CN108250351A - 一种耐高温耐黄变含氟环氧树脂的制备方法及应用 - Google Patents
一种耐高温耐黄变含氟环氧树脂的制备方法及应用 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明公开了一种耐高温耐黄变含氟环氧树脂的制备方法及应用。制备是以各种丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油醚、甲基丙烯酸缩水甘油醚或者各种脂环族环氧环丙烯酸酯作为环氧基提供物，以各种含氟丙烯酸酯单体作为氟元素提供物与甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯以及其他丙烯酸酯功能单体进行自由基聚合，制备出各种软化点，不同氟含量的，各种功能要求的耐高温耐黄变含氟环氧树脂；以及研究该含氟环氧树脂在涂料、油墨、航天航空等领域的应用。
Description
技术领域
本发明涉及化学领域中的一种耐高温耐黄变含氟环氧树脂的制备方法及应用。
背景技术
氟原子具有电负性大，摩尔极化率低的特点；同时氟原子间斥力大，C-F键长短，键能高，自由体积大。由于这些特性，将含氟基团引入环氧树脂中可显著降低材料的介电常数、吸水率和表面张力，改善材料的抗污性和电绝缘性能。
由于含氟聚合物有各种特殊性能，国内外很多研究人员对含氟环氧树脂做了研究，Alberto等(EP Pat.293889)公开了一系列含六氟异丙基的含氟环氧树脂的制备方法，指出了所发明的含氟环氧树脂具有疏水疏油的表面性质和低摩擦系数，固化物的介电常数为3.1-3.2；F.Montefusco等(F.Montefusco，R.Bongiovanni，et al.Polymer，2004，31：4663)报道了一种主链上含有氟烷基的新型环氧化合物，其具有良好的憎水性，适用于光纤涂层和印刷电路板等。Van de Grampel等(Van de Grampel，R.D.，Ming，W.，etal.Polymer，2005，46：10531)报道了一种含氟的环氧树脂涂料，固化成膜后表面张力明显降低。Lee(Lee，J.R.，Jin，F.L，et al.Surf.Coat.Technol.，2004，180：650.)和Misaki等(Masiki，T.，Hirohata，T.，et al.J.Polym.Sci.，1989，37：2617.)报道了带含氟基团的环氧树脂固化物比DGEBA具有更低介电常数和更优异的机械性能。王等(Wang，C.Z.，Zuo，Y.J.Appl.Poly.Sci.，2009，114，2528-2532.)用十二氟缩水甘油醚改性DGEBA环氧树脂，改性后的环氧树脂的吸水率大大降低，同时机械性能有所提高。
含氟环氧涂料具有优异的耐腐蚀、耐候、耐水、耐油性、自清洁等特性，使其在防水防污涂料领域得到了广泛的关注。目前的含氟环氧树脂主要是在主链段添加单个或者少了的氟原子，该类单体虽然能够提高涂料的耐热、耐腐蚀等性能，但是因其含氟量不高，对涂料的疏水性能、耐污性能提高不明显，并且合成方法复杂，成本高，限制了其使用范围；另外，通过添加小分子的含氟环氧树脂，虽然可以增加其相容性，但是使用量大，成本高，而且有一定的挥发性，污染环境；最后，从技术效果来看，短的含氟链难以迁移到涂料的表面，削弱了含氟基团改性的效果，因而大大地限制了含氟环氧涂料的应用范围。
本专利通过带环氧基团的双键和带氟元素的双键单体，通过各种丙烯酸酯的功能单体自由基聚合，可以合成不同软化点、不同特殊功能、不同环氧值、不用氟含量的环氧树脂，产品合成简单，无三废；属于环境友好型含氟环氧树脂的合成工艺。此产品创新点是通过自由基聚合的方法将环氧基团和氟元素同时引入到环氧树脂中；可得到不同要求适用于各种领域的环氧树脂，同时本专利合成的产品耐热温度高，无苯环，产品有很好的耐温和耐候耐黄变性能，生产无三废为等污染。
发明内容
