EP0000132B1 - Halogenhaltige Phosphorsäureester; polymere Präparate, welche diese als Flammschutzmittel enthalten - Google Patents

Halogenhaltige Phosphorsäureester; polymere Präparate, welche diese als Flammschutzmittel enthalten Download PDF

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Publication number
EP0000132B1
EP0000132B1 EP78100131A EP78100131A EP0000132B1 EP 0000132 B1 EP0000132 B1 EP 0000132B1 EP 78100131 A EP78100131 A EP 78100131A EP 78100131 A EP78100131 A EP 78100131A EP 0000132 B1 EP0000132 B1 EP 0000132B1
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Prior art keywords
phosphate
halogen
hydroxyl
bis
composition
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EP78100131A
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French (fr)
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EP0000132A1 (de
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James Andrew Albright
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Velsicol Chemical LLC
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Velsicol Chemical LLC
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/906—Polyurethane cellular product containing unreacted flame-retardant material

Definitions

  • This invention pertains to certain novel esters of pentavalent phosphorus acid and to plastic compositions containing these esters as flame retardants therefor.
  • any flame retardant in polymers or polymeric compositions is measured not only by the flame retardant capability of the additive but also by the ability of the additive to improve or modify, or at least not to detract from, other physical or mechanical properties of the polymer or polymeric composition.
  • the mere fact, therefore, that most flame retardants contain halogen and phosphorus atoms does not assure that any given halogenated or phosphorus-containing compound will impart usable flame retarding characteristics to all or even to any polymeric system.
  • U.S. Patent 3,132,169 to Birum et al. discloses flame retardant esters of pentavalent phosphorus acids, which esters contain both chlorine and bromine, and which are selected from the class consisting of a phosphate of the general formula wherein R is selected from the class consisting of hydrogen, alkyl and haloalkyl radicals of from 1 to 2 carbon atoms, R' is selected from the class consisting of hydrogen, alkyl and haloalkyl radicals of from 1 to 5 carbon atoms, R" is selected from the class consisting of R' and hydrocarbyloxymethyl radicals of from 1 to 8 carbon atoms, wherein one R" at a pair of adjacent carbon atoms must be hydrogen, and n is an integer from 0 to 1.
  • U.S. Patent 3,781,388 to Jenkner et al. discloses flameproofing agents having the general formula wherein R, is a halogen-containing alkyl radical containing 2 to 4 carbon atoms and 1 to 3 halogen atoms; R 2 is an alkyl radical containing 2 to 4 carbon atoms which may also optionally contain at least one halogen atom and/or at least one OH group; and R 3 is an alkyl group containing 2 to 4 carbon atoms and one OH group.
  • U.S. Patent 3,830,886 to Davis et al. discloses flame retardant additives of the general formula wherein n is zero or one; R is a lower alkyl; phenyl or alkylated phenyl having one to three lower alkyl substituents, R' is R or and at least one R" is Br or CI and each remaining R" is OH, Br, or Cl.
  • Birum et al. does not disclose that the compounds therein can contain hydroxyl substituents attached to the neopentyl group.
  • the indiscriminate substitution of a hydroxyl group for a halogen or hydrogen atom of a compound will often result in a dramatic decrease in the modified hydroxy substituted compound's hydrolytic and thermal stability.
  • Davis et al. discloses triesters of phosphorus acid in which one of the ester groups is a lower alkyl group.
  • Davis et al. state that "prior art fire-retardants suffer from a number of disadvantages such as their tendency to produce hydrogen halides such as HBr when heated” and that the "new compounds (of their invention) have unusual resistance to thermal and hydrolytic decomposition and are therefore superior fire-retardant additives for wood, textiles, plastics, and the like.”
  • Davis et al. appear to have achieved this unusual hydrolytic stability by using groups having no hydrogen containing carbon atoms in a beta position relative to halogen bearing carbon atoms.
  • the U.S. Patent 3,970,726 discloses polycyclic phosphateesters having the general formula wherein A is and B is wherein R, R' and R 2 are the same or different and are linear or branched primary radicals selected from alkyl having 1 to 6 carbon atoms, and haloalkyl and hydroxyalkyl having 2 to 6 carbon atoms; m and n are integers from 0 to about 4 and the sum of m plus n is from 1 to about 4.
  • polycyclic phosphateesters are disclosed as being useful as flame retardants especially for rigid polyurethane foams.
  • the phosphateesters disclosed are prepared from polycyclic phosphoro- halidites of the formulae wherein Z and Z 2 are bromine or OR 3 and R 3 is an alkyl or haloalkyl radical. (Column 2, lines 47-66).
  • These phosphate esters are prepared by the addition of a polycyclic phosphorohalidite to a primary aliphatic alcohol in the presence of chlorine. (Column 3, lines 34-38).
  • the French Patent 1,349,088 discloses halogenated polymeric diphosphates having the general formula wherein X is bromine or chlorine, R is hydrogen or hydrocarbyl halohydrocarbyl, hydrocarbyloxyalkyl or hydrocarbyl-C(O)O-alkyl and R' is hydrogen, alkyl or lower haloalkyl with the provision that R' is hydrogen when R is hydrocarbyloxyalkyl or hydrocarbyl-C(0)0-alkyl.
  • the compounds disclosed in this reference do not have the necessary hydroxyl group that is required by the present application and which is necessary for the compounds to be polymerizable into a polymeric backbone such as a polyurethane.
