CA1109176A - Flame-retardant polyolefin polymeric compositions containing 3,9-halophenoxy-2,4,8,10-tetraoxa-3,9- diphosphaspiro(5.5)undecane-3,9-dichalcogen - Google Patents
Flame-retardant polyolefin polymeric compositions containing 3,9-halophenoxy-2,4,8,10-tetraoxa-3,9- diphosphaspiro(5.5)undecane-3,9-dichalcogenInfo
- Publication number
- CA1109176A CA1109176A CA275,988A CA275988A CA1109176A CA 1109176 A CA1109176 A CA 1109176A CA 275988 A CA275988 A CA 275988A CA 1109176 A CA1109176 A CA 1109176A
- Authority
- CA
- Canada
- Prior art keywords
- tetraoxa
- undecane
- polymeric composition
- diphosphaspiro
- compound
- 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 abstract description 48
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 17
- 239000003063 flame retardant Substances 0.000 title claims description 47
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 230000000979 retarding effect Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- -1 bromophenoxy group Chemical group 0.000 claims description 28
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- RBFXDCLPWOLQRN-UHFFFAOYSA-N 3,9-bis(2,4,6-tribromophenoxy)-2,4,8,10-tetraoxa-3$l^{5},9$l^{5}-diphosphaspiro[5.5]undecane 3,9-dioxide Chemical compound BrC1=CC(Br)=CC(Br)=C1OP1(=O)OCC2(COP(=O)(OC=3C(=CC(Br)=CC=3Br)Br)OC2)CO1 RBFXDCLPWOLQRN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 3
- ZHHGLEAQWZWCRL-UHFFFAOYSA-N 3,9-bis(2,3,4,5,6-pentabromophenoxy)-2,4,8,10-tetraoxa-3$l^{5},9$l^{5}-diphosphaspiro[5.5]undecane 3,9-dioxide Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OP1(=O)OCC2(COP(=O)(OC=3C(=C(Br)C(Br)=C(Br)C=3Br)Br)OC2)CO1 ZHHGLEAQWZWCRL-UHFFFAOYSA-N 0.000 claims description 2
- LJAQGABBRKFNLD-UHFFFAOYSA-N 3,9-bis(sulfanylidene)-3,9-bis(2,4,6-tribromophenoxy)-2,4,8,10-tetraoxa-3lambda5,9lambda5-diphosphaspiro[5.5]undecane Chemical compound BrC1=C(OP2(OCC3(CO2)COP(OC3)(OC3=C(C=C(C=C3Br)Br)Br)=S)=S)C(=CC(=C1)Br)Br LJAQGABBRKFNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000009877 rendering Methods 0.000 claims description 2
- SIMBTBHUIKPPIM-UHFFFAOYSA-N 3,9-bis(2,3,4,6-tetrabromophenoxy)-2,4,8,10-tetraoxa-3lambda5,9lambda5-diphosphaspiro[5.5]undecane 3,9-dioxide Chemical compound BrC1=C(OP2(OCC3(CO2)COP(OC3)(OC3=C(C=C(C(=C3Br)Br)Br)Br)=O)=O)C(=C(C(=C1)Br)Br)Br SIMBTBHUIKPPIM-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000002156 mixing Methods 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 229940099514 low-density polyethylene Drugs 0.000 description 13
- 239000004702 low-density polyethylene Substances 0.000 description 13
- 229920001684 low density polyethylene Polymers 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 229920005669 high impact polystyrene Polymers 0.000 description 8
- 239000004797 high-impact polystyrene Substances 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OCSPARJUBMYNLY-UHFFFAOYSA-N 3,9-dichloro-2,4,8,10-tetraoxa-3$l^{5},9$l^{5}-diphosphaspiro[5.5]undecane 3,9-dioxide Chemical compound C1OP(Cl)(=O)OCC21COP(Cl)(=O)OC2 OCSPARJUBMYNLY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 235000014786 phosphorus Nutrition 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- NMBWHVSTNCSHJI-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-dichlorophosphoryloxybenzene Chemical group ClC1=C(Cl)C(Cl)=C(OP(Cl)(Cl)=O)C(Cl)=C1Cl NMBWHVSTNCSHJI-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000036366 Sensation of pressure Diseases 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
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- OOFVSLAKBNBEEH-UHFFFAOYSA-N dichloro-hydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(Cl)(Cl)=S OOFVSLAKBNBEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SVHOVVJFOWGYJO-UHFFFAOYSA-N pentabromophenol Chemical compound OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br SVHOVVJFOWGYJO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
- C07F9/657136—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s) the molecule containing more than one cyclic phosphorus atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- 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
- C08K5/5398—Phosphorus bound to sulfur
Landscapes
- 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)
Abstract
ABSTRACT OF THE DISCLOSURE
Polymeric compositions comprising a polyolefin polymer and a flame retarding amount of a compound of the formula:
Polymeric compositions comprising a polyolefin polymer and a flame retarding amount of a compound of the formula:
Description
1~91~
\
This invention relates to polymeric compositions, more particularly to synthetic resins comprising a polyolefin polymer and a flame retarding amount of a 3,9-bromophenoxy-
\
This invention relates to polymeric compositions, more particularly to synthetic resins comprising a polyolefin polymer and a flame retarding amount of a 3,9-bromophenoxy-
2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dichalcogen compound.
U~S. Patent 3,090,799 (hereinafter referred to as Wahl et al), discloses plasticizers comprising phosphoric acid esters of the generic formula:
O O
R10--P~ X / --OR2 in which Rl and R2 represent aliphatic, cycloaliphatic, heterocyclic or aromatic radicals, the hydrogen atoms of which can be substituted, for example, by halogen, ester, keto, nitrile, or amino groups. Rl and R2 can be identical or different. Because of the relatively high phosphoric acid content of the above compounds of Wahl et al, said compounds are stated by Wahl et al to impart a greater reduction in the combustibility for the same addition of plasticizer, in other words, smaller additions of Wahl et al's compounds are sufficient for producing the same effect.
The plasticizers of Wahl et al are stated as being useful in the production of shaped plastic compositions, such as foils, fiber and lacquer materials, as well as mold-ing materials, from organic compounds of high molecular weight, such as cellulose esters, cellulose ethers, polyvinyl com-pounds, for example, polyvinyl chloride, polyvinyl acetate, polystyrene, chlorinated rubber, alkyl resins, polyesters, polymers of acrylic acid and derivatives thereof, polyethylene polypropylene and other polymers and copolymers. Wahl et al further state that their phosphoric acid ester compounds may be used in any suitable thermoplastic resin.
The above discussion by Wahl et al is very generic and merely restates a general principle which is well known in the art of ~lame retardants, i.e., that phosphorus is capable when present in particular compounds of imparting flame `
retardant efficacy to materials treated therewith. However, it is also well known in the flame retardant art that there presently does not exist a universal flame retardant capable of imparting effective flame retardancy to all polymeric materials. Practitioners in the flame retardant art well recognize that although a compound may be an effective flame retardant for one polymer system, the same material may be ineffective for another. A flame retardant art practitiOner also knows that it takes inventive skill to determine what particular compound is capable of imparting flame retardant efficacy to a particular polymer system.
It has been discovered that a limited class of 3,9-halophenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-
U~S. Patent 3,090,799 (hereinafter referred to as Wahl et al), discloses plasticizers comprising phosphoric acid esters of the generic formula:
O O
R10--P~ X / --OR2 in which Rl and R2 represent aliphatic, cycloaliphatic, heterocyclic or aromatic radicals, the hydrogen atoms of which can be substituted, for example, by halogen, ester, keto, nitrile, or amino groups. Rl and R2 can be identical or different. Because of the relatively high phosphoric acid content of the above compounds of Wahl et al, said compounds are stated by Wahl et al to impart a greater reduction in the combustibility for the same addition of plasticizer, in other words, smaller additions of Wahl et al's compounds are sufficient for producing the same effect.
The plasticizers of Wahl et al are stated as being useful in the production of shaped plastic compositions, such as foils, fiber and lacquer materials, as well as mold-ing materials, from organic compounds of high molecular weight, such as cellulose esters, cellulose ethers, polyvinyl com-pounds, for example, polyvinyl chloride, polyvinyl acetate, polystyrene, chlorinated rubber, alkyl resins, polyesters, polymers of acrylic acid and derivatives thereof, polyethylene polypropylene and other polymers and copolymers. Wahl et al further state that their phosphoric acid ester compounds may be used in any suitable thermoplastic resin.
The above discussion by Wahl et al is very generic and merely restates a general principle which is well known in the art of ~lame retardants, i.e., that phosphorus is capable when present in particular compounds of imparting flame `
retardant efficacy to materials treated therewith. However, it is also well known in the flame retardant art that there presently does not exist a universal flame retardant capable of imparting effective flame retardancy to all polymeric materials. Practitioners in the flame retardant art well recognize that although a compound may be an effective flame retardant for one polymer system, the same material may be ineffective for another. A flame retardant art practitiOner also knows that it takes inventive skill to determine what particular compound is capable of imparting flame retardant efficacy to a particular polymer system.
It has been discovered that a limited class of 3,9-halophenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-
3,9-dichalcogen compounds impart an unusual high level of flame retardant efficacy to polyolefin polymers.
According to the present invention there is provided a polymeric composition comprising a polyole~in polymer and a flame retarding amount of a compound of the formula (I):
Brm X X
~ 0 ~ ~ I (I) wherein each X is identical and either oxygen or sulfur, pre-ferably oxygen, each m is an integer from 1 to 5, preferably from 1 to 4, and more preferably 3, n is an integer from 1 to 5, preferably from 1 to 4, and more preferably 3, I~ is also preferred that n equals m' it is thus especially preferred li~91~ , that m and n are both 3, whereby m plus n is 6. Further, it is preferred that both bromophenoxy groups be the same. Prefer-ably the compound contains at least ~5% by weight of bromine.
In another aspect of the invention there is provided a method of rendering a polyolefin polymer flame retardant which comprises incorporating a flame retarding amount of a compound of formula (I~ therein.
For purposes of illustration only, Table I, which follows is designated to further help describe the flame retardants of this invention and is neither meant nor should it be taken to be a complete listing of all the compounds within the scope of formula (I).
The numerical designations used in naming the compounds of this invention can be ascertained by reference to the following formula where the mem~ers of the hetero-cyclic and phenoxy rings are numbered.
~ O- Pg~ O _ ~ O~ 3- 0 ~ 4 r~
1~()917~i ~mmmmmmm ~ h ~llmmmmm h ~ h S~ h m ~mmmmmmm I I I I s~
~Illlmmm - ~ h S~ ~
H ~ mmmmmmm - ~ S l h h h ~mmmmmmm mmmmm . . - S~ h ~ h 5~ h S~
~mmmmmmm :~
i I t I I ~ ~
~Illllmm -~mmmmmmm X I O U~ O U~ O O U~
o C)
According to the present invention there is provided a polymeric composition comprising a polyole~in polymer and a flame retarding amount of a compound of the formula (I):
Brm X X
~ 0 ~ ~ I (I) wherein each X is identical and either oxygen or sulfur, pre-ferably oxygen, each m is an integer from 1 to 5, preferably from 1 to 4, and more preferably 3, n is an integer from 1 to 5, preferably from 1 to 4, and more preferably 3, I~ is also preferred that n equals m' it is thus especially preferred li~91~ , that m and n are both 3, whereby m plus n is 6. Further, it is preferred that both bromophenoxy groups be the same. Prefer-ably the compound contains at least ~5% by weight of bromine.
In another aspect of the invention there is provided a method of rendering a polyolefin polymer flame retardant which comprises incorporating a flame retarding amount of a compound of formula (I~ therein.
For purposes of illustration only, Table I, which follows is designated to further help describe the flame retardants of this invention and is neither meant nor should it be taken to be a complete listing of all the compounds within the scope of formula (I).
The numerical designations used in naming the compounds of this invention can be ascertained by reference to the following formula where the mem~ers of the hetero-cyclic and phenoxy rings are numbered.
~ O- Pg~ O _ ~ O~ 3- 0 ~ 4 r~
1~()917~i ~mmmmmmm ~ h ~llmmmmm h ~ h S~ h m ~mmmmmmm I I I I s~
~Illlmmm - ~ h S~ ~
H ~ mmmmmmm - ~ S l h h h ~mmmmmmm mmmmm . . - S~ h ~ h 5~ h S~
~mmmmmmm :~
i I t I I ~ ~
~Illllmm -~mmmmmmm X I O U~ O U~ O O U~
o C)
- 4 -11~91~6 The preferred compound within the scope o~ formula (I) is 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide.
In addition to the 3,9-bis-substituted compounds, an even larger number of 3,9-substituted compounds were the 3,9-substituents are different from each other are also included within the scope of this invention, The compounds of the present invention can be pre-pared by reacting a 3,9-dihalo-2,4,8,10-tetraoxa-3,9-diphos-phaspiro(5.5)-undecane-3,9-dioxide or disulfide with sub-stituted halophenols to yield the appropriate diphosphate ~-ester. The general reaction scheme is illustrated as follows:
Hal- P\ X /~ - Hal + ~ OU
~O-P~O~/\P-O-~ ~
wherein X has the meaning set forth above and wherein Hal indicates a halogen atom and Y is 1 to 5 bromo atoms. As an alternative reactant for the halophenol, the metal salts of the halophenol can be used. If it is desired that the two halophenol groups be different from each other, two different halophenol reactants should be employed. The reaction can be carried out by simply mixing the halophosphate and the halo-phenol or halophenol metal salt reactants together and heating the mixture gently at a temperature of 30 to 160C. for a period of time of from 1 to 12 hours. The above reaction can be conducted in the presence or absence of inert solvents.
Suitable inert solvents include aromatic solvents, e.g., benzene toluene, etc., and dipolar aprotic solvents, e.g., dimethyl~
formamide, dimethylsulfoxide, acetonitrile, and the iike.
Catalytic quantities of a metal salt or oxide such as magnesium oxide, magnesium chloride, calcium oxide, calcium chloride, titanium chloride, or vanadium acetate, or stochiometric quantities of a weak organic base such as pyridine or triethylamine, can be used to accelerate the completion of the reaction. The halophosphate starting reactant can be prepared by reacting pentaerythritol with a phosphorus oxyhalide.
The compounds within the scope of this invention can also be prepared according to the following reaction scheme:
~ OH + PXCl~ ~ OPC12 Reaction A Il 2 II + C(CHzH)4--~ ~ \ o X O
-Reaction B
wherein Y and X are as defined above. As an alternative reactant for the halophenol, the metal salts of the halo-phenol can be used. If it is desired that the two halophenol groups be different from each other, two different halophenol reactants should be employed. Reaction A can be carried out by refluxing the halophenol or halophenol metal salt with an e~cess amount of either phosphorous oxychloride or phosphorous thiochloride for a period of 1 to 48 hours, Catalytic quantities of a metal salt such as potassium chloride, sodium chloride, etc., or stochiometric quantities of a weak organic base such as pyridine or triethylamine, can be used to accelerate the completion of the reaction.
1~9~'76 To conduct Reaction B, two moles of the crude halo-phenyl dichlorophosphate or dichlorothiophosphate, II, are suspended or dissolved in an inert solvent. Suitable inert solvents include aromatic solvents, e.g., benzene, toluene, etc., and dipolar aprotic solvents, e.g., dimethylformamide, dimethylsulfoxide, acetonitrile, etc. One mole o~ penta-erythritol is added and the reactants are heated at 80 to 140C. for a period of 1 to 10 hours. The final product is separated by filtration, purified by standard techniques well known to those skilled in the art, e.g., washing, recrystallization, etc., and dried.
