CN111518133A - Reactive flame retardant, two-component polyurethane resin containing same and method for preparing same - Google Patents
Reactive flame retardant, two-component polyurethane resin containing same and method for preparing same Download PDFInfo
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- CN111518133A CN111518133A CN202010334508.0A CN202010334508A CN111518133A CN 111518133 A CN111518133 A CN 111518133A CN 202010334508 A CN202010334508 A CN 202010334508A CN 111518133 A CN111518133 A CN 111518133A
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- China
- Prior art keywords
- flame retardant
- polyurethane resin
- component polyurethane
- weight
- halogen
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 112
- 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 104
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 17
- 229920000570 polyether Polymers 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 16
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 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 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 4
- -1 phosphate ester Chemical class 0.000 claims description 4
- 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 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 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 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 9
- 150000001263 acyl chlorides Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 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 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl 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
- C08G18/388—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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a reactive flame retardant, two-component polyurethane resin containing the flame retardant, a method for preparing the flame retardant, and the fields of polymer synthesis and resin preparation. The method comprises the following steps: preparing dihydric alcohol containing phosphorus and halogen; and (3) preparing flame-retardant two-component polyurethane resin. The invention prepares the flame retardant simultaneously containing phosphorus, halogen and hydroxyl by carrying out ring-opening reaction on the epoxy compound containing halogen by using the monoalkyl phosphate containing 2 phosphorus hydroxyl groups. The prepared flame retardant has the advantages of wide raw material sources, simple and mild preparation conditions, high flame-retardant element content, low cost of the prepared polyurethane resin and high flame-retardant grade.
Description
Technical Field
The invention belongs to the field of polymer synthesis and resin preparation, and particularly relates to a reactive flame retardant, two-component polyurethane resin containing the flame retardant and a method for preparing the flame retardant.
Background
The polyurethane resin has the characteristics of high activity, simple and convenient use process and excellent performance, and is widely applied to the preparation of adhesives, coatings and high-performance glass fiber reinforced plastic composite materials. At present, flame retardants for polyurethane resins mainly comprise halogen-containing compounds, additive phosphorus and halogen-containing flame retardants without reactive groups, and inorganic fillers such as aluminum hydroxide, but halogen compounds can release toxic and harmful gases such as hydrogen halide when a resin cured product is combusted, the phosphorus-containing additive flame retardants and inorganic fillers can greatly affect the performance of the resin cured product when the addition amount of the phosphorus-containing additive flame retardants and inorganic fillers is large, and the additive flame retardants cannot be fixed on a polymer cross-linked network through chemical bonds and can slowly migrate to the surface of a product along with the use of the product, so that the flame retardant performance of the product is gradually reduced. Therefore, it is necessary to invent a flame retardant having a high phosphorus content and having a reactive group.
In the prior art, most of reactive phosphorus-containing flame retardants are prepared by using acyl chloride as a raw material and performing HCl removal reaction on the acyl chloride and excessive polyol under the action of alkali, for example, patent 201811209599.4 discloses a method for preparing a flame retardant by connecting Cl-containing CDOP (cyclic olefin phosphate) through ethylene glycol under the catalysis of alkali; patent 201810686423.1 and patent 02813115.0 disclose a technique for preparing phosphate alcohol compounds from phosphorus oxychloride, isooctanol and pentaerythritol under the action of negative pressure and an alkaline acid-binding agent respectively. The technology can indeed produce the phosphorus-containing flame retardant with high purity and containing hydroxyl reaction groups, but the acyl chloride is a dangerous product, and when the acyl chloride meets the air, the air immediately smokes to generate corrosive acid, and the hydrogen chloride produced in the reaction process also has severe corrosiveness on equipment and environment. The technology has extremely high requirements on equipment, process and reaction byproduct treatment, and is not suitable for industrial batch production.
Disclosure of Invention
The purpose of the invention is as follows: provides a reactive flame retardant, a two-component polyurethane resin containing the flame retardant and a method for preparing the flame retardant, which aim to solve the problems related to the background technology.
