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CN108047414A - Solvent-free leather polyurethane resin and preparation method and application - Google Patents

Solvent-free leather polyurethane resin and preparation method and application Download PDF

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Publication number
CN108047414A
CN108047414A CN201711500645.1A CN201711500645A CN108047414A CN 108047414 A CN108047414 A CN 108047414A CN 201711500645 A CN201711500645 A CN 201711500645A CN 108047414 A CN108047414 A CN 108047414A
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CN
China
Prior art keywords
resin
diisocyanate
component
solvent
synthetic leather
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201711500645.1A
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Chinese (zh)
Inventor
张初银
于吉鹏
付志朋
马元明
张兵
彭峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHEJIANG HUAFENG SYNTHETIC RESIN CO Ltd
Original Assignee
ZHEJIANG HUAFENG SYNTHETIC RESIN CO Ltd
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Priority to CN201711500645.1A priority Critical patent/CN108047414A/en
Publication of CN108047414A publication Critical patent/CN108047414A/en
Withdrawn legal-status Critical Current

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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
    • D06N3/146—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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, 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
    • 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
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • 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

Polyurethane resin the invention discloses a kind of uninanned platform leather and its preparation method and application, the polyurethane resin of the uninanned platform leather include Resin A component and resin B component；The Resin A component contains the water that the polyester ether polylol polyisocyanates performed polymer that weight percent is 20%~45% and weight percent are 0.3%~2.0%, and the resin B component contains the diisocyanate that weight percent is 20%~60%；The mass ratio of the Resin A component and resin B component is 3: 1~1: 3.The polyurethane resin of uninanned platform leather of the present invention need to only scratch a knife solventfree resin when producing synthetic leather, you can possess surface layer, adhesive layer and foaming layer structure, technical process is simple, and physical mechanical property is excellent.

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 20-45 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:
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 A component comprises the following components in percentage by mass:
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 4-35%.
The polyether ester polyol and 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 polyester polyol A is a mixture of 500-5000 number average molecular weight polyester diol of a polyadipic acid polyester and polyadipic acid polyester polyol; the mass ratio of the poly adipic acid polyester diol to the poly adipic acid polyester polyol is 3: 2-99: 1, the poly adipic acid polyester diol is a polycondensation product of adipic acid and micromolecular diol a, and the micromolecular diol a is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and diethylene glycol; the polyester polyol of the poly adipic acid series is a polymerization product of adipic acid, micromolecular dihydric alcohol a and micromolecular trihydric alcohol a; the functionality is 2.05-2.80, and the micromolecular dihydric alcohol a is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and diethylene glycol; the small molecule trihydric alcohol a is one or a mixture of two of glycerol, trimethylolpropane, trimethylolethane and hexanetriol:
the small molecular alcohol chain extender is a mixture of small molecular dihydric alcohol b and small molecular trihydric alcohol b, and the mass ratio of the small molecular dihydric alcohol b to the small molecular trihydric alcohol b is 7: 3-19: 5.
The micromolecular dihydric alcohol b is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, diethylene glycol and neopentyl glycol; the micromolecular trihydric alcohol b 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 polyhydric alcohol is more than one of poly adipic acid polyhydric alcohol, polycaprolactone polyhydric alcohol and polycarbonate polyhydric alcohol with the functionality of 2-3 and the number average molecular weight of 500-5000;
or,
the polyalcohol is a mixture of polyester diol and polyether polyol; the mass ratio of the polyester diol to the polyether polyol is 1: 9-9: 1;
the polyether polyol is a mixture of 5000-20000 number average molecular weight polyether diol, polyether triol and polyether tetraol, and the polyether diol, polyether triol and polyether tetraol respectively account for 40-75%, 10-50% and 0-20% of the polyether polyol by weight; the polyether diol is one or more of polyoxyethylene diol, polyoxypropylene-oxyethylene diol, polyoxybutylene diol and polytetrahydrofuran ether diol; the polyether triol is one or two of polypropylene oxide triol and polypropylene oxide-ethylene oxide triol; the polyether tetrahydric alcohol 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 500-5000.
