CN114456348A - 有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法 - Google Patents
有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法 Download PDFInfo
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Abstract
本发明涉及水性聚氨酯技术领域，具体为一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，包括以下步骤，步骤一：多元醇脱水，步骤二：预聚体反应，步骤三：亲水扩链，步骤四：丙酮降粘，步骤五：小分子扩链，步骤六：中和，步骤七：乳化和后扩链，步骤八：脱丙酮，本发明同时使用聚醚多元醇和聚酯多元醇，结合二者各自的优点，获得力学强度高、吸水率低的水性聚氨酯产品；使用脂肪族二异氰酸酯，以获得耐黄变特性；同时引入长链有机硅进行改性，降低表面能，获得优异的疏水效果，使得该水性聚氨酯乳液具有耐黄变、防水性能优异、力学性能佳等特点，十分适合用于皮革涂饰领域。
Description
技术领域
本发明涉及水性聚氨酯技术领域，具体为一种有机硅改性聚酯聚醚型皮 革涂饰用水性聚氨酯的制备方法。
背景技术
涂饰是天然皮革制造过程中的最后一道工序，也是较为关键的工序之一。 采用树脂涂饰可增加皮革的美观和耐用性能，提高皮革档次，遮盖皮革伤残， 赋予成品革美观的外表、舒适的手感和良好的力学性能，聚氨酯乳液作为皮 革涂饰剂具有良好的柔韧性、耐低温性和耐疲劳性等，其优点已得到业界公 认，最初的聚氨酯皮革涂饰剂是溶剂型湿固化聚氨酯，存在溶剂污染、成本 高等缺点，1972年，德国拜耳公司率先开发了水性聚氨酯皮革涂饰剂，我国 20世纪70年代中后期开始聚氨酯乳液涂饰剂的研制，目前水性聚氨酯皮革涂饰剂在软革行业已经普遍应用，有普通聚醚型芳香族聚氨酯、脂肪族不黄变、 有机硅改性水性聚氨酯光亮涂饰剂等品种，水性聚氨酯与以前使用的丙烯酸 酯乳液皮革涂饰剂相比，克服了丙烯酸酯树脂的”热粘冷脆”缺点，具有耐 低温性好、耐磨、耐折、手感柔软、丰满等特点，在皮革涂饰剂领域中占有 越来越重要的地位，具有重大发展潜力。
目前，皮革涂饰用聚氨酯主要分为聚酯型水性聚氨酯和聚醚型水性聚氨 酯，前者力学性能优异，但吸水率较高，后者耐水性能良好，但力学强度较 低，二者的结合使用，可以综合其优点，获得力学强度高、吸水率低的水性 聚氨酯产品，经过有机硅改性的水性聚氨酯乳液，可作为皮革防水光亮涂饰 剂，其涂膜表面光亮平滑、耐水、耐温，耐擦等级高，同时手感也更为爽滑， 适合有此种要求的皮革涂饰领域，为此我们提供一种有机硅改性聚酯聚醚型 皮革涂饰用水性聚氨酯的制备方法。
发明内容
本发明的目的在于提供一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨 酯的制备方法，包括以下步骤：
步骤一：多元醇脱水，取35-125份聚醚多元醇(PPG，MW＝2000g/mol) 和35-125份聚酯多元醇(PNA，MW＝2000g/mol)于四口烧瓶中，抽真空并升 温至120℃，除水3h，后降温至70℃；
步骤二：预聚体反应，取10-60份4,4'-二环己基甲烷二异氰酸酯、10-55 份异佛尔酮二异氰酸酯和0-15份长链羟基硅油(PDMS，MW＝4200g/mol)加 入步骤一中，通入氮气保护，于70℃下反应2h；
步骤三：亲水扩链，取9.38份2,2-二羟甲基丙酸，加入步骤二中，继续 反应3h，加入甲基丙酸1-3份；
步骤四：丙酮降粘，降温至50℃，向步骤三中加入50份丙酮降粘，搅拌 0.5h；
步骤五：小分子扩链，向步骤四中加入2.36份1,6-己二醇和5.36份三 羟甲基丙烷，升温至60℃，冷凝回流，反应2h，加入甲基丙二醇2-5份；
步骤六：中和，降温至室温，向步骤五中加入5.66份三乙胺，在600rpm 下搅拌0.5h；
步骤七：乳化和后扩链，取2-3份乙二胺滴入570-620份去离子水中， 将所得水溶液加入步骤六中，将分散盘的转速提高至1500rpm，乳化分散0.5h， 加入二甲基乙醇胺1-3份；
步骤八：脱丙酮，用旋转蒸发仪将步骤七所得乳液于42℃下旋蒸4h，脱 除丙酮，即得水性聚氨酯乳液，固含约30％。
优选的，脂肪族二异氰酸酯：4,4'-二环己基甲烷二异氰酸酯和异佛尔酮 二异氰酸酯，二者不含苯环。
优选的，异氰酸酯基团与脂环相连，无诱导效应，其反应活性相比于芳 香族异氰酸酯更低。
优选的，聚醚多元醇和聚酯多元醇混用，聚醚多元醇是主链含有醚键(R —O—R)，端基或侧基含有2个羟基(—OH)的低聚物。
优选的，聚醚多元醇为聚丙二醇，聚酯多元醇是由二元羧酸与二元醇等 通过缩聚反应得到的端基或侧基含有2个羟基(—OH)的聚酯多元醇。
优选的，聚酯多元醇为聚己二酸新戊二醇酯二醇。
优选的，引入相对分子质量(MW)为4200g/mol的羟基硅油，将其通过 化学反应接枝到聚氨酯的主链上。
优选的，以4,4'-二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯为异氰 酸酯组分，以聚丙二醇(MW＝2000g/mol)和聚己二酸新戊二醇酯二醇(MW＝2000 g/mol)为多元醇组分，以2,2-二羟甲基丙酸为亲水扩链剂，以1,6-己二醇 为小分子扩链剂，以三羟甲基丙烷为交联剂，以三乙胺为成盐剂，以乙二胺 为后扩链剂，引入长链羟基硅油。
与现有技术相比，本发明的有益效果是：
1.本发明同时使用聚醚多元醇和聚酯多元醇，结合二者各自的优点，获 得力学强度高、吸水率低的水性聚氨酯产品；使用脂肪族二异氰酸酯，以获 得耐黄变特性；同时引入长链有机硅进行改性，降低表面能，获得优异的疏 水效果，使得该水性聚氨酯乳液具有耐黄变、防水性能优异、力学性能佳等 特点，十分适合用于皮革涂饰领域。
2.本发明同时使用聚醚多元醇和聚酯多元醇，可综合二者各自的优点， 获得力学强度高、吸水率低的水性聚氨酯产品，最佳比例为1：1；使用4,4'- 二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯脂肪族二异氰酸酯，可获得 耐黄变特性，当4,4'-二环己基甲烷二异氰酸酯与异佛尔酮二异氰酸酯的质量 比为1.18时，取得的综合效果最佳，强度高、吸水率最低，伸长率优异；引 入长链有机硅进行改性，降低表面能，可使聚酯聚醚型聚氨酯乳液实现更为 优异的疏水效果，长链有机硅的引入量在3.2％时，所取得的综合性能最佳。
3.本发明获得的水性聚氨酯乳液具有耐黄变、防水性能优异、力学性能 佳等特点，十分适合用于皮革涂饰领域，同时使用聚醚多元醇和聚酯多元醇， 可综合二者各自的优点，获得力学强度高、吸水率低的水性聚氨酯产品；进 一步引入长链有机硅进行改性，可使聚酯聚醚型聚氨酯乳液实现更为优异的 疏水效果，所取得的综合性能更佳；使用4,4'-二环己基甲烷二异氰酸酯和异 佛尔酮二异氰酸酯脂肪族二异氰酸酯，可获得耐黄变特性，使产品应用领域 更为广泛，适应市场需求。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描 述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明 中的技术方案，本领域普通技术人员在没有做出创造性劳动前提下所获得的 所有其他实施例，都属于本发明保护的范围。
实施例一：
一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，包括以 下步骤：
步骤一：多元醇脱水，取80份聚醚多元醇(PPG，MW＝2000g/mol)和80 份聚酯多元醇(PNA，MW＝2000g/mol)于四口烧瓶中，抽真空并升温至120℃， 除水3h，后降温至70℃；
步骤二：预聚体反应，取36.47份4,4'-二环己基甲烷二异氰酸酯(HMDI)、 30.94份异佛尔酮二异氰酸酯(IPDI)和8.4份长链羟基硅油(PDMS，MW＝4200 g/mol)加入步骤一中，通入氮气保护，于70℃下反应2h；
步骤三：亲水扩链，取9.38份2,2-二羟甲基丙酸(DMPA)，加入步骤二 中，继续反应3h，加入甲基丙酸1-3份；
步骤四：丙酮降粘，降温至50℃，向步骤三中加入50份丙酮降粘，搅拌 0.5h；
步骤五：小分子扩链，向步骤四中加入2.36份1,6-己二醇(HDO)和5.36 份三羟甲基丙烷(TMP)，升温至60℃，冷凝回流，反应2h，加入甲基丙二 醇2-5份；
步骤六：中和，降温至室温，向步骤五中加入5.66份三乙胺(TEA)， 在600rpm下搅拌0.5h；
步骤七：乳化和后扩链，取2.23份乙二胺(EDA)滴入608.5份去离子 水中，将所得水溶液加入步骤六中，将分散盘的转速提高至1500rpm，乳化 分散0.5h，加入二甲基乙醇胺1-3份；
步骤八：脱丙酮，用旋转蒸发仪将步骤七所得乳液于42℃下旋蒸4h，脱 除丙酮，即得水性聚氨酯乳液，固含约30％。
脂肪族二异氰酸酯：4,4'-二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸 酯，二者不含苯环，异氰酸酯基团与脂环相连，无诱导效应，其反应活性相 比于芳香族异氰酸酯更低，聚醚多元醇和聚酯多元醇混用，聚醚多元醇是主 链含有醚键(R—O—R)，端基或侧基含有2个羟基(—OH)的低聚物，聚醚多元 醇为聚丙二醇，聚酯多元醇是由二元羧酸与二元醇等通过缩聚反应得到的端 基或侧基含有2个羟基(—OH)的聚酯多元醇，聚酯多元醇为聚己二酸新戊二 醇酯二醇，引入相对分子质量(MW)为4200g/mol的羟基硅油，将其通过化 学反应接枝到聚氨酯的主链上，以4,4'-二环己基甲烷二异氰酸酯和异佛尔酮 二异氰酸酯为异氰酸酯组分，以聚丙二醇(MW＝2000g/mol)和聚己二酸新戊 二醇酯二醇(MW＝2000g/mol)为多元醇组分，以2,2-二羟甲基丙酸为亲水扩 链剂，以1,6-己二醇为小分子扩链剂，以三羟甲基丙烷为交联剂，以三乙胺 为成盐剂，以乙二胺为后扩链剂，引入长链羟基硅油。
实施例2-7的具体操作方法如实施例1，具体配方如表1所示，各实施例 所取得的性能结果如表2所示；本发明关键术语定义，4,4'-二环己基甲烷二 异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)、聚己 二酸新戊二醇酯二醇(PNA)、羟基硅油(PDMS)、2,2-二羟甲基丙酸(DMPA)、 1,6-己二醇(HDO)、三羟甲基丙烷(TMP)、三乙胺(TEA)、乙二胺(EDA)。
表1各实施例所用原料配方
表2各实施例所取得的性能
通过对比实施例1、2、3可以发现：当使用PPG与PNA的质量比为1:1 时(实施例1)，取得的综合效果最佳，强度较高、吸水率最低，伸长率优异； 当PPG含量高时(实施例2)，力学强度较低；当PNA含量高时(实施例3)， 吸水率过高。
通过对比实施例1、4、5可以发现：长链有机硅PDMS的引入量在3.2％ 时(实施例1)所取得的综合性能最佳；当添加量升高至4.8％时(实施例4)， 由于过度的微相分离，导致其吸水率和力学性能均不佳；当PDMS的加入量为 0时(实施例5)，由于表面疏水性不足，导致其吸水率较高。
通过对比实施例1、6、7可以发现：当HMDI与IPDI的质量比为1.18时 (实施例1)，取得的综合效果最佳，强度较高、吸水率最低，伸长率优异； 当HMDI与IPDI的质量比为0.29时(实施例6)，断裂伸长率不佳；当HMDI 与IPDI的质量比为4.71时(实施例7)，拉伸强度与吸水率均不够理想，加 入甲基丙酸、甲基丙二醇和二甲基乙醇胺来提升水性聚氨酯的生产混料时内 部成分扩散效果，提升皮革的质地，综上所述，本发明最佳实施例为实施例1。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而 言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行 多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限 定。
Claims (8)
1.一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于，包括以下步骤：
步骤一：多元醇脱水，取35-125份聚醚多元醇(PPG，MW＝2000g/mol)和35-125份聚酯多元醇(PNA，MW＝2000g/mol)于四口烧瓶中，抽真空并升温至120℃，除水3h，后降温至70℃；
步骤二：预聚体反应，取10-60份4,4'-二环己基甲烷二异氰酸酯、10-55份异佛尔酮二异氰酸酯和0-15份长链羟基硅油(PDMS，MW＝4200g/mol)加入步骤一中，通入氮气保护，于70℃下反应2h；
步骤三：亲水扩链，取9.38份2,2-二羟甲基丙酸，加入步骤二中，继续反应3h，加入甲基丙酸1-3份；
步骤四：丙酮降粘，降温至50℃，向步骤三中加入50份丙酮降粘，搅拌0.5h；
步骤五：小分子扩链，向步骤四中加入2.36份1,6-己二醇和5.36份三羟甲基丙烷，升温至60℃，冷凝回流，反应2h，加入甲基丙二醇2-5份；
步骤六：中和，降温至室温，向步骤五中加入5.66份三乙胺，在600rpm下搅拌0.5h；
步骤七：乳化和后扩链，取2-3份乙二胺滴入570-620份去离子水中，将所得水溶液加入步骤六中，将分散盘的转速提高至1500rpm，乳化分散0.5h，加入二甲基乙醇胺1-3份；
步骤八：脱丙酮，用旋转蒸发仪将步骤七所得乳液于42℃下旋蒸4h，脱除丙酮，即得水性聚氨酯乳液，固含约30％。
2.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：脂肪族二异氰酸酯：4,4'-二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯，二者不含苯环。
3.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：异氰酸酯基团与脂环相连，无诱导效应，其反应活性相比于芳香族异氰酸酯更低。
4.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：聚醚多元醇和聚酯多元醇混用，聚醚多元醇是主链含有醚键(R—O—R)，端基或侧基含有2个羟基(—OH)的低聚物。
5.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：聚醚多元醇为聚丙二醇，聚酯多元醇是由二元羧酸与二元醇等通过缩聚反应得到的端基或侧基含有2个羟基(—OH)的聚酯多元醇。
6.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：聚酯多元醇为聚己二酸新戊二醇酯二醇。
7.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：引入相对分子质量(MW)为4200g/mol的羟基硅油，将其通过化学反应接枝到聚氨酯的主链上。
8.根据权利要求1所述的一种有机硅改性聚酯聚醚型皮革涂饰用水性聚氨酯的制备方法，其特征在于：以4,4'-二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯为异氰酸酯组分，以聚丙二醇(MW＝2000g/mol)和聚己二酸新戊二醇酯二醇(MW＝2000g/mol)为多元醇组分，以2,2-二羟甲基丙酸为亲水扩链剂，以1,6-己二醇为小分子扩链剂，以三羟甲基丙烷为交联剂，以三乙胺为成盐剂，以乙二胺为后扩链剂，引入长链羟基硅油。
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| CN115746243A (zh) * | 2022-11-11 | 2023-03-07 | 安徽聚合辐化化工有限公司 | 一种水性聚氨酯树脂及其制备方法 |
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