CN115354505B - Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof - Google Patents
Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof Download PDFInfo
- Publication number
- CN115354505B CN115354505B CN202211006429.2A CN202211006429A CN115354505B CN 115354505 B CN115354505 B CN 115354505B CN 202211006429 A CN202211006429 A CN 202211006429A CN 115354505 B CN115354505 B CN 115354505B
- Authority
- CN
- China
- Prior art keywords
- bio
- free polyurethane
- synthetic leather
- based solvent
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 97
- 239000004814 polyurethane Substances 0.000 title claims abstract description 97
- 239000002649 leather substitute Substances 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 239000002344 surface layer Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004744 fabric Substances 0.000 claims abstract description 43
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims description 32
- 229920005749 polyurethane resin Polymers 0.000 claims description 30
- 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 24
- 238000001035 drying Methods 0.000 claims description 19
- 238000007790 scraping Methods 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000003063 flame retardant Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000010409 ironing Methods 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 235000019482 Palm oil Nutrition 0.000 claims description 5
- 239000002540 palm oil Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000011527 polyurethane coating Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- ZBHSAYWIYAVUOP-UHFFFAOYSA-N 2-(benzylamino)-1-[3-(trifluoromethyl)phenyl]ethanol Chemical compound C=1C=CC(C(F)(F)F)=CC=1C(O)CNCC1=CC=CC=C1 ZBHSAYWIYAVUOP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000010345 tape casting Methods 0.000 description 8
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- -1 dimethylaminopropyl Chemical group 0.000 description 6
- 229940102253 isopropanolamine Drugs 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000010985 leather Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
-
- 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
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- 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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to the technical field of resin synthesis, and provides a bio-based solvent-free polyurethane surface layer resin for synthetic leather and a preparation method thereof. The method comprises the following steps: preparing modified bio-based polyester polyol, preparing wet-process polyurethane base cloth, preparing bio-based solvent-free polyurethane surface layer resin and synthetic leather. The biological base surface layer resin prepared by the invention has the advantages of folding resistance, damp and heat resistance, chemical corrosion resistance and soft hand feeling, is better in peel strength and mechanical property when used in the surface layer of synthetic leather, is energy-saving and environment-friendly, and meets the requirements of green chemical industry.
Description
Technical Field
The invention relates to the technical field of resin synthesis, in particular to a bio-based solvent-free polyurethane surface layer resin for synthetic leather and a preparation method thereof.
Background
The solvent-free polyurethane is a partially crosslinked polymer obtained based on two-component reaction molding techniques. The solvent-free polyurethane resin is not dissolved by using an organic solvent in the synthesis process, but reacts in situ on the fiber base cloth through high-speed shearing and blending, so that the film with the flexible porous structure is formed. Compared with the conventional film, the solvent-free polyurethane resin film has the advantages of quick forming, low energy consumption, excellent wear resistance, folding resistance, corrosion resistance, mechanical property and the like, and is increasingly used in various synthetic leather.
In the process of producing the solvent-free polyurethane synthetic leather, the surface layer still adopts water-based resin or traditional solvent-based resin, and the foaming layer adopts a solvent-free polyurethane in-situ forming process. The invention patent CN109957092A discloses a solvent-free polyurethane intermediate layer resin, a preparation method thereof and application thereof in sports and leisure shoe leather, wherein solvent-free polyurethane surface layer resin is coated on release paper through a dry normal line, and then the intermediate layer solvent-free polyurethane resin is coated until the intermediate layer solvent-free polyurethane resin is attached to base cloth in a semi-dry state to form synthetic leather. The method has high requirements on the process and equipment, and on-line regulation and control are difficult. The invention patent CN107190520B discloses a production method of flame-retardant heat-conducting type solvent-free polyurethane synthetic leather, which comprises the steps of directly scraping solvent-free polyurethane foaming slurry on release paper through a dry method, and curing the adhesive base cloth when the adhesive base cloth is in a semi-dry state to obtain the synthetic leather. This allows direct application of solvent-free polyurethane coatings to the surface of the base fabric, but there is still a need to regulate the curing time of the synthesis reaction, and there is a problem that the polyurethane penetrates into the base fabric resulting in uneven cloth cover, which also limits its application.
The synthesis of solvent-free polyurethanes is mainly carried out using polyols and isocyanates, which are mostly derived from the petrochemical industry, and polyurethanes synthesized based on bio-based materials are becoming an important point of research in order to respond to green chemical industry and to alleviate the dependence on petroleum. The polyol is taken as an important material for synthesizing polyurethane, and has larger occupation and larger influence on the performances such as flexibility, modulus and the like of polyurethane resin, so that the development of proper bio-based polyol is particularly important to be applied to solvent-free polyurethane surface layer resin and synthetic leather.
