CN115746688A - Powderable self-repairing flame-retardant low-VOC polyurethane coating key material and application thereof - Google Patents
Powderable self-repairing flame-retardant low-VOC polyurethane coating key material and application thereof Download PDFInfo
- Publication number
- CN115746688A CN115746688A CN202211354528.XA CN202211354528A CN115746688A CN 115746688 A CN115746688 A CN 115746688A CN 202211354528 A CN202211354528 A CN 202211354528A CN 115746688 A CN115746688 A CN 115746688A
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- Prior art keywords
- reacting
- stirring
- flame
- polyurethane
- coating
- Prior art date
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- 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 title claims abstract description 88
- 239000003063 flame retardant Substances 0.000 title claims abstract description 88
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 20
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
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- 238000000227 grinding Methods 0.000 claims description 14
- RBTCRFLJLUNCLL-UHFFFAOYSA-N (1-chloro-2-methyl-1-oxopropan-2-yl) acetate Chemical compound CC(=O)OC(C)(C)C(Cl)=O RBTCRFLJLUNCLL-UHFFFAOYSA-N 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 12
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 claims description 11
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 10
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 claims description 5
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- 239000011248 coating agent Substances 0.000 abstract description 70
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 10
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
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- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
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- 229960004889 salicylic acid Drugs 0.000 description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
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- 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 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/141—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 mixture of two or more polyurethanes in the same layer
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—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 two or more layers of polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/26—Vehicles, transportation
- D06N2211/263—Cars
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The invention discloses a preparation method and application of a powderable self-repairing flame-retardant low-VOC polyurethane coating. The powderable, self-repairing, flame-retardant and low-VOC polyurethane coating is applied to the finishing process of automobile cushion leather. The prepared polyurethane can be cured, the cured polyurethane can basically recover the original property in DEF, and simultaneously has better wear resistance and lower VOC (volatile organic Compounds), the problem of grain layer adhesion in the aging process of coating leather is solved, and the obtained automobile leather is partially self-repaired to recover the flame retardance under the conditions of abrasion or cutting.
Description
The invention relates to a division 2021114732965 filed on 12/06/2021.
Technical Field
The invention relates to a preparation and application method of a polyurethane coating, in particular to a preparation method of a powderable, self-repairing, flame-retardant and low-VOC polyurethane coating, and also relates to an application of the polyurethane coating in automobile cushion leather.
Background
The waterborne polyurethane has the advantages of safety, harmlessness and strong adhesive force, and can be widely applied to the fields of furniture, fabric coatings, automobile leather and the like. In the field of automobile leather, because most of polyurethane coating agents are liquid, the transportation difficulty of enterprises is increased, because polyurethane is cured and is not treated properly, and the original properties of the polyurethane coating agents are difficult to recover by adding water, but no powderable polyurethane coating agent exists in the current reports at home and abroad, so the improvement of the polyurethane coating agents is needed.
The invention discloses a preparation and application method of a flame-retardant wear-resistant low-VOC polyurethane coating, which is a patent granted in China with the publication number of CN112646475B, and comprises the steps of adding polyester diol, isocyanate and dibutyltin dilaurate into a reaction container, stirring at 75 to 90 ℃ for reaction to obtain a polyurethane prepolymer, adding hydrophilic chain extender dimethylolpropionic acid, a nitrogen-phosphorus intumescent flame retardant and an acetone solvent into the polyurethane prepolymer, and stirring at 70 to 90 ℃ for reaction for 1 to 2h; and adding triethylamine and water for emulsification for 20-60min, adding the substance A and epoxy-terminated polyether silicone oil, adjusting the pH to 6.5, stirring and reacting at 70-80 ℃ to obtain the flame-retardant wear-resistant low-VOC polyurethane coating, wherein the obtained polyurethane film obviously shows better flame retardance and wear resistance in the aspects of flame burning time, droplet resistance and the like, and the used polyurethane is waterborne polyurethane.
When the waterborne polyurethane is used as a coating material, the waterborne polyurethane is subjected to the actions of friction, collision, bending and the like, and the physical damages such as scratches, microcracks and the like appear on the surface of the waterborne polyurethane, so that the coating is damaged, the function of the waterborne polyurethane is lost, and the service life of the waterborne polyurethane is shortened. The self-repairing polymer material has the capability of repairing external physical damage, which is shown in that the functional function of the material is reduced, in order to prolong the service life of polyurethane, the polyurethane needs to be self-repaired, and particularly in the field of automobile leather, the automobile leather is frequently contacted with a human body and is continuously extruded, rubbed, bent and the like by the human body, so that the flame retardant property of the leather is reduced, and therefore, the repairable automobile leather is urgently needed.
The leather protein laboratory of cigarette desk university is dedicated to the research and development of automobile leather and matched chemical materials thereof for a long time, the Chinese invention patent with the patent number of CN201910405405.6 relates to a manufacturing process of antifouling, ultralow total carbon emission and abrasion-resistant cowhide automobile cushion leather, and the primary coating comprises water-based pigment paste, light-resistant coating, light-resistant acrylate resin coating, light-resistant waterborne polyurethane, flame-retardant coating and cationic oil; the intermediate coating comprises delustering polyurethane, bright polyurethane, a cross-linking agent, a material, wear-resistant polyurethane, carbodiimide, PTFE emulsion and a smoke inhibiting material; the top coat includes a hand feel agent and a cationic oil. The prepared cowhide automobile cushion leather further improves antifouling and wear-resisting performances and reduces total carbon emission on the basis of keeping flame retardance, light resistance and low atomization. Because the automobile leather is in close contact with people, the coating of the automobile leather is easy to fall off along with the long-term abrasion of the human body, and the standards of the existing automobile manufacturers for the automobile leather are different, so the abrasion resistance of the automobile leather needs to be further improved.
The market demand for leather for automobiles is very large, and with the prosperity of the automobile market, the business opportunity of automobile leather making is concerned by more and more leather enterprises.
In the use process of the automobile seat cushion, the small molecular compounds in the leather migrate to release special odor, and the released gas contains compounds such as formaldehyde, acetaldehyde, benzene, toluene and the like, so that the odor of the automobile leather needs to be reduced.
In leather processing, the grain side is arranged opposite to the grain side in an aging process, and the flesh side is arranged opposite to the flesh side, but after the last process is finished, the cohesiveness of the grain side of the leather is enhanced, the grain side and the grain side coating are mutually adhered in the arrangement process, and the problems of partial coating falling off or inconsistent color can be caused in separation.
In conclusion, it is necessary to research a relatively outstanding powderable, self-repairing, flame-retardant and low-VOC polyurethane coating, and to improve the defect that the flame retardant performance of automobile leather is reduced after the automobile leather is worn for a long time when the coating is used in the processing of the automobile leather.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a powderable self-repairing flame-retardant low-VOC polyurethane coating
The prepared polyurethane can be cured, and can basically recover the original property in DEF after being cured, and meanwhile, the polyurethane also has better wear-resisting property and lower VOC, solves the problem of grain layer adhesion in the process of coating leather and aging, and partially self-repairs the obtained automobile leather under the condition of abrasion or cutting to recover the flame retardance.
The technical scheme of the invention is as follows:
the preparation steps of the powderable polyurethane coating A and the self-repairing flame-retardant low-VOC polyurethane coating B are respectively as follows:
adding 18.6g of polytetrahydrofuran ether glycol and 11.8g of diisocyanate into a reaction vessel under the protection of nitrogen, heating the temperature of the system to 70-80 ℃, adding 0.24-0.31g of dibutyltin dilaurate, stirring for reaction for 2-4 h, adding 0.4-3.2 g of a chain extender into the system, and reacting for 2-3 h; cooling to 50 to 70 ℃, and adding 15 to 30mL of a viscosity reducer N, N-diethylformamide DEF; cooling to 40 ℃, adding 1.7 to 2.5g of triethylamine, reacting for 0.5 to 1h, adding 7 to 8g of bentonite, 1 to 2g of nano calcium carbonate and 1.6 to 2.4g of 4, 4-dinitrodiphenyl ether, and stirring at 60 to 70 ℃ for reacting for 1 to 2h to obtain viscous liquid; vacuum drying for 4h, grinding, sealing and storing to obtain the polyurethane coating A capable of being powdered;
adding 65 to 75mL of deionized water, 12 to 17g of epoxy resin E51, 0.9g of trimethylolpropane trimethacrylate and 1.4g of 3,4' -diaminodiphenyl ether into 1.7 to 4.3g of nitrogen-phosphorus intumescent flame retardant, stirring and reacting at 65 to 75 ℃ for 60 to 90min, and obtaining the repair flame-retardant low-VOC polyurethane coating B.
The diisocyanate is any one of 4,4' -diphenylmethane diisocyanate, isophorone diisocyanate and toluene diisocyanate.
The chain extender is any one of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 30-60min, raising the temperature of the system to 90-130 ℃, and reacting for 1-5h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45-50 ℃, keeping the temperature, stirring for 30-60 min, cooling to room temperature, dropwise adding 12.2 g of ethanolamine within 30-60min, and continuously reacting for 1-2 h to obtain a flame retardant intermediate A;
(2) Stirring 6.2-8.4 g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70-90 ℃ for reaction for 1-3h, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.5-3.6 g (KH 550) of 3-aminopropyltriethoxysilane into a reaction vessel, and stirring for reaction for 1-7h at 70-110 ℃ to obtain an intermediate B;
(3) Taking 4.2-8.6 g of the flame retardant intermediate A in the step (1), the intermediate B in the step (2) and sodium lignosulfonate, reacting at 60-70 ℃ for 1-2h under stirring, then adding 1.2-1.7 g of butyric anhydride and 0.6-1.2 g of 2, 4-dihydroxybenzaldehyde, reacting at 70-80 ℃ for 1-3h, then adding 0.5-1.2 g of ethylenediamine tetraacetic acid, 0.2-0.4 g of 4-carboxyphenylboronic acid and 0.1-0.4 g of 2-acetoxyisobutyryl chloride, and reacting at 70-80 ℃ for 2-3h to obtain the nitrogen-phosphorus intumescent flame retardant.
The finishing procedure comprises three times of primary coating, two times of intermediate coating and one time of top coating; the coating is carried out by roll coating, the roll coating temperature is 101 to 105 ℃, and the components of each layer of coating are as follows:
(a) The primer coating comprises the following components in parts by weight: 0.7 to 2.5 parts of water-based pigment paste, 32 parts of water and 0.2 to 0.5 part of cationic oil;
(b) The weight parts of the middle coating are as follows: 30 parts of water at the temperature of 40-50 ℃, 20-70 parts of extinction polyurethane, 7-18 parts of bright polyurethane, 2-4 parts of a cross-linking agent, 6-8 parts of a polyurethane coating which can be powdered, self-repairing and flame-retardant and has low VOC, 0.3-0.6 part of carbodiimide, 1.4-2.8 parts of a film forming accelerator, 0.1 part of trimethylolpropane, 0.1-0.2 part of vinyl trimethoxy silane and 0.05 part of p-phenylenediamine;
(c) The top coating comprises the following components in parts by weight: 16 parts of water, 1.6 to 2.1 parts of anti-bonding material, 5 to 7 parts of hand feeling agent and 0.2 to 0.3 part of cationic oil.
The preparation method of the anti-bonding material in the components used by the top coating comprises the following steps: adding 6 to 9 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 1 to 2h at 50 to 60 ℃, drying, adding 2.1 to 3.8 parts of phenylphosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1h at 60 to 65 ℃, distilling and removing the residual benzene, and drying the residue to obtain the anti-sticking material.
The preparation method of the film forming accelerant in the components used in the top coating comprises the following steps: 6g of polyethyleneimine and 8.2 to 9.4g of 2-acetoxyisobutyryl chloride are stirred and reacted for 1 to 2h at 50 to 60 ℃, then 1.1 to 1.4g of salicylic acid and 1.1 to 2.3g of semicarbazide are added, and the reaction is carried out at 50 to 70 ℃ for 30 to 90min to obtain the film forming accelerant.
The invention has the positive effects that:
(1) According to the invention, polytetrahydrofuran ether glycol and diisocyanate are used as a reaction catalyst, after triethylamine end capping treatment, nano calcium carbonate is loaded or dispersed in waterborne polyurethane under the synergistic assistance of 4, 4-dinitrodiphenyl ether, and the obtained material is intercalated in a space layer of montmorillonite, so that the possibility that different molecular chain polyurethane potentially polymerizes to form branched or reticular polyurethane under the close contact condition is prevented, the possibility of polymerization reaction after subsequent vacuum drying is reduced, the cured polyurethane, a flame retardant and a self-repairing material B are separately stored, the polyurethane transportation and the performance stability are facilitated, and the cured polyurethane basically recovers to the original properties under the DEF and stirring effects.
(2) Phosphoric acid is used as an acid source, pentaerythritol is used as a carbon source, and pentaerythritol phosphate is synthesized through an esterification reaction. Wherein the carbon source is heated to generate carbide to form the basis of a carbon layer; the acid source is heated to decompose, and the resultant can promote the dehydration of organic matter into charcoal. Adding POCl on the basis 3 An acid source in a supplementary system is added, ethanolamine is added as a gas source, the gas source is heated to generate non-combustible and flame-retardant gas which is distributed in the carbon layer to promote the carbon layer to foam, the distance between the heat source and the base material is increased, and the mass transfer and heat transfer effects during combustion are reduced, so that the better flame retardant property is achieved, and the synergistic effect of nitrogen and phosphorus is achieved; then boric acid is used as an acid source, tetrakis hydroxymethyl phosphonium sulfate is used as an acid source and a carbon source, a cage-shaped compound containing hydroxyl is synthesized under the catalysis of concentrated sulfuric acid, 3-aminopropyl triethoxysilane is used for reacting with the cage-shaped compound containing hydroxyl, silicon base is introduced, the synthesized intermediate B has both cage-shaped rigidity and an ethoxy side chain, and the mesomeric degree is improvedThe strength of the intermediate and the coordinated flame retardance of boron, phosphorus and silicon are achieved; the preparation method comprises the following steps of reacting a flame-retardant intermediate A with an intermediate B, wherein hydroxyl of the flame-retardant intermediate A reacts with hydroxyl on boron when heated, reacting and grafting the intermediate A and the intermediate B, dispersing a product obtained by the reaction on sodium lignosulfonate with a three-dimensional network space structure of polyphenols (chemical industry limited company of the Ministry of China) which is formed by connecting C-C bonds and C-O-C bonds in an equal form, uniformly dispersing the product, opening the chain of butyric anhydride by adopting butyric anhydride and unreacted hydroxyl in the product, reacting 2, 4-dihydroxybenzaldehyde with hydroxyl obtained by opening the ring, introducing carboxyl and aldehyde groups into the system, reacting ethylene diamine tetraacetic acid with the hydroxyl of the system, introducing carboxyl and increasing the rigidity of the system, reacting 4-carboxyphenylboronic acid and 2-acetoxyisobutyryl chloride with the hydroxyl and amino (imine) of the system, and enabling the obtained flame retardant to have a large amount of hydroxyl, carboxyl, aldehyde and imine, so that the subsequent flame-retardant lignin is conveniently dispersed in a three-dimensional structure of the flame-retardant system, facilitating the formation of a structural carbon layer, forming a compact flame-retardant carbon layer which is difficult to be coated in a compact and release a heat-insulating carbon layer in a short-release synergistic effect, and releasing nitrogen and phosphorus are difficult to simultaneously.
(3) The invention utilizes the interpenetrating of polyurethane and epoxy resin polymers to form an interlaced network polymer, wherein the epoxy resin participates in dispersing among polyurethane macromolecules, and performs the functions of intersecting and mutual cooperation. Epoxy resin and polyurethane are mutually intertwined to refine different structures, the intertwining among networks can obviously improve the dispersibility of the polyurethane and improve the property of the polyurethane, particularly under the action of the polyurethane on epoxy resin E51 (Jinan Yunbaihui Biotech Co., ltd.), polyurethane molecular chains and epoxy resin E51 molecular chains are mutually interlaced, and trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether are used for realizing the uniform chain distribution of the polyurethane and the epoxy resin without being intertwined too tightly due to the multi-branched chains and the large steric hindrance of the trimethylolpropane trimethacrylate and the 3,4' -diaminodiphenyl ether, so that the polyurethane and the epoxy resin can be repaired in time after being partially damaged, and simultaneously, the dispersibility of the trimethylolpropane trimethacrylate and the 3,4' -diaminodiphenyl ether is improved due to the poor dispersibility of the N, N-diethylformamide DEF compared with acetone and DMF on the polyurethane.
(4) In the film forming process, in order to accelerate the film forming of polyurethane, DEF, toluene and water molecules are required to be capable of volatilizing rapidly or releasing slowly subsequently, and polyethyleneimine is adopted to react with 2-acetoxyisobutyryl chloride. Although polyethyleneimine is a curing agent in the field, the effect is not particularly ideal in the aspect of polyurethane preparation, the imine of polyethyleneimine is reacted with the acyl chloride of 2-acetoxyisobutyryl chloride, semicarbazide is added to react with the residual acyl chloride, and the obtained compound is reacted with the hydroxyl and carboxyl of polyurethane in the polyurethane film forming process to accelerate the release of VOC. The amino can also react with the carbonyl of acetone, and particularly, the VOC release of polyurethane can be improved in a film-forming heating environment (such as drying in a drying tunnel in leather coating and finishing).
(5) The polyethyleneimine reacts with imine of 2-acetoxy isobutyryl chloride and acyl chloride, salicylic acid and semicarbazide are introduced, so that the film forming property of polyurethane is improved, and the wear resistance of the polyurethane is improved; reacting trifluoroacetamide with 1, 2-benzenediol in a water system, reacting amino of amide with phenolic hydroxyl, and performing modification reaction with phenyl phosphoryl dichloride in a benzene system to obtain the anti-sticking agent for sticking a deposited coating.
Detailed Description
The present invention is further illustrated by the following examples.
Example one
1. The polyurethane coating which can be powdered, self-repaired, flame-retardant and low in VOC is prepared according to the following steps:
(1) Adding 18.6g of polytetrahydrofuran ether glycol (with the molecular weight of 1000 g/mol) and 11.8g of 4,4' -diphenylmethane diisocyanate into a three-neck flask under the protection of nitrogen, raising the temperature of the system to 70 ℃, adding 0.24g of dibutyltin dilaurate, stirring for reaction for 2 hours, adding 0.4g of 2, 2-dimethylolpropionic acid, and reacting for 2 hours; cooling to 50 ℃, and adding 15mL of a viscosity reducer N, N-diethylformamide DEF; cooling to 40 ℃, adding 1.7g of triethylamine for reaction for 0.5h, adding 7g of bentonite, 1g of nano calcium carbonate and 1.6g of 4, 4-dinitrodiphenyl ether, and stirring at 60 ℃ for reaction for 1h to obtain viscous liquid; vacuum drying for 4h, grinding, sealing and storing to obtain the polyurethane coating A capable of being powdered;
(2) Self-repairing flame-retardant low-VOC polyurethane coating B: 65mL of deionized water, 12g of epoxy resin E51, 0.9g of trimethylolpropane trimethacrylate and 1.4g of 3,4' -diaminodiphenyl ether are added into 1.7g of the nitrogen-phosphorus intumescent flame retardant, and the mixture is stirred and reacted for 60min at the temperature of 65 ℃, so that the repair flame-retardant low-VOC polyurethane coating B is obtained.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 30min, raising the temperature of the system to 90 ℃, and reacting for 1h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45 ℃, keeping the temperature, stirring for 30min, cooling to room temperature, dropwise adding 12.2 g of ethanolamine within 30min, and continuously reacting for 1h to obtain a flame retardant intermediate A;
(2) Stirring 6.2g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70 ℃ for reaction for 1 hour, adding a sodium hydroxide solution (the mass fraction is 20%, the same applies below) to adjust the pH value to 6.0, adding 2.5g (KH 550) of 3-aminopropyltriethoxysilane into a reaction vessel, and stirring at 70 ℃ for reaction for 1 hour to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 4.2g of sodium lignosulfonate, stirring at 60 ℃ for reaction for 1h, adding 1.2g of butyric anhydride and 0.6g of 2, 4-dihydroxybenzaldehyde, reacting at 70 ℃ for 1h, adding 0.5g of ethylenediamine tetraacetic acid, 0.2g of 4-carboxyphenylboronic acid and 0.1g of 2-acetoxyisobutyryl chloride, and reacting at 70 ℃ for 2h to obtain the nitrogen-phosphorus intumescent flame retardant.
2. The following are examples of applications
Hanging, drying and dampening: carrying out a conventional process; (2021.06.15 Kraft automobile cushion leather of Henningson leather Co., ltd.)
Hanging, drying and dampening the cushion leather blank according to the factory process
The coating process comprises base coating, middle coating and top coating which are sequentially carried out, wherein the coating is roll coating, the roll coating temperature is 101 ℃, the base coating is roll-coated for three times, the middle coating is roll-coated for two times, and the top coating is roll-coated for one time, and each layer of coating comprises the following coating materials:
(a) The base coating comprises the following components in parts by weight: 0.7 part of aqueous pigment paste NEOSAN 2000 (Clainen chemical Co., ltd.), 32 parts of water, 0.2 part of cationic oil Euderm oil KWO-C0.4 part (cation, langsheng chemical);
(b) The middle coating comprises the following components in parts by weight: 30 parts of water at 40 ℃,20 parts of extinction polyurethane MATT 200 (polymer material Co., ltd., wenzhou State national Shibang), 7 parts of bright polyurethane HPV-C (Cyte Co., U.S.) and 2 parts of cross-linking agent XL-701 (Starer Co., U.S.), 6 parts of powderable, self-repairing and flame-retardant low-VOC polyurethane coating, 0.3 part of carbodiimide, 1.4 parts of film-forming accelerant, 0.1 part of trimethylolpropane, 0.1 part of vinyl trimethoxy silane and 0.05 part of p-phenylenediamine;
the polyurethane coating capable of being powdered, self-repaired, flame-retardant and low-VOC is prepared by stirring 100g of polyurethane coating A capable of being powdered and 18g of N, N-diethylformamide and 180g of polyurethane coating B capable of being self-repaired, flame-retardant and low-VOC at 40 ℃ for reaction for 1 hour, standing and layering for 2 hours, fully precipitating nano calcium carbonate and bentonite to obtain filtrate, and obtaining the polyurethane coating capable of being powdered, self-repaired, flame-retardant and low-VOC; the parts can be equal to g, and can also be properly adjusted according to the proportion;
the preparation method of the film forming accelerant comprises the following steps: 6g of polyethyleneimine and 8.2g of 2-acetoxyisobutyryl chloride are stirred to react for 1 hour at 50 ℃, 1.1g of salicylic acid and 1.1g of semicarbazide are added to react for 30 minutes at 50 ℃, and the film forming promoter is obtained.
(c) The top coating comprises the following components in parts by weight: 16 parts of water, 1.6 parts of an anti-bonding material, 5 parts of a hand feeling agent 2229W (Shandong Chunze commercial Co., ltd.) and 0.2 part of cationic oil Euderm oil KWO-C (cation, langsheng chemical);
the preparation method of the anti-bonding material comprises the following steps: adding 6 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 1 hour at 50 ℃, drying, adding 2.1 parts of phenyl phosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1 hour at 60 ℃, distilling and removing residual benzene, and drying the residual to obtain the anti-bonding material.
Example two
1. The self-repairing flame-retardant low-VOC polyurethane coating capable of being powdered is prepared according to the following steps:
(1) Adding 18.6g of polytetrahydrofuran ether glycol and 11.8g of isophorone diisocyanate into a reaction vessel protected by nitrogen, heating the system to 80 ℃, adding 0.31g of dibutyltin dilaurate, stirring for reaction for 4 hours, adding 3.2g of 2, 2-dimethylolbutyric acid into the system, and reacting for 3 hours; cooling to 70 ℃, and adding 30mL of a thickening agent N, N-diethylformamide DEF; cooling to 40 ℃, adding 2.5g of triethylamine, reacting for 1h, adding 8g of bentonite, 2g of nano calcium carbonate and 2.4g of 4, 4-dinitrodiphenyl ether, and stirring at 70 ℃ for reacting for 2h to obtain viscous liquid; vacuum drying for 4h, grinding, sealing and storing to obtain the polyurethane coating A capable of being powdered;
(2) Self-repairing flame-retardant low-VOC polyurethane coating B: 75mL of deionized water, 17g of epoxy resin E51, 0.9g of trimethylolpropane trimethacrylate and 1.4g of 3,4' -diaminodiphenyl ether are added into 4.3g of the nitrogen-phosphorus intumescent flame retardant, and the mixture is stirred and reacted for 90min at 75 ℃ to obtain the repair flame-retardant low-VOC polyurethane coating B.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 60min, raising the temperature of the system to 130 ℃, and reacting for 5h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, keeping the temperature, stirring for 60min, cooling to room temperature, dropwise adding 12.2 g of ethanolamine within 60min, and continuously reacting for 2h to obtain a flame retardant intermediate A;
(2) Stirring 8.4g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 90 ℃ for reaction for 3 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 3.6g (KH 550) of 3-aminopropyltriethoxysilane into a reaction vessel, and stirring at 110 ℃ for reaction for 7 hours to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 8.6g of sodium lignosulfonate, stirring at 70 ℃ for reacting for 2 hours, adding 1.7g of butyric anhydride and 1.2g of 2, 4-dihydroxybenzaldehyde, reacting at 80 ℃ for 3 hours, adding 1.2g of ethylenediamine tetraacetic acid, 0.4g of 4-carboxyphenylboronic acid and 0.4g of 2-acetoxyisobutyryl chloride, and reacting at 80 ℃ for 3 hours to obtain the nitrogen-phosphorus intumescent flame retardant.
2. The following are examples of applications
(2021.06.15 cow leather cushion leather embryo of Henningson leather Co., ltd. For automobile seat cushion leather, hanging, drying, and damping were carried out according to the process of Henningson leather Co., ltd. And also belonging to the conventional process in this field)
The coating process comprises the following steps of base coating, intermediate coating and top coating in sequence, wherein the coating is roll coating, the roll coating temperature is 105 ℃, the base coating is roll-rolled for three times, the intermediate coating is roll-rolled for two times, and the top coating is roll-rolled for one time, and each layer of coating comprises the following components:
(a) The base coating comprises the following components in parts by weight: 2.5 parts of aqueous pigment paste NEOSAN 2000 (Clainen chemical Co., ltd.), 32 parts of water and 0.5 part of cationic oil Euderm oil KWO-C (cationic, langsheng chemical);
(b) The middle coating comprises the following components in parts by weight: 30 parts of 50 ℃ water, 70 parts of extinction polyurethane MATT 200 (Wenzhou national Shibang high polymer material Co., ltd.), 18 parts of bright polyurethane HPV-C (Cyte corporation, cyst, USA), 4 parts of cross-linking agent XL-701 (Starer, USA), 8 parts of powderable, self-repairing and flame-retardant low-VOC polyurethane coating, 0.6 part of carbodiimide, 2.8 parts of film-forming accelerator, 0.1 part of trimethylolpropane, 0.2 part of vinyl trimethoxy silane and 0.05 part of p-phenylenediamine;
the polyurethane coating capable of being powdered, self-repairing, flame-retardant and low-VOC is prepared by stirring 100g of polyurethane coating A capable of being powdered, 25g of N, N-diethylformamide and 200g of self-repairing, flame-retardant and low-VOC polyurethane coating B at 50 ℃ for 2 hours, standing and layering for 2 hours, fully precipitating nano calcium carbonate and bentonite to obtain filtrate, and thus obtaining the polyurethane coating capable of being powdered, self-repairing, flame-retardant and low-VOC; the parts can be equal to g, and can also be properly adjusted according to the proportion;
(c) The top coating comprises the following components in parts by weight: 16 parts of water, 2.1 parts of an anti-bonding material, 7 parts of a hand feeling agent 2229W (Shandong and Sichuan commercial Co., ltd.) and 0.3 part of Euderm oil KWO-C (cation, langsheng chemical) of cationic oil;
the preparation method of the anti-bonding material comprises the following steps: adding 9 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 2 hours at the temperature of 60 ℃, drying, adding 3.8 parts of phenyl phosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1 hour at the temperature of 65 ℃, distilling and removing residual benzene, and drying the residual to obtain the anti-bonding material.
The preparation method of the film forming accelerant comprises the following steps: 6g of polyethyleneimine and 9.4g of 2-acetoxyisobutyryl chloride are stirred to react for 2 hours at the temperature of 60 ℃, 1.4g of salicylic acid is added, 2.3g of semicarbazide is added, and the reaction is carried out for 90 minutes at the temperature of 70 ℃ to obtain the film forming promoter.
Example three
1. The polyurethane coating which can be powdered, self-repaired, flame-retardant and low in VOC is prepared according to the following steps:
(1) Adding 18.6g of polytetrahydrofuran ether glycol and 11.8g of toluene diisocyanate into a reaction vessel protected by nitrogen, raising the temperature of the system to 75 ℃, adding 0.27g of dibutyltin dilaurate, stirring for reacting for 3 hours, adding 1.8g of 2, 2-dimethylolpropionic acid into the system, and reacting for 2.5 hours; cooling to 60 ℃, and adding 22.5mL of a viscosity reducer N, N-diethylformamide DEF; cooling to 40 ℃, adding 2.1g of triethylamine, reacting for 45min, adding 7.5g of bentonite, 1.5g of nano calcium carbonate and 2.0g of 4, 4-dinitrodiphenyl ether, and stirring at 65 ℃ for reacting for 1.5h to obtain viscous liquid; vacuum drying for 4h, grinding, sealing and storing to obtain the polyurethane coating A capable of being powdered;
(2) Self-repairing flame-retardant low-VOC polyurethane coating B: 70mL of deionized water, 14.5g of epoxy resin E51, 0.9g of trimethylolpropane trimethacrylate and 1.4g of 3,4' -diaminodiphenyl ether are added into 3.0g of nitrogen-phosphorus intumescent flame retardant, and the mixture is stirred and reacted for 75min at 70 ℃, so that the repair flame-retardant low-VOC polyurethane coating B is obtained.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 45min, raising the temperature of the system to 110 ℃, and reacting for 3h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45 ℃, keeping the temperature, stirring for 45min, cooling to room temperature, dropwise adding 12.2 g of ethanolamine within 45min, and continuously reacting for 1.5h to obtain a flame retardant intermediate A;
(2) Stirring 7.3 g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 80 ℃ for reaction for 2 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 3.0g (KH 550) of 3-aminopropyltriethoxysilane into a reaction vessel, and stirring at 90 ℃ for reaction for 4 hours to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 6.4g of sodium lignosulfonate, stirring and reacting for 1.5h at 65 ℃, then adding 1.45g of butyric anhydride and 0.9g of 2, 4-dihydroxybenzaldehyde, reacting for 2h at 75 ℃, then adding 0.8g of ethylenediamine tetraacetic acid, 0.3g of 4-carboxyphenylboronic acid and 0.25g of 2-acetoxyisobutyryl chloride, and reacting for 2.5h at 75 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
2. The following are examples of applications
The coating process comprises the following steps of base coating, middle coating and top coating in sequence, wherein the coating is roll coating, the roll coating temperature is 103 ℃, the base coating is roll-coated for three times, the middle coating is roll-coated for two times, and the top coating is roll-coated for one time, and the coating materials of each layer are as follows:
(a) The base coating comprises the following components in parts by weight: 1.6 parts of aqueous pigment paste NEOSAN 2000 (Clainen chemical Co., ltd.), 32 parts of water and 0.35 part of cationic oil Euderm oil KWO-C (cationic, langsheng chemical);
(b) The middle coating comprises the following components in parts by weight: 30 parts of water at the temperature of 45 ℃,45 parts of mat polyurethane MATT 200 (Wenzhou national Shibang high polymer material Co., ltd.), 12.5 parts of bright polyurethane HPV-C (Cyte corporation, cyst), 3 parts of cross-linking agent XL-701 (Starter, USA), 7 parts of polyurethane coating which can be powdered, self-repaired and flame-retardant and has low VOC, 0.45 part of carbodiimide, 2.1 parts of film forming accelerant, 0.1 part of trimethylolpropane, 0.15 part of vinyl trimethoxy silane and 0.05 part of p-phenylenediamine;
the polyurethane coating capable of being powdered, self-repaired, flame-retardant and low-VOC is prepared by stirring 100g of polyurethane coating A capable of being powdered, 22g of N, N-diethylformamide and 190g of self-repaired, flame-retardant and low-VOC polyurethane coating B at 45 ℃ for reaction for 1.5h, standing and layering for 2h, fully precipitating nano calcium carbonate and bentonite to obtain filtrate, and obtaining the polyurethane coating capable of being powdered, self-repaired, flame-retardant and low-VOC; the parts can be equal to g, and can also be properly adjusted according to the proportion;
the preparation method of the film forming accelerant comprises the following steps: reacting polyethyleneimine 6g and 2-acetoxyisobutyryl chloride 8.7g at 55 deg.C under stirring for 1.5h, adding salicylic acid 1.25g, adding semicarbazide 1.7g, and reacting at 60 deg.C for 60min to obtain film forming promoter.
(c) The top coating comprises the following components in parts by weight: 16 parts of water, 1.8 parts of an anti-bonding material, 6 parts of a hand feeling agent 2229W (Shandong Chuan Shanghai commercial Co., ltd.) and 0.25 part of Euderm oil KWO-C (cation, langsheng chemical) of cationic oil;
the preparation method of the anti-bonding material comprises the following steps: adding 7.5 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 1.5h at 55 ℃, drying, adding 3.0 parts of phenylphosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1h at 60 ℃, distilling and removing the residual benzene, and drying the residual to obtain the anti-bonding material.
Performance testing of polyurethane films:
GB/T5455-1997 textile burning performance test the flame burning time (afterflame time) of a film formed by the polyurethane coating is measured by a vertical method, the length of the sample is 20cm multiplied by 10cm, and the thickness is 1mm.
The VOC determination method comprises the following steps: the metal plate was baked in an oven at 105. + -. 2 ℃ for 30min and then placed in a desiccator until use. After polyurethane is mixed, the mixture is spread on a metal flat-bottom dish, placed for 24 hours under the conditions that the temperature is 23 +/-2 ℃ and the humidity is 50 +/-5 percent, and then dried in an oven at the temperature of 105 +/-2 ℃ for 60 minutes, and two tests are carried out in parallel. Weighing m before heating 1 (Metal Container m) 0 And sum of mass of reactants) and mass m after heating 2 (see 201710902448.6);
TABLE 1 curing of polyurethane coatings (step 1 preparation of polyurethane)
| Example one | Example two | Example three | |
| Curing conditions | Can be cured | Can be cured | Can be cured |
From table 1 (powderable polyurethane coating a) it can be seen that the polyurethane treated material can be cured as observed by experimental phenomena, the curing being seen visually.
TABLE 2 curing of polyurethane coatings (step 1 preparation of polyurethane)
The non-added bentonite, nano calcium carbonate and 4, 4-dinitrodiphenyl ether are experimental data obtained by adding DEF (stirring) to dissolve a solid in the process (8 g of cured polyurethane to calculate the amount of DEF required for normal temperature) for powdering the polyurethane coating a in the step (1), and the curing effect is determined according to the recovery amount of the solvent.
The process of the comparative example: adding 18.6g of polytetrahydrofuran ether glycol and 11.8g of toluene diisocyanate into a reaction vessel under the protection of nitrogen, heating the temperature of the system to 75 ℃, adding 0.27g of dibutyltin dilaurate, stirring for reaction for 3 hours, adding 1.8g of 2, 2-dimethylolpropionic acid into the system, and reacting for 2.5 hours; cooling to 60 ℃, and adding DEF22.5mL of a thickening agent N, N-diethylformamide; then cooling to 40 ℃, adding 2.1g of triethylamine, reacting for 0.5h, drying in vacuum, grinding, sealing and storing.
The chemical materials of unspecified factories related to the embodiment of the invention can be replaced by similar products of leather Limited company of the shinning industry of the eagle, and the wet heat stability is referred to as GBT 4689.8-1984, QB/T3812.5-1999 to measure the tensile strength and the maximum elongation at break, the dry friction color fastness, the wet friction color fastness, the coating adhesion fastness, the leather atomization performance, the leather wear resistance and the light resistance, see Shu from Zhengshanghan and Sunjuan (leather analysis and inspection technology, published in 2005 for 6 months); the dry heat shrinkage temperature is shown in Liujie, tang Ke Yong, china leather in the journal, 9 months 2001, oxygen index, vertical combustion method and smoke density, and can be tested by referring to the academic papers published in the Seeboang series or (Seeboang and the like, the influence of phosphorus flame retardant on the flame retardant property of leather [ J ], china leather, 8 months 2012 and TS-INT-002-2008 on-vehicle materials and parts total carbon emission determination method), and other tests can be carried out by referring to the light industry standard or the detection method of automobiles if the standards are unclear or not clear, or the test technology can be referred to the leather analysis and inspection technology published in 6 months 2005.
And (3) self-repairing flame-retardant test of leather: self-repairing of 1 cut A test sample is taken, the thickness of the test sample is 1.2cm, the depth of each 1cm part of the test sample is cut by a blade to be 0.02cm, a cut is dyed, the test sample is dried for 1 hour at 80 ℃ (an oven), and the test sample is tested after the repair effect is achieved (called 'cut' for short).
2, wear self-repairing: taking a test sample with the thickness of 1.2cm, carrying out 50 times of abrasion according to GB/T22374-2018, 100g/100r and the abrasion resistance performance, and drying for 1h at 80 ℃ (an oven) to test after the repairing effect is achieved (called grinding for short).
The powderable, self-repairing, flame-retardant and low-VOC polyurethane coating prepared according to the embodiment of the invention and the applied automobile leather and the existing similar automobile cushion leather are respectively detected, and the detection data are shown in Table 1.
TABLE 3 test data of automobile cushion leather manufacturing process
| Item | Example one | Example two | Example three | Comparative example automobile cushion leather detection result |
| Moist Heat stability/. Degree.C | 95 | 95 | 96 | 95 |
| Tensile strength/MPa | 17.5 | 17.6 | 17.8 | 17.2 |
| Maximum elongation at break/%) | 47 | 46 | 49 | 46 |
| Dry rub colour fastness/grade | 4.5 | 4.5 | 4.5 | 4.5 |
| Wet rub colour fastness/grade | 4.5 | 4.5 | 4.5 | 4.5 |
| Coating adhesion fastness/(N/10 mm) | 8.3 | 9.2 | 8.8 | 7.6 |
| Dry heatShrinkage temperature/. Degree.C | 170 | 170 | 170 | 162 |
| Light resistance/grade | 4.5 | 4.5 | 4.5 | 4.5 |
| Atomization value/mg | 2.1 | 2.7 | 2.3 | 2.8 |
| Oxygen index/% | 33.2 | 33.8 | 32.8 | 32.6 |
| Duration of continuous combustion/s | 1.2 | 1.1 | 1.8 | 2 |
| Smoldering time/s | 0.1 | 0.1 | Direct extinguishing | 0.2 |
| Tobacco density/% | 11.1 | 10.8 | 10.5 | 11.6 |
| Ultra low total carbon emission/. Mu.gC/g | 29.31 | 28.35 | 28.99 | 29.69 |
| Abrasion resistance (CS-10, 1000g,500 times) | No obvious damage and peeling | No obvious damage and peeling | Has no obvious damage and peeling | No obvious damage and peeling |
| Coating non-tackiness (%) | 98.3 | 97.8 | 98.0 | 97.6 |
Comparative example 202011643278, in which the VOCs are expressed as ultra low total carbon emissions, was used to determine the probability of grain adhesion from 100 pieces of cowhide upholstery leather using 3 skilled finish engineers, and the mutual non-adhesion of the coatings of the comparative example was averaged as a previous measurement by this team.
TABLE 4 leather test data of car seat without adding part of chemical materials (take example two as an example)
| Item | Detection result of automobile cushion leather prepared by the invention | Without addition of part of material |
| Abrasion resistance (CS-10, 1000g,500 times) | More damage and flaking | Non-addition film accelerator |
| Abrasion resistance (CS-10, 1000g,500 times) | Less damage and peeling | Without the addition of trimethylolpropane |
| Abrasion resistance (CS-10, 1000g,500 times) | Less damage and peeling | Without addition of vinyltrimethoxysilane |
| Abrasion resistance (CS-10, 1000g,500 times) | Less damage and peeling | Without addition of p-phenylenediamine |
| Abrasion resistance (CS-10, 1000g,500 times) | Less damage and peeling | Without addition of epoxy resin E51 |
| Coating non-tackiness (%) | 53.8 | Without addition of anti-adhesive material |
| Ultra-lowTotal carbon emission/. Mu.part C/part | 71.8 | Non-addition film accelerator |
| Oxygen index/% | 26.9 | Intumescent flame retardant without nitrogen and phosphorus |
| Density of smoke/%) | 32.5 | Intumescent flame retardant without adding nitrogen and phosphorus |
| Oxygen index/% | 29.1 | Adding nitrogen-phosphorus intumescent flame retardant and not adding butyric anhydride |
| Tobacco density/% | 35.2 | Adding nitrogen phosphorus intumescent flame retardant and not adding butyric anhydride |
| Oxygen index/% | 31.2 | Adding nitrogen phosphorus intumescent flame retardant, and not adding 2, 4-dihydroxy benzaldehyde |
| Tobacco density/% | 28.6 | Adding nitrogen-phosphorus intumescent flame retardant without adding 2, 4-dihydroxy benzaldehyde |
| Oxygen index/% | 31.6 | Adding nitrogen-phosphorus intumescent flame retardant and not adding ethylenediamine tetraacetic acid |
| Tobacco density/% | 24.6 | Adding nitrogen-phosphorus intumescent flame retardant and not adding ethylenediamine tetraacetic acid |
As can be seen from Table 4, the properties of no addition film accelerator, trimethylolpropane, vinyltrimethoxysilane, p-phenylenediamine, nitrogen phosphorus intumescent flame retardant are lower than those of the automotive leather in which the above materials are added, such as abrasion resistance, mutual non-adhesion of coatings, ultra-low total carbon emission, oxygen index and smoke density.
TABLE 5 self-repairing capability test data of automobile cushion leather (example two)
| Item | Detection result of automobile cushion leather prepared by the invention | Comparative example 202011643278 |
| Oxygen index/% (cut, unrepaired) | 30.8 | 29.5 |
| Oxygen index/% (milled, unrepaired) | 30.4 | 29.3 |
| Oxygen index/% (cut, repair) | 31.9 | 29.6 |
| Oxygen index/% (grind, repair) | 31.0 | 29.5 |
From table 5, it can be found that, for the invention, taking example two as an example, under the cutting and grinding condition, compared with the condition without cutting or grinding, the oxygen index is greatly reduced, and after repair, the oxygen index is much better than that of comparative repair, showing that the invention has self-repairing capability.
TABLE 6 self-repairing capability test data of automobile cushion leather without partial material (take example two as an example)
The cutting and grinding self-repairing abilities of the epoxy resin E51 and the trimethylolpropane trimethacrylate which are not added are reduced by 5 to 8 percent compared with the cutting and grinding self-repairing abilities of the materials (the percentage of the change range is calculated by taking the self-repairing as a benchmark), the self-repairing abilities of the epoxy resin E51 and the trimethylolpropane trimethacrylate can be really improved, and the fact that the cutting and grinding flame retardance (the oxygen index reduction range) of the materials is reduced by 2.3 to 3.5 percent compared with the repairing oxygen index without adding butyric anhydride and 2, 4-dihydroxybenzaldehyde is also shown to play a role in the cutting and grinding repairing.
Claims (2)
1. The preparation method of the nitrogen-phosphorus intumescent flame retardant required by the key material of the powderable self-repairing flame-retardant low-VOC polyurethane coating is characterized by comprising the following steps of:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 30-60min, raising the temperature of the system to 90-130 ℃, and reacting for 1-5h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45-50 ℃, keeping the temperature, stirring for 30-60 min, cooling to room temperature, dropwise adding 12.2 g of ethanolamine within 30-60min, and continuously reacting for 1-2 h to obtain a flame retardant intermediate A;
(2) Stirring 6.2 to 8.4g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70 to 90 ℃ for reaction for 1 to 3 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.5 to 3.6g of 3-aminopropyltriethoxysilane into a reaction vessel, and stirring for reaction for 1 to 7 hours at 70 to 110 ℃ to obtain an intermediate B;
(3) Taking 4.2-8.6 g of the flame retardant intermediate A in the step (1), the intermediate B in the step (2) and sodium lignosulfonate, reacting at 60-70 ℃ for 1-2h under stirring, then adding 1.2-1.7 g of butyric anhydride and 0.6-1.2 g of 2, 4-dihydroxybenzaldehyde, reacting at 70-80 ℃ for 1-3h, then adding 0.5-1.2 g of ethylenediamine tetraacetic acid, 0.2-0.4 g of 4-carboxyphenylboronic acid and 0.1-0.4 g of 2-acetoxyisobutyryl chloride, and reacting at 70-80 ℃ for 2-3h to obtain the nitrogen-phosphorus intumescent flame retardant.
2. A preparation method of a powderable polyurethane coating A and a self-repairing flame-retardant low-VOC polyurethane coating B which are required by key materials of the powderable self-repairing flame-retardant low-VOC polyurethane coating is characterized by comprising the following steps:
adding 18.6g of polytetrahydrofuran ether glycol and 11.8g of diisocyanate into a reaction vessel under the protection of nitrogen, heating the temperature of the system to 70-80 ℃, adding 0.24-0.31g of dibutyltin dilaurate, stirring for reaction for 2-4 h, adding 0.4-3.2 g of a chain extender into the system, and reacting for 2-3 h; cooling to 50 to 70 ℃, and adding 15 to 30mL of a thickening agent N, N-diethylformamide; cooling to 40 ℃, adding 1.7 to 2.5g of triethylamine, reacting for 0.5 to 1h, adding 7 to 8g of bentonite, 1 to 2g of nano calcium carbonate and 1.6 to 2.4g of 4, 4-dinitrodiphenyl ether, and stirring at 60 to 70 ℃ for reacting for 1 to 2h to obtain viscous liquid; vacuum drying for 4h, grinding, sealing and storing to obtain the polyurethane coating component A capable of being powdered;
adding 65-75mL of deionized water, 12-17g of epoxy resin E51, 0.9g of trimethylolpropane trimethacrylate and 1.4g of 3,4' -diaminodiphenyl ether into 1.7-4.3 g of nitrogen-phosphorus intumescent flame retardant, and stirring for reaction at 65-75 ℃ for 60-90min, wherein the component B is obtained from the repair flame-retardant low-VOC polyurethane coating component.
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| CN113956776A (en) | 2022-01-21 |
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