CN108276761B - Polyurethane resin for solvent-free leather, and preparation method and application thereof - Google Patents

Polyurethane resin for solvent-free leather, and preparation method and application thereof Download PDF

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CN108276761B
CN108276761B CN201711500719.1A CN201711500719A CN108276761B CN 108276761 B CN108276761 B CN 108276761B CN 201711500719 A CN201711500719 A CN 201711500719A CN 108276761 B CN108276761 B CN 108276761B
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resin
diisocyanate
polyether
diol
component
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CN108276761A (en
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于吉鹏
张初银
付志朋
马元明
吴晓敏
张兵
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Zhejiang Huafon Synthetic Resin Co ltd
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Zhejiang Huafon Synthetic Resin Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • 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
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • 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
    • D06N3/147—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a polyurethane resin of solvent-free synthetic leather, a preparation method and an application thereof, wherein a resin A component contains 30-45 wt% of polyether ester polyol-polyisocyanate prepolymer, 50-65 wt% of polyether polyol A and 0.3-2.0 wt% of water, and a resin B component contains 20-60 wt% of diisocyanate. The polyurethane resin of the solvent-free synthetic leather can have a surface layer, a bonding layer and a foaming layer structure only by blade coating a knife of the solvent-free resin when producing the synthetic leather, and has simple process and excellent physical and mechanical properties.

Description

Polyurethane resin for solvent-free leather, and preparation method and application thereof
Technical Field
The invention relates to a solvent-free polyurethane leather resin, a preparation method and application thereof
Background
Solvent-free polyurethane resins generally comprise two or more components which undergo chain extension, foaming and gelling reactions directly on a substrate during the production of synthetic leather.
The production process of the solvent-free polyurethane synthetic leather comprises the following steps:
(1) blade coating and drying the surface layer: respectively conveying two or more surface resin components to a mixing head according to a certain proportion, uniformly mixing, immediately injecting the mixture on release paper, coating the mixture into a film in a blade coating mode, and then entering a drying tunnel, wherein the polyurethane resin components rapidly react, the molecular weight of a polymer is rapidly increased, and a polyurethane synthetic leather surface layer with a characteristic group structure is rapidly generated;
(2) coating a foaming layer by blade coating: mixing two or more foaming layer resin components according to a certain proportion and coating the mixture on a surface layer in the same step (1), entering a drying tunnel after film forming, and attaching the semi-dry foaming layer to a base cloth;
(3) drying, curing and rolling.
The solvent-free polyurethane synthetic leather has no solvent participation in the production process, does not need to evaporate solvent or moisture, does not generate a large amount of organic waste liquid or waste water, is energy-saving and environment-friendly, has high production efficiency and low cost, and is an important direction for transformation development of the synthetic leather industry.
Chinese patent, application numbers 201610798749.4, 201610645186.5, 201610464914.2, 201610464885.X, 201610464957.0, 201511008510.4, 201510375189.7, 201410524279.3, 201410366764.2, 201410318120.6, 201410318118.9 and 200810168376.8 respectively disclose a solvent-free surface layer leather or a resin composition for leather and a preparation method thereof.
The Chinese patent application with application number of 201110254065.5 discloses that M material is polyester polyol prepolymer or polyether polyol prepolymer and auxiliary material, polyamine catalyst, etc., and N material is polymer polyisocyanate. Chinese patent ZL201210560235.7 discloses a method for preparing solvent-free multi-component polyurethane synthetic leather, wherein the polyol is one or more of polyether diol, polyether triol, polyester diol liquefied by heating or polyurethane prepolymer with hydroxyl. The preparation method is a one-step process, the physical properties of the produced synthetic leather products are poor, and the casting machine of the synthetic leather products needs to be provided with a plurality of raw material tanks, so that the production operability is poor.
The Chinese patent application with the application number of 201610798749.4 discloses a carbon fiber modified solvent-free polyurethane surface layer resin for sports shoe leather, and a preparation method and application thereof. The component A is composed of aliphatic isocyanate, oligomeric diol, organic silicon polyol, micromolecular diol, micromolecular triol, catalyst, light/heat stabilizer, flatting agent, defoaming agent, water removing agent and carbon fiber according to a specific proportion. The component B is composed of aliphatic diisocyanate, aliphatic triisocyanate, polytetrahydrofuran dihydric alcohol, micromolecular trihydric alcohol and a light/heat stabilizer according to a specific proportion. According to the patent application, aliphatic isocyanate is added into the component A, and the isocyanate in the component A is calculated according to the proportion to preferentially react with micromolecular dihydric alcohol and micromolecular trihydric alcohol to form a hydroxyl-terminated micromolecular prepolymer, so that the problem of compatibility between oligomer polyhydric alcohol and micromolecular polyhydric alcohol is solved, but the influence on the physical properties of synthetic leather products is very limited, and the physical properties of aliphatic solvent-free leather need to be improved by adding a carbon fiber material.
Disclosure of Invention
The invention aims to provide polyurethane resin for producing solvent-free synthetic leather by a one-step method and a preparation method thereof, so as to replace the traditional process of firstly making a wet-method base and then attaching a dry-method surface layer.
The solvent-free polyurethane resin for leather comprises a resin A component and a resin B component; the resin A component contains 30-45 wt% of polyether ester polyol-polyisocyanate prepolymer and 0.3-2.0 wt% of water, and the resin B component contains 20-60 wt% of diisocyanate.
The mass ratio of the resin A component to the resin B component is 3: 1-1: 3.
The resin A component comprises the following components in percentage by mass:
Figure BSA0000157143390000021
the resin B component comprises the following components in percentage by mass:
20 to 60 percent of diisocyanate;
30-80% of polyhydric alcohol;
0-1% of phosphoric acid;
preferably, the first and second liquid crystal materials are,
the resin B component comprises the following components in percentage by mass:
20 to 41 percent of diisocyanate;
58 to 80 percent of polyol;
0-1% of phosphoric acid;
the NCO content in the resin B component is 4-20%.
The polyether ester polyol-polyisocyanate prepolymer has the number average molecular weight of 10000-100000 and the functionality of 2-4,
preferably, the polyether ester polyol-polyisocyanate prepolymer is a prepolymer of polyether ester polyol and polyisocyanate, wherein the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methylcyclohexyl diisocyanate; the polyether ester polyol can be prepared by adopting a method reported in a patent document CN 105504259A;
the polyether polyol A is a mixture of polyether diol A, polyether triol A and polyether tetraol A with the number average molecular weight of 1000-10000, and the mass percentages of the polyether diol A, the polyether triol A and the polyether tetraol A in the polyether polyol A are respectively 40-70%, 10-50% and 0-30%;
the polyether diol A is one or more of polyoxyethylene diol, polyoxypropylene-oxyethylene diol, polyoxybutylene diol and polytetrahydrofuran ether diol; the polyether triol A is one or two of polyoxypropylene triol and polyoxypropylene-ethylene oxide triol; the polyether tetrahydric alcohol A is polyoxypropylene tetrahydric alcohol.
The small molecular alcohol chain extender is a mixture of small molecular dihydric alcohol and small molecular trihydric alcohol, and the mass ratio of the small molecular dihydric alcohol to the small molecular trihydric alcohol is 7: 3-19: 5.
The micromolecular dihydric alcohol is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, diethylene glycol and neopentyl glycol; the micromolecular trihydric alcohol is one or more of trimethylolpropane, trimethylolethane, glycerol, xylitol, sorbitol, mannitol and 1, 2, 6-hexanetriol.
The foam stabilizer is an organic silicon foam stabilizer.
The water is deionized water.
The durability auxiliary agent is more than one of ultraviolet absorbent, hindered amine light stabilizer or antioxidant; the ultraviolet absorbent is one or more of ultraviolet absorbents UV-1, UV-2, UV-320, UV-326, UV-327, UV-328, UV-571, UV-1130, UV-234, UV-1229 and UV-1164Z; the hindered amine light stabilizer is one or more of light stabilizer 292, light stabilizer 622 and light stabilizer 770; the antioxidant is one or more of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098, antioxidant 1135, antioxidant 1330, antioxidant 1024, antioxidant 3114 and antioxidant 168.
The catalyst is one or two of an amine catalyst and an organic metal catalyst; the amine catalyst is one or more of triethanolamine and triethylene diamine; the organic metal catalyst is one or more of organic tin, organic bismuth, organic potassium and organic zinc.
The diisocyanate is one or two of diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, dimethyl biphenyl diisocyanate, dimethyl diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methylcyclohexyl diisocyanate.
In the resin B, the resin B is a mixture of,
the polyalcohol is a mixture of polyester diol and polyether polyol B; the mass ratio of the polyester diol to the polyether polyol B is 1: 9-9: 1;
the polyether polyol B is a mixture of 5000-20000 number average molecular weight polyether diol B, polyether triol B and polyether tetraol B, and the polyether diol B, the polyether triol B and the polyether tetraol B respectively account for 40-75%, 10-50% and 0-20% of the polyether polyol by mass percent; the polyether diol B is one or more of polyoxyethylene diol, polyoxypropylene-oxyethylene diol, polyoxybutylene diol and polytetrahydrofuran ether diol; the polyether triol B is one or two of polyoxypropylene triol and polyoxypropylene-ethylene oxide triol; the polyether tetrahydric alcohol B is polyoxypropylene tetrahydric alcohol.
The polyester diol is one or more of poly adipic acid polyester diol, polycaprolactone polyester diol and polycarbonate polyester diol with the number average molecular weight of 500-3000;
the polyester diol of the polyadipic acid series is preferably polyethylene glycol adipate diol, polypropylene glycol adipate diol, 1, 4-butanediol adipate diol, diethylene glycol adipate diol and neopentyl glycol adipate diol.
The preparation method of the polyurethane resin for the solvent-free leather comprises the following steps:
(1) preparation of resin A component: adding a polyether ester polyol-polyisocyanate prepolymer and polyether polyol A into a reaction kettle, heating to 120-140 ℃, dehydrating for 5-6 h under the vacuum condition of-0.06 MPa-0.01 MPa, then cooling to 30-50 ℃, adding a small molecular alcohol chain extender, a foam stabilizer, a durability auxiliary agent, a catalyst and water, stirring for 2-4 h, detecting a hydroxyl value and a moisture content, when the hydroxyl value reaches 29-300 mgKOH/g and the moisture content is lower than 600ppm, obtaining a resin A component, and sealing and packaging for later use;
(2) preparation of the component B: adding diisocyanate, polyalcohol and phosphoric acid into a reaction kettle, stirring and reacting for 1.5-3.0 h at 90-110 ℃, sampling and detecting NCO content, reducing the temperature to 30-50 ℃ when the NCO content is 4-20%, discharging to obtain a resin B component, and sealing and packaging for later use.
The application method of the solvent-free polyurethane resin for leather used for preparing the solvent-free polyurethane synthetic leather comprises the following steps:
fully mixing the resin A component and the resin B component according to the mass ratio of 3: 1-1: 3, allowing the mixture to be used for 15-20 min, coating the mixed solvent-free AB material on release paper according to a set thickness, pre-drying the release paper in an oven, adhering base cloth in a semi-dry state, controlling the gap of a pressure roller to ensure that the solvent-free resin and the base cloth can be firmly adhered without breaking the foam hole, curing the mixture in a drying tunnel with the temperature controlled at 130-140 ℃ for 4-8 min, and rolling the cured mixture to obtain the integrated solvent-free polyurethane synthetic leather.
Compared with the prior art, the invention has the following advantages:
(1) the whole process only needs the knife coating and has no solvent resin, does not need to knife coat surface course resin and tie coat resin in addition, can possess surface course, tie coat and foaming layer structure, and simple process is convenient, and stoving, curing moreover, the whole production process of rolling does not have the solvent to participate in, need not evaporating solvent or moisture, also does not produce a large amount of organic waste liquid or waste water, and is energy-concerving and environment-protective, and production efficiency is high, and is with low costs.
(2) The mixing usable time of the resin A component and the resin B component can reach 15-20 min, and the production operability in the large-scale production process of the synthetic leather is improved.
(3) The resin A component of the invention is introduced with a proper amount of polyether ester polyol-polyisocyanate prepolymer, so that the parameters such as resin viscosity, molecular weight and the like are effectively adjusted, and the stability of the distribution ratio of the resin A component and the resin B component in production and processing is ensured.
(4) The solvent-free polyurethane synthetic leather has excellent physical and mechanical properties.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood that the specific materials, process conditions and results described in the examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example 1
30.00kg of polyether ester-toluene diisocyanate prepolymer (number average molecular weight 10000, functionality of 2), 26.00kg of polyoxypropylene diol (number average molecular weight 5000), 19.50kg of polyoxypropylene triol (number average molecular weight 9000) and 19.50kg of polyoxypropylene tetraol (number average molecular weight 10000) are heated to 120 ℃, dehydrated under vacuum condition of 0.01MPa for 6h, cooled to 30 ℃, added with 2.10kg of ethylene glycol, 0.90kg of trimethylolpropane, 0.70kg of organosilicon foam stabilizer, 0.3kg of deionized water and 0.65kg of ultraviolet absorbent UV-320, 0.30kg of light stabilizer 292, 0.05kg of antioxidant 245 and 0.30kg of organic tin metal catalyst are mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 85.2mgKOH/g and the moisture content is controlled to be 0.3 percent, the resin A component is prepared, and the mixture is sealed and packaged for standby;
16.55kg of toluene diisocyanate, 24.81kg of polyethylene glycol adipate glycol (with the number average molecular weight of 3000), 16.55kg of polyoxypropylene diol (with the number average molecular weight of 5000), 20.69kg of polyoxypropylene-ethylene oxide triol (with the number average molecular weight of 6000) and 4.14kg of polyoxypropylene tetraol (with the number average molecular weight of 10000) are put into a reaction kettle to be stirred and reacted for 3.0h at the temperature of 90 ℃, the NCO content is sampled and detected, and when the NCO content is 8.0 percent, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin component B is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 80, allowing the mixture to stand for 20min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 90-110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 6min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 2
45.00kg of polyether ester-diphenylmethane diisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 35.00kg of polytetrahydrofuran ether diol (number average molecular weight is 10000), 10.00kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 12000) and 5.00kg of polyoxypropylene tetraol (number average molecular weight is 20000) are heated to 140 ℃, and are dehydrated under the vacuum condition of 0.06MPa for 5h, then are cooled to 50 ℃, 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of organosilicon foaming agent are added for homogenization, 0.30kg of deionized water, 0.45kg of ultraviolet absorbent UV-320, 0.36kg of light stabilizer 292, 0.09kg of antioxidant 245 and 0.90kg of organic tin metal catalyst are added for mixing and stirring for 2h, the mghydroxyl value and the moisture content are detected, when the hydroxyl value reaches 62.1 KOH/g, and the moisture content is 0.3 percent, the resin component A is prepared and sealed and packaged for standby;
5.83kg of diphenylmethane diisocyanate, 24.77kg of methane diisocyanate, 5.83kg of polyethylene glycol adipate diol (number average molecular weight 1000), 39.37kg of polytetrahydrofuran ether diol (number average molecular weight 6000), 5.25kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 9000) and 7.87kg of polyoxypropylene tetraol (number average molecular weight 20000) are put into a reaction kettle to be stirred and reacted for 1.5 hours at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 14.3 percent, the temperature is reduced to 50 ℃ to discharge, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 33, allowing the mixture to stand for 15min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 90-110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 8min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 3
38.00kg of polyether ester-toluene diisocyanate prepolymer (the number average molecular weight is 30000 and the functionality is 3), 25.00kg of polyoxypropylene diol (the number average molecular weight is 20000), 25.00kg of polyoxypropylene triol (the number average molecular weight is 18000) are heated to 130 ℃, dehydrated for 5h under the vacuum condition of 0.04MPa, cooled to 40 ℃, added with 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of silicone foam stabilizer, 2.00kg of deionized water, 0.64kg of ultraviolet absorbent UV-320, 1.64kg of light stabilizer 292, 0.32kg of antioxidant 245 and 0.40kg of organic tin metal catalyst and mixed and stirred for 3h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 218.3mgKOH/g and the moisture content is 2 percent, the resin A component is prepared, and sealed and packaged for later use;
24.94kg of toluene diisocyanate, 32.30kg of polydiethylene glycol adipate (number average molecular weight 500), 1.79kg of polyoxypropylene diol (number average molecular weight 5000), 1.79kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 5000) and 0.60g of phosphoric acid are put into a reaction kettle and stirred for reaction at 100 ℃ for 2.0h, the NCO content is sampled and detected, and when the NCO content is 10.7%, the temperature is reduced to 30 ℃ for discharging, so that the component B of the polyurethane resin is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 153, allowing the mixture to stand for 10min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 80-90 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 4min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 4
40.0kg of polyether ester-diphenylmethane diisocyanate prepolymer (number average molecular weight is 20000, functionality is 4), 21.6kg of polytetrahydrofuran ether diol (number average molecular weight is 5000), 16.2kg of polyoxypropylene triol (number average molecular weight is 6000) and 16.2kg of polyoxypropylene tetraol (number average molecular weight is 5000) are heated to 120 ℃, dehydrated under the vacuum condition of 0.01MPa for 6h, then cooled to 30 ℃, 0.45kg of 1, 4-butanediol, 0.05kg of trimethylolpropane, 1.00kg of silicone foam stabilizer, 1.00kg of deionized water, 0.60kg of ultraviolet absorbent UV-320, 0.60kg of light stabilizer 292, 0.30kg of antioxidant 245 and 2.00kg of organic tin metal catalyst are added and mixed and stirred for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 89.7 KOH/g and the moisture content is controlled at 1 percent, the resin component A is prepared and sealed and packaged for standby;
2.39kg of diphenylmethane diisocyanate, 19.00kg of toluene diisocyanate, 8.55kg of polydiethylene glycol adipate (number average molecular weight of 500), 37.96kg of polytetrahydrofuran ether diol (number average molecular weight of 5000), 22.78kg of polyoxypropylene-oxyethylene triol (number average molecular weight of 15000), 15.19kg of polyoxypropylene tetraol (number average molecular weight of 6000) and 1.07g of phosphoric acid are put into a reaction kettle and stirred for reaction at 110 ℃ for 1.5 hours, the NCO content is detected by sampling, and when the NCO content is 12.7%, the temperature is reduced to 50 ℃ for discharging, thus obtaining the polyurethane resin B component.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 53, allowing the mixture to stand for 10min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 90-110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 6min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 5
30.00kg of polyether ester-isophorone cyanate ester prepolymer (number average molecular weight is 10000, functionality is 2), 26.00kg of polyoxypropylene diol (number average molecular weight is 5000), 19.50kg of polyoxypropylene triol (number average molecular weight is 9000) and 19.50kg of polyoxypropylene tetraol (number average molecular weight is 10000) are heated to 120 ℃, dehydrated under the vacuum condition of 0.01MPa for 6 hours, then cooled to 30 ℃, added with 2.10kg of ethylene glycol, 0.90kg of trimethylolpropane, 0.70kg of organosilicon foam stabilizer, 0.50kg of deionized water and 0.15kg of ultraviolet absorbent UV-320, 0.30kg of light stabilizer 292, 0.05kg of antioxidant 245 and 0.30kg of organic tin metal catalyst are mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 97.7mgKOH/g and the moisture content is 0.5 percent, the resin A component is prepared, and sealed and packaged for standby;
16.55kg of isophorone diisocyanate, 24.81kg of polyethylene glycol adipate glycol (number average molecular weight is 3000), 16.55kg of polyoxypropylene diol (number average molecular weight is 5000), 20.69kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 6000) and 4.14kg of polyoxypropylene tetraol (number average molecular weight is 10000) are put into a reaction kettle to be stirred and reacted for 3.0h at 90 ℃, the NCO content is sampled and detected, and when the NCO content is 15.3%, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 48, mixing for 20min, uniformly coating the mixed resin on release paper according to the set thickness, entering a drying tunnel with the temperature controlled at 110 ℃ for pre-reaction to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at the temperature of 130-140 ℃ for 6min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 6
45.00kg of polyether ester-dicyclohexylmethane diisocyanate prepolymer (number average molecular weight is 10000 and functionality is 4), 35.00kg of polytetrahydrofuran ether diol (number average molecular weight is 10000), 10.00kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 12000) and 5.00kg of polyoxypropylene tetraol (number average molecular weight is 20000) are heated to 140 ℃, dehydrated for 5h under the vacuum condition of 0.06MPa, cooled to 50 ℃, added with 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of silicone homogenizing agent, 0.30kg of deionized water, 0.45kg of ultraviolet absorbent UV-320, 0.36kg of light stabilizer 292, 0.09kg of antioxidant 245 and 0.90kg of metal catalyst and mixed and stirred for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 62.1 KOH/g and the moisture content reaches 0.3%, the resin component A is prepared and sealed and packaged for standby;
5.83kg of isophorone diisocyanate, 24.77kg of dicyclohexylmethane diisocyanate, 5.83kg of polyethylene glycol adipate diol (number average molecular weight 1000), 39.37kg of polytetrahydrofuran ether diol (number average molecular weight 6000), 5.25kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 9000) and 7.87kg of polyoxypropylene tetraol (number average molecular weight 20000) are put into a reaction kettle and stirred for reaction for 1.5 hours at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 10.0%, the temperature is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 46, allowing the mixture to stand for 15min, uniformly coating the mixed resin on release paper according to a set thickness, entering a drying tunnel with the temperature controlled at 100 ℃ for pre-reaction to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at the temperature of 130-140 ℃ for 8min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 7
40.00kg of polyether ester-dicyclohexylmethane diisocyanate prepolymer (the number average molecular weight is 30000 and the functionality is 3), 25.36kg of polyoxypropylene diol (the number average molecular weight is 20000), 25.00kg of polyoxypropylene triol (the number average molecular weight is 18000), heating to 130 ℃, dehydrating under the vacuum condition of 0.04MPa for 5h, cooling to 40 ℃, adding 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of silicone foam stabilizer, 0.3kg of deionized water, 0.64kg of ultraviolet absorbent UV-320, 0.68kg of light stabilizer 292, 0.32kg of antioxidant 245 and 1.00kg of organic tin metal catalyst, mixing and stirring for 3h, detecting the hydroxyl value and the moisture content, obtaining a resin A component when the hydroxyl value reaches 112.4mgKOH/g and the moisture content is 0.3%, and sealing and packaging for later use;
24.94kg of dicyclohexylmethane diisocyanate, 32.30kg of polydiethylene glycol adipate (number average molecular weight 500), 1.79kg of polyoxypropylene diol (number average molecular weight 5000), 1.79kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 5000) and 0.60g of phosphoric acid are put into a reaction kettle to be stirred and reacted for 2.0h at 100 ℃, the NCO content is sampled and detected, and when the NCO content is 4.1 percent, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin component B is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 205, allowing the mixture to stand for 20min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at the temperature of 130-140 ℃ for 4min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Example 8
40.0kg of polyether ester dicyclohexylmethane diisocyanate prepolymer (with the number average molecular weight of 20000 and the functionality of 4), 21.6kg of polytetrahydrofuran ether diol (with the number average molecular weight of 5000), 16.2kg of polyoxypropylene triol (with the number average molecular weight of 6000) and 16.2kg of polyoxypropylene tetraol (with the number average molecular weight of 5000) are heated to 120 ℃, dehydrated under the vacuum condition of-0.01 MPa for 6h, then cooled to 30 ℃, 0.45kg of 1, 4-butanediol, 0.05kg of trimethylolpropane, 1.00kg of silicone foam stabilizer, 1.00kg of deionized water, 0.60kg of ultraviolet absorbent UV-320, 0.60kg of light stabilizer 292, 0.30kg of antioxidant 245 and 2.00kg of organic tin metal catalyst are added and mixed and stirred for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 89.7 KOH/g and the moisture content reaches 1.0 percent, the resin A component is prepared, sealing and packaging for later use;
2.39kg of isophorone diisocyanate, 19.00kg of dicyclohexylmethane diisocyanate, 8.55kg of polydiethylene glycol adipate (number average molecular weight 500), 37.96kg of polytetrahydrofuran ether diol (number average molecular weight 5000), 22.78kg of polyoxypropylene-oxyethylene triol (number average molecular weight 15000), 15.19kg of polyoxypropylene tetraol (number average molecular weight 6000) and 07g of phosphoric acid are put into a reaction kettle and stirred for reaction for 1.5h at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 4.0%, the NCO is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 168, mixing for 10min, uniformly coating the mixed resin on release paper according to a set thickness, entering a drying tunnel with the temperature controlled at 80 ℃ for pre-reaction to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 140 ℃ for 6min after attaching, cooling, and rolling to obtain the integrated solvent-free polyurethane synthetic leather.
Comparative example 1
56.00kg of polyoxypropylene diol (with the number average molecular weight of 5000), 19.50kg of polyoxypropylene triol (with the number average molecular weight of 9000) and 19.50kg of polyoxypropylene tetraol (with the number average molecular weight of 10000) are heated to 120 ℃, dehydrated for 6 hours under the vacuum condition of-0.01 MPa, cooled to 30 ℃, added with 2.10kg of ethylene glycol, 0.90kg of trimethylolpropane, 0.70kg of organosilicon foam stabilizer, 0.3kg of deionized water, 0.65kg of ultraviolet absorbent UV-320, 0.30kg of light stabilizer 292, 0.05kg of antioxidant 245 and 0.30kg of organic tin metal catalyst and mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 88.6mgKOH/g and the moisture content is controlled to be 0.3 percent, the resin A component is prepared and sealed and packaged for standby application;
16.55kg of isophorone diisocyanate, 24.81kg of polyethylene glycol adipate glycol (number average molecular weight is 3000), 16.55kg of polyoxypropylene diol (number average molecular weight is 5000), 20.69kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 6000) and 4.14kg of polyoxypropylene tetraol (number average molecular weight is 10000) are put into a reaction kettle to be stirred and reacted for 3.0h at 90 ℃, the NCO content is sampled and detected, and when the NCO content is 8.0%, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 83, allowing the mixture to stand for 20min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 90-110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 2
45.00kg of polyester-diphenylmethane diisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 35.00kg of polyethylene glycol adipate (number average molecular weight is 3000), 10.00kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 12000) and 5.00kg of polyoxypropylene tetraol (number average molecular weight is 20000) are heated to 140 ℃, dehydrated under the vacuum condition of-0.06 MPa for 5h, then cooled to 50 ℃, 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of organosilicon foam stabilizer, 0.30kg of deionized water, 0.45kg of ultraviolet absorbent UV-320, 0.36kg of light stabilizer 292, 0.09kg of antioxidant 245 and 0.90kg of organic tin metal catalyst are added, mixed and stirred for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 76.3 KOH/g and the moisture content is 0.3 percent, the resin component A is prepared and sealed and packaged for standby;
5.83kg of diphenylmethane diisocyanate, 24.77kg of methane diisocyanate, 5.83kg of polyethylene glycol adipate diol (number average molecular weight 1000), 39.37kg of polytetrahydrofuran ether diol (number average molecular weight 6000), 5.25kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 9000) and 7.87kg of polyoxypropylene tetraol (number average molecular weight 20000) are put into a reaction kettle to be stirred and reacted for 1.5 hours at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 14.3 percent, the temperature is reduced to 50 ℃ to discharge, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 40, allowing the mixture to stand for 15min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 90-110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 8min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 3
38.00kg of polyether ester-toluene diisocyanate prepolymer (the number average molecular weight is 30000 and the functionality is 3), 25.00kg of polyoxypropylene diol (the number average molecular weight is 20000), 25.00kg of polyoxypropylene triol (the number average molecular weight is 18000) are heated to 130 ℃, dehydrated for 5h under the vacuum condition of 0.04MPa, cooled to 40 ℃, added with 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of silicone foam stabilizer, 0.64kg of ultraviolet absorbent UV-320, 0.64kg of light stabilizer 292, 1.32kg of antioxidant 245 and 1.40kg of organic tin metal catalyst and mixed and stirred for 3h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 96mgKOH/g and the moisture content is less than 500ppm, the resin A component is prepared, and sealed and packaged for standby application;
24.94kg of toluene diisocyanate, 32.30kg of polydiethylene glycol adipate (number average molecular weight 500), 1.79kg of polyoxypropylene diol (number average molecular weight 5000), 1.79kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 5000) and 0.60g of phosphoric acid are put into a reaction kettle and stirred for reaction at 100 ℃ for 2.0h, the NCO content is sampled and detected, and when the NCO content is 10.7%, the temperature is reduced to 30 ℃ for discharging, so that the component B of the polyurethane resin is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 67, allowing the mixture to stand for 10min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 80-90 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 4min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 4
40.0kg of polyether ester-diphenylmethane diisocyanate prepolymer (with the number average molecular weight of 20000 and the functionality of 4), 21.6kg of polytetrahydrofuran ether diol (with the number average molecular weight of 5000), 16.2kg of polyoxypropylene triol (with the number average molecular weight of 6000) and 16.2kg of polyoxypropylene tetraol (with the number average molecular weight of 5000) are heated to 120 ℃, dehydrated under the vacuum condition of-0.01 MPa for 6 hours, then cooled to 30 ℃, added with 0.45kg of 1, 4-butanediol, 0.05kg of trimethylolpropane, 2.50kg of organosilicon foam stabilizer, 1.00kg of deionized water and 2.00kg of organic tin metal catalyst, mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 89.7mgKOH/g and the moisture content is controlled to be 1%, the resin A component is prepared, and sealed and packaged for standby;
2.39kg of diphenylmethane diisocyanate, 19.00kg of toluene diisocyanate, 8.55kg of polydiethylene glycol adipate (number average molecular weight of 500), 37.96kg of polytetrahydrofuran ether diol (number average molecular weight of 5000), 22.78kg of polyoxypropylene-oxyethylene triol (number average molecular weight of 15000), 15.19kg of polyoxypropylene tetraol (number average molecular weight of 6000) and 1.07g of phosphoric acid are put into a reaction kettle and stirred for reaction at 110 ℃ for 1.5 hours, the NCO content is detected by sampling, and when the NCO content is 12.7%, the temperature is reduced to 50 ℃ for discharging, thus obtaining the polyurethane resin B component.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 53, allowing the mixture to stand for 10min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 90-110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 130-140 ℃ for 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 5
26.00kg of polyoxypropylene diol (with the number average molecular weight of 5000), 19.50kg of polyoxypropylene triol (with the number average molecular weight of 9000) and 49.50kg of polyoxypropylene tetraol (with the number average molecular weight of 10000) are heated to 120 ℃, dehydrated for 6 hours under the vacuum condition of-0.01 MPa, cooled to 30 ℃, added with 2.10kg of ethylene glycol, 0.90kg of trimethylolpropane, 0.70kg of organosilicon foam stabilizer, 0.50kg of deionized water, 0.15kg of ultraviolet absorbent UV-320, 0.30kg of light stabilizer 292, 0.05kg of antioxidant 245 and 0.30kg of organic tin metal catalyst, mixed and stirred for 2 hours, tested for the hydroxyl value and the moisture content, and when the hydroxyl value reaches 97.7mgKOH/g and the moisture content is 0.5 percent, the resin A component is prepared and sealed and packaged for standby application;
16.55kg of isophorone diisocyanate, 24.81kg of polyethylene glycol adipate glycol (number average molecular weight is 3000), 16.55kg of polyoxypropylene diol (number average molecular weight is 5000), 20.69kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 6000) and 4.14kg of polyoxypropylene tetraol (number average molecular weight is 10000) are put into a reaction kettle to be stirred and reacted for 3.0h at 90 ℃, the NCO content is sampled and detected, and when the NCO content is 15.3%, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 48, mixing for 20min, uniformly coating the mixed resin on release paper according to the set thickness, entering a drying tunnel with the temperature controlled at 110 ℃ for pre-reaction to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at the temperature of 130-140 ℃ for 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 6
45.00kg of polyether ester-toluene diisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 35.00kg of polytetrahydrofuran ether diol (number average molecular weight is 10000), 10.00kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 12000) and 5.00kg of polyoxypropylene tetraol (number average molecular weight is 20000) are heated to 140 ℃, and are dehydrated under the vacuum condition of-0.06 MPa for 5h, then are cooled to 50 ℃, 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of organosilicon foam stabilizer are added for homogenization, 0.30kg of deionized water, 0.45kg of ultraviolet absorbent UV-320, 0.36kg of light stabilizer 292, 0.09kg of antioxidant 245 and 0.90kg of organic tin metal catalyst are mixed and stirred for 2h, mghydroxyl value and moisture content are detected, when the hydroxyl value reaches 62.1 KOH/g and the moisture content reaches 0.3 percent, the resin component A is prepared and sealed and packaged for standby;
5.83kg of isophorone diisocyanate, 24.77kg of dicyclohexylmethane diisocyanate, 5.83kg of polyethylene glycol adipate diol (number average molecular weight 1000), 39.37kg of polytetrahydrofuran ether diol (number average molecular weight 6000), 5.25kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 9000) and 7.87kg of polyoxypropylene tetraol (number average molecular weight 20000) are put into a reaction kettle and stirred for reaction for 1.5 hours at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 10.0%, the temperature is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 46, allowing the mixture to stand for 15min, uniformly coating the mixed resin on release paper according to a set thickness, entering a drying tunnel with the temperature controlled at 100 ℃ for pre-reaction to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at the temperature of 130-140 ℃ for 8min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 7
40.00kg of polyether ester-dicyclohexylmethane diisocyanate prepolymer (the number average molecular weight is 30000 and the functionality is 3), 25.36kg of polyoxypropylene diol (the number average molecular weight is 20000), 25.00kg of polyoxypropylene triol (the number average molecular weight is 18000), heating to 130 ℃, dehydrating under the vacuum condition of 0.04MPa for 5h, cooling to 40 ℃, adding 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of organosilicon foam stabilizer, 0.94kg of ultraviolet absorbent UV-320, 0.68kg of light stabilizer 292, 0.32kg of antioxidant 245 and 1.00kg of organic tin metal catalyst, mixing and stirring for 3h, detecting the hydroxyl value and the moisture content, obtaining the resin A component when the hydroxyl value reaches 93.7mgKOH/g and the moisture content is less than 500ppm, and sealing and packaging for later use;
24.94kg of dicyclohexylmethane diisocyanate, 32.30kg of polydiethylene glycol adipate (number average molecular weight 500), 1.79kg of polyoxypropylene diol (number average molecular weight 5000), 1.79kg of polyoxypropylene-ethylene oxide triol (number average molecular weight 5000) and 0.60g of phosphoric acid are put into a reaction kettle to be stirred and reacted for 2.0h at 100 ℃, the NCO content is sampled and detected, and when the NCO content is 4.1 percent, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin component B is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 171, allowing the mixture to stand for 20min, uniformly coating the mixed resin on release paper according to a set thickness, pre-reacting in a drying tunnel with the temperature controlled at 110 ℃ to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at the temperature of 130-140 ℃ for 4min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 8
40.0kg of polyether ester dicyclohexylmethane diisocyanate prepolymer (with the number average molecular weight of 20000 and the functionality of 4), 21.6kg of polytetrahydrofuran ether diol (with the number average molecular weight of 5000), 16.2kg of polyoxypropylene triol (with the number average molecular weight of 6000) and 16.2kg of polyoxypropylene tetraol (with the number average molecular weight of 5000) are heated to 120 ℃, dehydrated under the vacuum condition of-0.01 MPa for 6 hours, then cooled to 30 ℃, and added with 0.45kg of 1, 4-butanediol, 0.05kg of trimethylolpropane, 2.50kg of organosilicon foam stabilizer, 1.00kg of deionized water and 2.00kg of organic tin metal catalyst for mixing and stirring for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 89.7mgKOH/g and the moisture content is 1.0%, the resin A component is prepared, and sealed and packaged for standby;
2.39kg of isophorone diisocyanate, 19.00kg of dicyclohexylmethane diisocyanate, 8.55kg of polydiethylene glycol adipate (number average molecular weight 500), 37.96kg of polytetrahydrofuran ether diol (number average molecular weight 5000), 22.78kg of polyoxypropylene-oxyethylene triol (number average molecular weight 15000), 15.19kg of polyoxypropylene tetraol (number average molecular weight 6000) and 07g of phosphoric acid are put into a reaction kettle and stirred for reaction for 1.5h at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 4.0%, the NCO is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 168, mixing for 10min, uniformly coating the mixed resin on release paper according to a set thickness, entering a drying tunnel with the temperature controlled at 80 ℃ for pre-reaction to a semi-dry state, then attaching base cloth, adjusting the attaching pressure according to the semi-dry state, curing at 140 ℃ for 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
The results of the physical property tests of the polyurethane synthetic leathers prepared in the application examples 1 to 4 and the comparative examples 1 to 4 are shown in table 1.
TABLE 1
Figure BSA0000157143390000141
The results of the physical property tests of the polyurethane synthetic leathers prepared in the application examples 5 to 8 and the comparative examples 5 to 8 are shown in table 2.
TABLE 2
Figure BSA0000157143390000151
In conclusion, the product of the invention integrates the solvent-free polyurethane resin for leather, is coated on the base cloth by the single-knife process, has simple and convenient process and good operability, and realizes the integration of the foaming layer, the bonding layer and the surface layer. As can be seen from Table 1, the examples have significantly improved physical properties such as peel strength, hydrolysis resistance, heat resistance and yellowing resistance compared with the comparative examples, and do not contain any organic solvent, do not pollute the environment, and do not affect the operational health.
Although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the embodiments, and equivalent changes or modifications made to the contents of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and the spirit of the present invention.

