CN113897032A - 一种用于纤维缠绕的环氧树脂复合材料及其制备方法 - Google Patents

一种用于纤维缠绕的环氧树脂复合材料及其制备方法 Download PDF

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CN113897032A
CN113897032A CN202111107354.2A CN202111107354A CN113897032A CN 113897032 A CN113897032 A CN 113897032A CN 202111107354 A CN202111107354 A CN 202111107354A CN 113897032 A CN113897032 A CN 113897032A
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epoxy resin
composite material
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resin composite
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林文丹
李刚
黄必文
郑斯祥
邓辉尧
邱诗砚
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Shanxi Yude New Materials Technology Co ltd
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Abstract

本发明提供一种用于纤维缠绕的环氧树脂复合材料及其制备方法,以双酚A型环氧树脂为主要基体树脂,辅以增韧型环氧树脂和浸润助剂提高复合材料的韧性、耐冲击性和界面结合力;同时,添加相应的活性稀释剂、固化剂、促进剂、疏水改性纳米填料等原料调整复合材料的粘度、可操作时间,以及耐热性等性能,获得了综合性能优良的用于纤维缠绕的环氧树脂复合材料,所述制备方法和施工方法简单,安全高效,能够满足工业生产的需要。

Description

一种用于纤维缠绕的环氧树脂复合材料及其制备方法
技术领域
本发明属于先进复合材料技术领域,特别涉及一种用于纤维缠绕的环氧树脂复合材料及其制备方法。
背景技术
纤维缠绕成型技术是在控制纤维张力和预定线型的条件下,将浸渍树脂胶液的连续纤维粗纱、编织物或纤维预浸带,往复缠绕在相应的芯模或内衬上,再固化制成一定形状的制品的方法,具有产品精度高、原材料浪费少、耐高温、耐摩擦、高比强、高比模等的性能优势,在航空航天、石油化工、汽车领域具有广泛的应用。
纤维缠绕成型技术常用的纤维材料主要有玻璃纤维、碳纤维、芳纶纤维等,相较于玻璃纤维和碳纤维而言,芳纶纤维具有相对密度小、高模量、耐剪切、高韧性等优异性能,但是,芳纶纤维表面与树脂的相容性差,复合材料界面性能比碳纤维和玻璃纤维低,导致层间剪切强度差,无法满足高力学性能的需求。
纤维缠绕成型技术常用的基体树脂为环氧树脂,环氧树脂具有力学性能高、粘接性能优异、固化收缩率小、耐化学腐蚀性等优点,是高性能树脂基复合材料优先考虑的基体树脂。然而,环氧树脂固化物性脆,韧性和耐冲击性能较差,通常需引入增韧剂调节体系韧性,但增韧剂的加入会影响基体力学性能并导致模量下降,难以实现模量与韧性的兼顾;同时,随着纤维复合材料应用的发展,对环氧树脂基体及其复合材料的性能,例如韧性、强度、界面性能、耐热性等都提出了更高的要求。
