CN113150345B - 一种高强度耐湿聚氨酯模压板及其制备方法 - Google Patents

一种高强度耐湿聚氨酯模压板及其制备方法 Download PDF

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CN113150345B
CN113150345B CN202110593772.0A CN202110593772A CN113150345B CN 113150345 B CN113150345 B CN 113150345B CN 202110593772 A CN202110593772 A CN 202110593772A CN 113150345 B CN113150345 B CN 113150345B
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张宗权
何辉春
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Guangdong Zongsheng New Materials Co ltd
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Abstract

本发明公开了一种高强度耐湿聚氨酯模压板及其制备方法。所述聚氨酯模压板是由多个预浸料热轧得到的;所述预浸料包括玻璃纤维布和树脂浸胶液。有益效果:(1)制备了瓜尔胶/聚二甲基硅氧烷作为聚氨酯树脂的内交联剂,利用亲和性和反应性,增强聚二甲基硅氧烷的相容性,抑制迁移;利用反应增加交联度协同提高抗拉强度和耐湿性;(2)利用以N‑(2‑羟乙基)马来酰亚胺作为聚氨酯树脂的扩链剂,与填料呋喃化聚多巴胺粒子反应,增加聚氨酯树脂之间的交联度,从而显著增加模压板的强度和耐湿性。(3)通过喷雾法制备粒径较小的聚多巴胺粒子,并通过表面呋喃化,增加呋喃化聚多巴胺粒子在树脂浸胶液中的分散性,保证树脂浸胶液的稳定性。

Description

一种高强度耐湿聚氨酯模压板及其制备方法
技术领域
本发明涉及聚氨酯模压板技术领域,具体为一种高强度耐湿聚氨酯模压板及其制备方法。
背景技术
聚氨酯是被誉为“第五大塑料”的高分子材料,由于其具有柔韧性好、结构可设计性等卓越的性能被广泛用于电子、建材、航天等多个领域。其中,利用热塑性聚氨酯树脂与玻璃纤维布复合形成模压板,两者间形成均匀连续相,赋予模压板以优良性能,易加工型、可重复利用性,使得模压板成为了手机外壳、笔记本电脑等电子产品外壳的主要耗材。目前市场上常见的模压板大多是以环氧树脂为主体的,但是环氧树脂弹性模量较差,分子设计性较弱。而聚氨酯树脂可以通过控制调节硬段和软段,从而获得不同的力学性能的聚氨酯树脂。
但是,聚氨酯模压板由于其亲水性基团较多,使得耐水性较差、强度低,极大的限制了其应用。一般采用大多使用石墨烯、碳纳米管等无机材料来增强力学强度,极少使用有机粒子。但是石墨烯等无机材料的添加,由于分散性不佳会降低浸胶液的稳定性,影响浸胶液在玻璃纤维布上的粘结性,且无机填料的增加会显著增加聚氨酯膜压板的表面粗糙度,影响产品美观。
因此,解决上述问题,制备一种高强度耐湿聚氨酯模压板具有重要意义。
发明内容
本发明的目的在于提供一种高强度耐湿聚氨酯模压板及其制备方法,以解决上述背景技术中提出的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种高强度耐湿聚氨酯模压板,所述聚氨酯模压板是由多个预浸料热轧得到的;所述预浸料包括玻璃纤维布和树脂浸胶液;所述树脂浸胶液的原料包括以下组分:按重量计,聚氨酯树脂100~125份、丙酮30~50份、固化剂5~10份、呋喃化聚多巴胺粒子6~8份。
