CN111101385B - A kind of preparation method of all-aqueous dry paste microfiber leather - Google Patents

A kind of preparation method of all-aqueous dry paste microfiber leather Download PDF

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CN111101385B
CN111101385B CN201911390032.6A CN201911390032A CN111101385B CN 111101385 B CN111101385 B CN 111101385B CN 201911390032 A CN201911390032 A CN 201911390032A CN 111101385 B CN111101385 B CN 111101385B
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island
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CN111101385A (en
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柴玉叶
刘若望
柴玉枝
许晓红
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Wenzhou University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • 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
    • D06N3/142—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 mixture of polyurethanes with other resins in the same layer
    • D06N3/144—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 mixture of polyurethanes with other resins in the same layer with polyurethane and polymerisation products, e.g. acrylics, PVC
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • 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
    • D06N3/145—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 two or more layers of polyurethanes
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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
    • D—TEXTILES; PAPER
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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
    • D06N3/147—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 isocyanates used
    • D06N3/148—(cyclo)aliphatic polyisocyanates
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    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
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    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1635—Elasticity
    • D—TEXTILES; PAPER
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    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention discloses a preparation method of full-water-based dry-pasting microfiber leather, which is characterized in that water-soluble polyvinyl alcohol is used as sea, nylon 6 is used as islands to prepare island-in-sea fibers, and the island-in-sea fibers are prepared into non-woven fabric by a carding needling method; then soaking the non-woven fabric by using mixed emulsion, wherein the mixed emulsion is a mixture of aqueous polyurethane emulsion and acrylic emulsion, and the aqueous polyurethane emulsion is formed by taking toluene-2, 4-diisocyanate and dibutyltin dilaurate as a catalyst and simultaneously adding a certain amount of polymer polyol and micromolecular polyol for reaction; wherein the polymer polyol is formed by reacting 1, 3-propanediol, 1, 5-glutaric acid, 3- (allyloxy) propane-1, 2-diol, and terephthalic acid; the acrylic emulsion is prepared by taking methyl methacrylate, ethyl acrylate and hydroxypropyl acrylate as reaction monomers. The finally prepared microfiber leather is soft, has plump hand feeling and high resilience; but also has large tensile load, tearing load and breaking elongation.

Description

一种全水性干贴超纤革制备方法A kind of preparation method of all-aqueous dry paste microfiber leather

技术领域technical field

本发明涉及合成革技术领域，更具体的说是涉及一种全水性干贴超纤革制备方法。The invention relates to the technical field of synthetic leather, in particular to a method for preparing all-water-based dry-applied microfiber leather.

背景技术Background technique

天然皮革由于受到资源的限制已不能满足人们日益增长的需求，作为天然皮革的替代品—合成革，以其良好的物理性能、手感和外观等特性，获得广泛的应用。其中超细纤维合成革是近年来发展起来的最新一代合成革产品，代表了合成革技术发展的主要方向。超细纤维合成革是以具有三维网状结构的超细纤维无纺布为增强材料，填充具有微孔结构的聚氨酯得到的。无论是内部微观结构，还是外观质感、物理特性以及穿着舒适性等方面，超细纤维合成革都能与天然皮革相媲美；而且在机械强度、耐化学性能、均一性、保型性等方面更优于天然皮革。目前，超细纤维合成革已广泛应用于高档运动鞋、箱包、服装、汽车内饰等各个领域，显示出广阔的发展前景。Due to the limitation of resources, natural leather can no longer meet the growing needs of people. As a substitute for natural leather—synthetic leather, it has been widely used for its good physical properties, hand feeling and appearance. Among them, microfiber synthetic leather is the latest generation of synthetic leather products developed in recent years, representing the main direction of synthetic leather technology development. Microfiber synthetic leather is obtained by using superfine fiber non-woven fabric with a three-dimensional network structure as a reinforcing material and filling polyurethane with a microporous structure. Microfiber synthetic leather is comparable to natural leather in terms of internal microstructure, appearance texture, physical properties, and wearing comfort; and it is better in terms of mechanical strength, chemical resistance, uniformity, and shape retention. Superior to natural leather. At present, microfiber synthetic leather has been widely used in various fields such as high-end sports shoes, bags, clothing, and automotive interiors, showing broad development prospects.

目前在超细纤维合成革的生产中，大多仍采用溶剂型聚氨酯浸渍超细纤维无纺布，再经湿法凝固、水洗、减量、干燥、后整理等工序，最终制得超细纤维合成革。溶剂型聚氨酯中大量的N，N－二甲基甲酰胺(DMF)等有机溶剂不仅造成了严重的环境污染，而且溶剂回收消耗了大量的能源和需要很大的设备投入。有机溶剂的环境污染已成为超细纤维合成革持续和快速发展所需要解决的关键问题。At present, in the production of ultra-fine fiber synthetic leather, most of them still use solvent-based polyurethane to impregnate ultra-fine fiber non-woven fabrics, and then undergo wet coagulation, water washing, weight reduction, drying, and post-finishing processes to finally obtain ultra-fine fiber synthetic leather. leather. A large amount of N, N-dimethylformamide (DMF) and other organic solvents in solvent-based polyurethane not only cause serious environmental pollution, but also consume a lot of energy and require a lot of equipment investment for solvent recovery. The environmental pollution of organic solvents has become a key problem to be solved for the sustainable and rapid development of microfiber synthetic leather.

发明内容Contents of the invention

针对现有技术存在的不足，本发明的目的在于提供一种全水性干贴超纤革制备方法，以水性聚氨酯浸渍超细纤维无纺布，无毒且安全；同时制得的超纤革具有拉伸负荷和撕裂负荷。Aiming at the deficiencies in the prior art, the purpose of the present invention is to provide a method for preparing fully water-based dry pasted microfiber leather, which is non-toxic and safe by impregnating superfine fiber non-woven fabric with water-based polyurethane; at the same time, the prepared microfiber leather has Tensile load and tear load.

为实现上述目的，本发明提供了如下技术方案：一种全水性干贴超纤革制备方法，包括以下步骤：In order to achieve the above object, the present invention provides the following technical solutions: a method for preparing fully water-based dry-applied microfiber leather, comprising the following steps:

步骤一：以水溶性聚乙烯醇做海，尼龙6做岛制成定岛海岛超细纤维，然后将该定岛海岛超细纤维通过梳理针刺法制成非织造布；Step 1: Use water-soluble polyvinyl alcohol to make the sea, and nylon 6 to make the island to make the superfine fiber of fixed island and sea island, and then make the superfine fiber of fixed island and sea island into a nonwoven fabric by carding and acupuncture;

步骤二：将非织造布送到湿法生产线中用混合乳液浸渍，得到水性基布；之后再将水性基布烘干，得到干燥后的水性基布；其中混合乳液为水性聚氨酯乳液和丙烯酸乳液的混合物，其质量比为8:1；Step 2: Send the nonwoven fabric to the wet production line and impregnate it with mixed emulsion to obtain a water-based base cloth; then dry the water-based base cloth to obtain a dried water-based base cloth; the mixed emulsion is water-based polyurethane emulsion and acrylic emulsion The mixture, its mass ratio is 8:1;

步骤三：将干燥后的水性基布放在碱液中进行碱减量处理，减量温度为85-95℃，减量时间为2-3h；减量结束后，用90-100℃的热水反复冲洗，直至水洗液呈中性，再定型烘干得到水性海岛超细贝斯；Step 3: Put the dried water-based fabric in lye for alkali reduction treatment, the reduction temperature is 85-95°C, and the reduction time is 2-3h; after the reduction is completed, use 90-100°C heat Rinse with water repeatedly until the washing liquid is neutral, then shape and dry to obtain water-based sea island ultra-fine bass;

步骤四，将水性海岛超细贝斯进行染色，磨皮处理；最后通过水性聚氨酯贴面，制得全水性干贴超纤革。Step 4: dye the water-based sea-island ultra-fine bass, and perform skin-brushing treatment; finally, through water-based polyurethane veneer, a fully water-based dry-applied microfiber leather is obtained.

作为本发明的进一步改进，步骤二中水性聚氨酯乳液包括下列重量份物质组成：As a further improvement of the present invention, the aqueous polyurethane emulsion in step 2 comprises the following components by weight:

甲苯-2,4-二异氰酸酯8份；8 parts of toluene-2,4-diisocyanate;

去离子水60份；60 parts of deionized water;

聚合物多元醇20份；20 parts of polymer polyols;

2,2-二甲基-1,3-丙二醇3份；3 parts of 2,2-dimethyl-1,3-propanediol;

二羟甲基丙酸2份；2 parts of dimethylolpropionic acid;

三乙胺2份；2 parts of triethylamine;

二月桂酸二丁基锡0.2份。0.2 parts of dibutyltin dilaurate.

作为本发明的进一步改进，所述聚合物多元醇的结构式为

Figure BDA0002344705410000031
所述聚合物多元醇的数均分子量为500-3000。As a further improvement of the present invention, the structural formula of the polymer polyol is
Figure BDA0002344705410000031
The number average molecular weight of the polymer polyol is 500-3000.

作为本发明的进一步改进，所述聚合物多元醇是由1,3-丙二醇、1,5-戊二酸、3-(烯丙氧基)丙烷-1,2-二醇和对苯二甲酸反应而成；As a further improvement of the present invention, the polymer polyol is formed by reacting 1,3-propanediol, 1,5-pentanedioic acid, 3-(allyloxy)propane-1,2-diol and terephthalic acid made;

其反应式为Its reaction formula is

Figure BDA0002344705410000032
Figure BDA0002344705410000032

作为本发明的进一步改进，所述聚合物多元醇的制备方法包括以下步骤：As a further improvement of the present invention, the preparation method of the polymer polyol comprises the following steps:

步骤一：在氮气保护下，将1,3-丙二醇、1,5-戊二酸和第一引发剂加入到装有溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为55-65℃的条件下进行反应，反应时间为13-15h；反应结束后，过滤提纯，制得第一初产物；Step 1: Under the protection of nitrogen, add 1,3-propanediol, 1,5-pentanedioic acid and the first initiator into the reaction vessel containing the solvent tetrahydrofuran, stir and mix, and mix well at a temperature of 55-65°C Under the conditions of reaction, the reaction time is 13-15h; after the reaction is finished, filter and purify to obtain the first initial product;

步骤二：在氮气保护下，将3-(烯丙氧基)丙烷-1,2-二醇、对苯二甲酸和第二引发剂加入到装有溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为70-80℃的条件下进行反应，反应时间为18-20h；反应结束后，过滤提纯，制得第二初产物；Step 2: Under the protection of nitrogen, add 3-(allyloxy)propane-1,2-diol, terephthalic acid and the second initiator into the reaction vessel containing the solvent tetrahydrofuran, stir and mix, and mix well Finally, the reaction is carried out at a temperature of 70-80°C, and the reaction time is 18-20h; after the reaction is completed, it is filtered and purified to obtain the second primary product;

步骤三：在氮气保护下，将第一初产物、第二初产物和第三引发剂加入到装有溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为85-95℃的条件下进行反应，反应时间为14-16h；反应结束后，过滤提纯，制得聚合物多元醇。Step 3: Under the protection of nitrogen, add the first primary product, the second primary product and the third initiator into the reaction vessel containing the solvent tetrahydrofuran, stir and mix, and mix uniformly and carry out at a temperature of 85-95°C Reaction, the reaction time is 14-16h; after the reaction, filter and purify to obtain polymer polyol.

作为本发明的进一步改进，所述第一引发剂为过氧化苯甲酰；所述第二引发剂为偶氮二异丁腈；所述第三引发剂为二苯甲基钾。As a further improvement of the present invention, the first initiator is benzoyl peroxide; the second initiator is azobisisobutyronitrile; and the third initiator is potassium benzhydryl.