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 a polyester 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 50-200mgKOH/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 4-35%, 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 in an oven, adhering base cloth in a semi-dry state, controlling the gap of a pressure roller, allowing the solvent-free resin and the base cloth to be firmly adhered without breaking the foam hole, curing in a drying tunnel at the temperature of 130-140 ℃ for 4-8 min, and rolling to obtain the 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
20.00kg of polyether ester polyol-toluene diisocyanate prepolymer (number average molecular weight is 10000, functionality is 2), 73.35kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 1000), 1.65kg of polyethylene glycol propylene glycol adipate (functionality is 2.80, number average molecular weight is 2000), heating to 120 ℃, dehydrating under vacuum condition of 0.01MPa for 6h, cooling to 30 ℃, adding 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 are mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 153.8mgKOH/g and the moisture content is 0.3 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
33.10kg of toluene diisocyanate and 49.62kg of polyethylene glycol adipate (with the number average molecular weight of 3000) 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 17.6 percent, the temperature is reduced to 30 ℃ to discharge, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 65, 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 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Example 2
35.00kg of polyether ester polyol-isophorone polyisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 58.00kg of polyethylene glycol butanediol adipate (number average molecular weight is 5000), 2.00kg of polyethylene glycol glycerol adipate (functionality is 2.05, number average molecular weight is 5000), heating to 140 ℃, dehydrating under the vacuum condition of-0.06 MPa for 5h, then cooling to 50 ℃, adding 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, mixing and stirring for 2h, detecting hydroxyl value and moisture content, and obtaining the resin A component when the hydroxyl value reaches 125.4 KOH/g and the moisture content is 16 percent, and sealing and packaging for later use.
8.06kg of toluene diisocyanate, 24.23kg of diphenylmethane diisocyanate and 28.06kg of polybutylene adipate (number average molecular weight 1000) 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 16 percent, the temperature is reduced to 50 ℃ for discharging, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 59, 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 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.
Example 3
33.40kg of polyether ester polyol-diphenylmethane diisocyanate prepolymer (number average molecular weight of 30000 and functionality of 3), 40.00kg of polyethylene glycol adipate (number average molecular weight of 3000), 15.00kg of polyethylene glycol-trimethylolpropane adipate (functionality of 2.3 and number average molecular weight of 3000) are heated to 130 ℃, dehydrated for 5h under the vacuum condition of-0.04 MPa, cooled to 40 ℃, added with 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of organosilicon foam stabilizer, 2.00kg of deionized water and 0.64kg of ultraviolet absorbent UV-320, 0.64kg of light stabilizer 292, 0.32kg of antioxidant 245 and 1.00kg of organic tin metal catalyst are mixed and stirred for 3 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 235.7mgKOH/g and the moisture content reaches 2.0 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
28.98kg of methane diisocyanate, 37.53kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.78g 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 11.6 percent, the temperature is reduced to 30 ℃ to discharge, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 152, 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 100 ℃ 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.
Example 4
40.00kg of polyether ester polyol-diphenylmethane diisocyanate prepolymer (number average molecular weight is 20000, functionality is 4), 37.80kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 2000), 16.20kg of polybutylene glycol propylene glycol adipate (functionality is 2.5, number average molecular weight is 3000) and heated to 120 ℃, and the mixture is dehydrated for 6h under the vacuum condition of-0.01 MPa, then cooled to 30 ℃, added with 1.6kg of glycol, 0.05kg of trimethylolpropane, 1.00kg of organosilicon foam stabilizer, 1.00kg of deionized water and 0.45kg of ultraviolet absorbent UV-320, 0.60kg of light stabilizer 292, 0.30kg of antioxidant 245 and 1.00kg 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 125.2mgKOH/g and the moisture content reaches 1.0 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
3.44kg of diphenylmethane diisocyanate, 27.34kg of toluene diisocyanate, 10.30kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.5g of phosphoric acid are put into a reaction kettle to be stirred and reacted for 1.5h at the temperature of 110 ℃, the NCO content is sampled and detected, and when the NCO content is 30.7 percent, the temperature is reduced to 50 ℃ to discharge, 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: 31, 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 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 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Example 5
30.00kg of polyether ester polyol-isophorone diisocyanate prepolymer (number average molecular weight is 10000, functionality is 2), 64.35kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 1000), 0.65kg of polyethylene glycol propylene glycol adipate (functionality is 2.80, number average molecular weight is 2000), heating to 120 ℃, dehydrating under vacuum condition of-0.01 MPa for 6h, cooling to 30 ℃ (C, adding 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 are mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 156.5mgKOH/g and the moisture content is 0.5 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
Adding 33.10kg of isophorone diisocyanate and 49.62kg of polyethylene glycol adipate (with the number average molecular weight of 3000) into a reaction kettle, stirring and reacting for 3.0h at 90 ℃, sampling and detecting the NCO content, and when the NCO content is 12.6%, reducing the temperature to 30 ℃ to discharge so as to obtain the polyurethane resin component B.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 93, 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 80 ℃ 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.
