CN113912985A - 一种高强高模环氧模塑料及其制备方法 - Google Patents

一种高强高模环氧模塑料及其制备方法 Download PDF

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CN113912985A
CN113912985A CN202111368108.2A CN202111368108A CN113912985A CN 113912985 A CN113912985 A CN 113912985A CN 202111368108 A CN202111368108 A CN 202111368108A CN 113912985 A CN113912985 A CN 113912985A
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于运花
冯德利
邓桢
李刚
杨小平
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Abstract

本发明涉及一种高强高模环氧模塑料及其制备方法,其解决了材料填料和树脂界面粘结性差、模塑料制品的强度和模量的性能较差的技术问题,本发明提供的高强高模环氧模塑料,其含有环氧树脂基体和填料,填料表面设有膜层,膜层为硅烷偶联剂水解基团与水性环氧树脂形成;本发明可用于高强高模环氧模塑料的制备领域。

Description

一种高强高模环氧模塑料及其制备方法
技术领域
本发明涉及一种复合材料,具体地说,涉及一种高强高模环氧模塑料及其制备方法。
背景技术
传统的界面增强方法使用硅烷偶联剂对无机填料进行表面改性,以改善树脂和无机填料间的亲和性及界面性能,而硅烷偶联剂与基体树脂虽有一定亲和性,但由于偶联剂本身化学结构与基体树脂的不同,导致其亲和性一般。虽偶联剂上的有机基团可与基体树脂进行一定程度上的交联,但亲和性不佳导致硅烷偶联剂处理后的填料在与基体树脂混合的过程中仍存在空隙、团聚和聚沉等现象,这最终使得填料与基体界面粘结不强,复合材料力学性能与未经偶联剂处理的相差不大。
公开号为CN109370160A的中国发明专利申请公开了一种粉末纤维改性的环氧模塑料及其制备方法;公开号为CN104017384A的中国发明专利申请公开了一种高压缩强度团状模塑料及其生产方法,这两种模塑料均采用传统方法使用硅烷偶联剂处理填料和树脂间的界面,但填料和树脂界面粘结性差,导致模塑料制品的强度和模量的性能较差。
发明内容
本发明就是为了解决现有材料填料和树脂界面粘结性差、模塑料制品的强度和模量的性能较差的技术问题,提供一种填料和树脂界面粘结性好、模塑料制品的强度和模量的性能较好的高强高模环氧模塑料及其制备方法。
为此,本发明提供一种高强高模环氧模塑料,其含有环氧树脂基体和填料,所述填料表面设有膜层,所述膜层为硅烷偶联剂水解基团与水性环氧树脂形成;所述高强高模环氧模塑料的压缩强度267.4~285.4MPa,拉伸强度81.7~85.6MPa,拉伸模量15.5~16.8GPa。
本发明同时提供一种高强高模环氧模塑料的制备方法,其包括如下步骤:(1)填料上浆:将增强纤维和矿物填料分别在水解后的硅烷偶联剂中浸泡后烘干,即可得到预处理的增强纤维和矿物填料;(2)将所述步骤(1)得到的预处理的增强纤维和矿物填料在水性环氧树脂浸润后烘干,即可得到上浆的增强纤维和矿物填料;(3)环氧树脂糊制备:将环氧树脂预热,加入固化剂,充分搅拌至完全溶解,即得到环氧树脂糊;(4)模塑料的制备:将所述步骤(2)中得到的上浆的增强纤维和矿物填料、所述步骤(3)中得到的环氧树脂糊、着色剂投入至捏合机,混合,得到高强高模环氧模塑料。
优选的,所述步骤(1)中,所述硅烷偶联剂为KH550、KH560、KH570中的一种或几种任意比例混合;所述增强纤维为玻璃纤维、芳纶纤维、玄武岩纤维、凯夫拉纤维中的一种或几种任意比例混合,其长度范围为300~800μm;所述矿物填料为钛酸钾晶须、硅微粉、碳酸钙晶须、滑石粉中的一种或几种任意比例混合,其粒径范围为5~50μm。
优选的,所述步骤(1)中,所述增强纤维和所述矿物填料的质量份数比为(15~25):(40~60)。
优选的,所述步骤(1)中,将增强纤维和矿物填料分别在水解后的硅烷偶联剂中浸泡,于烘箱80~120℃条件下烘干,即可得到预处理的增强纤维和矿物填料。
优选的,所述步骤(2)中,所述水性环氧树脂为改性的缩水甘油醚类树脂、缩水甘油脂类树脂、缩水甘油胺类树脂、脂环族环氧树脂中的一种或几种任意比例混合。
优选的,所述步骤(2)中,将预处理的增强纤维和矿物填料在水性环氧树脂浸润1~5分钟后于烘箱80~120℃条件下烘干,即可得到上浆的增强纤维和矿物填料。