  • Jenkner et al. disclose phosphates containing two haloalkyl groups of from 2 to 4 carbon atoms and a single hydroxyalkyl group of from 2 to 4 carbon atoms. These phosphates, however, are thermally and hydrolytically less stable, and therefore less useful than Applicant's instant compounds.
  • esters of pentavalent phosphorus acid of good thermal and hydrolytic stability having the formula wherein R and R' are haloalkyl containing from 2 to 6 carbon atoms and from 1 to 6 halogen atoms; n is or hydroxyl, provided that at least one X is hydroxyl, are preferred, with said compounds wherein n > 1 being more preferred.
  • Table I above is designed to further help describe the compounds of formula I and is neither meant nor should it be taken to be a complete listing of all the compounds within the scope of this invention.
  • n moles of the desired haloalkyl chlorophosphate and 1 mole of compound 11 are reacted under conditions such that they co-react to form compounds of formula I.
  • reaction temperatures range from about 20° to about 120°C.
  • the reaction can be carried out in the presence or absence of a solvent. If a solvent is used it should preferably be an inert organic solvent. Exemplary solvents include benzene, toluene, and chloroform.
  • Catalytic quantities of a metal salt or oxide such as magnesium oxide, magnesium chloride, calcium oxide, calcium chloride, titanium chloride, or vanadium acetate, or stoichiometric quantities of an organic base such as pyridine or triethylamine can be used.
  • liquid final product is washed with aqueous ammonia to remove any residual acidity.
  • aqueous ammonia wash is followed by a water wash.
  • the washed product is dried by standard techniques, e.g. at a temperature of from about 100° to about 130°C. until constant weight is achieved.
  • said solid product can be purified by washing or recrystallization by techniques which are well known to those skilled in the art, e.g., the solid product can be washed with water or organic solvents such as benzene, toluene, methanol, ethanol, etc., or crystallized from said solvent.
  • the purified solid product is then dried by standard techniques, e.g., at a temperature from about 50° to about 150°C. until constant weight is achieved.
  • the hydroxyl containing esters of pentavalent phosphorus acid of this invention as well as mixtures thereof are useful as reactive flame retardants in polymeric compositions selected from the group consisting of polyurethane, including flexible and rigid foams and elastomers, and polyester, both saturated and unsaturated polyester, including styrenated polyester.
  • polyurethane including flexible and rigid foams and elastomers
  • polyester both saturated and unsaturated polyester, including styrenated polyester.
  • polyurethanes means polymers containing repeated urethane linkages where R is aromatic or aliphatic group. These polymers are generally made by reacting a polyisocyanate with a compound having a plurality of active hydrogens (i.e., a compound having active hydrogen and which gives a positive Zerewitinoff test).
  • compositions are any polyurethane herein defined which one so desires to flame retard. It is to be understood that the polyurethanes used can be a "virgin" material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like or the polyurethanes can have additives (such as those mentioned and described herein).
  • polyesters means polycondensate products of the reaction of dibasic acids and/or anhydrides or derivatives therefrom with dihydroxy alcohols. This term includes both saturated and unsaturated polyesters. Unsaturated polyesters are so designated where part or all of the respective acids, anhydrides and/or alcohols contain crosslinkable ethylenic bonds.
  • dibasic acids and anhydrides include, without limitation, phthalic anhydride, maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 1,4,5,6,7,7-hexachlorobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid, i.e., chlor- endic acid, isophthalic acid and terephthalic acid.
  • dihydroxy alcohols include, without limitation, ethylene glycol, diethylene glycol, propylene glycol, butane glycol, butene diol, hexane diol, hexene diol, butyne diol, cyclohexane diol, cyclohexene diol, neopentyl glycol, hydrogenated bisphenol A, 2,2,4-trimethy)-1,3-pentanediot and 1,4-cyclohexanedimethanol.
  • polyesters which are resins derived from reactants used to give polyester resins and reactants used to give other polycondensate linkages.
  • reactants used to give polyester resins and reactants used to give other polycondensate linkages for example, there may be mentioned the reaction of dibasic anhydrides with dihydroxy alcohols and diamines to give polyester and polyamide links along the same molecular backbone.
  • those products formed by addition polymerization of reactants with ethylenic linkages before or after the polyester condensation reaction For example, the addition reaction of styrene with unsaturatioh in polyesters after polycondensation or the formation of an additional polymer with carboxylic acid or other condensable end-groups for further polymerization by polyesterification.
  • polyesters used in the present invention compositions is any polyesters herein defined and which one so desired to flame retard. It is to be understood that the polyesters used can be a "virgin" material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like or the polyesters can have additives (such as those mentioned and described herein).
  • the present flame retardants since they contain a free hydroxyl group, can be reacted and chemically bound into the polyurethane polymer matrix if they are added, for example, along with the polyol employed in making the polyurethane, to provide permanent non-fugitive flame retardancy.
  • the neopentyl moiety of the compounds of formula I contains only one hydroxyl group, e.g., compound 1 in Table I, these compounds can be used to control the polymer chain growth as chainstoppers. If the neopentyl moiety contains a plurality of hydroxyl groups, e.g., compound 7 in Table I.
