GB2085898A - Self-extinguishing polyolefinic compositions - Google Patents
Self-extinguishing polyolefinic compositions Download PDFInfo
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- GB2085898A GB2085898A GB8119166A GB8119166A GB2085898A GB 2085898 A GB2085898 A GB 2085898A GB 8119166 A GB8119166 A GB 8119166A GB 8119166 A GB8119166 A GB 8119166A GB 2085898 A GB2085898 A GB 2085898A
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- Prior art keywords
- parts
- bromo
- aromatic
- compound
- hydrocarbon
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000098 polyolefin Polymers 0.000 claims abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- BLAJPPMSXMTCLR-UHFFFAOYSA-N but-1-ene styrene Chemical compound CCC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 BLAJPPMSXMTCLR-UHFFFAOYSA-N 0.000 claims description 2
- XRERONKQLIQWGW-UHFFFAOYSA-N but-1-ene;styrene Chemical compound CCC=C.C=CC1=CC=CC=C1 XRERONKQLIQWGW-UHFFFAOYSA-N 0.000 claims description 2
- CYRHBNRLQMLULE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2Br)Br)=C1Br CYRHBNRLQMLULE-UHFFFAOYSA-N 0.000 claims 1
- WVJRAJZMOVQFEC-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5,6-dimethylbenzene Chemical group CC1=C(C)C(Br)=C(Br)C(Br)=C1Br WVJRAJZMOVQFEC-UHFFFAOYSA-N 0.000 claims 1
- WFPDYYHUULCORF-UHFFFAOYSA-N 1-bromoethoxybenzene Chemical compound CC(Br)OC1=CC=CC=C1 WFPDYYHUULCORF-UHFFFAOYSA-N 0.000 claims 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 239000013536 elastomeric material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- -1 aromatic bromine compound Chemical class 0.000 abstract description 17
- 239000000654 additive Substances 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000979 retarding effect Effects 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 17
- 229920001155 polypropylene Polymers 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical compound C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- 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 class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920001198 elastomeric copolymer Polymers 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- AQHVVFDSURVEDC-UHFFFAOYSA-N (2,3-dimethyl-2-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(CCC)C1=CC=CC=C1 AQHVVFDSURVEDC-UHFFFAOYSA-N 0.000 description 1
- NVRASYUHTRQZKB-UHFFFAOYSA-N 1,1,2,2,2-pentabromoethoxybenzene Chemical compound BrC(Br)(Br)C(Br)(Br)OC1=CC=CC=C1 NVRASYUHTRQZKB-UHFFFAOYSA-N 0.000 description 1
- QXWYPAKUEHGJSG-UHFFFAOYSA-N 1,3,5-tribromo-2-(2,3-dibromopropoxy)benzene Chemical compound BrCC(Br)COC1=C(Br)C=C(Br)C=C1Br QXWYPAKUEHGJSG-UHFFFAOYSA-N 0.000 description 1
- JRLUZLDQSVOQKP-UHFFFAOYSA-N C1(=CC=CC=C1)OC1=CC=CC=C1.[Br].[Br].[Br].[Br].[Br].[Br].[Br].[Br].[Br].[Br] Chemical compound C1(=CC=CC=C1)OC1=CC=CC=C1.[Br].[Br].[Br].[Br].[Br].[Br].[Br].[Br].[Br].[Br] JRLUZLDQSVOQKP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 239000008096 xylene 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K5/01—Hydrocarbons
-
- 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
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Self-extinguishing compositions substantially based on polyolefins, or on their polyblends with elastomers of the type EP, EPDM, SB, SBS, EVA comprise, as flame retarding additives, a combination of -from 1 to 5 parts of an aromatic bromine compound either alone or in admixture with an aliphatic-aromatic bromine compound; -from 0.5 to 5 parts of a compound of antimony or bismuth; -from 0.1 to 2 parts of an organic compound of the formula <IMAGE> where R = CH3 or C2H5; R' = CH3 and R'' = C6H5; and -from 0.1 to 3 parts of a melamine compound, all parts by wt. per 100 parts by wt. of polymer.
