CN113402698A - 一种植物基多官能度增韧型环氧树脂及其制备方法 - Google Patents
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Abstract
本发明公开了一种植物基多官能度增韧型环氧树脂,其特征在于,包括如下组分:如式1或2所示的植物多烯酚基缩水甘油醚;含有双羟基的化合物;催化剂;其中,所述植物多烯酚基缩水甘油醚与所述含有双羟基的化合物的摩尔比为2:1‑2;其中,所述催化剂用量为0.1%‑1%。本发明还公开了其制备方法。本发明所制备的植物基多官能度增韧型环氧树脂可以替代石油原材料所制备的固体环氧树脂,更加环保;增韧后的植物基多官能度增韧型环氧树脂柔韧性1mm,附着力1级,增韧效果明显改善。
Description
技术领域
本发明涉及环氧树脂防腐涂料制备领域,具体涉及一种植物基多官能度增韧型环氧树脂及其制备方法。
背景技术
环氧树脂防腐涂料是防腐蚀涂料中应用最广泛的涂料。一般而言,对组成中含有较多环氧基团的涂料统称为环氧漆,其树脂是分子结构至少含有两个环氧基的高分子化合物。适用于海上、工业区、化工厂、海岸、混凝土等严重腐蚀环境中钢铁构筑物的涂装,尤其适用于各种贮罐内表面的涂装。
用于环氧涂料的环氧树脂主要有双酚A型、双酚F型及酚醛环氧等树脂。环氧树脂防腐涂料的主要品种是双组分涂料,由基料和固化剂组成。
其它还有一些单组分自干型的品种,但是其性能与双组分涂料比较有不少的差距。
现有技术当中,用于生产环氧树脂防腐涂料的环氧树脂分子结构中含有活泼的环氧基团,它们可与多种类型的固化剂(芳香胺、脂肪胺、改性胺、聚酰胺等)发生交联反应而形成不溶的具有三向网状结构的高聚物。
环氧树脂固化物具有优良的耐化学品性能,收缩率低、粘接强度高、机械强度高、电绝缘性优良,因此广泛用于涂料、胶黏剂、油墨等领域,但是生产环氧树脂的原料石油是一次性资源,石油价格不断攀升,造成生产成本不断增加。
然而,环氧材料的冲击强度特性对很多应用不适合,为了更便于应用,需要增加环氧树脂交联密度,降低环氧树脂脆性,达到综合性能优良,成为当下最迫切的问题。
现有的环氧树脂的增韧途径主要是通过如下两类:
(1)利用橡胶弹性体、热塑性树脂、刚性无机填料、热致性液晶聚合物等形成两相结构进行增韧;
(2)利用热塑性塑料连续贯穿于环氧树脂网络中形成半互传网络聚合物来增韧;
其中,橡胶弹性体增韧环氧树脂是较早开始的一种增韧方法,但这种方法在提高韧性的同时,存在着降低材料模量和耐热性不足等缺点,因而限制了它在一些高性能领域的应用。
中国科学院化学所早期专利99108080.7公开了利用一种端羟基液体橡胶增韧的环氧树脂组合物,组合物固化后断裂能为689J/m2,抗弯强度为137.4Mpa,抗弯模量为2.35Gpa,具有明显的增韧效果。此方法仅是通过添加增韧剂满足性能,在更高的重防腐领域仍不能满足要求。
专利CN102924690公开了一种超支化聚醚型环氧树脂用于增韧增强的环氧树脂材料及其制备方法,但此工艺合成复杂,成本优势不明显,并不能在工业化产品中得到广泛推广。
涂料领域通常也是通过加入环氧树脂稀释剂,十二十四醇缩水甘油醚以及腰果酚基缩水甘油醚来增加树脂的韧性,但通过增韧的树脂,都是单官能度,不能与体系交联,形成致密的网,从而影响涂膜的防腐性能。
发明内容
为了克服现有技术的上述缺陷,本发明的目的在于提供一种植物基多官能度增韧型环氧树脂及其制备方法。通过简单的组分和合成工艺,帮助环氧树脂材料增韧提升交联密度和形成涂膜,所生产的环氧涂料具有优良的防腐和防水功能。
一种植物基多官能度增韧型环氧树脂,包括如下组分:
如式1或2所示的植物多烯酚基缩水甘油醚;
所述式1或2中的n=27-31;
含有双羟基的化合物;
催化剂;
其中,所述植物多烯酚基缩水甘油醚与所述含有双羟基的化合物的摩尔比为2:1-2;
其中,所述催化剂用量为0.1%-1%;
在本发明的一个优选实施例中,所述催化剂包括苄基三甲基溴化铵、苄基三乙基溴化铵、苄基三丁基溴化铵、四甲基溴化铵、四乙基溴化铵,四丙基溴化铵、四丁基溴化胺、十六烷基三甲基溴化铵、三氟化硼乙醚、三苯基膦、氢氧化钠或氢氧化钾中的任意一种或多种。
在本发明的一个优选实施例中,所述含有双羟基的化合物为双酚A、双酚S、聚丙二醇或聚乙二醇中的任意一种或多种。
一种植物基多官能度增韧型环氧树脂的制备方法,包括如下步骤:
将所述植物多烯酚基缩水甘油醚与所述含有双羟基的化合物加入反应釜当中后升温至60-100℃,后加入所述催化剂发生环氧开环反应,在80-120℃下保温2-8小时得所述植物基多官能度增韧型环氧树脂。
本发明的有益效果在于:
本发明所制备的植物基多官能度增韧型环氧树脂可以替代石油原材料所制备的固体环氧树脂,更加环保;
增韧后的植物基多官能度增韧型环氧树脂柔韧性1mm,附着力1级,增韧效果明显改善。
具体实施方式
实施例1
将一定量的植物多烯酚基缩水甘油醚293.7g与双酚A55.9g,催化剂四丁基溴化胺0.4g加入500ml反应烧瓶内釜,在120℃下,反应5小时;合成植物基多官能度增韧型环氧树脂。
实施例2
将一定量的植物多烯酚基缩水甘油醚293.7g与双酚A55.9g,催化剂氢氧化钠0.1g加入500ml反应烧瓶内釜,在100℃下,反应5小时;合成植物基多官能度增韧型环氧树脂。
实施例3
将一定量的植物多烯酚基缩水甘油醚293.7g与双酚A55.9g,催化剂三氟化硼乙醚0.1g加入500ml反应烧瓶内釜,在80℃下,反应3小时;合成植物基多官能度增韧型环氧树脂。
实施例4
将一定量的植物多烯酚基缩水甘油醚293.7g与双酚A55.9g,催化剂三苯基膦0.3g加入500ml反应烧瓶内釜,在120℃下,反应3小时;合成增韧型新型环氧树脂。
将本发明所制备的植物基多官能度增韧型环氧树脂刮膜制备200μm清漆膜;室温自干24小时;测试柔韧性、附着力,所得结果如表1所示:
由表1可知,增韧后的产品的附着力和柔韧性均有明显的提升。
以上描述了本发明的基本原理,主要技术特征和本发明的优越性,本发明不受上述实施例限制,在不脱离本发明原理和应用范围的前提下,本发明会有各种变化和改进,这些变化和改进,都落入要求保护的本发明范围内,本发明要求保护范围内由所附的权利要求及其等同物界定。
Claims (4)
2.如权利要求1所述的一种植物基多官能度增韧型环氧树脂,其特征在于,所述催化剂包括苄基三甲基溴化铵、苄基三乙基溴化铵、苄基三丁基溴化铵、四甲基溴化铵、四乙基溴化铵,四丙基溴化铵、四丁基溴化胺、十六烷基三甲基溴化铵、三氟化硼乙醚、三苯基膦、氢氧化钠或氢氧化钾中的任意一种或多种。
3.如权利要求1所述的一种植物基多官能度增韧型环氧树脂,其特征在于,所述含有双羟基的化合物为双酚A、双酚S、聚丙二醇或聚乙二醇中的任意一种或多种。
4.如权利要求1-3所述的一种植物基多官能度增韧型环氧树脂的制备方法,其特征在于,包括如下步骤:
将所述植物多烯酚基缩水甘油醚与所述含有双羟基的化合物加入反应釜当中后升温至60-100℃,后加入所述催化剂发生环氧开环反应,在80-120℃下保温2-8小时得所述植物基多官能度增韧型环氧树脂。
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CN114292568A (zh) * | 2021-12-15 | 2022-04-08 | 常熟耐素生物材料科技有限公司 | 一种植物多烯酚基低粘度无溶剂防腐涂料及其制备方法及应用 |
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JPH10218970A (ja) * | 1997-01-31 | 1998-08-18 | Asahi Chem Ind Co Ltd | 新規エポキシ樹脂 |
CN103449979A (zh) * | 2013-08-19 | 2013-12-18 | 上海美东生物材料有限公司 | 一种双酚环氧树脂及其制备方法 |
CN108373484A (zh) * | 2018-02-25 | 2018-08-07 | 李嘉顺 | 一种含磷腰果酚多缩水甘油醚及其制备方法 |
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JPH10218970A (ja) * | 1997-01-31 | 1998-08-18 | Asahi Chem Ind Co Ltd | 新規エポキシ樹脂 |
CN103449979A (zh) * | 2013-08-19 | 2013-12-18 | 上海美东生物材料有限公司 | 一种双酚环氧树脂及其制备方法 |
CN108373484A (zh) * | 2018-02-25 | 2018-08-07 | 李嘉顺 | 一种含磷腰果酚多缩水甘油醚及其制备方法 |
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CN114292568A (zh) * | 2021-12-15 | 2022-04-08 | 常熟耐素生物材料科技有限公司 | 一种植物多烯酚基低粘度无溶剂防腐涂料及其制备方法及应用 |
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