US20110065838A1 - Hydroxyphenyl Phosphine Oxide Mixtures and their use as Flame Retardants for Epoxy Resins - Google Patents

Hydroxyphenyl Phosphine Oxide Mixtures and their use as Flame Retardants for Epoxy Resins Download PDF

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US20110065838A1
US20110065838A1 US12/857,994 US85799410A US2011065838A1 US 20110065838 A1 US20110065838 A1 US 20110065838A1 US 85799410 A US85799410 A US 85799410A US 2011065838 A1 US2011065838 A1 US 2011065838A1
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mixture
composition
phosphine oxide
iii
alkoxyphenyl
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Larry D. Timberlake
Mark V. Hanson
James D. Sibecker
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Lanxess Solutions US Inc
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Chemtura Corp
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Priority to US12/857,994 priority Critical patent/US20110065838A1/en
Priority to PCT/US2010/045849 priority patent/WO2011031421A1/en
Priority to TW99129530A priority patent/TW201125873A/zh
Assigned to CHEMTURA CORPORATION reassignment CHEMTURA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HANSON, MARK V., SIEBECKER, JAMES D., TIMBERLAKE, LARRY D.
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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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix

Definitions

  • This application claims the benefit of the filing date of U.S. Provisional Application No. 61/241,562, filed Sep. 11, 2009, the entire contents of which are incorporated herein by reference.
  • This invention relates to hydroxyphenyl and alkoxyphenyl phosphine oxide mixtures and their use as flame retardants for epoxy resins.
  • Composite materials based on epoxy resins are used in a variety of applications and continue to have considerable importance because of their versatility.
  • a specific example of such an application is in the production of electrical laminates used in printed circuit boards (printed wiring boards, PWB).
  • PWB printed wiring boards
  • a key requirement of this and many other applications is flame resistance. Accordingly, it has been customary in the preparation of epoxy-containing laminates to incorporate various additives to improve the flame retardancy of the resulting laminate.
  • Many types of flame retardant substances have been used, however, the most common thus far used commercially have been halogen containing compounds, such as tetrabromobisphenol A.
  • levels of such bromine-containing flame retardant substances are required that provide a bromine content from 10 weight percent to 25 weight percent based on the total weight in the product.
  • halogen-containing fire retardant epoxy resins such as those containing tetrabromobisphenol A
  • tetrabromobisphenol A are considered to be safe and effective.
  • flame-retarded epoxy systems that are not based on halogen chemistry.
  • these replacement materials must still be able to meet the requirements of fire retardancy and to display the same advantages of mechanical properties, toughness, and solvent and moisture resistance that are offered by the halogenated materials currently used.
  • phosphorus-based fire retardant additives include Antiblaze® 1045 (Albright and Wilson Ltd, United Kingdom) which is a phosphonic acid ester. Phosphoric acid esters have also been used as additives, such as, for example, PX-200 (Diahachi, Japan). Other commercially available reactive phosphorus containing compounds disclosed as being suitable for epoxy resins include Sanko HCA and Sanko HCA-HQ (Sanko Chemical Co., Ltd., Japan).
  • Alkyl and aryl substituted phosphonic acid esters are particularly compatible with epoxy resins.
  • these phosphonic acid esters are often unsatisfactory as substitutes for halogenated flame retardants in epoxy resins for the production of electrical laminates.
  • these materials are known to be plasticizers and thus laminates formed therefrom tend to exhibit undesirably low glass transition temperatures (Tg).
  • Tg glass transition temperatures
  • An additional drawback is that the use of phosphonic acid esters in amounts sufficient to provide the necessary flame retardancy increases the tendency of the resulting cured epoxy resin to absorb moisture.
  • the moisture absorbency of cured laminate board is very significant, because laminates containing high levels of moisture tend to blister and fail, when subjected to the soldering operations typically employed in the manufacture of printed wiring boards.
  • EP 0 754 728 discloses a cyclic phosphonate as a flame retardant material, which is incorporated into an epoxy resin.
  • the cyclic phosphonate must be present in large quantities, such as in excess of 18 weight percent, in order for the resin system to meet UL 94 V-0 rating. This loading for the phosphonate compound may lead to a depression of the Tg or higher moisture absorption.
  • EP 1 116 774 utilizes a hydrogen phosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, in conjunction with triphenylphosphine oxide.
  • the epoxy resin base requires the use of non-standard epoxy resins, namely a xylene-modified novolak resin and naphthylene aralkyl and biphenyl-modified epoxy resins.
