CN111269390A - Polyurethane resin for synthetic leather surface layer and preparation method thereof - Google Patents
Polyurethane resin for synthetic leather surface layer and preparation method thereof Download PDFInfo
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- CN111269390A CN111269390A CN202010196173.0A CN202010196173A CN111269390A CN 111269390 A CN111269390 A CN 111269390A CN 202010196173 A CN202010196173 A CN 202010196173A CN 111269390 A CN111269390 A CN 111269390A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/4009—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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- 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
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/61—Polysiloxanes
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
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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
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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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- 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
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/146—Soilproof, soil repellent
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- 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)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane resin for a synthetic leather surface layer and a preparation method thereof, wherein the preparation method of the polyurethane resin comprises the following steps: adding polyether polyol, polyester polyol, polysiloxane a and part of solvent into a reaction kettle together, stirring at 40-55 ℃ until the solvent is completely dissolved, adding part of isocyanate, heating to 70-80 ℃, and carrying out prepolymerization reaction for 0.5-1 h; continuously adding the small-molecule chain extender, cooling to 50 ℃, stirring for 15-30 min, adding the catalyst, adding the rest of isocyanate, heating to 70-80 ℃, and continuously reacting for 0.5-1 h; and adding the solvent until the viscosity reaches 100-160 cps, cooling to 50 ℃, stirring for 1-1.5 h, and adding isocyanurate and polysiloxane b to obtain the polyurethane resin for the synthetic leather surface layer. The product of the invention has outstanding wear resistance and heat resistance, and the material does not turn white after being embossed at high temperature, has obvious antifouling effect after being applied to synthetic leather, and is not easy to be stained with ash.
Description
Technical Field
The present invention relates to a polyurethane resin. In particular to polyurethane resin which can be used as a synthetic leather surface layer material.
Background
The synthetic leather is a leather product which is close to the touch of genuine leather and is formed by combining base cloth such as non-woven fabric or woven cloth at the bottom layer, a foaming polyurethane microporous layer at the middle layer and a polyurethane coating at the surface layer. Wherein, the surface course is as the outermost material of synthetic leather, and the main effect includes: the appearance light sensation and the touch feeling of the synthetic leather are increased, so that the synthetic leather is closer to genuine leather, and the performances of wear resistance, scratch resistance, pollution resistance, yellowing prevention and the like of the synthetic leather are improved.
With the diversification of the demands of people, the market of the printable synthetic leather gradually develops, and at present, high-temperature embossing or high-temperature vacuum grain suction is generally adopted to form various patterns or decorative patterns on the synthetic leather. Therefore, compared with non-printed synthetic leather, the printed synthetic leather has the performance requirements of the common synthetic leather on light sensation, touch feeling, physical properties and the like and also has the requirements of high temperature resistance and deformation resistance. However, there are many problems faced in the field of printable synthetic leather, for example: the conventional synthetic leather has insufficient temperature resistance, and a surface layer is damaged or deformed after high-temperature embossing or high-temperature vacuum grain absorption; the damage of the surface structure after printing causes hard hand feeling, heavy glue feeling and large difference of corium feeling; micromolecular substances or assistants in the synthetic leather are precipitated and decomposed at high temperature to influence the surface effect of the material and the comprehensive physical properties of wear resistance, scratch resistance and the like.
Disclosure of Invention
The technical problem is as follows: in order to overcome the defects, the invention aims to provide a polyurethane resin for synthesizing a leather surface layer material, and polyurethane synthetic leather for embossing or embossing can be prepared by adopting a dry production process and taking the polyurethane resin as a surface layer coating.
The technical scheme is as follows: the polyurethane resin for the synthetic leather surface layer comprises the following components in percentage by mass:
the polysiloxane a is a polysiloxane polymer with a chain end provided with an isocyanate reactive group, and the number average molecular weight is 1000-2000;
the polysiloxane b is a polysiloxane polymer containing at least 2 reactive groups to isocyanate, and the number average molecular weight is 10000-20000.