作为本发明的进一步改进，所述水性聚氨酯乳液的制备方法为：根据设定的重量份配备原料，将甲苯-2,4-二异氰酸酯、聚合物多元醇、二月桂酸二丁基锡加入反应器内搅拌混合，混合均匀后在110-120℃的条件下反应3小时，接着加入2,2-二甲基-1,3-丙二醇和二羟甲基丙酸继续反应4小时；然后将温度降低至60℃，加入三乙胺继续反应30min；然后加入去离子水在转速为600r/min的条件下反应1小时，得到水性聚氨酯乳液。As a further improvement of the present invention, the preparation method of the water-based polyurethane emulsion is: prepare raw materials according to the set weight parts, add toluene-2,4-diisocyanate, polymer polyol, dibutyltin dilaurate into the reactor Stir and mix, mix well and react at 110-120°C for 3 hours, then add 2,2-dimethyl-1,3-propanediol and dimethylol propionic acid to continue the reaction for 4 hours; then lower the temperature to 60°C, add triethylamine and continue to react for 30 minutes; then add deionized water and react for 1 hour under the condition of rotating speed of 600r/min to obtain a water-based polyurethane emulsion.

作为本发明的进一步改进，所述丙烯酸乳液包括下列重量份物质组成丙烯酸单体20份As a further improvement of the present invention, the acrylic emulsion includes the following parts by weight of 20 parts of acrylic monomers:

十二烷基硫酸钠1份；1 part sodium lauryl sulfate;

过硫酸铵3份；3 parts of ammonium persulfate;

所述丙烯酸单体为甲基丙烯酸甲酯、丙烯酸乙酯和丙烯酸羟丙酯的混合物，其质量比为3:1:1。The acrylic acid monomer is a mixture of methyl methacrylate, ethyl acrylate and hydroxypropyl acrylate, and its mass ratio is 3:1:1.

作为本发明的进一步改进，所述丙烯酸乳液的制备方法为将丙烯酸单体、过硫酸铵和十二烷基硫酸钠加入到装有去离子水的反应容器中搅拌混合，混合均匀后在温度为80-90℃的条件下进行反应，反应时间为3-5h；反应结束后，用质量浓度为20％的氨水将体系pH调解至7.5-8.0，制得丙烯酸酯乳液。As a further improvement of the present invention, the preparation method of the acrylic acid emulsion is to add acrylic acid monomers, ammonium persulfate and sodium lauryl sulfate into a reaction vessel equipped with deionized water and stir and mix them. The reaction is carried out under the condition of 80-90° C., and the reaction time is 3-5 hours; after the reaction is completed, the pH of the system is adjusted to 7.5-8.0 with ammonia water with a mass concentration of 20%, to prepare an acrylate emulsion.

作为本发明的进一步改进，所述碱液为质量浓度为10％的氢氧化钠水溶液。As a further improvement of the present invention, the lye is an aqueous sodium hydroxide solution with a mass concentration of 10%.

本发明的有益效果：通过以水溶性聚乙烯醇作为海，以尼龙6作岛制成定岛海岛纤维，该定岛海岛纤维通过梳理针刺法制成非织造布，该非织造布即为超细纤维皮革的骨架材料；然后用混合乳液浸渍非织造布，混合乳液为水性聚氨酯乳液和丙烯酸乳液的混合物，没有使用有机溶剂型聚氨酯乳液，不含有机溶剂DMF，更加绿色环保，安全；作为本发明的新创点之一，该水性聚氨酯乳液是以甲苯-2,4-二异氰酸酯，以二月桂酸二丁基锡为催化剂，同时还加入了一定量的聚合物多元醇和小分子多元醇反应而成；其中聚合物多元醇是由1,3-丙二醇、1,5-戊二酸、3-(烯丙氧基)丙烷-1,2-二醇和对苯二甲酸反应而成，其分子结构式为

Figure BDA0002344705410000051
其数均分子量为500-3000；该聚合物多元醇中酯基，苯基，碳碳双键等官能团；通过将该水性聚氨酯溶液浸渍到非织造布的间隙中，通过聚氨酯黏连，使得非织造布从宏观上形成有机整体结构，具备类似真皮的质感；经过本发明的水性聚氨酯乳液浸渍后，制得的超纤革较为柔软，手感较好，回弹性较高，同时还具有较好的力学性能；作为本发明的创造性之一，除了用水性聚氨酯乳液对非织造布进行浸渍，还用了聚丙烯酸乳液进行浸渍，丙烯酸乳液是甲基丙烯酸甲酯、丙烯酸乙酯和丙烯酸羟丙酯作为反应单体，制备而成；在丙烯酸乳液的浸渍后，能够进一步提高超纤革的柔软度，回弹性，丰满度和力学性能。浸渍结束后，将干燥后的水性基布放在碱液中进行碱减量处理，再定型烘干得到水性海岛超细贝斯；最后将水性海岛超细贝斯进行染色，磨皮等处理，制得全水性干贴超纤革；最终制得的超纤革很柔软，手感丰满，同时具有较高的回弹性；还具有较大的拉伸负荷、撕裂负荷和断裂伸长率，能够满足实际生产生活的需求。Beneficial effects of the present invention: by using water-soluble polyvinyl alcohol as the sea and nylon 6 as the island to make fixed-island sea-island fibers, the fixed-island sea-island fibers are made into nonwoven fabrics by carding and acupuncture, and the nonwoven fabrics are super The skeleton material of fine fiber leather; then impregnate the non-woven fabric with mixed emulsion, the mixed emulsion is a mixture of water-based polyurethane emulsion and acrylic emulsion, without using organic solvent-based polyurethane emulsion, and does not contain organic solvent DMF, which is more green and safe; as this One of the innovations of the invention, the water-based polyurethane emulsion is formed by reacting toluene-2,4-diisocyanate with dibutyltin dilaurate as a catalyst, and adding a certain amount of polymer polyol and small molecule polyol. ; wherein the polymer polyol is formed by the reaction of 1,3-propanediol, 1,5-pentanedioic acid, 3-(allyloxy) propane-1,2-diol and terephthalic acid, and its molecular structure is
Figure BDA0002344705410000051
Its number-average molecular weight is 500-3000; functional groups such as ester groups, phenyl groups, and carbon-carbon double bonds in the polymer polyol; by impregnating the aqueous polyurethane solution into the gaps of the non-woven fabric, it is bonded by polyurethane to make the non-woven fabric The woven fabric forms an organic overall structure macroscopically, and has a texture similar to genuine leather; after being impregnated with the water-based polyurethane emulsion of the present invention, the prepared microfiber leather is relatively soft, has a good hand feeling, high resilience, and has good Mechanical properties; as one of the inventions of the present invention, in addition to impregnating the non-woven fabric with water-based polyurethane emulsion, polyacrylic acid emulsion is also used for impregnation, and the acrylic emulsion is methyl methacrylate, ethyl acrylate and hydroxypropyl acrylate as It is prepared from reactive monomers; after impregnated with acrylic emulsion, it can further improve the softness, resilience, fullness and mechanical properties of microfiber leather. After the impregnation, the dried water-based base cloth is placed in lye for alkali weight reduction treatment, and then shaped and dried to obtain the water-based sea-island ultra-fine bass; finally, the water-based sea-island ultra-fine bass is dyed, dermabrasion and other treatments to obtain Fully water-based dry paste microfiber leather; the final microfiber leather is very soft, full-feeling, and has high resilience; it also has a large tensile load, tear load and elongation at break, which can meet the actual production needs.

