CA1199745A - Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonate - Google Patents
Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonateInfo
- Publication number
- CA1199745A CA1199745A CA000309985A CA309985A CA1199745A CA 1199745 A CA1199745 A CA 1199745A CA 000309985 A CA000309985 A CA 000309985A CA 309985 A CA309985 A CA 309985A CA 1199745 A CA1199745 A CA 1199745A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- parts
- component
- carbon atoms
- weight
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 229920001955 polyphenylene ether Polymers 0.000 title claims description 15
- 125000004122 cyclic group Chemical group 0.000 title abstract description 9
- -1 poly-phenylene ether Chemical compound 0.000 claims abstract description 21
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 229920005669 high impact polystyrene Polymers 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004797 high-impact polystyrene Substances 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 230000000979 retarding effect Effects 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 3
- GMEVZRPQNQEJHG-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol Chemical compound C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 GMEVZRPQNQEJHG-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 1
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical compound N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- RLXOKISGPALBEB-UHFFFAOYSA-N OP(=O)OP(O)=O.OCC(CO)(CO)CO Chemical class OP(=O)OP(O)=O.OCC(CO)(CO)CO RLXOKISGPALBEB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PWZUUYSISTUNDW-VAFBSOEGSA-N quinestrol Chemical compound C([C@@H]1[C@@H](C2=CC=3)CC[C@]4([C@H]1CC[C@@]4(O)C#C)C)CC2=CC=3OC1CCCC1 PWZUUYSISTUNDW-VAFBSOEGSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 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
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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Flame retardant compositions comprising a poly-phenylene ether resin, a styrene resin and a cyclic phosphonate have excellent appearance and physical properties after molding. Especially useful is diphenyl pentaery-thritol diphosponate.
Flame retardant compositions comprising a poly-phenylene ether resin, a styrene resin and a cyclic phosphonate have excellent appearance and physical properties after molding. Especially useful is diphenyl pentaery-thritol diphosponate.
Description
~3~7~ 8CH 2513 This invention relates to flame retardant thermo-plastic compositions, and, more particularly, to compositions comprising a polyphenylene ether resin, a styrene resin, and a cyclic phosphonate.
Compositions comprising a polyphenylene ether resin and a styrene resin are well known as useful engin-eering thermoplastics, for molding, extrusion and the like.
They are described in Cize~, U. S. 3,383,435 issued May 14, 1968.
Such compositions are normally flammable, parti-cularly if high proportions of styrene resin are present, and aromatic phosphate compounds, e.gO, triphenyl phosphate, are used to retard or eliminate flammability. Haaf, U. S.
3,639,504 issued February 1, 1972 discloses that triphenyl phosphate has a tendency to reduce physical properties and describes the use of combinations of aromatic phosphates and aromatic halogen compounds to flame retard the composi-tion, without markedly lowering resistance to distortion by heat.
20_ Dialkyl pentaerythritol diphosphonates have been reported in Friedman, U. S. 3,141,032, dated July 14, 1964, to be generally superior as plasticizers and as flame retardan-ts for synthetic resins. However, it is disclosed that from 10 to 60 parts of the said phosphonate per 100 parts of resin (9.9 - 37.5 parts per 100 parts of the comkination, by weight) is the proper amount to use, with a stated preference of 30 parts per 100 parts of resin.
It has now been discovered that cyclic phosphonate compounds by themselves are effective non-plasticizing flame retardant additives for the compositions of polypheny-lene ethers and styrene resins, at an unexpectedly lower concentra~ion. Moreover, such cyclic phosphonate materials ,~
~ t7~ 8CH-2513 are just as effective in flame retardance in this system as triphenyl phosphate and provide compositions with substantially the same impact resistance as the polymer composition itself.
According to this invention there are provided flame retardant compositions comprising:
(a) a normally flammable composition comprising a polyphenylene ether resin and a styrene resin, and (b) an effective, flame-retardant amount of a compound of the formula fi / CH2 \ C CH ~ O O
O--CH2/ ~H2 -- /
wherein R is alkyl of from 1 to 18 carbon atoms, aryl or alkaryl.
