CN103641971B - Phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure and preparation method thereof - Google Patents
Phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure and preparation method thereof Download PDFInfo
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- CN103641971B CN103641971B CN201310689458.8A CN201310689458A CN103641971B CN 103641971 B CN103641971 B CN 103641971B CN 201310689458 A CN201310689458 A CN 201310689458A CN 103641971 B CN103641971 B CN 103641971B
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- alcohol
- phosphorus
- vulcabond
- phosphorus element
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 58
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 125000003368 amide group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000004185 ester group Chemical group 0.000 title abstract 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 37
- 239000011574 phosphorus Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 150000002148 esters Chemical group 0.000 claims description 13
- -1 phosphorous acid ester Chemical class 0.000 claims description 11
- FGYHQFZISBDLDR-UHFFFAOYSA-N OCCC[PH2]=O Chemical compound OCCC[PH2]=O FGYHQFZISBDLDR-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- FAUKXDZDINMBSZ-UHFFFAOYSA-N 3-bis(methylperoxy)phosphoryl-n-(hydroxymethyl)propanamide Chemical compound COOP(=O)(OOC)CCC(=O)NCO FAUKXDZDINMBSZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 claims description 3
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 claims description 3
- QFUAZGOBONNJEI-UHFFFAOYSA-N 4-diphenylphosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 QFUAZGOBONNJEI-UHFFFAOYSA-N 0.000 claims description 3
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical class N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 3
- PIZOTVJLMRCOJB-UHFFFAOYSA-N Oc1ccc(cc1)P(=O)c1ccccc1 Chemical compound Oc1ccc(cc1)P(=O)c1ccccc1 PIZOTVJLMRCOJB-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010985 leather Substances 0.000 abstract description 15
- 239000000835 fiber Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229920001410 Microfiber Polymers 0.000 description 15
- 239000002649 leather substitute Substances 0.000 description 15
- 239000004814 polyurethane Substances 0.000 description 15
- 229920002635 polyurethane Polymers 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 1
- DPXFJZGPVUNVOT-UHFFFAOYSA-N 3-[1,3-bis[3-(dimethylamino)propyl]triazinan-5-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCC1CN(CCCN(C)C)NN(CCCN(C)C)C1 DPXFJZGPVUNVOT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
- C08G18/3887—Phosphite compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/579—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them modified by compounds containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses phosphorus-nitrogen containing flame retardant of a kind of amido-containing acid ester structure and preparation method thereof, comprise the steps: the trivalent alcohol of the dibasic alcohol of phosphorus element-containing, phosphorus element-containing, catalysts and solvents, be uniformly mixed, then vulcabond is added, reaction, add the monohydroxy-alcohol reaction of phosphorus element-containing again, by solvent evaporate to dryness, the phosphorus-nitrogen containing flame retardant of described amido-containing acid ester structure can be obtained.The present invention is not a kind of phosphorus-nitrogen type expanding fire retardant, halogen-containing, containing heavy metal, nontoxic, is a kind of fire retardant of environmental protection; Building-up process is simply easy to control, and phosphorus nitrogen content is high, flame retardant effect is excellent, has remarkable consistency with urethane, well can be scattered in various urethane and use system; There is certain reticulated structure simultaneously, make it does not dissolved in toluene system, thus the fire-retardant superfine fiber chemical leather field that need produce through toluene decrement can be applied to.
Description
Technical field
The present invention relates to a kind of phosphorus-nitrogen containing flame retardant and preparation method thereof, particularly relate to phosphorus-nitrogen containing flame retardant of a kind of amido-containing acid ester structure and preparation method thereof.
Background technology
Superfine fiber chemical leather (being called for short: super fine leather) comprises superior automobile bearing circle leather, superior automobile seat leather, superior automobile door-plate leather and superior automobile panel board leather etc. in the application in automotive trim field, has the huge market space.Flame retardant properties is the key characteristic of automotive trim product, and this performance is all classified as the prerequisite pressure performance requriements of automotive trim product by each main engine plants.
