CN113549190A - 一种用于制备超纤革的聚氨酯底料 - Google Patents

一种用于制备超纤革的聚氨酯底料 Download PDF

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CN113549190A
CN113549190A CN202110903172.XA CN202110903172A CN113549190A CN 113549190 A CN113549190 A CN 113549190A CN 202110903172 A CN202110903172 A CN 202110903172A CN 113549190 A CN113549190 A CN 113549190A
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徐斌
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Abstract

本案涉及一种用于制备超纤革的聚氨酯底料，是由如下重量份的原料制成：400～500份多元醇、110～150份异氰酸酯、15～30份扩链剂、0.1～0.7份抗氧剂、0.001～0.002份阻聚剂磷酸、10～20份改性纳米粉体、500～800份N,N‑二甲基甲酰胺；其中，所述多元醇为聚酯多元醇和聚醚多元醇1:1的混合物。本发明通过在聚氨酯合成中添加自制的二醇以及改性纳米粉体，制得的聚氨酯树脂用于制备合成革时无需再添加其它助剂，即可与染色分子TiO2的粘结力强，遮盖力好。具有较高的拉伸强度和抗撕裂强度，同时满足了成革后不起皱且弯折无明显折痕的特点，可用于加工时下流行的小白鞋。

Description

一种用于制备超纤革的聚氨酯底料
技术领域
本发明属于合成革用树脂技术领域，具体涉及一种用于制备超纤革的聚氨酯底料。
背景技术
随着近年来皮革市场需求逐渐增长，国内现有产量与国内外市场需求之间存在的缺口将进一步扩大。在合成革应用过程中超纤可以替代聚氨酯湿法贝斯，用于制备鞋革、服装革、沙发革及握把革等。用超纤革用底料将超纤贝斯与干法面料结合制备得到的超纤革，其物性能够媲美于天然皮革。
超纤小白鞋一直风靡合成革市场，其具有良好的透气透湿性能、肉感强、风格种类多样及媲美于天然皮革等物性受到消费者广泛的喜爱。不同于其它用途的超纤革产品，超纤小白鞋对超纤革的物性要求非常高，即需要其具有较细的折痕、形状记忆性、高的粘结力与能与白色片有很好的相容性。这些性能中超纤底料染白色尤其重要，即需要白色片能够完全遮盖超纤贝斯的底色。通常超纤革染色是通过将干法面料染色，底料为清料，再与超纤贝斯贴合。这种染色方法对于干法面料的要求很高，即干法面料中通常加入诸如展色剂、流平剂、防浮色助剂、耐磨耐刮助剂等，如果此时再向其中加入色片，很容易导致不同批次干法面料呈现出展色的差异。由于超纤面料中加入多种助剂，这些助剂种类及添加量都会对最终超纤革的展色产生影响，这对超纤革的展色稳定性带来了挑战。而超纤底料在制备过程中并不添加过多的助剂，如果将色片加入超纤底料中对超纤革进行染色，做出的超纤革批次间展色差异则可忽略不计。因此，开发一种细折痕、形状记忆性佳、粘结力强及对于白色片(TiO2)遮盖力好的超纤小白鞋用聚氨酯底料是非常必要的。
发明内容
针对现有技术中的不足之处，本发明提供一种聚氨酯底料，其具有细折痕、形状记忆性能、粘结力强及对白色片TiO2的染色性能好等特性，将其用于超纤小白鞋中，能满足其对手感、物性及遮盖力的要求。
为实现上述目的，本发明提供如下技术方案：
一种用于制备超纤革的聚氨酯底料，是由如下重量份的原料制成：
Figure BDA0003200534050000021
其中，所述多元醇为聚酯多元醇和聚醚多元醇1:1的混合物；所述扩链剂为
Figure BDA0003200534050000022
进一步地，所述聚酯多元醇为PMA-2000、PBA-2000、PEA-2000中的一种或多种。
进一步地，所述聚醚多元醇为PPG-2000、PEG-2000及PTMG-2000中的一种或多种。
进一步地，所述异氰酸酯为六亚甲基二异氰酸酯、萘二异氰酸酯、4,4-二苯基甲烷二异氰酸酯及异佛尔酮二异氰酸酯中的一种或多种。
进一步地，所述抗氧剂为BHT或1010。
进一步地，所述改性纳米粉体为改性纳米氧化铝、改性纳米氧化锌、改性纳米氧化硅、改性纳米蒙脱土、改性纳米高岭土中的一种。
进一步地，所述改性纳米粉体为改性纳米高岭土，制备方法为：将纳米级淀粉加水糊化，然后维持温度在60℃，氮气氛围下，加入油酸和甲基丙烯酸三氟乙酯，同时加入一定量的0.1mol/L硝酸铈铵水溶液，搅拌反应3～4h；降温，向反应体系中加入一定量的纳米高岭土和尿素，超声处理1h，随后在室温下继续搅拌3～4h，离心分离去除溶液，产物烘干即得改性纳米高岭土。
进一步地，所述纳米级淀粉、油酸、甲基丙烯酸三氟乙酯的质量比为1:0.2:0.5～1，所述硝酸铈铵水溶液中硝酸铈铵的质量为甲基丙烯酸三氟乙酯2～4％。
进一步地，所述纳米高岭土和尿素的质量是所述纳米级淀粉的150～250％、70～100％。
相比于现有技术，本发明的有益效果是：本发明通过在聚氨酯合成中添加自制的二醇以及改性纳米粉体，制得的聚氨酯树脂用于制备合成革时无需再添加其它助剂，即可与染色分子TiO2的粘结力强，遮盖力好。具有较高的拉伸强度和抗撕裂强度，同时满足了成革后不起皱且弯折无明显折痕的特点，可用于加工时下流行的小白鞋。
具体实施方式
下面将结合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。
此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
本案提供一种用于制备超纤革的聚氨酯底料，是由如下重量份的原料制成：
400～500份多元醇、110～150份异氰酸酯、15～30份扩链剂、0.1～0.7份抗氧剂、0.001～0.002份阻聚剂磷酸、10～20份改性纳米粉体和500～800份N,N-二甲基甲酰(DMF)。
其中，所述多元醇为聚酯多元醇和聚醚多元醇1:1的混合物；所述扩链剂的合成方程式如下：
Figure BDA0003200534050000041
打磨镁条，剪碎成细屑，取1当量的镁屑加入反应瓶中，向瓶中通入氮气，随后在氮气氛围下加入适量溶剂THF；称取1当量氯甲基环己烷，将其中四分之一直接加入到反应瓶中，另外四分之三溶于适量THF后置于恒压滴液漏斗中，向反应瓶中加入一小粒碘，控制恒压滴液漏斗的滴加速度，滴加完成后反应3～4h，得到格式试剂；
在反应瓶中加入四氯化硅和THF，通入氮气20min，加入催化量的氰化亚铜，加热至60℃，将得到的格式试剂加入到反应瓶中，维持温度，搅拌反应4～5h，加入大量石油醚搅拌后过滤，滤液常压蒸馏提纯得到产物Ⅰ；
将产物Ⅰ和2当量的正丙醇胺加入到乙腈(MeCN)溶剂中，加入1当量的三乙胺，在80℃下反应6h，反应完成后洗涤、烘干得产物Ⅱ即本案所用扩链剂。
聚氨酯(PU)通常由多元醇、异氰酸酯、扩链剂和溶剂制得，关于多元醇的种类极多，研究也甚广，相比较而言，扩链剂的种类就比较少了。聚氨酯制备过程中最常采用的扩链剂如乙二醇、1,4-丁二醇、1,6-己二醇等等，对于提升聚氨酯材料的耐折性、形状记忆性等的能力欠缺。本发明以硅为单体核心，引入到聚氨酯树脂中，并用于制成超纤革，可赋予其防污性能及优良的耐老化性。然后合成一种具有环己烷的二醇，由于环己烷空间位阻效应，使聚合物不易形成规整的结晶，降低了整体PU树脂的结晶性能，从而使得染色分子更易穿插其中，使PU树脂满足超纤革性能要求的同时，也提高了超纤革的染色性能。然而，空间位阻较大，也会导致拉伸强度和断裂伸长率的降低。但是通过丙基醇延长碳链长度可有效解决此问题，因为较长的分子链运动更加容易，更易形成氢键，分子内氢键作用力增强则使得拉伸强度随之升高；而以四氯硅烷为起点合成的单体，其分子规整度相对较高，相应的断裂伸长率也较高。
所述改性纳米粉体为改性纳米高岭土，制备方法为：将20g纳米级淀粉加200ml水糊化，然后维持温度在60℃，氮气氛围下，加入4g油酸和12g甲基丙烯酸三氟乙酯，同时加入7.3ml的0.1mol/L硝酸铈铵水溶液，搅拌反应3～4h；降温，向反应体系中加入30g纳米高岭土和18g尿素，超声处理1h，随后在室温下继续搅拌3～4h，离心分离去除溶液，产物烘干即得改性纳米高岭土。
纳米粉体可作为聚氨酯树脂中的填料，用于提高与染料结合力度，然而纳米粉体与聚氨酯的分散相容性通常较差，因此需要对其进行适当化学改性。纳米级的氧化铝、氧化锌、氧化硅、蒙脱土与高岭土均可进行化学改性用于提高聚氨酯的性能，其中高岭土存储量丰富，由氧化硅和氧化铝构成的层状结果，改性方法通常是采用插层剂。本发明以尿素作为插层剂结合超声的方法可有效提高插层率，超声体系中还添加有聚合物链改性的纳米级淀粉，淀粉富含羟基、环氧基等可进一步提高与染料分子的结合力，采用具有长碳链结构的油酸和甲基丙烯酸三氟甲酯共同与糊化淀粉反应，提高聚合物的接枝率；羧基和三氟甲基引入到聚氨酯链中，通过氢键作用力使其与聚氨酯链结合。带羧基的长侧链也有利于进入到高岭土层状结构之间，从而提高改性淀粉与高岭土的相容性，使得其在聚氨酯体系中的分散性大大提高，进一步提高聚氨酯材料的形状记忆性和粘结力。
实施例1
准确称取214g的聚醚多元醇PPG-2000，214g的聚酯多元醇PEA-2000投入2000mL三口玻璃反应瓶中，再分别向瓶中加入0.001g阻聚剂磷酸、0.2g抗氧剂1010、23.5g扩链剂与500g溶剂DMF，将其充分搅拌均匀后再加入148.2g 4,4-二苯基甲烷二异氰酸酯(MDI)(R值为1)，再升温至75～80℃，使树脂反应增粘。随着粘度的增加，不断向反应瓶中加入溶剂DMF稀释，反应过程中补加少量MDI。树脂增粘反应结束后，使用甲醇对其进行终止，甲醇终止1小时后，加入11.5g改性纳米高岭土，继续搅拌1～2h，包料。最终所得树脂的粘度在20～24万cps，固含量为50％。
超纤革的制备方法如下：称取100g合成的聚氨酯底料，再向其中加入1g白色片TiO2与50g溶剂DMF，分散均匀后真空脱泡待用。称取100g干法面料，加入80g溶剂DMF，分散均匀后真空脱泡待用。将配好的干法面料涂于离型纸表面，置于110℃烘箱中完全干燥，再于其表面涂覆15mm后的真空脱泡后的聚氨酯底料，放110℃烘箱中烘120s，然后再将超纤贝斯贴于其上(半干贴)，压紧并放置在110℃烘箱中烘干。
实施例2：
准确称取220g的聚醚多元醇PEG-2000，220g的聚酯多元醇PBA-2000投入2000mL三口玻璃反应瓶中，再分别向瓶中加入0.001g阻聚剂磷酸、0.2g抗氧剂BHT、20g扩链剂与500g溶剂DMF，将其充分搅拌均匀后再加入120.7g MDI(R值为1)，再升温至75～80℃，使树脂反应增粘。随着粘度的增加，不断向反应瓶中加入溶剂DMF稀释，反应过程中补加少量MDI。树脂增粘反应结束后，使用甲醇对其进行终止，甲醇终止1小时后，加入12.5g改性纳米高岭土，冷却包料。最终所得树脂的粘度在20～24万(cps/℃)，固含量为50％。
本实施例的超纤革制备方法同实施例1。
实施例3：
准确称取225g的聚醚多元醇PTMG-2000，225g的聚酯多元醇PMA-2000投入2000mL三口玻璃反应瓶中，再分别向瓶中加入0.001g阻聚剂磷酸、0.2g抗氧剂BHT、21g扩链剂与500g溶剂DMF，将其充分搅拌均匀后再加入114.5g MDI(R值为1)，再升温至75～80℃，使树脂反应增粘。随着粘度的增加，不断向反应瓶中加入溶剂DMF稀释，反应过程中补加少量MDI。树脂增粘反应结束后，使用甲醇对其进行终止，甲醇终止1小时后，冷却包料。最终所得树脂的粘度在20～24万(cps/25℃)，固含量为50％。
本实施例的超纤革制备方法同实施例1。
对比例1：
同实施例1，区别在于将体系中的扩链剂替换成乙二醇。
对比例2
同实施例1，区别在于改性纳米粉体的制备为：将20g纳米级淀粉加200ml水糊化，加入30g纳米高岭土和18g尿素，超声处理1h，随后在室温下继续搅拌3～4h，离心分离去除溶液，产物烘干即得改性纳米高岭土。
通过表1示出的本发明各实施例提供的超纤革用聚氨酯底料与对比例相比具有优良的形状记忆性和染色性，断裂伸长率和拉伸强度较高，同时抗弯折，折痕较细不明显。
表1
Figure BDA0003200534050000071
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。

Claims (9)

1.一种用于制备超纤革的聚氨酯底料，其特征在于，是由如下重量份的原料制成：
Figure FDA0003200534040000011
其中，所述多元醇为聚酯多元醇和聚醚多元醇1:1的混合物；所述扩链剂为
Figure FDA0003200534040000012
2.如权利要求1所述的用于制备超纤革的聚氨酯底料，其特征在于，所述聚酯多元醇为PMA-2000、PBA-2000、PEA-2000中的一种或多种。
3.如权利要求1所述的用于制备超纤革的聚氨酯底料，其特征在于，所述聚醚多元醇为PPG-2000、PEG-2000及PTMG-2000中的一种或多种。
4.如权利要求1所述的用于制备超纤革的聚氨酯底料，其特征在于，所述异氰酸酯为六亚甲基二异氰酸酯、萘二异氰酸酯、4,4-二苯基甲烷二异氰酸酯及异佛尔酮二异氰酸酯中的一种或多种。
5.如权利要求1所述的用于制备超纤革的聚氨酯底料，其特征在于，所述抗氧剂为BHT或1010。
6.如权利要求1所述的用于制备超纤革的聚氨酯底料，其特征在于，所述改性纳米粉体为改性纳米氧化铝、改性纳米氧化锌、改性纳米氧化硅、改性纳米蒙脱土、改性纳米高岭土中的一种。
7.如权利要求6所述的用于制备超纤革的聚氨酯底料，其特征在于，所述改性纳米粉体为改性纳米高岭土，制备方法为：将纳米级淀粉加水糊化，然后维持温度在60℃，氮气氛围下，加入油酸和甲基丙烯酸三氟乙酯，同时加入一定量的0.1mol/L硝酸铈铵水溶液，搅拌反应3～4h；降温，向反应体系中加入一定量的纳米高岭土和尿素，超声处理1h，随后在室温下继续搅拌3～4h，离心分离去除溶液，产物烘干即得改性纳米高岭土。
8.如权利要求7所述的用于制备超纤革的聚氨酯底料，其特征在于，所述纳米级淀粉、油酸、甲基丙烯酸三氟乙酯的质量比为1:0.2:0.5～1，所述硝酸铈铵水溶液中硝酸铈铵的质量为甲基丙烯酸三氟乙酯2～4％。
9.如权利要求7所述的用于制备超纤革的聚氨酯底料，其特征在于，所述纳米高岭土和尿素的质量是所述纳米级淀粉的150～250％、70～100％。
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