CN107057032A - 一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法 - Google Patents

一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法 Download PDF

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CN107057032A
CN107057032A CN201710283286.2A CN201710283286A CN107057032A CN 107057032 A CN107057032 A CN 107057032A CN 201710283286 A CN201710283286 A CN 201710283286A CN 107057032 A CN107057032 A CN 107057032A
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polyurethane resin
spinning coating
performance water
based polyurethane
chain extender
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赵学庭
冯林林
戴家兵
李维虎
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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

本发明提供一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法，水性聚氨酯树脂包括以下原料组分及重量份：多元醇45～70份；多异氰酸酯15～35份；第一小分子扩链剂3～5份；阴离子型亲水扩链剂2～4份；催化剂0.1～0.2份；硅烷偶联剂0.5～2份；成盐剂2～4份；第二小分子扩链剂2～4份，本发明的高性能水性聚氨酯树脂乳液稳定性好，贮存时间长，采用本发明的水性聚氨酯树脂制备的纺织涂层不仅手感丰满爽滑、回弹良好，而且在纤维上的牢固性好，并且具有优异的耐水性。

Description

一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法
技术领域
本发明涉及高分子织物涂层剂的技术领域，特别是涉及一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法。
背景技术
随着水性聚氨酯合成技术的发展，其性能在不断改进，近年来，水性聚氨酯的应用领域不断拓展。目前，水性聚氨酯在纺织印染行业的应用越来越广泛，水性聚氨酯树脂能赋予织物优良的柔软度、丰满感、耐洗、耐磨、爽滑、手感好、回弹好等优异性能。但由于水性聚氨酯结构的可裁剪性以及原料的多样性，采用现有技术中的水性聚氨酯树脂所制备的纺织涂层存在耐水性和在纤维上的牢固性较差，手感和回弹性不理想等问题，导致水性聚氨酯型纺织涂层产品质量不佳。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法，用于解决采用现有技术中的水性聚氨酯树脂所制备的纺织涂层存在耐水性和在纤维上的牢固性较差，手感和回弹性不理想等问题，导致水性聚氨酯型纺织涂层产品质量不佳的问题。
为实现上述目的及其他相关目的，本发明提供一种用于纺织涂层的高性能水性聚氨酯树脂，所述水性聚氨酯树脂包括以下原料组分及重量份：
优选地，所述多元醇为50～65份。
优选地，所述多异氰酸酯为20～30份。
优选地，所述第一小分子扩链剂为4～5份。
优选地，所述阴离子型亲水扩链剂为3～4份。
优选地，所述催化剂为0.15～0.20份.
优选地，所述硅烷偶联剂为1～2份。
优选地，所述成盐剂为2～3份。
优选地，所述第二小分子扩链剂为3～4份。
优选地，所述水性聚氨酯树脂的固含量为30～40％。
优选地，所述水性聚氨酯树脂的固含量为35％。
优选地，所述多元醇包括脂肪族聚醚多元醇、端羟基聚硅氧烷二元醇。
优选地，所述脂肪族聚醚多元醇和所述端羟基聚硅氧烷二元醇的重量比例为40～50：6～10。
优选地，所述脂肪族聚醚多元醇选自聚氧化丙烯二醇和聚氧化丙烯三醇中的一种或者两种。
优选地，所述端羟基聚硅氧烷二元醇的结构式如下：
在结构式中，R1和R2均为CH3或CH2CH3或CH2CH2CH3，n为1～1000的整数。
优选地，所述端羟基聚硅氧烷二元醇的数均分子量为1000-3000，更优选为2000。
优选地，所述聚氧化丙烯二醇的数均分子量为1000或2000。
优选地，所述聚氧化丙烯三醇的数均分子量为2000或3000或4000。
优选地，所述多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和二环己基二异氰酸酯中的任意一种或者多种。
优选地，所述第一小分子扩链剂为乙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇中的任意一种或多种。
优选地，所述阴离子型亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸。
优选地，所述催化剂选自有机锌化合物、有机锡化合物、有机碱金属盐、叔胺及其盐化合物中的任意一种或两种。
更优选地，所述有机锌化合物选自异辛酸锌、辛酸锌和乙酰丙酮锌中的任意一种；所述有机锡化合物选自二丁基月桂酸锡和辛酸亚锡中的任意一种；所述有机碱金属盐为乙酸钠。
优选地，所述成盐剂为三乙胺；所述硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷，其结构式为：
优选地，所述第二小分子扩链剂选自乙二胺、1,4-环己二甲胺、异佛尔酮二胺中的一种或多种。
为实现上述目的及其他相关目的，本发明提供一种制备如权利要求1～8中任一项所述的用于纺织涂层的高性能水性聚氨酯树脂的方法，其特征在于，包括如下步骤：1)将所述多元醇与所述多异氰酸酯混合，温度调至80～90℃，反应2～3h；2)降温至40～50℃后，加入所述阴离子型亲水扩链剂、所述第一小分子扩链剂，再加入所述催化剂，混合后升温至70～80℃，混合反应2～4h，得到第一预聚体；3)将所述第一预聚体降温至40～50℃后，加入所述硅烷偶联剂，混合反应5～20min，得到第二预聚体；4)将所述第二预聚体降温至10～20℃，然后加入所述成盐剂进行中和，加入冰水混合物进行乳化反应后，调节温度至0～5℃，加入所述第二小分子扩链剂反应4～6min；5)减压蒸馏，获得水性聚氨酯树脂。
优选地，所述步骤2)中加入所述阴离子型亲水扩链剂、所述第一小分子扩链剂的同时加入用于调节溶液浓度的溶剂，所述溶剂为丙酮、丁酮、甲乙酮、N-甲基吡咯烷酮和N,N-二甲基甲酰胺中的一种或多种。溶剂的作用为调整反应溶液的粘度，其添加量根据反应需要酌情添加，优选为占聚氨酯树脂固体重量的30～50％，且溶剂在减压蒸馏阶段被蒸馏除去。
优选地，减压蒸馏的具体操作步骤为：在50～55℃，抽真空-0.07～-0.1MPa的条件下，蒸馏1～1.5h，测试固含量达标即可。
本发明选用聚氧化丙烯二醇和聚氧化丙烯三醇作为大分子多元醇的主要原料，同时加入少量端羟基聚硅氧烷二元醇，由于该大分子二元醇的羟基位于硅氧烷侧链上，当接入聚氨酯主链上时，硅氧烷容易向表面迁移，可显著提高涂膜的爽滑性、耐水性和手感；此外，硅氧烷水解生成的硅醇能与底材发生缩合反应可显著提高涂层的牢固性。大分子多元醇选用聚醚多元醇，在保证耐水性良好的同时增加涂层的手感和柔软度；同时，加入少量高分子量三官能度的聚醚多元醇即聚氧化丙烯三醇，由于聚醚多元醇分子量高可进一步提高涂层的手感，且三官能度为聚氨酯体系提供一定交联度，对水性聚氨酯树脂的综合性能有较大改善，使得获得的水性聚氨酯树脂不仅柔性好、还具有优良耐水性和牢固性。
同时本发明在合成过程中加入硅烷偶联剂γ-缩水甘油醚氧丙基三甲氧基硅烷，该硅烷偶联剂为含有三个硅氧键和环氧官能团的硅烷，由于硅氧烷在材料的表面富集会进一步提高材料的耐水性，同时环氧官能团的存在可以明显提高材料与基材的粘结强度。
如上所述，本发明的用于纺织涂层的高性能水性聚氨酯树脂及制备方法，具有以下有益效果：本发明的高性能水性聚氨酯树脂乳液稳定性好，贮存时间长，采用本发明的水性聚氨酯树脂制备的纺织涂层不仅手感丰满爽滑、回弹良好，而且在纤维上的牢固性好，并且具有优异的耐水性。
具体实施方式
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。
表1为实施例1-4中的水性聚氨酯树脂的各原料组分及其配比：
表1水性聚氨酯树脂的各原料组分及其配比
实施例1
1)向三口烧瓶中加入40g聚氧化丙烯二醇，16g聚氧化丙烯三醇，5g端羟基聚硅氧烷二元醇，再加入25g甲苯二异氰酸酯，升温至85℃，反应2h；
2)降温至50℃，加入3g乙二醇，4g二羟甲基丙酸，0.15g辛酸亚锡和丙酮40g，搅拌混合后，加热至80℃，反应3h；
3)降温至50℃，加入1gγ-缩水甘油醚氧丙基三甲氧基硅烷，反应20min；
4)降温至10℃，加入4g三乙胺中和，加入185g冰水混合物乳化分散，调节温度至4℃再加入4g乙二胺后扩链5min，并继续乳化分散；
5)通过减压蒸馏除去丙酮，获得水性聚氨酯树脂乳液。
实施例2
1)向三口烧瓶中加入30g聚氧化丙烯二醇，12g聚氧化丙烯三醇，7g端羟基聚硅氧烷二元醇，再加入15g二苯基甲烷二异氰酸酯，升温至80℃，反应2h；
2)降温至40℃，加入5g1,4-丁二醇，2g二羟甲基丙酸，0.1g辛酸锌和丁酮30g，搅拌混合后，加热至70℃，反应2h；
3)降温至45℃，加入0.5gγ-缩水甘油醚氧丙基三甲氧基硅烷，反应8min；
4)降温至10℃，加入2g三乙胺中和，加入180g冰水混合物乳化分散，调节温度至2℃再加入2g1,4-环己二甲胺后扩链4min，并继续乳化分散；
5)通过减压蒸馏除去丁酮，获得水性聚氨酯树脂乳液。
实施例3
1)向三口烧瓶中加入50g聚氧化丙烯二醇，10g聚氧化丙烯三醇，8g端羟基聚硅氧烷二元醇，再加入30g六亚甲基二异氰酸酯，升温至85℃，反应3h；
2)降温至45℃，加入4g2-甲基-1,3-丙二醇，3g二羟甲基丁酸，0.2g异辛酸锌和甲乙酮45g，搅拌混合后，加热至75℃，反应3h；
3)降温至40℃，加入1.5gγ-缩水甘油醚氧丙基三甲氧基硅烷，反应15min；
4)降温至15℃，加入3g三乙胺中和，加入185g冰水混合物乳化分散，调节温度至3℃再加入3g异佛尔酮二胺后扩链5min，并继续乳化分散；
5)通过减压蒸馏除去甲乙酮，获得水性聚氨酯树脂乳液。
实施例4
1)向三口烧瓶中加入45g聚氧化丙烯二醇，15g聚氧化丙烯三醇，10g端羟基聚硅氧烷二元醇，再加入35g二环己基二异氰酸酯，升温至90℃，反应3h；
2)降温至50℃，加入4g1,4-丁二醇，4g二羟甲基丁酸，0.2g乙酸钠和丙酮50g，搅拌混合后，加热至80℃，反应4h；
3)降温至50℃，加入1gγ-缩水甘油醚氧丙基三甲氧基硅烷，反应18min；
4)降温至20℃，加入4g三乙胺中和，加入190g冰水混合物乳化分散，调节温度至5℃再加入3g乙二胺后扩链6min，并继续乳化分散；
5)通过减压蒸馏除去丙酮，获得水性聚氨酯树脂乳液。
性能检测：
对实施例1-4的水性聚氨酯树脂进行性能参数测试，结果如表2所示：
表2水性聚氨酯树脂的基本特征参数测试结果
由表2可得知，本发明的水性聚氨酯树脂为乳液状态，固含量在34-36％，稳定性好，贮存时间长。
以涤纶春亚纺作为基布，将实施例1-4的水性聚氨酯树脂涂布在基布上形成纺织涂层，对纺织涂层进行性能评价，其测试结果见表3：
表3由实施例1-4的水性聚氨酯树脂制备的纺织涂层的性能检测结果
由表3可看出，本发明所制备的水性聚氨酯纺织涂层具有较高的剥离强度，与基布粘结牢度高，并且有较高的耐静水压性能，同时获得了较为理想的表面疏水性；此外由本发明的水性聚氨酯树脂制备的织物手感柔软爽滑，符合市场要求。
综上所述，本发明的高性能水性聚氨酯树脂乳液稳定性好，贮存时间长，采用本发明的水性聚氨酯树脂制备的纺织涂层不仅手感丰满爽滑、回弹良好，而且在纤维上的牢固性好，并且具有优异的耐水性。
所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
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)

1.一种用于纺织涂层的高性能水性聚氨酯树脂，其特征在于，所述水性聚氨酯树脂包括以下原料组分及重量份：
2.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述多元醇包括脂肪族聚醚多元醇、端羟基聚硅氧烷二元醇。
3.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和二环己基二异氰酸酯中的任意一种或者多种。
4.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述第一小分子扩链剂为乙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇中的任意一种或多种。
5.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述阴离子型亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸。
6.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述催化剂选自有机锌化合物、有机锡化合物、有机碱金属盐、叔胺及其盐化合物中的任意一种或两种。
7.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述成盐剂为三乙胺；所述硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷，其结构式为：
8.根据权利要求1所述的用于纺织涂层的高性能水性聚氨酯树脂，其特征在于：所述第二小分子扩链剂选自乙二胺、1,4-环己二甲胺、异佛尔酮二胺中的一种或多种。
9.一种制备如权利要求1～8中任一项所述的用于纺织涂层的高性能水性聚氨酯树脂的方法，其特征在于，包括如下步骤：
1)将所述多元醇与所述多异氰酸酯混合，温度调至80～90℃，反应2～3h；
2)降温至40～50℃后，加入所述阴离子型亲水扩链剂、所述第一小分子扩链剂，再加入所述催化剂，混合后升温至70～80℃，混合反应2～4h，得到第一预聚体；
3)将所述第一预聚体降温至40～50℃后，加入所述硅烷偶联剂，混合反应5～20min，得到第二预聚体；
4)将所述第二预聚体降温至10～20℃，然后加入所述成盐剂进行中和，加入冰水混合物进行乳化反应后，调节温度至0～5℃，加入所述第二小分子扩链剂反应4～6min；
5)减压蒸馏，获得水性聚氨酯树脂。
10.根据权利要求9所述的制备如权利要求1～8中任一项所述的用于纺织涂层的高性能水性聚氨酯树脂的方法，其特征在于：所述步骤2)中加入所述阴离子型亲水扩链剂、所述第一小分子扩链剂的同时加入用于调节溶液浓度的溶剂，所述溶剂为丙酮、丁酮、甲乙酮、N-甲基吡咯烷酮和N,N-二甲基甲酰胺中的一种或多种。
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CN110818875A (zh) * 2019-10-09 2020-02-21 江南大学 一种有机硅改性聚氨酯及其应用与其涂层织物制备方法
CN111019075A (zh) * 2019-11-29 2020-04-17 合肥科天水性科技有限责任公司 一种阴离子水性聚氨酯树脂、其制备方法和在涂料中的用途
CN111875774A (zh) * 2020-08-05 2020-11-03 辽宁恒星精细化工有限公司 一种织物用水性阻燃耐水压聚氨酯乳液制备方法
CN113429539A (zh) * 2021-05-31 2021-09-24 成都玉瓶科技有限公司 一种羟基聚硅氧烷改性水性聚氨酯乳液、超滑表面涂层及其制备方法
CN114851648A (zh) * 2022-04-19 2022-08-05 江门建滔积层板有限公司 一种高韧性耐高温cem-1板及其制备方法
CN116024826A (zh) * 2022-12-02 2023-04-28 中国第一汽车股份有限公司 一种轻薄罗布麻纤维功能面料及其制备方法

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