Disclosure of Invention
The invention aims to provide a bio-based solvent-free polyurethane surface layer resin for synthetic leather and a preparation method thereof, so as to solve at least one of the problems that the solvent-free polyurethane resin is excessively dependent on fossil raw materials in the synthesis process, the regulation and control of the solvent-free polyurethane leather synthesis process are difficult, and the like.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the preparation method of the bio-based solvent-free polyurethane surface layer resin for the synthetic leather comprises the following steps:
s1, preparing modified bio-based polyester polyol: adding a proper amount of diacid into castor oil under the atmosphere of protective gas, stirring and mixing uniformly, heating and reacting for a certain time, and then removing water in the polyol by bubbling and continuously introducing the protective gas, thus obtaining the modified bio-based polyester polyol;
s2, preparing wet polyurethane base cloth: immersing the base cloth into DMF water solution, taking out, ironing by an iron, putting the base cloth into DMF water solution to form a film after scraping polyurethane resin on a smooth surface, finally taking out, padding and drying to obtain wet polyurethane base cloth;
s3, preparing a bio-based solvent-free polyurethane surface layer resin: uniformly mixing liquefied diphenylmethane diisocyanate, polycarbonate diol and an antioxidant to obtain an NCO-containing end-capped prepolymer; the modified bio-based polyester polyol, the bio-based chain extender, the petroleum-based chain extender, the flame retardant, the flatting agent, the catalyst and the toner are sheared and mixed uniformly at a high speed, and then the component containing the OH end cap is obtained; uniformly mixing the NCO end-capped prepolymer and the OH end-capped component, spreading the mixture on release paper, and baking to obtain the bio-based solvent-free polyurethane surface layer resin;
s4, preparing the bio-based solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the smooth surface of the wet polyurethane base cloth, and drying to obtain the bio-based solvent-free polyurethane synthetic leather.
Preferably, the diacid in step S1 is one or more of adipic acid, oxalic acid and maleic acid; the mass ratio of the diacid to the castor oil is 3-10:100.
Preferably, the protective gas in step S1 includes nitrogen, helium or argon, and the heating reaction is performed for a period of time, specifically, for 6-10 hours at 120-200 ℃.
Preferably, in step S2:
the mass concentration of the DMF water solution is 20-50%;
the thickness of the wet polyurethane coating is 0.1-0.5 mm;
the temperature of the drying is 90-120 ℃.
Preferably, in step S3:
the polycarbonate diol comprises one or more of PCDL-1000, PCDL-1500, PCDL-2000 and PCDL-3000;
the liquefied diphenylmethane diisocyanate (MDI) includes any one of an isomer of MDI and carbodiimide-modified MDI;
the mass ratio of the liquefied MDI to the polycarbonate diol is 100:100-150.
Preferably, in step S3:
the bio-based chain extender comprises one or two of bio-based 1, 3-propanediol and palm oil;
the petroleum-based chain extender comprises one or more of ethanolamine, 1, 4-butanediol and ethylene glycol;
the flame retardant comprises one or more of modified DOPO, ammonium polyphosphate, nanometer aluminum hydroxide and aluminum oxide;
the catalyst comprises one or more of quaternary ammonium salt and organic bismuth;
the toner comprises one or two of graphite and carbon black.
The solvent-free polyurethane with excellent flame retardant property can be prepared by optimizing the formula of the flame retardant. In addition, the synthetic reaction rate can be regulated by regulating the viscosity of the prepolymer, and the film is endowed with good hand feeling and physical and mechanical properties.
Preferably, in step S3: the mass ratio of the modified bio-based polyester polyol to the bio-based chain extender to the petroleum-based chain extender to the flame retardant to the leveling agent to the catalyst to the toner is 100:15-25:20-30:50-80:1-3:0.2-1:1-5.
Preferably, in step S3: the ratio of the molar amount of-NCO in the NCO-terminated prepolymer to the molar amount of hydroxyl groups in the OH-terminated component is 0.9-1.05:1; the baking temperature is 100-130 ℃.
Preferably, in step S4: the thickness of the bio-based solvent-free polyurethane resin surface layer is 0.2-0.6 mm; the temperature of the drying is 110-150 ℃.
The invention also provides the bio-based solvent-free polyurethane surface layer resin for the synthetic leather, which is prepared by the preparation method, and the synthetic leather.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bio-based solvent-free polyurethane resin film is prepared by taking bio-based polyester polyol and a micromolecular chain extender as polyol raw materials and carrying out double-component in-situ blending polymerization. The synthetic processing has the beneficial effects that the synthetic processing can partially replace petroleum-based polyol, so that the dependence on fossil energy is reduced, the biodegradability is obviously improved, and the cost is saved. The bio-based polyester polyol also has unsaturated non-conjugated hydroxyl functional groups and more branched chains, which can improve the viscosity of the prepolymer, so that the crosslinking density of the system is improved, and the physical and mechanical properties of the solvent-free polyurethane resin film are effectively enhanced.
(2) The technology of layer-by-layer knife coating is adopted, namely the technology of sequentially knife coating wet resin and bio-based solvent-free polyurethane surface layer resin on the smooth surface of the base cloth, so that the on-line blending procedure in the conventional solvent-free polyurethane resin film synthesis process is omitted, the process is simple, and the operability is strong; meanwhile, the problems of cloth seepage and the like caused by direct coating are avoided. The base cloth treated by the wet resin has more hydrogen bond effect with the bio-based solvent-free polyurethane resin surface layer, so that the synthetic leather has higher peel strength and is not easy to delaminate.
(3) The bio-based solvent-free polyurethane surface layer resin prepared by the invention does not need an organic solvent in the production process, and the used raw material has high content of bio-renewable carbon, is an environment-friendly resin, has lower solvent residue and is an environment-friendly synthetic leather.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of bio-based solvent-free polyurethane surface layer resin for synthetic leather comprises the following steps:
(1) Preparation of modified biobased polyester polyol: oxalic acid is prepared by the following steps: adding oxalic acid into castor oil according to the mass ratio of 7:100, stirring and mixing uniformly, reacting for 6 hours at 120 ℃, then removing water in the polyol by bubbling and continuously introducing nitrogen, and stopping stirring and taking out to obtain the bio-based polyester polyol.
(2) Preparing wet polyurethane base cloth: immersing the base cloth into 40% DMF aqueous solution, taking out, ironing by an iron, spreading polyurethane resin with the thickness of 0.2 mm on a smooth surface, putting into 35 ℃ 35wt% DMF aqueous solution for film formation, finally taking out, padding, and drying at 100 ℃ to obtain the wet polyurethane base cloth.
(3) Preparing a bio-based solvent-free polyurethane surface layer resin: uniformly mixing liquefied MDI, PCDL-2000 and 2 parts of antioxidant H-07A according to the mass ratio of the liquefied MDI to the PCDL-2000 of 100:130 to obtain NCO-containing end-capped prepolymer; uniformly shearing and mixing modified bio-based polyester polyol, palm oil polyol, 1, 4-butanediol, modified DOPO, a leveling agent BYK-UV3500, an amine catalyst N, N-bis (dimethylaminopropyl) isopropanolamine and graphite at a mass ratio of 100:20:25:60:2:0.5:3 at a high speed to obtain an OH-terminated component; and shearing and mixing the NCO end-capped prepolymer and the OH end-capped component uniformly at a molar ratio of 1:1, then knife-coating the mixture on release paper, and baking the release paper at 110 ℃ to obtain the bio-based solvent-free polyurethane surface layer resin.
(4) Preparing bio-based solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the smooth surface of the wet polyurethane base cloth by using a graduated scale, wherein the thickness of the scraping surface layer is 0.4 millimeter, and drying at 130 ℃ to obtain the bio-based solvent-free polyurethane synthetic leather.
Example 2
A preparation method of bio-based solvent-free polyurethane surface layer resin for synthetic leather comprises the following steps:
(1) Preparation of modified biobased polyester polyol: maleic acid: adding maleic acid into castor oil at a mass ratio of 6:100, stirring and mixing uniformly, reacting for 6 hours at 150 ℃, then removing water in the polyol by bubbling and continuously introducing nitrogen, and stopping stirring and taking out to obtain the bio-based polyester polyol.
(2) Preparing wet polyurethane base cloth: immersing the base cloth into 40% DMF aqueous solution, taking out, ironing by an iron, spreading polyurethane resin with the thickness of 0.2 mm on a smooth surface, putting into 35 ℃ 35wt% DMF aqueous solution for film formation, finally taking out, padding, and drying at 100 ℃ to obtain the wet polyurethane base cloth.
(3) Preparing a bio-based solvent-free polyurethane surface layer resin: uniformly mixing liquefied MDI, PCDL-2000 and 2 parts of antioxidant H-07A according to the mass ratio of the liquefied MDI to the PCDL-2000 of 100:130 to obtain NCO-containing end-capped prepolymer; the preparation method comprises the steps of shearing and mixing modified bio-based polyester polyol, palm oil polyol, bio-based 1, 3-propylene glycol, 1, 4-butanediol, modified DOPO, a leveling agent BYK-UV3500, an amine catalyst N, N-bis (dimethylaminopropyl) isopropanolamine and graphite at a mass ratio of 100:3:17:25:60:2:0.5:3 uniformly, and obtaining an OH-terminated component; and shearing and mixing the NCO end-capped prepolymer and the OH end-capped component uniformly at a molar ratio of 1:1, then knife-coating the mixture on release paper, and baking the release paper at 110 ℃ to obtain the bio-based solvent-free polyurethane surface layer resin.
(4) Preparing bio-based solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the smooth surface of the wet polyurethane base cloth by using a graduated scale, wherein the thickness of the scraping surface layer is 0.4 millimeter, and drying at 130 ℃ to obtain the bio-based solvent-free polyurethane synthetic leather.
Example 3
A preparation method of bio-based solvent-free polyurethane surface layer resin for synthetic leather comprises the following steps:
(1) Preparation of modified biobased polyester polyol: under nitrogen atmosphere, adipic acid: adding adipic acid into castor oil at a mass ratio of 7.5:100, stirring and mixing uniformly, reacting for 6 hours at 160 ℃, then removing water in the polyol by bubbling and continuously introducing nitrogen, and stopping stirring and taking out to obtain the bio-based polyester polyol.
(2) Preparing wet polyurethane base cloth: immersing the base cloth into 40% DMF aqueous solution, taking out, ironing by an iron, spreading polyurethane resin with the thickness of 0.2 mm on a smooth surface, putting into 35 ℃ 35wt% DMF aqueous solution for film formation, finally taking out, padding, and drying at 100 ℃ to obtain the wet polyurethane base cloth.
(3) Preparing a bio-based solvent-free polyurethane surface layer resin: uniformly mixing liquefied MDI, PCDL-2000 and 2 parts of antioxidant H-07A according to the mass ratio of the liquefied MDI to the PCDL-2000 of 100:130 to obtain NCO-containing end-capped prepolymer; uniformly shearing and mixing modified bio-based polyester polyol, bio-based 1, 3-propylene glycol, 1, 4-butanediol, modified DOPO, a leveling agent BYK-UV3500, amine catalysts N, N-bis (dimethylaminopropyl) isopropanolamine and graphite at a mass ratio of 100:17:30:60:2:0.5:3 at high speed to obtain an OH-terminated component; and shearing and mixing the NCO end-capped prepolymer and the OH end-capped component uniformly at a molar ratio of 1:1, then knife-coating the mixture on release paper, and baking the release paper at 110 ℃ to obtain the bio-based solvent-free polyurethane surface layer resin.
(4) Preparing bio-based solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the smooth surface of the wet polyurethane base cloth by using a graduated scale, wherein the thickness of the scraping surface layer is 0.4 millimeter, and drying at 130 ℃ to obtain the bio-based solvent-free polyurethane synthetic leather.
Example 4
A preparation method of bio-based solvent-free polyurethane surface layer resin for synthetic leather comprises the following steps:
(1) Preparation of modified biobased polyester polyol: under nitrogen atmosphere, adipic acid: adding adipic acid into castor oil at a mass ratio of 7.5:100, stirring and mixing uniformly, reacting for 6 hours at 160 ℃, then removing water in the polyol by bubbling and continuously introducing nitrogen, and stopping stirring and taking out to obtain the bio-based polyester polyol.
(2) Preparing wet polyurethane base cloth: immersing the base cloth into 40% DMF aqueous solution, taking out, ironing by an iron, spreading polyurethane resin with the thickness of 0.2 mm on a smooth surface, putting into 35 ℃ 35wt% DMF aqueous solution for film formation, finally taking out, padding, and drying at 100 ℃ to obtain the wet polyurethane base cloth.
(3) Preparing a bio-based solvent-free polyurethane surface layer resin: uniformly mixing liquefied MDI, PCDL-2000 and 2 parts of antioxidant H-07A according to the mass ratio of the liquefied MDI to the PCDL-2000 of 100:130 to obtain NCO-containing end-capped prepolymer; uniformly shearing and mixing modified bio-based polyester polyol, palm oil polyol, 1, 4-butanediol, modified DOPO, a leveling agent BYK-UV3500, an amine catalyst N, N-bis (dimethylaminopropyl) isopropanolamine and graphite at a mass ratio of 100:17:30:60:2:0.5:3 at a high speed to obtain an OH-terminated component; and shearing and mixing the NCO end-capped prepolymer and the OH end-capped component uniformly at a molar ratio of 1:1, then knife-coating the mixture on release paper, and baking the release paper at 110 ℃ to obtain the bio-based solvent-free polyurethane surface layer resin.
(4) Preparing bio-based solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the smooth surface of the wet polyurethane base cloth by using a graduated scale, wherein the thickness of the scraping surface layer is 0.4 millimeter, and drying at 130 ℃ to obtain the bio-based solvent-free polyurethane synthetic leather.
Comparative example 1
A preparation method of solvent-free polyurethane surface layer resin for synthetic leather comprises the following steps:
(1) Preparing wet polyurethane base cloth: immersing the base cloth into 40% DMF aqueous solution, taking out, ironing by an iron, spreading polyurethane resin with the thickness of 0.2 mm on a smooth surface, putting into 35 ℃ 35wt% DMF aqueous solution for film formation, finally taking out, padding, and drying at 100 ℃ to obtain the wet polyurethane base cloth.
(2) Preparing solvent-free polyurethane surface layer resin: uniformly mixing liquefied MDI, PCDL-2000 and 2 parts of antioxidant H-07A according to the mass ratio of the liquefied MDI to the PCDL-2000 of 100:130 to obtain NCO-containing end-capped prepolymer; uniformly shearing and mixing PCDL-2000, 1, 4-butanediol, modified DOPO, a leveling agent BYK-UV3500, amine catalysts N, N-bis (dimethylaminopropyl) isopropanolamine and graphite at a mass ratio of 100:30:60:2:0.5:3 at high speed to obtain an OH-terminated component; and shearing and mixing the NCO end-capped prepolymer and the OH end-capped component uniformly at a molar ratio of 1:1, then knife-coating the mixture on release paper, and baking the release paper at 110 ℃ to obtain the solvent-free polyurethane surface layer resin.
(3) Preparing solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the surface of the wet polyurethane base cloth by using a graduated scale, wherein the thickness of the scraping surface layer is 0.4 mm, and drying at 130 ℃ to obtain the solvent-free polyurethane synthetic leather.
Comparative example 2
The preparation method of the solvent-free polyurethane interlayer resin for the synthetic leather comprises the following steps:
(1) Preparing solvent type polyurethane surface layer resin: the oily dry polyurethane resin with the thickness of 0.3 mm is coated on the release paper, and the solvent polyurethane surface layer resin is prepared after drying and molding in a baking oven at the temperature of 110 ℃.
(2) Preparing a solvent-free polyurethane interlayer resin: uniformly mixing liquefied MDI, PCDL-2000 and 2 parts of antioxidant H-07A according to the mass ratio of the liquefied MDI to the PCDL-2000 of 100:130 to obtain NCO-containing end-capped prepolymer; uniformly shearing and mixing PCDL-2000, 1, 4-butanediol, modified DOPO, a leveling agent BYK-UV3500 and amine catalyst N, N-bis (dimethylaminopropyl) isopropanolamine according to the mass ratio of 100:30:60:2:0.5 at high speed to obtain an OH-terminated component; and shearing and mixing the NCO end-capped prepolymer and the OH end-capped component uniformly at a molar ratio of 1:1, then knife-coating the mixture on release paper, and baking the release paper at 110 ℃ to obtain the solvent-free polyurethane layer resin.
(3) Preparing solvent-free polyurethane synthetic leather: fully mixing NCO-containing end-capped prepolymer and OH-containing end-capped component by a low-pressure casting machine, casting and coating the mixture on a solvent-type polyurethane surface layer, and pre-reacting for 60s in a baking oven at 110 ℃ to obtain a semi-finished film in a semi-dry state; and then directly attaching the base cloth on the semi-finished product film, and continuously reacting at 130 ℃ for 15min to enable the base cloth to be subjected to gel gradual solidification and molding, and separating paper and leather after cooling to obtain the solvent-free polyurethane synthetic leather.
In order to better embody the benefits of the present invention, the following performance tests were performed on the bio-based solvent-free polyurethane top resin films and synthetic leather obtained in examples 1 to 4 of the present invention and the solvent-free polyurethane resin films and synthetic leather obtained in comparative examples, and the test results are described below:
TABLE 1
Note that: the soft and hard hand feeling is detected by a soft and hard tester, and the higher the numerical value is, the softer the hand feeling is; tensile strength and elongation at break were measured by a universal tester.
TABLE 2
Note that: the test was carried out according to QB/T4197-2011 polyurethane resin for synthetic leather. The immediate peel strength was tested and after 24 hours of standing, the final peel strength was tested. The flame retardant properties of SFPU leather were tested according to the method of GB/8410-2006 combustion characteristics of automotive interior Material. The test was carried out according to QB/T4197-2011 polyurethane resin for synthetic leather.
As can be seen from the data in tables 1 and 2, the bio-based solvent-free polyurethane surface layer resin film prepared by the invention has better hand feeling than the comparative example, and the obtained synthetic leather has better flame retardance and higher peel strength. Comparative example 2 (solvent-containing facing) has significantly improved mechanical properties, hand and peel strength over comparative example 1 (solvent-free facing), while peel strength is less than in the examples and softness is similar. Compared with the solvent-free synthetic leather obtained by the conventional method, the biological-based synthetic leather synthesized by the technology has the advantages that part of performances are improved, the production requirements of the synthetic leather are met, and the biological-based synthetic leather is possible to market.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (8)
1. The preparation method of the bio-based solvent-free polyurethane synthetic leather is characterized by comprising the following steps of:
s1, preparing modified bio-based polyester polyol: adding a proper amount of diacid into castor oil under the atmosphere of protective gas, stirring and mixing uniformly, heating and reacting for a certain time, and then removing water in the polyol by bubbling and continuously introducing the protective gas, thus obtaining the modified bio-based polyester polyol; the diacid is one or more of adipic acid, oxalic acid and maleic acid, the mass ratio of the diacid to castor oil is 3-10:100, and the heating reaction is carried out for a certain time, specifically at 120-200 ℃ for 6-10 hours;
s2, preparing wet polyurethane base cloth: immersing the base cloth into DMF water solution, taking out, ironing by an iron, putting the base cloth into DMF water solution to form a film after scraping polyurethane resin on a smooth surface, finally taking out, padding and drying to obtain wet polyurethane base cloth;
s3, preparing a bio-based solvent-free polyurethane surface layer resin: uniformly mixing liquefied diphenylmethane diisocyanate, polycarbonate diol and an antioxidant to obtain an NCO-containing end-capped prepolymer; the modified bio-based polyester polyol, the bio-based chain extender, the petroleum-based chain extender, the flame retardant, the flatting agent, the catalyst and the toner are sheared and mixed uniformly at a high speed, and then the component containing the OH end cap is obtained; uniformly mixing the NCO end-capped prepolymer and the OH end-capped component, spreading the mixture on release paper, and baking to obtain the bio-based solvent-free polyurethane surface layer resin; the bio-based chain extender comprises one or two of bio-based 1, 3-propanediol and palm oil, the petroleum-based chain extender comprises one or more of ethanolamine, 1, 4-butanediol and ethylene glycol, and the ratio of the molar amount of-NCO in the NCO-terminated prepolymer to the molar amount of hydroxyl in the OH-terminated component is 0.9-1.05:1;
s4, preparing the bio-based solvent-free polyurethane synthetic leather: and (3) scraping the bio-based solvent-free polyurethane resin on the smooth surface of the wet polyurethane base cloth, and drying to obtain the bio-based solvent-free polyurethane synthetic leather.
2. The method for preparing a bio-based solvent-free polyurethane synthetic leather according to claim 1, wherein in step S2: the mass concentration of the DMF water solution is 20-50%; the thickness of the wet polyurethane coating is 0.1-0.5 mm; the temperature of the drying is 90-120 ℃.
3. The method for preparing a bio-based solvent-free polyurethane synthetic leather according to claim 1, wherein in step S3:
the polycarbonate diol comprises one or more of PCDL-1000, PCDL-1500, PCDL-2000 and PCDL-3000;
the liquefied diphenylmethane diisocyanate MDI includes any one of an isomer of MDI and carbodiimide-modified MDI;
the mass ratio of the liquefied MDI to the polycarbonate diol is 100:100-150.
4. The method for preparing a bio-based solvent-free polyurethane synthetic leather according to claim 1, wherein in step S3:
the flame retardant comprises one or more of ammonium polyphosphate, nanometer aluminum hydroxide, aluminum oxide and modified DOPO;
the catalyst comprises one or more of quaternary ammonium salt and organic bismuth;
the toner comprises one or two of graphite and carbon black.
5. The method for preparing a bio-based solvent-free polyurethane synthetic leather according to claim 1, wherein in step S3: the mass ratio of the modified bio-based polyester polyol to the bio-based chain extender to the petroleum-based chain extender to the flame retardant to the leveling agent to the catalyst to the toner is 100:15-25:20-30:50-80:1-3:0.2-1:1-5.
6. The method for preparing a bio-based solvent-free polyurethane synthetic leather according to claim 1, wherein in step S3:
the baking temperature is 100-130 ℃.
7. The method for preparing a bio-based solvent-free polyurethane synthetic leather according to claim 1, wherein in step S4:
the thickness of the bio-based solvent-free polyurethane resin surface layer is 0.2-0.6 mm;
the temperature of the drying is 110-150 ℃.
8. A bio-based solvent-free polyurethane synthetic leather, characterized in that it is produced according to the production method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211006429.2A CN115354505B (en) | 2022-08-22 | 2022-08-22 | Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211006429.2A CN115354505B (en) | 2022-08-22 | 2022-08-22 | Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115354505A CN115354505A (en) | 2022-11-18 |
| CN115354505B true CN115354505B (en) | 2024-03-08 |
Family
ID=84002056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211006429.2A Active CN115354505B (en) | 2022-08-22 | 2022-08-22 | Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115354505B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE750080A (en) * | 1969-05-07 | 1970-10-16 | Bayer Ag | ISOCYANATE PREPARATION PROCESS |
| DE2337457A1 (en) * | 1973-07-24 | 1975-02-13 | Basf Ag | APPRETURES FOR LEATHER |
| CN102995455A (en) * | 2011-09-14 | 2013-03-27 | 吴舒克 | Production process of anti-radiation PU (Poly Urethane) synthetic leather |
| CN103643533A (en) * | 2013-12-16 | 2014-03-19 | 上海华峰超纤材料股份有限公司 | Environment-friendly heat-insulating microfiber synthetic leather and preparation method thereof |
| CN104088161A (en) * | 2014-07-07 | 2014-10-08 | 旭川化学（苏州）有限公司 | Preparation method of solvent-free environment-friendly polyurethane automobile leather |
| CN105350342A (en) * | 2015-09-29 | 2016-02-24 | 安徽安利材料科技股份有限公司 | Preparation method of aqueous / solvent-free composite environmentally friendly polyurethane synthetic leather |
| CN107012692A (en) * | 2017-05-19 | 2017-08-04 | 陕西科技大学 | A kind of production method of bio-based no-solvent polyurethane synthetic leather |
| CN109021906A (en) * | 2018-06-11 | 2018-12-18 | 合肥安利聚氨酯新材料有限公司 | A kind of soccerballleather solventless polyurethane adhesive layer resin and the preparation method and application thereof |
| CN110964172A (en) * | 2019-11-06 | 2020-04-07 | 合肥科天水性科技有限责任公司 | Modified solvent-free bio-based polyurethane resin and application thereof |
| CN111732711A (en) * | 2020-07-01 | 2020-10-02 | 合肥安利聚氨酯新材料有限公司 | Preparation method and application of bio-based modified polyurethane resin |
| CN112592434A (en) * | 2020-12-15 | 2021-04-02 | 上海华峰新材料研发科技有限公司 | Bio-based aqueous photo-curing polyurethane resin and preparation method and application thereof |
| CN112851899A (en) * | 2021-01-07 | 2021-05-28 | 浙江禾欣科技有限公司 | Solvent-free polyurethane resin for high-flame-retardancy automobile leather and preparation method thereof |
-
2022
- 2022-08-22 CN CN202211006429.2A patent/CN115354505B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE750080A (en) * | 1969-05-07 | 1970-10-16 | Bayer Ag | ISOCYANATE PREPARATION PROCESS |
| DE2337457A1 (en) * | 1973-07-24 | 1975-02-13 | Basf Ag | APPRETURES FOR LEATHER |
| CN102995455A (en) * | 2011-09-14 | 2013-03-27 | 吴舒克 | Production process of anti-radiation PU (Poly Urethane) synthetic leather |
| CN103643533A (en) * | 2013-12-16 | 2014-03-19 | 上海华峰超纤材料股份有限公司 | Environment-friendly heat-insulating microfiber synthetic leather and preparation method thereof |
| CN104088161A (en) * | 2014-07-07 | 2014-10-08 | 旭川化学（苏州）有限公司 | Preparation method of solvent-free environment-friendly polyurethane automobile leather |
| CN105350342A (en) * | 2015-09-29 | 2016-02-24 | 安徽安利材料科技股份有限公司 | Preparation method of aqueous / solvent-free composite environmentally friendly polyurethane synthetic leather |