本发明涉及一种耐黄变耐高温含氟环氧树脂的制备方法及其在涂料中应用。
耐黄变耐高温含氟环氧树脂的制备方法 和技术方案。
本发明的耐黄变耐高温含氟树脂的制造方法的特征在于，将带环氧基团双键单体和带氟元素双键单体，其他丙烯酸酯功能单体与引发剂和分子量调节剂按一定比例混合溶解备用。
本发明的耐黄变耐高温含氟树脂的制造方法的特征在于，包括如下步骤：首先将带环氧基团双键和带氟元素双键混合单体、丙烯酸功能单体、引发剂、分子量调节剂投入混料器中，搅拌均匀，得到100份混合单体；然后在保护气的保护下，将添加有回流50-100份溶剂的反应釜搅拌加热至60-85℃，滴加上述混合单体，1-3小时内滴加完毕，滴加完毕后，回流，升温到85度保温反应1小时，然后补滴加入0.05份偶氮二异丁腈与6份溶剂混合液，在15分钟滴加完毕后保温1小时。然后将温度升高115℃，再保温1小时，得到共聚物溶液，将聚物溶液经过过滤后再进行真空脱溶剂，冷却得到不同分子量耐温耐黄变含氟环氧树脂。
所述带环氧基团丙烯酸酯和带氟元素丙烯酸酯混合比例在1：0.2-1之间。
所述引发剂用量与混合单体优选为0.4-5：100之间。
所述分子量调剂用量与混合单体优选为0.04-0.6：100之间。
所述溶剂用量与混合单体优选为0.5-1：1之间。
具体实施方式。
实施例1
一种耐黄变耐高温含氟树脂的制备方法，包括如下步骤：首先将甲基丙烯酸缩水甘油酯40份、丙烯酸三氟乙酯30份、甲基丙烯酸羟乙酯5份、甲基丙烯酸甲酯25、偶氮二异丁腈1份、3-巯基丙酸异辛酯0.2份投入混料器中，搅拌均匀，得到混合单体；然后在保护气的保护下，将添加有回流溶剂丙二醇甲醚醋酸酯53份的反应釜搅拌加热至60-85℃，滴加上述混合单体，2小时内滴加完毕，滴加完毕后，回流，升温到85度保温反应1小时然后15分钟内滴加入0.05g偶氮二异丁腈与6g丙二醇甲醚醋酸酯混合液。然后将温度升高115℃，再保温1.5小时，得到四元共聚物溶液，将四元共聚物溶液经过过滤后再进行真空脱溶剂，冷却得到半固体耐温耐黄变含氟环氧树脂，所得环氧树脂环氧值在0.28-0.32之间，氟元素含量10%左右。
相对于现有技术，本发明具有如下优点：
（1）本发明耐高温耐黄变型的含氟环氧树脂合成简单、通过自由基聚合反应分子量可调节。可生产固体或者液体的含氟环氧树脂，
（2）本发明耐高温耐黄变型的含氟环氧树脂还可含有羧基，可以溶于水做成水性环氧树脂，并具有较高的玻璃化转变温度、耐热性佳、耐黄变、固化膜耐水性、耐溶剂性及机械性能优异等特点，
（3）本发明耐高温耐黄变型的含氟环氧树脂具有优异的耐热性、耐黄变性及机械性能，合成过程中无三废，属于环境友好型环氧树脂。生产过程中基本上不产生废料。
实施例2
一种耐黄变耐高温含氟树脂的制备方法，包括如下步骤：首先将烯丙基缩水甘油醚20份、甲基丙烯酸缩水甘油酯20份、丙烯酸六氟丁酯30份、甲基丙烯酸羟乙酯5份、甲基丙烯酸甲酯25、偶氮二异丁腈1份、3-巯基丙酸异辛酯0.2份投入混料器中，搅拌均匀，得到混合单体；然后在保护气的保护下，将添加有回流溶剂丙二醇甲醚醋酸酯53份的反应釜搅拌加热至60-85℃，滴加上述混合单体，2小时内滴加完毕，滴加完毕后，回流，升温到85度保温反应1小时然后15分钟内滴加入0.05g偶氮二异丁腈与6g丙二醇甲醚醋酸酯混合液。然后将温度升高115℃，再保温1.5小时，得到四元共聚物溶液，将四元共聚物溶液经过过滤后再进行真空脱溶剂，冷却得到半固体耐温耐黄变含氟环氧树脂，所得环氧树脂环氧值在0.3-0.4之间，氟元素含量15%左右。
实施例3
一种耐黄变耐高温含氟树脂的制备方法，包括如下步骤：首先将3，4-环氧环己基甲基甲基丙烯酸酯20份、甲基丙烯酸缩水甘油酯20份、丙烯酸八氟戊酯40份、甲基丙烯酸羟乙酯5份、甲基丙烯酸甲酯15、偶氮二异丁腈1份、3-巯基丙酸异辛酯0.2份投入混料器中，搅拌均匀，得到混合单体；然后在保护气的保护下，将添加有回流溶剂丙二醇甲醚醋酸酯53份的反应釜搅拌加热至60-85℃，滴加上述混合单体，2小时内滴加完毕，滴加完毕后，回流，升温到85度保温反应1小时然后15分钟内滴加入0.05g偶氮二异丁腈与6g丙二醇甲醚醋酸酯混合液。然后将温度升高115℃，再保温1.5小时，得到四元共聚物溶液，将四元共聚物溶液经过过滤后再进行真空脱溶剂，冷却得到半固体耐温耐黄变含氟环氧树脂，所得环氧树脂环氧值在0.3-0.4之间，氟元素含量20%左右。
图1为耐黄变耐高温含氟环氧树脂结构通式
图2为实施例1耐黄变耐高温含氟环氧树脂
图3为实施例2耐黄变耐高温含氟环氧树脂
图4为实施例3耐黄变耐高温含氟环氧树脂。
Claims (8)
1.一种耐高温耐黄变含氟环氧树脂的制备方法，其特征在于所述含氟环氧树脂有如下结构式：
其中，R为-H或者-CH3，
其中，R1为含环氧基团丙烯酸酯单体结构，
其中，R2为丙烯酸酯特殊功能单体结构，
其中，R3为含氟元素的丙烯酸酯单体结构。
2.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法，其特征在于，所述自由基聚合中的环氧基提供单体为丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油醚、甲基丙烯酸缩水甘油醚、3,4-环氧环己基甲基甲基丙烯酸酯、3,4-环氧环己基甲基丙烯酸酯一种或者几种，等各种同时含有双键和环氧基的单体，作为自由基聚合中环氧基的提供单体。
3.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法，其特征在于，所述自由基聚合中的含氟元素提供单体为丙烯酸三氟乙酯、丙烯酸八氟戊酯、丙烯酸六氟丁酯、丙烯酸四氟丙酯一种或者几种，等各种同时含有双键和氟元素的单体，作为自由基聚合中氟元素的提供单体。
4.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法，其特征在于，所述自由基聚合中其他功能单体为甲基丙烯酸甲酯、甲基丙烯酸异冰片酯、N-羟甲基丙烯酰胺等一种或者几种高玻璃化温度单体，作为自由基聚合中高Tg玻璃化温度提供单体，甲基丙烯酸、丙烯酸等含有羧基的单体作为自由基聚合中水溶性提供单体。
5.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法，其特征在于，所述引发剂的用量为偶氮二异丁腈、过氧化二苯甲酰、二叔戊基过氧化物、过氧化二异丙苯或过氧化二叔丁基。
6.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法，其特征在于分子量调节剂为3-巯基丙酸异辛酯、叔十二烷基硫醇或正十二烷基硫醇。
7.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法，其特征在于，所述溶剂为DBE、乙二醇乙醚醋酸酯、乙二醇丁醚醋酸酯、二乙二醇丁醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇甲醚丙酸酯、二丙二醇甲醚、丙二醇甲醚、三甲苯或四甲苯。
8.根据权利要求1所述的耐高温耐黄变含氟环氧树脂的制备方法特征在于，包括如下步骤：首先将带环氧基团双键和带氟元素双键混合单体、丙烯酸功能单体、引发剂、分子量调节剂投入混料器中，搅拌均匀，得到100份混合单体；然后在保护气的保护下，将添加有回流50-100份溶剂的反应釜搅拌加热至60-85℃，滴加上述混合单体，1-3小时内滴加完毕，滴加完毕后，回流，升温到85度保温反应1小时，然后补滴加入0.05份偶氮二异丁腈与6份溶剂混合液，在15分钟滴加完毕后保温1小时，然后将温度升高115℃，再保温1小时，得到共聚物溶液，将聚物溶液经过过滤后再进行真空脱溶剂，冷却得到不同分子量耐温耐黄变含氟环氧树脂。
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