CN106188481A - A kind of automotive trim mesoporous modified polyurethane resin and preparation method thereof - Google Patents
A kind of automotive trim mesoporous modified polyurethane resin and preparation method thereof Download PDFInfo
- Publication number
- CN106188481A CN106188481A CN201610544579.7A CN201610544579A CN106188481A CN 106188481 A CN106188481 A CN 106188481A CN 201610544579 A CN201610544579 A CN 201610544579A CN 106188481 A CN106188481 A CN 106188481A
- Authority
- CN
- China
- Prior art keywords
- parts
- polyurethane resin
- modified polyurethane
- mesoporous
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001868 water Inorganic materials 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 hydroxyl 5 aminomethyl phenyl Chemical group 0.000 claims abstract description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013335 mesoporous material Substances 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 19
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 18
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 18
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001124 trientine Drugs 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 28
- 150000001298 alcohols Chemical class 0.000 claims description 19
- 235000013877 carbamide Nutrition 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 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 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 1
- 239000012757 flame retardant agent Substances 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000007761 roller coating Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 18
- 239000004814 polyurethane Substances 0.000 abstract description 18
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 238000009413 insulation Methods 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000005474 octanoate group Chemical group 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 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 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YADYSHISCDOTDA-UHFFFAOYSA-N azane;silicic acid Chemical compound N.O[Si](O)(O)O YADYSHISCDOTDA-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention discloses a kind of automotive trim mesoporous modified polyurethane resin and preparation method thereof, including following raw material components: presoma, silane coupler, phosphorous acid, 2 (2 hydroxyl 5 aminomethyl phenyl) BTA, BACN, methyl diphenylene diisocyanate, ethylene glycol, 1, 4 butanediols, polyester diol, toluene, N, N dimethylformamide, catalyst, methanol, ammonium hydrogen carbonate, presoma is by ammonium silicate, triethylene tetramine and zinc ammonia complex reaction prepare, zinc ammonia complex is by zinc sulfate, ammonia and water reaction prepare, BACN is by oxalic acid, water and urea reaction prepare.Mesoporous material in this invention can improve the mechanical strength of polyurethane product, increase polyurethane surface degree of functionality and hydrophilic, and meanwhile, mesoporous material gives the performances such as polyurethane excellent transparent, fungi-proofing, fire-retardant, peel strength, heat insulation, sound-absorbing.
Description
Technical field
The present invention relates to a kind of automotive trim mesoporous modified polyurethane resin and preparation method thereof.
Background technology
Polyurethane resin has the characteristics such as high intensity, anti tear, wear-resisting, solvent resistant, is widely used in daily life, workers and peasants
The fields such as industry production, medical science.Therefore, synthesis and the application thereof of polyurethane is increasingly taken seriously.
At present, there is fungi-proofing, fire-retardant, peel strength in polyurethane resin, heat insulation, sound-absorbing effect is undesirable.
Summary of the invention
It is an object of the invention to provide a kind of automotive trim preparation method with mesoporous modified polyurethane resin, the method
By changing reactant feed and processing mode, synthetic leather prepared by mesoporous modified polyurethane resin has fungi-proofing, fire-retardant, stripping
The performances such as intensity, heat insulation, sound-absorbing.
To achieve these goals, technical scheme is as follows.
A kind of mesoporous modified polyurethane resin of automotive trim, it is characterised in that: prepared by the reaction of following raw material components: front
Drive body, silane coupler, phosphorous acid, 2-(2-hydroxyl-5-aminomethyl phenyl) BTA, BACN, diphenylmethyl
Alkane diisocyanate, ethylene glycol, 1,4-butanediol, polyester diol, toluene, N,N-dimethylformamide, catalyst, first
Alcohol, ammonium hydrogen carbonate, raw materials quality portion rate be 5:0.5～1:0.3～0.8:0.2～0.5:1～5:37～83:7～15:3～
10:100～180:100～200:270～526:0.3～1.6:0.3～0.6:3～8；Wherein, described presoma is by silicic acid
Ammonium, triethylene tetramine and zinc ammonia complex reaction prepare, the portion rate of described ammonium silicate, triethylene tetramine and zinc ammonia complex
For 10:12～20:50～70；Described zinc ammonia complex is reacted by zinc sulfate, ammonia and water and prepares, described zinc sulfate, ammonia
The portion rate of gas and water is 10:30～60:20～50；Described BACN is prepared by oxalic acid, water and urea reaction, described
The portion rate of oxalic acid, water and carbamide be 100:70～90:60～80.
