EP0000132B1 - Halogenhaltige Phosphorsäureester; polymere Präparate, welche diese als Flammschutzmittel enthalten - Google Patents
Halogenhaltige Phosphorsäureester; polymere Präparate, welche diese als Flammschutzmittel enthalten Download PDFInfo
- Publication number
- EP0000132B1 EP0000132B1 EP78100131A EP78100131A EP0000132B1 EP 0000132 B1 EP0000132 B1 EP 0000132B1 EP 78100131 A EP78100131 A EP 78100131A EP 78100131 A EP78100131 A EP 78100131A EP 0000132 B1 EP0000132 B1 EP 0000132B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphate
- halogen
- hydroxyl
- bis
- composition
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims description 35
- 239000003063 flame retardant Substances 0.000 title description 38
- 150000002148 esters Chemical class 0.000 title description 6
- 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 description 24
- 229920000642 polymer Polymers 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- 229920000728 polyester Polymers 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000010452 phosphate Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000004814 polyurethane Substances 0.000 claims description 14
- 229920002635 polyurethane Polymers 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001188 haloalkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 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
- 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 description 3
- 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 2
- 150000001875 compounds Chemical class 0.000 description 41
- 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 16
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- -1 e.g. Polymers 0.000 description 11
- 230000003301 hydrolyzing effect Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 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
- 238000012360 testing method Methods 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-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
- 239000000395 magnesium oxide Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000008064 anhydrides Chemical class 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
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 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
- 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
- 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
- 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
- 125000002768 hydroxyalkyl group Chemical group 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000003367 polycyclic group Chemical group 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
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- 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 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
- 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
- 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
- CVPAHRJELRJUFI-UHFFFAOYSA-N [5-bromo-2-(3-bromopropyl)-2-chloropentyl] dihydrogen phosphate Chemical compound OP(O)(=O)OCC(Cl)(CCCBr)CCCBr CVPAHRJELRJUFI-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
- CPLPNZFTIJOEIN-UHFFFAOYSA-I [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O CPLPNZFTIJOEIN-UHFFFAOYSA-I 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
- 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
- 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
- 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
- 125000001246 bromo group Chemical group Br* 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- DJKGDNKYTKCJKD-UHFFFAOYSA-N chlorendic acid Chemical compound ClC1=C(Cl)C2(Cl)C(C(=O)O)C(C(O)=O)C1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-UHFFFAOYSA-N 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
- 229920001577 copolymer Polymers 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
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 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
- 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
- 125000001183 hydrocarbyl group Chemical group 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
- 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
- 239000012948 isocyanate Substances 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 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
- 239000002243 precursor Substances 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
- 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 Table
- 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 Table
- 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 R, 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 CI 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.
- 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.
- the U.S. Patent 3,970,726 discloses polycyclic phosphateesters having the general formula wherein A is and B is wherein R, R' and R 2 are the same or different and are linear or branched primary radicals selected from alkyl having 1 to 6 carbon atoms, and haloalkyl and hydroxyalkyl having 2 to 6 carbon atoms; m and n are integers from 0 to about 4 and the sum of m plus n is from 1 to about 4.
- polycyclic phosphateesters are disclosed as being useful as flame retardants especially for rigid polyurethane foams.
- the phosphateesters disclosed are prepared from polycyclic phosphoro- halidites of the formulae wherein Z and Z 2 are bromine or OR 3 and R 3 is an alkyl or haloalkyl radical. (Column 2, lines 47-66).
- These phosphate esters are prepared by the addition of a polycyclic phosphorohalidite to a primary aliphatic alcohol in the presence of chlorine. (Column 3, lines 34-38).
- the French Patent 1,349,088 discloses halogenated polymeric diphosphates having the general formula wherein X is bromine or chlorine, R is hydrogen or hydrocarbyl halohydrocarbyl, hydrocarbyloxyalkyl or hydrocarbyl-C(O)O-alkyl and R' is hydrogen, alkyl or lower haloalkyl with the provision that R' is hydrogen when R is hydrocarbyloxyalkyl or hydrocarbyl-C(0)0-alkyl.
- the compounds disclosed in this reference do not have the necessary hydroxyl group that is required by the present application and which is necessary for the compounds to be polymerizable into a polymeric backbone such as a polyurethane.
- 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 R and R' are haloalkyl containing from 2 to 6 carbon atoms and from 1 to 6 halogen atoms; n is or hydroxyl, provided that at least one X is hydroxyl, are preferred, with said compounds wherein n > 1 being more preferred.
- Table I above is designed to further help describe the compounds of formula I and is neither meant nor should it be taken to be a complete listing of all the compounds within the scope of this invention.
- n moles of the desired haloalkyl chlorophosphate and 1 mole of compound 11 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.
- Catalytic quantities of a metal salt or oxide such as magnesium oxide, magnesium chloride, calcium oxide, calcium chloride, titanium chloride, or vanadium acetate, 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° 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-(2,2,1)-5-heptene-2,3-dicarboxylic acid, i.e., chlor- endic 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-trimethy)-1,3-pentanediot and 1,4-cyclohexanedimethanol.
- 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 unsaturatioh 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 and described herein).
- the present flame retardants since they contain a free hydroxyl group, can 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 chainstoppers. If the neopentyl moiety contains a plurality of hydroxyl groups, e.g., compound 7 in Table I.
- 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 flame retardants within the scope of this invention may additionally be incorporated into or applied onto the 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 amount, 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 , Sbl 3 , SbOCI, As z 0 3 , As 2 0 5 , ZnB0 4 , BaB 2 0 4 -H 2 0, 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 disulfide and silicon carbide.
- materials such as glass, carbon, cellulosic
- 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.
- 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 cuoling 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 phosphate, is omitted. Samples of the laminate are subjected to Oxygen Index Test, ASTM D-2863-74. The results of said test are reported in Table III.
- thermogravimetric analyses TGA
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
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 |
---|---|
EP0000132A1 EP0000132A1 (de) | 1979-01-10 |
EP0000132B1 true EP0000132B1 (de) | 1981-08-05 |
Family
ID=25206695
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100131A Expired EP0000132B1 (de) | 1977-06-30 | 1978-06-09 | Halogenhaltige Phosphorsäureester; polymere Präparate, welche diese als Flammschutzmittel enthalten |
Country Status (5)
Country | Link |
---|---|
US (1) | US4133846A (de) |
EP (1) | EP0000132B1 (de) |
JP (1) | JPS5414926A (de) |
DE (1) | DE2860891D1 (de) |
IT (1) | IT1105474B (de) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US4339357A (en) * | 1978-09-05 | 1982-07-13 | Great Lakes Chemical Corporation | Intumescent composition |
EP0013713B1 (de) * | 1978-11-30 | 1984-04-11 | Mona Industries | Phosphor enthaltende oberflächenaktive Stoffe und ihre Herstellung |
US4556710A (en) * | 1983-03-18 | 1985-12-03 | The Dow Chemical Company | Primary hydroxyl-containing phosphono-s-triazines |
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 |
US4654105A (en) * | 1985-01-25 | 1987-03-31 | Stauffer Chemical Company | Process for producing laminated polyether urethane foam |
AU573110B2 (en) * | 1985-12-19 | 1988-05-26 | Dow Chemical Company, The | Halogenated phosphorate flame retardent for polyurethanes |
US4755547A (en) * | 1986-04-08 | 1988-07-05 | The Dow Chemical Company | Halogenated phosphate-phosphites and their acid halides and acids |
US4885381A (en) * | 1986-04-08 | 1989-12-05 | The Dow Chemical Company | Phosphate-phosphites acid halides |
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 |
ATE191733T1 (de) * | 1994-08-30 | 2000-04-15 | Akzo Nobel Nv | Verminderung des beschlagens in polyurethanschaum mittels phosphatestern |
US6136997A (en) * | 1994-11-01 | 2000-10-24 | Akzo Nobel Nv | Process for the formation of hydrocarbyl BIS(hydrocarbyl phosphate) |
US5750756A (en) * | 1994-11-01 | 1998-05-12 | 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 |
US7087667B2 (en) * | 2001-05-15 | 2006-08-08 | Teijin Chemicals, Ltd. | Flame-retardant resin composition and molded article therefrom |
EP2393874A2 (de) * | 2009-02-09 | 2011-12-14 | Icl-ip America Inc. | Flammschutzmittel enthaltende polyurethanschaumstoffzusammensetzung und herstellungsverfahren dafür, flammgeschützte zusammensetzung und daraus hergestellter polyurethanschaumstoff |
US11248101B2 (en) * | 2016-01-18 | 2022-02-15 | Basf Se | Process for producing porous materials |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE622006A (de) * | 1961-09-12 | |||
FR1349088A (fr) | 1962-03-07 | 1964-01-10 | Monsanto Chemicals | Ignifugeage de matières polymères au moyen d'esters phosphoriques halogénés |
US3830886A (en) * | 1968-06-13 | 1974-08-20 | Dow Chemical Co | Phosphorus compounds containing stable halogen |
JPS569512B2 (de) * | 1973-06-19 | 1981-03-02 | ||
SE7500950L (de) * | 1974-02-20 | 1975-08-21 | Ciba Geigy Ag | |
US3970726A (en) | 1975-01-23 | 1976-07-20 | Uniroyal, Inc. | Polycyclic phosphate esters and process for preparing same |
-
1977
- 1977-06-30 US US05/811,491 patent/US4133846A/en not_active Expired - Lifetime
-
1978
- 1978-06-09 EP EP78100131A patent/EP0000132B1/de not_active Expired
- 1978-06-09 DE DE7878100131T patent/DE2860891D1/de not_active Expired
- 1978-06-20 IT IT49952/78A patent/IT1105474B/it active
- 1978-06-30 JP JP7970678A patent/JPS5414926A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
DE2860891D1 (en) | 1981-11-05 |
JPS5414926A (en) | 1979-02-03 |
US4133846A (en) | 1979-01-09 |
IT7849952A0 (it) | 1978-06-20 |
EP0000132A1 (de) | 1979-01-10 |
IT1105474B (it) | 1985-11-04 |
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