-氨乙基氨丙基三甲氧基硅烷的重量比为2-3:20-30。
6.根据权利要求3-5中任一项所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,在改性氧化石墨烯的制备过程中,物料B、氧化石墨烯的重量比为3-10:20-48。
7.根据权利要求1-6中任一项所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,其原料按重量份包括:二甲基联苯二异氰酸酯38份、L-赖氨酸二异氰酸酯20份、聚四亚甲基醚二醇42份、环氧树脂6份、氯丁橡胶3份、甲基乙烯基苯基硅橡胶6份、二甲硫基甲苯二胺17份、1,2-二甲基咪唑0.4份、山梨醇6份、己二酸二辛酯5份、1H,1H,8H,8H-十二氟-1,8-辛二醇1份、硫磺0.6份、六氟双酚A 3份、复合填料10份。
8.根据权利要求1-7中任一项所述电路板专用阻燃防水聚氨酯复合材料,其特征在于,所述环氧树脂的环氧值为0.3-0.47。
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