WO2010133570A1 - Compositions ignifuges de guanidine phénylphosphinate - Google Patents

Compositions ignifuges de guanidine phénylphosphinate Download PDF

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WO2010133570A1
WO2010133570A1 PCT/EP2010/056775 EP2010056775W WO2010133570A1 WO 2010133570 A1 WO2010133570 A1 WO 2010133570A1 EP 2010056775 W EP2010056775 W EP 2010056775W WO 2010133570 A1 WO2010133570 A1 WO 2010133570A1
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alkyl
group
guanidine
phenyl
represent hydrogen
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PCT/EP2010/056775
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English (en)
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Rainer Xalter
Thomas Weiss
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Basf Se
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Publication of WO2010133570A1 publication Critical patent/WO2010133570A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C279/02—Guanidine; Salts, complexes or addition compounds 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
    • 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
    • C08K5/49—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 guanidine phenylphosphinates and mixtures of guanidine phenylphosphinates with dihydro-oxa- phosphaphenanthrene derivatives.
  • the compositions are especially useful for the manufac- ture of flame retardant compounds based on polyfunctional epoxides or polycondensates 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.
  • CTI comparative tracking index
  • the flame retardants are resistant to hydrolysis (leaching test: water, 70 0 C, 168 h), so contact with water may not diminish their flame retardant activity.
  • halogen containing flame retardants such as tetrabromobisphenol (TBBA)
  • TBBA tetrabromobisphenol
  • the invention relates to a composition, particularly a flame retardant composition, which comprises a) A guanidine 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-Ci-C 4 alkyl and
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl, phenyl, phenyl-Ci-C 4 alkyl, (Ci-C 4 alkyl) 1-3 phenyl and (Ci-C 4 alkyl) 1-2 hydroxyphenyl; 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 guanidine phenylphosphinate salt (I), wherein
  • RrR 5 represent hydrogen
  • R 1 -R5 represent substituents 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 R ⁇ -R ⁇ independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl and phenyl; 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 guanidine phenylphosphinate salt of the formula b) A polymer substrate.
  • a specific embodiment of the invention relates to a composition, which comprises a) A guanidine phenylphosphinate salt (I), wherein R 1 -R5 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
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl, phenyl, phenyl-CrC 4 alkyl, (Ci-C 4 alkyl) 1-3 phenyl and (Ci-C 4 alkyl) 1-2 hydroxyphenyl; 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 guanidine 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 a composition, particularly a flame retar- dant composition, which comprises a) A guanidinephenylphosphinate 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 - A -
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of CrC 4 alkyl, phenyl, phenyl-CrC 4 alkyl, (Ci-C 4 alk- yl)i -3 phenyl and (Ci-C 4 alkyl) 1-2 hydroxyphenyl;
  • the invention relates to a composition, which comprises the guanidine phenylphosphinate salt (I) in combination with an additional flame retardant selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphorylphenanthrene- 10-oxide (DOPO), salts of di-Ci-C 4 alkylphosphinic acid, triphenylphosphine oxide, and melamine phenylphosphonate.
  • DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene- 10-oxide
  • compositions particularly a flame retardant composition, which comprises a) The guanidine 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 guanidine 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-Ci-C 4 alkyl, e.g. hydroxymethyl or 1- or 2-hydroxyethyl and Ci-C 4 alkoxy, e.g. methoxy or ethoxy; and
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl, phenyl, phenyl-Ci-C 4 alkyl, e.g. benzyl or 1-or 2-phenethyl, (Ci-C 4 alkyl) 1-3 phenyl, e.g. tolyl or mesityl, and (Ci-C 4 alkyl) 1-2 hydroxyphenyl, e.g. 4-hydroxy- 3,5-di-tert-butylphenyl or 3-tert-butyl-4-hydroxy-5-methylphenyl.
  • guanidine phenylphosphinate salt (I) as defined above is obtainable by known methods, e.g. acid-base reaction of equivalent amounts of phenylphosphinic acid of the formula
  • R 6 -Rg are as defined above.
  • guanidine phenylphosphinate is prepared from guanidine and phenylphosphinic acid, for example by addition of both components as hot aqueous solutions, followed by subsequent crystallization, filtration, drying, and milling.
  • 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;
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl, phenyl, phenyl-CrC 4 alkyl, (Ci-C 4 alkyl) 1-3 phenyl and (Ci-C 4 alkyl) 1-2 hydroxyphenyl; particularly a guanidine phenylphosphinate salt (I), wherein RrR 5 represent hydrogen; or
  • RrR 5 represent a substituent selected from the group consisting of CrC 4 alkyl, hy- droxy-Ci-C 4 alkyl and CrC 4 alkoxy; and the other ones represent hydrogen; and
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of Ci-C 4 alkyl and phenyl.
  • the invention also relates to the guanidine phenylphosphinate salt (I) component of the formula
  • the method for preparing the guanidine phenylphosphinate salt (I) is also subject matter of the invention.
  • polymer substrate comprises within its scope thermoplastic polymers or thermo- sets.
  • thermoplastic polymers or thermo- sets.
  • suitable thermoplastic polymers is given below:
  • 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 polymethyl- ene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polymethyl- ene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably 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 copolymers (e.g.,
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ
  • propylene/butadiene copolymers isobutylene/isoprene co- polymers, 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 men- tioned in 1 ) above, for example polypropylene/ethylene-propylene
  • 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 including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred.
  • Stereo block polymers are also included.
  • 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
  • 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
  • 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. 7.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene- acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; s
  • 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.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes, which contain ethylene oxide as a co-monomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulphides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
  • Polyamides and co-polyamides 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, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g.
  • polyethylene glycol polypropylene glycol or poly- tetramethylene glycol
  • polyamides or co-polyamides modified with EPDM or ABS polyamides condensed during processing
  • RIM polyamide systems polyamides condensed during processing
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene ter- ephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block co-polyether 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 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.
  • 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 AP . H O 0H
  • bisphenol B
  • bisphenol S bisphenol TMC: bisphenol Z: , 4,4'-(2-norbornylidene)bis(2,6- dichlorophenol); or fluorene-9-bisphenol:
  • 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 diethylcarbonate, di-(halophenyl)carbonates, such as di-(chlorophenyl)carbonate, di-(bromophenyl)- carbonate, di-(trichlorophenyl)carbonate or di-(trichlorophenyl)carbonate, di-(alkylphenyl)car- bonates, 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 (Gen- eral 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, thermoplastic polyurethanes, polysulphones, polyacetals and PVC, including suitable compatibiliz- ing agents.
  • the polymer substrate may additionally contain thermoplastic poly- mers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof.
  • specific embodiments include polypropylene (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-styrene (AES), styrene-maleic anhydride (SMA) or high impact polystyrene (HIPS).
  • PP polypropylene
  • PE polyethylene
  • 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 phenols 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)-propane or
  • 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.
  • 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 R3 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.
  • Polyfunctional epoxide compounds are known. Many of them are commercially available from Huntsman Advanced Materials (brand name Araldite®). Examples of suitable polyfunctional 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; 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, ARALDITE GT 7304, ARALDITE GT 7004, ARALDITE GT 6084, ARALDITE GT 1999, ARALDITE GT 7077, ARALDITE GT 6097, ARALDITE GT 7097, ARALDITE GT 7008, ARALDITE GT 6099,
  • 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
  • Identical or different substituents may be present two or more times, whereas the substituents them- selves 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.
  • Ci-Ci 8 alkyl radical such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-n
  • Possible alkylene and alkoxy radicals can be derived formally from the above-mentioned al- kyl 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 -;
  • n 1-10.
  • aromatic groups are unsubstituted or substituted one or more times by alkyl, aryl, alkoxy, aryloxy or halogen, as described in more detail above.
  • guanidine phenylphosphinate (I) has curing properties. Therefore, a further embodiment of the invention relates to the preparation of well-cured laminates with excellent mechanical properties without use of any additional hardener components.
  • 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.
  • dodecenylsuccinic acid anhydride hexahydro- phthalic acid anhydride, tetrahydrophthalic acid anhydride, phthalic acid anhydride, pyro- mellitic acid anhydride, styrene-maleic acid anhydride copolymers, and derivatives thereof.
