EP0000132A1 - Halogen-substituted esters of phosphorous acid, polymeric compositions containing them as reactive flame retardants - Google Patents
Halogen-substituted esters of phosphorous acid, polymeric compositions containing them as reactive flame retardants Download PDFInfo
- Publication number
- EP0000132A1 EP0000132A1 EP78100131A EP78100131A EP0000132A1 EP 0000132 A1 EP0000132 A1 EP 0000132A1 EP 78100131 A EP78100131 A EP 78100131A EP 78100131 A EP78100131 A EP 78100131A EP 0000132 A1 EP0000132 A1 EP 0000132A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphate
- halogen
- hydroxyl
- compounds
- hydrogen
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000003063 flame retardant Substances 0.000 title abstract description 37
- 150000002148 esters Chemical class 0.000 title abstract description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 title 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 229920000728 polyester Polymers 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- SUZYULXHMUKEKF-UHFFFAOYSA-N [5,6-dibromo-3-(2,3-dibromopropyl)-3-hydroxy-2,2-dimethylhexyl] dihydrogen phosphate Chemical group OP(=O)(O)OCC(C)(C)C(O)(CC(Br)CBr)CC(Br)CBr SUZYULXHMUKEKF-UHFFFAOYSA-N 0.000 claims description 4
- GKUCOKYCEPATOG-UHFFFAOYSA-N [5,6-dichloro-3-(2,3-dichloropropyl)-3-hydroxy-2,2-dimethylhexyl] dihydrogen phosphate Chemical group OP(=O)(O)OCC(C)(C)C(O)(CC(Cl)CCl)CC(Cl)CCl GKUCOKYCEPATOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000000979 retarding effect Effects 0.000 claims description 3
- HDYKSDOJZARVPT-UHFFFAOYSA-N [2-[bis(2-chloroethoxy)phosphoryloxymethyl]-3-hydroxy-2-(hydroxymethyl)propyl] bis(2-chloroethyl) phosphate Chemical group ClCCOP(=O)(OCCCl)OCC(CO)(CO)COP(=O)(OCCCl)OCCCl HDYKSDOJZARVPT-UHFFFAOYSA-N 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 42
- 239000002253 acid Substances 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 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 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 230000003301 hydrolyzing effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- -1 e.g. Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KGRQEKWICBIUQP-UHFFFAOYSA-N [1,2-dibromo-4-(2,3-dibromopropyl)-6-hydroxy-5-methylheptan-4-yl] dihydrogen phosphate Chemical compound BrCC(Br)CC(C(C)C(O)C)(CC(Br)CBr)OP(O)(O)=O KGRQEKWICBIUQP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- DVASKQOEUNSJHT-UHFFFAOYSA-N 1,2-dibromo-3-[chloro(2,3-dibromopropoxy)phosphoryl]oxypropane Chemical compound BrCC(Br)COP(=O)(Cl)OCC(Br)CBr DVASKQOEUNSJHT-UHFFFAOYSA-N 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- COWMHTOCXHIQHS-UHFFFAOYSA-N 1,2-dichloro-3-[chloro(2,3-dichloropropoxy)phosphoryl]oxypropane Chemical compound ClCC(Cl)COP(Cl)(=O)OCC(Cl)CCl COWMHTOCXHIQHS-UHFFFAOYSA-N 0.000 description 1
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- JCJNVHVKDPMDAT-UHFFFAOYSA-N 1-chloro-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)C(O)Cl JCJNVHVKDPMDAT-UHFFFAOYSA-N 0.000 description 1
- XETKNKZXWYEULP-UHFFFAOYSA-N 1-chloro-2-[chloro(2-chloroethoxy)phosphoryl]oxyethane Chemical compound ClCCOP(Cl)(=O)OCCCl XETKNKZXWYEULP-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- LAXCMGSBLFNPKZ-UHFFFAOYSA-N P(O)(=O)(OP(=O)(O)O)OC(C(C(O)CCCl)(C(O)CCCl)C(O)CCCl)CCCl Chemical compound P(O)(=O)(OP(=O)(O)O)OC(C(C(O)CCCl)(C(O)CCCl)C(O)CCCl)CCCl LAXCMGSBLFNPKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004635 Polyester fiberglass Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- WBPYCLBJJVTWGW-UHFFFAOYSA-N [5,6-dibromo-3-(2,3-dibromopropyl)-2-hydroxyhexyl] dihydrogen phosphate Chemical compound OP(=O)(O)OCC(O)C(CC(Br)CBr)CC(Br)CBr WBPYCLBJJVTWGW-UHFFFAOYSA-N 0.000 description 1
- TWIFYPCALNMJGS-UHFFFAOYSA-N [5,6-dibromo-3-chloro-3-(2,3-dibromopropyl)-2,2-bis(hydroxymethyl)hexyl] dihydrogen phosphate Chemical compound OP(=O)(O)OCC(CO)(CO)C(Cl)(CC(Br)CBr)CC(Br)CBr TWIFYPCALNMJGS-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical compound I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HZZSYAYGZVNQDB-UHFFFAOYSA-N bis(3-bromopropyl) 2-chloroethyl phosphate Chemical compound BrCCCOP(=O)(OCCCl)OCCCBr HZZSYAYGZVNQDB-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- RVJVAMZRPQBPEE-UHFFFAOYSA-N cyclohex-2-ene-1,1-diol Chemical compound OC1(O)CCCC=C1 RVJVAMZRPQBPEE-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XRVUFNZZLJWIBD-UHFFFAOYSA-N hex-1-ene-1,1-diol Chemical compound CCCCC=C(O)O XRVUFNZZLJWIBD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010449 novaculite Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with 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 System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/906—Polyurethane cellular product containing unreacted flame-retardant material
Definitions
- This invention pertains to certain novel esters of pentavalent phosphorus acid and to plastic compositions containing these esters as flame retardants therefor.
