Classifications

• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/016—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
• • 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
  • C08K5/34922—Melamine; Derivatives thereof
• • 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
  • C08K5/34928—Salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5399—Phosphorus bound to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

• the invention relates to flame retardant formulations that can be used in polymers to flame-retardant compounds with outstanding
• plastics Due to their chemical composition, many plastics are easily combustible. In order to be able to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislative, plastics must therefore generally be equipped with flame retardants.
• thermoplastic polyesters in particular the salts of phosphinic acids
• WO-A-2005/059 018 describes a polybutylene terephthalate with a nitrogen-containing flame retardant, a phosphinate and a
• Ash-forming polymers are here polyetherimides, Polyphenylene ethers, polyphenylene sulfide, polysulfones, polyethersulfones,
• Polybutylene terephthalate, and phosphinates and a reaction product of a nitrogen-containing compound with phosphoric acid are preferred.
• PET Polyethylene terephthalate
• UL94 V-0 Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pages 14-18, Northbrook 1998) and a good one
• DE-A-10 2010 049968 describes flame-retardant polyesters with phosphinate, a phosphazene and a condensate of a nitrogen-containing compound with phosphoric acid as flame retardant. Only the addition of phosphazene achieves UL 94 V-0 and an elongation at break of more than 2% simultaneously. It will be a GWIT (Glow Wire Ignition Temperature) according to IEC 60695-2-13 of 775 ° C with 1 mm material thickness achieved.
• GWIT Low Wire Ignition Temperature
• a disadvantage of the described additives of flame retardants is a stronger wear of metal parts of the plasticizing unit and the nozzle during compounding. Similar problems can occur in the injection molding of polyester or high temperature polyamide compounds with certain phosphinates.
• WO-A-2009/109318 describes the preparation of flame-retardant, non-corrosive and readily flowable polyamide and polyester molding compositions.
• the flame retardant mixture used there consists of a phosphinic acid salt and a metal salt.
• DE-A-10 2010 048025 describes a flame retardant stabilizer combination for thermoplastics.
• the aforesaid combination consists of a salt of a dialkylphosphinic acid, a salt of a
• polyesters with this combination achieve UL94 V-0 with higher elongation at break, with a slight addition of phosphorous acid in PA6T / 66 resulting in low corrosion. Evidence of positive effects of such combination in polyester on the wear can not be found. It was therefore an object of the present invention to find flame retardant formulations for polymers which show a very good flame retardancy even with thin material thicknesses (applications), with which good mechanical properties of compounds are achieved and which have no detectable increased corrosion during processing.
• the invention therefore provides a flame retardant formulation for
• thermoplastic polymers comprising, as component A, from 20 to 97.9% by weight of a phosphinic acid salt of the formula (I) and / or of a diphosphinic acid salt of the formula (II) and / or polymers thereof,
• R 1 , R 2 are the same or different and are H or Ci-C6-alkyl, linear or
• R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, C 6 -C 10 -alkylarylene or C 7 -C 20 -arylalkylene;
• M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
• component B from 2 to 50% by weight of a phosphazenes of the general formula (III) or (IV)
• R 4 and R 4 ' are identical or different and are C 1 -C 20 -alkyl, C 6 -C 30 -aryl,
• Y represents the group -P (OPh) 4 or -P (O) (OPh) 2 ;
• component C 0.1 to 30 wt .-% of an inorganic zinc compound and as component D 0 to 50 wt .-% of a nitrogen-containing flame retardant.
• R 1 and R 2 are the same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
• R 3 is methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; Phenylene or naphthylene; Methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene,
• it contains flame retardant formulation
• the flame retardant formulation contains
• the flame retardant formulation contains
• the flame retardant formulation contains
• the phosphazenes are phenoxyphosphazenes.
• Melamine polyphosphates melampolyphosphates, melem polyphosphates and / or Melon polyphosphates and / or melamine condensation products such as melam, melem and / or melon;
• R 5 to R 7 are hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or -alkylcycloalkyl, optionally
• R 8 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or -alkylcycloalkyl, if appropriate
• R 9 to R 13 have the same groups as R 8 and -OR 8 ,
• n and n independently of one another 1, 2, 3 or 4,
• aromatic polycarboxylic acids benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine cyanurate, dicyandiamide and / or guanidine; and / or d) nitrogen-containing phosphates of the formulas (NH 4 ) y H3- y PO4 or
• Component C is preferably zinc oxide, zinc hydroxide, zinc oxide hydrate, zinc borate, basic zinc silicate and / or zinc stannate.