In the present invention, described silane coupler is the one of propyl trimethoxy silicane, VTES
Or several mixture；Described catalyst is the one in dibutyl tin laurate, triethanolamine, stannous octoate；Described poly-
Ester dihydroxylic alcohols is 10PE27 dihydroxylic alcohols, polypropylene glycol adipate dihydroxylic alcohols, polyethylene terephthalate two
One in unit alcohol, polyethylene terephthalate dihydroxylic alcohols.
A kind of automotive trim preparation method of mesoporous modified polyurethane resin, it is characterised in that comprise the following steps:
(1), be that 100:70～90:60～80 joins in reactor by oxalic acid, water and carbamide according to portion rate, mixing speed
130～200r/min, react 1～3h under the conditions of maintenance system temperature 25～46 DEG C, product through washing with alcohol, filtration, 60 DEG C ,-
0.1MPa is dried 2h, obtains BACN；
(2), be that 10:30～60:20～50 joins in reactor by zinc sulfate, ammonia and water according to portion rate, mixing speed
80～150r/min, react 0.5～2h under the conditions of maintenance system temperature 10～30 DEG C, product is through-30～-40 DEG C of lyophilizations 1
～3h, obtain zinc ammonia complex；While described cryodesiccated purpose is in order to make zinc ammonia complex rapid draing, reduce ammonia
The volatile quantity of gas.
(3), ammonium silicate, triethylene tetramine and zinc ammonia complex are joined ball according to portion rate 10:12～20:50～70
In type grinder, temperature 20～30 DEG C, under the conditions of 100～150r/min, griding reaction 1～3 h, i.e. obtains presoma；Institute
The purpose one side of the triethylene tetramine stated, for more preferable disperse silicic acid ammonium and zinc ammonia complex；On the other hand, in order to modify
Mesoporous material surface.
(4), presoma, silane coupler, phosphorous acid, 2-(2-hydroxyl-5-aminomethyl phenyl) BTA, novel resistance
Combustion agent, methyl diphenylene diisocyanate, ethylene glycol, 1,4-butanediol, polyester diol, toluene, N, N-dimethyl formyl
Amine, catalyst, methanol, ammonium hydrogen carbonate according to portion rate 5:0.5～1:0.3～0.8:0.2～0.5:1～5:37～83:7～
15:3～10:100～180:100～200:270～526:0.3～1.6:0.3～0.6:3～8 joins in reactor, in temperature
Spend 65～80 DEG C, react 1～3h under the conditions of 90～130r/min, i.e. obtain mesoporous material modified polyurethane resin.
This beneficial effect of the invention is:
1, while ammonium silicate and zinc ammonia complex can preferably be mixed in polyurethane building-up process, ammonium silicate and zinc ammonia
Complex can decompose generation nano silicon and nano zine oxide, and both are well disperseed in polyurethane body body,
Improve mesoporous material agglomeration in polyurethane.Also, the ammonia produced in ammonium silicate and zinc ammonia complex catabolic process exists
As pore creating material during nano silicon and zinc oxide generation, give the silicon dioxide generated and zinc oxide is mesoporous two
Silicon oxide and mesoporous zinc oxide；
2, owing to mesoporous silicon oxide and mesoporous zinc oxide are in building-up process, having ammonia to generate, ammonia and organic amine can be repaiied
Adorn newly-generated mesoporous material surface, obtain amine (ammonia) modified mesoporous material；
3, in polyurethane building-up process, ammonium carbonate along with the rising of reaction temperature, reaction of decomposing, generate carbon dioxide,
Water, ammonia, these materials can play the effect of the foaming agent of polyurethane, gives the excellent elasticity of polyurethane resin, sound absorption properties
Energy；
4, when under polyurethane is at fired state, on the one hand, phosphorous acid, as reducing agent, can consume oxygen；On the other hand, amine
(ammonia) modified mesoporous material can migrate to polyurethane surface, with the generation polycondensation reaction of (sub-) phosphoric acid, forms one at polyurethane surface
Layer flame-retardant layer；
5, when polyurethane is at fired state, on the one hand oxalic acid-carbamide fire retardant decomposes generation carbon dioxide, ammonia etc. is non-
Combustion-supporting property gas, on the other hand, oxalic acid-carbamide fire retardant can occur polyreaction when high temperature, forms one at polyurethane surface
Layer flame-retardant layer；
6, mesoporous silicon oxide and zinc oxide introduce, and due to crazing effect, improve the mechanical property of modified polyurethane.
This invention use presoma, BACN, methyl diphenylene diisocyanate, ethylene glycol, 1,4-butanediol,
The raw material such as polyester diol, ammonium hydrogen carbonate, be prepared for having excellent fungi-proofing, fire-retardant, peel strength, heat insulation, sound-absorbing effect etc. are excellent
The mesoporous modified polyurethane resin of the automotive trim of gesture.
The present invention can improve the mechanical strength of polyurethane product, increase polyurethane surface degree of functionality and hydrophilic, meanwhile,
Mesoporous material gives the performances such as polyurethane excellent transparent, fungi-proofing, fire-retardant, peel strength, heat insulation, sound-absorbing.
The present invention can apply automobile, building, sofa, household outer package, case and bag, fur clothing fungi-proofing, fire-retardant, peel off strong
The fields such as degree, heat insulation, sound-absorbing.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is described, in order to be better understood from the present invention.
Embodiment 1
(1), weigh 100 parts of oxalic acid, 82 parts of water and 67 parts of carbamide and join in reactor, mixing speed 165r/min, maintain body
Be to react 2h under the conditions of temperature 30 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 45 parts of ammonias and 39 parts of water and join in reactor, mixing speed 120r/min, maintain body
Being reaction 1h under the conditions of temperature 26 DEG C, product, through-35 DEG C of lyophilization 2h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 16 parts of triethylene tetramines and 65 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 26 DEG C, griding reaction 2 h under the conditions of 130r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.8 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.5 part of phosphorous acid, 0.3 part
2-(2-hydroxyl-5-aminomethyl phenyl) BTA, 3.5 parts of BACNs, 67 parts of methyl diphenylene diisocyanates, 12
Part ethylene glycol, 7 parts of 1,4-butanediols, 150 parts of polypropylene glycol adipate dihydroxylic alcohols, 155 parts of toluene, 440 parts of N, N-diformazans
Base Methanamide, 0.9 part of dibutyl tin laurate, 0.6 part of methanol, 5 parts of ammonium hydrogen carbonate join in reactor, in temperature 70
DEG C, react 2h under the conditions of 110r/min, i.e. obtain mesoporous material modified polyurethane resin.In table 1 is the automobile that embodiment 1 prepares
Adorn by the performance parameter of mesoporous modified polyurethane resin.
Embodiment 2
(1), weigh 100 parts of oxalic acid, 70 parts of water and 60 parts of carbamide and join in reactor, mixing speed 130r/min, maintain body
Be to react 1h under the conditions of temperature 25 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 30 parts of ammonias and 20 parts of water and join in reactor, mixing speed 80r/min, maintain body
Being reaction 0.5h under the conditions of temperature 10 DEG C, product, through-30 DEG C of lyophilization 1h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 12 parts of triethylene tetramines and 50 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 20 DEG C, griding reaction 1 h under the conditions of 100r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.5 part of VTES, 0.3 part of phosphorous acid, 0.2 part of 2-(2-hydroxyl-5-
Aminomethyl phenyl) BTA, 1 part of BACN, 37 parts of methyl diphenylene diisocyanates, 7 parts of ethylene glycol, 3 parts of 1,4-
Butanediol, 100 parts of polyethylene terephthalate dihydroxylic alcohols, 100 parts of toluene, 270 parts of N,N-dimethylformamides, 0.3 part three
Ethanolamine, 0.3 part of methanol, 3 parts of ammonium hydrogen carbonate join in reactor, temperature 65 DEG C, react 1h, i.e. under the conditions of 90r/min
Obtain mesoporous material modified polyurethane resin.
Embodiment 3
(1), weigh 100 parts of oxalic acid, 90 parts of water and 80 parts of carbamide and join in reactor, mixing speed 200r/min, maintain body
Be to react 3h under the conditions of temperature 46 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 60 parts of ammonias and 50 parts of water and join in reactor, mixing speed 150r/min, maintain body
Being reaction 2h under the conditions of temperature 30 DEG C, product, through-40 DEG C of lyophilization 3h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 20 parts of triethylene tetramines and 70 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 30 DEG C, griding reaction 3 h under the conditions of 150r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 1 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.8 part of phosphorous acid, 0.2～0.5
Part 2-(2-hydroxyl-5-aminomethyl phenyl) BTA, 5 parts of BACNs, 83 parts of methyl diphenylene diisocyanates, 15
Part ethylene glycol, 10 parts of 1,4-butanediols, 180 parts of polypropylene glycol adipate dihydroxylic alcohols, 200 parts of toluene, 526 parts of N, N-diformazans
Base Methanamide, 1.6 parts of dibutyl tin laurates, 0.6 part of methanol, 8 parts of ammonium hydrogen carbonate join in reactor, in temperature 80
DEG C, react 3h under the conditions of 130r/min, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 4
(1), weigh 100 parts of oxalic acid, 73 parts of water and 66 parts of carbamide and join in reactor, mixing speed 137r/min, maintain body
Be to react 3h under the conditions of temperature 28 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 35 parts of ammonias and 28 parts of water and join in reactor, mixing speed 85r/min, maintain body
Being reaction 0.8h under the conditions of temperature 13 DEG C, product, through-35 DEG C of lyophilization 1h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 15 parts of triethylene tetramines and 58 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 23 DEG C, griding reaction 3 h under the conditions of 110r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.7 part of VTES, 0.8 part of phosphorous acid, 0.3 part of 2-(2-hydroxyl-5-
Aminomethyl phenyl) BTA, 2 parts of BACNs, 56 parts of methyl diphenylene diisocyanates, 8 parts of ethylene glycol, 9 parts of 1,4-
Butanediol, 100 parts of polyethylene terephthalate dihydroxylic alcohols, 120 parts of toluene, 326 parts of N,N-dimethylformamides, 0.7 part three
Ethanolamine, 0.5 part of methanol, 6 parts of ammonium hydrogen carbonate join in reactor, temperature 68 DEG C, react under the conditions of 100r/min
1.5h, i.e. obtains mesoporous material modified polyurethane resin.
Embodiment 5
(1), weigh 100 parts of oxalic acid, 75 parts of water and 67 parts of carbamide and join in reactor, mixing speed 146r/min, maintain body
Be to react 2h under the conditions of temperature 30 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 33 parts of ammonias and 22 parts of water and join in reactor, mixing speed 90r/min, maintain body
Being reaction 1.2h under the conditions of temperature 18 DEG C, product, through-33 DEG C of lyophilization 2h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 15 parts of triethylene tetramines and 57 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 26 DEG C, griding reaction 2 h under the conditions of 130r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.7 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.4 part
2-(2-hydroxyl-5-aminomethyl phenyl) BTA, 4 parts of BACNs, 80 parts of methyl diphenylene diisocyanates, 14 parts
Ethylene glycol, 7 parts of 1,4-butanediols, 160 parts of polypropylene glycol adipate dihydroxylic alcohols, 180 parts of toluene, 470 parts of N, N-dimethyl
Methanamide, 1.4 parts of stannous octoates, 0.5 part of methanol, 4 parts of ammonium hydrogen carbonate join in reactor, at temperature 71 DEG C, 96r/min
Under the conditions of react 2h, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 6
(1), weigh 100 parts of oxalic acid, 80 parts of water and 76 parts of carbamide and join in reactor, mixing speed 150r/min, maintain body
Be to react 1h under the conditions of temperature 45 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 58 parts of ammonias and 49 parts of water and join in reactor, mixing speed 147r/min, maintain body
Being reaction 1.8h under the conditions of temperature 28 DEG C, product, through-39 DEG C of lyophilization 2h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 17 parts of triethylene tetramines and 66 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 24 DEG C, griding reaction 2 h under the conditions of 130r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.8 part of VTES, 0.6 part of phosphorous acid, 0.4 part of 2-(2-hydroxyl-5-
Aminomethyl phenyl) BTA, 3 parts of BACNs, 60 parts of methyl diphenylene diisocyanates, 9 parts of ethylene glycol, 5 parts of 1,4-
Butanediol, 160 parts of 10PE27 dihydroxylic alcohols, 170 parts of toluene, 326 parts of N,N-dimethylformamides, 1.6 parts of February
Dilaurylate, 0.5 part of methanol, 6 parts of ammonium hydrogen carbonate join in reactor, temperature 73 DEG C, anti-under the conditions of 123r/min
Answer 2h, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 7
(1), weigh 100 parts of oxalic acid, 84 parts of water and 73 parts of carbamide and join in reactor, mixing speed 150r/min, maintain body
Be to react 2.5h under the conditions of temperature 37 DEG C, product through 500mL washing with alcohol twice, filtrations, 60 DEG C ,-0.1MPa is dried 2h, must
To BACN；
(2), weigh 10 parts of zinc sulfate, 53 parts of ammonias and 46 parts of water and join in reactor, mixing speed 120r/min, maintain body
Being reaction 1.7h under the conditions of temperature 26 DEG C, product, through-37 DEG C of lyophilization 2.5h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 17 parts of triethylene tetramines and 66 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 21 DEG C, griding reaction 2.8 h under the conditions of 124r/min, i.e. obtain presoma；
(4) 5 parts of presomas, 0.8 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.4 part of 2-, are weighed
(2-hydroxyl-5-aminomethyl phenyl) BTA, 3 parts of BACNs, 41 parts of methyl diphenylene diisocyanates, 7 parts of second
Glycol, 8 parts of 1,4-butanediols, 140 parts of polyethylene terephthalate dihydroxylic alcohols, 100 parts of toluene, 270 parts of N, N-dimethyl
Methanamide, 1.6 parts of stannous octoates, 0.3 part of methanol, 3 parts of ammonium hydrogen carbonate join in reactor, at temperature 76 DEG C, 110r/min
Under the conditions of react 1h, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 8
(1), weigh 100 parts of oxalic acid, 83 parts of water and 75 parts of carbamide and join in reactor, mixing speed 170r/min, maintain body
Be to react 1.7h under the conditions of temperature 34 DEG C, product through 500mL washing with alcohol twice, filtrations, 60 DEG C ,-0.1MPa is dried 2h, must
To BACN；
(2), weigh 10 parts of zinc sulfate, 48 parts of ammonias and 44 parts of water and join in reactor, mixing speed 116r/min, maintain body
Being reaction 1.3h under the conditions of temperature 27 DEG C, product, through-32 DEG C of lyophilization 3h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 15 parts of triethylene tetramines and 65 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 26 DEG C, griding reaction 2h under the conditions of 130r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.7 part of VTES, 0.7 part of phosphorous acid, 0.4 part of 2-(2-hydroxyl-5-
Aminomethyl phenyl) BTA, 4 parts of BACNs, 72 parts of methyl diphenylene diisocyanates, 9 parts of ethylene glycol, 6 parts of 1,4-
Butanediol, 158 parts of 10PE27 dihydroxylic alcohols, 130 parts of toluene, 430 parts of N,N-dimethylformamides, 1.5 parts of February
Dilaurylate, 0.4 part of methanol, 5 parts of ammonium hydrogen carbonate join in reactor, temperature 73 DEG C, anti-under the conditions of 126r/min
Answer 2.3h, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 9
(1), weigh 100 parts of oxalic acid, 81 parts of water and 77 parts of carbamide and join in reactor, mixing speed 180r/min, maintain body
Be to react 2h under the conditions of temperature 29 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 36 parts of ammonias and 40 parts of water and join in reactor, mixing speed 130r/min, maintain body
Being reaction 1.9h under the conditions of temperature 17 DEG C, product, through-38 DEG C of lyophilization 1.5h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 17 parts of triethylene tetramines and 63 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 26 DEG C, griding reaction 2 h under the conditions of 130r/min, i.e. obtain presoma；
(4) 5 parts of presomas, 0.7 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.5 part of phosphorous acid, 0.3 part of 2-, are weighed
(2-hydroxyl-5-aminomethyl phenyl) BTA, 4 parts of BACNs, 67 parts of methyl diphenylene diisocyanates, 12 parts of second
Glycol, 7 parts of 1,4-butanediols, 180 parts of polyethylene terephthalate dihydroxylic alcohols, 180 parts of toluene, 390 parts of N, N-dimethyl
Methanamide, 1.3 parts of stannous octoates, 0.4 part of methanol, 5 parts of ammonium hydrogen carbonate join in reactor, at temperature 73 DEG C, 111r/min
Under the conditions of react 2.6h, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 10
(1), weigh 100 parts of oxalic acid, 82 parts of water and 71 parts of carbamide and join in reactor, mixing speed 180r/min, maintain body
Be to react 2.3h under the conditions of temperature 43 DEG C, product through 500mL washing with alcohol twice, filtrations, 60 DEG C ,-0.1MPa is dried 2h, must
To BACN；
(2), weigh 10 parts of zinc sulfate, 41 parts of ammonias and 44 parts of water and join in reactor, mixing speed 134r/min, maintain body
Being reaction 1.7h under the conditions of temperature 16 DEG C, product, through-38 DEG C of lyophilization 2.3h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 14 parts of triethylene tetramines and 63 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 22 DEG C, griding reaction 2.3 h under the conditions of 140r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.7 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.5 part
2-(2-hydroxyl-5-aminomethyl phenyl) BTA, 3 parts of BACNs, 63 parts of methyl diphenylene diisocyanates, 9 parts
Ethylene glycol, 9 parts of 1,4-butanediols, 150 parts of 10PE27 dihydroxylic alcohols, 170 parts of toluene, 350 parts of N, N-dimethyl
Methanamide, 1.5 parts of dibutyl tin laurates, 0.4 part of methanol, 4 parts of ammonium hydrogen carbonate join in reactor, temperature 77 DEG C,
React 2h under the conditions of 123r/min, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 11
(1), weigh 100 parts of oxalic acid, 89 parts of water and 75 parts of carbamide and join in reactor, mixing speed 190r/min, maintain body
Be to react 2h under the conditions of temperature 37 DEG C, product through 500mL washing with alcohol twice, filtration, 60 DEG C ,-0.1MPa is dried 2h, obtains
BACN；
(2), weigh 10 parts of zinc sulfate, 40 parts of ammonias and 41 parts of water and join in reactor, mixing speed 86r/min, maintain body
Being reaction 1.8h under the conditions of temperature 23 DEG C, product, through-36 DEG C of lyophilization 1h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 14 parts of triethylene tetramines and 60 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 29 DEG C, griding reaction 2h under the conditions of 135r/min, i.e. obtain presoma；
(4) 5 parts of presomas, 0.7 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.3 part of 2-, are weighed
(2-hydroxyl-5-aminomethyl phenyl) BTA, 4 parts of BACNs, 46 parts of methyl diphenylene diisocyanates, 7 parts of second
Glycol, 3 parts of 1,4-butanediols, 110 parts of polyethylene terephthalate dihydroxylic alcohols, 100 parts of toluene, 300 parts of N, N-dimethyl
Methanamide, 1.5 parts of stannous octoates, 0.6 part of methanol, 5 parts of ammonium hydrogen carbonate join in reactor, at temperature 75 DEG C, 97r/min
Under the conditions of react 2h, i.e. obtain mesoporous material modified polyurethane resin.
Embodiment 12
(1), weigh 100 parts of oxalic acid, 81 parts of water and 72 parts of carbamide and join in reactor, mixing speed 170r/min, maintain body
Be to react 1.5h under the conditions of temperature 30 DEG C, product through 500mL washing with alcohol twice, filtrations, 60 DEG C ,-0.1MPa is dried 2h, must
To BACN；
(2), weigh 10 parts of zinc sulfate, 35 parts of ammonias and 21 parts of water and join in reactor, mixing speed 88r/min, maintain body
Being reaction 1.5h under the conditions of temperature 18 DEG C, product, through-34 DEG C of lyophilization 1h, obtains zinc ammonia complex；
(3), weigh 10 parts of ammonium silicates, 16 parts of triethylene tetramines and 57 parts of zinc ammonia complex and join in ball-type grinder, in temperature
Spend 25 DEG C, griding reaction 3 h under the conditions of 140r/min, i.e. obtain presoma；
(4), weigh 5 parts of presomas, 0.7 part of (2,3-epoxy the third oxygen) propyl trimethoxy silicane, 0.4 part of phosphorous acid, 0.2 part
2-(2-hydroxyl-5-aminomethyl phenyl) BTA, 3 parts of BACNs, 50 parts of methyl diphenylene diisocyanates, 7 parts
Ethylene glycol, 4 parts of 1,4-butanediols, 120 parts of polyethylene terephthalate dihydroxylic alcohols, 130 parts of toluene, 270 parts of N, N-diformazans
Base Methanamide, 0.7 part of dibutyl tin laurate, 0.5 part of methanol, 8 parts of ammonium hydrogen carbonate join in reactor, in temperature 74
DEG C, react 1.5h under the conditions of 117r/min, i.e. obtain mesoporous material modified polyurethane resin.
Table 1
。
Claims (9)
1. the mesoporous modified polyurethane resin of automotive trim, it is characterised in that: prepared by the reaction of following raw material components: forerunner
Body, silane coupler, phosphorous acid, 2-(2-hydroxyl-5-aminomethyl phenyl) BTA, BACN, diphenyl methane
Diisocyanate, ethylene glycol, 1,4-butanediol, polyester diol, toluene, N,N-dimethylformamide, catalyst, methanol,
Ammonium hydrogen carbonate, raw materials quality portion rate is 5:0.5～1:0.3～0.8:0.2～0.5:1～5:37～83:7～15:3～10:
100～180:100～200:270～526:0.3～1.6:0.3～0.6:3～8；Wherein, described presoma by ammonium silicate,
Triethylene tetramine and zinc ammonia complex reaction prepare, and the portion rate of described ammonium silicate, triethylene tetramine and zinc ammonia complex is
10:12～20:50～70；Described zinc ammonia complex is reacted by zinc sulfate, ammonia and water and prepares, described zinc sulfate, ammonia
It is 10:30～60:20～50 with the portion rate of water；Described BACN is prepared by oxalic acid, water and urea reaction, described
The portion rate of oxalic acid, water and carbamide is 100:70～90:60～80.
The mesoporous modified polyurethane resin of automotive trim the most according to claim 1, it is characterised in that: described silane is even
Connection agent is one or more mixture of propyl trimethoxy silicane, VTES；Described catalyst is two
One in dibutyl tin laurate, triethanolamine, stannous octoate；Described polyester diol is 10PE27 binary
In alcohol, polypropylene glycol adipate dihydroxylic alcohols, polyethylene terephthalate dihydroxylic alcohols, polyethylene terephthalate dihydroxylic alcohols
One.
3. the automotive trim preparation method of mesoporous modified polyurethane resin described in a claim 1, it is characterised in that include
Following steps:
(1), be that 100:70～90:60～80 joins in reactor by oxalic acid, water and carbamide according to portion rate, mixing speed
130～200r/min, react 1～3h under the conditions of maintenance system temperature 25～46 DEG C, product through washing with alcohol, filtration, 60 DEG C ,-
0.1MPa is dried 2h, obtains BACN；
(2), be that 10:30～60:20～50 joins in reactor by zinc sulfate, ammonia and water according to portion rate, mixing speed
80～150r/min, react 0.5～2h under the conditions of maintenance system temperature 10～30 DEG C, product is through-30～-40 DEG C of lyophilizations 1
～3h, obtain zinc ammonia complex；
(3), according to portion rate 10:12～20:50～70, ammonium silicate, triethylene tetramine and zinc ammonia complex are joined ball-type to grind
In grinding machine, temperature 20～30 DEG C, under the conditions of 100～150r/min, griding reaction 1～3 h, i.e. obtains presoma；
(4), presoma, silane coupler, phosphorous acid, 2-(2-hydroxyl-5-aminomethyl phenyl) BTA, novel flame-retardant
Agent, methyl diphenylene diisocyanate, ethylene glycol, 1,4-butanediol, polyester diol, toluene, N,N-dimethylformamide,
Catalyst, methanol, ammonium hydrogen carbonate are according to portion rate 5:0.5～1:0.3～0.8:0.2～0.5:1～5:37～83:7～15:3
～10:100～180:100～200:270～526:0.3～1.6:0.3～0.6:3～8 joins in reactor, in temperature 65
～80 DEG C, react 1～3h under the conditions of 90～130r/min, i.e. obtain mesoporous material modified polyurethane resin.
The automotive trim the most according to claim 3 preparation method of mesoporous modified polyurethane resin, it is characterised in that: institute
In the preparation process of the BACN stated, oxalic acid uses the speed of 5mL/min to add to reactor.
The automotive trim the most according to claim 3 preparation method of mesoporous modified polyurethane resin, it is characterised in that: institute
In the preparation process of the zinc ammonia complex stated, ammonia adds in reactor with the speed of 2L/h.
The automotive trim the most according to claim 3 preparation method of mesoporous modified polyurethane resin, it is characterised in that: institute
In the preparation process of the presoma stated, ammonium silicate, zinc ammonia complex are solid.
The automotive trim the most according to claim 3 preparation method of mesoporous modified polyurethane resin, it is characterised in that: institute
In the preparation process of the mesoporous modified polyurethane resin stated, presoma adds to reactor when initially feeding intake.
The automotive trim the most according to claim 3 preparation method of mesoporous modified polyurethane resin, it is characterised in that: institute
In the preparation process of the mesoporous modified polyurethane resin stated, BACN adds to reactor at the end of final reaction.
The automotive trim the most according to claim 3 preparation method of mesoporous modified polyurethane resin, it is characterised in that: institute
The mesoporous modified polyurethane resin stated use roller coating, brush, spray, impregnating technique is coated on product surface.
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| CN201811118917.6A CN109265645A (en) | 2016-07-12 | 2016-07-12 | A kind of preparation method of mesoporous modified polyurethane resin for automobile interiors |
| CN201610544579.7A CN106188481B (en) | 2016-07-12 | 2016-07-12 | A kind of automotive trim mesoporous modified polyurethane resin and preparation method thereof |
| CN201811112674.5A CN109280145A (en) | 2016-07-12 | 2016-07-12 | A kind of preparation method of mesoporous modified polyurethane resin |
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| CN201811118917.6A Division CN109265645A (en) | 2016-07-12 | 2016-07-12 | A kind of preparation method of mesoporous modified polyurethane resin for automobile interiors |
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| CN201610544579.7A Expired - Fee Related CN106188481B (en) | 2016-07-12 | 2016-07-12 | A kind of automotive trim mesoporous modified polyurethane resin and preparation method thereof |
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| CN106905689A (en) * | 2017-03-27 | 2017-06-30 | 芜湖锐华暖通科技有限公司 | A kind of MULTILAYER COMPOSITE mute drain pipe fitting |
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- 2016-07-12 CN CN201811112674.5A patent/CN109280145A/en active Pending
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| CN1616354A (en) * | 2003-11-14 | 2005-05-18 | 湘潭大学 | Uniformly coordinating precipitation method for preparing nano zinc oxide |
| KR20070094312A (en) * | 2006-03-17 | 2007-09-20 | 마이크로코어텍(주) | Nano-porous silica beads with uniform pore size and their manufacturing process |
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| CN109265645A (en) | 2019-01-25 |
| CN106188481B (en) | 2018-09-28 |
| CN109280145A (en) | 2019-01-29 |
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