CN108797136B - A kind of polyurethane leather composition that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list - Google Patents
A kind of polyurethane leather composition that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list Download PDFInfo
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- CN108797136B CN108797136B CN201810684829.6A CN201810684829A CN108797136B CN 108797136 B CN108797136 B CN 108797136B CN 201810684829 A CN201810684829 A CN 201810684829A CN 108797136 B CN108797136 B CN 108797136B
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- China
- Prior art keywords
- polyurethane
- dialkyl group
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- thio
- fire
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 239000004814 polyurethane Substances 0.000 title claims abstract description 62
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- -1 thio hypophosphites Chemical class 0.000 title claims abstract description 48
- 239000010985 leather Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 241001365789 Oenanthe crocata Species 0.000 title claims abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims description 5
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000013005 condensation curing Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 55
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 238000005034 decoration Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 229910003202 NH4 Inorganic materials 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 229920001276 ammonium polyphosphate Polymers 0.000 description 7
- 239000002649 leather substitute Substances 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- SGPMZDLPUCDQQQ-UHFFFAOYSA-N 1-isocyano-3-(2,2,2-trihydroxyethyl)-7,9-dihydropurine-2,6,8-trione Chemical class OC(CN1C(N(C(C=2NC(NC1=2)=O)=O)[N+]#[C-])=O)(O)O SGPMZDLPUCDQQQ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 206010001557 Albinism Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000021167 banquet Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- KZVVGZKAVZUACK-BJILWQEISA-N rilpivirine hydrochloride Chemical compound Cl.CC1=CC(\C=C\C#N)=CC(C)=C1NC1=CC=NC(NC=2C=CC(=CC=2)C#N)=N1 KZVVGZKAVZUACK-BJILWQEISA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- 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
-
- 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
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1664—Releasability
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of polyurethane leather compositions that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list, using flame retardant polyurethane resin as superficial layer, the flame retardant polyurethane resin, by weight percentage, raw material composition include polyurethane matrix material system 65~90%；The thio hypophosphites 5~20% of dialkyl group list；At carbon component 1~15%；Shown in the thio hypophosphites structural formula of dialkyl group list such as following formula (I) or following formula (II), in formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4；Polyurethane leather composition provided by the invention can reach the inner decoration material for automobile combustion testing standard of FMVSS (american car security legislation) No.302.
Description
Technical field
The present invention relates to the technical fields of halogen-free anti-inflaming polyurethane, and in particular to a kind of no molten drop water stain-free is based on dialkyl group
The fire-retardant polyurethane leather composition of single thio hypophosphites.
Background technique
Polyurethane is a quasi polymer of main chain constitutional repeating unit Han-NHCOO-, english abbreviation PU, by isocyanates
(monomer) is polymerized with hydroxy compounds.Due to not dissolving in nonpolar solvent containing highly polar carbamate groups, have good
Good oil resistivity, toughness, wearability, resistance to ag(e)ing etc., is widely used multi-field.Wherein, it is as synthetic leather
A kind of important application of polyurethane material, it has soft glossy, naturally, soft, the strong appearance of kishke feel, has and base
The excellent mechanical performances such as material adhesive property is excellent, wear-resistant, flex endurant, anti-aging, resistance to fungi is good, while being also equipped with cold-resistant
The advantages that property is good, ventilative, washable, easy to process, cheap, is the ideal substitute of natural leather, answers extensively
For industries such as clothes, shoemaking, luggage, furniture, internal decorative material for vehicle, aircraft interior material, ship interior materials.
Application for furniture and vehicles interior material, relevant standard propose fire-retardant want higher to synthetic leather
It asks.Synthetic Leather is usually that polyurethane is impregnated with or is layered on the fiber base materials such as non-woven fabrics, textile, knitwear and shape
At, and it is different to constitute the combustion mechanism between the polyurethane resin of synthetic leather and fiber base material, therefore hinders Synthetic Leather
Burning is extremely difficult.