The flame retardants within the scope of this invention as well as mixtures thereof display an unobvious level of flame retardant efficacy in polyolefin polymeric compositions. Exemplary polyolefin polymers with which the flame retardants of this invention may be combined include homopolymers of ethylene, propylene, butene, and hexene and copolymers of two or more monomers, e.g., ethylene/propylene copolymers, ethylene/butene copolymers, and ethylene/hexene copolymers. A preferred class of polyolefin polymers which can be used with the flame retardants of this invention are propylene homo- and co-polymers thereof. A further des-cription of polyolefin polymers capable of being used in this invention can be found in Modern Plastics Encyclopedia, Vol, 52, No. 10A, McGraw-Hill, Inc., New York, ~ew York (1975), and the Encyclopedia of Polymer Science and Technology, Interscience Publishers, John Wiley & Sons, New York, N.Y.
(Vol, 2, Butylene Polymers- 1965, Vol. 6, Ethylene Polymers -1967 and Vol, 11, Propylene Polymers - lg69).
The flame retardants of this invention can be incorporated into or applied onto flammable polyolefin poly-meric material by techniques which are standard or known to g2 .
~ - 7 -`:
those skilled in the art. See for example, J. M. Lyons, "The Chemistry and Uses of Fire Retardants", Wiley-Inter-science, New York, 1970, and Z. E, Jolles, 'Bromine and Its Compounds", Academic Press, ~ew York, 1966. Depending on the substrate and the amount of flame re'ardancy desired, from about 1 to about 40 weight percent of the flame retardant compound of formula (I) can be incorporated therewith. How-ever, in most applications it is preferred to use from 1 to about 25 weight percent of said compounds within the scope of this invention. It should be noted that the optimum level of additive of the flame retardant within the scope of this invention depends upon the particular substrate being treated as well as the level of flame retardancy desired. For example, in polypropylene a flame retardant load level of from about 5 to about 25 percent by weight of the total polymeric com~
position is satisfactory.
In addition to the flame retardant compounds within the scope of this invention, the flame retardancy of a polymer can be further modified through the use of so-called synergists" or enhancing agents, although preferably no synergist or enhancing agent is used with the flame retardant phosphates of this invention. These "enhancing agents" com-prise 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, SbC13, SbBr3, SbI3, 2 3' 2 5~ ZnB04, BaB204.H20, 2.ZnO.3B203,3.5H O
and stannous oxide hydrate. The more preferred enhancing agent is antimony trioxide.
It is also within the scope of the present invention to employ other materials in the present invention compositions ~9:17~i where one so desired to achieve a particular end result.
Such materials include, without limitation, adhesion pro-motors; antioxidants; antistatic agents; antimicrobials colorants; heat stabilizers, light stabilizers and fillers.
The above mentioned materials, including filler, are more fully described in Modern Plastics Encyclopedia, ibid, 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 ~/O to about 75% and more specifically from about 1% to about 5~/O, 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 centi-grade, all weights are expressed in grams; and all volumes are expressed in milliliters.
Example Synthesis of 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide (compound 1 of Table I): !
The sodium salt of tribromophenol(282 grams) was partially dissolved and suspended in one liter of acetonitrile.
To this mixture 119 grams of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide was added over a one-half hour period. ~ slight exotherm was noted. Upon complete addition, the mixture was stirred and heated to 70C. for three hours. The resulting solid white mass was filtered and the l~U~
product washed thoroughly with two liters of warm water. The solid was subsequently washed twice with boiling acetone to yield 322 grams (81 percent) of a white solid, m.p, 282~ to 286qC. Percent bromine calculated: 54.0, percent bromine found: 52.06.
Example 2 Synthesis of 3,9-bis(2',3',4',5',6'-pentabromo-phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide (compound 6, Table I):
The sodium salt of pentabromophenol (460 grams) was suspended in about 3 liters of acetonitrile in a 5-liter flask.
To the above suspension was slowly added 133.7 grams (0.45 mole) of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5.5)undecane-3,9-dioxide. The reactants were stirred for half an hour and then heated gently. An additional liter of acetonitrile was added to the reaction system and then said system was heated up to 70C. and held at that temperature for 2.5 hours. The system was cooled, filtered, reslurried with water, refiltered with a centrifuge, and then air dried. The dried residue was given a boiling acetone wash, filtered through a centrifuge, and then dried at 95C. A yield of 69.7 percent (377 grams) was obtained. Melting point: 324 to 326¢.
Comparative Example 3 Synthesis of 3,9-bis(2',3',4',5',6'-pentachloro-phenoxy)-2,4j8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide.
Pentachlorophenol (97 grams, 0.364 mole), potassium chloride (3.6 grams), and phosphorus oxychloride (447 grams) were heated to the solutions refluxing temperature in a l-liter ~lask equipped with a magnetic stirrer. The reaction was re-fluxed for 16 hours, cooled to room temperature, and then lS~9176 filtered. Excess phosphorus oxychloride was removed under vacuum. The pentachlorophenyl dichlorophosphate residue (125 grams, 0.326 moles) was dissolved in toluene. Into this solution was added 22.2 grams (0.163 mole) of penta-erythritol. This reaction system was heated to reflux, held at the reflux temperature 2.75 hours, cooled to room tempera-ture, and then filtered. The residue was air dried and then dried for 2 hours at 110C. Yield: 117 5 grams (95.3%), Percent chlorine: theory: 46.9~/o' found: 46.44% melting point: greater than 380C.
Comparative Example 4 3,9-bis-~2 14',6'-trichlorophenoxy)-2, 4 ~ 8,10-tetraoxa-3,9-di-phosp~aspiro(5.5)undecane-3,9-dioxide.
The sodium salt of trichlorophenol (253 grams) was partially dissolved and suspended in 1 liter of acetonitrile.
To this mixture 171 grams of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide was added over a one-half hour period. A slight exotherm was noted. Upon con~
plete addition, the mixture was stirred and heated to 70C.
for three hours. The resulting solid white mass was filtered and the product washed thoroughly with warm water. The solid was subsequently washed twice with cold acetone to yield 181 grams (51 percent) of a white solid, m.p. 283 to 28~C, Percent chlorine calculated: 34.5 percent chlorine found:
30.9.
Comparative Example 5 3,9-bis(4'-chlorophenoxy~-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide Phosphorus oxychloride (3 kgm), potassium chloride ~40 grams), and p-chlorophenol (309 grams, 2.4 moles) were magnetically stirred in a 3 liter flask and heated to reflux.
11~917~
The reactants were refluxed for 12.75 hours and then cooled to room temperature. The reactants were filtered and excess phos-phorus oxychloride was removed under vacuum. The crude product (538 grams; 2.19 moles) was transferred to a 2 liter flask into which was also added 502 ml of toluene and 152 grams (1.09 moles) of pentaerythritol. These reactants were heated to reflux and then held there for 5.25 hours. The reactants were then cooled to room temperature, filtered, and the residue dried under vacuum at 80C. The product was washed with 3 liters of a 5~/O aqueous solution of acetone, filtered, and then air dried. Yield: 348 grams (66.5%), Acid number:
0.86, Percent chlorine: theory: 14.~/o; found: 15.06%.
Exam~le 6 A solution of 600 grams of polystyrene, 2670 grams of methylene chloride, and 60 grams of hexane, and 5 parts per hundred resin (phr) of Example 1 was prepared. To the above solution was added 3 grams of dicumyl peroxide as a flame retardant synergist. This mixture was poured into an aluminum dish and the methylene chloride was allowed to evaporate, Following this, the casting was steamed to produce a crude foam. This foam was then cut into sufficient specimens of appropriate sizes in order to subject said foam to various tests and the data obtained therefrom are reported in Table II.