- any flame retardant in polymers or polymeric compositions is measured not only by the flame retardant capability of the additive but also by the ability of the additive to improve or modify, or at least not to detract from, other physical or mechanical properties of the polymer or polymeric composition.
- the mere fact,, therefore, that most flame retardants contain halogen and phosphorus atoms does not assure that any given halogenated or phosphorus-containing compound will impart usable flame retarding characteristics to all or even to any polymeric system.
- U.S. Patent 3,132,169 to Birum et al. discloses flame retardant esters of pentavalent phosphorus acids, which esters contain both chlorine and bromine, and which are selected from the class consisting of a phosphate of the general formula wherein R is selected from the class consisting of hydrogen, alkyl and haloalkyl radicals of from 1 to 2 carbon atoms, R' is selected from the class consisting of hydrogen, alkyl and haloalkyl radicals of from 1 to 5 carbon atoms, R" is selected from the class consisting of R' and hydrocarbyloxymethyl radicals of from 1 to 8 carbon atoms, wherein one R" at a pair of adjacent carbon atoms must be hydrogen, and n is an integer from 0 to 1.
- U.S. Patent 3,781,388 to Jenkner et al. discloses flameproofing agents having the general formula wherein B 1 is a halogen-containing alkyl radical containing 2 to 4 carbon atoms and 1 to 3 halogen atoms; R 2 is an alkyl radical containing 2 to 4 carbon atoms which may also optionally contain at least one halogen atom and/or at least one OH group; and R 3 is an alkyl group containing 2 to 4 carbon atoms and one OH group.
- U.S. Patent 3,830,886 to Davis et al. discloses flame retardant additives of the general formula wherein n is zero or one; R is a lower alkyl, phenyl or alkylated phenyl having one to three lower alkyl substituents, R' is R or and at least one R" is Br or Cl and each remaining R" is OH, Br, or Cl.
- Birum et al. does not disclose that the compounds therein can contain hydroxyl substituents attached to the neopentyl group.
- the indiscriminate substitution of a hydroxyl group for a halogen or hydrogen atom of a compound will often result in a dramatic decrease in the modified hydroxy substituted compound's hydrolytic and thermal stability.
- the net result of this inventive skill is that one now can produce a reactive flame retardant capable of reactively being.
- Davis et al. discloses triesters of phosphorus acid in which one of the ester groups is a lower alkyl group.
- Davis et al. state that "prior art fire-retardants suffer from a number of disadvantages such as their tendency to produce hydrogen halides such as HBr when heated” and that the "new compounds (of their invention) have unusual resistance to thermal and hydrolytic decomposition and are therefore superior fire-retardant additives for wood, textiles, plastics, and the like.”
- Davis et al. appear to have achieved this unusual hydrolytic stability by using groups having no hydrogen containing carbon atoms in a beta position relative to halogen bearing carbon atoms.
- Jenkner et al. disclose phosphates containing two haloalkyl groups of from 2 to 4 carbon atoms and a single hydroxyalkyl group of from 2 to 4 carbon atoms. These phosphates, however, are thermally and hydrolytically less stable, and therefore less useful than Applicant's instant compounds.
- esters of pentavalent phosphorus acid of good thermal and hydrolytic stability having the formula wherein B and R' are haloalkyl containing from 2 to 6 carbon atoms and from 1 to 6 halogen atoms; n is an integer from 1 to 3; each X is independently selected from hydrogen, halogen, alkyl, or hydroxyl, provided that at least one X is hydroxyl. Also polyurethane or polyester polymeric compositions comprising a polyurethane or polyester polymer and a flame retarding amount of the above described compounds are provided.
- Each X is independently selected from hydrogen, hydroxyl, alkyl containing 1 to about 4 carbon atoms and halogen, preferably chlorine or bromine, provided that at least one X is hydroxyl, R and R' are lower haloalkyl groups containing from 2 to 6 carbon atoms and 1 to 6, preferably 1 to 3, halogen atoms, preferably chlorine or bromine.
- the haloalkyl groups can be branched or straight chain lower haloalkyl groups. Straight chain lower haloalkyl groups are preferred.
- n moles of the desired haloalkyl chlorophosphate and 1 mole of compound II are reacted under conditions such that they co-react to form compounds of formula I.
- reaction temperatures range from about 20° to about 120°C.
- the reaction can be carried out in the presence or absence of a solvent. If a solvent is used it should preferably be an inert organic solvent. Exemplary solvents include benzene, toluene, and chloroform.
- Catalytio quantities of a metal salt or oxide such as magnesium oxide, magnesium chloride, calcium oxide, calcium chloride, titanium chloride, or vanadium aoetate, or stoichiometric quantities of an organic base such as pyridine or triethylamine can be used.
- liquid final product is washed with aqueous ammonia to remove any residual acidity.
- aqueous ammonia wash is followed by a water wash.
- the washed product is dried by standard techniques, e.g. at a temperature of from about 100° to about 130°C. until constant weight is achieved.
- said solid product can be purified by washing or recrystallization by techniques which are well known to those skilled in the art, e.g., the solid product can be washed with water or organic solvents such as benzene, toluene, methanol, ethanol, etc., or crystallized from said solvent.
- the purified solid product is then dried by standard techniques, e.g., at a temperature from about 50 o to about 150°C. until constant weight is achieved.
- the hydroxyl containing esters of pentavalent phosphorus acid of this invention as well as mixtures thereof are useful as reactive flame retardants in polymeric compositions selected from the group consisting of polyurethane, including flexible and rigid foams and elastomers, and polyester, both saturated and unsaturated polyester, including styrenated polyester.
- polyurethane including flexible and rigid foams and elastomers
- polyester both saturated and unsaturated polyester, including styrenated polyester.
- polyurethanes means polymers containing repeated urethane linkages where R is aromatic or aliphatic group. These polymers are generally made by reacting a polyisocyanate with a compound having a plurality of active hydrogens (i.e., a compound having active hydrogen and which gives a positive Zerewitinoff test).
- compositions are any polyurethane herein defined which one so desires to flame retard. It is to be understood that the polyurethanes used can be a "virgin" material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like or the polyurethanes can have additives (such as those mentioned and described herein).
- polyesters means polycondensate products of the reaction of dibasic acids and/or anhydrides or derivatives therefrom with dihydroxy alcohols. This term includes both saturated and unsaturated polyesters. Unsaturated polyesters are so designated where part or all of the respective acids, anhydrides and/or alcohols contain crosslinkable ethylenic bonds.
- dibasic acids and anhydrides include, without limitation, phthalic anhydride, maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 1,4,5,6,7,7-hexachlorobicyclo-(2,2,l)-5-heptene-2,3-dicarboxylic acid, i.e., chlorendic acid, isophthalic acid and terephthalic acid.
- dihydroxy alcohols include, without limitation, ethylene glycol, diethylene glycol, propylene glycol, butane glycol, butene diol, hexane diol, hexene diol, butyne diol, cyclohexane diol, cyclohexene diol, neopentyl glycol, hydrogenated bisphenol A, 2,2,4-tri- mgthyl-1,3-pentanediol and 1,4-cyclohexanedimethanol.
- This term also includes oopolymers of polyesters which are resins derived from reactants used to give polyester resins and reactants used to give other polycondensate linkages.
- reactants used to give polyester resins and reactants used to give other polycondensate linkages For example, there may be mentioned the reaction of dibasic anhydrides with dihydroxy alcohols and diamines to give polyester and polyamide links along the same molecular backbone.
- those products formed by addition polymerization of reactants with ethylenic linkages before or after the polyester condensation reaction For example, the addition reaction of styrene with unsaturation in polyesters after polycondensation or the formation of an additional polymer with carboxylic acid or other condensable end-groups for further polymerization by polyesterification.
- polyesters used in the present invention compositions is any polyesters herein defined and which one so desired to flame retard. It is to be understood that the polyesters used can be a "virgin" material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like or the polyesters can have additives (such as those mentioned end described herein).
- the present Clame retardants since they contain a free hydroxyl group, cna be reacted and chemically bound into the polyurethane polymer matrix if they are added, for example, along with the polyol employed in making the polyurethane, to provide permanent non-fugitive flame retardancy.
- the neopentyl moiety of the compounds of formula I contains only one hydroxyl group, e.g., compound 1 in Table I, these compounds can be used to control the polymer chain growth as chain stoppers. If the neopentyl moiety contains a plurality of hydroxyl groups, e.g., compound 7 in Table I.
- these compounds can contribute,to the overall increase in chain length and may even be used as the sole polyol reactant to coreact with the toluene diisocyanate to form the polyurethane.
- the present flame retardants of formula I can be reacted and chemically bound into the polyester matrix if they are added, for example, along with the diol employed in making the polyester, to provide permanent non-fugitive flame retardancy. If the neopentyl moiety of the compounds of formula I contains only one hydroxyl group these compounds can generally be used to control the polymer chain growth as chain stoppers.
- neopentyl moiety contains a plurality of hydroxyl groups these compounds can generally contribute to the overall increase in chain length and may even be used as the sole diol reactants to coreact with the diacids or anhydrides to form the polyesters.
- the flame retardant phosphates of this invention Being bound into, or reacted into, the matrix of the polymer the flame retardant phosphates of this invention are not subject to solvent extraction or migration due to difference in vapor pressure, reaction to sunlight or other chemical influences. Additionally because the flame retardants of this.invention become an integral part of the polymer there is no significant change in physical properties such as is typically experienced by the use of additive type flame retardants, particularly when used in large amounts.
- the amount of flame retardant which is used in the compositions and in the methods of this invention is a flame retardant amcont, i.e., that amount necessary to produce measurable flame retardancy in the compositions which are so modified.
- the quantity of flame retardant employed in the compositions and methods of this invention can generally be from about 0.5 to about 50 percent or more by weight of the total composition.
- the flame retardant of the present invention will comprise from about 1 to about 25 percent by weight of the total composition.
- the flame retardancy of a polymer such as polystyrene can be further enhanced through the use of so called “synergists” or enhancing agents which, when used with the compounds of formula I, promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately.
- These "enhancing agents” comprise the oxides and halides of groups IVA and VA of the Periodic Table, and are further described in Modern Plastics Encyclopedia, ibid” as well as U.S. Patents 2,993,924; 2,996,528; 3,205,196 and 3,878,165.
- preferred enhancing agents include Sb 2 0 3 , SbCl 3 , SbBr 3 , SbI 3 , Sb0Cl, As 2 O 3 , As 2 O 5 , ZnBO 4 , BaB 2 O 4 ⁇ H 2 O, 2 ⁇ ZnO ⁇ 3B 2 O 3 ⁇ 3 ⁇ 5H 2 O and stannous oxide hydrate.
- the more preferred enhancing agent is antimony trioxide.
- the enhancing agent can be employed in concentrations as high as 30 percent by weight of the total composition, preferably up to 15 percent, and more preferably up to 10 percent, by weight of the total composition.