The technical scheme is as follows: the invention provides a reactive flame retardant, which is a compound obtained by reacting monoalkyl phosphate with a compound containing halogen and an epoxy structure.
The structure is as follows:
wherein R is C1-C18An alkyl chain of (a); m is an integer of 1 or 2; and X is Cl or Br.
The invention also provides a preparation method of the reactive flame retardant, which comprises the following steps: adding 1mol of monoalkyl phosphate into a ceramic reaction kettle, adding 2-4 mol of a compound containing halogen and an epoxy structure, and reacting at ambient temperature for 1-4 hours to obtain a flame retardant containing phosphorus and halogen;
the structure is as follows:
wherein R is C1-C18An alkyl chain of (a); m is an integer of 1 or 2; and X is Cl or Br.
As a preferred embodiment, the monoalkyl phosphate ester has the structure:
wherein R is C1-C18Alkyl chain of (2).
As a preferable scheme, the compound containing halogen and epoxy structure at least comprises one of epichlorohydrin and epibromohydrin.
The invention also provides a two-component polyurethane resin containing the flame retardant, which comprises a resin B material and a resin A material, and comprises the following components:
b, material B:
isocyanate 100 parts by weight
A material:
30-80 parts by weight of the flame retardant
20-80 parts of polyether polyol
0.2 to 1 weight percent of catalyst
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
As a preferable scheme, the isocyanate is one or more of diphenyl methylene diisocyanate, toluene diisocyanate, polymeric diphenyl methylene diisocyanate, hydrogenated diphenyl methylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
As a preferred embodiment, the polyether polyol structure corresponds to the general formula:
wherein R is1Is alkyl, x is an integer from 1 to 22, y is 0 or 1, and n is an integer from 2 to 4.
Preferably, the catalyst is an organic metal catalyst, and the organic amine catalyst is mixed according to a weight ratio of 1: (0.1-3).
Preferably, the organometallic catalyst includes at least one of tin laurate, stannous octoate, bismuth acetate, zinc acetate, potassium acetate, and potassium octoate.
Preferably, the organic amine catalyst comprises at least one of N, N-dimethylethanolamine, N-dimethylbenzylamine, triethylenediamine, dimethylcyclohexylamine, and tri-tertiary aminophenol.
Has the advantages that: the invention relates to a reactive flame retardant, two-component polyurethane resin containing the flame retardant and a method for preparing the flame retardant. Compared with the prior art, the invention has the following advantages: (1) the preparation process flow is simple, convenient and mild, complex equipment and harsh reaction conditions are not needed, and the energy consumption is obviously reduced; (2) the flame retardant prepared by the invention has high phosphorus and halogen contents, and the flame retardant property of the resin can be obviously improved by adding a small amount of the flame retardant; (3) the flame retardant is reactive, can be partially added as an auxiliary agent, can also be used as a curing agent in a large amount, and ensures the flame retardant property of the polyurethane resin without reducing the mechanical property of a resin cured product; (4) all raw materials are wide in source and low in price, and the product cost can be effectively reduced while the mechanical property and the flame retardant property are ensured.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
In the prior art, most of reactive phosphorus-containing flame retardants are prepared by using acyl chloride as a raw material and performing HCl removal reaction on the acyl chloride and excessive polyhydric alcohols under the action of alkali. The technology can indeed produce the phosphorus-containing flame retardant with high purity and containing hydroxyl reaction groups, but the acyl chloride is a dangerous product, and when the acyl chloride meets the air, the air immediately smokes to generate corrosive acid, and the hydrogen chloride produced in the reaction process also has severe corrosiveness on equipment and environment. The technology has extremely high requirements on equipment, process and reaction byproduct treatment, and is not suitable for industrial batch production.
