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EP2928952A1 - Matières moulables à base de polycarbonate ignifugées i - Google Patents

Matières moulables à base de polycarbonate ignifugées i

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Publication number
EP2928952A1
EP2928952A1 EP13798688.1A EP13798688A EP2928952A1 EP 2928952 A1 EP2928952 A1 EP 2928952A1 EP 13798688 A EP13798688 A EP 13798688A EP 2928952 A1 EP2928952 A1 EP 2928952A1
Authority
EP
European Patent Office
Prior art keywords
weight
alkyl
parts
component
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13798688.1A
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German (de)
English (en)
Inventor
Mathieu JUNG
Thomas Eckel
Vera Taschner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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Filing date
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Priority to EP13798688.1A priority Critical patent/EP2928952A1/fr
Publication of EP2928952A1 publication Critical patent/EP2928952A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/659—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having three phosphorus atoms as ring hetero atoms in the same ring
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to flame-retardant, impact-modified, high-temperature-stable polycarbonate (PC) acrylonitrile-butadiene-styrene (ABS) compositions having cyclic phosphazenes which have high modulus of elasticity, flowability, impact resistance, and high hydrolytic stability, and processes for their use Preparation and use of cyclic phosphazenes as flame retardants in polycarbonate compositions.
  • PC high-temperature-stable polycarbonate
  • ABS acrylonitrile-butadiene-styrene
  • EP 1 095 099 A1 describes polycarbonate-ABS molding compositions equipped with phosphazenes and phosphorus compounds which have excellent flame retardancy and very good mechanical properties, such as weld line strength or notched impact strength
  • EP 1 196 498 A1 describes phosphazene-treated molding compositions based on polycarbonate and graft polymers selected from the group of silicone, EP (D) M and acrylate rubbers as graft base, which have excellent flame retardancy and very good mechanical properties such as stress cracking resistance or notched impact strength.
  • EP 1 095 100 A1 describes polycarbonate / ABS molding compositions containing phosphazenes and inorganic nanoparticles which have excellent flame retardancy and very good mechanical properties.
  • EP 1 095 097 A1 describes phosphazene-modified polycarbonate-ABS molding compositions which have excellent flame retardancy and very good processing properties, the graft polymer being prepared by mass, solution or mass-suspension polymerization processes.
  • US2003 / 092802 Al discloses phenoxyphosphazenes and their preparation and use in polycarbonate-ABS molding compositions.
  • the phenoxyphosphazenes are preferably crosslinked and the Molding compounds are distinguished by good flame retardancy, good impact strength, high flexural modulus and high melt volume flow rate.
  • the ABS used is not described in detail. Furthermore, in this document the proportions of trimers, tetramers and higher oligomers of the present application are not described.
  • JP 1995 0038462 describes polycarbonate compositions containing graft polymers, phosphazenes as flame retardants and optionally vinyl copolymers. However, specific structures, compositions and amounts of the flame retardant are not mentioned.
  • JP19990176718 describes thermoplastic compositions consisting of aromatic polycarbonate, copolymer of aromatic vinyl monomers and vinyl cyanides, graft polymer of alkyl (meth) acrylates and rubber and phosphazene as flame retardants, which have good flowability.
  • the object of the present invention is therefore to provide a flame-retardant molding composition which is distinguished by a property combination of good notched impact strength, temperature stability, modulus of elasticity, flowability and stability to hydrolysis with a constant good UL94V0 classification at 1.5 mm.
  • the molding compositions are flame retardant and meet UL94 V-0 requirements even with thin wall thicknesses (i.e., wall thickness of 1.5 mm).
  • Bl optionally at least one graft polymer prepared in the emulsion polymerization process
  • B2) at least one graft polymer prepared in a bulk, suspension or solution polymerization process, B2) being present at at least 50% by weight, based on component B, 1.0-0.20.0 parts by weight, preferably 4.5-18.0 parts by weight, more preferably 6.0-15.0 parts by weight, more preferably 8.5-12.0 parts by weight.
  • Each R is the same or different and is an amine radical, in each case, optionally halogenated, preferably halogen-fluorinated, C i to Cg-alkyl, preferably methyl, ethyl, propyl or butyl, C to Cg alkoxy, preferably
  • Methoxy, ethoxy, propoxy or butoxy each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine and / or
  • Bromine substituted C 5 -C 3 -cycloalkyl, in each case optionally by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine and / or hydroxy-substituted, C 1 -C 20 -aryloxy, preferably phenoxy,
  • Naphthyloxy each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine and / or bromine, substituted C7 to C ⁇ 2 ⁇
  • Aralkyl preferably phenyl-Cj-C4-alkyl, or a halogen radical, preferably chlorine, or an OH radical.