  • Various other phosphorus compounds have also been used to prepare halogen-free flame retardant epoxy resins useful in the manufacture of composite materials.
  • phosphorus-carbon bonded moieties such as phosphine oxides
  • phosphine oxides have been disclosed in WO 01/42253; U.S. Pat. No. 4,345,059; EP 1 116 774; JP2000186186 and JP 05057991B4; all of which are incorporated herein by reference in their entirety.
  • Such phosphine oxides display benefits of improved resistance to moisture uptake when compared with other phosphorus compounds that contain P—O bonded moieties, as disclosed in WO 01/42253.
  • a key disadvantage of these compositions is that they are costly to prepare, because they utilize unique raw materials.
  • JP2000186186 discloses the use of pure bis(p-hydroxyphenyl)phenyl-phosphine oxide, which requires the use of a pure dichlorophenyl phosphine in its production.
  • JP 05057991 B4 discloses the production of tris-(m-gylcidyloxyphenyl)phosphine oxide by reacting the pure meta phenol with epichlorohydrin.
  • the phosphine oxides utilized in WO 01/42253 require lithium reagents and cryogenic reaction conditions, thus requiring special equipment for its manufacture.
  • a mixture of hydroxyarylphosphine oxides comprising (a) a mono(hydroxyaryl)phosphine oxide, (b) a bis(hydroxyaryl)phosphine oxide, (c) a tris(hydroxyaryl)phosphine oxide, and, optionally (d) a tri-aryl, alkyl or aralkyl-substituted phosphine oxide.
  • the mixture is produced by reacting a mixed Grignard reagent with phosphorus oxychloride and is said to be useful in the preparation of polyglycidyl ethers and as a flame retardant in epoxy resin compositions which can be processed into resin-impregnated composites.
  • U.S. Pat. No. 6,740,732 discloses phosphorus element-containing crosslinking agents for epoxy resin compositions based on isomeric mixtures of tris(2-hydroxyphenyl)phosphine oxides having the following general chemical structure:
  • R may be independently a hydrogen or a C 1 -C 10 alkyl group.
  • a novel composition comprising mixtures of ortho and para isomers of mono-, bis- and tris-(hydroxyphenyl) phosphine oxide compounds has now been developed and has been shown to be useful as a flame retardant in epoxy resin formulations.
  • the mixture can be produced from the direct reaction product of the manufacture of anisole from phenol and methyl bromide and hence is significantly less expensive to produce than many of the phosphorous containing flame retardants suggested in the prior art.
  • the invention resides in a hydroxyphenyl or alkoxyphenyl phosphine oxide composition
  • a hydroxyphenyl or alkoxyphenyl phosphine oxide composition comprising:
  • R is hydrogen or an alkyl group containing from 1 to 6 carbon atoms
  • R 1 and R 2 are the same or different and each is an alkyl group containing from 1 to 6 carbon atoms
  • each of x and y is an integer between 0 and 4
  • each OR group is in the ortho or para position with respect to the bond between the P atom and the associated phenyl group such that, for each mixture (i), (ii) and (iii), the ratio of the number of OR groups in the ortho-position with respect to the bond between the P atom and the associated phenyl group to the number of OR groups in the para-position with respect to the bond between the P atom and the associated phenyl group is between about 50:50 and about 0.1:99.9, preferably between about 20:80 and about 1:99.
  • each of x and y is zero and R is hydrogen.
  • said composition comprises about 10 to about 50 mole % of the first mixture (i), about 30 to about 60 mole % of the second mixture (ii) and about 10 to about 50 mole % of the third mixture (iii).
  • the invention resides in a method of producing the alkoxyphenyl phosphine oxide composition described herein, the method comprising:
  • the alkyl halide comprises methyl bromide and the oxidizing agent comprises hydrogen peroxide.
  • the method further comprises reacting the product of (d) with an acid to produce the corresponding hydroxyphenyl phosphine oxide composition wherein R in each of formulas (I), (II) and (III) is hydrogen.
  • the invention resides in an epoxy resin composition
  • an epoxy resin composition comprising the reaction product of producing the hydroxyphenyl phosphine oxide composition described herein, wherein R in each of formulas (I), (II) and (III) is hydrogen, and an epihalohydrin.
  • the invention resides in a curable epoxy resin composition
  • a curable epoxy resin composition comprising (a) an epoxy resin and (b) a cross-linking system comprising the hydroxyphenyl phosphine oxide composition described herein, wherein R in each of formulas (I), (II) and (III) is hydrogen.
  • hydroxyphenyl or alkoxyphenyl phosphine oxide composition comprising:
  • R is hydrogen or an alkyl group containing from 1 to 6 carbon atoms
  • R 1 and R 2 are the same or different and each is an alkyl group containing from 1 to 6 carbon atoms
  • each of x and y is an integer between 0 and 4
  • each OR group is in the ortho or para position with respect to the bond between the P atom and the associated phenyl group such that, for each mixture (i), (ii) and (iii), the ratio of the number of OR groups in the ortho-position with respect to the bond between the P atom and the associated phenyl group to the number of OR groups in the para-position with respect to the bond between the P atom and the associated phenyl group is between about 50:50 and about 0.1:99.9, preferably between about 20:80 and about 1:99, and most preferably between about 10:90 and 2:98.
