CN102230301B - 阳离子苯丙类表面施胶剂的制备方法 - Google Patents
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Abstract
阳离子苯丙类表面施胶剂的制备方法,制备步骤为,以质量份计:苯丙类高分子乳化剂a的合成;阳离子水性聚氨酯类高分子乳化剂b的合成;表面施胶剂的合成:在上述高分子乳化剂a或b,或者含a、b总质量浓度10-30%的混合液中,加入季铵化试剂,再用质量浓度0.1-1%的水溶性引发剂进行乳液聚合,聚合单体为由30-70%的苯乙烯和30-70%的甲基丙烯酸酯组成的混合物。该方法制备的表面施胶剂具有极低起泡性和极好抗水性,特别适合瓦楞纸板的表面施胶。
Description
技术领域
本发明属于造纸化学品领域,具体涉及一种造纸用表面施胶剂,其与氧化淀粉配合能有效的提高纸张的强度和抗水性,且表面施胶剂起泡性极低。
背景技术
纸张的表面施胶,其目的是提高纸张的表面性能和纸张的印刷性能。目前合成的表面施胶剂主要可分为三种类型:(1)、水溶性聚合物表面施胶剂(SMA及SAA类),其是采用有机溶剂作为介质的聚合溶液,缺点是对环境和使用者带来一定的污染;(2)、聚合物水分散液表面施胶剂(SAE类),采用乳液聚合,介质为水,环保以及抗水性好,缺点是起泡性高,需配合一定的消泡剂;(3)、聚氨酯水分散液表面施胶剂(PUD类),抗水性好,对纸张的强度提高显著,缺点是价格昂贵,制作工艺复杂,影响因素较多。合成的表面施胶剂与纤维的结合力是聚乙烯醇的100倍,与传统的施胶剂相比纸张具有更好的印刷型,施胶性,挺度和平滑度。
水分散体或者乳液,一般需要用乳化剂来稳定,否则容易引起结块,但也由此带来了乳液的抗水性能差和起泡性高的问题。CN 101177923A公开了一种苯丙乳液表面施胶剂,其应用了传统的乳液聚合工艺,虽然具有一定的抗水性,但是存在施胶剂的起泡性问题。JP 306690/2006提供一种即使对不含有内添施胶剂的纸也能提高施胶效果并且可以进行在少量的有机溶剂中的溶液聚合从而提高生产率的阳离子表面施胶剂,但其与硫酸铝的配合稳定性存在问题。
发明内容
解决的技术问题:本发明针对以上现有技术的不足和缺陷,提出一种具有极低起泡性和极好抗水性的表面施胶剂的制备方法,特别适合瓦楞纸板的表面施胶。
技术方案:本发明的目的通过以下技术方案实现:
阳离子苯丙类表面施胶剂的制备方法,制备步骤为,以质量份计:苯丙类高分子乳化剂a的合成:水溶性溶剂100份,苯乙烯20-60份,甲基丙烯酸酯5-20份,叔胺类甲基丙烯酸酯5-20份,在油溶性引发剂的存在下采用溶液聚合制得,聚合物加入冰醋酸中和,然后加入去离子水将固含量调至10%-30%;阳离子水性聚氨酯类高分子乳化剂b的合成:多元醇真空脱水,加入异氰酸酯及催化剂进行预聚反应,合成含异氰酸酯封端的预聚体,然后加入叔胺扩链剂扩链,用溶剂调节粘度,加入冰醋酸中和,用去离子水调节固含量为10%-30%;表面施胶剂的合成:在上述高分子乳化剂a或b,或者含a、b总质量浓度10-30%的混合液中,加入季铵化试剂,再用质量浓度0.1-1%的水溶性引发剂进行乳液聚合,聚合单体为由30-70%的苯乙烯和30-70%的甲基丙烯酸酯组成的混合物。
所述的水溶性溶剂为甲醇、乙醇、正丙醇、异丙醇、丙酮、丁酮、甲酸或乙酸。
所述的甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯或甲基丙烯酸异辛酯;叔胺类甲基丙烯酸酯为甲基丙烯酸二甲氨基乙酯。
所述的油溶性引发剂为过氧化苯甲酰或偶氮二异丁氰;水溶性引发剂为过硫酸铵、过硫酸钠、过硫酸钾、过硫酸盐-亚硫酸氢钠、双氧水-硫酸亚铁、双氧水-甲醛次硫酸氢钠、双氧水-抗坏血酸或水溶性偶氮类引发剂。
所述的多元醇为分子量在100-5000之间的聚丙二醇,聚乙二醇,聚四氢呋喃聚醚,聚酯多元醇,聚己内酯多元醇或聚碳酸酯多元醇中的一种或几种的混合物。
所述的催化剂为二月桂酸二丁基锡,辛酸亚锡,三乙胺,二亚乙烯三胺中的一种或几种的混合物。
所述的异氰酸酯为MDI,甲苯二异氰酸酯,HDI,PAPI,异氟尔酮二异氰酸酯中的一种或几种的混合物。
所述的叔胺扩链剂为N-甲基二乙醇胺、N,N二甲基乙醇胺、乙醇胺、二乙醇胺或三乙醇胺。
所述的调节粘度的溶剂为丙酮,丁酮,N,N-二甲基甲酰胺,甲基吡咯烷酮中的一种或几种的混合物。
所述的季铵化试剂为环氧氯丙烷、溴乙烷或苄基氯。
有益效果:与现有技术相比,本发明技术具有以下优点
(1)本发明中含有的有机溶剂少,安全环保;
(2)本发明不需要小分子乳化剂即可达到稳定,乳液的起泡性极低,稳定性好;
(3)本发明具有阳离子性,与淀粉或改性淀粉的相容性极好,能显著改善纸张的表面性能和印刷性。
具体实施方式
实施例1
在带有冷凝器、滴加装置、氮气口、搅拌器和温度计的500mL四口烧瓶中加入异丙醇100克,苯乙烯30克,丙烯酸二甲氨基乙酯10克,丙烯酸丁酯60克,正十二硫醇1克,过氧化苯甲酰1克,84℃聚合3小时,然后用5克冰醋酸中和15min,然后加入蒸馏水,最后抽真空回收异丙醇,得固含量20%的苯丙高分子乳化剂a。
在带有冷凝器、滴加装置、氮气口、搅拌器和温度计的500mL四口烧瓶中加入蒸馏水200克,高分子乳化剂a 50克,环氧氯丙烷0.5克,温度升至80度,滴加50克苯乙烯和50克丙烯酸丁酯的混合单体以及过硫酸铵的水溶液(1.8%质量含量)56克,聚合3小时,最后得到固含量30%,乳白色半透明的表面施胶剂。
实施例2
在带有冷凝器、滴加装置、氮气口、搅拌器和温度计的500mL四口烧瓶中加入50克聚乙二醇3000,真空脱水,然后加入30克甲苯二异氰酸酯及0.01克二月桂酸二丁基锡加入进行预聚反应,合成含异氰酸酯封端的预聚体,然后加入N,N二甲基乙醇胺扩链剂扩链,用丙酮调节粘度,加入冰醋酸中和,用去离子水调节固含量为20%,抽真空回收丙酮后得到高分子乳化剂b。
在带有冷凝器、滴加装置、氮气口、搅拌器和温度计的500mL四口烧瓶中加入蒸馏水200克,50克高分子乳化剂b,环氧氯丙烷0.5克,温度升至83度,滴加60克苯乙烯和40克丙烯酸异辛酯的混合单体以及过硫酸铵的水溶液(1.8%含量)56克,聚合3小时,最后得到固含量30%,乳白色半透明的表面施胶剂。
实验结果:
与硫酸铝的配伍性 | 施胶剂浓度0.2% COBB吸水值(g/m2) | 施胶剂浓度0.3% COBB吸水值(g/m2) | |
实施例1 | 中 | 36 | 29 |
实施例2 | 优 | 31 | 26 |
以上所述,仅是本发明的较佳实施例而已,并非对本发明的技术方案做任何形式上的限制。凡事依据本发明的技术试制对以上实施例所做的简单修改、同等变化与修饰,均在本发明的保护范围之内。
实施例3
阳离子苯丙类表面施胶剂的制备方法,制备步骤为:苯丙类高分子乳化剂a的合成:水溶性溶剂100g,苯乙烯20-60g,甲基丙烯酸酯5-20g,叔胺类甲基丙烯酸酯5-20g,在油溶性引发剂的存在下采用溶液聚合制得,聚合物加入冰醋酸中和,然后加入去离子水将固含量调至10%-30%;阳离子水性聚氨酯类高分子乳化剂b的合成:多元醇真空脱水,加入异氰酸酯及催化剂进行预聚反应,合成含异氰酸酯封端的预聚体,然后加入叔胺扩链剂扩链,用溶剂调节粘度,加入冰醋酸中和,用去离子水调节固含量为10%-30%;表面施胶剂的合成:在上述高分子乳化剂a或b,或者含a、b总质量浓度10-30%的混合液中,加入季铵化试剂,再用质量浓度0.1-1%的水溶性引发剂进行乳液聚合,聚合单体为由30-70%的苯乙烯和30-70%的甲基丙烯酸酯组成的混合物。所述的水溶性溶剂为甲醇、乙醇、正丙醇、异丙醇、丙酮、丁酮、甲酸或乙酸。所述的甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯或甲基丙烯酸异辛酯;叔胺类甲基丙烯酸酯为甲基丙烯酸二甲氨基乙酯。所述的油溶性引发剂为过氧化苯甲酰或偶氮二异丁氰;水溶性引发剂为过硫酸铵、过硫酸钠、过硫酸钾、过硫酸盐-亚硫酸氢钠、双氧水-硫酸亚铁、双氧水-甲醛次硫酸氢钠、双氧水-抗坏血酸或水溶性偶氮类引发剂。所述的多元醇为分子量在100-5000之间的聚丙二醇,聚乙二醇,聚四氢呋喃聚醚,聚酯多元醇,聚己内酯多元醇或聚碳酸酯多元醇中的一种或几种的混合物。所述的催化剂为二月桂酸二丁基锡,辛酸亚锡,三乙胺,二亚乙烯三胺中的一种或几种的混合物。所述的异氰酸酯为MDI,甲苯二异氰酸酯,HDI,PAPI,异氟尔酮二异氰酸酯中的一种或几种的混合物。所述的叔胺扩链剂为N-甲基二乙醇胺、N,N二甲基乙醇胺、乙醇胺、二乙醇胺或三乙醇胺。所述的调节粘度的溶剂为丙酮,丁酮,N,N-二甲基甲酰胺,甲基吡咯烷酮中的一种或几种的混合物。所述的季铵化试剂为环氧氯丙烷、溴乙烷或苄基氯。
Claims (1)
1.阳离子苯丙类表面施胶剂的制备方法,其特征在于制备步骤为:在带有冷凝器、滴加装置、氮气口、搅拌器和温度计的500mL四口烧瓶中加入50克聚乙二醇3000,真空脱水,然后加入30克甲苯二异氰酸酯及0.01克二月桂酸二丁基锡进行预聚反应,合成含异氰酸酯封端的预聚体,然后加入N,N二甲基乙醇胺扩链剂扩链,用丙酮调节粘度,加入冰醋酸中和,用去离子水调节固含量为20%,抽真空回收丙酮后得到高分子乳化剂b;在带有冷凝器、滴加装置、氮气口、搅拌器和温度计的500mL四口烧瓶中加入蒸馏水200克,50克高分子乳化剂b,环氧氯丙烷0.5克,温度升至83度,滴加60克苯乙烯和40克丙烯酸异辛酯的混合单体以及1.8%含量的过硫酸铵的水溶液56克,聚合3小时,最后得到固含量30%,乳白色半透明的表面施胶剂。
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