CN1693577A - Fire retarding polyurethane synthetic leather and its preparation method - Google Patents
Fire retarding polyurethane synthetic leather and its preparation method Download PDFInfo
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- CN1693577A CN1693577A CN 200510043502 CN200510043502A CN1693577A CN 1693577 A CN1693577 A CN 1693577A CN 200510043502 CN200510043502 CN 200510043502 CN 200510043502 A CN200510043502 A CN 200510043502A CN 1693577 A CN1693577 A CN 1693577A
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- China
- Prior art keywords
- flame retardant
- synthetic leather
- fire
- polyurethane
- retardant
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Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 59
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 58
- 239000002649 leather substitute Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 28
- 230000000979 retarding effect Effects 0.000 title claims description 25
- 239000003063 flame retardant Substances 0.000 claims abstract description 97
- 239000000654 additive Substances 0.000 claims abstract description 39
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 61
- 239000006185 dispersion Substances 0.000 claims description 29
- 239000003607 modifier Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229920001634 Copolyester Polymers 0.000 claims description 7
- 230000009970 fire resistant effect Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- -1 tribromoneoamyl alcohol Chemical class 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006757 chemical reactions by type Methods 0.000 claims description 5
- 239000012757 flame retardant agent Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 239000003340 retarding agent Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical class OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 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 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UUSVDJBYMWOMCY-UHFFFAOYSA-N 1,2-dibromobutane-1,1-diol Chemical class CCC(Br)C(O)(O)Br UUSVDJBYMWOMCY-UHFFFAOYSA-N 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims description 2
- BEUGUINOQBQTHY-UHFFFAOYSA-N P(=O)(OCC(O)CO)(O)O.N1=C(N)N=C(N)N=C1N Chemical compound P(=O)(OCC(O)CO)(O)O.N1=C(N)N=C(N)N=C1N BEUGUINOQBQTHY-UHFFFAOYSA-N 0.000 claims description 2
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 125000001246 bromo group Chemical class Br* 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000004970 Chain extender Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 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 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- PCIBVZXUNDZWRL-UHFFFAOYSA-N ethylene glycol monophosphate Chemical compound OCCOP(O)(O)=O PCIBVZXUNDZWRL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to a preparing technique for dispersing or copolymerizing additive fire retardant and/or reactive fire retardant in a solvent polyurethane system and its application to the production of polyurethane synthetic leather, belonging to the technical field of producing fire retardant synthetic leather. A fire retardant polyurethane synthetic leather has a composition of raw materials comprising fire retardant, and solvent polyurethane, where the fire retardant is additive fire retardant and/or reactive fire retardant. The invention succeeds in making higher fire retardant polyurethane synthetic leather, uneasy to fire and thoroughly eliminating the hidden trouble in the safety of polyurethane leather.
Description
One, affiliated technical field
The present invention relates to a kind of with additive flame retardant and/or reactive flame retardant be scattered in and/or react copolymerization in the solvent borne polyurethane system technology of preparing and be applied to the production of Synthetic Leather, belong to the technical field of preparation anti-flammability synthetic leather.This technology can be applicable to can obtain good flame-retardant effect in the preparation production of Synthetic Leather, polyurethane artificial leather and superfine fiber polyurethane leather.Adopt the polyurethane leather of this technology preparation to have and identical or close physical property, outward appearance and the feel of conventional polyurethanes leather, and has a stronger anti-flaming function, at seat, interior trim, furniture and other field of the fire-retardant requirement of higher safety is arranged, have wide promotion and application prospect.
Two, background technology
Polyurethane (PU) synthetic leather passes through years of development and makes things convenient for estimable advantages such as extensive with its good surface appearance feel and good, the wear-resisting anti-solvent of breathable moisture permeability tool, high strength, application, obtained using widely in each field such as industrial, civilian, military, closely bound up with people's production, life.Polyurethane leather adopts mainly that fabricbases such as polyurethane solutions and nonwoven fabric, nylon loop, woven are done, wet processes forms, this type of conventional urethane leather does not have flame-retarding characteristic, the shortcoming that exists common high molecular materials to be easy to burn, in that to bring for people's production, life comfortable and simultaneously easily, the very big potential safety hazard of also having hidden.