• component C is zinc stannate.
• the invention also relates to the use of a flame retardant formulation according to one or more of claims 1 to 11 as flame retardant,
• Intumescent coatings as flame retardants for wood and other cellulosic products, as reactive and / or non-reactive
• Polymer form mass for the production of flame-retardant polymer form bodies and / or for the flame-retardant finishing of polyester and cellulose pure and mixed fabrics by impregnation.
• the invention relates to the use of the flame retardant formulations according to the invention according to one or more of claims 1 to 12 in or for connectors, current-contacting parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breaker, lamp housing, LED lamp housing, capacitor housing , Bobbins, fans, protective contacts, plugs, in / on boards, housings for plugs, cables, flexible circuit boards, charging cables, engine covers, textile coatings and other products.
• power distributors Fl protection
• circuit boards potting compounds
• power connectors circuit breaker, lamp housing, LED lamp housing, capacitor housing , Bobbins, fans, protective contacts, plugs, in / on boards, housings for plugs, cables, flexible circuit boards, charging cables, engine covers, textile coatings and other products.
• the invention also encompasses a flame-retardant thermoplastic or thermosetting polymer molding composition, polymer moldings, films, filaments and fibers containing 0.5 to 45% by weight of flame retardant formulation according to one or more of claims 1 to 11, 10 to 95% by weight. % thermoplastic or thermosetting polymer or mixtures thereof, 0 to 55% by weight of additives and 0 to 55% by weight of filler or reinforcing materials, the sum of the components being 100% by weight.
• the invention comprises flame-retardant thermoplastic or thermosetting polymer molding compositions, polymer moldings, films, filaments and fibers, containing 5 to 30% by weight of flame retardant formulation according to one or more of claims 1 to 11, 20 to 95% by weight.
• thermoplastic or thermoset is preferred.
• Polymer molding composition polymer moldings, films, filaments and fibers, characterized in that these are polyesters, polyamides and / or
• the phenyl radicals may optionally be substituted.
• Phosphazenes for the purposes of the present application are described in Mark, J.A., Allcock, H.R., West, R., "Inorganic Polymers", Prentice Hall International, 1992, pages 61-141.
• the invention also relates to a flameproof plastic molding composition
• a flameproof plastic molding composition comprising an inventive anticorrosive flame retardant formulation
• the plastic is thermoplastic polymers of the type polystyrene HI (high-impact), polyphenylene ethers, polyamides, polyesters, polycarbonates and Blends or polymer blends of the type ABS (acrylonitrile-butadiene-styrene) or PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene) or PPE / HIPS
• M in formula (I) or (II) is magnesium, calcium, aluminum or zinc, more preferably aluminum or zinc.
• phosphinic acid salt includes salts of phosphinic and diphosphinic acids and their polymers.
• the phosphinic acid salts prepared in aqueous medium are essentially monomeric compounds. Depending on the
• Reaction conditions may also be polymeric
• Phosphinic salts arise.
• Suitable phosphinic acids as a constituent of the phosphinic acid salts are, for example:
• Dimethylphosphinic acid ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propyl-phosphinic acid, methane-di (methylphosphinic acid), benzene-1, 4- (dimethyl-phosphinic acid), methyl-phenyl-phosphinic acid, diphenylphosphinic acid.
• the salts of the phosphinic acids according to the invention can be prepared by known methods, as described in more detail, for example, in EP-A-0699708. The phosphinic acids are reacted, for example, in aqueous solution with metal carbonates, metal hydroxides or metal oxides.
• the aforementioned phosphinic acid salts can be used for the inventive
• Polyester compounds depending on the type of polymer used and the
• the phosphinic acid salts z. B. to achieve a better Dispersion in the polymer are ground to a finely divided form. If desired, it is also possible to use mixtures of different phosphinic acid salts.
• the phosphinic salts according to the invention are thermally stable, do not decompose the polymers during processing nor do they affect the production process of the plastic molding compound.
• the phosphinic acid salts are non-volatile under the usual polyester manufacturing and processing conditions.
• the polymers preferably originate from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the group of thermosetting polymers.
• thermoset polymers are epoxy resins.
• thermoset polymers are particularly preferably epoxy resins which have been cured with phenols, dicyandiamide, phenol derivatives (resoles), alcohols or amines, in particular phenol derivatives and dicyandiamide.
• thermoset polymers are particularly preferably epoxy resins which are mixed with phenols and / or dicyandiamide and / or a
• Catalyst are cured.
• the catalysts are preferably imidazole compounds.
• the epoxy resins are preferably polyepoxide compounds.
• the epoxy resins are preferably resins based on novolac.
• the epoxy resins are resins on the base
• Bisphenol-A Polymers which can be used according to the invention are thermosetting and thermoplastic polymers. Preferably, the polymers are polymers of mono- and
• Diolefins for example polypropylene, polyisobutylene, polybutene-1, poly-4-methyl-pentene-1, polyisoprene or polybutadiene and polymers of
• Cycloolefins such. From cyclopentene or norbornene; also polyethylene (which may be optionally crosslinked), e.g. High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density polyethylene and ultrahigh molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene Density (LLDPE), branched low density polyethylene (VLDPE), as well as mixtures thereof.
• HDPE High density polyethylene
• HDPE-HMW high density polyethylene
• HDPE-UHMW high density polyethylene and ultrahigh molecular weight
• MDPE medium density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density polyethylene Density
• VLDPE branched low density polyethylene
• the polymers are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as.
• LDPE low density polyethylene
• propylene-butene-1 copolymers propylene-butene-1 copolymers
• propylene-isobutylene copolymers propylene-isobutylene copolymers
• ethylene-butene-1 copolymers ethylene-butene-1 copolymers
• Ethylene-hexene copolymers ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers,
• Isobutylene-isoprene copolymers ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their
• the polymers are preferably hydrocarbon resins (eg C5-C9) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.
• the polymers are preferably polystyrene (polystyrene 143E (BASF), poly (p-methylstyrene), poly (alpha-methylstyrene).
• the polymers are copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene,
• Blends of high impact strength of styrene copolymers and another polymer such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
• the polymers are graft copolymers of styrene or alpha-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (resp.
• 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 alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, such as they z.
• the polymers are preferably halogen-containing polymers, such as.
• halogen-containing polymers such as.
• chlorinated rubber chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated Polyethylene, copolymers of ethylene and chlorinated ethylene,
• halogen-containing vinyl compounds such as. B. polyvinyl chloride
• Copolymers such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
• the polymers are preferably polymers which are derived from alpha, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethyl methacrylates which have been modified with butyl acrylate, polyacrylamides and polyacrylonitriles and copolymers of said monomers with one another or with other unsaturated monomers, such as Acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
• the polymers are preferably polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate,
• Polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins are examples of polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins.
• the polymers are preferably homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
• the polymers are preferably polyacetals, such as
• Polyoxymethylene as well as those polyoxymethylenes, the comonomers, such as.
• ethylene oxide Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• the polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.
• the polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.
• the polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2/12, polyamide 4 (poly-4-aminobutyric acid, Nylon® 4, Fa. DuPont), polyamide 4/6
• Ultramid ® A3, BASF polyamide 6/9 (poly (hexamethylene nonanediamid), nylon 6/9 ®, DuPont).
• Polyamide 6/10 poly (hexamethylene sebacamide), nylon ® 6/10, from DuPont
• polyamide 6/12 poly (hexamethylene dodecanediamide), nylon ® 6/12, from DuPont
• polyamide 6/66 poly (hexamethylene adipamide-co-caprolactam), nylon ® 6/66, Fa. DuPont
• polyamide 7 aminoheptanoic acid poly-7, nylon ® 7, Fa. DuPont
• Polydecamethylensebacamid Nylon ® 10,10, from DuPont.
• Polyamide 1 1 Poly-1 1 - aminoundecanoic acid, nylon ® 1 1, from DuPont.
• Polyamide 12 polylauryllactam
• Nylon ® 12 DuPont, Grillamid ® L20, from Ems Chemie
• aromatic polyamides starting from m-xylene diamine and adipic acid.
• Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid Polyhexamethylene isophthalamide polyhexamethylene terephthalamide) and
• an elastomer as modifier e.g. As poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide.
• Polypropylene glycol or polytetramethylene glycol Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
• the polymers are preferably polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and
• the polymers are preferably polyesters which differ from
• Derive dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones such as polyethylene terephthalate,
• Polybutylene terephthalate (Celanex ® 2500, Celanex ® 2002, from Celanese;. Ultradur ®, BASF), poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from polyethers having hydroxyl end groups; also with polycarbonates or MBS modified polyester.
• the polymers are preferably polycarbonates and
• the polymers are preferably polysulfones, polyethersulfones and polyether ketones.
• the polymers are preferably crosslinked polymers which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
• the polymers are drying and non-drying alkyd resins.
• the polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their halogen-containing, hardly combustible modifications.
• the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.
• the polymers are preferably alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins, isocyanates,
• Isocyanurates, polyisocyanates or epoxy resins are crosslinked.
• the polymers are preferably crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic
• Derive glycidyl compounds for. B. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, by conventional hardeners such. As anhydrides or amines can be crosslinked with or without accelerators.
• the polymers are preferably mixtures (polyblends) of the abovementioned polymers, such as e.g. PP / EPDM (polypropylene / ethylene-propylene-diene rubber), polyamide / EPDM or ABS (polyamide / ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC / EVA (polyvinyl chloride /
• Ethylene vinyl acetate Ethylene vinyl acetate
• PVC / ABS polyvinyl chloride / acrylonitrile-butadiene-styrene
• PVC / MBS polyvinyl chloride / methacrylate-butadiene-styrene
• PC / ABS polyvinylene vinyl acetate
• Methacrylate-butadiene-styrene PPO / HIPS (polyphenylene oxide / high impact
• the inventive combination of the components A and B and C and optionally D additives may be added, such.
• antioxidants UV absorbers and light stabilizers, metal deactivators, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, nucleating agents, fillers and reinforcing agents, other flame retardants and other additives.
• Suitable antioxidants include alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol; 1 .2 Alkylthiomethylphenole, z. B. 2,4-dioctylthiomethyl-6-tert-butylphenol; Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol; Tocopherols, e.g. For example, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E); Hydroxylated thiodiphenyl ethers, e.g. B.
• O, N and S benzyl compounds e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydi benzyl ether; Hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydrorybenzyl) -malonate; Hydroxybenzyl aromatics, e.g. B.
• Suitable UV absorbers and light stabilizers are, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole;
• 2-hydroxybenzophenones such as.
• Esters of optionally substituted benzoic acids such as.
• nickel compounds such as.
• Suitable metal deactivators are, for. B. ⁇ , ⁇ '-Diphenyloxalklarediamid, N-salicylal-N'-salicyloylhydrazin, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4 -hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) -oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis-phenylhydrazide, ⁇ , ⁇ '-diacetyl-adipic acid dihydrazide, N , N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic di
• Suitable peroxide-destroying compounds are, for. B. esters of .beta.-thionipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulphide, pentaerythritol tetrakis (.beta.-dodecylmercapto), propionate.
• esters of .beta.-thionipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester
• mercaptobenzimidazole the zinc salt of 2-mercaptobenzimidazole
• zinc dibutyl dithiocarbamate dioctadecyl disulphide
• pentaerythritol tetrakis
• Suitable polyamide stabilizers are, for. As copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
• Suitable basic co-stabilizers are melamine, polyvinylpyrrolidone,
• Suitable nucleating agents are for. For example, 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid.
• the fillers and reinforcing agents include, for.
• plasticizers As plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents and blowing agents.
• additional additives can be added to the polymers before, together with or after addition of the flame retardants.
• the dosage of these additives as well as the flame retardants can be carried out as a solid, in solution or melt, as well as in the form of solid or liquid mixtures or as masterbatches / concentrates.
• Lubricants and / or mold release agents may additionally be used as additives.
• the lubricants and / or mold release agents are long-chain fatty acids, their salts, their ester derivatives and / or amide derivatives,
• the lubricants and / or mold release agents are esters or salts of stearic acid, such as. As glycerol monostearate or calcium stearate.
• the lubricants and / or mold release agents are sodium stearate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium sulfate, sodium
• reaction products of montan wax acids with ethylene glycol are preferably a mixture of ethylene glycol mono-montan wax acid ester, ethylene glycol dimontane wax acid ester, montan wax acids and ethylene glycol.
• the lubricants and / or mold release agents are
• reaction products are particularly preferably a mixture of 1,3-budanediol mono-montan wax acid ester, 1,3-budanediol di-montan wax acid ester, montan wax acids, 1,3-butanediol, calcium montanate and the calcium salt.
• additives can be introduced into the plastic in a wide variety of process steps.
• polyamides already at the beginning or at the end of the polymerization / polycondensation or in a subsequent compounding process, the additives in the polymer melt
• the polymer is particularly preferably one or more polyesters and / or polyamides which may be provided with fillers and / or reinforcing materials.
• polyesters and polyamides are preferably in the form of shaped bodies, films, threads and / or fibers.
• inventive combinations of salts of dialkylphosphinic acids and phosphazenes with zinc-containing additives have a good flame retardancy, combined with improved stability in the processing of the molding compositions.
• This corrosion prevention effect has not been found to this extent in the prior art in any combination so far described.
• the flame retardant polyester compounds continue to contain
• the flame-retardant polyester compounds preferably contain more than one thermoplastic polyester. Particularly preferably, the flame-retardant polyester compounds contain PBT and PET in blends.
• the flame-resistant polyester compounds preferably also contain polycarbonates.
• the invention also relates to a process for the preparation of the flame-retardant polyester compounds or polyamide compounds according to the invention, characterized in that the components A to D in the abovementioned
• the invention relates to the use of fibers, films and
• thermoplastic polyesters are selected from the group of:
• Polyalkylene terephthalates according to the invention are reaction products of aromatic dicarboxylic acids or their reactive derivatives (eg dimethyl esters or anhydrides) and aliphatic,
• Polyalkylene terephthalates preferably to be used according to the invention can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, pages 695-710, Karl-Hanser-Verlag, Kunststoff 1973). Polyalkylene terephthalates preferably to be used according to the invention contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, of terephthalic acid residues.
• the polyalkylene terephthalates which are preferably used according to the invention may contain, in addition to terephthalic acid residues, up to 20 mol% of other aromatic dicarboxylic acids containing 8 to 14 carbon atoms or aliphatic dicarboxylic acids containing 4 to 12 carbon atoms, such as phthalic acid, isophthalic acid, naphthalene-2,6 dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic, cyclohexanedicarboxylic acid.
• polyalkylene terephthalates to be used according to the invention can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or
• 4-basic carboxylic acids e.g. in DE-A-19 00 270 are branched.
• Examples of preferred branching agents are
• Trimesic acid Trimellitic acid, trimethylolethane and -propane and pentaerythritol.
• polyalkylene terephthalates which are prepared solely from terephthalic acid and its reactive derivatives (eg
• Dialkyl esters and ethylene glycol and / or propanediol-1, 3 and / or butanediol-1, 4 are prepared (polyethylene and Polytrimethylen- and
• Polybutylene terephthalate and mixtures of these polyalkylene terephthalates.
• Preferred polybutylene terephthalates contain at least 80 mol%
• the preferred polybutylene terephthalates may further contain, in addition to 1,4-butanediol radicals, up to 20 mole% of other aliphatic diols having 2 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. Remains of
• Ethylene glycol propanediol 1, 3, 2-ethylpropanediol-1, 3, neopentyl glycol, pentanediol 1, 5, hexanediol-1 .6, cyclohexane-dimethanol-1, 4, 3-methylpentanediol-2,4,
• Polyalkylene terephthalates which are preferably used according to the invention are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components and / or butanediol-1,4.
• Particularly preferred copolyesters are poly (ethylene glycol / butanediol-1, 4) terephthalates.
• Suitable components C are those described in Mark, J.A., Allcock, H.R., West, R., "Inorganic Polymers", Prentice Hall International, 1992,
• the phosphazenes may also be a cross-linked phosphazene wherein at least one of the foregoing phosphazenes (V) and (VI) is cross-linked to at least one cross-linking group.
• the cross-linking group consists of an o-phenylene group, an m-phenylene group, a p-phenylene group, a biphenyl group or a group represented by the formula (XIII)
• A is a group -SO2, a group -S-, a group -O- or a group -C- (CH3) 2-, wherein each of said cross-linking groups is located between the two oxygen atoms that after the removal of the group R 1 , wherein the number of R 1 groups in the cross-linked phosphazene is 50 to 99.9%, based on the total number of R 1 groups in said phosphazene before cross-linking.
