CN109081885B - 一种用于金属表面处理领域的阳离子型聚丙烯酸酯乳液及其制备方法 - Google Patents
一种用于金属表面处理领域的阳离子型聚丙烯酸酯乳液及其制备方法 Download PDFInfo
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Abstract
本发明属于金属表面处理技术领域,提供一种用于金属表面处理领域的阳离子型聚丙烯酸酯乳液,其原料由如下重量份数的组份组成:水:280份;反应型乳化剂:18.6~24.8份;丙烯酸:1.5~2份;苯乙烯:150~180份;丙烯酸正丁酯:30~52份;10wt%的水溶性偶氮引发剂水溶液:14~16份;甲基丙烯酸缩水甘油酯:5份;丙烯酸羟乙酯:2份;消泡剂:0~1份。本发明所述制备工艺中不使用易引起阳离子乳化体系失稳的强电解质,所得乳液粒子为根据应用场景优化的核壳结构,且乳液中不含易引起金属表面处理涂层发生闪锈失效的游离小分子乳化剂,特别适于应用于金属表面处理领域中。
Description
技术领域
本发明属于金属表面处理技术领域,尤其涉及一种用于金属表面处理领域的阳离子型聚丙烯酸酯乳液及其制备方法。
背景技术
金属表面处理是指对金属产品如钢,铝,镀锌钢等裸露的金属表面进行处理,以使材料表面获得耐腐蚀,耐磨,绝缘等性能的过程。以化学方法进行金属表面处理所需的物料统称为金属表面处理剂,如用于普通钢材的防锈底漆,用于钢材,铝材及镀锌钢等表面的钝化剂和用于硅钢的绝缘涂料等。
目前,此类金属表面处理剂通常为半无机型,配方中包含金属盐类及金属氧化物成膜组分及有机聚合物,由聚合物提供涂层所需的部分性能,如耐水性,冲剪加工性能,表面润滑及与下道漆的附着力等。对于水性金属表面处理剂,有机聚合物可以水分散性聚合物乳液或以水溶性基团改性的聚合物水溶液两种形式引入,其中又以水性聚合物乳液较为常用。
阳离子型乳液中粒子带正电荷,与阴离子型乳液相比对金属基材具有更佳的附着力,且与无机组分具备更好的相容性,因此更适于在金属表面处理剂中使用。但由于阳离子型乳化剂发展相对较慢,种类较少,长期以来限制了阳离子型乳液相关技术的发展。目前,国内绝大部分金属表面处理剂仍使用技术较为成熟的阴离子型乳液进行生产。
在公开资料中,虽有一些阳离子型自由基乳液聚合工艺方案得到了报道,但大都用于日用化学品及造纸等领域中,对于阳离子乳液在金属表面处理中的应用仅有少量报道,如一些国外专利提到使用阳离子型乳液作为有机组分可获得性能良好的钝化剂,但并未对所使用阳离子乳液的具体组成及制备方法作出说明。
中国专利201210289703.1报道了一种阳离子-非离子混合型聚氨酯乳液及其制备方法,所得乳液中的聚合物为同时具有阳离子亲水基团和非离子亲水侧链的水性聚氨酯,特别适合用于镀锌钢板无铬钝化前处理领域,但该专利所述的聚氨酯制备工艺复杂,成本较高,且需自行合成所需的亲水扩链剂,较难在工业生产中推广。
中国专利申请201610913833.6公开了一种阳离子金属表面处理乳液及其制备方法,可获得阳离子型苯乙烯-甲基丙烯酸甲酯-丙烯酸异辛酯共聚物乳液,适于在金属表面处理剂生产中应用,但该专利申请所述乳液及制备方法基本为阳离子型聚丙烯酸酯乳液聚合的一般技术方法,并无明显的技术优化改进以使乳液在金属表面处理领域更加适用。
另外,上述公开资料中均使用水溶性盐类氧化-还原引发体系进行后消除引发(以甲醛合次硫酸氢钠和/或亚硫酸氢钠作为还原剂),经发明人实际测试,上述物料用于阳离子型自由基乳液聚合时,由于解离出的阴离子造成的干扰,体系极易发生乳化失效,造成乳液粒径过大,渣团大量产生等不良现象。
发明内容
鉴于现有技术中存在上述技术问题,本发明的目的是提供一种在性能及成本等方面特别适于在金属表面处理领域应用的阳离子型聚丙烯酸酯乳液及其制备方法,制备过程中不使用易引起阳离子乳化体系失稳的强电解质,乳液粒子为适于在金属表面处理领域应用的核壳结构,核区为具备较高玻璃化温度和强疏水特性的烯类单体共聚物,壳层为具备较低玻璃化温度和弱疏水特性的烯类单体共聚物;且乳液中不含易引起金属表面处理涂层发生闪锈失效的游离小分子乳化剂。
本发明为了实现上述目的而采取如下技术方案。
本发明提供一种用于金属表面处理领域的阳离子型聚丙烯酸酯乳液,其原料由如下重量份数的组份组成:
水: 280份;
反应型乳化剂: 18.6~24.8份;
丙烯酸: 1.5~2份;
苯乙烯: 150~180份;
丙烯酸正丁酯: 30~52份;
10wt%的水溶性偶氮引发剂水溶液: 14~16份;
甲基丙烯酸缩水甘油酯 5份;
丙烯酸羟乙酯: 2份;
消泡剂 0~1份。
进一步地,所述反应型乳化剂为马来酸双酯十八烷基聚(乙烯氧基)(20)醚-乙烯三甲基氯化铵(通用名R-303)。
进一步地,所述水溶性偶氮引发剂为偶氮二异丁脒盐酸盐。
本发明还提供上述阳离子型聚丙烯酸酯乳液的制备方法,具体步骤为:
1)在搅拌的同时依次将18~24份反应型乳化剂、1.0~1.5份丙烯酸、150~180份苯乙烯、20~40份丙烯酸正丁酯放入100份水中,搅拌乳化0.5小时后加入10份10wt%的水溶性偶氮引发剂水溶液,继续搅拌获得单体预乳化液;
2)取出上述单体预乳化液的5/6,作为预乳化液A;向剩余单体预乳化液中加入5份甲基丙烯酸缩水甘油酯、2份丙烯酸羟乙酯、0.5份丙烯酸、10~12份丙烯酸正丁酯,继续搅拌10~20分钟,获得预乳化液B;
3)将0.6~0.8份反应型乳化剂放入180份水中,搅拌下升温至76~85℃后,边搅拌边在2~3小时内加入全部预乳化液A,继续搅拌0.5小时后,再边搅拌边在1小时内加入全部预乳化液B,并继续搅拌0.5小时;
4)分两次加入4~6份10wt%的水溶性偶氮引发剂水溶液,两次间隔0.5小时,并继续保温0.5小时;
5)经过冷却、消泡和过滤后,获得阳离子型聚丙烯酸酯乳液。
进一步地,步骤1)和3)中的反应型乳化剂为马来酸双酯十八烷基聚(乙烯氧基)(20)醚-乙烯三甲基氯化铵(通用名R-303)。
进一步的,步骤1)和4)中的水溶性偶氮引发剂为偶氮二异丁脒盐酸盐。
进一步的,步骤5)的具体过程为:降温至30~40℃,加入0~1份消泡剂,继续搅拌15分钟,停止搅拌后,用160目尼龙滤网过滤,即获得阳离子型聚丙烯酸酯乳液。其中,所述消泡剂的型号为SN-Defoamer 2000。
通过上述方法制得的阳离子型聚丙烯酸酯乳液为包含质量分数为30~55%的有机高聚物粒子,0.5~1.5%助剂,余量为水的具有特征蓝光的乳白色液体。
由于采用了上述技术方案,本发明与现有技术相比,具有以下有益效果:
1)本发明所制备的乳液中,有机粒子为适于涂料使用的硬核软壳结构。其中,核区占聚合物总质量的70~90%,由以苯乙烯为主的具备较高玻璃化温度和强疏水特性的烯类单体共聚物组成,为涂层提供足够的硬度及疏水特性。壳层占聚合物总质量的10~30%,由低玻璃化温度的烯类单体共聚物组成,并富集有可交联的含羧基、羟基及酰胺基等活性基团的单体,以保证涂料对成膜性能及成膜后膜层与底材及面漆的附着力,同时降低了物料成本。
2)金属表面处理剂成膜后主要依靠阻隔作用为金属提供阻隔的防锈性能,因此涂层要求具备极强的耐水性及耐碱性。本发明所制备的乳液中使用含亲水基团单体及特殊表面活性单体提供乳液稳定所需的乳化作用,避免了小分子乳化剂遇水溶解渗透造成涂层失效的情况发生,且所得乳液具备机械稳定性优秀、低黏度、低泡等在金属表面处理剂实际生产中十分有价值的特性。3)本发明所述制备工艺,在乳液聚合阶段不使用传统无机盐类原料(甲醛合次硫酸氢钠、亚硫酸氢钠等),避免了因制备过程中解离的阴离子干扰造成的体系极易发生乳化失效,出现的乳液粒径过大,渣团大量产生等不良现象。由此,提升了所述阳离子型聚丙烯酸酯乳液的稳定性和实际生产中的工艺可操作性。