  • a preferred embodiment of the invention relates to a composition, which comprises as component b) a polyfunctional epoxide compound and 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 guanidine phenylphosphinate salt (I); b) About 30.0 - 95.0 wt% of a polyfunctional epoxide compound; and 0 - 60.0 wt% of a hardener compound. Additional Components
  • the instant invention further pertains to a composition, which comprises, in addition to the components a) and b), as defined above, as optional components, additional flame retar- dants and further additives selected from the group consisting of so-called anti-dripping agents and polymer stabilizers.
  • the composition contains additional flame retardants selected from the group consisting of phosphorus containing flame retardants, nitrogen containing flame retardants, halogenated flame retardants and inorganic flame retardants.
  • the guanidine phenylphosphinate salt (I) is combined in the flame retardant compositions of the invention with the phosphorus containing flame- retardant 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 d-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.
  • Representative examples of these compounds are compounds of the formulae:
  • 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:
  • 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.
  • the guanidine phenylphosphinate salt (I) is combined in the flame retardant compositions of the invention with a salt of di- Ci-C 4 alkylphosphinic acid, particularly the Ca 2+ , Zn 2+ , Or AI 3+ salt, as phosphorus containing flame retardant.
  • the di-Ci-C 4 alkylphosphinic acid has identical or different Ci-C 4 alkyl groups, such as dimethyl, diethyl, ethylmethyl or methyl-n-propylphosphinic acid.
  • Ci-C 4 alkyl groups such as dimethyl, diethyl, ethylmethyl or methyl-n-propylphosphinic acid.
  • Such products are known and commercially available (Exolit ® OP series, Clariant).
  • Particularly preferred are the aluminum salts of di-Ci-C 4 alkylphosphinic acid, such as di- methylphosphinic acid, diethylphosphinic acid (DEPAL) or methyl-ethylphospinic acid (MEPAL).
  • the guanidine phenylphosphinate salt (I) is combined in the flame retardant compositions of the invention with triphenylphosphine oxide as the phosphorus containing flame retardant.
  • the guanidine phenylphosphinate salt (I) is combined in the flame retardant compositions of the invention with the nitrogen containing flame retardant melamine phenylphosphonate, as described in U.S. Pat. Spec. No. 4,061,605 and EP-A-367 714.
  • the composition comprises as optional components further flame retardants selected from the group consisting of phosphorus containing flame retardants, nitrogen containing flame retardants, halogenated flame retardants and inorganic flame retardants.
  • additional flame retardants are known components, items of commerce or can be obtained by known methods.
  • Tetraphenyl resorcinol diphosphate (Fyrolflex ® RDP, Akzo Nobel), resorcinol diphosphate oligomer (RDP), triphenyl phosphate, ethylenediamine diphosphate (EDAP), diethyl-N,N- bis(2-hydroxyethyl)-aminomethyl phosphonate, hydroxyalkyl esters of phosphorus acids, salts of hypophosphoric acid (H 3 PO 2 ) comprising e.g. Ca 2+ , Zn 2+ , Or AI 3+ as cations, tetrakis(hydroxymethyl)phosphonium sulphide, ammonium polyphosphate and phosphazene flame-retardants.
  • Fyrolflex ® RDP Akzo Nobel
  • resorcinol diphosphate oligomer RDP
  • triphenyl phosphate ethylenediamine diphosphate
  • EDAP diethyl-N,N- bis(2-hydroxyeth
  • 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 and dimelamine pyrophosphate.
  • benzoguanamine tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimelamine phosphate, urea cyanurate, ammo- nium 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.
  • organohalogen flame retardants are, for example: Polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.), decabromodiphenyl oxide (DBDPO; Saytex ® 102E), tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370 ® , FMC Corp.), tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl)phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly- ⁇ -chloroethyl triphosphonate mixture, tetrabromobisphenol A bis(2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis(tetrabromophthalimide) (Saytex ® BT-93), bis(hexachlorocyclopentadieno)cyclo- o
  • the flame retardants mentioned above are routinely combined with an inorganic oxide synergist. Most common for this use are zinc or antimony oxides, e.g. Sb 2 U 3 or Sb 2 ⁇ 5 . Boron compounds are suitable, too.