For the fire-retardant finish of super fine leather, the technology of domestic and international main flow known is at present add in urethane China and foreign countries the flame-retardancy requirements that fire retardant has reached each the finished product client.In current superfine fiber chemical leather industry, fire retardant application is more is bromide fire retardant, because its flame retarding efficiency is high, has good synergistic effect with antimony, is the fire retardant that the cost performance of generally acknowledging in the industry is the highest; But the product applying this fire-retardant agent can discharge poisonous and hazardous gas in combustion in a large number, large to human injury.Especially prohibit the use the cry of halogen flame to grow to even greater heights in European Union area in Europe.
And flame retardant properties is only second to the novel environment friendly fire retardant mainly phosphorus-nitrogen containing flame retardant of halogen flame at present.Need in the superfine fiber chemical leather production process of current domestic main flow to carry out decrement treatment and high temperature washing process through high temperature toluene, current most of phosphorus-nitrogen containing flame retardant is difficult to still be retained in superfine fiber chemical leather after this condition process; On the other hand, phosphorus-nitrogen containing flame retardant and superfine fiber chemical leather flood the urethane poor compatibility used in production process, which results in fire retardant skewness in superfine fiber chemical leather, finally make the flame retardant effect of leather unstable.
Summary of the invention
The object of the invention is phosphorus-nitrogen containing flame retardant of openly a kind of amido-containing acid ester structure and preparation method thereof, to overcome the defect that prior art exists.
The preparation method of the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure of the present invention, comprise the steps: the trivalent alcohol of the dibasic alcohol of phosphorus element-containing, phosphorus element-containing, catalysts and solvents, be uniformly mixed, then vulcabond is added, react 0.5 ~ 2 hour at 50 ~ 100 DEG C, the monohydroxy-alcohol adding phosphorus element-containing again reacts 10 ~ 30 minutes, by solvent evaporate to dryness, can obtain the phosphorus-nitrogen containing flame retardant of described amido-containing acid ester structure;
The mol ratio of vulcabond and alcohol is:
The mole dosage of the trivalent alcohol of phosphorus element-containing is 50% ~ 6% of vulcabond;
The mole dosage of the dibasic alcohol of phosphorus element-containing is 0 ~ 94% of vulcabond;
The mole dosage of the monohydroxy-alcohol of phosphorus element-containing is 50% ~ 0 of vulcabond;
The consumption of described catalyzer is 0.05% ~ 5% of the total mass of vulcabond and alcohol;
Described solvent load is 5% ~ 500% of the total mass of vulcabond and alcohol, preferably 50% ~ 200%;
The trivalent alcohol of described phosphorus element-containing be selected from three (3-hydroxypropyl) phosphine oxide (trade name: FR-T), three (dipropylene glycol) phosphorous acid ester (No. CAS: 36788-39-3), trishydroxymethyl phosphine oxide (No. CAS: 1067-12-5) one or more;
The dibasic alcohol of described phosphorus element-containing is selected from N, one or more in two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl ester (No. CAS: 2781-11-5) of N-, two (3-hydroxypropyl) phosphine oxide (trade name: FR-D) of N, N-two (2-hydroxyethyl) AminomethylphosphoniAcid Acid dimethyl ester, two (4-hydroxyphenyl) phenyl phosphine oxide (No. CAS: 795-43-7) or normal-butyl;
The monohydroxy-alcohol of described phosphorus element-containing is selected from 1-oxo-4-methylol-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane, N-methylol-3-(dimethoxy phosphono) propionic acid amide, 4-hydroxyphenyl diphenyl phosphine oxide, one or more in ring octyl group (3-hydroxypropyl) phosphine oxide;
Described vulcabond is selected from tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), 1, one or more in hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), methyl cyclohexyl vulcabond (HTDI), two cyclohexyl methane diisocyanates (HMDI), tetramethylxylylene diisocyanate (TMXDI);
Described catalyzer is triethylamine, 1, one or more in 3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, cyclohexyl methyl tertiary amine, pentamethyl-two alkylene triamine, tetramethyl-Alkylenediamine, 4-methyl-diaminopropane, tetramethyl butane diamine, 4-methyl hexamethylene diamine;
Described solvent is one or more in 1-Methoxy-2-propyl acetate, vinyl acetic monomer, N-BUTYL ACETATE, acetone, methylethylketone, pimelinketone, tetrahydrofuran (THF), dioxane or dimethyl formamide.