Currently, including the basic flame-retardant system of two classes for the fire-retardant of Synthetic Leather: halogen system flame-retardant system and non-
Halogen flame-retardant system.Halogen system flame-retardant system is usually brominated flame-retardant collaboration antimony oxide, a large number of studies show that, it is added with bromine system
The polyurethane material of fire retardant can produce thick smoke and the harmful substances such as hydrogen bromide in burning, human body can be caused to suffocate.Therefore, it is
The safe and environment-friendly, halogen-free flame-retardant system of polyurethane exploitation has become a hot topic of research, and occurs the novel polyurethane that is applied in recent years
Halogen-free flame retardants.
According to the literature, mainly include two major classes primary structure applied to the halogen-free flame retardants of polyurethane: one kind is inorganic
Hydroxide system, including magnesium hydroxide and aluminium hydroxide；Another kind of is phosphorus nitrogen system flame-retardant system.For inorganic hydroxide body
System, fire retardation is limited, and in order to reach the requirement of various codes and standards, usual additive amount is very high, sometime up to entirely matches
The 80% of cube system due to inorganic hydroxide fire retardant and matrix resin and incompatible is dispersed in a manner of a kind of filler
In matrix resin, therefore, high filler loading capacity will substantially reduce the mechanical property of material.Sometimes for reduction inorganic hydroxide
Additive amount, also by the way of red phosphorus collaboration, but the application of red phosphorus can have the appearance color of material, and the combustion of red phosphorus
Burning is easy to produce the toxic gases such as hydrogen phosphide and a large amount of smog, therefore this is also not optimal solution.For phosphorus nitrogen system
Flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency, additive amount is greatly reduced and is able to achieve high fire-retardance
Property, it is the hot spot studied at present.
Apply more at present, high polymerization degree APP (APP) and organophosphorus compounds, high polymerization degree polyphosphoric acid
Ammonium (APP) flame-retardant system, it belongs to a kind of Intumscent Flame Retardant System, and since its anti-flammability is stronger, additive amount compares inorganic hydrogen
Oxide system will substantially reduce, but APP is due to its surface hydrophilic characteristic, and have certain water solubility, still with basis material
It is so incompatible, therefore the mechanical strength of the fire-retardant polyurethane material of APP system is still very low, while being easy migration precipitation, is making
Product surface generates the albinism being precipitated.Further, since the presence of ammonium ion, APP is easy the moisture absorption, polyurethane skin after a period of time
It after leather goods surface is with the presence of droplet or leather contact water, is formed in product surface water stain after dry, influences the appearance of product,
There is tacky feel simultaneously, reduces the sense of touch of polyurethane leather；And organophosphorus ester, some still have water solubility, though some
It is so water-soluble small, it overcomes to form water stain problem, but to belong to condensed phase fire-retardant for its fire retardant mechanism, belongs to non-expansion type, it is non-swollen
Swollen type flame-retardant system is for polyurethane material, and in kindling, drippage easy to form, molten drop will affect flame retardant effect, be extremely difficult to mark
Quasi- requirement.
Generally speaking, it is applied to major defect existing for the flame-retardant system of polyurethane leather material at present: poor fire,
Easy molten drop, the easy moisture absorption form the problems such as water stain and migration albefaction.Therefore, it is necessary to research and develop novel to be applied to the new of polyurethane material
The halogen-free flame-retardant system of type.
Summary of the invention
The present invention develops a kind of polyurethane leather that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, the material have the characteristics that high fire-retardance, without molten drop, water stain-free, resistance to migration, and can reach FMVSS (american car safety
Regulation) No.302 inner decoration material for automobile combustion testing standard.
Specific technical solution is as follows:
A kind of polyurethane leather composition that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list, with fire-retardant
Polyurethane resin as superficial layer, then with the fibrous layer as substrate is compound is prepared；
The flame retardant polyurethane resin, by weight percentage, raw material composition includes:
Polyurethane matrix material system 65~90%；
The thio hypophosphites 5~20% of dialkyl group list；
At carbon component 1~15%；
Shown in the thio hypophosphites of dialkyl group list, structural formula such as following formula (I) or following formula (II):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1
~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m be 1~
4；
It is described to be divided into insoluble insoluble cross-linked polymer at carbon group, shown in Crosslink structure such as following formula (III):
The present invention relates to the exploitations of halogen-free anti-inflaming polyurethane leather, using the novel thio secondary phosphorus of low aqueous solubility dialkyl group list
Hydrochlorate forms the expansibility flame-proof mechanism for being directed to polyurethane, solves existing fire retardant by special low aqueous solubility carbonific
It is that additive amount is big, forms the defect of precipitation and molten drop water stain, easy to migrate with polyurethane base material poor compatibility, the easy moisture absorption.This is novel
Flame-retardant system can be well adapted for polyurethane material, polyurethane skin of the halogen-free flameproof water stain-free without molten drop being had excellent performance
Leather.
It will elaborate below to the present invention.
The present invention is for the purpose of solving various defects existing for existing halogen-free anti-inflaming polyurethane, and inventor has carried out extensively
And in-depth study.Existing flame-retardant system aiming at the problem that flame retardant polyurethane material, new flame-retardant system is investigated, has as a result been sent out
The existing thio hypophosphites of dialkyl group list, which cooperates with, special can be well solved this problem at carbon component.
Shown in the structural formula such as above formula (I) or above formula (II) of the thio hypophosphites of dialkyl group list；Preferably, described two
The thio hypophosphites of alkyl list, R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tert-butyl, positive penta
Base, isopentyl, n-hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.Further preferably, the dialkyl group list is thio
Hypophosphites is selected from the thio hypo-aluminum orthophosphate of diethyl list.
The invention also discloses a kind of preparation processes of the thio hypophosphites of dialkyl group list, to prepare dialkyl group list sulphur
For generation aluminum phosphate, specifically:
(1) the thio sodium hypophosphite solution of dialkyl group list is reacted in acid condition with aluminum sulfate solution, obtains dialkyl group
The suspension of single thio hypo-aluminum orthophosphate sediment；
(2) suspension will be filtered, washed and dry, pulverize at 120 DEG C to certain partial size, obtain dialkyl group list sulphur
For hypo-aluminum orthophosphate combustion inhibitor.
It wherein, can be by commercially available acquisition, or by the following method as the thio sodium hypophosphite of dialkyl group list of raw material
Preparation:
(a) reacting Acidic phosphates in the presence of the concentrated sulfuric acid with phosphorus pentasulfide can be generated the thio secondary phosphorus of dialkyl group list
Acid；
(b) the thio hypophosphorous acid of dialkyl group list is reacted with sodium hydroxide generates the thio sodium hypophosphite of dialkyl group list soluble easily in water
Salt.
The thio hypophosphites of dialkyl group list is characterized in phosphorus content height, there are also the collaboration of element sulphur, good flame resistance, have compared with
High temperature of initial decomposition, water-soluble extremely low, resistance to migration is nonhygroscopic, is that a kind of novel can be applied to the engineerings such as nylon, polyester
In plastics, especially in the engineering plastics of fiberglass reinforced.It is not in inhale since water solubility is extremely low applied to polyurethane material
Tide and there is water stain problem, but due to being condensed phase fire retardant mechanism, so that polyurethane material is easy drippage, reduction in burning again
Flame retardant property, if reaching flame-retardancy requirements by improving additive amount, can not can be caused by flame-retardancy requirements as defined in standard
The reduction of material property.
Inventors discovered through research that being added in the presence of dialkyl group list thio hypophosphites suitably at carbon
Component becomes expansion type flame-retarding to the fire retardant mechanism of polyurethane material at this time, and under the action of expanding carbon-coating, material melts
Drop is also under control, it is shown that good anti-flammability.
As at charcoal component, the usually compounds such as compound of polyhydroxy, such as pentaerythrite, but these compounds by
In the presence of hydroxyl, although have it is good at carbon effect, it is water-soluble higher, will appear asking for the moisture absorption after being applied to polyurethane
The problems such as inscribing, surfaces of tacky, water stain and insulating properties caused to reduce.
It is studied through inventor, discovery is by two kinds of compounds of methylphosphonic acid and trihydroxyethyl isocyanuric ester in equivalent
Under the conditions of carry out polycondensation reaction, obtain heat cured carboxylate, when application is crushed to the carboxylate in the powder of certain particle size range
End, it is as described at carbon component.This at carbon component had at carbon effect, the association having had with the thio hypophosphites of dialkyl group list
The same sex, there are phosphorus and nitrogen in molecular structure, can reduce the additive amount of the thio hypophosphites of dialkyl group list, same to molecular configurational
In since there is no water suction group, it is nonhygroscopic, not will form water stain, surfaces of tacky will not be caused.
The preparation method at carbon component, specifically:
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, 150~
4~8h is reacted at 220 DEG C, and esterification prepolymer is made；
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed
It arrives.
In the preparation process of step (1) prepolymer, in order to accelerate reaction speed, need using phase transfer catalyst.Make
To be preferred, the phase transfer catalyst is selected from quaternary ammonium salt, such as tetrabutylammonium bromide.
In step (2), high-temperature polycondensation solidification is carried out to prepolymer, needs high vacuum, hot conditions.Preferably, taking out true
Sky to vacuum degree is not higher than 50KPa.The reaction can carry out in an oven, also can be used with the high-power of agitating function
Kneader.
It is block by the fire retardant obtained after condensation curing, in order to be added in basis material, it is also necessary to carry out powder
Broken processing controls average grain diameter D50 < 5 μm of fire retardant using mechanical crushing equipment.
Meanwhile also the water that esterification generates is drained in time.Prepolymer changes colour in order to prevent, and reaction can be in nitrogen
Atmosphere carries out.
It is further preferred that the flame retardant polyurethane resin, by weight percentage, raw material composition includes:
Polyurethane matrix material system 80~90%；
The thio hypophosphites 8~15% of dialkyl group list；
At carbon component 2~6%.
To further increase cooperative flame retardant effect, the total addition level of the phosphorus nitrogen sulphur composite flame retardant system is 14~19%,
By weight percentage, composition includes:
The thio hypophosphites 62.5~87.5% of dialkyl group list；
At carbon component 12.5~37.5%.
Average grain diameter D50 < 5 μm of the thio hypophosphites of dialkyl group list, are also crushed to average grain diameter D50 at carbon component
<5μm。
The polyurethane matrix material system, including polyurethane matrix material and solvent and curing agent, described is poly-
Urethane basis material is the resin synthesized by polyalcohol, isocyanates and chain extender, including polyester-type, polyether-type, poly- carbonic acid
Ester type, polycaprolactone type etc. can be individually, be also possible to two or more and be used in combination.
In halogen-free flameproof polyurethane resin material of the invention, before not influencing the physical property and flame retardant property of polyurethane
It puts, other auxiliary agents, such as anti-mildew agent, antistatic agent, lubricant, anti-UV agent, antioxidant can be added.
Preferably, the fibrous layer is selected from non-woven fabrics, textile or knitwear.
The method for preparing halogen-free anti-inflaming polyurethane leather composition is not particularly limited, and can be well known wet process or dry
Method.The halogen-free anti-inflaming polyurethane leather being prepared can be applied to the seat of the interior material of automobile, train, aircraft, steamer etc.
Sheet material, ground cushion, ceiling tile materials etc., the tables and chairs of furniture, the attending a banquet of chair, curtain, venetian blind, valance etc., the account of outdoor
Paulin, vehicle cover etc..
Compared with prior art, the present invention has the advantage that
The present invention provides a kind of polyurethane leather compositions fire-retardant based on the thio hypophosphites of dialkyl group list, with fire-retardant
For polyurethane resin as superficial layer, which includes by the thio hypophosphites of dialkyl group list and special at carbon component
The novel flame-retardant system of composition, the polyurethane resin of the halogen-free flameproof being prepared have high fire-retardance, without molten drop, water stain-free, resistance to
The features such as migration, the halogen-free anti-inflaming polyurethane leather being prepared can reach FMVSS (american car security legislation) No.302's
Inner decoration material for automobile combustion testing standard.
Specific embodiment
Following performance is investigated to material:
(1) flame retardant property
Inner decoration material for automobile combustion testing standard according to FMVSS (american car security legislation) No.302.
(2) water stain experiment
Flame retardant polyurethane leather sample is placed in polyurethane foam, 5ml water is placed on surface, is placed and is air-dried, and surface is observed
Whether water stain formation is had.
(3) resistance to migration experiment
Flame retardant polyurethane leather is cut into the sample of 18 × 25cm, is put into climatic chamber, is arranged 85 DEG C of temperature, phase
To humidity 85%, the state of specimen surface of the visual observations after 168 hours.
The preparation of flame retardance element
(1) preparation of the thio hypo-aluminum orthophosphate of diethyl list
The sulfuric acid of diethyl list thio the sodium hypophosphite aqueous solution 960g and concentration 30wt% of compound concentration 20wt% respectively
Desalted water 1000g is added into reactor, and the aqueous sulfuric acid 50g of concentration 25wt% is added by aluminum water solution 228g, is warming up to
80 DEG C, starts to synchronize the thio sodium hypophosphite aqueous solution of dropwise addition diethyl list and aluminum sulfate solution in proportion into reaction kettle, obtain
The thio hypo-aluminum orthophosphate sediment of diethyl list, is added dropwise to complete for 2 hours, keeps the temperature 1 hour, is then filtered, washed, dries, obtain two
The thio hypo-aluminum orthophosphate combustion inhibitor 166g (yield 95%) of ethyl list.
After tested, 345 DEG C of the initial decomposition temperature of product, solubility is 0.05% in water.
(2) preparation process at carbon component is as follows:
In the flask of 1L, 522 grams of (2 moles) trihydroxyethyl isocyanuric esters are added, leads to nitrogen protection, is heated to 150
DEG C trihydroxyethyl isocyanuric ester is melted, 2.7 grams of tetrabutylammonium bromide and 288g (3 moles) methylphosphonic acid is then added,
Strong stirring mixture, heating is raised to 210 DEG C from 150 DEG C within 6 hours, the water in reaction process is discharged, and condense metering,
210 DEG C keep the temperature 1 hour, are cooled to 150 DEG C, and melt is discharged to a metal tray, obtains a kind of faint yellow hair after melt is cooling
Crisp solids, for melting range from 100~120 DEG C, residual acid value is 7 milligrams of KOH/g.
Prepolymer is placed into vacuum drying oven together with pallet, is vacuumized, vacuum degree keeps 50KPa, is heated to 270
DEG C, it is kept for 2 hours, completes solidification, cooling discharge.Crushing material is stand-by to average grain diameter D50 < 5 micron.
Through analyzing:
Preparation at carbon component, phosphorus content are as follows: 10.5%, nitrogen content are as follows: 10.1% (phosphorus, nitrogen content be actual measurement
Value, slightly below calculated value), solubility < 0.1%, 1% weightlessness decomposition temperature is 320 DEG C.
Embodiment 1
It follows these steps to prepare and characterizes polyurethane leather:
(1) flame retardant polyurethane resin composition is prepared by formula as below:
Polyurethane resin substrate system 84%；
The thio hypo-aluminum orthophosphate 12% of diethyl list；
At carbon component 4%；
Wherein, by weight, the composition of polyurethane resin substrate system are as follows:
(2) it by above-mentioned flame retardant polyurethane compositions, is coated on polyester warp knitting cloth, forms 250 μm of thickness of coating,
Dry solidification 3 minutes in 120 DEG C of drying machine, and pricked with the cloth machine pressure of bundle, aging in 72 hours is carried out at 40 DEG C, obtains fire-retardant conjunction
Finished leather.
(3) correlated performance is tested.