- One level of synergist which is often used is an amount which is from about 25 to about 75 percent, preferably from about 33 to 67 percent, by weight of the flame retardant phosphates described above.
- Such materials include, without limitation, adhesion promoters, antioxidants, antistatic agents, antimicrobials, colorants, flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid., (in addition to the new class of flame retardants described herein), heat stabilizers, light stabilizers, pigments, plasticizers, preservatives, ultraviolet stabilizers and fillers.
- fillers there can be mentioned without limitation, materials such as glass, carbon, cellulosic fillers (wood flour, cork and shell flour), calcium carbonate (chalk, limestone, and precipitated calcium carbonate), metal flakes, metallic oxides (aluminum, beryllium oxide, and magnesia), metallic powders (aluminum, bronze, lead, stainless steel and zinc), polymers (comminuted polymers and elastomerplastic blends), silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica), silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate), and inorganic compounds such as barium ferrite, barium sulfate, molybdenum sidulfide and silicon carbide.
- materials such as glass, carbon, cellulos
- the amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely affect the desired results derived from the present invention compositions.
- the amount used can be zero (0) percent, based on the- total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about zero percent to about 75 percent and specifically from about one percent to about 50 percent.
- a rigid polyurethane foam is prepared using the following basic formulation:
- the polyol, surfactant, and fluorocarbon blowing agent are combined in a masterbatch based on 1000 grams of polyol to minimize loss of blowing agent.
- a polyester resin is prepared by mixing in a reaction vessel 148.12 grams of phthalic anhydride, 98.06 grams of maleic anhydride, 89.38 grams of ethylene glycol, 53.06 grams of diethylene glycol.
- the reaction vessel is then heated at 200°C. for two hours. Thereafter the temperature is lowered to 185°C. and 93.42 grams of bis-(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phosphate are added. Heating at 185°C. is continued for two hours. At the end of this period the vessel is cooled to 130°C. During cooling 0.1 grams of methyl hydroquinone inhibitor are added. After the vessel has reached 130°C.
- a polyester resin and fiberglass-polyester laminate are prepared substantially in accordance with the procedure of Example 3 except that the flame retardant additive, bis-(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phospheto is omitted. Samples of the laminate are subjected to Oxygen Indey Test, ASTM D-2863-74. The Table III.
- thermogravimetric analyses TGA
Abstract
Description
- This invention pertains to certain novel esters of pentavalent phosphorus acid and to plastic compositions containing these esters as flame retardants therefor.
- During the past several years, a large number of flame retardants have been developed for use with an almost equally large number of flammable materials. Cellulosic materials such as paper and wood and polymeric materials such as polyolefins, polyesters, polyurethane and polystyrene are just two examples of materials for which flame retardants have been developed. For any class of flammable materials, such as synthetic type polymers, those skilled in the art have long been aware that some flame retardant additives are more effective in polymers and polymeric compositions than other flame retardant additives. This is because the efficacy of any flame retardant in polymers or polymeric compositions is measured not only by the flame retardant capability of the additive but also by the ability of the additive to improve or modify, or at least not to detract from, other physical or mechanical properties of the polymer or polymeric composition. The mere fact,, therefore, that most flame retardants contain halogen and phosphorus atoms does not assure that any given halogenated or phosphorus-containing compound will impart usable flame retarding characteristics to all or even to any polymeric system. Furthermore, as those skilled in the art have improved the flame retardancy of many polymeric materials, they have been simultaneously required to provide the necessary flame retardancy with a minimal effect upon other properties of the polymer such as the light stability, processability, and flexural, tensile and impact strengths. Also, it has been the desire of those involved in the art of flame retardants to provide flame retardants having a durable lasting effect. Balancing all of the foregoing considerations and thereby developing polymeric compositions with good flame retardant characteristics as well as a satisfactory balance of other properties is, consequently, a task which has in the past and presently continues to require the exercise of a high degree of inventive skill.
- The prior art considered in the preparation of the instant application includes U.S. 3,132,169 to Birum et al., U.S. 3,324,205 to Carpenter et al., U.S. 3,385,801 to Birum et al., U.S. 3,391,226 to Birum et al., U.S. 3,433,856 to Friedman, U.S. 3,471,592 to Friedman, U.S. 3,781,388 to Jenkner et al., U.S. 3,830,886 to Davis-et al., and German Patent No. 2,416,663 to Burke.
- In particular, U.S. Patent 3,132,169 to Birum et al. discloses flame retardant esters of pentavalent phosphorus acids, which esters contain both chlorine and bromine, and which are selected from the class consisting of a phosphate of the general formula
- U.S. Patent 3,781,388 to Jenkner et al. discloses flameproofing agents having the general formula
-
- Birum et al. does not disclose that the compounds therein can contain hydroxyl substituents attached to the neopentyl group. As those skilled in the art of flame retardants know, the indiscriminate substitution of a hydroxyl group for a halogen or hydrogen atom of a compound will often result in a dramatic decrease in the modified hydroxy substituted compound's hydrolytic and thermal stability. However, by the use of a high degree of inventive skill, it was possible to effectuate a a substitution of a hydroxyl group for a halogen or hydrogen atom and still maintain the basic physical properties of the nonhydroxyl-containing compound. The net result of this inventive skill is that one now can produce a reactive flame retardant capable of reactively being. bound into a polymer chain, e.g., polyurethane and polyester, and thereby reducing the migration of the flame retardant and the subsequent flame retardancy loss of the polymeric composition. This result has long been sought after and much desired in the art of flame retardants.
