CN110183609B - Solvent-free polyurethane resin and application thereof - Google Patents
Solvent-free polyurethane resin and application thereof Download PDFInfo
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- CN110183609B CN110183609B CN201910326703.6A CN201910326703A CN110183609B CN 110183609 B CN110183609 B CN 110183609B CN 201910326703 A CN201910326703 A CN 201910326703A CN 110183609 B CN110183609 B CN 110183609B
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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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
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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
- C08G18/65—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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- 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
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1664—Releasability
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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
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1692—Weather resistance
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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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
A solvent-free polyurethane resin is formed by mixing a component A and a component B, wherein the component A comprises 30-70 parts by mass of polyether polyol, 30-70 parts by mass of sulfonate polyester polyol, 5-15 parts by mass of micromolecule chain extender, 0-5 parts by mass of cross-linking agent, 0.1-1.5 parts by mass of water, 0.025-0.05 part by mass of catalyst, 0.1-5 parts by mass of sulfonate chain extender and 0.1-2 parts by mass of foam stabilizer; the component B comprises 10-30 parts by mass of polyether polyol, 10-30 parts by mass of sulfonate polyester polyol and 40-60 parts by mass of isocyanate; the solvent-free polyurethane resin is applied to sulfonic acid type water-based resin, so that the initial peel strength and the hydrolysis retention rate are greatly improved.
Description
Technical Field
The invention belongs to the field of material industry, and particularly relates to a solvent-free polyurethane resin and application thereof.
Background
In recent years, the development of water-based synthetic leather and solvent-free synthetic leather is rapidly advanced, and a series of great progresses are made on the technical research and development and production process, so that a new opportunity is brought to the transformation and upgrading of the synthetic leather industry. The problems still exist in the prior solvent-free synthetic leather product are that the bonding strength of the water-based resin surface layer and the solvent-free polyurethane foaming layer is poor, the peel strength of the obtained synthetic leather product is low, and the synthetic leather product can not be applied to products with high requirements on peel strength.
Aiming at the defects in the prior art, the solvent-free polyurethane resin is improved, and the product is applied to sulfonic acid type water-based resin, so that the aim of improving the peel strength is fulfilled.
Disclosure of Invention
The invention aims to provide a solvent-free polyurethane resin which does not contain any organic solvent, has low energy consumption and high production efficiency, and has high peel strength with a water-based surface layer of sulfonic acid type water-based resin.
In order to solve the problems, the invention is realized by the following technical scheme:
a solvent-free polyurethane resin is formed by mixing a component A and a component B, wherein the component A comprises 30-70 parts by mass of polyether polyol, 30-70 parts by mass of sulfonate polyester polyol, 5-15 parts by mass of micromolecule chain extender, 0-5 parts by mass of cross-linking agent, 0.1-1.5 parts by mass of water, 0.025-0.05 part by mass of catalyst, 0.1-5 parts by mass of sulfonate chain extender and 0.1-2 parts by mass of foam stabilizer; the component B comprises 10-30 parts by mass of polyether polyol, 10-30 parts by mass of sulfonate polyester polyol and 40-60 parts by mass of isocyanate.
Optionally, the sulfonate-type chain extender is an adduct of a diaminoalkylsulfonate or an unsaturated diol with sodium bisulfite.
Optionally, the polyether polyol is one of polypropylene oxide glycol with the molecular weight of 1000-2000 and high-activity polyether triol with the molecular weight of 5000-6000.
Alternatively, the sulfonate polyester polyol has a molecular weight of 1000-. The sulfonate polyester polyol is prepared from the following components in parts by weight through dehydration, polycondensation and sulfonation: 40-80 parts of adipic acid, 30-60 parts of micromolecular dihydric alcohol and 0.01-0.06 part of tetrabutyl titanate catalyst, and the prepared polyester polyol is sulfonated to obtain sulfonate polyester polyol.
Optionally, the small-molecule chain extender is one or more of diethanolamine, ethylenediamine, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether.
Optionally, the cross-linking agent is one or more of glycerol, trimethylolpropane and triethanolamine.
Optionally, the catalyst is one or more of BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, Borchi Kat22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, MB20, and phenate, formate, hydrochloride, DBU, triethylene triamine, A1 of the above organometallic catalysts, and phenate, formate, isooctoate of the above amine catalysts.
Optionally, the foam stabilizer is a polyether modified silicone surfactant.
Another object of the present invention is to provide the use of the above solvent-free polyurethane resin for sulfonic acid-type aqueous resins.
In the invention, the solvent-free polyurethane resin prepared by the invention is applied to sulfonic acid type waterborne resin, so that the initial peel strength and the hydrolysis retention rate are greatly improved, and the production operation tolerance of waterborne/solvent-free synthetic leather is enhanced; the water-based/solvent-free synthetic leather does not contain any organic solvent, so that the synthetic leather has the advantages of environmental protection, soft hand feeling, fullness and the like, the physical properties of the synthetic leather can reach that the synthetic leather does not crack after being bent for 10 ten thousand times at normal temperature, is cold-resistant and does not crack after being bent for 8 ten thousand times at minus 10 ℃, the initial peel strength is more than 80N/3cm, the permanent peel strength is more than 100N/3cm, and the retention rate of the peel strength of 5 weeks under the constant temperature and humidity condition of 70 ℃ and 95 percent can reach more than 85 percent.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention 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.
(1) Preparation of component A:
dehydrating polyether polyol and sulfonate polyester polyol at 90-110 ℃ and-0.08 MPa-0.1 MPa for 3-5h for later use; adding the dehydrated polyether polyol and the dehydrated sulfonate polyester polyol into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, sequentially adding a chain extender, a cross-linking agent, water, a catalyst, a foam stabilizer and a sulfonate chain extender, and stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
putting isocyanate into a reaction kettle, stirring and mixing uniformly, then adding dehydrated polyether polyol and sulfonated polyester polyol, heating to 70-80 ℃, and stirring and reacting for 4-6 hours to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KT3010 sulfonic acid type water-based resin of fertilizer-combining water-based scientific materials Co., Ltd on release paper, and drying at 130 ℃ for 2 minutes for molding to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to a certain mass ratio to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to enable the solvent-free polyurethane resin to be crosslinked, cured and molded; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength), curing the prepared solvent-free synthetic leather at 70 ℃ for 24 hours, testing the peel strength (namely the permanent peel strength), the peel strength retention rate (70 ℃ multiplied by 95% humidity) for 5 weeks, and performing normal-temperature 23 ℃ multiplied by 10 ten thousand bending and cold-resistant-10 ℃ multiplied by 8 ten thousand bending.
The chemicals used in the examples and comparative examples are as follows:
polyether polyol: DP-4000 from Kunshan national chemical Co., Ltd.
Sulfonate polyester polyol: BY3301 available from Bai Yuan chemical Co., Ltd, Beijing.
Small-molecule chain extender: commercially available 1, 4-butanediol products.
A crosslinking agent: a commercially available trimethylolpropane product.
Catalyst: BiCAT 8124 organobismuth catalyst from leading chemicals USA.
Foam stabilizer: DC-193 polyether modified silicone foam stabilizer from American air chemical company.
Isocyanate: MDI-100 pure diphenylmethylene diisocyanate available from Funta Wanhua company.
Dimethylolpropionic acid: a commercially available product.
Description of the symbols
DP-4000 polyether polyol
BY3301 sulfonate polyester polyol
BiCAT 8124 organic bismuth catalyst
DC-193 polyether modified organic silicon foam stabilizer
A95 sulfonate type chain extender
MDI-100 pure diphenylmethylene diisocyanate.
Example 1
(1) Preparation of component A:
dehydrating DP-4000 and BY3301 at 90-110 deg.C and-0.08 MPa-0.1 MPa for 3-5 h; adding the dehydrated DP-400030 parts and BY 330170 parts into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, sequentially adding 5 parts of 1, 4-butanediol, 5 parts of trimethylolpropane, 0.1 part of water, BiCAT 81240.025 parts, DC-1930.1 parts and 950.1 parts of sulfonate chain extender A, and stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
adding MDI-10040 parts into a reaction kettle, uniformly stirring and mixing, then adding the dehydrated DP-400010 parts and BY 330130 parts, heating to 70-80 ℃, and stirring for reacting for 4-6h to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KT3010 sulfonic acid type water-based resin of fertilizer-combining water-based scientific materials Co., Ltd on release paper, and drying at 130 ℃ for 2 minutes for molding to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100/115 to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to crosslink, cure and form the polyurethane resin; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength) to be 32N/3cm, curing the prepared solvent-free synthetic leather at 70 ℃ for 24h, testing the peel strength (namely the permanent peel strength) to be 43N/3cm, testing the peel strength retention rate (70 ℃ multiplied by 95% humidity) at 5 weeks to be 86%, and testing the non-crack at the normal temperature of 23 ℃ multiplied by 10 ten thousand times and testing the non-crack at the cold resistance of-10 ℃ multiplied by 8 ten thousand times.
Example 2
(1) Preparation of component A:
dehydrating DP-4000 and BY3301 at 90-110 deg.C and-0.08 MPa-0.1 MPa for 3-5 h; adding DP-400040 parts and BY 330160 parts after dehydration into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, then sequentially adding 8 parts of 1, 4-butanediol, 2 parts of trimethylolpropane, 0.5 part of water, 81240.04 parts of BiCAT, DC-1930.8 parts and 952 parts of sulfonate chain extender, and stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
adding MDI-10042 parts into a reaction kettle, uniformly stirring and mixing, then adding the dehydrated DP-400020 parts and BY 330120 parts, heating to 70-80 ℃, and stirring for reacting for 4-6h to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KT3010 sulfonic acid type water-based resin of fertilizer-combining water-based scientific materials Co., Ltd on release paper, and drying at 130 ℃ for 2 minutes for molding to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100/124 to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to crosslink, cure and form the polyurethane resin; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength) to be 94N/3cm, curing the prepared solvent-free synthetic leather at 70 ℃ for 24h, testing the peel strength (namely the permanent peel strength) to be 117N/3cm, testing the peel strength retention rate (70 ℃ multiplied by 95% humidity) to be 87% at 5 weeks, and performing normal-temperature 23 ℃ multiplied by 10 ten thousand flex until no crack is formed, and performing cold-resistant-10 ℃ multiplied by 8 ten thousand flex until no crack is formed.
Example 3
(1) Preparation of component A:
dehydrating DP-4000 and BY3301 at 90-110 deg.C and-0.08 MPa-0.1 MPa for 3-5 h; adding the DP-400070 parts and the BY 330130 parts after dehydration into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, then sequentially adding 15 parts of 1, 4-butanediol, 0 part of trimethylolpropane, 1.5 parts of water, BiCAT 81240.05 parts, DC-1932 parts and 955 parts of a sulfonate chain extender A, and stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
adding MDI-10060 parts into a reaction kettle, uniformly stirring and mixing, then adding the dehydrated DP-400030 parts and BY 330110 parts, heating to 70-80 ℃, and stirring for reacting for 4-6h to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KT3010 sulfonic acid type water-based resin of fertilizer-combining water-based scientific materials Co., Ltd on release paper, and drying at 130 ℃ for 2 minutes for molding to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100/102 to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to crosslink, cure and form the polyurethane resin; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength) to be 121N/3cm, curing the prepared solvent-free synthetic leather at 70 ℃ for 24h, testing the peel strength (namely the permanent peel strength) to be 161N/3cm, testing the peel strength retention rate (70 ℃ multiplied by 95% humidity) at 5 weeks to be 85%, and testing the resistance to cracking at the normal temperature of 23 ℃ multiplied by 10 ten thousand times and testing the resistance to cracking at the cold resistance of-10 ℃ multiplied by 8 ten thousand times.
Example 4
(1) Preparation of component A:
dehydrating DP-4000 and BY3301 at 90-110 deg.C and-0.08 MPa-0.1 MPa for 3-5 h; adding DP-400040 parts and BY 330160 parts after dehydration into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, then sequentially adding 8 parts of 1, 4-butanediol, 2 parts of trimethylolpropane, 0.5 part of water, BiCAT 81240.04 parts, DC-1930.8 parts and 951 parts of a sulfonate chain extender, and stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
adding MDI-10042 parts into a reaction kettle, uniformly stirring and mixing, then adding the dehydrated DP-400020 parts and BY 330120 parts, heating to 70-80 ℃, and stirring for reacting for 4-6h to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KT3010 sulfonic acid type water-based resin of fertilizer-combining water-based scientific materials Co., Ltd on release paper, and drying at 130 ℃ for 2 minutes for molding to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100/108 to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to crosslink, cure and form the polyurethane resin; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength) to be 86N/3cm, curing the prepared solvent-free synthetic leather at 70 ℃ for 24h, testing the peel strength (namely the permanent peel strength) to be 102N/3cm, testing the peel strength retention rate (70 ℃ multiplied by 95% humidity) at 5 weeks to be 85%, and testing the non-crack at the normal temperature of 23 ℃ multiplied by 10 ten thousand times and testing the non-crack at the cold resistance of-10 ℃ multiplied by 8 ten thousand times.
Comparative example 1
(1) Preparation of component A:
dehydrating DP-4000 and BY3301 at 90-110 deg.C and-0.08 MPa-0.1 MPa for 3-5 h; adding DP-400040 parts and BY 330160 parts after dehydration into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, then sequentially adding 8 parts of 1, 4-butanediol, 2 parts of trimethylolpropane, 0.5 part of water, 81240.04 parts of BiCAT and DC-1930.8 parts, stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
adding MDI-10042 parts into a reaction kettle, uniformly stirring and mixing, then adding the dehydrated DP-400020 parts and BY 330120 parts, heating to 70-80 ℃, and stirring for reacting for 4-6h to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KT3010 sulfonic acid type water-based resin of fertilizer-combining water-based scientific materials Co., Ltd on release paper, and drying at 130 ℃ for 2 minutes for molding to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100/101 to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to crosslink, cure and form the polyurethane resin; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength) to be 25N/3cm, curing the prepared solvent-free synthetic leather at 70 ℃ for 24h, testing the peel strength (namely the permanent peel strength) to be 31N/3cm, testing the peel strength retention rate (70 ℃ multiplied by 95% humidity) to be 88% at 5 weeks, and performing normal-temperature 23 ℃ multiplied by 10 ten thousand flex until no crack is formed, and performing cold-resistant-10 ℃ multiplied by 8 ten thousand flex until no crack is formed.
Comparative example 2
(1) Preparation of component A:
dehydrating DP-4000 and BY3301 at 90-110 deg.C and-0.08 MPa-0.1 MPa for 3-5 h; adding the DP-400070 parts and the BY 330130 parts after dehydration into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, then sequentially adding 15 parts of 1, 4-butanediol, 0 part of trimethylolpropane, 1.5 parts of water, BiCAT 81240.05 parts, DC-1932 parts and 955 parts of a sulfonate chain extender A, and stirring and mixing for 4-6 hours to obtain a component A;
(2) preparation of component B:
adding MDI-10060 parts into a reaction kettle, uniformly stirring and mixing, then adding the dehydrated DP-400030 parts and BY 330110 parts, heating to 70-80 ℃, and stirring for reacting for 4-6h to obtain a component B;
(3) preparation of the solvent-free synthetic leather:
coating KTC716 carboxylic acid type water-based resin of fertilizer-containing water-based scientific materials Co., Ltd on release paper, drying at 130 ℃ for 2 minutes and forming to obtain a surface layer; fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100/102 to obtain solvent-free polyurethane resin, casting and coating the solvent-free polyurethane resin on a water-based surface layer, then putting the water-based surface layer into a 110 ℃ drying oven for pre-reaction for 60 seconds, attaching base cloth after the pre-reaction is finished, and then continuing to react for 7 minutes at the temperature of 100 ℃ and 150 ℃ to crosslink, cure and form the polyurethane resin; and (2) peeling off the release paper after curing and forming, rolling to obtain the high-peel solvent-free synthetic leather, testing the peel strength (namely the initial peel strength) to be 17N/3cm, curing the prepared solvent-free synthetic leather at 70 ℃ for 24h, testing the peel strength (namely the permanent peel strength) to be 35N/3cm, testing the peel strength retention rate (70 ℃ multiplied by 95% humidity) to be 75% at 5 weeks, and performing normal-temperature 23 ℃ multiplied by 10 ten thousand flex until no crack is formed, and performing cold-resistant-10 ℃ multiplied by 8 ten thousand flex until no crack is formed.
Table 1 shows a comparison of formulation compositions and performance results for solvent-free polyurethane resins of examples 1-4, comparative example 1 and comparative example 2.
As can be seen from table 1: (1) comparing examples 1 to 4 with comparative example 1, examples 1 to 4 are greater than the initial peel strength and the permanent peel strength in comparative example 1, and it is demonstrated that the application of the solvent-free polyurethane resin prepared according to the present invention to the sulfonic acid type aqueous resin greatly improves the initial peel strength and the permanent peel strength.
(2) Comparing examples 1 to 4 and comparative example 2, the peel strength of the solvent-free polyurethane resin of the present invention applied to the carboxylic acid type aqueous resin was far less high than that applied to the sulfonic acid type aqueous resin, because the carboxylic acid type aqueous resin exerts an inhibiting effect on the gel reaction of the sulfonic acid type solvent-free polyurethane resin.
TABLE 1 formulation compositions and performance results for solvent-free polyurethane resins of examples 1-4, comparative example 1, and comparative example 2
Claims (9)
1. The solvent-free synthetic leather is characterized in that the preparation method of the solvent-free synthetic leather comprises the following steps:
coating sulfonic acid type water-based resin on release paper, and drying and forming to obtain a surface layer;
mixing the component A and the component B, coating the mixture on the surface layer, and carrying out pre-reaction to obtain the solvent-free polyurethane resin layer;
adhering base cloth on the solvent-free polyurethane resin layer, and crosslinking, curing and molding the base cloth;
stripping the release paper after curing and forming to obtain the solvent-free synthetic leather;
the component A comprises 30-70 parts by mass of polyether polyol, 30-70 parts by mass of sulfonate polyester polyol, 5-15 parts by mass of micromolecule chain extender, 0-5 parts by mass of cross-linking agent, 0.1-1.5 parts by mass of water, 0.025-0.05 part by mass of catalyst, 0.1-5 parts by mass of sulfonate chain extender and 0.1-2 parts by mass of foam stabilizer;
the component B comprises 10-30 parts by mass of polyether polyol, 10-30 parts by mass of sulfonate polyester polyol and 40-60 parts by mass of isocyanate;
the preparation method of the component A comprises the following steps: dehydrating polyether polyol and sulfonate polyester polyol at 90-110 ℃ and-0.08 MPa-0.1 MPa for 3-5h for later use; adding the dehydrated polyether polyol and the dehydrated sulfonate polyester polyol into a reaction kettle, adjusting and keeping the temperature at 40-60 ℃, sequentially adding the micromolecule chain extender, the cross-linking agent, the water, the catalyst, the foam stabilizer and the sulfonate chain extender, and stirring and mixing for 4-6 hours to obtain a component A;
the preparation method of the component B comprises the following steps: adding isocyanate into a reaction kettle, stirring and mixing uniformly, then adding dehydrated polyether polyol and sulfonated polyester polyol, heating to 70-80 ℃, and stirring and reacting for 4-6 hours to obtain a component B.
2. Solvent-free synthetic leather according to claim 1, wherein: the sulfonate chain extender is an addition product of diaminoalkane sulfonate or unsaturated dihydric alcohol and sodium bisulfite.
3. Solvent-free synthetic leather according to claim 1, wherein: the polyether polyol in the component A and the component B is one of polypropylene oxide diol with the molecular weight of 1000-2000-one and polyether triol with the molecular weight of 5000-6000.
4. Solvent-free synthetic leather according to claim 1, wherein: the sulfonate polyester polyols in component A and component B have molecular weights of 1000-2000.
5. Solvent-free synthetic leather according to claim 1, wherein: the sulfonate polyester polyol in the component A and the component B is prepared by dehydrating, polycondensing and sulfonating the following components in parts by weight: 40-80 parts of adipic acid, 30-60 parts of micromolecular dihydric alcohol and 0.01-0.06 part of tetrabutyl titanate catalyst, and the prepared polyester polyol is sulfonated to obtain sulfonate polyester polyol.
6. Solvent-free synthetic leather according to claim 1, wherein: the small molecular chain extender is one or more of diethanolamine, ethylenediamine, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol and hydroquinone bis (2-hydroxyethyl) ether.
7. Solvent-free synthetic leather according to claim 1, wherein: the cross-linking agent is one or more of glycerol, trimethylolpropane and triethanolamine.
8. Solvent-free synthetic leather according to claim 1, wherein: the catalyst is BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, Borchi Kat22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, phenate, formate and hydrochloride of the organometallic catalysts, DBU, A1, phenate, formate and isooctoate of the amine catalysts, and one or more of the catalysts.
9. Solvent-free synthetic leather according to claim 1, wherein: the foam stabilizer is polyether modified organic silicon surfactant.
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| CN110835401B (en) * | 2019-09-24 | 2021-11-12 | 浙江禾欣科技有限公司 | Waterborne polyurethane surface layer resin and preparation method thereof |
| CN110964172B (en) * | 2019-11-06 | 2021-11-23 | 合肥科天水性科技有限责任公司 | Modified solvent-free bio-based polyurethane resin and application thereof |
| CN110951033A (en) * | 2019-12-19 | 2020-04-03 | 超然(福建)新材料科技有限公司 | Hydrolysis-resistant polyurethane resin and preparation method thereof |
| CN114892412A (en) * | 2022-06-02 | 2022-08-12 | 浙江昶丰新材料有限公司 | High-filler solvent-free water-based synthetic leather and preparation method thereof |
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