CN107400452A - 一种水性聚氨酯皮革涂饰剂及其制备方法 - Google Patents

一种水性聚氨酯皮革涂饰剂及其制备方法 Download PDF

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CN107400452A
CN107400452A CN201710527928.9A CN201710527928A CN107400452A CN 107400452 A CN107400452 A CN 107400452A CN 201710527928 A CN201710527928 A CN 201710527928A CN 107400452 A CN107400452 A CN 107400452A
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方晓俊
王之霖
潘宏梅
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Changzhou Date Art Decoration Materials Co Ltd
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Abstract

本发明公开了一种水性聚氨酯皮革涂饰剂及其制备方法，属于皮革助剂制备技术领域。本发明将纳米蒙脱土和无水乙醇混合并加入3‑氨丙基三甲氧基硅烷、二甲基二甲氧基硅烷搅拌、过滤，得滤渣后洗涤、冻干，制得改性纳米蒙脱土，再将聚己二酸丙二醇酯和聚醚多元醇加热反应后，加入异佛尔酮二异氰酸酯、2,2‑二羟甲基丙酸搅拌得预聚合混合液，再将改性纳米蒙脱土、有机溶剂混合分散后与催化剂、预聚合混合液、助剂等混合，即可得水性聚氨酯皮革涂饰剂，本发明所得水性聚氨酯皮革涂饰剂吸水率较小，具有较好的耐水性，喷涂在皮革表面后，与底层具有较强的粘接性能，且涂饰剂喷涂在皮革表表面后具有较好的机械性能，有效提高了皮革的耐用性。

Description

一种水性聚氨酯皮革涂饰剂及其制备方法
技术领域
本发明公开了一种水性聚氨酯皮革涂饰剂及其制备方法，属于皮革助剂制备技术领域。
背景技术
皮革涂饰剂是可通过揩、刷、喷或淋等方式在皮革表面形成薄膜或涂层的一种材料，主要包括聚丙烯酸酯、着色材料、溶剂和助剂。皮革涂饰剂可增加皮革的美观和耐用性能，提高皮革档次，增加皮革花色品种和扩大皮革使用范围。
在制革工业中，常用皮革涂饰剂有丙烯酸酯涂饰剂、酪素涂饰剂、硝化纤维涂饰剂和水性聚氨酯涂饰剂。其中水性聚氨酯涂饰剂以水为溶剂，产品无挥发性有机溶剂，具有无毒、成膜性能好、遮盖力强、弹性好等特点，涂饰的产品革手感舒适，且能大大提高合成革的档次，因此，其应用受到重点关注。如专利申请号CN201010589750.9公开了一种“单组份水性聚氨酯皮革涂饰剂的合成工艺”，该涂饰剂以聚醚三元醇、聚酯二元醇、甲苯二异氰酸酯为主要原料，经预聚、扩链、季铵化、乳化等过程制得稳定的自交联、自乳化型单组份水性聚氨酯皮革涂饰剂，该水性聚氨酯皮革涂饰剂使用后形成的胶膜耐热、耐磨性较好，但机械性能及耐水性不佳。又如专利申请号CN201210478167.X公开了一种“耐黄变皮革涂饰剂用水性聚氨酯分散体及其制备方法”，该分散体是以二环己基甲烷二异氰酸酯与异佛尔酮二异氰酸酯组成的二异氰酸酯混合物为起始原料，先以多元醇、二异氰酸酯混合物与交联剂反应生成预聚体，再于预聚体中添加亲水扩链剂进一步反应，并以小分子二元醇扩链，用三乙胺中和，并于水中分散后得到，该水性聚氨酯皮革涂饰剂侧重于耐黄变性能，其机械性能较低，与底层粘结性较差，且未提及耐水性能。
