CN104017169A - 一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法 - Google Patents

一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法 Download PDF

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CN104017169A
CN104017169A CN201410246512.6A CN201410246512A CN104017169A CN 104017169 A CN104017169 A CN 104017169A CN 201410246512 A CN201410246512 A CN 201410246512A CN 104017169 A CN104017169 A CN 104017169A
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廖学明
余晓梦
皮亚斌
杨浩
戴赛
罗运
吴雅
万欢
黄星
王龙
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Wuhan changyingtong Optoelectronic Technology Co., Ltd
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Abstract

本发明涉及一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,包括以下步骤:1)多元醇脱水;2)多元醇与多异氰酸酯混合催化反应1-4小时后,向体系中加入扩链剂、丙烯酸丁酯或苯乙烯单体继续反应3-5小时;3)加入羟基丙烯酸酯单体和阻聚剂,-NCO的转化率达到所需理论值时,即得到所需的水性聚氨酯树脂;4)调节pH在7-8之间,然后滴加含表面活性剂的水溶液,得到带蓝光的透明或半透明溶液;5)滴加含引发剂的水溶液,60-90℃下保温反应1-5小时,加入无水乙醇,得到含交联及杂化结构的核壳型水性聚氨酯乳液。本发明通过新的合成工艺,不使用丙酮等有机溶剂,也无需脱挥环节,得到完全以水为介质的聚氨酯乳液。

Description

一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法
技术领域
本发明属于水性涂料/油墨/胶黏剂领域,具体涉及一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法。
背景技术
自聚氨酯树脂问世以来,多以溶剂型应用于涂料、油墨及胶黏剂行业。现有聚氨酯涂料/油墨/胶黏剂存在诸多不足:如溶剂型聚氨酯涂料/油墨/胶黏剂体系中含有大量的有机溶剂污染环境、影响健康、生产成本高;单组份无溶剂型聚氨酯涂料/油墨/胶黏剂粘度高不利于施工;双组份聚氨酯涂料/油墨/胶黏剂的应用工艺复杂繁琐。上述几种聚氨酯体系也存在成膜后的耐温性差、硬度低、粘接强度和模量不高、外观不丰满等问题。
当前环境污染越来越严重,在人类环保意识日益增强的今天,对以水为介质的聚氨酯乳液的发展越来越受到重视,以水为溶剂,无毒、无污染,并且价格低廉。因此,水性聚氨酯乳液就成为聚氨酯工业发展的重要方向之一,可广泛应用于涂料、油墨、胶粘剂、织物涂层、皮革涂饰剂、纸张表面处理剂和纤维表面处理剂等。尽管市场上现在也有水性聚氨酯乳液,但多数仍然是用丙酮法或其他溶剂法合成的,产品后期虽然经过脱挥处理,却仍存在VOC超标的问题。
发明内容
本发明所要解决的技术问题是针对上述现有技术存在的不足而提供一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,本发明通过新的合成工艺,不使用丙酮等有机溶剂,也无需脱挥环节,得到完全以水为介质的聚氨酯乳液。