Preferred compositions are those in which the polyphenylene ether resin is of the formula ~' 0~-R n wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoininy unit, n is a positive integer equal to at least 50; and Rl, independently, is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals free of a ter-tiary alpha carbon atom, halohydrocarbon radicals having at least two carbon atoms between the ha:Logen atom and the phenyl nucleus and being free of a tertiary alpha carbon atoms, hydrocarbonoxy radicals beiny free of a tertiary alpha carbon ato~, or
Compositions comprising a polyphenylene ether resin and a styrene resin are well known as useful engin-eering thermoplastics, for molding, extrusion and the like.
They are described in Cize~, U. S. 3,383,435 issued May 14, 1968.
Such compositions are normally flammable, parti-cularly if high proportions of styrene resin are present, and aromatic phosphate compounds, e.gO, triphenyl phosphate, are used to retard or eliminate flammability. Haaf, U. S.
3,639,504 issued February 1, 1972 discloses that triphenyl phosphate has a tendency to reduce physical properties and describes the use of combinations of aromatic phosphates and aromatic halogen compounds to flame retard the composi-tion, without markedly lowering resistance to distortion by heat.
20_ Dialkyl pentaerythritol diphosphonates have been reported in Friedman, U. S. 3,141,032, dated July 14, 1964, to be generally superior as plasticizers and as flame retardan-ts for synthetic resins. However, it is disclosed that from 10 to 60 parts of the said phosphonate per 100 parts of resin (9.9 - 37.5 parts per 100 parts of the comkination, by weight) is the proper amount to use, with a stated preference of 30 parts per 100 parts of resin.
It has now been discovered that cyclic phosphonate compounds by themselves are effective non-plasticizing flame retardant additives for the compositions of polypheny-lene ethers and styrene resins, at an unexpectedly lower concentra~ion. Moreover, such cyclic phosphonate materials ,~
~ t7~ 8CH-2513 are just as effective in flame retardance in this system as triphenyl phosphate and provide compositions with substantially the same impact resistance as the polymer composition itself.
According to this invention there are provided flame retardant compositions comprising:
(a) a normally flammable composition comprising a polyphenylene ether resin and a styrene resin, and (b) an effective, flame-retardant amount of a compound of the formula fi / CH2 \ C CH ~ O O
O--CH2/ ~H2 -- /
wherein R is alkyl of from 1 to 18 carbon atoms, aryl or alkaryl.
Preferred compositions are those in which the polyphenylene ether resin is of the formula ~' 0~-R n wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoininy unit, n is a positive integer equal to at least 50; and Rl, independently, is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals free of a ter-tiary alpha carbon atom, halohydrocarbon radicals having at least two carbon atoms between the ha:Logen atom and the phenyl nucleus and being free of a tertiary alpha carbon atoms, hydrocarbonoxy radicals beiny free of a tertiary alpha carbon ato~, or
- 2 -~ .7~ 8CH-2513 halohydrocarbono~y radicals having at least two carhon atoms between the halogen atom and the phenyl nucleus and being free of a tertiary alpha carbon atoms.
Especially preferred resins are those in which Rl is alkyl of from 1 to 6 carbon atoms, especially methyl.
Special mention is made of compositions wherein each Rl is alkyl of from 1 to ~ carbon atoms. The component (a) can be made by those skilled in the art following the teachings of the above-mentioned Cizek patent, and the other references mentioned therein. These materials are also commercially available, e.g., from the General Electric Co., Pittsfield, Mass.
