CN112442162A - Phosphorus-containing flame retardant with hydroxyl and preparation method and application thereof - Google Patents
Phosphorus-containing flame retardant with hydroxyl and preparation method and application thereof Download PDFInfo
- Publication number
- CN112442162A CN112442162A CN201910804224.0A CN201910804224A CN112442162A CN 112442162 A CN112442162 A CN 112442162A CN 201910804224 A CN201910804224 A CN 201910804224A CN 112442162 A CN112442162 A CN 112442162A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- substituted
- unsubstituted
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 122
- 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 112
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 72
- 239000011574 phosphorus Substances 0.000 title claims abstract description 72
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000005805 hydroxylation reaction Methods 0.000 title description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 229920002379 silicone rubber Polymers 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229920005749 polyurethane resin Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 2
- 125000005568 organylene group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 125000005237 alkyleneamino group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- -1 methylene, ethylene, propylene, butylene Chemical group 0.000 description 2
- CVZGUJMLZZTPKH-UHFFFAOYSA-N octane-3,6-dione Chemical compound CCC(=O)CCC(=O)CC CVZGUJMLZZTPKH-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IPRPPFIAVHPVJH-UHFFFAOYSA-N (4-hydroxyphenyl)acetaldehyde Chemical compound OC1=CC=C(CC=O)C=C1 IPRPPFIAVHPVJH-UHFFFAOYSA-N 0.000 description 1
- VAIFYHGFLAPCON-UHFFFAOYSA-N 1,3-Diacetylpropane Chemical compound CC(=O)CCCC(C)=O VAIFYHGFLAPCON-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 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 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940118019 malondialdehyde Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- 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
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- 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
- C07F9/4056—Esters of arylalkanephosphonic acids
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides a phosphorus-containing flame retardant with hydroxyl and a preparation method and application thereof. The phosphorus-containing flame retardant has a structure shown in a formula I. The phosphorus-containing flame retardant containing hydroxyl provided by the invention has a hydroxyl functional group, so that the phosphorus-containing flame retardant can react with a high polymer monomer containing carboxyl, epoxy, isocyanate and other groups, when a high polymer compound is synthesized, the phosphorus-containing flame retardant containing hydroxyl is used as a reaction raw material, and a flame retardant unit is inserted into a high polymer chain segment in an embedding, crosslinking and other modes, so that the high polymer can be permanently flame-retardant.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and relates to a phosphorus-containing flame retardant with hydroxyl groups, and a preparation method and application thereof.
Background
Most of polymer materials are flammable materials, and in order to be safe, polymer products are increasingly required to have flame retardant capability. In order to improve the flame retardant property of the material, the method widely adopted at present is to add flame retardant into various polymer matrixes.
The traditional halogen flame retardant generates more smoke and releases irritant and corrosive gases during combustion, thereby polluting the environment and being harmful to human health; the current flame retardant development field shows the trends of no halogenation, high efficiency, low smoke and no toxicity. The phosphorus-containing flame retardant is one of the phosphorus flame retardants which are rapidly developed in recent years, and is an important halogen-free flame retardant with a wide application prospect. A small amount of the flame retardant is added into the polymer material, so that a good flame retardant effect can be achieved.
Phosphorus-containing flame retardants can be classified into additive and reactive types. The additive flame retardant is directly added into a polymer matrix, so that the material obtains a flame retardant effect, does not chemically react with the base material and other components in the base material, is physically dispersed in the base material to endow the flame retardancy, and the mechanical property of the flame-retardant matrix is often damaged and the quality of the material is influenced due to the large addition amount of the flame retardant. And because part of the added flame retardant is micromolecule flame retardant, micromolecule migration phenomenon can occur along with the prolonging of time, the flame retardant property of the material is reduced, and the water-soluble part of the added flame retardant loses the flame retardant property due to the fact that the added flame retardant is water-soluble and is dissolved in water.
