GB2078226A - Flame retardant mixture and resinous compositions including the mixture - Google Patents
Flame retardant mixture and resinous compositions including the mixture Download PDFInfo
- Publication number
- GB2078226A GB2078226A GB8105509A GB8105509A GB2078226A GB 2078226 A GB2078226 A GB 2078226A GB 8105509 A GB8105509 A GB 8105509A GB 8105509 A GB8105509 A GB 8105509A GB 2078226 A GB2078226 A GB 2078226A
- Authority
- GB
- United Kingdom
- Prior art keywords
- mixture
- phosphate
- flame retardant
- composition
- resinous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 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 20
- 239000003063 flame retardant Substances 0.000 title claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 mesityl groups Chemical group 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- 235000021317 phosphate Nutrition 0.000 claims abstract description 18
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 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 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 13
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012260 resinous material Substances 0.000 claims description 8
- 229920005669 high impact polystyrene Polymers 0.000 claims description 7
- 239000004797 high-impact polystyrene Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 150000001555 benzenes Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- SZQAOGPCUGHBPG-UHFFFAOYSA-N (2,4,6-trimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC(C)=C(OP(O)(O)=O)C(C)=C1 SZQAOGPCUGHBPG-UHFFFAOYSA-N 0.000 claims description 3
- TZNDMQPVWYWNFW-UHFFFAOYSA-N diphenyl (2,4,6-trimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC(C)=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 TZNDMQPVWYWNFW-UHFFFAOYSA-N 0.000 claims description 3
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 125000005023 xylyl group Chemical group 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 3
- 238000007706 flame test Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WRXFONORSZHETC-UHFFFAOYSA-N phenyl propan-2-yl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC1=CC=CC=C1 WRXFONORSZHETC-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- UETPRJJVZPVPQI-UHFFFAOYSA-N (2-propan-2-ylphenyl) dihydrogen phosphate Chemical class CC(C)C1=CC=CC=C1OP(O)(O)=O UETPRJJVZPVPQI-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- 150000000345 2,6-xylenols Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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
A flame retardant composition for resinous compositions, especially for mixtures of polyphenylene ethers and styrene resins, comprises a mixture of triaryl phosphates including at least one such phosphate wherein 1 or 2 of its 3 aryl groups are mesityl groups and its remaining group or groups are independently selected from phenyl and xylyl groups. In the resinous composition, the flame retardancy of the mixture per unit weight of phosphorus is greater than that of either triphenyl phosphate (TPP) or trimesityl phosphate (TMP) per se. <IMAGE>
Description
SPECIFICATION
Flame retardant mixture and resinous compositions including the mixture
This invention relates to a flame retardant mixture comprising a mixture of triaryl phosphates and to a resinous composition comprising a normally flammable resinous material and the flame retardant mixture.
Haaf, U. S. Patent 3,639,506, discloses a blend of polyphenylene ether and a styrene resin containing a flame retardant combination comprising an aromatic phosphate and an aromatic halogen compound. The Haaf patent discloses a wide variety of phosphates for use as the aromatic phosphate component of the blend, indicates a preference for triaryl phosphates, and states that the most preferred phosphate is triphenyl phosphate. Copper, U.S. Patent 3,883,613 discloses that trimesityl phosphate functions very effectively as a flame retardant per se in compositions of a polyphenylene ether and a styrene resin.
It has now been found that effective flame retardancy is provided by a new mixture of triaryl phosphates, which includes at least one such phosphate wherein 1 or 2 of its 3 aryl groups are mesityl groups and its remaining group or groups are independently selected from phenyl and xylyl groups. It has further been found that, in resinous compositions containing a normally flammable resin material and the mixture, the flame retardancy of the mixture, per unit weight of phosphorus, is greater than that of either triphenyl phosphate (TPP) or trimesityl phosphate (TMP) per se. Advantageously, this increased flame retardancy is obtained where the resin comprises a mixture of polyphenylene ethers and styrene resins, which are known in the art and are described in the above-referenced Haaf and Cooper patents and in Cizek, U.S. Patent 3,383,435.
Generally stated, the present invention provides in one aspect thereof a flame retardant mixture comprising 3 mixture of aromatic phosphates represented by the average formula:
where is a whole or fractional number from slightly more than 0 to slightly less than 3, andy is a whole or fractional number from 1 to2.
In another aspect, this invention provides a resinous composition comprising (A) a normally flammable resinous material and (B) a flame retardant amount of the flame retardant mixture set forth above.