较为优化地,所述呋喃化聚多巴胺粒子的平均粒径为80~200nm。
较为优化地,所述聚氨酯树脂的原料包括以下组分:按重量计,异氟尔酮二异氰酸酯28~35份、聚酯多元醇32~45份、瓜尔胶/聚二甲基硅氧烷8~12份、扩链剂8~15份。
较为优化地,所述瓜尔胶/聚二甲基硅氧烷的原材料包括以下组分:按重量计,异氰酸酯15~22份、氨基瓜尔胶22~32份、氨基聚二甲基硅氧烷30~45份。
较为优化地,所述扩链剂为N-(2-羟乙基)马来酰亚胺。
较为优化地,一种高强度耐湿聚氨酯模压板的制备方法,包括以下步骤:
步骤1:玻璃纤维布的预处理:将玻璃纤维布置于酸液中,洗涤干燥,得到预处理玻璃纤维布;
步骤2:将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布的两面,持续干燥,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,热轧,后固化得到模压板。
较为优化地,
步骤1:玻璃纤维布的预处理:将玻璃纤维布置于0.2~0.6mol/L的硫酸溶液中浸渍1~2小时,洗涤干燥,得到预处理玻璃纤维布;
步骤2:将聚氨酯树脂溶于丙酮中,加入呋喃化聚多巴胺粒子,搅拌混合30~40分钟,加入固化剂继续搅拌30~40分钟;得到树脂浸胶液;将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布两面,设置涂布速度为5~8m/min,在温度为80~100℃下持续干燥6~8小时,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,设置温度为160~210℃,压力为20~30kgf/cm2,时间为5~10分钟,热轧,后固化得到模压板。
较为优化地,所述呋喃化聚多巴胺粒子的制备方式为:将体积比为(35~38):(1~1.2):(15~18)的乙醇、氢氧化铵、去离子水混合搅拌10~20分钟,得到混合溶剂;将盐酸多巴胺溶解在去离子水中,得到25~50g/L的多巴胺溶液,将其以喷雾的方式射入混合溶剂中,搅拌24小时,离心分离,洗涤过滤干燥,得到聚多巴胺纳米粒子;将其分散在乙醇中,形成悬浮液,滴加三乙胺,调节pH=8.8~9.2,设置温度为58~65℃,滴加呋喃硫醇,反应8~10小时,过滤洗涤干燥,得到呋喃化聚多巴胺粒子。
较为优化地,聚氨酯树脂的制备方法为:将异氟尔酮二异氰酸脂、聚己内酯二醇和2,2-二羟甲基丁酸依次加入反应釜中,氮气氛围下,设置温度为80~82℃,反应2~3小时;加入瓜尔胶/聚二甲基硅氧烷,继续反应1~2小时;冷却至75~78℃,加入N-(2-羟乙基)马来酰亚胺、催化剂、甲乙酮,继续反应3~4小时扩链;冷却至38~45℃,加入三乙胺中和,过滤洗涤,得到聚氨酯树脂。
较为优化地,所述瓜尔胶/聚二甲基硅氧烷的制备方法为:将氨基聚二甲基硅氧烷、异氰酸酯、氨基瓜尔胶分别溶于丙酮溶剂中,得到15~20g/L的、30~40g/L的和10~15g/L的瓜尔胶溶液;将异氰酸酯溶液和氨基聚二甲基硅氧烷溶液混合均质20~40秒,得到混合溶液;将其滴入瓜尔胶溶液中,滴加时间为1~3小时,滴加结束后继续搅拌3~8分钟,得到瓜尔胶/聚二甲基硅氧烷。
本技术方案中,以玻璃纤维布为增强材料,将树脂浸胶液涂覆在玻璃纤维布的两面,初固化得到预浸料,再将多个预浸料在高温下热轧,得到模压板。利用设计制备的聚氨酯树脂、呋喃化聚多巴胺粒子协同增加模压板的耐湿性和强度。
