CN116804130A - Low-VOC TPO (thermoplastic polyolefin) automobile interior material and production process thereof - Google Patents
Low-VOC TPO (thermoplastic polyolefin) automobile interior material and production process thereof Download PDFInfo
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- CN116804130A CN116804130A CN202310494330.XA CN202310494330A CN116804130A CN 116804130 A CN116804130 A CN 116804130A CN 202310494330 A CN202310494330 A CN 202310494330A CN 116804130 A CN116804130 A CN 116804130A
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- parts
- tpo
- stirring
- water
- reaction
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 229920002397 thermoplastic olefin Polymers 0.000 title description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000010410 layer Substances 0.000 claims abstract description 54
- 239000003973 paint Substances 0.000 claims abstract description 51
- 239000004814 polyurethane Substances 0.000 claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 claims abstract description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 239000013530 defoamer Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 16
- 229920000098 polyolefin Polymers 0.000 claims abstract description 12
- 239000002344 surface layer Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 70
- 238000003756 stirring Methods 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 44
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002390 rotary evaporation Methods 0.000 claims description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims description 16
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 235000019766 L-Lysine Nutrition 0.000 claims description 12
- 239000004472 Lysine Substances 0.000 claims description 12
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000004595 color masterbatch Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003851 corona treatment Methods 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 230000037452 priming Effects 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 description 20
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/6775—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing halogen
-
- 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
- C09D5/002—Priming 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a low VOC TPO automobile interior material and a production process thereof, wherein the low VOC TPO automobile interior material comprises a polyolefin sponge layer, a TPO surface layer and a water paint layer from bottom to top, and the water paint layer comprises an aqueous primer layer and an aqueous finish paint layer, and is characterized in that: the aqueous primer layer comprises the following raw materials in parts by weight: 75-100 parts of modified polyurethane, 0.1-0.8 part of defoamer, 0.3-0.5 part of dispersant, 5-10 parts of nano calcium carbonate, 2-5 parts of silica sol, 1.2-2.0 parts of photoinitiator and 30-50 parts of deionized water; the TPO material is coated with the aqueous polyurethane paint, so that VOC emission can be reduced, and the hydrophobicity of a paint surface layer can be improved.
Description
Technical Field
The invention relates to the technical field of automobile interior materials, in particular to a low-VOC TPO automobile interior material and a production process thereof.
Background
The thermoplastic polyolefin elastomer (TPO) mainly comprises two components of rubber and polyolefin, has the advantages of high elasticity, high strength, high elongation, good low-temperature performance, excellent heat resistance, aging resistance and ultraviolet resistance, rubber elasticity at normal temperature, small density, large bending, high low-temperature impact resistance, easiness in processing, reusability and the like, and is widely applied to the fields of automobile parts, electronics and electricity, building sealing, sports equipment, mechanical industry and the like.
Polyolefin elastomer material surfaces often require a finish of paint to improve scratch resistance and provide good hand feel; however, the paint currently applied to the surface of the polyolefin elastomer is usually solvent polyurethane paint, toluene, butanone and other materials are often used as solvents, and the residual solvents of the product can cause exceeding of VOC.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low-VOC TPO automobile interior material and a production process thereof.
The aim of the invention can be achieved by the following technical scheme:
the low-VOC TPO automobile interior material sequentially comprises a polyolefin sponge layer, a TPO surface layer and a water paint layer from bottom to top, wherein the water paint layer comprises an aqueous primer layer and an aqueous finish paint layer, and the aqueous primer layer comprises the following raw materials in parts by weight: 75-100 parts of modified polyurethane, 0.1-0.8 part of defoamer (IOTA 1810), 0.3-0.5 part of dispersant (sodium dodecyl sulfate, sodium polyacrylate or stearic acid), 5-10 parts of nano calcium carbonate, 2-5 parts of silica sol, 1.2-2.0 parts of photoinitiator (2959) and 30-50 parts of deionized water;
the water-based finish paint layer comprises the following raw materials in parts by weight: 75-100 parts of modified polyurethane, 0.1-0.8 part of defoamer (IOTA 1810), 0.3-0.5 part of dispersant (sodium dodecyl sulfate, sodium polyacrylate or stearic acid), 2-5 parts of silica sol, 1.2-2.0 parts of photoinitiator (2959) and 30-50 parts of deionized water;
the modified polyurethane comprises the following steps:
adding polypropylene glycol, 1, 4-butanediol, dimethylolpropionic acid and dihydric alcohol into a three-neck flask, introducing nitrogen, heating to 80 ℃ and magnetically stirring at a rotating speed of 200r/min for 2 hours, adding isophorone diisocyanate and dibutyltin dilaurate, carrying out heat preservation reaction for 3 hours, adding acetone and triethylamine after the reaction is finished, stirring for 30 minutes, stirring at a rotating speed of 1000r/min at a constant speed, adding deionized water and ethylenediamine, stirring for 1 hour, preparing emulsion, and removing acetone at a temperature of 50 ℃ and a vacuum degree of 0.09MPa, thus preparing the modified polyurethane.
Further, the dosage ratio of the polypropylene glycol, the 1, 4-butanediol, the dimethylolpropionic acid, the isophorone diisocyanate, the triethylamine, the ethylenediamine and the dihydric alcohol is 20 g:4.10-4.12 g:2.02-2.06 g:22.23 g:1.57-1.60 g:1 g:4.24-4.32 g, and the dosage of the dibutyl tin dilaurate is 3-5% of the sum of the weight of the monomers.
Further, the dihydric alcohol comprises the following steps:
s1, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen, heating to 80 ℃, uniformly stirring at a rotating speed of 200r/min, adding L-lysine triisocyanate and dibutyltin dilaurate, uniformly stirring, carrying out heat preservation reaction for 3 hours, cooling to room temperature after the reaction is finished, adding diethanolamine, continuously stirring, carrying out reaction for 20min, and removing a solvent by rotary evaporation to obtain an intermediate 1;
in the step S1, alcohol hydroxyl on hexafluoro-n-butanol reacts with one isocyanate group on L-lysine triisocyanate, then the temperature is reduced to room temperature, and a second isocyanate on the L-lysine triisocyanate reacts with a secondary amine on diethanolamine to generate an intermediate 1, which is a dihydric alcohol containing fluorine bonds;
s2, adding itaconic acid and hydroxyethyl acrylate into a four-neck flask filled with toluene, heating to 60 ℃, adding p-toluenesulfonic acid under nitrogen atmosphere, stirring at a constant speed and reacting for 4 hours, heating to 70 ℃ after the reaction is finished, continuously stirring and reacting for 30 minutes, removing water by using anhydrous magnesium sulfate after the reaction is finished, evaporating out a solvent, and vacuumizing at 40 ℃ for 4 hours to obtain an intermediate 2;
in the step S2, one carboxyl group on itaconic acid and one hydroxyl group on hydroxyethyl acrylate react to generate an intermediate 2, the structure is shown as follows, an itaconic acid structure is introduced into the structure, an unsaturated carbon-carbon double bond is introduced,
s3, adding the intermediate 2 into a three-neck flask, then adding thionyl chloride, carrying out reflux reaction for 12 hours, removing residual thionyl chloride by rotary evaporation after the reaction is finished to obtain a filter cake, then adding the filter cake into tetrahydrofuran, filtering, and removing a solvent by rotary evaporation to obtain an intermediate 3;
in the step S3, intermediate 3 is synthesized through thionyl chloride, and acyl chloride is introduced into the structure of intermediate 3, wherein the structure of intermediate 3 is shown as follows:
step S4, adding the intermediate 3 into tetrahydrofuran, slowly dropwise adding the tetrahydrofuran into concentrated ammonia water under ice water bath, stirring the mixture at a constant speed for 24 hours at room temperature, decompressing and steaming out the tetrahydrofuran after the reaction is finished, extracting the tetrahydrofuran with dichloromethane for three times, washing an organic layer, drying and recrystallizing the organic layer, and then preparing the prepared compound into an intermediate 4 by adopting Huffman degradation reaction;
in the step S4, the intermediate 3 reacts with concentrated ammonia water to form amide, then the intermediate 4 is prepared by adopting Huffman degradation reaction, and amino is introduced into the structure of the intermediate 4, and the process is as follows:
and S5, adding the intermediate 4 and the intermediate 1 into tetrahydrofuran, stirring at a constant speed at room temperature, reacting for 30-45min, and removing the solvent by rotary evaporation to obtain dihydric alcohol, wherein the molar ratio of the intermediate 4 to the intermediate 1 is controlled to be 1:1.
In step S5, the amino group on intermediate 4 reacts with the remaining isocyanate group on intermediate 1 to produce a diol, which is a hydroxyl-terminated fluorine-containing itaconic acid-containing diol having a carbon-carbon double bond.
Further: in the step S1, the mol ratio of hexafluoro-n-butanol, L-lysine triisocyanate and diethanolamine is controlled to be 1:1:1, the dosage of dibutyltin dilaurate is 1-2% of the weight of hexafluoro-n-butanol, in the step S2, the dosage ratio of itaconic acid, hydroxyethyl acrylate, p-toluenesulfonic acid and toluene is controlled to be 0.1 mol:0.1 mol:0.02 g:20 mL, in the step S3, the mol ratio of intermediate 2 and thionyl chloride is controlled to be 0.1-0.2 mol:0.4-0.5 mol, and in the step S4, the dosage ratio of intermediate 3, concentrated ammonia water and tetrahydrofuran is controlled to be 0.1 mol:200 mL:50 mL.
A production process of a low VOC TPO automobile interior material comprises the following steps:
firstly, uniformly mixing 20-50 parts of semi-crosslinked TPO, 10-30 parts of polypropylene, 10-30 parts of polyethylene, 1-3 parts of light stabilizer (UV-119), 10-20 parts of nano calcium carbonate, 10-15 parts of stearic acid auxiliary agent and 5-10 parts of color master batch according to parts by weight, adding into an extruder, extruding to form a TPO film, and carrying out corona treatment to obtain a TPO surface layer;
secondly, uniformly mixing the modified polyurethane, the nano calcium carbonate, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to prepare the water-based primer;
thirdly, uniformly mixing the modified polyurethane, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to obtain the water-based finish paint;
fourthly, coating a water-based primer on one side surface of TPO, and applying ultraviolet light (1 kW,800 mJ/cm) 2 ) Irradiating for 30s to form a water-based finish paint layer, then coating the water-based finish paint, irradiating for 30s under ultraviolet light, and curing to form the water-based finish paintAnd (3) a layer, drying, and then compounding polyolefin sponge on the other side surface of the TPO to prepare the low-VOC TPO automobile interior material.
The invention has the beneficial effects that:
the TPO automotive interior material with low VOC is prepared by the invention, and the TPO material is coated with the aqueous polyurethane paint, so that on one hand, the VOC emission can be reduced, and on the other hand, the hydrophobic property of the paint surface layer can be improved; the waterborne polyurethane paint is prepared from a modified polyurethane matrix, hydrophilic dimethylolpropionic acid monomer and synthesized dihydric alcohol are introduced into the modified polyurethane in the synthesis process, the hydrophilic monomer is introduced into the waterborne paint, an organic solvent is not required to be used, VOC (volatile organic compound) can be reduced, the dihydric alcohol is hydroxyl-terminated fluorine-containing itaconic acid and carbon-carbon double bond-containing dihydric alcohol, the hydroxyl-terminated fluorine-containing itaconic acid and the carbon-carbon double bond-containing dihydric alcohol are introduced onto a polyurethane hard segment as a chain extender, the fluorine-containing chain segment can improve the hydrophobicity of the polyurethane paint surface, and the introduced itaconic acid structure and unsaturated double bond can endow the photocuring performance, so that the synthesized waterborne paint has the advantages of both the waterborne paint and the photocuring.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious 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
The aqueous primer layer comprises the following raw materials in parts by weight: 75 parts of modified polyurethane, 0.1 part of defoamer IOTA 1810,0.3 parts of dispersant sodium polyacrylate, 5 parts of nano calcium carbonate, 2 parts of silica sol, 1.2 parts of photoinitiator 2959 and 30 parts of deionized water;
the water-based finish paint layer comprises the following raw materials in parts by weight: 75 parts of modified polyurethane, 0.1 part of defoamer IOTA 1810,0.3 parts of dispersant sodium polyacrylate, 2 parts of silica sol, 1.2 parts of photoinitiator 2959 and 30 parts of deionized water;
the modified polyurethane comprises the following steps:
adding polypropylene glycol, 1, 4-butanediol, dimethylolpropionic acid and dihydric alcohol into a three-neck flask, introducing nitrogen, heating to 80 ℃ and magnetically stirring at a rotating speed of 200r/min for 2 hours, adding isophorone diisocyanate and dibutyltin dilaurate, carrying out heat preservation reaction for 3 hours, adding acetone and triethylamine after the reaction is finished, stirring for 30 minutes, stirring at a rotating speed of 1000r/min at a constant speed, adding deionized water and ethylenediamine, stirring for 1 hour, preparing an emulsion, removing acetone at a temperature of 50 ℃ and a vacuum degree of 0.09MPa, and preparing modified polyurethane, wherein the dosage ratio of the polypropylene glycol, the 1, 4-butanediol, the dimethylolpropionic acid, isophorone diisocyanate, the triethylamine, the ethylenediamine and the dihydric alcohol is 20 g:4.10 g:2.02 g:22.23 g:1.57 g:1 g:4.24 g, and the dosage of dibutyltin dilaurate is 3% of the weight of the monomer.
The dihydric alcohol comprises the following steps:
s1, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen, heating to 80 ℃, stirring at a constant speed at a rotating speed of 200r/min, adding L-lysine triisocyanate and dibutyltin dilaurate, stirring at a constant speed, reacting for 3 hours at a constant temperature, cooling to room temperature after the reaction is finished, adding diethanolamine, stirring continuously and reacting for 20 minutes, and removing a solvent by rotary evaporation to obtain an intermediate 1, wherein the molar ratio of hexafluoro-n-butanol, L-lysine triisocyanate and diethanolamine is controlled to be 1:1:1, and the dosage of dibutyltin dilaurate is 1% of the weight of hexafluoro-n-butanol;
s2, adding itaconic acid and hydroxyethyl acrylate into a four-neck flask filled with toluene, heating to 60 ℃, adding p-toluenesulfonic acid under nitrogen atmosphere, stirring at a constant speed and reacting for 4 hours, heating to 70 ℃ after the reaction is finished, continuously stirring and reacting for 30 minutes, removing water by using anhydrous magnesium sulfate after the reaction is finished, evaporating the solvent, vacuumizing for 4 hours at 40 ℃ to obtain an intermediate 2, and controlling the dosage ratio of itaconic acid, hydroxyethyl acrylate, p-toluenesulfonic acid and toluene to be 0.1 mol:0.02 g:20 mL;
s3, adding the intermediate 2 into a three-neck flask, then adding thionyl chloride, carrying out reflux reaction for 12h, removing residual thionyl chloride by rotary evaporation after the reaction is finished to obtain a filter cake, then adding the filter cake into tetrahydrofuran, filtering, removing a solvent by rotary evaporation to obtain an intermediate 3, and controlling the mol ratio of the intermediate 2 to the thionyl chloride to be 0.1 mol:0.4 mol;
step S4, adding the intermediate 3 into tetrahydrofuran, slowly dropwise adding the tetrahydrofuran into concentrated ammonia water under ice water bath, stirring at a constant speed for 24 hours at room temperature, decompressing and steaming out the tetrahydrofuran after the reaction is finished, extracting the tetrahydrofuran with dichloromethane for three times, washing an organic layer, drying and recrystallizing, preparing the prepared compound into the intermediate 4 by adopting Huffman degradation reaction, and controlling the dosage ratio of the intermediate 3, the concentrated ammonia water and the tetrahydrofuran to be 0.1 mol:200 mL:50 mL;
and S5, adding the intermediate 4 and the intermediate 1 into tetrahydrofuran, stirring at a constant speed at room temperature, reacting for 30min, and removing the solvent by rotary evaporation to obtain dihydric alcohol, wherein the molar ratio of the intermediate 4 to the intermediate 1 is controlled to be 1:1.
Example 2
The aqueous primer layer comprises the following raw materials in parts by weight: 85 parts of modified polyurethane, 0.3 part of defoamer IOTA 1810,0.4 parts of dispersant sodium dodecyl sulfate, 8 parts of nano calcium carbonate, 4 parts of silica sol, 1.5 parts of photoinitiator 2959 and 40 parts of deionized water;
the water-based finish paint layer comprises the following raw materials in parts by weight: 85 parts of modified polyurethane, 0.3 part of defoamer IOTA 1810,0.4 parts of dispersant sodium dodecyl sulfate, 4 parts of silica sol, 1.5 parts of photoinitiator 2959 and 40 parts of deionized water;
the modified polyurethane comprises the following steps:
adding polypropylene glycol, 1, 4-butanediol, dimethylolpropionic acid and dihydric alcohol into a three-neck flask, introducing nitrogen, heating to 80 ℃ and magnetically stirring at a rotating speed of 200r/min for 2 hours, adding isophorone diisocyanate and dibutyltin dilaurate, carrying out heat preservation reaction for 3 hours, adding acetone and triethylamine after the reaction is finished, stirring for 30 minutes, stirring at a rotating speed of 1000r/min at a constant speed, adding deionized water and ethylenediamine, stirring for 1 hour, preparing an emulsion, removing acetone at a temperature of 50 ℃ and a vacuum degree of 0.09MPa, and preparing modified polyurethane, wherein the dosage ratio of the polypropylene glycol, the 1, 4-butanediol, the dimethylolpropionic acid, isophorone diisocyanate, the triethylamine, the ethylenediamine and the dihydric alcohol is 20 g:4.11 g:2.04 g:22.23 g:1.58 g:1 g:4.30 g, and the dosage of dibutyltin dilaurate is 4% of the weight of the monomer.
The dihydric alcohol comprises the following steps:
s1, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen, heating to 80 ℃, stirring at a constant speed at a rotating speed of 200r/min, adding L-lysine triisocyanate and dibutyltin dilaurate, stirring at a constant speed, reacting for 3 hours at a constant temperature, cooling to room temperature after the reaction is finished, adding diethanolamine, stirring continuously and reacting for 20 minutes, and removing a solvent by rotary evaporation to obtain an intermediate 1, wherein the molar ratio of hexafluoro-n-butanol, L-lysine triisocyanate and diethanolamine is controlled to be 1:1:1, and the dosage of dibutyltin dilaurate is 1.5% of the weight of hexafluoro-n-butanol;
s2, adding itaconic acid and hydroxyethyl acrylate into a four-neck flask filled with toluene, heating to 60 ℃, adding p-toluenesulfonic acid under nitrogen atmosphere, stirring at a constant speed and reacting for 4 hours, heating to 70 ℃ after the reaction is finished, continuously stirring and reacting for 30 minutes, removing water by using anhydrous magnesium sulfate after the reaction is finished, evaporating the solvent, vacuumizing for 4 hours at 40 ℃ to obtain an intermediate 2, and controlling the dosage ratio of itaconic acid, hydroxyethyl acrylate, p-toluenesulfonic acid and toluene to be 0.1 mol:0.02 g:20 mL;
s3, adding the intermediate 2 into a three-neck flask, then adding thionyl chloride, carrying out reflux reaction for 12h, removing residual thionyl chloride by rotary evaporation after the reaction is finished to obtain a filter cake, then adding the filter cake into tetrahydrofuran, filtering, removing a solvent by rotary evaporation to obtain an intermediate 3, and controlling the mol ratio of the intermediate 2 to the thionyl chloride to be 0.1 mol:0.5 mol;
step S4, adding the intermediate 3 into tetrahydrofuran, slowly dropwise adding the tetrahydrofuran into concentrated ammonia water under ice water bath, stirring at a constant speed for 24 hours at room temperature, decompressing and steaming out the tetrahydrofuran after the reaction is finished, extracting the tetrahydrofuran with dichloromethane for three times, washing an organic layer, drying and recrystallizing, preparing the prepared compound into the intermediate 4 by adopting Huffman degradation reaction, and controlling the dosage ratio of the intermediate 3, the concentrated ammonia water and the tetrahydrofuran to be 0.1 mol:200 mL:50 mL;
and S5, adding the intermediate 4 and the intermediate 1 into tetrahydrofuran, stirring at a constant speed at room temperature, reacting for 45min, and removing the solvent by rotary evaporation to obtain dihydric alcohol, wherein the molar ratio of the intermediate 4 to the intermediate 1 is controlled to be 1:1.
Example 3
The aqueous primer layer comprises the following raw materials in parts by weight: 100 parts of modified polyurethane, 0.8 part of defoamer IOTA 1810,0.5 parts of dispersant stearic acid, 10 parts of nano calcium carbonate, 5 parts of silica sol, 2.0 parts of photoinitiator 2959 and 50 parts of deionized water;
the water-based finish paint layer comprises the following raw materials in parts by weight: 100 parts of modified polyurethane, 0.8 part of defoamer IOTA 1810,0.5 parts of dispersant stearic acid, 5 parts of silica sol, 2.0 parts of photoinitiator 2959 and 50 parts of deionized water;
the modified polyurethane comprises the following steps:
adding polypropylene glycol, 1, 4-butanediol, dimethylolpropionic acid and dihydric alcohol into a three-neck flask, introducing nitrogen, heating to 80 ℃ and magnetically stirring at a rotating speed of 200r/min for 2 hours, adding isophorone diisocyanate and dibutyltin dilaurate, carrying out heat preservation reaction for 3 hours, adding acetone and triethylamine after the reaction is finished, stirring for 30 minutes, stirring at a rotating speed of 1000r/min at a constant speed, adding deionized water and ethylenediamine, stirring for 1 hour, preparing an emulsion, removing acetone at a temperature of 50 ℃ and a vacuum degree of 0.09MPa, and preparing modified polyurethane, wherein the dosage ratio of the polypropylene glycol, the 1, 4-butanediol, the dimethylolpropionic acid, isophorone diisocyanate, the triethylamine, the ethylenediamine and the dihydric alcohol is 20 g:4.12 g:2.06 g:22.23 g:1.60 g:1 g:4.32 g, and the dosage of dibutyltin dilaurate is 5% of the weight of the monomer.
The dihydric alcohol comprises the following steps:
s1, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen, heating to 80 ℃, stirring at a constant speed at a rotating speed of 200r/min, adding L-lysine triisocyanate and dibutyltin dilaurate, stirring at a constant speed, reacting for 3 hours at a constant temperature, cooling to room temperature after the reaction is finished, adding diethanolamine, stirring continuously and reacting for 20 minutes, and removing a solvent by rotary evaporation to obtain an intermediate 1, wherein the molar ratio of hexafluoro-n-butanol, L-lysine triisocyanate and diethanolamine is controlled to be 1:1, and the dosage of dibutyltin dilaurate is 2% of the weight of hexafluoro-n-butanol;
s2, adding itaconic acid and hydroxyethyl acrylate into a four-neck flask filled with toluene, heating to 60 ℃, adding p-toluenesulfonic acid under nitrogen atmosphere, stirring at a constant speed and reacting for 4 hours, heating to 70 ℃ after the reaction is finished, continuously stirring and reacting for 30 minutes, removing water by using anhydrous magnesium sulfate after the reaction is finished, evaporating the solvent, vacuumizing for 4 hours at 40 ℃ to obtain an intermediate 2, and controlling the dosage ratio of itaconic acid, hydroxyethyl acrylate, p-toluenesulfonic acid and toluene to be 0.1 mol:0.02 g:20 mL;
s3, adding the intermediate 2 into a three-neck flask, then adding thionyl chloride, carrying out reflux reaction for 12h, removing residual thionyl chloride by rotary evaporation after the reaction is finished to obtain a filter cake, then adding the filter cake into tetrahydrofuran, filtering, removing a solvent by rotary evaporation to obtain an intermediate 3, and controlling the mol ratio of the intermediate 2 to the thionyl chloride to be 0.2 mol:0.5 mol;
step S4, adding the intermediate 3 into tetrahydrofuran, slowly dropwise adding the tetrahydrofuran into concentrated ammonia water under ice water bath, stirring at a constant speed for 24 hours at room temperature, decompressing and steaming out the tetrahydrofuran after the reaction is finished, extracting the tetrahydrofuran with dichloromethane for three times, washing an organic layer, drying and recrystallizing, preparing the prepared compound into the intermediate 4 by adopting Huffman degradation reaction, and controlling the dosage ratio of the intermediate 3, the concentrated ammonia water and the tetrahydrofuran to be 0.1 mol:200 mL:50 mL;
and S5, adding the intermediate 4 and the intermediate 1 into tetrahydrofuran, stirring at a constant speed at room temperature, reacting for 30-45min, and removing the solvent by rotary evaporation to obtain dihydric alcohol, wherein the molar ratio of the intermediate 4 to the intermediate 1 is controlled to be 1:1.
Example 4
The TPO automobile interior material with low VOC comprises a polyolefin sponge layer, a TPO surface layer and a water paint layer from bottom to top, wherein the water paint layer comprises an aqueous primer layer and an aqueous finish layer;
the production process of the automotive interior material comprises the following steps:
uniformly mixing 20 parts of semi-crosslinked TPO, 10 parts of polypropylene, 10 parts of polyethylene, 1 part of light stabilizer UV-119, 10 parts of nano calcium carbonate, 10 parts of stearic acid and 5 parts of color master batch according to parts by weight, adding into an extruder, extruding to form a TPO film, and carrying out corona treatment to obtain a TPO surface layer;
secondly, uniformly mixing the modified polyurethane, the nano calcium carbonate, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to prepare the water-based primer;
thirdly, uniformly mixing the modified polyurethane, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to obtain the water-based finish paint;
fourthly, coating a water-based primer on the surface of one side of TPO, and coating the TPO with ultraviolet light of 1kW,800mJ/cm 2 And (3) irradiating for 30s to form a water-based finish paint layer, coating the water-based finish paint layer, irradiating for 30s under ultraviolet irradiation, curing to form a water-based finish paint layer, drying, and compositing polyolefin sponge on the surface of the other side of the TPO to prepare the low-VOC TPO automotive interior material.
Example 5
The TPO automobile interior material with low VOC comprises a polyolefin sponge layer, a TPO surface layer and a water paint layer from bottom to top, wherein the water paint layer comprises an aqueous primer layer and an aqueous finish layer;
the production process of the automotive interior material comprises the following steps:
firstly, uniformly mixing 30 parts of semi-crosslinked TPO, 20 parts of polypropylene, 20 parts of polyethylene, 2 parts of light stabilizer UV-119, 15 parts of nano calcium carbonate, 12 parts of stearic acid and 8 parts of color master batch according to parts by weight, adding the mixture into an extruder, extruding the mixture to form a TPO film, and carrying out corona treatment to obtain a TPO surface layer;
secondly, uniformly mixing the modified polyurethane, the nano calcium carbonate, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to prepare the water-based primer;
thirdly, uniformly mixing the modified polyurethane, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to obtain the water-based finish paint;
fourthly, coating a water-based primer on the surface of one side of TPO, and coating the TPO with ultraviolet light of 1kW,800mJ/cm 2 Irradiating for 30s to form water-based paintAnd (3) coating a finish paint layer, coating a water-based finish paint, irradiating for 30s under ultraviolet irradiation, curing to form a water-based finish paint layer, drying, and compositing a polyolefin sponge on the surface of the other side of the TPO to prepare the low-VOC TPO automobile interior material.
Example 6
The TPO automobile interior material with low VOC comprises a polyolefin sponge layer, a TPO surface layer and a water paint layer from bottom to top, wherein the water paint layer comprises an aqueous primer layer and an aqueous finish layer;
the production process of the automotive interior material comprises the following steps:
firstly, uniformly mixing 50 parts of semi-crosslinked TPO, 30 parts of polypropylene, 30 parts of polyethylene, 3 parts of light stabilizer UV-119, 20 parts of nano calcium carbonate, 15 parts of stearic acid and 10 parts of color master batch according to parts by weight, adding the mixture into an extruder, extruding the mixture to form a TPO film, and carrying out corona treatment to obtain a TPO surface layer;
secondly, uniformly mixing the modified polyurethane, the nano calcium carbonate, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to prepare the water-based primer;
thirdly, uniformly mixing the modified polyurethane, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to obtain the water-based finish paint;
fourthly, coating a water-based primer on the surface of one side of TPO, and coating the TPO with ultraviolet light of 1kW,800mJ/cm 2 And (3) irradiating for 30s to form a water-based finish paint layer, coating the water-based finish paint layer, irradiating for 30s under ultraviolet irradiation, curing to form a water-based finish paint layer, drying, and compositing polyolefin sponge on the surface of the other side of the TPO to prepare the low-VOC TPO automotive interior material.
Comparative example 1
This comparative example was compared to example 4, and was coated with a solvent-borne polyurethane paint.
Comparative example 2
The VOC content and the water repellency of the interior materials prepared in examples 4 to 6 and comparative example 1 were measured according to the method prescribed by TS-BD-003 (test method for volatile organic compounds for parts in vehicles-bag method), and the results obtained are shown in Table 1;
TABLE 1
From the above table 1, it can be seen that the automobile interior materials prepared in examples 4 to 6 have lower VOC emissions, meet the environmental protection requirements, and have excellent hydrophobic properties.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (5)
1. The utility model provides a TPO automotive interior material of low VOC, from down upwards be polyolefin sponge layer, TPO top layer and water paint layer in proper order, the steam layer includes waterborne priming paint layer and waterborne finish paint layer, its characterized in that: the aqueous primer layer comprises the following raw materials in parts by weight: 75-100 parts of modified polyurethane, 0.1-0.8 part of defoamer, 0.3-0.5 part of dispersant, 5-10 parts of nano calcium carbonate, 2-5 parts of silica sol, 1.2-2.0 parts of photoinitiator (2959) and 30-50 parts of deionized water;
the water-based finish paint layer comprises the following raw materials in parts by weight: 75-100 parts of modified polyurethane, 0.1-0.8 part of defoamer, 0.3-0.5 part of dispersant, 2-5 parts of silica sol, 1.2-2.0 parts of photoinitiator (2959) and 30-50 parts of deionized water;
the modified polyurethane comprises the following steps:
adding polypropylene glycol, 1, 4-butanediol, dimethylolpropionic acid and dihydric alcohol into a three-neck flask, introducing nitrogen, heating to 80 ℃ and magnetically stirring at a rotating speed of 200r/min for 2 hours, adding isophorone diisocyanate and dibutyltin dilaurate, carrying out heat preservation reaction for 3 hours, adding acetone and triethylamine after the reaction is finished, stirring for 30 minutes, stirring at a rotating speed of 1000r/min at a constant speed, adding deionized water and ethylenediamine, stirring for 1 hour, preparing emulsion, and removing acetone at a temperature of 50 ℃ and a vacuum degree of 0.09MPa, thus preparing the modified polyurethane.
2. The low VOC TPO automotive interior material according to claim 1 wherein the polypropylene glycol, 1, 4-butanediol, dimethylolpropionic acid, isophorone diisocyanate, triethylamine, ethylenediamine and glycol are used in a ratio of 20 g: 4.10-4.12 g: 2.02-2.06 g: 22.23 g: 1.57-1.60 g: 1 g: 4.24-4.32g, and dibutyltin dilaurate is used in an amount of 3-5% based on the total weight of the monomers.
3. The low VOC TPO automotive interior material of claim 1 wherein the glycol comprises the steps of:
s1, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen, heating to 80 ℃, uniformly stirring at a rotating speed of 200r/min, adding L-lysine triisocyanate and dibutyltin dilaurate, uniformly stirring, carrying out heat preservation reaction for 3 hours, cooling to room temperature after the reaction is finished, adding diethanolamine, continuously stirring, carrying out reaction for 20min, and removing a solvent by rotary evaporation to obtain an intermediate 1;
s2, adding itaconic acid and hydroxyethyl acrylate into a four-neck flask filled with toluene, heating to 60 ℃, adding p-toluenesulfonic acid under nitrogen atmosphere, stirring at a constant speed and reacting for 4 hours, heating to 70 ℃ after the reaction is finished, continuously stirring and reacting for 30 minutes, removing water by using anhydrous magnesium sulfate after the reaction is finished, evaporating out a solvent, and vacuumizing at 40 ℃ for 4 hours to obtain an intermediate 2;
s3, adding the intermediate 2 into a three-neck flask, then adding thionyl chloride, carrying out reflux reaction for 12 hours, removing residual thionyl chloride by rotary evaporation after the reaction is finished to obtain a filter cake, then adding the filter cake into tetrahydrofuran, filtering, and removing a solvent by rotary evaporation to obtain an intermediate 3;
step S4, adding the intermediate 3 into tetrahydrofuran, slowly dropwise adding the tetrahydrofuran into concentrated ammonia water under ice water bath, stirring the mixture at a constant speed for 24 hours at room temperature, decompressing and steaming out the tetrahydrofuran after the reaction is finished, extracting the tetrahydrofuran with dichloromethane for three times, washing an organic layer, drying and recrystallizing the organic layer, and then preparing the prepared compound into an intermediate 4 by adopting Huffman degradation reaction;
and S5, adding the intermediate 4 and the intermediate 1 into tetrahydrofuran, stirring at a constant speed at room temperature, reacting for 30-45min, and removing the solvent by rotary evaporation to obtain the intermediate 5, wherein the molar ratio of the intermediate 4 to the intermediate 1 is controlled to be 1:1.
4. The low VOC TPO automotive interior material of claim 1 wherein: in the step S1, the mol ratio of hexafluoro-n-butanol, L-lysine triisocyanate and diethanolamine is controlled to be 1:1:1, the dosage of dibutyltin dilaurate is 1-2% of the weight of hexafluoro-n-butanol, in the step S2, the dosage ratio of itaconic acid, hydroxyethyl acrylate, p-toluenesulfonic acid and toluene is controlled to be 0.1 mol:0.1 mol:0.02 g:20 mL, in the step S3, the mol ratio of intermediate 2 and thionyl chloride is controlled to be 0.1-0.2 mol:0.4-0.5 mol, and in the step S4, the dosage ratio of intermediate 3, concentrated ammonia water and tetrahydrofuran is controlled to be 0.1 mol:200 mL:50 mL.
5. The process for producing a low VOC TPO automotive interior material according to claim 1 characterized by: the method comprises the following steps:
firstly, uniformly mixing 20-50 parts of semi-crosslinked TPO, 10-30 parts of polypropylene, 10-30 parts of polyethylene, 1-3 parts of light stabilizer (UV-119), 10-20 parts of nano calcium carbonate, 10-15 parts of stearic acid auxiliary agent and 5-10 parts of color master batch according to parts by weight, adding into an extruder, extruding to form a TPO film, and carrying out corona treatment to obtain a TPO surface layer;
secondly, uniformly mixing the modified polyurethane, the nano calcium carbonate, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to prepare the water-based primer;
thirdly, uniformly mixing the modified polyurethane, the silica sol, the photoinitiator and the deionized water, adding the defoamer and the dispersant, and uniformly stirring to obtain the water-based finish paint;
fourth step, in TPO oneThe side surfaces were coated with a water-borne primer under ultraviolet light (1 kW,800mJ/cm 2 ) Irradiating for 30s under irradiation to form an aqueous primer layer, then coating aqueous finish paint, irradiating for 30s under ultraviolet irradiation, forming an aqueous finish paint layer after curing, drying, and then compounding polyolefin sponge on the other side surface of the TPO to prepare the low-VOC TPO automotive interior material.
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