CN111748072A - 一种人造或合成革用水性自消光表处剂及制备方法 - Google Patents

一种人造或合成革用水性自消光表处剂及制备方法 Download PDF

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CN111748072A
CN111748072A CN202010683876.6A CN202010683876A CN111748072A CN 111748072 A CN111748072 A CN 111748072A CN 202010683876 A CN202010683876 A CN 202010683876A CN 111748072 A CN111748072 A CN 111748072A
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reacting
synthetic leather
extinction
chain extender
surface treating
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杨建军
唐慧
吴庆云
张建安
吴明元
刘久逸
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Anhui University
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Abstract

本发明公开了一种人造或合成革用水性自消光表处剂及制备方法，涉及水性涂料领域，包括将10g～20g聚合物多元醇、14.4g～43.1g多异氰酸酯和8.4g～25.2g端羟丙基聚二甲基硅氧烷在加入催化剂下，80℃～90℃条件下反应2h，降温至50℃后，加入1.6g～4.2g亲水扩链剂和2.6g～9.6g小分子扩链剂，在80℃下继续反应3h，用丙酮调节反应体系的粘度，防止凝胶的生成，冷却至40℃，加入1.1g～2.5g中和剂中和30min，加入1g～7.4g环氧树脂，在70℃反应1h，加入去离子水，在3000r/min的高转速下乳化30min，缓慢滴加0.8g～2.5g的乙二胺进行后扩链，得到人造革、合成革用水性自消光表处剂乳液；本发明所得表处剂使用后消光效果好，且硬度大、抗形变能力强、力学性能优异、耐摩耐刮。

Description

一种人造或合成革用水性自消光表处剂及制备方法
技术领域
本发明涉及水性涂料领域，具体涉及一种用于人造或合成革用的水性自消光表处剂。
背景技术
水性聚氨酯(WPU)亚光涂料具有色泽柔和、环保和更具高级感而越来越受到人们的喜爱。在人造革行业中，水性聚氨酯在人造革面料，中间层，贴合料和表面涂饰剂都有应用。
但是单一的水性聚氨酯在人造革表面不仅流平性不好、粘合力不足、表面颜色湿擦不合格，而且难以达到深度的消光效果。人们通过外添加消光剂的方法进行消光，但消光剂易发生沉降，使乳液的稳定性降低，且若混合不均则存在涂层的光泽有差异、涂层脆性增大等问题，部分消光粉体涂刷后，会导致皮革涂饰出现掉粉现象，消光不自然。
发明内容
本发明的目的在于克服现有技术的不足，提供了一种人造或合成革用水性自消光表处剂及制备方法，以解决现有技术中水性聚氨酯中添加消光剂导致皮革消光层光泽存在差异、涂层脆性大的技术问题。
本发明是通过以下技术方案实现的：
本发明提供了一种人造或合成革用水性自消光表处剂，所述表处剂的组成包括多元醇、有机硅和环氧树脂。
进一步，所述有机硅具体为端羟丙基聚二甲基硅氧烷。
本发明还提供一种权利上述表处剂的制备方法，该方法包括一下步骤：
步骤1、将10g～20g聚合物多元醇、14.4g～43.1g多异氰酸酯和8.4g～25.2g端羟丙基聚二甲基硅氧烷在加入催化剂下，80℃～90℃条件下反应2h；
步骤2、将步骤1所得产物降温至50℃后，加入1.6g～4.2g亲水扩链剂和2.6g～9.6g g 小分子扩链剂，在80℃下继续反应3h，用丙酮调节反应体系的粘度，防止凝胶的生成；
