GB2325933A - Flame retardant bis-[2,4-bis(dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds, method for their production & resin compositions of the same - Google Patents
Flame retardant bis-[2,4-bis(dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds, method for their production & resin compositions of the same Download PDFInfo
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- GB2325933A GB2325933A GB9711361A GB9711361A GB2325933A GB 2325933 A GB2325933 A GB 2325933A GB 9711361 A GB9711361 A GB 9711361A GB 9711361 A GB9711361 A GB 9711361A GB 2325933 A GB2325933 A GB 2325933A
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- -1 aryl diphosphate compounds Chemical class 0.000 title claims abstract description 59
- 239000003063 flame retardant Substances 0.000 title claims abstract description 17
- 239000011342 resin composition Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000001177 diphosphate Substances 0.000 claims description 20
- 235000011180 diphosphates Nutrition 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002952 polymeric resin Substances 0.000 claims description 10
- 229920003002 synthetic resin Polymers 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 9
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 239000000543 intermediate Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UXAFEFWYRQXVKX-UHFFFAOYSA-N 2,3-bis[3-(2,4-ditert-butylphenyl)-2,6-dimethylphenyl]benzene-1,4-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.CC(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C=1C(=C(C(=CC1)C)C=1C(=C(O)C=CC1O)C1=C(C(=CC=C1C)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)C)C UXAFEFWYRQXVKX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- ZOOOXFQDMBDASO-UHFFFAOYSA-N phosphono [2,3,4,6-tetrakis(2,6-dimethylphenyl)-5-hydroxyphenyl] hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1C(C(=C1C=2C(=CC=CC=2C)C)OP(O)(=O)OP(O)(O)=O)=C(O)C(C=2C(=CC=CC=2C)C)=C1C1=C(C)C=CC=C1C ZOOOXFQDMBDASO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BGGGMYCMZTXZBY-UHFFFAOYSA-N (3-hydroxyphenyl) phosphono hydrogen phosphate Chemical compound OC1=CC=CC(OP(O)(=O)OP(O)(O)=O)=C1 BGGGMYCMZTXZBY-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- IBTHQOWQFLAYAP-UHFFFAOYSA-N [2,4-bis[3-(2,4-ditert-butylphenyl)-2,6-dimethylphenyl]-5-hydroxyphenyl] phosphono hydrogen phosphate Chemical compound P(O)(=O)(OP(=O)(O)O)OC1=CC(O)=C(C=C1C1=C(C(=CC=C1C)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)C)C1=C(C(=CC=C1C)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)C IBTHQOWQFLAYAP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- RUZYUOTYCVRMRZ-UHFFFAOYSA-N doxazosin Chemical compound C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 RUZYUOTYCVRMRZ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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)
Abstract
Bis [2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds having the following formula 1 are flame retardants imparting heat resistance as well as flame retardance to plastic resins.
Description
BIS\2,SBlS(1,1-DIMETHYLETHYL)PHENYL-2,6- DIMETffYLPIlENYLi ARYL DIPHOSPHATE COMPOUND,
A METHOD FOR PRODUCING THE SAME AND RESIN
COMPOSITIONS CONTAINING THE SAME
This invention relates to a flame retardant, a method for producing them and resin compositions containing them, in particular, to bis [2,4
bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate
compound having the following formula 1, a novel organic compound for
the use of imparting flame retardant and heat resistant plastic resins, a
method for producing them and resin compositions containing them as a
flame retardant
Formula I
Recently, it is generally needed to reduce the inflammability of plastics, rubber, papers, and the like. In particular, various polymers having many excellent properties are widely used in the field of electric and clcctronic appliances, automobiles, airplanes and ships, so that the polymers are necessary to havc flame retardance currently.
In general, organophosphorous compounds are known as good name relarttanLs but have defects of relatively high volatility and low hcat resistance. Particularly, new high-perfonnance plastics such as engineering plastics and super-engineering plastics are processed around 300"C or above and hence flame retardants are required to have high heat resistance.
Aromatic organophosphate compounds were disclosed in USP
No. 4,134,876 as flame retardants having high heat resistance and low volatility. But the compounds have colors and a resin including the compound is not suitable for a base material of a final product due to the compounds' colors.
A compound having the following formula 7 was disclosed in
USP No. 5,122,558 and EP publication No. 509,506 and a compound having the following formula 8 was disclosed in JP publication No. 96208972. Polymeric resins have a tendency to be degraded by heat depending on the use of final products and in spite of their good flame retardance, the compounds are unsuitable to household electric appliances generating much heat due to their unsatisfactory heat resistance.
Formula 7
Formula 8
In the above formula 8, x is arylene group and RI, R2, R3 and RJ are substituted or unsubstituted alkyl group.
A method for producing aromatic diphosphate oligomer phosphate compound that uses phosphorous oxychloride and dihydroxylic phenol (formula 4) compound or monohydroxylic phenol compound(fonnula 9) as reactants was disclosed in USP No. 2,520,090 and EP EJo. 613,902. But the method described in the USP No. 2,520,09O has problems that residual phosphorous oxychloride must be removed after reaction and by-products such as various oligomers are generated. And the method described in
EP No. 613,902 has a problem that reaction intermediates must be purified after reaction between oxychloride and monohydroxylic phenol compound in order to supress fonnation ofthe oligomers, by-products.
Formula 4
Examples of the formula 4 are resorcinol and hydroquinone.
Formula 9
In the above formula 9, R1 is hydrogen atom or alkyl group with carbon number from 1 to 8 and R2 are alkyl group with carbon number from 1 to 8.
A method for producing powders of aromatic diphosphate compounds was disclosed in IJSP No. 5,420,327 and JP No. 2,552,780.
The aromatic diphosphate compounds have a purity of 90% or above by the method reacting phosphorous oxychloride and monohydroxylic phenol compound followed by reacting dihydroxylic phenol compound. It was described that the compounds wcrc superior to the prior non-halogen phosphate flame retardants, such as triphenyl phosphate(TPP) and resorcinol diphospliate(RDP) in flame retardance and heat resistance.
But the compounds have unsatisfactory heat resistance for the use of household electric appliances generating much heat.
In order to solve the problems as described above, an object of this
invention is to provide an aromatic diphosphatc compound, flame retardant showing excellent heat resistance by introducing tertiary butyl group.
This invention provides a method for producing the intermediate compound with 90% or above purily that makes it unnecessary to remove phosphorous oxychloride during reaction and reduces the formation of oligomers, by-product by imparting steric hindrance to monohydroxylic phenol compounds. This invention also provides resin compositions containing the compound as a flame retardant One aspect of this invention provides bis t2,4-bis(l,l- dimetylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compound having the following formula 1.
Formula 1
The bis [2,4-bis(1,1-dimetylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compound is preferably bis [2,4-bis(1,1-dimetylethyl)phenyl- 2,6-dimethylphenyl] resorcinol diphosphate compound having the following formula 2 or bis I2,4-bis(1,1 -dimetylethyl)phenyl-2,6- dimethylphenyl] hydroquinone diphosphate compound having the following formula 3.
Formula 2
Formula 3
And this invention also provides the use of the [2,4-bis(l,l- dimetylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds as flame retardants.
Another aspect of this invention provides a method for producing bis [2,4-bis(1,1 -dimetylethyl)phenyl-2 ,6-dimethylphcnyl] aryl diphosphate compound comprising the stcps of (a)forming a dichlorophosphate intermediate by reacting phosphorous oxychloride with a compound having the formula 5 in the presence of a catalyst, (b)forming a chlorophosphale inti:rrriediate by reacting the dichlorophosphate intermediate with a compound having the formula 6 in the presence of the catalyst, and (c)fonning the bis [2,4-bis(l -dimetylethyl)-2,6- dimethylphenyl] aryl diphosphate compound by reacting the chlorophosphate intermediate with a compound having the formula 4.
Formula 4
Formula 5
Formula 6
The compound having the formula 4 is preferably a resorcinol compound or a hydroquinone compound. A reaction in the method is shown by the following reaction formula 1.
Reaction formula 1
The Lewis acid catalyst is preferably MgC12 or Air13. This invention imparts heat resistance to the flame retardant by introducing the compound having tertiary butyl group.
In the step of fonning the dichlorophosphate intermediate by reacting phosphorous oxychloride with the compound having the formula
S in the presence of the catalyst, the dichlorophosphate intermediate having high purity can be obtained by substituting tertiary butyl group giving stearic hindrance, at the adjacent position to hydroxyl group of the monohydroxylic phenol compound, i. e. at 2(or 6) position of the monohydroxylic phenol compound. In case the monohydroxylic phenol compound has been substituted by tertiary butyl group at 2(or 6) position, it can be more substituted at 3, 4, 5 or 6(or 2) position. But the substitution of tertiary butyl group at 2(or 6) position causes the hydroxyl group of the monohydroxylic phenol compound to have low reactivity, so that it is the most preferable to substitute another tertiary butyl group at 4 position considering the reactivity and a production cost.
The third aspect of this invention provides resin compositions comprising a polymeric resin and a bis [2,4-bis(l,l-dimetylethyl)-2,6- dimethylphenyl] aryl diphosphate compound having the above formula 1 of 0.1-50% by weight of the weight of the polymeric resin. In the resin compositions, thc bis [2,4-bis(l,l -dimetylethyl)-2,6-dimethylphenyl] aryl diphosphate compound is prcfcrably a bis [2,4-bis(l,l-dimetylethyl)-2,6- dimethylphenyl] resorcinol diphosphate compound or a bis [2,4-bis(l,l- dimetylethyl)*2,6-dimetbylphenyl] hydroquinone diphosphate compound.
The polymeric resin is preferably selected from the group consisting of polyvinyl chloride, polyethylene, polypropylene, ABS resin, polystyrene, polymethylmetacrylate, polyamide, polycarbonate, polyurethane, phenol resin, melamine resin, unsaturated polyester and the mixtures thereof.
The most preferably, the polymeric resin comprises 90-10% by weight polycarbonate and 10-90% by weight ABS. The content of the aromatic organic compound having the formula 1 is controlled suitably depending on the use of a resin, and the ordinary content of the compound is 0.1 to 50% by weight of the weight of the resin. The flame retardant can be added to the polymeric resin by ordinary mixing method. If necessary, various additives such as antioxidants and packing agents can be added.
Figure 1 is an Infrared absorption spectrum of [2,4-bis(1,1- dimethyIethyl)phcnyl-2,6-dimethylphenyl] resorcinol diphosphate compound obtained in the Example 1 of this invention.
Figure 2 is an Infrared absorption spectrum of [2,4-bis(1,1- dimethylethyl)phenyl-2,6-dimethylphenyl] hydroquinone diphosphate compound obtained in the Example 2 of this invention.
This invention is further explained in more detail with reference to the following examples which do not limit this invention.
EXAMPLE 1 production of bis [2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] resorcinol diphosphate compound
268.2g 2,4-bis(l,l -dimethylethyl) phenol, 2.0g magnesium chloride and 1 00g xylene were added in a dried flask equipped with a thermometer, a cooling condenser, and an agitator and then heated.
When the temperature of the reactants rcachcd 1 500C, 1 99.3g phosphorous oxychloride was added through one hour. Hydrogen chloride was captured with water. The reaction was continued in 135"C after the addition of the phosphorous oxychloride. When the generation of HCl gas stopped, the temperature was raised up to 180 OC. Through maturation for 4 hours, 12,4-bis(l, I-dimcthylethyl) phenyl] dichlorophosphate intermediate was obtained. The [2,4-bis(1,l- dimethylethyl) phenyl] dichlorophosphate intermediate was cooled down to 700C. 158.9g xylenol and 2.0g magnesium chloride were added and then the temperature was slowly raised up to 1500C. When the generation of HC1 gas stopped, the temperature was raised up to 180 OC.
through maturation for 4 hours, [2,4-bis(l,l-dimethylethyl) phenyl-2,6dimethylphenyl] chlorophosphate intermediate was obtained. The [2, bis( 1,1 -dimethylethyl) phenyl-2,6-dimethylphenyl] ch lorophosphate intermediate was cooled down to 70 C. 71.6g resorcinol and 3.0g magnesium chloride were added and then the themperature was raised up to 150 C. When the generation of HCl gas stopped, the temperature was raised up to 180 C, the reaction was matured for 4 hours. After the reaction has finishcd, a product was washed with 400g of 5% hydrochloride solution in order to remove the catalyst and impurities, and subsequently was washed with water. The product was dried under a decompressed condition and 534g of a final product of which melting point is 450C was obtained.
The structure of a compound, a final product, was identified with
Infrared absorption(IR) spectrum and nuclear magnetic resonance(NMR) spectrum. IR spectrum was carried in a mixed plate form with potassium bromide by using Fouricr transform iriJiared(FT-IR) BRUKER IFS 66.
As shown in the Figure 1, the compound showed C-c stretching absorption bands at 1496cm and 1084cm-1, those of phenyl group, C-H3 deformation absorption bands at 1363cm-1 and 1399cm-1, those of CH3 in tertiary butyl group, a P=O stretching absorption band at 1308cm-1, and a
P-O-Ar stretching absorption band at 1130cm-1. H NMR spectrum was camed with a solvent, CHCl3 and with the internal standard of 7.24 CDC13, using BRUKER DRX 400. As a result, 6's were 1.28(18H, s), 1.34(18H, s), 7.01(9H, m), 7.15(3H, m), 7.36(2H, dd), and 7.43(2H, d). Therefore the compound was identified to have the structure as shown in the formula 2.
Production of a resin comEosition 10% by weight bis[2,4-bis(1,1-dimethylethyl)phenyl-2,6- dimethylphenyl] resorcinol diphosphate was added to a 100% by weight resin comprising 90% by weight polycarbonate and 10% by weight ABS and mixed by a mixing machine. The mixture was extruded with twin screw extruder and the extruded material was cooled and cut to be obtained in a pellet form. a test piece was made by injection molding. Flame rctartance, discoloration, heat deformation temperature, Izod impact strength, and pulling strength were measured on the test piece and results of the measurement were shown in table 1.
EXAMPLE 2 production of bis[2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] hydroquinone diphosphate compound
In the example I, the substantially same process was carried out except that resorcinol was replaced by hydroquinone. 530g of Bis [2,4bis(l,1-dimethylethyl)phenyl-2,6-dimethylphenyl] hydroquinone diphosphate having 49 C melting point was obtained. As a result of IR spectrum, the compound showed C=C stretching absorption bands at 1496cm and 1085cm~, those of phenyl group, CH3 deformation absorption band at 1363cm-1 and 1399cm-1, those of CH3 in tertiary butyl,
P=O stretching absorption band at 1307cm-1, and P-Ar stretching absorption band at 1158cm-1 as shown in the Figure 2. As a result of lH NMR spectrum, 6's were I .29(18H, s), 1.34(18H, s), 7.01(9H, m), 7.14(3H, m), 7.37(2H, dd), and 7.44(2H, d). Therefore the compound was identified to have the structure as shown in the formula 3.
Production of a resin composition
In the example 1, the substantially same process was carried out except that [2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] rcsorcinol diphosphate was replaced by [2,4-bis(1,1-dimethylethyl)phenyl- 2,6-dimethylphenyl] hydroquinone diphosphate. The result was shown in table 1.
COMPARATIVE EXAMPLE 1
In the production of the resin composition of example 1, the substantially same process was carried out except that bis[2,4-bis(l ,l - dimethylethyl)phenyl-2,6-dimethylphenyl 1 resorcinol diphosphate was rep laced by triphenyl phosphate(Junsei GR-grade reagent). The result was shown in table 1.
COMPARATIVE E?CAMPLt 2
In the production of the resin composition of example 2, the substantially same process was carried out except that bis[2,4-bis(l,1- dimethylethyl)phenyl-2,6-dimethylphenyl] hydroquinone diphosphate was replaced by tetrakis(2,6-dimethylphenyl) resorcinol diphosphate. The result was shown in table 1.
Test methods
1. flame retardanee flame retardance of the test pieces was evaluated by "inflammability test of plastic materials for machinery parts" in a test method of UL(Underwrites Laboratories Incoporaiion > 94. The test piece was 1 .6mm in thickness.
2. discoloration
discoloration of the test pieces was evaluated by visual test.
3. Vicat softening temperature
Vicar softening temperature of the test pieces was measured under a load of 1 kgf in compliance with ASTM D-1525.
4. Izod impact strength
Izod impact strength was measured in compliance with ASTM
D-256.
5. pulling strength
pulling strength was measured in compliance with ASTM D-638.
Table 1
example 1 example 2 comparative comparative example 1 example 2 flamc rciardance Vo V0 V1 ~ VE
discoloration not not discolored a little discolored discolored discolored Vicatsoftening 128 131 106 118 temperature( C) Izodimpact 61 60 50 51 strength (lcg-cmicm) pulling strength 610 620 550 590 (kg/cm2) As shown in the table 1, the resin compositions using bis [2,4bis(1,1-dimetylethyl)phenyl-2,6-dimethylphenyl] resorcinol diphosphate compound or bis [2,4-bis(1,1-dimetylethyl)phenyl-2,6-dimethylphenyl] hydroquinone diphosphate compound produced by the method described in this invention as flame retardant arc less discolored and have higher
Vicat softening temperature, impact strength and pulling strength than the resin composition using tripheyl phosphate or tetrakis[2,6-dimethylphenyl] resorcinol diphosphate.
Therefore, the aromatic diphosphate compounds described in this invention have excellent heat resistance as well as flame retardance enough to be used for flame retardants of plastic resins.
Claims (16)
1. A bis [2,4-bis(1,1-dimethylethyl) phenyl-216Aimethylphenyl) aryl diphosphate compound having the following formula 1:
Formula 1
2. The compound according to claim 1, wherein said bis [2,4bis( 1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compound is a bis [2,4-bis(1,1-dimethylethyl)phenyI-2,6-dimethylphenyl resorcinol diphosphate compound having the following formula 2:
Formula 2
3. Thc compound according to claim 1, wherein said bis [2,4 bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compound is a bis [2,4-bis(1,1 -dimethylethyl)pheny1-2, 6-dimethylphenyl] hydroquinone diphosphate compound having the following formula 3: Formula 3
4. The use of the bis [2,4-bis(1, dimetylethyl)phenyl-2,6- dimethylphenyl] aryl diphosphate compound according to any one of claim 1 to 3 as a flame retardant.
5 A method for producing a bis [2,4-bis(1,1-dimethylethyl)phenyl-2,6- dimethylphenyll aryl diphosphate compound comprising the steps of: (a) forming a dichlorophospbate intermediate by reacting phosphorous oxychloride with a compound having the formula 5 in the prcscnce of a catalyst;
(b)forming a chlorophosphate intermediate by reacting said dichlorophosphate intermediate with a compound having the formula 6 in the presence of a catalyst; and
(c)forming the bis [2,4-bis (1, -dimethylethyl)phenyl-2,6-dimethylphenyiJ aryl diphosphate compound by reacting said chlorophosphate intermediate with a compound having the formula 4.
Formula 4
Formula 5
Formula 6
6. The method according to claim 4, wherein said compound having the formula 4 is a resorcinol compound.
7. The method according to claim 4, wherein said compound having the formula 4 is a hydroquinone compound.
8. A resin composition comprising:
a polymeric resin of 100 parts by weight;and
a bis [2,4-bis (1, 1-dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compound having thc above formula 1 of 0.1-50 parts by weight of the weight of the polymeric resin.
9. The resin composition according to claim 8, wherein the bis [2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compound is a bis (2,4-bis(1,1-dimethyiethy1)pheny12,6-dimethyIphenyl] resorcinol diphosphate compound.
10. The resin composition according to claim 8, wherein the bis [2,4-bis (1,1 -dimethylethyl)phenyl- 2, 6-dimethyiphenyl] aryl diphosphate compound is a bis (2,4-bis (1,1 -dimethylethyl)phenyl-2,6-dimethyiphenyl] hydroquinone diphosphate compound.
11. The resin composition according to claim 8, wherein said polymeric resin is selected from the group consisting of polyvinyl chloride, polyethylene, polypropylene, ABS resin, polystyrene, polyamide, polymethyl metacrylate, polycarbonate, polyurethane, phenol resin, melamine resin, unsaturated polyester and the mixtures thereof.
12. The resin composition according to claim 8, wherein said polymeric resin comprises 90-10% by weight polycarbonate and 10-90% by weight ABS resin.
13. A flame retardant comprising a bis [2,4-bis (1, 1-dimethylethyl) phenyl-2,6dimethylphenyl] aryl diphosphate compound as claimed in any one of the claims 1 to 3.
14. A compound substantially as herein described with reference to formulae 1, 2 or 3 of the accompanying description.
15. A method for producing a compound substantially as hereinbefore described.
16. A resin composition substantially as hereinbefore described.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9711361A GB2325933A (en) | 1997-06-02 | 1997-06-02 | Flame retardant bis-[2,4-bis(dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds, method for their production & resin compositions of the same |
FR9706812A FR2763952A1 (en) | 1997-06-02 | 1997-06-03 | New bis-2,4-bis-1,1-di:methyl-ethyl-phenyl-2,6-di:methylphenyl aryl di:phosphate(s) |
DE19723221A DE19723221A1 (en) | 1997-06-02 | 1997-06-03 | BisÝ2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl¨ aryl diphosphate compound |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9711361A GB2325933A (en) | 1997-06-02 | 1997-06-02 | Flame retardant bis-[2,4-bis(dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds, method for their production & resin compositions of the same |
FR9706812A FR2763952A1 (en) | 1997-06-02 | 1997-06-03 | New bis-2,4-bis-1,1-di:methyl-ethyl-phenyl-2,6-di:methylphenyl aryl di:phosphate(s) |
DE19723221A DE19723221A1 (en) | 1997-06-02 | 1997-06-03 | BisÝ2,4-bis(1,1-dimethylethyl)phenyl-2,6-dimethylphenyl¨ aryl diphosphate compound |
Publications (2)
Publication Number | Publication Date |
---|---|
GB9711361D0 GB9711361D0 (en) | 1997-07-30 |
GB2325933A true GB2325933A (en) | 1998-12-09 |
Family
ID=27217438
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9711361A Withdrawn GB2325933A (en) | 1997-06-02 | 1997-06-02 | Flame retardant bis-[2,4-bis(dimethylethyl)phenyl-2,6-dimethylphenyl] aryl diphosphate compounds, method for their production & resin compositions of the same |
Country Status (3)
Country | Link |
---|---|
DE (1) | DE19723221A1 (en) |
FR (1) | FR2763952A1 (en) |
GB (1) | GB2325933A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2468814A1 (en) | 2010-12-22 | 2012-06-27 | Cheil Industries Inc. | Novel Phosphorus Compound, Method of Preparing the Same and Flame Retardant Thermoplastic Resin Composition Including the Same |
WO2016197915A1 (en) * | 2015-06-08 | 2016-12-15 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5508013B2 (en) | 2006-08-31 | 2014-05-28 | スプレスタ エルエルシー | Oligomer bisphosphate flame retardant and composition containing the same |
CN102341437B (en) * | 2009-03-09 | 2015-08-19 | Icl-Ip美国公司 | Fire-retardant polyolefin compositions |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5420327A (en) * | 1992-09-14 | 1995-05-30 | Akzo Nobel N.V. | Process for forming hydrocarbyl bisphosphate compound |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2901304B2 (en) * | 1990-02-13 | 1999-06-07 | 大八化学工業株式会社 | PVC resin film |
JP2552780B2 (en) * | 1991-04-16 | 1996-11-13 | 大八化学工業株式会社 | Method and application for producing aromatic diphosphate |
TW280824B (en) * | 1993-09-09 | 1996-07-11 | Ciba Geigy Ag | |
JPH08208972A (en) * | 1994-11-10 | 1996-08-13 | Toray Ind Inc | Thermoplastic resin composition |
-
1997
- 1997-06-02 GB GB9711361A patent/GB2325933A/en not_active Withdrawn
- 1997-06-03 DE DE19723221A patent/DE19723221A1/en not_active Withdrawn
- 1997-06-03 FR FR9706812A patent/FR2763952A1/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5420327A (en) * | 1992-09-14 | 1995-05-30 | Akzo Nobel N.V. | Process for forming hydrocarbyl bisphosphate compound |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2468814A1 (en) | 2010-12-22 | 2012-06-27 | Cheil Industries Inc. | Novel Phosphorus Compound, Method of Preparing the Same and Flame Retardant Thermoplastic Resin Composition Including the Same |
US8410203B2 (en) | 2010-12-22 | 2013-04-02 | Cheil Industries Inc. | Phosphorus compound, method of preparing the same and flame retardant thermoplastic resin composition including the same |
WO2016197915A1 (en) * | 2015-06-08 | 2016-12-15 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor |
Also Published As
Publication number | Publication date |
---|---|
DE19723221A1 (en) | 1998-12-10 |
FR2763952A1 (en) | 1998-12-04 |
GB9711361D0 (en) | 1997-07-30 |
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