WO2012064703A1 - Agent ignifugeant dérivé de dopo et hydrogrenats de synthèse pour compositions de résine époxy - Google Patents

Agent ignifugeant dérivé de dopo et hydrogrenats de synthèse pour compositions de résine époxy Download PDF

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WO2012064703A1
WO2012064703A1 PCT/US2011/059723 US2011059723W WO2012064703A1 WO 2012064703 A1 WO2012064703 A1 WO 2012064703A1 US 2011059723 W US2011059723 W US 2011059723W WO 2012064703 A1 WO2012064703 A1 WO 2012064703A1
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composition
synthetic
epoxy
acid
compound
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PCT/US2011/059723
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English (en)
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Kimberly Maxwell White
Monika Giesselbach
Rene G.E. Herbiet
Arthur G. Mack
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Albemarle Corporation
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • This invention relates to synthetic hydrogamets and 9,10-Dihydro-9-Oxa-10- Phosphaphenantrene-10-oxide derived additive flame-retardants, which are useful in epoxy resin compositions.
  • the epoxy resin compositions may be used in making prepregs or laminates for printed wiring boards and composite materials.
  • Epoxy resins are employed for a wide range of applications such as electronic components, electrical equipment, automotive parts and sporting equipment since the epoxy resins have desirable properties such as adhesiveness, heat resistance and moldability.
  • Flame- retardant agents in particular brominated epoxy resins compounds are employed for copper- clad laminates and sealants that are used in electronic components and electrical equipment.
  • halogen-containing compounds cause concerns about environment and human safety, and therefore flame-retardant agents that are more environmentally friendly are desirable.
  • organo-phosphorous flame retardants In the field of epoxy resins and laminates, organo -phosphorous flame retardants with reactive groups, such as those derived from 9,10- Dihydro-9-Oxa-lO-Phosphaphenantrene-lO-oxide (DOPO), are typically used in epoxy resin formulations because they react with the epoxy to form a phosphorus-modified epoxy resin.
  • DOPO 9,10- Dihydro-9-Oxa-lO-Phosphaphenantrene-lO-oxide
  • the technology for producing phosphorus-modified epoxy resins and their uses, including their use in forming prepregs, laminates and copper-clad laminates is well known in the art. See for example U.S. Pat. Nos.
  • additive organophosphorus flame retardants which do not have reactive groups, are typically not used in epoxy formulations, since it is believed that covalent bonding between the epoxy resin and a reactive organophosphorus flame retardant are needed to provide high glass transition temperatures and dimensional stability.
  • Commonly used mineral flame retardants for polymers such as aluminum trihydroxide (ATH), magnesium hydroxide (MDH) and silica have limited efficiency and use in epoxies.
  • Some mineral flame retardants require high loadings to pass relevant flame tests. In some cases, even when used at highest loadings, certain flame tests are too demanding for the mechanical, thermal, rheological or electrical properties of the final product.
  • ATH starts to decompose at about 200°C, which limits the application to epoxies that are processed at low temperatures.
  • silica is a very abrasive material, and quickly dulls the drilling bits that are required to drill holes in the printed wiring boards.
  • the present invention relates to a flame retardant epoxy composition
  • a flame retardant epoxy composition comprising:
  • A is a direct bond, C 6 -C i2 aryl, C 3 -Ci 2 cycloalkyl, or a C 3 -Ci 2 cycloalkenyl, wherein said cycloalkyl or cycloalkenyl may be optionally substituted by a Ci-C 6 alkyl;
  • each R 1 , R 2 , R 3 and R 4 are independently hydrogen, C]-Ci 5 alkyl, C 6 -Ci2 aryl, C 7 -Ci 5 aralkyl or C7-C15 alkaryl; or R 1 and R 2 or R 3 and R 4 taken together can form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring may be optional substituted by a CrQ alkyl; each m is independently 1, 2, 3 or 4
  • each R 5 and R 6 are independently hydrogen or a Ci-C 6 alkyl
  • each n is independently 0, 1 , 2, 3, 4 or 5;
  • n can not be 0;
  • This application provides, among other things, a synthetic hydrogarnet flame retardant comprised of synthetic hydrogarnet optionally modified by inclusion of silicate and/or phosphate ions in its crystal structure.
  • One embodiment of this invention is a synthetic hydrogarnet having the following formula: M n 3 M m 2(OH) 12 .
  • Another embodiment of this invention is a synthetic hydrogarnet characterized by (i) having the empirical formula M II 3 M lll 20y(OH)i 2- 5y-4 X (P04) y (Si0 4 )x wherein M 11 is one or a mixture of more than one alkaline earth metal, preferably Ca; and x and y are numbers in the range of 0 to about 1.5, with x + y in the range of 0 to about 1.5, preferably in the range of about 0.05 to about 1.5; a more preferred range is about 0.1 to about 1.5; even more preferred is about 0.05 to about 1.2.
  • the synthetic hydrogarnet may also have the following properties:
  • the synthetic hydrogarnets may be further characterized by having a surface moisture content of ⁇ 0.7 wt%, preferably ⁇ 0.5 wt%, as determined by infrared moisture balance at 105°C, and a sodium oxide content of ⁇ 0.5 wt% as determined by flame photometry.
  • the synthetic hydrogarnets can be represented by the following general formula (1):
  • Mg is a Group ⁇ metal atom, typically Ca, Sr, or Ba, or a mixture of at least two of these, or a mixture of any one or more of these with a minor proportion (i.e., less than about 50% by weight) of Mg
  • M m is a Group IIIA metal atom, especially aluminum, but which may be in admixture with small amounts (e.g., less than about 20 % by weight) of B, Ga, In, or Tl, or a mixture of any two or more of these
  • x and y are numbers in the range of 0 to about 1.5, with x + y in the range of 0 to about 1.5, preferably in the range of about 0.05 to about 1.5, more preferably in the range of about 0.1 to about 1.5, even more preferred is about 0.05 to about 1.2.
  • the product can be represented by the formula M !I 3 M !II 2 (OH)i2, where M H and M m are as in formula (1) above.
  • the synthetic hydrogarnet can be represented by the following general empirical formula: M u 3 M in 2 (OH) 12-4x (Si0 4 ) x (1A) wherein M 11 and M m are as in formula (1) above, and x is in the range of about 0.05 to about 1.5, preferably in the range of about 0.1 to about 1.5, more preferably in the range of about 0.05 to about 1.2.