第一,设计制备了聚氨酯树脂,聚氨酯通常含有羧基的硬段和氨基的软缎,而聚氨酯的耐水性取决于软缎的类型和亲水基的分布。常用于聚氨酯软缎改性的物质为疏水性的端羟基聚二甲基硅氧烷,但是该物质在改性过程中相容性差,从而分布不均匀,使得聚氨酯力学能力降低;同时该物质极易向聚氨酯表面迁移,影响其分散性,从而使得聚氨酯胶液产生不稳定性。因此,方案中利用异氰酸酯是强氢供体和受体,通过异氰酸基与氨基聚二甲基硅氧烷和氨基瓜尔多胶中氨基之间反应,得到瓜尔胶/聚二甲基硅氧烷,并以其为聚氨酯的内交联剂,利用瓜尔胶/聚二甲基硅氧烷链断中酯基与聚氨酯树脂原料中其他物质酯基的亲和性,利用分子链中残留的异氰酸基与聚氨酯树脂中的软段氨基反应、分子链中氨基与聚氨酯树脂中异氰酸基反应,通过亲和性和反应性,以此,增强聚二甲基硅氧烷的相容性,具体过程:由于瓜尔胶中羟基与聚氨酯原料中异氰酸盐可以形成更多的聚氨酯键,从而增加了聚氨酯树脂内部的交联度,抑制了吸水链断的膨胀,从而提高了耐湿性,也以此抑制了聚二甲基硅氧烷链断的迁移。需要说明的是,该物质的加入量不易过多,因为氨基与羧基之间会形成不稳定的氢键,会造成过度交联,扰乱分子排序,从而降低抗拉强度。
另外,以N-(2-羟乙基)马来酰亚胺作为扩链剂,形成聚氨酯的封端,与呋喃化聚多巴胺粒子反应,增加模压板强度。
第二,多巴胺是一种具有优异防水粘结力的粘合剂,将其加入在聚氨酯胶液中,可以增加其与玻璃纤维布的粘合力。且本方案中,制备了聚多巴胺粒子,并对其表面进行了改性,得到呋喃化聚多巴胺粒子,增加模压板的力学性能和耐湿性。
制备过程中以氮气喷雾的形式将盐酸多巴胺注入混合溶剂中,增加反应作用力,降低聚多巴胺粒子的粒径。从而在树脂浸胶液中更好的分散。该粒子增加了固化过程中的交联点,与氨酯树脂网络间有表面相互作用,从而抑制了聚合物链的迁移,增强了抗拉强度和耐热性;抑制了聚氨酯网络吸水降解,从而增强了耐湿性。具体:该粒子由于表面的呋喃环,与聚氨酯树脂中的马来酰胺在高温下会产生环加成反应,显著增加了树脂浸胶液固化使得交联度。从而显著增加模压板的强度和耐湿性。同时,也因为改性之后的反应性,形成了优异的相容性,提高了树脂胶液的粘聚力,获得了更高的强度。
与现有技术相比,本发明所达到的有益效果是:(1)制备了瓜尔胶/聚二甲基硅氧烷作为聚氨酯树脂的内交联剂,利用亲和性和反应性,增强聚二甲基硅氧烷的相容性,抑制迁移;利用反应增加交联度,瓜尔胶与聚二甲基硅氧烷协同提高了聚氨酯树脂的抗拉强度和耐湿性;(2)利用以N-(2-羟乙基)马来酰亚胺作为聚氨酯树脂的扩链剂,与呋喃化聚多巴胺粒子在高温固化过程中产生环加成反应,增加聚氨酯树脂之间的交联度,从而显著增加模压板的强度和耐湿性。(3)通过喷雾法制备粒径较小的聚多巴胺粒子,并通过表面呋喃化,以此增加呋喃化聚多巴胺粒子在树脂浸胶液中的分散性,保证树脂浸胶液的稳定性。
具体实施方式
下面将对本发明实施例中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,都属于本发明保护的范围。
实施例1:
步骤1:玻璃纤维布的预处理:将玻璃纤维布置于0.4mol/L的硫酸溶液中浸渍1~2小时,洗涤干燥,得到预处理玻璃纤维布;
步骤2:
(1)将乙醇、氢氧化铵、去离子水混合搅拌15分钟,体积比为36:1.1:16;将盐酸多巴胺溶解在去离子水中,得到30g/L的溶液,将喷雾的方式射入混合溶剂中,搅拌24小时,离心分离,洗涤过滤干燥,得到聚多巴胺纳米粒子;将其分散在乙醇中,形成悬浮液,滴加三乙胺,调节pH=9,设置温度为60℃,滴加呋喃硫醇,反应9小时,过滤洗涤干燥,得到呋喃化聚多巴胺粒子;