The group reactive to isocyanate is one or both of amino and hydroxyl.
Wherein:
the polyether glycol is one or more polyether diols obtained by ring-opening polymerization of alkylene oxide with 2-8 carbon atoms, and the number average molecular weight is 1000-3000.
The polyester polyol is one or more of polyester diols obtained by polymerizing aliphatic dibasic acid and aliphatic diol, and the number average molecular weight is 1000-3000.
The isocyanate is diisocyanate containing 2 isocyanate groups, and comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate.
The isocyanurate is a polymer containing an isocyanurate ring and having a polymerization degree of 3-7, and is obtained by carrying out auto-polymerization on aliphatic or aromatic diisocyanate.
The micromolecule chain extender is one or more than one of micromolecule substances which have 2-6 carbon atoms and at least contain 2 groups with reactivity to isocyanate.
The small molecular chain extender is a mixture of small molecular substances with 2-6 carbon atoms and containing 2 groups with reactivity to isocyanate and small molecular substances with 2-6 carbon atoms and containing more than 2 groups with reactivity to isocyanate, and the mass ratio of the small molecular substances to the small molecular chain extender is 25: 1-60: 1.
the micromolecule substance with 2-6 carbon atoms and 2 groups with reactivity to isocyanate comprises one or more than one of ethanolamine, ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol and neopentyl glycol;
the micromolecule substance with 2-6 carbon atoms and more than 2 groups with reactivity to isocyanate comprises one or two of trimethylolpropane and trihydroxypropane.
The preparation method of the polyurethane resin for the synthetic leather surface layer is obtained by adopting the following preparation steps in the presence of a solvent and a catalyst:
step 1, adding polyether polyol, polyester polyol, polysiloxane a and a part of solvent into a reaction kettle together, stirring at 40-55 ℃ until the polyether polyol, the polyester polyol, the polysiloxane a and the part of solvent are completely dissolved, adding a part of isocyanate, heating to 70-80 ℃, and carrying out prepolymerization reaction for 0.5-1 h;
step 2, continuously adding the small molecular chain extender, cooling to 50 ℃, stirring for 15-30 min, adding the catalyst, adding the rest of isocyanate, heating to 70-80 ℃, and continuously reacting for 0.5-1 h;
and 3, adding the solvent until the viscosity reaches 100-160 cps, cooling to 50 ℃, stirring for 1-1.5 h, and adding isocyanurate and polysiloxane b to obtain the polyurethane resin for the synthetic leather surface layer.
Has the advantages that: through the synergistic effect of the raw materials and the matching of the synthesis process, the product has outstanding wear resistance and heat resistance, and the material does not turn white after being embossed at high temperature.
In practical use, the product of the invention has good surface effect as synthetic leather surface forming material, has no obvious plastic feeling, has soft hand feeling, is similar to the touch of genuine leather, and has good wear-resisting, heat-resisting and antifouling effects in the long-term use process.
Detailed Description
The principles and features of the present invention are described below in conjunction with the following examples, all of which are intended to be commercially available or known.
The polyurethane resin comprises the following components in percentage by mass:
the polysiloxane a is a polysiloxane polymer with a chain end provided with an isocyanate reactive group, and the number average molecular weight is 1000-2000;
the polysiloxane b is a polysiloxane polymer containing at least 2 reactive groups to isocyanate, and the number average molecular weight is 10000-20000.
The polysiloxane b is one or two of amino and hydroxyl which have reactive groups for isocyanate.
The polyether glycol is one or more polyether diols obtained by ring-opening polymerization of alkylene oxide with 2-8 carbon atoms, and the number average molecular weight is 1000-3000.
The polyester polyol is one or more of polyester diols obtained by polymerizing aliphatic dibasic acid and aliphatic diol, and the number average molecular weight is 1000-3000.
Preferably, the polyester polyol is one or more polyester diols obtained by polymerizing 1, 6-adipic acid and linear chain or branched chain diols with 2-8 carbon atoms;
the isocyanate is diisocyanate containing 2 isocyanate groups, and comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate.
