CN107759759B - 一种合成革用封闭型无溶剂聚氨酯的制备方法及应用 - Google Patents

一种合成革用封闭型无溶剂聚氨酯的制备方法及应用 Download PDF

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CN107759759B
CN107759759B CN201711086990.5A CN201711086990A CN107759759B CN 107759759 B CN107759759 B CN 107759759B CN 201711086990 A CN201711086990 A CN 201711086990A CN 107759759 B CN107759759 B CN 107759759B
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马兴元
刘帅
张铭芮
赵昭
丁博
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Shaanxi University of Science and Technology
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Abstract

一种合成革用封闭型无溶剂聚氨酯的制备方法及应用，以摩尔份数计，首先，将真空脱水后的二元醇100～150份、甲乙酮肟10～20份、乙酰丙酮10～20份、丙二酸二乙酯10～20份混合均匀，再加入二异氰酸酯130～210份，搅拌混合均匀后，在70～90℃下反应60～120min，冷却后即可。本发明采用多种封闭剂同步聚合封闭的制备技术，可以得到粘度小于5000mPa·s的封闭型无溶剂聚氨酯，制备条件温和，清洁环保，使用这种封闭型无溶剂聚氨酯生产合成革，生产工艺简单稳定，可以消除传统合成革生产过程中的溶剂污染，同时具有节能高效的特点。

Description

一种合成革用封闭型无溶剂聚氨酯的制备方法及应用
技术领域
本发明涉及聚氨酯合成革技术领域，特别涉及一种合成革用封闭型无溶剂聚氨酯的制备方法及应用。
背景技术
聚氨酯合成革是模拟天然皮革的组织结构和使用性能，并可作为天然皮革代用品的复合材料。通常以无纺布模拟网状层，以发泡聚氨酯涂层模拟粒面层，所得到的合成革正、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皮革，广泛用于制作鞋、靴、箱包和球类等。
目前，聚氨酯合成革的生产采用溶剂型聚氨酯，在聚氨酯的制造和使用过程中都要用到大量的溶剂，如二甲基甲酰胺、甲苯和丁酮等，工过程会造成溶剂的污染。而且，会引起产品的DMF残留问题，最终造成产品安全问题。而这种产品安全问题，会限制产品进入高档市场。
为了解决聚氨酯合成革生产时的溶剂污染问题，目前主要采用水性聚氨酯或无溶剂聚氨酯替代溶剂型聚氨酯生产合成革。
发明内容
本发明的目的是提供一种合成革用封闭型无溶剂聚氨酯的制备方法和应用。
为达到上述目的，本发明采用的技术方案是：
一种合成革用封闭型无溶剂聚氨酯的制备方法，以摩尔份数计，首先，将真空脱水后的二元醇100～150份、甲乙酮肟10～20份、乙酰丙酮10～20份以及丙二酸二乙酯10～20份加入到带有氮气保护的反应器中，混合均匀，然后加入二异氰酸酯130～210份，搅拌混合均匀后，在70～90℃下反应60～120min，冷却后即得到合成革用封闭型无溶剂聚氨酯。
本发明进一步的改进在于，二元醇是聚醚二元醇、聚酯二元醇中的一种或两种。
本发明进一步的改进在于，二异氰酸酯是液体的具有两个-N＝C＝O官能团的异氰酸酯。
本发明进一步的改进在于，二异氰酸酯为甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种。
一种合成革用封闭型无溶剂聚氨酯在制备面层、发泡层和粘合层中的应用。
本发明进一步的改进在于，按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份混合均匀，采用刮涂法，涂布在离型纸上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即完全固化，形成面层。
本发明进一步的改进在于，按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份、发泡剂OBSH 1～2份混合均匀，采用刮涂法，涂布在面层上，控制涂布量为180～240g/m2，然后在130～160℃的条件下加热3～5min，即完全固化，形成发泡层。
本发明进一步的改进在于，按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆0～5份混合均匀，采用刮涂法，涂布在发泡层上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成粘合层。
与现有技术相比，本发明具有的有益效果：本发明采用多种封闭剂同步聚合封闭的制备技术，可以得到粘度小于5000mPa·s的封闭型无溶剂聚氨酯，制备条件温和，制备过程中和使用过程中都不使用任何溶剂，没有任何溶剂的污染问题，清洁环保。
使用本发明制备的封闭型无溶剂聚氨酯生产合成革，采用原有的溶剂型生产线，无需改造，即可生产环保型的合成革；在合成革的生产中，这种封闭型无溶剂聚氨酯可在不同的温度下，多种封闭剂依次解封，生产工艺稳定，操作简单，可以消除传统合成革生产过程中的溶剂污染，同时具有节能高效的特点。
具体实施方式
下面通过具体实施方式对本发明作进一步的详细说明，但本发明并不只限于这些例子。
一种合成革用封闭型无溶剂聚氨酯的制备方法，以摩尔份数计，首先，将真空脱水后的二元醇100～150份、甲乙酮肟10～20份、乙酰丙酮10～20份、丙二酸二乙酯10～20份加入到带有氮气保护的反应器中，混合均匀。然后，再加入二异氰酸酯130～210份，搅拌混合均匀后，在70～90℃的条件下反应60～120min，冷却后即可得到合成革用封闭型无溶剂聚氨酯。
采用的二元醇是聚醚二元醇或聚酯二元醇。也可以是一种二元醇或多种二元醇的混合物。
采用的二异氰酸酯组分是液体的具有两个-N＝C＝O官能团的异氰酸酯。如甲苯二异氰酸酯(TDI)、二苯基亚甲基二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)等。也可以是一种二异氰酸酯或多种二异氰酸酯的混合物。
由上述方法制得的合成革用封闭型无溶剂聚氨酯的应用方法：可作为聚氨酯合成革的面层树脂、发泡层树脂或粘合层树脂，控制一定的涂布量，然后在130～160℃的条件下加热3～5min，即可完全固化。具体应用方法如下：
封闭型无溶剂聚氨酯作为面层树脂使用时，按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份充分混合，采用刮涂法，刮涂在离型纸上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成面层。
封闭型无溶剂聚氨酯作为发泡层树脂使用时，按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份、发泡剂OBSH 1～2份充分混合，采用刮涂法，涂布在面层上，控制涂布量为180～240g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成发泡层。
封闭型无溶剂聚氨酯作为粘合层树脂使用时，按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆0～5份充分混合，采用刮涂法，涂布在发泡层上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成粘合层。
本发明采用多种封闭剂同步聚合封闭的制备技术，可以得到粘度小于5000mPa·s的封闭型无溶剂聚氨酯，制备条件温和，清洁环保，使用这种封闭型无溶剂聚氨酯生产合成革，生产工艺简单稳定，可以消除传统合成革生产过程中的溶剂污染，同时具有节能高效的特点。
实施例1
一种合成革用封闭型无溶剂聚氨酯的制备方法，以摩尔份数计，首先，将真空脱水后的二元醇100份、甲乙酮肟15份、乙酰丙酮20份以及丙二酸二乙酯10份加入到带有氮气保护的反应器中，混合均匀，然后加入二异氰酸酯210份，搅拌混合均匀后，在70℃下反应120min，冷却后即得到合成革用封闭型无溶剂聚氨酯。
其中，二元醇是聚醚二元醇。
二异氰酸酯为甲苯二异氰酸酯。
上述方法制得的合成革用封闭型无溶剂聚氨酯在制备面层中的应用：按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份混合均匀，采用刮涂法，涂布在离型纸上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即完全固化，形成面层。
实施例2
一种合成革用封闭型无溶剂聚氨酯的制备方法，以摩尔份数计，首先，将真空脱水后的二元醇120份、甲乙酮肟20份、乙酰丙酮10份以及丙二酸二乙酯15份加入到带有氮气保护的反应器中，混合均匀，然后加入二异氰酸酯130份，搅拌混合均匀后，在80℃下反应80min，冷却后即得到合成革用封闭型无溶剂聚氨酯。
其中，二元醇是聚酯二元醇。
二异氰酸酯为二苯基亚甲基二异氰酸酯。
上述方法制得的合成革用封闭型无溶剂聚氨酯在制备发泡层中的应用：按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份、发泡剂OBSH 1～2份混合均匀，采用刮涂法，涂布在面层上，控制涂布量为180～240g/m2，然后在130～160℃的条件下加热3～5min，即完全固化，形成发泡层。
实施例3
一种合成革用封闭型无溶剂聚氨酯的制备方法，以摩尔份数计，首先，将真空脱水后的二元醇130份、甲乙酮肟10份、乙酰丙酮13份以及丙二酸二乙酯18份加入到带有氮气保护的反应器中，混合均匀，然后加入二异氰酸酯160份，搅拌混合均匀后，在90℃下反应60min，冷却后即得到合成革用封闭型无溶剂聚氨酯。
其中，二元醇是聚醚二元醇与聚酯二元醇的混合物。
二异氰酸酯为二苯基亚甲基二异氰酸酯与异佛尔酮二异氰酸酯的混合物。
上述方法制得的合成革用封闭型无溶剂聚氨酯在制备粘合层中的应用：按质量份数计，将封闭型无溶剂聚氨酯100～120份，采用刮涂法，涂布在发泡层上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成粘合层。
实施例4
一种合成革用封闭型无溶剂聚氨酯的制备方法，以摩尔份数计，首先，将真空脱水后的二元醇150份、甲乙酮肟17份、乙酰丙酮18份以及丙二酸二乙酯20份加入到带有氮气保护的反应器中，混合均匀，然后加入二异氰酸酯180份，搅拌混合均匀后，在75℃下反应100min，冷却后即得到合成革用封闭型无溶剂聚氨酯。
其中，二元醇是聚酯二元醇。
二异氰酸酯为甲苯二异氰酸酯与二苯基亚甲基二异氰酸酯的混合物。
上述方法制得的合成革用封闭型无溶剂聚氨酯在制备粘合层中的应用：按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份混合均匀，采用刮涂法，涂布在发泡层上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成粘合层。

Claims (2)

1.一种合成革用封闭型无溶剂聚氨酯的制备方法，其特征在于：以摩尔份数计，首先，将真空脱水后的二元醇100～150份、甲乙酮肟10～20份、乙酰丙酮10～20份以及丙二酸二乙酯10～20份加入到带有氮气保护的反应器中，混合均匀，然后加入二异氰酸酯130～210份，搅拌混合均匀后，在70～90℃下反应60～120min，冷却后得到粘度小于5000mPa·s的合成革用封闭型无溶剂聚氨酯；其中，二元醇是聚醚二元醇、聚酯二元醇中的一种或两种；二异氰酸酯是液体的具有两个-N＝C＝O官能团的异氰酸酯；二异氰酸酯为甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或多种。
2.一种如权利要求1所述方法制得的合成革用封闭型无溶剂聚氨酯在制备面层、发泡层和粘合层中的应用；
按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份混合均匀，采用刮涂法，涂布在离型纸上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即完全固化，形成面层；
按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆1～5份、发泡剂OBSH 1～2份混合均匀，采用刮涂法，涂布在面层上，控制涂布量为180～240g/m2，然后在130～160℃的条件下加热3～5min，即完全固化，形成发泡层；
按质量份数计，将封闭型无溶剂聚氨酯100～120份、色浆0～5份混合均匀，采用刮涂法，涂布在发泡层上，控制涂布量为120～150g/m2，然后在130～160℃的条件下加热3～5min，即可完全固化，形成粘合层。
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