步骤3、将步骤2获得的产物冷却至40℃，加入1.1g～2.5g中和剂中和30min；
步骤4、步骤3的产物中加入1g～7.4g环氧树脂，在70℃反应1h；
步骤5、步骤4的产物中加入去离子水，在3000r/min的高转速下乳化30min；
步骤6、向步骤5的产物中缓慢滴加0.8g～2.5g的乙二胺进行后扩链，得到人造革、合成革用水性自消光表处剂乳液。
进一步，所述多异氰酸酯为甲苯二异氰酸酯、1，6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)、环己烷-1，4-二异氰酸酯、4，4-二环己基甲烷二异氰酸酯、4，4-二苯基甲烷二异氰酸酯中的至少一种。
进一步，所述聚多元醇的分子量为1000-2000；所述聚多元醇为聚四亚甲基醚二醇、聚四氢呋喃醚二醇、聚氧化丙烯二醇、聚己二酸1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇、聚碳酸酯二元醇中的至少一种。
进一步，所述催化剂为辛酸亚锡。
进一步，所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、2-[(2-氨乙基)氨基]磺酸钠中的至少一种。
进一步，所述小分子扩链剂为1,4-丁二醇。
进一步，所述中和剂为三乙胺。
进一步，所述聚多元醇和端羟丙基聚二甲基硅氧烷使用前在120℃下抽真空脱水2h，亲水扩链剂使用前在真空干燥箱中50℃下干燥1h，且所述聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2。
本发明相比现有技术具有以下优点：
1.本发明通过引入有机硅和环氧树脂制备人造革、合成革用水性自消光表处剂。利用有机硅聚合物的表面能低、与水性聚氨酯相容性差的特点和环氧树脂具有化学稳定性好、粘接力强、收缩率低、力学性能强和化学稳定性好的特点，合成了光泽度低、硬度大、抗形变能力强、力学性能优异、耐摩耐刮的胶膜，且由于没有外添消光粉，所以不会存在掉粉、易刮擦现象。
2.该方法简单可控，成本低廉，不需要复杂的生产设备，且其消光效果由涂料本身在成膜后自动产生，也不需要外加物理消光剂。
具体实施方式
下面将结合本发明实施例对本发明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。基于本发明中的实施例，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。
本发明提供的实施例：
实施例1
(1)制备人造革、合成革用水性自消光表处剂乳液，其中聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:4，环氧树脂添加量占聚氨酯预聚体总质量的2.5％。
(1.1)将聚四亚甲基醚二醇和端羟丙基聚二甲基硅氧烷在110℃抽真空脱水干燥2h后备用。在装有搅拌器、回流冷凝管及温度计的三口烧瓶中，加入10g聚四亚甲基醚二醇、16.8g 端羟丙基聚二甲基硅氧烷、33.3g异佛尔酮二异氰酸酯和两滴T-9，在80～90℃反应2h；聚四亚甲基醚二醇的分子量为2000；
(1.2)降温至50℃再加入3g二羟甲基丁酸和5.9g1，4-丁二醇，在80℃左右反应3h；视黏度情况加入丙酮降黏。实验采用二正丁胺法测定剩余－NCO基团，当－NCO的实际剩余含量达到理论剩余量的92％～98％时，反应即可停止。二羟甲基丁酸使用前在真空干燥箱中50℃下干燥1h；
(1.3)预聚体冷却至40℃，加入2g三乙胺中和30min；
(1.4)加入1.8g环氧树脂，70℃条件下反应1h左右；
(1.5)加入110ml去离子水，在3000r/min的高转速下乳化30min，最后向乳化好的乳液中缓慢滴加0.8g乙二胺(溶于10mL去离子水中)进行后扩链，制得人造革、合成革用水性自消光表处剂乳液。
实施例2
(1)制备人造革、合成革用水性自消光表处剂乳液，其中聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2，环氧树脂添加量占聚氨酯预聚体总质量的2.5％。
(1.1)将聚己二酸己二醇酯二醇和端羟丙基聚二甲基硅氧烷在110℃抽真空脱水干燥2h 后备用。在装有搅拌器、回流冷凝管及温度计的三口烧瓶中，加入10g聚己二酸己二醇酯二醇、8.4g端羟丙基聚二甲基硅氧烷、14.4g甲苯二异氰酸酯和两滴T-9，在80～90℃反应2h；聚己二酸己二醇酯二醇的分子量为2000；
(1.2)降温至50℃再加入1.6g二羟甲基丁酸和2.6g1，4-丁二醇，在80℃左右反应3h；视黏度情况加入丙酮降黏。实验采用二正丁胺法测定剩余－NCO基团，当－NCO的实际剩余含量达到理论剩余量的92％～98％时，反应即可停止。二羟甲基丁酸使用前在真空干燥箱中50℃下干燥1h；
(1.3)预聚体冷却至40℃，加入1.1g三乙胺中和30min；
(1.4)加入1g环氧树脂，70℃条件下反应1h左右；
(1.5)加入110ml去离子水，在3000r/min的高转速下乳化30min，最后向乳化好的乳液中缓慢滴加0.8g乙二胺(溶于10mL去离子水中)进行后扩链，制得人造革、合成革用水性自消光表处剂乳液。
实施例3
(1)制备人造革、合成革用水性自消光表处剂乳液，其中聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:1，环氧树脂添加量占聚氨酯预聚体总质量的2.5％。
(1.1)将聚碳酸酯二元醇和端羟丙基聚二甲基硅氧烷在110℃抽真空脱水干燥2h后备用。在装有搅拌器、回流冷凝管及温度计的三口烧瓶中，加入20g聚己二酸己二醇酯二醇、 8.4g端羟丙基聚二甲基硅氧烷、27.7g1，6-六亚甲基二异氰酸酯和两滴T-9，在80～90℃反应2h；聚碳酸酯二元醇的分子量为1000；
(1.2)降温至50℃再加入2.8g二羟甲基丙酸和5.3g1，4-丁二醇，在80℃左右反应3h；视黏度情况加入丙酮降黏。实验采用二正丁胺法测定剩余－NCO基团，当－NCO的实际剩余含量达到理论剩余量的92％～98％时，反应即可停止。二羟甲基丁酸使用前在真空干燥箱中50℃下干燥1h；
(1.3)预聚体冷却至40℃，加入2.1g三乙胺中和30min；
(1.4)加入1.6g环氧树脂，70℃条件下反应1h左右；
(1.5)加入110ml去离子水，在3000r/min的高转速下乳化30min，最后向乳化好的乳液中缓慢滴加1.7g乙二胺(溶于10mL去离子水中)进行后扩链，制得人造革、合成革用水性自消光表处剂乳液。
对实施例1～实施例3所得人造革、合成革用水性自消光表处剂为乳液状。其性能进行测试：
力学性能测试方法：按照国家标准GB/T16421-1996《塑料拉伸性能小试样试验方法》检测。稳定性测试：取2g人造革、合成革用水性自消光表处剂用离心机在3000rpm下离心15min。
光泽度测试：将10g人造革、合成革用水性自消光表处剂倒在聚四氟乙烯板上形成3cm ×3cm面积的乳液，先在室温下自干成膜，然后将膜板放在真空干燥箱里，在60℃下干燥24h，得到干燥的自消光胶膜；用光泽度仪测试所述自消光胶膜60度角光泽度。
耐刮擦性测试：在树脂中加入1％红色颜料，涂膜在皮革上，干燥后，将其固定在测试机上，磨棒上包上白布，对样品干摩擦20次(来回为一次)，测试后白布上的颜色进行色卡对比，级别越高，耐磨性越好。具体分级为：一级：掉色严重，二级：掉色，三级：轻微掉色，四
级：不掉色。
本发明实施例1～实施例3所得人造革、合成革用水性自消光表处剂测试性能如表1。
测试性能 实施例1 实施例2 实施例3
革表面光泽(60°) 0.6 0.4 0.7
耐刮擦 2级 3级 2级
触感 棉蜡感一般 棉蜡感稍丰富 棉蜡感一般
拉伸强度 18.25MPa 20.23MPa 19.05MPa
断裂伸长率 401.8％ 382.5％ 393.9％
乳液稳定性 略有沉淀 无明显沉淀 略有沉淀