与此同时,纤维缠绕成型技术对复合材料的粘度、浸润性和可操作时间具有较高的要求,如果复合材料在缠绕温度下粘度过高,或粘度增长过快,对纤维的浸润性会变差,导致复合材料与纤维的界面结合力较差,制备的产品难以拥有良好的性能。目前,研究如何制备一种粘度适中、可操作时间长、界面结合力高、耐热性以及耐冲击性的用于纤维缠绕的环氧树脂基复合材料仍然是该领域需要突破的技术重点。
发明内容
为了克服现有技术的不足,本发明提供了一种用于纤维缠绕的环氧树脂复合材料及其制备方法,以双酚A型环氧树脂为主要基体树脂,辅以增韧型环氧树脂和浸润助剂提高复合材料的韧性、耐冲击性和界面结合力,同时,添加相应的活性稀释剂、固化剂、促进剂、疏水改性纳米填料等原料调整复合材料的粘度、可操作时间,以及耐热性等性能,获得了综合性能优良的用于纤维缠绕的环氧树脂复合材料。
为了实现上述目的,本发明采用如下的技术方案,一种用于纤维缠绕的环氧树脂复合材料,包括A组分和B组分,所述A组分和B组分的质量比是100:20-30,其中,所述A组分包括以下重量份的原料:双酚A型环氧树脂100份,增韧型环氧树脂15-25份,浸润助剂10-20份,活性稀释剂40-60份,疏水改性纳米填料2-5份,偶联剂0-2份,消泡剂1-3份;
所述B组分包括以下重量份的原料:潜伏型固化剂20-30份,促进剂3-6份,润湿分散剂1-3份。
所述双酚A型环氧树脂的环氧当量为320-360g/eq,粘度为6000-8000cps;
所述增韧型环氧树脂是重均分子量为3000-5000g/mol的互穿网络结构的高分子树脂,其制备方法包括以下步骤:
(1)按照重量比1:5-6称取端羟基硅油和端羟基聚醚混合均匀,接着加入端羟基硅油和端羟基聚醚总质量1-2倍的有机溶剂N,N-二乙基乙酰胺混合均匀后得到混合溶液;
(2)按照羟基/NCO的摩尔比1:1.05-1.1称取二异氰酸酯,加热至70-80℃后,缓慢滴加步骤(1)制备得到的混合溶液,5-6h内滴完后,继续保温反应10-12h后,减压蒸馏除去溶剂以及未反应的二异氰酸酯,得到异氰酸酯封端的预聚物;
(3)将步骤(2)得到的异氰酸酯封端的预聚物与呋喃基改性环氧树脂按照环氧基/NCO的摩尔比1.1-1.2:1的比例混合均匀后,升温至70-80℃反应6-8h后,得到增韧型环氧树脂。
所述二异氰酸酯为芳族二异氰酸酯,选自二苯甲烷二异氰酸酯、甲苯二异氰酸酯、二甲基联苯二异氰酸酯的至少一种。
所述浸润助剂是重均分子量为400-600g/mol的聚合物,其通过端环氧基烯丙基聚醚与硅烷偶联剂通过硅氢反应制备而成,所述硅烷偶联剂为三乙氧基硅烷,三甲氧基硅烷的一种。
所述活性稀释剂为双官能环氧化合物,选自丁二醇二缩水甘油醚、己二醇二缩水甘油醚、乙二醇二缩水甘油醚、环己二醇二缩水甘油醚、新戊二醇二缩水甘油醚、二氧化环己烯乙烯、或二氧化双环戊二烯的至少一种;
所述疏水改性纳米填料的粒径为100-150nm,选自二氧化硅、二氧化钛、碳纳米管、石墨烯、碳酸钙的至少一种;所述疏水改性纳米填料是通过将纳米填料经过硅烷偶联剂混合改性制备而成的。
所述偶联剂选自硅烷偶联剂、钛酸酯偶联剂或铝酸酯偶联剂至少一种;
所述潜伏型固化剂为咪唑类潜伏型固化剂,选自1-氰乙基-2-乙基-4-甲基咪唑,2-十一烷基咪唑、2-十七烷基咪唑、1,3-二苯基-2甲基咪唑的氯化物的至少一种;
所述促进剂为乙酰丙酮铝或乙酰丙酮铬的一种。
本发明的另一个目的在于提供一种用于纤维缠绕的环氧树脂复合材料的制备方法,包括以下步骤:
(1)按照重量比将双酚A型环氧树脂、活性稀释剂、偶联剂和疏水改性纳米填料混合均匀,升温至30-40℃后,加入增韧型环氧树脂、浸润助剂和消泡剂,搅拌10-20min得到A组分;
(2)按照重量比将潜伏型固化剂、促进剂和润湿分散剂混合均匀后得到B组分,