具体实施方式detailed description

实施例1(制备聚合物多元醇)Embodiment 1 (preparation polymer polyol)

所述聚合物多元醇的制备方法包括以下步骤：The preparation method of described polymer polyol comprises the following steps:

步骤一：在氮气保护下，将8g1,3-丙二醇、15g1,5-戊二酸和5g第一引发剂过氧化苯甲酰加入到装有100ml溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为60℃的条件下进行反应，反应时间为14h；反应结束后，过滤提纯，制得第一初产物；Step 1: Under nitrogen protection, add 8g of 1,3-propanediol, 15g of 1,5-glutaric acid and 5g of the first initiator benzoyl peroxide into a reaction vessel containing 100ml of solvent tetrahydrofuran and stir to mix. The reaction was carried out at a temperature of 60° C., and the reaction time was 14 hours; after the reaction was completed, it was filtered and purified to obtain the first primary product;

步骤二：在氮气保护下，将16g3-(烯丙氧基)丙烷-1,2-二醇、20g对苯二甲酸和5g第二引发剂偶氮二异丁腈加入到装有100ml溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为75℃的条件下进行反应，反应时间为19h；反应结束后，过滤提纯，制得第二初产物；Step 2: under nitrogen protection, 16g3-(allyloxy) propane-1,2-diol, 20g terephthalic acid and 5g second initiator azobisisobutyronitrile are added to 100ml solvent tetrahydrofuran Stir and mix in a reaction vessel, mix evenly and react at a temperature of 75°C for 19 hours; after the reaction, filter and purify to obtain the second primary product;

步骤三：在氮气保护下，将3g第一初产物、5g第二初产物和0.5g第三引发剂二苯甲基钾加入到装有40ml溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为90℃的条件下进行反应，反应时间为15h；反应结束后，过滤提纯，制得聚合物多元醇。Step 3: under nitrogen protection, the first initial product of 3g, the second initial product of 5g and the third initiator benzhydryl potassium of 0.5g are added in the reaction vessel that 40ml solvent tetrahydrofuran is housed and stirred and mixed, after mixing uniformly The reaction is carried out at a temperature of 90° C., and the reaction time is 15 hours; after the reaction is completed, the polymer polyol is obtained by filtering and purifying.

其反应式为Its reaction formula is

Figure BDA0002344705410000061
Figure BDA0002344705410000061

聚合物多元醇的结构式为

Figure BDA0002344705410000062
The structural formula of polymer polyol is
Figure BDA0002344705410000062

实施例2(制备水性聚氨酯乳液)Embodiment 2 (preparation of aqueous polyurethane emulsion)

所述水性聚氨酯乳液包括下列重量份物质组成：Described water-based polyurethane emulsion comprises the following components by weight:

甲苯-2,4-二异氰酸酯8份；8 parts of toluene-2,4-diisocyanate;

去离子水60份；60 parts of deionized water;

聚合物多元醇20份；(由实施例1制得)20 parts of polymer polyols; (made by embodiment 1)

2,2-二甲基-1,3-丙二醇3份；3 parts of 2,2-dimethyl-1,3-propanediol;

二羟甲基丙酸2份；2 parts of dimethylolpropionic acid;

三乙胺2份；2 parts of triethylamine;

二月桂酸二丁基锡0.2份。0.2 parts of dibutyltin dilaurate.

所述水性聚氨酯乳液的制备方法为：根据设定的重量份配备原料，将甲苯-2,4-二异氰酸酯、聚合物多元醇(实施例1制得)、二月桂酸二丁基锡加入反应器内搅拌混合，混合均匀后在115℃的条件下反应3小时，接着加入2,2-二甲基-1,3-丙二醇和二羟甲基丙酸继续反应4小时；然后将温度降低至60℃，加入三乙胺继续反应30min；然后加入去离子水在转速为600r/min的条件下反应1小时，得到水性聚氨酯乳液。The preparation method of the water-based polyurethane emulsion is as follows: according to the set weight parts, the raw materials are equipped, and toluene-2,4-diisocyanate, polymer polyol (prepared in Example 1), and dibutyltin dilaurate are added to the reactor Stir and mix, mix well and react at 115°C for 3 hours, then add 2,2-dimethyl-1,3-propanediol and dimethylol propionic acid to continue the reaction for 4 hours; then lower the temperature to 60°C , adding triethylamine to continue the reaction for 30 minutes; then adding deionized water and reacting for 1 hour under the condition of a rotating speed of 600r/min to obtain an aqueous polyurethane emulsion.

实施例3(制备丙烯酸乳液)Embodiment 3 (preparation of acrylic acid emulsion)

所述丙烯酸乳液包括下列重量份物质组成The acrylic emulsion comprises the following components by weight

丙烯酸单体20份Acrylic monomer 20 parts

十二烷基硫酸钠1份；1 part sodium lauryl sulfate;

过硫酸铵3份；3 parts of ammonium persulfate;

所述丙烯酸单体为甲基丙烯酸甲酯、丙烯酸乙酯和丙烯酸羟丙酯的混合物，其质量比为3:1:1。The acrylic acid monomer is a mixture of methyl methacrylate, ethyl acrylate and hydroxypropyl acrylate, and its mass ratio is 3:1:1.

所述丙烯酸乳液的制备方法为将20g丙烯酸单体、3g过硫酸铵和1g十二烷基硫酸钠加入到装有100ml去离子水的反应容器中搅拌混合，混合均匀后在温度为85℃的条件下进行反应，反应时间为4h；反应结束后，用质量浓度为20％的氨水将体系pH调解至7.5-8.0，制得丙烯酸酯乳液。The preparation method of the acrylic acid emulsion is to add 20g of acrylic acid monomer, 3g of ammonium persulfate and 1g of sodium lauryl sulfate into a reaction vessel with 100ml of deionized water and stir and mix them. The reaction is carried out under certain conditions, and the reaction time is 4 hours; after the reaction is completed, the pH of the system is adjusted to 7.5-8.0 with ammonia water with a mass concentration of 20%, to prepare an acrylate emulsion.

实施例4Example 4

一种全水性干贴超纤革制备方法，其特征在于：包括以下步骤：A kind of preparation method of all-aqueous dry paste microfiber leather, it is characterized in that: comprise the following steps:

步骤一：以水溶性聚乙烯醇做海，尼龙6做岛制成定岛海岛超细纤维，然后将该定岛海岛超细纤维通过梳理针刺法制成非织造布；Step 1: Use water-soluble polyvinyl alcohol to make the sea, and nylon 6 to make the island to make the superfine fiber of fixed island and sea island, and then make the superfine fiber of fixed island and sea island into a nonwoven fabric by carding and acupuncture;

步骤二：将非织造布送到湿法生产线中用混合乳液浸渍，得到水性基布；之后再将水性基布在80℃的条件下烘干，烘干时间为1h，得到干燥后的水性基布；其中混合乳液为水性聚氨酯乳液(由实施例2制得)和丙烯酸乳液(由实施例3制得)的混合物，其质量比为8:1；Step 2: Send the nonwoven fabric to the wet production line and impregnate it with mixed emulsion to obtain a water-based base cloth; then dry the water-based base cloth at 80°C for 1 hour to obtain a dried water-based base cloth. Cloth; Wherein mixed emulsion is the mixture of aqueous polyurethane emulsion (made by embodiment 2) and acrylic acid emulsion (made by embodiment 3), and its mass ratio is 8:1;

步骤三：将干燥后的水性基布放在碱液中进行碱减量处理，减量温度为90℃，减量时间为2h；减量结束后，用95℃的热水反复冲洗，直至水洗液呈中性，再定型烘干，得到水性海岛超细贝斯；Step 3: Put the dried water-based fabric in lye for alkali reduction treatment. The reduction temperature is 90°C, and the reduction time is 2 hours. The liquid is neutral, and then shaped and dried to obtain a water-based island ultra-fine bass;

步骤四，将水性海岛超细贝斯进行染色，磨皮处理；最后通过水性聚氨酯贴面，制得全水性干贴超纤革。Step 4: dye the water-based sea-island ultra-fine bass, and perform skin-brushing treatment; finally, through water-based polyurethane veneer, a fully water-based dry-applied microfiber leather is obtained.

对比例1Comparative example 1

一种全水性干贴超纤革制备方法，其特征在于：包括以下步骤：A kind of preparation method of all-aqueous dry paste microfiber leather, it is characterized in that: comprise the following steps:

步骤一：以水溶性聚乙烯醇做海，尼龙6做岛制成定岛海岛超细纤维，然后将该定岛海岛超细纤维通过梳理针刺法制成非织造布；Step 1: Use water-soluble polyvinyl alcohol to make the sea, and nylon 6 to make the island to make the superfine fiber of fixed island and sea island, and then make the superfine fiber of fixed island and sea island into a nonwoven fabric by carding and acupuncture;

步骤二：将非织造布送到湿法生产线中用水性聚氨酯乳液浸渍，得到水性基布；之后再将水性基布在80℃的条件下烘干，烘干时间为1h，得到干燥后的水性基布；Step 2: Send the nonwoven fabric to the wet-laid production line for impregnation with water-based polyurethane emulsion to obtain a water-based base fabric; then dry the water-based base fabric at 80°C for 1 hour to obtain a dried water-based base fabric. fabric;

步骤三：将干燥后的水性基布放在碱液中进行碱减量处理，减量温度为90℃，减量时间为2h；减量结束后，用95℃的热水反复冲洗，直至水洗液呈中性，再定型烘干，得到水性海岛超细贝斯；Step 3: Put the dried water-based fabric in lye for alkali reduction treatment. The reduction temperature is 90°C, and the reduction time is 2 hours. The liquid is neutral, and then shaped and dried to obtain a water-based island ultra-fine bass;

步骤四，将水性海岛超细贝斯进行染色，磨皮处理；最后通过水性聚氨酯贴面，制得全水性干贴超纤革。Step 4: dye the water-based sea-island ultra-fine bass, and perform skin-brushing treatment; finally, through water-based polyurethane veneer, a fully water-based dry-applied microfiber leather is obtained.

其中水性聚氨酯乳液从浙江高得宝利新材料有限公司购买得到。Wherein the water-based polyurethane emulsion was purchased from Zhejiang Gaodebaoli New Material Co., Ltd.

性能测试Performance Testing

用万能试验机测试样的拉伸负荷、撕裂负荷和断裂伸长率；Test the tensile load, tear load and elongation at break of the sample with a universal testing machine;

试样的抗弯刚度用全自动织物硬挺度仪，按GB/T18318－2001《纺织品织物弯曲长度的测定》进行测试；用织物厚度仪测试样的压缩弹性率和比压缩弹性率。The flexural stiffness of the sample is tested with a fully automatic fabric stiffness tester according to GB/T18318-2001 "Determination of the Bending Length of Textile Fabrics"; the compressive modulus and specific compressive modulus of the sample are tested with a fabric thickness tester.

其结果如下表The results are as follows

性能performance 实施例4Example 4 对比例1Comparative example 1 拉伸负荷/NTensile load/N 168168 137137 撕裂负荷/NTear load/N 5151 3636 断裂伸长率/％Elongation at break/% 10201020 260260 抗弯刚度/(mN·cm)Bending stiffness/(mN cm) 649649 20352035 压缩弹性率/％Compression elastic rate/% 84.284.2 41.241.2 比压缩弹性率/％Specific compression elastic rate/% 4.54.5 2.32.3

柔软、丰满、回弹性是对超细纤维合成革基布手感的基本要求；本发明中分别以抗弯刚度、压缩弹性率和比压缩弹性率定量表征超细纤维合成革基布的柔软度、回弹性和丰满度。抗弯刚度越小，超纤革的手感越柔软；压缩弹性率越大，超纤革弹性的恢复能力越好，即回弹性越好；而比压缩弹性率越大，表示超纤革的手感越丰满。Softness, plumpness and resilience are the basic requirements to the feel of the microfiber synthetic leather base cloth; in the present invention, the softness, compression modulus and specific compression modulus of the microfiber synthetic leather base cloth are quantitatively characterized respectively Resilience and fullness. The smaller the bending stiffness, the softer the feel of the microfiber leather; the greater the compression elasticity, the better the recovery ability of the elasticity of the microfiber leather, that is, the better the resilience; and the greater the specific compression elasticity, it means the feel of the microfiber leather The more plump.

由上表可知，本发明制得的超纤革具有较小的抗弯强度，较大的压缩弹性率和比压缩弹性率，从而说明了本发明的超纤革很柔软，手感丰满，同时具有较高的回弹性，能够满足实际生产生活的需求。As can be seen from the above table, the microfiber leather prepared by the present invention has less flexural strength, larger compression modulus and specific compression modulus, thereby illustrating that the microfiber leather of the present invention is very soft, feels full, and has High resilience can meet the needs of actual production and life.

由上表可知，本发明制得的超纤革具有较大的拉伸负荷、撕裂负荷和断裂伸长率，进一步说明了本发明制得的超纤革具有优异的性能，能够满足实际生产生活的需求。As can be seen from the above table, the microfiber leather prepared by the present invention has a relatively large tensile load, tear load and elongation at break, further illustrating that the microfiber leather prepared by the present invention has excellent performance and can meet the requirements of actual production. the needs of life.

本发明的一种全水性干贴超纤革制备方法，以水溶性聚乙烯醇作为海，以尼龙6作岛制成定岛海岛纤维，该定岛海岛纤维通过梳理针刺法制成非织造布，该非织造布即为超细纤维皮革的骨架材料；A method for preparing fully water-based dry-applied microfiber leather of the present invention uses water-soluble polyvinyl alcohol as the sea and nylon 6 as the island to make fixed-island sea-island fibers, and the fixed-island sea-island fibers are made into nonwoven fabrics by carding and acupuncture , the non-woven fabric is the skeleton material of microfiber leather;

然后用混合乳液浸渍非织造布，混合乳液为水性聚氨酯乳液和丙烯酸乳液的混合物，没有使用有机溶剂型聚氨酯乳液，不含有机溶剂DMF，更加绿色环保，安全；作为本发明的新创点之一，该水性聚氨酯乳液是以甲苯-2,4-二异氰酸酯，以二月桂酸二丁基锡为催化剂，同时还加入了一定量的聚合物多元醇和小分子多元醇反应而成；其中聚合物多元醇是由1,3-丙二醇、1,5-戊二酸、3-(烯丙氧基)丙烷-1,2-二醇和对苯二甲酸反应而成，其分子结构式为

