WO2014179688A1 - Dérivés de di-dopo liés oar butadièn-2,3-diyle en tant que retardateurs de flamme - Google Patents

Dérivés de di-dopo liés oar butadièn-2,3-diyle en tant que retardateurs de flamme Download PDF

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WO2014179688A1
WO2014179688A1 PCT/US2014/036579 US2014036579W WO2014179688A1 WO 2014179688 A1 WO2014179688 A1 WO 2014179688A1 US 2014036579 W US2014036579 W US 2014036579W WO 2014179688 A1 WO2014179688 A1 WO 2014179688A1
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parts
weight
compound
alkyl
composition
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PCT/US2014/036579
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Scott Edward ANGELL
Kimberly A. WHITE
Yu Li ANGLELL
Arthur G. Mack
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Albemarle Corporation
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Priority to SG11201509015YA priority Critical patent/SG11201509015YA/en
Priority to JP2016512970A priority patent/JP2016529205A/ja
Priority to US14/888,561 priority patent/US20160060281A1/en
Priority to EP14729157.9A priority patent/EP2991995A1/fr
Priority to CA2911382A priority patent/CA2911382A1/fr
Publication of WO2014179688A1 publication Critical patent/WO2014179688A1/fr

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    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to novel, halogen-free flame-retardants derived from 9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-oxide (DOPO). This invention also relates to the use of the halogen free DOPO derived flame-retardants in polymers. BACKGROUND OF INVENTION
  • thermoplastic and thermoset polymers for example polyamides, polyesters, epoxy resins and polyurethanes
  • flame-retardants for many applications.
  • halogenated compounds more specifically, aromatic polybrominated compounds, have been used as flame-retardant additives in polymers. It is generally accepted that these products inhibit radical gas phase reactions from occurring in the flame when these products are ignited. This makes halogenated flame-retardants very commonly used additives for different types of polymeric materials.
  • halogenated flame-retardants have come under scrutiny because of ecological concerns. At this time, the flame-retardant industry is under pressure to change to flame-retardants that are perceived to be more environmentally friendly, such as organophosphorus flame-retardants.
  • organophosphorus compounds have been shown in the prior art to impart flame retardancy to polymers.
  • Most of the phosphorus-containing flame-retardants provide flame-retardant activity through a combination of vapor and condensed phase reactions, polymer carbonization promotion, and char formation.
  • organophosphorus flame-retardant materials There are usually problems associated with the use of organophosphorus flame-retardant materials.
  • One source of difficulty relates to the processing of polymers, which often requires high temperatures, potentially at temperatures above 210°C and often as high as 310-350°C.
  • flame-retardants often participate in decomposition or side reactions, which impart undesirable properties to the base polymer or polymer system.
  • Other flame-retardants become too volatile under processing conditions and are not effectively retained during processing.
  • the present invention relates to a compound, useful for a flame-retardant, having the following structure:
  • R 1 is C(R 4 ) 2 ; each R 2 and R 3 are independently hydrogen, C1-C15 alkyl, C 6 -Ci2 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R 2 and R 3 taken together can form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring may be optionally substituted by a Ci-C 6 alkyl; each R 4 is independently hydrogen, Ci-C 6 alkyl, C 6 -Ci 2 aryl or C3-C12 cycloalkyl; and each m is independently 1, 2, 3 or 4. DETAILED DESCRIPTION OF THE INVENTION
  • the present invention relates to a compound, useful for a flame-retardant additive, having the following structure:
  • R 1 is C(R 4 ) 2 ; each R 2 and R 3 are independently hydrogen, C1-C15 alkyl, C 6 -Ci2 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R 2 and R 3 taken together can form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring may be optionally substituted by a Ci-C 6 alkyl; each R 4 is independently hydrogen, Ci-C 6 alkyl, C 6 -Ci2 aryl or C3-C12 cycloalkyl; and each m is independently 1, 2, 3 or 4.
  • R 2 and R 3 are independently hydrogen or a Ci-C 6 alkyl. In another aspect, all R 4 substituents are hydrogen. In yet another aspect, R 2 and R 3 are hydrogen.
  • alkyl as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties.
  • 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 6 H 5 CH 2 -) and methylbenzyl (CH 3 C 6 H 4 CH 2 - ).
  • alkaryl indicates an "alkyl-aryl-" group.
  • alkaryl are methylphenyl-, dime thy lphenyl-, ethylphenyl- propylphenyl-, isopropylphenyl-, butylphenyl-, isobutylphenyl- and t-buty lphenyl-.