(3)按照重量比将A组分和B组分混合均匀,得到用于纤维缠绕的环氧树脂复合材料。
本发明的另一个目的在于提供一种用于纤维缠绕的环氧树脂复合材料的施工方法,包括以下步骤:
(1)将用于纤维缠绕的环氧树脂复合材料的A组分和B组分按照重量比混合均匀,通过真空脱泡处理后,升温至40-50℃置于胶槽中,对芳纶纤维进行浸渍缠绕得到制品;
(2)将制品置于烘箱中,以8-10℃/min的升温速率加热至90-100℃,保温60-80min后,再以3-5℃/min的升温速率加热至150-160℃,保温100-150min,即可。
与现有技术相比,本发明具有以下的有益效果:
(1)本发明提供了一种用于纤维缠绕的环氧树脂复合材料及其制备方法,以双酚A型环氧树脂为主要基体树脂,辅以增韧型环氧树脂和浸润助剂提高复合材料的韧性、耐冲击性和界面结合力,同时,添加相应的活性稀释剂、固化剂、促进剂、疏水改性纳米填料等原料调整复合材料的粘度、可操作时间,以及耐热性等性能,获得了综合性能优良的用于纤维缠绕的环氧树脂复合材料。
(2)本发明为了提高环氧树脂复合材料对芳纶纤维的浸润性,添加了具有环氧基和硅氧基的浸润助剂,有利于在树脂基体和芳纶纤维之间提供桥梁作用,且硅氧基具有较低的界面能与芳纶纤维的亲和性较环氧树脂基体强利于复合材料对芳纶纤维的浸润性,使得本发明的环氧树脂复合材料对芳纶纤维的浸润接触角小于45°,同时,所述浸润助剂有助于提高复合材料和纤维的层间剪切强度。
(3)本发明为了克服环氧树脂的脆性和耐冲击性差的缺点,选择添加增韧型环氧树脂和疏水改性纳米填料,二者协同改进了环氧树脂复合材料的韧性,所述增韧型环氧树脂具有特殊的互穿网络结构,且含有柔韧的硅氧基和聚醚链段,与其他组分的相容性高,使得最终的制品具有良好的力学性能和耐热性。
(4)本发明通过添加潜伏型固化剂和促进剂,调整复合材料的可操作时间,使得所述复合材料在40-50℃时具有较为适中的粘度(400-700cps),且在该温度下粘度翻倍的时间超过10h,具有良好的可操作时间。
(5)本发明还通过添加偶联剂、润湿分散剂、消泡剂等常用功能助剂,优化调整环氧树脂复合材料的施工性能,同时,所述制备方法和施工方法简单,安全高效,能够满足工业生产的需要。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为了进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。本发明所有原料,对其来源没有特别限制,在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。
制备例1
一种增韧型环氧树脂I的制备方法,包括以下步骤:
(1)按照重量比1:5称取端羟基硅油和端羟基聚醚混合均匀,接着加入端羟基硅油和端羟基聚醚总质量2倍的有机溶剂N,N-二乙基乙酰胺混合均匀后得到混合溶液;
(2)按照羟基/NCO的摩尔比1:1.05称取二异氰酸酯,加热至75℃后,缓慢滴加步骤(1)制备得到的混合溶液,6h内滴完后,继续保温反应10h后,减压蒸馏除去溶剂以及未反应的二异氰酸酯,得到异氰酸酯封端的预聚物;
(3)将步骤(2)得到的异氰酸酯封端的预聚物与呋喃基改性环氧树脂按照环氧基/NCO的摩尔比1.1:1的比例混合均匀后,升温至80℃反应6h后,得到增韧型环氧树脂I;所述二异氰酸酯为芳族二异氰酸酯,选自二苯甲烷二异氰酸酯;所述增韧型环氧树脂I的重均分子量为3963g/mol。
制备例2
一种增韧型环氧树脂II的制备方法,包括以下步骤:
(1)按照重量比1:6称取端羟基硅油和端羟基聚醚混合均匀,接着加入端羟基硅油和端羟基聚醚总质量1.5倍的有机溶剂N,N-二乙基乙酰胺混合均匀后得到混合溶液;
(2)按照羟基/NCO的摩尔比1:1.1称取二异氰酸酯,加热至80℃后,缓慢滴加步骤(1)制备得到的混合溶液,5h内滴完后,继续保温反应12h后,减压蒸馏除去溶剂以及未反应的二异氰酸酯,得到异氰酸酯封端的预聚物;
(3)将步骤(2)得到的异氰酸酯封端的预聚物与呋喃基改性环氧树脂按照环氧基/NCO的摩尔比1.2:1的比例混合均匀后,升温至70℃反应8h后,得到增韧型环氧树脂II;所述二异氰酸酯为芳族二异氰酸酯,选自甲苯二异氰酸酯;所述增韧型环氧树脂II的重均分子量为4756g/mol。
实施例1
一种用于纤维缠绕的环氧树脂复合材料,包括A组分和B组分,所述A组分和B组分的质量比是100:20,其中,所述A组分包括以下重量份的原料:双酚A型环氧树脂100份,增韧型环氧树脂I 20份,浸润助剂15份,活性稀释剂50份,疏水改性纳米填料3份,偶联剂2份,消泡剂3份;
所述B组分包括以下重量份的原料:潜伏型固化剂30份,促进剂6份,润湿分散剂3份;
所述双酚A型环氧树脂的环氧当量为360g/eq,粘度为7300cps;所述浸润助剂是重均分子量为480g/mol的聚合物,其通过端环氧基烯丙基聚醚与硅烷偶联剂通过硅氢反应制备而成,所述硅烷偶联剂为三乙氧基硅烷的一种;所述活性稀释剂为双官能环氧化合物,选自丁二醇二缩水甘油醚、二氧化双环戊二烯按照重量比1:1的混合物,所述疏水改性纳米填料的粒径为100nm,选自二氧化硅;所述疏水改性纳米填料是通过将纳米填料经过硅烷偶联剂混合改性制备而成的;所述偶联剂选自钛酸酯偶联剂;所述潜伏型固化剂为咪唑类潜伏型固化剂,选自1-氰乙基-2-乙基-4-甲基咪唑;所述促进剂为乙酰丙酮铝。
上述一种用于纤维缠绕的环氧树脂复合材料的制备方法,包括以下步骤:
(1)按照重量比将双酚A型环氧树脂、活性稀释剂、偶联剂和疏水改性纳米填料混合均匀,升温至40℃后,加入增韧型环氧树脂、浸润助剂和消泡剂,搅拌20min得到A组分;
(2)按照重量比将潜伏型固化剂、促进剂和润湿分散剂混合均匀后得到B组分,
(3)按照重量比将A组分和B组分混合均匀,得到用于纤维缠绕的环氧树脂复合材料。
实施例2
一种用于纤维缠绕的环氧树脂复合材料,包括A组分和B组分,所述A组分和B组分的质量比是100:30,其中,所述A组分包括以下重量份的原料:双酚A型环氧树脂100份,增韧型环氧树脂II 22份,浸润助剂18份,活性稀释剂53份,疏水改性纳米填料4份,偶联剂1份,消泡剂3份;
所述B组分包括以下重量份的原料:潜伏型固化剂25份,促进剂4份,润湿分散剂2份;
所述双酚A型环氧树脂的环氧当量为330g/eq,粘度为6809cps;所述浸润助剂是重均分子量为580g/mol的聚合物,其通过端环氧基烯丙基聚醚与硅烷偶联剂通过硅氢反应制备而成,所述硅烷偶联剂为三甲氧基硅烷的一种。
所述活性稀释剂为双官能环氧化合物,选自己二醇二缩水甘油醚、乙二醇二缩水甘油醚按照重量比1:2的混合物,所述疏水改性纳米填料的粒径为140nm,选自碳纳米管;所述疏水改性纳米填料是通过将纳米填料经过硅烷偶联剂混合改性制备而成的;所述偶联剂选自硅烷偶联剂;所述潜伏型固化剂为咪唑类潜伏型固化剂,选自2-十七烷基咪唑;所述促进剂为乙酰丙酮铬;
上述一种用于纤维缠绕的环氧树脂复合材料的制备方法,包括以下步骤:
(1)按照重量比将双酚A型环氧树脂、活性稀释剂、偶联剂和疏水改性纳米填料混合均匀,升温至35℃后,加入增韧型环氧树脂、浸润助剂和消泡剂,搅拌20min得到A组分;
(2)按照重量比将潜伏型固化剂、促进剂和润湿分散剂混合均匀后得到B组分,
(3)按照重量比将A组分和B组分混合均匀,得到用于纤维缠绕的环氧树脂复合材料。
实施例3
一种用于纤维缠绕的环氧树脂复合材料,包括A组分和B组分,所述A组分和B组分的质量比是100:25,其中,所述A组分包括以下重量份的原料:双酚A型环氧树脂100份,增韧型环氧树脂I15份,浸润助剂20份,活性稀释剂60份,疏水改性纳米填料5份,偶联剂2份,消泡剂3份;
所述B组分包括以下重量份的原料:潜伏型固化剂20份,促进剂3份,润湿分散剂3份;
所述双酚A型环氧树脂的环氧当量为348g/eq,粘度为7108cps;所述浸润助剂是重均分子量为465g/mol的聚合物,其通过端环氧基烯丙基聚醚与硅烷偶联剂通过硅氢反应制备而成,所述硅烷偶联剂为三乙氧基硅烷的一种;所述活性稀释剂为双官能环氧化合物,选自乙二醇二缩水甘油醚、新戊二醇二缩水甘油醚、二氧化环己烯乙烯按照重量比1:2:1的混合物;所述疏水改性纳米填料的粒径为130纳米,选自碳酸钙;所述疏水改性纳米填料是通过将纳米填料经过硅烷偶联剂混合改性制备而成的;所述偶联剂选自铝酸酯偶联剂;所述潜伏型固化剂为咪唑类潜伏型固化剂,选自1,3-二苯基-2甲基咪唑的氯化物;所述促进剂为乙酰丙酮铝;
上述一种用于纤维缠绕的环氧树脂复合材料的制备方法,包括以下步骤:
(1)按照重量比将双酚A型环氧树脂、活性稀释剂、偶联剂和疏水改性纳米填料混合均匀,升温至30℃后,加入增韧型环氧树脂、浸润助剂和消泡剂,搅拌20min得到A组分;
(2)按照重量比将潜伏型固化剂、促进剂和润湿分散剂混合均匀后得到B组分,
(3)按照重量比将A组分和B组分混合均匀,得到用于纤维缠绕的环氧树脂复合材料。
实施例4
一种用于纤维缠绕的环氧树脂复合材料,包括A组分和B组分,所述A组分和B组分的质量比是100:28,其中,所述A组分包括以下重量份的原料:双酚A型环氧树脂100份,增韧型环氧树脂II 18份,浸润助剂20份,活性稀释剂50份,疏水改性纳米填料4份,偶联剂1份,消泡剂3份;
所述B组分包括以下重量份的原料:潜伏型固化剂26份,促进剂5份,润湿分散剂2份;
所述双酚A型环氧树脂的环氧当量为352g/eq,粘度为6956cps;所述浸润助剂是重均分子量为508g/mol的聚合物,其通过端环氧基烯丙基聚醚与硅烷偶联剂通过硅氢反应制备而成,所述硅烷偶联剂为三甲氧基硅烷的一种;所述活性稀释剂为双官能环氧化合物,选自丁二醇二缩水甘油醚和新戊二醇二缩水甘油醚按照重量比2:1的混合物;所述疏水改性纳米填料的粒径为150纳米,选自二氧化钛;所述疏水改性纳米填料是通过将纳米填料经过硅烷偶联剂混合改性制备而成的;所述偶联剂选自硅烷偶联剂;所述潜伏型固化剂为咪唑类潜伏型固化剂,选自1-氰乙基-2-乙基-4-甲基咪唑;所述促进剂为乙酰丙酮铬;
上述一种用于纤维缠绕的环氧树脂复合材料的制备方法,包括以下步骤:
(1)按照重量比将双酚A型环氧树脂、活性稀释剂、偶联剂和疏水改性纳米填料混合均匀,升温至40℃后,加入增韧型环氧树脂、浸润助剂和消泡剂,搅拌20min得到A组分;
(2)按照重量比将潜伏型固化剂、促进剂和润湿分散剂混合均匀后得到B组分,
(3)按照重量比将A组分和B组分混合均匀,得到用于纤维缠绕的环氧树脂复合材料。
对比例1
不含增韧型环氧树脂II,双酚A型环氧树脂的重量份为118份,其余组分和配比、以及制备方法与实施例4完全一致。
对比例2
不含疏水改性纳米填料,增韧型环氧树脂II的重量份为22份,其余组分和配比、以及制备方法与实施例4完全一致。
对比例3
添加增韧型环氧树脂III 18份,其余组分和配比、以及制备方法与实施例4完全一致;所述增韧型环氧树脂III的制备方法,包括以下步骤:
(1)按照重量比1:10称取端羟基硅油和端羟基聚醚混合均匀,接着加入端羟基硅油和端羟基聚醚总质量1.5倍的有机溶剂N,N-二乙基乙酰胺混合均匀后得到混合溶液;
(2)按照羟基/NCO的摩尔比1:1.1称取二异氰酸酯,加热至80℃后,缓慢滴加步骤(1)制备得到的混合溶液,5h内滴完后,继续保温反应12h后,减压蒸馏除去溶剂以及未反应的二异氰酸酯,得到异氰酸酯封端的预聚物;
(3)将步骤(2)得到的异氰酸酯封端的预聚物与呋喃基改性环氧树脂按照环氧基/NCO的摩尔比1.2:1的比例混合均匀后,升温至70℃反应8h后,得到增韧型环氧树脂II;所述二异氰酸酯为芳族二异氰酸酯,选自甲苯二异氰酸酯;所述增韧型环氧树脂II的重均分子量为4923g/mol。
对比例4
添加增韧型环氧树脂IV 18份,其余组分和配比、以及制备方法与实施例4完全一致;所述增韧型环氧树脂III的制备方法,包括以下步骤:
(1)按照重量比1:10称取端羟基硅油和端羟基聚醚混合均匀,接着加入端羟基硅油和端羟基聚醚总质量1.5倍的有机溶剂N,N-二乙基乙酰胺混合均匀后得到混合溶液;
(2)按照羟基/NCO的摩尔比1:1.1称取二异氰酸酯,加热至80℃后,缓慢滴加步骤(1)制备得到的混合溶液,5h内滴完后,继续保温反应12h后,减压蒸馏除去溶剂以及未反应的二异氰酸酯,得到异氰酸酯封端的预聚物;
(3)将步骤(2)得到的异氰酸酯封端的预聚物与呋喃基改性环氧树脂按照环氧基/NCO的摩尔比1.2:1的比例混合均匀后,升温至70℃反应8h后,得到增韧型环氧树脂II;所述二异氰酸酯为异佛尔酮二异氰酸酯;所述增韧型环氧树脂II的重均分子量为4789g/mol。
对比例5
不添加浸润助剂,活性稀释剂的重量份为68份,其余组分和配比、以及制备方法与实施例4完全一致。
对比例6
添加浸润助剂I 20份,其余组分和配比、以及制备方法与实施例4完全一致,所述浸润助剂I为端环氧基烯丙基聚醚,重均分子量为487g/mol。
试样制品的制备:将实施例1-4和对比例1-6制备得到的环氧树脂复合材料通过真空脱泡处理后,升温至50℃置于胶槽中,对芳纶纤维进行浸渍缠绕得到制品;将制品置于烘箱中,以10℃/min的升温速率加热至100℃,保温80min后,再以5℃/min的升温速率加热至160℃,保温100min,即可。
测试实施例1-4和对比例1-6制备得到的环氧树脂复合材料的各项性能,测试结果见表1。
表1
Figure BDA0003272983410000091
从表1的试验数据可以发现,本发明提供了一种用于纤维缠绕的环氧树脂复合材料及其制备方法,所述环氧树脂复合材料具有适中的粘度和可操作时间,以及良好的韧性、耐冲击性、力学性能和耐热性;特别注意的是,通过添加了有环氧基和硅氧基的浸润助剂,有利于在树脂基体和芳纶纤维之间提供桥梁作用,提高了复合材料和纤维的层间剪切强度;以及添加了增韧型环氧树脂和疏水改性纳米填料,二者协同改进了环氧树脂复合材料的韧性和耐热性。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。

Claims (10)

1.一种用于纤维缠绕的环氧树脂复合材料,其特征在于:包括A组分和B组分,所述A组分和B组分的质量比是100:20-30,其中,所述A组分包括以下重量份的原料:双酚A型环氧树脂100份,增韧型环氧树脂15-25份,浸润助剂10-20份,活性稀释剂40-60份,疏水改性纳米填料2-5份,偶联剂0-2份,消泡剂1-3份;
所述B组分包括以下重量份的原料:潜伏型固化剂20-30份,促进剂3-6份,润湿分散剂1-3份。
2.根据权利要求1所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述双酚A型环氧树脂的环氧当量为320-360g/eq,粘度为6000-8000cps。
3.根据权利要求1所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述增韧型环氧树脂是重均分子量为3000-5000g/mol的互穿网络结构的高分子树脂,其制备方法包括以下步骤:
(1)按照重量比1:5-6称取端羟基硅油和端羟基聚醚混合均匀,接着加入端羟基硅油和端羟基聚醚总质量1-2倍的有机溶剂N,N-二乙基乙酰胺混合均匀后得到混合溶液;
(2)按照羟基/NCO的摩尔比1:1.05-1.1称取二异氰酸酯,加热至70-80℃后,缓慢滴加步骤(1)制备得到的混合溶液,5-6h内滴完后,继续保温反应10-12h后,减压蒸馏除去溶剂以及未反应的二异氰酸酯,得到异氰酸酯封端的预聚物;
(3)将步骤(2)得到的异氰酸酯封端的预聚物与呋喃基改性环氧树脂按照环氧基/NCO的摩尔比1.1-1.2:1的比例混合均匀后,升温至70-80℃反应6-8h后,得到增韧型环氧树脂。
4.根据权利要求3所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述二异氰酸酯为芳族二异氰酸酯,选自二苯甲烷二异氰酸酯、甲苯二异氰酸酯、二甲基联苯二异氰酸酯的至少一种。
5.根据权利要求1所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述浸润助剂是重均分子量为400-600g/mol的聚合物,其通过端环氧基烯丙基聚醚与硅烷偶联剂通过硅氢反应制备而成,所述硅烷偶联剂为三乙氧基硅烷,三甲氧基硅烷的一种。
6.根据权利要求1所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述活性稀释剂为双官能环氧化合物,选自丁二醇二缩水甘油醚、己二醇二缩水甘油醚、乙二醇二缩水甘油醚、环己二醇二缩水甘油醚、新戊二醇二缩水甘油醚、二氧化环己烯乙烯、或二氧化双环戊二烯的至少一种。
7.根据权利要求1所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述疏水改性纳米填料的粒径为100-150nm,选自二氧化硅、二氧化钛、碳纳米管、石墨烯、碳酸钙的至少一种;所述疏水改性纳米填料是通过将纳米填料经过硅烷偶联剂混合改性制备而成的。
8.根据权利要求1所述的一种用于纤维缠绕的环氧树脂复合材料,其特征在于:所述潜伏型固化剂为咪唑类潜伏型固化剂,选自1-氰乙基-2-乙基-4-甲基咪唑,2-十一烷基咪唑、2-十七烷基咪唑、1,3-二苯基-2甲基咪唑的氯化物的至少一种;所述促进剂为乙酰丙酮铝或乙酰丙酮铬的一种。
9.权利要求1-8所述的用于纤维缠绕的环氧树脂复合材料的制备方法,其特征在于:包括以下步骤:
(1)按照重量比将双酚A型环氧树脂、活性稀释剂、偶联剂和疏水改性纳米填料混合均匀,升温至30-40℃后,加入增韧型环氧树脂、浸润助剂和消泡剂,搅拌10-20min得到A组分;
(2)按照重量比将潜伏型固化剂、促进剂和润湿分散剂混合均匀后得到B组分,
(3)按照重量比将A组分和B组分混合均匀,得到用于纤维缠绕的环氧树脂复合材料。
10.权利要求1-8所述的用于纤维缠绕的环氧树脂复合材料的施工方法,其特征在于:包括以下步骤:
(1)将用于纤维缠绕的环氧树脂复合材料的A组分和B组分按照重量比混合均匀,通过真空脱泡处理后,升温至40-50℃置于胶槽中,对芳纶纤维进行浸渍缠绕得到制品;
(2)将制品置于烘箱中,以8-10℃/min的升温速率加热至90-100℃,保温60-80min后,再以3-5℃/min的升温速率加热至150-160℃,保温100-150min,即可。
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