CN106939138B - 一种抗剥离低聚物水性环氧涂料的制备方法 - Google Patents
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Abstract
本发明公开了一种抗剥离低聚物水性环氧涂料的制备方法,本发明的抗剥离低聚物水性环氧涂料相比于传统水性环氧树脂涂料具有更好的附着力,抗剥离强度高,耐水、酸、碱、盐、汽油性强,铅笔硬度高,拉伸强度高,各原料在水溶液中分散性好,无结块无沉积,涂覆在基材表面平整性好,无颗粒。
Description
技术领域
本发明属于涂料领域,具体涉及一种抗剥离低聚物水性环氧涂料的制备方法。
背景技术
环氧树脂具有优异的耐化学腐蚀性,对众多底材具有极佳的附着力,能与多种固化剂固化,涂膜的致密性好、刚性强、耐热耐磨性都很好,在防腐涂料中占据着重要地位,通过添加不同的填料和调整固化剂品种,可以制成性能各异的环氧树脂防腐涂料、适用于不同的防腐场合,达到良好的保护效果。每年世界上约有 40%的环氧树脂应用于制造环氧涂料,大部分应用于防腐领域。在我国,大约有 30%~40%的环氧树脂被加工成各种各样的涂料,在船舶、土木工程、家用电器、机电工业等领域有着广泛的用途。
环氧树脂用于防腐蚀涂料中以液体树脂所占份额最大,但目前工业上使用的涂料大部分是溶剂型涂料,常规溶剂型涂料多以芳烃、酯类、醇类、酮类等作为溶剂,这些溶剂均具有不同程度的毒性,而且挥发物直接排入空气,对环境污染较重。随着人们环保意识的增强,不含有机溶剂或低 VOC 的新型防腐蚀涂料如粉末涂料、无溶剂涂料和水性涂料等绿色涂料相继被开发。粉末涂料因固化条件较为苛刻,从而限制了它的发展;无溶剂环氧涂料在无溶剂化涂料领域是比较成功的,只是近年来在活性稀释剂的低毒性和固化剂的安全可靠性等方面受到了挑战,正在改善之中;而水性环氧涂料除了秉承溶剂型涂料的诸多优点外,正在向提高性能、减少污染、扩大应用等方面发展,其领域己涵盖机车、航空、食品、建筑等,因此水性环氧涂料是近年来发展十分迅速的一个领域;
环氧树脂固化物因脆性大,抗冲击性、耐酸碱性、柔韧性及耐温性差,限制了环氧树脂涂料的应用,因此对环氧树脂的改性一直是对环氧树脂防腐涂料研究的重点之一,而为了提高其力学性能,往往在其中加入各种膨润土、石墨烯等无机填料,但是这些无机填料与环氧树脂的相容性较差,容易造成涂料的贮存稳定性差,且容易形成结块,降低了涂料的品质,且传统的水性环氧树脂涂料与基材的附着力等级为2级,虽然能够满足实际生产生活中对涂膜的要求,但是对于一些需要经常擦拭、表面平整性较差的基材来说,还是需要更强的剥离强度才能满足对基材的持久性保护,因此,本发明的目的就是提供一种更高附着力、成品分散性好、不结块的水性环氧树脂涂料。
发明内容
本发明的目的在于进一步提高传统水性环氧树脂的抗剥离强度,解决无机填料与环氧树脂间的分散性较差的问题,提供一种抗剥离低聚物水性环氧涂料的制备方法。
为实现上述目的,本发明采用以下技术方案:
一种抗剥离低聚物水性环氧涂料的制备方法,包括以下步骤:
(1)取2-3重量份的羊毛脂,加入到其重量57-60倍的无水乙醇中,在80-85℃下保温搅拌4-10分钟;
(2)取27-32重量份的正硅酸乙酯,加入到其重量30-40倍的去离子水中,搅拌1-2小时,与上述羊毛脂的乙醇溶液混合,搅拌反应40-50分钟,与10-13重量份的氯乙酸混合,送入到反应釜中,在110-120℃的保温反应1-2小时,出料冷却,得酯化溶胶分散液;
(3)取1-3重量份的γ-氨丙基三乙氧基硅烷,与上述酯化溶胶分散液混合,升高温度为60-65℃,超声30-40分钟,过滤,将沉淀水洗,常温干燥,得氨基酯化溶胶;