(2)将氨基聚二甲基硅氧烷、异氰酸酯、氨基瓜尔胶分别溶于丙酮溶剂中,得到18g/L的、35g/L的和12g/L的瓜尔胶溶液;将异氰酸酯溶液和氨基聚二甲基硅氧烷溶液混合均质30秒,得到混合溶液;将其滴入瓜尔胶溶液中,滴加时间为1.5小时,滴加结束后继续搅拌5分钟,得到瓜尔胶/聚二甲基硅氧烷,备用;将异氟尔酮二异氰酸脂、聚己内酯二醇和2,2-二羟甲基丁酸依次加入反应釜中,氮气氛围下,设置温度为81℃,反,2.5小时;加入瓜尔胶/聚二甲基硅氧烷,继续反应1.5小时;冷却至76℃,加入N-(2-羟乙基)马来酰亚胺、催化剂、甲乙酮,继续反应3.5小时扩链;冷却至40℃,加入三乙胺中和,过滤洗涤,得到聚氨酯树脂。
(3)将聚氨酯树脂溶于丙酮中,加入呋喃化聚多巴胺粒子,搅拌混合35分钟,加入固化剂继续搅拌35分钟;得到树脂浸胶液;
(4)将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布两面,设置涂布速度为6m/min,在温度为90℃下持续干燥7小时,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,设置温度为180℃,压力为25kgf/cm2,热轧时间为8分钟,热轧,后固化得到模压板。
本实施例中,所述聚氨酯模压板的原料包括以下组分:按重量百分比,玻璃纤维布65%、树脂浸胶液35%;所述树脂浸胶液的原料包括以下组分:按重量计,聚氨酯树脂110份、丙酮42份、异氰酸酯固化剂6份、呋喃化聚多巴胺粒子7份;所述聚氨酯树脂的原料包括以下组分:按重量计,异氟尔酮二异氰酸酯31份、聚酯多元醇36份、瓜尔胶/聚二甲基硅氧烷10份、N-(2-羟乙基)马来酰亚胺12份;所述瓜尔胶/聚二甲基硅氧烷的原材料包括以下组分:按重量计,异氰酸酯18份、氨基瓜尔胶28份、氨基聚二甲基硅氧烷40份;所述呋喃化聚多巴胺粒子的平均粒径为92nm。
实施例2:
步骤1:玻璃纤维布的预处理:将玻璃纤维布置于0.2mol/L的硫酸溶液中浸渍1小时,洗涤干燥,得到预处理玻璃纤维布;
步骤2:
(1)将乙醇、氢氧化铵、去离子水混合搅拌10分钟,体积比为35:1:15;将盐酸多巴胺溶解在去离子水中,得到25g/L的溶液,将喷雾的方式射入混合溶剂中,搅拌24小时,离心分离,洗涤过滤干燥,得到聚多巴胺纳米粒子;将其分散在乙醇中,形成悬浮液,滴加三乙胺,调节pH=8.8,设置温度为58℃,滴加呋喃硫醇,反应8小时,过滤洗涤干燥,得到呋喃化聚多巴胺粒子;
(2)将氨基聚二甲基硅氧烷、异氰酸酯、氨基瓜尔胶分别溶于丙酮溶剂中,得到15g/L的、30g/L的和10g/L的瓜尔胶溶液;将异氰酸酯溶液和氨基聚二甲基硅氧烷溶液混合均质20秒,得到混合溶液;将其滴入瓜尔胶溶液中,滴加时间为小时,滴加结束后继续搅拌3分钟,得到瓜尔胶/聚二甲基硅氧烷,备用;将异氟尔酮二异氰酸脂、聚己内酯二醇和2,2-二羟甲基丁酸依次加入反应釜中,氮气氛围下,设置温度为80℃,反应2小时;加入瓜尔胶/聚二甲基硅氧烷,继续反应1小时;冷却至75℃,加入N-(2-羟乙基)马来酰亚胺、催化剂、甲乙酮,继续反应3小时扩链;冷却至38℃,加入三乙胺中和,过滤洗涤,得到聚氨酯树脂。
(3)将聚氨酯树脂溶于丙酮中,加入呋喃化聚多巴胺粒子,搅拌混合30分钟,加入固化剂继续搅拌30分钟;得到树脂浸胶液;
(4)将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布两面,设置涂布速度为8m/min,在温度为80℃下持续干燥6小时,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,设置温度为160℃,压力为20kgf/cm2,热轧时间为10分钟,热轧,后固化得到模压板。
