CN107973894A - 一种综合性能高环保型改性水性聚氨酯的制备方法 - Google Patents

一种综合性能高环保型改性水性聚氨酯的制备方法 Download PDF

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CN107973894A
CN107973894A CN201711283830.XA CN201711283830A CN107973894A CN 107973894 A CN107973894 A CN 107973894A CN 201711283830 A CN201711283830 A CN 201711283830A CN 107973894 A CN107973894 A CN 107973894A
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张成华
吴中阳
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Suining City Ming Chuan Lingerling Technology Co Ltd
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Abstract

本发明提供了一种综合性能高环保型改性水性聚氨酯的制备方法，包括以下步骤：(1)分别制备聚酯类预聚体和聚醇类预聚体；(2)共混，得复合聚氨酯预聚体；(3)用聚硅氧烷低聚物改性复合聚氨酯预聚体，得有机硅改性聚氨酯；(4)用中和剂中和有机硅改性聚氨酯；(5)去离子水分散乳液，得综合性能高环保型改性水性聚氨酯；(6)抽真空去除溶剂，出产品，其操作容易，易于规模化生产。本发明采用不同预聚体，通过物理共混改性聚氨酯预聚体，再与聚硅氧烷加成聚合、扩链反应制成有机硅改性聚氨酯共聚物，克服有机硅氧烷与聚氨酯相容性很差的技术难题，产品综合性能较高。

