CN111254719B - 一种聚氨酯合成革用无氟拨水剂及其制备方法 - Google Patents
一种聚氨酯合成革用无氟拨水剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚氨酯合成革用无氟拨水剂，按重量份计算，包括如下组分：39.5％‑70％的有效固形份A、29.5％‑60％的溶剂B和0.05‑0.5％的助剂C；所述有效固形份A为如下式1所示，式中，PMS为单羟基有机硅与异氰酸酯基反应生成的链段；PSI‑PU为双羟基有机硅、聚酯多元醇与二异氰酸酯反应生成的聚氨基甲酸酯链段，含有氨基甲酸酯重复单元2‑14个；F为3‑8个官能度的多元醇Y与异氰酸酯基反应生成的链段；m和n表示3‑8的整数，助剂C为不含有反应基团的改性有机硅。本发明还公开了其制备方法。本发明制备的拨水剂具有优异的拨水性能，少量添加于聚氨酯合成革中能明显提高聚氨酯合成革的耐水解性能。
Description
技术领域
本发明涉及一种无氟拨水剂及其制备方法，具体涉及一种聚氨酯合成革用无氟拨水剂及其制备方法。
背景技术
天然皮革优良的特性已被人们广泛用于生产日用品和工业品等领域，由于天然皮革资源的日益紧缺和人们环保意识的逐渐增强，以及随着工业技术的不断进步，性能优良的聚氨酯合成革成为取代天然皮革的最佳选择。目前，聚氨酯合成革在服装革、箱包革、鞋革上的应用特别广泛。但由于普通聚氨酯树脂中含有大量的易水解基团(如酯基)，在一定条件下容易水解，因而其耐水解性能较差。
一般在聚氨酯树脂中加入一定量的助剂来提高聚氨酯合成革制品的耐水解性能。这种助剂一般是有机氟类的化合物，因为含氟化合物的自由能低，具有难附着的特性，将其添加于聚氨酯合成革制品中，能起到很好的阻碍水分子对易水解基团的进攻，起到拨水效果，提高聚氨酯合成革制品的耐水解性能。但是有机氟化合物中的PFOS(全氟辛基磺酰化合物)和PFOA(全氟辛酸)等在环境中具有高持久性，在环境中聚集和人体与动物组织中积累，对人体健康和环境产生潜在的危险。
因此含有这类有害物质的助剂在全球很多国家遭到禁用，寻找可以替代的不含氟类表面活性剂成为行业亟待解决的首要问题。
有机硅类化合物的主链十分柔顺，其分子间的作用力比碳氢化合物要弱得多，因此比同分子量的碳氢化合物粘度低，表面张力弱，表面能小，成膜能力强。这种低表面张力和低表面能使它获得多方面应用：疏水、消泡、泡沫稳定、防粘、润滑等各项优异性能。因此可以使用有机硅类助剂代替氟系助剂来达到相似的拨水效果。
现有公开的发明当中的无氟拨水剂仅用作纺织品的后处理，市场上现有用在聚氨酯合成革上的无氟拨水剂具有稳定性不太好，效果不理想等诸多缺陷。
发明内容
为了克服现有技术的上述缺陷，本发明的目的之一在于提供一种聚氨酯合成革用无氟拨水剂。用于解决现有拨水剂的诸多不足之处。本发明的拨水剂能显著提高聚氨酯合成革的耐水解性能。
本发明的另一目的在于提供一种制备所述合成革用无氟拨水剂的方法。
为了实现本发明的目的之一，所采用的技术方案是：
一种聚氨酯合成革用无氟拨水剂，其中，所述拨水剂按重量份计算，包括如下组分：
39.5％-70％的有效固形份A；
29.5％-60％的溶剂B；
0.05-0.5％的助剂C；
其中，
所述有效固形份A为如下式1所示：
(PMS)m(PSI-PU)nF
式1
式中，PMS为单羟基有机硅与异氰酸酯基反应生成的链段；
PSI-PU为双羟基有机硅、聚酯多元醇与二异氰酸酯反应生成的聚氨基甲酸酯链段，含有氨基甲酸酯重复单元2-14个；
F为3-8个官能度的多元醇Y与异氰酸酯基反应生成的链段。m和n表示3-8的整数。
在本发明的一个优选实施例中，所述m和n为相等的整数。
在本发明的一个优选实施例中，所述溶剂B为有机溶剂。
在本发明的一个优选实施例中，所述助剂C为不含用反应性基团的改性有机硅。所述助剂C用来提高聚氨酯树脂浆料和泼水剂的相容性，有利于拨水剂在浆料中均匀分散。
在本发明的一个优选实施例中，所述单羟基有机硅为数均分子量300-1000g/mol，官能度为1的如式2所示的单羟基有机硅：
式2；