| CN107012692A (en) * | 2017-05-19 | 2017-08-04 | 陕西科技大学 | A kind of production method of bio-based no-solvent polyurethane synthetic leather |
| CN109021906A (en) * | 2018-06-11 | 2018-12-18 | 合肥安利聚氨酯新材料有限公司 | A kind of soccerballleather solventless polyurethane adhesive layer resin and the preparation method and application thereof |
| CN110964172A (en) * | 2019-11-06 | 2020-04-07 | 合肥科天水性科技有限责任公司 | Modified solvent-free bio-based polyurethane resin and application thereof |
| CN111732711A (en) * | 2020-07-01 | 2020-10-02 | 合肥安利聚氨酯新材料有限公司 | Preparation method and application of bio-based modified polyurethane resin |
| CN112592434A (en) * | 2020-12-15 | 2021-04-02 | 上海华峰新材料研发科技有限公司 | Bio-based aqueous photo-curing polyurethane resin and preparation method and application thereof |
| CN112851899A (en) * | 2021-01-07 | 2021-05-28 | 浙江禾欣科技有限公司 | Solvent-free polyurethane resin for high-flame-retardancy automobile leather and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A review of graphene based transparent conducting films for use in solar photovoltaic applications;Nurul Nazli Rosli et al.;《Renewable and Sustainable Energy Reviews》;第99卷(第2019期);83-99 * |
| 有机硅改性无溶剂聚氨酯树脂在合成革中的应用;王海峰;;安徽化工(第01期);89-93 * |
| 耐酸碱无溶剂型双组分聚氨酯自流平地坪涂料的研制;刁贵强;张绮旎;封科军;陈灵智;陈文燕;黄志润;;电镀与涂饰(第22期);27-31 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115354505A (en) | 2022-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105399921A (en) | High solid content flame retardant wet-method foaming polyurethane used for synthetic leather and preparation method and application thereof | |
| CN110835401A (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
| CN110804147A (en) | Bio-based waterborne polyurethane resin and application thereof | |
| CN114381191A (en) | Hydroxyl silicone oil modified waterborne polyurethane coating with high tensile strength and high water resistance coating film | |
| CN114736596B (en) | Quick-drying type single-component polyurethane waterproof coating and preparation method thereof | |
| CN109666122A (en) | Epoxy soybean oil modified urethanes leather finishing agent and preparation method thereof | |
| CN114085349A (en) | Silicone-modified polyurethane resin and method for producing same | |
| CN112831018B (en) | Solvent-free synthetic leather polyurethane composite material and preparation method thereof | |
| CN115354505B (en) | Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof | |
| CN116143994B (en) | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather | |
| CN116410433B (en) | Silicon-containing polyurethane resin, preparation method thereof and synthetic leather bass | |
| CN112961307B (en) | Solvent-free polyurethane resin, impregnation slurry, and preparation method and application thereof | |
| CN115716904A (en) | Organic silicon modified bio-based polyurethane, preparation method thereof and synthetic leather containing organic silicon modified bio-based polyurethane | |
| CN107236511B (en) | Polyurethane adhesive composition for shoes and preparation method thereof | |
| KR101824627B1 (en) | Non-solvent polyurethane and method for manufacturing synthetic leather of car seat using thereof | |
| CN110951028B (en) | Polyurethane resin and preparation method and application thereof | |
| CN109705310B (en) | Polyurethane resin for waterproof breathable leather and preparation method thereof | |
| CN113788925A (en) | Waterborne polyurethane resin and preparation method and application thereof | |
| CN110952335B (en) | Weather-resistant island-fixing fiber base cloth and preparation method and application thereof | |
| CN112761001A (en) | Environment-friendly space leather and preparation method and application thereof | |
| KR20130105407A (en) | Method for producing polyurethane foam seat, polyurethane foam seat and leathery sheet-shaped article | |
| TW201943753A (en) | Irreversible solvent-free polyurethane resin and artificial leather comprising the same | |
| CN113583200B (en) | Low-temperature-sensitivity aqueous polyurethane resin | |
| CN110066378B (en) | Fluorine-containing organic silicon modified polyurethane resin for clothing leather and preparation method thereof | |
| CN112940221A (en) | Polyurethane resin of soft synthetic leather for clothes and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |