CN110938191A - 一种水性环氧固化剂的制备方法 - Google Patents
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Abstract
本发明公开了一种水性环氧固化剂的制备方法,包括以下步骤:1)在N2保护下,将聚氧化乙烯类化合物升温至140℃脱水2h,再加入一定量的缩水甘油醚类化合物混合均匀;2)在步骤1)混合后体系中,引入一定量的催化剂,在120~180℃反应4‑6h得到中间产物;3)将步骤2)得到的中间产物中缓慢滴加胺类物质,在70℃~90℃反应1‑2h,再加水稀释得到水性环氧固化剂;通过化学改性法制备水性环氧固化剂,在固化剂分子链中引入了聚氧化乙烯链段,提高了水性环氧固化剂储存稳定性,产品毒性低,与水性环氧树脂相容性好,便于大规模推广使用。
Description
技术领域
本发明涉及化工产品开发领域,特别涉及一种水性环氧固化剂的制备方法。
背景技术
环氧树脂作为三大通用热固性树脂之一,具有优良的工艺性能、机械性能和物理性能,广泛应用于机械电子、航空航天、交通和建筑等领域。单纯的环氧树脂没有很大的利用价值,只有在加入固化剂及其他一些改性成分后使之形成三维网状结构的高聚合物材料才能够得到一系列优良的物理机械性能。
水性双组分环氧涂料替代双组分溶剂型环氧涂料用于船舶、交通、工业防护等领域防腐将大幅减少挥发性有机物排放,有利于保护环境。分子链段中接上适量亲水在水体系有一定稳定性的环氧乳液基本上是以小分子的形式存在,在实际应用中不存在应用价值或应用价值小。水性环氧固化剂可以将每个环氧分子连接起来,形成3D网状的大分子,漆膜才具备综合性能,水性环氧固化剂是双组分水性环氧涂料的重要组成,所以合成性能优异的水性环氧固化剂非常重要。
目前市场上水性环氧固化剂质量参差不齐,未经改性的胺类固化剂会存在挥发性大、毒性大、多元胺伯胺含量高,生成的碳酸盐会导致漆膜发白,而且未经改性的多元胺存在相容性差等问题。本发明制备的水性环氧固化剂稳定性好,毒性低,相容性好,适合大规模推广应用。
发明内容
为了解决现有的水性环氧固化剂挥发性大、毒性大、多元胺伯胺含量高的问题,本发明提供一种稳定性好、毒性低、相容性好的水性环氧乳液的制备方法。
为了实现上述目的,本发明提供的技术方案是:一种水性环氧固化剂的制备方法,其特征在于,包括以下步骤:
1)在N2保护下,将聚氧化乙烯类化合物升温至140℃脱水2h,再加入一定量的缩水甘油醚类化合物混合均匀;
2)在步骤1)混合后体系中,引入一定量的催化剂,在120~180℃反应4-6h得到中间产物;
3)将步骤2)得到的中间产物中缓慢滴加胺类物质,在70℃~90℃反应1-2h,再加水稀释得到水性环氧固化剂。
在上述制备方法中,所述步骤1)中的聚氧化乙烯类化合物为聚乙二醇、聚丙二醇和聚醚多元醇其中的一种或者多种。
在上述制备方法中,作为优选的技术方案,所述步骤1)中聚氧化乙烯类化合物和缩水甘油醚类化合物的摩尔比为1:3~1:1。
作为优选的技术方案,所述步骤1)中的缩水甘油醚类化合物为单缩水甘油醚,二缩水甘油醚及环氧树脂中的一种或者多种。
在上述技术方案中,所述步骤3)中的胺类物质为脂肪胺、脂环胺、聚醚胺和芳香胺中的一种或者多种。
作为优选的技术方案,所述步骤3)中的胺类物质添加量为缩水甘油醚类化合物摩尔数的0.5~2倍。
进一步的,所述步骤3)中的加水量为水性环氧固化剂总量的20~40%。
在上述技术方案中,作为优选的技术方案,所述步骤3)中水性环氧固化剂的活性氢当量为150~300g/eq。
本发明相对于现有技术的有益效果是:通过化学改性法制备水性环氧固化剂,在固化剂分子链中引入了聚氧化乙烯链段,提高了水性环氧固化剂储存稳定性,产品毒性低,与水性环氧树脂相容性好,便于大规模推广使用。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是,对于这些实施方式的说明用于帮助理解本发明,但并不构成对本发明的限定。此外,下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例一:
1)在N2保护下,称量200g聚乙二醇(4000分子量)升温至140℃脱水2h,再加入17.1g的烯丙基缩水甘油醚类化合物混合均匀;
2)在步骤1)混合后体系中,加入0.6g的过硫酸钾,180℃反应4h得到中间产物PEG-AGE;
3)将步骤2)得到的中间产物PEG-AGE中缓慢滴加60g聚醚胺,70℃反应2h,再加入68g水稀释得到水性环氧固化剂,该固化剂固含量为80%,活性氢当量为195g/eq。
实施例二:
1)在N2保护下,称量300g聚醚多元醇(2000分子量)升温至140℃脱水2h,再加入24.6g的邻甲苯基缩水甘油醚类化合物混合均匀;
2)在步骤1)混合后体系中,加入1g的三氟化硼乙醚络合物,120℃反应6h得到中间产物PMPO-CGE;
3)将步骤2)得到的中间产物PMPO-CGE中缓慢滴加31g二乙烯三胺,90℃反应1.5h,再加入237g水稀释得到水性环氧固化剂,该固化剂固含量为60%,活性氢当量为300g/eq。
实施例三:
1)在N2保护下,称量200g聚丙二醇(2000分子量)升温至140℃脱水2h,再加入32.8g的苄基缩水甘油醚类化合物混合均匀;
2)在步骤1)混合后体系中,加入0.6g的过硫酸钾,160℃反应6h得到中间产物PPG-BGE;
3)将步骤2)得到的中间产物PPG-BGE中缓慢滴加10.7g邻甲苯胺,80℃反应1h,再加入104g水稀释得到水性环氧固化剂,该固化剂固含量为70%,活性氢当量为150g/eq。
实施例四:
1)在N2保护下,称量200g聚乙二醇(6000分子量)升温至140℃脱水2h,再加入35.6g的E51环氧树脂混合均匀;
2)在步骤1)混合后体系中,加入1g的三氟化硼乙胺络合物,180℃反应5h得到中间产物PEG-EP;
3)将步骤2)得到的中间产物PEG-EP中缓慢滴加8.5g异佛尔酮二胺,70℃反应2h,再加入61g水稀释得到水性环氧固化剂,该固化剂固含量为80%,活性氢当量为225g/eq。
表1
表1为实施例一至实施例四制备得到的水性环氧固化剂样品指标。
以上对本发明的实施方式作了详细说明,但本发明不限于所描述的实施方式。对于本领域的技术人员而言,在不脱离本发明原理和精神的情况下,对这些实施方式进行多种变化、修改、替换和变型,仍落入本发明的保护范围内。
Claims (8)
1.一种水性环氧固化剂的制备方法,其特征在于,包括以下步骤:
1)在N2保护下,将聚氧化乙烯类化合物升温至140℃脱水2h,再加入一定量的缩水甘油醚类化合物混合均匀;
2)在步骤1)混合后体系中,引入一定量的催化剂,在120~180℃反应4-6h得到中间产物;
3)将步骤2)得到的中间产物中缓慢滴加胺类物质,在70℃~90℃反应1-2h,再加水稀释得到水性环氧固化剂。
2.根据权利要求1所述的水性环氧固化剂的制备方法,其特征在于:所述步骤1)中的聚氧化乙烯类化合物为聚乙二醇、聚丙二醇和聚醚多元醇其中的一种或者多种。
3.根据权利要求1或2所述的水性环氧固化剂的制备方法,其特征在于:所述步骤1)中聚氧化乙烯类化合物和缩水甘油醚类化合物的摩尔比为1:3~1:1。
4.根据权利要求1所述的水性环氧固化剂的制备方法,其特征在于:所述步骤1)中的缩水甘油醚类化合物为单缩水甘油醚,二缩水甘油醚及环氧树脂中的一种或者多种。
5.根据权利要求1所述的水性环氧固化剂的制备方法,其特征在于:所述步骤3)中的胺类物质为脂肪胺、脂环胺、聚醚胺和芳香胺中的一种或者多种。
6.根据权利要求1或5所述的水性环氧固化剂的制备方法,其特征在于:所述步骤3)中的胺类物质添加量为缩水甘油醚类化合物摩尔数的0.5~2倍。
7.根据权利要求1所述的水性环氧固化剂的制备方法,其特征在于:所述步骤3)中的加水量为水性环氧固化剂总量的20~40%。
8.根据权利要求1所述的水性环氧固化剂的制备方法,其特征在于:所述步骤3)中水性环氧固化剂的活性氢当量为150~300g/eq。
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