Example 6
45.00kg of polyether ester polyol-isophorone polyisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 30.00kg of polyethylene glycol butanediol adipate (number average molecular weight is 5000), 20.00kg of polyethylene glycol glycerol adipate (functionality is 2.05, number average molecular weight is 5000), heating to 140 ℃, dehydrating under the vacuum condition of-0.06 MPa for 5h, then cooling to 50 ℃, adding 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, mixing and stirring for 2h, detecting hydroxyl value and moisture content, and obtaining the resin A component when the hydroxyl value reaches 72.6 mghydroxyl/g and the moisture content is 0.3 percent, and sealing and packaging for later use.
8.06kg of isophorone diisocyanate, 24.23kg of dicyclohexylmethane diisocyanate and 28.06kg of polybutylene adipate (number average molecular weight 1000) 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 14%, the temperature is reduced to 50 ℃ for discharging, thus obtaining the polyurethane resin component B.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 39, 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 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 8min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Example 7
38.00kg of polyether ester polyol-isophorone polyisocyanate prepolymer (number average molecular weight of 30000 and functionality of 3), 40.00kg of polyethylene glycol adipate (number average molecular weight of 3000), 10.00kg of polyethylene glycol adipate trimethylolpropane (functionality of 2.3 and number average molecular weight of 3000) are heated to 130 ℃, dehydrated for 5h under the vacuum condition of-0.04 MPa, cooled to 40 ℃, added with 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of organosilicon foam stabilizer, 0.3kg of deionized water and 1.68kg of ultraviolet absorbent UV-320, 0.64kg of light stabilizer 292, 1.32kg of antioxidant 245 and 1.00kg of organic tin metal catalyst are mixed and stirred for 3 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 127.8mgKOH/g and the moisture content reaches 0.3 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
28.98kg of dicyclohexylmethane diisocyanate, 37.53kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.78g 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 4.5 percent, the temperature is reduced to 30 ℃ to discharge, thus obtaining the polyurethane resin component B.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 213, 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 ℃ 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 5min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Example 8
40.00kg of polyether ester polyol-isophorone polyisocyanate prepolymer (number average molecular weight is 20000, functionality is 4), 37.80kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 2000), 16.20kg of polybutylene glycol propylene glycol adipate (functionality is 2.5, number average molecular weight is 3000) and heated to 120 ℃, and the mixture is dehydrated for 6h under the vacuum condition of-0.01 MPa, then cooled to 30 ℃, added with 0.6kg of glycol, 0.05kg of trimethylolpropane, 0.50kg of organosilicon foam stabilizer, 2.0kg of deionized water and 0.30kg of ultraviolet absorbent UV-320, 0.25kg of light stabilizer 292, 0.30kg of antioxidant 245 and 2.00kg 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 169.4mgKOH/g and the moisture content reaches 2.0 percent, the resin A component is prepared, and the mixture is sealed and packaged for standby.
3.44kg of isophorone diisocyanate, 27.34kg of dicyclohexylmethane diisocyanate, 10.30kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.5g 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 20.3 percent, the temperature is reduced to 50 ℃ for discharging, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 63, allowing the mixture to stand for 10min, uniformly coating the mixed resin on release paper according to a set thickness, entering a drying tunnel with the temperature controlled at 90 ℃ 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 4min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 1
20.00kg of polyether polyol-isophorone diisocyanate prepolymer (number average molecular weight is 10000, functionality is 2), 73.35kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 1000), 1.65kg of polyethylene glycol dipropylene glycol glycerol adipate (functionality is 2.80, number average molecular weight is 2000), heating to 120 ℃, dehydrating under the vacuum condition of 0.01MPa for 6h, cooling to 30 ℃, adding 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 153.8mgKOH/g and the moisture content is 0.3 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
33.10kg of dicyclohexylmethane diisocyanate and 49.62kg of polyethylene glycol adipate (with the number average molecular weight of 3000) 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 17.6 percent, the temperature is reduced to 30 ℃ to discharge, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 66, 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 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 2
35.00kg of polyether-isophorone polyisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 58.00kg of polytetrahydrofuran ether glycol (number average molecular weight is 5000), 2.00kg of polyoxypropylene glycol (functionality is 2.05, number average molecular weight is 5000), heating to 140 ℃, dehydrating under vacuum condition of-0.06 MPa for 5h, cooling to 50 ℃, adding 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of silicone 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, mixing and stirring for 2h, detecting hydroxyl value and moisture content, when the hydroxyl value reaches 125.4mgKOH/g and the moisture content is 16%, preparing the resin A component, sealing and packaging for later use.
8.06kg of toluene diisocyanate, 24.23kg of diphenylmethane diisocyanate and 28.06kg of polytetrahydrofuran ether glycol (number average molecular weight 1000) are put into a reaction kettle, stirred and reacted for 1.5h at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 16 percent, the temperature is reduced to 50 ℃ for discharging, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 59, 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 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.
Comparative example 3
33.40kg of polyether ester-diphenylmethane diisocyanate prepolymer (number average molecular weight of 30000 and functionality of 3), 40.00kg of polyethylene glycol adipate (number average molecular weight of 3000), 15.00kg of polyethylene glycol adipate (functionality of 2.3 and number average molecular weight of 3000) are heated to 130 ℃, dehydrated under the vacuum condition of-0.04 MPa for 5h, cooled to 40 ℃, added with 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of silicone foam stabilizer, 1.64kg of ultraviolet absorbent UV-320, 1.64kg of light stabilizer 292, 0.32kg of antioxidant 245 and 1.00kg of organic tin metal catalyst, mixed and stirred for 3h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 111.0mgKOH/g and the moisture content is less than 500ppm, the resin A component is prepared, and sealed and packaged for later use.
28.98kg of methane diisocyanate, 37.53kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.78g 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 11.6 percent, the temperature is reduced to 30 ℃ to discharge, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 72, 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 100 ℃ 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 4
40.00kg of polyether ester-diphenylmethane diisocyanate prepolymer (number average molecular weight is 20000, functionality is 4), 37.80kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 2000), 16.20kg of polybutylene glycol propylene glycol adipate (functionality is 2.5, number average molecular weight is 3000) are heated to 120 ℃, the mixture is dehydrated under the vacuum condition of-0.01 MPa for 6h, then the temperature is reduced to 30 ℃, 1.6kg of ethylene glycol, 0.05kg of trimethylolpropane, 1.00kg of organosilicon foam stabilizer and 1.00kg of deionized water, 2.35kg 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 125.2mgKOH/g and the moisture content is 1.0%, the resin A component is prepared, and sealed and packaged for later use.
3.44kg of diphenylmethane diisocyanate, 27.34kg of toluene diisocyanate, 10.30kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.5g of phosphoric acid are put into a reaction kettle to be stirred and reacted for 1.5h at the temperature of 110 ℃, the NCO content is sampled and detected, and when the NCO content is 30.7 percent, the temperature is reduced to 50 ℃ to discharge, 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: 31, 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 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 6min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 5
64.35kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 1000), 30.65kg of polyethylene glycol dipropylene glycol glycerol adipate (functionality is 2.80, number average molecular weight is 2000), the temperature is raised to 120 ℃, the dehydration is carried out for 6h under the vacuum condition of-0.01 MPa, then the temperature is reduced to 30 ℃, 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 are added for mixing and stirring for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 140.6mgKOH/g and the moisture content is 0.5 percent, the resin A component is prepared, and sealed and packaged for standby application.
Adding 33.10kg of isophorone diisocyanate and 49.62kg of polyethylene glycol adipate (with the number average molecular weight of 3000) into a reaction kettle, stirring and reacting for 3.0h at 90 ℃, sampling and detecting the NCO content, and when the NCO content is 12.6%, reducing the temperature to 30 ℃ to discharge so as to obtain the polyurethane resin component B.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 84, 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 80 ℃ 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-isophorone polyisocyanate prepolymer (number average molecular weight is 10000, functionality is 4), 30.00kg of polyethylene glycol butanediol adipate (number average molecular weight is 5000), 20.00kg of polyethylene glycol glycerol adipate (functionality is 2.05, number average molecular weight is 5000), heating to 140 ℃, dehydrating for 5h under the vacuum condition of-0.06 MPa, cooling to 50 ℃, adding 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.60kg of organosilicon foam stabilizer, 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 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 53.9mgKOH/g and the moisture content is less than 500ppm, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
8.06kg of isophorone diisocyanate, 24.23kg of dicyclohexylmethane diisocyanate and 28.06kg of polybutylene adipate (number average molecular weight 1000) 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 14%, the temperature is reduced to 50 ℃ for discharging, thus obtaining the polyurethane resin component B.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 29, 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 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 140 ℃ for 8min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 7
38.00kg of polyether-isophorone diisocyanate prepolymer (number average molecular weight 30000 and functionality of 3), 40.00kg of polyethylene glycol adipate (number average molecular weight 3000), 10.00kg of polyethylene glycol adipate trimethylolpropane (functionality of 2.3 and number average molecular weight 3000) are heated to 130 ℃, dehydrated for 5h under the vacuum condition of-0.04 MPa, cooled to 40 ℃, added with 4.50kg of ethylene glycol, 0.50kg of trimethylolpropane, 2.00kg of organosilicon foam stabilizer, 0.3kg of deionized water and 1.68kg of ultraviolet absorbent UV-320, 0.64kg of light stabilizer 292, 1.32kg of antioxidant 245 and 1.00kg of organic tin metal catalyst are mixed and stirred for 3 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 127.8mgKOH/g and the moisture content reaches 0.3 percent, the resin A component is prepared, and the resin A component is sealed and packaged for standby.