Three, summary of the invention
In view of above-mentioned prior art present situation, the present inventor is through studying for a long period of time, a kind of special preparation technology of final employing is scattered in and/or reacts copolymerization in the solvent borne polyurethane system with additive flame retardant and/or reactive flame retardant grinding, and utilizes above-mentioned technology successfully to make the Synthetic Leather with higher flame-retarding characteristic.
Technical solution of the present invention is as follows:
(1) a kind of fire retarding polyurethane synthetic leather of the present invention, its special character is that the raw material components of this Synthetic Leather includes fire retardant, solvent borne polyurethane;
The raw material components fire retardant of this Synthetic Leather is additive flame retardant or reactive flame retardant or additive flame retardant and reactive flame retardant;
(2) described additive flame retardant dispersion (fire-retardant dispersion) raw material components prescription is as follows:
100 parts of polyurethane resin solutions (weight portion)
Additive flame retardant 10-150 part
Dispersion aids 2-30 part
Modifier 1-15 part
Solvent 30-90 part;
The capital equipment that adopts is as follows:
High speed dispersor, drying equipment, high pressure homogenization machine, sand mill etc.;
Above-mentioned additive flame retardant comprises one or more in following: magnesium hydroxide, aluminium hydroxide, Firebrake ZB, APP, iron oxide red, iron oxide yellow, melamine, melamine phosphate, red phosphorus, antimony oxide, zinc oxide, magnesia, expanded graphite, aluminum phosphate, magnesium phosphate, trbasic zinc phosphate, TCEP, TCBP, TBC, deca-BDE, decabromodiphenyl, phosphoric acid ester derivant and other additive flame retardant agent materials;
Assistant packet contains solvent, modifier, dispersion aids, and wherein solvent comprises one or more in following: acetone, butanone, cyclohexanone, ethyl acetate, dimethylformamide, oxolane etc.; Modifier comprises that phosphate is that modifier, silicon are that modifier, titanate esters are modifier etc.; Dispersion aids comprises one or more in following: acrylic acid series dispersant, silicon are that dispersant, fluorine are dispersant etc.;
(3) preparation additive flame retardant dispersion technical process is as follows:
1. the additive flame retardant agent material being carried out drying dewaters;
2. the order of pressing solvent, modifier, dispersion aids, additive flame retardant adds high speed dispersor, selects processing temperature and time according to the material viscosity and the performance of different formulations;
3. polyurethane resin solution is added above-mentioned mixed system, fully mix dispersion;
4. fully grind by high pressure homogenization machine and/or sand mill, this process is capable of circulation carries out;
5. the dispersion grinding effect reaches metering packing after the standard.
(4) described reactive flame retardant copolymerization polyurethane system (fire-resistant copolyesters system) raw material group
Divide prescription as follows:
Solvent (DMF) 100 parts (weight portions) is joined
Reactive flame retardant 10-25 part
Isocyanates 5-20 part
Polyalcohol 5-25 part
Catalyst 0.001-0.03 part;
Described reactive flame retardant comprises one or more in following: melamine methylol, hydroxyethyl phosphate and derivative thereof, dibromoneopentyl glycol and ester derivative thereof, tribromoneoamyl alcohol, dibromo butanediol and ester derivative thereof, tetrabromobisphenol A, tetrabromobisphenol A two (hydroxyethyl ether), phosphorus-containing polyol etc., and present technique also is suitable for the reaction-type flame-retarding agent material that other contain active hydrogen simultaneously;
Catalyst comprises one or more in following: phosphoric acid, triphenyl phosphite, stannous octoate, dibutyl tin laurate or its compound;
(5) preparation feedback type fire retardant copolymerization polyurethane system technical process is as follows:
1. the reaction-type flame-retarding agent material carries out drying and dewaters, and moisture content is less than 0.3%;
2. the order of pressing solvent, catalyst, polyalcohol, reactive flame retardant adds reactor, fully stirs and control 40～60 ℃ of uniform temperatures;
3. isocyanates is added reactor in batches, total inventory is determined according to the viscosity situation of reaction system in temperature≤90 of strict control reaction system ℃;
4. back cooling, metering, packing react completely.
The capital equipment that adopts is as follows:
Dry water removal device, reactor, baking oven (drying room) etc.