4)本发明所述生产工艺无需多次进行预乳化及多次升降温,与现有资料中公开的核-壳乳液合成工艺相比更为节能环保,简单可行。
具体实施方式
下面结合具体实施例来说明本发明的技术方案和技术效果。除非特别说明,本发明中所用的技术手段均为本领域技术人员所公知的方法。另外,实施方案应理解为说明性的,而非限制本发明的范围。
实施例1:
本实施例中,制备本专利所述的用于金属表面处理领域的阳离子型聚丙烯酸酯乳液,具体制备方法为:
1)向分散釜中投入100份(以质量份数计,下同)去离子水,在搅拌下依次加入18份反应型乳化剂R-303(马来酸双酯十八烷基聚(乙烯氧基)(20)醚-乙烯三甲基氯化铵)、1.5份丙烯酸、150份苯乙烯、40份丙烯酸正丁酯,高速搅拌乳化0.5小时后加入10份偶氮二异丁脒盐酸盐10%水溶液,继续搅拌5分钟,获得单体预乳化液;
2)自分散釜取出上述单体预乳化液的5/6,作为预乳化液A;向剩余单体预乳化液中加入5份甲基丙烯酸缩水甘油酯、2份丙烯酸羟乙酯、0.5份丙烯酸、10份丙烯酸正丁酯,继续搅拌10~20分钟,获得预乳化液B;
3)向带有夹套水浴装置、搅拌装置及加料装置的反应釜中投入180份去离子水及0.6份反应型乳化剂R-303,搅拌下升温至76~85℃后,在2~3小时内向反应釜中匀速泵入全部上述预乳化液A,期间维持搅拌速度及温度不变;其后,维持在上述温度继续搅拌约0.5小时,再用约1小时泵入全部上述预乳化液B,并同样维持搅拌速度及温度不变;单体加料全部完成后,维持在上述温度继续搅拌约0.5小时;
4)之后分两次加入4份偶氮二异丁脒盐酸盐10%水溶液,两次加料间隔0.5小时;加料完毕后,继续保温0.5小时;
5)保温结束后,降温至30~40℃,加入0.5份SN-Defoamer 2000消泡剂,继续搅拌15分钟,停止搅拌后,用160目尼龙滤网过滤,即制成所述用于金属表面处理的阳离子型聚丙烯酸酯乳液。
对得到的阳离子型聚丙烯酸酯乳液进行性能测试,所得乳液部分性能测试结果如下:(测试方法依照GB/T11525-2002《合成树脂乳液试验方法》进行)
外观 | 不挥发物/% | pH值 | 粘度/mpa·s |
均匀乳白色蓝光 | 40.9% | 2.7 | 88 |
冻融稳定性 | 贮存稳定性 | 稀释稳定性/% | 机械稳定性 |
>5 | 通过 | >99 | 未测试 |
粒径/μm | 残存单体/% | 最低成膜温度/℃ | 粗粒子/% |
0.087(平均值) | 1.8(质量法) | 29.4 | 0 |
实施例2:
本实施例中,制备本专利所述的用于金属表面处理领域的阳离子型聚丙烯酸酯乳液,具体制备方法为:
1)向分散釜中投入100份(以质量份数计,下同)去离子水,在搅拌下依次加入24份反应型乳化剂R-303(马来酸双酯十八烷基聚(乙烯氧基)(20)醚-乙烯三甲基氯化铵)、1.5份丙烯酸、180份苯乙烯、20份丙烯酸正丁酯,高速搅拌乳化0.5小时后加入12份偶氮二异丁脒盐酸盐10%水溶液,继续搅拌5分钟,获得单体预乳化液;
2)自分散釜取出上述单体预乳化液的5/6,作为预乳化液A;向剩余单体预乳化液中加入5份甲基丙烯酸缩水甘油酯、2份丙烯酸羟乙酯、0.5份丙烯酸、12份丙烯酸正丁酯,继续搅拌10~20分钟,获得预乳化液B;
3)向带有夹套水浴装置、搅拌装置及加料装置的反应釜中投入180份去离子水及0.8份反应型乳化剂R-303,搅拌下升温至76~85℃后,在2~3小时内向反应釜中匀速泵入全部上述预乳化液A,期间维持搅拌速度及温度不变;其后,维持在上述温度继续搅拌约0.5小时,再用约1小时泵入全部上述预乳化液B,并同样维持搅拌速度及温度不变;单体加料全部完成后,维持在上述温度继续搅拌约0.5小时;
4)之后分两次加入6份偶氮二异丁脒盐酸盐10%水溶液,两次加料间隔0.5小时;加料完毕后,继续保温0.5小时;
5)保温结束后,降温至30~40℃,加入0.5份SN-Defoamer 2000消泡剂,继续搅拌15分钟,停止搅拌后,用160目尼龙滤网过滤,即制成所述用于金属表面处理的阳离子型聚丙烯酸酯乳液。
所得乳液部分性能测试结果如下:(测试方法依照GB/T11525-2002《合成树脂乳液试验方法》进行)
外观 | 不挥发物/% | pH值 | 粘度/mpa·s |
均匀乳白色蓝光 | 39.9% | 2.6 | 170 |
冻融稳定性 | 贮存稳定性 | 稀释稳定性/% | 机械稳定性 |
>5 | 通过 | >99 | 未测试 |
粒径/μm | 残存单体/% | 最低成膜温度/℃ | 粗粒子/% |
0.172(平均值) | 4.1(质量法) | 31.2 | 0 |
实施例3:
本实施例中,制备本专利所述的用于金属表面处理领域的阳离子型聚丙烯酸酯乳液,具体制备方法为:
1)向分散釜中投入100份(以质量份数计,下同)去离子水,在搅拌下依次加入18份反应型乳化剂R-303(马来酸双酯十八烷基聚(乙烯氧基)(20)醚-乙烯三甲基氯化铵)、1.0份丙烯酸、150份苯乙烯、40份丙烯酸正丁酯,高速搅拌乳化0.5小时后加入10份偶氮二异丁脒盐酸盐10%水溶液,继续搅拌5分钟,获得单体预乳化液;
2)自分散釜取出上述单体预乳化液的5/6,作为预乳化液A;向剩余单体预乳化液中加入1份丙烯酸羟乙酯、0.5份丙烯酸、15份丙烯酸正丁酯,继续搅拌10~20分钟,获得预乳化液B;
3)向带有夹套水浴装置、搅拌装置及加料装置的反应釜中投入180份去离子水及0.6份反应型乳化剂R-303,搅拌下升温至76~85℃后,在2~3小时内向反应釜中匀速泵入全部上述预乳化液A,期间维持搅拌速度及温度不变;其后,维持在上述温度继续搅拌约0.5小时,再用约1小时泵入全部上述预乳化液B,并同样维持搅拌速度及温度不变;单体加料全部完成后,维持在上述温度继续搅拌约0.5小时;
4)之后分两次加入4份偶氮二异丁脒盐酸盐10%水溶液,两次加料间隔0.5小时;加料完毕后,继续保温0.5小时;
5)保温结束后,降温至30~40℃,加入0.5份SN-Defoamer 2000消泡剂,继续搅拌15分钟,停止搅拌后,用160目尼龙滤网过滤,即制成所述用于金属表面处理的阳离子型聚丙烯酸酯乳液。
所得乳液部分性能测试结果如下:(测试方法依照GB/T11525-2002《合成树脂乳液试验方法》进行)
外观 | 不挥发物/% | pH值 | 粘度/mpa·s |
均匀乳白色蓝光 | 402% | 4.1 | 56 |
冻融稳定性 | 贮存稳定性 | 稀释稳定性/% | 机械稳定性 |
>5 | 通过 | >99 | 未测试 |
粒径/μm | 残存单体/% | 最低成膜温度/℃ | 粗粒子/% |
0.103(平均值) | 2.2(质量法) | 28.7 | 0 |
Claims (6)
1.一种用于金属表面处理领域的阳离子型聚丙烯酸酯乳液,其特征在于,其原料由如下重量份数的组份组成:
其中,所述反应型乳化剂为马来酸双酯十八烷基聚(乙烯氧基)20醚-乙烯三甲基氯化铵;
其制备方法包括如下具体步骤:
1)在搅拌的同时依次将18~24份反应型乳化剂、1.0~1.5份丙烯酸、150~180份苯乙烯、20~40份丙烯酸正丁酯放入100份水中,搅拌乳化0.5小时后加入10份10wt%的水溶性偶氮引发剂水溶液,继续搅拌获得单体预乳化液;
2)取出上述单体预乳化液的5/6,作为预乳化液A;向剩余单体预乳化液中加入5份甲基丙烯酸缩水甘油酯、2份丙烯酸羟乙酯、0.5份丙烯酸、10~12份丙烯酸正丁酯,继续搅拌10~20分钟,获得预乳化液B;
