CN103897135B - 一种高固含量水性聚氨酯乳液的制备方法 - Google Patents
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Abstract
本发明公开了一种高固含量水性聚氨酯乳液的制备方法。目前的制备方法对水性聚氨酯乳液含固量的提升效果有限。本发明的高含固量水性聚氨酯乳液粒子具有亲水性不同的核壳结构,其制备方法包括将聚合物多元醇脱水后,与二异氰酸酯,亲水扩链剂、小分子扩链剂反应后得到粘稠预聚体A,将预聚体A与按相同步骤合成的不含或少含亲水单体的预聚体B混合均匀,加入中和剂中和,在高速搅拌下分散于去离子水中,经后扩链剂扩链,得到高含固量的水性聚氨酯乳液。该高含固量的水性聚氨酯乳液具有水合层薄、粘度低、稳定性好、含固量高的优点,该高含固量水性聚氨酯乳液的制备方法具有不受配方及原料限制、适应性广、工艺简单具备可行性、可控性强的优点。
Description
技术领域
本发明涉及水性聚氨酯领域,具体地说是一种高固含量水性聚氨酯乳液的制备方法。
背景技术
溶剂型聚氨酯因其优异的性能被广泛运用于木制品的表面防护、胶粘剂、人造革等领域,但溶剂型聚氨酯在生产、施工和固化过程中需要加入大量的挥发性有机溶剂,危害健康安全、对环境造成污染。
近几年来,世界各国都已经逐渐重视有机废气中挥发性有机物(VOC)的危害性,关于控制VOC的法规日渐严厉,部分西方发达国家已经明确规定了有机物的排放种类、排放量。不同于溶剂型聚氨酯,水性聚氨酯以水为介质,水不燃、不爆、无毒、无味,不会污染环境,且施工条件好,生产与应用安全,不会危害施工与操作人员的身体健康;同时,水便宜,易得,故能显著降低产品的成本,因而已越来越引起人们的重视。其中,高固含量水性聚氨酯具有干燥快、加工能耗低等显著优点,替代溶剂型聚氨酯可行性高。
水性聚氨酯乳液的固含量较难提高的根本原因在于大部分水性聚氨酯采用的是内乳化工艺,由于亲水基团分布的不可控性而不可避免的存在一定厚度的水合层,油相与水相的界限不是很清晰,因此如何减少普通内乳化法制备水性聚氨酯体系的水合层厚度,是提高内乳化法水性聚氨酯含固量的一个关键,而对这一部分的内容国内外都少有研究。
目前国内外关于高固含量水性聚氨酯的制备主要有以下几个方面,是采用新型亲水扩链剂或连续法后扩链工艺。公开号为CN101597369A的中国专利申请,采用含脂环族磺酸型亲水性扩链剂,将其作为扩链剂引入到水性聚氨酯分子中,得到高固含量水性聚氨酯分散体。公开号为CN101605831A的中国专利申请,其采用连续乳化后扩链工艺,制成高固含量水性聚氨酯分散体。公开号为CN101432327A的中国专利申请,同样是采用连续乳化后扩链工艺,并辅助以必要的表面活性剂、分散剂、增稠剂等制成超高固含量聚氨酯分散体的密封剂组合物。此外,公开号为CN103087291A的中国专利申请也公开了一种通过大小粒径乳液粒子复合的方式制备高固含量水性聚氨酯乳液的方法。S.K.Lee等人报道了通过控制亲水基团的位置,将亲水基团接到软段以及分子链末端使亲水基团具有更低的自由能,有利于提高含固量(Highsolidandhighstabilitywaterbornepolyurethanesviaionicgroupsinsoftsegmentsandchaintermini.JournalofColloidandInterfaceScience336(2009)208–214)。在上述专利申请中,新型亲水扩链剂原料来源目前有较大限制,并且预聚体粘度大,需求溶剂较多;连续乳化后扩链工艺对工艺控制要求极高,且不适用于小批量、多品种的高固含量聚氨酯分散体生产;大小粒径乳液复合的方法对粒径控制的要求比较高,控制亲水基团位置对含固量的提升效果有限。
发明内容
为解决目前普通内乳化法制备水性聚氨酯存在含固量难以提高的技术缺陷,本发明提供一种高固含量水性聚氨酯乳液的制备方法,其通过控制水合层厚度制备出高固含量的水性聚氨酯乳液,使水性聚氨酯乳液具有水合层薄、含固量高、粘度低、分散稳定性好的特性,可应用于家具工业、人造革行业和胶粘剂工业等对环保、能耗和施工条件有较高要求的领域。
本发明通过以下技术方案实现:一种高固含量水性聚氨酯乳液的制备方法,其包含如下步骤:1)将40~70质量份的分子量为500~4000聚合物二元醇或聚合物多元醇中的一种或多种升温至90~120℃,真空脱水30~90min,降温到55~75℃后加入15~40质量份的二异氰酸酯,在氮气保护下搅拌均匀,搅拌时间为0.5~1h,然后加入0.01~0.05质量份的二月桂酸二丁基锡、辛酸亚锡中至少一种作为催化剂,在60~90℃下反应1~3h,得到澄清透明的反应物;
2)以2,2-二羟甲基丙酸(DMPA)、2,2-二羟甲基丁酸(DMBA)、乙二氨基乙磺酸钠、乙二羟基乙磺酸钠中至少一种作为亲水扩链剂,以1,4-丁二醇、一缩二乙二醇、2-甲基丙二醇、3-甲基戊二醇、新戊二醇、1,6-己二醇、2-甲基-2-乙基丙二醇、三羟甲基丙烷或它们中的多种作为小分子扩链剂,以丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮或它们中的多种作为溶剂;将3~7质量份的亲水扩链剂、1~4.5质量份的小分子扩链剂、0.1~50质量份的溶剂加入到步骤1)得到的反应物中,在60~90℃下反应1~3h;降温到45~70℃,得到澄清粘稠的预聚体A;
3)采用与预聚体A相同的制备步骤制备预聚体B,制备预聚体B时亲水扩链剂用量为0.01~2.9质量份,其它原料所用的质量份数不变,使制得的预聚体B的亲水性弱于预聚体A,将预聚体A和预聚体B按质量比1:0.3~2.0混合后,充分搅拌15~300秒,得到均匀的混合预聚体,控制混合预聚体的pH值为6~8,然后在800~2000r/min的高速搅拌下分散于去离子水中,得到高含固量的水性聚氨酯初乳液;
以乙二胺、丁二胺、异佛尔酮二胺、己二胺、戊二胺、哌嗪、环己二胺、水合肼、N,N’-二甲基乙二胺或它们中的多种为后扩链剂,将其活性官能团(如OH或NH2)与水性聚氨酯初乳液中NCO摩尔比为0.01~0.8:1的后扩链剂滴加到水性聚氨酯初乳液中,搅拌0.5~2h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。该水性聚氨酯乳液粒子具有亲水性能存在差异的核壳结构,其中壳的亲水性较好,核的亲水性比壳弱或没有亲水性。
进一步,所述的二异氰酸酯优选为甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、4,4’一亚甲基一二环己基二异氰酸酯(H12MDI)、苯二甲撑二异氰酸酯(XDI)、2,2,4-三甲基己烷二异氰酸酯(TMHDI)或它们中的多种。
进一步,加入与酸值对应的中和剂将混合预聚体中和至pH值为6~8,所述的中和剂优选为三乙胺、三正丁胺、氢氧化钠、二乙醇胺、三乙醇胺或它们中的多种。
进一步,所述的聚合物多元醇选自聚醚多元醇、聚酯多元醇中的一种或多种;所述的聚合物二元醇选自聚醚二元醇、聚酯二元醇中的一种或多种。
本发明具有的有益效果:本发明将亲水单体含量少或基本不含亲水单体的预聚体B包裹在正常亲水单体含量的预聚体A中,从而形成具有核壳结构亲水性不同的乳液,充分利用壳预聚体的亲水性提供亲水性能,核的亲水性弱的特性减少结合水,减薄水合层,从而得到粘度低、稳定性好、含固量高的水性聚氨酯乳液,最终成品水性聚氨酯乳液的含固量可以达到55~60%以上。本发明制备高含固量水性聚氨酯乳液的方法不受配方及原料限制,适应性广、工艺简单具备可行性、可控性强,适合多种的水性聚氨酯树脂生产。
具体实施方式
通过下面的实施例来进一步说明本发明的技术方案,但本发明不限于这些实施例,这些实施例仅为本发明的优选实施例。
实施例1
将50g500分子量的聚己二酸丁二醇酯二醇在110℃下,真空脱水1.5h,降温到65℃,加入39gTDI,氮气保护下,搅拌0.5h,加入二月桂酸二丁基锡0.015g,在80℃下,反应2h;加入5gDMPA,1g1,4-丁二醇,2g新戊二醇,10g丁酮,5gN-甲基吡咯烷酮,在80℃下,反应3h,降温到50℃,得到澄清透明的粘稠预聚体A,与由15g500分子量聚己二酸丁二醇酯二醇、9gTDI、0.005g二月桂酸二丁基锡、0.3g1,4-丁二醇,0.6g新戊二醇,3g丁酮,1.5gN-甲基吡咯烷酮按相同步骤反应得到的预聚体B混合均匀,加入3.7gTEA中和,在800~2000r/min的高速搅拌下分散于110g去离子水中,加入3g乙二胺后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例2
将300g4000分子量的聚丙二醇在110℃下,真空脱水1h,降温到65℃,加入66gTDI,氮气保护下,搅拌0.5h,加入辛酸亚锡0.08g,在80℃下,反应3h;加入15gDMPA,3g2-甲基丙二醇,2g3-甲基戊二醇,50g丁酮,在80℃下,反应2h,降温到55℃,得到澄清透明的粘稠预聚体A,与由200g4000分子量聚丙二醇、28gTDI、辛酸亚锡0.04g、3g2-甲基丙二醇,2g3-甲基戊二醇,50g丁酮按相同步骤反应得到的预聚体B混合均匀,加入11gTEA中和,在800~2000r/min的高速搅拌下分散于330g去离子水中,加入10.2g戊二胺后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例3
将50g500分子量的聚己二酸丁二醇酯二醇在110℃下,真空脱水1.5h,降温到65℃,加入50gIPDI,氮气保护下,搅拌0.5h,加入辛酸亚锡0.02g,在80℃下,反应2h;加入5gDMPA,1g1,4-丁二醇,2g新戊二醇,10g丁酮,5gN-甲基吡咯烷酮,在80℃下,反应3h,降温到50℃,得到澄清透明的粘稠预聚体A,与由50g500分子量聚己二酸丁二醇酯二醇、38gIPDI、辛酸亚锡0.02g、1g1,4-丁二醇,2g新戊二醇,10g丁酮,5gN-甲基吡咯烷酮按相同步骤反应得到的预聚体B混合均匀,加入3.7gTEA中和,在800~2000r/min的高速搅拌下分散于135g去离子水中,加入8g己二胺后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例4
将150g2000分子量的聚丙二醇,50g聚醚多元醇N330在110℃下,真空脱水1h,降温到65℃,加入160gIPDI,氮气保护下,搅拌0.5h,加入0.15g辛酸亚锡,在80℃下,反应2h;加入30gDMBA,15g一缩二乙二醇,2g三羟甲基丙烷,在70℃下,反应3h,降温到45℃,得到澄清透明的粘稠预聚体A,与由300g2000分子量聚丙二醇、100g聚醚多元醇N330,140gIPDI、0.3g辛酸亚锡、15gDMBA,12g一缩二乙二醇,4g三羟甲基丙烷,按相同步骤反应得到的预聚体B混合均匀,加入5g氢氧化钠中和,在800~2000r/min的高速搅拌下分散于360g去离子水中,加入12g丁二胺后扩链,搅拌1h,得到高含固量的水性聚氨酯乳液。
实施例5
将200g2000分子量的聚四氢呋喃醚二醇在110℃下,真空脱水1h,降温到65℃,加入60gIPDI,15gH12MDI氮气保护下,搅拌0.5h,加入0.18g辛酸亚锡,在80℃下,反应2h;加入20gDMPA,5g1,6-己二醇,100g丁酮,在80℃下,反应2.5h,降温到50℃,得到澄清透明的粘稠预聚体A,与由200g2000分子量聚丙二醇、33.3gIPDI、6.4gH12MDI、0.15g辛酸亚锡、5g1,6-己二醇,40g丁酮按相同步骤反应得到的预聚体B混合均匀,加入11g三正丁胺中和,在800~2000r/min的高速搅拌下分散于345g去离子水中,加入5g乙二胺和3gN,N’-二甲基乙二胺后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例6
将200g2000分子量的聚四氢呋喃醚二醇在110℃下,真空脱水1h,降温到65℃,加入43.5gTDI,29gMDI氮气保护下,搅拌0.5h,加入0.1g辛酸亚锡,在80℃下,反应2h;加入12gDMPA,10g新戊二醇,80g丁酮,30gN,N-二甲基甲酰胺,在85℃下,反应2.5h,降温到50℃,得到澄清透明的粘稠预聚体A,与由200g2000分子量聚己二酸新戊二醇酯二醇、50gTDI,0.1g辛酸亚锡、10g1,4-丁二醇,70g丁酮按相同步骤反应得到的预聚体B混合均匀,加入7gTEA中和,在800~2000r/min的高速搅拌下分散于355g去离子水中,加入8g异佛尔酮二胺后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例7
将200g2000分子量的聚四氢呋喃醚二醇在110℃下,真空脱水1h,降温到65℃,加入43.5gTDI,29gMDI氮气保护下,搅拌0.5h,加入0.1g辛酸亚锡,在80℃下,反应2h;加入16g乙二氨基乙磺酸盐,10g新戊二醇,150g丁酮,130gN,N-二甲基甲酰胺,在85℃下,反应2.5h,降温到50℃,得到澄清透明的粘稠预聚体A,与由100g2000分子量聚己二酸新戊二醇酯二醇、25gTDI,0.05g辛酸亚锡、5g1,4-丁二醇,35g丁酮按相同步骤反应得到的预聚体B混合均匀,在800~2000r/min的高速搅拌下分散于270g去离子水中,加入6g异佛尔酮二胺和2g水合肼(浓度为10-15%)后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例8
将300g4000分子量的聚丙二醇在110℃下,真空脱水1h,降温到65℃,加入32gHDI、44.4gIPDI,氮气保护下,搅拌0.5h,加入辛酸亚锡0.08g,在80℃下,反应3h;加入15gDMPA,5g乙二羟基乙磺酸钠,3g2-甲基丙二醇,2g3-甲基戊二醇,50g丁酮,在80℃下,反应2h,降温到55℃,得到澄清透明的粘稠预聚体A,与由200g4000分子量聚丙二醇、28gTDI、辛酸亚锡0.04g、3g2-甲基丙二醇,2g3-甲基戊二醇,50g丁酮按相同步骤反应得到的预聚体B混合均匀,加入11gTEA中和,在800~2000r/min的高速搅拌下分散于330g去离子水中,加入6.8g哌嗪后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
实施例9
将200g2000分子量的聚四氢呋喃醚二醇在110℃下,真空脱水1h,降温到65℃,加入50gXDI,12gTMHDI氮气保护下,搅拌0.5h,加入0.18g辛酸亚锡,在80℃下,反应2h;加入20gDMPA,5g1,6-己二醇,100g丁酮,在80℃下,反应2.5h,降温到50℃,得到澄清透明的粘稠预聚体A,与由200g2000分子量聚丙二醇、33.3gIPDI、6.4gH12MDI、0.15g辛酸亚锡、5g1,6-己二醇,40g丁酮按相同步骤反应得到的预聚体B混合均匀,加入11g三正丁胺中和,在800~2000r/min的高速搅拌下分散于345g去离子水中,加入5g乙二胺和4g环己二胺后扩链,搅拌1h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
Claims (4)
1.一种高固含量水性聚氨酯乳液的制备方法,其包含如下步骤:
1)将40~70质量份的分子量为500~4000聚合物二元醇或聚合物多元醇中的一种或多种升温至90~120℃,真空脱水30~90min,降温到55~75℃后加入15~40质量份的二异氰酸酯,在氮气保护下搅拌均匀,搅拌时间为0.5~1h,然后加入0.01~0.05质量份的二月桂酸二丁基锡、辛酸亚锡中至少一种作为催化剂,在60~90℃下反应1~3h,得到澄清透明的反应物;
2)以2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、乙二氨基乙磺酸钠、乙二羟基乙磺酸钠中至少一种作为亲水扩链剂,以1,4-丁二醇、一缩二乙二醇、2-甲基丙二醇、3-甲基戊二醇、新戊二醇、1,6-己二醇、2-甲基-2-乙基丙二醇、三羟甲基丙烷或它们中的多种作为小分子扩链剂,以丙酮、丁酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮或它们中的多种作为溶剂;将3~7质量份的亲水扩链剂、1~4.5质量份的小分子扩链剂、0.1~50质量份的溶剂加入到步骤1)得到的反应物中,在60~90℃下反应1~3h;降温到45~70℃,得到澄清粘稠的预聚体A;
3)采用与预聚体A相同的制备步骤制备预聚体B,制备预聚体B时亲水扩链剂用量为0.01~2.9质量份,其它原料所用的质量份数不变,使制得的预聚体B的亲水性弱于预聚体A,将预聚体A和预聚体B按质量比1:0.3~2.0混合后,充分搅拌15~300秒,得到均匀的混合预聚体,控制混合预聚体的pH值为6~8,然后在800~2000r/min的高速搅拌下分散于去离子水中,得到高含固量的水性聚氨酯初乳液;
以乙二胺、丁二胺、异佛尔酮二胺、己二胺、戊二胺、哌嗪、环己二胺、水合肼、N,N’-二甲基乙二胺或它们中的多种为后扩链剂,将其活性官能团与水性聚氨酯初乳液中NCO摩尔比为0.01~0.8:1的后扩链剂滴加到水性聚氨酯初乳液中,搅拌0.5~2h,减压脱去溶剂,得到高含固量的水性聚氨酯乳液。
2.根据权利要求1所述的高固含量水性聚氨酯乳液的制备方法,其特征在于,所述的二异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、4,4’一亚甲基一二环己基二异氰酸酯、苯二甲撑二异氰酸酯、2,2,4-三甲基己烷二异氰酸酯或它们中的多种。
3.根据权利要求1所述的高固含量水性聚氨酯乳液的制备方法,其特征在于,加入与酸值对应的中和剂将混合预聚体中和至pH值为6~8,所述的中和剂为三乙胺、三正丁胺、氢氧化钠、二乙醇胺、三乙醇胺或它们中的多种。
4.根据权利要求1所述的高固含量水性聚氨酯乳液的制备方法,其特征在于,所述的聚合物多元醇选自聚醚多元醇、聚酯多元醇中的一种或多种;所述的聚合物二元醇选自聚醚二元醇、聚酯二元醇中的一种或多种。
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CN102898613A (zh) * | 2012-11-09 | 2013-01-30 | 陕西邦希化工有限公司 | 水溶性有机硅改性聚氨酯树脂的制备方法 |
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