  • 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.
  • all the foregoing groups derived from hydrocarbons may have up to about 1 to about 20 carbon atoms (e.g., C1-C2 0 alkyl, C6-C2 0 aryl, C7-C2 0 alkaryl, C7-C2 0 aralkyl) or 1 to about 12 carbon atoms (e.g., C1-C12 alkyl, C 6 -Ci2 aryl, C7-C12 alkaryl, C7-C12 aralkyl), or 1 to about 8 carbon atoms, or 1 to about 6 carbon atoms.
  • carbon atoms e.g., C1-C2 0 alkyl, C6-C2 0 aryl, C7-C2 0 alkaryl, C7-C2 0 aralkyl
  • 1 to about 12 carbon atoms e.g., C1-C12 alkyl, C 6 -Ci2 aryl, C7-C12 alkaryl,
  • This invention also related to a flame-retardant polymer composition
  • a flame-retardant polymer composition comprising a polymer and the flame-retardant amount of the compounds of Formula I.
  • Polymer that may be used in the flame-retardant polymer composition include, but are not limited to: polyolefins, polyesters, polyethers, polyketones, polyamides, polyvinylchlorides, natural and synthetic rubbers, polyurethanes, polystyrenes, poly(meth)acrylates, phenolic resins, polybenzoxazine, polyacetals, poly aery lonitriles, polybutadienes, polystyrenes, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, polyphenylene oxide, polycarbonates, cellulose, cellulose derivatives, cyanate esters, polyphenylene esters, polybutadiene resins, butadiene- styrene resins
  • the polymers are polyesters, phenolic resins, phenol triazine novolaks, cresol triazine novolaks, triazine phenol epoxy novolaks, triazine cresol epoxy novolaks, polyamides, polyurethanes, polystyrene, epoxy resins or mixtures thereof.
  • the flame -retardant composition further comprises at least one conventional additive, such as heat stabilizers, light stabilizers, ultra-violet light absorbers, anti-oxidants, anti-static agents, preservatives, adhesion promoters, 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-retardant additives, smoke suppressants and mixtures thereof.
  • at least one conventional additive such as heat stabilizers, light stabilizers, ultra-violet light absorbers, anti-oxidants, anti-static agents, preservatives, adhesion promoters, fillers, pigments, dyes
  • the other flame-retardant additives which may be used with the compounds of formulas Formula I include, but are not limited to, nitrogen-containing synergists such as ammonium polyphosphate, melamine, melamine phosphate, melamine cyanurate, melamine pyrophosphate, melamine polyphosphate, Melam (1,3,5- triazine-2,4,6-triamine-n-(4,6- diamino-l,3,5-triazine-2-yl), Melem(-2, 5, 8-triamino- 1,3,4, 6,7,9, 9b-Heptaazaphenalene), Melon (poly[8-amino-l,3,4,6,7,9,9b-Heptaazaphenalene-2,5-diyl)imino] phosphate and cyanurate derivatives of guanidine and piperazine, phosphazene compound, polyphophazenes, antimony oxide, silica, talc, hydrotalcite,
  • the amount of compound of Formula I added to the polymer as a flame-retardant may be varied over a wide range. Usually from about 0.1 to about 150 parts by weight of the compounds of Formula I are used per 100 parts by weight of polymer. Preferably about 0.5 to about 100 parts of the compounds of Formula I are used per 100 parts by weight of polymer, or from about 2 to about 70 parts by weight per 100 parts by weight of polymer or from about 2 to about 50 parts by weight per 100 parts by weight of polymer.
  • Masterbatches of polymer containing the compounds of Formula I of this invention, which are blended with additional amounts of substrate polymer, can contain even higher concentrations of the compounds of Formula I, e.g., from about 100 to about 1000, or from about 100 to about 500, or from about 100 to about 250 parts by weight of the compounds of Formula I per 100 parts by weight of polymer.
  • the amount of the phosphorus compounds of Formula I in the flame- retardant polymer 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.
  • Polypheny lene oxides and sulfides and blends of these polymers with polystyrene graft polymers or styrene copolymers such as high impact polystyrene, EPDM copolymers with rubbers, as well as blends of polyphenylene oxide with polyamides and polyesters.
  • Polyurethanes which are derived from polyethers, polyesters or poly butadiene with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand including polyisocyanurates, as well as precursors thereof.