Each material and proportion are shown in Table 1 in embodiment, and the performance test results of obtained material are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, in addition to the thio hypo-aluminum orthophosphate of diethyl list and at the ratio adjustment of carbon component, mentions
The ratio of the high thio hypo-aluminum orthophosphate of diethyl list keeps flame-retardant system total amount constant.Other materials and proportion are shown in Table 1, acquired
Material the results are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, in addition to the thio hypo-aluminum orthophosphate of diethyl list and at the ratio adjustment of carbon component, mentions
Height keeps flame-retardant system total amount constant at the ratio of carbon component.Other materials and proportion are shown in Table 1, and obtained material result is shown in
Table 1.
Embodiment 4
Implementation process is same as Example 1, in addition to formula rate adjustment, reduces flame-retardant system sum-rate.Other materials
And proportion is shown in Table 1, obtained material the results are shown in Table 1.
Embodiment 5
Implementation process is same as Example 1, in addition to formula rate adjustment, improves flame-retardant system sum-rate.Other materials
And proportion is shown in Table 1, obtained material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, in addition to not using into carbon group exceptionally.Other materials and proportion are shown in Table 1, acquired
Material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than without using the thio hypo-aluminum orthophosphate of diethyl list.Other materials and proportion
It is shown in Table 1, obtained material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than only using ammonium polyphosphate, does not use the thio hypo-aluminum orthophosphate of diethyl list
With at carbon component.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, in addition to the thio hypo-aluminum orthophosphate of diethyl list is substituted for diethyl hypo-aluminum orthophosphate
Outside salt.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Table 1
Claims (9)
1. a kind of polyurethane leather composition that no molten drop water stain-free is fire-retardant based on the thio hypophosphites of dialkyl group list, feature exist
In, using flame retardant polyurethane resin as superficial layer, then with the fibrous layer as substrate is compound is prepared；
The flame retardant polyurethane resin, by weight percentage, raw material composition includes:
Polyurethane matrix material system 65~90%；
The thio hypophosphites 5~20% of dialkyl group list；
At charcoal component 1~15%；
Shown in the thio hypophosphites of dialkyl group list, structural formula such as following formula (I) or following formula (II):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K or NH4, m is 1~4；
It is described to be divided into insoluble insoluble cross-linked polymer at charcoal group, shown in Crosslink structure such as following formula (III):
2. the no molten drop water stain-free according to claim 1 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that the thio hypophosphites of dialkyl group list, R1、R2Independently selected from methyl, ethyl, n-propyl, just
Butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
3. the no molten drop water stain-free according to claim 1 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that the thio hypophosphites of dialkyl group list, average grain diameter D50 < 5 μm.
4. the no molten drop water stain-free according to claim 1 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that the preparation process at charcoal component, specifically:
(1) trihydroxyethyl isocyanuric ester and methylphosphonic acid of equivalent, under phase transfer catalyst effect, at 150~220 DEG C
Esterification prepolymer is made in 4~8h of lower reaction；
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed.
5. the no molten drop water stain-free according to claim 4 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that
The phase transfer catalyst is selected from quaternary ammonium salt；
It is described to vacuumize, until vacuum degree is not higher than 50KPa；
The crushing, until average grain diameter D50 < 5 μm.
6. the no molten drop water stain-free according to claim 1 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that the polyurethane matrix material system is selected from polyester polyurethane system, polyether polyurethane body
At least one of system, polycarbonate polyurethane system.
7. according to claim 1~6 it is any it is described without molten drop water stain-free based on fire-retardant poly- of the thio hypophosphites of dialkyl group list
Urethane leather composition, which is characterized in that by weight percentage, the raw material composition of the flame retardant polyurethane resin includes:
Polyurethane matrix material system 80~90%；
The thio hypophosphites 8~15% of dialkyl group list；
At charcoal component 2~6%.
8. the no molten drop water stain-free according to claim 1 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that the fibrous layer is non-woven fabrics or knitwear.
9. the no molten drop water stain-free according to claim 1 polyurethane leather fire-retardant based on the thio hypophosphites of dialkyl group list
Composition, which is characterized in that by wet process or dry method that the superficial layer and the fibrous layer is compound.
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