CN105542108A - 超细纤维合成革用易染色聚氨酯树脂及其制备方法 - Google Patents

超细纤维合成革用易染色聚氨酯树脂及其制备方法 Download PDF

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CN105542108A
CN105542108A CN201510971522.0A CN201510971522A CN105542108A CN 105542108 A CN105542108 A CN 105542108A CN 201510971522 A CN201510971522 A CN 201510971522A CN 105542108 A CN105542108 A CN 105542108A
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杜明兵
张其斌
杨银龙
吴勇
诸葛磊
刘国
胡雪丽
彭超豪
王贺玲
蔡肖燕
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Shanghai Huafeng Super Fiber Technology Co.,Ltd.
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Abstract

本发明公开了一种超细纤维合成革用易染色聚氨酯树脂及其制备方法，制备方法包括如下步骤：以异氰酸酯、多元醇和扩链剂为起始原料，进行反应，然后将反应产物稀释，获得所述的超细纤维合成革用易染色聚氨酯树脂，其中，多元醇和扩链剂中的一种以上，含有酰胺基、仲氨基或者叔氨基基团。本发明聚氨酯上染率高，基布染色均一性好，且上色后的色牢度高，色彩鲜艳，染料使用量低，可以大大降低生产成本，具有实际应用价值。

Description

超细纤维合成革用易染色聚氨酯树脂及其制备方法
技术领域
本发明涉及一种聚氨酯树脂及其制备方法。
背景技术
目前，超细纤维合成革分为不定岛超细纤维和定岛超细纤维合成革，是代替天然皮革最为理想的材料。其基底层为超细纤维与聚氨酯(PU)弹性体的复合无纺布材料，超细纤维三维交联在一起，起到骨架和支撑作用，聚氨酯分布在纤维的四周，使整个合成革基布形成一个整体。面层也采用聚氨酯树脂造面，所得产品不论从内部微孔结构,还是外观质感、物理特性以及穿着舒适性等方面,都能与高级天然皮革相媲美，现已被广泛的应用于服装、制鞋、汽车等领域。
超细纤维合成革中的锦纶超细纤维和聚氨酯(PU)树脂，结构不同，染色差异大，从而造成了超纤合成革染色的难点。同时定岛超细纤维相比不定岛超细纤维，上染率更高，如果使用常规的聚氨酯树脂，染色不均一，会使染色后基布发花。
发明内容
本发明的目的在于提供一种超细纤维合成革用易染色聚氨酯树脂的制备方法，解决现有聚氨酯树脂难染色、匀染性差和色牢度差的缺陷。
本发明的制备方法，包括如下步骤：
以异氰酸酯、多元醇和扩链剂为起始原料，进行反应，然后将反应产物稀释，获得所述的超细纤维合成革用易染色聚氨酯树脂，其中，多元醇和扩链剂中的一种以上，含有酰胺基、仲氨基或者叔氨基基团；
具体的，本发明的方法，包括如下步骤：
(1)将异氰酸酯加入多元醇和溶剂中，65～75℃预聚80～100min；
异氰酸酯与多元醇的摩尔比为：异氰酸酯∶多元醇＝2:1～8:1
溶剂中，多元醇的重量含量为40％～80％；
所述的多元醇为聚酯多元醇或聚醚多元醇中的一种以上；
其中，所述的聚醚多元醇为二官能团聚醚胺(PEA)或者是二官能团聚醚胺(PEA)和聚四氢呋喃二醇(PTMG)；
当选用二官能团聚醚胺(PEA)和聚四氢呋喃二醇(PTMG)时，重量比为：
聚四氢呋喃二醇∶二官能团聚醚胺＝4～6∶1；
(2)然后加入具有可染基团的扩链剂、小分子扩链剂和溶剂，并分批加入异氰酸酯，50～100℃，优选65～75℃反应，异氰酸酯的加入量，使反应物的粘度为80～200Pa·s(25℃)，然后加入溶剂稀释至粘度为60～180Pa·s(25℃)加入终止剂反应20～40min，即可获得所述的超细纤维合成革用易染色聚氨酯树脂；
具有可染基团的扩链剂的重量用量为多元醇的0.1％～10％，优选1～5％；
小分子扩链剂的重量用量为具有可染基团的扩链剂的1～15倍；
以步骤(1)中的多元醇为基准，溶剂中，多元醇的重量含量为45％～70％；
二官能团聚醚胺(PEA)常用分子量为230～5000，优选D230(分子量：230)、D2000(分子量：2000)；
聚四氢呋喃二醇(PTMG)常用的分子量为850～3000，优选为PTMG2000(分子量：2000)；
所述聚酯多元醇优选聚酯二醇，所述的聚酯二醇为己二酸系聚酯多元醇，如：己二酸和丁二醇反应而得的PBA1000、PBA2000、PBA3000等，或者为己二酸和乙二醇反应而得的PEA1000、PEA2000、PEA3000等，或者己二酸和己二醇反应而成的PHA1000、PHA2000、PHA3000等；
上述的异氰酸酯优选二苯基甲烷二异氰酸酯MDI；
所述的具有可染基团的扩链剂选自N-叔丁基二乙醇胺(TBDEA)、N,N'-双(2-羟乙基)对苯二甲酰胺(HETA)，N,N'-二(2-羟乙基)草酰胺(HEOA)或N,N'-二(2-羟乙基)丁二酰胺(HEDA)中的一种；
所述的小分子扩链剂优选乙二醇(EG)或丁二醇(BG)中的一种；
所述的溶剂选自N,N-二甲基甲酰胺(DMF)、甲苯、丁酮、异丙醇、异丁醇的一种或多种；
所述的封端剂甲醇和乙醇中的一种或多种；
采用本发明制备的易染色聚氨酯树脂，分子软硬段区域中，引入可染基团，引入酰胺基、仲氨基或者叔氨基基团中的一种或一种以上；
引入聚醚胺，提高了软段区域的上染率；引入酰胺基，使树脂具有和纤维类似结构；引入叔氨基，提高与染料的结合牢度。
本发明通过在聚氨酯树脂中引入可与染料结合的基团，使产品在满足基本性能要求的同时，还提高染色性能。与现有报道的染色聚氨酯树脂相比，应用到定岛、不定岛超细纤维合成革染色过程中，聚氨酯上染率高，基布染色均一性好，且上色后的色牢度高，色彩鲜艳，染料使用量低，可以大大降低生产成本，具有实际应用价值。
具体实施方式
下面结合具体实施例对本发明内容作进一步描述，本发明的试验条件可以根据需要进行相应调整，而不限于本实施例的试验条件。
实施例1
(1)将聚四氢呋喃二醇(PTMG2000)(100g)、二官能团聚醚胺(PEA)D2000(20g)、溶剂N,N-二甲基甲酰胺(DMF)(100g)投入反应瓶中，混合均匀，投入MDI(12g)70℃预聚80min；
(2)预聚完成后，加入乙二醇EG(11g)、N-叔丁基二乙醇胺TBDEA(1.5g)和DMF(280g)，分批加入MDI(51g)，80℃反应，MDI反应完后，补加MDI使粘度涨到90Pa·s(25℃)粘度时，停止加入；
然后加入DMF(80g)稀释至反应物的粘度60Pa·s(25℃)，加入甲醇0.05g终止剂反应30min，降温至50℃后出料，即可获得所述的超细纤维合成革用易染色聚氨酯树脂，树脂固体质量分数为(30±1)％。
用到合成革基布上，采用GB/T29865-2013方法检测，DatacolorsF650电脑测色配色仪SCT-混料透射测色配色***测试，和常规染色基布相比，结果如下：上染率可以提高30％以上，染色均一，色牢度提高1级，染料使用量减少30％。
实施例2
(1)将聚四氢呋喃二醇(PTMG2000)(120g)、二官能团聚醚胺(PEA)D230(10g)和DMF(100g)投入反应瓶中，搅拌使其混合均匀，投入MDI(20g)，升温至60℃预聚90min；
(2)预聚完成后，加入乙二醇(EG)(10g)、N,N'-二(2-羟乙基)丁二酰胺(HEDA)(5g)、DMF(320g)到反应瓶中，分批投入MDI(52g)，保持70℃反应，MDI反应完后，补加MDI使粘度涨到100Pa·s(25℃)粘度时，停止加入；
加入DMF(80g)稀释至粘度80Pa·s(25℃)，加入甲醇(0.05g)终止剂反应30min，降温至50℃后出料,所得到的树脂固体质量分数为(30±1)％。
用到合成革基布上，采用GB/T29865-2013方法检测，DatacolorsF650电脑测色配色仪SCT-混料透射测色配色***测试，结果如下：上染率可以提高20％以上，染色均一，色牢度提高1级，染料使用量减少20％。
实施例3
(1)将聚四氢呋喃二醇(PTMG)2000(120g)、二官能团聚醚胺(PEA)D2000(30g)、DMF(100g)投入反应瓶中，搅拌使其混合均匀，投入MDI(14g)，升温至80℃预聚60min；
(2)加入乙二醇(EG)(14g)、N-叔丁基二乙醇胺(TBDEA)(1g)和DMF(380g)，N,N'-二(2-羟乙基)草酰胺(HEOA)(4g)，分批加入MDI(70g)，保持75℃反应，MDI反应完后，补加MDI使粘度涨到140Pa·s(25℃)粘度时，停止加入；
加入DMF(80g)稀释至粘度120Pa·s(25℃)，加入甲醇(0.05g)终止剂反应30min，降至50℃后出料,得到的树脂固体质量分数为(30±1)％。
用到合成革基布上，采用GB/T29865-2013方法检测，DatacolorsF650电脑测色配色仪SCT-混料透射测色配色***测试，结果如下：上染率可以提高60％以上，染色均一，色牢度提高1.5级，染料使用量减少60％。
实施例4
(1)将四氢呋喃二醇(PTMG2000)(100g)、二官能团聚醚胺(PEA)D2000(20g)、己二酸和己二醇反应生成的己二酸系聚酯多元醇PHA2000(30g)、DMF(100g)投入反应瓶中搅拌使其混合均匀，投入MDI(14g)，升温至70℃预聚90min；
(2)预聚完成后，加入乙二醇EG(8g)、N-叔丁基二乙醇胺(TBDEA)(4g)、双(2-羟乙基)对苯二甲酰胺HETA(3g)、DMF(320g)到反应瓶中搅匀，分批投入MDI(46g)，保持70℃反应，MDI反应完后，补加MDI使粘度涨到160Pa·s(25℃)粘度时，停止加入；
加入DMF(80g)稀释至粘度140Pa·s(25℃)，加入甲醇(0.05g)终止剂反应30min，降温至50℃后出料,所得到的树脂固体质量分数为(30±1)％。
用到合成革基布上，采用GB/T29865-2013方法检测，DatacolorsF650电脑测色配色仪SCT-混料透射测色配色***测试，结果如下：上染率可以提高50％以上，染色均一，色牢度提高1.5级，染料使用量减少50％。

Claims (10)

1.超细纤维合成革用易染色聚氨酯树脂的制备方法，其特征在于，包括如下步骤：以异氰酸酯、多元醇和扩链剂为起始原料，进行反应，然后将反应产物稀释，获得所述的超细纤维合成革用易染色聚氨酯树脂，其中，多元醇和扩链剂中的一种以上，含有酰胺基、仲氨基或者叔氨基基团。
2.超细纤维合成革用易染色聚氨酯树脂的制备方法，其特征在于，包括如下步骤：(1)将异氰酸酯加入多元醇和溶剂中预聚；
所述的多元醇为聚酯多元醇或聚醚多元醇中的一种以上；
其中，所述的聚醚多元醇为二官能团聚醚胺(PEA)或者是二官能团聚醚胺(PEA)和聚四氢呋喃二醇(PTMG)；
(2)然后加入具有可染基团的扩链剂、小分子扩链剂和溶剂，反应，加入溶剂稀释，加入终止剂反应20～40min，即可获得所述的超细纤维合成革用易染色聚氨酯树脂。
3.根据权利要求2所述的方法，其特征在于，当选用二官能团聚醚胺(PEA)和聚四氢呋喃二醇(PTMG)时，重量比为：聚四氢呋喃二醇∶二官能团聚醚胺＝4～6∶1。
4.根据权利要求2所述的方法，其特征在于，具有可染基团的扩链剂的重量用量为多元醇的0.1％～10％，小分子扩链剂的重量用量为具有可染基团的扩链剂的1～15倍。
5.根据权利要求2所述的方法，其特征在于，以步骤(1)中的多元醇为基准，溶剂中，多元醇的重量含量为45％～70％。
6.根据权利要求2所述的方法，其特征在于，二官能团聚醚胺(PEA)分子量为230～5000；聚四氢呋喃二醇(PTMG)分子量为850～3000。
7.根据权利要求2所述的方法，其特征在于，所述聚酯多元醇为聚酯二醇。
8.根据权利要求1所述的方法，其特征在于，所述的异氰酸酯为二苯基甲烷二异氰酸酯MDI。
9.根据权利要求1～8任一项所述的方法，其特征在于，所述的具有可染基团的扩链剂选自N-叔丁基二乙醇胺(TBDEA)、N,N'-双(2-羟乙基)对苯二甲酰胺(HETA)，N,N'-二(2-羟乙基)草酰胺(HEOA)或N,N'-二(2-羟乙基)丁二酰胺(HEDA)中的一种。
10.根据权利要求1～9任一项所述方法制备的超细纤维合成革用易染色聚氨酯树脂。
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