CN112626882B - 一种合成革用水性聚氨酯发泡层的制备方法 - Google Patents

一种合成革用水性聚氨酯发泡层的制备方法 Download PDF

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CN112626882B
CN112626882B CN202011443877.XA CN202011443877A CN112626882B CN 112626882 B CN112626882 B CN 112626882B CN 202011443877 A CN202011443877 A CN 202011443877A CN 112626882 B CN112626882 B CN 112626882B
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waterborne polyurethane
synthetic leather
foaming layer
acid
foam
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CN112626882A (zh
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林炜
吴尖辉
魏涛
王春华
张龙
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Sichuan University
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Sichuan University
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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Abstract

本发明公开了一种合成革用水性聚氨酯发泡层的制备方法，首先以木浆为原料制备出带电荷的纤维素纳米纤维，同时多异氰酸酯与大分子二元醇、亲水扩链剂以及小分子扩链剂先后通过加成聚合和酸碱中和反应得到阳离子或阴离子型水性聚氨酯，然后将带电荷纤维素纳米纤维与一定量的交联剂加入到带相反电荷的离子型水性聚氨酯乳液中，在高速搅拌的条件下纤维素纳米纤维和水性聚氨酯纳米颗粒通静电相互作用在气液界面自组装一层双分子层从而得到稳定的Pickering泡沫，再以其为模板，经干燥固化后即可得到合成革用水性聚氨酯发泡层。制备过程绿色环保，简单易于大规模工业化，且所得发泡层泡孔致密均一，手感丰满厚实。

Description

一种合成革用水性聚氨酯发泡层的制备方法
技术领域
本发明涉及合成革制造领域，具体涉及一种合成革用水性聚氨酯发泡层的制备方法。
背景技术
我国是合成革的生产大国，据统计，2018年合成革的产量达到70亿平米，占世界总量的70％，且到2027年，每年还将以7％的年增长率继续增长。究其原因主要有以下三点：1.人们对动物的保护意识增强，迫使企业寻找真皮革的替代品，如特斯拉在2016年开始用合成革代替真皮革作为汽车内饰，并于今年年底完成全部汽车革“去动物化”。2.与真皮革相比，合成革的价格更便宜。3.更为重要的是，合成革的各项性能如透气、透湿、外感、手感等方面均与真皮革接近，使其能够成为真皮革的理想替代品。
然而以湿法和干法制造工艺为主的传统合成革企业所使用的聚氨酯树脂均为溶剂型的，浆料中有机溶剂的挥发不仅使经济遭受很大的损失，而且还会给环境造成严重的污染。如湿法工艺所用溶剂型聚氨酯的固含量在17％左右，需要加入大量的有机溶剂N,N-二甲基甲酰胺(DMF)，尽管目前的精馏技术能够回收 98％的DMF，但是由于使用的DMF量太大，最终无序排放的DNF量还是相当大的。而干法工艺所使用的溶剂多为几种溶剂的混合物如DMF、丁酮、乙酸酯类、甲苯和甲缩醛等，这给溶剂的回收带来了很大的困难，最终回收率仅为50％左右。据估计，合成革行业每年共需溶剂约340万吨，其中至少有100～150万吨溶剂被无序排放，每吨按1.2万元计算，无序排放100万吨所造成的经济损失便高达120亿元。更重要的是，随着生活水平的提高，人们对革制品的生态性提出了更高的要求，欧盟的REACH法规规定，对服装革、汽车内饰革和家具革等合成革制品提出了零偶氮、零甲醛和零重金属的要求，且对其中的挥发性有机溶剂(VOC)的含量限制在5mg/kg以下。因此，无论是从环境、成本还是对外出口的角度来看，传统的基于溶剂型聚氨酯合成革制造工艺均很难满足相应的要求。
使用水性聚氨酯代替溶剂型聚氨酯制造生态合成革，是从源头上消除溶剂污染解决上述问题的理想方案。水性聚氨酯是以水为溶剂的聚氨酯乳液，为了使聚氨酯能够均匀分散在水中，往往需要在其结构中引入一定量的亲水基团，根据亲水基团的不同，可将水性聚氨酯分为阴离子型(羧基、磺酸基)、阳离子型(季铵盐) 和非离子型(聚乙二醇)三类。目前在合成革领域应用最多的是阴离子型水性聚氨酯，其次是阳离子型水性聚氨酯，而非离子型水性聚氨酯并不多见。水性聚氨酯直接涂覆在基布上所形成的涂层比较扁薄、致密，无法达到与真皮革类似的透气透湿性、良好的手感以及丰满度，在基布表面涂覆一层具有多孔结构的水性聚氨酯发泡层是解决上述问题的有效途径。目前常用的发泡方法主要有化学发泡和物理发泡两类，化学发泡法主要是利用发泡剂在高温下分解释放大量的气体，进而促使聚氨酯基体发泡，但所用的发泡剂多为不溶于水的有机物且发泡温度较高，一般超过200℃，故而不适用于水性聚氨酯体系。物理发泡则主要是通过强烈的机械搅拌将气体引入到聚氨酯基体中，然后在稳泡剂、匀泡剂等的作用下得到聚氨酯泡沫，这也是目前工业上水性聚氨酯发泡所用的方法。但此法的工艺要求很高、成本过大、对水性聚氨酯固含量的要求要超过50％，且所得泡沫的稳定性和泡沫孔径的均匀性均有待进一步提高。因此，发泡层的制备一直以来都是制约水性聚氨酯合成革发展的关键技术。
Pickering泡沫是一类由具有特定润湿性的固体粒子吸附在气液界面所形成的泡沫，表现出良好的泡沫稳定性和孔径均匀性，其孔径的大小还可以通过改变固体粒子的表面润湿性和浓度等因素来调节。因此，以Pickering泡沫为模板来制备多孔泡沫材料逐渐受到人们的广泛关注，如To Ngai等人利用疏水的二氧化硅纳米颗粒与亲水的聚合物如玉米蛋白和聚(N-异丙基丙烯酰胺)等协同稳定的 Pickering泡沫为模板，通过往连续相中加入交联剂如戊二醛将结构交联固化，然后在室温下干燥即可得到多孔的轻质材料，研究表明这类材料在3D打印和模具成型等领域表现出潜在的应用前景(Sheng,Y.；Lin,K.；Binks,B.P.