Preferred compositions also include those in which the styrene resin has at least 25 percent by weight units derived from a compound of the formula:
~(Op wherein R2 is hydrogen, alkyl of from 1 to 6 carbon atoms or halogen, Z is vinyl, halogen, or lower alkyl~ and p is 0 or ~ whole number equal to the number of replaceable hydrogen atoms in the benzene nucleus. Preferred such styrene resins will be those in which p is 0 and ~2 is hydrogen. Typical styrene resins include, by way of example~ homopolymers such as polystyrene and polychloro-styrene, the modified polystyrenes such as rubber modified polystyrenes (high impact polystyrenes), and the styrene containing copolymers, such as the styrene-acrylonitrlle copolymers (SAN), styrene-butadiene copolymers, styrene/
ethylenepropylene-butadiene terpolymers (EPDM), styrene maleic anhydride copolymers (SMA), styrene-acrylonitrile-,~
~ ~ ~ ~ ~ 8CH 2513 alpha-alkyl styrene copolymers, styrene-acrylonitrile-butadene terpolymers (ABS), poly-alpha-methyl styrene, copolymers of ethylvinyl benzene and divinyl benzene, and the like.
The flame retardant cyclic phosphonates will include compounds wherein ~ is straight a branched-chain alkyl of from about l to about 18 carbon atoms, e.g., methyl, ethyl, propyl, i-propyl, n-decyl, hexadecyl, octadecyl, and the like, aryl e.g. phenyl, naphthyl, and the like, or alkaryl, e.g., benzyl, phenethyl, and the like, containing up to about 18 carbon atoms. Preferably, in the cyclic phosphonate, R will be methyl, decyl and, especially preferably phenyl.
The cyclic phosphonates can be made by those skilled in the art, e.g., by following the procedure hereinafter, or in U. S. 3,141,032 for example.
~he manner of adding the flame retardant component (b~ to the composition (a) is not critical.
Preferably, however, such component is added as part of ; a blend premix, the latter being passed through an ex truder with extrusion temperature being maintained between about 450 and 640F. depending on the composition.
The s-trands emerging from the extruder may be cooled, chppped into pellets, molded to a desired shape.
The concentration of the flame retardant additi~e (b) can vary, but is dependent to a large extent on the concentration of the styrene resin and the particular styrene resin used. Lower concentrations of styrene resin or less flammable styrene resins require a lower c ncen~ration of flame retardant. Moreover, ~D~O~ ~r ~ ~
30 ~ cyclic ~ 7*~e~-wh~eh higher contents o~ phosphorous can be used in ]ower amounts. In general, however, amounts of from about l to about 10 parts by weight of component ~ S 8CH 2513 (b) can be used. However, to secure the major ad~antayes, only from about 2 to about 10 parts per 100 parts by weight of (a) and (b) combined will be used.
Conventional additives, e.g., reinforcements, pigments~ stabilizers, lubricants, and the like can also be included in conventional amounts.
The following examples illustrate the present invention. In each report~ flame retardant properties are determined following procedures established by the Underwriters' Laboratory Bulletin, No. 9~. To meet a V-l rating, bars measuring 2 1/2" x 1/2" x 1/8"
thick are twice ignited for 10 seconds each time.
The compositions shall:
A. Not have any specimens which burn with flaming combustion for more than 30 seconds after each application of the tes-t flame~
B. Not have a total flaming combustion time exceeding 250 seconds for the 10 flame applications for each set of 5 specimens.
C. Not have any specimens which burn with flaming or glowing combustion up to the holding clamp.
D. Not have any specimens which drip flaming particles that ignite the dry absorbent surgical cotton located 12 inches (305 mm) below the test specimen.
E. Not have any specimens with glowing combustion which persists beyond 60 seconds after the second removal of the test f]ame.
E ~MPI.ES 1 - 3 Cornpositions comprising polyphenylene ether resin, polystyrene resin and a cyclic phosphonate of the formula o / 0 ~ CH2 \ CH - 0 0 R ~ P C P ~ R
O--CH2/ \CH2--O /
are preblended, extruded at 530F and chopped into molding granules. The granules are injection molded at 500F ~cylinder) and 180F (mold) in a 3 oz. Newbury injection molding machine. Physical properties and burn ~est results for these and for ~omparison examples are set forth in the Table:
"c"
Especially preferred resins are those in which Rl is alkyl of from 1 to 6 carbon atoms, especially methyl.