Description
SPECIFICATION
Self-extinguishing polyolefinic compositions
The present invention concerns self-extinguishing compositions substantially based on polymers or copolymers of ethylene and alpha-olefins, possibly in admixture with elastomers of EP (ethylene-propylene) EPDM (ethylene-propylene diene monomer), EVA (ethylene-vinyl acetate)
SB (styrene-butene), SBS (styrene-butene-styrene) type, and comprising:
A) a bromo hydrocarbon either alone or in admixture with other halogenated hydrocarbons;
B) a compound of antimonium, or bismuth and
C) an organic compound having the formula
where R = CH3 or C2H5;
R' = CH3 and R" = C6H5.
It is known that plastic resins tend to expand into all the application fields and that this expansion finds an obstacle where difficulty burning materials are requested. To avoid this drawback, hundreds of solutions in a patent crowded field) have been suggested which foresee the addition, to the basic polymers, of flame retardant compounds and compositions comprising generally antimony trioxide and halogenated hydrocarbons.
According to US Patent n" 3.419.518 (BASF) molding material based on propylene polymers and antimony trioxide, which contains chlorinated paraffins or aromatic bromo-hydrocarbons is rendered self-extinguishing with large amounts (above 15%) of said antimony and halogenated compounds whereby the mechanical and electrical properties of the basic polymer are deteriorated: moreover bromo substituted phenols are said to have an unpleasant odor whereby the patented compositions contain from 0.2 to 10% b.w. (on the polymer weight) of antimony trioxide and from 1 to 13% of a brominated cycloalkane.
French patent publication 2.064.294 (Phillips Petroleum) describes flame-retardant compositions based on a polymer (f.i. polypropylene) and containing from 0.5 to 20% of a cycloaliphatic bromo-hydrocarbon, from 0.1 to 20% of a polymeric hydrocarbon (which can take the above formula 1, in a simplified case), and from 0.1 to 20% of antimony trioxide.
British Patent no 1.270.318 (BASF) describes flame-resistant molding compositions based on propylene polymers and comprising:
A) from 0.5 to 9% of an aliphatic bromo-hydrocarbon; B) from 0.2 to 7 of antimony trioxide; C) from 0.05 to 3% of an organic phosphite and D) from 0.2 to 6% of a mixture of an alkane polyol with an organic compound which in a simplified case can take the above formula 1).
British Patent 1.439.948 (BASF) describes compositions which further contain from 0.1 to 3% of a barium or cadmium salt of an alkanoic or alkenoic acid in addition to the above compounds from A) to D) of the above British Patent 1.270.318.
British Patent 1.529.236 (BASF) describes nonflammable molded compositions based on propylene polymers and containing: A) from 37 to 47% of a Diels-Alder adduct; B) from 7 to 20% antimony trioxide, and from 10 to 20% melamine.
The above and many others prior Patents suggest thus the use of aliphatic or cyclo-aliphatic bromo-hydrocarbons which are thermally unstable and on heating decompose with the formation of the corresponding hydrogen halides. This unstability is considered advantageous in the burning phase but is inconvenient during the preparation and working of the polymer compositions (mixing, granulation and moulding): indeed the weak stability of said non-aromatic bromo-hydrocarbons may cause their thermal decomposition during working the olefin polymers whereby the compositions based on said polymers, particularly on their polyblends with elastomers and containing non-aromatic bromo-hydrocarbons may show the drawbacks deriving from the toxicity of the thermal decomposition products freed by said non-aromatic compounds, and from the measures to adopt in the composition preparation and working also because of the appearance of the corrosion phenomena in the machinery utilized for such working.
Object of the present invention is now a very specific self-extinguishing polyolefin composition containing additives which, though singularly per sè known, are happely coordinated in order to surprisingly allow the advantageous use of thermically stable aromatic bromo-hydrocarbons in such a low concentration that the physical and chemical properties of the basic polymers are not at all deteriorated.
The compositions according to the invention comprise now:
I) a polymer or copolymer of ethylene or alpha-olefins, or their polyblends with elastomeric copolymers of the type EP, EPDM, SB, SBS, EVA and the like, and per 100 parts by weight of said polymers,
II) from 1 to 5% of aromatic bromo hydrocarbon, optionally in admixture with an aliphaticaromatic bromo hydrocarbon; III) Yrnm 0.5 to 5% of an antimonium or bismuth compound;
IV) from 0.01 to 2 parts of an organic compound having the formula
where R is CH3 or C2H5; R' is CH3 and
R" is C6H5; and
V) from 0.1 to 3 parts of a triazinic compound, particularly of melamine.
