WO2010057851A1 - Compositions d'agent ignifugeant à base de phénylphosphinates de mélamine - Google Patents

Compositions d'agent ignifugeant à base de phénylphosphinates de mélamine Download PDF

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WO2010057851A1
WO2010057851A1 PCT/EP2009/065228 EP2009065228W WO2010057851A1 WO 2010057851 A1 WO2010057851 A1 WO 2010057851A1 EP 2009065228 W EP2009065228 W EP 2009065228W WO 2010057851 A1 WO2010057851 A1 WO 2010057851A1
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alkyl
formula
melamine
hydroxy
compounds
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PCT/EP2009/065228
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English (en)
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Sabine Fuchs
Thomas Weiss
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Basf Se
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Priority to CN2009801469095A priority Critical patent/CN102224219A/zh
Priority to EP09749153A priority patent/EP2367901A1/fr
Priority to US13/129,408 priority patent/US8877838B2/en
Priority to JP2011536840A priority patent/JP5409798B2/ja
Publication of WO2010057851A1 publication Critical patent/WO2010057851A1/fr

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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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)
    • 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
    • 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
    • C07F9/65719—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, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • 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'

Definitions

  • the present invention relates to flame retardant polymer compositions which comprise melamine phenylphosphinates and mixtures of melamine phenylphosphinates with dihydro- oxa-phosphaphenanthrene derivatives.
  • the compositions are especially useful for the manufacture of flame retardant compounds based on polyfunctional epoxides or polycon- densates like polyesters, polyamides and polycarbonates.
  • Flame retardants are added to polymeric materials (synthetic or natural) to enhance the flame retardant properties of the polymers. Depending on their composition, flame retardants may act in the solid, liquid or gas phase either chemically, e.g. as a spumescent by liberation of nitrogen, and/or physically, e.g. by producing a foam coverage. Flame retardants interfere during a particular stage of the combustion process, e.g. during heating, decomposition, ignition or flame spread.
  • the invention relates to a composition, particularly a flame retardant composition, which comprises a) A melamine phenylphosphinate salt of the formula
  • RrR 5 independently of one another represent hydrogen or a substituent selected from the group consisting of CrC 4 alkyl, hydroxy, hydroxy-CrC 4 alkyl and Ci-C 4 alkoxy; and b) A polymer substrate.
  • composition defined above for use as a flame retardant is another embodiment of the invention.
  • a preferred embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises a) A melamine phenylphosphinate salt (I), wherein
  • RrR 5 represent hydrogen
  • RrR 5 represent a substituent selected from the group consisting of Ci-C 4 alkyl, hydroxy-Ci-C 4 alkyl and Ci-C 4 alkoxy; and the other ones represent hydrogen; and b) A polymer substrate.
  • a more preferred embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises a) The melamine phenylphosphinate salt of the formula
  • a specific embodiment of the invention relates to a composition, which comprises a) A melamine phenylphosphinate salt (I), wherein
  • RrR 5 independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl, hydroxy, hydroxy-Ci-C 4 alkyl and Ci-C 4 alkoxy; and b) A polymer substrate selected from the group consisting of polyfunctional epoxide compounds, hardener compounds and thermoplastic polymers.
  • a more specific embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises a) The melamine phenylphosphinate salt of the formula
  • a polymer substrate selected from the group consisting of polyfunctional epoxide compounds and hardener compounds.
  • a preferred embodiment of the invention relates to composition, particularly a flame retardant composition, which comprises a) The melamine phenylphosphinate salt of the formula
  • a polymer substrate selected from the group consisting of polyfunctional epoxide compounds and hardener compounds.
  • a highly preferred embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises a) The melamine phenylphosphinate salt of the formula
  • a polymer substrate selected from the group consisting of polyfunctional epoxide compounds and hardener compounds;
  • compositions according to the invention attain the desirable V-O rating, according to UL- 94 (Underwriter's Laboratories Subject 94) and other excellent ratings in related test methods, especially in glass fibre reinforced formulations where conventional FR systems tend to fail.
  • composition as defined above, comprises the following components:
  • RrR 5 independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl, e.g. methyl, ethyl, n- or isopropyl, or n-, iso- or tert-butyl, hydroxy, hydroxy-CrC 4 alkyl, e.g. hydroxymethyl or 1- or 2-hydroxyethyl and Ci-C 4 alkoxy, e.g. methoxy or ethoxy.