Therefore, the development of a phosphorus-containing flame retardant which can really realize safety, environmental protection and flame retardance is needed to meet the application requirements.
Disclosure of Invention
The invention aims to provide a phosphorus-containing flame retardant with hydroxyl and a preparation method and application thereof. The phosphorus-containing flame retardant containing hydroxyl provided by the invention has a hydroxyl functional group, so that the phosphorus-containing flame retardant can react with a high polymer monomer containing carboxyl, epoxy, isocyanate and other groups, when a high polymer compound is synthesized, the phosphorus-containing flame retardant containing hydroxyl is used as a reaction raw material, and a flame retardant unit is inserted into a high polymer chain segment in an embedding, crosslinking and other modes, so that the high polymer can be permanently flame-retardant.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a phosphorus-containing flame retardant with hydroxyl groups, wherein the phosphorus-containing flame retardant has a structure represented by formula I:
wherein Z is1、Z2Each independently is preferably a phosphorus-containing group.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently is preferably an inert group, a sulfur atom, an oxygen atom or-H.
X1Selected from any organylene group that satisfies a chemical environment.
a. b, c, d, f, g, h are each independently an integer preferably from 0 to 5, e.g., 1, 2, 3, 4, etc., and a, b are not simultaneously 0, f, g are not simultaneously 0, g, h are not simultaneously 0, while b + c + h ≦ 5 (e.g., b + c + h ≦ 4, b + c + h ≦ 3, b + c + h ≦ 2, etc.) and a + d + g ≦ 5 (e.g., a + d + g ≦ 4, a + d + g ≦ 3, a + d + g ≦ 2, etc.).
e is an integer from 0 to 100, such as 2,5, 10, 20, 30, 40, 50, 60, 70, 80, 90, and the like.
The phosphorus-containing flame retardant with hydroxyl can participate in the reaction for preparing a high polymer base material, such as the reaction with carboxyl to prepare polyester and the like; the phosphorus-containing flame retardant with hydroxyl groups provided by the invention exists in the polymer matrix resin in the form of molecular chain fragments, so that the phenomenon of micromolecule precipitation can be avoided, and the phenomenon that some additive flame retardants lose flame retardance due to water solubility is avoided.
The phosphorus-containing flame retardant with hydroxyl provided by the invention is phenolic hydroxyl when the hydroxyl is connected with an aromatic group, and the hydroxyl also comprises the phenolic hydroxyl.
Preferably, Z1、Z2Each independently preferably
R1Is methyl or ethyl.
Preferably, a + b.gtoreq.2, more preferably a + b.gtoreq.2.
Preferably, said M1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 linear alkylene group may be methylene, ethylene, propylene, butylene, etc.
The C3-C5 may be C3, C4, C5, etc.
The C1-C3 may be C1, C2, C3, etc.
Preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
Preferably, Y1、Y2Each independently is preferably-H or ═ O.
Preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1-C30 can be C2, C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C6-C30 can be C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like.
The C5-C7 may be C6 or the like.
The C1-C5 may be C1, C2, C3, C4, C5, etc.
The following description is merely an explanation of structures such as alkyleneamino groups, and R does not particularly denote any meaning.
The alkyleneamino group refers to-R-NH-, wherein R is alkylene.
The alkylene acyl refers to-R-C (O) -, wherein R is alkylene.
The alkylene ester group means-R-COO-wherein R represents an alkylene group.
The arylene amine group means-Ar-NH-, wherein Ar represents an arylene group.
The aryleneacyl group means-Ar-C (O) -, wherein Ar represents an arylene group.
The arylene ester group means-Ar-COO-in which Ar represents an arylene group.
Preferably, said R is2、R3、R4、R5、R6、R7、R8、R9Independently of one another, they are preferably C1-C6 linear or branched alkylene radicals.
The C1-C6 may be C2, C3, C4, C5, etc.
Preferably, n, m, i, k are each independently integers preferably from 0 to 30, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.