(4)取0.3-0.5重量份的十六烷基二甲基叔胺、30-36重量份的四氢呋喃混合,搅拌均匀,得催化混合溶液;
(5)取上述氨基酯化溶胶,与10-12重量份的、30-35%的甲醛溶液混合,搅拌均匀,加入上述催化混合溶液,在70-75℃下保温搅拌36-50分钟,得氨基低聚物溶胶;
(6)取1-2重量份的聚乙二醇、24-30重量份的环氧树脂E44混合,搅拌均匀,送入到反应釜中,调节反应釜温度为56-70℃,保温搅拌10-20分钟,通入氮气,加入0.1-0.2重量份的三氟化硼***,搅拌反应3-4小时,出料,降低温度为35-40℃,加入4-5重量份的油酸,保温搅拌1-2小时,得油酸改性环氧树脂预聚物;
(7)将上述氨基低聚物溶胶、油酸改性环氧树脂预聚物混合,加入到混合料重量4-6倍的去离子水中,在70-75℃下保温搅拌4-6小时,得酰胺化低聚物环氧树脂溶胶;
(8)取上述酰胺化低聚物环氧树脂溶胶,与140-150重量份的环氧树脂E44、3-4重量份的二苯基甲烷二异氰酸酯混合,升高温度为60-70℃,保温搅拌110-130分钟,加入混合料重量65-80%的去离子水、0.6-1%的蓖麻油酸、0.4-1%的司盘80,搅拌均匀,再经过胶体磨研磨、均质机乳化,即得所述抗剥离低聚物水性环氧涂料。
所述的步骤(8)中,胶体磨的研磨时间为30-40分钟,均质机乳化的压力为40-60MPa、乳化时间为20-30分钟。
所述抗剥离低聚物水性环氧涂料的使用方法为:在使用前,将抗剥离低聚物水性环氧涂料与其重量20-25%的固化剂混合,搅拌均匀,即可进行涂覆。
所述的固化剂为甲基六氢邻苯二甲酸酐。
本发明的优点:
本发明首先采用正硅酸乙酯为前驱体,与羊毛脂的乙醇溶液混合水解,之后与氯乙酸混合,使得氯乙酸与乙醇在水解溶胶液中发生酯化,得到酯化溶胶分散液,然后将其通过γ-氨丙基三乙氧基硅烷处理,得到氨基酯化溶胶,然后以氨基低聚物溶胶、甲醛为原料,十六烷基二甲基叔胺为催化剂,四氢呋喃为溶剂,经过脱水缩合,得到氨基低聚物溶胶;
然后将环氧树脂E44、聚乙二醇共混,以三氟化硼***为催化剂制备环氧树脂预聚物,然后采用油酸处理,得到羧基化环氧树脂;
之后将氨基低聚物溶胶、油酸改性环氧树脂预聚物混合交联,得酰胺化低聚物环氧树脂溶胶,最后将酰胺化低聚物环氧树脂溶胶与环氧树脂、助剂等进行混合分散,得到本发明的抗剥离低聚物水性环氧涂料;
本发明将正硅酸乙酯的水解与氯乙酸、乙醇的酯化反应同步进行,使得形成的溶胶与酯化料有效的结合,不仅将溶胶表面有机化,而且提高了酯化料的强度和力学性能,从而可以提高成品涂膜的表面的力学性能;
本发明采用氯乙酸乙酯溶胶、甲醛为原料,十六烷基二甲基叔胺为催化剂,四氢呋喃为溶剂,经过加成缩合,得到氨基低聚物溶胶,其具有很高的粘结强度,能够有效的提高涂料与基材间的粘结性,提高涂膜的附着力和抗剥离强度,增强涂膜对基材的保护性能;
本发明将氨基低聚物溶胶、油酸改性环氧树脂预聚物混合交联,氨基低聚物溶胶为碱性溶胶,油酸改性环氧树脂预聚物为酸性预聚物,两者可以形成有效的交联,生成酰胺化交联产物,而交联产物经过酰胺化后,可以很好的实现水溶性,使得各原料在水溶液中能够很好的分散,从而能够使得成品均匀性好,无结块,涂层平整光滑无颗粒。
具体实施方式
实施例1
一种抗剥离低聚物水性环氧涂料的制备方法,包括以下步骤:
(1)取2重量份的羊毛脂,加入到其重量57倍的无水乙醇中,在80℃下保温搅拌4分钟;
(2)取27重量份的正硅酸乙酯,加入到其重量30倍的去离子水中,搅拌1小时,与上述羊毛脂的乙醇溶液混合,搅拌反应40分钟,与10重量份的氯乙酸混合,送入到反应釜中,在110℃的保温反应1小时,出料冷却,得酯化溶胶分散液;
(3)取1重量份的γ-氨丙基三乙氧基硅烷,与上述酯化溶胶分散液混合,升高温度为60℃,超声30分钟,过滤,将沉淀水洗,常温干燥,得氨基酯化溶胶;
(4)取0.3重量份的十六烷基二甲基叔胺、30重量份的四氢呋喃混合,搅拌均匀,得催化混合溶液;
(5)取上述氨基酯化溶胶,与10重量份的、30%的甲醛溶液混合,搅拌均匀,加入上述催化混合溶液,在70℃下保温搅拌36分钟,得氨基低聚物溶胶;
(6)取1重量份的聚乙二醇、24重量份的环氧树脂E44混合,搅拌均匀,送入到反应釜中,调节反应釜温度为56℃,保温搅拌10分钟,通入氮气,加入0.1重量份的三氟化硼***,搅拌反应3小时,出料,降低温度为35℃,加入4重量份的油酸,保温搅拌1小时,得油酸改性环氧树脂预聚物;
(7)将上述氨基低聚物溶胶、油酸改性环氧树脂预聚物混合,加入到混合料重量4倍的去离子水中,在70℃下保温搅拌4小时,得酰胺化低聚物环氧树脂溶胶;
(8)取上述酰胺化低聚物环氧树脂溶胶,与140重量份的环氧树脂E44、3重量份的二苯基甲烷二异氰酸酯混合,升高温度为60℃,保温搅拌110分钟,加入混合料重量65%的去离子水、0.6%的蓖麻油酸、0.4%的司盘80,搅拌均匀,再经过胶体磨研磨、均质机乳化,胶体磨的研磨时间为30分钟,均质机乳化的压力为40MPa、乳化时间为20分钟,即得所述抗剥离低聚物水性环氧涂料。
所述抗剥离低聚物水性环氧涂料的使用方法为:在使用前,将抗剥离低聚物水性环氧涂料与其重量25%的甲基六氢邻苯二甲酸酐混合,搅拌均匀,即可进行涂覆。
本发明实施例1涂料的性能测试:
涂料无结块无沉积,涂层平整光滑无颗粒;
附着力:1级;
涂膜耐腐蚀性能:
蒸馏水/d浸泡边缘起泡:14.3;
3%氯化钠溶液/d浸泡边缘起泡:21;
10%氢氧化钠溶液/d浸泡边缘起泡:17.5;
10%盐酸溶液/d浸泡边缘起泡:5;
汽油/d浸泡边缘起泡:6;
铅笔硬度:4H;
拉伸强度/PMa:110;
实施例2
一种抗剥离低聚物水性环氧涂料的制备方法,包括以下步骤:
(1)取3重量份的羊毛脂,加入到其重量60倍的无水乙醇中,在85℃下保温搅拌10分钟;
(2)取32重量份的正硅酸乙酯,加入到其重量40倍的去离子水中,搅拌2小时,与上述羊毛脂的乙醇溶液混合,搅拌反应40分钟,与13重量份的氯乙酸混合,送入到反应釜中,在120℃的保温反应2小时,出料冷却,得酯化溶胶分散液;
(3)取3重量份的γ-氨丙基三乙氧基硅烷,与上述酯化溶胶分散液混合,升高温度为65℃,超声40分钟,过滤,将沉淀水洗,常温干燥,得氨基酯化溶胶;
(4)取0.5重量份的十六烷基二甲基叔胺、36重量份的四氢呋喃混合,搅拌均匀,得催化混合溶液;
(5)取上述氨基酯化溶胶,与12重量份的、35%的甲醛溶液混合,搅拌均匀,加入上述催化混合溶液,在75℃下保温搅拌50分钟,得氨基低聚物溶胶;
(6)取2重量份的聚乙二醇、30重量份的环氧树脂E44混合,搅拌均匀,送入到反应釜中,调节反应釜温度为70℃,保温搅拌20分钟,通入氮气,加入0.2重量份的三氟化硼***,搅拌反应4小时,出料,降低温度为40℃,加入5重量份的油酸,保温搅拌2小时,得油酸改性环氧树脂预聚物;
(7)将上述氨基低聚物溶胶、油酸改性环氧树脂预聚物混合,加入到混合料重量6倍的去离子水中,在75℃下保温搅拌6小时,得酰胺化低聚物环氧树脂溶胶;
(8)取上述酰胺化低聚物环氧树脂溶胶,与150重量份的环氧树脂E44、4重量份的二苯基甲烷二异氰酸酯混合,升高温度为70℃,保温搅拌130分钟,加入混合料重量80%的去离子水、1%的蓖麻油酸、1%的司盘80,搅拌均匀,再经过胶体磨研磨、均质机乳化,胶体磨的研磨时间为30分钟,均质机乳化的压力为60MPa、乳化时间为30分钟即得所述抗剥离低聚物水性环氧涂料。
在使用前,将抗剥离低聚物水性环氧涂料与其重量25%的甲基六氢邻苯二甲酸酐混合,搅拌均匀,即可进行涂覆。
本发明实施例2涂料的性能测试:
涂料无结块无沉积,涂层平整光滑无颗粒;
附着力:1级;
涂膜耐腐蚀性能:
蒸馏水/d浸泡边缘起泡:14;
3%氯化钠溶液/d浸泡边缘起泡:20.5;
10%氢氧化钠溶液/d浸泡边缘起泡:18;
10%盐酸溶液/d浸泡边缘起泡:5;
汽油/d浸泡边缘起泡:6.5;
铅笔硬度:4H;2
拉伸强度/PMa:108.5;
传统水性环氧树脂涂料的性能测试:
附着力:2级;
涂膜耐腐蚀性能:
蒸馏水/d浸泡边缘起泡:4;
3%氯化钠溶液/d浸泡边缘起泡:6;
10%氢氧化钠溶液/d浸泡边缘起泡:5;
10%盐酸溶液/d浸泡边缘起泡:2;
汽油/d浸泡边缘起泡:2.5;
铅笔硬度:2H;
拉伸强度/PMa:77。
由此可以看出,本发明的抗剥离低聚物水性环氧涂料相比于传统水性环氧树脂涂料具有更好的附着力,抗剥离强度高,耐水、酸、碱、盐、汽油性强,铅笔硬度高,拉伸强度高,各原料在水溶液中分散性好,无结块无沉积,涂覆在基材表面平整性好,无颗粒。
Claims (3)
1.一种抗剥离低聚物水性环氧涂料的制备方法,其特征在于,包括以下步骤:
(1)取2-3重量份的羊毛脂,加入到其重量57-60倍的无水乙醇中,在80-85℃下保温搅拌4-10分钟;
(2)取27-32重量份的正硅酸乙酯,加入到其重量30-40倍的去离子水中,搅拌1-2小时,与上述羊毛脂的乙醇溶液混合,搅拌反应40-50分钟,与10-13重量份的氯乙酸混合,送入到反应釜中,在110-120℃下保温反应1-2小时,出料冷却,得酯化溶胶分散液;
(3)取1-3重量份的γ-氨丙基三乙氧基硅烷,与上述酯化溶胶分散液混合,升高温度为60-65℃,超声30-40分钟,过滤,将沉淀水洗,常温干燥,得氨基酯化溶胶;
(4)取0.3-0.5重量份的十六烷基二甲基叔胺、30-36重量份的四氢呋喃混合,搅拌均匀,得催化混合溶液;
(5)取上述氨基酯化溶胶,与10-12重量份的、30-35%的甲醛溶液混合,搅拌均匀,加入上述催化混合溶液,在70-75℃下保温搅拌36-50分钟,得氨基低聚物溶胶;
(6)取1-2重量份的聚乙二醇、24-30重量份的环氧树脂E44混合,搅拌均匀,送入到反应釜中,调节反应釜温度为56-70℃,保温搅拌10-20分钟,通入氮气,加入0.1-0.2重量份的三氟化硼***,搅拌反应3-4小时,出料,降低温度为35-40℃,加入4-5重量份的油酸,保温搅拌1-2小时,得油酸改性环氧树脂预聚物;
(7)将上述氨基低聚物溶胶、油酸改性环氧树脂预聚物混合,加入到混合料重量4-6倍的去离子水中,在70-75℃下保温搅拌4-6小时,得酰胺化低聚物环氧树脂溶胶;
(8)取上述酰胺化低聚物环氧树脂溶胶,与140-150重量份的环氧树脂E44、3-4重量份的二苯基甲烷二异氰酸酯混合,升高温度为60-70℃,保温搅拌110-130分钟,加入混合料重量65-80%的去离子水、0.6-1%的蓖麻油酸、0.4-1%的司盘80,搅拌均匀,再经过胶体磨研磨、均质机乳化,即得所述抗剥离低聚物水性环氧涂料;胶体磨的研磨时间为30-40分钟,均质机乳化的压力为40-60MPa、乳化时间为20-30分钟。
2.根据权利要求1所述的一种抗剥离低聚物水性环氧涂料的制备方法,其特征在于,所述抗剥离低聚物水性环氧涂料的使用方法为:在使用前,将抗剥离低聚物水性环氧涂料与其重量20-25%的固化剂混合,搅拌均匀,即可进行涂覆。
3.根据权利要求2所述的一种抗剥离低聚物水性环氧涂料的制备方法,其特征在于,所述的固化剂为甲基六氢邻苯二甲酸酐。
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