优选的,所述步骤(3)中,所述环氧树脂为缩水甘油醚类树脂、缩水甘油脂类树脂、缩水甘油胺类树脂、脂环族环氧树脂中的一种或几种任意比例混合;所述固化剂为双氰胺、甲基纳迪克酸酐、4,4'-二氨基二苯砜、2-苯基咪唑中的一种或几种任意比例混合。
优选的,所述步骤(3)中,将环氧树脂预热至70~100℃,加入固化剂,充分搅拌至完全溶解即得到环氧树脂糊;所述环氧树脂与所述固化剂的质量份数比为(15~25):(5~15)。
优选的,所述步骤(4)中,着色剂为绝缘炭黑;所述上浆后的增强纤维和矿物填料、所述环氧树脂糊和所述着色剂的质量份数比为:(15~25):(40~60):(0.5~1)。
本发明具有以下有益效果:
本发明通过水性环氧树脂对硅烷偶联剂处理后的填料上浆,使得填料和树脂基体拥有了最佳的亲和性,改善了填料在环氧树脂基体中的分散性和相容性,填料和树脂基体间有更致密的固化交联网络,模塑料的分散性和界面性能得到了明显的提升。此方法解决了传统硅烷偶联剂处理填料的缺陷,制得的模塑料力学性能相比硅烷偶联剂处理的具有更高的强度和模量。
附图说明
图1是本发明中KH550与上浆后填料表面接触角示意图;
图2是本发明中硅烷偶联剂KH550处理后填料表面接触角示意图。
具体实施方式
下面结合实施例对本发明做进一步描述。
各实施方式中,复合材料的拉伸强度、压缩强度和拉伸模量通过美国Instron-1121万能材料试验机测试得到,体积电阻率通过数字超高阻、微电流测量仪:EST212测试得到,压缩强度测试标准为GB/T 2567-2008;拉伸强度和拉伸模量测试标准为GB/T 2567-2008;体积电阻率测试标准为GB 1410—2006。
实施例1
填料上浆:19.5份长度300μm玻璃纤维和45份粒径为25μm钛酸钾晶须浸泡于水解后的KH550溶液中3h,过滤、在烘箱110℃下烘干。将KH550处理后玻璃纤维和钛酸钾晶须浸润于水性TDE-85树脂中4min,放于烘箱100℃烘干8min。
环氧树脂糊制备:将10份环氧树脂TDE-85与10份环氧树脂E51,预热至80℃,加入15份固化剂4,4’-二氨基二苯砜DDS,充分搅拌至完全溶解。
将玻璃纤维、钛酸钾晶须、树脂糊加入捏合机中,加入绝缘炭黑0.5份,捏合60分钟,每隔20分钟将料取出重新投料其中,得到环氧模塑料。
实施例2
填料上浆:29份长度400μm凯夫拉纤维和40份粒径为30μm的硅微粉浸泡于水解后的KH560溶液中3h,过滤后于烘箱110℃下烘干。将KH560处理后玻璃纤维和钛酸钾晶须浸润于水性E51树脂中3min,放于烘箱80℃烘干10min。
树脂糊的配置:将10份环氧树脂E51与15份环氧树脂TDE-85混合均匀,预热至80℃,加入5份固化剂甲基纳迪克酸酐,充分搅拌至混合均匀。
称取按凯夫拉纤维、硅微粉、树脂糊加入捏合机中,加入绝缘炭黑1份,捏合60分钟,每隔20分钟将料取出重新投料其中,得到环氧模塑料。
实施例3
填料上浆:39.5份长度600μm的KH550处理过玄武岩纤维和35份长度20μm的滑石粉浸泡于水解后的KH570溶液中3h,过滤后于烘箱110℃下烘干。将KH570处理后玻璃纤维和钛酸钾晶须浸润于水性AFG-90树脂中2min,放于烘箱120℃烘干5min。
树脂糊的配置:将10份环氧树脂AFG-90与5份环氧树脂E51混合均匀,预热至100℃,加入10份固化剂双氰胺,充分搅拌至混合均匀。
将玄武岩纤维、滑石粉、树脂糊加入捏合机中,加入绝缘炭黑0.5份,捏合60分钟,每隔20分钟将料取出重新投料其中,得到环氧模塑料。
对比例
本对比例与实施例1的区别在于,所使用的填料仅经过KH550处理,进行环氧模塑料的制备。
表1:实施例1~3与对比例所制得材料的性能
Figure BDA0003361604760000051
从表1中可以看出,经过偶联剂和上浆处理后的强度和模量有显著的提高,强度的提高这是由于填料和树脂基体间有更致密的固化交联网络,界面性能更强,受到应力的作用后,连续相的应力更有利于传递到增强相,模量的提高主要归因于填料的分散性得到了明显的改善,使得模塑料制品受力更加均匀,不容易变形。
以环氧树脂作为测量液体,对填料进行接触角测量,从图1和图2可以看出,经过偶联剂处理的填料接触角远大于KH550和上浆处理的,表明经过上浆后的填料与树脂间的浸润性得到的提高,更有利于填料在树脂间的分散。
惟以上所述者,仅为本发明的具体实施例而已,当不能以此限定本发明实施的范围,故其等同组件的置换,或依本发明专利保护范围所作的等同变化与修改,皆应仍属本发明权利要求书涵盖之范畴。

Claims (10)

1.一种高强高模环氧模塑料,其含有环氧树脂基体和填料,其特征是,所述填料表面设有膜层,所述膜层为硅烷偶联剂水解基团与水性环氧树脂形成;所述高强高模环氧模塑料的压缩强度267.4~285.4MPa,拉伸强度81.7~85.6MPa,拉伸模量15.5~16.8GPa。
2.如权利要求1所述的高强高模环氧模塑料的制备方法,其特征是,包括如下步骤:
(1)填料上浆:将增强纤维和矿物填料分别在水解后的硅烷偶联剂中浸泡后烘干,即可得到预处理的增强纤维和矿物填料;
(2)将所述步骤(1)得到的预处理的增强纤维和矿物填料在水性环氧树脂浸润后烘干,即可得到上浆的增强纤维和矿物填料;
(3)环氧树脂糊制备:将环氧树脂预热,加入固化剂,充分搅拌至完全溶解,即得到环氧树脂糊;
(4)模塑料的制备:将所述步骤(2)中得到的上浆的增强纤维和矿物填料、所述步骤(3)中得到的环氧树脂糊、着色剂投入至捏合机,混合,得到高强高模环氧模塑料。
3.根据权利要求2所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(1)中,所述硅烷偶联剂为KH550、KH560、KH570中的一种或几种任意比例混合;所述增强纤维为玻璃纤维、芳纶纤维、玄武岩纤维、凯夫拉纤维中的一种或几种任意比例混合,其长度范围为300~800μm;所述矿物填料为钛酸钾晶须、硅微粉、碳酸钙晶须、滑石粉中的一种或几种任意比例混合,其粒径范围为5~50μm。
4.根据权利要求3所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(1)中,所述增强纤维和所述矿物填料的质量份数比为(15~25):(40~60)。
5.根据权利要求4所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(1)中,将增强纤维和矿物填料分别在水解后的硅烷偶联剂中浸泡,于烘箱80~120℃条件下烘干,即可得到预处理的增强纤维和矿物填料。
6.根据权利要求2所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(2)中,所述水性环氧树脂为改性的缩水甘油醚类树脂、缩水甘油脂类树脂、缩水甘油胺类树脂、脂环族环氧树脂中的一种或几种任意比例混合。
7.根据权利要求6所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(2)中,将预处理的增强纤维和矿物填料在水性环氧树脂浸润1~5分钟后于烘箱80~120℃条件下烘干,即可得到上浆的增强纤维和矿物填料。
8.根据权利要求2所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(3)中,所述环氧树脂为缩水甘油醚类树脂、缩水甘油脂类树脂、缩水甘油胺类树脂、脂环族环氧树脂中的一种或几种任意比例混合;所述固化剂为双氰胺、甲基纳迪克酸酐、4,4'-二氨基二苯砜、2-苯基咪唑中的一种或几种任意比例混合。
9.根据权利要求2所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(3)中,将环氧树脂预热至70~100℃,加入固化剂,充分搅拌至完全溶解即得到环氧树脂糊;所述环氧树脂与所述固化剂的质量份数比为(15~25):(5~15)。
10.根据权利要求2所述的高强高模环氧模塑料的制备方法,其特征在于,所述步骤(4)中,着色剂为绝缘炭黑;所述上浆后的增强纤维和矿物填料、所述环氧树脂糊和所述着色剂的质量份数比为:(15~25):(40~60):(0.5~1)。
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