WO2005049722A1 - Flame retardant containing organophosphorous compound, its preparation process, and flame retardant resin composition comprising same - Google Patents
Flame retardant containing organophosphorous compound, its preparation process, and flame retardant resin composition comprising same Download PDFInfo
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- WO2005049722A1 WO2005049722A1 PCT/KR2004/001237 KR2004001237W WO2005049722A1 WO 2005049722 A1 WO2005049722 A1 WO 2005049722A1 KR 2004001237 W KR2004001237 W KR 2004001237W WO 2005049722 A1 WO2005049722 A1 WO 2005049722A1
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- WIPO (PCT)
- Prior art keywords
- flame retardant
- dihydroxydiphenylmethane
- preparing
- compound
- condensed
- Prior art date
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- 150000002903 organophosphorus compounds Chemical class 0.000 title claims abstract description 87
- 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 83
- 239000003063 flame retardant Substances 0.000 title claims abstract description 83
- 239000011342 resin composition Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 51
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 claims abstract description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 34
- -1 oxy phosphorous chloride Chemical compound 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012442 inert solvent Substances 0.000 claims description 8
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 125000005023 xylyl group Chemical group 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 32
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 125000004437 phosphorous atom Chemical group 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000002485 combustion reaction Methods 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 15
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 229910052698 phosphorus Inorganic materials 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- 239000003517 fume Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 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 11
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 229920000265 Polyparaphenylene Polymers 0.000 description 9
- 229920005668 polycarbonate resin Polymers 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000004431 polycarbonate resin Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007850 degeneration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass 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
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- 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
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 241000546339 Trioxys Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MCIXCJIARTZWCW-UHFFFAOYSA-N n-(1,5-dimethyl-3-oxo-2-phenylpyrazol-4-yl)-2-hydroxybenzamide Chemical compound O=C1N(C=2C=CC=CC=2)N(C)C(C)=C1NC(=O)C1=CC=CC=C1O MCIXCJIARTZWCW-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011227 reinforcement additive Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229940089401 xylon Drugs 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
-
- 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
- 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 System
- 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
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Definitions
- the present invention relates to a flame retardant, and particularly to a flame retardant comprising an organophosphorus compound having a low viscosity and a low volatility, a method for preparing the same, and a flame retardant resin composition comprising the same.
- the conventional flame retardant for inflammable resin is generally composed of an organic halide due to economic grounds.
- the flame retardant resin comprising the organic halide has a demerit in that it generates a poisonous gas when it burns.
- an acid gas and a pollutant chemical material are generated, which is serious problems due to an increase in the consumption of the plastics.
- One proposal thereof is a flame retardant essentially consisting of an organophosphorus compound.
- the flame retardant is generally requested to have high flame retardancy, as well as a low cost, miscibility with the resin, to be non- migrative, have a low volatility, and to be non-hydrolytic or to have non-ester changeable properties.
- Triphenyl phosphate is known to be the simplest and cheapest compound among the organophosphorus compounds thus far, but it has demerits in that it evaporates with smoke during the shaping process at high temperatures to degenerate the working environment since it tends to be easily volatilized due to its low molecular weight. Further, also due to its low molecular weight, it has additional demerits in that the softening point of the resin comprising the same decreases and the mechanical strength thereof decreases, and migration of the flame retardant from the resin occurs.
- Japanese Patent Publication No. Sho 51-19858 Japanese Laid-open Patent Publication No. Sho 59-202240, and Japanese Patent Publication No. Hei 2-18336 disclose condensed organophosphorus compounds having 2 or more phosphorus atoms in one molecule.
- Such a condensed organophosphorus compound is widely employed as a flame retardant for polyphenylene ether resin, polyphenylene ether-polystyrene mixed resin, polycarbonate resin, and polycarbonate- ABS mixed resin, and so on.
- the condensed organophosphorus compound is in the form of either a highly viscous liquid or a glass phase solid having a low softening point, rendering it difficult to handle.
- the highly condensed organophosphorus compound causes a remarkable increase in viscosity of a material comprising the same, and thus, in order to apply it as a flame retardant, a pre-treatment process such as pre-heating is required to decrease the viscosity. Accordingly, handling and processing properties should be improved.
- the present invention is to provide a flame retardant comprising an organophosphorus compound as a main component, which has low volatility, prevents degeneration of a working environment, and has remarkably improved handling property due to its low viscosity, and a flame retardant resin composition comprising the same.
- One aspect of the present invention relates to a flame retardant having a low viscosity and a low volatility comprising an organophosphorus compound represented by the following formula 1 as a main component:
- R is a phenyl, tolyl, or xylyl group
- a divalent phenol of dihydroxydiphenylmethane comprised in the organophosphorus compound comprises 60% or less of 4,4'-dihydroxydiphenylmethane and 40% or more of the total amount of 2,2'-dihydroxyldiphenylmethane and 2,4'-dihydroxyldiphenylmethane, and a flame retardant resin composition comprising the same.
- Another aspect of the present invention relates to a method for preparing a flame retardant comprising the organophosphorus compound represented by the Formula 1, comprising the steps of: condensing a phenol and a formaldehyde in the presence of an acidic catalyst selected from the group consisting of a diluted sulfuric acid, paratoluene sulfonic acid, and phosphoric acid to prepare a dihydroxydiphenylmethane composition comprising 60% or less of 4,4-dihydroxydiphenylmethane and 40% or more cf the total amount of 2,2'-dihydroxydiphenylmethane and 2,4'-dihydroxydiphenylmethane; and reacting the dihydroxydiphenylmethane composition with an oxy phosphorous chloride to obtain a compound represented by the following Formula 2, and then removing the excessive amount of oxy phosphorus chloride and reacting the compound with monovalent phenols.
- an acidic catalyst selected from the group consisting of a diluted sulfuric acid, parato
- FIG. 1 shows an infrared absorption spectrum cf dihydroxy diphenylmethane prepared by the method of one embodiment (Example 1-1) according to the present invention
- FIG. 2 shows an infrared absorption spectrum cf a dihydroxy diphenylmethane prepared by the method of one embodiment (Example 1-2) according to the present invention
- FIG. 3 shows an infrared absorption spectrum cf a condensed organophosphorus compound prepared by the conventional method (Comparative Example 1);
- Fig. 4 shows an infrared absorption spectrum of a condensed organophosphorus compound prepared by the conventional method (Comparative Example 2). Best Mode
- Embodiments cf the present invention will now be described in detail with reference to the accompanying drawings.
- One aspect cf the present invention provides a flame retardant comprising an organophosphorus compound represented by the following Formula 1 as a main component:: [21] ⁇ Formula 1> R - O O - R
- R is a phenyl, tolyl, or xylyl group
- a divalent phenol of dihydroxydiphenylmethane comprised in the organophosphorus compound comprises 60% or less of 4,4'-dihydroxydiphenylmethane and 40% or more of the total amounts of 2,2'-dihydroxyldiphenylmethane and 2,4'-dihydroxyldiphenylmethane.
- Another aspect of the present invention relates to a method for preparing a flame retardant comprising an organophosphorus compound represented by the Formula 1, which method comprises the steps of: condensing a phenol and a formaldehyde in the presence of an acidic catalyst selected from the group consisting cf a diluted sulfuric acid, paratoluene sulfonic acid, and phosphoric acid to prepare dihydroxydiphenylmethane composition comprising 60% or less of 4,4-dihydroxy diphenylmethane and 40% or more cf the total amount of 2,2'-dihydroxy diphenylmethane and 2,4'-dihydroxy diphenylmethane; and reacting the dihydroxydiphenylmethane composition with an oxy phosphorous chloride to obtain a compound represented by the following Formula 2, and then removing the excessive amount of oxy phosphorus chloride and reacting the compound with monovalent phenols:
- the flame retardant according to the present invention comprises 70% by weight or more, more preferably 80% by weight or more, of an organophosphorus compound represented by the Formula 1, having two phosphorus atoms per molecule (hereinafter, referred to as a condensed compound, excepting Examples); and 30% by weight or less, more preferably 20% by weight or less, of a highly condensed organophosphorus compound having three (3) or more phosphorus atoms per molecule (hereinafter, referred to as a highly condensed compound, excepting Examples); and a non- condensed organophosphorus compound having only one phosphorus atom per molecule (hereinafter, referred as a non-condensed compound, excepting Examples).