The same processing conditions as above were used to maXe additional polystyrene foam samples having different flame retardant load levels. These samples were tested in the same manner and the results obtained are also tabulated in Table II, 17~
The flame retardant of Example I (4~O of the total mixture by weight) was dry mixed with high impact polystyrene (HIPS) resin (52% by weight), and ~O by weight antimony oxide (Cosden 825* TV-K brand HIPS Cosden Oil & Chemical Co., Big Springs, Texas). The mixture was melt blended in a compounding machine under the following conditions: temperature: 240C., rpm: 100 to 120, and mixing time: 2 to 3 minutes (Prep-Center*
brand compounding machine, C.W. Braebender Instruments, Inc., S. Hackensack, New Jersey). The discharge mass was cooled, ground, let down to a flame retardant load level of l~/o by weight and 3.6% by weight antimony oxide by dry blending the ground concentrate discharge mass with the HIPS resin, and then injection molded using a 30-ton Newbury 1 ounce injection molding machine under the following parameters: screw speed:
250 rpm, injection pressure: initial: 2000 pounds per square inch (psi), internal barrel temperature: rear zone: 440F., front zone: 470F.; cycle time: 60 seconds (sec.); total injection time: 20 sec., total stroke time: 5 sec. The final HIPS polymeric composition was subjected to various tests' and the data obtained therefrom are reported in Table II.
The same processing conditions as above were used to make additional HIPS Polymeric samples having different flame retardant and antimony oxide load levels. Using the same injection molding conditions as above save that the internal barrel temperature rear and front zones were 420 and 470F.
respectively, HIPS samples were also prepared with neither flame retardant additive nor antimony oxide present. The absence of the prior melt blending step and the difference in the rear and front zone internal barrel temperatures have no impact on the flame retarding efficacy of the HIPS base resin.
* trademark B
11'~176 These samples were tested in the same manner and the results obtained are also tabulated in Table II.
Example 8 The flame retardant o~ Example l (36% of the total mixture by weight) was dry mixed with low density polyethylene (LDPE) resin (64% by weight) (Union Carbide 3900 brand LDPE, Union Carbide Corp., New York, New York). The mixture was melt blended in a Brabender Prep-Center compounding machine under the following conditions: temperature: 220C., rpm: lO0~
and mixing time: 2 to 3 minutes. The discharge mass was cooled, ground, let down to a flame retardant load level of l~/o bv weight flame retardant by dry blending the ground concentrate discharge mass with the LDPE resin, and then injection molded using a 30-ton Newbury l ounce injection molding machine under the following parameters: screw speed: 250 rpm; injection pressure: initial: 2000 psi; internal barrel temperature:
rear zone: 410F., front zone: 440 F.; cycle time. 60 sec,, total injection time: 20 sec., total stroke time: 3 sec. The final LDPE polymeric composition was subjected to various tests and the data obtained therefrom are reported in Tables II and III.
Using the same injection molding conditions as above, additional LDPE samples were prepared without any flame retardant additive present. The absence o~ the prior melt blending step has no impact on the flame retarding efficacy of the LDPE base resin. These samples were tested in the same manner and the results obtained are also reported in Tables II and III.
Example 9 The flame retardant of Example 1 (3~/O of the total mixture by weight) was dry mixed with polypropylene resin (7~/O by wei~ht) (Hercules 6823 brand polypropylene, Hercules, Inc., Wilmington, Delaware). The mixture was melt blended in a Brabender Prep~Center compounding machine under the following conditions: temperature: 220C.; rpm: 100, and mixing time:
1 to 2 minutes. The discharge mass was cooled, ground, let down to a flame retardant load level of 12.5% by weight flame retardant by dry blending the ground concentrate discharge mass with the polypropylene resin and then injection molded using a 30-ton Newbury 1 ounce injection molding machine under the following parameters: screw speed: 250 rpm' injection pressure: initial: 2000 psi, internal barrel temperature:
rear zone: 410F., front zone: 440 F,; cycle time: 45 sec., total injection time: 20 sec.; total stroke time: 4.5 sec.
The final polypropylene polymeric composition was subjected to various tests and the data obtained therefrom are reported in Tables II and III.
The same processing conditions as above, save that in the case of compound of Example 2 the compounding parameters were: temperature: 225C., rpm: 120, and mixing time: 2 to 3 minutes and cycle time was 60 seconds and the stroke time was 4.5 seconds, and in the case of compound of Example 3 the mixing time was 2 to 3 minutes, the cycle time was 60 seconds and the total stroke time was 4 seconds. The different parameters used in preparing these additional polypropylene polymeric samples have no impact on the flame retardant efficacy of the flame retardant additive. Also, using the same-injection molding conditions as above, additional polypropylene poly-meric samples were prepared without any flame retardant additive present, The absence of the prior melt blending step has no impact on the flame retardant efficacy of the flame retardant additive. These samples were tested in the same manner and the results obtained are also reported in Tables II and III.
Table II clearly demonstrates that the flame retardant compounds within the scope of this invention, as exemplified by Example 1, are not universal flame retardants capable of imparting effective flame retardancy to all polymeric mate-rials treated therewith. However, Table II clearly depicts this invention's discovery of the unobvious flame retardant efficacy of the flame retardant compounds within the scope o~ this invention, as exemplified by compounds of Examples 1 and 2 in polyolefins, as exemplified by low density poly-ethylene and polypropylene~ As vividly displayed in Table II, of the various polymeric compositions containing an exemplary flame retardant compound within the scope of this invention, only flame retarded polyolefins exhibit an exceptionally high increment in Oxygen Index. These beneficial results are achieved without the use of an "enhancing" agent.
Other flame retardant compounds within the scope of this invention which also impart an exceptionally high incre-ment in Oxygen Index to flame retarded polyolefins include 3,9-bis(2',4' r 5',6'-tetrabromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide, and 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)-undecane-3,9-disulfide.
.
~ V - 16 -7~i . I ~ O
o <; . ~ .
US U~ o O . ' 'd ~ .
O e e -,~ . . I' a C ~ ,~
H ,_~ --' S I h 1_~ ~ . 5~ . 5 .
a~
~3 0~ ~ èi~ ' ,-1~ O . U') u~ o J ~o O O
'C ~ O O ~ O C`~ ~ O ~ ~ O
E-lJJ a) o o o o ~:1 - -- h h ~ ~ ~
.,1 O O O 0 5:: ,~ C~ oo C~l oo oo C`l C`l o X p~ ~ ~ ~1 ~( ~( ~ ,(r-l a) o e n o a ,~
.~
o aJ
,. ~,, .. . al C O ' a~
~ z ~ ~ ~
O H
I I I t LI m ~ -r( ~ 3 I I I I o E~ ' X I I I I 1~
~ ~ , , , , o ~ ~ 3 C~
O tn I
~ " ~ a u~
~rl O rl h ~rl bO
~1 ~ C G ~ ~ ~1 ¢ U7 h - h C~ ~ h o C~ ~ ~ W ,~
aJ ~ ~ a~ o o o e ~ ~ h > ~ ~ h h h ~ ~ O H ~ O h O O H H H H a~ a o 3 O
¦:~1 X ,_1~, al P ( ~1 ~1:: X X X Ei ~ ~' P-' ~LI r aJ Q.
O O
G
~10~17~
Example 10 The compound of Example 4 (36% of the total mixture by weight) was dry mixed with LDPE resin (64% by weight) (Union Carbide 3900 brand LDPE, Union Carbide Corp., ~ew York, New York). The mixture was melt blended in a Brabender Prep-Center compounding machine under the following conditions:
temperature: 220~C., rpm: 100; and mixing time: 2 to 3 minutes.
The discharge mass was cooled, ground, let down to a flame retardant load level of l8/O by weight flame retardant by dry blending the ground concentrate discharge mass with the LDPE
resin, and then injection molded using a 30-ton Newbury 1 ounce injection molding machine under the following para-meters: screw speed: 250 rpm; injection pressure: initial:
2000 psi; internal barrel temperature: rear zone: 410F., front zone: 440F.; cycle time: 60 sec., total injection time: 20 sec., total stroke time: 3.5 sec. The final LDPE
polymeric composition was subjected to various tests and the data obtained therefrom are reported in Table III.
