CN110591044B - High-physical-property low-fogging waterborne surface layer polyurethane resin and preparation method thereof - Google Patents
High-physical-property low-fogging waterborne surface layer polyurethane resin and preparation method thereof Download PDFInfo
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- CN110591044B CN110591044B CN201910799959.9A CN201910799959A CN110591044B CN 110591044 B CN110591044 B CN 110591044B CN 201910799959 A CN201910799959 A CN 201910799959A CN 110591044 B CN110591044 B CN 110591044B
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- polyurethane resin
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- diol
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 94
- 239000002344 surface layer Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 150000007974 melamines Chemical class 0.000 claims abstract description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 63
- 150000002009 diols Chemical class 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- -1 poly adipic acid-1, 4-butanediol ester Chemical class 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 229920000515 polycarbonate Polymers 0.000 claims description 16
- 239000004417 polycarbonate Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000010695 polyglycol Substances 0.000 claims description 15
- 229920000151 polyglycol Polymers 0.000 claims description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- XGJZQNMUVTZITK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexamethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CON(OC)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 XGJZQNMUVTZITK-UHFFFAOYSA-N 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 239000002649 leather substitute Substances 0.000 abstract description 56
- 239000010410 layer Substances 0.000 abstract description 23
- 238000005187 foaming Methods 0.000 abstract description 22
- 239000010985 leather Substances 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 28
- 238000000576 coating method Methods 0.000 description 28
- 229920002635 polyurethane Polymers 0.000 description 24
- 239000004814 polyurethane Substances 0.000 description 24
- 239000012948 isocyanate Substances 0.000 description 16
- 150000002513 isocyanates Chemical class 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 229920003002 synthetic resin Polymers 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000013065 commercial product Substances 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- 238000007790 scraping Methods 0.000 description 7
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 5
- 125000003827 glycol group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- JVUAOHHLYDUVMM-UHFFFAOYSA-N C(CCCCCCC)OC(CCCCCCCCC)=O.[Bi] Chemical compound C(CCCCCCC)OC(CCCCCCCCC)=O.[Bi] JVUAOHHLYDUVMM-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000009864 tensile test Methods 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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
- 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
-
- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- 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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- 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)
Abstract
The invention discloses a high-physical-property low-fogging water-based surface layer polyurethane resin and a preparation method thereof, wherein the high-physical-property low-fogging water-based surface layer polyurethane resin is prepared from the following raw materials in percentage by weight: 5.0 to 30.0 percent of polydiol, 3.0 to 15.0 percent of diisocyanate, 1.0 to 5.0 percent of chain extender, 0.01 to 0.03 percent of catalyst, 0.2 to 1.0 percent of antioxidant, 5.0 to 20.0 percent of acetone, 50.0 to 80.0 percent of deionized water, 3.0 to 8.0 percent of N-methyl pyrrolidone, 0.5 to 3.0 percent of triethylamine, 0.1 to 1.0 percent of ethylenediamine and 0.01 to 0.2 percent of melamine derivative. The invention is matched with a solvent-free foaming layer for use, the fogging problem of the leather surface is obviously improved, the surface layer of the synthetic leather product has good adhesion with the foaming layer, and the physical properties such as peel strength, wear resistance, solvent resistance and the like are excellent integrally.
Description
Technical Field
The invention relates to a high-physical-property low-fogging waterborne surface layer polyurethane resin and a preparation method thereof, belonging to the technical field of materials for synthetic leather, in particular to the field of polyurethane resin for synthetic leather.
Background
Polyurethane resin has been applied to the synthetic leather industry for over fifty years, and the traditional synthetic leather consists of an oily dry-method polyurethane resin surface layer and an oily wet-method polyurethane resin foaming layer and can be applied to various fields of clothes, shoe materials, bags, home decoration, automobiles and the like. In recent years, with the beginning of the country to limit VOC emission, aqueous polyurethane resins and solvent-free polyurethane resins, which are superior in terms of environmental protection, have been rapidly developed.
In order to realize all-round environmental protection of polyurethane resin, developers have used aqueous polyurethane resin as a surface layer and solvent-free polyurethane resin as a foaming layer to produce environment-friendly synthetic leather, but the patents are few.
Patent CN201410797159.0 discloses an environment-friendly polyurethane clothing leather and a preparation method thereof, and the formed leather product has good hydrolysis resistance, low-temperature flexibility, wear resistance, scratch resistance, soft hand feeling and strong real leather feeling, and can meet the application requirements in the clothing field.
Patent CN201510634193.0 discloses a preparation method of water-based/solvent-free composite environment-friendly polyurethane synthetic leather, and the developed product has strong stereoscopic impression of patterns, soft hand feeling and hydrolysis resistance.
Patent CN201610464625.2 discloses ecological microfiber-imitated polyurethane synthetic leather for automobiles and a preparation method thereof, wherein the ecological microfiber-imitated polyurethane synthetic leather comprises a microfiber-imitated base material, a water-based surface layer and a solvent-free foaming layer, the performance of the prepared leather exceeds that of solvent type polyurethane resin synthetic leather in some aspects, and the performance of the prepared leather is mainly embodied by solvent-free polyurethane resin.
However, in the manner of combining the aqueous surface layer and the solvent-free foaming layer disclosed in the above patent documents, it is difficult to avoid the migration of small molecules in the solvent-free polyurethane resin to the leather surface, which easily causes the fogging of the leather surface and seriously affects the product appearance.
At present, synthetic leather combining aqueous surface layer polyurethane and a solvent-free polyurethane foaming layer is rarely available in the market, the main reason is that the leather surface is easy to fog, and the comprehensive performance of the product is difficult to meet the requirement, for example, the traditional aqueous polyurethane material has poor water resistance and heat resistance, and after the aqueous polyurethane material is combined with the solvent-free polyurethane resin foaming layer, the mechanical strength is difficult to meet the requirement, so that the application of combining the aqueous polyurethane resin surface layer and the solvent-free polyurethane resin foaming layer is limited.
Disclosure of Invention
The invention aims to provide a high-physical-property low-fogging waterborne surface layer polyurethane resin and a preparation method thereof, so as to overcome the defects in the prior art.
The high-physical-property low-fogging waterborne surface layer polyurethane resin is prepared from the following raw materials in percentage by weight:
preferably, the high-physical-property low-fogging waterborne surface layer polyurethane resin is prepared from the following raw materials in percentage by weight:
the polyglycol comprises a mixture of polyester diol and polyether diol;
the polyester dihydric alcohol is more than one of polycarbonate dihydric alcohol, poly adipic acid-1, 4-butanediol ester dihydric alcohol and poly adipic acid-ethylene glycol ester dihydric alcohol, the number average molecular weight of the polycarbonate dihydric alcohol is 1000-2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol ester dihydric alcohol is 1000-3000, and the number average molecular weight of the poly adipic acid-ethylene glycol ester dihydric alcohol is 2000-3000;
the polyether diol is more than one of polytetrahydrofuran diol and polyoxypropylene diol, the number average molecular weight of the polytetrahydrofuran diol is 1000-2000, and the number average molecular weight of the polyoxypropylene diol is 400-2000;
the mass ratio of the polyester diol to the polyether diol is 3: 5-2: 7;
the diisocyanate is more than one of diphenylmethane diisocyanate and toluene diisocyanate;
the chain extender consists of nonionic dihydric alcohol and ionic dihydric alcohol;
the non-ionic dihydric alcohol is more than one of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol and diethylene glycol;
the ionic dihydric alcohol is more than one of 2, 2-dimethylolbutyric acid and 2, 2-dimethylolpropionic acid;
the mass ratio of the nonionic dihydric alcohol to the ionic dihydric alcohol is 1: 1-2: 3;
the catalyst is an organic bismuth catalyst, is selected from more than one of bismuth isooctanoate and bismuth octodecanoate, and is purchased from European EGE chemical company;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:1, and the antioxidant 1010 and the antioxidant 168 are both purchased from Pasteur Germany.
The melamine derivative is more than one of methyl-etherified hexamethoxy melamine, n-butyl-etherified melamine and high imino n-butyl-etherified melamine.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) mixing polyglycol and antioxidant at 50-55 deg.c in vacuum, adding diisocyanate and reacting at 65-75 deg.c for 1-3 hr;
(2) adding a chain extender, and stirring for 15-30 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 50-70 minutes at 70-80 ℃, adding propanol to adjust the viscosity to 2000-5000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 0.5-2 hours, and evaporating acetone to dryness to obtain the high-physical-property low-fogging aqueous surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the water-based surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a base material, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
the base material is a non-woven fabric material and is used as a supporting surface of the synthetic leather;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
The invention is used in combination with the solvent-free polyurethane resin, so as to solve the problem that the leather surface is fogged due to the migration of residual isocyanate, added auxiliary agents, fillers and other micromolecules in the solvent-free polyurethane resin to the leather surface in the prior art, improve the adhesion between the surface layer and the foaming layer, and improve the physical properties such as the peeling strength, the wear resistance, the solvent resistance and the like of the synthetic leather.
According to the invention, the matched melamine derivative is introduced into the aqueous surface layer polyurethane resin, and in the reaction process of preparing the synthetic leather from the aqueous polyurethane surface layer and the solvent-free polyurethane foaming layer, a compact reticular cross-linked structure is formed at the layer interface and in the surface layer resin, so that the physical performance of the synthetic leather is improved, especially the compact reticular cross-linked structure has an effective inhibiting effect on the migration process of free isocyanate, added auxiliaries, fillers and other small molecules in the solvent-free polyurethane resin to the leather surface, so that the physical barrier is realized, meanwhile, the reticular structure can adsorb and rivet the small molecules, and the molecular migration difficulty is greatly increased. The synthetic leather surface layer made of the water-based surface layer resin is matched with the solvent-free foaming layer for use, so that the fogging problem of the leather surface can be obviously improved, and the appearance level of the product is improved. Meanwhile, the surface layer of the synthetic leather product has good adhesion with the foaming layer, and the physical properties such as peel strength, wear resistance, solvent resistance and the like are excellent on the whole.
Detailed Description
The following examples are given to illustrate the present invention and should not be construed as limiting the scope of the present invention. The implementation conditions used in the examples may be modified or adjusted according to the conditions and requirements of the particular manufacturer.
Example 1
The raw materials comprise: (weight)
The polyglycol is a mixture of poly adipic acid-1, 4-butanediol ester dihydric alcohol and polytetrahydrofuran dihydric alcohol, the number average molecular weight of the poly adipic acid-1, 4-butanediol ester dihydric alcohol is 1000, the number average molecular weight of the polytetrahydrofuran dihydric alcohol is 1000, and the mass ratio of the two is 3: 5;
the diisocyanate is toluene diisocyanate;
the chain extender is a mixture of 1, 4-butanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is bismuth isooctanoate;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The melamine derivative is high imino n-butyl etherified melamine.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 50 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 1 hour at 65 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 15 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 50 minutes at 70 ℃, adding propanol to adjust the viscosity to 3000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 1 hour, and evaporating acetone to obtain the high-physical-property low-fogging water-based surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Example 2
The raw material composition of the high-physical-property low-fogging water-based surface layer polyurethane resin is as follows:
the polyglycol is a mixture of polycarbonate diol, poly adipic acid-glycol ester diol and polyoxypropylene diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-glycol ester diol is 2000, the number average molecular weight of the polyoxypropylene diol is 1000, and the mass ratio of the polycarbonate diol to the poly adipic acid-glycol ester diol is 1:2: 5;
the diisocyanate is diphenylmethane diisocyanate;
the chain extender is a mixture of ethylene glycol, 1, 6-hexanediol and 2, 2-dimethylolpropionic acid, and the mass ratio of the substances is 2:1: 3;
the catalyst is bismuth octodecanoate;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The melamine derivative is methylated hexamethoxy melamine.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 3 hours at 75 ℃;
(2) slowly adding ionic and nonionic glycol chain extenders, and stirring for 30 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting at 80 ℃ for 70 minutes, adding propanol to adjust the viscosity to 5000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 2 hours, and evaporating acetone to obtain the high-physical-property low-fogging water-based surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Example 3
The raw material composition of the high-physical-property low-fogging water-based surface layer polyurethane resin is as follows:
the polyglycol is a mixture of polycarbonate diol, poly adipic acid-1, 4-butanediol diol ester diol and polytetrahydrofuran diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol diol ester diol is 2000, the number average molecular weight of the polytetrahydrofuran diol is 2000, and the mass ratio of the polycarbonate diol to the polytetrahydrofuran diol is 1:1: 7;
the diisocyanate is a mixture of diphenylmethane diisocyanate and toluene diisocyanate, and the mass ratio of the diisocyanate to the toluene diisocyanate is 9: 1;
the chain extender is a mixture of 1, 6-hexanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is a mixture of bismuth isooctanoate and bismuth octyldecanoate, and the mass ratio of the materials is 4: 1;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The melamine derivative is a mixture of methyl-etherified hexamethoxy melamine and n-butyl-etherified melamine, and the mass ratio of the melamine derivative is 1: 2.
The preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 2 hours at 70 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 25 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 60 minutes at 75 ℃, adding propanol to adjust the viscosity to 4000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 1.5 hours, and evaporating acetone to obtain the high-physical-property low-fogging aqueous surface layer polyurethane resin.
The high-physical-property low-fogging waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Comparative example 1
The raw materials comprise:
the polyglycol is a mixture of polycarbonate diol, poly adipic acid-1, 4-butanediol diol ester diol and polytetrahydrofuran diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol diol ester diol is 2000, the number average molecular weight of the polytetrahydrofuran diol is 2000, and the mass ratio of the polycarbonate diol to the polytetrahydrofuran diol is 1:1: 7;
the diisocyanate is a mixture of diphenylmethane diisocyanate and toluene diisocyanate, and the mass ratio of the diisocyanate to the toluene diisocyanate is 9: 1;
the chain extender is a mixture of 1, 6-hexanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is a mixture of bismuth isooctanoate and bismuth octyldecanoate, and the mass ratio of the materials is 4: 1;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The preparation method comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 2 hours at 70 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 25 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 60 minutes at 75 ℃, adding propanol to adjust the viscosity to 4000 mPa.S/25 ℃;
(4) slowly cooling to room temperature, respectively adding triethylamine and diethylamine, then adding deionized water for emulsification, stirring and dispersing for 1.5 hours, and evaporating acetone to obtain the aqueous surface layer polyurethane resin.
The waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Comparative example 2
The raw materials comprise:
the polyglycol is a mixture of polycarbonate diol, poly adipic acid-1, 4-butanediol diol ester diol and polytetrahydrofuran diol, the number average molecular weight of the polycarbonate diol is 2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol diol ester diol is 2000, the number average molecular weight of the polytetrahydrofuran diol is 2000, and the mass ratio of the polycarbonate diol to the polytetrahydrofuran diol is 1:1: 7;
the diisocyanate is a mixture of diphenylmethane diisocyanate and toluene diisocyanate, and the mass ratio of the diisocyanate to the toluene diisocyanate is 9: 1;
the chain extender is a mixture of 1, 6-hexanediol and 2, 2-dimethylolbutyric acid, and the mass ratio of the substances is 1: 1;
the catalyst is a mixture of bismuth isooctanoate and bismuth octyldecanoate, and the mass ratio of the materials is 4: 1;
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168, and the weight ratio is 1: 1.
The preparation method comprises the following steps:
(1) adding polyglycol and antioxidant into a reactor to be stirred, controlling the temperature to be 55 ℃, keeping vacuum, stirring uniformly, then adding diisocyanate, and reacting for 2 hours at 70 ℃;
(2) slowly adding the ionic and nonionic glycol chain extenders, and stirring for 25 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 60 minutes at 75 ℃, adding propanol to adjust the viscosity to 4000 mPa.S/25 ℃;
(4) slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine, then adding deionized water for emulsification, stirring and dispersing for 1.5 hours, and evaporating acetone to obtain the aqueous surface layer polyurethane resin.
The waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating and scraping the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Comparative example 3
The waterborne surface layer polyurethane resin adopts a JF-PDY-846HY type product produced by Zhejiang Huafeng synthetic resin Co.
The waterborne surface layer polyurethane resin can be matched with solvent-free polyurethane resin for use to prepare the environment-friendly synthetic leather.
The solvent-free polyurethane resin can be a commercial product, such as solvent-free polyurethane resin produced by Zhejiang Huafeng synthetic resin Co., Ltd, and is prepared from a polyol A component with the trade name of JF-NS-6010A, an isocyanate prepolymer B component with the trade name of JF-NS-6010B, a dibutyltin dilaurate catalyst with the trade name of JF-NS-C010 and the like.
The preparation method of the environment-friendly synthetic leather comprises the following steps:
(1) coating the aqueous surface layer polyurethane resin on release paper, drying at 80 ℃ until the release paper is nearly dry, and then drying at 120 ℃ for 4min until the release paper is completely dry;
(2) mixing a polyol A component with a catalyst, injecting the mixture into a tank A of a polyurethane low-pressure coating machine, adding an isocyanate prepolymer B component with the brand number of F-NS-6010B into a tank B of the polyurethane low-pressure coating machine, setting the temperature of a storage tank A and the temperature of a storage tank B to be 20 ℃, mixing the component A and the component B, then coating the mixture on the aqueous surface layer polyurethane resin obtained in the step (1) according to the thickness of 0.3mm, baking the mixture to be in a semi-dry state at 90 ℃, attaching a non-woven fabric substrate, and baking the mixture for 3min at 140 ℃ until the mixture is cured;
(3) and (3) baking at 150 ℃ for 1min, taking out and cooling to room temperature, and peeling off the release paper to obtain the environment-friendly synthetic leather combining the water-based surface layer and the solvent-free foaming layer.
Detection test
In order to verify that the synthetic leather surface layer made of the high-physical-property low-fogging waterborne surface layer polyurethane resin and the solvent-free resin synthetic leather foaming layer are combined for use, the synthetic leather surface layer has excellent performance. The following describes and shows the performance test methods, test results, and the like of each example and comparative example, respectively.
The performance test method comprises the following steps:
(1) repeated peel test of release paper: using mirror-surface release paper, repeating the preparation process of the environment-friendly synthetic leather until the release paper is torn when the synthetic leather is peeled off, and stopping and recording the using times of the release paper;
(2) repeated peel test of release film: repeating the preparation process of the environment-friendly synthetic leather by using the mirror-surface release film until the surface of the release film is damaged when the synthetic leather is peeled off, and stopping and recording the use times of the release film;
(3) testing the migration resistance of the synthetic leather: placing the environment-friendly synthetic leather in a constant temperature and humidity test machine with the humidity of 95% and the temperature of 70 ℃, continuously observing the phenomenon of fog precipitation, and recording days for starting the fog precipitation (the days for the fog precipitation are more than 10 days, which meets the requirements of the market solvent type mirror surface synthetic leather);
(4) and (3) testing the peel strength: attaching a hot melt adhesive with the width of 3cm on the surface of the environment-friendly synthetic leather, cutting, testing by using a universal tensile testing machine, and recording the peel strength;
(5) TABER abrasion resistance test: cutting the environment-friendly synthetic leather into round sample pieces, fixing the round sample pieces on a GT-7012-T type TABER abrasion tester, testing under the conditions of using an H22 grinding wheel and a 750g weight, continuously observing the damage condition of the leather surface, stopping the machine and recording the number of test turns when more than 2 points of damage appear on the leather surface;
(6) MEK resistance test: 5 drops of pure MEK are dripped on the surface of the environment-friendly synthetic leather, the MEK dripping position generates a swelling phenomenon, a metal key is used for scraping the swelling position every 10 seconds, and if the surface is damaged, the time is recorded.
The test results are shown in tables 1 and 2.
TABLE 1 test results of repeated peeling of release paper/release film and migration resistance of synthetic leather
TABLE 2 test results of peel strength, TABER abrasion resistance and hydrolysis resistance of synthetic leather
In conclusion, the high-physical-property low-fogging waterborne surface layer polyurethane resin prepared by the invention has high bonding property with the solvent-free foaming layer polyurethane resin, the surface of the prepared environment-friendly synthetic leather does not fog or precipitate, and the repeated use times of release paper and release film on a production line are greatly improved. Meanwhile, the environment-friendly synthetic leather has high peel strength, high wear resistance and high solvent resistance. The excellent performance of the invention is beneficial to widening the application range of the waterborne polyurethane resin and further developing the environmental-friendly synthetic leather product.
Although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the embodiments, and equivalent changes or modifications made to the contents of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and the spirit of the present invention.
Claims (5)
1. The high-physical-property low-fogging waterborne surface layer polyurethane resin is characterized by being prepared from the following raw materials in percentage by weight:
the polyglycol comprises a mixture of polyester diol and polyether diol;
the polyester dihydric alcohol is more than one of polycarbonate dihydric alcohol, poly adipic acid-1, 4-butanediol ester dihydric alcohol and poly adipic acid-ethylene glycol ester dihydric alcohol, the number average molecular weight of the polycarbonate dihydric alcohol is 1000-2000, the number average molecular weight of the poly adipic acid-1, 4-butanediol ester dihydric alcohol is 1000-3000, and the number average molecular weight of the poly adipic acid-ethylene glycol ester dihydric alcohol is 2000-3000;
the polyether diol is more than one of polytetrahydrofuran diol and polyoxypropylene diol, the number average molecular weight of the polytetrahydrofuran diol is 1000-2000, and the number average molecular weight of the polyoxypropylene diol is 400-2000;
the diisocyanate is more than one of diphenylmethane diisocyanate and toluene diisocyanate;
the chain extender consists of nonionic dihydric alcohol and ionic dihydric alcohol;
the non-ionic dihydric alcohol is more than one of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol and diethylene glycol;
the ionic dihydric alcohol is more than one of 2, 2-dimethylolbutyric acid and 2, 2-dimethylolpropionic acid;
the melamine derivative is more than one of methyl-etherified hexamethoxy melamine, n-butyl-etherified melamine and high imino n-butyl-etherified melamine;
the preparation method of the high-physical-property low-fogging waterborne surface layer polyurethane resin comprises the following steps:
(1) mixing polyglycol and antioxidant in vacuum, adding diisocyanate and reacting;
(2) adding a chain extender;
(3) adding N-methyl pyrrolidone and a catalyst, reacting, and adding propanol to adjust viscosity;
(4) and cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing, and evaporating acetone to dryness to obtain the high-physical-property low-fogging water-based surface layer polyurethane resin.
2. The polyurethane resin for the high-physical-property low-fogging water-based surface layer as claimed in claim 1, wherein the mass ratio of the polyester diol to the polyether diol is 3:5 to 2: 7.
3. The high-physical-property low-fogging waterborne surface layer polyurethane resin according to claim 1, characterized in that the amount ratio of the nonionic diol to the ionic diol is 1: 1-2: 3.
4. The high-physical-property low-fogging waterborne surface layer polyurethane resin as claimed in claim 1, wherein the catalyst is an organic bismuth catalyst, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the weight ratio is 1: 1.
5. The preparation method of the polyurethane resin for the high-physical-property low-fogging water-based surface layer as claimed in claim 1, characterized by comprising the following steps: (1) mixing polyglycol and antioxidant at 50-55 deg.c in vacuum, adding diisocyanate and reacting at 65-75 deg.c for 1-3 hr;
(2) adding a chain extender, and stirring for 15-30 minutes;
(3) adding N-methyl pyrrolidone and a catalyst, reacting for 50-70 minutes at 70-80 ℃, adding propanol to adjust the viscosity to 2000-5000 mPa.S/25 ℃;
(4) and slowly cooling to room temperature, respectively adding triethylamine, diethylamine and melamine derivatives, adding deionized water for emulsification, stirring and dispersing for 0.5-2 hours, and evaporating acetone to dryness to obtain the high-physical-property low-fogging aqueous surface layer polyurethane resin.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1214773A (en) * | 1968-05-03 | 1970-12-02 | Bayer Ag | Process for treating sheet structures with aqueous polyurethane dispersions and colloidal solutions |
| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| JP2009001713A (en) * | 2007-06-22 | 2009-01-08 | Dainichiseika Color & Chem Mfg Co Ltd | Coating material for skin layer of synthetic artificial leather and method for producing synthetic artificial leather |
| CN102875767A (en) * | 2011-07-12 | 2013-01-16 | 上海诺科生物科技有限公司 | Synthetic method of environment-friendly type waterborne polyurethane resin for artificial leather |
| CN103435773A (en) * | 2013-09-11 | 2013-12-11 | 侯马飞 | Polyurethane resin for synthetic leather with high water pressure resistance |
| CN103755917A (en) * | 2013-12-26 | 2014-04-30 | 浙江华峰合成树脂有限公司 | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof |
| CN104312407A (en) * | 2013-03-22 | 2015-01-28 | 吴小再 | Aqueous polyurethane paint preparation method |
| CN104327710A (en) * | 2013-03-22 | 2015-02-04 | 吴小再 | Preparation method of paint having simple preparation process |
| CN104356912A (en) * | 2013-03-22 | 2015-02-18 | 吴小再 | Preparation method of coating |
| CN107840937A (en) * | 2017-10-31 | 2018-03-27 | 上海华峰新材料研发科技有限公司 | Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application |
-
2019
- 2019-08-28 CN CN201910799959.9A patent/CN110591044B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1214773A (en) * | 1968-05-03 | 1970-12-02 | Bayer Ag | Process for treating sheet structures with aqueous polyurethane dispersions and colloidal solutions |
| AT291185B (en) * | 1968-05-03 | 1971-07-12 | Bayer Ag | Process for coating or finishing flat structures |
| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| JP2009001713A (en) * | 2007-06-22 | 2009-01-08 | Dainichiseika Color & Chem Mfg Co Ltd | Coating material for skin layer of synthetic artificial leather and method for producing synthetic artificial leather |
| CN102875767A (en) * | 2011-07-12 | 2013-01-16 | 上海诺科生物科技有限公司 | Synthetic method of environment-friendly type waterborne polyurethane resin for artificial leather |
| CN104312407A (en) * | 2013-03-22 | 2015-01-28 | 吴小再 | Aqueous polyurethane paint preparation method |
| CN104327710A (en) * | 2013-03-22 | 2015-02-04 | 吴小再 | Preparation method of paint having simple preparation process |
| CN104356912A (en) * | 2013-03-22 | 2015-02-18 | 吴小再 | Preparation method of coating |
| CN103435773A (en) * | 2013-09-11 | 2013-12-11 | 侯马飞 | Polyurethane resin for synthetic leather with high water pressure resistance |
| CN103755917A (en) * | 2013-12-26 | 2014-04-30 | 浙江华峰合成树脂有限公司 | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof |
| CN107840937A (en) * | 2017-10-31 | 2018-03-27 | 上海华峰新材料研发科技有限公司 | Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Suzana M.Caki＇ca等.Glycolyzed poly(ethylene terephthalate) waste and castor oil-based polyols for waterborne polyurethane adhesives containing hexamethoxymethyl melamine.《Progress in Organic Coatings》.2015,第78卷357-368. * |
| 三聚氰胺及其衍生物改性聚氨酯的制备与研究;林强;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20161015(第10期);B018-2 * |
| 合成革用水性聚氨酯的制备;王震 等;《聚氨酯工业》;20110428;第26卷(第2期);40-43 * |
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