其中R1为-CH3或者-CH2CH3。
在本发明的一个优选实施例中，所述双羟基有机硅为单端双羟基有机硅或双端双羟基有机硅中的任意一种或多种。
在本发明的一个优选实施例中，所述的单端双羟基有机硅为如式3所示的分子量为300-4000g/mol的单端双羟基有机硅：
式3；
其中R2为-CH3或者-CH2CH3。
在本发明的一个优选实施例中，所述的双端双羟基有机硅为如式4所示的分子量为1000-3000g/mol的双端双羟基有机硅：
式4；
其中R3为-CH3或者-CH2CH3。
在本发明的一个优选实施例中，所述的聚酯多元醇为分子量为500-2000g/mol的聚碳酸酯二元醇或分子量为500-2000g/mol的聚己内酯二醇中的任意一种或者两种以上的混合。
在本发明的一个优选实施例中，所述二异氰酸酯为脂肪族二异氰酸酯、芳香族二异氰酸酯或芳香族二异氰酸酯的衍生物中的任意一种或两种以上的混合。
在本发明的一个优选实施例中，所述脂肪族二异氰酸酯为1,6-己二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)或甲基环己基二异氰酸酯(HTDI)中的任意一种或两种以上的混合。
在本发明的一个优选实施例中，所述芳香族二异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)或苯二亚甲基二异氰酸酯(XDI)，萘二异氰酸酯(NDI)中的任意一种或两种以上的混合。
在本发明的一个优选实施例中，所述芳香族二异氰酸酯的衍生物为是液化MDI或TDI二聚体中的任意一种或两种以上的混合。
在本发明的一个优选实施例中，所述的3-8个官能度的多元醇为三羟甲基丙烷、甘油、三羟甲基乙烷、1,2,6-己三醇、季戊四醇、木糖醇、甘露醇或蔗糖中的任意一种或两种以上的混合。
在本发明的一个优选实施例中，所述的溶剂B为甲苯、丁酮、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮中的任意一种或两种以上的混合。
为了实现本发明的目的之二，所采用的技术方案是：
一种聚氨酯合成革用无氟拨水剂的制备方法，包括以下步骤：
步骤1：
将N个所述双羟基有机硅和所述聚酯多元醇的混合物与(N+1)个所述二异氰酸酯混合，放入部分溶剂B中反应，反应到体系中的羟基完全反应，体系中NCO的重量百分比NCO％达到理论值后得所述预聚体聚氨基甲酸酯链段PSI-PU；
步骤2：将所述多元醇Y分批缓慢加入到步骤1的体系中，反应1-2小时后，测量体系中NCO的重量百分比NCO％达到理论值；
然后投入所述的的单羟基有机硅，反应终点用红外光谱测试仪测试无NCO基团的特征峰确定；
步骤3：
在所述步骤2的反应产物当中加入剩余溶剂B和助剂C搅拌均匀，至所需浓度得所述聚氨酯合成革用无氟拨水剂。
在本发明的一个优选实施例中，
所述步骤(1)中的N为：1-7；
所述步骤(1)中的双端基有机硅的重复单元数为：1-7；
所述步骤(1)中的聚酯多元醇的重复单元数为：0-3；
所述步骤(1)中的异氰酸酯是分批加入到反应体系中；
所述步骤(1)的反应温度控制在50-80℃。
在本发明的一个优选实施例中，
所述步骤(2)中预聚体PSI-PU和多元醇F的比例为3-8，是根据多元醇Y的特征基团数来确定；
所述步骤(2)的反应温度控制在40-60℃；
所述步骤(3)的助剂C加入量为0.05％-0.5％，优选为0.1-0.2％；
所述步骤(3)的所需浓度为40％-70％，优选为50％-70％。
本发明的有益效果在于：
(1)本发明制得的拨水剂具有显著的拨水效果，加入少量本发明的拨水剂于合成革中就能显著提高合成革的耐水解性能；
(2)本发明拨水剂的制备过程简单，成本低，易于工业化生产，具有良好的应用前景和经济效益；
(3)本发明制得的拨水剂使用方便，使用时可以直接加入制备合成革的聚氨酯树脂浆料中，搅拌均匀即可。
具体实施方式
下面结合具体实施例对本发明进一步详细说明。
实施例1