  • the synthetic hydrogarnet can be represented by the following general empirical formula: M i, 3 M m 2 O y (OH) 1 2-5 y (P0 4 ) y (IB) wherein M n and M m are as in formula (1) above, and y is in the range of about 0.05 to about 1.5, preferably in the range of about 0.1 to about 1 .5, more preferably in the range of about 0.05 to about 1.2. '
  • Another embodiment is synthetic hydroga nets thatmay be represented by the following general empirical formula (2):
  • M 11 is a Group IIA metal atom, typically Ca, Sr, or Ba, or a mixture of at least two of these, or a mixture of any one or more of these with a minor proportion (i.e., less than about 50% by weight) of Mg; and where x and y are numbers in the range of 0 to about 1.5, with x + y in the range of about 0 to about 1.5, preferably in the range of about 0.05 to about 1.5; more preferably in the range of about 0.1 to about 1.5, even more preferably in the range of about 0.05 to about 1.2.
  • the product can be represented by the formula n Al 2 (OH)i 2 , where n is as in formula (2) above.
  • the synthetic hydrogarnet can be represented by the following general empirical formula:
  • M 1 ' is as in formula (2) above, and x is in the range of about 0.05 to about 1.5, preferably in the range of about 0.1 to about 1.5, more preferably in the range of about 0.05 to about 1.2.
  • the synthetic hydrogarnet can be represented by the following general empirical formula: M II 3 Al 2 0 y (OH) ,2-5 y (P0 4 ) y (2B) wherein M 11 is as in formula (2) above, and y is in the range of about 0.05 to about 1.5, preferably in the range of about 0.1 to about 1.5, more preferably in the range of about 0.05 to about 1.2.
  • Another embodiment is a synthetic hydrogarnet represented by the following general empirical formula (3):
  • the synthetic hydrogamets of this invention are flame retardants of increased effectiveness and are further characterized by having enhanced thermal stability. It is also believed that by virtue of the inclusion of silicate and/or phosphate in the crystal structure, the resultant crystal growth characteristics of the synthetic hydrogamets can be influenced in a favorable manner. This in turn could have a beneficial influence on various characteristics of the synthetic hydrogamets, such as purity.
  • the synthetic hydrogamets may be produced by agitating a mixture formed from:
  • a Group IIA metal source especially an alkaline earth metal source
  • a source of silicon especially an aqueous silicate solution, as for example, (i) one or more of the solutions of, e.g., NaSi0 3 or Na Si 3 0 7 such as are commercially-available as "water glass” and/or (ii) amorphous or crystalline silicon dioxide in powder form), and/or
  • a source of phosphorus especially an aqueous phosphate solution, e.g., phosphoric acid, alkali or ammonium phosphate salts such as Na 3 P0 4 , Na HP(3 ⁇ 4, NaH 2 P0 4 , alkali or ammonium diphosphate salts such as Na 4 P 2 C > 7, and/or alkali or ammonium polyphosphate salts
  • a source of phosphorus especially an aqueous phosphate solution, e.g., phosphoric acid, alkali or ammonium phosphate salts such as Na 3 P0 4 , Na HP(3 ⁇ 4, NaH 2 P0 4 , alkali or ammonium diphosphate salts such as Na 4 P 2 C > 7, and/or alkali or ammonium polyphosphate salts
  • the process being further characterized in that the proportions of the Group IIIA metal source and the Group IIA metal source used in forming the mixture are in a molar ratio of Group IIA metal: Group IIIA metal in the range of about 1 : 1 to about 2:1.
  • the source of silicon used in fonning the mixture provides silicate in amounts in the range of about 0.05 to about 1.5 moles of silicate per mole of modified synthetic inorganic hydrogarnet prepared, and/or when present, the source of phosphorus used in forming the mixture provides phosphate in amounts in the range of about 0.05 to about 1.5 moles of phosphate per mole of modified synthetic inorganic hydrogarnet prepared.
  • Preferred proportions of the source of silicon used in forming the mixture and/or the source of phosphorus used in forming the mixture provide silicate and/or phosphate in amounts in the range of about 0.1 to about 1.5 moles, more preferably in the range of about 0.05 to about 1.2 moles, of silicate and/or phosphate per mole of modified synthetic inorganic hydrogarnet prepared.
  • each atom of silicon from the silicon source forms one silicate ion in the modified synthetic hydrogarnet
  • each atom of phosphorus from the phosphorus source forms one phosphate ion in the modified synthetic hydrogarnet.
  • a preferred process for producing the synthetic hydrogarnets of this invention relates to the incorporation therein of suitable amounts of silicate and/or phosphate.
  • This process comprises: agitating a mixture formed from a aluminum source, a calcium source, water, a source of silicon and/or phosphorus, and an alkali metal hydroxide, and heating said agitated mixture at a temperature in the range of about 50 to 100°C, the aluminum source being (i) aluminum hydroxide, boehmite, pseudo boehmite, aluminum oxide, or mixtures of any two or more of the foregoing, and (ii) in powder form, the calcium source being (i) an inorganic salt, hydroxide, or oxide of calcium, including hydrates thereof, and (ii) in powder form;
  • the proportions of aluminum source and calcium source used in forming the mixture provide a molar ratio of Ca:Al in the range of about 1 : 1 to about 2: 1, and the source of silicon used in forming the mixture provides silicate in amounts in the range of about 0.05 to about 1.5 moles, preferably in the range of about 0.1 to about 1.5 moles, more preferably in the range of about 0.05 to about 1.2 moles, of silicate per mole of synthetic flame retardant produced, and/or the source of phosphorus used in forming the mixture provides phosphate in amounts in the range of about 0.05 to about 1.5 moles, preferably in the range of about 0.1 to about 1.5 moles, more preferably about 0.05 to about 1.2 moles, of phosphate per mole of synthetic flame retardant produced.
  • the application also provides a di-dopo compound having the following structure:
  • A is a direct bond, C 6 -Cs2 aryl, C3-C12 cycloalkyl, or a C 3 -C] 2 cycloalkenyl, wherein said cycloalkyl or cycloalkenyl may be optional substituted by a C
  • both n subscripts are 1 or 2 and A is a direct bond, in another aspect, both n subscripts are 1 and A is a C 6 -Ci2 aryl.
  • R 1 , R 2 , R 3 and R 4 are independently hydrogen or a C ⁇ -C alkyl.
  • R 5 and R 6 are each independently hydrogen or methyl.
  • alkyl as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, pentyl and hexyl.
  • aryl as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, such as phenyl, naphthyl, indenyl, and fluorenyl. "Aryl” encompasses fused ring groups wherein at least one ring is aromatic.
  • aralkyl indicates an "aryl-alkyl-" group.
  • Non-limiting example of an aralkyl group is benzyl (C ⁇ CH?-) and meihylbenzyJ (CH3C6H4CH2- ).
  • alkaryl indicates an "alkyl-aryl-" group.
  • alkaryl are methylphenyl-, dimethylphenyl-, ethylphenyl- propylphenyl-, isopropylphenyl-, butylphenyl-, isobutylphenyl- and t-butylphenyl-.