  • Polyamides including copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene iso-phthalamide, as well as copolymers thereof with polyethers, such as with polyethylene glycol, polypropylene glycol or poly tetramethy lene glycols.
  • Polyesters which are derived from dicarboxylic acids and di-alcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-l,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoates as well as block-copolyether-esters derived from polyethers having hydroxyl end groups.
  • Polystyrene and graft copolymers of styrene for example styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with random copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for instance the terpolymers of styrene known as ABS, MBS, ASA or AES terpolymers.
  • Epoxy resins are compounds that are prepared by polyaddition reaction of an epoxy resin component and a crosslinking (hardener) component.
  • the epoxy resin components used are aromatic polyglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, polyglycidyl ethers of phenol-formaldehyde resins and of cresol-formaldehyde resins, polyglycidyl ethers of phthalic, isophthalic and terephthalic acid, and also of trimellitic acid, N-glycidyl compounds of aromatic amines and of heterocyclic nitrogen bases, and also di- and polyglycidyl compounds of polyhydric aliphatic alcohols.
  • the hardeners used are polyamines such as dicyandiamide (DICY), phenolic novolacs, cresol novolacs, triethylenetetramine, aminoethylpiperazine and isophoronediamine, polyamidoamines, polybasic acids or anhydrides thereof, for example phthalic anhyride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride or phenols.
  • the cross-linking may also be affected by polymerization using suitable catalysts or promoters, such as 2-phenylimidazole, 2-methylimidazole, benzyl dimethylamine (BDMA), etc.
  • Polyesters are particularly suitable.
  • the flame-retardant additive of Formula I may be incorporated into the polymer by a variety of mixing techniques, such as solution blending and melt blending.
  • melt blending equipment include twin screw extruders, single screw extruders, Banbury mixers, roll mixers, kneaders, etc.
  • the melt blending temperature depends on the resin being used and is within the range from about 150°C to about 400°C.
  • the extrudate exits through small die holes, and the strands of molten composition are cooled by passing through a water bath.
  • the cooled strands can be pelletized.
  • the pellets can be used to prepare molded articles. In some instances, it is necessary to dry the composition prior to molding.
  • a further technique is to add the flame- retardant to finished polymer granules or powders and to process the mixture directly to provide a plastic article.
  • the method used in producing a plastic article from the flame-retardant resin composition of the present invention is not particularly limited, and any method commonly used may be employed. Exemplary such methods include moldings such as injection molding, blow molding, extrusion, sheet forming, thermal molding, rotational molding, and lamination.
  • the phosphorus flame retardants of Formula I may be used in thermoset applications such as laminates for printed circuit boards (PCB) and composites for aerospace. A number of different formulations and components may be used to produce these laminates and composites including the resins systems discussed below.
  • Cyanate ester resins are derived from cyanate ester monomers and will form a triazine structure upon curing. They may be used alone or with other materials such as epoxies monomers or resin, bismaleimides (discussed below) to form BT resins, and other resins used in the PCB and composite areas.
  • a non-limiting exemplary structure of a cyanate ester is a composition shown below in Formula II:
  • each Arl and Ar2 are independently phenylene, biphenylene, naphthylene and anthrylene; each XI and X2 are independently Ci-Cs alkylene, Ci-Cs haloalkylene, C3-Ci 6 cycloalkylene, -S-, carbonyl, or carboxyl; and each Rl is independently hydrogen or a Ci-Cs alkyl and n is a whole number from 0 to 10.
  • Cyanate esters and resins are commercial materials.
  • Non-limiting examples of cyanate esters are dicyanatobenzenes, tricyanatobenzenes, dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato-biphenyl, bis(cyanatophenyl)methanes and alkyl derivatives thereof, bis(dihalocyanatophenyl)propanes, bis(cyanatophenyl)ethers, bis(cyanatophenyl)sulfides, bis(cyanatophenyl)propanes, phosphorus-containing cyanate esters (e.g., tris(cyanatophenyl)phosphites, tris(cyanatophenyl)phosphates, and the like), bis(halocyanatophenyl)methanes, cyanated novolac, bis[cyanatophenyl(methylethylidene)]benzene, cyanated bisphenol-terminated thermoplastic
  • Preferred cyanate ester monomers from which the triazines are prepared include bisphenol-A cyanate esters, bisphenol-E cyanate esters, tetramethylbisphenol-F cyanate esters, bisphenol-M cyanate esters, phenol Novolac cyanate esters, bisphenol-C cyanate esters, dicyclopentadienyl-bisphenol cyanate esters, Novolac cyanate esters, and the like, as well as mixtures of any two or more thereof.