- the flame retardant according to the present invention has a low viscosity as well as a low volatility.
- the condensed compound represented by the Formula 1 sufficiently improves the volatility and the migrative properties of the organophosphorus compound.
- a highly condensed compound just increases the viscosity, but does not remarkably improve volatility and migration-preventing properties.
- the attempts to decrease the amount of the non- condensed compound have been carried out by substantially increasing the amount of highly condensed compound, which causes an increase in viscosity of the organophosphorus compound.
- the amount of the non-condensed compound together with the highly condensed compound remains as small as possible, so that the problems caused by the high viscosity are solved. Further, the viscosity of the condensed compound is suitably controlled by changing the kinds and the compositions cf the bivalent phenol.
- the viscosity cf the condensed compound decreases when the dihydroxydiphenylmethane composition is employed as the bivalent phenol, excepting resorcin and hydroquinone having comparatively smaller molecular weight. Further, it is surprisingly found that the viscosity decreases when the amount of 4,4'-dihydroxydiphenylmethane is 60% or less and the total amount of 2,2'- dihydroxydiphenylmethane and 2,4'- dihydroxydiphenylmethane is 40% or more. When the amount of 4,4'-dihydroxydiphenylmethane is more than 60%, the viscosity of the condensed compound improperly increases.
- the flame retardant having a low volatility and a low viscosity comprising the organophosphorus compound according to the present invention is prepared by combining a process for preparing a dihydroxydiphenylmethane composition and a process for preparing a condensed phosphorus compound using the obtained dihydroxydiphenylmethane, while suppressing the generation of the non-condensed compound together with the highly condensed compound.
- the dihydroxydiphenylmethane would be prepared by the condensed reaction between the excess cf phenol and the formaldehyde in the presence cf an acidic catalyst, in this case it is typically hard to avoid generation of a highly condensed polymer of tri- or more valence phenols, so-called poly nuclear units.
- the organophosphorus compound is prepared using a material comprising a large amount of the polynuclear units, it causes problems in that the generated material has a high viscosity, and in the worst case, a gelling process occurs during the preparation process.
- the condensed units that do not fall within the polynuclear unit are also used for resin material. Such condensed units may be used prior to removing the polynuclear units via a purification process, and they are called bisphenol-F.
- the dihydroxydiphenylmethane composition comprises 49% by weight of 4,4-dihydroxydiphenylmethane, 41% by weight of 2,4-dihydroxydiphenylmethane, 6.5% by weight of 2,2'-dihydroxydiphenylmethane, and 3.5% by weight of tri-nuclear units.
- the dihydroxydiphenylmethane composition is used to prepare a condensed organophosphorus compound.
- a sufficient amount of an oxy phosphorus chloride is reacted with the dihydroxydiphenylmethane composition in the presence cf a catalyst cf magnesium chloride, and an excess amount of oxy phosphorus chloride is removed, and then mono-valence phenols are added to complete the reaction.
- the reaction with the mono- valence phenols is carried out using an excess amount of phenols under a mild reaction condition in order to avoid generation of a highly condensed organophosphorus compound and a non-condensed organophosphorus compound.
- the excess amount of phenol is removed by vacuum evaporation after washing, neutralizing, and dehydrating.
- the example of the phenols according to the present invention may include, but is not limited to, phenol, ortho-cresol, para-cresol, 2,4-xylenol, or 2,6-xylenol, and is preferably phenol.
- a flame retardant comprising the phosphorus compound as a main component has good compatibility with polyphenylene ether-polystyrene mixed resin, polycarbonate resin, or polycarbonate- ABS mixed resin, and provides a good flame retardant effect to these resins.
- the polyphenylene ether-polystyrene mixed resin is a resin wherein the polymer compound obtained by oxidation polymerization cf 2,6-xylenol is mixed with polystyrene or high-impact polystyrene in order to improve the processibility and impact resistance. It is a so-called polymer alloy having heat resistance.
- the polycarbonate resin is a polymer compound polycondensed by blowing a phosgene into an alkali salt aqueous solution of bisphenol-A containing a tiny amount cf mono-phenol as a terminal group, and having transparency and impact resistance.
- the polycarbonate- ABS mixed resin is a polymer alloy of polycarbonate and ABS resin.
- ABS resin is very difficult to make flame retardant by an organophosphorus compound alone, but a polymer alloy thereof is easily made flame retardant by an organophosphorus compound alone.
- the condensed phosphorus compound cf the present invention is added in an amount of 5 to 30% by weight, more preferably 7 to 25% by weight, and still more preferably 10 to 20% by weight, to achieve the object of providing the flame retardant and the flame retardant resin composition cf the present invention.
- the flame retardant condensed phosphorus compound When the flame retardant condensed phosphorus compound is added in an amount of less than 5% by weight, the flame retardant effect is not sufficient. When more than 30% by weight is added, it is not preferably due to the possibility of degeneration of the resin physical properties.
- the degeneration of physical properties cf the resin means that heat resistance, tensile strength, or hardness of the resin is degenerated.
- the flame-retardant resin composition may further comprise one or more conventional additives for the resin such as a flame retardant of the organophosphorus compound other than the flame retardant of the present invention, an antioxidant, a photo stabilizer, a dye, a pigment, a plasticizer, a filler, and a reinforcement additive.
- a flame retardant of the organophosphorus compound other than the flame retardant of the present invention an antioxidant, a photo stabilizer, a dye, a pigment, a plasticizer, a filler, and a reinforcement additive.
- a dihydroxydiphenylmethane composition is basically prepared by condensation of phenol and formaldehyde in the presence of an acidic catalyst. However, if the condensation reaction is carried out as a homogeneous reaction, using an excessive amount cf phenol is unavoidable in order to inhibit generation of polynuclear units, production efficiency per volume of a reactor decreases, and a large amount of phenol must be recovered, thus making the process uneconomical.
- formaldehyde source a formaldehyde polymer or trioxy acid, so called formalin and paraform, is used, and formalin is preferable.
- the formalin can be loaded in a non-homogeneous mixture of sufficiently mixed phenol and acidic catalyst. It is preferable to use a somewhat smaller amount of formalin than a theoretical amount required for dihydroxydiphenylmethane composition, i.e. 40 to 95%, more preferably 60 to 90%.
- phenol is used with very low excessiveness that cannot be expected in a homogeneous reaction designed to inhibit the generation of polynuclear units, making the process very economical.
- the temperature of the condensation reaction is preferably low and within a range that does not make reaction speed significantly low.
- Reaction temperature is preferably 20 to 120 °C , more preferably 40 to 110 °C , and still more preferably 50 to 100 °C .
- an inert solvent that does not disturb non-homogeneity of the reaction can be added.
- cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, chlorinated hydrocarbon, and the like can be exemplified.
- the reaction mixture is stood to separate a lower layer comprising a mixture cf water and a catalyst cf phosphoric acid, and an upper layer comprising a dihydroxydiphenylmethane composition dissolved in an inert solvent that is employed if necessary.
- the dihydroxydiphenylmethane composition in the upper layer is washed, and then the employed solvent and excess phenol can be removed by distillation.
- the dihydroxydiphenylmethane composition is prepared by the above process, it can be employed as an inexpensive divalent phenol in the present invention.
- the dihydroxydiphenylmethane composition prepared by the above process is used to prepare the condensed compound of the present invention.
- the present invention uses a process for preparing a condensed compound designed so as to inhibit the generation of a highly condensed compound and a non-condensed compound.
- the condensation reaction is carried out in two chemical steps (i) and (ii).
- the common process wherein divalent phenol, phenol, and oxy phosphorus chloride are simultaneously reacted in the presence of a catalyst such as magnesium chloride cannot obtain an organophosphorus compound of the present invention.
- a catalyst such as magnesium chloride
- 2 molecules of oxy phosphorus chloride are condensed at both terminals of divalent phenol.
- the main product cf this step is represented by the following Chemical Formula 2:
- the reaction mixture passed through these chemical steps is washed and neutralized to remove a catalyst and an acidic material.
- an organic solvent can be used.
- cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, and the like can be exemplified.
- the excess amount of phenol employed can be finally removed by vacuum distillation.
