CN106573945A - 基于dopo的杂化阻燃剂 - Google Patents
基于dopo的杂化阻燃剂 Download PDFInfo
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- CN106573945A CN106573945A CN201580025437.3A CN201580025437A CN106573945A CN 106573945 A CN106573945 A CN 106573945A CN 201580025437 A CN201580025437 A CN 201580025437A CN 106573945 A CN106573945 A CN 106573945A
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- retardant
- oxygen
- polymeric material
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 53
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 47
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229920000728 polyester Polymers 0.000 claims abstract description 20
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 29
- -1 flame-retardant compound Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 230000000996 additive effect Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000002952 polymeric resin Substances 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 abstract 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
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- 239000011159 matrix material Substances 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- BVMWIXWOIGJRGE-UHFFFAOYSA-N NP(O)=O Chemical compound NP(O)=O BVMWIXWOIGJRGE-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- UIFYLQRSDQQZKW-UHFFFAOYSA-N P(O)(O)=O.P(O)(O)=O.OCC(CO)(CO)CO Chemical class P(O)(O)=O.P(O)(O)=O.OCC(CO)(CO)CO UIFYLQRSDQQZKW-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- SYULDULNBJYSGR-UHFFFAOYSA-N [O].P1CCCCC1 Chemical compound [O].P1CCCCC1 SYULDULNBJYSGR-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003921 pyrrolotriazines Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
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Abstract