  • Polybenzoxazines are made from benzoxazine monomer, which upon heating or curing, causes the heterocyclic oxazine ring to open forming the polymer where the nitrogen is in the main chain of the polymer.
  • a non-limiting exemplary structure of a benzoxazine monomer is a composition shown below in Formul
  • each X3 and X4 are independently Ci-Cs alkylene, Ci-Cs haloalkylene, C3-C16 cycloalkylene, -S-, carbonyl, or carboxyl; and each R 4 is independently a C1-C3 alkyl or a phenyl and n is a whole number from 0 to 10.
  • Another component that may be added in the laminate or composite formulation is bismaleimides. They are typically used in conjunction with the cyanate monomers to form the so called BT (bismaleimide-triazine) resins.
  • X is alkylene, cycloalkylene, arylene, polyarylene, heteroarylene, polyheteroarylene or bisarylene; wherein bisarylene is -Ar-Y-Ar-, and Ar is arylene, Y is a direct bond, -0-, -S- or Ci to C alkylene; R 5 is hydrogen or a Ci to C 6 alkyl, and n is 2 to 10.
  • Exemplary bismaleimides contemplated for use in the practice of the present invention are selected from the group consisting of N,N'-m-phenylene bismaleimide, N,N'-p- phenylene bismaleimide, N,N'-m-toluene bismaleimide, N,N'-4,4'-biphenylene bismaleimide, N,N'-4,4'-[3,3'-dimethyl-biphenylene]bismaleimide, N,N'-4,4'-[3,3'- dimethyldiphenylmethane] bis maleimide, N,N'-4,4'-[3,3'- diethyldiphenylmethanejbismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'- diphenylpropane bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-3,3'- diphen
  • the epoxy resin can be selected from known epoxy resins. Examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a xylene novolak type epoxy resin, triglycidyl isocyanurate, an alicyclic epoxy resin, a dicyclopentadiene.
  • novolak type epoxy resin a biphenyl aralkyl novolak type epoxy resin, a phenol aralkyl novolak type epoxy resin, a naphthol aralkyl novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a brominated bisphenol A type epoxy resin, a brominated phenol novolak type epoxy resin, a trifunctional phenol type epoxy resin, a tetrafunctional phenol type epoxy resin, a naphthalene type epoxy resin and a phosphorus -containing epoxy resin.
  • Preferred examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a brominated bisphenol A type epoxy resin, a brominated phenol novolak type epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl novolak type epoxy resin, a biphenyl aralkyl novolak type epoxy resin and a naphthol aralkyl novolak type epoxy resin.
  • These epoxy resins may be used alone or in combination.
  • the above epoxy resin curing agent can be selected from generally known epoxy resin curing agents. Examples thereof include imidazole derivatives such as 2- methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, l-cyanoethyl-2- phenylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5 - dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine and 4-methyl-N,N- dimethylbenzylamine; and phosphine compounds such as phosphonium compounds.
  • imidazole derivatives such as 2- methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, l-cyanoethyl-2- phenylimidazole, 1 -cyanoethyl
  • Polyphenylene oxide also called polyphenylene ether
  • exemplary polyphenylene oxides have the structure: [-Ph-0-] n wherein Ph is an optionally substituted phenyl ring, and n falls in the range of about 10 up to about 200; with n in the range of about 10-100 is preferred.
  • Ph is an optionally substituted phenyl ring
  • n falls in the range of about 10 up to about 200; with n in the range of about 10-100 is preferred.
  • Styrene maleic anhydride also known as SMA is a copolymer consisting of styrene and maleic anhydride monomers.
  • the copolymer is typically formed by a radical polymerization, using an organic peroxide as the initiator resulting is an alternating monomer arrangement. It has a transparent appearance, high heat resistance, high dimensional stability, and the reactivity of the anhydride groups.
  • SB styrene-butadiene
  • SBS styrene-butadiene-styrene
  • FG1901X and FG 1924 from Kraton Polymers
  • ethylene propylene diene monomer liquid rubbers and vinyl-terminated polybutadiene rubber
  • the laminate or composite formulation may contain other additives known in the art such as an inorganic filler, a color pigment, an antifoamer, a surface conditioner, other flame retardants, an ultraviolet absorber, antioxidants and flow regulators, as required.