28.98kg of dicyclohexylmethane diisocyanate, 37.53kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.78g 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 4.5 percent, the temperature is reduced to 30 ℃ to discharge, thus obtaining the polyurethane resin component B.
Fully mixing the resin A component and the resin B component according to the mass ratio of 100: 213, 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 ℃ 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 5min after attaching, cooling, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 8
40.00kg of polyether ester-isophorone polyisocyanate prepolymer (number average molecular weight is 20000, functionality is 4), 37.80kg of polyethylene glycol propylene glycol adipate (number average molecular weight is 2000), 16.20kg of polybutylene glycol glycerol adipate (functionality is 2.5, number average molecular weight is 3000) are heated to 120 ℃, the mixture is dehydrated under the vacuum condition of-0.01 MPa for 6h, then the temperature is reduced to 30 ℃, 0.6kg of ethylene glycol, 0.05kg of trimethylolpropane, 1.35kg of organosilicon foam stabilizer, 2.0kg of deionized water and 2.00kg of organic tin metal catalyst are added for mixing and stirring for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 169.4mgKOH/g and the moisture content is 2.0%, the resin A component is prepared, and sealed and packaged for later use.
3.44kg of isophorone diisocyanate, 27.34kg of dicyclohexylmethane diisocyanate, 10.30kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.5g 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 20.3 percent, the temperature is reduced to 50 ℃ for discharging, thus obtaining the component B of the polyurethane resin.
Fully mixing the resin A component and the resin E component according to the mass ratio of 100: 63, allowing the mixture to stand for 10min, uniformly coating the mixed resin on release paper according to a set thickness, entering a drying tunnel with the temperature controlled at 90 ℃ 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 4min 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
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
In conclusion, the high-temperature-resistant integrated polyurethane resin provided by the invention is coated on the base cloth by a single-knife process, the process is simple and convenient, the operability is good, and the integration of the foaming layer, the bonding layer and the surface layer is realized. As can be seen from Table 1, the examples have significantly improved peel strength, tensile strength, heat resistance and yellowing resistance as compared with the comparative examples, and do not contain any organic solvent, do not pollute the environment, and do not affect the health of the operation.
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 (11)

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 contains 20-45 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.
2. The polyurethane resin of solvent-free synthetic leather according to claim 1, wherein the resin A component comprises the following components in percentage by mass:
the resin A component comprises the following components in percentage by mass:
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 4-35%.
3. The polyurethane resin of the solvent-free synthetic leather according to claim 2, wherein the polyether ester polyol-polyisocyanate prepolymer has a number average molecular weight of 10000-100000 and a functionality of 2-4;
the polyether ester polyol-polyisocyanate prepolymer is a prepolymer of polyether ester polyol and polyisocyanate, wherein the prepolymer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, triphenylmethane triisocyanate, dimethyl triphenylmethane tetraisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methyl cyclohexyl diisocyanate.
4. The polyurethane resin for solvent-free synthetic leather according to claim 2, wherein the polyester polyol a is a mixture of a 500-5000 number average molecular weight polyacyl polyester diol and a polyacyl polyester polyol; the mass ratio of the poly adipic acid polyester diol to the poly adipic acid polyester polyol is 3: 2-99: 1, the poly adipic acid polyester diol is a polycondensation product of adipic acid and micromolecular diol a, and the micromolecular diol a is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and diethylene glycol; the polyester polyol of the poly adipic acid series is a polymerization product of adipic acid, micromolecular dihydric alcohol a and micromolecular trihydric alcohol a; the functionality is 2.05-2.80, and the micromolecular dihydric alcohol a is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and diethylene glycol; the small molecule trihydric alcohol a is one or a mixture of two of glycerol, trimethylolpropane, trimethylolethane and hexanetriol.
5. The polyurethane resin of the solvent-free synthetic leather according to claim 2, wherein the mass ratio of the small molecular diol b to the small molecular triol b is 7: 3-19: 5.
6. The polyurethane resin of the solvent-free synthetic leather according to claim 5, wherein the small molecular diol b is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, diethylene glycol and neopentyl glycol; the micromolecular trihydric alcohol b is one or more of trimethylolpropane, trimethylolethane, glycerol, xylitol, sorbitol, mannitol and 1, 2, 6-hexanetriol.
7. The polyurethane resin of solvent-free synthetic leather according to claim 2, wherein the foam stabilizer is a silicone foam stabilizer;
the defoaming agent is one or more of fluorine defoaming agent and siloxane defoaming agent;
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.
8. The polyurethane resin for solvent-free synthetic leather according to claim 2, wherein in the resin B, the polymeric polyol is at least one of a polyacylohexanepolyol, a polycaprolactonepolyol, and a polycarbonate polyol having a functionality of 2 to 3 and a number average molecular weight of 500 to 5000.
9. The polyurethane resin for solvent-free synthetic leather according to claim 2, wherein in the resin B, the polymeric polyol is a mixture of polyester diol and polyether polyol; the mass ratio of the polyester diol to the polyether polyol is 1: 9-9: 1;
the polyether polyol is a mixture of 5000-20000 number average molecular weight polyether diol, polyether triol and polyether tetraol, and the polyether diol, polyether triol and polyether tetraol respectively account for 40-75%, 10-50% and 0-20% of the polyether polyol by weight; 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 500-5000.
10. The method for preparing the polyurethane resin of the solvent-free synthetic leather according to any one of claims 1 to 9, comprising the following steps:
(1) preparation of resin A component: adding a polyether ester polyol-polyisocyanate prepolymer and a polyester 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 uniform foaming agent, a durability auxiliary agent, a catalyst and water, stirring for 2-4 h, detecting a hydroxyl value and a water content, when the hydroxyl value reaches 50-200mgKOH/g and the water 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 4-35%, discharging to obtain a resin B component, and sealing and packaging for later use.
11. Use of the polyurethane resin of solvent-free synthetic leather according to any one of claims 1 to 9, for preparing solvent-free polyurethane synthetic leather, 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, 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 in an oven, adhering base cloth in a semi-dry state, controlling the gap of a pressure roller, allowing the solvent-free resin and the base cloth to be firmly adhered without breaking the foam hole, curing in a drying tunnel at the temperature of 130-140 ℃ for 4-8 min, and rolling to obtain the solvent-free polyurethane synthetic leather.
CN201711500645.1A 2017-12-29 2017-12-29 Solvent-free leather polyurethane resin and preparation method and application Withdrawn CN108047414A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679059A (en) * 2018-12-11 2019-04-26 万华化学集团股份有限公司 A kind of polyurethane-polyurea water dispersion and the preparation method and application thereof
CN110592965A (en) * 2019-08-26 2019-12-20 安徽安利材料科技股份有限公司 High-foaming high-stripping solvent-free shoe leather and preparation method thereof
CN112375206A (en) * 2020-12-22 2021-02-19 浙江兆泽实业有限公司 High-physical-property solvent-free polyurethane fabric resin for leather and preparation method thereof

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CN105504213A (en) * 2016-01-29 2016-04-20 李善军 Solvent-free polyurethane composition for synthetic leather

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CN105504213A (en) * 2016-01-29 2016-04-20 李善军 Solvent-free polyurethane composition for synthetic leather

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679059A (en) * 2018-12-11 2019-04-26 万华化学集团股份有限公司 A kind of polyurethane-polyurea water dispersion and the preparation method and application thereof
CN109679059B (en) * 2018-12-11 2021-07-23 万华化学集团股份有限公司 Polyurethane-polyurea aqueous dispersion and preparation method and application thereof
CN110592965A (en) * 2019-08-26 2019-12-20 安徽安利材料科技股份有限公司 High-foaming high-stripping solvent-free shoe leather and preparation method thereof
CN112375206A (en) * 2020-12-22 2021-02-19 浙江兆泽实业有限公司 High-physical-property solvent-free polyurethane fabric resin for leather and preparation method thereof

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Application publication date: 20180518