Practice of this invention will be better understood by referring to the following detailed description.
Aromatic phosphates which may be included in the mixture of aromatic phosphates include, for example, triphenyl phosphate (TPP), diphenyl mesityl phosphate (DPMP), dimesityl phenyl phosphate (DMPP), trimesityl phosphate (TMP), trixylyl phosphate (TXP), dixylyl mesityl phosphate (DXMP), dimesityl xylyl phosphate (DMXP), and trimesityl phosphate.
In a preferred embodiment,57 is 2 and the flame retardant mixture comprises at least 2 compounds selected from the group consisting of (a) triphenyl phosphate (TPP), (b) diphenyl mesityl phosphate (DPMP), (c) dimesityl phenyl phosphate (DMPP) and (d) trimesityl phosphate (TMP) subject to the proviso that at least one of said two compounds is selected from the group consisting of DPMP and DMPP. Preferably the mixture comprises at least 3 of said compounds, and more preferably all 4 of said compounds.
In another preferred embodimentB is 1 and the flame retardant mixture comprises at least 2 compounds selected from the group consisting of (a) trixylyl phosphate (TXP), (b) dixylyl mesityl phosphate (DXMP), (c) dimesityl xylyl phosphate (DMXP) and (d) trimesityl phosphate (TMP) subject to the proviso that at least one of said 2 compounds is selected from the group consisting of DXMP and
DMXP. Preferably the mixture comprises at least 3 of said compounds, and more preferably 4 of said compounds.
The flame retardant mixture may further include, in addition to the mixture having the above average formula, (isopropyl phenyl) phosphates, e.g. tri(isopropyl phenyl) phosphate, such as commercially available Kronitex K-SO.
The resin normally flammable resinous material of the resinous composition includes one or more normally flammable resins which are capable of being improved with respect to flame retardancy by the addition thereto of substituted or unsubstituted triarylphosphates. It is well known in the art that such resins include for example, polyvinyl chlorides, polyphenylene ethers, cellulosic resins, and many polyesters.
In a preferred embodiment, the normally flammable resinous material comprises
(i) a polyphenylene ether of the formula
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; Q is a monovalent substituent selected from hydrogen, a hydrocarbon radical, a halohydrocarbon radical having at least two carbon atoms between the halogen atom and the phenol nucleus, a hydrocarbonoxy radical, and a halohydrocarbonoxy radical having at least two carbon atoms between the halogen atom and the phenol nucleus, Q' and 0" are the same as 0 and in addition, halogen, with the proviso that Q, 0' and 0" are all free of a tertiary alpha-carbon atom and n is a whole number of at least 50; and
(ii) a styrene resin.
Polyphenylene ethers represented by the formula of component (i) above and methods for their formulation may be found in U.S. Patent Nos. 3,306,874 and 3,306,875 of Allan S. Hay and U. S.
Patent Nos. 3,257,357 and 3,257,358 of Gelu Stamatoff.
The styrene resin (ii), as is described in the above noted Cizek patent, has at least 25 percent by weight polymer units derived from the compound having the formula:
where R1 is a hydrogen, (lower)alkyl or halogen; Z is a member selected from the class consisting of vinyl, halogen, and (lower)alkyl; and p is a whole number equal to O to the number of replaceable hydrogen atoms on the benzene nucleus.Typical styrene resins include, by way of example, homopolymers such as polystyrene and polychlorostyrene, the modified polystyrenes such as rubber modified polystyrenes (high impact styrenes), and the styrene containing copolymers such as the styrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers, styrene-acrylonitrile-alpha-alkyl styrene copolymers, styrene-acrylonitrile-butadiene copolymers (ABS), poly-alpha-methyl styrene, copolymers of ethylvinyl benzene and divinyl benzene, and the like. (Lower)alkyl groups contain up to 6 carbon atoms.
A preferred ratio of polyphenylene ether to styrene resin comprises 20 to 80% by weight of the latter. The polyphenylene ether is preferably poly(2,6-dimethyl-1 ,4-phenylene)ether. The styrene resin is preferably a rubber modified high impact polystyrene as is described in the Cizek patent.
The manner of adding the flame retardant mixture to the normally flammable resinous composition is not critical. Preferably, each component is added as a part of a premix, the latter being passed through an extruder with extrusion temperature being maintained between about 4500 and 6400 F., dependent upon the composition. The strands emerging from the extruder may be cooled, chopped into pellets, re-extruded, chopped into pellets and molded to a desired shape.
