CN113801434A - 一种高抗冲发泡环氧树脂材料及其制备方法 - Google Patents
一种高抗冲发泡环氧树脂材料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种高抗冲发泡环氧树脂材料及其制备方法，以重量份数计，高抗冲发泡环氧树脂材料包括以下组分：环氧树脂30～40份、填充料43～52份、二氰二胺6～8份、偶氮二甲酰胺0.5～1.5份、氧化锌0.25～0.75份、硬脂酸锌0.25～0.75份、硫化剂0.5～1份、固化剂0.5～1份和乳液状的乙烯丙烯酸甲酯共聚物6～9份；所述乳液状的乙烯丙烯酸甲酯共聚物按照以下方法制得：将水、甲基丙烯酸乳液和过硫酸钾混合，通入乙烯，反应，得到乳液状乙烯丙烯酸甲酯共聚物。本发明在上述用量的组分的共同作用下，具有就较高抗冲强度。还具有优异拉伸强度、剪切强度、弯曲强度和粘结强度。
Description
技术领域
本发明属于环氧树脂材料，尤其涉及一种高抗冲发泡环氧树脂材料及其制备方法。
背景技术
环氧树脂发泡胶条未固化之前柔软，可塑性非常好，能适用于各种复杂形状的空腔，从而使它的加工工艺非常简单。发泡之后具有泡孔均一，质轻密度低，比表面积大，导热率低，机械性能、耐候性和耐化学腐蚀性良好等诸多优点，广泛的用于保温，消音，隔振等领域，是环氧树脂材料主要的应用方向之一。但是，环氧树脂的固有缺点，比如质脆，耐冲击性能差，限制了它的应用。所以，发泡环氧树脂胶条材料增韧改性一直都是环氧树脂领域的热门研究课题。
发明内容
有鉴于此，本发明的目的在于提供一种高抗冲发泡环氧树脂材料及其制备方法，该环氧树脂材料具有较高抗冲强度。
本发明提供了一种高抗冲发泡环氧树脂材料，以重量份数计，包括以下组分：
环氧树脂30～40份、填充料43～52份、二氰二胺6～8份、偶氮二甲酰胺0.5～1.5份、氧化锌0.25～0.75份、硬脂酸锌0.25～0.75份、硫化剂0.5～1份、固化剂0.5～1份和乳液状的乙烯丙烯酸甲酯共聚物6～9份；
所述乳液状的乙烯丙烯酸甲酯共聚物按照以下方法制得：
将水、叔丁醇、甲基丙烯酸乳液和过硫酸钾混合，通入乙烯，反应，得到乳液状的乙烯丙烯酸甲酯共聚物。
在本发明中，所述水、叔丁醇、甲基丙烯酸乳液和过硫酸钾的质量比为(1500～1800):(250～350):(20～40):(1.0～1.5)。具体实施例中，所述水、叔丁醇、甲基丙烯酸乳液和过硫酸钾的质量比为1600:300:25:1.1。
在本发明中，所述乙烯的压力为15～22MPa。具体实施例中，所述乙烯的压力为20MPa。
在本发明中，所述反应的温度为75～85℃，时间为5～7h。具体实施例中，所述反应的温度为80℃，时间为5.5h。
在本发明中，所述环氧树脂选自107B和/或E51。
在本发明中，所述填充料选自硫酸钡、碳酸钙和钛白粉中的一种或多种。
所述硫化剂优选选自BiBp。
所述固化剂选自二甲氨基丙脲。
本发明提供了一种上述技术方案所述高抗冲发泡环氧树脂材料的制备方法，包括以下步骤:
将环氧树脂、填充料、二氰二胺、偶氮二甲酰胺、氧化锌、硬脂酸锌、硫化剂、固化剂和乳液状乙烯丙烯酸甲酯共聚物在90～110℃熔融，混合均匀后挤出成型，得到高抗冲发泡环氧树脂材料。
在本发明中，所述乙烯丙烯酸甲酯共聚物为乳液状，相比颗粒状态的物料，在液态基材中更容易加工使用及分散均匀，其含有的官能团能与环氧树脂发生架桥反应，两者的界面结合是一种化学键结合而不是简单的物理交联缠绕，两者相互作用，在微观领域会形成软硬相间的串联结构，使材料有很好的抗拉强度和抗冲强度。
本发明按照GB/T1040.1-2006、GB/T1040.2-2006制备试样并测试拉伸强度、冲击强度和弯曲强度；本发明按照GB/T7124-2008制备剪切试样并测试剪切强度；本发明按照GB/T2791-1995制备粘结强度试样并测试粘结强度；试样固化时的温度为180℃，时间15min。
本发明提供了一种高抗冲发泡环氧树脂材料，以重量份数计，包括以下组分：环氧树脂30～40份、填充料43～52份、二氰二胺6～8份、偶氮二甲酰胺0.5～1.5份、氧化锌0.25～0.75份、硬脂酸锌0.25～0.75份、硫化剂0.5～1份、固化剂0.5～1份和乳液状的乙烯丙烯酸甲酯共聚物6～9份；所述乳液状的乙烯丙烯酸甲酯共聚物按照以下方法制得：将水、甲基丙烯酸乳液和过硫酸钾混合，通入乙烯，反应，得到乙烯丙烯酸甲酯共聚物。本发明在上述用量的组分的共同作用下，具有就较高的抗冲强度。还具有优异的拉伸强度、剪切强度、弯曲强度和粘结强度。
具体实施方式
为了进一步说明本发明，下面结合实施例对本发明提供的一种高抗冲发泡环氧树脂材料及其制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
预备实施例
将纯水1600g、叔丁醇300g、甲基丙烯酸乳液25g、过硫酸钾1.1g加入反应釜中，然后通入乙烯气体，保持压力20MPa，在80℃下反应5.5h后取出白色乳液，得到乙烯丙烯酸甲酯共聚物，即A料。
实施例1～3
按照表1中所示的原料种类和用量，以重量份数计：
将环氧树脂、碳酸钙、二氰二胺、偶氮二甲酰胺AC、氧化锌、硬脂酸锌、硫化剂BiBp、固化剂和乙烯丙烯酸甲酯共聚物投入压注机，90℃-110℃熔融，混合，挤出成型，得到高抗冲发泡环氧树脂材料；
对比例1
按照表1中所述物料种类和用量，按照实施例的工艺条件，制得环氧树脂材料；
对比例2
按照表1，将环氧树脂、碳酸钙、二氰二胺、4,4'-氧代双苯磺酰肼OBSH、氧化锌、硬脂酸锌、硫化剂BiBp、固化剂和白色乳液状态的乙烯丙烯酸甲酯共聚物料投入压注机，90℃-110℃熔融，混合，挤出成型，得到环氧树脂材料；
表1实施例和对比例制备的环氧树脂材料采用的原料及用量及性能测试结果
由以上实施例可知，本发明提供了一种高抗冲发泡环氧树脂材料，以重量份数计，包括以下组分：环氧树脂30～40份、填充料43～52份、二氰二胺6～8份、偶氮二甲酰胺0.5～1.5份、氧化锌0.25～0.75份、硬脂酸锌0.25～0.75份、硫化剂0.5～1份、固化剂0.5～1份和乳液状的乙烯丙烯酸甲酯共聚物6～9份；所述乳液状的乙烯丙烯酸甲酯共聚物按照以下方法制得：将水、甲基丙烯酸乳液和过硫酸钾混合，通入乙烯，反应，得到乙烯丙烯酸甲酯共聚物。本发明在上述用量的组分的共同作用下，具有就较高的抗冲强度。还具有优异的拉伸强度、剪切强度、弯曲强度和粘结强度。实验结果表明：环氧树脂材料的拉伸强度为32.0～32.4MPa，弯曲强度为54.1～54.6MPa，剪切强度为16.8～17.5MPa，抗冲强度为7.2～7.6KJ/m2，粘结强度为32.0～33.6KN/m。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种高抗冲发泡环氧树脂材料，以重量份数计，包括以下组分：
环氧树脂30～40份、填充料43～52份、二氰二胺6～8份、偶氮二甲酰胺0.5～1.5份、氧化锌0.25～0.75份、硬脂酸锌0.25～0.75份、硫化剂0.5～1份、固化剂0.5～1份和乳液状的乙烯丙烯酸甲酯共聚物6～9份；
所述乳液状的乙烯丙烯酸甲酯共聚物按照以下方法制得：
将水、叔丁醇、甲基丙烯酸乳液和过硫酸钾混合，通入乙烯，反应，得到乳液状的乙烯丙烯酸甲酯共聚物。
2.根据权利要求1所述的高抗冲发泡环氧树脂材料，其特征在于，所述水、叔丁醇、甲基丙烯酸乳液和过硫酸钾的质量比为(1500～1800):(250～350):(20～40):(1.0～1.5)。
3.根据权利要求1所述的高抗冲发泡环氧树脂材料，其特征在于，所述乙烯的压力为15～22MPa。
4.根据权利要求1所述的高抗冲发泡环氧树脂材料，其特征在于，所述反应的温度为75～85℃，时间为5～7h。
5.根据权利要求1所述的高抗冲发泡环氧树脂材料，其特征在于，所述环氧树脂选自107B和/或E51。
6.根据权利要求1所述的高抗冲发泡环氧树脂材料，其特征在于，所述填充料选自硫酸钡、碳酸钙和钛白粉中的一种或多种。
7.一种权利要求1～6任一项所述高抗冲发泡环氧树脂材料的制备方法，包括以下步骤:
将环氧树脂、填充料、二氰二胺、偶氮二甲酰胺、氧化锌、硬脂酸锌、硫化剂、固化剂和乳液状乙烯丙烯酸甲酯共聚物在90～110℃熔融，混合均匀后挤出成型，得到高抗冲发泡环氧树脂材料。
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