  • alkenyl as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon double bond wherein alkyl is as defined above. Examples of alkenyl include, but are not limited to, ethenyl and propenyl.
  • cycloalkyl includes non- aromatic saturated cyclic alkyl moieties wherein alkyl is as defined above.
  • examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • cycloalkenyl includes non- aromatic cyclic alkenyl moieties wherein alkenyl is as defined above.
  • examples of cycloalkyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl.
  • all the foregoing groups derived from hydrocarbons may have up to about 1 to about 20 carbon atoms (e.g., Ci-C 20 alkyl, C 6 -C 2 o aryl, C7-C20 alkaryl, C7-Q20 aralkyl) or 1 to about 12 carbon atoms (e.g., Ci-Cn alkyl, C -C) 2 aryl, C7-C12 alkaryl, C7-C 1 2 aralkyl), or 1 to about 8 carbon atoms, or 1 to about 6 carbon atoms.
  • Ci-C 20 alkyl, C 6 -C 2 o aryl, C7-C20 alkaryl, C7-Q20 aralkyl e.g., Ci-Cn alkyl, C -C) 2 aryl, C7-C12 alkaryl, C7-C 1 2 aralkyl
  • 1 to about 8 carbon atoms e.g., Ci-Cn alkyl,
  • A is a direct bond, C 6 -Ci 2 aryl, C3-C12 cycloalkyl, or a C3-C12 cycloalkenyl, wherein said cycloalkyl or cycloalkenyl may be optional substituted by a C C 6 alkyl; each R , R , R and R 4 are independently hydrogen, C1-C15 alkyl, C 6 -C i2 aryl, O7-C 15 aralkyl or G7-C15 alkaryl; or R 1 and R 2 or R 3 and R 4 taken together can form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring may be optional substituted by a C i-Q alkyl; each m is independently 1 , 2, 3 or 4; each R 5 and R 6 are independently hydrogen or a Ci -C 6 alkyl; and each n is independently 0, 1, 2, 3, 4 or 5; with the proviso that when A is a direct bond
  • One base that may be used is an alkali metal base such as alkali metal alkoxides, alkali metal amides and alkali metal alkyl amides.
  • Alkali metals for the base include lithium, sodium and potassium.
  • the bases that may be used include, but are not limited to, potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium t-butoxide, sodium t-butoxide, lithium diisopropyl amide and mixtures thereof.
  • Preferred are potassium t-butoxide and sodium methoxide.
  • Any suitable amount of base may be used in the process of this invention. Such suitable amounts include from about 0.1 to about 10 equivalence, or about 0.5 to about 5 equivalence, based on the amount of the compound of Formula A.
  • the process may also contain an optional solvent.
  • solvents may include, but are not limited to, heptane, hexane, petroleum ether, methylcyclohexane; toluene, xylene, ethyl benzene, tetrahydrofuran, dimethyl sulfoxide (DMSO), 1,4-dioxane, dimethyl formamide (DMF), dimethylacetamide (DMAc), acetonitrile, ethylene glycol, dimethyl ether, ethylene glycol diethyl ether or mixtures thereof.
  • DMSO dimethyl sulfoxide
  • DMF dimethyl formamide
  • DMAc dimethylacetamide
  • acetonitrile ethylene glycol, dimethyl ether, ethylene glycol diethyl ether or mixtures thereof.
  • the process may be conducted at temperatures ranging from about -10°C to about
  • the catalyst that may be used is any suitable catalyst for dehydration and/or Arbuzov reactions.
  • General suitable catalysts are, alky halides, alkali halides, alkaline earth metal halides, transition metals and their halides or acid catalysts such as methyl p-toluenesulfonate, ethyl p-toluenesulfuonate.
  • Arbuzov reaction catalysts are especially suitable.
  • the process may optionally use a solvent, preferably a high boiling point solvent and an optional entrainer.
  • the purity of the compounds of Formual I, when combined with epoxies should be greater than about 95%, or about 98% or about 99%.
  • the purity levels can be measured by using NMR spectroscopy.
  • NMR spectroscopy One skilled in the art of NMR spectroscopy can develop a procedure for measuring the purity of the compound of Formula I and one procedure may be found in PCT/US 10/35359.
  • the compound of formula I is grounded or milled prior to combining with the polymer.
  • the d 50 particle size after grinding or milling may be less than about 15 pm, or less than 10 ⁇ , or less than about 5 ⁇ , or less than about 3 pm or less than about 2 pm.
  • the d 50 particle size may even be less than 1 pm, such as about 100 nm to 800 ran.
  • a particle size of d 50 is the median particle size, where half the particles are above the value and half the particles are below the value. Any suitable milling or grinding technique may be used such as jet milling.
  • the compound of Formula I have a monomodal particle size distribution, preferably when the d 50 particle size is greater than about 2 pm so that the compound may be more homogenously blended with the polymer.
  • a Coulter LS-230 counter or equivalent is used with its small volume module. The operating instructions of the manufacturer are followed.
  • a Horiba laser light scattering instrument e.g., Horiba LA900 Model 7991
  • the procedure involves weighing the sample, typically an amount in the range of about 0.01 gram to about 0.015 gram, into a clean dry aluminum cup that has been washed with deionized water before use.
  • the instrument autosampler disperses a 0.05 g sample in water using 0.4 mL of 1% Triton X-100 surfactant and ultrasonic treatment. This suspension is circulated through a measuring cell where the powder particles scatter a beam of laser light. Detectors in the instrument measure intensity of the light scattered.
  • the computer in the instrument calculates mean particle size, average particle size and particle size distribution from such measurements.
  • the compound of Formula I is substantially or completely free of organic bases because organic bases may deleteriously affect its use as a flame retardant, especially when used in epoxies.
  • Substantially free of organic bases means that the levels are less than about 10,000 ppm, or less than about 1000 ppm, or less than about 100 ppm or less than about 10 ppm.
  • One method to have the compound of Formula I be substantially or completely free of an organic base is not to use the any organic base in the reaction to produce the compound.
  • One method to determine the amount of organic base, if any, is NMR spectroscopy.
  • An organic base is an organic compound, which acts as a base.
  • Organic bases are usually, but not always, proton acceptors. They usually contain nitrogen atoms, which can be readily protonated.
  • Amines and nitrogen-containing heterocyclic compounds are typically organic bases. Examples include, but are not limited to pyridine, methyl amine, trimethylamine, triethylamine, tripropylamine, tributylamine, N-ethylmorpholine, imidazole, benzimidazole, histidine, phosphazene bases and carbonates or hydroxides of some organic cations.
  • DOPO because DOPO may deleteriously affect its use as a flame retardant.
  • Substantially free of DOPO means that the levels are less than about 50,000 ppm, or less than about 20,000 ppm, or less than about 10,000 ppm or less than about 1000 ppm or less than about 100 ppm.
  • a preferred method to reduce the DOPO is to wash the product with water or water miscible solvents such as alcohols (e.g., isopropanol), aldehydes or ketones (e.g., acetone) before and/or after filtration. DOPO levels may be measured by using NMR spectroscopy.
  • the amount of solvent remaining in the compound of Formual I after purification should be less than about 1000 ppm, or less than about 100 ppm, or less than about 50 ppm, The amount of solvent may be measured by using NMR spectroscopy.
  • One method to reduce the amount of solvent in the compound of Formula I is drying under vacuum or with nitrogen sweep at temperature from about 100°C to 170°C for about 2 to about 24 hours. If the compound is grounded or milled, it is preferred to do at temperatures above room temperature, such as by hot air jet milling to further reduce volatiles.
  • any suitable epoxy resin useful in the art may be used in the present invention as the epoxy compound.
  • Representative epoxy resins suitable for use in the present invention 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.
  • an epoxy resin which possesses an average functionality 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 groups. Examples of heterocyclic epoxy compounds are diglycidylhydantoin or triglycidyl isocyanurate (TGIC).
  • 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, polybenzoxazine, resorcinol, 4,4'-biphenyl, dihydroxynaphthylene, and epoxy resins derived from novolacs, such as, phenol: formaldehyde novolac, creso 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, creso formaldehyde novolac, bis
  • 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.
  • Epoxy novolac resins are readily commercially available, for example, under the trade names D.E.NTM, QUAT EX.TM (Trademarks of the Dow Chemical Company), TactixTM 742 (Trademarks of Ciba) and Epon 1M (trademark of Resolution Performance Products).
  • the materials of commerce generally comprise mixtures of various glycidoxyphenyl and methyl-, ethyl- propyl- glycidoxyphenyl groups.
  • the amount of the compound of Formula I in the flame retardant epoxy composition is about 0.1 to about 100 parts, or about 1 to 70 parts, by weight per 100 parts by weight of the epoxy compound.
  • the amount of the phosphorus compound of Formula I in the flame retardant epoxy composition is selected so the composition will contain about 0.5 wt% to about 10 wt % or about 1.2 wt% to about 7 wt%, or about 1.5 wt% to about 5 wt% phosphorous content, based on the total weight of the composition.
  • the amount of the synthetic hydrogamet in the flame retardant epoxy composition is about 0.1 to about 100 parts, or about 1 to 70 parts, by weight per 100 parts by weight of the epoxy compound.
  • the phosphorus-containing flame retardant epoxy composition has an epoxy equivalence of generally about 100 g eq to about 1000 g eq., or about 100 g/eq to about 800 g/eq or about 150 g/eq to about 500 g/eq.
  • Dispersants or wetting agents may also be used in the flame retardant epoxy composition, Dispersant are compounds that are used to suspend or disperse particles in a liquid medium and are usually polymer or oligomeric in nature. A discussion of dispersants may be found in Kirl-Othmer Encyclopedia of Chemical Technology, John Wiley and Sons, Vol. 8, page 672-697, 5 th edition 2004. Any suitable dispersant may be used in the flame retardant epoxy composition.
  • Non-limiting examples of suitable dispersants are alkylammonium salts of a polycarboxylic acid; alkylammoniums salt of a fatty acid; alkanolammonium salts of an acidic polymer; propylene glycol methyl ether acetate or polyethylene glycol monomethyl ether both optionally containing small amounts of polyphosphoric acids or polyphosphate oligomers; or mixtures thereof.
  • the alkylammonium salt of a polycarboxylic acid may be represented by the following formula: N(R' V -C(0)-R 12 -(COOH) n wherein each R 1 1 is independently a Cj-Cie alkyl, C3-C18 cycloalkyl, C 6 -Cis aryl or a C 7 -C 18 aralkyl; R !2 is a Q-Cioo hydrocarbylene group, optionally containing ether linkages, and n is 1 to about 50.
  • R !2 is a Q-Cioo hydrocarbylene group, optionally containing ether linkages, and n is 1 to about 50.
  • R is a Ci-Cig alkyl. In another embodiment, R is C2-C20 alkylene. In another embodiment, n is 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10,
  • quaternary ammonium cations include tetraalkyl(Cn 8 ) ammoniums, such as trimethylethyl-, triethylmethyl-, trimethylhexyl-, trimethyloctyl-, tributyloctyl-, trimethyldecyl-, trimethyltetradecyl-, trimethylcetyl- and methyltrioctyl- ammoniums.
  • polycarboxylic acids that may be used to form the anion include, but are not limited to anions of polycarboxylic acid derived from: oxalic acid, malonic acid, succinic acid glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tiidecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicocanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, citric acid, aconitic acid, propane- 1 , 2, 3-tricarbox
  • Another dispersant which is used in the present invention, is an alkyl ammonium salt of a fatty acid. It may be represented by the following formula:
  • each R 13 is independently a Cj-C 18 alkyl, C 3 -Cig cycloalkyl, C 6 -Ci 8 aryl or a C -Cis aralkyl; R i4 is a C C 30 alkyl, or Q-C30 alkenyl.
  • Fatty acids may be converted into quaternary ammonium salts either through neutralization with a quaternary ammonium hydroxide or through anion exchange with a quaternary ammonium carbonate.
  • the fatty acid anion is derived from unsaturated fatty acids. Examples of such unsaturated fatty acids, include, but are not limited to: myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid or mixtures thereof.
  • quaternary ammonium cations include, but are not limited to tetraalkylfCi-Cig) ammoniums, such as trimethylethyl-, triethylmethyl-, trimethylhexyl-, trimethyloctyl-, tributyloctyl-, trimethyldecyl-, trimethyltetradecyl-, trimethylcetyl- and methyl trio ctyl -ammoniums .
  • Another dispersant which is used in the present invention, is an alkanolammonium salt of an acidic polymer. It may be represented by the following formula:
  • each R 15 is independently a Cj-Cj 8 alkyl, C 3 -Ci 8 cycloalkyl, Ce-Cjg aryl, C7-C18 aralkyl, Ci-C J5 hydro xyalkyl, C 3 -C 1 g hydroxycycloalkyl C 6 -Ci 8 hydroxyaryl or a C 7 -Cis hydroxyaralkyl; provided that at least one R 15 contains a hydroxy group; Z is a carboxyl- containing polymer having a number average molecular weight (Mn) of 1000 to 100,000.
  • Mn number average molecular weight
  • Alkanolammonium salt of an acidic polymer are known in the art.
  • U.S. Patent No. 6,680,266, herein incorporated by reference discloses many such alkylammonium acidic polymer compounds and how they are prepared.
  • Carboxyl-containing polymers may be converted into quaternary ammonium salts either through neutralization with a quaternary ammonium hydroxide or through anion exchange with a quaternary ammonium carbonate.
  • R i5 hydroxyalkyl groups include, but are not limited to: hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl and hydroxyoctyl.
  • Suitable examples of quaternary alkanolammonium cations that may be used, include, but are not limited to: trihydiOxyalkyl(C2-C 8 ) aIkyI(C]-C 6 ) ammoniums, such as trihydroxyethylhexyl ammonium; trihydroxymethyl ethyl ammonium; trihydroxy ethylpentyl ammonium; trihydroxymethylbutyl ammonium; stearyltrihydroxyethyl ammonium; dialkyl(Cg-Ci 8 )dihydiOxyethylammonium salts such as dilauryldihydroxy ethylammonium.
  • the carboxyl-containing polymers have an Mn of about 1 ,000 to about 100,000, or about 3,000 to about 30,000 and an Mw of generally about 1,100 to about 150,000, or about 3,300 to about 40,000.
  • the polymers have an acid value of usually at least about 250, or about 500 to about 970, or about 550 to about 900, or about 700 to about 780.
  • an acidic polymer is an ethylenically unsaturated carboxyl- containing monomer or a copolymer of an ethylenically unsaturated carboxyl-containing monomer with at least one other polymerizable monomer.
  • Suitable ethylenically unsaturated carboxyl-containing monomers include, but are not limited to ⁇ , ⁇ -unsaturated monocarboxylic acids, such as (meth)acrylic and crotonic acids; dicarboxylic acids, such as maieic, fumaric, itaconic, citraconic, mesaconic, methylenemalonic and cinnamic acids, tricarboxylic acids, such as aconitic acid; dicarboxylic anhydrides, such as maieic, itaconic and citraconic anhydrides; half esters of dicarboxylic acid as mentioned above with monohydric alcohol (e.g.
  • alkanols, cellosolves and carbitols, containing 2 to 16 carbon atoms such as monobutyl maleate, monoethylcarbitol maleate and the like, fumarates and itaconates corresponding to these maleates; as well as combinations of two or more of these monomers.
  • an acidic polymer is a carboxyl-containing polyester.
  • Such resins are derived from the reaction of a dicarboxylic acid or anhydride with a polyhydric compound.
  • Polycarboxylic acids such as phthalic acid, maieic acid, fumaric acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, succinic acid, dodecylsuccinic acid, nadic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, as well as adhydrides of such acids where they exist are useful.
  • phthalic acid isophthalic acid, terephthalic acid, hexahydrophthalic acid, succinic acid, dodecylsuccinic acid, maieic acid, nadic acid, their anhydrides where they exist, and mixtures thereof.
  • Polyhydric alcohols which are reacted with the polycarboxylic acid or anhydride include glycerol, trimethylol ethane, tnmethylolpropane, pentaerythritol, sorbitol, mannitol, ethylene glycol, diethylene glycol, 2,3-butylene glycol and oxyalkylated derivatives thereof.
  • Commercial examples of such dispersant are the line of dispersants and wetting agents are typically available from suppliers such as Avecia Additives and BYK Chemie, such as Byk® W903, W935, W961 , and W969. The choice of a particular type of surfactant, wetting agent or dispersant depends upon the resin and the desired properties of the laminate or printed wiring board.
  • the amounts of the dispersant or wetting agent can vary, typically the amount on a weight basis added to the composition is in the range of about 0.01wt% to about 4wt% or in the range of about 0.1 wt% to about 2wt%, based on the total weight of the composition.
  • the synthetic hydrogamets may also be at least partially coated with a silane coating agent.
  • silanes that may be used are: aminopropyltriethoxysilane, aminoethylaminpropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylsilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyle)-3- aminopropyltrimethoxysi 1 ane, N-(2 - aminoethyl )-3 -ami nopropylmethyl dimethoxysilane, N- (2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-cyclohexyl-3-aminopropyl- trimethoxysilane, benzylaminoethylaminopropyltrimethoxysilane, vinylbenzylamino- ethy
  • the synthetic hydrogarnets may be coated with the silane by any suitable method.
  • One method is spray coating, where the silane is sprayed on well agitated synthetic hydrogarnets using mixing equipment from manufactures such as such Loedige, Littleford Day, Hosokawa Alpine, and Thyssen Henschel.
  • Example of commercial silanes that may be used are the line of multifunctional silanes Dynasylan ⁇ from Degussa (Evonik industries AG).
  • the present invention also relates to a cured flamed retardant epoxy resin comprising the flame-retardant epoxy resin composition above reacted with a curing or polymer initiation agent.
  • the aforementioned curing or polymerization initializing agents are not limited to a specific curing or polymerization initializing agent as long as the agent helps polymerization of the epoxy resin in the flame retardant epoxy composition.
  • polymerization initializing agents examples include cationic polymerization initializing agents such as methane sulfonic acid, aluminum chloride, stannum chloride, trifluoroboron ethylamine complex, trifluoroboron ethylether complex and the like; radical polymerization initializing agents such as benzoyl peroxide, dicumyl peroxide, azo bis-isobutyronitrile and the like; and anionic polymerization initializing agents such as methoxy potassium, triethyl amine, 2-dimethyl aminophenol and the like and mixtures thereof.
  • cationic polymerization initializing agents such as methane sulfonic acid, aluminum chloride, stannum chloride, trifluoroboron ethylamine complex, trifluoroboron ethylether complex and the like
  • radical polymerization initializing agents such as benzoyl peroxide, dicumyl peroxide, azo bis-isobutyronitrile and the like
  • the aforementioned epoxy curing agents include any agent known by a person skilled in the art. Examples, include but are not limited to: ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, meta phenylene diamine, para phenylene diamine, para xylene diamine, 4,4'-diamino diphenyl methane, 4,4'-diamino diphenyl propane, 4,4' ⁇ diamino diphenyl ether, 4,4'-diamino diphenyl sulfone, 4,4'-diamino dicyclohexane, bis (4-aminophenyl) phenyl methane, 1,5-diamino naphthalene, meta xylylene diamine, para xylylene diamine, 1,1 -bis (4-aminophenyl) cyclohexane, dicyan diamide, phenol/formaldehyde novolac
  • the amount of curing agent that may be used is based on the molar equivalence of curing functional groups in the curing agent to the molar equivalence of un-reacted epoxy groups in the flame-retardant epoxy resin composition.
  • the curing agent amount may be from about 0,1 equivalence to about 10 equivalence or about 0.3 equivalence to about 5 equivalence, or about 0.7 equivalence to about 2 equivalence based on the equivalence of unreacted epoxy groups in the phosphorus-containing epoxy resin.
  • the polymerization initializing agents may be added in concentrations ranging from about 0.01 wt% to about 10 wt %, or about 0.05 to about 5%, or about 0.1 wt% to about 2 wt%, based on the total weight of the fiame-retardant epoxy resin composition.
  • the curing temperature may be carried out generally between about 25°C to about 250°C, or about 70°C to about 240°C or about 150°C to about 220°C.
  • epoxy curing agent promoters may also be used to promote curing of the flame retardant epoxy composition. These epoxy curing agent promoter are often based on imidazoles. Examples of such epoxy curing agent promoters include, but are not limited to: 1 -methylimidazole, 2-methylimidazole, 1,2-dimethylirnidazole, 1,2,4,5-tetramethylirnidazole, 2-ethyl-4-methylimidazole, 2-phenyIimidazole, 1 -cyanoethyl-2-phenylimidazole, l-(4,6- diamino-s-triazinyl-2-ethyl)-2-phenylimidazole or mixtures thereof.
  • the epoxy curing agent promoter may be added in concentrations ranging from about 0.0001 wt% to about 5 wt %, or about 0.01 to about 3%, or about 0.1 wt% to about 2 wt%, or about 0.15 wt% to about 1 wt%, based on the weight of curing agent used. Higher concentrations of promoter may be used with different curing agents, such as DICY, dicyandiamide, where promoter concentrations are more typically in the 5-25 wt% range, based on weight of curing agent.
  • the aforementioned cured flamed retardant epoxy resin and/or flame-retardant epoxy compositions of the invention may also contain other conventional additives, such as heat stabilizers, light stabilizers, ultra-violet light absorbers, anti-oxidants, anti-static agents, preservatives, adhesion promoters, coupling agents such as amino-, vinyl- or alkyl silanes or maleic acid grafted polymers; sodium stearate or calcium stearate, ; metal scavengers or deactivators fillers, pigments, dyes, lubricants, mold releasers, blowing agents, fungicides, plasticizers, processing aids, acid scavengers, dyes, pigments, nucleating agents, wetting agents, dispersing agents, synergists, mineral fillers, reinforcing agents such as glass fiber, glass flake, carbon fiber, or metal fiber; whiskers such as potassium titanate, aluminum borate, or calcium silicate; inorganic fillers and other fire-retard
  • the other fire retardant additives include, but are not limited to, ammonium polyphosphate, nitrogen-containing synergists such as melamine polyphosphate, antimony oxide, silica, hydrated alumina such as aluminum hydroxide (ATH), boehmite, bismuth oxide, molybdenum oxide, or mixtures of these compounds with zinc, aluminum and/or magnesium oxide or salts.
  • ammonium polyphosphate nitrogen-containing synergists such as melamine polyphosphate, antimony oxide, silica, hydrated alumina such as aluminum hydroxide (ATH), boehmite, bismuth oxide, molybdenum oxide, or mixtures of these compounds with zinc, aluminum and/or magnesium oxide or salts.
  • fillers and reinforcing agents include fused silica powder; crystalline silica powder; alumina; silicon nitride; aluminum nitride; boron nitride; magnesia; titanium oxide; calcium carbonate; magnesium carbonate; calcium silicate; glass fiber; asbestos, talc, kaolin, bentonite, wollastonite, glass fiber, glass fabrics, glass matt, milled glass fiber, glass beads (solid or hollow), silicon carbide whiskers and mixtures thereof. Many of these materials are enumerated in the Encyclopedia of Materials Science and Engineering, Vol. # 3, pp. 1745 1759, MIT Press, Cambridge, Mass.
  • Non limiting examples of these additional flame retardants are mineral flame retardants like aluminum hydroxides, magnesium hydroxides, boehmites, layered double hydroxides (LDH), organically modified LDHs, clays, organically modified nano-clays, zinc borates, zinc stannates and zinc hydroxy stannates, brominated flame retardants, phosphorus containing flame retardants, nitrogen containing flame retardants and the like.
  • mineral flame retardants like aluminum hydroxides, magnesium hydroxides, boehmites, layered double hydroxides (LDH), organically modified LDHs, clays, organically modified nano-clays, zinc borates, zinc stannates and zinc hydroxy stannates, brominated flame retardants, phosphorus containing flame retardants, nitrogen containing flame retardants and the like.
  • the aforementioned cured flamed retardant epoxy resin and/or flame-retardant epoxy composition of the invention may be used to form prepreg and/or laminates.
  • Typical procedures for forming prepregs and laminates for printed wiring boards involve such operations as:
  • An epoxy- containing formulation such as one containing the flame retardant epoxy composition of the present invention is formulated with solvents and curing or polymerization agents and optionally other conventional additives described above.
  • the formulation is applied to or impregnated into a substrate by rolling, dipping, spraying, other known techniques and/or combinations thereof.
  • the substrate is an inorganic or organic reinforcing agent in the form of fibers, fleece, fabric, or textile material, e.g., typically a woven or non- woven fiber mat containing, for instance, glass fibers or paper.
  • the impregnated substrate is "B-staged” by heating at a temperature sufficient to draw off solvent in the epoxy formulation and optionally to partially cure the epoxy formulation, so that the impregnated substrate cooled to room temperature is dry to the touch and can be handled easily.
  • the "B-staging” step is usually carried out at a temperature of from 90°C to 240°C and for a time of from 1 minute to 15 minutes.
  • the impregnated substrate that results from B-staging is called a "prepreg.”
  • the temperature is most commonly 100°C for composites and 130°C to 200°C for electrical laminates.
  • One or more sheets of prepreg are stacked or laid up in alternating layers with one or more sheets of a conductive material, such as copper foil, if an electrical laminate is desired.
  • a conductive material such as copper foil
  • the laid-up sheets are pressed at high temperature and pressure for a time sufficient to cure the resin and form a laminate.
  • the temperature of this lamination step is usually between 100°C and 240°C, and is most often between 165°C and 200°C.
  • the lamination step may also be carried out in two or more stages, such as a first stage between 100°C and 150°C and a second stage at between 165°C and 200°C.
  • the pressure is usually between 50 N/cm 2 and 500 N/cm 2 .
  • the lamination step is usually carried out for a time of from 1 minute to 200 minutes, and most often for 45 minutes to 120 minutes.
  • the lamination step may optionally be carried out at higher temperatures for shorter times (such as in continuous lamination processes) or for longer times at lower temperatures (such as in low energy press processes).
  • the resulting laminate for example, a copper-clad laminate
  • the temperature of post-treatment is usually between 120°C and 250°C.
  • the post- treatment usually is between 30 minutes and 12 hours.
  • the solvent for the epoxy resin in step A above is a ketone such as 2- butanone or methyl ethyl ketone (MEK).
  • MEK methyl ethyl ketone
  • any other suitable type of conventionally-used solvent for forming these formulations can be employed.
  • such other solvents include, but are not limited to acetone, methyl isobutyl ketone (MIBK), 2-methoxy ethanol, 1 -methoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, toluene, N,N- dimethylformamide, and mixtures thereof EXAMPLES
  • the initial charges to the 20-liter vessel were 4 liters of water, followed by 4 kg Solvay liquor with NaOH cone, of 50 wt.%, 11.7 kg of a 20% solids slurry of unmilled Ca(OH) 2 and 680 g of water glass (Na 2 Si 3 0 7 ) sodium silicate solution, having a calculated Si0 2 concentration of 27 wt% (available from Riedel-de Haen).
  • This mixture was heated while stirring to 95°C at a rate of about 15°C per minute. At reaching the desired temperature, 1850 grams of fine precipitated aluminum trihydrate were added.
  • Example 1 The procedure in Example 1 above was followed except that the Ca(OH) 2 was milled prior to combining with the other components.
  • the d 50 of the final product was about 1.1 ⁇ .
  • a 4-neck 5L half-jacketed reactor was fitted with an addition funnel, thermocouple, mechanical stirrer and nitrogen flow.
  • the reactor was charged with potassium t-butoxide (tBuOK) (230 g, 2.05 mol) and 1.5 L of anhydrous DMSO as solvent.
  • tBuOK potassium t-butoxide
  • DOPO DOPO
  • Higli purity DOPO was loaded into a reactor and a given amount of mixed xylenes was then pumped into the reactor.
  • a 2.62 wt% Nal/EG solution was prepared and charged to the reactor. The were then agitated and heated to 198°C in 5-6 hours while the pressure was maintained at 40-41 psig. Once the contents reached the reaction temperature, a co-feed containing the 2.62 wt% Nal/EG and mixed xylenes was started. The co-feed lasted a minimum of about 14 hours.
  • the xylene feed rate was on the order of llb/min. After an 1 1.5-hour feed and 2-hour hold, the reactor became full. It was cooled to 190°C, and a sample of the reactor slurry was collected. NMR results indicated that the DOPO conversion was about 72% at this point. The reactor was re-heated to 1 7-1 9°C, and the co-feed was conducted for another 5 hours, followed with 2.5 hour hold. The DOPO conversion was then about 93% at the end of the second co-feed, the reaction mixture was quenched with IPA and cooled slowly to ⁇ 100°C.
  • the DiDOPO flame retardant of Example 3 (6H- Dibenz[c,e][l,2]oxaphosphorin, 6,6'-( l,2-ethanediyl)bis-, 6,6'-dioxide) containing 13.5 wt% P was ground using a jet mill to reduce the particle size of the compound to a d 50 of about 2-4 ⁇ prior to combining with the polymer.
  • a flame retardant resin mixture containing 3.0 wt% P based on solids content, excluding mass contribution from the mineral filler. With the mineral filler (silica or hydroga net), the resin mixture contained 2.1 wt% P based on overall solids content.
  • the resin mixture was prepared by blending 128.8 g of 50 wt% NPCN 703 solution, 62.7 g of 50 wt% SD-1702 solution, 27.4 g flame retardant and 0.083 g 2- phenylimidazole promoter. An additional 30 g ME was added to the mixture. The novolac to promoter ratio was about 378. About 0.5-1 mL of the resin mixture was added to a hot cure plate (Thermo-electric company) at about 170-172°C. A tongue depressor was split in half lengthwise, and half of the depressor was used to move the resin on the hot plate until stiffness was noted and then lifting the resin with the flat part of the depressor until string formation ceased. The gel time was 1 minute 47 seconds, determined by the point where resin "strings" could no longer be pulled from the resin mixture and the epoxy became “tack free.” The resin mixture was mixed thoroughly using a high shear mixer stirred at 5,700 rpm for about 20 minutes.
  • An 1 1 inch by 1 1 inch square woven glass fabric (7628 glass with 643 finish from BGF Industries) was cut to size from a large roll and stapled to wood supports (12 inches long, 1 inch wide and 1/16 inch thick) on the top and bottom ends of the fabric.
  • the wood supports contained holes in the corners for inserting paper clips on one end for hanging the fabric in the B-stage oven.
  • the A-stage, or resin varnish, was painted on the front and back of the fabric. Paper clips were unfolded and inserted into the both holes of one wood support.
  • the resin-saturated fabric was hung from aluminum supports in a laboratory fume hood and allowed to drip dry for about one minute before hanging in a pre-heated (to 170 °C) forced air Blue M oven (Lab Safety Supply Inc., a unit of General Signal) for 55 seconds.
  • the edges of the B-staged prepreg were removed by reducing the sheet dimensions to 10 inch by 10 inch.
  • the sheet was cut into four 5 inch by 5 inch sheets and weighed before stacking the four layers of prepreg between two layers of Pacothane release film (Insulectro Corp.) and two steel plates (1/8 inch thick, 12 inch by 12 inch square dimensions).
  • the laminate was formed in the hot press at 5,000 psig for 1 hour.
  • the resulting laminate was 0.035 inches thick, contained 50 wt% resin and underwent 1 1 wt% resin overflow during pressing.
  • Five 0.5 inch wide coupons were cut from the laminate using a diamond saw, and the coupon edges were smoothed with sandpaper.
  • the flammability of the coupons were screened by AST D3801- 06 using an Atlas UL-94 burn chamber, resulting in a burn rating with 218 seconds total burn time for the two ignitions on all five coupons. Burn times for most coupons exceeded 30 seconds during the first ignition, and a second ignition was not performed. Several coupons burned slowly to the clamp.
  • Example 7 were prepared similarly to examples 5-6, but a 1 :1 wt%:wt% mixture of
  • XP-7866 and melamine polyphosphate (Melapur 200 (M-200) from BASF Corporation) was used.
  • the resin mixture retained the targeted 3.0 wt% P based on solids content, excluding mass contribution from the mineral filler. With the mineral filler, the resin mixture contained 2.1 wt% P based on overall solids content.
  • the flame retardant of Example 4 (6H-Dibenz[c,e][l,2]oxaphosphorin, 6,6'-(l ,2- ethanediyl)bis-, 6,6'-dioxide) containing 13.5 wt% P was ground by Fluid Energy Corporation using a jet mill to reduce the particle size of the compound to a d 50 of about 2-4 ⁇ prior to combining with the polymer.
  • the flame retardant of Example 4 was used to prepare laminates in Examples 8-10.
  • the laminates of Example 8-10 was prepared similarly to the laminate in Example 7 with the exception of the novolac to promoter ratio was about 794.
  • Example 8 For the laminate of Example 8, a UL-94 V-l rating with 79 seconds total burn time was obtained for the two ignitions on all five coupons. These results were obtained from a 0.029 inches thick laminate, containing 41 wt% resin.
  • Example 9 The laminate of Example 9 was prepared similarly to the laminate in Example 9 with the exception that 0.5 wt% of Byk Chemie W-903 dispersing agent was added prior to high shear mixing. A UL-94 V-l rating with 53 seconds total burn time was obtained for the two ignitions on all five coupons. These results were obtained from a 0.029 inches thick laminate, containing 46 wt% resin.
  • Example 10 The laminate of Example 10 was prepared similarly to the laminate in Example 10 with the exception that 0.8 wt% of Byk Chemie W-903 dispersing agent was added prior to high shear mixing. A UL-94 V-0 rating with 43 seconds total burn time was obtained for the two ignitions on all five coupons. These results were obtained from a 0.032 inches thick laminate, containing 49 wt% resin.
  • Laminate Tg measurements were performed similarly to what is described in IPC method IPC-TM-650 (method 2.4.25c), using a 20°C /mm temperature rate rise in N 2 with the following differences.
  • the isothermal hold temperatures were 200°C for laminates based on DEN-438 resin, 220°C for laminates based on NPCN-703 and 250°C for laminates based on NPCN-703 resin with no flame retardant.
  • the TA Instrument software analyzer was used to determine the glass transition temperature. In some cases a third scan was performed to determine the delta Tg between the first, second and third scans.
  • a hole saw was used to drill out laminate sample disks of a size proportioned to fit inside a standard aluminum DSC pan.
  • sample edges were gently sanded to for fitting into the pan, and the most in tact surface of the laminate was positioned facing the bottom of the pan.
  • the sample weight (-40-50 mg) was recorded and a sample pan lid added using a plunger press to seal the lid onto the pan. An empty sealed pan was added to the reference platform.
  • thermogravimetric analyses were performed on a TA Instruments Q500 TGA instrument.
  • the TGA is connected to a PC, which provides user interface and operational system control.
  • the temperature scale was calibrated using certified Curie temperatures of alumel and nickel reference standards.
  • the microbalance was calibrated using certified reference weights. Both of these calibrations were performed according to the instrument manufacturers recommended procedures.
  • the samples contained about 10 mg to 12 mg, which were heated at 10 °C/min in under nitrogen from room temperature to 500 °C in platinum sample pans.
  • a raw data file containing the sample weight and temperature data is saved to the PC hard drive during the measurement. After the TGA measurement is finished the raw data file is analyzed for 1%, 2%, 5%, weight loss temperatures.

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Abstract

La présente invention concerne des hydrogrenats de synthèse et des adjuvants ignifugeants dérivés du 9,10-dihydro-9-oxa-10-phosphaphénantrène-10-oxyde, pouvant être employés dans les compositions de résine époxy. Les compositions de résine époxy peuvent être employées dans la fabrication de pré-imprégnés ou de laminés pour les circuits imprimés et les matériaux composites.
PCT/US2011/059723 2010-11-12 2011-11-08 Agent ignifugeant dérivé de dopo et hydrogrenats de synthèse pour compositions de résine époxy WO2012064703A1 (fr)

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WO2016008074A1 (fr) * 2014-07-14 2016-01-21 中国科学院宁波材料技术与工程研究所 Nylon haute température ignifuge sans halogène
JP2017110014A (ja) * 2014-11-10 2017-06-22 江蘇雅克科技股▲ふん▼有限公司 Ｄｏｐｏ誘導体とエポキシ樹脂組成物の高周波基板への適用
CN107082909A (zh) * 2017-04-18 2017-08-22 三峡大学 一种含dopo的对苯二酚双磷酸酯阻燃剂的制备方法及其应用
CN109400650A (zh) * 2018-11-14 2019-03-01 湖北省兴发磷化工研究院有限公司 一种阻燃剂dopo-ita的合成方法
CN109535388A (zh) * 2018-11-21 2019-03-29 苏州生益科技有限公司 含磷环氧树脂组合物及应用其制备的半固化片和层压板
CN110218327A (zh) * 2019-05-31 2019-09-10 福建师范大学 一种超支化含磷聚硅氧硼烷阻燃剂及其制备方法
CN110951216A (zh) * 2019-11-29 2020-04-03 陕西生益科技有限公司 一种热固性树脂组合物以及使用其的预浸料和层压板
CN111234235A (zh) * 2020-02-24 2020-06-05 桂林理工大学 一种低聚硅氧磷酸酯阻燃剂及其制备方法和应用

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CN103113718A (zh) * 2013-02-11 2013-05-22 中国能源建设集团山西省电力勘测设计院 一种高强度隔热酚醛环氧树脂组合物
WO2016008074A1 (fr) * 2014-07-14 2016-01-21 中国科学院宁波材料技术与工程研究所 Nylon haute température ignifuge sans halogène
JP2017110014A (ja) * 2014-11-10 2017-06-22 江蘇雅克科技股▲ふん▼有限公司 Ｄｏｐｏ誘導体とエポキシ樹脂組成物の高周波基板への適用
US9956742B2 (en) 2014-11-10 2018-05-01 Jiangsu Yoke Technology Co., Ltd DOPO derivative and composite of epoxy applied in high-frequency substrate
CN107082909A (zh) * 2017-04-18 2017-08-22 三峡大学 一种含dopo的对苯二酚双磷酸酯阻燃剂的制备方法及其应用
CN109400650B (zh) * 2018-11-14 2024-03-15 湖北省兴发磷化工研究院有限公司 一种阻燃剂dopo-ita的合成方法
CN109400650A (zh) * 2018-11-14 2019-03-01 湖北省兴发磷化工研究院有限公司 一种阻燃剂dopo-ita的合成方法
CN109535388A (zh) * 2018-11-21 2019-03-29 苏州生益科技有限公司 含磷环氧树脂组合物及应用其制备的半固化片和层压板
CN109535388B (zh) * 2018-11-21 2021-02-09 苏州生益科技有限公司 含磷环氧树脂组合物及应用其制备的半固化片和层压板
CN110218327B (zh) * 2019-05-31 2021-03-16 福建师范大学 一种超支化含磷聚硅氧硼烷阻燃剂及其制备方法
CN110218327A (zh) * 2019-05-31 2019-09-10 福建师范大学 一种超支化含磷聚硅氧硼烷阻燃剂及其制备方法
CN110951216A (zh) * 2019-11-29 2020-04-03 陕西生益科技有限公司 一种热固性树脂组合物以及使用其的预浸料和层压板
CN110951216B (zh) * 2019-11-29 2022-12-20 陕西生益科技有限公司 一种热固性树脂组合物以及使用其的预浸料和层压板
CN111234235A (zh) * 2020-02-24 2020-06-05 桂林理工大学 一种低聚硅氧磷酸酯阻燃剂及其制备方法和应用
CN111234235B (zh) * 2020-02-24 2022-05-13 桂林理工大学 一种低聚硅氧磷酸酯阻燃剂及其制备方法和应用

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