  • R in each of formulas (I), (II) and (III) is hydrogen or an alkyl group containing from 1 to 3 carbon atoms, especially hydrogen or a methyl group.
  • the present composition will generally comprise isomers of formulas (I), (II) and (III) in which R is an alkyl group.
  • the composition is generally converted to an active form, in which some or all of the R groups are hydrogen. Such conversion is readily achieved by treating the composition with an acid, such as hydrogen bromide.
  • each of R 1 and R 2 in formulas (I), (II) and (III) is an alkyl group containing from 1 to 3 carbon atoms, especially a methyl group.
  • each of x and y in formulas (I), (II) and (III) is generally either zero or 1, especially zero.
  • the present composition comprises from about 10 to about 50, such as from about 15 to about 30, mole % of the first mixture (i), from about 30 to about 60, such as from about 40 to about 55, mole % of the second mixture (ii) and from about 10 to about 50, such as from about 15 to about 30, mole % of the third mixture (iii).
  • the present composition can readily be produced by a process in which phenol is initially reacted with an alkyl halide having 1 to 6 carbon atoms, generally methyl bromide, in the presence of an alkali metal base, such as sodium or potassium hydroxide, to produce a first product mixture comprising an alkoxybenzene and an alkali metal halide.
  • the reaction is typically conducted at a temperature of about 50° C. to about 90° C. for about 1 to about 3 hours and can be represented as follows:
  • the first product mixture is then contacted with an oxidizing agent, such as hydrogen peroxide, under conditions such that the alkali metal halide reacts with the alkoxybenzene to produce a mixture of mew and para-haloalkoxybenzenes.
  • an oxidizing agent such as hydrogen peroxide
  • the oxidation reaction is typically conducted at a temperature of about 20° C. to about 40° C. for about 1 to about 4 hours and can be represented as follows:
  • the resulting mixture of meta and para-haloalkoxybenzenes is isolated by phase separation and, optionally, distillation, without separation of the individual isomers, and then dried to remove trace moisture.
  • the isomers have the same boiling points.
  • the dried mixture of meta and para-haloalkoxybenzenes is then mixed with an unsubstituted or alkyl-substituted halobenzene, such as benzyl chloride.
  • the resultant mixture is then reacted with magnesium followed by phosphorus oxychloride to produce the required composition wherein R in formulas (I), (H) and (III) is an alkyl group containing from 1 to 6 carbon atoms.
  • the reaction is a Grignard type reaction and is typically conducted by adding the haloalkoxybenzene/halobenzene mixture to a suspension of magnesium in an ether-based solvent at a 1:1 molar ratio. Then the phosphorus oxychloride is added to the formed Grignard reagent at a molar ratio of at least 1:3 (POCl 3 :Grignard).
  • the reaction is generally carried out at a temperature of about 60° C. to about 110° C. for about 1 to about 3 hours for each step.
  • mixture (ii) the overall reaction can be represented as follows:
  • the Grignard product will also normally contain triphenyl phosphine oxide compounds of the formula IV:
  • the present composition can contain up to 10 wt % of triphenyl phosphine oxide without substantial deleterious effect on the utility of the composition in producing epoxy resin compositions.
  • the mixture of alkoxyphenyl phosphine oxide isomers produced by the Grignard reaction can be converted to a mixture of hydroxyphenyl phosphine oxide isomers by reacting the as-synthesized product with an acid, normally hydrogen bromide. This is conveniently effected by refluxing the alkoxyphenyl phosphine oxide isomers with 48% HBr for several hours and not only converts the product to its active hydroxyl form but also generates alkyl bromide, in this case methyl bromide, that can be recycled to the initial reaction with phenol.
  • an acid normally hydrogen bromide
  • the resultant hydroxyphenyl phosphine oxide composition can be used either (a) directly to produce curable, flame retardant epoxy resins or (b) as a crosslinking agent to produce cured, flame retardant epoxy resins.
  • the present hydroxyphenyl phosphine oxide composition is conveniently reacted with an epihalohydrin, such as epichlorohydrin, to produce the corresponding glycidyl ether derivatives.
  • epihalohydrin such as epichlorohydrin
  • ether derivatives are epoxy resins and can be cured with standard hardeners such as a combination of dicyandiamide and 2-methylimidazole.
  • standard hardeners such as a combination of dicyandiamide and 2-methylimidazole.
  • the present phenolic mixtures can also act as hardeners themselves.
  • Other phenolic hardeners include, but are not limited to, phenolic resins obtained from the reaction of phenols or alkyl-substituted phenols with formaldehyde, such as phenol novolaks, cresol novolaks, and resoles.
  • hardeners include amines, anhydrides, and combinations involving amines with Lewis acids.