Compared with prior art, the invention has the beneficial effects as follows:
1. fire retardant of the present invention is not a kind of phosphorus-nitrogen type expanding fire retardant, halogen-containing, containing heavy metal, nontoxic, is a kind of fire retardant of environmental protection;
2. fire-retardant FRW process of the present invention is simply easy to control, and the catalyzer Nitrogen element adopted in synthesis and the monohydroxy-alcohol of end-blocking contain phosphoric, have the advantages that phosphorus nitrogen content is high, flame retardant effect is excellent;
3. fire retardant of the present invention contains carbamate structures, has remarkable consistency with urethane, well can be scattered in various urethane and use system;
4. fire retardant of the present invention makes its molecule have certain reticulated structure by adding trivalent alcohol, makes it does not dissolved in toluene system, thus can be applied to the fire-retardant superfine fiber chemical leather field that need produce through toluene decrement.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited.
Embodiment 1
Trivalent alcohol by described phosphorus element-containing: 215 gram of three (dipropylene glycol) phosphorous acid ester, catalyzer: 1, 3, 5-tri-(dimethylamino-propyl) Hexahydrotriazine 0.2854 gram and solvent dimethylformamide 2853.8 grams add in reaction vessel, after stirring, add vulcabond: ditan-4, 4 '-vulcabond 250.26 grams, and be warming up to 100 DEG C, and react 2 hours in this temperature, add the monohydroxy-alcohol of phosphorus element-containing again: N-methylol-3-(dimethoxy phosphono) propionic acid amide 105.5 grams, react 30 minutes, after solvent evaporate to dryness is obtained white powder, it is exactly the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure.When in polyurethane ultrafine fiber synthetic leather containing 30%(mass percentage) this fire retardant time, when the method provided by GB8410-2006 carries out combustion testing, the combustionvelocity of polyurethane ultrafine fiber synthetic leather is 51mm/min, meet the requirement of automotive trim product flame retardant properties in this standard, and adopt the polyurethane ultrafine fiber synthetic leather of this fire retardant in combustion without molten drop.
Embodiment 2
Dibasic alcohol by described phosphorus element-containing: 150 grams of (N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl ester of N-, the trivalent alcohol of phosphorus element-containing: 37.82 grams of trishydroxymethyl phosphine oxides, catalyzer: triethylamine 8.81 grams and solvent dioxane 400 grams add in reaction vessel, after stirring, add vulcabond: ditan-4, 4 '-vulcabond 250.26 grams, and be warming up to 75 DEG C, and react 1.5 hours in this temperature, add the monohydroxy-alcohol of phosphorus element-containing again: N-methylol-3-(dimethoxy phosphono) propionic acid amide 2.616 grams, react 20 minutes, after solvent evaporate to dryness is obtained white powder, it is exactly the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure.When in polyurethane ultrafine fiber synthetic leather containing 30%(mass percentage) this fire retardant time, when the method provided by GB8410-2006 carries out combustion testing, the combustionvelocity of polyurethane ultrafine fiber synthetic leather is 16mm/min, meet the requirement of automotive trim product flame retardant properties in this standard, and adopt the polyurethane ultrafine fiber synthetic leather of this fire retardant in combustion without molten drop.
Embodiment 3
Dibasic alcohol by described phosphorus element-containing: 291.66 grams of two (4-hydroxyphenyl) phenyl phosphine oxides, the trivalent alcohol of phosphorus element-containing: 8.4 grams of trishydroxymethyl phosphine oxides, catalyzer: cyclohexyl methyl tertiary amine 23.41 grams and solvent propylene glycol methyl ether acetate 23.41 grams add in reaction vessel, after stirring, add vulcabond: 1, hexamethylene-diisocyanate 168.19 grams, and be warming up to 50 DEG C, and react 0.5 hour in this temperature, after solvent evaporate to dryness is obtained colourless transparent liquid, be exactly the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure.When in polyurethane ultrafine fiber synthetic leather containing 30%(mass percentage) this fire retardant time, when the method provided by GB 8410-2006 carries out combustion testing, the combustionvelocity of polyurethane ultrafine fiber synthetic leather is 63mm/min, meet the requirement of automotive trim product flame retardant properties in this standard, and adopt the polyurethane ultrafine fiber synthetic leather of this fire retardant in combustion without molten drop.
Embodiment 4
Dibasic alcohol by described phosphorus element-containing: 154.46 grams of two (3-hydroxypropyl) phosphine oxides of normal-butyl, the trivalent alcohol of phosphorus element-containing: 44.86 gram of three (3-hydroxypropyl) phosphine oxide (molecular weight: 224.3), catalyzer: tetramethyl butane diamine 0.724 gram and solvent cyclohexanone 482.79 grams add in reaction vessel, after stirring, add vulcabond: two cyclohexyl methane diisocyanates 262.35 grams, and be warming up to 65 DEG C, and react 1 hour in this temperature, add the monohydroxy-alcohol of phosphorus element-containing again: ring octyl group (3-hydroxypropyl) phosphine oxide 2.16 grams, react 10 minutes, after solvent evaporate to dryness is obtained colourless transparent liquid, it is exactly the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure.When in polyurethane ultrafine fiber synthetic leather containing 30%(mass percentage) this fire retardant time, when the method provided by GB 8410-2006 carries out combustion testing, the combustionvelocity of polyurethane ultrafine fiber synthetic leather is 47mm/min, meet the requirement of automotive trim product flame retardant properties in this standard, and adopt the polyurethane ultrafine fiber synthetic leather of this fire retardant in combustion without molten drop.
Embodiment 5
Dibasic alcohol by described phosphorus element-containing: 68.18 grams of N, two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid dimethyl ester of N-, the trivalent alcohol of phosphorus element-containing: 89.72 gram of three (3-hydroxypropyl) phosphine oxide, catalyzer: cyclohexyl methyl tertiary amine 12.81 grams and solvents tetrahydrofurane 853.9 grams add in reaction vessel, after stirring, add vulcabond: naphthalene-1, 5-vulcabond 210.19 grams, and be warming up to 60 DEG C, and react 2 hours in this temperature, add the monohydroxy-alcohol of phosphorus element-containing again: 4-hydroxyphenyl diphenyl phosphine oxide 58.86 grams, react 25 minutes, after solvent evaporate to dryness is obtained colourless transparent liquid, it is exactly the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure.When in polyurethane ultrafine fiber synthetic leather containing 30%(mass percentage) this fire retardant time, when the method provided by GB 8410-2006 carries out combustion testing, the combustionvelocity of polyurethane ultrafine fiber synthetic leather is 41mm/min, meet the requirement of automotive trim product flame retardant properties in this standard, and adopt the polyurethane ultrafine fiber synthetic leather of this fire retardant in combustion without molten drop.
Claims (6)
1. the preparation method of the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure, it is characterized in that, comprise the steps: the trivalent alcohol of the dibasic alcohol of phosphorus element-containing, phosphorus element-containing, catalysts and solvents, be uniformly mixed, then add vulcabond, reaction, then add the monohydroxy-alcohol reaction of phosphorus element-containing, by solvent evaporate to dryness, the phosphorus-nitrogen containing flame retardant of described amido-containing acid ester structure can be obtained;
The trivalent alcohol of described phosphorus element-containing be selected from three (3-hydroxypropyl) phosphine oxide, three (dipropylene glycol) phosphorous acid ester, trishydroxymethyl phosphine oxide one or more;
The dibasic alcohol of described phosphorus element-containing is selected from N, one or more in two (2-hydroxyethyl) the AminomethylphosphoniAcid Acid diethyl ester of N-, two (3-hydroxypropyl) phosphine oxide of N, N-two (2-hydroxyethyl) AminomethylphosphoniAcid Acid dimethyl ester, two (4-hydroxyphenyl) phenyl phosphine oxide or normal-butyl;
The monohydroxy-alcohol of described phosphorus element-containing is selected from 1-oxo-4-methylol-2, one or more in 6,7-trioxa-1-phosphabicyclo [2.2.2] octane, N-methylol-3-(dimethoxy phosphono) propionic acid amide, 4-hydroxyphenyl diphenyl phosphine oxide, ring octyl group (3-hydroxypropyl) phosphine oxide;
Described vulcabond is selected from tolylene diisocyanate, ditan-4,4 '-vulcabond, 1, one or more in hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, methyl cyclohexyl vulcabond, two cyclohexyl methane diisocyanates, tetramethylxylylene diisocyanate.
