CN115448859B - 一种硫醇环氧固化剂及其制备方法 - Google Patents
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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Abstract
本发明公开了一种硫醇环氧固化剂,它是由质量百分比的5‑35%酚类物质、5‑25%醛类物质、15‑40%的含羟基的仲胺、20‑55%的巯基羧酸、3‑8%的强酸性阳离子交换树脂制成。本发明通过大量实验筛选出各种反应原料组成和反应具体步骤,制备得到的硫醇环氧固化剂,与环氧树脂搭配,无需加入促进剂即可实现低温快干,且固化后漆膜硬度高,附着力好,具有优良的防腐性能,适用于低温条件下的户外防腐施工。
Description
技术领域
本发明涉及一种硫醇环氧固化剂及其制备方法。
背景技术
环氧树脂是一种常见的热固性树脂,其分子结构中含有活泼的环氧基团,通过加入固化剂使其交联固化。环氧树脂固化收缩率低,固化物具有优异的热稳定性、力学性能、粘接性、介电性能,被广泛应用于涂料、胶粘剂、复合材料等领域。
在环氧双组分体系中,固化剂的结构特点对环氧体系的性能起到关键作用。固化剂有硫醇、胺、酸酐等多个种类。其中胺类和酸酐类等都需要在常温(20℃)或中高温下才能固化,因而不能应用于低温环境。
硫醇类固化剂是一类低温固化剂,但是一般的硫醇(如常见市售聚硫醇CAPCURE3-800)单独使用活性很低,在室温下几乎不与环氧树脂反应。为实现低温固化性能,需要与叔胺类催化剂配合使用。一旦加入叔胺类催化剂,硫醇与环氧基的反应快速进行,甚至在-10℃的低温下也能使环氧树脂发生固化,难以控制。
发明内容
发明目的:本发明的目的是提供一种硫醇环氧固化剂;本发明另一个目的是提供该固化剂的制备方法。
技术方案:为实现以上目的,本发明采用的技术方案是:
一种硫醇环氧固化剂,它是由下列质量百分比的原料制成:5-35%酚类物质、5-25%醛类物质、15-40%的含羟基的仲胺、20-55%的巯基羧酸、3-8%的强酸性阳离子交换树脂。
作为优选方案,以上所述的硫醇环氧固化剂,所述的酚类物质为苯酚、对叔丁基苯酚、腰果酚、壬基酚、十二烷基酚、邻甲基苯酚、间甲基苯酚、对甲基苯酚、萘酚、双酚A中的一种或几种混合物。
作为优选方案,以上所述的硫醇环氧固化剂,所述的醛类物质为甲醛、乙醛、正丁醛、苯甲醛中的一种或几种混合物。
作为优选方案,以上所述的硫醇环氧固化剂,所述的含羟基的仲胺包括但不限于二乙醇胺、二异丙醇胺、二丁醇胺、N-羟乙基哌嗪。
作为优选方案,以上所述的硫醇环氧固化剂,所述的巯基羧酸包括但不限于3-巯基丙酸、3-巯基丁酸、4-巯基丁酸、巯基乙酸、10-巯基癸酸、12-巯基十二酸。
本发明所述的硫醇环氧树脂固化剂的制备方法,其包括以下步骤:
1)按质量百分比将酚类物质、含羟基的仲胺投入反应釜中,搅拌均匀;
2)升温至50~60℃;
3)向反应釜中滴加计量好的醛类物质,期间控制温度50℃-80℃;
4)滴加完成后,温度升至80℃-100℃,保温1~3小时;
5)冷却釜内物料温度至50~60℃;
6)向反应釜中加入计量好的巯基羧酸和强酸性阳离子交换树脂;
7)升温至100~110℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
作为优选方案,以上所述的硫醇环氧固化剂的制备方法,其包括以下步骤:
1)按质量百分比将酚类物质、含羟基的仲胺投入反应釜中,搅拌均匀;
2)升温至50℃;
3)向反应釜中滴加计量好的醛类物质,期间控制温度50℃-70℃;
4)滴加完成后,温度升至80℃-100℃,保温3小时;
5)冷却釜内物料温度至60℃;
6)向反应釜中加入计量好的巯基羧酸和强酸性阳离子交换树脂;
7)升温至100℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
本发明主要是通过以下几点方案来改进现有技术的不足:
1、本发明通过化学接枝使产物同时含有叔胺基和巯基,得到一款可在低温下单独使用的硫醇类环氧固化剂,简化了下游的配方设计和生产流程。
2、本发明以酚为起始原料,得到的最终产物含苯环核心骨架,与常见市售硫醇类固化剂相比,固化物具有更优越的刚性和耐热性。适用于冬季户外的防腐、地坪、灌浆等工程建设场景。
3、本发明可以通过原料选型和投料配比实现产物分子结构的多样性,从而设计出适用于不同使用需求的产品,实用性更强。
有益效果:本发明和现有技术相比具有以下优点:
本发明通过大量实验筛选出各种反应原料组成和反应具体步骤,制备得到的硫醇环氧固化剂,与环氧树脂搭配,无需加入叔胺促进剂即可实现低温快干,且固化后漆膜硬度高,附着力好,具有优良的防腐性能,适用于低温条件下的户外防腐施工。
具体实施方式
实施例1
1、一种硫醇环氧固化剂,它是由下列质量百分比的原料制成:7.8%的苯酚、7.5%的甲醛、26.3%的二乙醇胺、53.2%的3-巯基丙酸、5.2%的强酸性阳离子交换树脂。
2、硫醇环氧固化剂的制备方法,其包括以下步骤:
1)按质量百分比将7.8%的苯酚、26.3%的二乙醇胺投入反应釜中,搅拌均匀;
2)升温至50℃;
3)向反应釜中分批加入7.5%的甲醛,期间控制温度50℃-70℃;
4)投料完成后,温度升至80℃-100℃,保温3小时;
5)冷却釜内物料温度至60℃;
6)向反应釜中加入53.2%的3-巯基丙酸和5.2%强酸性阳离子交换树脂;
7)升温至100℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
实施例2
1、一种硫醇环氧固化剂,它是由下列质量百分比的原料制成:33%的壬基酚、16%的苯甲醛、20%的二异丙醇胺、28%的巯基乙酸、3%的强酸性阳离子交换树脂。
2、硫醇环氧固化剂的制备方法,其包括以下步骤:
1)按质量百分比将33%的壬基酚、20%的二异丙醇胺投入反应釜中,搅拌均匀;
2)升温至50℃;
3)向反应釜中滴入16%的苯甲醛,期间控制温度50℃-70℃;
4)投料完成后,温度升至80℃-100℃,保温3小时;
5)冷却釜内物料温度至60℃;
6)向反应釜中加入28%的巯基乙酸和3%的强酸性阳离子交换树脂;
7)升温至100℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
实施例3
1、一种硫醇环氧固化剂,它是由下列质量百分比的原料制成:14%的邻甲酚、19%的正丁醛、33%的N-羟乙基哌嗪、31%的4-巯基丁酸、3%的强酸性阳离子交换树脂。
2、硫醇环氧固化剂的制备方法,其包括以下步骤:
1)按质量百分比将14%的邻甲酚、33%的N-羟乙基哌嗪投入反应釜中,搅拌均匀;
2)升温至50℃;
3)向反应釜中滴入19%的正丁醛,期间控制温度50℃-70℃;
4)投料完成后,温度升至80℃-100℃,保温3小时;
5)冷却釜内物料温度至60℃;
6)向反应釜中加入31%的4-巯基丁酸和3%的强酸性阳离子交换树脂;
7)升温至100℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
对比实施例1
1、去掉实施例1中3-巯基丙酸的酯化步骤,即利用苯酚、甲醛和二乙醇胺制备一款不含巯基的胺类环氧固化剂。它由下列质量百分比的原料制成:19%的苯酚、18%的甲醛、63%的二乙醇胺。
2、不含巯基的胺类环氧固化剂的制备方法,其包括以下步骤:
1)按质量百分比将19%苯酚、63%的二乙醇胺投入反应釜中,搅拌均匀;
2)升温至50℃;
3)向反应釜中分批加入18%的甲醛,期间控制温度50℃-70℃;
4)投料完成后,温度升至80℃-100℃,保温3小时;
5)保温完成后开启真空,除去反应生成的水;
6)冷却。得到成品不含巯基的胺类环氧固化剂。
实施例4性能测试
将环氧树脂(江苏三木化工股份有限公司生产828)与以上实施例1~3和对比实施例1制得的环氧固化剂1:1混合均匀,然后涂布于马口铁板成膜,膜厚40μm。
同时相同条件测试一款市售聚硫醇CAPCURE 3-800(CAPCURE 3-800单独与环氧树脂828搭配无法有效固化,因此搭配5%叔胺催化剂DMP-30测试)。实施例1~3、对比实施例1、聚硫醇CAPCURE 3-800和DMP-30(叔胺催化剂)搭配使用分别测得基本性能如下表。
注:硬度按国标GB/T6739-1996规定方法测试;附着力按国标GB/T9286-88规定方法测试;耐盐雾按国标GB/T1771-91规定方法测试。
以上性能检测结果表明,本发明制备得到的硫醇环氧固化剂与环氧树脂搭配固化,具有低温快干的特性,且固化后漆膜硬度高,附着力好,具有优良的防腐性能,适用于低温条件下的户外防腐施工。
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 (4)
1.一种硫醇环氧固化剂,其特征在于:它是由下列质量百分比的原料制成:
5-35%酚类物质、5-25%醛类物质、15-40%的含羟基的仲胺、20-55%的巯基羧酸、3-8%的强酸性阳离子交换树脂;
所述的酚类物质为苯酚、壬基酚、邻甲酚;
所述的醛类物质为甲醛、苯甲醛、正丁醛;
所述的含羟基的仲胺为二乙醇胺、二异丙醇胺、N-羟乙基哌嗪;
所述的巯基羧酸为3-巯基丙酸、巯基乙酸、4-巯基丁酸。
2.权利要求1所述的硫醇环氧固化剂的制备方法,其特征在于,包括以下步骤:
1)按质量百分比将酚类物质、含羟基的仲胺投入反应釜中,搅拌均匀;
2)升温至50~60℃;
3)向反应釜中滴加计量好的醛类物质,期间控制温度50℃-80℃;
4)滴加完成后,温度升至80℃-100℃,保温1~3小时;
5)冷却釜内物料温度至50~60℃;
6)向反应釜中加入计量好的巯基羧酸和强酸性阳离子交换树脂;
7)升温至100~110℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
3.根据权利要求2所述的硫醇环氧固化剂的制备方法,其特征在于,包括以下步骤:
1)按质量百分比将酚类物质、含羟基的仲胺投入反应釜中,搅拌均匀;
2)升温至50℃;
3)向反应釜中滴加计量好的醛类物质,期间控制温度50℃-70℃;
4)滴加完成后,温度升至80℃-100℃,保温3小时;
5)冷却釜内物料温度至60℃;
6)向反应釜中加入计量好的巯基羧酸和强酸性阳离子交换树脂;
7)升温至100℃,同时蒸出反应生成的水;
8)至反应无水生成后,过滤除去强酸性阳离子交换树脂,得到成品硫醇环氧固化剂。
4.根据权利要求2或3所述的硫醇环氧固化剂的制备方法,其特征在于,所述的酚类物质、醛类物质、含羟基仲胺的摩尔量比为1:1:1或1:2:2或1:3:3,所述的巯基羧酸的摩尔数与酚类物质和含羟基仲胺中的羟基的摩尔数相等。
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