The polymer under I) is preferably selected from of polyethylenes (having low, medium or high density), polypropylenes consisting essentially of isotactic molecules, plastic ethylenepropylene copolymers; the above polymer can be blended with 2-20% of elastomeric copolymers of the type EP, EPDM, SB, SBS, EVA and the like.
According to an advantageous feature of the invention the bromine aromatic compoud 11) is selected from the group octa-, nona-, or deca- bromine diphenyl; octanona-, or deca-bromine diphenyl oxide; bis-, tris-, or penta-bromo phenoxyethane; tetrabromine xylene, tetrabromine bisphenol A and nitrogen containing aromatic bromine compounds particularly bis (tetrabromine phtalimmide) ethane (BTFE). The additional aromatic-aliphatic bromo-hydrocarbon contains bromine both in the aliphatic and aromatic group and is preferably a derivative of propylic ether of phenol or bis-phenol A. The Compound Ill is preferably selected from of antimonium trioxide (Sb203), and of oxides, sulphurs, halides and organic salts of bismuth particularly BiOCI. Bi(NO3)3.5H2O, Bi(SO4)3, (BiO)2.SO4, BiPO4, (BiO)2.CO3.
The organic (synergic) compound of formula (1) is preferably (2,3-dimethyl- 2,3 diphenil)hexane or butane.
The different features and advantages of the invention will better appear from the following non-limitative examples, the powdery components of which were mixed in a 1 liter rotating glass flask in a nitrogen atmosphere at room temperature.
The homogeneous mix so obtained was then extruded in a small extruder at about 190"C; 200 g of the so granulated extruded product were moulded in a small press at about 180"C under a pressure of 2.5 Kg/cm2 during 6 minutes obtaining 3 mm thick laminae. The selfextinguishing capacity of these laminae was determined by measuring the oxygen index according to ASTM D-2863 which expresses the minimum percentage of oxygen in an oxygennitrogen mixture, necessary for the test sample to burn in a continuous manner.
On groups of 5 test samples having thickness of 1 /4, 1/8 or 1/16 inch the tests according to rules of the UL-94 "Vertical Burning Test" were carried out which allow for a given period to classify the material at the levels 94-V-0, 94-V-1 and 94-V-2.
Example 1 (comparison)
100 parts of polypropylene (P.P.) having a melt-index (M.I.) of 5 were mixed in the dry state in a 1 liter rotating flask in a nitrogen atmosphere, at room temperature with: -7.5 parts of decabromodiphenyl oxide; -2.5 parts antimony trioxide
The thus obtained mix was then granulated in an extruder which had a screw with a diameter of 45 mm and a length/diameter ratio of 25, was heated at 190"C and was rotated at 30 rev./min 500 g of said granulated mix so obtained were compression moulded at 180"C in form of a 3 mm thick lamina from which the test samples according to rule UL-94 are obtained.
The test results of this and of the other examples are recorded in Table I.
Example 2
By proceeding as in example 1 test samples were prepared from: 100 parts of a propylene homopolymer of M.l. = 5: -4.5 parts of decabromo-diphenyloxide ("BROMKAL" 81 by Kalk A.G.) -2.5 parts Sb203 --0.4 parts of 2.3 dimethyl 2.3 diphenylbutane -1 part melamine.
Example 3
By proceeding as in example 1 test laminae were prepared from a mix of: -100 parts of a mix consisting of 90 parts of polypropylene (M.l. = 5) and of 10 parts of an
EVA coplymer containing 45% vinylacetate; -1.9 parts of bis(4(2,3 dibromopropyl)- 3,5 dibrnmophenyl) propane ("BROMKAL" 66-8); -1.9 parts decabromodiphenyl; -1.9 parts Sb2O3, --0.3 parts (2,3 dimethyl 2,3 diphenyl)butane; and -0.9 part melamine.
Example 4.