  • Ci-C 4 alkyl e.g. methyl, ethyl, n- or isopropyl, or n-, iso- or tert-butyl
  • hydroxy, hydroxy-CrC 4 alkyl e.g. hydroxymethyl or 1- or 2-hydroxyethyl
  • Ci-C 4 alkoxy e.g. methoxy or ethoxy.
  • the melamine phenylphosphinate salt (I) as defined above is obtainable by known methods, e.g. acid-base reaction of equivalent amounts of melamine with phenylphosphinic acid of the formula
  • melamine phenylphosphinate is prepared from mela- mine and phenylphosphinic acid, for example by addition of both components as hot aqueous solutions, followed by subsequent crystallization, filtration, drying, and milling.
  • a further embodiment of the invention relates to the melamine phenylphosphinate salt (I) component of the formula
  • RrR 5 independently of one another represent hydrogen or a substituent selected from the group consisting of CrC 4 alkyl, hydroxy, hydroxy-CrC 4 alkyl and Ci-C 4 alkoxy, particularly a melamine phenylphosphinate salt (I), wherein RrR 5 represent hydrogen; or
  • RrR 5 represent a substituent selected from the group consisting of Ci-C 4 alkyl, hydroxy-Ci-C 4 alkyl and Ci-C 4 alkoxy; and the other ones represent hy- drogen.
  • the invention also relates to the melamine phenylphosphinate salt (I) component of the formula
  • the method for preparing the melamine phenylphosphinate salt (I) is also subject matter of the invention.
  • the melamine phenylphosphinate salt (I) is combined in the flame retardant compositions of the invention with oxaphosphorinoxide or a derivative thereof, as represented by the formula
  • the phosphorous atom and one oxygen atom are part of a cyclic structure, particularly a five or six membered ring, and at least one group of the partial formula
  • the oxaphosphorinoxide (II) is represented by the following structural formula:
  • DOPO 6H-dibenz[c,e][1 ,2]oxaphosphorin-6-oxide, 3,4:5,6-dibenzo-2H-1 ,2- oxaphosphorin-2-oxide or 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide, abbreviated as DOPO (CA. RN 35948-25-5).
  • DOPO 6H-dibenz[c,e][1 ,2]oxaphosphorin-6-oxide, 3,4:5,6-dibenzo-2H-1 ,2- oxaphosphorin-2-oxide or 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide, abbreviated as DOPO (CA. RN 35948-25-5).
  • Such compound is commercially available from Sanko Co, Ltd. under the trade name Sanko-HCA.
  • Two different structural formulae may be assigned to DOPO and its hydrolysis product:
  • Suitable derivatives of oxaphosphorinoxide are 9,10-dihydro-9-oxa-10-phosphorylphenan- threne-10-oxide (DOPO), salts of DOPO, such as the zinc salts
  • phenyl groups may be substituted by additional substituents and R represents Ci-Ci 8 alkyl or C 6 -Ci 2 aryl, which may be substituted by further substituents.
  • Representative compounds (lib) are compounds of the formula:
  • R 1 represents hydrogen or Ci-C 4 alkyl
  • R a represents hydrogen or d-C 4 alkyl; or represents alkoxyalkyl, such as the compounds of the formula:
  • Aryl such as the compounds of the formulae:
  • R represents arylalkyl
  • R represents alkoxyalkyl substituted by hydroxy, such as the compound of the formula
  • suitable derivatives of oxaphosphorinoxide are characterized by the presence of two groups of the partial formula
  • phenyl groups may be substituted by further substituents.
  • X represents C 2 -C 6 alkylene and Ri and Ri' represent hydrogen or d-C 4 alkyl;
  • R and R' represent hydrogen or Ci-C 4 alkyl
  • x represents a numeral from 2 to 4 and R represents CrC 4 alkyl or C ⁇ -Cio aryl or to- syl;
  • R represents hydroxy or amino
  • n a numeral from two to six and R represents the ester group from a polyhydroxy alcohol, such as di-, tri- or tetrahydroxy alcohol, e.g. ethylene glycol, trimethylol propane, pentaerythritol or dipentaerythritol, as obtained by reaction of DOPO with acrylic acid-R-esters and subsequent transesterifica- tion:
  • a polyhydroxy alcohol such as di-, tri- or tetrahydroxy alcohol, e.g. ethylene glycol, trimethylol propane, pentaerythritol or dipentaerythritol
  • R represents CrC 4 alkyl, as obtained by reaction of:
  • suitable derivatives of oxaphosphorinoxide are characterized by the presence of three groups of the partial formula (A). These groups are connected with a trivalent group Y, such as compounds of the formula
  • phenyl groups may be substituted by further substituents.
  • Representative examples of these compounds are compounds of the formulae: obtainable by condensation of melamine with DOPO and formaldehyde; or
  • suitable derivatives of oxaphosphorinoxide are characterized by the presence of more than three groups of the partial formula (A), according to the structural formulae
  • n numerals from 1.to 30, or more preferably from 2 to 10.
  • oxaphosphorinoxides as defined above are known compounds or can be prepared by known methods. Some of them are commercially available.
  • polymer substrate comprises within its scope thermoplastic polymers or thermo- sets.
  • polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, poly- but-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadi- ene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be cross linked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE linear low density polyethylene
  • ULDPE ultrahigh molecular weight polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, pref- erably polyethylene and polypropylene, can be prepared by different and especially by the following methods: a) Radical polymerisation (normally under high pressure and at elevated temperature). b) Catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • ligand typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, and amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler- Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyl- ene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin co- polymers (e.g.
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ
  • propylene/butadiene copolymers isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethyl- ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-no- rbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers,
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • the homopolymers and copolymers mentioned above may have a stereo structure in- eluding syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred.
  • Stereo block polymers are also included.
  • Polystyrene poly (p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred.
  • Stereo block polymers are also included; a) Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, sty- rene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni- trile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a Homopolymers and copolymers may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sul- phochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichloro- hydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvi- nylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobut
  • Polymers derived from ⁇ , ⁇ -unsatu rated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacry- lonitriles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • 1 1.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl ben- zoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 above. 12.
  • Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes, which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulphides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyam- ide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olef
  • Polyureas Polyureas, polyimides, polyamide imides, polyether imides, polyester imides, polyhydan- toins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate
  • PAN polyhydroxybenzoates
  • block copolyether esters derived from hydroxyl-terminated polyethers and also polyesters modified with polycarbonates or MBS.
  • Blends of the aforementioned polymers for example PP/EPDM, Polyam- ide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, Polyam- ide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate
  • Polycarbonates are obtainable by interfacial processes or by melt processes (catalytic transesterification).
  • the polycarbonate may be either branched or linear in structure and may include any functional substituents.
  • Polycarbonate copolymers and polycarbonate blends are also within the scope of the invention.
  • the term polycarbonate should be interpreted as inclusive of copolymers and blends with other thermoplastics. Methods for the manufacture of polycarbonates are known, for example, from U.S. Patent Specification Nos. 3,030,331; 3, 169, 121; 4, 130,458; 4,263,201; 4,286,083; 4,552, 704; 5,210,268; and 5,606,007. A combination of two or more polycarbonates of different molecular weights may be used.
  • polycarbonates obtainable by reaction of a diphenol, such as bisphenol A, with a carbonate source.
  • a diphenol such as bisphenol A
  • suitable diphenols are:
  • Bisphenol A , bisphenol AF:
  • bisphenol C bisphenol E: bisphenol F: , bisphenol M:
  • the carbonate source may be a carbonyl halide, a carbonate ester or a haloformate.
  • Suitable carbonate halides are phosgene or carbonylbromide.
  • Suitable carbonate esters are dialkyl- carbonates, such as dimethyl- or diethylcarbonate, diphenyl carbonate, phenyl-alkylphenyl- carbonate, such as phenyl-tolylcarbonate, dialkylcarbonates, such as dimethyl- or diethylcar- bonate, di-(halophenyl)carbonates, such as di-(chlorophenyl)carbonate, di-(bromo- phenyl)carbonate, di-(trichlorophenyl)carbonate or di-(trichlorophenyl)carbonate, di-(alkyl- phenyl)carbonates, such as di-tolylcarbonate, naphthylcarbonate, dichloronaphthylcarbonate and others
  • the polymer substrate mentioned above which comprises polycarbonates or polycarbonate blends is a polycarbonate-copolymer, wherein isophthalate/terephthalate-resorcinol segments are present.
  • polycarbonates are commercially available, e.g. Lexan® SLX (General Electrics Co. USA).
  • Other polymeric substrates of component b) may additionally contain in the form as admixtures or as copolymers a wide variety of synthetic polymers including polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly(meth)acrylates, thermo- plastic polyurethanes, polysulphones, polyacetals and PVC, including suitable compatibiliz- ing agents.
  • the polymer substrate may additionally contain thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof.
  • thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof.
