CN114479015A - 一种水性环氧树脂固化剂及其制备方法与应用 - Google Patents
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Abstract
Description
技术领域
本发明属于高分子化学领域,具体涉及一种水性环氧树脂固化剂及其制备方法与应用。
背景技术
近年来,随着国家政策的驱动以及人们环保意识的不断增强,水性环氧树脂涂料的应用越来越广泛,种类也越来越多,但是市面上大多都是脂肪族胺制备的水性环氧固化剂,而芳香胺制备的水性环氧固化剂的种类却很少。
苯胺,又称阿尼林,是一种芳香族胺,水溶性较差,是最重要的胺类物质之一。作为常见的大宗原材料,苯胺的用途非常广泛,在染料、药物、树脂、橡胶硫化促进剂等领域有着非常重要的应用。苯胺因为其活性低、疏水性较强,很难制备水性环氧固化剂,因此目前多以聚苯胺的形式制备水性固化剂,例如中国专利文献CN105647378A以聚苯胺的形式制备水性环氧固化剂,但是由于聚苯胺的疏水性更强、韧性更差,其制备的水性固化剂的工艺繁琐且成膜性能不好。
因此,研究直接以苯胺或改性后的苯胺制备水性环氧树脂固化剂具有重要意义。
发明内容
本发明的目的是提供一种水性环氧树脂固化剂及其制备方法,该水性环氧树脂固化剂以苯胺及苯胺衍生物在一定条件下与含有聚醚链段等亲水基团的化合物反应后,再与多聚甲醛和多元胺在一定条件下反应得到,并进而提供该环氧树脂固化剂的应用。
本发明是通过以下技术方案来实现的:
第一方面,本发明提供一种水性环氧树脂固化剂,具有如下所示的结构式:
其中,n为1或2;
R1、R2分别为H、C1~C10羧基、C1~C10酯基、C1~C10羟基或C1~C50聚醚链段,但不同时为H;
n为1时,R3为H、C1~C10烷基、C1~C10氨基、C1~C10羟基或C1~C10羧基,n为2时,R3不存在;
R4为H、卤素、C1~C10烷基或-CH2-NH-R3;R4’为H、卤素、C1~C10烷基或-CH2-NH-R3;
R5,R6彼此独立地为H或卤素。
优选地,上述水性环氧树脂固化剂中,R1为H、C1~C5羧基、C1~C8羟基、C1~C8酯基、或C2~C30聚醚链段;R2为H、C1~C5羧基、C1~C8羟基、C1~C8酯基、或C2~C30聚醚链段;n为1时,R3为H、C1~C6烷基、C1~C10氨基、C1~C5羧基或C1~C8羟基,n为2时,R3不存在;R4为H或-CH2-NH-R3;R4’为H或-CH2-NH-R3;R5,R6彼此独立地为H。
根据本发明的第二个方面,提供一种制备上述水性环氧树脂固化剂的方法,该方法包括使以下原料反应而制备上述水性环氧树脂固化剂:
c)甲醛溶液(优选的浓度范围20wt%~40wt%)或甲醛聚合物;
d)一元胺或多元胺;
其中,R1、R2分别为H、C1~C10羧基、C1~C10酯基、C1~C10羟基或C1~C50聚醚链段,但不同时为H;
n为1时,R3为H、C1~C10烷基、C1~C10氨基、C1~C10羟基或C1~C10羧基,n为2时,R3不存在;
R4为H、卤素、C1~C10烷基或-CH2-NH-R3;R4’为H、卤素、C1~C10烷基或-CH2-NH-R3;
R5,R6彼此独立地为H或卤素;
R7为H、C1~C10羟基或C2~C10环氧基;
R8为H或甲基;
R为C1~C10烷基、C1~C10酯基或C1~C50聚醚链段;
R’为C1-C5烷基或C1-C5羟烷基。
优选地,上述水性环氧树脂固化剂的制备方法中,R1为H、C1~C5羧基、C1~C8羟基、C1~C8酯基、或C2~C30聚醚链段;R2为H、C1~C5羧基、C1~C8羟基、C1~C8酯基、或C2~C30聚醚链段;n为1时,R3为H、C1~C6烷基、C1~C10氨基、C1~C5羧基或C1~C8羟基,n为2时,R3不存在;R4为H或-CH2-NH-R3;R4’为H或-CH2-NH-R3;R5,R6彼此独立地为H;R7为C2~C6环氧基;R为C1~C5烷基、C1~C8酯基或C2~C30聚醚链段。
优选地,上述水性环氧树脂固化剂的制备方法中,