Special mention is made of compositions wherein each Rl is alkyl of from 1 to ~ carbon atoms. The component (a) can be made by those skilled in the art following the teachings of the above-mentioned Cizek patent, and the other references mentioned therein. These materials are also commercially available, e.g., from the General Electric Co., Pittsfield, Mass.
Preferred compositions also include those in which the styrene resin has at least 25 percent by weight units derived from a compound of the formula:
~(Op wherein R2 is hydrogen, alkyl of from 1 to 6 carbon atoms or halogen, Z is vinyl, halogen, or lower alkyl~ and p is 0 or ~ whole number equal to the number of replaceable hydrogen atoms in the benzene nucleus. Preferred such styrene resins will be those in which p is 0 and ~2 is hydrogen. Typical styrene resins include, by way of example~ homopolymers such as polystyrene and polychloro-styrene, the modified polystyrenes such as rubber modified polystyrenes (high impact polystyrenes), and the styrene containing copolymers, such as the styrene-acrylonitrlle copolymers (SAN), styrene-butadiene copolymers, styrene/
ethylenepropylene-butadiene terpolymers (EPDM), styrene maleic anhydride copolymers (SMA), styrene-acrylonitrile-,~
~ ~ ~ ~ ~ 8CH 2513 alpha-alkyl styrene copolymers, styrene-acrylonitrile-butadene terpolymers (ABS), poly-alpha-methyl styrene, copolymers of ethylvinyl benzene and divinyl benzene, and the like.
The flame retardant cyclic phosphonates will include compounds wherein ~ is straight a branched-chain alkyl of from about l to about 18 carbon atoms, e.g., methyl, ethyl, propyl, i-propyl, n-decyl, hexadecyl, octadecyl, and the like, aryl e.g. phenyl, naphthyl, and the like, or alkaryl, e.g., benzyl, phenethyl, and the like, containing up to about 18 carbon atoms. Preferably, in the cyclic phosphonate, R will be methyl, decyl and, especially preferably phenyl.
The cyclic phosphonates can be made by those skilled in the art, e.g., by following the procedure hereinafter, or in U. S. 3,141,032 for example.
~he manner of adding the flame retardant component (b~ to the composition (a) is not critical.
Preferably, however, such component is added as part of ; a blend premix, the latter being passed through an ex truder with extrusion temperature being maintained between about 450 and 640F. depending on the composition.
The s-trands emerging from the extruder may be cooled, chppped into pellets, molded to a desired shape.
The concentration of the flame retardant additi~e (b) can vary, but is dependent to a large extent on the concentration of the styrene resin and the particular styrene resin used. Lower concentrations of styrene resin or less flammable styrene resins require a lower c ncen~ration of flame retardant. Moreover, ~D~O~ ~r ~ ~
30 ~ cyclic ~ 7*~e~-wh~eh higher contents o~ phosphorous can be used in ]ower amounts. In general, however, amounts of from about l to about 10 parts by weight of component ~ S 8CH 2513 (b) can be used. However, to secure the major ad~antayes, only from about 2 to about 10 parts per 100 parts by weight of (a) and (b) combined will be used.
Conventional additives, e.g., reinforcements, pigments~ stabilizers, lubricants, and the like can also be included in conventional amounts.
The following examples illustrate the present invention. In each report~ flame retardant properties are determined following procedures established by the Underwriters' Laboratory Bulletin, No. 9~. To meet a V-l rating, bars measuring 2 1/2" x 1/2" x 1/8"
thick are twice ignited for 10 seconds each time.
The compositions shall:
A. Not have any specimens which burn with flaming combustion for more than 30 seconds after each application of the tes-t flame~
B. Not have a total flaming combustion time exceeding 250 seconds for the 10 flame applications for each set of 5 specimens.
C. Not have any specimens which burn with flaming or glowing combustion up to the holding clamp.
D. Not have any specimens which drip flaming particles that ignite the dry absorbent surgical cotton located 12 inches (305 mm) below the test specimen.
E. Not have any specimens with glowing combustion which persists beyond 60 seconds after the second removal of the test f]ame.
E ~MPI.ES 1 - 3 Cornpositions comprising polyphenylene ether resin, polystyrene resin and a cyclic phosphonate of the formula o / 0 ~ CH2 \ CH - 0 0 R ~ P C P ~ R
O--CH2/ \CH2--O /
are preblended, extruded at 530F and chopped into molding granules. The granules are injection molded at 500F ~cylinder) and 180F (mold) in a 3 oz. Newbury injection molding machine. Physical properties and burn ~est results for these and for ~omparison examples are set forth in the Table:
"c"
3~S
Table. - Compositions Comprising Polyphenylene Ether, _ Styrene Resin And Cyclic Phosphonate.
Example 1 2 3 3A* 3B*
Compositions (p-ts. per hundred wt.) Poly(2,6-dimethyl~1,4-phenylene)ethera 35 35 35 35 35 Polystyrene resinb 65 65 65 65 65 Cyclic phosphonate R = CH3 2.5 -- -- __ __ R = ClO~I21 6 5 4.1 Triphenyl phosphate -- -- -- 7.0 Properties -Heat Distortion temp.
at 266 psi, F 240 232 238 201 228 Izod impact, ft.-lbs./
in. notch 4.1 -- 4.3 4.6 3.6 Gardner impact, in.-lbs. -- 90 170 170 110 20 Melt viscosity at 1,500 sec. 1630 1400 -- -- 1550 UL 94 Rating V-l V-l V-l V-l Burns * Control a PPO , General Electric CoO
b FG 834 M rubber modi~ied polystyrene, Foster Grant Co.
c Sample from ~eston Chemical CorpO
d See U.S. 3,141,032 e See procedure herein f Conventional plasticizing Elame retardant agen-t.
~', ,', ~3g~ 8CH-2513 Phenyl phosphonic dichloride, 116.95 g is added to a suspension of 407 85 g of pentaerythritol in 400 ml of acetone/triethylamine, cooled to 0-5C. The addition is fast enough to maintain the reaction temperature below 10C. The thick mass was stirred and allowed to warm to 25C during 15~20 minutes, then refluxed for 13 hours, cooled, filtered and the cake was sucked dry. Then a product is obtained in 69.3% yield, m.p., after recrystallization of 268-270C. The produce has an analysis corresponding to the formula:
O O--CH2 CH2-- 0\
C H5 - P \ f - C6H5 corresponding materials can be prepared by following the procedures of U.S. 3,141,032.
Many varia~ions will suggest themselves to those skilled in this art in the light of the above-detailed description. All such obvious variations are within the full intended scope of the invention as defined by the appended claims.
_ 8
Table. - Compositions Comprising Polyphenylene Ether, _ Styrene Resin And Cyclic Phosphonate.
Example 1 2 3 3A* 3B*
Compositions (p-ts. per hundred wt.) Poly(2,6-dimethyl~1,4-phenylene)ethera 35 35 35 35 35 Polystyrene resinb 65 65 65 65 65 Cyclic phosphonate R = CH3 2.5 -- -- __ __ R = ClO~I21 6 5 4.1 Triphenyl phosphate -- -- -- 7.0 Properties -Heat Distortion temp.
at 266 psi, F 240 232 238 201 228 Izod impact, ft.-lbs./
in. notch 4.1 -- 4.3 4.6 3.6 Gardner impact, in.-lbs. -- 90 170 170 110 20 Melt viscosity at 1,500 sec. 1630 1400 -- -- 1550 UL 94 Rating V-l V-l V-l V-l Burns * Control a PPO , General Electric CoO
b FG 834 M rubber modi~ied polystyrene, Foster Grant Co.
c Sample from ~eston Chemical CorpO
d See U.S. 3,141,032 e See procedure herein f Conventional plasticizing Elame retardant agen-t.
~', ,', ~3g~ 8CH-2513 Phenyl phosphonic dichloride, 116.95 g is added to a suspension of 407 85 g of pentaerythritol in 400 ml of acetone/triethylamine, cooled to 0-5C. The addition is fast enough to maintain the reaction temperature below 10C. The thick mass was stirred and allowed to warm to 25C during 15~20 minutes, then refluxed for 13 hours, cooled, filtered and the cake was sucked dry. Then a product is obtained in 69.3% yield, m.p., after recrystallization of 268-270C. The produce has an analysis corresponding to the formula:
O O--CH2 CH2-- 0\
C H5 - P \ f - C6H5 corresponding materials can be prepared by following the procedures of U.S. 3,141,032.
Many varia~ions will suggest themselves to those skilled in this art in the light of the above-detailed description. All such obvious variations are within the full intended scope of the invention as defined by the appended claims.
_ 8
Claims (36)
1. A flame retardant composition comprising (a) a normally flammable composition comprising a polyphenylene ether resin and a styrene resin, and (b) an effective, flame-retardant amount of up to 9.9 parts by weight per 100 parts by weight of (a) and (b) combined, of a compound of the formula wherein R is alkyl of from 1 to 18 carbon atoms, aryl or alkaryl.
2. A composition as defined in claim 1 wherein said polyphenylene ether resin is of the formula wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer equal to at least 50; and R1, independently, is a mono-valent substituent selected from hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus and being free of a tertiary alpha carbon atom, hydrocarbonoxy radicals being free of a tertiary alpha carbon atom, or halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus and being free of a tertiary alpha carbon atoms.
3. A composition as defined in Claim 2 wherein each R1 is alkyl of from 1 to 6 carbon atoms.
4. A composition as defined in Claim 3 wherein each R1 is methyl.
5. A composition as defined in Claim 1 wherein the styrene resin comprises from 20 to 80 parts by weight per 100 parts by weight of component (a).
6. A composition as defined in Claim 1 wherein said styrene resin has at least 25 percent by weight units derived from a compound of the formula:
wherein R2 is hydrogen, alkyl of from 1 to 6 carbon atoms or halogen; Z is vinyl, halogen, or lower alkyl, and p is 0 or a whole number equal to the number of replaceable hydrogen atoms in the benzene nucleus.
wherein R2 is hydrogen, alkyl of from 1 to 6 carbon atoms or halogen; Z is vinyl, halogen, or lower alkyl, and p is 0 or a whole number equal to the number of replaceable hydrogen atoms in the benzene nucleus.
7. A composition as defined in Claim 6 wherein p is 0 and R2 is hydrogen.
8. A composition as defined in Claim 1 wherein, in component (b), R is methyl.
9. A composition as defined in Claim 1 wherein in component (b), R is decyl.
10. A composition as defined in claim 1 wherein the amount of component (b) is from 2 to 9.9 parts by weight per 100 parts by weight of (a) and (b) combined.
11. A composition as defined in claim 1 wherein, in component (b), R is phenyl.
12. A flame retardant composition comprising:
(a) a normally flammable composition comprising a polyphenylene ether resin and a styrene resin, said styrene resin being in an amount of from 20 to 80 parts by weight per 100 parts of component (a); and (b) a flame retardant compound of the formua wherein R is alkyl of from 1 to 18 carbon atoms, aryl or alkaryl, said flame retardant compound comprising from 2 to 9.9 parts by weight per 100 parts by weight of components (a) and (b) combined.
(a) a normally flammable composition comprising a polyphenylene ether resin and a styrene resin, said styrene resin being in an amount of from 20 to 80 parts by weight per 100 parts of component (a); and (b) a flame retardant compound of the formua wherein R is alkyl of from 1 to 18 carbon atoms, aryl or alkaryl, said flame retardant compound comprising from 2 to 9.9 parts by weight per 100 parts by weight of components (a) and (b) combined.
13. A composition as defined in claim 12 wherein, in component (b), R is methyl.
14. A composition as defined in claim 12 wherein, in component (b), R is decyl.
15. A composition as defined in claim 12 wherein, in component (b), R is phenyl.
16. A fire retardant composition comprising (a) a blend of (1) a polyphenylene ether resin and (2) a styrene resin, and (b) an effective fire retardant amount of a pentaerythrityl phosphonate, represented by wherein R is selected from alkyl of 1 to 18 carbon atoms, aryl and aralkyl.
17. A composition of claim 16 wherein R is selected from methyl, phenyl and benzyl.
18. A composition of claim 16 wherein the styrene resin is a rubber-modified high impact polystyrene thermo-plastic resin.
19. A composition of claim 16 wherein the phosphonate is present in 5 to 9.9% by weight of the composition.
20. A flame retardant composition comprising (a) a normally flammable composition comprising a polyphenylene ether resin and a styrene resin, and (b) an effective, flame-retardant amount of a compound of the formula wherein R is alkyl of from 1 to 18 carbon atoms, aryl or alkaryl.
21. A composition as defined in claim 20 wherein said polyphenylene ether resin is of the formula wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer equal to to at least 50; and R1 independently, is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus and being free of a tertiary alpha carbon atom, hydrocarbonoxy radicals being free of a tertiary alpha carbon atom, or halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus and being free of a tertiary alpha carbon atom.
22. A composition as defined in claim 21 wherein each R1 is alkyl of from 1 to 6 carbon atoms.
23. A composition as defined in claim 22 wherein each R1 is methyl.
24. A composition as defined in claim 20 wherein the styrene resin comprises from 20 to 80 parts by weight per 100 parts by weight of component (a).
25. A composition as defined in claim 20 wherein said styrene resin has at least 25 percent by weight units derived from a compound of the formula:
wherein R2 is hydrogen, alkyl of from 1 to 6 carbon atoms or halogen; Z is vinyl, halogen, or lower alkyl, and p is 0 or a whole number equal to the number of replaceable hydrogen atoms in the benzene nucleus.
wherein R2 is hydrogen, alkyl of from 1 to 6 carbon atoms or halogen; Z is vinyl, halogen, or lower alkyl, and p is 0 or a whole number equal to the number of replaceable hydrogen atoms in the benzene nucleus.
26 A composition as defined in claim 25 wherein p is 0 and R2 is hydrogen.
27. A composition as defined in claim 20 wherein, in component (b), R is methyl.
28. A composition as defined in claim 20 wherein, in component (b), R is decyl.
29. A composition as defined in claim 20 wherein the amount of component (b) is from 2 to 10 parts by weight per 100 parts by weight of (a) and (b) combined.
30. A composition as defined in claim 20 wherein, in component (b), R is phenyl.
31. A flame retardant polyphenylene ether resin/rubber modified, high-impact polystyrene thermoplastic composition comprising an effective flame retarding amount of a pentaerythirtyl phosphonate compound represented by the formula wherein R is methyl, phenyl, or benzyl.
32. The composition of claim 31 wherein said molding composition comprises a homogeneous blend of 20 to 80 percent polyphenylene ether resin and 20 to 80 percent of rubber-modified, high-impact po]ystyrene resin.
33. The composition of claim 31 wherein each R is methyl.
34. The composition of claim 31 wherein each R
is phenyl.
is phenyl.
35. The composition of claim 31 wherein each R
is benzyl.
is benzyl.
36. The composition of claim 31 wherein the phosphonate is present in at least about 5% by weight of the composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83105677A | 1977-09-06 | 1977-09-06 | |
| US831,056 | 1977-09-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1199745A true CA1199745A (en) | 1986-01-21 |
Family
ID=25258195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000309985A Expired CA1199745A (en) | 1977-09-06 | 1978-08-24 | Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonate |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5460354A (en) |
| AU (1) | AU3955078A (en) |
| CA (1) | CA1199745A (en) |
| DE (1) | DE2836771A1 (en) |
| FR (1) | FR2401956A1 (en) |
| GB (1) | GB2003888B (en) |
| NL (1) | NL7809098A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4402882A (en) * | 1980-09-02 | 1983-09-06 | Ciba-Geigy Corporation | Process for the production of diphosphaspiro compounds |
| DE3105946A1 (en) | 1981-02-18 | 1982-08-19 | Basf Ag, 6700 Ludwigshafen | SELF-EXTINGUISHING THERMOPLASTIC MOLDS |
| EP0075863A1 (en) * | 1981-09-25 | 1983-04-06 | General Electric Company | Improved polyphenylene ether and polyalkenyl aromatic resin compositions |
| US6797754B2 (en) | 2002-05-06 | 2004-09-28 | Cheil Industries Inc. | Flame retardant styrenic compositions containing oxaphospholane compound as flame retardant |
| CN1267500C (en) | 2001-05-15 | 2006-08-02 | 帝人化成株式会社 | Flame-retardant resin composition and molded article therefrom |
| US7365114B2 (en) * | 2002-09-25 | 2008-04-29 | Cheil Industries Inc. | Flameproof styrenic resin composition |
| KR100505317B1 (en) * | 2003-08-04 | 2005-08-02 | 제일모직주식회사 | Flameproof Thermoplastic Resin Composition |
| AU2003304381A1 (en) | 2003-08-04 | 2005-02-15 | Cheil Industries Inc. | Flameproof thermoplastic resin composition |
| JP2007520572A (en) | 2003-08-14 | 2007-07-26 | チェイル インダストリーズ インコーポレイテッド | Flame retardant rubber reinforced polystyrene resin composition |
| KR100506067B1 (en) | 2003-08-14 | 2005-08-03 | 제일모직주식회사 | Flameproof Thermoplastic Resin Composition |
| JP4790804B2 (en) | 2005-08-08 | 2011-10-12 | チェイル インダストリーズ インコーポレイテッド | Flame retardant molding composition |
| KR100817399B1 (en) | 2005-12-29 | 2008-03-27 | 제일모직주식회사 | Flameproof thermoplastic Resin Composition |
| US20090163627A1 (en) * | 2007-12-20 | 2009-06-25 | Cheil Industries Inc. | Symmetric Cyclic Phosphonate Compound, Method of Preparing the Same and Flame Retardant Styrenic Resin Composition Including the Same |
| JP5502819B2 (en) * | 2011-08-24 | 2014-05-28 | 帝人株式会社 | Flame retardant resin composition and molded product therefrom |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3141031A (en) * | 1960-08-23 | 1964-07-14 | Ethyl Corp | Olefin cobalt carbonyl compounds |
| US3997505A (en) * | 1974-01-02 | 1976-12-14 | Michigan Chemical Corporation | Flame retardant polymeric compositions containing pentaerythritol cyclic diphosphates or diphosphoramidates |
| CH596332A5 (en) * | 1975-07-15 | 1978-03-15 | Ciba Geigy Ag |
-
1978
- 1978-08-21 GB GB7833991A patent/GB2003888B/en not_active Expired
- 1978-08-23 DE DE19782836771 patent/DE2836771A1/en not_active Withdrawn
- 1978-08-24 CA CA000309985A patent/CA1199745A/en not_active Expired
- 1978-09-05 FR FR7825476A patent/FR2401956A1/en not_active Withdrawn
- 1978-09-05 AU AU39550/78A patent/AU3955078A/en active Pending
- 1978-09-05 JP JP10818578A patent/JPS5460354A/en active Pending
- 1978-09-06 NL NL7809098A patent/NL7809098A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2836771A1 (en) | 1979-03-15 |
| AU3955078A (en) | 1980-03-13 |
| GB2003888B (en) | 1982-02-03 |
| GB2003888A (en) | 1979-03-21 |
| FR2401956A1 (en) | 1979-03-30 |
| JPS5460354A (en) | 1979-05-15 |
| NL7809098A (en) | 1979-03-08 |
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