CN111777738B - 一种植物油衍生物改性的两性聚氨酯复鞣剂及其制备方法 - Google Patents

一种植物油衍生物改性的两性聚氨酯复鞣剂及其制备方法 Download PDF

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CN111777738B
CN111777738B CN202010738291.XA CN202010738291A CN111777738B CN 111777738 B CN111777738 B CN 111777738B CN 202010738291 A CN202010738291 A CN 202010738291A CN 111777738 B CN111777738 B CN 111777738B
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王学川
蓝晓梅
刘新华
朱兴
韩庆鑫
王园园
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Abstract

发明本公开了一种植物油衍生物改性两性聚氨酯复鞣剂及其制备方法，首先将二异氰酸酯、聚四氢呋喃二醚醇和催化剂混合均匀进行预聚反应，升温后先后加入阴离子扩链剂2,2‑二羟甲基丙酸，阳离子扩链剂N‑甲基二乙醇胺，再将蓖麻油酸加入到体系中反应一定的时间后，降温进行中和，乳化，最后得到蓖麻油酸改性两性聚氨酯复鞣剂。本发明提供的蓖麻油酸改性的两性聚氨酯复鞣剂中同时含有阴、阳离子基团，可有效提高无铬鞣特别是有机无铬鞣制坯革或者毛皮对皮革化料的吸收率，进而改善无铬鞣皮革和毛皮的耐湿热稳定性、手感、撕裂强度等性能。

Description

一种植物油衍生物改性的两性聚氨酯复鞣剂及其制备方法
技术领域
本发明涉及皮革复鞣剂技术领域，具体涉及一种植物油衍生物改性的两性聚氨酯复鞣剂及其制备方法。
背景技术
目前，皮革行业中最常使用的铬鞣方法存在严重的污染问题。因此，研发无铬的生态皮革制造技术如非铬金属鞣制和非金属鞣制，是皮革行业未来的发展方向。但是，与铬鞣革纤维相比，非金属鞣革纤维呈强负电性，缺乏带正电的金属离子使其表面上离子化，因此会降低非金属鞣制皮革纤维与皮革的传统阴离子试剂的反应性。故而研究可提高非金属鞣制坯革等电点的皮革复鞣剂是现阶段研究人员的主要工作。目前，已有研究人员研发出用于皮革无铬鞣的非金属鞣剂，本发明研究的复鞣剂即为该鞣剂的配套复鞣剂。
聚氨酯本身可用于皮革复鞣，当其用于皮革和毛皮复鞣时多为单一的阴离子或阳离子性。而两性聚氨酯中不仅同时含有阴阳离子，还具有较强耐酸碱性，较好生物降解性，将其应用于皮革和毛皮复鞣工艺，可有效提高后续阴离子材料的结合率。
蓖麻油酸分子中含有羟基和双键，可作为扩链剂可用于聚氨酯的合成。将蓖麻油酸引入聚氨酯不仅可以提高天然可再生资源的利用率，还可对皮革和毛皮起到一定的加脂作用。
将蓖麻油酸引入两性聚氨酯，并将其运用于皮革的复鞣工序，且复鞣过程中具有加脂功能的复鞣剂尚未有相关研究。
发明内容
本发明目的在于提供一种可提高非金属鞣制皮坯正电性的植物油衍生物改性两性聚氨酯复鞣剂及其制备方法。
为实现上述目的，本发明所采用的技术方案为:在N2的保护，温度为60~90℃条件下，二异氰酸酯与聚四氢呋喃二醚醇在催化剂作用下预聚2~3 h，升温至80~100℃后分别将阴、阳离子扩链剂加入到体系中进行反应2~4 h，再加入植物油衍生物反应2~4 h，降温至40~50℃时进行中和，乳化，最后得到植物油衍生物改性的两性聚氨酯复鞣剂。
二异氰酸酯、聚四氢呋喃二醚醇的物质的量比为(2~4):1；阴、阳离子扩链剂的质量分别为二异氰酸酯与聚四氢呋喃二醚醇质量的5~10%。
具体地，包括如下步骤：在N2的保护，60~90℃条件下，将一定量二异氰酸酯与聚四氢呋喃二醚醇混合，使其反应得到聚氨酯预聚体；升温分别加入2,2-二羟甲基丙酸和N-甲基二乙醇胺进行扩链反应，再加入蓖麻油酸进行改性；降温加入三乙胺中和羧基，最后加入蒸馏水高速搅拌乳化，得到蓖麻油酸改性的两性聚氨酯复鞣剂。
进一步地，所述的反应物比例为二异氰酸酯：聚四氢呋喃二醚醇：2,2-二羟甲基丙酸：N-甲基二乙醇胺：蓖麻油酸=16:5:(3~3.5):(3~4):(2~3)。。
进一步地，所述的二异氰酸酯为二苯甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、己二异氰酸酯HDI、异氟尔酮二异氰酸酯IPDI中的任一种。
进一步地，扩链时，反应温度为80~100℃，反应时间为2~4 h。
进一步地，加入蓖麻油酸改性时，反应温度为80~100℃，反应时间为2~4 h。
本发明的有益效果为：
1.将蓖麻油酸引入两性聚氨酯，合成了新型两性聚氨酯，可将其用于皮革复鞣。该复鞣剂中同时含有阴、阳离子基团，可有效提高有机无铬鞣鞣制皮革和毛皮的等电点，进而提高皮革和毛皮对皮革整饰材料的吸收率，还可起到一定加脂作用。
2.合成路线简单，反应温度较低、反应时间较短，在常压下即可进行。该产物由于引入了植物油衍生物，因此具有良好的生物可降解性，可减少环境污染。
具体实施方式
下面结合具体实施例对本发明进行详细阐述，但是本发明不局限于以下实施例。
实施例1:由IPDI为异氰酸酯合成蓖麻油酸改性的两性聚氨酯
将异氟尔酮二异氰酸酯(IPDI)、聚四氢呋喃二醚醇(PTMG-1000)、二月桂酸二丁基锡(DBTDL)在60℃下反应3 h得到聚氨酯预聚体；升温至80℃，加入二羟甲基丙酸（DMPA）和N~甲基二乙醇胺(MDEA)分别反应3 h；再加入蓖麻油酸（RA）反应3 h；再将温度降至40℃，加入三乙胺中和，蒸馏水乳化，即得到半透明泛蓝光的两性聚氨酯乳液。
IPDI: PTMG-1000:DMPA:MEDA: RA的摩尔比=16: 5: 3: 3: 3。
实施例2:将异氰酸酯由IPDI换成二苯甲烷二异氰酸酯（MDI）
将二苯甲烷二异氰酸酯（MDI）、PTMG-1000、DBTDL在65℃下反应2 h得到聚氨酯预聚体；升温至85℃，加入DMPA和MDEA分别反应2 h；再加入RA反应2 h；再将温度降至45℃，加入三乙胺中和，蒸馏水乳化，即得到半透明泛蓝光的两性聚氨酯乳液。
MDI: PTMG-1000:DMPA:MEDA: RA的摩尔比=16: 5: 3: 4: 2
实施例3:将异氰酸酯由IPDI换成甲苯二异氰酸酯（TDI）
将甲苯二异氰酸酯（TDI）、PTMG-1000DBTDL在75℃下反应3 h得到聚氨酯预聚体；升温至90℃，加入DMPA和MDEA分别反应3 h；再加入RA反应2 h；再将温度降至50℃，加入三乙胺中和，蒸馏水乳化，即得到半透明泛蓝光的两性聚氨酯乳液。
TDI: PTMG-1000:DMPA:MEDA: RA的摩尔比= 16: 5: 3: 3.5: 3
实施例4:将异氰酸酯由IPDI换成己二异氰酸酯（HDI）
将己二异氰酸酯（HDI）、PTMG-1000、DBTDL在80℃下反应4 h得到聚氨酯预聚体；升温至95℃，加入DMPA和MDEA分别反应3.5 h；再加入RA反应3 h；再将温度降至45℃，加入三乙胺中和，蒸馏水乳化，即得到半透明泛蓝光的两性聚氨酯乳液。
HDI: PTMG-1000:DMPA:MEDA: RA的摩尔比= 16: 5: 3.5: 3.5: 2
对比例1:用等摩尔量的PTMG-1000代替RA
将己二异氰酸酯（HDI）、PTMG-1000、DBTDL在60℃下反应3 h得到聚氨酯预聚体；升温至80℃，加入DMPA和MDEA分别反应3 h；再将温度降至40℃，加入三乙胺中和，蒸馏水乳化，即得到半透明泛蓝光的两性聚氨酯乳液。
将实施例1与对比例1制备的两性聚氨酯用于皮革行业的复鞣工序，以不加任何复鞣剂的皮革作为空白样，并测定复鞣后皮革的收缩温度（Ts），撕裂强度，表1表2分别为两性聚氨酯的复鞣工序和所得的结果。
Figure DEST_PATH_IMAGE001
Figure 205746DEST_PATH_IMAGE002
对比例1与实施例1相比较，其区别在于将蓖麻油酸替换为了等摩尔量的PTMG-1000，比较发现蓖麻油加入后聚氨酯热力学性能得到了提升。
以上实施例仅用于说明本发明的技术方案，而非对其限制，其依然可以对前述所实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换，而这些修改或替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (5)

1.一种植物油衍生物改性两性聚氨酯复鞣剂的制备方法，其特征在于，包括如下步骤：
1）60~90℃条件下，将异氰酸酯与聚四氢呋喃醚二醇混合，反应得到聚氨酯预聚体；
2）升温至80~100℃，分别加入2,2-二羟甲基丙酸和N-甲基二乙醇胺进行扩链反应；扩链反应完成后，再加入蓖麻油酸反应；
3）降温加入三乙胺进行中和，最后加入蒸馏水高速搅拌乳化。
2.如权利要求1所述的方法，其特征在于，异氰酸酯、聚四氢呋喃醚二醇、2,2-二羟甲基丙酸、N-甲基二乙醇胺、蓖麻油酸的摩尔比为16:5:(3~3.5):(3~4):(2~3)。
3.如权利要求1所述的方法，其特征在于，所述异氰酸酯为二苯甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI、己二异氰酸酯HDI、异佛 尔酮二异氰酸酯IPDI中的一种。
4.如权利要求1所述的方法，其特征在于，制备聚氨酯预聚体时，反应温度为60~90℃，反应时间为2~4 h；扩链时，反应温度为80~100℃，反应时间为2~4 h；加入蓖麻油酸后，反应温度为80~100℃，反应时间为2~4 h；反应体系在N2保护下进行。
5.权利要求1~4任一项所述方法得到的植物油衍生物改性两性聚氨酯复鞣剂。
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