  • Specific embodiments include polypropyl- ene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glycol-modified polycyclohexylenemethylene terephthalate (PCTG), polysulphone (PSU), polymethylmethacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile- ethylene-propylene-sty
  • polymer substrate of component b) consists of a polyfunctional epoxide compound, wherein at least two epoxy groups of the partial formula
  • Ri and R 3 both represent hydrogen and R 2 represents hydrogen or methyl; or wherein q represents zero or 1 , R 1 and R 3 together form the -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - groups and R 2 represents hydrogen.
  • polyfunctional epoxide compounds are: I) Polyglycidyl esters and poly( ⁇ -methylglycidyl) esters obtainable by reacting a compound having at least two carboxyl groups in the molecule with epichlorohydrin and/or glyceroldichlorohydrin and/or ⁇ -methylepichlorohydrin. The reaction is carried out in the presence of bases.
  • Suitable compounds having at least two carboxyl groups in the molecule are aliphatic polycarboxylic acids, such as glutaric, adipic, pimelic, suberic, azelaic, sebacic or dimerized or trimerized linoleic acid. Cycloaliphatic polycarboxylic acids are suitable, e.g.
  • Aromatic polycarboxylic acids are suitable, such as phthalic, isophthalic, trimellitic and pyromellitic acid. Likewise suitable are carboxyl-terminated adducts of, for example, trimellitic acid and polyols such as glycerol or 2,2-bis(4-hydroxycyclohexyl)propane.
  • Polyglycidyl ethers or poly( ⁇ -methylglycidyl) ethers obtainable by reacting a compound having at least two free alcoholic hydroxyl groups and/or phenolic hydroxyl groups with a suitably substituted epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst with subsequent treatment under alkaline conditions.
  • Ethers of this type are derived, for example, from straight-chained alcohols, such as ethyleneglycol, diethyleneglycol and higher poly(oxyethylene) glycols, propane-1 ,2- diol, or poly(oxypropylene) glycols, propane-1 ,3-diol, butane-1 ,4-diol, poly(oxytetra- methylene) glycols, pentane-1 ,5-diol, hexane-1 ,6-diol, hexane-2,4,6-triol, glycerol, 1 ,1 ,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins.
  • straight-chained alcohols such as ethyleneglycol, diethyleneglycol and higher poly(oxyethylene) glycols, propane-1 ,2- diol, or poly(oxyprop
  • cycloaliphatic alcohols such as 1 ,3- or 1 ,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hy- droxycyclohexyl)-propane or 1 ,1-bis(hydroxymethyl)cyclohex-3-ene, or they possess aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethyl- amino)diphenylmethane.
  • cycloaliphatic alcohols such as 1 ,3- or 1 ,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hy- droxycyclohexyl)-propane or 1 ,1-bis(hydroxymethyl)cyclohex-3-ene, or they possess aromatic nuclei, such as N,N-bis(2-hydroxye
  • the epoxy compounds may also be derived from mononuclear phenols, such as re- sorcinol or hydroquinone; or they are based on polynuclear phenols, such as bis(4- hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hy- droxyphenyl)-propane or 4,4'-dihydroxydiphenyl sulphone, or on condensates of phe- nols with formaldehyde that are obtained under acidic conditions, such as phenol No- volak®.
  • mononuclear phenols such as re- sorcinol or hydroquinone
  • polynuclear phenols such as bis(4- hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hy- droxyphenyl)-
  • Poly(N-glycidyl) compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least two amino hydrogen atoms.
  • amines are, for example, aniline, toluidine, n-butylamine, bis(4-aminophenyl)meth- ane, m-xylylenediamine or bis(4-methylaminophenyl)methane, and also N,N,O-trigly- cidyl-m-aminophenol or N,N,O-triglycidyl-p-aminophenol.
  • the poly(N-glycidyl) compounds also include N,N'-diglycidyl derivatives of cycloal- kylene-ureas, such as ethylene urea or 1 ,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.
  • N,N'-diglycidyl derivatives of cycloal- kylene-ureas such as ethylene urea or 1 ,3-propyleneurea
  • N,N'-diglycidyl derivatives of hydantoins such as of 5,5-dimethylhydantoin.
  • Poly(S-glycidyl) compounds such as di-S-glycidyl derivatives derived from dithiols, such as ethane-1 ,2-dithiol or bis(4-mercaptomethylphenyl) ether.
  • Epoxy compounds having a radical of the formula A, in which R 1 and R 3 together are -CH 2 -CH 2 - and n is 0 are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether or 1 ,2-bis(2,3-epoxycyclopentyloxy) ethane.
  • An example of an epoxy resin having a radical of the formula A in which R 1 and R 3 together are -CH 2 -CH 2 - and n is 1 is (3,4-epoxy-6-methylcy- clohexyl)methyl S' ⁇ '-epoxy- ⁇ '-methylcyclohexanecarboxylate.
  • Suitable polyfunc- tional epoxides are: a) Liquid bisphenol A diglycidyl ethers, such as ARALDITE GY 240, ARALDITE GY 250, ARALDITE GY 260, ARALDITE GY 266, ARALDITE GY 2600, ARALDITE MY 790, DER ® 332, DER331 , Hexion ® EPR 158, Tactix ® 123, TACTIX138, Epon ® 826; b) Solid bisphenol A diglycidyl ethers such as ARALDITE GT 6071 , ARALDITE GT 7071 , ARALDITE GT 7072, ARALDITE GT 6063, ARALDITE GT 7203, ARALDITE GT 6064,
  • N,N,O-triglycidyl ethers of p-aminophenol such as ARALDITE MY 0510
  • m Tetraglycidyl-4,4'-methylenebenzamine or N,N,N',N'-tetraglycidyldiaminophenylmethane, such as ARALDITE MY 720, ARALDITE MY 721
  • n N,N,N',N'-tetraglycidyl-m-xylidenediamine, such as Tetrad ® -X
  • Triglycidyl ether of 1 ,1 ,2,-tris(4-hydroxyphenyl)ethane such as Tactix ® 742.
  • Suitable polyfunctional epoxide compounds preferably comprise at least two groups of the formula
  • X 1 , X 2 and X 3 are cyclohexylene, phenylene or naphthylene which can be unsubsti- tuted or substituted and Xi is additionally an unsubstituted or substituted radical of the partial formula and X 2 is additionally an unsubstituted or substituted
  • Identical or different substituents may be present two or more times, whereas the substituents themselves may likewise be further substituted.
  • a suitable alkyl radical is a Ci-Ci 8 alkyl radical, such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-do- decyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, and their branched isomers.
  • Possible alkylene and alkoxy radicals can be derived formally from the above-mentioned alkyl radicals by removing a further hydrogen atom or, respectively, by adding an oxygen atom.
  • Suitable aryl radicals are those having 6-20 carbon atoms, such as phenylene, biphenylene or naphthylene.
  • Possible arylene and aryloxy radicals can be derived formally from the abovementioned aryl radicals by removing a further hydrogen atom or, respectively, by adding an oxygen atom.
  • Y 2 is a direct bond or the groups -SO 2 -, -CO-, -S-, -SO-, CH 2 -, -C(CH 3 ) 2 - or -C(CF 3 ) 2 -; and n is 1-10.
  • aromatic rings are unsubstituted or substituted one or more times by alkyl, aryl, alkoxy, aryloxy or halogen, as described in more detail above.
  • a hardener component is present in the composition.
  • a suitable hardener compound is any of the known hardeners for epoxy resins.
  • the amine, phenolic and anhydride hardeners are particularly preferred, such as polyamines, e.g.
  • a preferred embodiment of the invention relates to a composition, which comprises as component b) a polyfunctional epoxide compound a hardener compound that contains at least two amino groups, such as dicyandiamide.
  • a particularly preferred embodiment of the invention relates to a composition, which comprises a) about 0.05 - 30.0 wt.% of melamine phenylphosphinate salt (I); b) about 60.0 - 95.0 wt% of a polyfunctional epoxide compound; and 0.10 - 40.0 wt% of a hardener compound.
  • the instant invention further pertains to a composition, which comprises, in addition to the components a) and b), as defined above, further additives selected from the group consisting of so-called anti-dripping agents, polymer stabilizers and additional flame-retardants, such as phosphorus containing flame-retardants, nitrogen containing flame-retardants, halogenated flame-retardants and inorganic flame-retardants.
  • further additives selected from the group consisting of so-called anti-dripping agents, polymer stabilizers and additional flame-retardants, such as phosphorus containing flame-retardants, nitrogen containing flame-retardants, halogenated flame-retardants and inorganic flame-retardants.
  • the invention relates to a composition, which com- prises in addition to the melamine phenylphosphinate salt (I) of Component a) , optionally combined with oxaphosphorinoxide or derivatives thereof, further additives selected from the group consisting of polymer stabilizers and additional flame retardants.
  • the invention relates to a composition which additionally comprises as additional component so-called anti-dripping agents.
  • anti-dripping agents reduce the melt flow of the thermoplastic polymer and inhibit the formation of drops at high temperatures.
  • Various references such as U.S. Patent Specification No. 4,263,201, describe the addition of anti-dripping agents to flame retardant compositions.
  • Suitable additives that inhibit the formation of drops at high temperatures include glass fibers, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibers, glass spheres and the like.
  • PTFE polytetrafluoroethylene
  • the addition of polysiloxanes of different structures has been proposed in various references; cf. U.S. Patent Specification Nos. 6,660, 787, 6,727,302 or 6, 730, 720.
  • Stabilizers are preferably halogen-free and selected from nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabiliz- ers, quinone methide stabilizers and monoacrylate esters of 2,2'-alkylidenebisphenol stabilizers.
  • the composition comprises an additional flame retardant component.
  • additional flame-retardants are known components, items of commerce or can be obtained by known methods.
  • Other representative phosphorus containing flame-retardants, in addition to the ones defined above, are for example:
  • Tetraphenyl resorcinol diphosphate (Fyrolflex ® RDP, Akzo Nobel), resorcinol diphosphate oligomer (RDP), tetrakis(hydroxymethyl)phosphonium sulphide, triphenyl phosphate, diethyl- N,N-bis(2-hydroxyethyl)-aminomethyl phosphonate, hydroxyalkyl esters of phosphorus acids, salts of hypophosphoric acid (H 3 PO 2 ) wherin e.g.
  • Ca 2+ , Zn 2+ , or Al 3+ function as cations, ammonium polyphosphate (APP) or (Hostaflam ® AP750), resorcinol diphosphate oligomer (RDP), phosphazene flame-retardants and ethylenediamine diphosphate (EDAP).
  • APP ammonium polyphosphate
  • Hostaflam ® AP750 resorcinol diphosphate oligomer
  • RDP resorcinol diphosphate oligomer
  • EDAP ethylenediamine diphosphate
  • Nitrogen containing flame-retardants are, for example, isocyanurate flame-retardants, such as polyisocyanurate, esters of isocyanuric acid or isocyanurates.
  • isocyanurate flame-retardants such as polyisocyanurate, esters of isocyanuric acid or isocyanurates.
  • Representative examples are hydroxyalkyl isocyanurates, such as tris-(2-hydroxyethyl)isocyanurate, tris(hydroxy- methyl)isocyanurate, tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl isocyanurate.
  • Nitrogen containing flame-retardants include further melamine-based flame-retardants.
  • Representative examples are: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate, dimelamine pyrophosphate.
  • benzoguanamine tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, urea cyanurate, ammonium polyphosphate, a condensation product of melamine from the series melem, melam, melon and/or a higher condensed compound or a reaction product of melamine with phosphoric acid or a mixture thereof.
  • Representative inorganic flame retardants include, for example, aluminum trihydroxide (ATH), boehmite (AIOOH), magnesium dihydroxide (MDH), zinc borates, CaCO 3 , layered silicates and layered double hydroxides (modified by organic substituents, and mixtures thereof.
  • ATH aluminum trihydroxide
  • AIOOH boehmite
  • MDH magnesium dihydroxide
  • CaCO 3 layered silicates and layered double hydroxides (modified by organic substituents, and mixtures thereof.
  • organohalogen flame retardants are, for example:
  • the above-mentioned additional flame retardant classes are advantageously contained in the composition of the invention in an amount from about 0.5% to about 45.0% by weight of the organic polymer substrate; for instance about 1.0% to about 40.0%; for example about 5.0% to about 35.0% by weight of the polymer or based on the total weight of the composition.
  • composition according to the invention may additionally contain one or more conventional additives, for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-hydroxy-benzophenone, 2-(2'-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)- 1 ,3,5-triazine groups.
  • additives for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-hydroxy-benzophenone, 2-(2'
  • Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles.
  • Preferred specific antioxidants include octadecyl 3-(3,5-di-tert-butyl- 4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] (IRGANOX 1010), tris(3,5-di-tert-butyl-4-hydroxyphenyl)iso- cyanurate (IRGANOX 31 14), 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)ben- zene (IRGANOX 1330), triethyleneglycol-bis[3-(3- ter
  • Specific processing stabilizers include tris(2,4-di- tert-butylphenyl) phosphite (IRGAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10- tetraoxa-3,9-diphosphaspiro[5.5]undecane (IRGAFOS 126), 2,2',2"-nitrilo[triethyl-tris- (3,3',5,5'-tetra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di- tert-butylphenyl)[1 ,1-biphenyl]-4,4'-diylbisphosphonite (IRGAFOS P-EPQ).
  • Specific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phenol (TINUVIN 234), 2-(5-chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol
  • TINUVIN 326 2-(2H-benzotriazole-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol
  • TINUVIN 329 2-(2H-benzotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol
  • TINUVIN 350 2,2'- methylenebis(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol)
  • TINUVIN 360 2,2'- methylenebis(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol
  • TINUVIN 360 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol
  • TINUVIN 1577 2-(2'-hydroxy- 5'-methyl
  • CHIMASSORB 81 I .S-bis-P'-cyano-S'.S'-diphenylacryloyOox ⁇ -bis- ⁇ '-cyano- 3',3'- diphenylacryloyl)oxy]methyl ⁇ -propane (Uvinul® 3030, BASF), ethyl-2-cyano-3,3- diphenylacrylate (UVINUL 3035), and (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL 3039).
  • the additives mentioned above are preferably contained in an amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative to the weight of the polymer substrate b).
  • the incorporation of the components defined above into the polymer component is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
  • the addi- tive components a) and b) and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder, or as a solution or dispersion or suspension or melt.
  • the addition of the additive components to the polymer substrate can be carried out in customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders. The process is preferably carried out in an extruder by introducing the additive during processing.
  • Particularly preferred processing machines are single-screw extruders, contra-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co-kneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
  • Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffex- trusion, Vol. 1 Unen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
  • the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
  • the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), preferably 25 - 300 rpm.
  • the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
  • the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
  • the additive components a) and optional further additives can also be sprayed onto the polymer substrate b).
  • the additive mixture dilutes other additives, for example the conventional additives indicated above, or their melts so that they can be sprayed also together with these additives onto the polymer substrate.
  • Addition by spraying during the deactivation of the polymerisation catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst.
  • spherically polymerised polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
  • the additive components a) and optional further additives can also be added to the polymer in the form of a master batch ("concentrate") which contains the components in a concentration of, for example, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% by weight incorporated in a polymer.
  • concentration a master batch
  • the polymer is not necessarily of identical structure than the polymer where the additives are added finally.
  • the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices.
  • Incorporation can take place prior to or during the shaping operation.
  • the materials containing the additives of the invention described herein preferably are used for the production of molded articles, for example roto-molded articles, injection molded articles, profiles and the like, and especially a fibre, spun melt non-woven, film or foam.
  • a preferred embodiment of the invention furthermore relates to a process for the production of an epoxy resin composition having flame retardant properties which comprises mixing at least one polyfunctional epoxide compound b), an effective amount of at least one melamine phosphinate salt (I), optionally combined with oxaphosphorinoxide or a derivative thereof, and a hardener compound, optionally in the presence of a suitable accelerator, such as methyl imidazole.
  • a suitable accelerator such as methyl imidazole.
  • the invention relates to a mixture, which comprises the melamine phenylphosphinate salt of the formula (I 1 ) in combination with 6H-dibenz[c,e][1 ,2]- oxazaphosphorin-6-oxide of the formula (II): or a derivative thereof.
  • the components (I 1 ) and (II) are admixed to the polyfunctional epoxide compound in concen- trations of 0.05 - 30.0 wt.%, preferably 0.1 - 20.0 wt.% for component a) and 0.5 - 40.0 wt.%, preferably 1.0 - 25 wt.% for component b).
  • the preferred ratio of components a) : b) is in the range 10 : 1 - 1 : 10, preferably 5 : 1 - 1 : 5.
  • a further embodiment of the invention relates to a process for imparting flame retardancy to a hardened polyfunctional epoxide composition, which process comprises adding the above- defined flame retardant mixture and a hardener compound to the polyfunctional epoxide.
  • a further embodiment of the invention relates to a process for imparting flame retardancy to a polymer substrate, which process comprises adding component a) to the polymer substrate b).
  • the following examples illustrate the invention, but are not to be construed to limit the scope thereof.
  • DOPO 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • Standard procedure A resin formulation is prepared using different amounts of Araldite® ECN 1280 resin. 9.2 parts of DICY (solution in solvent mixture of DMF and methoxy-2-propanol), 0.3 parts of methylimidazole accelerator and 60 parts methoxy-2-propanol are added to the resin composition, followed by the above-mentioned flame retardants. After complete mixing of the above mixture in a glass jar at 70 0 C and continuous stirring for a period of 30 min, flame retardant components, melamine phenylphosphinate or melamine phenylphosphinate and DOPO are added and mixed thoroughly with the above mentioned mixture until a homogeneous composition is obtained.
  • the composition is coated onto a piece of glass cloth and heated to 170 0 C for about 1 - 3 min in a forced draft oven.
  • the time in the forced draft oven is varied slightly from sample to sample in order to control resin flow of the final laminate.
  • the fibre material, now in the shape of a non-tacky prepreg is cut into 7 strips ( ⁇ 180 x 180 mm) which are stacked upon each other in a distance holder, to assure the manufacture of laminates with uniform thickness of 1.5 mm.
  • the strips are covered with two Teflon® plates of 1 mm thickness on the upper and the lower side of the prepreg stack.
  • the stack is placed on a hot press, and the stacked prepregs are subjected to elevated temperature and pressure according to the following general schedule:

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Abstract

La présente invention porte sur des compositions de polymère ignifugeant qui comprennent des phénylphosphinates de mélamine et des mélanges comprenant des dérivés de dihydro-oxa-phosphaphénanthrène. Les compositions sont particulièrement utiles pour la fabrication de composés ignifugeants à base de produits de polycondensation comme des polyesters, des polyamides et des polycarbonates et d'époxydes polyfonctionnels.
PCT/EP2009/065228 2008-11-24 2009-11-16 Compositions d'agent ignifugeant à base de phénylphosphinates de mélamine WO2010057851A1 (fr)

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CN2009801469095A CN102224219A (zh) 2008-11-24 2009-11-16 蜜胺苯基次膦酸盐阻燃剂组合物
EP09749153A EP2367901A1 (fr) 2008-11-24 2009-11-16 Compositions d'agent ignifugeant à base de phénylphosphinates de mélamine
US13/129,408 US8877838B2 (en) 2008-11-24 2009-11-16 Melamine phenylphosphinate flame retardant compositions
JP2011536840A JP5409798B2 (ja) 2008-11-24 2009-11-16 メラミンフェニルホスフィン酸塩の難燃剤組成物

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010035103A1 (de) 2010-08-23 2012-02-23 Catena Additives Gmbh & Co. Kg Flammschutzmittelzusammensetzungen enthaltend Triazin-interkalierte Metall-Phosphate
US20130338264A1 (en) * 2011-03-11 2013-12-19 Basf Se Condensation products of melamine and phenylphosphonic acid and their use as flame retardants
WO2014060003A1 (fr) 2012-10-16 2014-04-24 Wolfgang Wehner Phosphates azino-métalliques utilisés comme agents ignifuges
WO2014060004A1 (fr) 2012-10-16 2014-04-24 Wolfgang Wehner Procédé de production de métal-hydroxydiphényl-2' -(thio)phosphinates et de métal-diphénylène-(thio)phosphonates, compositions les contenant et leur utilisation comme agents ignifuges
WO2014124990A1 (fr) * 2013-02-13 2014-08-21 Floridienne S.A. Composition de produit ignifuge
AT509959B1 (de) * 2010-05-28 2015-02-15 Sunpor Kunststoff Gmbh Flammgeschützte expandierbare polymerisate
EP2927302A1 (fr) 2014-04-03 2015-10-07 Basf Se Moyen de protection contre les flammes à base de liaisons de di-, tri- et tétra-aryléthane substituées
EP2947115A1 (fr) 2014-05-22 2015-11-25 Basf Se Mélanges ignifuges sans halogène pour polyoléfine en mousse
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EP2947115A1 (fr) 2014-05-22 2015-11-25 Basf Se Mélanges ignifuges sans halogène pour polyoléfine en mousse
WO2015180165A1 (fr) * 2014-05-30 2015-12-03 Dupont (China) Research & Development And Management Co., Ltd. Agents ignifugeants, leurs procédés de préparation et compositions thermoplastiques associées
DE102015009598A1 (de) 2015-07-24 2017-01-26 Trupti Dave-Wehner Verfahren zur Herstellung eines halogenfreien Flammschutzmittels
WO2021048155A1 (fr) 2019-09-11 2021-03-18 Clariant International Ltd Composition ignifuge, composition de moulage polymère la comprenant et son utilisation

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US20110288206A1 (en) 2011-11-24
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JP5409798B2 (ja) 2014-02-05
EP2367901A1 (fr) 2011-09-28
US8877838B2 (en) 2014-11-04

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