CN116478381B - Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof - Google Patents
Bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and preparation method thereof Download PDFInfo
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 70
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 70
- 150000002009 diols Chemical class 0.000 title claims abstract description 67
- 239000002649 leather substitute Substances 0.000 title claims abstract description 25
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 22
- 239000010985 leather Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- KKADPXVIOXHVKN-UHFFFAOYSA-N 4-hydroxyphenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=C(O)C=C1 KKADPXVIOXHVKN-UHFFFAOYSA-N 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- -1 ester diol Chemical class 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- BLAKAEFIFWAFGH-UHFFFAOYSA-N acetyl acetate;pyridine Chemical compound C1=CC=NC=C1.CC(=O)OC(C)=O BLAKAEFIFWAFGH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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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 bio-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and a preparation method thereof, wherein 500-100 parts by weight of low molecular weight bio-based diol is heated to 120-130 ℃, vacuum dehydration is carried out for 2 hours, then the temperature is reduced to below 80 ℃, then 100ppm of catalyst and 1000-2500 parts by weight of epsilon-caprolactone are added, the temperature is raised to 160 ℃ under the protection of nitrogen, the temperature is kept for 6 hours, then the temperature is reduced to 140 ℃, impurities are removed in vacuum, and then the temperature is reduced to 80 ℃ for discharging, thus obtaining the bio-based polycaprolactone diol. According to the invention, low molecular weight bio-based dihydric alcohol is used for replacing dihydric alcohol of petrochemical products, so that the dependency degree of the petrochemical products can be reduced, and excellent products with better low temperature resistance can be obtained by modifying polycaprolactone, and the product has high product competitiveness and application value.
Description
Technical Field
The invention belongs to the technical field of new polyurethane materials, and particularly relates to a substance-based polycaprolactone diol, polyurethane resin for leather, synthetic leather and a preparation method thereof.
Background
Polycaprolactone belongs to a high-end raw material in the polyurethane industry, has hydrolysis resistance, high strength and high chemical resistance, and is widely applied to coatings, adhesives, synthetic leather, waterborne polyurethane, spray polyurea, thermoplastic elastomer, casting elastomer and the like. However, the existing polycaprolactone is usually polymerized with caprolactone by using dihydric alcohols in petrochemical products, such as pentanediol, etc. With the improvement of the living standard of people, the consumption of petrochemical resources is increased, petrochemical products are non-renewable resources, the risk of petroleum exhaustion is faced in the future, and the main direction of future technology is to replace the petrochemical products with renewable resources completely or partially. In addition, low temperature resistance of polycaprolactone products obtained by polymerization of petrochemical diols with caprolactone is poor, and therefore improvements are needed.
Disclosure of Invention
Based on the background situation, the invention provides a bio-based polycaprolactone diol, polyurethane resin for bio-based polycaprolactone diol base leather, synthetic leather and a preparation method thereof in order to solve the problem of dependency of polycaprolactone diol on petrochemical products. The hydrolysis resistance, cold resistance, flex resistance and chemical resistance of the modified polyurethane are greatly improved compared with the traditional polycaprolactone diol. Can be widely applied to the fields of paint, adhesive, synthetic leather, aqueous polyurethane, spray polyurea, thermoplastic elastomer, casting elastomer, high-performance polyurethane foam plastic and the like.
The technical problems to be solved by the invention are realized by the following technical scheme:
a bio-based polycaprolactone diol comprises 500-100 parts by weight of low molecular weight bio-based diol, 1000-2500 parts by weight of epsilon-caprolactone and 100ppm of catalyst (the sum of the weight of relatively low molecular weight bio-based diol and epsilon-caprolactone); the molecular weight of the low molecular weight bio-based diol ranges from 500 to 1100.
Further improved, the chemical formula of the low molecular weight bio-based diol is as follows:
H-[O-CH 2 CH 2 CH 2 -] P the value range of the OHP is 9-18.
The synthetic leather prepared from the bio-based polycaprolactone diol is characterized by comprising 100-200 parts by weight of the bio-based polycaprolactone diol, 20-22.1 parts by weight of ethylene glycol, 700 parts by weight of solvent and 105 parts by weight of diphenylmethane diisocyanate;
further improved, the structural formula of the bio-based polycaprolactone diol is shown as follows:
H-[O-CH 2 CH 2 CH 2 CH 2 CH 2 -CO] m -[O-CH 2 CH 2 CH 2 -O] p -[CO-CH 2 CH 2 CH 2 CH 2 CH 2 ] n -OH
wherein m and n are caprolactone repeating units, p is a bio-base diol 1.3-propanediol repeating unit, the value range of p is 9-18, the value range of m is 5-8, and the value range of n is 5-8.
Further improved, the epsilon-caprolactone is an industrial grade product with the purity of 95.00-99.99 percent.
Further improved, the catalyst is one or more of tetraisobutyl titanate, tetraisopropyl titanate, dibutyl tin dilaurate and stannous octoate.
A preparation method of bio-based polycaprolactone diol comprises the following steps:
heating 500-100 parts by weight of low molecular weight bio-based dihydric alcohol to 120-130 ℃, dehydrating in vacuum for 2 hours, then reducing the temperature to below 80 ℃, then adding 100ppm of catalyst and 1000-2500 parts by weight of epsilon-caprolactone, heating to 160 ℃ under the protection of nitrogen, preserving heat for 6 hours, then reducing the temperature to 140 ℃, removing impurities in vacuum, reducing the temperature to 80 ℃ and discharging to obtain the bio-based polycaprolactone dihydric alcohol.
The polyurethane resin for the bio-based polycaprolactone diol leather comprises 200 parts by weight of bio-based polycaprolactone diol, 20-22.1 parts by weight of ethylene glycol, 700 parts by weight of solvent, 105 parts by weight of diphenylmethane diisocyanate and 0.3-0.5 part by weight of methanol; the bio-based polycaprolactone diol is as shown in any one of claims 1-5.
Further improved, the solvent is one or more of N, N-dimethylformamide, toluene, butanone, ethyl acetate, dimethyl carbonate and butyl acetate.
A preparation method of polyurethane resin for bio-based polycaprolactone diol leather comprises the following steps:
adding 200 parts by weight of bio-based polycaprolactone dihydric alcohol, 20-22.1 parts by weight of ethylene glycol and 700 parts by weight of solvent into a reaction kettle, stirring for 30 minutes, adding 105 parts by weight of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 kiloCPS/25 ℃, and adding 0.3-0.5 part by weight of methanol to terminate the reaction to obtain the polyurethane resin for the bio-based polycaprolactone dihydric alcohol leather; the bio-based polycaprolactone diol is as described above.
A synthetic leather, the method of making the synthetic leather comprising: adding 100 parts by weight of polyurethane resin for bio-based polycaprolactone diol leather, 5 parts by weight of color paste, 50 parts by weight of dimethylformamide and 50 parts by weight of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating the mixture on release paper, putting the release paper into a baking oven for baking, then coating a layer of resin, baking the release paper until the release paper is semi-dried, attaching the release paper to a base, and putting the release paper into the baking oven for baking after attaching the release paper to obtain synthetic leather; the polyurethane resin for bio-based polycaprolactone diol-based leather is as described above.
The invention has the advantages that:
according to the invention, low molecular weight bio-based dihydric alcohol is used for replacing dihydric alcohol of petrochemical products, so that the dependency degree of the petrochemical products can be reduced, and excellent products with better low temperature resistance can be obtained by modifying polycaprolactone, and the product has high product competitiveness and application value.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention as defined in the claims.
The testing method comprises the following steps:
the number average molecular weight Mn of the product was determined by GPC with tetrahydrofuran as mobile phase and polystyrene as standard reference.
The hydroxyl number was determined by the acetic anhydride-pyridine method using industry standard HG 2709-1995-T.
Mobility was determined by industry standard HG/T4454-2012.
The synthetic leather was cut into 35 x 70mm size samples.
The elongation at break and the tensile strength are tested by a universal tensile machine according to national standard GB/T1040-1992.
The normal low temperature flex test is carried out by a normal low temperature flex tester according to QB/T2714-2005.