以上可知，控制聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2时，所制备的人造革、合成革用水性自消光表处剂性能较优。所以以下实施案例是通过控制聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2时，改变环氧树脂添加量制备人造革、合成革用水性自消光表处剂，并对其性能进行测试。
实施例4
(1)制备人造革、合成革用水性自消光表处剂乳液，其中聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2，环氧树脂添加量占聚氨酯预聚体总质量的5％。
(1.1)将聚己二酸1，4-丁二醇酯二醇和端羟丙基聚二甲基硅氧烷在110℃抽真空脱水干燥2h后备用。在装有搅拌器、回流冷凝管及温度计的三口烧瓶中，加入20g聚己二酸1，4- 丁二醇酯二醇、16.8g端羟丙基聚二甲基硅氧烷、36.7g异佛尔酮二异氰酸酯和两滴T-9，在80～ 90℃反应2h；聚己二酸1，4-丁二醇酯二醇的分子量为2000；
(1.2)降温至50℃再加入3.7g二羟甲基丁酸和5g1，4-丁二醇，在80℃左右反应3h；视黏度情况加入丙酮降黏。实验采用二正丁胺法测定剩余－NCO基团，当－NCO的实际剩余含量达到理论剩余量的92％～98％时，反应即可停止。二羟甲基丁酸使用前在真空干燥箱中50℃下干燥1h；
(1.3)预聚体冷却至40℃，加入2.5g三乙胺中和30min；
(1.4)加入4.2g环氧树脂，70℃条件下反应1h左右；
(1.5)加入220ml去离子水，在3000r/min的高转速下乳化30min，最后向乳化好的乳液中均缓慢滴加1.8g乙二胺(溶于10mL去离子水中)进行后扩链，制得人造革、合成革用水性自消光表处剂乳液。
实施例5
(1)制备人造革、合成革用水性自消光表处剂乳液，其中聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2，环氧树脂添加量占聚氨酯预聚体总质量的7.5％。
(1.1)将聚碳酸酯二元醇和端羟丙基聚二甲基硅氧烷在110℃抽真空脱水干燥2h后备用。在装有搅拌器、回流冷凝管及温度计的三口烧瓶中，加入15g聚碳酸酯二元醇、25.2g端羟丙基聚二甲基硅氧烷、40g甲苯二异氰酸酯和两滴T-9，在80～90℃反应2h；聚碳酸酯二元醇的分子量为1000；
(1.2)降温至50℃再加入4.2g二羟甲基丙酸和9.6g1，4-丁二醇，在80℃左右反应3h；视黏度情况加入丙酮降黏。实验采用二正丁胺法测定剩余－NCO基团，当－NCO的实际剩余含量达到理论剩余量的92％～98％时，反应即可停止。二羟甲基丙酸使用前在真空干燥箱中50℃下干燥1h；
(1.3)预聚体冷却至40℃，加入1.3g三乙胺中和30min；
(1.4)加入7.4g环氧树脂，70℃条件下反应1h左右；
(1.5)加入150g去离子水，在3000r/min的高转速下乳化30min，最后向乳化好的乳液中均缓慢滴加2.5g乙二胺(溶于10mL去离子水中)进行后扩链，制得人造革、合成革用水性自消光表处剂乳液。
本发明实施例2、实施例4和实施例5所得人造革、合成革用水性自消光表处剂测试性能如表2。
测试性能 实施例2 实施例4 实施例5
革表面光泽(60°) 0.4 0.2 0.5
耐刮擦 3级 4级 3级
触感 棉蜡感稍丰富 棉蜡感丰富 棉蜡感稍丰富
拉伸强度 20.23MPa 24.56MPa 23.05MPa
断裂伸长率 382.5％ 365.2％ 378.1％
乳液稳定性 无明显沉淀 无明显沉淀 无明显沉淀
表2
综上可知，控制聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2，环氧树脂添加量占聚氨酯预聚体总质量的5％时，所制备的人造革、合成革用水性自消光表处剂性能最优。对比中国专利CN107722236A公布的一种合成革用有机硅改性自消光水性聚氨酯，其方法只是单纯利用有机硅改性其消光性能，其他性能并未得到有效改善，而该实施案例中不仅消光性能更好，且由于环氧树脂的引入，其力学性能和耐刮擦性均比较优异。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

1.一种人造或合成革用水性自消光表处剂，其特征在于，所述表处剂的组成包括多元醇、有机硅和环氧树脂。
2.根据权利要求1所述的表处剂，其特征在于，所述有机硅具体为端羟丙基聚二甲基硅氧烷。
3.一种权利要求2所述表处剂的制备方法，其特征在于，该方法包括一下步骤：
步骤1、将10g～20g聚合物多元醇、14.4g～43.1g多异氰酸酯和8.4g～25.2g端羟丙基聚二甲基硅氧烷在加入催化剂下，80℃～90℃条件下反应2h；
步骤2、将步骤1所得产物降温至50℃后，加入1.6g～4.2g亲水扩链剂和2.6g～9.6g小分子扩链剂，在80℃下继续反应3h，用丙酮调节反应体系的粘度，防止凝胶的生成；
步骤3、将步骤2获得的产物冷却至40℃，加入1.1g～2.5g中和剂中和30min；
步骤4、步骤3的产物中加入1g～7.4g环氧树脂，在70℃反应1h；
步骤5、步骤4的产物中加入去离子水，在3000r/min的高转速下乳化30min；
步骤6、向步骤5的产物中缓慢滴加0.8g～2.5g的乙二胺进行后扩链，得到人造革、合成革用水性自消光表处剂乳液。
4.根据权利要求3所述的方法，其特征在于，所述多异氰酸酯为甲苯二异氰酸酯、1，6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)、环己烷-1，4-二异氰酸酯、4，4-二环己基甲烷二异氰酸酯、4，4-二苯基甲烷二异氰酸酯中的至少一种。
5.根据权利要求4所述的方法，其特征在于，所述聚多元醇的分子量为1000-2000；所述聚多元醇为聚四亚甲基醚二醇、聚四氢呋喃醚二醇、聚氧化丙烯二醇、聚己二酸1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇、聚碳酸酯二元醇中的至少一种。
6.根据权利要求5所述的方法，其特征在于，所述催化剂为辛酸亚锡。
7.根据权利要求6所述的方法，其特征在于，所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、2-[(2-氨乙基)氨基]磺酸钠中的至少一种。
8.根据权利要求7所述的方法，其特征在于，所述小分子扩链剂为1,4-丁二醇。
9.根据权利要求8所述的方法，其特征在于，所述中和剂为三乙胺。
10.根据权利要求3-9任一所述的方法，其特征在于，所述聚多元醇和端羟丙基聚二甲基硅氧烷使用前在120℃下抽真空脱水2h，亲水扩链剂使用前在真空干燥箱中50℃下干燥1h，且所述聚多元醇和端羟丙基聚二甲基硅氧烷摩尔比为1:2。
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CN114644879A (zh) * 2022-03-10 2022-06-21 吉林大学 一种抗空蚀、防污、防腐多功能涂料及涂层
CN115058176A (zh) * 2022-05-31 2022-09-16 广东粤港澳大湾区黄埔材料研究院 一种环氧改性自消光水性聚氨酯乳液及其制备方法

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唐慧等: "环氧树脂改性含硅自消光水性聚氨酯树脂的制备及性能", 《精细化工》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114644879A (zh) * 2022-03-10 2022-06-21 吉林大学 一种抗空蚀、防污、防腐多功能涂料及涂层
CN115058176A (zh) * 2022-05-31 2022-09-16 广东粤港澳大湾区黄埔材料研究院 一种环氧改性自消光水性聚氨酯乳液及其制备方法

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