  • the composition consists only of the components A to F.
  • the composition is free of inorganic flame retardants and flame retardant synergists, in particular aluminum hydroxide, aluminum oxide and arsenic and antimony oxides.
  • the composition is free from further organic flame retardants, in particular bisphenol A diphosphate oligomers, resorcinol diphosphate oligomers, triphenyl phosphate, octamethyl resorcinol diphosphate and tetrabromo bisphenol A diphosphate oligocarbonate.
  • organic flame retardants in particular bisphenol A diphosphate oligomers, resorcinol diphosphate oligomers, triphenyl phosphate, octamethyl resorcinol diphosphate and tetrabromo bisphenol A diphosphate oligocarbonate.
  • the preferred embodiments can be carried out individually or else linked to one another.
  • the invention also provides processes for the preparation of the molding compositions and the use of the molding compositions for the production of moldings, and the use of cyclic phosphazenes having a defined oligomer distribution for the preparation of the compositions according to the invention.
  • the molding compositions of the invention can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films.
  • moldings are films, profiles, housing parts of any kind, e.g. for household appliances such as juice presses, coffee machines, blenders; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.
  • household appliances such as juice presses, coffee machines, blenders
  • office machines such as monitors, flat screens, notebooks, printers, copiers
  • Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.
  • the molding compositions according to the invention can also be used, for example, for the production of the following moldings or moldings: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, housings of electrical appliances containing small transformers, housings for information processing and transmission equipment, housings and panels for medical applications Equipment, enclosures for safety devices, moldings for plumbing and bathroom equipment, grille covers and garden tools.
  • Aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for example, see Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, 1964 and DE-AS 1 495 626, DE -A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396, for the preparation of aromatic polyester carbonates, eg DE-A 3 007 934) ,
  • Heteroatom-containing rings may be condensed
  • B is in each case C 1 to C 12 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
  • x each independently 0, 1 or 2
  • p 1 or 0
  • R 5 and R 6 are individually selectable for each X 1 , independently of one another hydrogen or C 1 -C 8 -alkyl, preferably hydrogen, methyl or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyl) - C ⁇ C j -alkanes, bis- (hydroxyphenyl) -C5 -C6 -cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl ) -sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) -sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) -diisopropyl-benzenes and their nuclear-brominated and / or nuclear-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1, 1 - Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-) hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane.
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol-A
  • the diphenols can be used individually or as any mixtures. The diphenols are known from
  • Chain terminators suitable for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert.
  • alkylphenols such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-
  • the amount of chain terminators to be used is generally between 0.5 mol%, and 10 mol%, based on the molar sum of the diphenols used in each case.
  • thermoplastic aromatic polycarbonates have average molecular weights (weight average M w , as measured by GPC (gel permeation chromatography) with polycarbonate standard) of 15,000 to 80,000 g / mol, preferably 19,000 to 32,000 g / mol, particularly preferably 22,000 to 30,000 g / mol.
  • thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by the incorporation of 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three and more phenolic groups. Preference is given to using linear polycarbonates, more preferably based on bisphenol-A.
  • Both homopolycarbonates and copolycarbonates are suitable.
  • inventive copolycarbonates according to component A it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, based on the total amount of diphenols to be used, of hydroxyaryloxy endblocked polydiorganosiloxanes. These are known (US 3 419 634) and can be prepared by literature methods.
  • polydiorganosiloxane-containing copolycarbonates are also suitable.
  • the preparation of the polydiorganosiloxane-containing copolycarbonates is described, for example, in DE-A 3 334 782.
  • Aromatic Dicarbon Tartihalogemde for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • a carbonyl halide preferably phosgene, is additionally used as the bifunctional acid derivative.
  • chain terminators for the preparation of the aromatic polyester are in addition to the aforementioned monophenols nor their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by Ci to C22-alkyl groups or by halogen atoms, as well as aliphatic C2 to C22 Monocarbonklarechloride into consideration.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
  • one or more aromatic hydroxycarboxylic acid may additionally be used.