综上所述，现有水性聚氨酯皮革涂饰剂普遍存在耐水性差，机械强度低和与底层粘接性差的缺陷，未解决这些缺陷，亟待开发一种与底层粘结性能良好，机械强度较高，且具有优异耐水性能的新型水性聚氨酯皮革涂饰剂。
发明内容
本发明主要解决的技术问题：针对现有水性聚氨酯皮革涂饰剂普遍存在耐水性差，机械强度低和与底层粘接性差的缺陷，提供了一种水性聚氨酯皮革涂饰剂及其制备方法。
为了解决上述技术问题，本发明所采用的技术方案是：
一种水性聚氨酯皮革涂饰剂，所述皮革涂饰剂由下述重量份原料制备：
30～50份聚醚多元醇，10～12份聚己二酸丙二醇酯，4.2～5.0份异佛尔酮二异氰酸酯，1.0～1.2份2,2-二羟甲基丙酸，0.010～0.012份改性纳米蒙脱土，0.01～0.02份催化剂，18～20份有机溶剂，0.6～0.8份成盐剂，0.4～0.5份小分子扩链剂，40～50份去离子水。
所述聚醚多元醇为聚丙二醇、聚乙二醇、聚四氢呋喃二醇中的一种或多种。
所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的任意一种。
所述有机溶剂为丙酮、甲乙酮、N-甲基吡咯烷酮，N,N-二甲基甲酰胺中的一种或多种。
所述成盐剂为三乙胺、三乙醇胺中的任意一种。
所述小分子扩链剂为乙二胺、己二胺、丙二醇、1,4-丁二醇中的一种或多种。
所述改性纳米蒙脱土为：将纳米蒙脱土和无水乙醇混合，再滴加3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷，在70～80℃下以800～1000r/min搅拌4～6h，冷却至室温后过滤洗涤干燥制得，所述纳米蒙脱土、3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷的质量比为1：2：1。
一种水性聚氨酯皮革涂饰剂的制备方法，具体步骤为：
S1.取纳米蒙脱土超声分散在无水乙醇中，再滴加3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷，在70～80℃下以800～1000r/min搅拌4～6h，冷却至室温后过滤洗涤干燥，得改性纳米蒙脱土；
S2.将聚己二酸丙二醇酯与聚醚多元醇装入烧瓶中并加热至80～90℃，搅拌10～15min后加入异佛尔酮二异氰酸酯，保温搅拌1～2h，再加入2,2-二羟甲基丙酸，继续搅拌2～3h，得预聚合混合液；
S3.将改性纳米蒙脱土超声分散在有机溶剂中，并与催化剂加入预聚合混合液中，以800～1000r/min搅拌1～2h，冷却至50～60℃，再加入成盐剂、有机溶剂，继续搅拌20～30min后，降温至10～15℃，再加入小分子扩链剂、去离子水，以1800～2000r/min搅拌1～2h，得水性聚氨酯皮革涂饰剂。
本发明的有益效果是：
本发明利用3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷改性纳米蒙脱土，在纳米蒙脱土表面接枝疏水基团并增加活性反应位点，再通过原位聚合法将改性纳米蒙脱土引入到聚氨酯中，通过改性纳米蒙脱土作为成核剂，增加聚氨酯的结晶度，同时改性纳米蒙脱土以剥离单片层形式无规律地存在于聚氨酯基体中，增加了基体的交联度，由线型分子结构发展成交联的三维网状结构，改善了材料的机械强度和与底层粘接性能，同时形成的氢键变多，交联点之间的链长变短，水分子难以渗入到分子链间进行溶胀，并且聚氨酯中的亲水基团被交联后形成的三维网状结构包围，进而降低吸水率，改善耐水性能。
具体实施方式
首先取0.8～1.0g纳米蒙脱土，加入250～300mL无水乙醇中，以300W超声波超声分散30～40min，再滴加1.6～2.0g3-氨丙基三甲氧基硅烷，0.8～1.0g二甲基二甲氧基硅烷，在70～80℃下以800～1000r/min搅拌4～6h，冷却至室温后过滤，得滤渣，将滤渣用无水乙醇洗涤滤渣2～3次后再用去离子水洗涤2～3次，并置于冷冻干燥箱中冷冻干燥，得改性纳米蒙脱土，随后取10～12g聚己二酸丙二醇酯，30～50g聚醚多元醇，装入烧瓶中并加热至80～90℃，以300～400r/min搅拌10～15min，再加入4.2～5.0g异佛尔酮二异氰酸酯，保温搅拌1～2h后加入1.0～1.2g2,2-二羟甲基丙酸，继续搅拌2～3h，得预聚合混合液，再取0.010～0.012g改性纳米蒙脱土加入9～10g有机溶剂中，以300W超声波超声分散10～15min，得改性纳米蒙脱土分散液，将改性纳米蒙脱土分散液与0.01～0.02g催化剂加入预聚合混合液中，以800～1000r/min搅拌1～2h，冷却至50～60℃，再加入0.6～0.8g成盐剂，9～10g有机溶剂，继续搅拌20～30min后，降温至10～15℃，再加入40～50mL质量分数为1%小分子扩链剂水溶液，以1800～2000r/min搅拌1～2h，得水性聚氨酯皮革涂饰剂。所述聚醚多元醇为聚丙二醇、聚乙二醇、聚四氢呋喃二醇中的一种或多种。所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的任意一种。所述有机溶剂为丙酮、甲乙酮、N-甲基吡咯烷酮，N,N-二甲基甲酰胺中的一种或多种。所述成盐剂为三乙胺、三乙醇胺中的任意一种。所述小分子扩链剂为乙二胺、己二胺、丙二醇、1,4-丁二醇中的一种或多种。
实例1
首先取0.8g纳米蒙脱土，加入250mL无水乙醇中，以300W超声波超声分散30，再滴加1.6g3-氨丙基三甲氧基硅烷，0.8g二甲基二甲氧基硅烷，在70℃下以800r/min搅拌4h，冷却至室温后过滤，得滤渣，将滤渣用无水乙醇洗涤滤渣2次后再用去离子水洗涤2次，并置于冷冻干燥箱中冷冻干燥，得改性纳米蒙脱土，随后取10g聚己二酸丙二醇酯，30g聚醚多元醇，装入烧瓶中并加热至80℃，以300r/min搅拌10min，再加入4.2g异佛尔酮二异氰酸酯，保温搅拌1h后加入1.0g2,2-二羟甲基丙酸，继续搅拌2h，得预聚合混合液，再取0.010g改性纳米蒙脱土加入9g有机溶剂中，以300W超声波超声分散10min，得改性纳米蒙脱土分散液，将改性纳米蒙脱土分散液与0.01g催化剂加入预聚合混合液中，以800r/min搅拌1h，冷却至50℃，再加入0.6g成盐剂，9g有机溶剂，继续搅拌20min后，降温至10℃，再加入40mL质量分数为1%小分子扩链剂水溶液，以1800r/min搅拌1h，得水性聚氨酯皮革涂饰剂。所述聚醚多元醇为聚丙二醇。所述催化剂为二月桂酸二丁基锡。所述有机溶剂为丙酮。所述成盐剂为三乙胺。所述小分子扩链剂为乙二胺。
实例2
