CN108164674B - Solvent-free non-yellowing high-transparency and bending-resistant polyurethane leather resin and preparation method and application thereof - Google Patents
Solvent-free non-yellowing high-transparency and bending-resistant polyurethane leather resin and preparation method and application thereof Download PDFInfo
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- CN108164674B CN108164674B CN201711475375.3A CN201711475375A CN108164674B CN 108164674 B CN108164674 B CN 108164674B CN 201711475375 A CN201711475375 A CN 201711475375A CN 108164674 B CN108164674 B CN 108164674B
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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
- D06N3/147—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
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- 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
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- 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
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- 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
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- 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
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
The invention discloses a solvent-free non-yellowing high-transparency and bending-resistant polyurethane leather resin and a preparation method and application thereof, wherein the solvent-free non-yellowing high-transparency and bending-resistant polyurethane leather resin comprises a resin A component and a resin B component; the resin A component and the resin B component are 3: 1-1: 2 in mass percentage, the resin A component contains 30-45 wt% of polyether polyol-aliphatic polyisocyanate prepolymer, and the resin B component contains 15-60 wt% of aliphatic diisocyanate.
Description
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), forming a film, then feeding the film into a drying tunnel, and attaching the semi-dry foaming layer to 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 composed of polyester polyol prepolymer or polyether polyol prepolymer, auxiliary material, polyamine catalyst and the like, 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.
Chinese patent application with application number of 201610798749.4 discloses carbon fiber modified solvent-free polyurethane for sneaker leather
The existing non-yellowing solvent-free polyurethane surface layer resin for leather is difficult to prepare high-transparency and high-flexibility-resistant surface layer leather, and has insufficient aesthetic property.
Disclosure of Invention
The invention aims to provide a solvent-free non-yellowing high-transparency and bright-flexing-resistant polyurethane resin, a preparation method and application thereof, so as to solve the problems of non-yellowing solvent-free synthetic leather.
The solvent-free, non-yellowing, high-transparency, bright and bending-resistant polyurethane resin comprises a resin A component and a resin B component; the mass ratio of the resin A component to the resin B component is 3: 1-1: 2.
The resin A component contains 30-45 wt% of polyether polyol-aliphatic polyisocyanate prepolymer, and the resin B component contains 15-60 wt% of aliphatic diisocyanate;
preferably, the resin A component consists of the following components in percentage by mass:
the resin B component comprises the following components in percentage by mass:
15-60% of aliphatic diisocyanate;
30-85% of polyol;
0-1% of phosphoric acid;
preferably:
the resin B component comprises the following components in percentage by mass:
15 to 41 percent of aliphatic diisocyanate;
58 to 85 percent of polyol;
0-1% of phosphoric acid;
the NCO content in the resin B component is 4-10%.
The polyether polyol-aliphatic polyisocyanate prepolymer has the number average molecular weight of 10000-100000 and the functionality of 2-4;
preferably, the polyether ester polyol-aliphatic polyisocyanate prepolymer is a prepolymer of polyether ester polyol and aliphatic polyisocyanate, wherein the aliphatic diisocyanate is one or more of 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 5000-20000, 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 polypropylene oxide triol and polypropylene oxide-ethylene oxide triol; the polyether tetrahydric alcohol a is polyoxypropylene tetrahydric alcohol.
The micromolecular alcohol chain extender is one or a mixture of micromolecular dihydric alcohol and micromolecular trihydric alcohol;
the micromolecular dihydric alcohol is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, diethylene glycol and neopentyl glycol; the small molecule 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 defoaming agent is one or more of fluorine defoaming agent and siloxane defoaming agent.
The durability auxiliary agent is a mixture of an ultraviolet absorber, a hindered amine light stabilizer and an antioxidant, and the ultraviolet absorber, the hindered amine light stabilizer and the antioxidant respectively account for 30-50%, 40-60% and 10-20% of the durability auxiliary agent by mass percent; 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 aliphatic diisocyanate is one or two of 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 polyhydric alcohol is one or a mixture of polyester diol and polyether polyol B;
wherein: the polyether glycol B is selected from one or a mixture of polyether glycol B, polyether triol B and polyether tetraol B, and the polyether glycol B, the polyether triol B and the polyether tetraol B respectively account for 40-75%, 10-50% and 0-20% of the polyether glycol B by mass;
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 trihydric alcohol and polyoxypropylene-ethylene oxide trihydric alcohol; 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 poly adipic 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 polyether polyol has a functionality of 2-4 and a number average molecular weight of 5000-20000;
the preparation method of the solvent-free non-yellowing high-transparency and high-flexibility polyurethane resin comprises the following steps of:
(1) preparation of resin A component: adding a polyether ester polyol-aliphatic 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, cooling to 30-50 ℃, adding a small molecular alcohol chain extender, a foam stabilizer, a durability auxiliary agent, a catalyst and a defoaming agent, stirring for 2-4 h, detecting a hydroxyl value and a water content, when the hydroxyl value reaches 25-95 mgKOH/g and the water content is lower than 500ppm, preparing a resin A component, and sealing and packaging for later use;
(2) preparation of the component B: adding aliphatic diisocyanate, polyalcohol and phosphoric acid into a reaction kettle, stirring and reacting for 1.5-3.0 h at 90-110 ℃, sampling and detecting the NCO content, reducing the temperature to 30-50 ℃ when the NCO content is 4-10%, discharging to obtain a resin B component, and sealing and packaging for later use.