  • the present flame retardants of formula I can be reacted and chemically bound into the polyester matrix if they are added, for example, along with the diol employed in making the polyester, to provide permanent non-fugitive flame retardancy. If the neopentyl moiety of the compounds of formula I contains only one hydroxyl group these compounds can generally be used to control the polymer chain growth as chain stoppers.
  • neopentyl moiety contains a plurality of hydroxyl groups these compounds can generally contribute to the overall increase in chain length and may even be used as the sole diol reactants to coreact with the diacids or anhydrides to form the polyesters.
  • the flame retardant phosphates of this invention Being bound into, or reacted into, the matrix of the polymer the flame retardant phosphates of this invention are not subject to solvent extraction or migration due to difference in vapor pressure, reaction to sunlight or other chemical influences. Additionally because the flame retardants of this invention become an integral part of the polymer there is no significant change in physical properties such as is typically experienced by the use of additive type flame retardants, particularly when used in large amounts.
  • the flame retardants within the scope of this invention may additionally be incorporated into or applied onto the above polymers by techniques which are standard or known to those skilled in the art as described, for example, in J. M. Lyons, "The Chemistry and Use of Fire Retardants", Wiley Interscience, New York (1970) or Z. E. Jolles, "Bromine and Its Compounds", Academic Press, New York (1966).
  • the amount of flame retardant which is used in the compositions and in the methods of this invention is a flame retardant amount, i.e., that amount necessary to produce measurable flame retardancy in the compositions which are so modified.
  • the quantity of flame retardant employed in the compositions and methods of this invention can generally be from about 0.5 to about 50 percent or more by weight of the total composition.
  • the flame retardant of the present invention will comprise from about 1 to about 25 percent by weight of the total composition.
  • the flame retardancy of a polymer such as polystyrene can be further enhanced through the use of so called “synergists” or enhancing agents which, when used with the compounds of formula I, promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately.
  • These "enhancing agents” comprise the oxides and halides of groups IVA and VA of the Periodic Table, and are further described in Modern Plastics Encyclopedia, ibid., as well as U.S. Patents 2,993,924; 2,996,528; 3,205,196 and 3,878,165.
  • preferred enhancing agents include Sb 2 0 3 , SbCl 3 , SbBr 3 , Sbl 3 , SbOCI, As z 0 3 , As 2 0 5 , ZnB0 4 , BaB 2 0 4 -H 2 0, 2 ⁇ ZnO ⁇ 3B 2 O 3 ⁇ 3 ⁇ 5H 2 O and stannous oxide hydrate.
  • the more preferred enhancing agent is antimony trioxide.
  • the enhancing agent can be employed in concentrations as high as 30 percent by weight of the total composition, preferably up to 15 percent, and more preferably up to 10 percent, by weight of the total composition.
  • One level of synergist which is often used is an amount which is from about 25 to about 75 percent, preferably from about 33 to 67 percent, by weight of the flame retardant phosphates described above.
  • Such materials include, without limitation, adhesion promoters, antioxidants, antistatic agents, antimicrobials, colorants, flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid., (in addition to the new class of flame retardants described herein), heat stabilizers, light stabilizers, pigments, plasticizers, preservatives, ultraviolet stabilizers and fillers.
  • fillers there can be mentioned without limitation, materials such as glass, carbon, cellulosic fillers (wood flour, cork and shell flour), calcium carbonate (chalk, limestone, and precipitated calcium carbonate), metal flakes, metallic oxides (aluminum, beryllium oxide, and magnesia), metallic powders (aluminum, bronze, lead, stainless steel and zinc), polymers (comminuted polymers and elastomerplastic blends), silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica), silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate), and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.
  • materials such as glass, carbon, cellulosic
  • the amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely affect the desired results derived from the present invention compositions.
  • the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about zero percent to about 75 percent and specifically from about one percent to about 50 percent.
  • the polyol, surfactant, and fluorocarbon blowing agent are combined in a masterbatch based on 1000 grams of polyol to minimize loss of blowing agent.
  • a polyester resin is prepared by mixing in a reaction vessel 148.12 grams of phthalic anhydride, 98.06 grams of maleic anhydride, 89.38 grams of ethylene glycol, 53.06 grams of diethylene glycol.
  • the reaction vessel is then heated at 200°C. for two hours. Thereafter the temperature is lowered to 185°C. and 93.42 grams of bis-(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phosphate are added. Heating at 185°C. is continued for two hours. At the end of this period the vessel is cooled to 130°C. During cuoling 0.1 grams of methyl hydroquinone inhibitor are added. After the vessel has reached 130°C.
  • a polyester resin and fiberglass-polyester laminate are prepared substantially in accordance with the procedure of Example 3 except that the flame retardant additive, bis-(2,3-dibromopropyl)-2,3-dimethyl-3-hydroxypropyl phosphate, is omitted. Samples of the laminate are subjected to Oxygen Index Test, ASTM D-2863-74. The results of said test are reported in Table III.
  • thermogravimetric analyses TGA

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Claims (14)

1. Phosphat der allgemeinen Formel
Figure imgb0025
in der R und R' unabhängig voneinander aus niederen Halogenalkylen mit 2 bis 6 Kohlenstoffatomen und 1 bis 6 Halogenatomen ausgewählt sind, n eine ganze Zahl von 1 bis 3 bedeutet, und jedes X unabhängig aus Wasserstoff, Halogen, Alkyl und Hydroxyl mit der Maßgabe ausgewählt ist, daß mindestens eine X Hydroxyl bedeutet.
2. Phosphat nach Anspruch 1, dadurch gekennzeichnet, daß das Halogen Chlor oder Brom ist.
3. Phosphat nach Anspruch 2, dadurch gekennzeichnet, daß die genannten Halogenalkyle geradkettige Halogenalkyle sind.
4. Phosphat nach Anspruch 2, dadurch gekennzeichnet, daß jedes X unabhängig aus Wasserstoff, Halogen und Hydroxyl mit der Maßgabe ausgewählt ist, daß mindestens ein X Hydroxyl bedeutet.
5. Phosphat nach Anspruch 4, dadurch gekennzeichnet, daß es Bis(2.3-dibrompropyl)-2.2-dimethyl-3-hydroxypropylphosphat ist.
6. Phosphat nach Anspruch 4, dadurch gekennzeichnet, daß es Bis(2.3-dichlorpropyl)-2,2-dimethyl-3-hydroxypropylphosphat ist.
7. Phosphat nach Anspruch 4, dadurch gekennzeichnet, daß es Tetrakis(2-chioräthyi)-pentaery- thritoldiphosphat ist.
8. Polymere Zusammensetzung enthaltend ein aus Polyester- und Polyurethanpolymeren ausgewähltes Polymer und eine flammhemmende Menge eines Phosphates der allgemeinen Formel
Figure imgb0026
in der R und R' unabhängig voneinander ausgewählt sind aus niedrigen Halogenalkylen mit 2 bis 6 Kohlenstoffatomen und 1 bis 6 Halogenatomen, n eine ganze Zahl von 1 bis 3 bedeutet und X unabhängig aus Wasserstoff, Halogen, Alkyl und Hydroxyl mit der Maßgabe ausgewählt ist, daß mindestens ein X Hydroxyl bedeutet.
9. Zusammensetzung nach Anspruch 8, dadurch gekennzeichnet, daß Halogen Chlor oder Brom bedeutet.
10. Zusammensetzung nach Anspruch 9, dadurch gekennzeichnet, daß das Halogenalkyl ein geradkettiges Halogenalkyl ist.
11. Zusammensetzung nach Anspruch 9, dadurch gekennzeichnet, daß X unabhängig aus Wasserstoff, halogen und Hydroxyl mit der Maßgabe ausgewählt ist, daß mindestens ein X Hydroxyl bedeutet.
12. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß das Phosphat Bis(2.3-dibrompropyl)-2.2-dimethyl-3-hydroxypropylphosphat ist.
13. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß das Phosphat Bis(2.3-di- chlorpropyl)-2.2-dimethyl-3-hydroxypropylphosphat ist.
14. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß das Phosphat Tetrakis(2- chloräthyl)-pentaerythitoldiphosphat ist.
EP78100131A 1977-06-30 1978-06-09 Halogenhaltige Phosphorsäureester; polymere Präparate, welche diese als Flammschutzmittel enthalten Expired EP0000132B1 (de)

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US05/811,491 US4133846A (en) 1977-06-30 1977-06-30 Hydroxyl containing phosphates and polyphosphates
US811491 2007-06-11

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US (1) US4133846A (de)
EP (1) EP0000132B1 (de)
JP (1) JPS5414926A (de)
DE (1) DE2860891D1 (de)
IT (1) IT1105474B (de)

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EP0013713B1 (de) * 1978-11-30 1984-04-11 Mona Industries Phosphor enthaltende oberflächenaktive Stoffe und ihre Herstellung
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US4654105A (en) * 1985-01-25 1987-03-31 Stauffer Chemical Company Process for producing laminated polyether urethane foam
AU573110B2 (en) * 1985-12-19 1988-05-26 Dow Chemical Company, The Halogenated phosphorate flame retardent for polyurethanes
US4755547A (en) * 1986-04-08 1988-07-05 The Dow Chemical Company Halogenated phosphate-phosphites and their acid halides and acids
US4885381A (en) * 1986-04-08 1989-12-05 The Dow Chemical Company Phosphate-phosphites acid halides
US5420327A (en) * 1992-09-14 1995-05-30 Akzo Nobel N.V. Process for forming hydrocarbyl bisphosphate compound
US5457221A (en) * 1993-03-03 1995-10-10 Akzo Nobel N.V. Process for the manufacture of poly (hydrocarbylene aryl phosphate) compositions
ATE191733T1 (de) * 1994-08-30 2000-04-15 Akzo Nobel Nv Verminderung des beschlagens in polyurethanschaum mittels phosphatestern
US6136997A (en) * 1994-11-01 2000-10-24 Akzo Nobel Nv Process for the formation of hydrocarbyl BIS(hydrocarbyl phosphate)
US5750756A (en) * 1994-11-01 1998-05-12 Akzo Nobel Nv Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate)
US5728859A (en) * 1996-10-31 1998-03-17 Akzo Nobel N.V. Process for making monohydroxy-terminated phosphate compositions
US6262135B1 (en) * 1999-04-12 2001-07-17 Akzo Nobel Nv Polyurethane foam containing a blend of monomeric and oligomeric flame retardants
US6399685B1 (en) 2000-12-11 2002-06-04 Albemarle Corporation Purification of arylene polyphosphate esters
US7087667B2 (en) * 2001-05-15 2006-08-08 Teijin Chemicals, Ltd. Flame-retardant resin composition and molded article therefrom
EP2393874A2 (de) * 2009-02-09 2011-12-14 Icl-ip America Inc. Flammschutzmittel enthaltende polyurethanschaumstoffzusammensetzung und herstellungsverfahren dafür, flammgeschützte zusammensetzung und daraus hergestellter polyurethanschaumstoff
US11248101B2 (en) * 2016-01-18 2022-02-15 Basf Se Process for producing porous materials

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FR1349088A (fr) 1962-03-07 1964-01-10 Monsanto Chemicals Ignifugeage de matières polymères au moyen d'esters phosphoriques halogénés
US3830886A (en) * 1968-06-13 1974-08-20 Dow Chemical Co Phosphorus compounds containing stable halogen
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US3970726A (en) 1975-01-23 1976-07-20 Uniroyal, Inc. Polycyclic phosphate esters and process for preparing same

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JPS5414926A (en) 1979-02-03
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IT7849952A0 (it) 1978-06-20
EP0000132A1 (de) 1979-01-10
IT1105474B (it) 1985-11-04

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