- Davis et al. discloses triesters of phosphorus acid in which one of the ester groups is a lower alkyl group. Davis et al. state that "prior art fire-retardants suffer from a number of disadvantages such as their tendency to produce hydrogen halides such as HBr when heated" and that the "new compounds (of their invention) have unusual resistance to thermal and hydrolytic decomposition and are therefore superior fire-retardant additives for wood, textiles, plastics, and the like." Davis et al. appear to have achieved this unusual hydrolytic stability by using groups having no hydrogen containing carbon atoms in a beta position relative to halogen bearing carbon atoms.
- Applicant has found, contrary to the teachings of the prior art, that the instant compounds possess unusual hydrolytic stability despite the fact that they may possess halogen atoms adjacent to the beta carbon atoms.
- Jenkner et al. disclose phosphates containing two haloalkyl groups of from 2 to 4 carbon atoms and a single hydroxyalkyl group of from 2 to 4 carbon atoms. These phosphates, however, are thermally and hydrolytically less stable, and therefore less useful than Applicant's instant compounds.
- In accordance with this invention there are provided esters of pentavalent phosphorus acid of good thermal and hydrolytic stability having the formula
- Compounds within the scope of this invention have formula I above. Each X is independently selected from hydrogen, hydroxyl, alkyl containing 1 to about 4 carbon atoms and halogen, preferably chlorine or bromine, provided that at least one X is hydroxyl, R and R' are lower haloalkyl groups containing from 2 to 6 carbon atoms and 1 to 6, preferably 1 to 3, halogen atoms, preferably chlorine or bromine. The haloalkyl groups can be branched or straight chain lower haloalkyl groups. Straight chain lower haloalkyl groups are preferred. Compounds of Formula I, wherein X is independently selected from hydrogen, halogen, preferably chlorine or bromine,
- Compounds within the scope of this invention are prepared according to the general reaction scheme:
- Depending on the physical condition of the final end product various product purification and isolation procedures can be used. In the case of a liquid final product, said liquid product is washed with aqueous ammonia to remove any residual acidity. The aqueous ammonia wash is followed by a water wash. The washed product is dried by standard techniques, e.g. at a temperature of from about 100° to about 130°C. until constant weight is achieved.
- When a solid product is attained, said solid product can be purified by washing or recrystallization by techniques which are well known to those skilled in the art, e.g., the solid product can be washed with water or organic solvents such as benzene, toluene, methanol, ethanol, etc., or crystallized from said solvent. The purified solid product is then dried by standard techniques, e.g., at a temperature from about 50o to about 150°C. until constant weight is achieved.
- The hydroxyl containing esters of pentavalent phosphorus acid of this invention as well as mixtures thereof are useful as reactive flame retardants in polymeric compositions selected from the group consisting of polyurethane, including flexible and rigid foams and elastomers, and polyester, both saturated and unsaturated polyester, including styrenated polyester. A detailed description of the polyurethane and polyester polymeric compositions capable of being used with the flame retardants of formula I can be found in Modern Plastics Encyclopedia, Vol. 52, No. 10A, McGraw-Hill, Inc., New York, NY (1975), said Encyclopedia being incorporated herein by reference.
- Generally the term polyurethanes means polymers containing repeated urethane linkages
- Thus the polyurethanes used in the present invention compositions are any polyurethane herein defined which one so desires to flame retard. It is to be understood that the polyurethanes used can be a "virgin" material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like or the polyurethanes can have additives (such as those mentioned and described herein).
- Generally the term polyesters means polycondensate products of the reaction of dibasic acids and/or anhydrides or derivatives therefrom with dihydroxy alcohols. This term includes both saturated and unsaturated polyesters. Unsaturated polyesters are so designated where part or all of the respective acids, anhydrides and/or alcohols contain crosslinkable ethylenic bonds.
- Examples of dibasic acids and anhydrides-include, without limitation, phthalic anhydride, maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 1,4,5,6,7,7-hexachlorobicyclo-(2,2,l)-5-heptene-2,3-dicarboxylic acid, i.e., chlorendic acid, isophthalic acid and terephthalic acid.
- Examples of dihydroxy alcohols include, without limitation, ethylene glycol, diethylene glycol, propylene glycol, butane glycol, butene diol, hexane diol, hexene diol, butyne diol, cyclohexane diol, cyclohexene diol, neopentyl glycol, hydrogenated bisphenol A, 2,2,4-tri- mgthyl-1,3-pentanediol and 1,4-cyclohexanedimethanol.
- This term also includes oopolymers of polyesters which are resins derived from reactants used to give polyester resins and reactants used to give other polycondensate linkages. For example, there may be mentioned the reaction of dibasic anhydrides with dihydroxy alcohols and diamines to give polyester and polyamide links along the same molecular backbone. Also, those products formed by addition polymerization of reactants with ethylenic linkages before or after the polyester condensation reaction. For example, the addition reaction of styrene with unsaturation in polyesters after polycondensation or the formation of an additional polymer with carboxylic acid or other condensable end-groups for further polymerization by polyesterification.
- Thus the polyesters used in the present invention compositions is any polyesters herein defined and which one so desired to flame retard. It is to be understood that the polyesters used can be a "virgin" material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like or the polyesters can have additives (such as those mentioned end described herein).
- It is an advantage of this invention that the present Clame retardants, since they contain a free hydroxyl group, cna be reacted and chemically bound into the polyurethane polymer matrix if they are added, for example, along with the polyol employed in making the polyurethane, to provide permanent non-fugitive flame retardancy. If the neopentyl moiety of the compounds of formula I contains only one hydroxyl group, e.g., compound 1 in Table I, these compounds can be used to control the polymer chain growth as chain stoppers. If the neopentyl moiety contains a plurality of hydroxyl groups, e.g., compound 7 in Table I. these compounds can contribute,to the overall increase in chain length and may even be used as the sole polyol reactant to coreact with the toluene diisocyanate to form the polyurethane. Likewise, the present flame retardants of formula I can be reacted and chemically bound into the polyester matrix if they are added, for example, along with the diol employed in making the polyester, to provide permanent non-fugitive flame retardancy. If the neopentyl moiety of the compounds of formula I contains only one hydroxyl group these compounds can generally be used to control the polymer chain growth as chain stoppers. If the neopentyl moiety contains a plurality of hydroxyl groups these compounds can generally contribute to the overall increase in chain length and may even be used as the sole diol reactants to coreact with the diacids or anhydrides to form the polyesters.
- Being bound into, or reacted into, the matrix of the polymer the flame retardant phosphates of this invention are not subject to solvent extraction or migration due to difference in vapor pressure, reaction to sunlight or other chemical influences. Additionally because the flame retardants of this.invention become an integral part of the polymer there is no significant change in physical properties such as is typically experienced by the use of additive type flame retardants, particularly when used in large amounts.
- The flame retardants within the scope of this invention above polymers by techniques which are standard or known to those skilled in the art as described, for example, in J. M. Lyons, "The Chemistry and Use of Fire Retardants", Wiley Interscience, New York (1970) or Z. E. Jolles, "Bromine and Its Compounds", Academic Press, New York (1966).
- The amount of flame retardant which is used in the compositions and in the methods of this invention is a flame retardant amcont, i.e., that amount necessary to produce measurable flame retardancy in the compositions which are so modified. Depending upon the particular compound and the particular polymer with which it is combined, the quantity of flame retardant employed in the compositions and methods of this invention can generally be from about 0.5 to about 50 percent or more by weight of the total composition. Generally, for most compositions, the flame retardant of the present invention will comprise from about 1 to about 25 percent by weight of the total composition.
- In addition to the flame retardant compounds within the scope of this invention, the flame retardancy of a polymer such as polystyrene can be further enhanced through the use of so called "synergists" or enhancing agents which, when used with the compounds of formula I, promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These "enhancing agents" comprise the oxides and halides of groups IVA and VA of the Periodic Table, and are further described in Modern Plastics Encyclopedia, ibid" as well as U.S. Patents 2,993,924; 2,996,528; 3,205,196 and 3,878,165. Without limitation, preferred enhancing agents include Sb203, SbCl3, SbBr3, SbI3, Sb0Cl, As2O3, As2O5, ZnBO4, BaB2O4·H2O, 2·ZnO·3B2O3·3·5H2O and stannous oxide hydrate. The more preferred enhancing agent is antimony trioxide. The enhancing agent can be employed in concentrations as high as 30 percent by weight of the total composition, preferably up to 15 percent, and more preferably up to 10 percent, by weight of the total composition. One level of synergist which is often used is an amount which is from about 25 to about 75 percent, preferably from about 33 to 67 percent, by weight of the flame retardant phosphates described above.
- It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promoters, antioxidants, antistatic agents, antimicrobials, colorants, flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid., (in addition to the new class of flame retardants described herein), heat stabilizers, light stabilizers, pigments, plasticizers, preservatives, ultraviolet stabilizers and fillers.
- In this latter category, i.e., fillers, there can be mentioned without limitation, materials such as glass, carbon, cellulosic fillers (wood flour, cork and shell flour), calcium carbonate (chalk, limestone, and precipitated calcium carbonate), metal flakes, metallic oxides (aluminum, beryllium oxide, and magnesia), metallic powders (aluminum, bronze, lead, stainless steel and zinc), polymers (comminuted polymers and elastomerplastic blends), silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica), silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate), and inorganic compounds such as barium ferrite, barium sulfate, molybdenum sidulfide and silicon carbide.
- The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid., and which publication is incorporated herein by reference.
- The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely affect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the- total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about zero percent to about 75 percent and specifically from about one percent to about 50 percent.
- The following examples are provided for the purpose of further illustration only and are not intended to be limitations on the disclosed invention. Unless otherwise specified, all temperatures are expressed in degrees centigrade; all weights are expressed in grams; and all volumes are expressed in milliliters. /
- To a mechanically stirred solution of 516 grams of bis (2,3-dibromopropyl) chlorophosphate and 104 grams of neopentyl glycol is added 0.1 grams of magnesium oxide. The solution is heated slowly to 80°C. and held at that temperature for four hours until the hydrogen chloride evolution ceases. The reaction mixture is heated to 95°C. for one hour using an aspirator vacuum to remove residual hydrogen chloride. Upon cooling to 40°C., the reaction mixture is washed with aqueous ammonia and two additional times with water. Volatile impurities are removed by steam distillation. The product is dried, treated with Celite®(1) and Celkate® (2) and filtered. The structure of the resulting 495 grams of a clear light yellow liquid is confirmed by NMR and IR analysis.
- (1)brand of diatomaceous earth filter aid.
- (2)brand of magnesium silicate filter aid.
- To a mechanically stirred solution of 406 grams of bis-(2,3-dichloropropyl)chlorophosphate and 125 grams of neopentyl glycol was added 0.1 gram of magnesium oxide. The solution was slowly heated to 65°C. and held between 65°C. and 75°C. for seven hours until the hydrogen chloride evolution ceased. After cooling overnight, the product was washed with aqueous ammonia and two additional times with water. Volatile impurities were removed by steam distillation. The product was dried, treated with Celite and Celkate and filtered. The structure of the resulting 360 grams of a yellow liquid was confirmed by NMR and IR analysis.
- To a mechanically stirred solution of 652 grams of bis-(2,3-dibromopropyl)chlorophosphate and 195 grams of chloropentaerythritol was added 0.1 grams of magnesium oxide. The solution was heated to 70°C. and held at this temperature for five hours. After cooling to 40°C., the product was washed with aqueous ammonia and two additional times with water. The product was dried, treated with Celite and Celkate and filtered. The structure of the resulting 754 grams of product was confirmed by NMR and IR analysis.
- To a mechanically stirred solution of 282 grams of bis-(2-chloroethyl)chlorophosphate and 54.4 grams of pentaerythritol was added 0.1 grams of magnesium oxide. The solution was heated to 80°C. and held at that temperature for six hours until the hydrogen chloride evolution ceased. After cooling the solution to room temperature, the product was washed with aquous ammonia and two additional times with water. The product was dried to a constant weight, treated with Celite and Celkate and filtered. The structure of the resulting 110 grams of a colorless liquid was confirmed by NMR and IR analysis.
-
- The following procedure is used to prepare the foam:
- 1. The polyisocyanate is weighed into a tared, 10 ounce, paper cup (allowances being made for holdup) and the cup set aside while the remaining ingredients are weighed out and mixed.
- 2. The polyol masterbatch is weighed out, in the proper amount to give 100 grams of polyol, in a one quart, untreated, paper cup.
- 3. The 10 grams of the flame retardant of Example 1 are then weighed into the same one quart cup.
- 4. The contents of the one quart cup are mixed at 1000 rpm for 5 seconds.
- 5. The polyisocyanate is then added and stirring at 1000 rpm continues for 10 seconds.
- 6. The mix is poured into a five-pound, untreated, paper tub and allowed to rise.
- After the foam is tack-free, and substantially cured, it is set aside for at least seven days prior to subjecting said foam to an Oxygen Index Test, ASTM D-2863-74. The results of said test are reported in Table II.
-
- A polyester resin is prepared by mixing in a reaction vessel 148.12 grams of phthalic anhydride, 98.06 grams of maleic anhydride, 89.38 grams of ethylene glycol, 53.06 grams of diethylene glycol. The reaction vessel is then heated at 200°C. for two hours. Thereafter the temperature is lowered to 185°C. and 93.42 grams of bis-(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phosphate are added. Heating at 185°C. is continued for two hours. At the end of this period the vessel is cooled to 130°C. During cooling 0.1 grams of methyl hydroquinone inhibitor are added. After the vessel has reached 130°C. 235.7 grams of styrene are added. The vessel is then cooled to room temperature, and a fiberglass-polyester laminate is formed containing 25.9% by weight of fiberglass..Samples of this laminate are then subjected to Oxygen Index Test, ASTM D-2863-74. The results of said test are reported in Table III.
- A polyester resin and fiberglass-polyester laminate are prepared substantially in accordance with the procedure of Example 3 except that the flame retardant additive, bis-(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phospheto is omitted. Samples of the laminate are subjected to Oxygen Indey Test, ASTM D-2863-74. The Table III.
- The hydrolytic stability of bis-(2,3-dibromopropyl)-2,2-dimethyl-3-hydroxypropyl phosphate of Example 1, bis-(bromopropyl)-chloroethyl phosphate, tris-(2-chloroethyl) phosphate, and bis-(2,3-dibromopropyl)-2-hydroxypropyl phosphate is determined by the following procedure:
- A magnetically stirred emulsion containing 4 grams of one of the above three compounds, 1 gram of an emulsifier (Emcol AM2-100, Witco Chemical Corporation, New York, New York), and 45 grams of water are heated at 100oC. for 44 hours. The acid number of the emulsion is then determined by titration with a standard potassium hydroxide solution and the results are tabulated in Table IV. A compound's acid number is inversely proportional to the hydrolytic stability of that compound, i.e., the larger a compound's acid number, the poorer will be said compound's hydrolytic stability.
- As exemplified by bis(2,3-dibromopropyl)-2,3dimethyl-3-hydroxypropyl phosphate in Table IV below, the hydrolytic stability of the compounds within the scope of this invention is unobviously better than the hydrolytic stability of close prior art compounds. This increase in hydrolytic stability possessed by the compounds within the scope of this invention has eignificant commercial and practical implications.
- The thermal stability of the same compounds tested in Example 8 is determined by the procedure set forth in Section 9-951, "Thermogravimetric Analyzer", of "Instruction Manual 990, Thermal Analyzer and Modules", E. I. Du Pont De Nemours and Co. (Inc.), Instrument Products Division, Wilmington, Delaware 19898. The results of the thermogravimetric analyses (TGA) of the three compounds at several different weight losses are tabulated in Table V.
- As exemplified by bis(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phosphate, in Table V, compounds within the scope of formula I possess superior thermal stability than that possessed by prior art compounds.
Claims (14)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/811,491 US4133846A (en) | 1977-06-30 | 1977-06-30 | Hydroxyl containing phosphates and polyphosphates |
US811491 | 2007-06-11 |
Publications (2)
Publication Number | Publication Date |
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EP0000132A1 true EP0000132A1 (en) | 1979-01-10 |
EP0000132B1 EP0000132B1 (en) | 1981-08-05 |
Family
ID=25206695
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP78100131A Expired EP0000132B1 (en) | 1977-06-30 | 1978-06-09 | Halogen-substituted esters of phosphorous acid, polymeric compositions containing them as reactive flame retardants |
Country Status (5)
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US (1) | US4133846A (en) |
EP (1) | EP0000132B1 (en) |
JP (1) | JPS5414926A (en) |
DE (1) | DE2860891D1 (en) |
IT (1) | IT1105474B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0013713A1 (en) * | 1978-11-30 | 1980-08-06 | Mona Industries | Phosphorus containing surface active agents and their preparation |
GB2185027A (en) * | 1985-12-19 | 1987-07-08 | Dow Chemical Co | Phosphorus-containing flame-retardant polyurethanes |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4339357A (en) * | 1978-09-05 | 1982-07-13 | Great Lakes Chemical Corporation | Intumescent composition |
US4205022A (en) * | 1978-09-05 | 1980-05-27 | Velsicol Chemical Corporation | 2,2-Bis(haloalkyl)-3-hydroxy-1-propyl phosphoric acids |
US4265791A (en) * | 1978-09-05 | 1981-05-05 | Velsicol Chemical Corporation | Novel phosphoric acid |
US4556710A (en) * | 1983-03-18 | 1985-12-03 | The Dow Chemical Company | Primary hydroxyl-containing phosphono-s-triazines |
US4654105A (en) * | 1985-01-25 | 1987-03-31 | Stauffer Chemical Company | Process for producing laminated polyether urethane foam |
US4652485A (en) * | 1985-01-25 | 1987-03-24 | Stauffer Chemical Company | Laminated heat-sealed polyether urethane foam |
US4616044A (en) * | 1985-01-25 | 1986-10-07 | Stauffer Chemical Company | Heat laminatable polyether urethane foam |
US4885381A (en) * | 1986-04-08 | 1989-12-05 | The Dow Chemical Company | Phosphate-phosphites acid halides |
US4755547A (en) * | 1986-04-08 | 1988-07-05 | The Dow Chemical Company | Halogenated phosphate-phosphites and their acid halides and acids |
US5420327A (en) * | 1992-09-14 | 1995-05-30 | Akzo Nobel N.V. | Process for forming hydrocarbyl bisphosphate compound |
US5457221A (en) * | 1993-03-03 | 1995-10-10 | Akzo Nobel N.V. | Process for the manufacture of poly (hydrocarbylene aryl phosphate) compositions |
US5958993A (en) * | 1994-08-30 | 1999-09-28 | Akzo Novel Nv | Fog reduction in polyurethane foam using phosphate esters |
US5750756A (en) * | 1994-11-01 | 1998-05-12 | Akzo Nobel Nv | Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) |
US6136997A (en) * | 1994-11-01 | 2000-10-24 | Akzo Nobel Nv | Process for the formation of hydrocarbyl BIS(hydrocarbyl phosphate) |
US5728859A (en) * | 1996-10-31 | 1998-03-17 | Akzo Nobel N.V. | Process for making monohydroxy-terminated phosphate compositions |
US6262135B1 (en) * | 1999-04-12 | 2001-07-17 | Akzo Nobel Nv | Polyurethane foam containing a blend of monomeric and oligomeric flame retardants |
US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
EP1408085B1 (en) * | 2001-05-15 | 2008-06-18 | Teijin Chemicals, Ltd. | Flame retardant resin composition and molded article therefrom |
CN102307938B (en) * | 2009-02-09 | 2013-11-06 | Icl-Ip美国公司 | Polyurethane foam composition containing flame-retardant, and process for making same, flame retardant composition and polyurethane foam made therefrom |
CN108473658B (en) * | 2016-01-18 | 2022-08-26 | 巴斯夫欧洲公司 | Method for producing porous material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1349088A (en) | 1962-03-07 | 1964-01-10 | Monsanto Chemicals | Fireproofing of polymeric materials with halogenated phosphoric esters |
US3970726A (en) | 1975-01-23 | 1976-07-20 | Uniroyal, Inc. | Polycyclic phosphate esters and process for preparing same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE622006A (en) * | 1961-09-12 | |||
US3830886A (en) * | 1968-06-13 | 1974-08-20 | Dow Chemical Co | Phosphorus compounds containing stable halogen |
JPS569512B2 (en) * | 1973-06-19 | 1981-03-02 | ||
SE7500950L (en) * | 1974-02-20 | 1975-08-21 | Ciba Geigy Ag |
-
1977
- 1977-06-30 US US05/811,491 patent/US4133846A/en not_active Expired - Lifetime
-
1978
- 1978-06-09 EP EP78100131A patent/EP0000132B1/en not_active Expired
- 1978-06-09 DE DE7878100131T patent/DE2860891D1/en not_active Expired
- 1978-06-20 IT IT49952/78A patent/IT1105474B/en active
- 1978-06-30 JP JP7970678A patent/JPS5414926A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1349088A (en) | 1962-03-07 | 1964-01-10 | Monsanto Chemicals | Fireproofing of polymeric materials with halogenated phosphoric esters |
US3970726A (en) | 1975-01-23 | 1976-07-20 | Uniroyal, Inc. | Polycyclic phosphate esters and process for preparing same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0013713A1 (en) * | 1978-11-30 | 1980-08-06 | Mona Industries | Phosphorus containing surface active agents and their preparation |
GB2185027A (en) * | 1985-12-19 | 1987-07-08 | Dow Chemical Co | Phosphorus-containing flame-retardant polyurethanes |
Also Published As
Publication number | Publication date |
---|---|
DE2860891D1 (en) | 1981-11-05 |
US4133846A (en) | 1979-01-09 |
EP0000132B1 (en) | 1981-08-05 |
JPS5414926A (en) | 1979-02-03 |
IT7849952A0 (en) | 1978-06-20 |
IT1105474B (en) | 1985-11-04 |
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