By proceeding as in example 1 with a mix of: -100 parts polypropylene (M.l. = 3); -5 parts of a mixture consisting of 3 parts of decabromodiphenyloxide and of 1.5 p. of 2,4,6 tribromophenoxy-2,3 dibromopropane -2.5 parts Sb2O3; --0,5 parts (2,3 diphenyl 2, 3 dimethyl) hexane; , melamine cyanurate -1.5 parts
Example 5
By proceeding as in example 1, laminae were prepared from a mix of: 100 parts of a polyblend consisting of 91 parts of polypropylene and 9 parts of EP copolymer and having a
Melt Index = 10; 3 p. of nonabromodiphenil (BROMKAL-80); 1 p. of BROMKAL 66-8 1 part of bismuth basic carbonate (BiO2)CO3; and 0.9 part melamine.
Table I
Results of the self-extinguishing tests
Example 1 2 3 4 5
Oxygen index 23 26.5 27 27.5 27.5
UL 94 test sample 1/8" burning 94-V2 94-V-2 94-V-2 94-V-2
With the compositions of examples 2-5 according to the invention (low content of aromatic bromo hydrocarbons thanks to the happy combination of critically selected additives) no decomposition products and corrosion phenomena were observed during the preparation and the moulding of the mixes because of the thermal stability of said aromatic bromo hydrocarbons: on the contrary same decomposition products and corrosion phenomena are not seldom with the aliphatic or cyclo-aliphatic bromo hydrocarbons recommended in the Prior Art.
Claims (6)
1. Polyolefinic compositions for the manufacture of self-extinguishing articles, comprising a polymer or copolymer of ethylene and/or alphaolefin; a bromo-hydrocarbon, a compound of antimonium; an organic compound of the type:
where R = CH3 or C2Hs, R' = CH3, R" = C6H5 wherein the composition contains 100 parts of said olefin polymer or copolymer:
from 1 to 5 parts of a thermally stable aromatic bromo-hydrocarbon;
from 0.5 to 5 parts of antimonium trioxide or a compound of bismuth;
from 0.1 to 2 parts of the above organic compound (1) and
from 0.1 to 3 parts of a triazinic derivative.
2. A composition as claimed in claim 1, wherein the polymer or copolymer includes from 2 to 20% of an elastomeric material selected from ethylene propylene copolymers, ethylene propylene diene monomer, ethylene-vinyl acetate, styrene butene and styrene-butene-styrene.
3. A composition as claimed in claim 1, wherein the triazinic derivative is melamine.
4. A composition according to any one of claims 1 to 3, wherein the aromatic bromohydrocarbon is selected from octanona-, or deca-bromodiphenyl; octa-, nona-, or deca-bromodiphenyl oxide, bis, tris or penta, bromo-phenoxy-ethane, tetrabromoxylene, tetrabromobisphenol
A.
5. A composition according to claim 4, in which from 0.1 to 2 parts of the aromatic-bromo hydrocarbon are substituted with an aliphatic-aromatic bromo-hydrocarbon in which bromine is present both in the aliphatic and aromatic groups.
6. A composition as claimed in claim 1, substantially as hereinbefore described in any one of Examples 2 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT25311/80A IT1133878B (en) | 1980-10-14 | 1980-10-14 | SELF-EXTINGUISHING POLYOLEFINIC COMPOSITIONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2085898A true GB2085898A (en) | 1982-05-06 |
| GB2085898B GB2085898B (en) | 1984-08-22 |
Family
ID=11216301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8119166A Expired GB2085898B (en) | 1980-10-14 | 1981-06-22 | Self-extinguishing polyolefinic compositions |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3124644A1 (en) |
| FR (1) | FR2491937A1 (en) |
| GB (1) | GB2085898B (en) |
| IT (1) | IT1133878B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0065160A2 (en) * | 1981-04-30 | 1982-11-24 | Montedison S.p.A. | Self extinguishing polyolefinic compositions |
| EP0144015A1 (en) * | 1983-11-14 | 1985-06-12 | MONTEDIPE S.p.A. | Self-extinguishing compositions based on ethylene vinylacetate copolymers suitable for the preparation of foamed materials |
| US4607077A (en) * | 1985-05-07 | 1986-08-19 | Hercules Incorporated | Phosphazene flame retardants for reaction injection molded poly(dicyclopentadiene) |
| EP1239005A1 (en) * | 2001-02-27 | 2002-09-11 | Bromine Compounds Ltd. | Fire-retardant polyolefin compositions |
| US6737456B2 (en) | 2001-02-27 | 2004-05-18 | Bromine Compounds Ltd. | Fire-retardant polyolefin compositions |
| WO2004041919A2 (en) * | 2002-11-04 | 2004-05-21 | Ciba Specialty Chemicals Holding Inc. | Flame retardant compositions |
| EP1449880A1 (en) * | 2001-10-24 | 2004-08-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | FLAME−RETARDANT STYRENE RESIN COMPOSITION |
| EP1449879A1 (en) * | 2001-10-24 | 2004-08-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | FLAME−RETARDANT STYRENE RESIN COMPOSITION |
| WO2012096962A1 (en) * | 2011-01-11 | 2012-07-19 | Dow Global Technologies Llc | Antioxidant compounds for polyolefin resins |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1221822A (en) * | 1967-10-10 | 1971-02-10 | Bakelite Xylonite Ltd | Improvements in and relating to polymer compositions |
| FR2109757A5 (en) * | 1970-10-01 | 1972-05-26 | Basf Ag | |
| DE2506831A1 (en) * | 1975-02-18 | 1976-08-26 | Basf Ag | FIRE-COMBUSTIBLE MOLDING COMPOUNDS BASED ON POLYMERIZED PROPYLENE |
-
1980
- 1980-10-14 IT IT25311/80A patent/IT1133878B/en active
-
1981
- 1981-06-19 FR FR8112109A patent/FR2491937A1/en not_active Withdrawn
- 1981-06-22 GB GB8119166A patent/GB2085898B/en not_active Expired
- 1981-06-23 DE DE19813124644 patent/DE3124644A1/en not_active Withdrawn
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0065160A2 (en) * | 1981-04-30 | 1982-11-24 | Montedison S.p.A. | Self extinguishing polyolefinic compositions |
| EP0065160A3 (en) * | 1981-04-30 | 1983-06-08 | Montedison S.P.A. | Self extinguishing polyolefinic compositions |
| EP0144015A1 (en) * | 1983-11-14 | 1985-06-12 | MONTEDIPE S.p.A. | Self-extinguishing compositions based on ethylene vinylacetate copolymers suitable for the preparation of foamed materials |
| US4607077A (en) * | 1985-05-07 | 1986-08-19 | Hercules Incorporated | Phosphazene flame retardants for reaction injection molded poly(dicyclopentadiene) |
| EP1239005A1 (en) * | 2001-02-27 | 2002-09-11 | Bromine Compounds Ltd. | Fire-retardant polyolefin compositions |
| US6737456B2 (en) | 2001-02-27 | 2004-05-18 | Bromine Compounds Ltd. | Fire-retardant polyolefin compositions |
| EP1449879A1 (en) * | 2001-10-24 | 2004-08-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | FLAME−RETARDANT STYRENE RESIN COMPOSITION |
| EP1449880A1 (en) * | 2001-10-24 | 2004-08-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | FLAME−RETARDANT STYRENE RESIN COMPOSITION |
| EP1449879A4 (en) * | 2001-10-24 | 2005-01-05 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame-retardant styrene resin composition |
| EP1449880A4 (en) * | 2001-10-24 | 2005-01-05 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame-retardant styrene resin composition |
| WO2004041919A2 (en) * | 2002-11-04 | 2004-05-21 | Ciba Specialty Chemicals Holding Inc. | Flame retardant compositions |
| WO2004041919A3 (en) * | 2002-11-04 | 2004-10-14 | Ciba Sc Holding Ag | Flame retardant compositions |
| US7138448B2 (en) | 2002-11-04 | 2006-11-21 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
| CN100387645C (en) * | 2002-11-04 | 2008-05-14 | 西巴特殊化学品控股有限公司 | Flame retardant compositions |
| AU2003283310B2 (en) * | 2002-11-04 | 2009-11-12 | Basf Se | Flame retardant compositions |
| WO2012096962A1 (en) * | 2011-01-11 | 2012-07-19 | Dow Global Technologies Llc | Antioxidant compounds for polyolefin resins |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2491937A1 (en) | 1982-04-16 |
| GB2085898B (en) | 1984-08-22 |
| IT1133878B (en) | 1986-07-24 |
| IT8025311A0 (en) | 1980-10-14 |
| DE3124644A1 (en) | 1982-06-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |