CN106867384A - 一种适用于合成革的水性抗撕裂助剂 - Google Patents
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Abstract
本发明公开了一种适用于合成革的水性抗撕裂助剂,涉及合成革功能助剂技术领域,由如下重量份数的原料制成:50wt%聚四氟乙烯乳液15‑20份、水解聚马来酸酐3‑5份、聚乙烯醇树脂3‑5份、纳米陶瓷胶粉2‑3份、活性白土2‑3份、海泡石纤维1‑2份、聚氧化乙烯1‑2份、石棉绒0.5‑1份、聚合氯化铝0.5‑1份、分子筛原粉0.5‑1份、硫化猪油0.3‑0.5份、纳米氧化锌0.05‑0.2份、水50‑100份。本发明抗撕裂助剂添加于水性聚氨酯浆料后,能在保证合成革原有柔软度的基础上有效提高所制合成革的抗撕裂性能,增强合成革的使用质量,从而延长合成革的使用寿命。
Description
技术领域:
本发明涉及合成革功能助剂技术领域,具体涉及一种适用于合成革的水性抗撕裂助剂。
背景技术:
合成革,模拟天然革的组成和结构并可作为其代用材料的塑料制品。通常以经浸渍的无纺布为网状层,微孔聚氨酯层作为粒面层制得。其正、反面都与皮革十分相似,并具有一定的透气性,比普通人造革更接近天然革,广泛用于制作鞋、靴、箱包和球类等。
功能助剂是提高合成革使用质量、保证使用寿命的功能性添加剂。抗撕裂助剂属于合成革的主要功能助剂之一,以增强合成革的抗撕裂性。目前,常用抗撕裂助剂通常由高分子材料组成,与合成革制备浆料的相容性差,因此难以发挥其本身具有的优异抗撕裂性能。针对这一问题,亟需开发新型合成革加工用抗撕裂助剂。
发明内容:
本发明所要解决的技术问题在于提供一种通过提高使用安全性、增强与合成革制备浆料共混相容性以发挥优异抗撕裂性能的适用于合成革的水性抗撕裂助剂。
本发明所要解决的技术问题采用以下的技术方案来实现:
一种适用于合成革的水性抗撕裂助剂,由如下重量份数的原料制成:
50wt%聚四氟乙烯乳液15-20份、水解聚马来酸酐3-5份、聚乙烯醇树脂3-5份、纳米陶瓷胶粉2-3份、活性白土2-3份、海泡石纤维1-2份、聚氧化乙烯1-2份、石棉绒0.5-1份、聚合氯化铝0.5-1份、分子筛原粉0.5-1份、硫化猪油0.3-0.5份、纳米氧化锌0.05-0.2份、水50-100份。
其制备方法包括如下步骤:
(1)向水中加入聚乙烯醇树脂和聚氧化乙烯,并以5℃/min的升温速度升温至回流状态保温混合10-15min,再加入硫化猪油和纳米氧化锌,继续回流保温混合10-15min,然后自然冷却至室温,即得物料I;
(2)向纳米陶瓷胶粉中加入活性白土和海泡石纤维,并以5℃/min的升温速度升温至75-80℃保温混合10-15min,再加入石棉绒和分子筛原粉,继续以5℃/min的升温速度升温至115-120℃保温混合5-10min,然后自然冷却至室温,即得物料II;
(3)向物料I中加入物料II、50wt%聚四氟乙烯乳液、水解聚马来酸酐和聚合氯化铝,并以5℃/min的升温速度升温至回流状态保温混合10-15min,然后自然冷却至室温,所得混合溶液送入球磨机中,经研磨后过200-300目筛。
所述50wt%聚四氟乙烯乳液由水溶性改性聚四氟乙烯加水制成,其具体制备方法为:向水中加入超细聚四氟乙烯粉末和乙烯基二茂铁,充分分散后静置15-30min,再加入聚乙烯醇缩丁醛和N-羟甲基丙烯酰胺,并以5℃/min的升温速度升温至回流状态保温混合0.5-1h,然后加入氢化蓖麻油和聚二甲基二烯丙基氯化铵,继续回流保温混合15-30min,待以5℃/min的降温速度降温至0-5℃后保温静置1-2h,再次以5℃/min的升温速度升温至回流状态保温混合10-15min,所得混合液送入球磨机中,8-12h后过100-200目筛,所得滤液经加热浓缩至固含量达到50%。