首先取0.9g纳米蒙脱土，加入275mL无水乙醇中，以300W超声波超声分散35min，再滴加1.8g3-氨丙基三甲氧基硅烷，0.9g二甲基二甲氧基硅烷，在75℃下以900r/min搅拌5h，冷却至室温后过滤，得滤渣，将滤渣用无水乙醇洗涤滤渣2次后再用去离子水洗涤2次，并置于冷冻干燥箱中冷冻干燥，得改性纳米蒙脱土，随后取11g聚己二酸丙二醇酯，40g聚醚多元醇，装入烧瓶中并加热至85℃，以350r/min搅拌13min，再加入4.6g异佛尔酮二异氰酸酯，保温搅拌1h后加入1.1g2,2-二羟甲基丙酸，继续搅拌2h，得预聚合混合液，再取0.011g改性纳米蒙脱土加入9g有机溶剂中，以300W超声波超声分散13min，得改性纳米蒙脱土分散液，将改性纳米蒙脱土分散液与0.01g催化剂加入预聚合混合液中，以900r/min搅拌1h，冷却至55℃，再加入0.7g成盐剂，9g有机溶剂，继续搅拌25min后，降温至13℃，再加入45mL质量分数为1%小分子扩链剂水溶液，以1900r/min搅拌1h，得水性聚氨酯皮革涂饰剂。所述聚醚多元醇为聚乙二醇。所述催化剂为二月桂酸二丁基锡。所述有机溶剂为甲乙酮。所述成盐剂为三乙胺。所述小分子扩链剂为己二胺。
实例3
首先取1.0g纳米蒙脱土，加入300mL无水乙醇中，以300W超声波超声分40min，再滴加2.0g3-氨丙基三甲氧基硅烷，1.0g二甲基二甲氧基硅烷，在80℃下以1000r/min搅拌6h，冷却至室温后过滤，得滤渣，将滤渣用无水乙醇洗涤滤渣3次后再用去离子水洗涤3次，并置于冷冻干燥箱中冷冻干燥，得改性纳米蒙脱土，随后取12g聚己二酸丙二醇酯，50g聚醚多元醇，装入烧瓶中并加热至90℃，以400r/min搅拌15min，再加入5.0g异佛尔酮二异氰酸酯，保温搅拌2h后加入1.2g2,2-二羟甲基丙酸，继续搅拌3h，得预聚合混合液，再取0.012g改性纳米蒙脱土加入10g有机溶剂中，以300W超声波超声分散15min，得改性纳米蒙脱土分散液，将改性纳米蒙脱土分散液与0.02g催化剂加入预聚合混合液中，以1000r/min搅拌2h，冷却至60℃，再加入0.8g成盐剂，10g有机溶剂，继续搅拌30min后，降温至15℃，再加入50mL质量分数为1%小分子扩链剂水溶液，以2000r/min搅拌2h，得水性聚氨酯皮革涂饰剂。所述聚醚多元醇为聚四氢呋喃二醇。所述催化剂为辛酸亚锡。所述有机溶剂为N-甲基吡咯烷酮。所述成盐剂为三乙醇胺。所述小分子扩链剂为丙二醇。
对比例：山东某新材料有限公司生产的水性聚氨酯皮革涂饰剂。
利用喷枪将本发明实例1～3所得水性聚氨酯皮革涂饰剂和对比例水性聚氨酯皮革涂饰剂分别喷涂在四块边长为5cm的正方形皮革表面，待喷涂完成后，将四块皮革于温度为70℃下烘干，制得皮革试样。对制得的四块皮革试样进行性能检测，其检测结果如表1所示：
表1
检测项目 实例1 实例2 实例3 对比例
铅笔硬度（H） 2 2 2 1
附着力（级） 0 0 0 2
抗冲击性能（J/m2） 68.9 69.6 70.4 64.3
吸水率（%） 9.2 8.5 7.9 14.2
拉伸强度（MPa） 47.2 48.9 49.7 38.3
检验方法：
铅笔硬度：根据GB/T6739标准，使用涂膜铅笔划痕硬度仪测定四块皮革试样涂饰面的铅笔硬度；
附着力：根据GB/T9286标准，通过划格实验的方法测定四块皮革试样涂膜的附着力；
吸水率：根据HG/T3856标准，测定四块皮革试样涂饰面的吸水率；
拉伸性能：将四块皮革试样分别裁剪成长为25mm、宽为6mm大小试样，将裁剪后的皮革试样依次放置在万能材料实验机上测试其拉伸性能；
冲击性能：根据GB/T1732标准，通过用漆膜冲击器测定四块皮革试样涂饰面的抗冲击性能。
综上所述，本发明所得水性聚氨酯皮革涂饰剂吸水率较小，具有较好的耐水性，喷涂在皮革表面后，与底层具有较强的粘接性能，且涂饰剂喷涂在皮革表表面后具有较好的机械性能，有效提高了皮革的耐用性，具有较好的应用前景。

Claims (8)

1.一种水性聚氨酯皮革涂饰剂，其特征在于，所述皮革涂饰剂由下述重量份原料制备：
30～50份聚醚多元醇，10～12份聚己二酸丙二醇酯，4.2～5.0份异佛尔酮二异氰酸酯，1.0～1.2份2,2-二羟甲基丙酸，0.010～0.012份改性纳米蒙脱土，0.01～0.02份催化剂，18～20份有机溶剂，0.6～0.8份成盐剂，0.4～0.5份小分子扩链剂，40～50份去离子水。
2.如权利要求1所述的一种水性聚氨酯皮革涂饰剂，其特征在于，所述聚醚多元醇为聚丙二醇、聚乙二醇、聚四氢呋喃二醇中的一种或多种。
3.如权利要求1所述的一种水性聚氨酯皮革涂饰剂，其特征在于，所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的任意一种。
4.如权利要求1所述的一种水性聚氨酯皮革涂饰剂，其特征在于，所述有机溶剂为丙酮、甲乙酮、N-甲基吡咯烷酮，N,N-二甲基甲酰胺中的一种或多种。
5.如权利要求1所述的一种水性聚氨酯皮革涂饰剂，其特征在于，所述成盐剂为三乙胺、三乙醇胺中的任意一种。
6.如权利要求1所述的一种水性聚氨酯皮革涂饰剂，其特征在于，所述小分子扩链剂为乙二胺、己二胺、丙二醇、1,4-丁二醇中的一种或多种。
7.如权利要求1所述的一种水性聚氨酯皮革涂饰剂，其特征在于，所述改性纳米蒙脱土为：将纳米蒙脱土和无水乙醇混合，再滴加3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷，在70～80℃下以800～1000r/min搅拌4～6h，冷却至室温后过滤洗涤干燥制得，所述纳米蒙脱土、3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷的质量比为1：2：1。
8.如权利要求1～7任意一项所述的一种水性聚氨酯皮革涂饰剂的制备方法，其特征在于，具体步骤为：
S1.取纳米蒙脱土超声分散在无水乙醇中，再滴加3-氨丙基三甲氧基硅烷和二甲基二甲氧基硅烷，在70～80℃下以800～1000r/min搅拌4～6h，冷却至室温后过滤洗涤干燥，得改性纳米蒙脱土；
S2.将聚己二酸丙二醇酯与聚醚多元醇装入烧瓶中并加热至80～90℃，搅拌10～15min后加入异佛尔酮二异氰酸酯，保温搅拌1～2h，再加入2,2-二羟甲基丙酸，继续搅拌2～3h，得预聚合混合液；
S3.将改性纳米蒙脱土超声分散在有机溶剂中，并与催化剂加入预聚合混合液中，以800～1000r/min搅拌1～2h，冷却至50～60℃，再加入成盐剂、有机溶剂，继续搅拌20～30min后，降温至10～15℃，再加入小分子扩链剂、去离子水，以1800～2000r/min搅拌1～2h，得水性聚氨酯皮革涂饰剂。
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CN117143511A (zh) * 2023-10-30 2023-12-01 福建兴宇树脂有限公司 一种高耐候汽车内饰革用聚氨酯涂层材料及其制备方法
CN117143511B (zh) * 2023-10-30 2024-02-13 福建兴宇树脂有限公司 一种高耐候汽车内饰革用聚氨酯涂层材料及其制备方法

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Application publication date: 20171128