CN111925494B - 一种高粘性水性聚氨酯及其制备方法 - Google Patents
一种高粘性水性聚氨酯及其制备方法 Download PDFInfo
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- CN111925494B CN111925494B CN202010857039.0A CN202010857039A CN111925494B CN 111925494 B CN111925494 B CN 111925494B CN 202010857039 A CN202010857039 A CN 202010857039A CN 111925494 B CN111925494 B CN 111925494B
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Abstract
Description
技术领域
本发明涉及有机高分子合成技术领域,更具体的说是涉及一种高粘性水性聚氨酯及其制备方法。
背景技术
水性聚氨酯是一种以去离子水代替有机溶剂作为分散介质的新型聚氨酯体系,也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水性聚氨酯以水为溶剂,无污染、安全可靠、机械性能优良、相容性好、易于改性等优点。
目前水性聚氨酯品种繁多,可以按多种方法分类:1.以外观分,水性聚氨酯可分为聚氨酯乳液、聚氨酯分散液、聚氨酯水溶液;2.按使用形式分,单组分及双组分。可直接使用,或无需交联剂即可得到所需使用性能的水性聚氨酯称为单组分水性聚氨酯胶粘剂。若单独使用不能获得所需的性能,必须添加交联剂;或者一般单组分水性聚氨酯添加交联剂后能提高粘接性能,在这些情况中,水性聚氨酯主剂和交联剂二者就组成双组分体系;3.以亲水性基团的性质分, 根据聚氨酯分子侧链或主链上是否含有离子基团,即是否属离子键聚合物(离聚物),水性聚氨酯可分为阴离子型、阳离子型、非离子型。含阴、阳离子的水性聚氨酯又称为离聚物型水性聚氨酯。
随着人们环保意识的增强、各国对环境污染问题的日益重视,水性聚氨酯正逐步取代溶剂型聚氨酯,广泛应用于涂料、粘合剂、皮革价格、纺织、油墨印刷等诸多领域。在油墨印刷领域中,油墨是用于印刷的重要材料,普通的胶印油墨中都含有矿物油,并且对人体有害。而水性聚氨酯油墨不含有挥发性有机溶剂,安全、无毒,被大量用于食品、药品、儿童玩具中的软包装印刷。但目前现有的油墨用水性聚氨酯存在诸多问题,如:稳定性较差,保质期短;附着牢度差;这些问题的存在大大限制了水性聚氨酯在油墨印刷中的使用。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种高粘性水性聚氨酯及其制备方法,该水性聚氨酯不含有有机溶剂,安全无毒,粘性高;同时又具有较长的稳定性;还有较高的附着牢度,特别适合应用于油墨印刷领域。
为实现上述目的,本发明提供了如下技术方案:一种高粘性水性聚氨酯,包括下列重量份物质组成:
异佛尔酮二异氰酸酯 8-25份
聚合物多元醇 10-30份
小分子多元醇 2-6份;
去离子水 30-80份;
含有羧基的第一亲水扩链剂 1-5份;
含有磺酸基的第二亲水扩链剂 1-5份;
中和剂1-5份;
催化剂0.4-1份;
改性剂1-3份;
所述聚合物多元醇为聚四氢呋喃醚二醇和物质A的混合物,其质量比为3:1;
其中物质A的结构式为
所述改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物,其质量比为2:3:1。
作为本发明的进一步改进,所述聚四氢呋喃醚二醇的数均分子量为500-5000;所述物质A的数均分子量为1000-6000。
作为本发明的进一步改进,所述小分子多元醇为1,4丁二醇、二羟甲基丙酸和物质B的混合物,其质量比为2:1:1;
其中物质B的结构式为
作为本发明的进一步改进,第一亲水扩链剂为二羟甲基丁酸、噻吩-2,3-二羧酸和2-氨基-5-乙酰氨基苯甲酸的混合物,其质量比为3:1:2。
作为本发明的进一步改进,所述第二亲水扩链剂为乙二胺基丙磺酸钠、2-氨基苯酚-4-磺酸钠和3-氨基-2-4-氯苯基-2-羟基丙烷磺酸钠的混合物,其质量比为1:2:1。
作为本发明的进一步改进,所述中和剂为三乙醇胺。
作为本发明的进一步改进,所述催化剂为有机锌类催化剂、有机铋类催化剂和有机银类催化剂中至少一种。
作为本发明的进一步改进,一种高粘性水性聚氨酯的制备方法,包括以下步骤:
步骤一:根据设定的重量份配备原料,将聚合物多元醇、小分子多元醇、异佛尔酮二异氰酸酯、催化剂和改性剂加入到反应容器中,于60-90℃下反应3-5小时,得到预聚体;
步骤二:加入第一亲水扩链剂,于60-90℃下反应2~4小时;
步骤三:降温至30-50℃,加入中和剂反应10-40分钟,得到离聚体;
步骤四:剧烈搅拌下,将去离子水加入到离聚体中,然后搅拌5-20分钟,得到水性聚氨酯预分散液;
步骤五:将第二亲水扩链剂加入到水性聚氨酯预分散液中反应20-60分钟,得到高粘性水性聚氨酯。
本发明的有益效果:通过是以异佛尔酮二异氰酸酯作为异氰酸酯,以聚四氢呋喃醚二醇和物质A作为聚合物多元醇,同时加入小分子多元醇,第一扩链剂,第二扩链剂和改性剂等物质反应制得,物质A的结构式为
改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物; 在小分子多元醇选择了1,4丁二醇、二羟甲基丙酸和物质B;而物质B的结构式为:
本发明制得的水性聚氨酯,以去离子水作为溶剂,不含有任何有机溶剂,无毒环保,安全,能够保证使用者的健康;同时稳定性高,保质期为6个月以上,使用时间长;还具有高粘性,能够附着在各种基材上,附着牢度高,不容易脱落,特别适合应用于油墨印刷领域。
具体实施方式
实施例1
物质A的制备
将10g(0.025mol)聚乙二醇二丙烯酸酯(Mn=400)、5g(0.025mol)丙二醛50%水溶液,0.28g(0.0025mol)1,4-二叠氮双环[2.2.2]辛烷(DABCO)催化剂和0.014g对羟基苯酚阻聚剂加入到50mL丙酮溶剂中搅拌混合,混合均匀后再温度为70℃的条件下反应96小时;反应结束后,减压蒸馏除去溶剂,加入二氯甲烷,并用无水硫酸镁干燥24小时候,过滤,滤液通过减压蒸馏出去二氯甲烷,粗产物用乙醚沉淀,得到物质A;Mn(GPC)=3500,PDI(GPC)=1.8;物质A中含有较多的羟基,活泼双键和酯键;
其反应式为:
实施例2
一种高粘性水性聚氨酯,包括下列重量份物质组成:
异佛尔酮二异氰酸酯18份
聚合物多元醇20份
小分子多元醇4份;
去离子水60份;
含有羧基的第一亲水扩链剂3份;
含有磺酸基的第二亲水扩链剂3份;
中和剂2份
催化剂0.7份;
改性剂2份;
所述聚合物多元醇为聚四氢呋喃醚二醇和物质A的混合物,其质量比为3:1;
其中物质A的结构式为
物质A由实施例1制得;聚四氢呋喃醚二醇的数均分子量为2500;
所述改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物,其质量比为2:3:1。
所述小分子多元醇为1,4丁二醇、二羟甲基丙酸和物质B的混合物,其质量比为2:1:1;
其中物质B的结构式为
所述第一亲水扩链剂为二羟甲基丁酸、噻吩-2,3-二羧酸和2-氨基-5-乙酰氨基苯甲酸的混合物,其质量比为3:1:2。
所述第二亲水扩链剂为乙二胺基丙磺酸钠、2-氨基苯酚-4-磺酸钠和3-氨基-2-4-氯苯基-2-羟基丙烷磺酸钠的混合物,其质量比为1:2:1。
所述中和剂为三乙醇胺。
所述催化剂为有机锌类催化剂。
一种高粘性水性聚氨酯的制备方法,其特征在于:包括以下步骤:
步骤一:根据设定的重量份配备原料,将聚合物多元醇、小分子多元醇、异佛尔酮二异氰酸酯、催化剂和改性剂加入到反应容器中,于80℃下反应4小时,得到预聚体;
步骤二:加入第一亲水扩链剂,于80℃下反应3小时;
步骤三:降温至40℃,加入中和剂反应25分钟,得到离聚体;
步骤四:剧烈搅拌下,将去离子水加入到离聚体中,然后搅拌15分钟,得到水性聚氨酯预分散液;
步骤五:将第二亲水扩链剂加入到水性聚氨酯预分散液中反应40分钟,得到高粘性水性聚氨酯。
实施例3
一种高粘性水性聚氨酯,包括下列重量份物质组成:
异佛尔酮二异氰酸酯10份
聚合物多元醇14份
小分子多元醇5份;
去离子水45份;
含有羧基的第一亲水扩链剂2份;
含有磺酸基的第二亲水扩链剂2份;
中和剂2份
催化剂0.5份;
改性剂2份;
所述聚合物多元醇为聚四氢呋喃醚二醇和物质A的混合物,其质量比为3:1;
其中物质A的结构式为
物质A由实施例1制得;
所述聚四氢呋喃醚二醇的数均分子量为5000;
所述改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物,其质量比为2:3:1。
所述小分子多元醇为1,4丁二醇、二羟甲基丙酸和物质B的混合物,其质量比为2:1:1;
其中物质B的结构式为
所述第一亲水扩链剂为二羟甲基丁酸、噻吩-2,3-二羧酸和2-氨基-5-乙酰氨基苯甲酸的混合物,其质量比为3:1:2。
所述第二亲水扩链剂为乙二胺基丙磺酸钠、2-氨基苯酚-4-磺酸钠和3-氨基-2-4-氯苯基-2-羟基丙烷磺酸钠的混合物,其质量比为1:2:1。
所述中和剂为三乙醇胺。
所述催化剂为有机铋类催化剂。
一种高粘性水性聚氨酯的制备方法,其特征在于:包括以下步骤:
步骤一:根据设定的重量份配备原料,将聚合物多元醇、小分子多元醇、异佛尔酮二异氰酸酯、催化剂和改性剂加入到反应容器中,于70℃下反应4小时,得到预聚体;
步骤二:加入第一亲水扩链剂,于70℃下反应3小时;
步骤三:降温至40℃,加入中和剂反应20分钟,得到离聚体;
步骤四:剧烈搅拌下,将去离子水加入到离聚体中,然后搅拌10分钟,得到水性聚氨酯预分散液;
步骤五:将第二亲水扩链剂加入到水性聚氨酯预分散液中反应30分钟,得到高粘性水性聚氨酯。
实施例4
一种高粘性水性聚氨酯,包括下列重量份物质组成:
异佛尔酮二异氰酸酯24份
聚合物多元醇30份
小分子多元醇2份;
去离子水70份;
含有羧基的第一亲水扩链剂4份;
含有磺酸基的第二亲水扩链剂4份;
中和剂5份
催化剂1份;
改性剂3份;
所述聚合物多元醇为聚四氢呋喃醚二醇和物质A的混合物,其质量比为3:1;
其中物质A的结构式为
所述物质A由实施例1制得;
所述聚四氢呋喃醚二醇的数均分子量为1000。
所述改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物,其质量比为2:3:1。
所述小分子多元醇为1,4丁二醇、二羟甲基丙酸和物质B的混合物,其质量比为2:1:1;
其中物质B的结构式为
所述第一亲水扩链剂为二羟甲基丁酸、噻吩-2,3-二羧酸和2-氨基-5-乙酰氨基苯甲酸的混合物,其质量比为3:1:2。
所述第二亲水扩链剂为乙二胺基丙磺酸钠、2-氨基苯酚-4-磺酸钠和3-氨基-2-4-氯苯基-2-羟基丙烷磺酸钠的混合物,其质量比为1:2:1。
所述中和剂为三乙醇胺。
所述催化剂为有机银类催化剂。
一种高粘性水性聚氨酯的制备方法,其特征在于:包括以下步骤:
步骤一:根据设定的重量份配备原料,将聚合物多元醇、小分子多元醇、异佛尔酮二异氰酸酯、催化剂和改性剂加入到反应容器中,于90℃下反应4小时,得到预聚体;
步骤二:加入第一亲水扩链剂,于90℃下反应4小时;
步骤三:降温至40℃,加入中和剂反应40分钟,得到离聚体;
步骤四:剧烈搅拌下,将去离子水加入到离聚体中,然后搅拌20分钟,得到水性聚氨酯预分散液;
步骤五:将第二亲水扩链剂加入到水性聚氨酯预分散液中反应50分钟,得到高粘性水性聚氨酯。
对比例1
一种高粘性水性聚氨酯,包括下列重量份物质组成:
异佛尔酮二异氰酸酯10份
聚合物多元醇14份
小分子多元醇5份;
去离子水45份;
含有羧基的第一亲水扩链剂2份;
含有磺酸基的第二亲水扩链剂2份;
中和剂2份
催化剂0.5份;
所述聚合物多元醇为聚四氢呋喃醚二醇;
所述聚四氢呋喃醚二醇的数均分子量为5000;
所述小分子多元醇为1,4丁二醇、二羟甲基丙酸和物质B的混合物,其质量比为2:1:1;
其中物质B的结构式为
所述第一亲水扩链剂为二羟甲基丁酸、噻吩-2,3-二羧酸和2-氨基-5-乙酰氨基苯甲酸的混合物,其质量比为3:1:2。
所述第二亲水扩链剂为乙二胺基丙磺酸钠、2-氨基苯酚-4-磺酸钠和3-氨基-2-4-氯苯基-2-羟基丙烷磺酸钠的混合物,其质量比为1:2:1。
所述中和剂为三乙醇胺。
所述催化剂为有机锌类催化剂。
一种高粘性水性聚氨酯的制备方法,其特征在于:包括以下步骤:
步骤一:根据设定的重量份配备原料,将聚合物多元醇、小分子多元醇、异佛尔酮二异氰酸酯和催化剂加入到反应容器中,于70℃下反应4小时,得到预聚体;
步骤二:加入第一亲水扩链剂,于70℃下反应3小时;
步骤三:降温至40℃,加入中和剂反应20分钟,得到离聚体;
步骤四:剧烈搅拌下,将去离子水加入到离聚体中,然后搅拌10分钟,得到水性聚氨酯预分散液;
步骤五:将第二亲水扩链剂加入到水性聚氨酯预分散液中反应30分钟,得到水性聚氨酯。
性能测试
用粘度计对对实施例2-4和对比例1制得的水性聚氨酯试样进行粘度测试;
根据GB/T6753.3-1986对实施例2-4和对比例1制得的水性聚氨酯试样进行稳定性能测试;
由上表可知,本发明制得的水性聚氨酯中不含有任何有机溶剂,无毒,安全,环保;且粘度高,能够紧密粘结(附着)在各种基物上,不容易脱落或分离;同时稳定性强,保质期大于6个月,经济价值高,提高了水性聚氨酯的应用范围。
根据GB/T 13217.7-2009液体油墨附着牢度检验方法对实施例2-4和对比例1制得水性聚氨酯进行附着牢度测试;其中附着牢度的评价均是分1-5级。其中1级为最差,5级为最好,3级以上为合格
附着牢度,是指油墨印迹在承印物上的附着力;经过附着牢度测试,实施例2-4制得的水性聚氨酯的附着牢度均在4级以上,附着力较强,且能够与附着在各种不同的附着底物上,应用范围十分广泛,特别适合油墨印刷领域。
根据GB/T 528-1992对实施例2-4和对比例1制得的水性聚氨酯进行拉伸强度测试;
经过对试样进行拉伸强度测试,我们惊喜的发现实施例2-4制得的水性聚氨酯也具有较大的拉伸强度,这进一步增大了水性聚氨酯的应用范围
本发明的一种高粘性水性聚氨酯,是以异佛尔酮二异氰酸酯作为异氰酸酯原料,以聚四氢呋喃醚二醇和物质A作为聚合物多元醇,同时加入小分子多元醇,第一扩链剂,第二扩链剂和改性剂等物质反应制得, 异佛尔酮二异氰酸酯是一种常见的异氰酸酯原料,是脂肪族不变黄异氰酸酯,与羟基、胺等含活泼氢化合物发生反应,其为无色,从而使得最终制得的水性聚氨酯可以为无色;同时它能提高水性聚氨酯的耐光学,耐化学品性,使得最终制成的水性聚氨酯具有较强的稳定性,保质期更长,延长使用时间,提高经济价值;作为本发明的创造性之一,在聚合物多元醇上选择了聚四氢呋喃醚二醇和物质A,其中聚四氢呋喃醚二醇是一种常见的生产聚氨酯的原料,本发明中聚四氢呋喃醚二醇的分子量为500-5000,这使得聚四氢呋喃醚二醇具有不错的溶解度,易于与异佛尔酮二异氰酸酯反应;而物质A是聚乙二醇二丙烯酸酯和丙二醛反应而成,物质A的结构式为,数均分子量为1000-6000;物质A中除了较多的羟基,还具有活泼的碳碳双键和酯基;羟基和碳碳双键的性质十分活泼,这使得物质A不仅能与异氰酸酯发生聚合反应,也能与改性剂,第一扩链剂等物质发生聚合反应,反应更加充分,使得最终形成的水性聚氨酯具有较高粘度,粘度是评价水性聚氨酯使用性能的一个重要参数,目前现有的水性聚氨酯的粘性较低,不易于粘结(附着)在各种基物上,这大大限制了水性聚氨酯的发展;而聚四氢呋喃醚二醇和物质A的协同作用下,使得本发明的水性聚氨酯具有高粘性,能够紧密贴合(附着)在各种基物上,附着力强;
作为本发明的另一个新创点,就是加入改性剂进行进一步改性处理,改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物;其中2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸中含有羟基,羧基,硅基等基团,羟基,羧基这些活泼基团的存在,有利于改性剂与异佛尔酮二异氰酸酯和聚合物多元醇之间充分反应,而硅基的存在有助于提高水性聚氨酯的稳定性,延长其使用时间;二乙二醇二乙烯基醚中含有碳碳双键等基团,易与物质A之间发生聚合反应;4-(环氧乙基甲氧基)苯乙酰胺中作为一种辅助改性剂,具有环氧,酰胺基团;能够提高各种助剂与异氰酸酯之间的协同性,保证各种助剂能够发挥其应有的作用;在这三种物质的共同作用下,不仅提高水性聚氨酯的附着牢度,同时还提高了水性聚氨酯的稳定性,延长水性聚氨酯的使用寿命;此外我们还惊喜的发现改性剂的加入有助于提高水性聚氨酯的拉伸强度,提高水性聚氨酯的应用范围。
在小分子多元醇选择了1,4丁二醇、二羟甲基丙酸和物质B;其中1,4丁二醇、二羟甲基丙酸是两种常见的合成聚氨酯的原料;而物质B的结构式为
物质B不仅含有多个羟基,能与异氰酸酯进行反应,进一步扩链;还具有多个碳碳双键,能够与物质A之间发生加聚反应,提高协同作用;在这三种物质的共同作用下,有助于进一步提高水性聚氨酯的粘性。
此外,本发明中还加入第一扩链剂和第二扩链剂进行扩链,第一扩链剂中含有羧基,第二扩链剂中含有磺酸基团;这使得最终制得的水性聚氨酯中同时含有羧酸基团和磺酸基团;由于这两个基团的存在,进一步提高了水性聚氨酯的稳定性,还也提高了水性聚氨酯的拉伸强度,具有很好的推广应用价值。
本发明制得的水性聚氨酯,以去离子水作为溶剂,不含有任何有机溶剂,无毒环保,安全,能够保证使用者的健康;同时稳定性高,保质期为6个月以上,使用时间长;还具有高粘性,能够附着在各种基材上,附着牢度高,不容易脱落,特别适合应用于油墨印刷领域。
以上所述仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理前提下的若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (6)
1.一种高粘性水性聚氨酯,其特征在于:包括下列重量份物质组成:
异佛尔酮二异氰酸酯8-25份
聚合物多元醇10-30份
小分子多元醇2-6份;
去离子水30-80份;
含有羧基的第一亲水扩链剂1-5份;
含有磺酸基的第二亲水扩链剂1-5份;
中和剂1-5份
催化剂0.4-1份;
改性剂1-3份;
所述聚合物多元醇为聚四氢呋喃醚二醇和物质A的混合物,其质量比为3:1;
其中物质A的结构式为
所述改性剂为2-[(2-羧基-5-羟基苯基)-二(苯基)硅烷基]-4-羟基苯甲酸、二乙二醇二乙烯基醚和4-(环氧乙基甲氧基)苯乙酰胺的混合物,其质量比为2:3:1;
所述聚四氢呋喃醚二醇的数均分子量为500-5000;所述物质A的数均分子量为1000-6000;
所述小分子多元醇为1,4丁二醇、二羟甲基丙酸和物质B的混合物,其质量比为2:1:1;
其中物质B的结构式为
2.根据权利要求1所述的一种高粘性水性聚氨酯,其特征在于:第一亲水扩链剂为二羟甲基丁酸、噻吩-2,3-二羧酸和2-氨基-5-乙酰氨基苯甲酸的混合物,其质量比为3:1:2。
3.根据权利要求1所述的一种高粘性水性聚氨酯,其特征在于:所述第二亲水扩链剂为乙二胺基丙磺酸钠、2-氨基苯酚-4-磺酸钠和3-氨基-2-4-氯苯基-2-羟基丙烷磺酸钠的混合物,其质量比为1:2:1。
4.根据权利要求1所述的一种高粘性水性聚氨酯,其特征在于:所述中和剂为三乙醇胺。
5.根据权利要求1所述的一种高粘性水性聚氨酯,其特征在于:所述催化剂为有机锌类催化剂、有机铋类催化剂和有机银类催化剂中至少一种。
6.根据权利要求1至5任意一项所述的一种高粘性水性聚氨酯的制备方法,其特征在于:包括以下步骤:
步骤一:根据设定的重量份配备原料,将聚合物多元醇、小分子多元醇、异佛尔酮二异氰酸酯、催化剂和改性剂加入到反应容器中,于60-90℃下反应3-5小时,得到预聚体;
步骤二:加入第一亲水扩链剂,于60-90℃下反应2~4小时;
步骤三:降温至30-50℃,加入中和剂反应10-40分钟,得到离聚体;
步骤四:剧烈搅拌下,将去离子水加入到离聚体中,然后搅拌5-20分钟,得到水性聚氨酯预分散液;
步骤五:将第二亲水扩链剂加入到水性聚氨酯预分散液中反应20-60分钟,得到高粘性水性聚氨酯。
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