Preferably, the phosphorus-containing flame retardant with hydroxyl has a structure shown in formula II, formula III, formula IV, formula V or formula VI:
wherein M is1Is selected from C1-C3 linear alkylene, C3 branched alkylene or phenyl.
M2Selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs a linear or branched alkyl group of C1-C6, R2、R3、R4、R5、R6、R7、R8、R9Each independently is preferably a C1-C6 (e.g., C2, C3, C4, C5) straight or branched chain alkylene group, and each of n, m, i, k independently is preferably an integer of 0-30, such as 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.
R1Is methyl or ethyl.
R、R'、R”、RV、RPEach independently is preferably a substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight or branched alkylene group.
Y1、Y2Each independently is preferably-H or ═ O.
a. b, g and h are preferably 0, 1 or 2 independently, a and b are not 0 at the same time, a + b is 2, f and g are not 0 at the same time, and g and h are not 0 at the same time.
e is an integer from 0 to 20, e.g., 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 19, etc., and f is 0 or 1.
The invention does not limit the preparation method of the phosphorus-containing flame retardant with hydroxyl, and any preparation method capable of obtaining the compound of the invention can be adopted, and the preparation method is exemplified as follows:
in a second aspect, the present invention provides a method for preparing a phosphorus-containing flame retardant having hydroxyl groups according to the first aspect, the method comprising:
the phosphorus-containing flame retardant with hydroxyl is obtained by the addition reaction of a compound containing a-P-H bond and a compound containing an unsaturated bond and/or a cyclic group.
In a third aspect, the present invention provides a use of the phosphorus-containing flame retardant having hydroxyl groups according to the first aspect for preparing a polyurethane resin, a phenol resin, a polyester resin, a polyamide resin, an alkyd resin or a silicone rubber resin.
The phosphorus-containing flame retardant with hydroxyl provided by the invention can be used as a preparation raw material for preparing polyurethane resin, phenolic resin and silicon rubber, reacts with other components in the raw material, and participates in the reaction process.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phosphorus-containing flame retardant with hydroxyl can participate in the reaction for preparing a high polymer base material, such as the reaction with carboxyl to prepare polyester and the like; the phosphorus-containing flame retardant with hydroxyl groups provided by the invention exists in the polymer matrix resin in the form of molecular chain fragments, so that the phenomenon of micromolecule precipitation can be avoided, and the phenomenon that some additive flame retardants lose flame retardance due to water solubility is avoided.
(2) The phosphorus-containing flame retardant with hydroxyl provided by the invention has good flame retardant performance and mechanical performance, such as polyurethane resin, phenolic resin, polyester resin, polyamide resin, alkyd resin or silicone rubber resin and the like prepared from the phosphorus-containing flame retardant with hydroxyl.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of pentanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝6.60-6.62(s,2H,-OH),3.40-3.45(d,12H,-P-O-CH3),1.7-1.8(s,2H,-CH2),1.3-1.32(s,6H,-CH3).
Preparation example 2
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of 2, 5-hexanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),1.36-1.40(t,4H,-C-C 2H-C 2H-C-),1.20-1.22(s,6H,-CH3).
Preparation example 3
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of 2, 6-heptanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),1.35-1.40(t,4H,-C 2H-CH2-C 2H-),1.30-1.33(m,2H,-CH2-C 2H-CH2-),1.19-1.21(s,6H,-CH3).
Preparation example 4
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of 3, 6-octanedione and 50mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating and refluxing, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),1.36-1.40(m,8H,-C 2H-C-C 2H-C 2H-C-C 2H-),0.98-1.02(t,6H,-CH3).
Preparation example 5
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of glyoxal and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to 50 ℃, continuing to react for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝6.20-6.22(d,2H,-OH),3.70-3.76(m,2H,-CH-),3.48-3.52(d,12H,-P-O-CH3).
Preparation example 6
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of malondialdehyde and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to 50 ℃, continuing to react for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝3.40-3.45(d,12H,-P-O-CH3),3.34-3.38(d,2H,-CH-),1.46-1.52(m,2H,-CH-C 2H-CH-).
Preparation example 7
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of dimethyl phosphite, 1mol of o-phthalaldehyde and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to reflux, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(400MHz,DMSO-d6):δ＝7.10-7.14(s,4H,ph-H),4.58-4.62(s,2H,-CH-P),3.40-3.45(d,12H,-P-O-CH3).
Preparation example 8
A phosphorus-containing flame retardant with hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 1mol of dimethyl phosphite, 1mol of p-hydroxyphenylacetaldehyde and 20mL of ethanol into a three-neck flask with a magnetic stirring thermometer, stirring, controlling the temperature to be below 5 ℃ in an ice-water bath, dropwise adding 2mol of triethylamine, gradually heating to reflux, continuously reacting for 1h, and carrying out reduced pressure distillation to obtain the reactive flame retardant with the structure.
1H NMR(CDCl3400MHz, TMS): δ ═ 9.21-9.45(s, H, -OH),7.01-7.03(d,2H, H with the phenyl ring near-CH-), 6.65-6.68(d,2H, H with the phenyl ring near the hydroxyl group), 4.52-4.55(s,1H, -CH-),3.44-3.48(d,6H, -P-O-CH-), and3).
the phosphorus-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of polyurethane resin:
examples 1 to 8
A polyurethane particle is prepared by the following steps:
40 parts by weight of phosphorus-containing flame retardant, 100 parts by weight of isophorone diisocyanate, 55 parts by weight of hydroxyl-terminated polytetrahydrofuran having a molecular weight of 2000, 5 parts by weight of ethylene glycol and 1 part by weight of catalyst were mixed and extruded by a twin-screw extruder to obtain polyurethane particles.
Wherein the phosphorus-containing flame retardant is provided in preparation examples 1-8.
Comparative example 1
The phosphorus-containing flame retardant was replaced with a hydroxyl-terminated polytetrahydrofuran having a molecular weight of 2000.
Comparative examples 2 to 3
On the basis of comparative example 1, triphenyl phosphate, which is a flame retardant, was added in an amount of 40 parts by weight (comparative example 2) and 75 parts by weight (comparative example 3).
Performance testing
The polyurethane particles provided in examples 1 to 8 and comparative examples 1 to 3 were subjected to a performance test as follows:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: the method is carried out according to the regulation of GB/T528-2009, the test speed (500 +/-50) mm/min and the thickness of a sample are 10 mm;
(3) flame retardant stability: the polyurethane composition was soaked in water for 1 hour and dried to measure its flammability again.
The results of the tests on the examples and comparative examples are shown in Table 1:
TABLE 1
| Sample (I) | Combustibility | Tensile strength/MPa | Elongation at break/% | Combustibility after immersion in water |
| Example 1 | V-0 | 40.5 | 210 | V-0 |
| Example 2 | V-0 | 39.8 | 215 | V-0 |
| Example 3 | V-0 | 37.8 | 224 | V-0 |
| Example 4 | V-0 | 37.5 | 229 | V-0 |
| Example 5 | V-0 | 42.5 | 198 | V-0 |
| Example 6 | V-0 | 41.6 | 205 | V-0 |
| Example 7 | V-0 | 54.2 | 175 | V-0 |
| Example 8 | V-0 | 55.9 | 174 | V-0 |
| Comparative example 1 | V-2 | 32.1 | 264 | V-2 |
| Comparative example 2 | V-1 | 35.7 | 174 | V-2 |
| Comparative example 3 | V-0 | 36.4 | 124 | V-1 |
As can be seen from the examples and performance tests, the reactive flame retardant with hydroxyl groups provided by the invention can participate in the preparation process of polyurethane resin, and has stability; meanwhile, the flame retardant property of the material can reach V-0 level, and the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant property can not be reduced because the flame retardant is dissolved in water in operations such as washing and the like. As is clear from the comparison of examples 1 to 8, the tensile strength of the finally obtained polyurethane resin was high and was 54.2MPa or more when the phosphorus-containing flame retardants provided in preparation examples 7 to 8 were selected, and the elongation at break was good and was 210% or more when the phosphorus-containing flame retardants provided in preparation examples 1 to 4 were selected.
The phosphorus-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of silicon rubber:
examples 9 to 16
A silicone rubber composition is prepared by the following steps:
60 parts by weight of phenyltrimethoxysilane, 60 parts by weight of vinyltrimethoxysilane, 80 parts by weight of a reactive flame retardant with hydroxyl and 10 parts by weight of benzenesulfonic acid are mixed at 60 ℃ for 8 hours, and then 10 parts by weight of a catalyst is added to be mixed to obtain the silicone rubber.
The phosphorus-containing flame retardants were the phosphorus-containing flame retardants provided in preparation examples 1-8, respectively.
Comparative example 4
The only difference from example 9 was that the reactive flame retardant having hydroxyl groups was replaced with 100 parts by weight of polyphosphate.
And (3) performance testing:
the samples provided in examples 9-16 and comparative example 4 were tested for performance by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: according to the regulation of GB/T528-2009;
(3) flame retardant stability: after soaking the silicone rubber composition in water for 1h, it was dried and its flammability was measured again.
Test results for examples and comparative examples table 2:
TABLE 2
The embodiment and the performance test show that the phosphorus-containing flame retardant with hydroxyl can participate in the preparation of the silicon rubber, and simultaneously, the phosphorus-containing flame retardant with hydroxyl exists as a molecular chain segment, so that the mechanical property of the silicon rubber can be enhanced, wherein the tensile strength is more than 1.5MPa and can reach more than 1.8 MPa; the flame retardant property of the material can reach V-0 level; the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant performance can not be reduced because the flame retardant is dissolved in water in operations such as water washing and the like.
The phosphorus-containing flame retardant with hydroxyl prepared by the invention is applied to the preparation of polyester resin:
examples 17 to 24
A polyester composition is prepared by the following steps:
a polyester composition was prepared by mixing 50 parts by weight of maleic anhydride, 10 parts by weight of ethylene glycol, 40 parts by weight of a phosphorus-containing flame retardant having hydroxyl groups, 50 parts by weight of poly (1, 4-cyclohexylenedimethylene) terephthalate, and 10 parts by weight of polyethylene terephthalate.
The phosphorus-containing flame retardants were the phosphorus-containing flame retardants provided in preparation examples 1-8, respectively.
Comparative example 5
The only difference from example 17 was that the reactive flame retardant having a hydroxyl group was replaced with 40 parts by weight of ethylene glycol.
Comparative example 6
The difference from comparative example 5 is that 30 parts by weight of aluminum tris (diethylphosphinate) were added on the basis of comparative example 5.
And (3) performance testing:
the samples provided in examples 17-24 and comparative examples 5-6 were tested for performance by the following method:
(1) combustibility: testing according to UL-94 vertical burning test standard;
(2) tensile strength and elongation: according to the GB/T1040-2006;
(3) flame retardant stability: after soaking the polyester composition in water for 1h, it was dried and its flammability was measured again.
Test results for examples and comparative examples table 3:
TABLE 3
As can be seen from the examples and performance tests, the phosphorus-containing flame retardant with hydroxyl can participate in the preparation of polyester, and simultaneously, the phosphorus-containing flame retardant with hydroxyl exists as a molecular chain segment, so that the mechanical property of the polyester composition can be enhanced, wherein the tensile strength is more than 36.4MPa and can reach more than 37.9 MPa; the flame retardant property of the material can reach V-0 level; the phosphorus-containing flame retardant provided by the invention has good flame retardant stability, and the flame retardant performance can not be reduced because the flame retardant is dissolved in water in operations such as water washing and the like.