The difference in parameters used to prepare the various LDPE samples of Examples 8 and,10 has no impact on the flame retarding efficacy of the flame retardant additive.
Example 11 The compound of Example 4 (25% of the total mixture by weight) was dry mixed with polypropylene resin (75% by weight) (Hercules 6823 brand polypropylene, Hercules, Inc , Wilmington, Delaware). The mixture was melt blended in a Brabender Prep-Center compounding machine under the following conditions: temperature: 220C., rmpo 100, and mixing time:
2 to 3 minutes. The discharge mass was cooled, ground, let down to a flame retardant load level of 12.5% by weight flame retardant by dry blending the ground concentrate discharge mass with the polypropylene resin, and then injection molded ~,A
9~7~
using a 30-ton Newbury 1 ounce injection molding machine under the following parameters: screw speed: 250 rpm' injection pres-sure: initial: 2000 psi, internal barrel temperature: rear zone: 410 F., front zone: 440F., cycle time: 60 sec., total injection time: 20 sec.' total stroke time: 4.5 sec.
The final polypropylene po.lymeric composition was subjected to various tests and the data obtained therefrom are reported in Table III.
The same processing conditions as above, save that the compounding temperature was 210C,, the rpm was 120, and the total stroke time was 4 seconds, were used to prepare additional polypropylene samples containing compound B. The difference in parameters used to prepare the various polypro-pylene samples of Examples 9 and 11 has no impact on the flame retarding efficacy of the polypropylene base resin.
917~ 1 O ~ O O ~ O
a .
. ~ .. ..
~n o o Ln u~ o _, ~ ~ ~ ~ ~ ~, O -.,1 C) C O O o o ~ ~ o o o æ~ ~ o o ~ ~ o E~
a bO
.
,~
O
~ .. ~ . .
.~1 I I O H
.~ ~ X X X X U~ a) ~ ~ ~`~
~ I I C~ . ~ X X X X ~
. f~ I I ~ W
,1 O O
~ . - X
.~ , o - V) ~ C ~ ~ ~q C W
h ~ P~ ~ ., E ~ p~
E j r~ h S-O ~ ~ ~ P~ ~ ~ ~ ~ ~ ,~ ~
~ ~ ~ ~ ~E3 O o U~ O
a:~ v . , ~4 .
'~
i7~ii Based on this disclosure, many other modifications and ramifications will naturally suggest themselves to those skilled in the art. These are intended to be comprehended as within the scope of this invention.
,, ,~
In addition to the 3,9-bis-substituted compounds, an even larger number of 3,9-substituted compounds were the 3,9-substituents are different from each other are also included within the scope of this invention, The compounds of the present invention can be pre-pared by reacting a 3,9-dihalo-2,4,8,10-tetraoxa-3,9-diphos-phaspiro(5.5)-undecane-3,9-dioxide or disulfide with sub-stituted halophenols to yield the appropriate diphosphate ~-ester. The general reaction scheme is illustrated as follows:
Hal- P\ X /~ - Hal + ~ OU
~O-P~O~/\P-O-~ ~
wherein X has the meaning set forth above and wherein Hal indicates a halogen atom and Y is 1 to 5 bromo atoms. As an alternative reactant for the halophenol, the metal salts of the halophenol can be used. If it is desired that the two halophenol groups be different from each other, two different halophenol reactants should be employed. The reaction can be carried out by simply mixing the halophosphate and the halo-phenol or halophenol metal salt reactants together and heating the mixture gently at a temperature of 30 to 160C. for a period of time of from 1 to 12 hours. The above reaction can be conducted in the presence or absence of inert solvents.
Suitable inert solvents include aromatic solvents, e.g., benzene toluene, etc., and dipolar aprotic solvents, e.g., dimethyl~
formamide, dimethylsulfoxide, acetonitrile, and the iike.
Catalytic quantities of a metal salt or oxide such as magnesium oxide, magnesium chloride, calcium oxide, calcium chloride, titanium chloride, or vanadium acetate, or stochiometric quantities of a weak organic base such as pyridine or triethylamine, can be used to accelerate the completion of the reaction. The halophosphate starting reactant can be prepared by reacting pentaerythritol with a phosphorus oxyhalide.
The compounds within the scope of this invention can also be prepared according to the following reaction scheme:
~ OH + PXCl~ ~ OPC12 Reaction A Il 2 II + C(CHzH)4--~ ~ \ o X O
-Reaction B
wherein Y and X are as defined above. As an alternative reactant for the halophenol, the metal salts of the halo-phenol can be used. If it is desired that the two halophenol groups be different from each other, two different halophenol reactants should be employed. Reaction A can be carried out by refluxing the halophenol or halophenol metal salt with an e~cess amount of either phosphorous oxychloride or phosphorous thiochloride for a period of 1 to 48 hours, Catalytic quantities of a metal salt such as potassium chloride, sodium chloride, etc., or stochiometric quantities of a weak organic base such as pyridine or triethylamine, can be used to accelerate the completion of the reaction.
1~9~'76 To conduct Reaction B, two moles of the crude halo-phenyl dichlorophosphate or dichlorothiophosphate, II, are suspended or dissolved in an inert solvent. Suitable inert solvents include aromatic solvents, e.g., benzene, toluene, etc., and dipolar aprotic solvents, e.g., dimethylformamide, dimethylsulfoxide, acetonitrile, etc. One mole o~ penta-erythritol is added and the reactants are heated at 80 to 140C. for a period of 1 to 10 hours. The final product is separated by filtration, purified by standard techniques well known to those skilled in the art, e.g., washing, recrystallization, etc., and dried.
The flame retardants within the scope of this invention as well as mixtures thereof display an unobvious level of flame retardant efficacy in polyolefin polymeric compositions. Exemplary polyolefin polymers with which the flame retardants of this invention may be combined include homopolymers of ethylene, propylene, butene, and hexene and copolymers of two or more monomers, e.g., ethylene/propylene copolymers, ethylene/butene copolymers, and ethylene/hexene copolymers. A preferred class of polyolefin polymers which can be used with the flame retardants of this invention are propylene homo- and co-polymers thereof. A further des-cription of polyolefin polymers capable of being used in this invention can be found in Modern Plastics Encyclopedia, Vol, 52, No. 10A, McGraw-Hill, Inc., New York, ~ew York (1975), and the Encyclopedia of Polymer Science and Technology, Interscience Publishers, John Wiley & Sons, New York, N.Y.
(Vol, 2, Butylene Polymers- 1965, Vol. 6, Ethylene Polymers -1967 and Vol, 11, Propylene Polymers - lg69).
The flame retardants of this invention can be incorporated into or applied onto flammable polyolefin poly-meric material by techniques which are standard or known to g2 .
~ - 7 -`:
those skilled in the art. See for example, J. M. Lyons, "The Chemistry and Uses of Fire Retardants", Wiley-Inter-science, New York, 1970, and Z. E, Jolles, 'Bromine and Its Compounds", Academic Press, ~ew York, 1966. Depending on the substrate and the amount of flame re'ardancy desired, from about 1 to about 40 weight percent of the flame retardant compound of formula (I) can be incorporated therewith. How-ever, in most applications it is preferred to use from 1 to about 25 weight percent of said compounds within the scope of this invention. It should be noted that the optimum level of additive of the flame retardant within the scope of this invention depends upon the particular substrate being treated as well as the level of flame retardancy desired. For example, in polypropylene a flame retardant load level of from about 5 to about 25 percent by weight of the total polymeric com~
position is satisfactory.
In addition to the flame retardant compounds within the scope of this invention, the flame retardancy of a polymer can be further modified through the use of so-called synergists" or enhancing agents, although preferably no synergist or enhancing agent is used with the flame retardant phosphates of this invention. These "enhancing agents" com-prise 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, SbC13, SbBr3, SbI3, 2 3' 2 5~ ZnB04, BaB204.H20, 2.ZnO.3B203,3.5H O
and stannous oxide hydrate. The more preferred enhancing agent is antimony trioxide.
It is also within the scope of the present invention to employ other materials in the present invention compositions ~9:17~i where one so desired to achieve a particular end result.
Such materials include, without limitation, adhesion pro-motors; antioxidants; antistatic agents; antimicrobials colorants; heat stabilizers, light stabilizers and fillers.
The above mentioned materials, including filler, are more fully described in Modern Plastics Encyclopedia, ibid, 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 ~/O to about 75% and more specifically from about 1% to about 5~/O, 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 centi-grade, all weights are expressed in grams; and all volumes are expressed in milliliters.
Example Synthesis of 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide (compound 1 of Table I): !
The sodium salt of tribromophenol(282 grams) was partially dissolved and suspended in one liter of acetonitrile.
To this mixture 119 grams of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide was added over a one-half hour period. ~ slight exotherm was noted. Upon complete addition, the mixture was stirred and heated to 70C. for three hours. The resulting solid white mass was filtered and the l~U~
product washed thoroughly with two liters of warm water. The solid was subsequently washed twice with boiling acetone to yield 322 grams (81 percent) of a white solid, m.p, 282~ to 286qC. Percent bromine calculated: 54.0, percent bromine found: 52.06.
Example 2 Synthesis of 3,9-bis(2',3',4',5',6'-pentabromo-phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide (compound 6, Table I):
The sodium salt of pentabromophenol (460 grams) was suspended in about 3 liters of acetonitrile in a 5-liter flask.
To the above suspension was slowly added 133.7 grams (0.45 mole) of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5.5)undecane-3,9-dioxide. The reactants were stirred for half an hour and then heated gently. An additional liter of acetonitrile was added to the reaction system and then said system was heated up to 70C. and held at that temperature for 2.5 hours. The system was cooled, filtered, reslurried with water, refiltered with a centrifuge, and then air dried. The dried residue was given a boiling acetone wash, filtered through a centrifuge, and then dried at 95C. A yield of 69.7 percent (377 grams) was obtained. Melting point: 324 to 326¢.
Comparative Example 3 Synthesis of 3,9-bis(2',3',4',5',6'-pentachloro-phenoxy)-2,4j8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide.
Pentachlorophenol (97 grams, 0.364 mole), potassium chloride (3.6 grams), and phosphorus oxychloride (447 grams) were heated to the solutions refluxing temperature in a l-liter ~lask equipped with a magnetic stirrer. The reaction was re-fluxed for 16 hours, cooled to room temperature, and then lS~9176 filtered. Excess phosphorus oxychloride was removed under vacuum. The pentachlorophenyl dichlorophosphate residue (125 grams, 0.326 moles) was dissolved in toluene. Into this solution was added 22.2 grams (0.163 mole) of penta-erythritol. This reaction system was heated to reflux, held at the reflux temperature 2.75 hours, cooled to room tempera-ture, and then filtered. The residue was air dried and then dried for 2 hours at 110C. Yield: 117 5 grams (95.3%), Percent chlorine: theory: 46.9~/o' found: 46.44% melting point: greater than 380C.
Comparative Example 4 3,9-bis-~2 14',6'-trichlorophenoxy)-2, 4 ~ 8,10-tetraoxa-3,9-di-phosp~aspiro(5.5)undecane-3,9-dioxide.
The sodium salt of trichlorophenol (253 grams) was partially dissolved and suspended in 1 liter of acetonitrile.
To this mixture 171 grams of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide was added over a one-half hour period. A slight exotherm was noted. Upon con~
plete addition, the mixture was stirred and heated to 70C.
for three hours. The resulting solid white mass was filtered and the product washed thoroughly with warm water. The solid was subsequently washed twice with cold acetone to yield 181 grams (51 percent) of a white solid, m.p. 283 to 28~C, Percent chlorine calculated: 34.5 percent chlorine found:
30.9.
Comparative Example 5 3,9-bis(4'-chlorophenoxy~-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide Phosphorus oxychloride (3 kgm), potassium chloride ~40 grams), and p-chlorophenol (309 grams, 2.4 moles) were magnetically stirred in a 3 liter flask and heated to reflux.
11~917~
The reactants were refluxed for 12.75 hours and then cooled to room temperature. The reactants were filtered and excess phos-phorus oxychloride was removed under vacuum. The crude product (538 grams; 2.19 moles) was transferred to a 2 liter flask into which was also added 502 ml of toluene and 152 grams (1.09 moles) of pentaerythritol. These reactants were heated to reflux and then held there for 5.25 hours. The reactants were then cooled to room temperature, filtered, and the residue dried under vacuum at 80C. The product was washed with 3 liters of a 5~/O aqueous solution of acetone, filtered, and then air dried. Yield: 348 grams (66.5%), Acid number:
0.86, Percent chlorine: theory: 14.~/o; found: 15.06%.
Exam~le 6 A solution of 600 grams of polystyrene, 2670 grams of methylene chloride, and 60 grams of hexane, and 5 parts per hundred resin (phr) of Example 1 was prepared. To the above solution was added 3 grams of dicumyl peroxide as a flame retardant synergist. This mixture was poured into an aluminum dish and the methylene chloride was allowed to evaporate, Following this, the casting was steamed to produce a crude foam. This foam was then cut into sufficient specimens of appropriate sizes in order to subject said foam to various tests and the data obtained therefrom are reported in Table II.
The same processing conditions as above were used to maXe additional polystyrene foam samples having different flame retardant load levels. These samples were tested in the same manner and the results obtained are also tabulated in Table II, 17~
The flame retardant of Example I (4~O of the total mixture by weight) was dry mixed with high impact polystyrene (HIPS) resin (52% by weight), and ~O by weight antimony oxide (Cosden 825* TV-K brand HIPS Cosden Oil & Chemical Co., Big Springs, Texas). The mixture was melt blended in a compounding machine under the following conditions: temperature: 240C., rpm: 100 to 120, and mixing time: 2 to 3 minutes (Prep-Center*
brand compounding machine, C.W. Braebender Instruments, Inc., S. Hackensack, New Jersey). The discharge mass was cooled, ground, let down to a flame retardant load level of l~/o by weight and 3.6% by weight antimony oxide by dry blending the ground concentrate discharge mass with the HIPS resin, and then injection molded using a 30-ton Newbury 1 ounce injection molding machine under the following parameters: screw speed:
250 rpm, injection pressure: initial: 2000 pounds per square inch (psi), internal barrel temperature: rear zone: 440F., front zone: 470F.; cycle time: 60 seconds (sec.); total injection time: 20 sec., total stroke time: 5 sec. The final HIPS polymeric composition was subjected to various tests' and the data obtained therefrom are reported in Table II.
The same processing conditions as above were used to make additional HIPS Polymeric samples having different flame retardant and antimony oxide load levels. Using the same injection molding conditions as above save that the internal barrel temperature rear and front zones were 420 and 470F.
respectively, HIPS samples were also prepared with neither flame retardant additive nor antimony oxide present. The absence of the prior melt blending step and the difference in the rear and front zone internal barrel temperatures have no impact on the flame retarding efficacy of the HIPS base resin.
* trademark B
11'~176 These samples were tested in the same manner and the results obtained are also tabulated in Table II.
Example 8 The flame retardant o~ Example l (36% of the total mixture by weight) was dry mixed with low density polyethylene (LDPE) resin (64% by weight) (Union Carbide 3900 brand LDPE, Union Carbide Corp., New York, New York). The mixture was melt blended in a Brabender Prep-Center compounding machine under the following conditions: temperature: 220C., rpm: lO0~
and mixing time: 2 to 3 minutes. The discharge mass was cooled, ground, let down to a flame retardant load level of l~/o bv weight flame retardant by dry blending the ground concentrate discharge mass with the LDPE resin, and then injection molded using a 30-ton Newbury l ounce injection molding machine under the following parameters: screw speed: 250 rpm; injection pressure: initial: 2000 psi; internal barrel temperature:
rear zone: 410F., front zone: 440 F.; cycle time. 60 sec,, total injection time: 20 sec., total stroke time: 3 sec. The final LDPE polymeric composition was subjected to various tests and the data obtained therefrom are reported in Tables II and III.
Using the same injection molding conditions as above, additional LDPE samples were prepared without any flame retardant additive present. The absence o~ the prior melt blending step has no impact on the flame retarding efficacy of the LDPE base resin. These samples were tested in the same manner and the results obtained are also reported in Tables II and III.
Example 9 The flame retardant of Example 1 (3~/O of the total mixture by weight) was dry mixed with polypropylene resin (7~/O by wei~ht) (Hercules 6823 brand polypropylene, Hercules, Inc., Wilmington, Delaware). The mixture was melt blended in a Brabender Prep~Center compounding machine under the following conditions: temperature: 220C.; rpm: 100, and mixing time:
1 to 2 minutes. The discharge mass was cooled, ground, let down to a flame retardant load level of 12.5% by weight flame retardant by dry blending the ground concentrate discharge mass with the polypropylene resin and then injection molded using a 30-ton Newbury 1 ounce injection molding machine under the following parameters: screw speed: 250 rpm' injection pressure: initial: 2000 psi, internal barrel temperature:
rear zone: 410F., front zone: 440 F,; cycle time: 45 sec., total injection time: 20 sec.; total stroke time: 4.5 sec.
The final polypropylene polymeric composition was subjected to various tests and the data obtained therefrom are reported in Tables II and III.
The same processing conditions as above, save that in the case of compound of Example 2 the compounding parameters were: temperature: 225C., rpm: 120, and mixing time: 2 to 3 minutes and cycle time was 60 seconds and the stroke time was 4.5 seconds, and in the case of compound of Example 3 the mixing time was 2 to 3 minutes, the cycle time was 60 seconds and the total stroke time was 4 seconds. The different parameters used in preparing these additional polypropylene polymeric samples have no impact on the flame retardant efficacy of the flame retardant additive. Also, using the same-injection molding conditions as above, additional polypropylene poly-meric samples were prepared without any flame retardant additive present, The absence of the prior melt blending step has no impact on the flame retardant efficacy of the flame retardant additive. These samples were tested in the same manner and the results obtained are also reported in Tables II and III.
Table II clearly demonstrates that the flame retardant compounds within the scope of this invention, as exemplified by Example 1, are not universal flame retardants capable of imparting effective flame retardancy to all polymeric mate-rials treated therewith. However, Table II clearly depicts this invention's discovery of the unobvious flame retardant efficacy of the flame retardant compounds within the scope o~ this invention, as exemplified by compounds of Examples 1 and 2 in polyolefins, as exemplified by low density poly-ethylene and polypropylene~ As vividly displayed in Table II, of the various polymeric compositions containing an exemplary flame retardant compound within the scope of this invention, only flame retarded polyolefins exhibit an exceptionally high increment in Oxygen Index. These beneficial results are achieved without the use of an "enhancing" agent.
Other flame retardant compounds within the scope of this invention which also impart an exceptionally high incre-ment in Oxygen Index to flame retarded polyolefins include 3,9-bis(2',4' r 5',6'-tetrabromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide, and 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)-undecane-3,9-disulfide.
.
~ V - 16 -7~i . I ~ O
o <; . ~ .
US U~ o O . ' 'd ~ .
O e e -,~ . . I' a C ~ ,~
H ,_~ --' S I h 1_~ ~ . 5~ . 5 .
a~
~3 0~ ~ èi~ ' ,-1~ O . U') u~ o J ~o O O
'C ~ O O ~ O C`~ ~ O ~ ~ O
E-lJJ a) o o o o ~:1 - -- h h ~ ~ ~
.,1 O O O 0 5:: ,~ C~ oo C~l oo oo C`l C`l o X p~ ~ ~ ~1 ~( ~( ~ ,(r-l a) o e n o a ,~
.~
o aJ
,. ~,, .. . al C O ' a~
~ z ~ ~ ~
O H
I I I t LI m ~ -r( ~ 3 I I I I o E~ ' X I I I I 1~
~ ~ , , , , o ~ ~ 3 C~
O tn I
~ " ~ a u~
~rl O rl h ~rl bO
~1 ~ C G ~ ~ ~1 ¢ U7 h - h C~ ~ h o C~ ~ ~ W ,~
aJ ~ ~ a~ o o o e ~ ~ h > ~ ~ h h h ~ ~ O H ~ O h O O H H H H a~ a o 3 O
¦:~1 X ,_1~, al P ( ~1 ~1:: X X X Ei ~ ~' P-' ~LI r aJ Q.
O O
G
~10~17~
Example 10 The compound of Example 4 (36% of the total mixture by weight) was dry mixed with LDPE resin (64% by weight) (Union Carbide 3900 brand LDPE, Union Carbide Corp., ~ew York, New York). The mixture was melt blended in a Brabender Prep-Center compounding machine under the following conditions:
temperature: 220~C., rpm: 100; and mixing time: 2 to 3 minutes.
The discharge mass was cooled, ground, let down to a flame retardant load level of l8/O by weight flame retardant by dry blending the ground concentrate discharge mass with the LDPE
resin, and then injection molded using a 30-ton Newbury 1 ounce injection molding machine under the following para-meters: screw speed: 250 rpm; injection pressure: initial:
2000 psi; internal barrel temperature: rear zone: 410F., front zone: 440F.; cycle time: 60 sec., total injection time: 20 sec., total stroke time: 3.5 sec. The final LDPE
polymeric composition was subjected to various tests and the data obtained therefrom are reported in Table III.
The difference in parameters used to prepare the various LDPE samples of Examples 8 and,10 has no impact on the flame retarding efficacy of the flame retardant additive.
Example 11 The compound of Example 4 (25% of the total mixture by weight) was dry mixed with polypropylene resin (75% by weight) (Hercules 6823 brand polypropylene, Hercules, Inc , Wilmington, Delaware). The mixture was melt blended in a Brabender Prep-Center compounding machine under the following conditions: temperature: 220C., rmpo 100, and mixing time:
2 to 3 minutes. The discharge mass was cooled, ground, let down to a flame retardant load level of 12.5% by weight flame retardant by dry blending the ground concentrate discharge mass with the polypropylene resin, and then injection molded ~,A
9~7~
using a 30-ton Newbury 1 ounce injection molding machine under the following parameters: screw speed: 250 rpm' injection pres-sure: initial: 2000 psi, internal barrel temperature: rear zone: 410 F., front zone: 440F., cycle time: 60 sec., total injection time: 20 sec.' total stroke time: 4.5 sec.
The final polypropylene po.lymeric composition was subjected to various tests and the data obtained therefrom are reported in Table III.
The same processing conditions as above, save that the compounding temperature was 210C,, the rpm was 120, and the total stroke time was 4 seconds, were used to prepare additional polypropylene samples containing compound B. The difference in parameters used to prepare the various polypro-pylene samples of Examples 9 and 11 has no impact on the flame retarding efficacy of the polypropylene base resin.
917~ 1 O ~ O O ~ O
a .
. ~ .. ..
~n o o Ln u~ o _, ~ ~ ~ ~ ~ ~, O -.,1 C) C O O o o ~ ~ o o o æ~ ~ o o ~ ~ o E~
a bO
.
,~
O
~ .. ~ . .
.~1 I I O H
.~ ~ X X X X U~ a) ~ ~ ~`~
~ I I C~ . ~ X X X X ~
. f~ I I ~ W
,1 O O
~ . - X
.~ , o - V) ~ C ~ ~ ~q C W
h ~ P~ ~ ., E ~ p~
E j r~ h S-O ~ ~ ~ P~ ~ ~ ~ ~ ~ ,~ ~
~ ~ ~ ~ ~E3 O o U~ O
a:~ v . , ~4 .
'~
i7~ii Based on this disclosure, many other modifications and ramifications will naturally suggest themselves to those skilled in the art. These are intended to be comprehended as within the scope of this invention.
,, ,~
Claims (19)
1. A polymeric composition comprising a polyolefin polymer and a flame retarding amount of a compound of the formula:
wherein each X is identical and is oxygen or sulfur, m is an integer from 1 to 5 and n is an integer from 1 to 5.
wherein each X is identical and is oxygen or sulfur, m is an integer from 1 to 5 and n is an integer from 1 to 5.
2. A polymeric composition according to claim 1, wherein said compound contains at least 45%, by weight, bromine.
3. A polymeric composition according to claim 1 or 2, wherein m is an integer from 1 to 4 and wherein n is an integer from 1 to 4.
4. A polymeric composition according to claim 1 or 2, wherein m equals n, and m and n are integers from 1 to 4.
5. A polymeric composition according to claim 1 or 2, wherein each bromophenoxy group is the same and m and n are integers from 1 to 4.
6. A polymeric composition according to claim 1 or 2, wherein m and n are both 3.
7. A polymeric composition according to claim 1 or 2, wherein m plus n is 6.
8. A polymeric composition according to claim 1, wherein said compound is selected from 3,9-bis(2',4',6'-tri-bromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)-undecane-3,9-dioxide; 3,9-bis(2',3',4',5',6'-pentabromo-phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide and 3,9-bis(2',4',5',6'-tetrabromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide, and 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-disulfide.
9. A polymeric composition according to claim 8, wherein said polyolefin polymer is selected from polypro-pylene, polyethylene and copolymers thereof.
10. A polymeric composition according to claim 9, wherein said compound is 3,9-bis(2',4',6'-tribromophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane-3,9-dioxide.
11. A polymeric composition according to claim 1 or 2, wherein said compound is present in an amount from about 1 to about 40 weight percent of the total composition.
12. A method of rendering a polyolefin polymer flame retardant which comprises incorporating in said polymer a flame retarding amount of a compound of formula:
wherein each X is identical and is oxygen or sulphur and m and n are integers from 1 to 5.
wherein each X is identical and is oxygen or sulphur and m and n are integers from 1 to 5.
13. A method according to claim 12, wherein said com-pound contains at least 45%, by weight, of bromine.
14. A method according to claim 12 or 13, wherein m and n are integers from 1 to 4.
15. A method according to claim 12 or 13, wherein m and n are equal, and are integers from 1 to 4.
16. A method according to claim 12 or 13, wherein each bromophenoxy group is the same and m and n are integers from 1 to 4.
17. A method according to claim 12 or 13, wherein m and n are both 3.
18. A method according to claim 12 or 13, wherein m plus n is 6.
19. A method according to claim 12 or 13, wherein from 1 to 40%, by weight, of said compound is incorporated in said polymer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US68575476A | 1976-05-13 | 1976-05-13 | |
US685,754 | 1976-05-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1109176A true CA1109176A (en) | 1981-09-15 |
Family
ID=24753542
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA275,988A Expired CA1109176A (en) | 1976-05-13 | 1977-04-12 | Flame-retardant polyolefin polymeric compositions containing 3,9-halophenoxy-2,4,8,10-tetraoxa-3,9- diphosphaspiro(5.5)undecane-3,9-dichalcogen |
Country Status (8)
Country | Link |
---|---|
JP (1) | JPS534061A (en) |
BE (1) | BE854449A (en) |
CA (1) | CA1109176A (en) |
DE (1) | DE2719737A1 (en) |
FR (1) | FR2351148A1 (en) |
GB (1) | GB1570654A (en) |
IT (1) | IT1082057B (en) |
NL (1) | NL7704714A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5630936U (en) * | 1979-08-20 | 1981-03-25 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1155901B (en) * | 1959-11-17 | 1963-10-17 | Agfa Ag | Softeners for cellulose derivatives |
-
1977
- 1977-04-12 CA CA275,988A patent/CA1109176A/en not_active Expired
- 1977-04-29 NL NL7704714A patent/NL7704714A/en not_active Application Discontinuation
- 1977-05-03 DE DE19772719737 patent/DE2719737A1/en not_active Ceased
- 1977-05-06 GB GB1910977A patent/GB1570654A/en not_active Expired
- 1977-05-10 BE BE177430A patent/BE854449A/en unknown
- 1977-05-12 IT IT2349077A patent/IT1082057B/en active
- 1977-05-13 FR FR7714824A patent/FR2351148A1/en active Granted
- 1977-05-13 JP JP5445177A patent/JPS534061A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
IT1082057B (en) | 1985-05-21 |
DE2719737A1 (en) | 1977-11-17 |
JPS534061A (en) | 1978-01-14 |
GB1570654A (en) | 1980-07-02 |
BE854449A (en) | 1977-11-10 |
NL7704714A (en) | 1977-11-15 |
JPS5550497B2 (en) | 1980-12-18 |
FR2351148A1 (en) | 1977-12-09 |
FR2351148B1 (en) | 1981-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1109182A (en) | Flame retardant composition of poly-phenylene ether, styrene resin and cyclic phosphate | |
US3997505A (en) | Flame retardant polymeric compositions containing pentaerythritol cyclic diphosphates or diphosphoramidates | |
US3932321A (en) | Flame-retardant polymer composition | |
JPH0873726A (en) | Flame-retardant thermoplastic resin composition | |
CA1073920A (en) | Process for the production of organic phosphorus compounds and their use as flameproofing agents | |
EP0000132A1 (en) | Halogen-substituted esters of phosphorous acid, polymeric compositions containing them as reactive flame retardants | |
JP4585659B2 (en) | Flame retardant resin composition and molded product therefrom | |
CA1199745A (en) | Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonate | |
US3978167A (en) | Pentaerythritol cyclic diphosphates and diphosphoramidates | |
EP0924249B1 (en) | Phosphoric ester, process for preparing the same and use thereof | |
US4520152A (en) | Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonate | |
CA1075257A (en) | Pentaerythritol cyclic diphosphates and diphosphoramidates | |
CA1109176A (en) | Flame-retardant polyolefin polymeric compositions containing 3,9-halophenoxy-2,4,8,10-tetraoxa-3,9- diphosphaspiro(5.5)undecane-3,9-dichalcogen | |
EP1262519B1 (en) | Flame-retardant resin composition and molded article obtained therefrom | |
EP0617042B1 (en) | Organic phosphorus compounds and flame-retarded resin compositions containing the same | |
CA1052027A (en) | Flame retardant polymeric compositions containing pentaerythritol cyclic diphosphates and diphosphoramidates | |
US4274998A (en) | Diester of 3,5,3',5'-tetrabromo-bisphenol A with halogenated aromatic carboxylic acid | |
Yang et al. | Synthesis and properties of 4‐hydroxy‐2, 3, 5, 6‐tetrabromobenzyl phosphonates and effects of their flame retardance on impact polystyrene | |
US3901847A (en) | Flame retardant polymer composition | |
WO1996013545A1 (en) | Flame retarded, stabilized polyester composition | |
US4301062A (en) | Diester of 3,5,3',5'-tetrabromo-bisphenol A with halogenated aromatic carboxylic acid | |
US3468982A (en) | Propene-3-phosphonates and polymers thereof | |
US4390477A (en) | Diphenyl pentaerythritol diphosphonate | |
US3345392A (en) | Organophosphorus-copper complex compounds | |
CA2042008C (en) | Phosphorus compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |