WO1998035970A1 - Process for making and using bisaryl diphosphates - Google Patents
Process for making and using bisaryl diphosphates Download PDFInfo
- Publication number
- WO1998035970A1 WO1998035970A1 PCT/US1998/002968 US9802968W WO9835970A1 WO 1998035970 A1 WO1998035970 A1 WO 1998035970A1 US 9802968 W US9802968 W US 9802968W WO 9835970 A1 WO9835970 A1 WO 9835970A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bisphenol
- reacting
- diphosphorotetrahalide
- catalyst
- bisaryl
- Prior art date
Links
- 239000001177 diphosphate Substances 0.000 title claims abstract description 54
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 title claims abstract description 54
- 235000011180 diphosphates Nutrition 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 51
- 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 claims abstract description 114
- 239000002952 polymeric resin Substances 0.000 claims abstract description 51
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000011874 heated mixture Substances 0.000 claims abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 239000011574 phosphorus Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 125000006267 biphenyl group Chemical group 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000000047 product Substances 0.000 description 25
- 235000021317 phosphate Nutrition 0.000 description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 239000012467 final product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 229920005669 high impact polystyrene Polymers 0.000 description 8
- 239000004797 high-impact polystyrene Substances 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 8
- 229920006380 polyphenylene oxide Polymers 0.000 description 8
- 229920007019 PC/ABS Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- -1 polybutylene terephthalate Polymers 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 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 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Chemical group 0.000 description 2
- 239000007862 dimeric product Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
-
- 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
Definitions
- the present invention relates generally to the manufacture and use of bisaryl diphosphates , and more particularly to an improved process for making and using bisphenol A bis(diphenyl)-phosphate without purification.
- Bisaryl diphosphates such as bisphenol A bis (diphenyl) - phosphate can be effective flame retardants for polymer resins.
- polyphenylene oxide/high-impact polystyrene (“PPO/HIPS”) and polycarbonate/acrylonitrile- adosiene-styrene (“PC/ABS”) blends can be improved with bisaryl diphosphate flame retardants.
- bisphenol A bis (diphenyl)-phosphate can be obtained by catalytically reacting a phosphorus oxyhalide with bisphenol A and then reacting the intermediate with phenol.
- Prior art processes for making and using bisaryl diphosphates include one or more steps to remove the catalyst from the diphosphate. The most common method employed for catalyst removal has been by aqueous washing which leads to emulsions with the product. However, the residual water must generally be removed prior to use as a flame retardant.
- Prior art processes for making and using bisaryl diphosphates also disclose that the triaryl phosphate content of the final products should be reduced. Accordingly, prior art processes typically employed a non-reactive solvent to reduce triaryl phosphates.
- a method of effectively and economically making flame retarded polymer resins by adding to the polymer resin a catalytically synthesized bisaryl diphosphate that has not been purified to remove catalyst from the product, so that the synthesized bisaryl diphosphate provided to the resin contains the catalyst (or the residue of the catalyst) used to make the bisaryl diphosphate.
- the flame retarded polymer resins referred to above are made using a bisaryl diphosphate that is the product of a process in which a dihydric aromatic compound (such as bisphenol A) is semi-continuously added to a heated catalyst/phosphorus oxyhalide mixture (such as a mixture of phosphorus oxychloride and MgCl) over a period of 0.5 hours to 12.0 hours.
- a dihydric aromatic compound such as bisphenol A
- a heated catalyst/phosphorus oxyhalide mixture such as a mixture of phosphorus oxychloride and MgCl
- the resulting intermediate is then reacted with an alcohol (such as phenol) to form the desired bisaryl diphosphate.
- the dihydric aromatic compound e.g. , bisphenol A
- the alcohol e.q . , phenol
- One object of the present invention is to provide improved methods of flame retarding polymer resins.
- Another object of the present invention is to provide new polymer resins that have been flame retarded at a minimum cost.
- Still another object of the present invention is to provide improved methods of manufacturing bisaryl diphosphate compounds for use as flame retardants in polymer resins.
- one aspect of the present invention provides a method of making flame retarded polymer resins by blending a catalytically prepared bisaryl diphosphate into a polymer resin without removing the catalyst (or catalyst residue) from the bisaryl diphosphate.
- polymer resins that have been flame retarded in this way possess characteristics that compare favorably with those of resins made with bisaryl diphosphates only after removing the catalyst from the bisaryl diphosphate. While the
- the bisaryl diphosphate/catalyst mixture may be used as a flame retardant in a wide variety of polymer resins.
- Preferred polymer resins include polyphenylene oxide (PPO) , high-impact polystyrene (HIPS) , polycarbonate (PC), polyurethane (PU) , polyvinyl chloride (PVC) , acrylonitrile-butadiene-styrene (ABS) , and polybutylene terephthalate (PBT) , but a wide range of other polymer resins may also be used.
- Blends of these and other resins such as polyphenylene oxide/high-impact polystyrene blends (PPO/HIPS) and polycarbonate/acrylonitrile-butadiene-styrene blends (PC/ABS) may also advantageously be made and used.
- the flame retardant may be added in the range of 5-30%, preferably, 10-20%.
- the bisaryl diphosphate/catalyst mixtures that are formulated into the polymer resins, in the preferred embodiments the bisaryl diphosphate is made by the two-step process illustrated below.
- a phosphorus oxyhalide is reacted with a dihydric aromatic compound in the presence of a catalyst.
- the dihydric aromatic is preferably semi-continuously added to a heated mixture of phosphorus oxyhalide and catalyst over a period of time of 0.5 hours to 12 hours.
- reaction mixture is heated to reflux temperatures in order to evolve the hydrogen chloride by-product gas and convert the dihydric aromatic compound into the corresponding diphosphorotetrachloridate.
- the crude step 1 intermediate is reacted with an alcohol to form the desired flame-retardant product.
- the reaction is heated to sufficient temperatures to convert the intermediate to product.
- a subsurface nitrogen sparge is introduced to remove the by-product hydrogen chloride.
- the phosphorus oxyhalide is of the formula POX-,, where X is bromine or chlorine.
- X is bromine or chlorine.
- the most preferred phosphorus oxyhalide is phosphorus oxychloride, although phosphorus oxybromide can be used.
- the preferred dihydric aromatic compounds include resorcinol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, bisphenol methane, biphenols, and other substituted dihydric aromatic compounds. It is preferred that there be no more than one substituent ortho to each hydroxyl group on the dihydric aromatic compound.
- the most preferred dihydric aromatic compound is bisphenol A.
- the ratio of the phosphorus oxyhalide to the dihydric compound is used to control the degree of polymerization in the final product. The preferred range is between one-half and five moles of phosphorus oxyhalide per mole of dihydric compound, although ratios outside this range may be used. The preferred range is merely representative of the process in its preferred embodiments.
- the preferred catalysts promote the reaction and are soluble in the final product, although nonsoluble catalysts may be used. Many of the preferred catalysts are metal halide salts, but other types of compounds may be used to catalyze the reaction. Examples of preferred catalysts include aluminum chloride, magnesium chloride, calcium chloride, zinc chloride and titanium tetrachloride. The most preferred catalyst for use in this invention is magnesium chloride.
- the amount of catalyst needed in the reaction is in the range of 0.01-2.0 wt% based on the weight of dihydric aromatic compound. The most preferred range is 0.1-0.75 wt%
- the excess phosphorus oxyhalide may be removed by distillation.
- the distillation can be at reduced pressure, or at atmospheric pressure using elevated temperatures.
- the phosphorus oxyhalide is removed with reduced pressure and elevated temperatures.
- the pressure is less than 20 torr and the temperature is between 150 and 180°C.
- any alcohol may be used.
- Preferred alcohols are aromatic alcohols, although aliphatic alcohols may also be used — either alone or in combination with an aromatic alcohol.
- Preferred alcohols for use in the invention include ortho-cresol , meta-cresol, para-cresol, xylenols, phenol, halo-phenols and other substituted phenols. It is preferred that there be no more than one substituent ortho to each hydroxyl group on an aromatic alcohol.
- the more preferred alcohols are monohydric aromatic alcohols, most preferably phenol.
- the ratio of alcohol to the diphosphorotetrachloridate intermediate is preferably at least 4 moles per mole based on reaction stoichiometry .
- Excesses of up to 10% are desired to increase the reaction rate and account for loss of the aromatic compound from the reactor.
- the preferred range is a 1-3% excess above stoichiometric requirements.
- the alcohol is preferably added to the hot mixture from the first step in a semi-continuous fashion.
- the compound is added over the course of 0.5 to 12 hours.
- the reaction is conducted at a temperature such that the alcohol reacts with the step 1 intermediate. This temperature varies according to the substituents on both the alcohol and the dihydric aromatic compound from the first step.
- the reaction components are bisphenol A, phosphorus oxychloride, and phenol
- the preferred temperature range for the reaction of step 1 intermediate is 140-240°C with the most preferable range being 150-180°C.
- the reaction temperature may be held constant after the addition of alcohol, or it may be increased to increase the reaction rate.
- the excess alcohol is distilled from the mixture, preferably under reduced pressure.
- the temperature, pressure and other reaction conditions for the distillation depend on the dihydric aromatic compound and alcohol being used, but when the reaction components are bisphenol A and phenol, the most preferred method is stripping in a wiped-film or falling-film evaporator using absolute pressures of less than 10 torr and temperatures of 165-220°C.
- the present invention may be embodied in a process for the preparation of a bisaryl diphosphate as described below: 1.
- the reaction mixture is heated to promote reaction and evolve the by-product hydrogen chloride gas.
- a nitrogen sparge may be introduced to the reaction to enhance evolution of hydrogen chloride.
- the aromatic/aliphatic group in the phosphoryl compound (the "R" group in the formula above) is derived from the reaction of an alcohol with a phosphorus oxyhalide. Suitable alcohols are identical to those listed above. The dihydric aromatic compound is also selected from those listed above.
- the dihydric aromatic compound is added to the hot phosphoryl compound in the temperature range of 100-240°C. Typical addition times range from 0.5 to 12 hours. When the reaction is complete, any volatile compounds are removed by distillation under reduced pressure in a wiped-film or falling-film evaporator in the temperature range of 165-220°C.
- the bisaryl diphosphate used to flame retard the polymer resin is the product of a specific process for catalytically preparing bisaryl diphosphates.
- the process includes the semi-continuous addition of the dihydric aromatic compound to the phosphorus oxyhalide to reduce triaryl phosphate content, with semi-continuous addition being the addition of the dihydric aromatic compound to the heated catalyst/phosphorus oxyhalide mixture over a period of 0.5 hours to 12.0 hours.
- the resulting product is then reacted with an alcohol to form the desired bisaryl diphosphate.
- the semi-continuous addition of the dihydric aromatic compound reduces the decomposition of this compound, particularly in the case of bisphenol A.
- the step 1 intermediate product therefore contains fewer decomposition products. Since these decomposition products are converted to triaryl phosphates in the second reaction, the use of the semi-continuous addition is effective to minimize the triaryl phosphate content in the final product. This is especially true when bisphenol A is used as the dihydric aromatic compound.
- the bisaryl diphosphate used to flame retard the polymer resin is the product of a process for catalytically preparing bisaryl diphosphates in which a dry dihydric aromatic compound (e.q .. dry BPA) is used.
- a dry dihydric aromatic compound e.q .. dry BPA
- the dihydric aromatic compound has a moisture content of ⁇ 200ppm water.
- the bisaryl diphosphate used to flame retard the polymer resin is the product of a process for catalytically preparing bisaryl diphosphates in which a dry alcohol (e.g. , dry phenol) is used.
- a dry alcohol e.g. , dry phenol
- the phenol has a moisture content of ⁇ 300ppm.
- the effect of excess water is an increase in acidity of the final product which causes hydrolytic instability when formulated in PC/ABS .
- the effect of water in phenol is thus different than the effect of water in BPA.
- Acid POCI3 Dime Water is therefore substantially eliminated from the POCl_ in the most preferred embodiments.
- the POCl span is sufficiently water-free to assure that the dimer and acids levels in the POC1-, are less than 0.2% by weight.
- Step 1 Phosphorus oxychloride (3347.8g, 21.881 moles), magnesium chloride (2.85g, 0.030 moles), and bisphenol A (1425.4g, 6.24 moles) were charged into a flask equipped with a stirrer, heating mantle, temperature controller, and a reflux condenser vented to a caustic scrubber. The contents were heated to reflux for 6.75 hours and the reaction monitored for completion by liquid chromatography . After the reaction was complete, the flask was equipped for distillation and vacuum gradually applied until the pressure was less than 20 torr. The temperature of the flask contents was allowed to increase to 180°C during this process. When the temperature reached 180°C, the distillation was stopped and the material was subsequently used in the second step.
- Step 2 A portion of the step 1 intermediate (1095.8g) from the above reaction was charged into a flask equipped with a stirrer, heating mantle, temperature controller, and a reflux condenser vented to a caustic scrubber. The contents were heated to 180°C and phenol (832.7g, 8.85 moles) was charged into an addition funnel. The phenol was added over the course of 3.5 hours. An hour after the addition was complete, a subsurface nitrogen sparge was introduced into the reactor. The reaction was monitored for completion by liquid chromatography . When the reaction was complete, vacuum was applied to the reactor for 1.0 hour to remove the bulk of the excess phenol. The product was analyzed by liquid chromatography and found to contain 96.1% by area bisaryl diphosphate (monomer and higher oligomers) and 4.5 wt% triphenyl phosphate.
- Step 1 Phosphorus oxychloride (671. Og, 4.38 moles) and magnesium chloride (0.58g, 0.0061 moles) were charged into a flask equipped with a stirrer, heating mantle, temperature controller, and a reflux condenser vented to a water absorber. The flask contents were heated to 100°C. Bisphenol A (288.5g, 1.26 moles) was placed in a solids addition funnel and added to the flask over the course of 3 hours. At that time, the flask contents were heated to reflux and the reaction monitored for completion by liquid chromatography. After the reaction was complete, the flask was equipped for distillation and vacuum gradually applied until the pressure was less than 20 torr. The temperature of the flask contents was allowed to increase to 180°C during this process. When the temperature reached 180°C, the distillation was stopped and the material was subsequently used in the second step.
- Step 2 The contents of the flask from step 1 were heated to 165°C. Phenol (432.6g, 4.60 moles) was charged into an addition funnel wrapped with heat tape. The phenol was added to the reactor over the course of 2 hours. An hour after the addition was complete, a subsurface nitrogen sparge was introduced into the reactor. The reaction was monitored for completion by liquid chromatography. When the reaction was complete, vacuum was applied to the evaporator to remove the remaining phenol. The final product was analyzed by liquid chromatography and found to contain 98.7% by area bisaryl diphosphate (monomer and higher oligomers) and 0.76 wt% triphenyl phosphate.
- Step 1 Phosphorus oxychloride and bisphenol A were reacted under magnesium chloride catalysis as described in Example 2, Step 1 (semi-continuous addition of BPA).
- the bisphenol A was analyzed for moisture prior to the reaction.
- Two different reactions were run using two different water levels in the bisphenol A.
- the product of both reactions was analyzed by liquid chromatography to determine the amount of monomeric and dimeric product.
- the table below shows that use of dry bisphenol A results in a step 1 intermediate product that has a higher content of the monomeric product relative to the dimeric product.
- Step 1 Two reactions were run to generate step 1 intermediate product as described in Example 2, Step 1 (semi-continuous addition of BPA). In both cases, bisphenol A with a moisture content of ⁇ 200 ppm water was used. Normalized area % monomer content of the final product was >81%.
- Step 2 The material from each of the step 1 reactions was reacted with phenol as described in Example 2, Step 2. The two reactions used phenol which had two different levels of moisture. The product was analyzed by liquid chromatography for the monomeric and dimeric content and analyzed by titration for acidity. The data in the table below show that the increased moisture in the phenol had no impact on the normalized monomer content in the final product. However, the acidity of the final product was affected.
- the bisphenol A bis (diphenyl) phosphate produced in the above examples is compounded into various polymer resins using a Berstorff 25 mm twin screw extruder equipped with a • -• 4 inch wide, variable speed, DC drive belt feeder.
- the twin screw extruder settings are tabulated below.
- the bisphenol A bis (diphenyl) phosphate is heated in a 4-liter stainless steel resin kettle to approximately 80°C. 0 While the bisphenol A bis (diphenyl) phosphate is heating, the belt feeder containing the polymer resin is calibrated to deliver the required feed rate into the throat of the extruder .
- the heated Zenith pump is calibrated to deliver the desired feed rate of bisphenol A bis(diphenyl) phosphate into the third barrel of the twin screw extruder.
- the pumping system is then connected to the extruder by attaching the feedlines into the injection port located at the third barrel.
- the polymer resin is fed into the twin screw extruder at the throat.
- the resin is allowed to pass through the extruder for several minutes before the bisphenol A bis (diphenyl) phosphate is added in order to ensure that any residual clean out material is purged from the extruder.
- the pumping system is started and bisphenol A bis (diphenyl) phosphate is injected into the extruder through the feedlines and the injection port.
- the melt pressure measured at the interface between the seventh barrel and the die, is used as an indication that the bisphenol A bis (diphenyl) phosphate is being incorporated into the polymer resin.
- the base polymer resin generally has a melt pressure reading 100-200 psi greater than the bisphenol A bis(di ⁇ henyl) phosphate formulated polymer resin. Once the bisphenol A bis(diphenyl) phosphate is incorporated into the polymer resin, the melt pressure drops 100-200 psi due to bisphenol A bis(diphenyl) phosphate's ability to improve the flow properties of the polymer resin.
- the material passes through the extruder die and strands through a water bath used for cooling.
- the cooled strands of formulated polymer resin are pellitized and used for molding flammability and physical test bars.
- PPO/HIPS 20% bisphenol A bis(diphenyl) phosphate & 80% PPO/HIPS
- PC/ABS 11% bisphenol A bis (diphenyl) phosphate £ ⁇ 89% PC/ABS
- PBT 10% bisphenol A bis(diphenyl) phosphate & 90% PBT.
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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)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002281106A CA2281106A1 (en) | 1997-02-14 | 1998-02-10 | Process for making and using bisaryl diphosphates |
EP98906465A EP0971935A4 (en) | 1997-02-14 | 1998-02-10 | Process for making and using bisaryl diphosphates |
IL13137998A IL131379A0 (en) | 1997-02-14 | 1998-02-10 | A flame retardant polymer resin containing bisaryl diphosphate and a method for making the same |
BR9808644-8A BR9808644A (en) | 1997-02-14 | 1998-02-10 | Process for the manufacture and use of bisaryl diphosphates |
JP53598698A JP2001512510A (en) | 1997-02-14 | 1998-02-10 | Methods for producing and using bisaryldiphosphates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US3873497P | 1997-02-14 | 1997-02-14 | |
US60/038,734 | 1997-02-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998035970A1 true WO1998035970A1 (en) | 1998-08-20 |
Family
ID=21901584
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/002968 WO1998035970A1 (en) | 1997-02-14 | 1998-02-10 | Process for making and using bisaryl diphosphates |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0971935A4 (en) |
JP (1) | JP2001512510A (en) |
KR (1) | KR20000071089A (en) |
CN (1) | CN1252073A (en) |
BR (1) | BR9808644A (en) |
CA (1) | CA2281106A1 (en) |
IL (1) | IL131379A0 (en) |
WO (1) | WO1998035970A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000077012A1 (en) * | 1999-06-11 | 2000-12-21 | Albemarle Corporation | Bisphenol-a bis(diphenyl phosphate)-based flame retardant |
US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
US6420465B1 (en) | 2000-10-16 | 2002-07-16 | Bayer Aktiengesellschaft | Process for preparing phosphoric acid esters |
US6489502B2 (en) | 2000-10-16 | 2002-12-03 | Bayer Aktiengesellschaft | Process for preparing phosphoric acid esters |
US6706907B1 (en) | 1999-08-18 | 2004-03-16 | Daihachi Chemical Industry Co. Ltd. | Method of purifying organic phosphoric ester |
WO2005049722A1 (en) * | 2003-11-19 | 2005-06-02 | Songwon Industrial Co.,Ltd | Flame retardant containing organophosphorous compound, its preparation process, and flame retardant resin composition comprising same |
WO2010075276A1 (en) | 2008-12-22 | 2010-07-01 | Icl-Ip America Inc. | Water miscible solvent based process for purifying a bisphosphate |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6613928B1 (en) * | 1999-07-27 | 2003-09-02 | Daihachi Chemical Industry Co., Ltd. | Process for the preparation of condensed phosphoric esters |
JP4536185B2 (en) * | 1999-11-05 | 2010-09-01 | 大八化学工業株式会社 | Method for producing condensed phosphate ester |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
US4267127A (en) * | 1978-07-29 | 1981-05-12 | Bayer Aktiengesellschaft | Process for the production of phosphoric acid triesters |
US5135973A (en) * | 1989-02-27 | 1992-08-04 | Polyplastics Co., Ltd. | Flame-retardant polyester resin composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9325575D0 (en) * | 1993-12-14 | 1994-02-16 | Dow Benelux | Flame retardant styrenic polymer compositions |
WO1997012925A1 (en) * | 1995-09-29 | 1997-04-10 | Toshiba Chemical Corporation | Halogen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
EP0918780A4 (en) * | 1996-06-13 | 1999-07-21 | Great Lakes Chemical Corp | Process to prepare aryldiphosphoric esters |
-
1998
- 1998-02-10 BR BR9808644-8A patent/BR9808644A/en not_active Application Discontinuation
- 1998-02-10 WO PCT/US1998/002968 patent/WO1998035970A1/en not_active Application Discontinuation
- 1998-02-10 IL IL13137998A patent/IL131379A0/en unknown
- 1998-02-10 JP JP53598698A patent/JP2001512510A/en active Pending
- 1998-02-10 EP EP98906465A patent/EP0971935A4/en not_active Withdrawn
- 1998-02-10 CN CN98804140A patent/CN1252073A/en active Pending
- 1998-02-10 KR KR1019997007376A patent/KR20000071089A/en not_active Application Discontinuation
- 1998-02-10 CA CA002281106A patent/CA2281106A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
US4267127A (en) * | 1978-07-29 | 1981-05-12 | Bayer Aktiengesellschaft | Process for the production of phosphoric acid triesters |
US5135973A (en) * | 1989-02-27 | 1992-08-04 | Polyplastics Co., Ltd. | Flame-retardant polyester resin composition |
Non-Patent Citations (1)
Title |
---|
See also references of EP0971935A4 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000077012A1 (en) * | 1999-06-11 | 2000-12-21 | Albemarle Corporation | Bisphenol-a bis(diphenyl phosphate)-based flame retardant |
US6319432B1 (en) | 1999-06-11 | 2001-11-20 | Albemarle Corporation | Bisphenol-A bis(diphenyl phosphate)-based flame retardant |
US6706907B1 (en) | 1999-08-18 | 2004-03-16 | Daihachi Chemical Industry Co. Ltd. | Method of purifying organic phosphoric ester |
US6420465B1 (en) | 2000-10-16 | 2002-07-16 | Bayer Aktiengesellschaft | Process for preparing phosphoric acid esters |
US6489502B2 (en) | 2000-10-16 | 2002-12-03 | Bayer Aktiengesellschaft | Process for preparing phosphoric acid esters |
US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
WO2002048158A1 (en) * | 2000-12-11 | 2002-06-20 | Albemarle Corporation | Purification of arylene polyphosphate esters |
WO2005049722A1 (en) * | 2003-11-19 | 2005-06-02 | Songwon Industrial Co.,Ltd | Flame retardant containing organophosphorous compound, its preparation process, and flame retardant resin composition comprising same |
WO2010075276A1 (en) | 2008-12-22 | 2010-07-01 | Icl-Ip America Inc. | Water miscible solvent based process for purifying a bisphosphate |
US8299149B2 (en) | 2008-12-22 | 2012-10-30 | Icl-Ip America Inc. | Water miscible solvent based process for purifying a bisphosphate |
Also Published As
Publication number | Publication date |
---|---|
JP2001512510A (en) | 2001-08-21 |
EP0971935A4 (en) | 2000-04-19 |
CA2281106A1 (en) | 1998-08-20 |
IL131379A0 (en) | 2001-01-28 |
CN1252073A (en) | 2000-05-03 |
BR9808644A (en) | 2000-05-23 |
EP0971935A1 (en) | 2000-01-19 |
KR20000071089A (en) | 2000-11-25 |
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