所述水、超细聚四氟乙烯粉末、乙烯基二茂铁、聚乙烯醇缩丁醛、N-羟甲基丙烯酰胺、氢化蓖麻油和聚二甲基二烯丙基氯化铵的质量比为50-100:15-20:0.1-0.2:3-5:0.5-1:0.3-0.5:0.05-0.1。
所述纳米陶瓷胶粉由如下重量份数的原料制成:氢化松香季戊四醇酯3-5份、陶瓷微粉3-5份、烯丙基缩水甘油醚2-3份、六羟甲基三聚氰胺六甲醚1-2份、C5加氢石油树脂1-2份、微晶蜡0.5-1份、松节油0.5-1份、马来酸酐接枝相容剂0.05-0.1份,其具体制备方法为:向氢化松香季戊四醇酯中加入烯丙基缩水甘油醚和C5加氢石油树脂,并以5℃/min的升温速度升温至115-120℃保温混合15-30min,再加入微晶蜡和马来酸酐接枝相容剂,继续在115-120℃保温混合15-30min,待以10℃/min的降温速度降温至50-60℃后加入陶瓷微粉、六羟甲基三聚氰胺六甲醚和松节油,充分混合,所得混合物转入-5-0℃环境中静置1-2h,最后送入纳米研磨机中,经充分研磨后制得粒径在30-50nm的纳米陶瓷胶粉。
本发明的有益效果是:本发明所制抗撕裂助剂以水作为稀释溶剂,大大提高使用安全性,并利于与水性聚氨酯浆料共混相容,且共混相容性好;该抗撕裂助剂添加于水性聚氨酯浆料后,能在保证合成革原有柔软度的基础上有效提高所制合成革的抗撕裂性能,增强合成革的使用质量,从而延长合成革的使用寿命。
具体实施方式:
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
实施例1
(1)向100份水中加入3份聚乙烯醇树脂和2份聚氧化乙烯,并以5℃/min的升温速度升温至回流状态保温混合10min,再加入0.5份硫化猪油和0.15份纳米氧化锌,继续回流保温混合15min,然后自然冷却至室温,即得物料I;
(2)向3份纳米陶瓷胶粉中加入2份活性白土和1份海泡石纤维,并以5℃/min的升温速度升温至75-80℃保温混合10min,再加入1份石棉绒和0.5份分子筛原粉,继续以5℃/min的升温速度升温至115-120℃保温混合10min,然后自然冷却至室温,即得物料II;
(3)向物料I中加入物料II、20份50wt%聚四氟乙烯乳液、5份水解聚马来酸酐和0.5份聚合氯化铝,并以5℃/min的升温速度升温至回流状态保温混合15min,然后自然冷却至室温,所得混合溶液送入球磨机中,经研磨后过300目筛。
50wt%聚四氟乙烯乳液的制备:向100份水中加入20份超细聚四氟乙烯粉末和0.15份乙烯基二茂铁,充分分散后静置30min,再加入3份聚乙烯醇缩丁醛和0.5份N-羟甲基丙烯酰胺,并以5℃/min的升温速度升温至回流状态保温混合1h,然后加入0.3份氢化蓖麻油和0.1份聚二甲基二烯丙基氯化铵,继续回流保温混合15min,待以5℃/min的降温速度降温至0-5℃后保温静置1h,再次以5℃/min的升温速度升温至回流状态保温混合10min,所得混合液送入球磨机中,8h后过200目筛,所得滤液经加热浓缩至固含量达到50%。
纳米陶瓷胶粉的制备:向5份氢化松香季戊四醇酯中加入2份烯丙基缩水甘油醚和1份C5加氢石油树脂,并以5℃/min的升温速度升温至115-120℃保温混合30min,再加入1份微晶蜡和0.05份马来酸酐接枝相容剂,继续在115-120℃保温混合15min,待以10℃/min的降温速度降温至50-60℃后加入5份陶瓷微粉、1份六羟甲基三聚氰胺六甲醚和0.5份松节油,充分混合,所得混合物转入-5-0℃环境中静置2h,最后送入纳米研磨机中,经充分研磨后制得粒径在30-50nm的纳米陶瓷胶粉。
实施例2
(1)向100份水中加入5份聚乙烯醇树脂和1份聚氧化乙烯,并以5℃/min的升温速度升温至回流状态保温混合10min,再加入0.3份硫化猪油和0.1份纳米氧化锌,继续回流保温混合15min,然后自然冷却至室温,即得物料I;