  • Representative inorganic flame retardants include, for example, aluminum trihydroxide (ATH), boehmite (AIOOH), magnesium dihydroxide (MDH), zinc borates, CaCO ⁇ , (organically modified) layered silicates, (organically modified) layered double hydroxides, and mixtures thereof.
  • 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.
  • 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.
  • 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.
  • Stabilizers are preferably halogen-free and selected from the group consisting of nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers and monoacrylate esters of 2,2'-alky- lidenebisphenol stabilizers.
  • 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 sta- bilizers 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'-methylene- bis(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol) (TINUVIN 360), and 2-(4,6- diphenyl-1 ,3,5-triazin-2-y
  • 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 additive 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.
  • 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.
  • 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. If a plurality of components is added, these can be premixed or added individually.
  • 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 po- lymerisation catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst.
  • 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.
  • a further embodiment of the invention relates to a mixture, which comprises A guanidine phenylphosphinate salt (I), wherein 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
  • R 6 -Rg independently of one another represent hydrogen or a substituent selected from the group consisting of CrC 4 alkyl, phenyl, phenyl-CrC 4 alkyl,
  • the invention in combination with an additional flame retardant, particularly a flame retardant selected from the group consisting of phosphorus containing flame retardants, nitrogen containing flame retardants, halogenated flame retardants and inorganic flame retardants.
  • a flame retardant selected from the group consisting of phosphorus containing flame retardants, nitrogen containing flame retardants, halogenated flame retardants and inorganic flame retardants.
  • the invention relates to a mixture, which comprises a guanidine phenylphosphinate salt (I 1 ) in combination with an additional flame retardant selected from the group of oxaphosphorinoxide or a derivative thereof, as represented by the formula (II), salts of di-CrC 4 alkylphosphinic acid, triphenylphosphine oxide, and melamine phenylphosphinate.
  • the components (I 1 ) and (II) are admixed to the polyfunctional epoxide compound in concentrations of 0.05 - 30.0 wt
  • a further embodiment of the invention relates to a process for imparting flame retardancy to a polymer substrate, which process comprises adding to a polymer substrate the above defined guanidine phenylphosphinate salt (I).
  • a preferred 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 retardants and flame retardant mixtures and a hardener compound to the polyfunctional epoxide.
  • Typical applications for such flame retarded epoxide compositions include, but are not limited to, epoxy-glass cloth laminate composites used e.g. for the manufacture of printed circuit boards (PCB's), or used as structural elements in transportation vehicles (trains, planes, ships, automotives, etc.) and in construction applications (dry walls, floorings, beams, etc.).
  • PCB's printed circuit boards
  • construction applications dry walls, floorings, beams, etc.
  • a further embodiment of the invention relates to a process for imparting flame retardancy to a any polymer substrate, which process comprises adding component a) to the polymer sub- strate b).
  • Phenylphosphonic acid Aldrich Germany
  • o-Cresol Novolac epoxy resin Araldite® ECN 1280, Huntsman Advanced Materials, Basel, Switzerland;
  • Dicyandiamide (DICY), accelerator: methylimidazole, both from Aldrich, Germany; Solvents: Methoxy-2-propanol and dimethylformamide, Merck Eurolab, Germany;
  • DOPO 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • Phenylphosphinic acid (2.00 mol, 284.2 g) is dissolved at room temperature in 1.50 1 ethanol.
  • the solution is heated to 65°C, and guanidine carbonate (1.00 mol, 180.2 g) is added in small portions over a period of 35 min. Subsequent portions are added in the moment when the carbon dioxide evolution caused by the addition of previous portions has ceased. After complete addition, the mixture is stirred for another 90 min at 65°C.
  • the clear, colourless solution is concentrated to dryness in a rotary evaporator.
  • the solid residue is dried at 60 0 C in a circulating air oven over night and subsequently for 17 h in a vacuum oven at 130 0 C. 400.3 g (1.99 mol, 99.4%) of the desired product are obtained as a colourless crystalline solid.
  • a saturated hot aqueous solution of phenylphosphonic acid (800 mmol, 126 g) is added to a saturated solution of melamine (800 mmol, 101.0 g) in 90 0 C hot water under vigorous stirring. After 10 min, the reaction mixture is allowed to cool slowly to room temperature (later on to 4°C) slowly. The procedure yields 205.0 g (721 mmol, 90.2 %) of the desired product as colorless crystals (needles).
  • a resin formulation is prepared by dissolving at 95°C in 100 parts of Araldite® ECN 1280 resin in 25 parts of methoxy-2-propanol. 0.04 parts of 2-methylimidazole, various amounts of phenylphosphinic acid guanidine salt and additional amounts of methoxy-2-propanol are added to this solution. A clear resin solution is obtained after 60 min at 95°C. To this solution 9.15 parts of DICY dissolved in a 1 :1 mixture of methoxy-2-propanol and DMF are added.
  • the formulation is hot coated onto a piece of glass cloth (type 7628) and heated to 170 0 C for about 1 - 3 min in a forced draft oven.
  • the fiber, now a non-tacky prepreg is cut into seven strips ( ⁇ 180 x 180 mm) which are stacked on top of each other in a distance holder to as- sure the manufacture of laminates with uniform thickness of 1.5 mm.
  • the strips are covered and with two PTFE plates of 1 mm thickness on the upper and lower sides of the prepreg stack.
  • the stack is placed on a hot press, and the stacked prepregs are subjected to a pressure of 3 bar at 170 0 C for a period of 2 h.
  • the resulting laminate is removed from the press, cooled to ambient temperature, and sepa- rated from the distance holder and PTFE plates.
  • the laminate is cut to a piece of
  • the laminate is cut into five strips (125 x 13.0 mm), conditioned for 48 h at 23°C and 50% relative humidity, and tested in the previously described UL-94 flammability test.
  • the data obtained in this test are presented in the Table below.
  • TGA measurements are performed according to IPC-TM-650 2.4.24.6 on a Mettler TGA/DSC1 by using small pieces (about 15 mg) cut from the laminate. Samples are heated from room temperature to 550 0 C at a rate of 10°C/min under a nitrogen flow of 30 cm 3 /min.
  • TMA Thermomechanical analysis
  • TMA measurements are performed on a Mettler TMA 40 by using small disks (0 5.3 mm) cut from the laminate. Delamination temperatures and times are determined according to IPC- TM-650 2.4.24.1 and glass transition temperatures (Tg) according to IPC-TM-650 2.4.24C. Samples are heated from room temperature to 288°C at a rate of 10°C/min and maintained at this temperature for 1 h or a shorter time period in the event that the sample decomposes.
  • Laminates are prepared as described above.
  • Laminates are prepared as described above.
  • Laminate is prepared as described above. DOPO is added to the resin solution in combination with guanidine phenylphosphinate.
  • Laminates are prepared as described above. Exolit® OP 930, triphenyl- phosphine oxide, melamine phenylphosphonate, MELAPUR 200 and ATH are added together with the hardener (DICY).
  • Example 5 shows that guanidine phenylphosphinate has curing properties. In contrast to Referential Example 2 where no curing was achieved under the manufacturing conditions employed, Example 5 demonstrates the preparation of well-cured laminates with excellent mechanical properties without use of any additional hardener components.

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Abstract

L'invention porte sur des compositions polymères ignifuges comprenant de la guanidine phénylphosphinate et sur des mélanges contenant d'autres produits ignifuges. Ces compositions sont particulièrement utiles pour la fabrication de composés ignifuges à base d'époxydes polyfonctionnels ou de polycondensés tels que des polyesters, polyamides et polycarbonates.
PCT/EP2010/056775 2009-05-19 2010-05-18 Compositions ignifuges de guanidine phénylphosphinate WO2010133570A1 (fr)

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WO2012072739A1 (fr) * 2010-12-02 2012-06-07 Basf Se Compositions ignifuges au phosphinate anticorrosion
WO2019083006A1 (fr) * 2017-10-27 2019-05-02 積水化学工業株式会社 Composition de résine durcissable, objet durci, agent adhésif, et film adhésif

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012072739A1 (fr) * 2010-12-02 2012-06-07 Basf Se Compositions ignifuges au phosphinate anticorrosion
WO2019083006A1 (fr) * 2017-10-27 2019-05-02 積水化学工業株式会社 Composition de résine durcissable, objet durci, agent adhésif, et film adhésif

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