CN110272530A - 一种多粒径羧酸型水性聚氨酯的制备方法及应用 - Google Patents

一种多粒径羧酸型水性聚氨酯的制备方法及应用 Download PDF

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CN110272530A
CN110272530A CN201910436811.9A CN201910436811A CN110272530A CN 110272530 A CN110272530 A CN 110272530A CN 201910436811 A CN201910436811 A CN 201910436811A CN 110272530 A CN110272530 A CN 110272530A
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carboxylic acid
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李维虎
汪飞
戴家兵
赵曦
王刚
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Abstract

本发明公开了一种多粒径羧酸型水性聚氨酯的制备方法，包括以下步骤，在至少两个反应釡中同时加入多元醇和多异氰酸酯反应；将所述反应釜降温后加入亲水扩链剂、小分子醇类扩链剂和催化剂反应；在所述反应釜中加入稀释剂后降温获得多个预聚体并混合均匀；加入胺类扩链剂，经纯化处理获得多粒径羧酸型水性聚氨酯。本发明通过多粒径工艺，可以将羧酸型水性聚氨酯树脂的固含量做到50％以上，储存稳定性达到三个月以上，解决了羧酸型水性聚氨酯无法制备高固含水性聚氨酯的问题，使用该工艺制备的高固水性聚氨酯用于丰满的手感，发泡更加均匀细腻，做出来的贝斯强度更高，耐热性能更强；本发明制备出的产品也不含有机溶剂，具有环保健康的优点。