(2)向2份纳米陶瓷胶粉中加入2份活性白土和1份海泡石纤维,并以5℃/min的升温速度升温至75-80℃保温混合10min,再加入0.5份石棉绒和0.5份分子筛原粉,继续以5℃/min的升温速度升温至115-120℃保温混合10min,然后自然冷却至室温,即得物料II;
(3)向物料I中加入物料II、20份50wt%聚四氟乙烯乳液、3份水解聚马来酸酐和0.5份聚合氯化铝,并以5℃/min的升温速度升温至回流状态保温混合15min,然后自然冷却至室温,所得混合溶液送入球磨机中,经研磨后过300目筛。
50wt%聚四氟乙烯乳液的制备:向100份水中加入20份超细聚四氟乙烯粉末和0.2份乙烯基二茂铁,充分分散后静置30min,再加入5份聚乙烯醇缩丁醛和0.5份N-羟甲基丙烯酰胺,并以5℃/min的升温速度升温至回流状态保温混合1h,然后加入0.5份氢化蓖麻油和0.05份聚二甲基二烯丙基氯化铵,继续回流保温混合15min,待以5℃/min的降温速度降温至0-5℃后保温静置1h,再次以5℃/min的升温速度升温至回流状态保温混合10min,所得混合液送入球磨机中,8h后过200目筛,所得滤液经加热浓缩至固含量达到50%。
纳米陶瓷胶粉的制备:向3份氢化松香季戊四醇酯中加入2份烯丙基缩水甘油醚和2份C5加氢石油树脂,并以5℃/min的升温速度升温至115-120℃保温混合30min,再加入0.5份微晶蜡和0.05份马来酸酐接枝相容剂,继续在115-120℃保温混合15min,待以10℃/min的降温速度降温至50-60℃后加入5份陶瓷微粉、1份六羟甲基三聚氰胺六甲醚和0.5份松节油,充分混合,所得混合物转入-5-0℃环境中静置2h,最后送入纳米研磨机中,经充分研磨后制得粒径在30-50nm的纳米陶瓷胶粉。
实施例3
(1)向100份水中加入5份聚乙烯醇树脂和1份聚氧化乙烯,并以5℃/min的升温速度升温至回流状态保温混合10min,再加入0.3份硫化猪油和0.1份纳米氧化锌,继续回流保温混合15min,然后自然冷却至室温,即得物料I;
(2)向2份纳米陶瓷粉中加入2份活性白土和1份海泡石纤维,并以5℃/min的升温速度升温至75-80℃保温混合10min,再加入0.5份石棉绒和0.5份分子筛原粉,继续以5℃/min的升温速度升温至115-120℃保温混合10min,然后自然冷却至室温,即得物料II;
(3)向物料I中加入物料II、20份50wt%聚四氟乙烯乳液、3份水解聚马来酸酐和0.5份聚合氯化铝,并以5℃/min的升温速度升温至回流状态保温混合15min,然后自然冷却至室温,所得混合溶液送入球磨机中,经研磨后过300目筛。
50wt%聚四氟乙烯乳液的制备:向100份水中加入20份超细聚四氟乙烯粉末和0.2份乙烯基二茂铁,充分分散后静置30min,再加入5份聚乙烯醇缩丁醛和0.5份N-羟甲基丙烯酰胺,并以5℃/min的升温速度升温至回流状态保温混合1h,然后加入0.5份氢化蓖麻油和0.05份聚二甲基二烯丙基氯化铵,继续回流保温混合15min,待以5℃/min的降温速度降温至0-5℃后保温静置1h,再次以5℃/min的升温速度升温至回流状态保温混合10min,所得混合液送入球磨机中,8h后过200目筛,所得滤液经加热浓缩至固含量达到50%。
实施例4
将等量实施例1、实施例2和实施例3所制抗撕裂助剂添加到等量水性聚氨酯浆料(如表1)中,并设置不添加抗撕裂助剂的对照例,经相同加工工艺制得PU合成革,再对合成革的抗撕裂性能进行测定,结果如表2所示。
表1水性聚氨酯浆料配方
原料 | 实施例1 | 实施例2 | 实施例3 | 对照例 |
水性聚氨酯乳液/kg | 55 | 55 | 55 | 55 |
填充剂/kg | 5 | 5 | 5 | 5 |
增稠剂/kg | 3 | 3 | 3 | 3 |
水性色浆/kg | 3 | 3 | 3 | 3 |
柔软剂/kg | 2 | 2 | 2 | 2 |
渗透剂/kg | 1.5 | 1.5 | 1.5 | 1.5 |
流平剂/kg | 0.5 | 0.5 | 0.5 | 0.5 |