The applicant states that the present invention is illustrated by the above examples of the phosphorus-containing flame retardant with hydroxyl groups of the present invention and the preparation method and application thereof, but the present invention is not limited to the above detailed methods, i.e. it does not mean that the present invention must be implemented by relying on the above detailed methods. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A phosphorus-containing flame retardant with hydroxyl groups is characterized by having a structure shown as a formula I:
wherein Z is1、Z2Each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
a. b, c, d, f, g and h are respectively and independently selected from integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and meanwhile, b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5;
e is an integer of 0 to 100.
2. The phosphorus-containing flame retardant having hydroxyl groups as claimed in claim 1, wherein Z is1、Z2Each independently preferably
R1Is any one of saturated or unsaturated alkyl, aryl or heteroaryl, further preferably methyl, ethyl or phenyl;
preferably, a + b.gtoreq.2, more preferably a + b.gtoreq.2.
3. The phosphorus-containing flame retardant having hydroxyl group according to claim 1 or 2, wherein M is1Selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
4. Phosphorus-containing flame retardant having hydroxyl groups according to any of claims 1 to 3, wherein M is2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2、R3、R4、R5、R6、R7、R8、R9Each independently of the others is preferably a linear or branched alkylene group having from C1 to C10, L2、Y2、Z2Is connected to R2、R3、R4、R5、R6、R7、R8、R9N, m, i, k are each independently an integer preferably from 0 to 100.
5. The phosphorus-containing flame retardant having hydroxyl groups as claimed in any of claims 1 to 4, wherein Y is1、Y2Each independently is preferably-H or ═ O;
preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 linear or branched alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamine, substituted or unsubstituted C1-C30 alkyleneacyl, substituted or unsubstituted C1-C30 alkyleneester, substituted or unsubstituted C6-C30 alkyleneamine, substituted or unsubstituted C6-C30 aryleneacyl or C6-C30 aryleneester, further preferably substituted or unsubstituted C1-C5 linear or branched alkylene, substituted or unsubstituted C1-C5 alkyleneamine, substituted or unsubstituted C1-C5 alkyleneacyl or substituted or unsubstituted C1-C5 alkyleneester, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", RVEach independently is preferably a substituted or unsubstituted C1-C10 straight or branched chain alkylene group.
6. The phosphorus-containing flame retardant having hydroxyl groups according to any one of claims 1 to 5, wherein R is2、R3、R4、R5、R6、R7、R8、R9Independently of one another, they are preferably C1-C6 linear or branched alkylene radicals.
7. Phosphorus-containing flame retardant with hydroxyl groups according to any of claims 1 to 6, characterized in that n, m, i, k are each independently preferably an integer from 0 to 30.
8. Phosphorus-containing flame retardant with hydroxyl groups according to any of claims 1 to 7, characterized in that the phosphorus-containing flame retardant with hydroxyl groups preferably has the structure according to formula II, formula III, formula IV, formula V or formula VI:
wherein M is1Selected from C1-C3 linear alkylene, C3 branched alkylene or phenyl;
M2selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs a linear or branched alkyl group of C1-C6, R2、R3、R4、R5、R6、R7、R8、R9Each independently is a linear or branched alkylene group preferably having C1-C6, and each of n, m, i and k independently is an integer preferably having 0-30;
R1is a firstOr ethyl;
R、R'、R”、RV、RPeach independently a linear or branched alkylene group preferably having C1-C10 which may be substituted or unsubstituted;
Y1、Y2each independently is preferably-H or ═ O;
a. b, g and h are preferably 0, 1 or 2 independently, a and b are not 0 at the same time, a + b is 2, f and g are not 0 at the same time, and g and h are not 0 at the same time;
e is an integer of 0 to 20, and f is 0 or 1.
9. Use of a phosphorus containing flame retardant with hydroxyl groups according to any of claims 1 to 8 for the preparation of polyurethane resins, phenolic resins, polyester resins, alkyd resins or silicone rubber resins.
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