本实施例中,所述聚氨酯模压板的原料包括以下组分:按重量百分比,玻璃纤维布60%、树脂浸胶液40%;所述树脂浸胶液的原料包括以下组分:按重量计,聚氨酯树脂100份、丙酮30份、异氰酸酯固化剂5份、呋喃化聚多巴胺粒子6份;所述聚氨酯树脂的原料包括以下组分:按重量计,异氟尔酮二异氰酸酯28份、聚酯多元醇32份、瓜尔胶/聚二甲基硅氧烷8份、N-(2-羟乙基)马来酰亚胺8份;所述瓜尔胶/聚二甲基硅氧烷的原材料包括以下组分:按重量计,异氰酸酯15份、氨基瓜尔胶22份、氨基聚二甲基硅氧烷30份;所述呋喃化聚多巴胺粒子的平均粒径为80nm。
实施例3:步骤1:玻璃纤维布的预处理:将玻璃纤维布置于0.6mol/L的硫酸溶液中浸渍1~2小时,洗涤干燥,得到预处理玻璃纤维布;
步骤2:
(1)将乙醇、氢氧化铵、去离子水混合搅拌20分钟,体积比为38:1.2:18;将盐酸多巴胺溶解在去离子水中,得到25~50g/L的溶液,将喷雾的方式射入混合溶剂中,搅拌24小时,离心分离,洗涤过滤干燥,得到聚多巴胺纳米粒子;将其分散在乙醇中,形成悬浮液,滴加三乙胺,调节pH=9.2,设置温度为65℃,滴加呋喃硫醇,反应10小时,过滤洗涤干燥,得到呋喃化聚多巴胺粒子;
(2)将氨基聚二甲基硅氧烷、异氰酸酯、氨基瓜尔胶分别溶于丙酮溶剂中,得到20g/L的、40g/L的和115g/L的瓜尔胶溶液;将异氰酸酯溶液和氨基聚二甲基硅氧烷溶液混合均质40秒,得到混合溶液;将其滴入瓜尔胶溶液中,滴加时间为3小时,滴加结束后继续搅拌8分钟,得到瓜尔胶/聚二甲基硅氧烷,备用;将异氟尔酮二异氰酸脂、聚己内酯二醇和2,2-二羟甲基丁酸依次加入反应釜中,氮气氛围下,设置温度为82℃,反应3小时;加入瓜尔胶/聚二甲基硅氧烷,继续反应2小时;冷却至78℃,加入N-(2-羟乙基)马来酰亚胺、催化剂、甲乙酮,继续反应4小时扩链;冷却至45℃,加入三乙胺中和,过滤洗涤,得到聚氨酯树脂。
(3)将聚氨酯树脂溶于丙酮中,加入呋喃化聚多巴胺粒子,搅拌混合40分钟,加入固化剂继续搅拌40分钟;得到树脂浸胶液;
(4)将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布两面,设置涂布速度为5m/min,在温度为100℃下持续干燥8小时,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,设置温度为210℃,压力为30kgf/cm2,热轧时间为5分钟,热轧,后固化得到模压板。
本实施例中,所述聚氨酯模压板的原料包括以下组分:按重量百分比,玻璃纤维布70%、树脂浸胶液30%;所述树脂浸胶液的原料包括以下组分:按重量计,聚氨酯树脂125份、丙酮50份、异氰酸酯固化剂10份、呋喃化聚多巴胺粒子8份;所述聚氨酯树脂的原料包括以下组分:按重量计,异氟尔酮二异氰酸酯35份、聚酯多元醇45份、瓜尔胶/聚二甲基硅氧烷12份、N-(2-羟乙基)马来酰亚胺15份;所述瓜尔胶/聚二甲基硅氧烷的原材料包括以下组分:按重量计,异氰酸酯22份、氨基瓜尔胶32份、氨基聚二甲基硅氧烷45份;所述呋喃化聚多巴胺粒子的平均粒径为200nm。
实施例4:不加入瓜尔胶/聚二甲基硅氧烷;将氨基瓜尔胶与氨基聚二甲基硅氧烷直接加入;其余与实施例1相同。
本实施例中,所述聚氨酯树脂的原料包括以下组分:按重量计,异氟尔酮二异氰酸酯31份、聚酯多元醇36份、氨基瓜尔胶4份、氨基聚二甲基硅氧烷6份、N-(2-羟乙基)马来酰亚胺12份。
实施例5:不加入瓜尔胶;其余与实施例1相同;
实施例6:将扩链剂N-(2-羟乙基)马来酰亚胺替换为1,4-二丁醇;其余与实施例1相同;
实施例7:不加入呋喃化聚多巴胺粒子;其余与实施例1相同;
实施例8:不对聚多巴胺粒子呋喃化,直接用聚多巴胺粒子,其余与实施例1相同;
实验:取实施例1~8制备的一种高强度耐湿聚氨酯模压板裁剪成8cm×8cm的正方形,(1)采用GB/T528-1992标准测试方法,采用万能材料实验机测试拉伸强度(MPa)和弯曲模量(GPa);(2)将浸泡前的聚氨酯模压板称重计为m1;将其常温浸泡在蒸馏水中7天,取出后表面水分用吸水纸除去称重计为m2,吸湿率=(m2-m1)/m1×100%,所得结果如下表所示:
Figure BDA0003090222420000081
结论:对比实施例1~3的数据可以看出,所制备的聚氨酯模压板的拉上强度均在350MPa以上,弯曲模量均在16GPa以上,吸湿率小于1%,具有良好的耐湿性。
对比实施例4的数据可以发现,力学性能下降,原因是:将氨基瓜尔胶与氨基聚二甲基硅氧烷直接加入,使得聚二甲基硅氧烷的迁移不能被抑制,从而相容性差,使得力学性能下降;且由于聚二甲基硅氧烷不被锚固在聚氨酯内部交联网络中,降低了内部的溶胀,增加了吸湿率。在对比实施例5的数据,可以发现,力学性能大幅下降,吸湿率上升明显,原因是:由于瓜尔胶中羟基与聚氨酯原料中异氰酸盐可以形成更多的聚氨酯键,从而增加了聚氨酯树脂内部的交联度,抑制了吸水链断的膨胀,从而提高了耐湿性,也以此抑制了聚二甲基硅氧烷链断的迁移。两种物质间存在协同作用。
同样的,对比实施例6-8的数据可以发现,力学性能下降,吸湿率上升。原因是:聚多巴胺粒子是防水性粘合剂多巴胺所制备的,将其加入在聚氨酯胶液中,可以增加其与玻璃纤维布的粘合力,与聚氨酯树脂间有作用力,可以增加力学性能。同时利用以N-(2-羟乙基)马来酰亚胺作为聚氨酯树脂的扩链剂,与呋喃化聚多巴胺粒子在高温固化过程中产生环加成反应,增加聚氨酯树脂之间的交联度,从而显著增加模压板的强度和耐湿性。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (6)

1.一种高强度耐湿聚氨酯模压板,其特征在于:所述聚氨酯模压板是由多个预浸料热轧得到的;所述预浸料包括玻璃纤维布和树脂浸胶液;所述树脂浸胶液的原料包括以下组分:按重量计,聚氨酯树脂100~125份、丙酮30~50份、固化剂5~10份、呋喃化聚多巴胺粒子6~8份;
所述聚氨酯树脂的制备方法为:将异氟尔酮二异氰酸脂、聚己内酯二醇和2,2-二羟甲基丁酸依次加入反应釜中,氮气氛围下,设置温度为80~82℃,反应2~3小时;加入瓜尔胶/聚二甲基硅氧烷,继续反应1~2小时;冷却至75~78℃,加入N-(2-羟乙基)马来酰亚胺、催化剂、甲乙酮,继续反应3~4小时扩链;冷却至38~45℃,加入三乙胺中和,过滤洗涤,得到聚氨酯树脂;
所述瓜尔胶/聚二甲基硅氧烷的制备方法为:将氨基聚二甲基硅氧烷、异氰酸酯、氨基瓜尔胶分别溶于丙酮溶剂中,得到15~20g/L、30~40g/L和10~15g/L的溶液;将异氰酸酯溶液和氨基聚二甲基硅氧烷溶液混合均质20~40秒,得到混合溶液;将其滴入瓜尔胶溶液中,滴加时间为1~3小时,滴加结束后继续搅拌3~8分钟,得到瓜尔胶/聚二甲基硅氧烷;
所述呋喃化聚多巴胺粒子的制备方式为:将体积比为(35~38):(1~1.2):(15~18)的乙醇、氢氧化铵、去离子水混合搅拌10~20分钟,得到混合溶剂;将盐酸多巴胺溶解在去离子水中,得到25~50g/L的多巴胺溶液,将其以喷雾的方式射入混合溶剂中,搅拌24小时,离心分离,洗涤过滤干燥,得到聚多巴胺纳米粒子;将其分散在乙醇中,形成悬浮液,滴加三乙胺,调节pH=8.8~9.2,设置温度为58~65℃,滴加呋喃硫醇,反应8~10小时,过滤洗涤干燥,得到呋喃化聚多巴胺粒子。
2.根据权利要求1所述的一种高强度耐湿聚氨酯模压板,其特征在于:所述呋喃化聚多巴胺粒子的平均粒径为80~200nm。