• the foregoing examples of the halogen-free phosphazene can be used either alone or in combination.
• Phosphazene includes a mixture of phosphazene compounds in which a phenoxy group and / or an alkoxy group has been introduced in a mixture of the cyclic and straight-chain chlorophosphazenes, e.g. B.
• Hexachlorocyclotriphosphazenes octachlorocyclotetraphosphazenes and the like.
• the chlorophosphazenes are prepared by reacting ammonium chloride and phosphorus pentachloride at 120 - 130 ° C with each other.
• cross-linked phosphazene examples include
• Phenoxyphosphazenes having a 4,4'-diphenylene group cross-linked structure and the like Phenoxyphosphazenes having a 4,4'-diphenylene group cross-linked structure and the like.
• Phenoxy groups are substituted; and straight-chain phosphazenes substituted by phenoxy groups.
• Phosphoric acids are compounds which are formed by reacting melamine or the condensed melamine compounds, such as melam, Meiern or melon, etc., with phosphoric acid. Examples of these are dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, Melamine polyphosphate, melampolyphosphate, melon polyphosphate and
• component D is um
• Mineral particulate fillers based on talc, wollastonite, kaolin and / or glass fibers are particularly preferably used according to the invention.
• mineral fillers are preferably used, in particular talc, wollastonite or kaolin.
• needle-shaped mineral fillers may also be used with particular preference. Under needle-shaped mineral fillers is
• the mineral has a length to diameter ratio of from 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, most preferably from 4: 1 to 12: 1.
• the mean particle size of the suitable acicular minerals according to the invention is preferably less than 20 microns, more preferably less than 15 microns, most preferably less than 10 microns.
• the filler and / or reinforcing material may optionally
• Primer system based on silane.
• pretreatment is not essential.
• polymer dispersions, film formers, branching agents and / or glass fiber processing aids may be used in addition to silanes.
• Particularly preferred reinforcing materials are glass fibers, generally having a fiber diameter between 7 and 18 microns, preferably between 9 and 15 microns, are added as continuous filaments or as cut or ground glass fibers.
• the fibers can with a suitable sizing system and a primer or adhesion promoter system z.
• Preferred adhesion promoters are silane compounds from the group
• Aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as a substituent are aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as a substituent.
• the silane compounds are generally used in amounts of 0.05 to 2 wt .-%, preferably 0.25 to 1, 5 wt .-% and in particular 0.5 to 1 wt .-% based on the mineral Filler, used for surface coating.
• the particulate fillers may have a smaller d97 or d50 value than those originally used due to the processing into the molding compound or molding in the molding compound or in the molding
• the glass fibers Due to the processing, the glass fibers can be shorter due to the molding composition or molding in the molding compound or in the molding
• Molding compositions in addition to the components A to D contain at least one lubricant and mold release agent.
• Long-chain fatty acids for example stearic acid or behenic acid
• their salts for example Ca or Zn stearate
• their ester derivatives or amide derivatives for example ethylene bisstearylamide
• montan waxes mixturetures from straight-chain, saturated
• Carboxylic acids with chain lengths of 28 to 32 carbon atoms and low molecular weight polyethylene or polypropylene waxes.
• PETS pentaerythritol tetrastearate
• Molding compounds in addition to the components A to D contain other additives.
• Usual additives are for. B. stabilizers (for example
• UV stabilizers UV stabilizers, heat stabilizers, gamma ray stabilizers,
• Hydrolysis stabilizers antistatic agents, other flame retardants, emulsifiers, nucleating agents, plasticizers, processing aids,
• Impact modifiers dyes and pigments.
• the additives can be used alone or mixed or in the form of masterbatches, or can be premixed in the melt or applied to the surface thereof.
• UV stabilizers for example, sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as various substituted representatives of these groups and mixtures thereof can be used.
• aromatic secondary amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as various substituted representatives of these groups and mixtures thereof
• suitable UV stabilizers are various UV stabilizers.
• impact modifiers are generally copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or
• Methacrylic acid esters having 1 to 18 carbon atoms in the alcohol component.
• Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide, zinc sulfide and carbon black, furthermore organic pigments, such as phthalocyanines,
• Quinacridones, perylenes and dyes such as nigrosine and anthraquinones are added as colorants and other colorants.