  • the inorganic filler include silicas such as natural silica, fused silica, amorphous silica and hollow silica, white carbon, titanium white, aerosil, alumina, talc, natural mica, synthetic mica, kaolin, clay, calcined clay, calcined kaolin, calcined talc, mica; metal hydrates such as aluminum hydroxide, heat-treated aluminum hydroxide (obtained by heat-treating aluminum hydroxide and reducing part of crystal water), boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, barium sulfate, E-glass, A-glass, NE-glass,
  • the average particle diameter of the inorganic filler is preferably 0.1 to 10 um. Inorganic fillers having different particle size distributions or different average particle diameters may be used in combination as required.
  • the amount of the inorganic filler is not specially limited. The amount of the inorganic filler per 100 parts by weight of the resin components is preferably 10 to 300 parts by weight, particularly preferably 30 to 200 parts by weight.
  • the base substrate material used in the present invention can be selected from known base substrate materials which are used for various printed wiring board materials and composites. Examples thereof include inorganic fibers such as E glass, D glass, S glass, NE glass and quartz, and organic fibers such as polyimide, polyamide and polyester.
  • the base material is properly selected according to intended use or performance as required. These base materials maybe used alone or in combination.
  • the form of the base material is typically a woven fabric, a nonwoven fabric, roving, a chopped strand mat or a surfacing mat.
  • the thickness of the base material is not specially limited. Generally, it is about 0.01 to 0.3 mm.
  • base materials surface-treated with a silane-coupling agent or the like and physically-opening-treated woven fabrics can be preferably used in view of heat resistance after moisture absorption.
  • a film of polyimide, polyamide, polyester or the like may be also used. The thickness of the film is not specially limited and it is preferably about 0.002 to 0.05 mm.
  • a film surface-treated by plasma treatment or the like may be used.
  • the aforementioned flamed retardant may especially be used to form prepreg and/or laminates with epoxy compounds.
  • Typical procedures for forming prepregs and laminates for printed wiring boards involve such operations as:
  • An epoxy-containing formulation such as one containing the aforementioned flame- retardant with an epoxy compound 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.
  • D) 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, l-methoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, toluene, ⁇ , ⁇ -dimethylformamide, and mixtures thereof.
  • the curing or polymerization initializing agents that may be used for preparing the laminates 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 phosphorus-containing epoxy resin.
  • 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 cured epoxy resin.
  • 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 epoxy compositions. These epoxy curing agent promoters are often based on imidazoles. Examples of such epoxy curing agent promoters include, but are not limited to: 1- methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, l-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 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. Amounts
  • the amount of Flame retardant of Formula I used in the laminate or composite formulation is typically about 1% to about 30wt%, or about 3% to about 25wt%, or about 5% to about 20wt%, based on the total weight of the resins in the composite or laminate formulation.
  • the cyanate ester resin may be used alone or is typically combined with an epoxy or a bismaleimide monomer.
  • the amount of the epoxy resin is preferably about 10 to about 90% by weight, particularly preferably about 30% to 70% by weight, based on the total amount of the cyanate ester compound and the epoxy resin.
  • the amount of the maleimide compound is preferably about 5% to about 75% by weight, particularly preferably about 10 to about 70% by weight, based on the total amount of the cyanate ester resin and the maleimide compound.
  • the polybenzoxazines may be used alone or in combination with the other components typically within the same amounts used for the cyanate esters.
  • thermoset embodiments of the present invention are shown below.
  • the present invention also relates to a thermoset composition
  • a thermoset composition comprising: (a) 0-50 parts by weight of at least one cyanate ester, (b) 0-50 parts by weight of at benzoxazine monomer; (c) 0-50 parts by weight of at least one bismaleimide, (d) 10-100 parts by weight of at least one epoxy compound; and (e) 5-60 parts by weight of the phosphorus compound having the formula I.
  • a thermoset composition comprising: (a) 0-50 parts by weight of at least one cyanate ester, (b) 0-50 parts by weight of at benzoxazine monomer; (c) 0-50 parts by weight of at least one bismaleimide, (d) 10-100 parts by weight of at least one epoxy compound; and (e) 5-60 parts by weight of the phosphorus compound having the formula I.
  • R 2 and R 3 in Formula I are independently hydrogen or a Ci-C 6 alkyl.
  • a further embodiment is wherein R 2 and R 3 in
  • compositions comprises (a) 10-50 parts by weight of at least one cyanate ester, (b) 10-50 parts by weight of at benzoxazine monomer; (c) 10-50 parts by weight of at least one bismaleimide, (d) 10-100 parts by weight of at least one epoxy compound; and (e) 5-60 parts by weight of the phosphorus compound having formula I.
  • the present invention also relates to a thermoset composition
  • a thermoset composition comprising: (a) 30-100 parts by weight of at least styrene -butadiene (SB) rubber, (b) 0-50 parts by weight of a styrene-butadiene-styrene (SBS) rubber; (c) 0-50 parts by weight of at least one bismaleimide, (d) 0-50 parts by weight of a maleic anhydride grafted styrene-butadiene polymer; ( e) 0-50 parts of an ethylene propylene diene monomer liquid rubber, (f) 0-50 parts of a vinyl -terminated polybutadiene rubber and (g) 0-50 parts of a polyphenylene oxide resin and (h) 5-60 parts of the phosphorus compound of Formula I .
  • SB styrene -butadiene
  • SBS styrene-butadiene-styrene
  • R 2 and R 3 in Formula I are independently hydrogen or a Ci-C 6 alkyl.
  • a further embodiment is wherein R 2 and R 3 in Formula I are hydrogen and all R 4 substituents in Formula I are hydrogen.
  • Another embodiment is a composition comprises (a) 10-50 parts by weight of at least one cyanate ester, (b) 10-50 parts by weight of at benzoxazine monomer; (c) 10-50 parts by weight of at least one bismaleimide, (d) 10-100 parts by weight of at least one epoxy compound; and (e) 5-60 parts by weight of the phosphorus compound having formula I.
  • the compounds of the present invention may be produced by reacting approximately 2 equivalents of the chloro-dopo compound of Formula A with approximately one equivalent of the butyne diol compound of Formula B, optionally in presence of a base to neutralize the HC1 produced and an optional solvent, to form the compound of the present invention, wherein R 1 , R 2 and R 3 are defined above.
  • the reaction temperature may be from about - 20°C to about 100°C.
  • Any suitable optional base may be used to neutralize the HC1 produced in the reaction including organic or inorganic bases.
  • any optional suitable solvent may be used in the reaction.
  • suitable solvent may include: include, but are not limited to heptane, hexane, chloroform, chlorobenzene, petroleum ether, methylcyclohexane; dichloromethane, toluene, xylenes, ethyl benzene, tetrahydrofuran, DMSO, 1,4-dioxane, acetonitrile, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or mixtures thereof.
  • a 4000-mL, 5-neck reaction vessel with circulating oil jacket was equipped with a mechanical stirrer, a condenser, a thermocouple, and a 1000-ml addition funnel.
  • the addition funnel was equipped with a short section of Teflon tubing for smooth delivery to the reactor and a glass plug at the top.
  • a nitrogen line with a bubbler was fitted to the top of the condenser.
  • DOPO-C1 (531.63g, 2.266mol) was dissolved in dichloromethane (1645g) and transferred to the reactor.
  • the oil jacket of the reaction vessel was cooled to -15°C.
  • the condenser was cooled to 10°C. Once the thermocouple indicated that the interior temperature of the reaction vessel was 0°C, the solution was slowly added to the reaction vessel to maintain a temperature of less than 15°C. After addition, the mixture was allowed to come to room temperature.
  • a flame-retardant resin mixture containing 3.0 wt P was prepared by adding 126.3 g of 85wt DEN 438 solution, 126.0 g of 50wt SD-1702 solution, 52.0 g flame-retardant compound and 0.161 g 2-phenylimidazole promoter. The novolac to promoter ratio was about 392.
  • An additional 80 g MEK was added to the resin solution. The flame-retardant completely dissolved in the solution with heating at about 40°C.
  • An 11 inch by 11 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 3 minutes.
  • 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 0.032 inches thick, contained 42 wt resin and underwent 7 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 ASTM D3801- 06 using an Atlas UL-94 burn chamber, resulting in a V-0 rating with 48 seconds total burn time for the two ignitions on all five coupons.
  • Example 2 The procedure used in Example 2 was used to develop prophetic laminate formulas for Examples 3-11 in Table 2 (wt basis) with the exception that a higher functional o-cresol Novolac type epoxy resin (Nan Ya NPCN-703) is used in place of the phenol epoxy novolac resin and in some examples silica and/or melamine polyphosphate (Melapur 200 (M-200) from BASF Corporation) are used in the resin mixtures.
  • PER is the phosphorus flame retardant produced in Example 1
  • compositions are processed according to the following procedure.
  • the web would be impregnated with the slurry, metered to the correct thickness, and then solvent would be removed (evaporated to form a prepreg).
  • the lamination process entails a stack-up of 6 prepreg layers between two sheets of copper foils (Oak Mitsui TOC 500 LZ or Circuit Foil TWS) uncoated or previously coated with the adhesive layer. This stack-up would then be densified and cured via fiat bed lamination; typical cure temperature ranges were between about 325° F. (163° C.) and about 475° F. (246° C.) and pressure between 300- 1200 psi.
  • PFR is the phosphorus flame retardant produced in Example 1 , Kraton® D-l 1 18 a sytyrene-butadiene (SB) diblock copolymer (20%) and styrene- butadiene-styrene (SBS) tribloek copolymer (80%) from Kraton Polymers.
  • Trilene 65 is an ethylene propylene cliene monomer liquid rubber from Crompton Corp.
  • B-3000 is a vinyl- terminated polybuiadiene .from Nippon Soda
  • Varox® DCP is a dicumyl peroxide curing agent from RT Vanderbilt
  • Meiapur 200 is a melamine polyphosphate from BASF Corp.
  • MGZ-6R is a silica coated magnesium hydroxide from Sakai Chemicals.
  • Naugard® XL is an antioxidant (l,2-dioxoet ane-l,2-diyl)bis(iminoethane-2J.-diyl) bis[3-i3,5-di-tcit-but.y.l- -hydroxyphe.nyljpropai5oa e], from Addivam Corporation.
  • A74NT is a aminosikrse from GelesL Inc.
  • PFR is the phosphorus flame retardant produced in Example 1
  • AroCy® L-10 and XU378 are Cyanate Esters based on bisphenol E and Bisphenol-M from Huntsman Corp.
  • BM-200 is 4,4-diphenylmethane bismaleimide from Otsuka Chemical.
  • Araldite® LZ8282 is a benzoxazine resin based on bisphenol F from Huntsman Corp.
  • NPCN-703 is 60 wt an o-cresol Novolac type epoxy resin from Nan Ya Plastics Corp.
  • NC- 3000H is a biphenyl aralkyl novolak type epoxy resin from Nippon Kayaku Co.
  • YPXTM 100F is a polypheny lene ether from Mitsubishi Gas Chemical Co.
  • DelacalTM NFR HP is a nitrogen synergists comprising constituents of Melem and Melam from Delamin Limited.
  • MGZ-6R is a silica coated magnesium hydroxide from Sakai Chemicals.
  • SMA® 1000 is a styrene-maleic anhydride copolymer with styrene/maleic anhydride molar ratios of 1 : 1 from Cray Valley USA.
  • Kraton ⁇ D-1118 a styrene-butadierie (SB) diblock copolymer (20%) and styrene- butadiene-styrene (SBS) tri block copolymer (80%) from Kraton Polymers.
  • SB styrene-butadierie
  • SBS styrene- butadiene-styrene
  • BM-200 is 4,4- dipbeny] methane bismaleimide from Otsuka Chemical.
  • YPXTM 100F is a polyphenylene ether from Mitsubishi Gas Chemical Co. Ricon® 156MA17 from Sartomer (subsidiary of the Arkema group) is a polybutadiene resin with maleic anhydride additions.
  • Kraton® FG1901X is a maleic anhydride grafted polybutadiene-styrene copolymer from Kraton Polymers.
  • MGZ-6R is a silica coated magnesium hydroxide from Sakai Chemicals.
  • SMA® 1000 is a styrene-maleic anhydride copolymer with styrene/maleic anhydride molar ratios of 1 : 1 from Cray Valley USA.

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Abstract

La présente invention concerne de nouveaux retardateurs de flamme exempts d'halogène, dérivés du 9,10-dihydro-9-oxa-10-phosphaphénanthrène-10-oxyde (DOPO) de la structure ci-après : Cette invention concerne également l'utilisation des compositions dérivées de DOPO exemptes d'halogène en tant que retardateurs de flamme dans des polymères, et un procédé de préparation des composés ci-dessus par réaction d'un composé de formule A avec un composé de formule B :
PCT/US2014/036579 2013-05-03 2014-05-02 Dérivés de di-dopo liés oar butadièn-2,3-diyle en tant que retardateurs de flamme WO2014179688A1 (fr)

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SG11201509015YA SG11201509015YA (en) 2013-05-03 2014-05-02 Butadien2,3-diyl linked di-dopo derivatives as flame retardants
JP2016512970A JP2016529205A (ja) 2013-05-03 2014-05-02 難燃剤としてのブタジエン２，３−ジイル結合ｄｉ−ｄｏｐｏ誘導体
US14/888,561 US20160060281A1 (en) 2013-05-31 2014-05-02 Butadien2,3-diyl linked di-dopo derivatives as flame retardants
EP14729157.9A EP2991995A1 (fr) 2013-05-03 2014-05-02 Dérivés de di-dopo liés oar butadièn-2,3-diyle en tant que retardateurs de flamme
CA2911382A CA2911382A1 (fr) 2013-05-03 2014-05-02 Derives de di-dopo lies oar butadien-2,3-diyle en tant que retardateurs de flamme

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CN104558684A (zh) * 2015-01-21 2015-04-29 三峡大学 一种含dopo的双氧己内磷酸酯阻燃剂，制备方法及其应用
JP2017165827A (ja) * 2016-03-15 2017-09-21 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板
CN109161000A (zh) * 2018-07-27 2019-01-08 武汉工程大学 一种新型化合物dopo-ma在环氧树脂体系中的应用
WO2019006774A1 (fr) * 2017-07-05 2019-01-10 中国科学院宁波材料技术与工程研究所 Procédé de préparation d'un composé didopo
CN109721710A (zh) * 2018-07-27 2019-05-07 武汉工程大学 一种新型化合物dopo-ma及其合成方法
CN109796688A (zh) * 2018-12-31 2019-05-24 安徽天康(集团)股份有限公司 一种云母带矿物绝缘波纹铜护套防火阻燃电缆
CN110964320A (zh) * 2019-12-25 2020-04-07 艾蒙特成都新材料科技有限公司 一种阻燃马来酰亚胺组合物及其覆铜板的制备方法

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JP7100799B2 (ja) * 2018-01-12 2022-07-14 昭和電工マテリアルズ株式会社 熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び高速通信対応モジュール
JP7274114B2 (ja) * 2018-01-12 2023-05-16 株式会社レゾナック 熱硬化性樹脂組成物、プリプレグ、積層板、プリント配線板及び高速通信対応モジュール
CN111635616B (zh) * 2019-03-01 2021-07-30 广东生益科技股份有限公司 无卤阻燃热固性树脂组合物、印刷电路用预浸料及覆金属层压板
TWI757816B (zh) * 2020-08-05 2022-03-11 國立中興大學 磷系化合物及其製備方法、阻燃不飽和樹脂組成物及固化物
CN113322533B (zh) * 2021-06-28 2022-11-22 中车青岛四方机车车辆股份有限公司 一种本征阻燃聚乙烯醇纤维及其制备方法
KR102615736B1 (ko) * 2021-08-11 2023-12-20 세진하이텍(주) 열반사 단열재 판넬 및 이의 제조방법
WO2023145960A1 (fr) * 2022-01-31 2023-08-03 株式会社ダイセル Composition de résine thermodurcissable, composition de résine pour carte de circuit imprimé, et composition de résine pour substrat de carte de circuit imprimé

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558684A (zh) * 2015-01-21 2015-04-29 三峡大学 一种含dopo的双氧己内磷酸酯阻燃剂，制备方法及其应用
JP2017165827A (ja) * 2016-03-15 2017-09-21 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板
WO2019006774A1 (fr) * 2017-07-05 2019-01-10 中国科学院宁波材料技术与工程研究所 Procédé de préparation d'un composé didopo
CN109161000A (zh) * 2018-07-27 2019-01-08 武汉工程大学 一种新型化合物dopo-ma在环氧树脂体系中的应用
CN109721710A (zh) * 2018-07-27 2019-05-07 武汉工程大学 一种新型化合物dopo-ma及其合成方法
CN109796688A (zh) * 2018-12-31 2019-05-24 安徽天康(集团)股份有限公司 一种云母带矿物绝缘波纹铜护套防火阻燃电缆
CN110964320A (zh) * 2019-12-25 2020-04-07 艾蒙特成都新材料科技有限公司 一种阻燃马来酰亚胺组合物及其覆铜板的制备方法
CN110964320B (zh) * 2019-12-25 2022-06-07 艾蒙特成都新材料科技有限公司 一种阻燃马来酰亚胺组合物及其覆铜板的制备方法

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