Description

一种综合性能高环保型改性水性聚氨酯的制备方法
技术领域
本发明涉及高分子技术领域，特别地涉及到一种采用综合性能高环保型改性水性聚氨酯的方法。
背景技术
随着人们环保意识的增强，材料安全问题越加重视，对包装复合用粘合剂、皮革涂层等其他生活用品提出越来越高的标准和要求。水性聚氨酯(WPU)是采用水作为分散介质的聚氨酯乳液，除具有溶剂型聚氨酯优异性能外，还具有使用简单、无毒、无环境污染等优点，其产品成功应用于轻纺、皮革、木材加工、建筑、造纸等行业。但是由于水性聚氨酯采用水作为溶剂，介质水的表面张力太大、热焓高，使得其成膜过程中表面铺展较差、干燥时间长，成膜与基材复合差，力学性能降低；而促使水性聚氨酯稳定分散在介质水中的亲水性基团，会引起水性聚氨酯成膜耐水性差且易吸水；水性聚氨酯乳化分散时高粘度有机相会导致的分散困难、乳液粒径大和乳液固含量较低。
国内外对水性聚氨酯的改性有从分子尺度进行多元醇分子设计改性，或将特定分子结构或者元素引入多元醇改变大分子主链以改进各种应用性能，或在微观尺度进行纳米复合提升力学性能，或利用可再生资源降低成本，或在成膜过程引入特定官能团反应进行交联以提升成膜特性等。
有机硅很早就已被用于聚氨酯的改性，因其分子链当中的Si-O-Si键具有较大的内聚能而具有耐高温，耐水解等优良的性能，且该链属于柔性链，具有低温柔顺性好、表面张力低、生物相容性好等优点用它对聚氨酯预聚体进行物理或化学的改性，可以提高胶粘剂的综合性能。其中以硅氧键(-SiO-Si-)为骨架组成的聚硅氧烷应用最广。聚氨酯嵌段共聚物兼具有聚硅氧烷和聚氨酯两者的优异性能，表现出良好的低温柔顺性、介电性、表面富集性和优良的生物相容性等，克服了聚硅氧烷机械性能差的缺点，也弥补了聚氨酯耐候性差的不足。
通常由于有机硅氧烷与聚氨酯链段溶度参数相差很大，相容性很差，采用物理共混方式则存在严重的相分离状态甚至涂膜分层，由此力学性能和乳液贮存稳定性差。
发明内容
本发明目的在于采用不同预聚体，通过物理共混的方法改性聚氨酯预聚体，克服单一预聚体在耐水，耐高温、柔性差的缺点，并用带有活性端基的聚硅氧烷与预聚体通过加成聚合和扩链反应制成有机硅改性聚氨酯共聚物，克服有机硅氧烷与聚氨酯相容性很差的技术难题。
本发明为解决上述技术问题所采用的技术方案为：
一种综合性能高环保型改性水性聚氨酯的制备方法，包括以下工艺步骤：
(1)预聚反应：将低聚物多元醇、多元异氰酸酯、聚乙酰胺、酸性二羟基化合物和小分子扩链剂在通N2的保护下加入反应釜中，控制温度反应；具体包括，
(11)分别将聚醚多元多元醇和聚酯多元醇与多元异氰酸酯、酸性二羟基化合物和小分子扩链剂在通N2的保护下加入反应釜中，温度控制为75-85℃，反应1-3小时，制得聚酯类预聚体和聚醇类预聚体；
(2)扩链：继续在反应釜中投入2，2-双羟甲基丙酸、丙酮进行扩链封端反应，控制温度60-70℃，搅拌，搅拌转速为280r/min，反应2-3小时，制得聚氨酯预聚体；
具体包括：将步骤(11)所述的聚酯类预聚体和聚醇类预聚体分别在反应釜中进行扩链反应，然后共混制得复合聚氨酯预聚体。
(3)有机硅改性预聚体：将步骤(2)所述的聚氨酯预聚体加入到溶剂中，在N2保护下加入7％～10％聚硅氧烷低聚物，升温后调整温度到70～90℃，加入扩链剂，保温反应，制得有机硅改性聚氨酯预聚体；。
(4)中和反应：在步骤(3)所述的有机硅改性聚氨酯预聚体加入中和剂进行中和，得有机硅改性聚氨酯预聚体乳液；
具体地，降温30℃以下，加入中和剂进行中和；所述的中和剂为5％的三乙胺。
(5)水分散：调节温度为0～20℃，将去离子水滴入步骤(4)所述的有机硅改性聚氨酯预聚体乳液中进行乳化，然后加入扩链剂，强烈搅拌，转速控制为127min，扩链8-15min，反应完抽真空去除溶剂，得到综合性能高环保型改性水性聚氨酯。
上述小分子扩链剂为1，4-丁二醇和乙二胺；
上述多元异氰酸酯包括：异佛尔酮二异氰酸酯、甲苯2，4-二异氰酸酯；
上述低聚物多元醇包括：聚四氢呋喃二醇；
上述聚硅氧烷低聚物是聚二甲基硅氧烷；
上述聚二甲基硅氧烷为部分甲基被取代后的聚硅氧烷的一种或两种；
上述溶剂为二氧六环和四氢呋喃混合液、N，N’-二甲基甲酰胺和二甲亚砜混合液的任一种。
发明的有益效果
本发明综合性能高环保型改性水性聚氨酯综合性能高。本发明采用不同种多元醇合成不同的预聚体，然后通过物理共混的方法改性聚氨酯预聚体，克服单一预聚体在耐水、耐高温、柔性差的缺点，得到综合性能高的水性聚氨酯预聚体。
本发明综合性能高环保型改性水性聚氨酯应用范围广，其耐候性能佳，机械性能良好，从而解决目前水性聚氨酯产品应用的技术难点。
本发明综合性能高环保型改性水性聚氨酯的制备方法工艺简单，条件易于控制，容易实现规模化生产。
下面结合实施例，对本发明进一步说明。
具体实施方式
实施例1
本实施例提供了一种综合性能高环保型改性水性聚氨酯的制备方法，具体地包括以下步骤：
1、制备预聚体
(1)制备预聚体A：在5装有温度计、回流冷凝管、搅拌器的三口烧瓶中，将聚己二酸丁二醇酯(分子量M＝21行真空脱水后，加入1，4-丁二醇4.5克、异佛尔酮二异氰酸酯49.2克，聚乙酰胺12克，催化剂二月桂酸二丁基锡0.15克，在80℃反应3小时，测定NCO含量小于5.2％时，降温到60℃，加入二羟甲基丙酸9.6克，丙酮50克，于70℃反应3小时，到所定的NCO时得到预聚体A。
(2)预聚体B：在5装有温度计、回流冷凝管、搅拌器的三口烧瓶中，将聚醚多元醇PPG(分子量M＝21行真空脱水后，加入1，4-丁二醇4.5克、异佛尔酮二异氰酸酯49.2克，催化剂二月桂酸二丁基锡0.15克，在80℃反应3小时，测定NCO含量小于5.2％时，降温60℃，加入二羟甲基丙酸9.6克，丙酮50克，于70℃反应3小时，到所定的NCO时得到预聚体B。
2、制备复合聚氨酯预聚体
在5装有温度计、回流冷凝管、搅拌器的三口烧瓶中加入预聚体A70克、预聚体B30克加入聚硅氧烷低聚物(PDMS)5.6克、丙酮10克于70℃反应3小时。
3、中和
降温到30℃加入三乙胺3.5克进行中和反应，得乳液。
4、水分散
将乳液降温于20℃以下，在高速分散情况下加入去离子水114克进行乳化，然后加入乙二胺1.4克和去离子水5.6克的混和液进行扩链反应，得粗产品。
5、除去溶剂
将粗产品真空脱去丙酮得到40％(wt)的有机硅改性聚氨酯树脂。
实施例2
1、制备预聚体
(1)制备预聚体A：在5装有温度计、回流冷凝管、搅拌器的三口烧瓶中，将聚己二酸丁二醇酯(分子量M＝21行真空脱水后，加入1，4-丁二醇4.5克、甲苯二异氰酸酯38.6克，聚乙酰胺12克，催化剂二月桂酸二丁基锡0.14克，在80℃反应3小时，测定NCO含量小于6.9％时，降温60℃，加入二羟甲基丙酸9.4克，丙酮50克，于70℃反应3小时，到所定的NCO时得到预聚体A。
(2)制备预聚体B：在5装有温度计、回流冷凝管、搅拌器的三口烧瓶中，将聚醚多元醇PPG(分子量M＝21行真空脱水后，加入1，4-丁二醇4.5克、甲苯二异氰酸酯38.6克，催化剂二月桂酸二丁基锡0.15克，在80℃反应3小时，测定NCO含量小于6.9％时，降温60℃，加入二羟甲基丙酸9.4克，丙酮50克，于70℃反应3小时，到所定的NCO，得到预聚体B。
2、制备复合聚氨酯预聚体
在5装有温度计、回流冷凝管、搅拌器的三口烧瓶中加入预聚体A70克、预聚体B30克加入聚硅氧烷低聚物(PDMS)5.3克、丙酮10克于70℃反应3小时。
3、中和
降温于30℃加入三乙胺3.7克进行中和反应。
4、水分散
降温小于20℃以下，在高速分散情况下加入去离子水115克进行乳化，然后加入乙二胺1.4克和去离子水5.6克的混和液进行扩链反应。
5、除去溶剂
真空脱去丙酮得到40％(wt)的有机硅改性聚氨酯树脂。
实施例3
本实施例与实施例1基本相同，其区别在于：的步骤“1、制备预聚体”中“(2)制备预聚体B”中用聚四氢呋喃二醇(PTMG)取代聚醚多元醇。
本发明并不限于上述实施例，凡是能实现本发明目的的所有等同的实施方式，均在本发明的保护范围之内。

Claims (8)

1.一种综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，包括以下工艺步骤：
(1)预聚反应：将低聚物多元醇、多元异氰酸酯、聚乙酰胺、酸性二羟基化合物和小分子扩链剂在通N2的保护下加入反应釜中，控制温度；
(2)扩链：继续在反应釜中投入2，2-双羟甲基丙酸、丙酮进行扩链封端反应，制得聚氨酯预聚体；
(3)有机硅改性预聚体：将步骤(2)所述的聚氨酯预聚体加入到溶剂中，在N2保护下加入7％～10％聚硅氧烷低聚物和扩链剂，保温反应，制得有机硅改性聚氨酯预聚体；
(4)中和反应：在步骤(3)所述的有机硅改性聚氨酯预聚体加入中和剂进行中和，得有机硅改性聚氨酯预聚体乳液；
(5)水分散：将去离子水滴入步骤(4)所述的有机硅改性聚氨酯预聚体乳液中进行乳化，然后加入扩链剂，强烈搅拌，扩链，反应完抽真空去溶剂，得到综合性能高环保型改性水性聚氨酯。
2.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，
所述步骤(1)还包括：
(11)分别将聚醚多元多元醇和聚酯多元醇与多元异氰酸酯、酸性二羟基化合物和小分子扩链剂在通N2的保护下加入反应釜中，温度控制为75-85℃，反应1-3小时，制得聚酯类预聚体和聚醇类预聚体；
所述步骤(2)还包括：
(22)将步骤(11)所述的聚酯类预聚体和聚醇类预聚体分别在反应釜中进行扩链反应，然后共混制得复合聚氨酯预聚体。
3.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，所述步骤(2)包括：控制温度60-70℃，搅拌，搅拌转速为280r/min，反应2-3小时。
4.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，所述步骤(3)还包括：在N2保护下加入7％～10％聚硅氧烷低聚物，升温后调整温度到70～90℃，加入扩链剂。
5.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，所述步骤(4)还包括：降温30℃以下，加入中和剂进行中和；所述的中和剂为5％的三乙胺。
6.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，所述步骤(5)包括：调节温度为0～20℃，将去离子水滴入步骤(4)所述的有机硅改性聚氨酯预聚体乳液中进行乳化，然后加入扩链剂，强烈搅拌，转速控制为1200～1700r/min，扩链8-15min，得到综合性能高环保型改性水性聚氨酯。
7.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，步骤(1)所述小分子扩链剂为1，4-丁二醇和乙二胺；所述多元异氰酸酯包括：异佛尔酮二异氰酸酯、甲苯2，4-二异氰酸酯；所述低聚物多元醇包括：聚四氢呋喃二醇。
8.根据权利要求1所述的综合性能高环保型改性水性聚氨酯的制备方法，其特征在于，步骤(3)所述聚硅氧烷低聚物是聚二甲基硅氧烷；所述聚二甲基硅氧烷为部分甲基被取代后的聚硅氧烷的一种或两种；所述溶剂为二氧六环和四氢呋喃混合液、N，N’-二甲基甲酰胺和二甲亚砜混合液的任一种。
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CN108178822A (zh) * 2017-12-29 2018-06-19 何俊 一种环保型改性水性聚氨酯的制备方法
CN109553747A (zh) * 2018-12-05 2019-04-02 长春工业大学 一种高固含可生物降解水性聚氨酯的制备方法
CN109734875A (zh) * 2018-12-24 2019-05-10 上海东大化学有限公司 一种氨基硅烷偶联剂改性水性聚氨酯及其制备方法
US11407904B2 (en) 2019-02-11 2022-08-09 King Fahd University Of Petroleum And Minerals Waterborne polyurethane containing polyhedral oligomeric silsesquioxane

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CN107629188A (zh) * 2017-09-07 2018-01-26 绵阳凤面科技有限公司 一种综合性能高环保型改性水性聚氨酯的制备方法

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CN107629188A (zh) * 2017-09-07 2018-01-26 绵阳凤面科技有限公司 一种综合性能高环保型改性水性聚氨酯的制备方法

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CN108178822A (zh) * 2017-12-29 2018-06-19 何俊 一种环保型改性水性聚氨酯的制备方法
CN109553747A (zh) * 2018-12-05 2019-04-02 长春工业大学 一种高固含可生物降解水性聚氨酯的制备方法
CN109553747B (zh) * 2018-12-05 2021-06-08 长春工业大学 一种高固含可生物降解水性聚氨酯的制备方法
CN109734875A (zh) * 2018-12-24 2019-05-10 上海东大化学有限公司 一种氨基硅烷偶联剂改性水性聚氨酯及其制备方法
US11407904B2 (en) 2019-02-11 2022-08-09 King Fahd University Of Petroleum And Minerals Waterborne polyurethane containing polyhedral oligomeric silsesquioxane

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