抗撕裂助剂/kg | 0.5 | 0.5 | 0.5 | 0 |
表2利用本发明所制抗撕裂助剂的合成革抗撕裂性能
测试项目 | 实施例1 | 实施例2 | 实施例3 | 对照例 |
经向撕裂负荷/N | 28 | 30 | 22 | 15 |
纬向撕裂负荷/N | 23 | 21 | 17 | 12 |
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种适用于合成革的水性抗撕裂助剂,其特征在于,由如下重量份数的原料制成:
50wt%聚四氟乙烯乳液15-20份、水解聚马来酸酐3-5份、聚乙烯醇树脂3-5份、纳米陶瓷胶粉2-3份、活性白土2-3份、海泡石纤维1-2份、聚氧化乙烯1-2份、石棉绒0.5-1份、聚合氯化铝0.5-1份、分子筛原粉0.5-1份、硫化猪油0.3-0.5份、纳米氧化锌0.05-0.2份、水50-100份。
2.根据权利要求1所述的适用于合成革的水性抗撕裂助剂,其特征在于,其制备方法包括如下步骤:
(1)向水中加入聚乙烯醇树脂和聚氧化乙烯,并以5℃/min的升温速度升温至回流状态保温混合10-15min,再加入硫化猪油和纳米氧化锌,继续回流保温混合10-15min,然后自然冷却至室温,即得物料I;
(2)向纳米陶瓷胶粉中加入活性白土和海泡石纤维,并以5℃/min的升温速度升温至75-80℃保温混合10-15min,再加入石棉绒和分子筛原粉,继续以5℃/min的升温速度升温至115-120℃保温混合5-10min,然后自然冷却至室温,即得物料II;
(3)向物料I中加入物料II、50wt%聚四氟乙烯乳液、水解聚马来酸酐和聚合氯化铝,并以5℃/min的升温速度升温至回流状态保温混合10-15min,然后自然冷却至室温,所得混合溶液送入球磨机中,经研磨后过200-300目筛。
3.根据权利要求1或2所述的适用于合成革的水性抗撕裂助剂,其特征在于:所述50wt%聚四氟乙烯乳液由水溶性改性聚四氟乙烯加水制成,其具体制备方法为:向水中加入超细聚四氟乙烯粉末和乙烯基二茂铁,充分分散后静置15-30min,再加入聚乙烯醇缩丁醛和N-羟甲基丙烯酰胺,并以5℃/min的升温速度升温至回流状态保温混合0.5-1h,然后加入氢化蓖麻油和聚二甲基二烯丙基氯化铵,继续回流保温混合15-30min,待以5℃/min的降温速度降温至0-5℃后保温静置1-2h,再次以5℃/min的升温速度升温至回流状态保温混合10-15min,所得混合液送入球磨机中,8-12h后过100-200目筛,所得滤液经加热浓缩至固含量达到50%。
4.根据权利要求3所述的适用于合成革的水性抗撕裂助剂,其特征在于:所述水、超细聚四氟乙烯粉末、乙烯基二茂铁、聚乙烯醇缩丁醛、N-羟甲基丙烯酰胺、氢化蓖麻油和聚二甲基二烯丙基氯化铵的质量比为50-100:15-20:0.1-0.2:3-5:0.5-1:0.3-0.5:0.05-0.1。
5.根据权利要求1所述的适用于合成革的水性抗撕裂助剂,其特征在于:所述纳米陶瓷胶粉由如下重量份数的原料制成:氢化松香季戊四醇酯3-5份、陶瓷微粉3-5份、烯丙基缩水甘油醚2-3份、六羟甲基三聚氰胺六甲醚1-2份、C5加氢石油树脂1-2份、微晶蜡0.5-1份、松节油0.5-1份、马来酸酐接枝相容剂0.05-0.1份,其具体制备方法为:向氢化松香季戊四醇酯中加入烯丙基缩水甘油醚和C5加氢石油树脂,并以5℃/min的升温速度升温至115-120℃保温混合15-30min,再加入微晶蜡和马来酸酐接枝相容剂,继续在115-120℃保温混合15-30min,待以10℃/min的降温速度降温至50-60℃后加入陶瓷微粉、六羟甲基三聚氰胺六甲醚和松节油,充分混合,所得混合物转入-5-0℃环境中静置1-2h,最后送入纳米研磨机中,经充分研磨后制得粒径在30-50nm的纳米陶瓷胶粉。
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