CN114044872B - Polyurethane resin for synthetic leather, water-absorbing moisture-permeable degradable synthetic leather and preparation method thereof - Google Patents
Polyurethane resin for synthetic leather, water-absorbing moisture-permeable degradable synthetic leather and preparation method thereof Download PDFInfo
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- CN114044872B CN114044872B CN202111201826.0A CN202111201826A CN114044872B CN 114044872 B CN114044872 B CN 114044872B CN 202111201826 A CN202111201826 A CN 202111201826A CN 114044872 B CN114044872 B CN 114044872B
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- Prior art keywords
- polyol
- synthetic leather
- polyurethane resin
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- solvent
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 49
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 100
- 150000003077 polyols Chemical class 0.000 claims abstract description 91
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 31
- 239000004417 polycarbonate Substances 0.000 claims abstract description 31
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002521 macromolecule Polymers 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 32
- -1 polyethylene terephthalate Polymers 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 4
- 150000003384 small molecules Chemical class 0.000 claims 1
- 230000001739 rebound effect Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000002689 soil Substances 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 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 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- C08G18/40—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
- C08G18/30—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
- C08G18/65—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
-
- 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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- 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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0065—Organic pigments, e.g. dyes, brighteners
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/121—Permeability to gases, adsorption
- D06N2209/123—Breathable
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
- D06N2209/1614—Biodegradable
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1635—Elasticity
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The application relates to polyurethane resin for synthetic leather, water-absorbing and moisture-permeable degradable synthetic leather and a preparation method thereof. According to the application, the polycarbonate, the micromolecular polyol and the macromolecule polyol are subjected to transesterification reaction to prepare the blended polyol component, the blended polyol component has the rigidity of the polycarbonate and the flexibility characteristic of the macromolecule polyol, and is applied to polyurethane resin for synthetic leather, so that the prepared synthetic leather has a slow rebound effect and good hand feeling. Meanwhile, the prepared synthetic leather has water absorption and moisture permeability, and the synthetic leather product is buried in soil after being worn and abandoned, can be biodegraded by microorganisms in the soil, and does not cause environmental pollution.
Description
Technical Field
The application belongs to the technical field of synthetic leather, and particularly relates to polyurethane resin for synthetic leather, water-absorbent and moisture-permeable degradable synthetic leather and a preparation method thereof.
Background
The traditional polyurethane synthetic leather mainly comprises polyester and polyether polyol, and polycaprolactone and polycarbonate polyol are used in a few cases. The polyester polyol commonly used has the characteristics of excellent oil resistance, excellent adhesive property, high tensile strength, good temperature resistance and the like, but has poor hydrolysis resistance. Polyether polyols have good hydrolysis resistance, but have poor adhesion, low tensile strength, and are readily oxidized under ultraviolet light. The cost of producing conventional polyester and polyether polyols is lower, which makes them useful in a wider range of polyurethane materials, but their benefits are limited. The polycarbonate polyol is used as a substitute product of polyester and polyether polyol, and has the advantages of excellent hydrolytic stability, good chemical resistance, long service life, good thermal stability and better mechanical property. However, polycarbonate polyols are produced at a higher cost than polyether and polyester polyols, and are therefore used mainly in the high-end fields of automobiles, leather, shoes and the like.
Traditional polycarbonate polyols are mainly derived from the petroleum industry, i.e. formed by condensation of aromatic or aliphatic diols with highly toxic phosgene followed by transesterification. Commercially available polyurethane resins use almost all petroleum-based polyols and have no sustainable development. The commercial polyurethane synthetic leather has the advantages of popular touch feeling, texture, service life and aging resistance for consumers, but has the defects of lower slow rebound effect than leather, poorer water absorption and moisture permeability and no biodegradation. The sweat discharged by human body still gathers on the skin surface due to the poor water absorption and moisture permeability, bacteria are easy to grow, and the skin care product is uncomfortable to wear and is easy to infect skin diseases such as eczema. If the polyurethane synthetic leather product cannot be degraded by microorganisms after being discarded, the polyurethane synthetic leather product is like white pollution caused by plastics, seriously threatens the health of human bodies, and has no sustainable development.