Claims (9)

1. The polyurethane resin of the solvent-free synthetic leather is characterized by comprising a resin A component and a resin B component;
the resin A component comprises the following components in percentage by mass:
Figure FSB0000196914470000011
the resin B component comprises the following components in percentage by mass:
20 to 60 percent of diisocyanate;
30-80% of polyhydric alcohol;
0-1% of phosphoric acid;
the NCO content in the resin B component is 4-20%;
the polyether ester polyol-polyisocyanate prepolymer has the number average molecular weight of 10000-100000 and the functionality of 2-4;
the polyether polyol A is a mixture of polyether diol A, polyether triol A and polyether tetraol A with the number average molecular weight of 1000-10000, and the mass percentages of the polyether diol A, the polyether triol A and the polyether tetraol A in the polyether polyol A are 40-70%, 10-50% and 0-30% respectively.
2. The polyurethane resin of claim 1, wherein the polyether ester polyol-polyisocyanate prepolymer is a prepolymer of polyether ester polyol and polyisocyanate, wherein the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, and methylcyclohexyl diisocyanate.
3. The polyurethane resin of the solvent-free synthetic leather according to claim 1, wherein the polyether diol A is one or more of polyoxyethylene diol, polyoxypropylene-oxyethylene diol, polyoxybutylene diol and polytetrahydrofuran ether diol; the polyether triol A is one or two of polyoxypropylene triol and polyoxypropylene-ethylene oxide triol; the polyether tetrahydric alcohol A is polyoxypropylene tetrahydric alcohol.
4. The polyurethane resin of solvent-free synthetic leather according to claim 3, wherein the small molecule alcohol chain extender is a mixture of small molecule dihydric alcohol and small molecule trihydric alcohol, and the mass ratio of the small molecule dihydric alcohol to the small molecule trihydric alcohol is 7: 3-19: 5.
5. The polyurethane resin of solvent-free synthetic leather according to claim 1, wherein the foam stabilizer is a silicone foam stabilizer;
the durability auxiliary agent is more than one of ultraviolet absorbent, hindered amine light stabilizer or antioxidant, and the ultraviolet absorbent is more than one of ultraviolet absorbent UV-1, UV-2, UV-320, UV-326, UV-327, UV-328, UV-571, UV-1130, UV-234, UV-1229 and UV-1164Z; the hindered amine light stabilizer is one or more of light stabilizer 292, light stabilizer 622 and light stabilizer 770; the antioxidant is one or more of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098, antioxidant 1135, antioxidant 1330, antioxidant 1024, antioxidant 3114 and antioxidant 168, and the catalyst is one or two of amine catalyst and organic metal catalyst; the amine catalyst is one or more of triethanolamine and triethylene diamine; the organic metal catalyst is one or more of organic tin, organic bismuth, organic potassium and organic zinc;
the diisocyanate is one or two of diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, dimethyl biphenyl diisocyanate, dimethyl diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methylcyclohexyl diisocyanate.
6. The polyurethane resin for solvent-free synthetic leather according to claim 1, wherein in the resin B, the polyol is a mixture of polyester diol and polyether polyol B; the mass ratio of the polyester diol to the polyether polyol B is 1: 9-9: 1.
7. The polyurethane resin of the solvent-free synthetic leather according to claim 6, wherein in the resin B, the polyether polyol B is a mixture of 5000-20000 number average molecular weight polyether diol B, polyether triol B and polyether tetraol B, and the mass percentages of the polyether diol B, the polyether triol B and the polyether tetraol B in the polyether polyol are respectively 40-75%, 10-50% and 0-20%; the polyether diol B is one or more of polyoxyethylene diol, polyoxypropylene-oxyethylene diol, polyoxybutylene diol and polytetrahydrofuran ether diol; the polyether triol B is one or two of polyoxypropylene triol and polyoxypropylene-ethylene oxide triol; the polyether tetrahydric alcohol B is polyoxypropylene tetrahydric alcohol;
the polyester diol is one or more of poly adipic acid polyester diol, polycaprolactone polyester diol and polycarbonate polyester diol with the number average molecular weight of 500-3000.
8. The method for preparing the polyurethane resin of the solvent-free synthetic leather according to any one of claims 1 to 7, comprising the following steps:
(1) preparation of resin A component: adding a polyether ester polyol-polyisocyanate prepolymer and polyether polyol A into a reaction kettle, heating to 120-140 ℃, dehydrating for 5-6 h under the vacuum condition of-0.06 MPa-0.01 MPa, then cooling to 30-50 ℃, adding a small molecular alcohol chain extender, a foam stabilizer, a durability auxiliary agent, a catalyst and water, stirring for 2-4 h, detecting a hydroxyl value and a moisture content, when the hydroxyl value reaches 29-300 mgKOH/g and the moisture content is lower than 600ppm, obtaining a resin A component, and sealing and packaging for later use;
(2) preparation of the component B: adding diisocyanate, polyalcohol and phosphoric acid into a reaction kettle, stirring and reacting for 1.5-3.0 h at 90-110 ℃, sampling and detecting NCO content, reducing the temperature to 30-50 ℃ when the NCO content is 4-20%, discharging to obtain a resin B component, and sealing and packaging for later use.
9. The application of the polyurethane resin of the solvent-free synthetic leather according to any one of claims 1 to 7, which is used for preparing the solvent-free polyurethane synthetic leather, and the application method comprises the following steps:
fully mixing the resin A component and the resin B component according to the mass ratio of 3: 1-1: 3, mixing for 15-20 min, coating the mixed solvent-free A, B component on release paper according to a set thickness, pre-drying in an oven, attaching base cloth in a semi-dry state, controlling the gap of a pressure roller to ensure that the solvent-free resin and the base cloth can be firmly attached without breaking the foam hole, curing in a drying tunnel with the temperature controlled at 130-140 ℃ for 4-8 min, and rolling to obtain the solvent-free polyurethane synthetic leather.
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