2. method according to claim 1, it is characterized in that, comprise the steps: the trivalent alcohol of the dibasic alcohol of phosphorus element-containing, phosphorus element-containing, catalysts and solvents, be uniformly mixed, then vulcabond is added, react 0.5 ~ 2 hour at 50 ~ 100 DEG C, then the monohydroxy-alcohol adding phosphorus element-containing reacts 10 ~ 30 minutes.
3. method according to claim 1, is characterized in that, the mol ratio of vulcabond and alcohol is: the mole dosage of the trivalent alcohol of phosphorus element-containing is 50% ~ 6% of vulcabond; The mole dosage of the dibasic alcohol of phosphorus element-containing is 0 ~ 94% of vulcabond; The mole dosage of the monohydroxy-alcohol of phosphorus element-containing is 50% ~ 0 of vulcabond; The consumption of described catalyzer is 0.05% ~ 5% of the total mass of vulcabond and alcohol; Described solvent load is 5% ~ 500% of the total mass of vulcabond and alcohol.
4. method according to claim 1, it is characterized in that, described catalyzer is triethylamine, 1, one or more in 3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, cyclohexyl methyl tertiary amine, pentamethyl-two alkylene triamine, tetramethyl-Alkylenediamine, 4-methyl-diaminopropane, tetramethyl butane diamine, 4-methyl hexamethylene diamine.
5. method according to claim 4, is characterized in that, described solvent is one or more in 1-Methoxy-2-propyl acetate, vinyl acetic monomer, N-BUTYL ACETATE, acetone, methylethylketone, pimelinketone, tetrahydrofuran (THF), dioxane or dimethyl formamide.
6. the phosphorus-nitrogen containing flame retardant of amido-containing acid ester structure prepared by the method according to any one of Claims 1 to 5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345324A (en) * | 1999-02-26 | 2002-04-17 | Ucb公司 | Phosphorus-comprising materials, their preparation and use |
| WO2012126179A1 (en) * | 2011-03-23 | 2012-09-27 | Dow Global Technologies Llc | Phosphorous-containing flame retardants for polyurethane foams |
| CN103073986A (en) * | 2012-12-19 | 2013-05-01 | 烟台万华聚氨酯股份有限公司 | Advanced flame-retardant polyurethane spray foam material and preparation method thereof |
| CN103443186A (en) * | 2011-03-23 | 2013-12-11 | 陶氏环球技术有限责任公司 | Phosphorous Flame Retardants for Polyurethane Foam |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345324A (en) * | 1999-02-26 | 2002-04-17 | Ucb公司 | Phosphorus-comprising materials, their preparation and use |
| WO2012126179A1 (en) * | 2011-03-23 | 2012-09-27 | Dow Global Technologies Llc | Phosphorous-containing flame retardants for polyurethane foams |
| CN103443186A (en) * | 2011-03-23 | 2013-12-11 | 陶氏环球技术有限责任公司 | Phosphorous Flame Retardants for Polyurethane Foam |
| CN103073986A (en) * | 2012-12-19 | 2013-05-01 | 烟台万华聚氨酯股份有限公司 | Advanced flame-retardant polyurethane spray foam material and preparation method thereof |
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