；Ngai,T., Ultra-stable aqueous foams induced by interfacial co-assemblyof highly hydrophobic particles and hydrophilic polymer.Journal of Colloidand Interface Science 2020,579, 628-636.)。有研究表明，与二氧化硅等球形的稳定剂相比，具有一定长径比的纳米纤维彼此之间会形成相互交叉的三维网状结构，故以其为稳定剂能够制备更为稳定的泡沫。同时，三维网状本身也是多孔结构，因此以纳米纤维稳定的Pickering 泡沫成为制备合成革用水性聚氨酯发泡层的理想模板选择。
纤维素是D-葡萄糖单元以β-1,4糖苷键连接而成的大分子多糖，是地球上含量最为丰富的天然有机高分子，具有来源广泛、价格低廉、绿色环保以及优异的力学性能等优点，在合成革领域也有广泛的应用，常作为填料与聚氨酯树脂混合使用，起到降低生产成本和提高力学性能的作用。以纤维素为原料制备的纤维素纳米纤维是一类直径在3-50nm，长度为几个微米，长径比大于50的纳米纤维材料，具有高弹性模量(130-150GPa)、高强度(2-6GPa)、良好的生物降解性和低热膨胀系数(4-6ppm K-1)等优点。根据所带电荷的不同，纤维素纳米纤维可以分为阳离子型和阴离子型两类，这些带电荷的纤维素纳米纤维能够通过静电相互作用与其它带相反电荷的粒子在气液界面自组装形成双分子层最终得到稳定的Pickering泡沫。如Lars
Figure GDA0003185625100000031
等人以季铵盐改性后的纤维素纳米纤维和含羧基阴离子的吲哚美辛协同稳定制备出超稳定的Pickering泡沫(
Figure GDA0003185625100000032
K.； Wohlert,J.；Müllertz,A.；
Figure GDA0003185625100000033
L.；Svagan,A.J.,Cellulose Nanopaper and Nanofoam forPatient-Tailored Drug Delivery.Advanced Materials Interfaces 2017,4 (9),1600655.)。与之类似，用于合成革领域的水性聚氨酯均为带电的离子型纳米粒子，从理论上来说，这些离子型聚氨酯能够通过静电相互作用与带相反电荷的纤维素纳米纤维在气液界面自组装形成双分子层，进而得到两者协同稳定的 Pickering泡沫。
发明内容
本发明公开了一种合成革用水性聚氨酯发泡层的制备方法，首先以木浆为原料制备出带电荷的纤维素纳米纤维，同时多异氰酸酯与大分子二元醇、亲水扩链剂以及小分子扩链剂先后通过聚加成和酸碱中和反应得到阳离子或阴离子型水性聚氨酯，然后将带电荷纤维素纳米纤维与一定量的交联剂加入到带相反电荷的离子型水性聚氨酯乳液中，在高速搅拌的条件下纤维素纳米纤维和水性聚氨酯纳米颗粒通静电相互作用在气液界面自组装一层双分子层从而得到稳定的 Pickering泡沫，再以其为模板，经干燥固化后即可得到合成革用水性聚氨酯发泡层。具体制备方法如下：
(1)制备带电荷的纤维素纳米纤维：Ⅰ.制备带负电荷的纤维素纳米纤维，按质量份数计，将100份木浆纤维质量分数为60％的浆液、1～10份TEMPO与10～60 份NaBr混合均匀，然后在搅拌的条件下往其中缓慢加入20～120份的次氯酸钠质量分数为37％的溶液，在pH为8～10的条件下反应，直到pH无明显变化为止。待反应结束后，再通过离心、透析和冷冻干燥，即可得到含羧基的阴离子型纤维素纳米纤维。Ⅱ.制备带正电荷的纤维素纳米纤维，将2,3-环氧丙基三甲基氯化铵与木浆按照质量比(0.1～10):1加入到有机溶剂A中，然后加入一定量的碱性物质B在温度为50～90℃的条件下反应至少2h。待反应结束后，利用去离子水反复洗涤多次，最终得到阳离子型纤维素纳米纤维。
(2)制备离子型水性聚氨酯：按质量份数计，首先将30～80份大分子二元醇在110℃下真空干燥1h，然后将温度降低到70℃，往其中加入20～40份二异氰酸酯在无水的情况下反应1h，得到异氰酸酯基团封端的聚氨酯预聚体，将温度升高到80℃℃后往其中加入含叔胺基团或含羧基的二元醇类亲水单体和几滴二丁基锡二月桂酸酯作为催化剂继续反应2～4小时，并不时地加入一定量的有机溶剂 C调节反应体系的粘度。待反应完成之后，再往其中加入小分子扩链剂继续反应 2～4小时，然后将温度降低至50℃，接下来往其中加入与叔胺或者羧基等摩尔质量的酸性或碱性物质D酸碱中和30min，最后将其分散在一定量的去离子水中，减压蒸馏出去残余的溶剂得到离子型水性聚氨酯分散液。
(3)制备Pickering泡沫和水性聚氨酯发泡层：将上述步骤(1)中所制备的带正电荷的纤维素纳米纤维与一定量的交联剂加入到步骤(2)中带负电荷的水性聚氨酯乳液中，或者将上述步骤(1)中所制备的带负电荷的纤维素纳米纤维与一定量的交联剂加入到步骤(2)中带正电荷的水性聚氨酯乳液中，在大力搅拌下使纤维素纳米纤维与水性聚氨酯纳米颗粒通过静电相互作用一起在气/液界面自组装形成双分子层从而得到稳定的Pickering泡沫，在室温下放置一段时间，让交联剂将泡沫的结构交联固化，最后除去溶剂水便得到阳离子型水性聚氨酯发泡层。
所述的一种合成革用水性聚氨酯发泡层的制备方法，其特征在于步骤(1)中所用的木浆为磨盘机械浆、硫酸盐木浆、烧碱法浆、亚硫酸盐木浆、磨石磨木浆和热磨机械浆中的一种。所用的有机溶剂A为甲酰胺、四甲基亚砜、乙腈、异丙醇、正丁醇和四氢呋喃中的一种。所用的碱性物质B为二乙胺、三乙胺、三正丙胺、二异丙胺、三己胺和氢氧化钠中的一种。
所述的一种合成革用水性聚氨酯发泡层的制备方法，其特征在于步骤(2)中所用的二异氰酸酯为异佛尔酮二异氰酸酯、1,3-苯二异氰酸酯、2,6-甲苯二异氰酸酯、六亚甲基二异氰酸酯和1,4-环己烷二异氰酸酯中的一种。所用的大分子二元醇为聚四氢呋喃醚二醇、聚乙二醇、聚碳酸酯二醇、聚丙二醇、聚硅氧烷二醇和聚ε-己内酯二元醇中的一种或几种的混合。所用的有机溶剂C为无水的四氢呋喃和丙酮中的一种。所用的亲水单体为N-甲基二乙醇胺、3-二甲氨基-1,2-丙二醇、二乙醇胺、间甲苯基二乙醇胺、N-丁基二乙醇胺、二羟甲基丙酸、二羟甲基丁酸、酒石酸、含羧基半酯二元醇、二氨基苯甲酸、乙二胺基乙磺酸盐中的一种。所用的小分子扩链剂为赖氨酸、1,4-丁二醇、1,6-己二醇、二甘醇、1,4-丁二胺、乙二胺和肼等中的一种。所用的酸性物质D为乙酸、丙酸、苯甲酸、丙烯酸和乳酸中的一种。
所述的一种合成革用水性聚氨酯发泡层的制备方法，其特征在于步骤(3)中所用的交联剂为氮丙啶、三羟甲基三聚氰胺、六甲氧基亚甲基三聚氰胺、聚碳化二亚胺、环氧树脂和三乙烯四胺中的一种。
本发明与现有技术相比，具有如下有益效果：
1.由纤维素纳米纤维和水性聚氨酯纳米颗粒协同稳定的Pickering泡沫具有非常好的稳定性，无须添加稳泡剂、增稠剂等其它助剂。
2.以纤维素纳米纤维和水性聚氨酯纳米颗粒协同稳定的Pickering泡沫为模板制得的水性聚氨酯发泡层的工艺简单，适合工业化生产，且所得产品外观无瑕疵、泡孔结构致密、规则，很好地解决现有机械发泡法制备的水性聚氨酯发泡层所存在的孔径不稳定以及均一性不好的问题。
3.泡孔孔径可控，可以根据需要，通过调节纤维素纳米纤维的表面润湿性、浓度和长径比等因素得到不同泡孔直径的泡沫。
4.所得的水性聚氨酯发泡层在室温下即可固化成型，能耗低，可以降低生产成本。
具体实施方式
下面给出本发明的四个实施方案，以具体说明合成革用水性聚氨酯发泡层的制备方法。
实施例1
本实施例按照下述步骤制备合成革用水性聚氨酯发泡层：
(1)制备阴离子型纤维素纳米纤维
将0.5g TEMPO和5g NaBr加入到20g质量分数为15％的烧碱法木浆中，然后在搅拌的条件下往上述混合液中缓慢加入80mL NaClO质量分数为37％溶液，不断往体系中加入1M的NaOH溶液，始终维持pH在10左右，室温下反应直到体系的pH不再发生变化，然后将混合液离心、透析后冷冻干燥，最终得到含羧基的阴离子型纤维素纳米纤维。
(2)制备阳离子型水性聚氨酯
首先将10g(5mmol)聚碳酸酯二醇在110℃下减压脱水干燥1h。然后将温度降到70℃，在氮气保护下加入5.77g(26mmol)异佛尔酮二异氰酸酯，在搅拌的条件下反应1h，然后往其中加入0.95g(8mmol)N-甲基二乙醇胺和三滴催化剂二丁基锡二月桂酸酯，反应2h后，加入1.08g(12mmol)1,4-丁二醇继续反应 2h。将温度降至50℃，往其中加入0.48g(8mmol)乙酸反应半小时，将其倒入 42g去离子水中，高速搅拌30min，即得到固含量为30％的阳离子型水性聚氨酯乳液。
(3)制备Pickering泡沫和水性聚氨酯发泡层
将0.4g含羧基的阴离子纤维素纳米纤维和0.6g三羟甲基三聚氰胺加入到 10mL阳离子水性聚氨酯乳液中，在高速剪切力的作用下乳化2min，得到稳定的Pickering泡沫，然后在室温下放置4h等完全交联固化之后，再将其转移至80℃的烘箱中真空干燥至恒重，最终得到水性聚氨酯发泡层。
实施例2
本实施例按照下述步骤制备合成革用水性聚氨酯发泡层：
(1)制备阴离子型纤维素纳米纤维
将0.6g TEMPO和6g NaBr加入到15g质量分数为15％的硫酸盐木浆中，然后在搅拌的条件下往上述混合液中缓慢加入90mL NaClO质量分数为37％溶液，不断往体系中加入1M的NaOH溶液，始终维持pH在10左右，室温下反应直到体系的pH不再发生变化，然后将混合液离心、透析后冷冻干燥，最终得到含羧基的阴离子型纤维素纳米纤维。
(2)制备阳离子型水性聚氨酯
首先将14g(7mmol)聚四氢呋喃醚二醇在110℃下减压脱水干燥1h。然后将温度降到70℃，在氮气保护下加入4.15g(25mmol)1,4-环己烷二异氰酸酯，在搅拌的条件下反应1h，然后往其中加入0.83g(7mmol)3-二甲氨基-1,2-丙二醇和三滴催化剂二丁基锡二月桂酸酯，反应2h后，加入0.99g(11mmol)1,4- 丁二醇继续反应2h。将温度降至50℃，往其中加入0.59g(8mmol)丙酸反应半小时，将其倒入46g去离子水中，高速搅拌30min，即得到固含量为30％的水性聚氨酯乳液。
(3)制备Pickering泡沫和水性聚氨酯发泡层
将0.5g含羧基的阴离子纤维素纳米纤维和0.5g六甲氧基亚甲基三聚氰胺加入到10mL阳离子水性聚氨酯乳液中，在高速剪切力的作用下乳化2min，得到稳定的Pickering泡沫，然后在室温下放置5h等完全交联固化之后，再将其转移至80℃的烘箱中真空干燥至恒重，最终得到水性聚氨酯发泡层。
实施例3
本实施例按照下述步骤制备合成革用水性聚氨酯发泡层：
(1)制备阳离子型纤维素纳米纤维
往10g质量分数为20％的硫酸盐木浆中加入5g 2,3-环氧丙基三甲基氯化铵，然后加入2mL1M的氢氧化钠溶液，将体系的pH调至碱性，接着往其中加入100 mL异丙醇溶剂，在50℃下反应2h。待反应结束后，用去离子水反复洗涤多遍，最终得到阳离子型纤维素纳米纤维。
(2)制备阴离子型水性聚氨酯
首先将8g(4mmol)聚碳酸酯二醇在110℃下减压脱水干燥2h。然后将温度降低到75℃，在氮气保护下加入3.84g(24mmol)1,3-苯二异氰酸酯，在搅拌的条件下反应1h，然后往其中加入0.89g(6mmol)二羟甲基丁酸和三滴催化剂二丁基锡二月桂酸酯，反应2h后，加入1.65g(14mmol)1,4-丁二醇继续反应2h。将温度降至50℃，往其中加入1.61g(6mmol)三己胺反应半小时，将其倒入37 g去离子水中，高速搅拌30min，即得到固含量为30％的水性聚氨酯乳液。
(3)制备Pickering泡沫和水性聚氨酯发泡层
将0.5g阳离子纤维素纳米纤维和0.4g氮丙啶加入到10mL阴离子水性聚氨酯乳液中，在高速剪切力的作用下乳化2min，得到稳定的Pickering泡沫，然后在室温下放置5h等完全交联固化之后，再将其转移至80℃的烘箱中真空干燥至恒重，最终得到水性聚氨酯发泡层。
实施例4
本实施例按照下述步骤制备合成革用水性聚氨酯发泡层：
(1)制备阳离子型纤维素纳米纤维
往10g质量分数为25％的磨盘机械浆中加入8g 2,3-环氧丙基三甲基氯化铵，然后加入2mL1M的氢氧化钠溶液，将体系的pH调至碱性，接着往其中加入100 mL正丁醇溶剂，在65℃下反应3h。待反应结束后，用去离子水反复洗涤多遍，最终得到阳离子型纤维素纳米纤维。
(2)制备阴离子型水性聚氨酯
首先将14g(7mmol)聚硅氧烷二醇在110℃下减压脱水干燥2h。然后将温度降低到80℃，在氮气保护下加入3.98g(26mmol)1,4-环己烷二异氰酸酯，在搅拌的条件下反应1h，然后往其中加入0.9g(6mmol)酒石酸和三滴催化剂二丁基锡二月桂酸酯，反应2h后，继续往其中加入1.90g(13mmol)赖氨酸反应2h。将温度降至50℃，往其中加入1.08g(12mmol)三乙胺反应半小时，将其倒入49g去离子水中，高速搅拌30min，即得到固含量为30％的水性聚氨酯乳液。
(3)制备Pickering泡沫和水性聚氨酯发泡层
将0.6g阳离子纤维素纳米纤维和0.5g聚碳化二亚胺加入到10mL阴离子水性聚氨酯乳液中，在高速剪切力的作用下乳化2min，得到稳定的Pickering泡沫，然后在室温下放置5h等完全交联固化之后，再将其转移至80℃的烘箱中真空干燥至恒重，最终得到水性聚氨酯发泡层。

Claims (4)

1.一种合成革用水性聚氨酯发泡层的制备方法，其特征在于具体包含以下几个步骤：
(1)制备带电荷的纤维素纳米纤维：Ⅰ.制备带负电荷的纤维素纳米纤维，按质量份数计，将100份木浆纤维质量分数为60％的浆液、1～10份TEMPO与10～60份NaBr混合均匀，然后在搅拌的条件下往其中缓慢加入20～120份的次氯酸钠质量分数为37％的溶液，在pH为8～10的条件下反应，直到pH无明显变化为止；待反应结束后，再通过离心、透析和冷冻干燥，即可得到带负电的纤维素纳米纤维；Ⅱ.制备带正电荷的纤维素纳米纤维，将2,3-环氧丙基三甲基氯化铵与木浆按照质量比(0.1～10):1加入到有机溶剂A中，然后加入一定量的碱性物质B在温度为50～90℃的条件下反应至少2h；待反应结束后，用去离子水反复洗涤多次，最终得到带正电的纤维素纳米纤维；
(2)制备离子型水性聚氨酯：按质量份数计，首先将30～80份大分子二元醇在110℃下真空干燥1h，然后将温度降低到70℃，往其中加入20～40份二异氰酸酯在无水的情况下反应1h，得到异氰酸酯基团封端的聚氨酯预聚体，将温度升高到80℃后往其中加入含叔胺基团或含羧基的二元醇类亲水单体和几滴二丁基锡二月桂酸酯作为催化剂继续反应2～4小时，并不时地加入一定量的有机溶剂C调节反应体系的粘度， 待反应完成之后，再往其中加入小分子扩链剂继续反应2～4小时，然后将温度降低至50℃，接下来往其中加入与叔胺或者羧基等摩尔质量的酸性或碱性物质D酸碱中和30min，最后将其分散在一定量的去离子水中，减压蒸馏出去残余的溶剂得到离子型水性聚氨酯分散液；
(3)制备Pickering泡沫和水性聚氨酯发泡层：将上述步骤(1)中所制备的带正电荷的纤维素纳米纤维与一定量的交联剂加入到步骤(2)中带负电荷的水性聚氨酯乳液中，或者将上述步骤(1)中所制备的带负电荷的纤维素纳米纤维与一定量的交联剂加入到步骤(2)中带正电荷的水性聚氨酯乳液中，在大力搅拌下使纤维素纳米纤维与水性聚氨酯纳米颗粒通过静电相互作用一起在气/液界面自组装形成双分子层从而得到稳定的Pickering泡沫，在室温下放置一段时间，让交联剂将泡沫的结构交联固化，最后除去溶剂水便得到阳离子型水性聚氨酯发泡层。
2.根据权利要求1所述的一种合成革用水性聚氨酯发泡层的制备方法，其特征在于步骤(1)中所用的木浆为磨盘机械浆、硫酸盐木浆、烧碱法浆、亚硫酸盐木浆、磨石磨木浆和热磨机械浆中的一种； 所用的有机溶剂A为甲酰胺、四甲基亚砜、乙腈、异丙醇、正丁醇和四氢呋喃中的一种； 所用的碱性物质B为二乙胺、三乙胺、三正丙胺、二异丙胺、三己胺和氢氧化钠中的一种。
3.根据权利要求1所述的一种合成革用水性聚氨酯发泡层的制备方法，其特征在于步骤(2)中所用的二异氰酸酯为异佛尔酮二异氰酸酯、1,3-苯二异氰酸酯、2,6-甲苯二异氰酸酯、六亚甲基二异氰酸酯和1,4-环己烷二异氰酸酯中的一种； 所用的大分子二元醇为聚四氢呋喃醚二醇、聚乙二醇、聚碳酸酯二醇、聚丙二醇、聚硅氧烷二醇和聚ε-己内酯二元醇中的一种或几种的混合； 所用的有机溶剂C为无水的四氢呋喃和丙酮中的一种。所用的亲水单体为N-甲基二乙醇胺、3-二甲氨基-1,2-丙二醇、二乙醇胺、间甲苯基二乙醇胺、N-丁基二乙醇胺、二羟甲基丙酸、二羟甲基丁酸、酒石酸、含羧基半酯二元醇、二氨基苯甲酸、乙二胺基乙磺酸盐中的一种； 所用的小分子扩链剂为赖氨酸、1,4-丁二醇、1,6-己二醇、二甘醇、1,4-丁二胺、乙二胺和肼等中的一种； 所用的酸性物质D为乙酸、丙酸、苯甲酸、丙烯酸和乳酸中的一种。
4.根据权利要求1所述的一种合成革用水性聚氨酯发泡层的制备方法，其特征在于步骤(3)中所用的交联剂为氮丙啶、三羟甲基三聚氰胺、六甲氧基亚甲基三聚氰胺、聚碳化二亚胺、环氧树脂和三乙烯四胺中的一种。
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