3.根据权利要求1所述的一种高强度耐湿聚氨酯模压板,其特征在于:所述聚氨酯树脂的原料包括以下组分:按重量计,异氟尔酮二异氰酸酯28~35份、聚酯多元醇32~45份、瓜尔胶/聚二甲基硅氧烷8~12份、扩链剂8~15份。
4.根据权利要求3所述的一种高强度耐湿聚氨酯模压板,其特征在于:所述瓜尔胶/聚二甲基硅氧烷的原材料包括以下组分:按重量计,异氰酸酯15~22份、氨基瓜尔胶22~32份、氨基聚二甲基硅氧烷30~45份。
5.根据权利要求1所述的一种高强度耐湿聚氨酯模压板,其特征在于:所述聚氨酯模压板的制备方法包括以下步骤:
步骤1:玻璃纤维布的预处理:将玻璃纤维布置于酸液中,洗涤干燥,得到预处理玻璃纤维布;
步骤2:将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布的两面,持续干燥,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,热轧,后固化得到模压板。
6.根据权利要求5所述的一种高强度耐湿聚氨酯模压板,其特征在于:包括以下步骤:
步骤1:玻璃纤维布的预处理:将玻璃纤维布置于0.2~0.6mol/L的硫酸溶液中浸渍1~2小时,洗涤干燥,得到预处理玻璃纤维布;
步骤2:将聚氨酯树脂溶于丙酮中,加入呋喃化聚多巴胺粒子,搅拌混合30~40分钟,加入固化剂继续搅拌30~40分钟;得到树脂浸胶液;将预处理玻璃纤维布置于涂布机上,将树脂浸胶液均匀涂覆在预处理玻璃纤维布两面,设置涂布速度为5~8m/min,在温度为80~100℃下持续干燥6~8小时,初固化得到预浸料;
步骤3:将至少一层的预浸料叠加置于热压辊中,设置温度为160~210℃,压力为20~30kgf/cm2,时间为5~10分钟,热轧,后固化得到模压板。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031783A (ja) * 1999-05-14 2001-02-06 Toray Ind Inc プリプレグ及び繊維強化複合材料
EP1642620A1 (fr) * 2004-10-04 2006-04-05 L'oreal, S.A. Composition cosmétique capillaire à base de particules creuses et de polyuréthane fixant siliconé
CN101076562A (zh) * 2004-10-11 2007-11-21 拜尔材料科学股份公司 玻璃纤维增强的聚合物组合物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031783A (ja) * 1999-05-14 2001-02-06 Toray Ind Inc プリプレグ及び繊維強化複合材料
EP1642620A1 (fr) * 2004-10-04 2006-04-05 L'oreal, S.A. Composition cosmétique capillaire à base de particules creuses et de polyuréthane fixant siliconé
CN101076562A (zh) * 2004-10-11 2007-11-21 拜尔材料科学股份公司 玻璃纤维增强的聚合物组合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
聚氨酯R-RIM中的增强材料及其增强效果;薛建;《聚氨酯工业》(第02期);3-10 *

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