(6) a kind of fire retarding polyurethane synthetic leather preparation method, its special character is that additive flame retardant and/or reactive flame retardant grinding are scattered in and/or react copolymerization in the solvent borne polyurethane system, make the Synthetic Leather with higher flame-retarding characteristic;
The polyurethane resin that is used for the present invention can be the solubility polyurethane resin of any kind, comprise polyester-type, polyether-type, poly-carbon type and copoly type etc. by the polyalcohol classification, poly-carbon type is meant polycarbonate type, and copoly type is meant polyester, polyethers, poly-carbon copoly type; Comprise toluene di-isocyanate(TDI) (TDI type), methyl diphenylene diisocyanate (MDI type), hexamethylene diisocyanate (HDI type), isophorone diisocyanate (IPDI type), hydrogenated diphenyl methane diisocyanate (H by the isocyanates classification
12The MDI type) and copoly type etc.; Comprise alcohols chain extender and amine chain extender etc. by the chain extender classification.
The preparation technology of fire retarding polyurethane synthetic leather
Basic craft course:
Fire retardant preparation → nonwoven fabric → impregnation → solidify → extract out → wash → dye napping → the make face that oils → polish
Different cultivars and purposes according to product prepare fire retarding polyurethane synthetic leather through above-mentioned technical process, the acquisition of anti-flammability mainly lean against " impregnation " and " making face " two procedures with " fire-retardant dispersion " and/or " fire-resistant copolyesters system " by height stir disperse to join impregnation with and the face made from realizing in the polyurethane feed liquid, its addition requires to adjust according to different anti-flammabilitys, thereby obtains different anti-flammability products.
The present invention adopts special preparation technology that additive flame retardant and/or reactive flame retardant grinding are scattered in and/or react copolymerization in the solvent borne polyurethane system, successfully made Synthetic Leather with higher flame-retarding characteristic, overcome the conventional urethane leather and do not had the shortcoming that flame-retarding characteristic exists common high molecular materials to be easy to burn, thoroughly eliminated the Synthetic Leather potential safety hazard.
Four, the specific embodiment
Embodiment 1:
A kind of fire retarding polyurethane synthetic leather, its raw material components includes additive flame retardant, solvent borne polyurethane, additive flame retardant dispersion (fire-retardant dispersion) raw material components prescription is: polyurethane resin solution 100 parts (according to weight portions) is joined 10 parts of additive flame retardant magnesium hydroxides, 2 parts of acrylic acid series dispersion aidss, phosphate is 1 part of a modifier, 30 parts of solvent acetone;
Additive flame retardant preparation technology is:
A. the additive flame retardant agent material being carried out drying with drying equipment dewaters;
B. the order of pressing solvent, modifier, dispersion aids, additive flame retardant adds high speed dispersor, selects processing temperature and time according to the material viscosity and the performance of different formulations;
C. polyurethane resin solution is added above-mentioned mixed system, fully mix dispersion;
D. fully grind by high pressure homogenization machine and/or sand mill, this process is capable of circulation carries out;
E. the dispersion grinding effect reaches metering packing after the standard.
Fire retarding polyurethane synthetic leather preparation method basic craft course is: fire retardant preparation → nonwoven fabric → impregnation → solidify → extract out → wash → dye napping → the make face that oils → polish, " impregnation " and " making face " two procedures " fire-retardant dispersion " stirred by height disperse to join impregnation with and the face of making realize in the polyurethane feed liquid.
Embodiment 2:
A kind of fire retarding polyurethane synthetic leather, its raw material components includes reactive flame retardant, solvent borne polyurethane, reactive flame retardant copolymerization polyurethane system (fire-resistant copolyesters system) material component prescription is as follows: 10 parts of 100 parts of (according to weight portion) reactant ligands of solvent (DMF) type fire retardant melamine methylols, 5 parts of isocyanates, 5 parts of polyalcohols, 0.001 part of phosphoric acid catalyst;
Reactive flame retardant preparation technology is:
A. the reaction-type flame-retarding agent material carries out drying with dry water removal device and dewaters;
B. the order of pressing solvent, catalyst, polyalcohol, reactive flame retardant adds reactor, fully stirs and control 40 ℃ of uniform temperatures;
C. isocyanates is added reactor in batches, 70～85 ℃ of the temperature of strict control reaction system are determined total inventory according to the viscosity situation of reaction system;
D. the back metering packing reacts completely.
Fire retarding polyurethane synthetic leather preparation method basic craft course is: fire retardant preparation → nonwoven fabric → impregnation → solidify → extract out → wash → dye napping → the make face that oils → polish, " impregnation " and " making face " two procedures " fire-resistant copolyesters system " stirred by height disperse to join impregnation with and the face of making realize in the polyurethane feed liquid.