所述组分a)选自苯胺、N-甲基苯胺、N-乙基苯胺、卤代苯胺(卤素选自氟、氯、溴、碘)和烷基(例如C1-C6烷基)代苯胺中的至少一种,优选为苯胺;
所述组分b)选自丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、烯丙醇、聚乙二醇二缩水甘油醚和聚丙二醇二缩水甘油醚中的至少一种;
所述组分c)选自甲醛溶液、三聚甲醛或多聚甲醛;
所述组分d)选自脂肪族多元胺及其衍生物、脂环胺及其衍生物和芳香族胺及其衍生物中的至少一种;所述脂肪族多元胺选自乙二胺、二乙烯三胺、三乙烯四胺、己二胺和辛二胺中的至少一种;所述脂环胺选自异佛尔酮二胺、1,3-环己二甲胺、4,4’-二氨基二环己基甲烷和环己胺中的至少一种;所述芳香族胺选自间苯二甲胺。
进一步地,制备上述水性环氧树脂固化剂的方法包括以下步骤:
(1)取选定质量的组分a)与组分b)加入到反应容器中,加热(例如加热至80~120℃)搅拌下反应(例如反应2~6h),制备得到中间产物;
(2)取选定质量的组分c)和组分d)加入到所述反应容器中,加热(例如反应温度为80~120℃)搅拌下反应(例如反应2~6h),制备得到固化剂产物;
(3)将所述固化剂产物降温(例如降温至室温),加入去离子水,即得水性环氧树脂固化剂。
优选地,上述制备方法中,所述组分a)选自苯胺、N-甲基苯胺、N-乙基苯胺、卤代苯胺(卤素选自氟、氯、溴、碘)和烷基(例如C1-C6烷基)代苯胺中的至少一种,优选为苯胺;所述组分b)选自丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、烯丙醇、聚乙二醇二缩水甘油醚和聚丙二醇二缩水甘油醚中的至少一种;所述组分c)选自甲醛溶液、三聚甲醛或多聚甲醛;所述组分d)选自脂肪族多元胺及其衍生物、脂环胺及其衍生物和芳香族胺及其衍生物中的至少一种;所述脂肪族多元胺选自乙二胺、二乙烯三胺、三乙烯四胺、己二胺和辛二胺中的至少一种;所述脂环胺选自异佛尔酮二胺、1,3-环己二甲胺、4,4’-二氨基二环己基甲烷和环己胺中的至少一种;所述芳香族胺选自间苯二甲胺。
优选地,上述制备方法中,组分a)与组分b)的摩尔比为1:(0.5~2.5),优选为1:(1~2),比如可以为1:0.7或1:1.6;和/或,组分a)、组分c)与组分d)三者的摩尔比为1:(0.5~2):(0.5~2),优选为1:(0.8~1.2):(0.8~1.2),比如可以为1:0.6:0:6、1:1:1、1:1.5:1.5或1:1.8:1.8,其中组分c)的摩尔量以甲醛计。
第三方面,本发明还提供上述水性环氧树脂固化剂或上述制备方法制备得到的水性环氧树脂固化剂在制备水性涂料中的应用。
第四方面,本发明提供一种水性涂料,采用上述水性环氧树脂固化剂或上述制备方法制备得到的水性环氧树脂固化剂制备而成。
由水性环氧树脂固化剂制备水性涂料的方法是本领域所熟知的。
本发明的技术方案具有如下优点:
(1)本发明创造性地对苯胺进行改性、进而利用苯胺及其衍生物通过一定的工艺制备得到水性环氧固化剂。该水性环氧固化剂可以依靠苯胺上活泼氢和侧链上活泼氢与环氧树脂进行交联,增加了体系的交联密度,进一步提高了体系的性能。该水性环氧树脂固化剂具有很好的耐酸效果,可以应用于水性地坪、水性钢结构防腐涂料领域,具有明显的应用价值。
(2)本发明以含有羧基、羟基、酯基或聚醚结构的化合物分别可以制备得到离子型和非离子型水性环氧固化剂,可以适用于不同的配方体系。
(3)本发明以不同的一元胺或多元胺、以不同结构的含有氨基的化合物可以制备不同链段长度、不同体系、不同力学强度、不同性能的水性环氧树脂固化剂,因而可以满足各种不同的应用需求。
(4)本发明的水性环氧树脂固化剂既可以单独使用,也可以与其他环氧树脂固化剂配合使用,应用范围广。
附图说明
为了使本发明的内容更容易被清楚的理解,下面根据本发明的具体实施例并结合附图,对本发明作进一步详细的说明,其中:
图1为本发明实施例1的水性环氧树脂固化剂的IR图;
图2为本发明实施例2的水性环氧树脂固化剂的IR图;
图3为本发明实施例3的水性环氧树脂固化剂的IR图;
图4为本发明实施例4的水性环氧树脂固化剂的IR图。
图5为本发明实施例5的水性环氧树脂固化剂的IR图。
具体实施方式
通过具体实施例对本发明做进一步说明,本发明所述实施例只是作为对本发明的说明,并不限制本发明的范围。
本发明实施例中用到的主要化学品名称、缩写及来源如下表所示。非特殊标明下,所用试剂均为化学分析纯。
表1
实施例1
本实施例水性环氧树脂固化剂的制备方法包括以下步骤:(1)将9.3g(0.1mol)的苯胺和30g(0.053mol)的聚乙二醇二缩水甘油醚,加入到三口反应容器中,搅拌均匀,加热至80℃下,反应2h得中间产物;(2)将3g多聚甲醛(含有0.1mol甲醛)和6g(0.1mol)乙二胺加入到步骤(1)中的三口反应容器中,在80℃搅拌下反应2h,制备得到固化剂产物;(3)将上述固化剂产物降至室温,加入46.5g去离子水,即得水性环氧树脂固化剂,其理论结构式如下所示,IR图如图1所示。经过IR图分析确认实际结构式与理论结构式相同。
实施例2
本实施例水性环氧树脂固化剂的制备方法包括以下步骤:(1)将9.3g(0.1mol)的苯胺和56g(0.1mol)的聚乙二醇二缩水甘油醚,加入到三口反应容器中,搅拌均匀,加热至120℃下,反应4h得中间产物;(2)将6g多聚甲醛(含有0.2mol甲醛)和20.6g(0.2mol)二乙烯三胺加入到步骤(1)中的三口反应容器中,在120℃搅拌下反应4h,制备得到固化剂产物;(3)将上述固化剂产物降至室温,加入87.7g去离子水,即得水性环氧树脂固化剂。其理论结构式如下所示,IR图如图2所示。经过IR图分析确认实际结构式与理论结构式相同。
实施例3
本实施例水性环氧树脂固化剂的制备方法包括以下步骤:(1)将9.3g(0.1mol)的苯胺和7.2g(0.1mol)的丙烯酸,加入到三口反应容器中,搅拌均匀,加热至80℃下,反应2h得中间产物;(2)将3g多聚甲醛(含有0.1mol甲醛)和6g(0.1mol)乙二胺加入到步骤(1)中的三口反应容器中,在80℃搅拌下反应4h,制备得到固化剂产物;(3)将上述固化剂产物降至室温,加入23.7g去离子水,即得水性环氧树脂固化剂。其理论结构式如下所示,IR图如图3所示。经过IR图分析确认实际结构式与理论结构式相同。
实施例4
本实施例水性环氧树脂固化剂的制备方法包括以下步骤:(1)将9.3g(0.1mol)的苯胺和23.2g(0.2mol)的丙烯酸羟乙酯,加入到三口反应容器中,搅拌均匀,加热至80℃下,反应2h得中间产物;(2)将3g多聚甲醛(含有0.1mol甲醛)和6g(0.1mol)乙二胺加入到步骤(1)中的三口反应容器中,在80℃搅拌下反应4h,制备得到固化剂产物;(3)将上述固化剂产物降至室温,加入39.7g去离子水,即得水性环氧树脂固化剂。其理论结构式如下所示,IR图如图4所示。经过IR图分析确认实际结构式与理论结构式相同。
实施例5
本实施例水性环氧树脂固化剂的制备方法包括以下步骤:(1)将9.3g(0.1mol)的苯胺和30g(0.053mol)的聚乙二醇二缩水甘油醚,加入到三口反应容器中,搅拌均匀,加热至80℃下,反应2h得中间产物;(2)将6g多聚甲醛(含有0.2mol甲醛)和12g(0.2mol)乙二胺加入到步骤(1)中的三口反应容器中,在80℃搅拌下反应2h,制备得到固化剂产物;(3)将上述固化剂产物降至室温,加入53.7g去离子水,即得水性环氧树脂固化剂,其理论结构式如下所示,IR图如图5所示。经过IR图分析确认实际结构式与理论结构式相同。
分别将实施例1-5制备的水性环氧树脂固化剂、某市售水性环氧树脂固化剂与环氧树脂乳液wanpro0901按照一定配比混合均匀后,刮涂漆膜样板,进行耐酸性能测试,测试方法为《GB/T9274-1988色漆和清漆耐液体介质的测定》中丙法,具体测试结果如表2所示。
表2
编号 | 耐10%H<sub>2</sub>SO<sub>4</sub>(d) |
实施例1 | 10 |
实施例2 | 12 |
实施例3 | 7 |
实施例4 | 8 |
实施例5 | 12 |
市售固化剂 | 3 |
从表2中的测试结果可以看出,本发明实施例1-5的水性环氧树脂固化剂制备的环氧树脂固化物漆膜的耐酸性能较好,完全满足环氧树脂地坪材料的应用需求,具有一定的应用领域。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (9)
2.根据权利要求1所述的水性环氧树脂固化剂,其特征在于,R1为H、C1~C5羧基、C1~C8羟基或C2~C30聚醚链段;R2为H、C1~C5羧基、C1~C8羟基或C2~C30聚醚链段;n为1时,R3为H、C1~C6烷基、C1~C10氨基、C1~C5羧基或C1~C8羟基,或在n等于2时R3不存在;R4为H或-CH2-NH-R3;R4’为H或-CH2-NH-R3;R5,R6彼此独立地为H。
3.一种制备权利要求1或2所述的水性环氧树脂固化剂的方法,其特征在于,该方法包括使以下原料反应而制备水性环氧树脂固化剂:
c)甲醛溶液或甲醛聚合物;
d)一元胺或多元胺;
其中,R1、R2分别为H、C1~C10羧基、C1~C10酯基、C1~C10羟基或C1~C50聚醚链段,但不同时为H;
n为1时,R3为H、C1~C10烷基、C1~C10氨基、C1~C10羟基或C1~C10羧基,n为2时,R3不存在;
R4为H、卤素、C1~C10烷基或-CH2-NH-R3;R4’为H、卤素、C1~C10烷基或-CH2-NH-R3;
R5,R6彼此独立地为H或卤素;
R7为H、C1~C10羟基或C2~C10环氧基;
R8为H或甲基;
R为C1~C10烷基、C1~C10酯基或C1~C50聚醚链段;
R’为C1-C5烷基或C1-C5羟烷基。
4.根据权利要求3所述的方法,其特征在于,R1为H、C1~C5羧基、C1~C8羟基、C1~C8酯基、或C2~C30聚醚链段;R2为H、C1~C5羧基、C1~C8羟基、C1~C8酯基、或C2~C30聚醚链段;n为1时,R3为H、C1~C6烷基、C1~C10氨基、C1~C5羧基或C1~C8羟基,n为2时,R3不存在;R4为H或-CH2-NH-R3;R4’为H或-CH2-NH-R3;R5,R6彼此独立地为H;R7为C2~C6环氧基;R为C1~C5烷基、C1~C8酯基或C2~C30聚醚链段。
5.根据权利要求3或4所述的方法,其特征在于,
所述组分a)选自苯胺、N-甲基苯胺、N-乙基苯胺、卤代苯胺和烷基代苯胺中的至少一种,优选为苯胺;
所述组分b)选自丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、烯丙醇、聚乙二醇二缩水甘油醚和聚丙二醇二缩水甘油醚中的至少一种;
所述组分c)选自甲醛溶液、三聚甲醛或多聚甲醛;
所述组分d)选自脂肪族多元胺、脂环胺和芳香族胺中的至少一种;所述脂肪族多元胺选自乙二胺、二乙烯三胺、三乙烯四胺、己二胺和辛二胺中的至少一种;所述脂环胺选自异佛尔酮二胺、1,3-环己二甲胺、4,4’-二氨基二环己基甲烷和环己胺中的至少一种;所述芳香族胺选自间苯二甲胺。
6.根据权利要求3-5中任一项所述的方法,其特征在于该方法包括:
(1)取选定质量的组分a)与组分b)加入到反应容器中,加热(例如加热至80~120℃)搅拌下反应(例如反应2~6h),制备得到中间产物;
(2)取选定质量的组分c)和组分d)加入到所述反应容器中,加热(例如反应温度为80~120℃)搅拌下反应(例如反应2~6h),制备得到固化剂产物;
(3)将所述固化剂产物降温(例如降温至室温),加入去离子水,即得水性环氧树脂固化剂。
7.根据权利要求3-6中任一项所述的方法,其特征在于,组分a)与组分b)的摩尔比为1:(0.5~2.5),优选为1:(1~2);和/或,
组分a)、组分c)与组分d)三者的摩尔比为1:(0.5~2):(0.5~2),优选为1:(0.8~1.2):(0.8~1.2),其中组分c)的摩尔量以甲醛计。
8.权利要求1-2中任一项所述的水性环氧树脂固化剂或权利要求3-8中任一项所述的方法制备得到的水性环氧树脂固化剂在制备水性涂料中的应用。
9.一种水性涂料,其特征在于,采用权利要求1-2中任一项所述的水性环氧树脂固化剂或权利要求3-7中任一项所述的方法制备得到的水性环氧树脂固化剂制备而成。
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