Figure BDA0002344705410000101
其数均分子量为500-3000；该聚合物多元醇中酯基，苯基，碳碳双键等官能团；通过将该水性聚氨酯溶液浸渍到非织造布的间隙中，通过聚氨酯黏连，使得非织造布从宏观上形成有机整体结构，具备类似真皮的质感；经过本发明的水性聚氨酯乳液浸渍后，制得的超纤革较为柔软，手感较好，回弹性较高，同时还具有较好的力学性能；作为本发明的创造性之一，除了用水性聚氨酯乳液对非织造布进行浸渍，还用了聚丙烯酸乳液进行浸渍，丙烯酸乳液是甲基丙烯酸甲酯、丙烯酸乙酯和丙烯酸羟丙酯作为反应单体，制备而成；在丙烯酸乳液的浸渍后，能够进一步提高超纤革的柔软度，回弹性，丰满度和力学性能。浸渍结束后，将干燥后的水性基布放在碱液中进行碱减量处理，再定型烘干得到水性海岛超细贝斯；最后将水性海岛超细贝斯进行染色，磨皮等处理，制得全水性干贴超纤革；最终制得的超纤革很柔软，手感丰满，同时具有较高的回弹性；还具有较大的拉伸负荷、撕裂负荷和断裂伸长率，能够满足实际生产生活的需求。Then impregnate the non-woven fabric with the mixed emulsion, the mixed emulsion is a mixture of water-based polyurethane emulsion and acrylic emulsion, does not use organic solvent polyurethane emulsion, does not contain organic solvent DMF, is more green, environmentally friendly and safe; as one of the new innovations of the present invention , the water-based polyurethane emulsion is formed by reacting toluene-2,4-diisocyanate with dibutyltin dilaurate as a catalyst, and adding a certain amount of polymer polyol and small molecule polyol; the polymer polyol is It is formed by the reaction of 1,3-propanediol, 1,5-pentanedioic acid, 3-(allyloxy)propane-1,2-diol and terephthalic acid, and its molecular structure is
Figure BDA0002344705410000101
Its number-average molecular weight is 500-3000; functional groups such as ester groups, phenyl groups, and carbon-carbon double bonds in the polymer polyol; by impregnating the aqueous polyurethane solution into the gaps of the non-woven fabric, it is bonded by polyurethane to make the non-woven fabric The woven fabric forms an organic overall structure macroscopically, and has a texture similar to genuine leather; after being impregnated with the water-based polyurethane emulsion of the present invention, the prepared microfiber leather is relatively soft, has a good hand feeling, high resilience, and has good Mechanical properties; as one of the inventions of the present invention, in addition to impregnating the non-woven fabric with water-based polyurethane emulsion, polyacrylic acid emulsion is also used for impregnation, and the acrylic emulsion is methyl methacrylate, ethyl acrylate and hydroxypropyl acrylate as It is prepared from reactive monomers; after impregnated with acrylic emulsion, it can further improve the softness, resilience, fullness and mechanical properties of microfiber leather. After the impregnation, the dried water-based base cloth is placed in lye for alkali weight reduction treatment, and then shaped and dried to obtain the water-based sea-island ultra-fine bass; finally, the water-based sea-island ultra-fine bass is dyed, dermabrasion and other treatments to obtain Fully water-based dry paste microfiber leather; the final microfiber leather is very soft, full-feeling, and has high resilience; it also has a large tensile load, tear load and elongation at break, which can meet the actual production needs.

以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above descriptions are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, some improvements and modifications without departing from the principles of the present invention should also be regarded as the protection scope of the present invention.

Claims (8)

1.一种全水性干贴超纤革制备方法，其特征在于：包括以下步骤：1. a kind of all-aqueous dry pasting microfiber leather preparation method is characterized in that: comprise the following steps: 步骤一：以水溶性聚乙烯醇做海，尼龙6做岛制成定岛海岛超细纤维，然后将该定岛海岛超细纤维通过梳理针刺法制成非织造布；Step 1: Use water-soluble polyvinyl alcohol to make the sea, and nylon 6 to make the island to make the superfine fiber of fixed island and sea island, and then make the superfine fiber of fixed island and sea island into a nonwoven fabric by carding and acupuncture; 步骤二：将非织造布送到湿法生产线中用混合乳液浸渍，得到水性基布；之后再将水性基布烘干，得到干燥后的水性基布；其中混合乳液为水性聚氨酯乳液和丙烯酸乳液的混合物，其质量比为8:1；Step 2: Send the nonwoven fabric to the wet production line and impregnate it with mixed emulsion to obtain a water-based base cloth; then dry the water-based base cloth to obtain a dried water-based base cloth; the mixed emulsion is water-based polyurethane emulsion and acrylic emulsion The mixture, its mass ratio is 8:1; 步骤三：将干燥后的水性基布放在碱液中进行碱减量处理，减量温度为85-95℃，减量时间为2-3h；减量结束后，用90-100℃的热水反复冲洗，直至水洗液呈中性，再定型烘干得到水性海岛超细贝斯；Step 3: Put the dried water-based fabric in lye for alkali reduction treatment, the reduction temperature is 85-95°C, and the reduction time is 2-3h; after the reduction is completed, use 90-100°C heat Rinse with water repeatedly until the washing liquid is neutral, then shape and dry to obtain water-based sea island ultra-fine bass; 步骤四，将水性海岛超细贝斯进行染色，磨皮处理；最后通过水性聚氨酯贴面，制得全水性干贴超纤革；Step 4: Dye the water-based sea-island ultra-fine bass, and perform skin-brushing treatment; finally, through the water-based polyurethane veneer, make a fully water-based dry-applied microfiber leather; 步骤二中水性聚氨酯乳液包括下列重量份物质组成：甲苯-2,4-二异氰酸酯8份；去离子水60份；聚合物多元醇20份；2,2-二甲基-1,3-丙二醇3份；The water-based polyurethane emulsion in step 2 includes the following components by weight: 8 parts of toluene-2,4-diisocyanate; 60 parts of deionized water; 20 parts of polymer polyol; 2,2-dimethyl-1,3-propanediol 3 copies; 二羟甲基丙酸2份；三乙胺2份；二月桂酸二丁基锡0.2份；2 parts of dimethylol propionic acid; 2 parts of triethylamine; 0.2 part of dibutyltin dilaurate; 所述聚合物多元醇的结构式为The structural formula of the polymer polyol is
Figure FDA0003761800390000011
Figure FDA0003761800390000011
 所述聚合物多元醇的数均分子量为500-3000。The number average molecular weight of the polymer polyol is 500-3000. 2.根据权利要求1所述的一种全水性干贴超纤革制备方法，其特征在于：所述聚合物多元醇是由1,3-丙二醇、1,5-戊二酸、3-(烯丙氧基)丙烷-1,2-二醇和对苯二甲酸反应而成；2. a kind of all-water-based dry paste microfiber leather preparation method according to claim 1, is characterized in that: described polymer polyol is made of 1,3-propanediol, 1,5-glutaric acid, 3-( Allyloxy)propane-1,2-diol reacted with terephthalic acid; 其反应式为Its reaction formula is
Figure FDA0003761800390000021
Figure FDA0003761800390000021
 3.根据权利要求2所述的一种全水性干贴超纤革制备方法，其特征在于：所述聚合物多元醇的制备方法包括以下步骤：3. a kind of all water-based dry pasting microfiber leather preparation method according to claim 2, is characterized in that: the preparation method of described polymer polyol comprises the following steps: 步骤一：在氮气保护下，将1,3-丙二醇、1,5-戊二酸和第一引发剂加入到装有溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为55-65℃的条件下进行反应，反应时间为13-15h；反应结束后，过滤提纯，制得第一初产物；Step 1: Under the protection of nitrogen, add 1,3-propanediol, 1,5-pentanedioic acid and the first initiator into the reaction vessel containing the solvent tetrahydrofuran, stir and mix, and mix well at a temperature of 55-65°C Under the conditions of reaction, the reaction time is 13-15h; after the reaction is finished, filter and purify to obtain the first initial product; 步骤二：在氮气保护下，将3-(烯丙氧基)丙烷-1,2-二醇、对苯二甲酸和第二引发剂加入到装有溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为70-80℃的条件下进行反应，反应时间为18-20h；反应结束后，过滤提纯，制得第二初产物；Step 2: Under the protection of nitrogen, add 3-(allyloxy)propane-1,2-diol, terephthalic acid and the second initiator into the reaction vessel containing the solvent tetrahydrofuran, stir and mix, and mix well Finally, the reaction is carried out at a temperature of 70-80°C, and the reaction time is 18-20h; after the reaction is completed, it is filtered and purified to obtain the second primary product; 步骤三：在氮气保护下，将第一初产物、第二初产物和第三引发剂加入到装有溶剂四氢呋喃的反应容器中搅拌混合，混合均匀后在温度为85-95℃的条件下进行反应，反应时间为14-16h；反应结束后，过滤提纯，制得聚合物多元醇。Step 3: Under the protection of nitrogen, add the first primary product, the second primary product and the third initiator into the reaction vessel containing the solvent tetrahydrofuran, stir and mix, and mix uniformly and carry out at a temperature of 85-95°C Reaction, the reaction time is 14-16h; after the reaction, filter and purify to obtain polymer polyol. 4.根据权利要求3所述的一种全水性干贴超纤革制备方法，其特征在于：所述第一引发剂为过氧化苯甲酰；所述第二引发剂为偶氮二异丁腈；所述第三引发剂为二苯甲基钾。4. a kind of all-aqueous dry paste microfiber leather preparation method according to claim 3 is characterized in that: described first initiator is benzoyl peroxide; Described second initiator is azobisisobutyl Nitrile; The third initiator is potassium benzhydryl. 5.根据权利要求4所述的一种全水性干贴超纤革制备方法，其特征在于：所述水性聚氨酯乳液的制备方法为：根据设定的重量份配备原料，将甲苯-2,4-二异氰酸酯、聚合物多元醇、二月桂酸二丁基锡加入反应器内搅拌混合，混合均匀后在110-120℃的条件下反应3小时，接着加入2,2-二甲基-1,3-丙二醇和二羟甲基丙酸继续反应4小时；然后将温度降低至60℃，加入三乙胺继续反应30min；然后加入去离子水在转速为600r/min的条件下反应1小时，得到水性聚氨酯乳液。5. The preparation method of a kind of all-water-based dry paste microfiber leather according to claim 4, characterized in that: the preparation method of the water-based polyurethane emulsion is: prepare raw materials according to the set weight parts, and toluene-2,4 - Add diisocyanate, polymer polyol, dibutyltin dilaurate into the reactor and stir to mix. After mixing evenly, react at 110-120°C for 3 hours, then add 2,2-dimethyl-1,3- Propylene glycol and dimethylolpropionic acid continued to react for 4 hours; then lowered the temperature to 60°C, added triethylamine and continued to react for 30 minutes; then added deionized water and reacted for 1 hour at a speed of 600r/min to obtain waterborne polyurethane lotion. 6.根据权利要求5所述的一种全水性干贴超纤革制备方法，其特征在于：所述丙烯酸乳液包括下列重量份物质组成6. A method for preparing fully water-based dry-applied microfiber leather according to claim 5, characterized in that: said acrylic emulsion comprises the following components by weight 丙烯酸单体20份Acrylic monomer 20 parts 十二烷基硫酸钠1份；1 part sodium lauryl sulfate; 过硫酸铵3份；3 parts of ammonium persulfate; 所述丙烯酸单体为甲基丙烯酸甲酯、丙烯酸乙酯和丙烯酸羟丙酯的混合物，其质量比为3:1:1。The acrylic acid monomer is a mixture of methyl methacrylate, ethyl acrylate and hydroxypropyl acrylate, and its mass ratio is 3:1:1. 7.根据权利要求6所述的一种全水性干贴超纤革制备方法，其特征在于：所述丙烯酸乳液的制备方法为将丙烯酸单体、过硫酸铵和十二烷基硫酸钠加入到装有去离子水的反应容器中搅拌混合，混合均匀后在温度为80-90℃的条件下进行反应，反应时间为3-5h；反应结束后，用质量浓度为20％的氨水将体系pH调解至7.5-8.0，制得丙烯酸酯乳液。7. a kind of all-aqueous dry pasting superfiber leather preparation method according to claim 6 is characterized in that: the preparation method of described acrylic acid emulsion is that acrylic acid monomer, ammonium persulfate and sodium lauryl sulfate are added to Stir and mix in a reaction vessel equipped with deionized water, and react at a temperature of 80-90°C after mixing evenly, and the reaction time is 3-5h; Adjust to 7.5-8.0 to prepare acrylate emulsion. 8.根据权利要求7所述的一种全水性干贴超纤革制备方法，其特征在于：所述碱液为质量浓度为10％的氢氧化钠水溶液。8. A method for preparing fully water-based dry-applied microfiber leather according to claim 7, characterized in that: the lye is an aqueous sodium hydroxide solution with a mass concentration of 10%.
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