Disclosure of Invention
The application aims to solve the technical problem of overcoming the defects of the prior art and providing the biodegradable polyurethane resin for the synthetic leather with good slow rebound effect, good water absorption and moisture permeability and the preparation method thereof.
The second object of the application is to provide a water-absorbing moisture-permeable degradable synthetic leather and a preparation method thereof.
In order to achieve the above purpose, the application adopts the following technical scheme:
the raw material formula of the solvent polyurethane resin comprises isocyanate, a polyol component and a solvent, wherein the polyol component is prepared by conducting transesterification reaction on polycarbonate, micromolecular polyol and high-molecular polyol in the presence of a catalyst, and the polycarbonate is prepared by reacting carbon dioxide with an epoxy compound.
The epoxy compound is selected from the group consisting of ethylene oxide, propylene oxide, 1, 2-butylene oxide.
In some embodiments of the application, the polycarbonate is selected from the group consisting of polyethylene carbonate, polypropylene carbonate, polybutylene carbonate, and has a number average molecular weight of 800 to 1500.
In the present application, the polycarbonate is produced as a polycarbonate in CO 2 And an epoxy compound is used as a raw material to synthesize the completely degradable environment-friendly material, has the characteristics of green and environment protection, and accords with the sustainable development characteristic of the polyurethane material.
In some embodiments of the application, the mass ratio of the polycarbonate to the small molecular polyol to the high molecular polyol is 6.6-10:0.53-1:6-8. Preferably, the mass ratio of the polycarbonate to the micromolecular polyol to the macromolecule polyol is 10-15:1:8-13. Further preferably, the mass ratio of the polycarbonate to the polymer polyol is 1.1 to 1.25:1.
In some embodiments of the application, the small molecule polyol is selected from neopentyl glycol, 1, 6-hexanediol, ethylene glycol. The addition of the small molecule polyol aids in the transesterification reaction.
In some embodiments of the application, the polymeric polyol is selected from polyethylene glycol, silicone polyol, polycaprolactone polyol, and other polyester polyols selected from polyethylene terephthalate glycol, polymethyl adipate glycol, and 1, 4-butanediol polyglutaric acid glycol.
Preferably, the polyethylene glycol has a number average molecular weight of 500 to 2000 and a functionality of 2 to 3.
Preferably, the organic silicon polyol is any one or a combination of a plurality of anionic, cationic, nonionic and complex ionic dihydroxy organic silicon polyols, and the number average molecular weight of the organic silicon polyol is 500-2000.
Preferably, the polycaprolactone polyol has a number average molecular weight of 500 to 2000 and a functionality of 2 to 3.
Preferably, the number average molecular weight of the polyethylene terephthalate glycol, the polymethyl adipate glycol and the 1, 4-butanediol polyglutaric acid glycol is respectively 1000-2000, and the functionality is 2-5.
In some embodiments of the application, the transesterification reaction is carried out at 220-280℃and the reaction is terminated when the hydroxyl number of the system is detected to be 25-27 mgKOH/g and the acid number is below 0.45 mgKOH/g.
In some embodiments of the application, the isocyanate is one or more of 4, 4-diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), naphthalene Diisocyanate (NDI), toluene Diisocyanate (TDI), and isophorone diisocyanate (IPDI). Preferably, the isocyanate is a combination of two or more of 4, 4-diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), naphthalene Diisocyanate (NDI), toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI).
In some embodiments of the application, the raw material formulation of the polyurethane resin further comprises a small molecule polyol, a catalyst and an auxiliary agent.
Preferably, the small molecule polyol is one or a combination of a plurality of neopentyl glycol, 1, 6-hexanediol and ethylene glycol. More preferably, the small molecular polyol is neopentyl glycol, 1.6-hexanediol and ethylene glycol, and the mass ratio of the neopentyl glycol to the ethylene glycol is 5.5-6.5:3.5-4.5:1.
In some preferred and specific embodiments, the raw material formulation of the polyurethane resin comprises the following components in parts by weight:
preferably, the auxiliary agent is an antioxidant.
Preferably, the catalyst is one or a combination of several of organotin, organobismuth and lead oxide.
Preferably, the solvent is an organic solvent, such as including but not limited to N, N-Dimethylformamide (DMF).
The application adopts a second technical scheme that: the preparation method of the solvent polyurethane resin comprises the following steps:
(1) Preparation of polyol component
The polycarbonate, the micromolecular polyol and the macromolecule polyol are subjected to transesterification reaction at 220-280 ℃ in the presence of a catalyst, and the reaction is ended when the hydroxyl value of the system is 25-27 mgKOH/g, so as to obtain the polyol component;
(2) Preparation of solvent type polyurethane resin
Mixing the auxiliary agent, the polyol component, the micromolecular polyol and the solvent, adding isocyanate for reaction, and adding a terminator for termination reaction after the reaction is finished.
In some embodiments, in step (1), nitrogen is bubbled into the system during the transesterification reaction to accelerate the reaction.
In some preferred and specific embodiments, the specific implementation of step (1) is: adding polycarbonate, micromolecular polyol, high-molecular polyol and a catalyst into a reaction kettle, heating to 220-280 ℃ under the protection of inert gas to perform transesterification, and then blowing inert gas into the system to accelerate the transesterification.
Preferably, under the protection of the inert gas, the inert gas is positioned above the liquid level, and the flow rate of the inert gas is 0.2 to 0.5 L.min -1 。
Preferably, the inert gas is blown in, the inert gas is positioned below the liquid level, and the flow rate of the inert gas is 0.5-2 L.min -1 。
Preferably, after the inert gas protection is carried out for 2.5-4 hours, inert gas is blown into the system.
Preferably, the inert gas includes, but is not limited to, nitrogen.
In some preferred and specific embodiments, in step (2), the reaction is carried out at 65-85 ℃.
Preferably, the terminator includes, but is not limited to, methanol.
According to a third technical scheme adopted by the application, the synthetic leather is prepared from the solvent polyurethane resin.
According to a fourth technical scheme adopted by the application, the preparation method of the synthetic leather comprises the following steps: and mixing the solvent type polyurethane resin, lignocellulose, filler, pigment and solvent to obtain slurry, coating the slurry on the surface of the base cloth, curing in water, washing with water, and drying to obtain the synthetic leather.
In some preferred and specific embodiments, the slurry comprises 100 parts of the solvent-based polyurethane resin, 25 to 35 parts of lignocellulose, 15 to 25 parts of calcium carbonate, 0.5 to 1.5 parts of pigment, and 100 to 120 parts of solvent.
The lignocellulose is favorable for assisting the foaming of polyurethane resin, improving the dimensional stability of the synthetic leather and reducing the expansion coefficient.
Due to the application of the technical scheme, compared with the prior art, the application has the following advantages:
according to the application, the polycarbonate, the micromolecular polyol and the macromolecule polyol are subjected to transesterification reaction to prepare the blended polyol component, the blended polyol component has the rigidity of the polycarbonate and the flexibility characteristic of the macromolecule polyol, and is applied to polyurethane resin for synthetic leather, so that the prepared synthetic leather has a slow rebound effect and good hand feeling. Meanwhile, hydrophilic groups in the prepared polyurethane resin can form a hydrogen bond structure with water emitted by a human body, so that the water vapor emitted by the human body can be discharged in time, and the wearing comfort is kept. The synthetic leather product is buried in soil after being worn and abandoned, can be biodegraded by microorganisms in the soil, and does not cause environmental pollution.
The polyurethane resin prepared by the application is prepared by a one-step method, has simple process, low cost and energy consumption and excellent processability, and does not generate waste in the production process.
