CN107849186B - 涂料添加剂 - Google Patents
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Abstract
本发明提供一种涂料添加剂(共)聚合物,按所述(共)聚合物的总干重计,包含按干重计以下量作为(共)聚合单元,从20%到60%至少一种乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体,和从40%到80%至少一种水溶性烯系不饱和单体。其进一步提供一种涂料调配物,按所述涂料调配物的总干重计,包含按干重计,高于0.04%所述乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体。
Description
技术领域
本发明提供一种涂料添加剂和包含所述涂料添加剂的涂料调配物。
背景技术
如甲基丙烯酸乙酰乙酰氧基乙酯(AAEM)的乙酰乙酰氧基或乙酰乙酰胺官能性单体通常用于制备可用于制造具有良好硬度和化学与抗粘连性的自交联、室温固化乳液共聚物。一旦并入到共聚物中,AAEM单体的乙酰乙酰氧基官能基可通过“氧化固化”或与所添加的如二胺的交联剂反应来交叉结合以产生固化膜。由于类似化学,乙酰乙酰氧基官能基也可用于与甲醛反应。
由于技术限制,AAEM通常在涂布粘合剂中聚合以实现其以上作用。这限制了AAEM的使用。
因此,希望提供一种包含乙酰乙酰氧基或乙酰乙酰胺官能性单体且可分开地添加到涂料的涂料添加剂。出人意料的是,乙酰乙酰氧基官能基在通过涂料添加剂而不是通过涂料粘合剂添加时具有高许多的效果。
发明内容
本发明提供一种涂料添加剂(共)聚合物,按(共)聚合物的总干重计,包含按干重计以下量作为(共)聚合单元,从20%到60%至少一种乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体,和从40%到80%至少一种聚乙二醇修饰的烯系不饱和单体。
本发明进一步提供一种涂料调配物,按涂料调配物的总干重计,包含按干重计高于0.04%乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体。
具体实施方式
本发明的涂料添加剂为(共)聚合物,按(共)聚合物的总干重计,包含按干重计以下量作为(共)聚合单元:从20%到60%,优选从25%到55%,并且更优选从30%到45%的至少一种乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体;和从40%到80%,优选从45%到75%,并且更优选从55%到70%的至少一种水溶性烯系不饱和单体。
乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体
乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体为具有至少一个烯系不饱和性官能基和至少一个连接到烯系不饱和性官能基的乙酰乙酰基部分且具有以下结构的单体:
其中R1选自H、具有1到10个碳原子的烷基和苯基;
其中A具有以下结构:
其中R2选自H、具有1到10个碳原子的烷基、苯基、卤基、CO2CH3和CN;R3选自H、具有1到10个碳原子的烷基、苯基和卤基;R4选自具有1到10个碳原子的亚烷基和亚苯基;以及R5选自具有1到10个碳原子的亚烷基和亚苯基;
其中a、m、n和q独立地选自0和1;和
其中X和Y中的每一个选自-NH-和-O-;以及
其中B选自A、具有1到10个碳原子的烷基、苯基和杂环基。
乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体的合适的实例包括(甲基)丙烯酸乙酰乙酰氧基烷酯,如(甲基)丙烯酸乙酰乙酰氧基乙酯、(甲基)丙烯酸乙酰乙酰氧基丙酯、(甲基)丙烯酸乙酰乙酰氧基丁酯和(甲基)丙烯酸丙2,3-二(乙酰乙酰氧酯);乙酰乙酸烯丙酯;乙酰乙酸乙烯酯;以及具有以下结构的乙酰乙酰胺:
其中R6选自H和甲基。
优选地,乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体选自(甲基)丙烯酸乙酰乙酰氧基乙酯、(甲基)丙烯酸乙酰乙酰氧基丙酯、(甲基)丙烯酸乙酰乙酰氧基丁酯、乙酰乙酸烯丙酯、(甲基)丙烯酸丙2,3-二(乙酰乙酰氧酯)和其任何组合。
水溶性烯系不饱和单体
水溶性烯系不饱和单体为具有以下结构的单体:
D-(CH2CH2O)h-(CH2CH(CH3)O)k-E;
其中h为从0到150,优选从23到100,并且更优选从25到50的整数;以及k为从0到30,优选从0到20,并且更优选从0到10的整数;
其中D为烯系不饱和基团,且选自甲基丙烯酸酯(CH2=C(CH3)CO2-)、甲基丙烯酰胺(CH2=C(CH3)CONH-)、丙烯酸酯(CH2=CHCO2-)、丙烯酰胺(CH2=CHCONH-)、乙烯基醚(CH2=CH-O-)和烯丙基醚(CH2=CHCH2-O-);以及
其中E为封端基团,且选自H,具有1到4个碳原子的烷基和包括膦酸、磷酸、硫酸和磺酸的锂、钠、钾和铵盐的阴离子盐基团。
水溶性烯系不饱和单体的合适的实例包括甲氧基聚乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸羟丙酯、乙烯基磺酸钠(SVS)、对苯乙烯磺酸钠(SSS)、丙烯酰胺(AM)和(甲基)丙烯酸N-羟基甲酯。可商购的产品包括可购自Zhejiang Huangmachemical industry group Co.,Ltd.的HOMASYTERTM MPEG-MA和可购自Evonik IndustriesAG的VISIOMERTM MPEG 1005MA W、VISIOMERTM MPEG 2005MA W、VISIOMERTM MPEG 5005MA W。
优选地,水溶性烯系不饱和单体选自甲氧基聚乙二醇甲基丙烯酸酯、聚乙二醇(甲基)丙烯酸酯和其组合。
聚合过程
用于制备(共)聚合物的乳液或溶液聚合在所属领域中是众所周知的。常规表面活性剂可用作阴离子和/或非离子乳化剂,如碱金属烷基硫酸盐或铵烷基硫酸盐、烷基磺酸、脂肪酸和乙氧基化烷基酚。按总单体的干重计,所用表面活性剂的量通常是按干重计0.1%至6%。可使用热引发方法或氧化还原引发方法。可使用常规自由基引发剂,且合适的实例包括氢过氧化物、叔丁基氢过氧化物、t-戊基氢过氧化物、铵和碱金属过硫酸盐,其中包括钠和钾,按总单体的干重计,通常在按干重计0.01%到3.0%的水平下。可以类似水平使用结合有适合还原剂,如连二亚硫酸钠、异抗坏血酸和亚硫酸氢钠,的使用相同引发剂的氧化还原体系,任选地组合如铁和铜的金属离子,任选地另外包括金属络合剂。可使用链转移剂,如硫醇,来调整(共)聚合物的分子量。单体混合物可以无掺杂的添加或以水中乳液的形式添加。在反应期间,单体混合物可使用均匀或变化的组合物以单次添加或以多次添加或连续地添加。在任一阶段之前、期间或之后可添加其它成分,如自由基引发剂、氧化剂、还原剂、链转移剂、中和剂、表面活性剂和分散剂。
涂料调配物
按涂料调配物的总干重计,可以高于0.04%,优选从0.1%到2%,并且更优选从0.2%到1.5%的干重百分比将乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体添加至涂料添加剂。
实例
I.原材料
II.测试方法
1.甲醛(HCHO)消除效果测试
在黑色乙烯基板上使用200nm薄膜机向下抽吸涂料调配物,且在水平位置上风干一天。在板的背侧上使用200nm薄膜机进一步向下抽吸涂料调配物,且在水平位置上风干7天。切割5cm×1cm涂料膜以用于测试。
涂料膜样本用夹子固定,且放置到充分密封的测试瓶中。通过穿过瓶盖的小孔将甲醛注射到测试瓶中。在24小时中,在室温下,将3-甲基-2-苯并噻唑啉酮腙(MBTH)溶液注射到测试瓶中以吸附甲醛残余物。在另一2小时中,通过分光光度计方法测试吸附溶液中的甲醛含量。溶液中保留的甲醛含量越少,涂料膜的甲醛消除效果越高。甲醛消除效果以百分比表示。百分比越高,甲醛消除效果越高。
III.实验实例
1.涂料添加剂1到2的制备
通过将370g去离子水(DI)、80g(99.0%活性)(甲基)丙烯酸乙酰乙酰氧基乙酯和162.8g HOMASYTERTM MPEG-MA聚乙二醇修饰的甲基丙烯酸酯混合来制备单体混合物。
将1600g去离子水添加到3升四颈圆底烧瓶,所述圆底烧瓶配备有浆搅拌棒、温度计、氮气入口和回流冷凝器,且接着在氮气气氛下在搅拌下加热到78℃。接着,将含1.5g硫酸亚铁的10g DI水添加到烧瓶,且接着用6g DI水冲洗烧瓶。接着,将含1.8g亚硫酸氢钠的8g DI水添加到烧瓶,且接着用2g DI水冲洗烧瓶。在5min之后,在60min内,将单体混合物馈送到烧瓶中,与含1.4g过硫酸钠的72g DI水和含26g亚硫酸氢钠的66g DI水一起共馈送。温度降低到66℃,且添加含1.06g过硫酸钠的10g DI水并保持15min。接着使温度进一步冷却到40℃,且接着将含15g氢过氧化物(35%活性)的10g DI水添加到烧瓶中并保持5min。使烧瓶冷却到室温,且接着在高效搅拌下添加22g乙醇胺(50%活性)。所制备的产物为具有10.1%固体和3.54的pH值的涂料添加剂1的(共)聚合物分散液。
涂料添加剂2的(共)聚合物分散液根据以上程序来制备,其中仅将单体混合物改变成370g去离子水(DI)、40g(99.0%活性)(甲基)丙烯酸乙酰乙酰氧基乙酯和217.5gHOMASYTERTM MPEG-MA修饰的甲基丙烯酸酯。所制备的涂料添加剂2的(共)聚合物分散液具有9.58%固体和3.89的pH值。
2.粘合剂1到3的制备
由含有501.7g DI水、23.94g十二烷基苯磺酸钠(DS-4,22.5%活性)、747g丙烯酸丁酯、652.9g甲基丙烯酸甲酯、22.41g甲基丙烯酸和74.7g甲基丙烯酸乙酰乙酰氧基乙酯的单体混合物来制备粘合剂1。将47.2g单体混合物添加到含有1317.9g DI水和10.64g DS-4(22.5%活性)的混合物的锅,将加热到85℃。接着,将溶解于50g DI水中的2.26g过硫酸钠(SPS)添加作为引发剂。十分钟后,历经90min将单体混合物的其余部分与溶解于50g DI水中的1.13g SPS一起在独立馈送中逐渐添加到锅。在完成馈送之后,使锅中的混合物冷却到60℃,且通过添加溶解于12.5g DI水中的0.75g叔丁基氢过氧化物随后溶解于12.5g DI水中的0.45g异抗坏血酸(IAA)冲洗30min。接着,使混合物冷却到室温,且添加氢氧化铵以调整pH值到约9.0。
根据以上程序来制备粘合剂2,其中仅将单体混合物改变成501.7g DI水、23.94g十二烷基苯磺酸钠(DS-4,22.5%活性)、747g丙烯酸丁酯、725.2g甲基丙烯酸甲酯、22.41g甲基丙烯酸和2.39g甲基丙烯酸乙酰乙酰氧基乙酯。
根据以上程序来制备粘合剂3,其中仅将单体混合物改变成501.7g DI水、23.94g十二烷基苯磺酸钠(DS-4,22.5%活性)、747g丙烯酸丁酯、727.6g甲基丙烯酸甲酯和22.41g甲基丙烯酸。
3.涂料调配物1到10的制备
根据表1的程序来制备涂料调配物1到10,其中详细差异展示于表2中。
表1.涂料配方
IV.结果
表2
涂料 | 粘合剂 | 添加剂 | 涂料中的AAEM(%) | 甲醛消除效果 |
比较涂料1* | 1(5%AAEM) | - | 1.38% | 85.47% |
2 | 3(0%AAEM) | 1(40%AAEM) | 0.69% | 90.34% |
3 | 3(0%AAEM) | 1(40%AAEM) | 0.35% | 90.35% |
4 | 3(0%AAEM) | 1(40%AAEM) | 0.17% | 83.84% |
5 | 3(0%AAEM) | 1(40%AAEM) | 0.04% | 77.34% |
比较涂料6* | 3(0%AAEM) | 1(40%AAEM) | 0.02% | 65.95% |
比较涂料7* | 2(0.16%AAEM) | - | 0.04% | 62.16% |
8 | 3(0%AAEM) | 2(20%AAEM) | 0.04% | 76.77% |
比较涂料9* | 3(0%AAEM) | 2(20%AAEM) | 0.02% | 62.80% |
*涂料1、6、7和9为比较涂料调配物。
粘合剂1含有5%AAEM,而粘合剂3不含AAEM。本发明的涂料2到5包含粘合剂3,且因此在粘合剂组合物中不包含AAEM,但其在添加剂中包含不同AAEM负载。比较涂料1包含粘合剂1,且因此在粘合剂组合物中包含AAEM,但其在添加剂中并不包含任何AAEM。本发明的涂料2到5中的总AAEM负载比比较涂料1低许多。为了实现类似甲醛消除效果,如果是在添加剂中而不是在粘合剂组合物中添加AAEM,则涂料中的AAEM负载可显著较少。具体地说,比较涂料1具有与本发明的涂料4类似的甲醛消除效果,且按涂料组合物的总干重计,比较涂料1中的AAEM负载按干重计为1.38%,而本发明的涂料4中的AAEM负载按干重计仅为0.17%。
比较涂料7和9与本发明的涂料8也证明相同趋势。
粘合剂2含有0.16%AAEM。本发明的涂料8和比较涂料9包含粘合剂3,且因此在粘合剂组合物中不包含AAEM,但其在添加剂中包含不同AAEM负载。比较涂料7包含粘合剂2,且因此在粘合剂组合物中包含AAEM,但其在添加剂中并不包含任何AAEM。本发明的涂料8和比较涂料7包含相等量的AAEM,唯一差异是,在比较涂料7中是在粘合剂中添加AAEM,而在本发明的涂料8中是在添加剂中添加AAEM。本发明的涂料8与比较涂料7的甲醛消除效果相比具有显著更好的甲醛消除效果。再次证明,为了实现类似甲醛消除效果,如果AAEM是添加在添加剂中而不是在粘合剂组合物中,则涂料中的AAEM负载可显著地较少。具体地说,比较涂料7具有与比较涂料9类似的甲醛消除效果,且按涂料组合物的总干重计,比较涂料7中的AAEM负载按干重计为0.04%,而比较涂料9中的AAEM负载按干重计仅为0.02%。
另一方面,涂料调配物中的AAEM负载限制涂料的甲醛消除效果,且按涂料组合物的总干重计,将仅在按干重计高于0.04%的范围下起作用。
Claims (11)
1.一种涂料调配物,其包含添加剂聚合物,按所述聚合物的总干重计,所述添加剂聚合物包含按干重计的以下量作为聚合单元,从20%到60%至少一种乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体,和从40%到80%至少一种水溶性烯系不饱和单体,
其中所述水溶性烯系不饱和单体选自N-羟基甲基(甲基)丙烯酰胺、乙烯基磺酸钠盐、对苯乙烯磺酸钠或具有以下结构:
D-(CH2CH2O)h-(CH2CH(CH3)O)k-E
其中h为从0到150的整数;以及k为从0到30的整数;
其中D为烯系不饱和基团,选自CH2=C(CH3)CO2–、CH2=C(CH3)CONH–、CH2=CHCO2–、CH2=CHCONH–、CH2=CH-O–和CH2=CHCH2-O–;以及
其中E为封端基团,且选自H,具有1到4个碳原子的烷基、以及选自膦酸、磷酸、硫酸和磺酸的锂、钠、钾和铵盐的阴离子盐基团;
按所述涂料调配物的总干重计,所述涂料调配物包含按干重计,高于0.04%乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体作为共聚单元。
2.根据权利要求1所述的涂料调配物,其中h为从23到100的整数;以及k为从0到20的整数。
3.根据权利要求1所述的涂料调配物,其中h为从25到50的整数;以及k为从0到10的整数。
4.根据权利要求1所述的涂料调配物,其中按所述聚合物的总干重计,其包含按干重计的以下量作为聚合单元,从30%到45%至少一种乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体。
5.根据权利要求1所述的涂料调配物,其中按所述聚合物的总干重计,其包含按干重计的以下量作为聚合单元,从55%到70%至少一种水溶性烯系不饱和单体。
7.根据权利要求6所述的涂料调配物,其中所述乙酰乙酰氧基官能性烯系不饱和单体和所述乙酰乙酰胺官能性烯系不饱和单体选自(甲基)丙烯酸乙酰乙酰氧基乙酯、(甲基)丙烯酸乙酰乙酰氧基丙酯、(甲基)丙烯酸乙酰乙酰氧基丁酯、乙酰乙酸烯丙酯、(甲基)丙烯酸2,3-二(乙酰乙酰氧基)丙酯和其任何组合。
8.根据权利要求1所述的涂料调配物,其中所述水溶性烯系不饱和单体选自甲氧基聚乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸羟丙酯、乙烯基磺酸钠盐、对苯乙烯磺酸钠、丙烯酰胺和N-羟基甲基(甲基)丙烯酰胺。
9.根据权利要求1所述的涂料调配物,其中所述水溶性烯系不饱和单体选自甲氧基聚乙二醇甲基丙烯酸酯、聚乙二醇甲基丙烯酸酯和其组合。
10.根据权利要求1所述的涂料调配物,其中按所述涂料调配物的总干重计,其包含按干重计,从0.1%到2%所述乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体。
11.根据权利要求1所述的涂料调配物,其中按所述涂料调配物的总干重计,其包含按干重计,从0.2%到1.5%所述乙酰乙酰氧基或乙酰乙酰胺官能性烯系不饱和单体。
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