(1)将400g单端双羟基有机硅(1mol)、400g聚碳酸酯二元醇(0.4mol)和500g N,N-二甲基甲酰胺、500g甲苯投入到5L的四口反应瓶中，搅拌，于50-80℃的温度下分批加入278.4g甲苯二异氰酸酯(TDI)(1.6mol)反应，至NCO重量百分比达到0.81％，(2)然后以滴加的方式加入6.13g甘油，40-60℃反应1-2H，测量NCO的重量百分比达到0.40％后，投入100g的单羟基硅油(0.2mol)，反应终点用红外光谱仪检测无NCO基团特征峰确定。(3)再加入189.3g N,N-二甲基甲酰胺和4.75g改性有机硅油，搅拌均匀，得到聚氨酯合成革用无氟拨水剂1。
实施例2
(1)将800g双端双羟基有机硅(0.4mol)和200g聚己内酯二元醇(0.1mol)和500gN,N-二甲基甲酰胺和500g甲苯投入到5L的四口反应瓶中，搅拌，于50-80℃的温度下分批加入104.4g甲苯二异氰酸酯(TDI)(0.6mol)反应，至NCO重量百分比达到0.40％，(2)然后以滴加的方式加入3.07g甘油，40-60℃反应1-2H，测量NCO的重量百分比达到0.20％后，投入50g的单羟基硅油(0.1mol)，反应终点用红外光谱仪检测无NCO基团特征峰确定。(3)再加入162g N,N-二甲基甲酰胺和4.65g改性有机硅油，搅拌均匀，得到聚氨酯合成革用无氟拨水剂2。
实施例3
(1)将400g单端双羟基有机硅(1mol)和800g N,N-二甲基甲酰胺投入到5L的四口反应瓶中，搅拌，于50-80℃的温度下分批加入348g甲苯二异氰酸酯(TDI)(2mol)反应，至NCO重量百分比达到5.43％，(2)然后以滴加的方式加入44.67g三羟甲基丙烷，40-60℃反应1-2H，测量NCO的重量百分比达到2.64％后，投入500g的单羟基硅油(1mol)，反应终点用红外光谱仪检测无NCO基团特征峰确定。(3)再加入63g N,N-二甲基甲酰胺和2.16g改性有机硅油，搅拌均匀，得到聚氨酯合成革用无氟拨水剂3。
实施例4
(1)将400g单端双羟基有机硅(1mol)和1000g N,N-二甲基甲酰胺投入到5L的四口反应瓶中，搅拌，于50-80℃的温度下分批加入348g甲苯二异氰酸酯(TDI)(2mol)反应，至NCO重量百分比达到4.81％，(2)然后以滴加的方式加入30.67g甘油，40-60℃反应1-2H，测量NCO的重量百分比达到2.36％后，投入500g的单羟基硅油(1mol)，反应终点用红外光谱仪检测无NCO基团特征峰确定。(3)再加入283.5g N,N-二甲基甲酰胺和5.14g改性有机硅油，搅拌均匀，得到聚氨酯合成革用无氟拨水剂4。
实施例5
(1)将600g单端双羟基有机硅(1.5mol)和800g N,N-二甲基甲酰胺投入到5L的四口反应瓶中，搅拌，于50-80℃的温度下分批加入522g甲苯二异氰酸酯(TDI)(3mol)反应，至NCO重量百分比达到6.56％，(2)然后以滴加的方式加入46g甘油，40-60℃反应1-2H，测量NCO的重量百分比达到3.20％后，投入750g的单羟基硅油(1.5mol)，反应终点用红外光谱仪检测无NCO基团特征峰确定。(3)再加入24g N,N-二甲基甲酰胺和5.49g改性有机硅油，搅拌均匀，得到聚氨酯合成革用无氟拨水剂5。
使用本发明的拨水剂与进口的拨水剂A-750(韩国NURI公司)比较：
采用如下的两种方法对拨水剂的性能进行测试：
(1)取两份相同的聚氨酯树脂浆料制备合成革，制备时分别按照重量比为拨水剂/聚氨酯浆料＝0.5/100加入本发明的拨水剂和A-750，将制得的合成革产品取部分完全浸入10％氢氧化钠溶液，25℃，24小时，取出洗净，烘干，对比浸泡前后的合成革制品的剥离强度，测试损失率X：
X＝(1-浸泡后剥离强度/浸泡前剥离强度)×100％
实验做3个数据取平均值。X值大，表明树脂水解严重，拨水效果差。
(2)取两份相同的聚氨酯树脂浆料制备合成革，制备时分别按照重量比为拨水剂/聚氨酯树脂浆料＝0.5/100加入本发明的拨水剂和A-750，将制得的合成革裁取10cm*2cm的样条，将样条竖直放置，下部1cm浸入水中，水沿着样条向上润湿，纪录水线超出水面5cm所需的润湿时间，用t表示。浸润时间越长，表明拨水剂效果越好。测试结果如下表1所示：
表1
| 名称 | 损失率X(％) | 浸润时间t(min) |
| 拨水剂1 | 4.1 | 40 |
| 拨水剂2 | 4.0 | 41 |
| 拨水剂3 | 3.0 | 50 |
| 拨水剂4 | 3.4 | 45 |
| 拨水剂5 | 2.7 | 55 |
| A-750 | 5.0 | 30 |
从表1可以看出，实施例1-5制得的拨水剂的拨水效果都比进口的A-750(有效固形份70％左右)好。
因此，本发明所制得的拨水剂具有优异的拨水性能，加入本发明的拨水剂，使得聚氨酯合成革制品具有很好的耐水解性能。
以上所述仅为本发明的部分较佳实施例，对于本技术领域的技术人员来说，在不脱离本发明技术原理的情况下，还可以做出若干改进和变化，这些改进和变化也应视为本发明的涵盖范围。
Claims (6)
1.一种聚氨酯合成革用无氟拨水剂，其特征在于，所述拨水剂按重量份计算，包括如下组分：
39.5%-70%的有效固形份A；
29.5%-60%的溶剂B；
0.05-0.5%的助剂C；
其中，
所述有效固形份A为如下式1所示：
(PMS)m(PSI-PU)n F
式1
式1中，所述PMS为单羟基有机硅与异氰酸酯基反应生成的链段；
所述PSI-PU为由双羟基有机硅和聚酯多元醇组成混合物与二异氰酸酯反应生成的聚氨基甲酸酯链段，含有氨基甲酸酯重复单元2-14个；
F为3-8个官能度的多元醇Y与异氰酸酯基反应生成的链段；
所述m和n表示3-8的整数，所述m和n为相等的整数；
所述溶剂B为有机溶剂；所述助剂C为不含反应性基团的改性有机硅；所述单羟基有机硅为数均分子量300-1000g/mol，官能度为1的如式2所示的单羟基有机硅：
式2；
其中R1为-CH3或者-CH2CH3；
所述双羟基有机硅为单端双羟基有机硅或双端双羟基有机硅中的任意一种或多种；
所述的聚酯多元醇为分子量为500-2000g/mol的聚碳酸酯二元醇或分子量为500-2000g/mol的聚己内酯二醇中的任意一种或者两种以上的混合；
所述二异氰酸酯为脂肪族二异氰酸酯、芳香族二异氰酸酯或芳香族二异氰酸酯的衍生物中的任意一种或两种以上的混合。
2.如权利要求1所述的一种聚氨酯合成革用无氟拨水剂，其特征在于，所述的单端双羟基有机硅为如式3所示的分子量为300-4000g/mol的单端双羟基有机硅：
式3；
其中R2为-CH3或者-CH2CH3。
3.如权利要求1所述的一种聚氨酯合成革用无氟拨水剂，其特征在于，所述的双端双羟基有机硅为如式4所示的分子量为1000-3000g/mol的双端双羟基有机硅：
式4；
其中R3为-CH3或者-CH2CH3。
4.如权利要求1所述的一种聚氨酯合成革用无氟拨水剂，其特征在于，
所述脂肪族二异氰酸酯为1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯或甲基环己基二异氰酸酯中的任意一种或两种以上的混合；
所述芳香族二异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或苯二亚甲基二异氰酸酯，萘二异氰酸酯中的任意一种或两种以上的混合；
所述芳香族二异氰酸酯的衍生物为液化二苯基甲烷二异氰酸酯或甲苯二异氰酸酯二聚体中的任意一种或两种以上的混合。
5.如权利要求1所述的一种聚氨酯合成革用无氟拨水剂，其特征在于，所述的3-8个官能度的多元醇为三羟甲基丙烷、甘油、三羟甲基乙烷、1,2,6-己三醇、季戊四醇、木糖醇、甘露醇或蔗糖中的任意一种或两种以上的混合。
6.如权利要求1所述的一种聚氨酯合成革用无氟拨水剂，其特征在于，所述的溶剂B为甲苯、丁酮、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮中的任意一种或两种以上的混合。
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