  • Amine hardeners include, but are not limited to, alkyl amines, aryl amines, amides, biguanide derivatives, melamine and guanamine derivatives, methylene-dianiline, diaminodiphenylsulfone, imidazoles, ethylenediamine, diethylenetriamine, polyamides, polyamidoamines, imidazolines, polyetheramines, araliphatic amines, dicyandiamide, and m-phenylenediamine.
  • Combinations of nitrogen-containing catalyst with Lewis acids include the heterocyclic secondary and tertiary amines and the Lewis acids include oxides and hydroxides of zinc, tin, silicon, aluminum, boron, and iron.
  • Other curing agents include carboxylic acids and anhydrides, amino-formaldehyde resins, and amine-boron complexes. Many types of curing agents that would be useful can be found in any basic epoxy resin text.
  • the resins described herein may be formulated with additional additives and fillers to affect cure rate, enhance flame retardancy, and increase the physical properties of the cured epoxy resin composition.
  • fillers and reinforcing agents include mica, talc, kaolin, bentonite, wollastonite, glass fiber, glass fabrics glass matt, milled glass fiber, glass heads (solid or hollow), silica, or silicon carbide whiskers and so forth. Many of these materials are enumerated in the Encyclopedia of Materials Science and Engineering, Vol. #3, pp. 1745-1759, MIT Press, Cambridge, Mass. (1986), the disclosure of which is incorporated herein by reference. Combinations of fillers are preferred in some embodiments; whereas in other embodiments, the reinforcing agent makes up most of the final composite, as in the case of glass fabric used in prepregs and laminates for printed wiring boards.
  • the curable epoxy resin described herein may be formulated with other flame-retardant materials as co-additives to improve their performance.
  • co-FR materials could be either inorganic or organic and can be reactive or additive based compounds.
  • inorganic additive type materials include, but are not limited to, aluminum trihydrate (ATH), magnesium hydroxide, barium hydroxide, calcium carbonate, titanium dioxide, and silicon dioxide.
  • organic based additives or reactives include, but are not limited to, triphenyl phosphate, resorcinol bis(di-2,6-xylyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), DOPO-based epoxy resins, bisphenol A bis(diphenyl-phosphate), melamine, melamine phosphate, melamine borate and many others familiar to one skilled in the art.
  • triphenyl phosphate resorcinol bis(di-2,6-xylyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), DOPO-based epoxy resins, bisphenol A bis(diphenyl-phosphate), melamine, melamine phosphate, melamine borate and many others familiar to one skilled in the art.
  • the present hydroxyphenyl phosphine oxide composition can be used as a crosslinking agent for epoxy resins, either alone or in combination with a phenolic co-crosslinking composition.
  • Suitable phenolic co-crosslinking compositions comprise novolac resins, such as phenol-formaldehyde resins, cresol-formaldehyde resins, and mixtures thereof.
  • a polymer of a phenol, nitrogen heteroaryl compound and aldehyde is also suitable.
  • Examples include benzoguanamine-phenol-formaldehyde resins, acetoguanamine-phenol-formaldehyde resins, melamine-phenol-formaldehyde resins, benzoguanamine-cresol-formaldehyde resins, acetoguanamine-cresol-formaldehyde resins, melamine-cresol-formaldehyde resins, and mixtures thereof.
  • epoxy resins suitable for use with the present hydroxyphenyl phosphine oxide composition are presented in Epoxy Resins Chemistry and Technology, Second Edition edited by Clayton A. May (Marcel Dekker, Inc. New York, 1988), Chemistry and Technology of Epoxy Resins edited by B. Ellis (Blackie Academic & Professional, Glasgow, 1993), Handbook of Epoxy Resins by H. E. Lee and K. Neville (McGraw Hill, New York, 1967), and EP 1116774 A2.
  • Suitable epoxy resins are, but not limited to, epoxy resins based on bisphenols and polyphenols, such as, bisphenol A, tetramethylbisphenol A, bisphenol F, bisphenol S, tetrakisphenylolethane, resorcinol, 4,4′-biphenyl, dihydroxynaphthylene, and epoxy resins derived from novolacs, such as, phenol:formaldehyde novolac, cresol:formaldehyde novolac, bisphenol A novolac, biphenyl-, toluene-, xylene, or mesitylene-modified phenol:formaldehyde novolac, aminotriazine novolac resins and heterocyclic epoxy resins derived from p-amino phenol and cyanuric acid.
  • novolacs such as, phenol:formaldehyde novolac, cresol:formaldehyde novolac, bisphenol A novolac
  • aliphatic epoxy resins derived from 1,4-butanediol, glycerol, and dicyclopentadiene skeletons are suitable, for example. Many other suitable epoxy resin systems are available and would also be recognized as being suitable by one skilled in the art.
  • an epoxy resin which possesses on average more than 1 and preferably at least 1.8, more preferably at least 2 epoxy groups per molecule.
  • the epoxy resin is a novolac epoxy resin with at least 2.5 epoxy groups per molecule.
  • the epoxy resin may be any saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compound which possesses more than one 1,2-epoxy group. Examples of heterocyclic epoxy compounds are diglycidylhydantoin or triglycidyl isocyanurate (TGIC).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Fireproofing Substances (AREA)
US12/857,994 2009-09-11 2010-08-17 Hydroxyphenyl Phosphine Oxide Mixtures and their use as Flame Retardants for Epoxy Resins Abandoned US20110065838A1 (en)

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US12/857,994 US20110065838A1 (en) 2009-09-11 2010-08-17 Hydroxyphenyl Phosphine Oxide Mixtures and their use as Flame Retardants for Epoxy Resins
PCT/US2010/045849 WO2011031421A1 (en) 2009-09-11 2010-08-18 Hydroxyphenyl phosphine oxide mixtures and their use as flame retardants for epoxy resins
TW99129530A TW201125873A (en) 2009-09-11 2010-09-01 Hydroxyphenyl phosphine oxide mixtures and their use as flame retardants for epoxy resins

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US20110065869A1 (en) * 2009-09-11 2011-03-17 Timberlake Larry D Hydroxyphenyl phosphine oxide mixtures and their use as flame retardant's for epoxy resins
WO2012158353A1 (en) 2011-05-19 2012-11-22 Chemtura Corporation Aluminum phosphorus acid salts as epoxy resin cure inhibitors
WO2022040633A1 (en) * 2020-08-21 2022-02-24 The University Of Southern Mississippi Phenylphosphine oxide and oxygen stable epoxy polymers and methods of synthesis

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US8865862B2 (en) * 2009-09-11 2014-10-21 Chemtura Corporation Hydroxyphenyl phosphine oxide mixtures and their use as flame retardants for epoxy resins
US9388340B2 (en) * 2009-09-11 2016-07-12 Chemtura Corporation Preparation of hydroxyphenyl phosphine oxide mixtures
CN104004015A (zh) * 2014-06-06 2014-08-27 清华大学 二烃基次膦酸的制备方法
US9534108B2 (en) 2015-03-13 2017-01-03 Chemtura Corporation Flame retardant epoxy resins comprising phosphorus containing flame retardants
CN112409572A (zh) * 2019-08-22 2021-02-26 苏州巨峰新材料科技有限公司 含磷阻燃低热膨胀系数环氧树脂及其制备方法和所涉及的中间产物以及应用
TWI860749B (zh) 2023-06-14 2024-11-01 南亞塑膠工業股份有限公司 磷系耐燃劑、製品及其製造方法

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US8404161B2 (en) * 2009-09-11 2013-03-26 Chemtura Corporation Hydroxyphenyl phosphine oxide mixtures and their use as flame retardant's for epoxy resins
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US11884772B2 (en) 2020-08-21 2024-01-30 The University Of Southern Mississippi Phenylphosphine oxide and oxygen stable epoxy polymers and methods of synthesis

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IL218156A0 (en) 2012-07-31
BR112012001128A2 (pt) 2017-10-17
EP2475716B1 (en) 2017-04-19
TW201125873A (en) 2011-08-01
JP5559322B2 (ja) 2014-07-23
RU2012105465A (ru) 2013-08-27
WO2011031421A1 (en) 2011-03-17
WO2011031834A1 (en) 2011-03-17
CA2767940A1 (en) 2011-03-17
CN102471534A (zh) 2012-05-23
EP2475716A1 (en) 2012-07-18
KR20120089450A (ko) 2012-08-10
US20110065869A1 (en) 2011-03-17
US8404161B2 (en) 2013-03-26
CN102471534B (zh) 2013-10-16

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