本发明涉及新型且改进的不含卤素的阻燃化合物,其具有式(I)的结构:其中:R1和R2独立地为氢、C1‑C6烷基、‑P(O)(OR3)2、‑P(O)OR3R4、‑P(O)R3 2,其中R3和R4独立地为C1‑C4烷基、C6‑C12芳基、C7‑C15芳烷基或C7‑C15烷芳基;或者R1和R2一起形成不饱和环状环,其任选地被烷基取代;各k独立地为1至2的整数;各X独立地为氧(O)或硫(S);v为0或1;各Y独立地为C1‑C4亚烷基、C6亚芳基、C7‑C15亚芳烷基、C7‑C15亚烷芳基、氧(O)、氮(NR),其中R为H或C1‑C4烷基;n为0、1或2,条件是当Y为氧(O)或氮(NR)时n为1;各Z独立地为C1‑C4亚烷基、C6亚芳基、C7‑C15亚芳烷基或C7‑C15亚烷芳基;m独立地为0、1或2;条件是当Y为氧(O)或氮(N)时m不可为0;各Q独立地为C1‑C4亚烷基;t为1至2的整数;W为氧(O)或硫(S)。该化合物尤其适合作为用于热塑性聚酯的阻燃添加剂。
Description
技术领域
本发明总体涉及新型阻燃剂9,10-二氢-9-氧杂-10-磷杂菲化合物。
背景技术
多种含磷化合物由于它们作为阻燃(flame retardant)添加剂的适用性而已经被进行了研究。特别地,已经探索了DOPO(9,l0-二氢-9-氧杂-磷杂菲-10-氧化物)及其衍生物作为阻燃剂,并已知其主要通过气相阻燃机理起作用。
例如,由EP 1506968已知,可以有效合成基于DOPO的膦酸酯,而US4228064展现了基于DOPO的膦酸酯和亚膦酸酯作为用于聚苯醚配方的阻燃添加剂的功用。此外,EP2557085描述了基于DOPO的膦酰胺化物(phosphonamidate)的合成以及它们在聚氨酯泡沫体中的应用。
此外,由DE 10330774和EP 2284208已知,可使DOPO与不饱和的二羧酸反应,且随后与其它适合于建立酯键的含P衍生物共聚,以获得具有不同P含量的阻燃性聚酯。这些基于DOPO的聚合物可例如在纤维应用中用作用于聚对苯二甲酸乙二醇酯(PET)的阻燃添加剂,或在工程塑料中用作独立的阻燃性聚酯。
尽管所报道的DOPO衍生物中的一些的热稳定性使得能够将它们在如对于聚酯加工通常所使用的升高的温度下熔融加工,但这些衍生物都未被证明在热解时形成炭(char)(这是将提高它们作为阻燃添加剂的功效的性质)。
已知含有季戊四醇二膦酸酯(炭前体单元)、具有DOPO作为侧基的聚合物和/或低聚物(通常没有报道分子量),如例如Wang X.等在Materials Chemistry and Physics2011,125,536-541中等所报道的。然而,对于所有报道的结构,都没有解决具有卤化端基的问题。由于以下事实,这可能是一个问题:对于相对低分子量的添加剂,端基的重要性增加。
季戊四醇磷酸酯醇(PEPA)已知为这样的阻燃添加剂:其具有相对低的热稳定性(在200℃左右分解),主要以凝聚相起作用,在热解时形成最高达40重量%的炭。PEPA的衍生物主要用作聚烯烃如聚丙烯的阻燃添加剂,如US5420326中所描述的。
US 4801625描述了PEPA衍生物,其与其它聚合物添加剂(如产生惰性气体的化合物(如三聚氰胺)或其它含磷衍生物(如多磷酸铵))组合而使聚烯烃为阻燃性的。WO 91/04295教导了PEPA衍生物用于获得烟被抑制的不饱和聚酯树脂组合物的用途。
发明内容
可能,要求耐燃性(flame resistance)的合成聚合物的最重要类别之一是热塑性聚酯,其具有许多应用如工程塑料以及熔纺纤维。任何待添加至这样的聚合物的阻燃添加剂应具有足够的热稳定性以承受住该聚合物的熔融加工所通常需要的温度。因此,对于用于在高温下加工的热塑性塑料的新型且改进的不含卤素的阻燃剂仍然存在需求。这样的化合物应在其阻燃作用方面为有效的,且不应负面影响聚合物基质的期望性质例如熔融粘度(可加工性)、机械性质或熔纺纤维的能力。
根据本发明的一个方面,提供了具有式(I)的结构的阻燃化合物:
其中R1和R2可独立地为氢、C1-C6烷基、-P(O)(OR3)2、-P(O)OR3R4、-P(O)R3 2,其中R3和R4可独立地为C1-C4烷基、C6-C12芳基、C7-C15芳烷基、C7-C15烷芳基;或者R1和R2一起可形成不饱和环状环,其可被烷基基团取代;各k可独立地为1至2的整数;各X可独立地为氧(O)或硫(S);v可为0或1;各Y可独立地为C1-C4亚烷基、C6亚芳基、C7-C15亚芳烷基、C7-C15亚烷芳基、氧(O)、氮(NR),其中R为H或C1-C4烷基;n可为0、1或2,条件是当Y为氧(O)或氮(NR)时n为1;各Z可独立地为C1-C4亚烷基、C6亚芳基、C7-C15亚芳烷基或C7-C15亚烷芳基;m可独立地为0、1或2;条件是当Y为氧(O)或氮(N)时m不可为0;各Q可独立地为C1-C4亚烷基;t为1至2的整数;W可为氧(O)或硫(S)。
本发明的有利实施方案在从属权利要求中定义和/或在于此在下文中描述。
惊讶地发现,以上定义的化合物(其基于DOPO-和PEPA-类型部分的组合,且因此可被设想为“杂化阻燃剂”)呈现出在阻燃化合物中、特别是在用于热塑性聚酯的阻燃添加剂中高度合乎需要的数种特性的组合。这样的有利的性质包括,但不限于:高的热稳定性(使得能够熔融共混)、至少约150℃且稍低于多数聚酯的熔融加工温度的高的熔融温度,从而允许该添加剂在聚合物基质中更均匀的分散。
优选地,该化合物的热稳定性为约270℃至约335℃,更优选为约280℃至约330℃,最优选为约290℃至约325℃,且熔融温度优选为约150℃至约260℃,更优选为约160℃至约240℃,最优选为约170℃至约230℃。当暴露于火焰或火时,本发明的化合物同时在气相中以及在凝聚相中呈现出杂化阻燃活性。换句话说,在一个分子中组合了不同的阻燃机理,并因此可将该不同的阻燃机理包含在聚合物中而无需混合两种不同的阻燃化合物。
思量到的是,本发明的化合物对于改善某些热固性聚合物的耐燃性可为有用的。
然而,特别地,本发明的化合物对于制造这样的热塑性聚酯材料是有用的:尽管添加剂负载相对低,但是其具有良好的耐燃性。
因此,根据本发明的另一方面,提供具有改善的耐燃性的聚合物材料(此后也被称为“耐燃性聚合物材料”),其包含至少一种热塑性聚合物树脂和至少一种具有如以上定义的式(I)的结构的阻燃化合物,并且任选地包含任何常规添加剂。
在一些实施方案中,所述热塑性聚合物树脂可为聚烯烃、聚碳酸酯或环氧树脂。根据另一实施方案,所述热塑性聚合物树脂为聚酯树脂。
根据一个实施方案,所述耐燃性聚合物材料可以另外包含基于氮的阻燃性试剂作为第二阻燃成分。
根据一个实施方案,所述聚合物材料为适于工程塑料应用的形式。根据另一实施方案,所述聚合物材料为纤维形式(尤其是用于织物应用)。
以下,术语“自由基(radical)”有时与“基团(group)”或“部分”或“取代基”可互换地使用,例如“烷基自由基”等同于如在有机化学中常用的“烷基基团”。
除非另作说明,此处所用的术语“烷基”包括具有直链或支链部分的饱和单价烃自由基,例如但不限于:甲基、乙基、丙基、异丙基、丁基或异丁基。
除非另作说明,此处所用的术语“亚烷基”包括具有直链或支链部分的饱和二价烃自由基,例如但不限于:亚甲基、亚乙基、亚丙基、亚异丙基、亚丁基或亚异丁基。
除非另作说明,此处所用的术语“芳基”包括由芳族烃通过除去一个氢而得到的芳族自由基,例如但不限于苯基或萘基。
除非另作说明,此处所用的术语“亚芳基”包括由芳族烃通过除去两个氢而得到的芳族二价自由基,例如但不限于亚苯基。
除非另作说明,此处所用的术语“芳烷基”表示“芳基烷基”基团,例如但不限于:苄基(C6H5-CH2-)或甲基苄基(CH3-C6H4-CH2-)。
除非另作说明,此处所用的术语“烷芳基”表示“烷基芳基”基团,例如但不限于:甲基苯基(CH3-C6H4-)、二甲基苯基((CH3)2-C6H3-)或异丙基苯基((CH3)2C-C6H4-)。
除非另作说明,此处关于化合物所用的术语“热稳定性”特征在于指示“分解温度”,其应被理解为化合物显著的(在惰性气氛下5%重量损失)热分解开始时的阀值温度。
在该阻燃化合物的一个实施方案中,n和m两者均为0,X独立地为氧(O)或硫(S),Q为亚甲基(-CH2-),t为1,W为氧(O)。在另一个实施方案中,R1和R2两者独立地为氢或C1-C6烷基。在另一个实施方案中,Y为亚甲基(-CH2-),n为1,m为0,X为氧(O),Q为亚甲基(-CH2-),t为1,W为氧(O)。在又一个实施方案中,X独立地为氧(O)或硫(S),Y为氧(-O-)或氮(-NH-),n为1,Z为亚甲基(-CH2-),m为2,Q为亚甲基(-CH2-),t为1,W为氧(O)。
可用于本发明的式(I)化合物的具体实例为:
根据另一方面,制造式(I)的杂化阻燃化合物的方法包括在碱的存在下使式(A)的化合物与式(B)的化合物反应:
其中R1、R2、m、X、v、Y、n和Z如以上定义,T可为氢或选自Cl、Br或I的卤素,条件是当T为氢时,n和m两者均为0;
其中Q、t、W如以上定义,且L为羟基(-OH)。
可使用的碱为任何能够在亲核取代反应中除去卤化氢的合适的碱,例如叔胺。通常合适的碱包括,但不限于,三乙胺或N-甲基咪唑。
可使用任何合适量的碱,包括:基于式A的化合物的量,约1至约10当量,或约1至约5当量。
该方法可任选地在溶剂中进行。可使用的溶剂包括,但不限于:氯仿、二氯甲烷、四氢呋喃、乙腈、甲苯、或其混合物。
该方法可在范围约-5℃至约110℃的温度下进行。
可用于制造式(I)的杂化阻燃化合物的另一方法包括在碱的存在下使式(A)的化合物(其中R1、R2、m、X、v、Y、n和Z如上定义,T为羟基(-OH)且m不可为0)与式(B)的化合物(其中Q、t、W如上定义且L为选自Cl、Br或I的卤素)反应。
一种可使用的碱为碱金属碱,如碱金属醇盐、碱金属氨化物(alkali metalamide)和碱金属烷基氨化物(alkali metal alkyl amide)。可使用的碱的实例包括但不限于,甲醇钠、甲醇钾、乙醇钠、乙醇钾、叔丁醇钠、叔丁醇钾、二异丙基氨基锂、及其混合物。
该方法可任选地在溶剂中进行。可使用的溶剂包括,但不限于,四氢呋喃、乙腈、甲苯、二甲苯;N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜、或其混合物。
该方法可在范围约-5℃至约75℃的温度下进行。
优选的是,当与聚酯组合时,式(I)的化合物的纯度应大于95%,更优选98%或最优选99%。
在本发明中,“热塑性聚酯树脂”被定义为基于至少一种脂族或芳族二羟基化合物和至少一种芳族二羧酸的聚酯。在各种实施方案中使用的热塑性聚酯没有限制且可变化。尤其优选的聚酯为聚对苯二甲酸丁二醇酯(通常简称为PBT)、聚对苯二甲酸乙二醇酯(通常简称为PET)和聚萘二甲酸乙二醇酯(通常简称为PEN)或这些的任意组合。术语“热塑性聚酯”还包括热塑性共聚酯弹性体,例如,但不限于,共聚醚酯(通常简称为COPES或TPE-E)。其它没有具体描述的聚酯也被这些实施方案所涵盖,且可与以上描述的杂化阻燃体系组合以产生本发明的阻燃聚酯。该类型的产品例如为(BASF,PBT)和(DSM,TPE-E)。
根据本发明的杂化阻燃成分的总含量可在耐燃性聚合物材料(此后也简称为“组合物”)的实施方案之间变化,并可基于耐燃性聚合物材料的期望性质而改变。
例如,在一些实施方案中,尤其是在颗粒形式或模塑形式的聚合物材料的情况中,阻燃成分的总含量优选低于所述组合物总重量的30%重量,更优选低于所述组合物总重量的25%重量,最优选低于所述组合物总重量的20%重量,使得机械性质和电学性质对于多数期望的应用是令人满意的。然而,为了实现令人满意的阻燃性质,阻燃成分的总含量优选不低于所述组合物总重量的14%重量。
在其它实施方案中,尤其是在纤维形式的聚合物材料的情况中,阻燃成分的总含量优选低于所述组合物总重量的15%重量,更优选低于所述组合物总重量的10%重量,甚至更优选低于所述组合物总重量的7%重量。然而,为了实现令人满意的阻燃性质,阻燃成分的总含量优选高于所述组合物总重量的5%重量。
将理解,所述耐燃性聚合物材料可包括另外的添加剂以提供例如颜色,或改善由所述阻燃聚酯呈现出的一种或多种性质。这样的另外的添加剂的实例包括,但不限于以下实例:耐火性添加剂、加工助剂、热和加工稳定剂、UV稳定剂、防滴剂(例如但不限于PTFE(聚四氟乙烯))、颜料、分散剂、成核剂和其它通常与聚酯或聚酯纤维一起使用的添加剂。在可商购获得的聚合物树脂中通常包含这样的添加剂。
在一个实施方案中,所述耐燃性聚合物材料进一步包含基于氮的阻燃性试剂作为第二阻燃成分。这样的基于氮的阻燃性试剂是普遍知晓的,且可包括,但不限于,具有高的氮含量的对称的三嗪衍生物、络合物和缩合产物。尤其适合的基于氮的阻燃性试剂为如下的那些:其具有允许将它们在超过200℃的温度下进行熔融加工的合适的热稳定性。此外,所述基于氮的阻燃性试剂必须与所述聚酯树脂以及与本发明中所用的其它添加剂成分相容。另外,它们不应在被引入所述聚酯树脂中时迁移到表面,它们应当是能以适于熔融加工的细粒度分布获得的,且它们不应在被引入所述聚酯树脂中时导致变色或气味。
附图说明
通过参照结合附图考虑的本发明的多种实施方案的以下描述,本发明的上述以及其它特征和目的以及其实现方式将变得更明晰且本发明本身将被更好理解,其中:
图1显示产品和622+实施例1(14重量%)的DSC曲线。
具体实施方案
实施例
以下实施例说明了本发明。然而应理解,此处所描述的以及在权利要求中所叙述的发明不旨在被以下实施例的细节所限制。
实施例1
DOPO-PEPA的合成
在该实施例中,将500g 9,10-二氢-9-氧杂-磷杂菲-10-氧化物(DOPO)和458g季戊四醇磷酸酯醇(PEPA)置于1.5L二氯甲烷(DCM)中。向该搅拌着的悬浮液中加入221mL N-甲基咪唑(NMI),随后滴加248mL的四氯化碳(CCl4),历时1小时。在加入CCl4期间,将温度保持在15-20℃之间。随后,将反应混合物回流6小时。冷却后,在真空下蒸馏二氯甲烷,并将产物用水(2L)沉淀出来。搅拌3小时后,过滤出作为白色粉末的产物并在真空下在60℃下干燥至恒重,得到744g(82%)的DOPO-PEPA。
熔点:m.p.=222℃(基于DSC,加热速率=5℃min-1)
热稳定性:T5%=338℃;T63.%=700℃
磷含量:15.71重量%
1H-NMR,δ(ppm):3.98-4.09(m,2H);4.48(d,=6.5Hz,);7.34-7.40(m,2H),7.51(t,=7.7Hz,lH);7.65(dt,J=3.8Hz,J=7.4Hz,1H);7.85-7.95(m,2H);8.20-8.27(m,2H)
13C-NMR,δ(ppm):37.48,61.87,75.02,119.95,120.65,121.92,124.86,125.39,126.03,128.91,130.03,131.06,134.41,136.35,148.87。
31P-NMR,δ(ppm):-7.18;10.96。
实施例2
DOPS-PEPA的合成
在该实施例中,将10g 6-氯-6H-二苯并[c,e][1,2]氧磷杂环己烷(DOPCl)和1.6gS8在100mL甲苯中的悬浮液加热以回流5小时。在将其冷却至室温后,加入3.7mL N-甲基咪唑(NMI),随后加入8.4g季戊四醇磷酸酯醇(PEPA)。在加入期间将温度保持在15-20℃之间。随后,将反应混合物回流3小时。在将其冷却至室温后,将沉淀的产物过滤出,用水(2x300mL)和醇(2x 300mL)清洗。将所获得的白色粉末在真空下在60℃下干燥至恒重,得到12.3g(70%)的DOPS-PEPA。
熔点:m.p.=200℃(基于DSC,加热速率=5℃min-1)
热稳定性:T5%=296℃;T64.%=700℃
磷含量:15.10重量%
1H-NMR,δ(ppm):3.99-4.09(m,2H);4.33-4.42(m,);7.36-7.41(m,2H),7.52(t,=8.0Hz,1H);7.63-7.67(m,1H);7.85(t,=8.0Hz,1H);7.95-8.02(m,1H),8.18-8.22(m,2H)
13C-NMR,δ(ppm):37.28,61.83,74.94,119.96,122.24,124.73,125.10,125.58,126.03,128.93,130.81,131.02,134.13,134.35,148.77。
31P-NMR,δ(ppm):-7.27;77.03。
实施例3和4
阻燃性TPE-E(Arnitel)
熔融加工:
在螺杆直径为24mm且L/D比为40的同向旋转双螺杆挤出机(HaakePolylab OS,PTW24/40型,Germany)上制备多种组合物。使用重力给料系统(Three Tec,Switzerland)进行材料的投配。所有的组合物是在相同的螺杆转速下加工的。对于所有配方,熔体的测量温度为230℃。使复合物熔体通过喷嘴,在水浴中冷却至室温并切割成颗粒。将该颗粒在真空烘箱中在100℃下干燥12小时。将所分析的颗粒在50%的相对湿度下调理72小时。所得配混物如下:
实施例3:Arnitel具有18重量%的DOPO-PEPA(实施例1)(2.8重量%P含量),m.p.=224℃。
实施例4:Arnitel具有14重量%的DOPO-PEPA(实施例1)(2.2重量%P含量)以及4重量%的Melapur MC 50(氰脲酸三聚氰胺),m.p.=224℃。
对比例5:Arnitel不含阻燃添加剂(0重量%P含量),m.p.=218℃。
对比例6:Arnitel含有卤化阻燃添加剂(0重量%P含量),m.p.=226℃。
对比例7:Arnitel含有基于氮的阻燃添加剂(0重量%P含量),m.p.=216℃。
ASTM D3801UL94–垂直燃烧测试
将经干燥的颗粒压缩模塑成1mm厚的板并切割成ASTM D3801UL94–垂直燃烧测试(V-0、V-1或V-2)所需的尺寸(125±5mm长,13.0±0.5mm宽)。
表1.UL94垂直燃烧测试
组合物 | 等级 |
对比例5 | 无等级 |
对比例6 | V2 |
对比例7 | V2 |
实施例3 | V0 |
实施例4 | V0 |
差示扫描量热法(DSC)
进行差示扫描量热法测量以评价配方(图1)。使用第一次加热循环(使用5℃min-1的加热速率)来评估如以上报道的配混物的熔点。在以10℃min-1的冷却速率冷却后,将所述配方以10℃min-1的加热速率再次加热。在第二次加热循环中,只有实施例3的组合物显示出与原始的TPE(对比例5)相同的熔点。在第二次加热循环中热塑性组合物的熔融温度的降低强烈暗示热塑性链段的分子量的恶化并因此在其期望的机械和物理性质方面的降低。这些测量结果表明了对于所述聚合物基质,实施例1的添加剂良好的相容性以及无负面作用。鉴于组合物在汽车工业中主要应用于引擎盖下应用并且从可回收性角度来看,其对升高温度的耐受性是重要的。
实施例8
阻燃性PET纤维
将粘度为1.40g cm-3的准备好用于纺丝(纺丝即用,ready-to-spin)的PET颗粒与5重量%的来自实施例1的杂化阻燃剂预混合,并通过包含直径为13mm且长径比(L/D)为25的单螺杆挤出机的料斗引入喷丝头中。使用具有0.5mm的直径和4的长径比(L/D)的单丝喷丝头。将所述PET组合物在具有270℃的熔体温度的情况下并且在1650m min-1的卷绕速度下纺丝。以5.5的拉伸比获得的单丝PET组合物具有Φ=59μm的直径和36分特克斯的纤维线密度。所获得的阻燃性PET纤维(实施例8)具有0.8重量%的相应P含量,而对比例9是作为不添加阻燃剂的对照实施例制备的。
表2.阻燃性PET纤维实施例8和对比例9的物理性质
为了评估耐燃性,将所述PET纤维以0.13±0.03g cm-2的密度编织成织物。从每个实施例中切割出长度为10cm的五个样品,其平均重量为1±0.02g。对所述100±5mm长的紧紧卷起的样品根据ASTM D3801UL94–垂直燃烧测试(V-0、V-1或V-2)中所述的测试程序和材料分类进行垂直燃烧测试,并且结果列于表2中。
实施例10
阻燃性PBT
在螺杆直径为24mm且L/D比为40的同向旋转双螺杆挤出机(HaakePolylab OS,PTW24/40型,Germany)上制备多种组合物。使用重力给料系统(Three Tec,Switzerland)进行材料的投配。所有的组合物是在相同的螺杆转速下加工的。使复合物熔体通过喷嘴,在水浴中冷却至室温并切割成颗粒。将该颗粒在真空烘箱中在80℃下干燥12小时。将所分析的颗粒在50%的相对湿度下调理72小时。
所得配混物如下:
实施例10:具有20重量%的DOPO-PEPA(实施例1)(3.2wt%P含量)以及4.5重量%的Melapur MC 50(氰脲酸三聚氰胺)。
对比例11:不含阻燃添加剂(0重量%P含量)。
ASTM D3801UL94–垂直燃烧测试
将经干燥的颗粒压缩模塑成为1mm厚的板并切割成ASTM D3801UL94–垂直燃烧测试(V-0、V-1或V-2)所需的尺寸(125±5mm长,13.0±0.5mm宽)。
表1.UL94垂直燃烧测试
组合物 | 等级 |
对比例11 | 无等级 |
实施例10 | V0 |
Claims (11)
1.阻燃化合物,其具有式I的结构:
其中:
R1和R2独立地为氢、C1-C6烷基、-P(O)(OR3)2、-P(O)OR3R4、或-P(O)R3 2,其中R3和R4独立地为C1-C4烷基、C6-C12芳基、C7-C15芳烷基或C7-C15烷芳基;或者R1和R2一起形成不饱和环状环,所述环状环任选地被烷基基团取代;
各k独立地为1至2的整数;
各X独立地为氧(O)或硫(S);
v为0或1;
各Y独立地为C1-C4亚烷基、C6亚芳基、C7-C15亚芳烷基、C7-C15亚烷芳基、氧(O)、氮(NR),其中R为H或C1-C4烷基;
n为0、1或2,条件是当Y为氧(O)或氮(NR)时,n为1;
各Z独立地为C1-C4亚烷基、C6亚芳基、C7-C15亚芳烷基或C7-C15亚烷芳基;
m独立地为0、1或2;条件是当Y为氧(O)或氮(N)时,m不能为0;
各Q独立地为C1-C4亚烷基;
t为1至2的整数;
W为氧(O)或硫(S)。
2.根据权利要求1的阻燃化合物,其选自:
-DOPO-PEPA;和
-DOPS-PEPA。
3.具有改善的耐燃性的聚合物材料,其包含至少一种热塑性聚合物树脂、至少一种根据权利要求1或2的阻燃化合物并且任选地包含任何常规的添加剂。
4.根据权利要求3的聚合物材料,其中所述热塑性聚合物树脂为热塑性聚酯树脂。
5.根据权利要求3或4的聚合物材料,其进一步包含基于氮的阻燃性试剂作为第二阻燃成分。
6.根据权利要求3至5之一的聚合物材料,其为颗粒形式或模塑形式。
7.根据权利要求6的聚合物材料,其中阻燃成分(I)的总含量为所述组合物的总重量的14%至30%重量。
8.根据权利要求3至5之一的聚合物材料,其为纤维形式。
9.根据权利要求8的聚合物材料,其中阻燃成分(I)的总含量为所述组合物的总重量的5%至20%重量。
10.根据权利要求3或4的聚合物材料,其中所述阻燃化合物作为表面层沉积。
11.制造根据权利要求1的阻燃化合物的方法,所述方法包括在碱的存在下使式(A)的化合物与式(B)的化合物反应:
其中:
a)R1、R2、m、X、v、Y、n和Z如以上定义,T可为氢或选自Cl、Br或I的卤素,条件是当T为氢时,n和m两者均为0;和其中Q、t、W如以上定义,且L为羟基(-OH);或者
b)R1、R2、m、X、v、Y、n和Z如以上定义,T为羟基(-OH)且m不同于0,和其中Q、t、W如上定义且L为选自Cl、Br或I的卤素。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110564114A (zh) * | 2019-08-14 | 2019-12-13 | 上海工程技术大学 | 一种阻燃材料的制备方法 |
CN111763232A (zh) * | 2020-05-09 | 2020-10-13 | 北京工商大学 | 一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂及其制备方法 |
CN111763232B (zh) * | 2020-05-09 | 2022-11-04 | 北京工商大学 | 一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂及其制备方法 |
CN113372616A (zh) * | 2021-06-17 | 2021-09-10 | 武汉工程大学 | 一种含三嗪环的膨胀型阻燃剂及其制备方法 |
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EP3119790B1 (en) | 2018-07-11 |
DK3119790T3 (en) | 2018-10-22 |
US20170081590A1 (en) | 2017-03-23 |
KR102452800B1 (ko) | 2022-10-17 |
US10072212B2 (en) | 2018-09-11 |
KR20160137575A (ko) | 2016-11-30 |
CN106573945B (zh) | 2019-08-23 |
EP2921498A1 (en) | 2015-09-23 |
EP3119790A1 (en) | 2017-01-25 |
WO2015140105A1 (en) | 2015-09-24 |
ES2687348T3 (es) | 2018-10-24 |
JP2017514890A (ja) | 2017-06-08 |
JP6462107B2 (ja) | 2019-01-30 |
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