Detailed Description
As described in the background, the polyurethane resin or synthetic leather currently on the market is basically made of petroleum-based polyols, and has no sustainable development. In recent years scientists use CO 2 The new generation of poly-carbon is prepared as raw materialAcid ester polyols, which have high environmental and economic benefits. Greenhouse gas CO 2 The polycarbonate polyol is widely available in nature, has rich and renewable raw material sources, and can be used as a main raw material for producing the polycarbonate polyol. Current CO 2 Is considered as a pollutant, carbon emissions are of concern in countries around the world, but in the near future, CO 2 Will be considered an important resource. Compared with petroleum-based polyurethane, CO 2 The carbon emissions in the base polyurethane are significantly reduced, which is an important indicator of the sustainable development of the polyurethane production industry as green polyol. In recent years scientists have also sought alternative products to petroleum-based polyurethanes from nature, such as the preparation of polyurethane materials using vegetable oils of abundant origin, but from a social development perspective they compete with grain production and the worldwide vegetable oil supply market is very fluctuating and not sustainable. Using CO 2 The production of polyurethane as a polyol feedstock does not compete with the vegetable oil market. CO is processed by 2 Experiments have proven that the use of base polycarbonate polyols in polyurethane materials is viable, and that this technique has technical, environmental and economic advantages over traditional formulations.
The polycarbonate polyol has a good rigid structure, and other types of common polyols have good flexibility, and if the common polyol and the carbonate polyol can form a blending structure, the polyurethane synthetic leather prepared from the polycarbonate polyol has good slow rebound effect. Based on this, the inventors innovatively put CO 2 The base polycarbonate, the micromolecular polyol and the macromolecule polyol are subjected to transesterification reaction to obtain a blended polyol component, the blended polyol component is used as a raw material in polyurethane resin for synthetic leather, the prepared synthetic leather has good slow rebound effect, hydrophilic chemical groups (such as hydroxyl groups) in the polyol component can freely form hydrogen bonds with water vapor discharged from a human body to assist the water vapor to be discharged out of the body, so that the skin is kept dry and comfortable to wear, and meanwhile, the polyurethane resin prepared by matching the polyol component with other components can be completely degraded by microorganisms in soil and cannot cause white similar to plasticsColor contamination, with sustainable development.
In some embodiments of the application, the polyol component is prepared by the following process: 1000 to 1500 parts of polycarbonate, 50 to 200 parts of micromolecular polyol and 800 to 1300 parts of other polyols are put into a reaction kettle, 0.05 to 0.1 part of catalyst is added, a nitrogen pipe is placed above the liquid level, and the nitrogen flow is set to be 0.2 to 0.5 L.min -1 Slowly heating to 220-280 deg.c for reaction for 3 hr, and setting the flow rate of nitrogen gas below the liquid level at 0.5-2 L.min -1 . And continuously performing transesterification reaction, continuously testing the hydroxyl value and the acid value in the reaction process until the measured hydroxyl value is between 25 and 27mgKOH/g and the acid value is below 0.45mgKOH/g, and cooling and packaging the prepared polyol component.
The polyurethane resin is prepared by the following steps: taking weight as unit, 450-600 parts of polyol component, 130-160 parts of isocyanate, 8-20 parts of micromolecular polyol, 0.2-0.6 part of auxiliary agent, 0.05-0.1 part of catalyst and 400-500 parts of solvent are put into a reaction bottle for 1000-1200 r.min -1 Stirring until uniform. And then adding isocyanate into a reaction bottle to keep the R value between 0.9 and 0.95, and raising the reaction temperature to between 65 and 85 ℃ to thicken the reaction, wherein a small amount of isocyanate can be added in the reaction process to promote the tackifying reaction. Adding the rest solvent in the tackifying process, adding the terminator methanol when the viscosity of the resin reaches 20-24 ten thousand (cps/DEG C), and continuously stirring for 1h to cool the wrapper. The solid content of the final polyurethane resin is controlled between 40 and 50 percent.
The synthetic leather is prepared by the following steps: 100g of the polyurethane resin and a plastic bottle are taken, 25 to 35g of lignocellulose, 15 to 25g of filler, 0.5 to 1.5g of pigment and 100 to 120g of solvent are added into the polyurethane resin and the plastic bottle, and the polyurethane resin and the plastic bottle are mixed with 3000 r.min -1 Uniformly dispersed at high speed under the stirring speed, and then standing for deaeration for standby. The leather substrate was soaked in 25% DMF aqueous solution to remove surface impurities, pressurized with water using a water press, ironed to semi-dry using an iron, and then padded with a 1.5mm thick gauge. Pouring a small amount of the slurry to be used on the surface of the base fabric, scraping the base fabric, and then placing the base fabric in water for fillingAnd (5) performing separate solidification, washing, drying and other treatments to obtain the polyurethane synthetic leather.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Further, it is understood that various changes and modifications of the present application may be made by those skilled in the art after reading the contents of the present application, and such equivalents are also within the scope of the present application as defined in the appended claims.
Example 1
The synthetic leather provided by the embodiment is prepared by the following method:
(1) Preparation of polyol component
1000 parts of polyethylene carbonate (molecular weight 800), 100 parts of neopentyl glycol and 900 parts of polyethylene glycol (PEG-1000) are put into a 4kg reaction kettle, 0.05 part of catalyst is added, a nitrogen pipe is placed above the liquid level, and the nitrogen flow is set at 0.2 L.min -1 Slowly heating to 270 ℃ for reaction for 3 hours, then placing a nitrogen pipe below the liquid level, and setting the nitrogen flow to be 1 L.min -1 . And continuously carrying out transesterification reaction, continuously testing the hydroxyl value and the acid value in the reaction process until the tested hydroxyl value is about 26mgKOH/g and the acid value is below 0.3mgKOH/g, and cooling and packaging the prepared polyol component.
(2) Preparation of polyurethane resin
480 parts of a polyol component, 4.9 parts of neopentyl glycol, 3.3 parts of 1, 6-hexanediol, 0.8 part of ethylene glycol, 0.2 part of an antioxidant, 0.06 part of a catalyst and 400 parts of a solvent DMF are put into a 4kg reaction bottle, and the reaction time is 1200 r.min -1 Stirring until uniform. Then adding 60 parts of 4, 4-diphenylmethane diisocyanate and 60 parts of hexamethylene diisocyanate (R=1) into a reaction bottle, and raising the reaction temperature to 65-85 ℃ to make the reaction be thickened, wherein a small amount of isocyanate can be added in the reaction process to promote the tackifying reaction. Adding the rest solvent DMF in the tackifying process, adding 3 parts of terminator methanol when the viscosity of the resin reaches 20-24 ten thousand (cps/DEG C), continuously stirring for 1h, and cooling the wrapper to obtain the polyurethane resin with the solid content of 40-50%.
(3) Preparation of synthetic leather
100 parts of the synthetic polyurethane resin and a plastic bottle are taken, 30 parts of lignocellulose, 20 parts of calcium carbonate, 1 part of carbon black and 110 parts of solvent DMF are added into the mixture, and 3000 r.min -1 Uniformly dispersed at high speed under the stirring speed, and then standing for deaeration for standby. The leather substrate was soaked in 25% DMF aqueous solution to remove surface impurities, pressurized with water using a water press, ironed to semi-dry using an iron, and then padded with a 1.5mm thick gauge. Pouring a little of the slurry to be used on the surface of the base cloth, scraping and coating the slurry, then placing the slurry in water for full solidification, and then performing water washing, drying and other treatments to obtain the polyurethane synthetic leather.
Example 2
The synthetic leather provided in this example was prepared in the same manner as in example 1 in step (3).
The polyol component of step (1) is prepared as follows: 1200 parts of polypropylene carbonate (molecular weight: 850), 80 parts of 1, 4-butanediol and 1000 parts of anionic dihydroxy organosilicon polyol (molecular weight: 800) are put into a 4kg reaction kettle, 0.07 part of catalyst is added, a nitrogen pipe is placed above the liquid level, and the nitrogen flow is set at 0.3 L.min -1 Slowly heating to 270 ℃ for reaction for 3 hours, then placing a nitrogen pipe below the liquid level, and setting the nitrogen flow to be 0.6 L.min -1 . And continuously carrying out transesterification reaction, continuously testing the hydroxyl value and the acid value in the reaction process until the tested hydroxyl value is about 26mgKOH/g and the acid value is below 0.3mgKOH/g, and cooling and packaging the prepared polyol component.
The polyurethane resin of step (2) is prepared as follows: 500 parts of polyol component, 4.9 parts of neopentyl glycol, 3.3 parts of 1, 6-hexanediol, 0.8 part of ethylene glycol, 0.3 part of antioxidant, 0.07 part of catalyst and 420 parts of solvent DMF are put into a 4kg reaction bottle, and the reaction time is 1000 r.min -1 Stirring until uniform. Then 70 parts of naphthalene diisocyanate and 65 parts of toluene diisocyanate (R=1) are added into a reaction bottle, the reaction temperature is raised to 65-85 ℃ to make the reaction be thickened, and a small amount of isocyanate can be added in the reaction process to promote the tackifying reaction. Adding the residual solvent DMF in the tackifying process, and waiting for the resin to be stickyWhen the temperature reaches 20-24 ten thousand (cps/DEG C), adding 3 parts of terminator methanol, continuously stirring for 1h, cooling and packaging to obtain the polyurethane resin with the solid content of 40-50%.
Example 3
The synthetic leather provided in this example was prepared in the same manner as in example 1 in step (3).
The polyol component of step (1) is prepared as follows: 1500 parts of polybutylenecarbonate (molecular weight 800), 150 parts of ethylene glycol and 1200 parts of polymethyl propylene glycol adipate (molecular weight 1000) are put into a 4kg reaction kettle, 0.08 part of catalyst is added, a nitrogen pipe is arranged above the liquid level, and the nitrogen flow is set at 0.4 L.min -1 Slowly heating to 280 deg.c for reaction for 3 hr, setting nitrogen pipe below the liquid level and nitrogen flow rate of 2L min -1 . And continuously carrying out transesterification reaction, continuously testing the hydroxyl value and the acid value in the reaction process until the tested hydroxyl value is about 27mgKOH/g and the acid value is below 0.45mgKOH/g, and cooling and packaging the prepared polyol component.
The polyurethane resin of step (2) is prepared as follows: 550 parts of a polyol component, 4.9 parts of neopentyl glycol, 3.3 parts of 1, 6-hexanediol, 0.8 part of ethylene glycol, 0.5 part of an antioxidant, 0.08 part of a catalyst and 500 parts of a solvent DMF are put into a 4kg reaction bottle, and the reaction is carried out at 1100 r.min -1 Stirring until uniform. Then 150 parts (R=1) of isophorone diisocyanate is added into the reaction bottle, the reaction temperature is raised to 65-85 ℃ to make the isophorone diisocyanate react and thicken, and a small amount of isocyanate can be added in the reaction process to promote the tackifying reaction. Adding the rest solvent DMF in the tackifying process, adding 3 parts of terminator methanol when the viscosity of the resin reaches 20-24 ten thousand (cps/DEG C), continuously stirring for 1h, and cooling the wrapper to obtain the polyurethane resin with the solid content of 40-50%.
Comparative example 1
The synthetic leather provided in this comparative example was prepared substantially as in example 1, except that: polyurethane resin was prepared using polyethylene adipate instead of polyol component.
Comparative example 2
The synthetic leather provided in this comparative example was prepared substantially as in example 1, except that: in the step (2), 9 parts of 1.4-butanediol were used instead of 4.9 parts of neopentyl glycol, 3.3 parts of 1.6-hexanediol and 0.8 part of ethylene glycol.
Comparative example 3
The synthetic leather provided in this comparative example was prepared substantially as in example 1, except that: in the step (2), 120 parts of 4, 4-diphenylmethane diisocyanate was substituted for 60 parts of hexamethylene diisocyanate and 60 parts of 4, 4-diphenylmethane diisocyanate.
Comparative example 4
The synthetic leather provided in this comparative example was prepared substantially as in example 1, except that: a mixture of 1000 parts of commercially available polypropylene carbonate glycol and 1000 parts of polyethylene glycol was used in place of the polyol component.
Comparative example 5
The synthetic leather provided in this comparative example was prepared substantially as in example 1, except that: in the preparation process of the step (1), no small molecular polyol is added, namely, only 1000 parts of polyethylene carbonate and 1000 parts of polyethylene glycol (PEG-1000) are adopted for carrying out transesterification reaction to prepare a polyol component. As a result, the transesterification reaction proceeds with difficulty. And thus is not used for the subsequent preparation of polyurethane resin.