In a preferred embodiment of the invention, the isocyanate is diphenylmethane diisocyanate;
the isocyanurate is a polymer containing an isocyanurate ring and having a polymerization degree of 3-7, and is obtained by carrying out auto-polymerization on aliphatic or aromatic diisocyanate.
In a preferred embodiment of the present invention, the isocyanurate is a polymer containing an isocyanurate ring having a polymerization degree of 3 obtained by the polymerization of hexamethylene diisocyanate;
the micromolecule chain extender is one or more than one of micromolecule substances which have 2-6 carbon atoms and at least contain 2 groups with reactivity to isocyanate.
The small molecular chain extender is a mixture of small molecular substances with 2-6 carbon atoms and containing 2 groups with reactivity to isocyanate and small molecular substances with 2-6 carbon atoms and containing more than 2 groups with reactivity to isocyanate, and the mass ratio of the small molecular substances to the small molecular chain extender is 25: 1-60: 1.
the micromolecule substance with 2-6 carbon atoms and 2 groups with reactivity to isocyanate comprises one or more than one of ethanolamine, ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol and neopentyl glycol;
the micromolecule substance with 2-6 carbon atoms and more than 2 groups with reactivity to isocyanate comprises one or two of trimethylolpropane and trihydroxypropane.
The solvent is one or more than one of N, N-dimethylformamide, toluene, butanone and ethyl acetate, and the mass ratio of the polyurethane resin to the solvent is 3: 10-3: 5;
furthermore, the polyurethane resin can be further improved by adding additives known in the field, such as one or more of an anti-aging agent, a leveling agent, a chain terminator and a flame retardant;
the anti-aging agents include ultraviolet absorbers, light stabilizers, antioxidants, such as: one or more of an ultraviolet absorber UV-320, an ultraviolet absorber UV-326, an ultraviolet absorber UV-327, an ultraviolet absorber UV-328, an ultraviolet absorber UV-1130, a light stabilizer 292, a light stabilizer 770, a light stabilizer 622, an antioxidant 245, an antioxidant 1010, an antioxidant 1035, an antioxidant 1076 and an antioxidant 1098, wherein the addition amount of the anti-aging agent is 0.2-2.0% of the mass of the polyurethane resin;
the leveling agent comprises an organic silicon type leveling agent and an acrylic acid type leveling agent, and the addition amount of the leveling agent is 0.2-0.6% of the mass of the polyurethane resin;
the chain terminator is a small molecular monohydric alcohol such as methanol, ethanol or a mixture of the methanol and the ethanol, and the addition amount of the chain terminator is 0.3-1% of the mass of the polyurethane resin;
the flame retardant comprises one or more of halogenated phosphate, halogenated hydrocarbon, melamine and derivatives, and inorganic flame retardants, and the addition amount of the flame retardant is 0.5-10% of the mass of the polyurethane resin;
the polyurethane resin for the synthetic leather surface layer is prepared by adopting the following preparation steps in the presence of a solvent and a catalyst:
step 1, adding polyether polyol, polyester polyol, polysiloxane a and a part of solvent into a reaction kettle together, stirring at 40-55 ℃ until the polyether polyol, the polyester polyol, the polysiloxane a and the part of solvent are completely dissolved, adding a part of isocyanate, heating to 70-80 ℃, and carrying out prepolymerization reaction for 0.5-1 h;
step 2, continuously adding the small molecular chain extender, cooling to 50 ℃, stirring for 15-30 min, adding the catalyst, adding the rest of isocyanate, heating to 70-80 ℃, and continuously reacting for 0.5-1 h;
and 3, adding the solvent until the viscosity reaches 100-160 cps, cooling to 50 ℃, stirring for 1-1.5 h, and adding isocyanurate and polysiloxane b to obtain the polyurethane resin for the synthetic leather surface layer.
Wherein the content of the first and second substances,
the molar ratio (R value) of the isocyanate group in the step 1 to the isocyanate reactive group is 0.4-0.8; the added solvent amount has no special requirement, and the raw materials can be fully dissolved;
the viscosity test in the step 3 is carried out by adopting a rotary viscometer at the temperature of 25 ℃;
preferably, an auxiliary agent is added in the step 1 or 3, an anti-aging auxiliary agent is added in the step 1, and a leveling agent, a chain terminator and a flame retardant are added in the step 3;
the catalyst is an environment-friendly metal catalyst and an amine catalyst, the metal catalyst comprises one or more of metal organic bismuth, organic zinc, silver oxide and organic tin, and the amine catalyst comprises one or more of heat-sensitive delayed DBU hydrochloride amine and gel amine catalyst;
the addition amount of the catalyst is 0.05-0.15% of the mass of the polyurethane resin;
example 1
(1) Adding 17.2kg of neopentyl glycol adipate diol with the number average molecular weight of 1000, 35kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 1.9kg of amino-terminated polysiloxane with the number average molecular weight of 1000 and 100kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the mixture is completely dissolved, adding 5kg of diphenylmethane diisocyanate, heating to 70 ℃, and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 6kg of diethylene glycol and 0.1kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 19.3kg of diphenylmethane diisocyanate, heating to 70 ℃, and continuously reacting for 0.5 h;
(3) supplementing the remaining 200kg of solvent N, N-dimethylformamide until the viscosity reaches 110cps, cooling to 50 ℃, stirring for 1h, adding 5.2kg of hexamethylene diisocyanate, performing auto-polymerization to obtain a polymer with the polymerization degree of 3 and 10.3kg of hydroxyl-terminated siloxane with the number average molecular weight of 20000 to obtain the polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group in the step (1) to the isocyanate group-reactive group is 0.55;
the adding amount of the catalyst in the step (2) is 0.1 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Example 2
(1) Adding 20kg of adipic acid-1, 4-butanediol ester with the number average molecular weight of 2000, 26kg of polytetramethylene ether glycol with the number average molecular weight of 3000, 1.5kg of hydroxyl-terminated polysiloxane with the number average molecular weight of 2000 and 80kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 40 ℃ until the mixture is completely dissolved, adding 3.8kg of diphenylmethane diisocyanate, heating to 70 ℃, and carrying out prepolymerization reaction for 0.5 h;
(2) continuously adding 9.7kg of 1, 4-butanediol and 0.3kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 29kg of diphenylmethane diisocyanate, heating to 70 ℃, and continuously reacting for 0.5 h;
(3) adding the remaining 100kg of solvent N, N-dimethylformamide until the viscosity reaches 118cps, cooling to 50 ℃, stirring for 1h, adding 3kg of hexamethylene diisocyanate, carrying out self polymerization to obtain a polymer with the polymerization degree of 3 and 6.7kg of hydroxyl-terminated siloxane with the number average molecular weight of 20000 to obtain the polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group to the isocyanate-reactive group in the step (1) is 0.78;
the adding amount of the catalyst in the step (2) is 0.05 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Example 3
(1) Adding 14.4kg of adipic acid-ethylene glycol-1, 4-butanediol ester dihydric alcohol with the number average molecular weight of 3000, 32.8kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 0.3kg of amino-terminated polysiloxane with the number average molecular weight of 1000 and 100kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 55 ℃ until the materials are completely dissolved, adding 4.3kg of diphenylmethane diisocyanate, heating to 80 ℃ and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 5kg of ethanolamine and 0.2kg of trimethylolpropane, cooling to 50 ℃, stirring for 15min, adding a catalyst of dibutyltin dilaurate, supplementing 21.9kg of diphenylmethane diisocyanate, heating to 80 ℃, and continuously reacting for 1 h;
(3) adding the remaining 100kg of solvent N, N-dimethylformamide until the viscosity reaches 120cps, cooling to 50 ℃, stirring for 1.5h, adding 4.1kg of hexamethylene diisocyanate, performing self polymerization to obtain a polymer with the polymerization degree of 3 and 17kg of trihydroxy siloxane with the number average molecular weight of 10000 to obtain polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group in the step (1) to the isocyanate-reactive group is 0.80;
the adding amount of the catalyst in the step (2) is 0.15 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Example 4
(1) Adding 14.9kg of neopentyl glycol adipate diol with the number average molecular weight of 1000, 29.3kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 1.5kg of hydroxyl-terminated polysiloxane with the number average molecular weight of 2000 and 100kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the hydroxyl-terminated polysiloxane and the solvent N, N-dimethylformamide are completely dissolved, adding 4.8kg of diphenylmethane diisocyanate, heating to 80 ℃, and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 5.9kg of ethanolamine and 0.1kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 27kg of diphenylmethane diisocyanate, heating to 80 ℃, and continuously reacting for 1 h;
(3) adding the rest 140kg of solvent N, N-dimethylformamide until the viscosity reaches 115cps, cooling to 50 ℃, stirring for 1h, adding 3.5kg of hexamethylene diisocyanate, performing self polymerization to obtain a polymer with the polymerization degree of 3 and 13kg of trihydroxy siloxane with the number average molecular weight of 10000 to obtain polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group in the step (1) to the isocyanate-reactive group is 0.63;
the adding amount of the catalyst in the step (2) is 0.1 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Example 5
(1) Adding 16.9kg of adipic acid-1, 4-butanediol ester with the number average molecular weight of 2000, 35kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 1.5kg of hydroxyl-terminated polysiloxane with the number average molecular weight of 2000 and 110kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the mixture is completely dissolved, adding 3.1kg of diphenylmethane diisocyanate, heating to 80 ℃, and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 5.7kg of 1, 4-butanediol and 0.2kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 20kg of diphenylmethane diisocyanate, heating to 80 ℃, and continuously reacting for 1 h;
(3) adding the remaining 120kg of solvent N, N-dimethylformamide until the viscosity reaches 117cps, cooling to 50 ℃, stirring for 1h, adding 4.2kg of hexamethylene diisocyanate, performing self polymerization to obtain a polymer with the polymerization degree of 3 and 13.4kg of trihydroxy siloxane with the number average molecular weight of 10000 to obtain polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group to the isocyanate-reactive group in the step (1) is 0.46;
the adding amount of the catalyst in the step (2) is 0.05 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Comparative example 1
(1) Adding 14.9kg of neopentyl glycol adipate diol with the number average molecular weight of 1000, 29.3kg of polytetramethylene ether glycol with the number average molecular weight of 2000 and 100kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the solvents are completely dissolved, adding 4.8kg of diphenylmethane diisocyanate, heating to 80 ℃, and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 5.9kg of ethanolamine and 0.1kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 27kg of diphenylmethane diisocyanate, heating to 80 ℃, and continuously reacting for 1 h;
(3) adding the rest 140kg of solvent N, N-dimethylformamide until the viscosity reaches 122cps, cooling to 50 ℃, and stirring for 1h to obtain polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group in the step (1) to the isocyanate-reactive group is 0.65;
the adding amount of the catalyst in the step (2) is 0.1 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Comparative example 2
(1) Adding 14.9kg of neopentyl glycol adipate diol with the number average molecular weight of 1000, 29.3kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 1.5kg of hydroxyl-terminated polysiloxane with the number average molecular weight of 2000 and 100kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the hydroxyl-terminated polysiloxane and the solvent N, N-dimethylformamide are completely dissolved, adding 4.8kg of diphenylmethane diisocyanate, heating to 80 ℃, and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 5.9kg of ethanolamine and 0.1kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 27kg of diphenylmethane diisocyanate, heating to 80 ℃, and continuously reacting for 1 h;
(3) adding the rest 140kg of solvent N, N-dimethylformamide until the viscosity reaches 124cps, cooling to 50 ℃, and stirring for 1h to obtain polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group in the step (1) to the isocyanate-reactive group is 0.63;
the adding amount of the catalyst in the step (2) is 0.1 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Comparative example 3
(1) Adding 14.9kg of neopentyl glycol adipate diol with the number average molecular weight of 1000, 29.3kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 1.5kg of hydroxyl-terminated polysiloxane with the number average molecular weight of 2000 and 100kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the hydroxyl-terminated polysiloxane and the solvent N, N-dimethylformamide are completely dissolved, adding 4.8kg of diphenylmethane diisocyanate, heating to 80 ℃, and carrying out prepolymerization reaction for 1 hour;
(2) continuously adding 5.9kg of ethanolamine and 0.1kg of trimethylolpropane, cooling to 50 ℃, stirring for 30min, adding a catalyst of dibutyltin dilaurate, supplementing 27kg of diphenylmethane diisocyanate, heating to 80 ℃, and continuously reacting for 1 h;
(3) adding the rest 140kg of solvent N, N-dimethylformamide until the viscosity reaches 117cps, cooling to 50 ℃, stirring for 1h, and adding 13kg of trihydroxy siloxane with number average molecular weight of 10000 to obtain polyurethane resin for the synthetic leather surface layer;
wherein:
the molar ratio (R value) of the isocyanate group in the step (1) to the isocyanate-reactive group is 0.63;
the adding amount of the catalyst in the step (2) is 0.1 wt%;
0.5 wt% of antioxidant 1010 added in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added when the viscosity in the step (3) meets the requirement;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
Comparative example 4
(1) Adding 14.9kg of neopentyl glycol adipate diol with the number average molecular weight of 1000, 29.3kg of polytetramethylene ether glycol with the number average molecular weight of 2000, 1.5kg of hydroxyl-terminated polysiloxane with the number average molecular weight of 2000 and 240kg of solvent N, N-dimethylformamide into a reaction kettle, stirring at 50 ℃ until the hydroxyl-terminated polysiloxane and the solvent are completely dissolved, adding a catalyst dibutyltin dilaurate, 31.8kg of diphenylmethane diisocyanate, 5.9kg of ethanolamine, 0.1kg of trimethylolpropane and 3.5kg of hexamethylene diisocyanate into the reaction kettle, performing self-polymerization to obtain a polymer with the polymerization degree of 3, and heating 13kg of trihydroxysiloxane with the number average molecular weight of 10000 to 80 ℃ for reaction for 3 hours;
wherein:
the adding amount of the catalyst in the step (2) is 0.1 wt%;
0.5 wt% of antioxidant 1010 is added at the early stage of the reaction in the step (1), and 0.3 wt% of flatting agent BYK-333 and 0.3 wt% of methanol are added at the later stage of the reaction in the step (1) when the viscosity reaches 117 cps;
the amounts of the catalyst and the auxiliary added are calculated based on the mass of the polyurethane resin.
The properties of the obtained polyurethane resin for the synthetic leather surface layer are respectively tested by the following test methods, and the properties are shown in the following table:
and (3) testing the wear resistance: coating polyurethane resin on release paper by using a 20-filament single knife, attaching a base material with a foaming layer and base cloth to prepare a synthetic leather sample, curing for 24 hours, and then carrying out wear resistance test according to QB/T4545 regulation, wherein the revolution when the surface layer is damaged is recorded by adopting an H18 grinding wheel and 1000g load;
softening point test: scraping polyurethane resin into a film with the thickness of 15 filaments, suspending the film in an oven after the film is dried, and recording the temperature of the film with deformation as a softening point;
and (3) surface effect test: embossing and shaping a synthetic leather sample at a high temperature of 180 ℃, sealing and placing for 6 months at normal temperature, and observing the surface precipitation phenomenon of the leather sample;
antifouling test: and (3) placing the synthetic leather sample outdoors for 1 week to check the surface dust deposition condition, coating the surface of the synthetic leather sample with a marker pen, wiping the surface with a wet towel, and observing whether the surface can be wiped off.
From the tests of the embodiment and the comparative example, when the polyurethane resin obtained by the technical scheme of the invention is used for synthesizing leather surface materials, the heat resistance of the product is obviously improved by utilizing the synergistic effect of all raw materials and combining the preparation processes, the heat resistance of the preferred embodiment can reach 195 ℃, and the surface effect is still kept very good and no whitening phenomenon occurs after embossing treatment is carried out at a high temperature of 180 ℃; the wear resistance of the wear-resistant alloy is greatly improved, and the data of the embodiment and the comparative example can be obviously seen; more surprisingly, the product has obvious antifouling effect after being applied to synthetic leather, is not easy to be stained with dust, and is not easy to have oil stain remained on the surface. In addition, the products of examples 1-5 are used as synthetic leather surface layer forming materials, the synthetic leather has good surface effect, no obvious plastic feeling, soft hand feeling and similar touch feeling to real leather, in the long-time actual use process, the wear-resistant and antifouling effects are kept good, and the minimum retention rate of the wear-resistant and antifouling performance can still reach more than 80% after 12 months.
Claims (10)
1. The polyurethane resin for the synthetic leather surface layer is characterized by comprising the following components in percentage by mass:
the polysiloxane a is a polysiloxane polymer with a chain end provided with an isocyanate reactive group, and the number average molecular weight is 1000-2000;
the polysiloxane b is a polysiloxane polymer containing at least 2 reactive groups to isocyanate, and the number average molecular weight is 10000-20000.
2. The polyurethane resin for synthetic leather top layer according to claim 1, wherein the isocyanate, the group reactive thereto, is one or both of an amino group and a hydroxyl group.
3. The polyurethane resin for the synthetic leather top layer according to claim 1, wherein the polyether polyol is one or more polyether diols obtained by ring-opening polymerization of alkylene oxide having 2 to 8 carbon atoms, and the number average molecular weight is 1000 to 3000.
4. The polyurethane resin for the synthetic leather top layer according to claim 1, wherein the polyester polyol is one or more of polyester diols obtained by polymerization of aliphatic dibasic acid and aliphatic diol, and the number average molecular weight is 1000 to 3000.
5. The polyurethane resin for synthetic leather top layer according to claim 1, wherein the isocyanate is diisocyanate containing 2 isocyanate groups, and comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, and p-phenylene diisocyanate.
6. The polyurethane resin for synthetic leather top layer according to claim 1, wherein the isocyanurate is a polymer containing an isocyanurate ring having a degree of polymerization of 3 to 7, which is obtained by the self-polymerization of an aliphatic or aromatic diisocyanate.
7. The polyurethane resin for synthetic leather top layer according to claim 1, wherein the small molecule chain extender is one or more of small molecule substances having 2 to 6 carbon atoms and at least 2 groups reactive to isocyanate.
8. The polyurethane resin for the synthetic leather top layer according to claim 7, wherein the small molecule chain extender is a mixture of a small molecule substance having 2 to 6 carbon atoms and containing 2 groups reactive to isocyanate and a small molecule substance having 2 to 6 carbon atoms and containing more than 2 groups reactive to isocyanate, and the mass ratio of the two substances is 25:1 to 60: 1.
9. the polyurethane resin for the synthetic leather top layer according to claim 8, wherein the small molecular substance having 2 to 6 carbon atoms and 2 groups reactive with isocyanate comprises one or more of ethanolamine, ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, and neopentyl glycol;
the micromolecule substance with 2-6 carbon atoms and more than 2 groups with reactivity to isocyanate comprises one or two of trimethylolpropane and trihydroxypropane.
10. The method for preparing the polyurethane resin for the synthetic leather top layer according to claim 1, wherein the polyurethane resin for the synthetic leather top layer is prepared by the following steps in the presence of a solvent and a catalyst:
step 1, adding polyether polyol, polyester polyol, polysiloxane a and a part of solvent into a reaction kettle together, stirring at 40-55 ℃ until the polyether polyol, the polyester polyol, the polysiloxane a and the part of solvent are completely dissolved, adding a part of isocyanate, heating to 70-80 ℃, and carrying out prepolymerization reaction for 0.5-1 h;
step 2, continuously adding the small molecular chain extender, cooling to 50 ℃, stirring for 15-30 min, adding the catalyst, adding the rest of isocyanate, heating to 70-80 ℃, and continuously reacting for 0.5-1 h;
and 3, adding the solvent until the viscosity reaches 100-160 cps, cooling to 50 ℃, stirring for 1-1.5 h, and adding isocyanurate and polysiloxane b to obtain the polyurethane resin for the synthetic leather surface layer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150241A (en) * | 2021-03-12 | 2021-07-23 | 扬州工业职业技术学院 | Polyurethane resin for anti-doodling leather and preparation method thereof |
| CN113336913A (en) * | 2021-07-23 | 2021-09-03 | 浙江禾欣科技有限公司 | Polyurethane resin with explosion-proof needle function and preparation method thereof |
| CN113861375A (en) * | 2021-10-22 | 2021-12-31 | 东莞市米儿塑胶原料有限公司 | Anti-yellowing TPU and preparation method of TPU protective film |
| CN115716904A (en) * | 2022-11-28 | 2023-02-28 | 广州市斯洛柯高分子聚合物有限公司 | Organic silicon modified bio-based polyurethane, preparation method thereof and synthetic leather containing organic silicon modified bio-based polyurethane |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140162073A1 (en) * | 2012-11-06 | 2014-06-12 | Rohm And Haas Company | Aqueous leather coating composition and method for coating leather |
| CN104628980A (en) * | 2015-02-05 | 2015-05-20 | 上海汇得化工有限公司 | Solvent-free polyurethane resin for synthetic leather and method for preparing synthetic leather from polyurethane resin |
| CN106008891A (en) * | 2016-05-20 | 2016-10-12 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for solvent-free crease-free microfiber mirror-surface synthetic leather and preparation method and application of polyurethane resin |
| CN106519177A (en) * | 2015-09-11 | 2017-03-22 | 安徽安利材料科技股份有限公司 | Method for manufacturing embossed solvent-free polyurethane synthetic leather |
-
2020
- 2020-03-19 CN CN202010196173.0A patent/CN111269390B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140162073A1 (en) * | 2012-11-06 | 2014-06-12 | Rohm And Haas Company | Aqueous leather coating composition and method for coating leather |
| CN104628980A (en) * | 2015-02-05 | 2015-05-20 | 上海汇得化工有限公司 | Solvent-free polyurethane resin for synthetic leather and method for preparing synthetic leather from polyurethane resin |
| CN106519177A (en) * | 2015-09-11 | 2017-03-22 | 安徽安利材料科技股份有限公司 | Method for manufacturing embossed solvent-free polyurethane synthetic leather |
| CN106008891A (en) * | 2016-05-20 | 2016-10-12 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for solvent-free crease-free microfiber mirror-surface synthetic leather and preparation method and application of polyurethane resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150241A (en) * | 2021-03-12 | 2021-07-23 | 扬州工业职业技术学院 | Polyurethane resin for anti-doodling leather and preparation method thereof |
| CN113336913A (en) * | 2021-07-23 | 2021-09-03 | 浙江禾欣科技有限公司 | Polyurethane resin with explosion-proof needle function and preparation method thereof |
| CN113336913B (en) * | 2021-07-23 | 2022-05-13 | 浙江禾欣科技有限公司 | Polyurethane resin with explosion-proof needle function and preparation method thereof |
| CN113861375A (en) * | 2021-10-22 | 2021-12-31 | 东莞市米儿塑胶原料有限公司 | Anti-yellowing TPU and preparation method of TPU protective film |
| CN115716904A (en) * | 2022-11-28 | 2023-02-28 | 广州市斯洛柯高分子聚合物有限公司 | Organic silicon modified bio-based polyurethane, preparation method thereof and synthetic leather containing organic silicon modified bio-based polyurethane |
| CN116496692A (en) * | 2023-03-21 | 2023-07-28 | 河南新旭体育设施有限公司 | Polyurethane plastic runway spouted surface material with excellent weather resistance |
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