- composition of the condensed organophosphorus compound prepared by the step (b) employing the dihydroxydiphenylmethane composition prepared by the step (a), oxy phosphorus chloride and phenol is as follows:
- TPP Non-condensed compound
- a compound having 3 phosphorus atoms in one molecule (highly condensed compound): 11.0 wt%
- a compound having 4 phosphorus atoms in one molecule (highly condensed compound): 1.5 wt%
- TPP is triphenylphosphate
- R in Chemical Formula 1 is a phenyl group.
- step (a) cf preparing dihydroxydiphenylmethane composition plays an important role in terms of low viscosity.
- a flame retardant resin composition is prepared, and any method commonly used in the art can be used without limitation.
- the example of the present invention employed a Henschel mixer and an extrusion molder to prepare a test piece.
- Example 1-1 Preparation cf dihydroxydiphenylmethane composition
- the reaction mixture was aged for 1 hour and stood to separate the contents cf the flask into 2 layers. After removing the upper layer containing a mixture cf water and phosphoric acid, the residue was washed twice with 750 g of water. Excess phenol and toluene were removed under reduced pressure, and the residue was cooled to obtain 1001 g of dihydroxydiphenylmethane composition in an almost white crystal form.
- the obtained compound was found to comprise 49 wt% of 4,4-dihydroxydiphenylmethane, 41 wt% cf 2,4'-dihydroxydiphenylmethane, 6.5 wt% of 2,2'-dihydorxydiphenylmethane, and 3.5 wt% cf tri-nuclear units, and it contained trace amounts of phenol and quaternary- nuclear units.
- the infrared absorption spectrum cf the dihydroxydiphenylmethane composition is shown in Fig. 1.
- Example 2 Preparation of flame retardant polyphenylene ether-polvstyrene mixed resin [97] To 100 parts by weight cf a non-flame retardant polyphenylene ether-polystyrene mixed resin that did not contain an organophosphorus compound (Xylon: Japan, Asahi Corporation), 12 parts by weight of the condensed organophosphorus compound obtained in Example 1-2 were added and mixed in a Henschel mixer.
- organophosphorus compound Xylon: Japan, Asahi Corporation
- the mixture was injected into an extrusion molder at 300 °C to mold a test piece for a combustion test having a length of 125mm, a width of 13 mm, and a thickness of 2 mm. No fume generation was observed in the Henschel mixer or the extrusion molder.
- a combustion test was carried out according to 'Test for Flammability of Plastic Materials-UL94' of American Underwriters Laboratories. Combustion tests for the other Examples and Comparative Examples were carried out, and the results are shown in Table 1.
- the condensed organophosphorus compound obtained in Example 1-2 had low viscosity, and could be easily drawn from a reactor even at room temperature of 25 °C .
- Example 2 The same procedure was carried out as in Example 2, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 2 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 1, to prepare a test piece, and a combustion test was carried out using the same. No smoke generation was observed in the Henschel mixer or the extrusion molder. However, since the condensed organophosphorus compound prepared in Comparative Example 1 had high viscosity and could not be drawn from the reactor, it was heated to 70 °C .
- Comparative Example 4 Preparation of flame retardant polycarbonate resin composition using the crude product of Comparative Example 1 [105] The same procedure was carried out as in Example 3, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 3 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 1, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 78% compared with those which did not contain a flame retardant.
- Comparative Example 5 Preparation of flame retardant polycarbonate- ABS mixed resin using the crude product of Comparative Example 1
- Example 4 The same procedure was carried out as in Example 4, except that 18 parts by weight of the condensed organophosphorus compound employed in Example 4 were replaced with 18 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 1, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder.
- Example 2 The same procedure was carried out as in Example 2, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 2 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 2, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder. However, since the condensed organophosphorus compound prepared in Comparative Example 2 had slightly high viscosity and could not be drawn from the reactor, it was heated to 40 °C .
- Comparative Example 7 Preparation of flame retardant polycarbonate resin composition using the crude product of Comparative Example 2
- Example 3 The same procedure was carried out as in Example 3, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 3 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 2, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 72% compared with those which did not contain flame retardant.
- Comparative Example 8 Preparation of flame retardant polycarbonate- ABS mixed resin using the crude product of Comparative Example 2
- Example 4 The same procedure was carried out as in Example 4, except that 18 parts by weight of the condensed organophosphorus compound employed in Example 4 were replaced with 18 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 2, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder.
- Example 2 The same procedure was carried out as in Example 2, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 2 were replaced with 12 parts by weight of triphenylphosphate, to prepare a test piece, and a combustion test was carried out using the same. Significant fume generation was observed in the Henschel mixer and the extrusion molder.
- Example 3 The same procedure was carried out as in Example 3, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 3 were replaced with 12 parts by weight of triphenylphosphate, to prepare a test piece, and a combustion test was carried out using the same. Significant fume generation was observed in the Henschel mixer and the extrusion molder. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 69% compared with those which did not contain a flame retardant.
- Example 4 The same procedure was carried out as in Example 4, except that 18 parts by weight of the condensed organophosphorus compound employed in Example 4 were replaced with 18 parts by weight of triphenylphosphate, to prepare a test piece, and a combustion test was carried out using the same. Significant fume generation was observed in the Henschel mixer and the extrusion molder.
- PPE-PS a polyphenylene ether-polystyrene mixed resin
- PC-ABS polycarbonate- ABS mixed resin
- V-0 and V-l indicate grades according to combustion test (TJL-94 Vertical Burning Test).
- the flame retardant comprising a condensed organophosphorus compound represented by the Formula 1 as a main component and prepared by the combination of two steps as exemplified in Examples 1-1 and 1-2, has a low viscosity, a low solidifying point, and a low volatility, and can be easily handled, and thus can largely decrease or remove fuming during the processes of preparing a flame retardant resin composition and a molded product, thereby improving the working environment.
- dihydroxydiphenylmethane that is a starting material of a condensed organophosphorus compound can be prepared by a simple method to provide divalent phenol with low cost, economical effects are offered to a flame retardant.
Abstract
Disclosed are a flame retardant comprising a main component of an organo phosphorus compound, wherein a divalent phenol of dihydroxydiphenylmethane comprised in the organo phosphorus compound comprises 60% or less of 4,4'-dihydroxydiphenylmethane and 40% or more of a total amount of 2,2'-dihydroxyldiphenylmethane and 2,4'-dihydroxyldiphenylmethane; a method of preparing the same, and a flame retardant resin composition comprising the same. The obtained flame retardant has a low viscosity and volatility and it is easy to handle it, and thereby it facilitates easy preparation of the same.
Description
Description FLAME RETARDANT CONTAINING ORGANOPHOSPHOROUS COMPOUND, ITS PREPARATION PROCESS, AND FLAME RETARDANT RESIN COMPOSITION COMPRISING SAME Technical Field
[1] The present invention relates to a flame retardant, and particularly to a flame retardant comprising an organophosphorus compound having a low viscosity and a low volatility, a method for preparing the same, and a flame retardant resin composition comprising the same. Background Art
[2] The conventional flame retardant for inflammable resin is generally composed of an organic halide due to economic grounds. However, the flame retardant resin comprising the organic halide has a demerit in that it generates a poisonous gas when it burns. Further, when waste plastic materials consisting of the organic halide are burned, an acid gas and a pollutant chemical material are generated, which is serious problems due to an increase in the consumption of the plastics. Accordingly, it is highly demanded to provide a new flame retardant having a high stability, other than the organic halide. One proposal thereof is a flame retardant essentially consisting of an organophosphorus compound. The flame retardant is generally requested to have high flame retardancy, as well as a low cost, miscibility with the resin, to be non- migrative, have a low volatility, and to be non-hydrolytic or to have non-ester changeable properties.
[3] Triphenyl phosphate is known to be the simplest and cheapest compound among the organophosphorus compounds thus far, but it has demerits in that it evaporates with smoke during the shaping process at high temperatures to degenerate the working environment since it tends to be easily volatilized due to its low molecular weight. Further, also due to its low molecular weight, it has additional demerits in that the softening point of the resin comprising the same decreases and the mechanical strength thereof decreases, and migration of the flame retardant from the resin occurs.
[4] In order to solve the afore-mentioned problems caused by the low molecular weight organophosphorus compound, Japanese Patent Publication No. Sho 51-19858, Japanese Laid-open Patent Publication No. Sho 59-202240, and Japanese Patent
Publication No. Hei 2-18336 disclose condensed organophosphorus compounds having 2 or more phosphorus atoms in one molecule. Such a condensed organophosphorus compound is widely employed as a flame retardant for polyphenylene ether resin, polyphenylene ether-polystyrene mixed resin, polycarbonate resin, and polycarbonate- ABS mixed resin, and so on. Typically, the condensed organophosphorus compound is in the form of either a highly viscous liquid or a glass phase solid having a low softening point, rendering it difficult to handle.
[5] Although a non-condensed organophosphorus compound having only one phosphorus atom per molecule such as triphenyl phosphate has problems in volatility and migration as mentioned above, such problems can be sufficiently improved by the condensed organophosphorus compound having two phosphorus atoms per molecule. Japanese Laid-open Patent Publication No. Sho 59-202240 discloses a large amount of a highly condensed organophosphorus compound having 3 or more phosphorus atoms per molecule in order to decrease the amount of non-condensed organophosphorus having a low molecular weight and having only one phosphorus atom per molecule. However, the highly condensed organophosphorus compound causes a remarkable increase in viscosity of a material comprising the same, and thus, in order to apply it as a flame retardant, a pre-treatment process such as pre-heating is required to decrease the viscosity. Accordingly, handling and processing properties should be improved.
[6] Further, as bivalent phenols that can be used as the condensed organophosphorus compound, resorcin, hydroquinone, bisphenol-A, bisphenol-F, or bisphenol-S can be mentioned. However, these are expensive, and thus increase the cost compared with the conventional triphenyl phosphate. Disclosure
[7] The present invention is to provide a flame retardant comprising an organophosphorus compound as a main component, which has low volatility, prevents degeneration of a working environment, and has remarkably improved handling property due to its low viscosity, and a flame retardant resin composition comprising the same.
[8] One aspect of the present invention relates to a flame retardant having a low viscosity and a low volatility comprising an organophosphorus compound represented by the following formula 1 as a main component:
[9] < [Formula 1>
R - O O - R
[10] wherein R is a phenyl, tolyl, or xylyl group;
[11] wherein a divalent phenol of dihydroxydiphenylmethane comprised in the organophosphorus compound comprises 60% or less of 4,4'-dihydroxydiphenylmethane and 40% or more of the total amount of 2,2'-dihydroxyldiphenylmethane and 2,4'-dihydroxyldiphenylmethane, and a flame retardant resin composition comprising the same.
[12] Another aspect of the present invention relates to a method for preparing a flame retardant comprising the organophosphorus compound represented by the Formula 1, comprising the steps of: condensing a phenol and a formaldehyde in the presence of an acidic catalyst selected from the group consisting of a diluted sulfuric acid, paratoluene sulfonic acid, and phosphoric acid to prepare a dihydroxydiphenylmethane composition comprising 60% or less of 4,4-dihydroxydiphenylmethane and 40% or more cf the total amount of 2,2'-dihydroxydiphenylmethane and 2,4'-dihydroxydiphenylmethane; and reacting the dihydroxydiphenylmethane composition with an oxy phosphorous chloride to obtain a compound represented by the following Formula 2, and then removing the excessive amount of oxy phosphorus chloride and reacting the compound with monovalent phenols.
[13] <Formula 2>
? CH2 ? 2(CI P-0- @f ^ -O-P i Cl)2
Description of Drawings
[14] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate an embodiment of the invention, and together with the description, serve to explain the principles cf the invention.
[15] FIG. 1 shows an infrared absorption spectrum cf dihydroxy diphenylmethane prepared by the method of one embodiment (Example 1-1) according to the present invention;
[16] FIG. 2 shows an infrared absorption spectrum cf a dihydroxy diphenylmethane prepared by the method of one embodiment (Example 1-2) according to the present
invention; [17] FIG. 3 shows an infrared absorption spectrum cf a condensed organophosphorus compound prepared by the conventional method (Comparative Example 1); and [18] Fig. 4 shows an infrared absorption spectrum of a condensed organophosphorus compound prepared by the conventional method (Comparative Example 2). Best Mode [19] Embodiments cf the present invention will now be described in detail with reference to the accompanying drawings. [20] One aspect cf the present invention provides a flame retardant comprising an organophosphorus compound represented by the following Formula 1 as a main component:: [21] <Formula 1> R - O O - R
R - O - - O - R
o o
[22] wherein R is a phenyl, tolyl, or xylyl group;
[23] wherein a divalent phenol of dihydroxydiphenylmethane comprised in the organophosphorus compound comprises 60% or less of 4,4'-dihydroxydiphenylmethane and 40% or more of the total amounts of 2,2'-dihydroxyldiphenylmethane and 2,4'-dihydroxyldiphenylmethane.
[24] Another aspect of the present invention relates to a method for preparing a flame retardant comprising an organophosphorus compound represented by the Formula 1, which method comprises the steps of: condensing a phenol and a formaldehyde in the presence of an acidic catalyst selected from the group consisting cf a diluted sulfuric acid, paratoluene sulfonic acid, and phosphoric acid to prepare dihydroxydiphenylmethane composition comprising 60% or less of 4,4-dihydroxy diphenylmethane and 40% or more cf the total amount of 2,2'-dihydroxy diphenylmethane and 2,4'-dihydroxy diphenylmethane; and reacting the dihydroxydiphenylmethane composition with an oxy phosphorous chloride to obtain a compound represented by the following Formula 2, and then removing the excessive amount of oxy phosphorus chloride and reacting the compound with monovalent phenols:
[25] <Formula 2>
[26] The flame retardant according to the present invention comprises 70% by weight or more, more preferably 80% by weight or more, of an organophosphorus compound represented by the Formula 1, having two phosphorus atoms per molecule (hereinafter, referred to as a condensed compound, excepting Examples); and 30% by weight or less, more preferably 20% by weight or less, of a highly condensed organophosphorus compound having three (3) or more phosphorus atoms per molecule (hereinafter, referred to as a highly condensed compound, excepting Examples); and a non- condensed organophosphorus compound having only one phosphorus atom per molecule (hereinafter, referred as a non-condensed compound, excepting Examples). Hence, the flame retardant according to the present invention has a low viscosity as well as a low volatility.
[27] The inventors found that the condensed compound represented by the Formula 1 sufficiently improves the volatility and the migrative properties of the organophosphorus compound. A highly condensed compound just increases the viscosity, but does not remarkably improve volatility and migration-preventing properties. As mentioned above, the attempts to decrease the amount of the non- condensed compound have been carried out by substantially increasing the amount of highly condensed compound, which causes an increase in viscosity of the organophosphorus compound.
[28] According to the present invention, the amount of the non-condensed compound together with the highly condensed compound remains as small as possible, so that the problems caused by the high viscosity are solved. Further, the viscosity of the condensed compound is suitably controlled by changing the kinds and the compositions cf the bivalent phenol.
[29] According to the present invention, it is found that the viscosity cf the condensed compound decreases when the dihydroxydiphenylmethane composition is employed as the bivalent phenol, excepting resorcin and hydroquinone having comparatively smaller molecular weight. Further, it is surprisingly found that the viscosity decreases when the amount of 4,4'-dihydroxydiphenylmethane is 60% or less and the total amount of 2,2'- dihydroxydiphenylmethane and 2,4'- dihydroxydiphenylmethane is 40% or more. When the amount of 4,4'-dihydroxydiphenylmethane is more than 60%, the viscosity of the condensed compound improperly increases.
[30] On the other hand, there is close relationship between the amount cf 4,4'-dihydroxydiphenylmethane and the solidifying point of the condensed compound. For example, as the solidifying point of the condensed compound derived from 4,4'-dihydroxydiphenylmethane having purity of 97% is 7 °C , it is hard to handle it in the winter season. Further, the solidifying point of the condensed compound derived from the composition containing 4,4'-dihydroxydiphenylmethane having purity of 55% is -8 °C , it is not hard to handle it due to the solidification even in the winter season. Accordingly, the viscosity of the flame retardant can be controlled both by the condensed compound and by the dihydroxydiphenylmethane comprised in the condensed compound.
[31] The flame retardant having a low volatility and a low viscosity comprising the organophosphorus compound according to the present invention is prepared by combining a process for preparing a dihydroxydiphenylmethane composition and a process for preparing a condensed phosphorus compound using the obtained dihydroxydiphenylmethane, while suppressing the generation of the non-condensed compound together with the highly condensed compound.
[32] Although the dihydroxydiphenylmethane would be prepared by the condensed reaction between the excess cf phenol and the formaldehyde in the presence cf an acidic catalyst, in this case it is typically hard to avoid generation of a highly condensed polymer of tri- or more valence phenols, so-called poly nuclear units. When the organophosphorus compound is prepared using a material comprising a large amount of the polynuclear units, it causes problems in that the generated material has a high viscosity, and in the worst case, a gelling process occurs during the preparation process. The condensed units that do not fall within the polynuclear unit are also used for resin material. Such condensed units may be used prior to removing the polynuclear units via a purification process, and they are called bisphenol-F.
[33] However, 2,2'-dihydroxydiphenylmethane and 2,4'-dihydroxydiphenylmethane substantially disappear, and thereby 4,4-dihydroxydiphenylmethane is highly concentrated in the bisphenol-F. If the bisphenol-F is used for the organophosphorus compound of the present invention, the resultant condensed compound has a high viscosity and a high solidifying point, which is not suitable for the present invention.
[34] It is possible to achieve the object cf the present invention of providing the low viscosity and low volatility organo phosphorus compound by designing the process of preparing the dihydroxydiphenylmethane composition so as to generate polynuclear units and 4,4'-dihydroxydiphenylmethane in as small amount as possible. According to
one embodiment cf the present invention, the dihydroxydiphenylmethane composition comprises 49% by weight of 4,4-dihydroxydiphenylmethane, 41% by weight of 2,4-dihydroxydiphenylmethane, 6.5% by weight of 2,2'-dihydroxydiphenylmethane, and 3.5% by weight of tri-nuclear units. Accordingly, a condensed phenol comprising quaternary or higher nuclear units is seldom seen. Although all organo phosphorus compounds generated from the tri-nuclear units are highly condensed compounds, there are no problems to obtain a low viscosity organo phosphorus compound when the tri-nuclear units are present in an amount of 5% by weight or less.
[35] According to one embodiment cf the present invention, the dihydroxydiphenylmethane composition is used to prepare a condensed organophosphorus compound. For example, a sufficient amount of an oxy phosphorus chloride is reacted with the dihydroxydiphenylmethane composition in the presence cf a catalyst cf magnesium chloride, and an excess amount of oxy phosphorus chloride is removed, and then mono-valence phenols are added to complete the reaction. The reaction with the mono- valence phenols is carried out using an excess amount of phenols under a mild reaction condition in order to avoid generation of a highly condensed organophosphorus compound and a non-condensed organophosphorus compound. The excess amount of phenol is removed by vacuum evaporation after washing, neutralizing, and dehydrating. The example of the phenols according to the present invention may include, but is not limited to, phenol, ortho-cresol, para-cresol, 2,4-xylenol, or 2,6-xylenol, and is preferably phenol.
[36] A flame retardant comprising the phosphorus compound as a main component has good compatibility with polyphenylene ether-polystyrene mixed resin, polycarbonate resin, or polycarbonate- ABS mixed resin, and provides a good flame retardant effect to these resins. The polyphenylene ether-polystyrene mixed resin is a resin wherein the polymer compound obtained by oxidation polymerization cf 2,6-xylenol is mixed with polystyrene or high-impact polystyrene in order to improve the processibility and impact resistance. It is a so-called polymer alloy having heat resistance. The polycarbonate resin is a polymer compound polycondensed by blowing a phosgene into an alkali salt aqueous solution of bisphenol-A containing a tiny amount cf mono-phenol as a terminal group, and having transparency and impact resistance.
[37] Further, the polycarbonate- ABS mixed resin is a polymer alloy of polycarbonate and ABS resin. The ABS resin composed of an acryl monomer, butadiene, and styrene has impact resistance, is prepared by various methods, and is useful for a polymer alloy. ABS resin is very difficult to make flame retardant by an organophosphorus
compound alone, but a polymer alloy thereof is easily made flame retardant by an organophosphorus compound alone. The condensed phosphorus compound cf the present invention is added in an amount of 5 to 30% by weight, more preferably 7 to 25% by weight, and still more preferably 10 to 20% by weight, to achieve the object of providing the flame retardant and the flame retardant resin composition cf the present invention. When the flame retardant condensed phosphorus compound is added in an amount of less than 5% by weight, the flame retardant effect is not sufficient. When more than 30% by weight is added, it is not preferably due to the possibility of degeneration of the resin physical properties. The degeneration of physical properties cf the resin means that heat resistance, tensile strength, or hardness of the resin is degenerated.
[38] The flame-retardant resin composition may further comprise one or more conventional additives for the resin such as a flame retardant of the organophosphorus compound other than the flame retardant of the present invention, an antioxidant, a photo stabilizer, a dye, a pigment, a plasticizer, a filler, and a reinforcement additive.
[39] The best mode for carrying out the present invention is explained in detail hereinafter.
[40] Firstly, preparation cf the dihydroxydiphenylmethane composition of the present invention (the step (a)), wherein the dihydroxydiphenylmethane composition having a suitable composition for preparing a low viscosity condensed organophosphorus compound is prepared, is explained. Secondly, preparation of a condensed organo compound using the obtained dihydroxydiphenylmethane composition (the step (b)), wherein a condensed organophosphorus compound is prepared while inhibiting the generation of a highly condensed compound and a non-condensed compound in order to realize low viscosity and low volatility, is explained. The steps (a) and (b) are designed so as to satisfy the object of the present invention, hence they are considered as necessary parts in this invention. Thirdly, the flame retardant having a main component of condensed compound obtained from the steps (a) and (b) is prepared. Any conventional methods can be applied for this step.
[41] The step (a) is now explained. A dihydroxydiphenylmethane composition is basically prepared by condensation of phenol and formaldehyde in the presence of an acidic catalyst. However, if the condensation reaction is carried out as a homogeneous reaction, using an excessive amount cf phenol is unavoidable in order to inhibit generation of polynuclear units, production efficiency per volume of a reactor decreases, and a large amount of phenol must be recovered, thus making the process
uneconomical.
[42] In order to decrease excessiveness cf the amount cf phenol, it is preferable to carry out the condensation reaction as a non-homogeneous reaction. In order to carry out the non-homogeneous reaction, diluted sulfuric acid, paratoluene sulfonic acid aqueous solution or phosphoric acid is used as an acidic catalyst, and phosphoric acid is preferable. And, it is preferable to employ a significantly larger amount of phosphoric acid than a usual catalyst amount. The phosphoric acid is used in an amount of 5 to 200% by weight, more preferably 20 to 150% by weight, and most preferably 40 to 100% by weight, based on the amount of phenol.
[43] As a formaldehyde source, a formaldehyde polymer or trioxy acid, so called formalin and paraform, is used, and formalin is preferable. The formalin can be loaded in a non-homogeneous mixture of sufficiently mixed phenol and acidic catalyst. It is preferable to use a somewhat smaller amount of formalin than a theoretical amount required for dihydroxydiphenylmethane composition, i.e. 40 to 95%, more preferably 60 to 90%. Thus, phenol is used with very low excessiveness that cannot be expected in a homogeneous reaction designed to inhibit the generation of polynuclear units, making the process very economical.
[44] In order to make the composition of the dihydroxydiphenylmethane composition suitable for the present invention, the temperature of the condensation reaction is preferably low and within a range that does not make reaction speed significantly low. Reaction temperature is preferably 20 to 120 °C , more preferably 40 to 110 °C , and still more preferably 50 to 100 °C . In order to carry out the condensation reaction smoothly and inhibit the generation of polynuclear units, an inert solvent that does not disturb non-homogeneity of the reaction can be added.
[45] As preferable inert solvents, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, chlorinated hydrocarbon, and the like can be exemplified. After completion of the reaction, the reaction mixture is stood to separate a lower layer comprising a mixture cf water and a catalyst cf phosphoric acid, and an upper layer comprising a dihydroxydiphenylmethane composition dissolved in an inert solvent that is employed if necessary. The dihydroxydiphenylmethane composition in the upper layer is washed, and then the employed solvent and excess phenol can be removed by distillation. When the dihydroxydiphenylmethane composition is prepared by the above process, it can be employed as an inexpensive divalent phenol in the present invention.
[46] Then, in the step (b), the dihydroxydiphenylmethane composition prepared by the
above process is used to prepare the condensed compound of the present invention. As mentioned above, the present invention uses a process for preparing a condensed compound designed so as to inhibit the generation of a highly condensed compound and a non-condensed compound.
[47] For this, the condensation reaction is carried out in two chemical steps (i) and (ii). The common process wherein divalent phenol, phenol, and oxy phosphorus chloride are simultaneously reacted in the presence of a catalyst such as magnesium chloride cannot obtain an organophosphorus compound of the present invention. In the chemical step (i), 2 molecules of oxy phosphorus chloride are condensed at both terminals of divalent phenol. The main product cf this step is represented by the following Chemical Formula 2:
[48] <Chemical Formula 2> 9 CH2 9 2(d )- P-0- <gT " -0-P i Cl);
[49] For this, a somewhat excess amount of oxy phosphorus chloride is used. The excess oxy phosphorus chloride is recovered and removed by distillation after completion of the reaction. In order to carry out the reaction smoothly and to conveniently recover and remove oxy phosphorus chloride, if necessary, an inert solvent can be added. As preferable inert solvents, xylene, ethylbenzene, chlorobenzene, and the like can be exemplified. In the chemical step (ii), the chemical step (i) is completed, and excess oxy phosphorus chloride is removed and then excess phenol is added. In order to make condensation reaction conditions as mild as possible, and inhibit unnecessary esterffication or generation of a highly condensed compound and a non-condensed compound due to non-homogeneity, it is preferable to carry out the reaction using an excess amount of phenol at a low temperature as long as reaction speed is not lowered.
[50] The reaction mixture passed through these chemical steps is washed and neutralized to remove a catalyst and an acidic material. In order to decrease the viscosity and specific gravity of the reaction mixture and carry out the post-treatment process smoothly, an organic solvent can be used. As preferable organic solvents, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, and the like can be exemplified. The excess amount of phenol employed can be finally removed by vacuum distillation.
[51] For example, the composition of the condensed organophosphorus compound
prepared by the step (b) employing the dihydroxydiphenylmethane composition prepared by the step (a), oxy phosphorus chloride and phenol is as follows:
[52] Non-condensed compound (TPP): 3.5 wt%
[53] Condensed compound (corresponding to Chemical Formula 1): 84.0 wt%
[54] A compound having 3 phosphorus atoms in one molecule (highly condensed compound): 11.0 wt%
[55] A compound having 4 phosphorus atoms in one molecule (highly condensed compound): 1.5 wt%
[56] A compound having 5 phosphorus atoms in one molecule (highly condensed compound): trace amount
[57] Wherein TPP is triphenylphosphate, and R in Chemical Formula 1 is a phenyl group.
[58] Since only highly condensed compounds are produced from a small amount of tri- nuclear units existing in the dihydroxydiphenylmethane composition, the step (a) cf preparing dihydroxydiphenylmethane composition plays an important role in terms of low viscosity.
[59] Finally, in the step (c), a flame retardant resin composition is prepared, and any method commonly used in the art can be used without limitation. The example of the present invention employed a Henschel mixer and an extrusion molder to prepare a test piece.
[60] The present invention is explained with reference to Examples and Comparative Examples hereinafter. Preparation of an organophosphorus compound and then preparation cf a resin composition are described. Examples 1-1, 1-2, and Comparative Examples 1 and 2 relate to preparation of condensed organophosphorus compounds, and Examples 2 to 4 relate to preparation of resin compositions using condensed organophosphorus compounds prepared in Examples 1-2 and combustion tests thereof. In Comparative Example 3 and thereafter, preparation of resin compositions using an organophosphorus compound that is compared with the organophosphorus compound of the present invention and combustion tests thereof are described.
[61] Example 1-1: Preparation cf dihydroxydiphenylmethane composition
[62] Into a 5000 ml five-necked flask made of hard glass, equipped with a stirrer, a thermometer, a reflux cooler, a load lot, and a gas inhaler, 1880 g of phenol (20 mol), 1000 g of toluene, and 908 g of phosphoric acid were introduced. Nitrogen gas was infused through a gas inhaler, the flask was heated while stirring to elevate the temperature cf the mixture to 60 °C , and then 429 g cf 35% formalin (5 mol) were
slowly loaded on the load lot. Approximately 5 hours were required for loading of the formalin.
[63] After completion of the loading, the reaction mixture was aged for 1 hour and stood to separate the contents cf the flask into 2 layers. After removing the upper layer containing a mixture cf water and phosphoric acid, the residue was washed twice with 750 g of water. Excess phenol and toluene were removed under reduced pressure, and the residue was cooled to obtain 1001 g of dihydroxydiphenylmethane composition in an almost white crystal form.
[64] As a result cf liquid chromatography analysis, the obtained compound was found to comprise 49 wt% of 4,4-dihydroxydiphenylmethane, 41 wt% cf 2,4'-dihydroxydiphenylmethane, 6.5 wt% of 2,2'-dihydorxydiphenylmethane, and 3.5 wt% cf tri-nuclear units, and it contained trace amounts of phenol and quaternary- nuclear units. The infrared absorption spectrum cf the dihydroxydiphenylmethane composition is shown in Fig. 1.
[65] Example 1-2: Preparation cf condensed organophosphorus compound
[66] Into a 5000 ml four-necked flask made of hard glass, equipped with a stirrer, a thermometer, a reflux cooler connected to a gas treating unit in the upper part, and a gas inhaler, 1001 g of the dihydroxydiphenylmethane composition obtained in Example 1-1, 3833 g cf oxy phosphorus chloride, and 3 g cf magnesium chloride were introduced. Nitrogen gas was infused through a gas inhaler, and the flask was heated while stirring to carry out first condensation.
[67] The reaction was somewhat endothermic, and was carried out at 107 °C while oxy phosphorus chloride was refluxed and hydrogen chloride gas was smoothly generated. Simultaneously with the reaction, the temperature of the reaction mixture was slowly elevated but was maintained at 107 °C to complete the first condensation. The completion of the reaction was determined by NMR analysis of the reaction mixture and stopping of generation of hydrogen chloride gas.
[68] Approximately 6 hours were required for completing the condensation reaction. Then, the reflux cooler was replaced with a vacuum distiller, and an excess amount cf oxy phosphorus chloride was removed with a vacuum distiller with the gas inhaler closed. Again, the gas inhaler was opened, the vacuum distiller was replaced with a reflux cooler, and then 1833 g of phenol were added. The contents cf the flask were heated to 125 °C , and the next condensation was carried out.
[69] The progress and completion cf the reaction were determined by stopping of generation of hydrogen chloride gas, NMR analysis, and liquid chromatography
analysis. Approximately 7 hours were required for completion of the reaction. After completion of the reaction, 1150 g of toluene were added, and then the reaction mixture was transferred to a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a reflux cooler, a load lot, and an outlet in the lower part. 810 g of water were added through a load lot while stirring, the flask was heated, and the mixture was boiled at about 87 °C . [70] After stirring for 30 minutes, the reaction mixture was stood. After removing the aqueous solution in the lower layer, 810 g of water were added through a load lot, and the same procedure was repeated. Then, 800 g of 1% sodium bicarbonate aqueous solution were added through a load lot and the same procedure was repeated. Finally, 810 g of water were added through a load lot, and the same procedure was repeated. The reaction mixture was dehydrated by azeotropic distillation with toluene, and filtered to remove pollutants. Toluene and excess phenol were removed by distillation from the filtrate. The distillation was carried out with an increasing depressurization degree, finally under 50 Torr, 130 °C . The residue was cooled to obtain 2978 g of a somewhat viscous light yellowish transparent liquid. The viscosity was 118 centipoise at 70 °C , and the solidifying point was -9 °C . The analysis results by liquid chromatography are as follows: [71] A compound having 1 phosphorus atom in one molecule: 3.2%
[72] A compound having 2 phosphorus atoms in one molecule: 84.4%
[73] A compound having 3 phosphorus atoms in one molecule: 10.8%
[74] A compound having 4 phosphorus atoms in one molecule: 1.5%
[75] A compound having 5 phosphorus atoms in one molecule: trace amount
[76] Phenol: trace amount
[77] Wherein % means weight %, and phosphorus contents were 9.6%. The infrared absorption spectrum is shown in Fig. 2. [78] Comparative Example 1 : Preparation of condensed organophosphorus compound using 4.4'-dihydroxydiphenylmethane having high purity [79] The same procedure as in Example 1-2 was carried out, except that 1001 g of dihydroxydiphenylmethane composition employed in Example 1-2 were replaced with 151.5 g of bisphenol-F comprising 97% of 4,4'-dihydroxydiphenylmethane, and a total of 3% of 2,4'-dihydroxydiphenylmethane and 2,2'-dihydroxydiphenylmethane was used, to obtain 332.7 g of condensed organophosphorus compound. The obtained compound was a somewhat yellowish and significantly viscous liquid, and had a viscosity cf 902 centipoise at 70 °C , and a solidifying point of 7 °C . The analysis
results by liquid chromatography are as follows: [80] A compound having 1 phosphorus atom in one molecule: 3.3%
[81] A compound having 2 phosphorus atoms in one molecule: 86.7%
[82] A compound having 3 phosphorus atoms in one molecule: 9.0%
[83] A compound having 4 phosphorus atoms in one molecule: 0.9%
[84] A compound having 5 phosphorus atoms in one molecule: trace amount
[85] Phenol: trace amount
[86] Wherein % means weight %, and the contents of phosphorus were 9.5%. The infrared absorption spectrum is shown in Fig. 3. [87] Comparative Example 2: Preparation of a condensed organophosphorus compound using bisphenol A [88] The same procedure as in Example 1-2 was carried out, except that 1001 g of dihydroxydiphenylmethane composition was changed to 167.5 g of commercial bisphenol- A, to obtain 482.6 g of condensed organophosphorus compound. The obtained compound was a viscous light yellowish liquid, with a viscosity of 318 centipoise at 70 °C . The analysis results by liquid chromatography are as follows: [89] A compound having 1 phosphorus atom in one molecule: 3.5%
[90] A compound having 2 phosphorus atoms in one molecule: 86.1%
[91] A compound having 3 phosphorus atoms in one molecule: 9.2%
[92] A compound having 4 phosphorus atoms in one molecule: 1.0%
[93] A compound having 5 phosphorus atoms in one molecule: trace amount
[94] Phenol: trace amount
[95] Wherein % means weight %, and the contents of phosphorus were 9.0%. The infrared absorption spectrum is shown in Fig. 4. [96] Example 2: Preparation of flame retardant polyphenylene ether-polvstyrene mixed resin [97] To 100 parts by weight cf a non-flame retardant polyphenylene ether-polystyrene mixed resin that did not contain an organophosphorus compound (Xylon: Japan, Asahi Corporation), 12 parts by weight of the condensed organophosphorus compound obtained in Example 1-2 were added and mixed in a Henschel mixer. The mixture was injected into an extrusion molder at 300 °C to mold a test piece for a combustion test having a length of 125mm, a width of 13 mm, and a thickness of 2 mm. No fume generation was observed in the Henschel mixer or the extrusion molder. For the test piece, a combustion test was carried out according to 'Test for Flammability of Plastic Materials-UL94' of American Underwriters Laboratories. Combustion tests for the
other Examples and Comparative Examples were carried out, and the results are shown in Table 1. The condensed organophosphorus compound obtained in Example 1-2 had low viscosity, and could be easily drawn from a reactor even at room temperature of 25 °C .
[98] Example 3: Preparation of flame retardant polycarbonate resin composition
[99] To 100 parts by weight cf a non-flame retardant polycarbonate that did not contain an organophosphorus compound (Eupirone: Japan, Mitsubishi Gas Chemical Company), 12 parts by weight of the condensed organophosphorus compound obtained in Example 1-2 were added, and the resultant was molded to a test piece of the same shape as in Example 2 with an extrusion molder at 300 °C by the same procedure as in Example 2. No fume generation was observed in the Henschel mixer or the extrusion molder. A combustion test was carried out by the same procedure as in Example 2. The results are shown in Table 1. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 82% compared with those which did not contain a flame retardant.
[100] Example 4: Preparation of flame-retardant polycarbonate- ABS mixed resin
[101] 45 parts by weight cf a non-flame retardant polycarbonate that did not contain an organophosphorus compound, 55 parts by weight of non-flame retardant ABS resin (Dore Company) that did not contain an organophosphorus compound, and 18 parts by weight of the condensed organophosphorus compound obtained in Example 1-2 were mixed in a Henschel mixer, and a test piece for a combustion test was prepared by the same procedure as in Example 2. No fume generation was observed in the Henschel mixer or the extrusion molder.
[102] Comparative Example 3: Preparation of flame retardant polyphenylene ether- polvstyrene mixed resin using the crude product cf Comparative Example 1
[103] The same procedure was carried out as in Example 2, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 2 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 1, to prepare a test piece, and a combustion test was carried out using the same. No smoke generation was observed in the Henschel mixer or the extrusion molder. However, since the condensed organophosphorus compound prepared in Comparative Example 1 had high viscosity and could not be drawn from the reactor, it was heated to 70 °C .
[104] Comparative Example 4: Preparation of flame retardant polycarbonate resin composition using the crude product of Comparative Example 1
[105] The same procedure was carried out as in Example 3, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 3 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 1, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 78% compared with those which did not contain a flame retardant.
[106] Comparative Example 5: Preparation of flame retardant polycarbonate- ABS mixed resin using the crude product of Comparative Example 1
[107] The same procedure was carried out as in Example 4, except that 18 parts by weight of the condensed organophosphorus compound employed in Example 4 were replaced with 18 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 1, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder.
[108] Comparative Example 6: Preparation of flame retardant polyphenylene ether- polvstyrene mixed resin using the crude product cf Comparative Example 2
[109] The same procedure was carried out as in Example 2, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 2 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 2, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder. However, since the condensed organophosphorus compound prepared in Comparative Example 2 had slightly high viscosity and could not be drawn from the reactor, it was heated to 40 °C .
[110] Comparative Example 7: Preparation of flame retardant polycarbonate resin composition using the crude product of Comparative Example 2
[111] The same procedure was carried out as in Example 3, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 3 were replaced with 12 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 2, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 72% compared with those which did not
contain flame retardant.
[112] Comparative Example 8: Preparation of flame retardant polycarbonate- ABS mixed resin using the crude product of Comparative Example 2
[113] The same procedure was carried out as in Example 4, except that 18 parts by weight of the condensed organophosphorus compound employed in Example 4 were replaced with 18 parts by weight of the condensed organophosphorus compound prepared in Comparative Example 2, to prepare a test piece, and a combustion test was carried out using the same. No fume generation was observed in the Henschel mixer or the extrusion molder.
[114] Comparative Example 9: Preparation of flame retardant polyphenylene ether- polystyrene mixed resin using triphenylphosphate
[115] The same procedure was carried out as in Example 2, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 2 were replaced with 12 parts by weight of triphenylphosphate, to prepare a test piece, and a combustion test was carried out using the same. Significant fume generation was observed in the Henschel mixer and the extrusion molder.
[116] Comparative Example 10: Preparation of flame retardant polycarbonate resin composition using triphenylphosphate
[117] The same procedure was carried out as in Example 3, except that 12 parts by weight of the condensed organophosphorus compound employed in Example 3 were replaced with 12 parts by weight of triphenylphosphate, to prepare a test piece, and a combustion test was carried out using the same. Significant fume generation was observed in the Henschel mixer and the extrusion molder. The average molecular weight of the test piece was measured by a viscosimetric method to have decreased to 69% compared with those which did not contain a flame retardant.
[118] Comparative Example 11: Preparation of flame retardant polycarbonate- ABS mixed resin using triphenylphosphate
[119] The same procedure was carried out as in Example 4, except that 18 parts by weight of the condensed organophosphorus compound employed in Example 4 were replaced with 18 parts by weight of triphenylphosphate, to prepare a test piece, and a combustion test was carried out using the same. Significant fume generation was observed in the Henschel mixer and the extrusion molder.
[120] Table 1
[121]
[122] PPE-PS: a polyphenylene ether-polystyrene mixed resin
[123] PC: polycarbonate resin
[124] PC-ABS: polycarbonate- ABS mixed resin
[125] TPP: triphenylphosphate
[126] In the Table, V-0 and V-l indicate grades according to combustion test (TJL-94 Vertical Burning Test).
[127] As shown in the Examples and the Comparative Examples, the flame retardant comprising a condensed organophosphorus compound represented by the Formula 1 as a main component and prepared by the combination of two steps as exemplified in Examples 1-1 and 1-2, has a low viscosity, a low solidifying point, and a low volatility, and can be easily handled, and thus can largely decrease or remove fuming during the processes of preparing a flame retardant resin composition and a molded product, thereby improving the working environment. In addition, according to the present invention, since dihydroxydiphenylmethane that is a starting material of a condensed organophosphorus compound can be prepared by a simple method to provide divalent phenol with low cost, economical effects are offered to a flame retardant.
Claims
[1] A flame retardant comprising an organophosphorus compound represented by the following formula 1 as a main component: <Formula 1> R - O O - R I C H J I R - O - P - O -< O YQV O - P - O - R o o wherein R is a phenyl, tolyl, or xylyl group; wherein a divalent phenol of dihydroxydiphenylmethane in the organophosphorus composition comprises 60% or less of 4,4'-dihydroxydiphenylmethane and 40% or more of a total amount cf 2,2'-dihydroxyldiphenylmethane and 2,4'-dihydroxyldiphenylmethane.
[2] The flame retardant according to claim 1, wherein the organophosphorus compound represented by the formula 1 is contained in an amount of 70% by weight or more, based on the total weight of the flame retardant.
[3] The flame retardant according to claim 1, wherein R is phenyl in the Formula 1.
[4] A flame retardant resin composition comprising the flame retardant according to claim 1.
[5] The flame retardant resin composition according to claim 4, wherein the flame retardant is contained in an amount of 5-30% by weight of the composition.
[6] A method for preparing a flame retardant comprising an organophosphorus compound represented by the following Formula 1, comprising: (a) condensing a phenol and a formaldehyde in the presence cf an acidic catalyst selected from the group consisting of a diluted sulfuric acid, paratoluene sulfonic acid, and phosphoric acid to prepare a dihydroxydiphenylmethane composition comprising 60% or less of 4,4-dihydroxy diphenylmethane and 40% or more of a total amount of 2,2'-dihydroxydiphenylmethane and 2,4'-dihydroxydiphenylmethane; and (b) reacting the dihydroxydiphenylmethane composition with an oxy phosphorous chloride to obtain a compound represented by the following Formula 2, and then removing an excessive amount of oxy phosphorus chloride and reacting the compound with monovalent phenols: <Formula 1>
R - O O - R
[7] The method for preparing the flame retardant according to claim 6, wherein the acidic catalyst is phosphoric acid. [8] The method for preparing the flame retardant according to claim 7, wherein the phosphoric acid is added in an amount of 5-200% by weight. [9] The method for preparing the flame retardant according to claim 6, wherein the phenol is reacted in an amount of 40-95% by weight of the theoretical amount required for the dihydroxy diphenylmethane. [10] The method for preparing the flame retardant according to claim 6, wherein the dihydroxy diphenylmethane is reacted in an inert solvent. [11] The method for preparing the flame retardant according to claim 10, wherein the inert solvent is selected from the group consisting cf cyclohexane, methyl cy- clohexane, benzene, toluene, xylene, ethylbenzene, and chlorinated hydro- carbonate. [12] The method for preparing the flame retardant according to claim 6, wherein the dihydroxydiphenylmethane composition is reacted at a temperature cf 20 to 120 °C . [13] The method for preparing the flame retardant according to claim 6, wherein the catalyst used for preparing the condensed organophosphorus compound is magnesium chloride. [14] The method for preparing the flame retardant according to claim 6, further comprising post-treatment steps of washing and neutralizing the reaction mixture. [15] The method for preparing the flame retardant according to claim 14, wherein the post-treatment is carried out in an inert solvent selected from the group consisting of cyclohexane, benzene, toluene, xylene, ethyl benzene, and
chlorinated hydrocarbonate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020030082090A KR20050048218A (en) | 2003-11-19 | 2003-11-19 | Flame retardant containing organophosphorous compound, its preparation process, and flame retardant resin composition containing the same |
| KR10-2003-0082090 | 2003-11-19 |
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| Publication Number | Publication Date |
|---|---|
| WO2005049722A1 true WO2005049722A1 (en) | 2005-06-02 |
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ID=34617251
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2004/001237 WO2005049722A1 (en) | 2003-11-19 | 2004-05-25 | Flame retardant containing organophosphorous compound, its preparation process, and flame retardant resin composition comprising same |
Country Status (2)
| Country | Link |
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| KR (1) | KR20050048218A (en) |
| WO (1) | WO2005049722A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015041614A1 (en) * | 2013-09-20 | 2015-03-26 | Aditya Birla Chemicals (Thailand) Ltd | Improved manufacturing process for dihydroxydiphenylmethane with high selectivity for 2,4'- dihydroxydiphenylmethane |
| CN107629086A (en) * | 2017-09-25 | 2018-01-26 | 浙江万盛股份有限公司 | A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants |
| US10246551B2 (en) * | 2015-02-26 | 2019-04-02 | International Business Machines Corporation | Flame-retardant polymers derived from polyols and polyacids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
| SU449027A1 (en) * | 1972-10-11 | 1974-11-05 | Предприятие П/Я Р-6830 | The method of obtaining 4,4-dioxydiphenylmethane |
| EP0331173A1 (en) * | 1988-03-04 | 1989-09-06 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing 4,4'-dihydroxydiphenylmethane |
| US5455292A (en) * | 1992-08-06 | 1995-10-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Hydrolytically stable, halogen-free flame retardant resin composition |
| WO1998035970A1 (en) * | 1997-02-14 | 1998-08-20 | Great Lakes Chemical Corporation | Process for making and using bisaryl diphosphates |
| WO1999055771A1 (en) * | 1998-04-29 | 1999-11-04 | Great Lakes Chemical Corporation | Continuous process for the manufacture of phosphoric acid esters |
| WO2002032911A1 (en) * | 2000-10-16 | 2002-04-25 | Bayer Aktiengesellschaft | Method for producing phosphoric acid esters |
-
2003
- 2003-11-19 KR KR1020030082090A patent/KR20050048218A/en not_active Application Discontinuation
-
2004
- 2004-05-25 WO PCT/KR2004/001237 patent/WO2005049722A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
| SU449027A1 (en) * | 1972-10-11 | 1974-11-05 | Предприятие П/Я Р-6830 | The method of obtaining 4,4-dioxydiphenylmethane |
| EP0331173A1 (en) * | 1988-03-04 | 1989-09-06 | Mitsubishi Petrochemical Co., Ltd. | Process for preparing 4,4'-dihydroxydiphenylmethane |
| US5455292A (en) * | 1992-08-06 | 1995-10-03 | Asahi Kasei Kogyo Kabushiki Kaisha | Hydrolytically stable, halogen-free flame retardant resin composition |
| WO1998035970A1 (en) * | 1997-02-14 | 1998-08-20 | Great Lakes Chemical Corporation | Process for making and using bisaryl diphosphates |
| WO1999055771A1 (en) * | 1998-04-29 | 1999-11-04 | Great Lakes Chemical Corporation | Continuous process for the manufacture of phosphoric acid esters |
| WO2002032911A1 (en) * | 2000-10-16 | 2002-04-25 | Bayer Aktiengesellschaft | Method for producing phosphoric acid esters |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015041614A1 (en) * | 2013-09-20 | 2015-03-26 | Aditya Birla Chemicals (Thailand) Ltd | Improved manufacturing process for dihydroxydiphenylmethane with high selectivity for 2,4'- dihydroxydiphenylmethane |
| US10683250B2 (en) | 2013-09-20 | 2020-06-16 | Aditya Birla Chemicals (Thailand) Ltd. | Manufacturing process for dihydroxydiphenylmethane with high selectivity for 2,4′-dihydroxydiphenylmethane |
| US10246551B2 (en) * | 2015-02-26 | 2019-04-02 | International Business Machines Corporation | Flame-retardant polymers derived from polyols and polyacids |
| CN107629086A (en) * | 2017-09-25 | 2018-01-26 | 浙江万盛股份有限公司 | A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants |
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| KR20050048218A (en) | 2005-05-24 |
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