Example 1
500 g of bio-based dihydric alcohol with the molecular weight of 500-700 (H-650 of DuPont company of U.S.) is added into a reaction kettle, the temperature is raised to 120-130 ℃, the mixture is dehydrated for 2 hours in vacuum, then the temperature is reduced to below 80 ℃, then 100ppm stannous octoate and 1500 g of caprolactone are added, the mixture is heated to 160 ℃ under the protection of nitrogen, the mixture is kept for 6 hours for reaction, then the mixture is cooled to 140 ℃ and the impurities are removed in vacuum for 3 hours, and the mixture is discharged after the temperature is reduced to 80 ℃. The test acid value was 0.25mgKOH/g, and the hydroxyl value was: 55.85mgKOH/g to obtain the bio-based polycaprolactone diol BP-1.
Adding the bio-based polycaprolactone diol BP-1200 g, ethylene glycol 20 g and dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding diphenylmethane diisocyanate 105 g, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the bio-based polycaprolactone diol-based polyurethane resin BPU-1.
Adding 100 g of BPU-1, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-1 from the baking oven for cooling, and stripping the release paper to obtain the synthetic leather SL-1 prepared from the bio-based polycaprolactone diol.
Example 2
500 g of bio-based dihydric alcohol with the molecular weight of 500-700 (H-650 of DuPont company of U.S.) is added into a reaction kettle, the temperature is raised to 120-130 ℃, the mixture is dehydrated in vacuum for 2 hours, then the temperature is reduced to below 80 ℃, then 100ppm stannous octoate and 2500 g of caprolactone are added, the mixture is heated to 160 ℃ under the protection of nitrogen, the mixture is kept for 6 hours, the mixture is cooled to 140 ℃ and the impurities are removed in vacuum for 3 hours, and the mixture is discharged after the temperature is reduced to 80 ℃. The test acid value was 0.23mgKOH/g, and the hydroxyl value was: 37.63mgKOH/g to give biobased polycaprolactone diol BP-2.
Adding the bio-based polycaprolactone diol BP-2200 g, ethylene glycol 22.1 g and dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding diphenylmethane diisocyanate 105 g, stirring uniformly, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.5g of methanol to terminate the reaction to obtain the polyurethane resin BPU-2 for the bio-based polycaprolactone diol leather.
Adding 100 g of BPU-2, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-2 prepared from the bio-based polycaprolactone diol from the oven, cooling, and stripping the release paper.
Example 3
Adding 1000 g of bio-based dihydric alcohol with 900-1100 molecular weight (H-1000 of DuPont company of America) into a reaction kettle, heating to 120-130 ℃, vacuum dehydrating for 2 hours, then reducing the temperature to below 80 ℃, adding 100ppm stannous octoate and 1000 g of caprolactone, heating to 160 ℃ under the protection of nitrogen, preserving heat for 6 hours, then cooling to 140 ℃, vacuum removing impurities for 3 hours, and discharging after reducing the temperature to 80 ℃. The test acid value was 0.29mgKOH/g, and the hydroxyl value was: 56.24mgKOH/g to obtain the bio-based polycaprolactone diol BP-3.
Adding the bio-based polycaprolactone diol BP-3200 g, 20 g of ethylene glycol and 700 g of dimethylformamide into a reaction kettle, stirring for 30 minutes, adding 105 g of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the polyurethane resin BPU-3 for the bio-based polycaprolactone diol leather.
Adding 100 g of BPU-3, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-3 prepared from the bio-based polycaprolactone diol after cooling from the oven, and stripping the release paper.
Comparative example 1
5.2 g of neopentyl glycol, 100ppm of stannous octoate and 995 g of caprolactone are added into a reaction kettle, the mixture is stirred and heated to 70 ℃, the mixture is dehydrated in vacuum for 2 hours, the mixture is heated to 160 ℃ after being pumped in nitrogen to break vacuum, the mixture is reacted for 6 hours in a heat preservation way, the mixture is cooled to 140 ℃ and is discharged after the mixture is cooled to 80 ℃ after the mixture is cooled to remove impurities in vacuum for 3 hours. The test acid value was 0.29mgKOH/g, and the hydroxyl value was: 56.24mgKOH/g to obtain the bio-based polycaprolactone diol BP-4.
Adding the polycaprolactone dihydric alcohol BP-4200 g, the ethylene glycol 20 g and the dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding the diphenylmethane diisocyanate 105 g, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding the methanol 0.3g to terminate the reaction to obtain the polyurethane resin BPU-4 for the polycaprolactone dihydric alcohol leather.
Adding 100 g of BPU-4, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-4 prepared from polycaprolactone diol from the oven, cooling, and stripping the release paper.
Comparative example 2
5.2 g of neopentyl glycol, 100ppm of stannous octoate and 1495 g of caprolactone are added into a reaction kettle, stirred and heated to 70 ℃, dehydrated in vacuum for 2 hours, heated to 160 ℃ after being pumped in nitrogen to break vacuum, and reacted for 6 hours in a heat preservation mode, cooled to 140 ℃ and removed in vacuum for 3 hours, and discharged after being cooled to 80 ℃. The test acid value was 0.23mgKOH/g, and the hydroxyl value was: 38.13mgKOH/g to give polycaprolactone diol BP-5.
Adding the polycaprolactone dihydric alcohol BP-5200 g, ethylene glycol 22.1 g and dimethylformamide 700 g into a reaction kettle, stirring for 30 minutes, adding 105 g of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the system viscosity to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the polyurethane resin BPU-5 for the polycaprolactone dihydric alcohol leather.
Adding 100 g of BPU-5, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-5 prepared from polycaprolactone diol from the oven, cooling, and stripping the release paper.
Comparative example 3
1000 g of polytetrahydrofuran dihydric alcohol with the molecular weight is added into a reaction kettle, the temperature is raised to 120-130 ℃, the vacuum dehydration is carried out for 2 hours, then the temperature is reduced to below 80 ℃, then 100ppm stannous octoate and 1000 g of caprolactone are added, the temperature is raised to 160 ℃ under the protection of nitrogen, the temperature is kept for 6 hours, the reaction is carried out, the temperature is reduced to 140 ℃, the vacuum impurity removal is carried out for 3 hours, and the material is discharged after the temperature is reduced to 80 ℃. The test acid value was 0.29mgKOH/g, and the hydroxyl value was: 57.34mgKOH/g to obtain polyether ester diol BP-6.
Adding the above polyether-ester diol BP-3200 g, 20 g of ethylene glycol and 700 g of dimethylformamide into a reaction kettle, stirring for 30 minutes, adding 105 g of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the viscosity of the system to 12 ten thousand CPS/25 ℃, and adding 0.3g of methanol to terminate the reaction to obtain the polyurethane resin BPU-6 for the polyether-ester diol leather.
Adding 100 g of BPU-6, 5g of color paste, 50 g of dimethylformamide and 50 g of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating on release paper, putting into a baking oven for baking, coating a layer of resin, baking to be semi-dry, attaching to a bass, and putting into the baking oven for baking after attaching. And taking out the synthetic leather SL-6 prepared from polyether ester diol from the baking oven, cooling, and stripping the release paper.
The synthetic leather samples prepared in the above examples were subjected to performance test comparison, and the results are shown in the following table:
description: the normal temperature flexibility test condition is 20 ℃, and the low temperature flexibility test condition is-20 ℃.
As can be seen from the above table, in the embodiments 1 to 3, the larger the ratio of caprolactone in the bio-based polycaprolactone diol, the larger the final strength of the product, the elongation at break and the number of times of normal temperature flex resistance are not much affected, but the number of times of low temperature flex resistance is reduced. The tensile strength was reduced as compared with comparative examples 2 and 3, the elongation was not changed much, the number of normal temperature flex resistance was increased as compared with comparative examples 2 to 3 in examples 1 to 3, and the increase was relatively large as compared with comparative examples 1 to 2 in examples 1 to 3 in the low temperature flex resistance test. Example 3 the product of example 3 has a lower modulus, better hand feel, and more excellent low temperature flexure resistance than comparative example 3, and is more suitable for soft super cold resistant synthetic leather products. Example 3 had a slight decrease in tensile strength compared to comparative example 2, with other properties being substantially equal. Demonstrating that the performance in synthetic leather is very similar in bio-based polycaprolactone diol prepared with 1000 molecular weight bio-based diol and in polyether ester prepared with 1000 molecular weight polytetrahydrofuran diol. From the above experimental data, the bio-based polycaprolactone diol prepared by taking the bio-based diol as the initiator can replace or partially replace petrochemical polyether ester diol in actual production and life, and the bio-based product is used for replacing petrochemical products in the field of synthetic leather, so that the bio-based polycaprolactone diol has more excellent performance in low-temperature cold resistance and can reduce the dependency degree on the petrochemical products.
The above detailed description is only specific for the practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and various changes made by those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. The bio-based polycaprolactone diol is characterized by comprising 500-100 parts by weight of low molecular weight bio-based diol, 1000-2500 parts by weight of epsilon-caprolactone and 100ppm of catalyst;
the molecular weight of the low molecular weight bio-based diol ranges from 500 to 1100; the chemical formula of the low molecular weight bio-based diol is shown as follows:
the value range of P is 9-18.
2. The bio-based polycaprolactone diol of claim 1, wherein the bio-based polycaprolactone diol has the structural formula:
H-[O-CH 2 CH 2 CH 2 CH 2 CH 2 -CO] m -[O-CH 2 CH 2 CH 2 -O] p -[CO-CH 2 CH 2 CH 2 CH 2 CH 2 ] n -OH wherein m, n is a caprolactone repeating unit, p is a bio-based diol 1.3-propanediol repeating unit, the value of p ranges from 9 to 18, the value of m ranges from 5 to 8, and the value of n ranges from 5 to 8.
3. The biobased polycaprolactone diol of claim 1, wherein the epsilon-caprolactone is an industrial grade product having a purity of 95.00 to 99.99%.
4. The bio-based polycaprolactone diol of claim 1, wherein the catalyst is one or more of tetraisobutyl titanate, tetraisopropyl titanate, dibutyltin dilaurate, stannous octoate.
5. The preparation method of the bio-based polycaprolactone diol is characterized by comprising the following steps of:
heating 500-100 parts by weight of low molecular weight bio-based dihydric alcohol to 120-130 ℃, dehydrating in vacuum for 2 hours, then reducing the temperature to below 80 ℃, then adding 100ppm of catalyst and 1000-2500 parts by weight of epsilon-caprolactone, heating to 160 ℃ under the protection of nitrogen, preserving heat for 6 hours, then reducing the temperature to 140 ℃, removing impurities in vacuum, reducing the temperature to 80 ℃ and discharging to obtain the bio-based polycaprolactone dihydric alcohol according to any one of claims 1-4.
6. The polyurethane resin for the bio-based polycaprolactone diol leather is characterized by comprising 200 parts by weight of bio-based polycaprolactone diol, 20-22.1 parts by weight of ethylene glycol, 700 parts by weight of solvent, 105 parts by weight of diphenylmethane diisocyanate and 0.3-0.5 part by weight of methanol; the bio-based polycaprolactone diol is as shown in any one of claims 1-4.
7. The polyurethane resin for bio-based polycaprolactone diol leather according to claim 6, wherein the solvent is one or more of N, N-dimethylformamide, toluene, butanone, ethyl acetate, dimethyl carbonate, and butyl acetate.
8. The preparation method of the polyurethane resin for the bio-based polycaprolactone diol leather is characterized by comprising the following steps of: adding 200 parts by weight of bio-based polycaprolactone dihydric alcohol, 20-22.1 parts by weight of ethylene glycol and 700 parts by weight of solvent into a reaction kettle, stirring for 30 minutes, adding 105 parts by weight of diphenylmethane diisocyanate, uniformly stirring, heating to 50-90 ℃, increasing the viscosity of the system to 12 kiloCPS/25 ℃, and adding 0.3-0.05 part by weight of methanol by mass for terminating reaction to obtain the polyurethane resin for the bio-based polycaprolactone dihydric alcohol leather; the bio-based polycaprolactone diol is as described in any one of claims 1-4.
9. The synthetic leather is characterized by comprising the following preparation method: adding 100 parts by weight of polyurethane resin for bio-based polycaprolactone diol leather, 5 parts by weight of color paste, 50 parts by weight of dimethylformamide and 50 parts by weight of butanone into a dispersing cup, uniformly stirring, defoaming by a centrifugal machine, coating the mixture on release paper, putting the release paper into a baking oven for baking, then coating a layer of resin, baking the release paper until the release paper is semi-dried, attaching the release paper to a base, and putting the release paper into the baking oven for baking after attaching the release paper to obtain synthetic leather; a polyurethane resin for bio-based polycaprolactone diol-based leather is shown in claim 6.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2093853A (en) * | 1981-02-27 | 1982-09-08 | Daicel Chem | Lactone polymer and polyurethane obtained therefrom |
CN101824132A (en) * | 2010-04-21 | 2010-09-08 | 浙江深蓝轻纺科技有限公司 | Weak solvent aliphatic polyurethane resin for synthetic leather and preparation method thereof |
CN103788584A (en) * | 2013-12-31 | 2014-05-14 | 金发科技股份有限公司 | Thermoplastic polyether ester elastomer composition as well as preparation method and application thereof |
CN113025184A (en) * | 2021-02-08 | 2021-06-25 | 合肥科天水性科技有限责任公司 | High-adhesion waterborne polyurethane coating resin and preparation method thereof |
CN115160547A (en) * | 2022-07-27 | 2022-10-11 | 湖南聚仁化工新材料科技有限公司 | Polycaprolactone polyol, preparation method thereof and coating |
CN115260433A (en) * | 2022-06-24 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Bio-based high-damping thermoplastic polyurethane elastomer material and preparation method and application thereof |
CN115572366A (en) * | 2022-09-06 | 2023-01-06 | 中国科学院宁波材料技术与工程研究所 | Pressure-resistant temperature-sensitive thermoplastic polylactic acid-based polyurethane elastomer and preparation method and application thereof |
CN115651171A (en) * | 2022-11-04 | 2023-01-31 | 万华化学集团股份有限公司 | Continuous preparation method of polycaprolactone polyol |
-
2023
- 2023-04-19 CN CN202310417187.4A patent/CN116478381B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2093853A (en) * | 1981-02-27 | 1982-09-08 | Daicel Chem | Lactone polymer and polyurethane obtained therefrom |
CN101824132A (en) * | 2010-04-21 | 2010-09-08 | 浙江深蓝轻纺科技有限公司 | Weak solvent aliphatic polyurethane resin for synthetic leather and preparation method thereof |
CN103788584A (en) * | 2013-12-31 | 2014-05-14 | 金发科技股份有限公司 | Thermoplastic polyether ester elastomer composition as well as preparation method and application thereof |
CN113025184A (en) * | 2021-02-08 | 2021-06-25 | 合肥科天水性科技有限责任公司 | High-adhesion waterborne polyurethane coating resin and preparation method thereof |
CN115260433A (en) * | 2022-06-24 | 2022-11-01 | 中国科学院宁波材料技术与工程研究所 | Bio-based high-damping thermoplastic polyurethane elastomer material and preparation method and application thereof |
CN115160547A (en) * | 2022-07-27 | 2022-10-11 | 湖南聚仁化工新材料科技有限公司 | Polycaprolactone polyol, preparation method thereof and coating |
CN115572366A (en) * | 2022-09-06 | 2023-01-06 | 中国科学院宁波材料技术与工程研究所 | Pressure-resistant temperature-sensitive thermoplastic polylactic acid-based polyurethane elastomer and preparation method and application thereof |
CN115651171A (en) * | 2022-11-04 | 2023-01-31 | 万华化学集团股份有限公司 | Continuous preparation method of polycaprolactone polyol |
Non-Patent Citations (2)
Title |
---|
刁晓倩,翁云宣.国内生物基材料产业发展现状.《生物工程学报》.2016,第32卷(第6期),第715-725页. * |
袁洁 , 贺江平.不同二元醇单体对聚氨酯性能的影响研究.《纺织科学与工程学报》.2018,第35卷(第2期),第65-69页. * |
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