For the synthetic leathers of examples 1 to 3 and comparative examples 1 to 4, water absorption perspective was tested with reference to the GB/T21655.2-2009 standard; the biodegradability is tested according to GB/T19277-2003 standard, and the higher the 45-day biodegradation rate is, the better is; the slow rebound effect was measured as follows, and the results are shown in table 1.
The detection method of slow rebound comprises the following steps: and the prepared synthetic leather is folded in half, and if the crease can be recovered within 10min, the slow rebound effect is excellent. If the crease cannot be recovered within 10 minutes, the slow rebound effect is poor.
Table 1 shows the performance test of the synthetic leather of examples 1 to 3 and comparative examples 1 to 4
The above embodiments are provided to illustrate the technical concept and features of the present application and are intended to enable those skilled in the art to understand the content of the present application and implement the same, and are not intended to limit the scope of the present application. All equivalent changes or modifications made in accordance with the spirit of the present application should be construed to be included in the scope of the present application.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (7)
1. A solvent polyurethane resin for synthetic leather is characterized in that: the raw material formula of the polyurethane resin comprises the following components in parts by weight:
450-600 parts of a polyol component;
130-160 parts of isocyanate;
8-20 parts of small molecule polyalcohol;
0.2-0.6 part of auxiliary agent;
0.05-0.1 part of a catalyst;
550-750 parts of solvent;
the polyol component is prepared by transesterification reaction of polycarbonate, small molecular polyol and high molecular polyol in the presence of a catalyst, wherein the polycarbonate is prepared by reacting carbon dioxide with an epoxy compound;
the number average molecular weight of the polycarbonate is 800-1500;
the transesterification reaction is carried out at 220-280 ℃, and when the hydroxyl value of the system is detected to be 25-27 mgKOH/g, the reaction is ended;
the high molecular polyol is selected from polyethylene glycol, organosilicon polyol, polycaprolactone polyol, polyethylene terephthalate glycol, polymethyl propylene glycol adipate glycol and 1, 4-butanediol polyglutaric acid glycol;
the mass ratio of the polycarbonate to the micromolecular polyol to the macromolecule polyol is 6.6-10:0.53-1:6-8;
the small molecular polyol is selected from neopentyl glycol, 1, 6-hexanediol and ethylene glycol;
the isocyanate is 4, 4-diphenyl methane diisocyanate;
in the polyurethane resin, the micromolecular polyol is a combination of neopentyl glycol, 1.6-hexanediol and ethylene glycol according to a mass ratio of 5.5-6.5:3.5-4.5:1.
2. The solvent-based polyurethane resin according to claim 1, wherein: the polycarbonate is selected from the group consisting of polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate.
3. The solvent-based polyurethane resin according to claim 1, wherein: the auxiliary agent is an antioxidant.
4. A method for producing the solvent-based polyurethane resin according to any one of claims 1 to 3, comprising the steps of:
(1) Preparation of polyol component
Carrying out transesterification on polycarbonate, micromolecular polyalcohol and macromolecule polyalcohol in the presence of a catalyst at 220-280 ℃, and ending the reaction when the hydroxyl value of a system is 25-27 mgKOH/g to obtain the polyalcohol component;
(2) Preparation of solvent type polyurethane resin
Mixing the auxiliary agent, the polyol component, the micromolecular polyol, the catalyst and the solvent, adding isocyanate for reaction, and adding a terminator for termination reaction after the reaction is finished.
5. A synthetic leather prepared from the solvent-based polyurethane resin according to any one of claims 1 to 3.
6. A method of making a synthetic leather according to claim 5, comprising the steps of: mixing the solvent polyurethane resin, lignocellulose, the filler, the pigment and the solvent according to any one of claims 1-3 to obtain slurry, coating the slurry on the surface of a base fabric, curing in water, washing with water, and drying to obtain the synthetic leather.
7. The method for producing synthetic leather according to claim 6, wherein: the slurry comprises 100 parts of the solvent polyurethane resin, 25-35 parts of lignocellulose, 15-25 parts of filler, 0.5-1.5 parts of pigment and 100-120 parts of solvent.
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