3)将0.6~0.8份反应型乳化剂放入180份水中,搅拌下升温至76~85℃后,边搅拌边在2~3小时内加入全部预乳化液A,继续搅拌0.5小时后,再边搅拌边在1小时内加入全部预乳化液B,并继续搅拌0.5小时;
4)分两次加入4~6份10wt%的水溶性偶氮引发剂水溶液,两次间隔0.5小时,并继续保温0.5小时;
5)经过冷却、消泡和过滤后,获得阳离子型聚丙烯酸酯乳液。
2.根据权利要求1所述的阳离子型聚丙烯酸酯乳液,其特征在于,所述水溶性偶氮引发剂为偶氮二异丁脒盐酸盐。
3.一种如权利要求1或2所述阳离子型聚丙烯酸酯乳液的制备方法,其特征在于,其具体步骤为:
1)在搅拌的同时依次将18~24份反应型乳化剂、1.0~1.5份丙烯酸、150~180份苯乙烯、20~40份丙烯酸正丁酯放入100份水中,搅拌乳化0.5小时后加入10份10wt%的水溶性偶氮引发剂水溶液,继续搅拌获得单体预乳化液;
2)取出上述单体预乳化液的5/6,作为预乳化液A;向剩余单体预乳化液中加入5份甲基丙烯酸缩水甘油酯、2份丙烯酸羟乙酯、0.5份丙烯酸、10~12份丙烯酸正丁酯,继续搅拌10~20分钟,获得预乳化液B;
3)将0.6~0.8份反应型乳化剂放入180份水中,搅拌下升温至76~85℃后,边搅拌边在2~3小时内加入全部预乳化液A,继续搅拌0.5小时后,再边搅拌边在1小时内加入全部预乳化液B,并继续搅拌0.5小时;
4)分两次加入4~6份10wt%的水溶性偶氮引发剂水溶液,两次间隔0.5小时,并继续保温0.5小时;
5)经过冷却、消泡和过滤后,获得阳离子型聚丙烯酸酯乳液。
4.根据权利要求3所述的制备方法,其特征在于,步骤5)的具体过程为:降温至30~40℃,加入0~1份消泡剂,继续搅拌15分钟,停止搅拌后,用160目尼龙滤网过滤,即获得阳离子型聚丙烯酸酯乳液。
5.根据权利要求4所述的制备方法,其特征在于,所述消泡剂的型号为SN-Defoamer2000。
6.根据权利要求3所述的制备方法,其特征在于,制得的阳离子型聚丙烯酸酯乳液为包含质量分数为30~55%的有机高聚物粒子,0.5~1.5%助剂,余量为水的具有特征蓝光的乳白色液体。
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JPS60221450A (ja) * | 1984-04-19 | 1985-11-06 | Nippon Steel Corp | 金属表面処理組成物 |
CN102775578A (zh) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | 阳离子-非离子混合型水性聚氨酯乳液及其制备方法 |
CN106543350A (zh) * | 2016-10-20 | 2017-03-29 | 中山市巴德富化工科技有限公司 | 一种阳离子金属表面处理乳液及其制备方法 |
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US3873349A (en) * | 1971-03-12 | 1975-03-25 | Nippon Kokan Kk | Process of treating surfaces of metals |
JPS60221450A (ja) * | 1984-04-19 | 1985-11-06 | Nippon Steel Corp | 金属表面処理組成物 |
CN102775578A (zh) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | 阳离子-非离子混合型水性聚氨酯乳液及其制备方法 |
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