Description

一种多粒径羧酸型水性聚氨酯的制备方法及应用
技术领域
本发明属于材料工业领域，具体涉及一种多粒径羧酸型水性聚氨酯的制备方法及应用。
背景技术
水性聚氨酯领域从亲水基团来划分，主要为季铵盐类阳离子型水性聚氨酯、羧酸型水性聚氨酯、磺酸型水性聚氨酯和非离子型水性聚氨酯。目前羧酸型水性聚氨酯树脂很难做到固含量45％以上，磺酸型水性聚氨酯很容易制得高固含水性聚氨酯，但是耐水解性能较差，部分领域性能上无法满足。
本申请针对现有技术存在的缺陷，提出一种多粒径羧酸型水性聚氨酯的制备方法，解决了羧酸型水性聚氨酯无法制备高固含水性聚氨酯的问题，使用该工艺制备的高固水性聚氨酯用于丰满的手感，发泡更加均匀细腻，做出来的贝斯强度更高，耐热性能更强。
发明内容
本发明旨在提供一种多粒径羧酸型高固贝斯水性聚氨酯的制备方法及应用，制备出的多粒径羧酸型水性聚氨酯可以将羧酸型水性聚氨酯树脂的固含量做到50％以上，储存稳定性达到三个月以上。
为解决上述问题，本发明是通过以下技术方案实现的：一种多粒径羧酸型水性聚氨酯的制备方法，包括以下步骤，
在至少两个反应釡中同时加入多元醇和多异氰酸酯反应；
将所述至少两个反应釜降温后加入亲水扩链剂、小分子醇类扩链剂和催化剂反应；
在所述至少两个反应釜中加入稀释剂后降温获得多个预聚体并混合均匀；
加入胺类扩链剂，经纯化处理获得多粒径羧酸型水性聚氨酯。
可选地，所述多元醇包括聚四氢呋喃醚多元醇、聚酯醚多元醇、聚环氧丙烷多元醇和聚硅氧烷多元醇中的任意一种或多种。
可选地，所述多异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1，6-己二异氰酸酯和苯二亚甲基二异氰酸酯任意一种或多种。
可选地，所述胺类扩链剂为乙二胺、己二胺、异佛尔酮二胺中的一种或者多种。
可选地，所述亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸一种或两种；
和/或，所述小分子醇类扩链剂包括乙二醇、2-甲基-1,3-丙二醇、一缩二乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二甘醇、三羟甲基丙烷中的任意一种或多种。
可选地，在所述至少两个反应釜中所述亲水扩链剂在体系中所占比例之差大于0.5％。
可选地，所述催化剂选为有机铋催化剂。
可选地，所述多个预聚体之间具有相互嵌合的结构。
可选地，所述稀释剂为丙酮。
可选地，加入所述稀释剂之前，反应体系降温至40-50℃。
可选地，所述纯化处理包括减压蒸馏。
可选地，所述多元醇的分子量为1000-4000。
一种利用所述方法制备的多粒径羧酸型水性聚氨酯树脂在服装革、沙发革和太空革贝斯的用途。
本发明通过多粒径工艺，可以将羧酸型水性聚氨酯树脂的固含量做到50％以上，储存稳定性达到三个月以上，解决了羧酸型水性聚氨酯无法制备高固含水性聚氨酯的问题，使用该工艺制备的高固水性聚氨酯用于丰满的手感，发泡更加均匀细腻，做出来的贝斯强度更高，耐热性能更强；本发明制备出的产品也不含有机溶剂，具有环保健康的优点。多釜工艺操作较简单，原理易懂。
具体实施方式
下面通过几个具体的实施例对本发明作进一步的说明，但需要指出的是本发明的实施例中所描述的具体的物料配比、工艺条件及结果等仅用于说明本发明，并不能以此限制本发明的保护范围，凡是根据本发明的精神实质所作的等效变化或修饰，都应该涵盖在本发明的保护范围内。
一种多粒径羧酸型水性聚氨酯的制备方法，包括以下步骤，在至少两个反应釡中同时加入一定量多元醇和多异氰酸酯反应；将所述至少两个反应釜降温后加适量入亲水扩链剂、小分子醇类扩链剂和催化剂反应，其中，各反应釜中亲水扩链剂在体系中所占比例之差大于0.5％，而且每个反应釜中加入两种类型的扩链剂；在所述至少两个反应釜中加入稀释剂整粘度后将至少两个反应釡的预聚体混合在一起，搅拌，然后降温至-5～5℃加入成盐剂中和15-30分钟；加水后再缓慢加入适量胺类扩链剂，减压蒸馏，获得多粒径羧酸型水性聚氨酯。
在一实施例中，同时制备两个反应釜水性聚氨酯，两个反应釜均加入78g的分子量为3000的聚四氢呋喃二元醇和20g甲苯二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后一釜加入2g的二羟甲基丙酸和3g的1,4-丁二醇和少量丙酮在80℃下反应1小时，另一釜加入5g的二羟甲基丙酸和1g的1,4-丁二醇和少量丙酮在80℃下反应1小时，然后加入0.1g的有机铋催化剂在60℃下反应3小时，测定NCO含量，达到理论值后加入适量稀释剂调整粘度，然后降温至20℃，将两个反应釜预聚体合并在一起并搅拌均匀，然后加入5.28g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入3.6g的乙二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品1。
在一实施例中，同时制备两个反应釜水性聚氨酯，两个反应釜均加入50g的分子量为2000的聚四氢呋喃二元醇和20g分子量为2000的聚硅氧烷二元醇与17.8g的甲苯二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后一釜加入3.1g的二羟甲基丙酸和1.88g的1,6-己二醇和少量丙酮在80℃下反应1小时，另一釜加入5.1g的二羟甲基丙酸和0.12g的1,6-己二醇和少量丙酮在80℃下反应1小时，然后加入0.1g的有机铋催化剂在60℃下反应3小时，测定NCO含量，达到理论值后加入适量丙酮调整粘度，然后降温至5℃，将两个反应釜预聚体合并在一起并搅拌均匀，加入6.18g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入6.4g的异佛尔酮二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品2。
在一实施例中，同时制备两个反应釜水性聚氨酯，两个反应釜均加入75g的分子量为2000的聚酯醚二元醇和26g的异佛尔酮二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后一釡加入2.6g的二羟甲基丙酸和1.8g的一缩二乙二醇和少量丙酮在80℃下反应2小时，另一釜加入4.24g的二羟甲基丙酸和0.5g的一缩二乙二醇和少量丙酮在80℃下反应2小时，然后加入0.15g的Coscat83催化剂在70℃下反应3小时，测定NCO含量，达到理论值后加入适量丙酮调整粘度，然后降温至15℃，将两个反应釜预聚体合并在一起并搅拌均匀，加入5.15g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入11.08g的异佛尔酮二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品3。
在一实施例中，在单釡中制备水性聚氨酯，加入78g的分子量为3000的聚四氢呋喃二元醇和20g甲苯二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后加入3.5g的二羟甲基丙酸和2g的1,4-丁二醇和少量丙酮在80℃下反应1小时，然后加入0.1g的有机铋催化剂在60℃下反应3小时，测定NCO含量，达到理论值后加入适量稀释剂调整粘度，然后降温至20℃，然后加入2.64g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入3.2g的乙二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品4。
在一实施例中，在单釡中制备水性聚氨酯，加入50g的分子量为2000的聚四氢呋喃二元醇和20g分子量为2000的聚硅氧烷二元醇与17.8g的甲苯二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后加入4.1g的二羟甲基丙酸和1g的1,6-己二醇和少量丙酮在80℃下反应1小时，然后加入0.1g的有机铋催化剂在60℃下反应3小时，测定NCO含量，达到理论值后加入适量丙酮调整粘度，然后降温至5℃，加入3.09g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入3.2g的异佛尔酮二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品5。
在一实施例中，在单釡中制备水性聚氨酯，加入75g的分子量为2000的聚酯醚二元醇和26g的异佛尔酮二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后加入3.42g的二羟甲基丙酸和1.03g的一缩二乙二醇和少量丙酮在80℃下反应2小时，然后加入0.15g的有机铋催化剂(型号为Coscat83)在70℃下反应3小时，测定NCO含量，达到理论值后加入适量丙酮调整粘度，然后降温至15℃，加入2.58g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入5.54g的异佛尔酮二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品6。
在一实施例中，此实施例是为了考察在单釡、双釜和三釜这三种反应情况下，所制得的产品的性能优劣。同时制备三釜水性聚氨酯，三釜均加入78g的分子量为3000的聚四氢呋喃二元醇和20g甲苯二异氰酸酯在90℃下反应2小时，测定NCO含量，达到理论值后降温至50℃，然后一釜加入2g的二羟甲基丙酸和3g的1,4-丁二醇和少量丙酮在80℃下反应1小时，另一釜加入3g的二羟甲基丙酸和2.33g的1,4-丁二醇和少量丙酮在80℃下反应1小时，最后一釡加入4g的二羟甲基丙酸和1.66g的1,4-丁二醇和少量丙酮在80℃下反应1小时，然后加入0.1g的有机铋催化剂在60℃下反应3小时，测定NCO含量，达到理论值后加入适量稀释剂调整粘度，然后降温至20℃，将两个反应釜预聚体合并在一起并搅拌均匀，然后加入6.78g的三乙胺，中和30分钟后，在高速剪切下(1400转/分钟以上)下加入0-5℃的冰水，再缓慢加入4.8g的乙二胺，所得的树脂经减压蒸馏除去丙酮后，得到样品7。此对比例中的亲扩链剂的量还可以是其他比例的量。
将以上7个样品分别在500-800转/分钟的高速剪切下加入润湿剂、木质纤维素、发泡剂、稳泡剂和固化剂，发泡至原体积的1.5倍，制成粘度为15000mpas-18000mpas的发泡浆料，将无纺布烫平，然后在无纺布上涂覆上制作好的发泡浆料，涂布量为600g/㎡，然后将涂覆发泡浆料的无纺布通过凝固槽中的凝固液(弱酸溶液)进行凝聚，使水性聚氨酯破乳并与木质素一起形成多空填充物，然后通过水洗槽清洗去残留在上面的凝固液，然后放在100-120℃的烘箱中烘2小时，烘干后获得水性太空革贝斯。
将所得水性太空革贝斯进行一下测试：
耐磨测试采用马丁代尔耐磨仪进行测试。
耐碱测试采用10％的氢氧化钠在70℃下浸泡72小时。
表1实施例1-3所得样品的性能测试
表2对比例4-7所得样品的性能测试
从以上样品1-7的性能测试对比可知，采用两釡或两釜以上同时进行双粒径或更多粒径工艺的制备的产品性能比单釜合成出来的产品性能更好。
本发明是通过至少两个预聚体混合而达到了多粒径工艺，加入胺类扩链剂的目的是进行后扩链，性能会更好。此处需要说明，用更多粒径，效果也会相对更好。
本发明的原理：水性聚氨酯树脂可以通过亲水扩链剂(二羟甲基丙酸或二羟甲基丁酸)来控制粒径大小，本发明即通过控制亲水扩链剂的用量来合成出至少两种不同粒径的预聚体，然后混合在一起，进行中和、乳化及后扩链。至少两种不同粒径的树脂在成膜时，小粒径分子会嵌入到大分子粒径之间，成膜时会更加致密，所以会拥有更高的物性，其中在剥离强度上表现最为明显。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