The resin for the solvent-free non-yellow high-transparency high-brightness bending-resistant polyurethane leather can be used for preparing the solvent-free non-yellow high-transparency high-brightness bending-resistant polyurethane synthetic leather, and the application method comprises the following steps:
and (2) fully mixing the resin A component and the resin B component according to the mass ratio of 3: 1-1: 2, allowing the mixture to be used for 15-20 min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 4-8 min in a drying tunnel with the temperature controlled at 120-140 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and bending-resistant polyurethane synthetic leather.
Compared with the prior art, the invention has the following advantages:
(1) the solvent-free non-yellowing high-transparency bright-bending-resistant polyurethane leather disclosed by the invention is coated on a synthetic leather surface layer, so that the synthetic leather has high transparency and high brightness, the aesthetic degree is endowed, the physical and mechanical properties such as bending resistance and the like of the non-yellowing synthetic leather are further improved, the normal-temperature folding strength is more than or equal to 20 ten thousand, the folding resistance at minus 20 ℃ is more than or equal to 5 ten thousand, the hydrolysis resistance reaches 8 weeks, and the yellowing resistance grade is more than or equal to 4.
(2) The mixing service life of the resin A component and the resin B component can reach 15-20 min, and the production operability in the synthetic leather production process is improved.
(3) The component A of the resin is introduced with a proper amount of polyether ester prepolymer, so that the parameters such as viscosity, molecular weight and the like of the resin are effectively adjusted, and the stability of the distribution ratio of the component A of the resin and the component B of the resin during production and processing is ensured.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood that the specific material ratios, 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 polyol-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-0.01 MPa for 6 hours, then cooled to 30 ℃, 2.10kg of ethylene glycol, 0.90kg of trimethylolpropane, 0.70kg of silicone foam stabilizer, 0.50kg of siloxane foam suppressor, 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 and mixed and stirred for 2 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 66.5mgKOH/g and the moisture content is lower than 500ppm, the resin component A 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 5.8%, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin B component is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 0.94:1, mixing for 20min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 8min in a drying tunnel with the temperature controlled at 120 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and bright-flexing-resistant polyurethane synthetic leather.
Example 2
45.00kg of polyether ester polyol-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 under 0.06MPa vacuum condition for 5h, cooled to 50 ℃, added with 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of organosilicon foam stabilizer, 0.30kg of siloxane defoamer, 0.45kg of ultraviolet absorbent UV-320, 0.36kg of light stabilizer 292, 0.09kg of antioxidant 245 and 0.90kg of metal catalyst, mixed and stirred for 2h, the hydroxyl value and the moisture content are detected, and when the hydroxyl value reaches 43.4 KOH/g, when the water content is lower than 500ppm, 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 detected by sampling, and when the NCO content is 10.0%, the NCO is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 2.4:1, mixing for 15min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 4min in a drying tunnel with the temperature controlled at 140 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and anti-bending polyurethane synthetic leather.
Example 3
38.00kg of polyether ester polyol-dicyclohexylmethane diisocyanate prepolymer (number average molecular weight of 30000 and functionality of 3), 25.36kg of polyoxypropylene diol (number average molecular weight of 20000), 25.00kg of polyoxypropylene triol (number average molecular weight of 18000), heating to 130 ℃, dehydrating under 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, 2.00kg of siloxane defoamer, and 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 are mixed and stirred for 3 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 93.6mgKOH/g and the moisture content is lower than 500ppm, the resin A component is prepared, and the mixture is sealed and packaged for standby application;
24.94kg of dicyclohexylmethane diisocyanate, 32.30kg of polyethylene glycol adipate (number average molecular weight of 500), 1.79kg of polyoxypropylene diol (number average molecular weight of 5000), 1.79kg of polyoxypropylene-ethylene oxide triol (number average molecular weight of 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%, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin component B is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 1:3, allowing the mixture to stand for 20min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 6min in a drying tunnel with the temperature controlled at 130 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and anti-bending polyurethane synthetic leather.
Example 4
40.0kg of polyether ester polyol-dicyclohexylmethane diisocyanate prepolymer (number average molecular weight is 20000 and 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 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 siloxane foam suppressor, 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, mixed and stirred for 2h, hydroxyl value and moisture content are detected, when hydroxyl value reaches 27.4 KOH/g, when the water content is lower than 500ppm, the resin component A 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 1.5 hours at 110 ℃, the NCO content is sampled and detected, and when the NCO content is 4.0%, the temperature is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 2.0:1, mixing for 10min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 6min in a drying tunnel with the temperature controlled at 130 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and bright-flexing-resistant polyurethane synthetic leather.
Comparative example 1
30.00kg of polyether polyol-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 silicone foam stabilizer, 0.50kg of siloxane foam suppressor, 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, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 66.5mgKOH/g and the moisture content is lower than 500ppm, the resin A component is prepared, sealing and packaging for later use;
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 5.8%, the temperature is reduced to 30 ℃ to discharge, so that the polyurethane resin B component is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 0.9:1, mixing for 20min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 8min in a drying tunnel with the temperature controlled at 120 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and bright-flexing-resistant polyurethane synthetic leather.
Comparative example 2
55.00kg of polytetrahydrofuran ether diol (with the number average molecular weight of 10000), 30.00kg of polypropylene oxide-ethylene oxide triol (with the number average molecular weight of 12000) and 10.00kg of polypropylene oxide tetraol (with the number average molecular weight of 20000) are heated to 140 ℃, dehydrated for 5h under the vacuum condition of-0.06 MPa, then cooled to 50 ℃, 2.47kg of 1, 4-butanediol, 0.13kg of trimethylolpropane, 0.30kg of silicone foam stabilizer, 0.30kg of siloxane foam suppressor, 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 and mixed and stirred for 2h, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 44.0mgKOH/g and the moisture content is lower than 500ppm, the 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 detected by sampling, and when the NCO content is 10.0%, the NCO is reduced to 50 ℃ for discharging, so that the polyurethane resin B component is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 2.7:1, mixing for 15min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 4min in a drying tunnel with the temperature controlled at 140 ℃, and rolling to obtain the solvent-free high-transparency polyurethane synthetic leather.
Comparative example 3
38.00kg of polyether ester polyol-dicyclohexylmethane diisocyanate prepolymer (number average molecular weight of 30000 and functionality of 3), 25.36kg of polyoxypropylene diol (number average molecular weight of 20000), 25.00kg of polyoxypropylene triol (number average molecular weight of 18000), heating to 130 ℃, dehydrating under 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, 2.00kg of siloxane defoamer, and 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 are mixed and stirred for 3 hours, the hydroxyl value and the moisture content are detected, when the hydroxyl value reaches 93.6mgKOH/g and the moisture content is lower than 500ppm, the resin A component is prepared, and the mixture is sealed and packaged for standby application;
24.94kg of dicyclohexylmethane diisocyanate, 32.30kg of polydiethylene glycol adipate (with the number average molecular weight of 500) and 0.60g of phosphoric acid are put into a reaction kettle to be stirred and reacted for 2.0h at the temperature of 100 ℃, the NCO content is sampled and detected, and when the NCO content is 4.5 percent, the NCO content is reduced to 30 ℃ to discharge, so that the component B of the polyurethane resin is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 1:2.9, allowing the mixture to stand for 20min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 6min in a drying tunnel with the temperature controlled at 130 ℃, and rolling to obtain the solvent-free polyurethane synthetic leather.
Comparative example 4
40.0kg of polyether ester polyol-dicyclohexylmethane diisocyanate prepolymer (number average molecular weight is 20000 and 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 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 siloxane foam suppressor, 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, mixed and stirred for 2h, hydroxyl value and moisture content are detected, when hydroxyl value reaches 27.4 KOH/g, when the water content is lower than 500ppm, the resin component A is prepared and sealed and packaged for standby;
2.39kg of isophorone diisocyanate, 19.00kg of dicyclohexylmethane diisocyanate, 37.96kg of polytetrahydrofuran ether diol (number average molecular weight is 5000), 22.78kg of polyoxypropylene-ethylene oxide triol (number average molecular weight is 15000), 15.19kg of polyoxypropylene tetraol (number average molecular weight is 6000) and 07g of phosphoric acid 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 5.9%, the temperature is reduced to 50 ℃ to discharge, so that the polyurethane resin B component is obtained.
And (2) fully mixing the resin A component and the resin B component according to the mass ratio of 2.6:1, mixing for 10min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 6min in a drying tunnel with the temperature controlled at 130 ℃, 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. Wherein the yellowing resistance test method is specified by the method B in QB/T4672-2014; hydrolysis resistance test method is specified by method A in QB/T4671-2014, and the wet heat treatment time is 5 weeks. Refractive index test according to
TABLE 1
In conclusion, the solvent-free, yellowing-free, high-transparency, bright and bending-resistant polyurethane leather resin is coated on a synthetic leather surface layer, so that the synthetic leather has the performances of smoothness, transparency, yellowing resistance and the like, compared with a comparative example, the bending resistance and the hydrolysis resistance are greatly different, the comprehensive performance is better, and the resin does not contain any organic solvent, does not pollute the environment and does not influence the operation and work 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 (5)
1. The solvent-free non-yellowing high-transparency and high-flexibility-resistant resin for polyurethane leather is characterized by comprising a resin A component and a resin B component; the mass ratio of the resin A component to the resin B component is 3: 1-1: 2;
the resin A component comprises the following components in percentage by mass:
the resin B component comprises the following components in percentage by mass:
15-60% of aliphatic diisocyanate;
30-85% of polyol;
0-1% of phosphoric acid;
the NCO content in the resin B component is 4-10%;
the polyether ester polyol-aliphatic polyisocyanate prepolymer has the number average molecular weight of 10000-100000 and the functionality of 2-4;
the preparation method of the solvent-free non-yellowing high-transparency and high-brightness flexing-resistant polyurethane leather resin is characterized by comprising the following steps of:
(1) preparation of resin A component: adding a polyether ester polyol-aliphatic 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 a defoaming agent, stirring for 2-4 h, detecting a hydroxyl value and a water content, when the hydroxyl value reaches 25-95 mgKOH/g and the water content is lower than 500ppm, obtaining a resin A component, and sealing and packaging for later use;
(2) preparation of the component B: adding aliphatic 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 4-10%, discharging to obtain a resin B component, and sealing and packaging for later use;
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 5000-20000, 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 polypropylene oxide triol and polypropylene oxide-ethylene oxide triol; the polyether tetrahydric alcohol a is polyoxypropylene tetrahydric alcohol;
in the resin B, the polyhydric alcohol is a mixture of polyester diol and polyether polyol B;
wherein: the polyether polyol B is selected from one or a mixture of 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 B 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;
the poly adipic acid polyester diol is selected from poly ethylene glycol adipate diol, poly propylene glycol adipate diol, poly 1, 4-butanediol adipate diol, poly diethylene glycol adipate diol and poly neopentyl glycol adipate diol; the polyether polyol B has a functionality of 2-4 and a number average molecular weight of 5000-20000.
2. The resin for the solvent-free non-yellowing high-transparency and high-flex-resistance polyurethane leather according to claim 1, wherein the polyether ester polyol-aliphatic polyisocyanate prepolymer is a prepolymer of polyether ester polyol and aliphatic polyisocyanate, wherein the aliphatic diisocyanate is one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methylcyclohexyl diisocyanate.
3. The resin for the solvent-free non-yellowing high-transparency bright-flex-resistant polyurethane leather as claimed in claim 1, wherein the small molecular alcohol chain extender is one or a mixture of small molecular diol and small molecular triol.
4. The resin for solvent-free non-yellowing high-transparency and high-flex-resistance polyurethane leather according to claim 1, wherein the aliphatic diisocyanate is one or two of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate and methylcyclohexyl diisocyanate.
5. The application of the resin for the solvent-free non-yellowing high-transparency bright-flex-resistant polyurethane leather as claimed in any one of claims 1 to 4, which is used for preparing the solvent-free non-yellowing high-transparency bright-flex-resistant polyurethane synthetic leather, and the application method comprises the following steps:
and (2) fully mixing the resin A component and the resin B component according to the mass ratio of 3: 1-1: 2, allowing the mixture to be used for 15-20 min, uniformly coating the mixed resin on a synthetic leather surface layer according to a set thickness, curing for 4-8 min in a drying tunnel with the temperature controlled at 120-140 ℃, and rolling to obtain the solvent-free non-yellowing high-transparency and anti-bending polyurethane synthetic leather.
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