• carbon black is preferred.
• a nucleating agent z For example, sodium or calcium phenylphosphinate, alumina or silica and preferably talc can be used.
• processing aids for example, copolymers of at least one [ct] olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol can be used. Preference is given here
• plasticizers are dioctyl phthalate,
• Dibenzyl phthalate butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.
• the flame-retardant polyester compounds according to the invention preferably also contain carbodiimides.
• the components A, B, C and D can be in thermoplastic polyester
• the components C and D can also be separated via a
• the flame-retardant additives A, B, C and D can also already be added to the polyester composition during the polycondensation.
• the flame-retardant polyester compounds are suitable for the production of
• polyesters Commercially available polyesters (granules), component A:
• PBT Polybutylene terephthalate
• Ultradur ® 4500 BASF, D.
• Component B is a compound having Component B:
• Depal Aluminum salt of diethylphosphinic acid, hereinafter referred to as Depal.
• Component C Aluminum salt of diethylphosphinic acid, hereinafter referred to as Depal.
• Component E Flamtard ® H, stannate, from William Blythe, UK.
• Component F PPG fiberglass HP 3786 EC 10 4, 5 MM component G: lubricants: Licowax E ®, montan wax, Clariant, CH. 2. Preparation, Processing and Testing of Flame Resistant Polyester Compounds
• the flameproofing components were mixed with the polymer granules and possibly additives in the ratio indicated in the tables and on a twin-screw extruder (Leistritz ZSE 27 HP-44D type) at temperatures of 240 to 280 ° C incorporated.
• the homogenized polymer strand was
• the flammability of the specimens was assessed by determining the oxygen index (LOI according to ASTM D 2863-77).
• the platelet method set up at DKI (Deutsches Kunststoffinstitut, Darmstadt) is used for model investigations for the comparative evaluation of metallic materials and the corrosion and wear intensity of plasticizing molding compounds.
• DKI Deutsches Kunststoffinstitut, Darmstadt
• two specimens are placed in pairs in the nozzle so that they have a rectangular gap of 12 mm length, 10 mm width and a height of 0.1 to a maximum of 1 mm adjustable height for the passage of
• plastic melt is extruded (or sprayed) from a plasticizing unit with the appearance of large local
• a wear parameter is the weight loss of the specimens, which is determined by differential weighing of the specimens with an A & D "Electronic Balance"
• Sample plate removed and physically / chemically cleaned of the adhering plastic.
• the physical cleaning is done by removing the hot plastic mass by rubbing with a soft material (cotton).
• the chemical cleaning is carried out by heating the specimens at 60 ° C in m-cresol for 10 minutes. After boiling still adhering plastic mass is removed by rubbing with a soft cotton swab.
• the glow-wire resistance was determined by means of the glow-wire test GWIT (GlowWire-Ignition-Temperature) according to IEC 60695-2-13.
• the GWIT test is performed on 3 test specimens (for example on 60 x 60 X geometry plates
• Lubricant (% by weight) 0.3 0.3 0.3 0.3 0.3
• the flame-retardant polyester compounds according to the invention are also distinguished by a high oxygen index and high tracking resistance.
• the flame retardant polyamide composition has a
• Tracking immunity [Tracking Index (CTI)] measured according to the International Electrotechnical Commission Standard IEC-601 12/3 of greater than or equal to 600 volts.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fireproofing Substances (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=56148397

Family Applications (1)

Country Status (8)

Families Citing this family (17)

Family Cites Families (24)

• 2015
  • 2015-06-24 DE DE102015211728.6A patent/DE102015211728A1/de not_active Withdrawn
• 2016
  • 2016-06-16 TW TW105118988A patent/TWI707903B/zh not_active IP Right Cessation
  • 2016-06-20 CN CN201680010343.3A patent/CN107250267B/zh active Active
  • 2016-06-20 WO PCT/EP2016/064116 patent/WO2016207087A1/de not_active Ceased
  • 2016-06-20 EP EP16730832.9A patent/EP3313920A1/de not_active Withdrawn
  • 2016-06-20 KR KR1020187002208A patent/KR102546391B1/ko active Active
  • 2016-06-20 US US15/738,497 patent/US11053375B2/en not_active Expired - Fee Related
  • 2016-06-20 JP JP2017559395A patent/JP6986450B2/ja not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events