The invention mainly uses monoalkyl phosphate containing 2 phosphorus hydroxyl groups to carry out ring-opening reaction on an epoxy compound containing halogen, so as to prepare the flame retardant simultaneously containing phosphorus, halogen and hydroxyl groups. The specific synthesis process is as follows: adding n mol number of monoalkyl phosphate into a ceramic reaction kettle, adding 2n-4n mol number of compound containing halogen and epoxy structure, and reacting for 1h at ambient temperature to obtain the flame retardant containing phosphorus and halogen. Wherein, in order to improve the phosphorus content of the flame retardant, the value range of the molar ratio between the monoalkyl phosphate and the halogen and epoxy structure compound is 1: (2-4), the flame retardant property and the flame retardant grade of the polyurethane resin are greatly improved. The compound containing halogen and epoxy structure has the best flame retardant effect of epichlorohydrin and epoxy bromohydrin, and the halogen and phosphorus element generate synergistic effect, so that the flame retardant property and the flame retardant grade of the polyurethane resin are improved. The structure is as follows:
wherein R is C1-C18An alkyl chain of (a); m is an integer of 1 or 2; and X is Cl or Br.
Based on the flame retardant, the flame retardant is applied to two-component flame-retardant polyurethane resin, and specifically comprises a resin B material and a resin A material, wherein the flame retardant comprises the following components:
b, material B:
isocyanate 100 parts by weight
A material:
30-80 parts of flame retardant
20-80 parts of polyether polyol
0.2 to 1 weight percent of catalyst
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature. The flame retardant is a reactive type, can be partially added as an auxiliary agent, can also be used as a curing agent in a large amount, and can ensure the flame retardant property of the polyurethane resin without reducing the mechanical property of a resin cured product.
As the two-component flame-retardant polyurethane resin, the isocyanate can be one or more of diphenyl methylene diisocyanate, toluene diisocyanate, polymeric diphenyl methylene diisocyanate, hydrogenated diphenyl methylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
The polyether polyol structure conforms to the general formula:
wherein R is1Is alkyl, x is an integer from 1 to 22, y is 0 or 1, and n is an integer from 2 to 4.
The C atom with positive charge in the isocyanate group is easily attacked by nucleophilic reagent, and nucleophilic addition reaction occurs to coordinate the electron-deficient carbon atom with the nucleophilic center of the active hydrogen compound, so that polarization is generated to cause the reaction to proceed. The flame retardant can also be regarded as a polyether polyol, the reaction process of which can be expressed as follows:
based on the above reaction, the reactive flame retardant or polyether polyol can be subjected to a crosslinking reaction with diisocyanate to be cured to form a resin material.
The effect of the catalyst on the above reaction was further investigated. The catalyst can be one or more of organic metal catalysts and organic amine catalysts. The organic metal catalyst at least comprises one of tin laurate, stannous octoate, bismuth acetate, zinc acetate, potassium acetate and potassium octoate. The organic amine catalyst at least comprises one of N, N-dimethylethanolamine, N-dimethylbenzylamine, triethylene diamine, dimethylcyclohexylamine and tri-tertiary aminophenol. As a preferable scheme, when the catalyst is an organic metal catalyst, the organic amine catalyst is mixed according to the weight ratio of 1: (0.1 to 3) the curing effect is the best.
Compared with the prior art, the invention solves the following problems: (1) the raw materials have wide sources and low price, and the used monoalkyl phosphate and the production technology thereof are widely used in the industries of pesticides, emulsifiers and the like; (2) the production process is simple, convenient and mild, the reaction only needs to be stirred for 1 hour at normal temperature and normal pressure in the ceramic kettle, no additional equipment is needed for assistance, and no byproducts or industrial three wastes are produced; (3) the preparation method has the advantages that the high-phosphorus-content reactive flame retardant is prepared, so that the flame retardant property and the flame retardant grade of the polyurethane resin are greatly improved; (4) the flame retardant is reactive, can be partially added as an auxiliary agent, can also be used as a curing agent in a large amount, and ensures the flame retardant property of the polyurethane resin without reducing the mechanical property of a resin cured product.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
10mol of monomethyl phosphate (R is methyl) and 20mol of epichlorohydrin are added into a ceramic kettle and stirred for 1h at ambient temperature to obtain the flame retardant (X is Cl in the structure, m = 1), the phosphorus content of the flame retardant is 11.15%, the chlorine content is 25.54%, and the molecular weight is 278 g/mol.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
100 parts by weight of toluene diisocyanate
Material A (polyol component)
30 parts by weight of flame retardant
70 parts by weight of polyether triol (R1 is propyl, x =1, y =0, n = 3)
0.1 part by weight of tin laurate
0.1 part by weight of tri-tertiary aminophenol
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Example 2
10mol of monobutyl phosphate (R is butyl) and 40mol of epoxy bromopropane are added into a ceramic kettle and stirred for 1h at ambient temperature to obtain the flame retardant (X is Br, m =2 in the structure), wherein the flame retardant contains 4.52% of phosphorus, 18.66% of bromine and 686g/mol of molecular weight.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
100 parts by weight of polymeric diphenylmethylene diisocyanate (crude MDI)
Material A (polyol component)
50 parts by weight of flame retardant
Polyether tetrahydric alcohol (R1 is pentyl, x =2, y =1, n = 4) 30 parts by weight
20 parts by weight of polyether glycol (R1 is an ethyl group, x =22, y =1, n = 2)
0.5 part by weight of bismuth acetate
0.5 part by weight of N, N-dimethylbenzylamine
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Example 3
10mol of octadecyl phosphate (R is octadecyl) and 20mol of propylene bromide oxide are added into a ceramic kettle and stirred for 1h at ambient temperature to obtain the flame retardant (X is Br, m =1 in the structure), the phosphorus content of the flame retardant is 4.83%, the bromine content of the flame retardant is 19.92%, and the molecular weight of the flame retardant is 642 g/mol.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
Isofluoroketone diisocyanate 100 parts by weight
Material A (polyol component)
80 parts by weight of flame retardant
20 parts by weight of polyether tetrahydric alcohol (R1 is amyl, x =1, y =0, n = 4)
0.2 part by weight of stannous octoate
0.5 part by weight of triethylene diamine
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Example 4
Adding 10mol of dodecyl phosphate (R is dodecyl) and 40mol of epichlorohydrin into a ceramic kettle, and stirring for 1h at ambient temperature to obtain the flame retardant (X is Cl, m =2 in the structure), wherein the flame retardant contains 5.18% of phosphorus, 11.87% of chlorine and 598g/mol of molecular weight.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
50 parts by weight of diphenylmethylene diisocyanate (MDI)
Hydrogenated Diphenylmethylene diisocyanate (HMDI) 50 parts by weight
Material A (polyol component)
Flame retardant 20 parts by weight
60 parts by weight of polyether triol (R1 is propyl, x =1, y =0, n = 3)
20 parts by weight of polyether glycol (R1 is ethyl, x =12, y =1, n = 3)
0.6 part by weight of potassium caprylate
0.1 part by weight of dimethylcyclohexylamine
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Example 5
10mol of monomethyl phosphate (R is methyl) and 20mol of epichlorohydrin are added into a ceramic kettle and stirred for 1h at ambient temperature to obtain the flame retardant (X is Cl in the structure, m = 1), the phosphorus content of the flame retardant is 11.15%, the chlorine content is 25.54%, and the molecular weight is 278 g/mol.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
100 parts by weight of toluene diisocyanate
Material A (polyol component)
30 parts by weight of flame retardant
70 parts by weight of polyether triol (R1 is propyl, x =1, y =0, n = 3)
0.2 part by weight of tin laurate
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Example 6
10mol of monomethyl phosphate (R is methyl) and 20mol of epichlorohydrin are added into a ceramic kettle and stirred for 1h at ambient temperature to obtain the flame retardant (X is Cl in the structure, m = 1), the phosphorus content of the flame retardant is 11.15%, the chlorine content is 25.54%, and the molecular weight is 278 g/mol.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
100 parts by weight of toluene diisocyanate
Material A (polyol component)
30 parts by weight of flame retardant
70 parts by weight of polyether triol (R1 is propyl, x =1, y =0, n = 3)
0.2 part by weight of tri-tertiary aminophenol
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Example 7
10mol of monomethyl phosphate (R is methyl) and 60mol of epichlorohydrin are added into a ceramic kettle and stirred for 1h at ambient temperature to obtain the flame retardant (X is Cl in the structure, m = 1), the phosphorus content of the flame retardant is 4.76%, the chlorine content is 32.72%, and the molecular weight is 651 g/mol.
The flame-retardant two-component polyurethane resin has the following formula:
material B (isocyanate component)
100 parts by weight of toluene diisocyanate
Material A (polyol component)
30 parts by weight of flame retardant
70 parts by weight of polyether triol (R1 is propyl, x =1, y =0, n = 3)
0.1 part by weight of tin laurate
0.1 part by weight of tri-tertiary aminophenol
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
Comparative examples 1 to 4
Commercially available flame retardants 1 to 4 were purchased to replace the reactive flame retardants in the formulations of examples 1 to 4, respectively, and the resins of comparative examples 1 to 4 were prepared according to the formulations of examples 1 to 4, and the prepared resins were introduced into a mold to be cured at room temperature after being mixed uniformly.
Example of detection
The resins obtained in the above examples and comparative examples were subjected to mechanical tests and flame retardancy tests, wherein the flame retardancy test standards were as follows: UL94: 2011V 0, V1 and V2.
The test data for the examples are as follows:
the test data for the comparative examples are as follows:
from the test data in the table, it can be seen that, compared with the commercial flame retardant, on the premise of the same and larger addition amount, the flame retardant of the invention has obviously improved flame retardant grade and mechanical property compared with the comparative examples in the examples 1 and 3; under the condition of the same and smaller addition amount, compared with the comparative example, the flame retardant disclosed by the invention has the same flame retardant grade on the examples 2 and 4, but the mechanical property is obviously improved. In addition, compared with the examples 5 and 6, the synergistic catalytic effect of the compound catalyst is far greater than that of the compound catalyst when the compound catalyst is used alone.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (10)
2. A preparation method of a reactive flame retardant is characterized by comprising the following steps: adding 1mol of monoalkyl phosphate into a ceramic reaction kettle, adding 2-4 mol of a compound containing halogen and an epoxy structure, and reacting at ambient temperature for 1-4 hours to obtain a flame retardant containing phosphorus and halogen;
the structure is as follows:
wherein R is C1-C18An alkyl chain of (a); m is an integer of 1 or 2; and X is Cl or Br.
4. The method of claim 2, wherein the compound containing halogen and epoxy structure comprises at least one of epichlorohydrin and epibromohydrin.
5. The two-component polyurethane resin containing the flame retardant is characterized by comprising a resin B material and a resin A material, and the two-component polyurethane resin comprises the following components:
b, material B:
isocyanate 100 parts by weight
A material:
30 to 80 parts by weight of the flame retardant of claim 1
20-80 parts of polyether polyol
0.2 to 1 weight percent of catalyst
And uniformly mixing the prepared resin, and introducing the resin into a mold to be cured under the condition of room temperature.
6. The two-component polyurethane resin containing the flame retardant according to claim 5, wherein the isocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, polymeric diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate trimer.
8. The two-component polyurethane resin containing the flame retardant according to claim 5, wherein the catalyst is an organic metal catalyst, and the organic amine catalyst is present in an amount of 1: (0.1-3).
9. The two-component polyurethane resin containing the flame retardant as claimed in claim 8, wherein the organometallic catalyst comprises at least one of tin laurate, stannous octoate, bismuth acetate, zinc acetate, potassium acetate, and potassium octoate.
10. The two-component polyurethane resin containing the flame retardant according to claim 8, wherein the organic amine catalyst comprises at least one of N, N-dimethylethanolamine, N-dimethylbenzylamine, triethylenediamine, dimethylcyclohexylamine, and tri-tertiary aminophenol.
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CN1203236A (en) * | 1998-04-27 | 1998-12-30 | 欧育湘 | Di (1,3-dihalo-2-propyl)-2,2-dimethyl-3-halopropyl phosphate |
CN107011377A (en) * | 2017-05-03 | 2017-08-04 | 南通书创药业科技有限公司 | A kind of preparation method of β oxo-phosphoric acids ester |
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