Embodiment 3:
A kind of fire retarding polyurethane synthetic leather, its raw material components includes additive flame retardant and reactive flame retardant, solvent borne polyurethane, additive flame retardant dispersion (fire-retardant dispersion) raw material components prescription is: polyurethane resin solution 100 parts (according to weight portions) is joined 150 parts of additive flame retardant APP, silicon is 30 parts of dispersants, silicon is 15 parts of modifier, 90 parts of solvents (DMF); Reactive flame retardant copolymerization polyurethane system (fire-resistant copolyesters system) raw material components prescription is as follows: 25 parts of 100 parts of (according to weight portion) reactant ligands of solvent (DMF) type fire retardant tribromoneoamyl alcohols, 20 parts of isocyanates, 25 parts of polyalcohols, 0.03 part of triphenyl phosphite catalyst;
Additive flame retardant and reactive flame retardant and fire retarding polyurethane synthetic leather preparation method with
Embodiment 1,2 is identical.
Embodiment 4:
A kind of fire retarding polyurethane synthetic leather, its raw material components includes additive flame retardant and reactive flame retardant, solvent borne polyurethane, additive flame retardant dispersion (fire-retardant dispersion) raw material components prescription is: polyurethane resin solution 100 parts (according to weight portions) is joined 80 parts of additive flame retardant melamine phosphates, fluorine is 15 parts of dispersants, titanate esters is 8 parts of modifier, 60 parts of solvents tetrahydrofurane; Reactive flame retardant copolymerization polyurethane system (fire-resistant copolyesters system) raw material components prescription is as follows: 17 parts of 100 parts of (according to weight portion) reactant ligands of solvent (DMF) type fire retardant phosphorus-containing polyols, 13 parts of isocyanates, 16 parts of polyalcohols, 0.01 part of stannous octoate catalyst;
Additive flame retardant and reactive flame retardant and fire retarding polyurethane synthetic leather preparation method with
Embodiment 1,2 is identical.
The fire retarding polyurethane synthetic leather of the embodiment of the invention 1,2,3,4 preparations has higher flame-retarding characteristic, overcome the conventional urethane leather and do not had the shortcoming that flame-retarding characteristic exists common high molecular materials to be easy to burn, thoroughly eliminated the Synthetic Leather potential safety hazard.
Following table is that the flame-retarding characteristic (oxygen index (OI)) of different flame retardant combination and consumption products obtained therefrom is given an example, purpose is to further specify different flame retardant combination and consumption to the influence of product flame-retarding characteristic (oxygen index (OI)), does not represent this patent only to be applicable to listed fire retardant scope in the table.
Product laboratory sample flame-retarding characteristic (oxygen index (OI)) and fire retardant consumption (percentage by weight) table
Annotate: 1, the fire retardant consumption is meant each fire retardant shared percentage by weight in sample in the table.
2, the fire retardant kind title of each alphabetical representative:
A: magnesium hydroxide B: aluminium hydroxide C: iron oxide red
D: antimony oxide E: aluminum phosphate F: deca-BDE
G: red phosphorus H: tetrabromobisphenol A I: dibromoneopentyl glycol
J: melamine K: hydroxyethyl phosphate L: expanded graphite
M: APP N: Firebrake ZB
Claims (10)
1, a kind of fire retarding polyurethane synthetic leather is characterized in that the raw material components of this Synthetic Leather includes fire retardant, solvent borne polyurethane.
2, according to the described a kind of fire retarding polyurethane synthetic leather of claim 1, the raw material components fire retardant that it is characterized in that this Synthetic Leather is additive flame retardant or reactive flame retardant or additive flame retardant and reactive flame retardant.
3, according to the described a kind of fire retarding polyurethane synthetic leather of claim 2, it is characterized in that described additive flame retardant dispersion raw material components is as follows according to the weight portion prescription: 100 parts of polyurethane resin solutions, join additive flame retardant 10-150 part, assistant packet contains dispersion aids 2-30 part, modifier 1-15 part, solvent 30-90 part.
4, according to the described a kind of fire retarding polyurethane synthetic leather of claim 3, it is characterized in that described additive flame retardant comprises one or more in following: magnesium hydroxide, aluminium hydroxide, Firebrake ZB, APP, iron oxide red, iron oxide yellow, melamine, melamine phosphate, red phosphorus, antimony oxide, zinc oxide, magnesia, expanded graphite, aluminum phosphate, magnesium phosphate, trbasic zinc phosphate, TCEP, TCBP, TBC, deca-BDE, ten bromines connect benzene, phosphoric acid ester derivant and other additive flame retardant agent materials; Auxiliary agent comprises solvent, modifier, dispersion aids, and wherein solvent comprises one or more in following: acetone, butanone, cyclohexanone, ethyl acetate, dimethylformamide, oxolane; Modifier comprises one or more in following: phosphate is that modifier, silicon are that modifier, titanate esters are modifier; Dispersion aids comprises one or more in following: acrylic acid series dispersant, silicon are that dispersant, fluorine are dispersant.
5, according to the described a kind of fire retarding polyurethane synthetic leather of claim 2, it is characterized in that described reactive flame retardant copolymerization polyurethane system raw material components is as follows according to the weight portion prescription: 100 parts of solvents, reactive flame retardant 10-25 part, isocyanates 5-20 part, polyalcohol 5-25 part, catalyst 0.001-0.03 part.
6, according to the described a kind of fire retarding polyurethane synthetic leather of claim 5, it is characterized in that described reactive flame retardant comprises one or more in following: melamine methylol, hydroxyethyl phosphate and derivative thereof, dibromoneopentyl glycol and ester derivative thereof, tribromoneoamyl alcohol, dibromo butanediol and ester derivative thereof, tetrabromobisphenol A, two, the phosphorus-containing polyol of tetrabromobisphenol A, present technique also is suitable for other reaction-type flame-retarding agent materials simultaneously; Catalyst is one or more in following: phosphoric acid, triphenyl phosphite, stannous octoate, dibutyl tin laurate or its compound.
7, a kind of fire retarding polyurethane synthetic leather preparation method is characterized in that additive flame retardant and/or reactive flame retardant grinding are scattered in and/or react copolymerization in the solvent borne polyurethane system, makes the Synthetic Leather with higher flame-retarding characteristic.
8, according to the described a kind of fire retarding polyurethane synthetic leather preparation method of claim 7, it is characterized in that its basic craft course is: fire retardant preparation → nonwoven fabric → impregnation → solidify → extract out → wash → dye napping → the make face that oils → polish, " impregnation " and " making face " two procedures " fire-retardant dispersion " and/or " fire-resistant copolyesters system " stirred by height disperse to join impregnation with and the face of making realize in the polyurethane feed liquid.
9,, it is characterized in that described additive flame retardant preparation technology is according to the described a kind of fire retarding polyurethane synthetic leather preparation method of claim 8:
A. the additive flame retardant agent material being carried out drying with drying equipment dewaters;
B. the order of pressing solvent, modifier, dispersion aids, additive flame retardant adds high speed dispersor, selects processing temperature and time according to the material viscosity and the performance of different formulations;
C. polyurethane resin solution is added above-mentioned mixed system, fully mix dispersion;
D. fully grind by high pressure homogenization machine and/or sand mill, this process is capable of circulation carries out;
E. the dispersion grinding effect reaches metering packing after the standard.
10,, it is characterized in that described reactive flame retardant preparation technology is according to the described a kind of fire retarding polyurethane synthetic leather preparation method of claim 8:
A. the reaction-type flame-retarding agent material carries out drying with dry water removal device and dewaters;
B. the order of pressing solvent, catalyst, polyalcohol, reactive flame retardant adds reactor, fully stirs and control 40～60 ℃ of uniform temperatures;
C. isocyanates is added reactor in batches, total inventory is determined according to the viscosity situation of reaction system in temperature≤90 of strict control reaction system ℃;
D. the back metering packing reacts completely.
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