1.一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于，包括以下步骤，
在至少两个反应釡中同时加入多元醇和多异氰酸酯反应；
将所述至少两个反应釜降温后加入亲水扩链剂、小分子醇类扩链剂和催化剂反应；
在所述至少两个反应釜中加入稀释剂后降温获得多个预聚体并混合均匀；
加入胺类扩链剂，经纯化处理获得多粒径羧酸型水性聚氨酯。
2.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：所述多元醇包括聚四氢呋喃醚多元醇、聚酯醚多元醇、聚环氧丙烷多元醇和聚硅氧烷多元醇中的任意一种或多种。
3.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：所述多异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1，6-己二异氰酸酯和苯二亚甲基二异氰酸酯任意一种或多种。
4.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：所述胺类扩链剂为乙二胺、己二胺、异佛尔酮二胺中的一种或者多种。
5.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：所述亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸一种或两种；
和/或，所述小分子醇类扩链剂包括乙二醇、2-甲基-1,3-丙二醇、一缩二乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二甘醇、三羟甲基丙烷中的任意一种或多种。
6.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：在所述至少两个反应釜中所述亲水扩链剂在体系中所占比例之差大于0.5％。
7.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：所述催化剂选为有机铋催化剂。
8.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：所述多个预聚体之间具有相互嵌合的结构。
9.根据权利要求1所述的一种多粒径羧酸型水性聚氨酯的制备方法，其特征在于：加入所述稀释剂之前，反应体系降温至40-50℃。
10.一种如权利要求1-9任一项所述方法制备的多粒径羧酸型水性聚氨酯树脂在服装革、沙发革和太空革贝斯的用途。
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Publication number Priority date Publication date Assignee Title
CN111454420A (zh) * 2020-04-13 2020-07-28 齐鲁工业大学 一种高固含羧酸型水性聚氨酯的制备方法
CN113896858A (zh) * 2021-09-30 2022-01-07 明新孟诺卡(江苏)新材料有限公司 一种mdi型水性聚氨酯的制备方法
CN114907545A (zh) * 2022-06-06 2022-08-16 合肥科天水性科技有限责任公司 一种特柔软合成革干法机械发泡涂层用高固含水性聚氨酯

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