The concentration of the flame retardant mixture in the resinous composition is not critical and is dependent to a large extent upon the degree of flammability of the normally flammable resin composition. Where the last-mentioned composition comprises a polyphenylene ether and a styrene resin, the degree of flammability is dependent to a large extent upon the concentration of the styrene resin and the particular styrene resin used. Lower concentrations of styrene resin or less flammable styrene resins may include a lower concentration of the flame retardant. In general, a small concentration of the flame retardant is desirable, 0.5 to 1 5 parts per 100 parts of polymer (phr.) generaily being acceptable and between 1 and 10 phr being preferred where the styrene content permits.
This invention is further illustrated by the following non-limiting examples.
Preparation of a mixture of mesityl xylyl phosphates from a mixture of polymethylphenols for uses in the Exampies.
To a 250 ml flask equipped with a stirrer, reflux condenser, thermometer, and heater was added 396 gm of a mixture of polymethylphenols. The mixture consisted of 75% 2,4,6-trimethylphenol, 23% 2,4 and 2,6-dimethylphenols and 2,3,6-trirnethylphenol and anisoles. The phenolics were combined with 153 g of phosphorus oxychloride and 8 gm of magnesium chloride at 250C. This mixture was heated to 2500C for six hours and hydrogen chloride was continuously evolved. After purging the reaction mass with nitrogen, it was purified by vacuum distilling unreacted phenolics.
Gas chromatographic analysis indicated the still pot contained 95% of a mixture of triaryl phosphates after the phenolics were removed and the yield of mixed mesityl xylyl phosphates was 78%.
The product mixture is transparent and glassy and has a pour point near 800C. It is hereinafter designated the "mesityl xylyl phosphate mixture."
EXAMPLE 1 Poly(2,6-dimethyl-l ,4-phenylene)ether, 400 parts; 600 parts of rubber modified high impact polystyrene Foster Grant 834; 5 parts of diphenyl decyl phosphite, 1 5 parts of polyethylene, and 130 parts of the mesityl xylyl phosphate mixture are blended in a Waring blender and extruded in a 28 mm
Werner Pfleiter extruder (rear, 5400 F.; front 5550F.; die, 5500 F.). The extruded pellets are again extruded under the same conditions and then molded into standard test bars on a 3 oz Newbury injection molding machine (nozzle, front, rear, all 4500 F.; die, 1700 F.). For comparison purposes, a second composition is made in exactly the same way except that half the mesityl xylyl phosphate mixture is replaced with 65 g of triphenyl phosphate and a third composition is made with 130 g of a commercial grade of isopropylphenyl phosphate mixture.
Test bars 1/16" thick of all compositions are tested for flammability, igniting the bars in a gas flame and measuring the time required for extinction of the flame in each bar according to the procedure of the U.L. 94 test, as modified. The molded pieces are also subjected to physical property measurements, the heat distortion temperature being measured by ASTM method D-648.
The results of the flame test on 5 bars and the physical properties are set forth in Table 1:
TABLE 1
Flammability and Physical Properties of
Polyphenylene Ether and Polystyrene Compositions
Containing The Mesityl Xylyl Phosphate Mixture
Composition A B C
Formulation (parts by weight) poly(2,6-dimethyl-l,4- phenylene)ether 400 400 400
high impact polystyrene 600 600 600
mesityl xylyl phosphate mixture 1 30 65
triphenyl phosphate - 65
tri isopropyl phenyl phosphate - - 130
decyl diphenyl phosphite 5 5 5
polyethylene 15 1 5 1 5 Flame Test
Average time to extinction (sec.) 1 sot ignition 14 12 9
Average time to extinction (sec.)
2nd ignition 8 10 14
Physical Properties
Heat distortion temp., OF at 264 psi 204 195 184 Meltviscosityat5400Fand 1500 sec-l 1400 1200 1150
Notched Izod Impact, ft.lbs./in. 3.3 3.3 2.6
Yellowness Index 32 32 28
Composition A according to this invention, has a significantly higher heat distortion temperature and is comparable in other properties.
EXAMPLE 2 Poly(2,6-dimethyl-1 ,4-phenylene)ether, 550.0 parts, 450.0 g. of rubber modified high impact polystyrene, 1 5 parts of polyethylene, 10 parts of diphenyl decyl phosphite, 1.5 parts of zinc sulfide, 1.5 parts of zinc oxide and 35 parts of the mesityl xylyl phosphate mixture are extruded and molded as described in Example 1. A second composition is prepared in the same way except that the half mesityl xylyl phosphate mixture is replaced by 18 parts of triphenyl phosphate and a third composition is prepared from 35 parts of triphenyl phosphate.
The average flame-out time (U.L. 94 test, first ignition) is measured on five 1/16" thick bars, and the physical properties, including heat distortion temperature, are measured. The results are set forth in
Table 2:
TABLE 2
Flammability and Physical Properties of
Polyphenylene Ether and Polystyrene Compositions
Containing The Mesityl Xylyl Phosphate Mixture
Composition D E F
Formulation (parts by weight) poly!2,6-dimethyl-1,4- phenylene)ether 550 550 550
high impact polystyrene 450 450 450
mesityl xylyl phosphate mixture 35 18
triphenyl phosphate - 17 35
polyethylene 15 1 5 15
diphenyl decyl phosphite 10 10 10
zinc sulfide 1.5 1.5 1.5
zinc oxide 1.5 1.5 1.5
Flame Test
Time to extinction (sec.)
average of 5, st ignition 14 17 17
Physical Properties
Heat distortion temp., OF. at 264 psi. 245 237 236
Melt viscosity at 5400F and 1500 sec-4 2290 2400 2550
Yellowness Index 31 29 29
Notched Izod Impact, ft.lbs./in. 2.9 3.7 2.5
Compostion D according to this invention, has a significantly higher heat distortion temperature
and is comparable in other properties.
It is obvious that modifications can be made in light of the above examples. For instance, poly(2,6 diphenyl- 1 ,4-phenylene)ether can be substituted for the poly(2,6-dimethyl-1 ,4-phenylene)ether. For the
rubber modified high impact polystyrene, there can be substituted homopolystyrene or a 80:20
copolymer of styrene and methyl methacrylate.
In addition, the compositions of this invention may be formulated with other additives, for
conventional purposes, such as pigments, plasticizers, fillers, reinforcements and the like. Furthermore,
third component resins such as polyethylene may be added in minor concentrations without departing from the spirit or scope thereof. The compositions are useful to form films, fibers, molded articles, and the like, in accordance with conventional practice.
Claims (12)
1. A flame retardant mixture comprising a mixture of aromatic phosphates represented by the average formula:
wheres is a whole or fractional number from slightly more than 0 to slightly less than 3 andy is a whole or fractional number from 1 to 2.
2. A mixture as claimed in Claim 1 which comprises at least 2 compounds selected from (a) triphenyl phosphate (TTP), (b) diphenyl mesityl phosphate (DPMP), (c) dimesityl phenyl phosphate (DMPP) and (d) trimesityl phosphate (TMP), at least one of said two compounds being DPMP or DMPP.
3. A mixture as claimed in Claim 1, wheminy= 1, which comprises at least 2 compounds selected from (a) trixylyl phosphate (TXP), (b) dixylyl mesityl phosphate (DXMP), (c) dimesityl xylyl phosphate (DMXP) and (d) trimesityl phosphate (TMP) at least one of said 2 compounds being DXMP or DMXP.
4. A mixture as claimed in any preceding Claim which additionally includes tri(isopropyl phenyi) phosphate.
5. A mixture as claimed in Claim 1 and substantially as hereinbefore described.
6. A resinous composition comprising (a) a normally flammable resinous material and (b) a flame retardant amount of the flame retardant mixture of any one of Claims 1 to 5.
7. A resinous composition as claimed in Claim 6 wherein the normally flammable resinous material comprises
(i) a polyphenylene ether of the formula
wherein the oxygen ether atom of each unit is connected to the benzene nucleus of the next adjoining unit; Q is hydrogen, a hydrocarbon radical, a halohydrocarbon radical having at least two carbon atoms between the halogen atom and the phenol nucleus, a hydrocarbonpxy radical, or a halohydrocarbonoxy radical having at least two carbon atoms between the halogen atom and the phenol nucleus; 0' and Q", which can be the same or different, are the same as Q or can be halogen, with the proviso that Q, Q' and
Q" are all free of a tertiary alpha-carbon atom, and n at least 50; and
(ii) a styrene resin.
8. A resinous composition as claimed in Claim 7 wherein the styrene resin is present in an amount of from 80 to 20% by weight of the weight of components (i) and (ii) in the composition, and has at least 25% by weight of units derived from a vinyl aromatic compound of the formula
wherein R1 is hydrogen, alkyl or halogen, Z is vinyl, halogen or alkyl and p is O or a whole number equal to the number of replaceable hydrogen atoms on the benzene nucleus.
9. A resinous composition as claimed in any of Claims 6 to 8 wherein the flame retardant mixture amounts to 0.5 to 1 5 parts by weight per 100 parts by weight of the normally flammable resinous material.
10. A resinous composition as claimed in Claim 9 wherein the flame retardant composition amounts to 1 to 10 parts by weight per 100 parts by weight of the normally flammable resinous material.
11. A resinous composition as claimed in any one of Claims 7 to 10 wherein the polyphenylene ether is poly(1 ,6-dimethyl-1 ,4-phenylene)ether.
12. A resinous composition as claimed in any one of Claims 7 to 11 wherein the styrene resin is a rubber-modified high impact polystyrene.
1 3. A resinous composition as claimed in Claim 6 and substantially as hereinbefore described with reference to either of the Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16163780A | 1980-06-20 | 1980-06-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2078226A true GB2078226A (en) | 1982-01-06 |
| GB2078226B GB2078226B (en) | 1984-03-07 |
Family
ID=22582059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8105509A Expired GB2078226B (en) | 1980-06-20 | 1981-02-20 | Flame retardant mixture and resinous compositions including the mixture |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5730737A (en) |
| AU (1) | AU7195281A (en) |
| BR (1) | BR8103133A (en) |
| DE (1) | DE3123090A1 (en) |
| FR (1) | FR2485027A1 (en) |
| GB (1) | GB2078226B (en) |
| NL (1) | NL8102963A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0085201A1 (en) * | 1982-02-01 | 1983-08-10 | FMC Corporation | Flame retardant polyphenylene ether-styrene thermoplastic resin compositions |
| EP0086760A2 (en) * | 1982-02-16 | 1983-08-24 | FMC Corporation | Mixed phenyl/mesityl phosphate ester composition |
| EP0090524A1 (en) * | 1982-03-26 | 1983-10-05 | General Electric Company | Thermal oxidation stabilizer composed of phosphite derivatives of an alcohol and PPE monomer still bottoms, and PPE compositions containing said phosphites |
| US4511498A (en) * | 1982-02-16 | 1985-04-16 | Fmc Corporation | Mixed phenyl/mesityl phosphate ester composition |
| WO2001074937A1 (en) * | 2000-03-30 | 2001-10-11 | General Electric Company | Transparent, flame retardant poly(arylene ether) blends |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5695850A (en) * | 1993-01-29 | 1997-12-09 | Crow; William R. | Performance enhancing athletic shoe components and methods |
| US6589630B1 (en) | 1995-03-23 | 2003-07-08 | William R. Crow | Performance enhancing shoe components and methods |
| US6120880A (en) * | 1995-03-23 | 2000-09-19 | Crow; William R. | Performance enhancing athletic shoe components and methods |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2126850A (en) * | 1934-07-26 | 1938-08-16 | Celanese Corp | Conductor and filaments therefor containing organic derivative of cellulose |
| DE2756458A1 (en) * | 1976-12-21 | 1978-06-22 | Gen Electric | DRIP-RETARDED, PLASTICIZED THERMOPLASTIC COMPOSITION |
| DE1768076A1 (en) * | 1967-05-16 | 1972-02-03 | Koppers Co Inc | Usually liquid phosphate ester preparation |
| US3639506A (en) * | 1969-05-21 | 1972-02-01 | Gen Electric | Flame retardant composition of polyphenylene ether styrene resin aromatic phosphate and aromatic halogen compound |
| US3773864A (en) * | 1970-12-16 | 1973-11-20 | Monsanto Co | Triaryl phosphates |
| GB1413475A (en) * | 1971-11-05 | 1975-11-12 | Burmah Oil Trading Ltd | Production of cyclic esters lactones |
| DE2708447A1 (en) * | 1976-03-06 | 1977-09-08 | Ciba Geigy Ag | FLAME RETARDANT POLYMER COMPOSITIONS |
| JPS53137239A (en) * | 1977-04-30 | 1978-11-30 | Ciba Geigy Ag | Polymer composition |
| GB2027712B (en) * | 1978-07-21 | 1983-03-23 | Ciba Geigy Ag | Triary phosphates |
| US4233199A (en) * | 1979-07-03 | 1980-11-11 | Visvaldis Abolins | Flame resistant thermoplastic compositions with well balanced physical properties |
-
1981
- 1981-02-20 GB GB8105509A patent/GB2078226B/en not_active Expired
- 1981-05-20 BR BR8103133A patent/BR8103133A/en unknown
- 1981-06-11 DE DE19813123090 patent/DE3123090A1/en not_active Ceased
- 1981-06-17 FR FR8111923A patent/FR2485027A1/en active Granted
- 1981-06-18 AU AU71952/81A patent/AU7195281A/en not_active Abandoned
- 1981-06-19 JP JP9406881A patent/JPS5730737A/en active Pending
- 1981-06-19 NL NL8102963A patent/NL8102963A/en not_active Application Discontinuation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0085201A1 (en) * | 1982-02-01 | 1983-08-10 | FMC Corporation | Flame retardant polyphenylene ether-styrene thermoplastic resin compositions |
| EP0086760A2 (en) * | 1982-02-16 | 1983-08-24 | FMC Corporation | Mixed phenyl/mesityl phosphate ester composition |
| EP0086760A3 (en) * | 1982-02-16 | 1984-02-22 | Fmc Corporation | Mixed phenyl/mesityl phosphate ester composition |
| US4511498A (en) * | 1982-02-16 | 1985-04-16 | Fmc Corporation | Mixed phenyl/mesityl phosphate ester composition |
| EP0090524A1 (en) * | 1982-03-26 | 1983-10-05 | General Electric Company | Thermal oxidation stabilizer composed of phosphite derivatives of an alcohol and PPE monomer still bottoms, and PPE compositions containing said phosphites |
| WO2001074937A1 (en) * | 2000-03-30 | 2001-10-11 | General Electric Company | Transparent, flame retardant poly(arylene ether) blends |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8103133A (en) | 1982-02-09 |
| GB2078226B (en) | 1984-03-07 |
| FR2485027A1 (en) | 1981-12-24 |
| AU7195281A (en) | 1981-12-24 |
| DE3123090A1 (en) | 1982-03-25 |
| FR2485027B1 (en) | 1985-05-10 |
| NL8102963A (en) | 1982-01-18 |
| JPS5730737A (en) | 1982-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4526917A (en) | Flame retardant mixture of triaryl phosphates and resinous compositions thereof | |
| CA1109182A (en) | Flame retardant composition of poly-phenylene ether, styrene resin and cyclic phosphate | |
| US3883613A (en) | Flame retardant composition of polyphenylene ether, styrene resin and trimesityl phosphate and process for the preparation thereof | |
| EP1424356B1 (en) | Flame retardant resin compositions | |
| JP2003531234A (en) | Highly flowable polyphenylene ether compound | |
| EP1651718B1 (en) | Flameproof thermoplastic resin composition | |
| US4405739A (en) | Polyphenylene ether resins and compositions heat stabilized with phosphite compounds | |
| US4350793A (en) | Flame-retardant composition of polyphenylene ether, polystyrene resin and polyphosphonate | |
| US5973041A (en) | Resinous compositions containing aromatic bisphosphoramidates as flame retardants | |
| US6124385A (en) | Halogen-free flame resistant polystyrol moulding materials | |
| GB2341184A (en) | Thermoplastic flameproof polymer blend composition | |
| EP1654321B1 (en) | Flameproof rubber-reinforced styrenic resin composition | |
| CA1199745A (en) | Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonate | |
| JP2003529654A (en) | Transparent flame-retardant poly (arylene ether) blend | |
| US6194496B1 (en) | Flame-resistant thermoplastic moulding materials with improved processing behavior | |
| JP2004176071A (en) | Additive for thermoplastic resin and flame-retardant resin composition | |
| GB2078226A (en) | Flame retardant mixture and resinous compositions including the mixture | |
| US4520152A (en) | Flame retardant composition of polyphenylene ether, styrene resin and cyclic phosphonate | |
| EP1543070B1 (en) | Flameproof styrenic resin composition | |
| EP0129824B1 (en) | Flame retardant blends of abs resin and polyphenylene ether | |
| US4390477A (en) | Diphenyl pentaerythritol diphosphonate | |
| US20020137824A1 (en) | Flameproof styrene-containing graft resin compositions having a particular nitrile content distribution | |
| WO1988003542A1 (en) | Flame retarded modified polyphenylene esters having improved flow characteristics | |
| US4483953A (en) | Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite | |
| GB2076831A (en) | Compositions of a polyphenylene ether resin and a copolymer of styrene and bromostyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960220 |