本发明为解决上述提出的问题所采用的技术方案为:
一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,包括以下步骤:
1)多元醇脱水:对多元醇进行脱水处理,得到不含水的多元醇;
2)聚氨酯树脂合成与扩链:向步骤1)所得不含水的多元醇中加入催化剂混合均匀,再加入多异氰酸酯搅拌均匀,再升温至50-80℃下反应,反应1-4小时后,向体系中加入扩链剂,并加入良溶剂或者可反应性单体继续反应3-5小时;本步骤所述可反应性单体为丙烯酸酯单体和或苯乙烯单体;
3)接枝并引入可交联结构:将经步骤2)扩链反应后的体系中加入羟基丙烯酸酯单体和阻聚剂,通过滴定法检测-NCO的转化率,当达到所需理论值时,即得到所需的水性聚氨酯树脂;
4)中和与分散:加入胺类中和剂中和步骤3)所得的水性聚氨酯树脂,调节pH在7-8之间,然后滴加含表面活性剂的水溶液,伴以充分搅拌,控制滴加的时间为30-60分钟,继而得到带蓝光的透明或半透明溶液;
5)杂化反应:往步骤4)所得的溶液体系中滴加含引发剂的水溶液,引发可反应性单体,控制滴加的时间为30-60分钟,在60-90℃下保温反应1-5小时,然后加入无水乙醇搅拌分散均匀,得到带有蓝光的半透明乳液,即为含交联及杂化结构的核壳型水性聚氨酯乳液。
上述各反应原料及助剂用量按重量百分数计,各组分配比为:多异氰酸酯7.0-16,多元醇10-19,丙烯酸酯3.5-8.5,苯乙烯4.5-7.5,羟基丙烯酸酯3.0-5.0,扩链剂0.5-3.5,催化剂0.05-1,阻聚剂0.07-1.5,胺类中和剂1.0-3.0,表面活性剂0.05-0.15,引发剂0.05-0.3,去离子水50-80,无水乙醇10-20,所述去离子水分别用于溶解表面活性剂和引发剂,配制表面活性剂水溶液和引发剂水溶液。
按上述方案,所述多元醇的数均分子量在500-5000之间,粘度在600-3000mPa.S(25℃)之间。所述多元醇包括聚酯多元醇、聚醚多元醇、植物油多元醇、松香酯多元醇及聚烯烃多元醇。更为具体地,所述多元醇为聚己二酸乙二醇内二醇酯(PDA)、聚己二酸乙二醇酯(PEA)、聚己二酸丁二醇酯二醇(PBA)、聚己内酯(PCL)、聚碳酸酯二元醇(PCDL)、聚四亚甲基醚二醇(PTMEG)、聚乙二醇(PEG)和聚醚多元醇(PPG)中的一种或几种按任意比例的混合物。尤以聚己内酯(PCL)与聚四亚甲基醚二醇(PTMEG)两种混合使用、聚己内酯(PCL)单独使用效果最佳。
按上述方案,所述步骤1)中的脱水处理是将一种或几种按任意比例的多元醇混合后,加热至50-80℃,然后抽真空至0.098-0.1MPa,升温至100-120℃保温2-3小时,所得产物密闭备用。
按上述方案,所述步骤2)中的催化剂包括叔胺类和有机金属类化合物;更为具体地,所述催化剂为三亚乙基二胺、双(二甲氨基乙基)醚、2-(2-二甲氨基-乙氧基)乙醇、辛酸亚锡、二月桂酸二丁基锡、羧酸钾、有机汞以及有机铅中一种。尤以辛酸亚锡、二月桂酸二丁基锡中的一种作为最佳选择。
按上述方案,所述步骤2)中的多异氰酸酯包括二异氰酸酯、三异氰酸酯和多异氰酸酯。更为具体地,所述多异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、三甲基-1,6-六亚甲基二异氰酸酯(TMHDI)、异佛尔酮二异氰酸酯(IPDI)和二(二异氰酸酯甲基)环己烷(HXDI)的一种或几种按任意比例的混合物,尤以其中的一种或两种混合使用效果最佳。
按上述方案,所述步骤2)中的扩链剂包括小分子二元醇、二元胺及乙醇胺类化合物。更为具体地,所述扩链剂为1,4-丁二醇、乙二醇、1,2-丙二醇、1,3-丙二醇、一缩二乙二醇、1,6-己二醇、3,3’-二氯-4,4’-二氨基二苯基甲烷(MOCA)、二甲硫基甲苯二胺DMTDA、二乙基甲苯二胺(DETDA)、乙醇胺、二乙醇胺、三乙醇胺、二羟甲基丙酸及二羟甲基丁酸中一种或几种。
按上述方案,所述步骤2)加入扩链剂时,可以同时添加适量调节粘度的良溶剂,有利于反应充分与散热,所述良溶剂为N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、丙酮、环己酮中一种或几种。。
按上述方案,所述步骤2)的丙烯酸酯和步骤3)中的羟基丙烯酸酯均包括(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯及环氧丙烯酸酯等。本发明选用环氧丙烯酸酯或(甲基)丙烯酸羟丙酯作为功能单体封端。
按上述方案,所述步骤3)中阻聚剂为对苯二酚、2,6-二叔丁基对甲酚、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、丁基或辛基化苯胺及亚磷酸酯的一种或几种按任意比例的混合物。选择其中的一种或与亚磷酸酯复合使用效果尤佳。
按上述方案,所述步骤4)中胺类中和剂为氨水、三乙胺、二乙醇胺中一种或几种。。
按上述方案,所述步骤4)中表面活性剂十二烷基磺酸钠或十二烷基硫酸钠等。
按上述方案,所述步骤4)中中和的温度为30-50℃,反应时间为30-90分钟,加入胺类中和剂的过程中边加边搅拌。
按上述方案,所述步骤5)中引发剂为偶氮二异丁氰、偶氮二异庚氰、过硫酸铵或过硫酸钾中的任意一种或几种。。
上述制备方法制备得到的含交联及杂化结构的核壳型水性聚氨酯乳液,可以作为清漆或配制成水性涂料与水性油墨,应用于建材、家具及印刷包装等领域。
与现有技术相比,本发明的有益效果是:
第一,本发明所述的聚氨酯乳液主体树脂中引入了可交联单体及乳液体系中引入了杂化结构,使其具有良好的成膜性和冻融稳定性;
第二,本发明所述聚氨酯乳液可以根据应用的需要加,用去离子水、乙醇等稀释不破乳,方便应用;
第三,本发明通过新的合成工艺,不使用丙酮等有机溶剂,也无需脱挥环节,得到完全以水为介质的聚氨酯乳液,VOC含量为零或趋近于零。
本发明所述聚氨酯乳液对铝箔、纸张、木材、PET和印刷油墨等具有良好的附着力,膜柔韧性好、耐黄变、高温不回粘、低温不裂纹,涂膜透亮丰满。
附图说明
图1实施例1中核壳型水性聚氨酯乳液的制备方法的官能团反应示意图。
图2本发明制备的核壳型水性聚氨酯乳液的电镜图。
图3本发明制备的核壳型水性聚氨酯乳液作为胶粘剂使用示意图。
具体实施方式
为进一步阐明本发明技术,下面结合具体实施例进行详细描述,本发明包括但不限于以下实施例。
本发明通过滴定法测定NCO的含量确定反应程度,其方法依据为《HG-T2409-1992聚氨酯预聚体中异氰酸酯基含量的测定》,当NCO含量达到理论值时即表示反应结束,出料,得到所需的含交联及杂化结构的水性聚氨酯树脂。
本发明中官能团反应示意图如图1所示。
实施例1
本实施例中各反应原料及助剂用量按重量百分数计,各组分配比为:异佛尔酮二异氰酸酯(IPDI):甲苯二异氰酸酯(TDI):聚已内酯多元醇(PCL):聚四亚甲基醚二醇醇(PTMEG):1,4-丁二醇(DBO):二羟甲基丙酸(DMPA):丙烯酸-2-羟基丙酯HPA:十二烷基硫酸钠(SDS):过硫酸铵(APS):苯乙烯(St):三乙胺(TEA):催化剂(二月桂酸二丁基锡):阻聚剂(对苯二酚):去离子水:无水乙醇为50:26:60:60:6:15:50:1.5:1.75:78:16:0.5:0.75:550:150;所述去离子水分别用于溶解表面活性剂和引发剂,配制表面活性剂水溶液和引发剂水溶液;多元醇PCL和PTMEG的数均相对分子质量为1000,25℃时粘度在600mPa.S左右。
本实施例所述含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,各原料按上述配比,具体步骤如下:
1)多元醇脱水:将PTMEG和PCL投入反应釜混合后,升温,至温度达到50℃时,启动真空泵,使反应釜内真空度缓慢的升至0.098-0.1MPa,控制釜内温度为110℃左右保温3小时,产物出料后置于密闭储槽中备用;
2)聚氨酯树脂合成与扩链:将步骤1)所得产物投入反应釜,再加入催化剂二月桂酸二丁基锡,室温下搅拌混合均匀,再加入IPDI和TDI搅拌均匀后在70℃下反应,反应3小时后,向体系中加入扩链剂DBO和DMPA、苯乙烯单体,反应5小时;
3)接枝并引入可交联结构:将步骤2)扩链反应后的体系加入HPA和对苯二酚,反应4小时后,滴定-NCO基团的转化率,当达到所需理论值时,停止反应,得到所需的水性聚氨酯树脂;
4)中和分散:待步骤3)所得水性聚氨酯树脂降温到30℃加入TEA,调节体系pH值在7-8之间,滴加SDS的水溶液,强力搅拌分散1小时,控制SDS的水溶液的滴加时间为1小时,得到有蓝光的透明或半透明液体;
5)杂化反应:往步骤4)所得溶液体系中滴加溶解有APS的水溶液,控制滴加时间60min,置于90℃下保温反应3小时,加入无水乙醇搅拌分散均匀,得到有蓝光的半透明或乳白色液体,即得到所需的新型水性聚氨酯乳液。
如图2所示,本发明制备的水性聚氨酯乳液产物粒径为350nm左右,为核壳结构。
如图3所示,本发明尤其适用于两种基材间的粘结,基材1通常为塑料,可以为PET膜、PE膜、PP膜、PS膜、PC膜等;基材2通常为铝箔、卡纸、UV固化油墨等,作为粘结在基材1上的外包装。
表1水性聚氨酯乳液性能指标
外观 半透明有蓝光液体
固含(%) 30
PH值 7.5
附着力 ≤1
硬度 ≥H
粘度(涂-4杯,25℃) 15.6秒
实施例2
本实施例中各反应原料及助剂用量按重量百分数计,各组分配比为:异佛尔酮二异氰酸酯(IPDI):聚已内酯多元醇(PCL):1,4-丁二醇(DBO):二羟甲基丙酸(DMPA):丙烯酸羟乙酯(HEA):十二烷基硫酸钠(SDS):过硫酸铵(APS):良溶剂DMAc:二乙醇胺:催化剂(二月桂酸二丁基锡):阻聚剂(对苯二酚):去离子水:无水乙醇为76:120:5:20:50:1.2:1.8:100:16:1.5:2.5:600:200;所述去离子水分别用于溶解表面活性剂和引发剂,配制表面活性剂水溶液和引发剂水溶液。其中,PCL的数均相对分子质量为600-1000,25℃时粘度在600mPa.S左右。
本实施例所述含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,各原料按上述配比,具体步骤如下:
1)多元醇脱水处理:将PCL投入反应釜混合后,升温,至温度达到70℃时,启动真空泵,使反应釜内真空度缓慢的升至0.098-0.1MPa,控制釜内温度为120℃左右保温3小时,产物出料后置于密闭储槽中备用;
2)聚氨酯树脂合成与扩链:将步骤1)所得产物投入反应釜,再加入催化剂二月桂酸二丁基锡,室温下搅拌混合均匀,再加入IPDI搅拌均匀后在50℃下反应,反应1小时后,向体系中加入扩链剂DBO和DMPA、良溶剂DMAc,反应3小时;
3)接枝并引入可交联结构:将步骤2)扩链反应后的体系加入HEA和阻聚剂,反应5小时后,滴定-NCO基团的转化率,当达到所需理论值时,停止反应,得到所需的水性聚氨酯树脂;
4)中和分散:待步骤3)所得水性聚氨酯树脂降温到40℃加入二乙醇胺,调节体系pH值在7-8之间,滴加SDS的水溶液,强力搅拌分散3小时,控制SDS的水溶液的滴加时间为0.5小时,得到有蓝光的透明或半透明液体;
5)杂化反应:往步骤4)所得溶液体系中滴加溶解有APS的水溶液,控制滴加时间为30min,置于60℃下保温反应5小时,加入无水乙醇搅拌分散均匀,得到有蓝光的半透明或乳白色液体,即得到所需的新型水性聚氨酯乳液。
表2水性聚氨酯乳液性能指标
外观 半透明有蓝光液体/乳白色液体
固含(%) 35
PH值 7.1
附着力 ≤1
硬度 ≥H
粘度(涂-4杯,25℃) 17秒
实施例3
本实施例中各反应原料及助剂用量按重量百分数计,各组分配比为:4,4'-二环己基甲烷二异氰酸酯(HMDI):六亚甲基二异氰酸酯(HDI):聚乙二醇(PEG):聚四亚甲基醚二醇(PTMEG):1,4-丁二醇(DBO):二羟甲基丁酸(DMBA):丙烯酸羟丙酯(HPA):十二烷基硫酸钠(SDS):过硫酸铵(APS):良溶剂丙酮:三乙胺(TEA):催化剂(二月桂酸二丁基锡):阻聚剂(对苯二酚):去离子水:无水乙醇为50:26:60:60:6:15:50:1.5:1.75:78:16:0.5:0.75:550:150;所述去离子水分别用于溶解表面活性剂和引发剂,配制表面活性剂水溶液和引发剂水溶液。其中,多元醇PEG、PTMEG的数均相对分子质量为800-1000,25℃时粘度在600mPa.S左右。
本实施例所述含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,各原料按上述配比,具体步骤如下:
1)多元醇脱水处理:将PEG、PTMEG投入反应釜混合后,升温,至温度达到70℃时,启动真空泵,使反应釜内真空度缓慢的升至0.098-0.1MPa,控制釜内温度为120℃左右保温3小时,产物出料后置于密闭储槽中备用;
2)聚氨酯树脂合成与扩链:将步骤1)所得产物投入反应釜,再加入催化剂二月桂酸二丁基锡,室温下搅拌混合均匀,再加入HMDI和HDI搅拌均匀后在60℃下反应,反应2小时后,向体系中加入扩链剂DBO和DMPA、良溶剂丙酮,反应5小时;
3)接枝并引入可交联结构:将步骤2)扩链反应后的体系加入HPA和对苯二酚,反应4小时后,滴定-NCO基团的转化率,当达到所需理论值时,停止反应,得到所需的水性聚氨酯树脂;
4)中和分散:待步骤3)所得水性聚氨酯树脂降温到30℃加入TEA,调节体系pH值在7-8之间,滴加SDS的水溶液,强力搅拌分散1.5小时,控制SDS的水溶液的滴加时间为1小时,得到有蓝光的透明或半透明液体;
5)杂化反应:往步骤4)所得溶液体系中滴加溶解有APS的水溶液,控制滴加时间为50min,置于80℃下保温反应2小时,加入无水乙醇搅拌分散均匀,得到有蓝光的半透明乳白色液体,即得到所需的新型水性聚氨酯乳液。
表3水性聚氨酯乳液性能指标
外观 半透明有蓝光液体/乳白色液体
固含(%) 40
PH值 7.4
附着力 ≤1
硬度 ≥H
粘度(涂-4杯,25℃) 18.5秒
实施例4
本实施例中各反应原料及助剂用量按重量百分数计,各组分配比为:异氟尔酮二异氰酸酯(IPDI):4,4'-二环己基甲烷二异氰酸酯(HMDI):聚乙二醇(PEG):聚四亚甲基醚二醇(PTMEG):二羟甲基丙酸(DMPA):丙烯酸羟乙酯(HEA):十二烷基硫酸钠(SDS):过硫酸铵(APS):良溶剂DMF:三乙胺(TEA):催化剂(二月桂酸二丁基锡):阻聚剂(对苯二酚):去离子水:无水乙醇为50:26:60:60:20:50:1.5:1.75:60:25:16:0.5:0.75:550:150;所述去离子水分别用于溶解表面活性剂和引发剂,配制表面活性剂水溶液和引发剂水溶液。其中,多元醇PEG、PTMEG的数均相对分子质量为1000,25℃时粘度在600mPa.S左右。
本实施例所述含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,各原料按上述配比,具体步骤如下:
1)多元醇脱水处理:将PEG、PTMEG投入反应釜混合后,升温,至温度达到70℃时,启动真空泵,使反应釜内真空度缓慢的升至0.098-0.1MPa,控制釜内温度为120℃左右保温3小时,产物出料后置于密闭储槽中备用;
2)聚氨酯树脂合成与扩链:将步骤1)所得产物投入反应釜,再加入催化剂二月桂酸二丁基锡,室温下搅拌混合均匀,再加入IPDI和HMDI搅拌均匀后在60℃下反应,反应2小时后,向体系中加入扩链剂DMPA、良溶剂DMF,反应5小时;
3)接枝并引入可交联结构:将步骤2)扩链反应后的体系加入HEA和对苯二酚,反应4小时后,滴定-NCO基团的转化率,当达到所需理论值时,停止反应,得到所需的水性聚氨酯树脂;
4)中和分散:待步骤3)所得水性聚氨酯树脂降温到30℃加入TEA,调节体系pH值在7-8之间,滴加SDS的水溶液,强力搅拌分散1.5小时,控制SDS的水溶液的滴加时间为1小时,得到有蓝光的透明或半透明液体;
5)杂化反应:往步骤4)所得溶液体系中滴加溶解有APS的水溶液,控制滴加时间为50min,置于80℃下保温反应2小时,加入无水乙醇搅拌分散均匀,得到有蓝光的半透明乳白色液体,即得到所需的新型水性聚氨酯乳液。
表4水性聚氨酯乳液性能指标
外观 半透明有蓝光液体/乳白色液体
固含(%) 30
PH值 7.7
附着力 ≤1
硬度 ≥H
粘度(涂-4杯,25℃) 14.6秒
以上所述为本发明的较佳实施例,对于上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

1.一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于包括以下步骤: 
1)多元醇脱水:对多元醇进行脱水处理,得到不含水的多元醇; 
2)聚氨酯树脂合成与扩链:向步骤1)所得不含水的多元醇中加入催化剂混合均匀,再加入多异氰酸酯搅拌均匀,再升温至50-80℃下反应,反应1-4小时后,向体系中加入扩链剂,并加入良溶剂或者可反应性单体继续反应3-5小时;本步骤所述可反应性单体为丙烯酸酯单体和或苯乙烯单体; 
3)接枝并引入可交联结构:将经步骤2)扩链反应后的体系中加入羟基丙烯酸酯单体和阻聚剂,通过滴定法检测-NCO的转化率,当达到所需理论值时,即得到所需的水性聚氨酯树脂; 
4)中和与分散:加入胺类中和剂中和步骤3)所得的水性聚氨酯树脂,调节pH在7-8之间,然后滴加含表面活性剂的水溶液,伴以充分搅拌,控制滴加的时间为30-60分钟,继而得到带蓝光的透明或半透明溶液; 
5)杂化反应:往步骤4)所得的溶液体系中滴加含引发剂的水溶液,引发可反应性单体,控制滴加的时间为30-60分钟,在60-90℃下保温反应1-5小时,然后加入无水乙醇搅拌分散均匀,得到带有蓝光的半透明乳液,即为含交联及杂化结构的核壳型水性聚氨酯乳液。 
2.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于各组分配比为:多异氰酸酯7.0-16,多元醇10-19,丙烯酸酯3.5-8.5、苯乙烯4.5-7.5,羟基丙烯酸酯3.0-5.0,扩链剂0.5-3.5,催化剂0.05-1,阻聚剂0.07-1.5,胺类中和剂1.0-3.0,表面活性剂0.05-0.15,引发剂0.05-0.3,去离子水50-80,无水乙醇10-20,所述去离子水分别用于溶解表面活性剂和引发剂,配制表面活性剂水溶液和引发剂水溶液。 
3.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述多元醇的数均分子量在500-5000之间,粘度在600-3000mPa.S(25℃)之间;所述多元醇包括聚酯多元醇、聚醚多元醇、植物油多元醇、松香酯多元醇及聚烯烃多元醇。 
4.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述步骤1)中的脱水处理是将一种或几种按任意比例的多元醇混合后,加热至50-80℃,然后抽真空至0.098-0.1MPa,升温至100-120℃保温2-3小时,所得产物密闭备用。 
5.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述步骤2)中的催化剂包括叔胺类和有机金属类化合物;所述步骤2)中的扩链剂包括小分子二元醇、二元胺及乙醇胺类化合物。 
6.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法, 其特征在于所述步骤2)中的多异氰酸酯包括二异氰酸酯、三异氰酸酯和多异氰酸酯。 
7.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述步骤2)加入扩链剂时,可以同时添加适量调节粘度的良溶剂;所述良溶剂为N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、丙酮、环己酮中一种。 
8.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述步骤2)的丙烯酸酯和步骤3)中的羟基丙烯酸酯均包括(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯及环氧丙烯酸酯。 
9.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述步骤3)中阻聚剂剂为对苯二酚、2,6-二叔丁基对甲酚、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、丁基或辛基化苯胺及亚磷酸酯的一种或几种按任意比例的混合物。 
10.根据权利要求1所述的一种含交联及杂化结构的核壳型水性聚氨酯乳液的制备方法,其特征在于所述步骤4)中胺类中和剂为氨水、三乙胺、二乙醇胺中一种,表面活性剂十二烷基磺酸钠或十二烷基硫酸钠;所述步骤4)中中和的温度为30-50℃,反应时间为30-90分钟,加入胺类中和剂的过程中边加边搅拌;所述步骤5)中引发剂为偶氮二异丁氰、偶氮二异庚氰、过硫酸铵或过硫酸钾中的任意一种。 
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105622857A (zh) * 2016-04-01 2016-06-01 武汉大学 一种互穿网络结构水性聚氨酯纳米复合材料的制备方法
CN109735219A (zh) * 2018-12-21 2019-05-10 广东华润涂料有限公司 双组分水性聚氨酯涂料组合物以及由其形成的低光泽度涂层
CN113710759A (zh) * 2019-04-02 2021-11-26 Ppg工业俄亥俄公司 耐污涂料组合物
CN114933690A (zh) * 2022-06-10 2022-08-23 山西晋川合成材料股份有限公司 利用核壳结构制备耐污紫外固化树脂的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102924664A (zh) * 2012-11-20 2013-02-13 江苏日出化工有限公司 一种核壳含氟聚氨酯-丙烯酸酯乳胶制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102924664A (zh) * 2012-11-20 2013-02-13 江苏日出化工有限公司 一种核壳含氟聚氨酯-丙烯酸酯乳胶制备方法

Cited By (5)

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CN105622857A (zh) * 2016-04-01 2016-06-01 武汉大学 一种互穿网络结构水性聚氨酯纳米复合材料的制备方法
CN109735219A (zh) * 2018-12-21 2019-05-10 广东华润涂料有限公司 双组分水性聚氨酯涂料组合物以及由其形成的低光泽度涂层
CN109735219B (zh) * 2018-12-21 2021-04-20 广东华润涂料有限公司 双组分水性聚氨酯涂料组合物以及由其形成的低光泽度涂层
CN113710759A (zh) * 2019-04-02 2021-11-26 Ppg工业俄亥俄公司 耐污涂料组合物
CN114933690A (zh) * 2022-06-10 2022-08-23 山西晋川合成材料股份有限公司 利用核壳结构制备耐污紫外固化树脂的方法

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