  • the aromatic polyester carbonates can be branched both linearly and in a known manner (see DE-A 2 940 024 and DE-A 3 007 934), linear polyester carbonates being preferred.
  • branching agents are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0 , 01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or difunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl ) ethane
  • the proportion of carbonate structural units can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture.
  • Component B preferably contains the components Bl and B2 in the following proportions:
  • Bl 0-50% by weight, preferably 10-45% by weight, particularly preferably 10-30% by weight;
  • B2 50-100% by weight, preferably 55-90% by weight, particularly preferably 70-90% by weight;
  • the component Bl is a graft polymer prepared by the emulsion polymerization method, in a preferred embodiment,
  • Bl .l 5 to 95 wt .-%, preferably 10 to 70 wt .-%, particularly preferably 20 to 60 wt .-%, based on the component Bl, a mixture of
  • Bl .l .1) 65 to 85 wt .-%, preferably 70 to 80 wt .-%, based on Bl .l, of at least one monomer selected from the group of vinyl aromatics (such as styrene, a-methyl styrene), nuclear-substituted vinylaromatic (such as p-methylstyrene, p-chlorostyrene) and methacrylic acid (C1-C8) alkyl esters (such as methyl methacrylate, ethyl methacrylate) and Bl .l.) 2) 15 to 35 wt .-%, preferably 20 to 30 wt .-%, based on Bl .l, of at least one monomer selected from the group of vinyl cyanides (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (meth) acrylic acid (C 1 -C 8) alkyl esters (such as Meth
  • the graft base preferably has a glass transition temperature ⁇ 0 ° C, more preferably ⁇ - 20 ° C, particularly preferably ⁇ -60 ° C.
  • the graft particles in component B 1 preferably have an average particle size (d.sub.50 value) of 0.05 to 5 .mu.m, preferably of 0.1 to 1.0 .mu.m, more preferably of 0.2 to 0.5 .mu.m.
  • the average particle size dso is the diameter, above and below which each 50 wt .-% of the particles are. Unless explicitly stated otherwise in the present application, it is determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
  • Preferred monomers B 1.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers Bl .1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B 1.1.1 styrene and Bl .1.2 acrylonitrile.
  • Suitable graft bases B1.2 for the graft polymers B1 are diene rubbers, diene-vinyl block copolymer rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene - And ethylene / vinyl acetate rubbers and mixtures of such rubbers or silicone-acrylate composite rubbers in which the silicone and the acrylate components are chemically linked together (eg by grafting).
  • Preferred graft bases B1.2 are diene rubbers (for example based on butadiene or isoprene), diene-vinyl block copolymer rubbers (for example based on butadiene and styrene blocks), Copolymers of diene rubbers with other copolymerizable monomers (eg according to B 1.1.1 and Bl .1.2) and mixtures of the abovementioned rubber types.
  • Especially preferred are pure polybutadiene rubber and styrene-butadiene block copolymer rubber.
  • the gel fraction of the graft polymers is at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 75% by weight (measured in acetone).
  • the gel content of the graft polymers unless otherwise stated in the present invention, determined at 25 ° C as insoluble in acetone as a solvent insoluble fraction (M. Hoffmann, H. Krömer, R. Kuhn, polymer analysis I and II, Georg Thieme Verlag, Stuttgart 1977).
  • the graft polymers Bl are prepared by free-radical polymerization.
  • the graft polymer Bl is generally free due to its production, i. non-chemically bonded to the rubber base copolymer of B 1.1.1 and Bl .1.2, which is characterized in that it can be dissolved in suitable solvents (such as acetone).
  • Component Bl preferably comprises a free copolymer of B 1.1.1 and Bl. 1.2 which has a weight-average molecular weight (Mw), determined by gel permeation chromatography using polystyrene as standard, of preferably 30,000 to 150,000 g / mol, more preferably 40,000 to 120,000 g / mol.
  • Mw weight-average molecular weight
  • compositions of the invention may optionally contain graft polymers prepared by the bulk, solution or suspension polymerization process.
  • these are graft polymers of
  • B2.1.1 65 to 85 wt .-%, preferably 70 to 80 wt .-%, based on the mixture B.2.1, at least one monomer selected from the group of vinyl aromatics (such as styrene, ⁇ -methyl styrene), ring-substituted vinyl aromatic (such as p-methylstyrene, p-chlorostyrene) and methacrylic acid (C 1 -C 8) -alkyl esters (such as methyl methacrylate, ethyl methacrylate) and
  • B2.1.2 15 to 35 wt .-%, preferably 20 to 30 wt .-% based on the mixture B2.1, at least one monomer selected from the group of vinyl cyanides (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (Meth ) acrylic acid (Cl-C8) -alkyl (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example, maleic anhydride and N-phenyl-maleimide) to B2.2) 95 to 5 wt .-%, preferably 20 to 7 wt .-%, particularly preferably 15 to 8 wt .-%, most preferably 13 to 7 wt .-%, based on the component B2, at least one graft.
  • vinyl cyanides such as unsaturated nitriles such as
  • the graft base preferably has a glass transition temperature ⁇ 0 ° C, preferably ⁇ -20 ° C, more preferably ⁇ -60 ° C.
  • the graft particles in the component B2 preferably have an average particle size (D50 value) of 0.1 to 10 ⁇ m, preferably of 0.2 to 2 ⁇ m, particularly preferably of 0.3 to 1.0 ⁇ m, very particularly preferably of 0 , 3 to 0.6 ⁇ on.
  • Preferred monomers B2.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B2.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B2.1.1 styrene and B2.1.2 acrylonitrile.
  • Suitable graft bases B2.2 for the graft polymers B2 are, for example, diene rubbers, diene-vinyl block copolymer rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and mixtures of such rubbers.
  • Preferred graft bases B2.2 are diene rubbers (for example based on butadiene or isoprene), diene-vinyl block copolymer rubbers (for example based on butadiene and styrene blocks), copolymers of diene rubbers with further copolymerizable monomers (for example according to B2.1.1 and B2 .1.2) and mixtures of the aforementioned rubber types.
  • Particularly preferred as the graft base B2.2 are styrene-butadiene block copolymer rubbers and mixtures of styrene-butadiene block copolymer rubbers with pure polybutadiene rubber.
  • the gel content of the graft polymers B2 is preferably 10 to 35 wt .-%, more preferably 15 to 30 wt .-%, most preferably 17 to 23 wt .-% (measured in acetone).
  • Particularly preferred polymers B2 are, for example, ABS polymers prepared by free-radical polymerization, which in a preferred embodiment up to 10 wt .-%, particularly preferably up to 5% by weight, more preferably 2 to 5% by weight, based in each case on the graft polymer B2, of n-butyl acrylate.
  • the graft polymer B2 generally comprises free, i. non-chemically bonded to the rubber base copolymer of B2.1.1 and B2.1.2, which is characterized in that it can be dissolved in suitable solvent (for example, acetone).
  • suitable solvent for example, acetone
  • Component B2 preferably contains free copolymer of B2.1.1 and B2.1.2 which has a weight-average molecular weight (Mw), determined by gel permeation chromatography using polystyrene as standard, of preferably 50,000 to 200,000 g / mol, particularly preferably 70,000 to 150,000 g / mol , more preferably from 80,000 to 120,000 g / mol.
  • Mw weight-average molecular weight
  • Phosphazenes according to component C which are used according to the present invention, are cyclic phosphazenes according to formula (X)
  • R is the same or different and for
  • halogenated preferably halogen-halogenated, more preferably monohalogenated, C 1 - to Cg-alkyl, preferably methyl
  • alkyl optionally in each case by alkyl, preferably C 1 -C 4 -alkyl, and / or
  • Halogen preferably chlorine and / or bromine, substituted C5 to Cg-cycloalkyl, optionally in each case by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine and / or hydroxyl-substituted, C 2 -C 2 () -aryloxy, preferably phenoxy, naphthyloxy,
  • alkyl preferably Ci-C4-alkyl, and / or halogen, preferably chlorine and / or bromine, substituted C7- to Ci 2-aralkyl, preferably phenyl-Ci-C4-alkyl, or
  • halogen radical preferably chlorine or fluorine
  • k 1, 2 or 3.
  • the proportion of this phosphorus halogen-substituted phosphazene is preferably less than 1000 ppm, more preferably less than 500ppm
  • the phosphazenes can be used alone or as a mixture, i. the radical R may be the same or 2 or more radicals in the formula (X) may be different.
  • the radicals R of a phosphazene are preferably identical.
  • the phosphazenes of component C fulfill all three aforementioned conditions with regard to the proportions (C 2 -C 4).
  • n the weighted arithmetic mean of k is defined according to the following formula:
  • n is in the range from 1.10 to 1.75, preferably from 1.15 to 1.50, more preferably from 1.20 to 1.45, and particularly preferably from 1.20 to 1.40 ( Area limits included).
  • the phosphazenes and their preparation are described for example in EP-A 728 81 1, DE-A 1 961668 and WO 97/40092.
  • the oligomer compositions of the phosphazenes in the respective blend samples can also be detected and quantified after compounding by means of 31 P NMR (chemical shift, ⁇ trimer: 6.5 to 10.0 ppm, ⁇ tetramer: -10 to -13.5 ppm; ⁇ higher oligomers: -16.5 to -25.0 ppm).
  • Component D comprises one or more thermoplastic vinyl (co) polymers or polyalkylene terephthalates.
  • Suitable as vinyl (co) polymers D are polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (Ci-Cg) - alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) unsaturated Carboxylic acids. Particularly suitable are (co) polymers of
  • D. l 50 to 99 preferably 60 to 80 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth) acrylic acid (Ci-C8) - Alkyl esters, such as methyl methacrylate, ethyl methacrylate), and D.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (Ci-C8) alkyl esters, such as Methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids such as maleic acid, and / or derivatives such as anhydrides and imides, unsaturated
  • the vinyl (co) polymers D are resinous, thermoplastic and rubber-free.
  • the copolymer of D.I. styrene and D.2 acrylonitrile is particularly preferred.
  • the (co) polymers according to D are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights M w (weight average, determined by light scattering or sedimentation) of between 15,000 and 200,000 g / mol, more preferably between 100,000 and 150,000 g / mol.
  • D is a copolymer of 77% by weight of styrene and 23% by weight of acrylonitrile having a weight-average molecular weight M w of 130,000 g / mol.
  • compositions according to the invention comprise one or a mixture of two or more different polyalkylene terephthalates.
  • Polyalkylene terephthalates in the context of the invention are polyalkylene terephthalates which are derived from terephthalic acid (or its reactive derivatives, eg dimethyl esters or anhydrides) and alkanediols, cycloaliphatic or araliphatic diols and mixtures thereof, for example based on propylene glycol, butanediol, pentanediol, hexanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, and cyclohexyldimethanol, wherein the diol component according to the invention has more than 2 carbon atoms. Accordingly, as component D, preference is given to using polybutylene terephthalate and / or polytrimethylene terephthalate, most preferably polybutylene terephthalate.
  • the polyalkylene terephthalates according to the invention may also contain up to 5% by weight of isophthalic acid as the monomer of the diacid.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 3 to 21 C atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser Verlag, Kunststoff 1973 ).
  • Preferred polyalkylene terephthalates contain at least 80, preferably at least 90 mol%, based on the diol component, 1,3-propanediol and / or butanediol-1,4-radicals.
  • the preferred polyalkylene terephthalates may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene, dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic, cyclohexanedicarboxylic.
  • the preferred polyalkylene terephthalates may contain, in addition to propanediol-1,3- or butanediol-1,4-radicals, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g.
  • the polyalkylene terephthalates may be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or of tri or tetrabasic carboxylic acids, e.g. in DE-A 19 00 270 and US-A 3,692,744 are branched.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. It is advisable to use no more than 1 mol% of the branching agent, based on the acid component.
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid or its reactive derivatives (for example its dialkyl esters, such as dimethyl terephthalate) and 1,3-propanediol and / or 1,4-butanediol (polypropylene tantphthalate and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates
  • Preferred polyalkylene terephthalates 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; particularly preferred copolyesters are poly (propylene glycol 1, 3-butanediol-1, 4) terephthalates.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight ) at 25 ° C.
  • the polyesters prepared according to the invention can also be used in admixture with other polyesters and / or further polymers, mixtures of polyalkylene terephthalates with other polyesters preferably being used here.
  • the composition may contain other conventional polymer additives such as flame retardant synergists other than anti-dripping agents, lubricants and mold release agents (e.g., pentaerythritol tetrastearate), nucleating agents, stabilizers (e.g., UV / light stabilizers, thermal stabilizers, antioxidants, transesterification inhibitors, antihydrolysis agents), antistatic agents (e.g., carbon blacks, carbon fibers, carbon nanotubes, and the like) organic antistats such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers) as well as dyes, pigments, fillers and reinforcing materials, in particular glass fibers, mineral reinforcing materials and carbon fibers.
  • flame retardant synergists other than anti-dripping agents e.g., lubricants and mold release agents (e.g., pentaerythritol tetrastearate), nucleating agents, stabilize
  • Stabilizers used are preferably sterically hindered phenols and phosphites or mixtures thereof, such as, for example, Irganox® B900 (Ciba Specialty Chemicals). Pentaerythritol tetrastearate is preferably used as a mold release agent. Furthermore, carbon black is preferably added as a black pigment (eg black pearls). Particularly preferred molding compositions comprise as component E, in addition to optional further additives, a mold release agent, more preferably pentaerythritol tetrastearate, in 0.1 to 1.5 parts by weight, preferably 0.2 to 1.0 parts by weight, more preferably 0.3 to 0.8 parts by weight.
  • Particularly preferred molding compositions contain, as component E, in addition to optional further additives, at least one stabilizer, for example selected from the group of sterically hindered phenols, phosphites and mixtures thereof and more preferably Irganox® B900, in 0.01 to 0.5 parts by weight, preferably 0.03 to 0.4 parts by weight, particularly preferably 0.06 to 0.3 parts by weight.
  • at least one stabilizer for example selected from the group of sterically hindered phenols, phosphites and mixtures thereof and more preferably Irganox® B900, in 0.01 to 0.5 parts by weight, preferably 0.03 to 0.4 parts by weight, particularly preferably 0.06 to 0.3 parts by weight.
  • PTFE component F
  • pentaerythritol tetrastearate and Irganox B900 with a phosphorus-based flame retardant, as component C
  • polytetrafluoroethylene (PTFE) or PTFE-containing compositions such as masterbatches of PTFE are used as anti-dripping agents with polymers or copolymers containing styrene or methyl methacrylate, as a powder or as a coagulated mixture, e.g. with component B, used.
  • PTFE polytetrafluoroethylene
  • PTFE-containing compositions such as masterbatches of PTFE are used as anti-dripping agents with polymers or copolymers containing styrene or methyl methacrylate, as a powder or as a coagulated mixture, e.g. with component B, used.
  • the fluorinated polyolefins used as Antidrippingstoff are high molecular weight and have glass transition temperatures of above -30 ° C, usually of about 100 ° C, fluorine contents, preferably from 65 to 76, in particular from 70 to 76 wt .-%, average particle diameter d 50 of 0 , 05 to 1000, preferably 0.08 to 20 ⁇ .
  • fluorinated polyolefins used as Antidrippingstoff are high molecular weight and have glass transition temperatures of above -30 ° C, usually of about 100 ° C, fluorine contents, preferably from 65 to 76, in particular from 70 to 76 wt .-%, average particle diameter d 50 of 0 , 05 to 1000, preferably 0.08 to 20 ⁇ .
  • Polyolefins have a density of from 1.2 to 2.3 g / cn.
  • Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers.
  • the fluorinated polyolefins are known (see “Vinyl and Related Polymers” by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484-494; "Fluoropolymers” by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Vol.
  • They can be prepared by known methods, for example by polymerization of tetrafluoroethylene in an aqueous medium with a free-radical-forming catalyst, for example sodium, potassium or ammonium peroxidisulfate at pressures of 7 to 71 kg / cm ⁇ and at temperatures from 0 to 200 ° C, preferably at temperatures of 20 to 100 ° C. (See, for example, U.S. Patent 2,393,967 for details).
  • a free-radical-forming catalyst for example sodium, potassium or ammonium peroxidisulfate
  • the density of these materials may be between 1.2 and 2.3 g / cw, the average particle size between 0.05 and 1000 ⁇ .
  • the inventively preferred fluorinated polyolefins have average particle diameter of 0.05 to 20 ⁇ , preferably 0.08 to 10 ⁇ , and a density of 1.2 to 1.9 g / cw? -
  • Suitable fluorinated polyolefins F which can be used in powder form are tetrafluoroethylene polymers having an average particle diameter of from 100 to 1000 ⁇ m and densities of 2.0 g / cw? to 2.3 g / cn
  • Suitable tetrafluoroethylene polymer powders are commercially available products and are available, for example, from DuPont under the trade name Teflon®.
  • Particularly preferred flame-retardant compositions comprise as component F, in addition to optional further additives, a fluorinated polyolefin in 0.05 to 5.0 parts by wt., Preferably 0.1 to 2.0 parts by wt., Particularly preferably 0.1 to 1.0 Parts by weight.
  • a fluorinated polyolefin in 0.05 to 5.0 parts by wt., Preferably 0.1 to 2.0 parts by wt., Particularly preferably 0.1 to 1.0 Parts by weight.
  • Linear polycarbonate based on bisphenol A having a weight-average molecular weight M w of 27500 g / mol (determined by GPC in dichloromethane with polycarbonate as standard).
  • Component B2 ABS-type n-butyl acrylate-modified graft polymer prepared by the mass polymerization method having an A: B: S ratio of 21: 10: 65% by weight and having an n-butyl acrylate content of 4% by weight.
  • the dso value of the graft particle diameter determined by ultracentrifugation is 0.5 ⁇ m.
  • the graft base on which the grafted polymer is based is a styrene-butadiene block copolymer rubber (SBR).
  • SBR styrene-butadiene block copolymer rubber
  • the gel content of the graft polymer measured in acetone is 20% by weight.
  • the weight average molecular weight M w of the free, ie not chemically bound to the rubber or included in the rubber particles in acetone insoluble form for acetone by GPC with polystyrene as standard in dimethylformamide at 20 ° C is 110 kg / mol ,
  • Thermostabilizer Irganox® B900 (mixture of 80% Irgafos® 168 and 20% Irganox® 1076; BASF AG; Ludwigshafen / Irgafos® 168 (tris (2,4-di-tert-butylphenyl) phosphite) / Irganox® 1076 (2,6-di-tert-butyl-4- (octadecanoxycarbonylethyl) phenol) Component F
  • the feedstocks listed in Table 1 are compounded on a twin-screw extruder (ZSK-25) (Werner and Pfleiderer) at a speed of 225 rpm and a throughput of 20 kg / h at a machine temperature of 260 ° C granulated.
  • ZSK-25 twin-screw extruder
  • the finished granules are processed on an injection molding machine to the corresponding test specimens (melt temperature 240 ° C, mold temperature 80 ° C, flow front speed 240 mm / s).
  • the IZOD notched impact strength was measured according to ISO 180 / 1A on single-sided molded test bars of the dimension 80 mm x 10 mm x 4 mm.
  • the tensile elastic modulus was determined according to ISO 527 on 170 mm x 10 mm x 4 mm geometry shoulder bars.
  • the heat resistance was measured in accordance with ISO 306 (Vicat softening temperature, method B with 50 N load and a heating rate of 120 K / h) on single-sided test bars of dimension 80 mm xlO mm x 4 mm.
  • melt flowability was determined according to ISO 11443 (melt viscosity). Melt flowability was evaluated by melt volume flow rate (MVR) measured according to ISO 1133 at a temperature of 260 ° C and with a 5 kg punch load.
  • MVR melt volume flow rate
  • the fire behavior was measured according to UL 94V on bars measuring 127 x 12.7 x 1.5 mm.
  • compositions of Examples 1, 2 and 3 with 100% to 58%) ABS in the mass polymerization based on the total ABS content solve the object of the invention, ie a combination of good impact strength, temperature stability, E Modulus, flowability ( ⁇ 300 Pas at 1000s -1 ) and hydrolysis stability ( ⁇ 50% deviation from the MVR 260 ° C / 5kg starting point after storage for 7d / 95 ° C / 100% relative humidity), with a UL94V 0 classification at 1, 5 mm.

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Abstract

La présente invention concerne des compositions et des matières moulables à base de polycarbonate (PC) et d'ABS ignifugées, stables à haute température et à résilience modifiée, présentant un module élevé d'élasticité, une bonne fluidité et une stabilité à l'hydrolyse élevée et contenant : A) 55 à 95 parties en poids de polycarbonate aromatique et/ou de polyester carbonate aromatique, B) 1,0 à 20,0 parties en poids de polymère greffé modifié par un caoutchouc, C) 1,0 à 20,0 parties en poids d'au moins un phosphazène cyclique de formule (X), où k vaut 1 ou est un nombre entier de 1 à 10, de préférence de 1 à 8 et de façon particulièrement préférée de 1 à 5, la proportion de trimère (k=1) allant de 60 à 98% en moles, rapportée au composant C, et R est identique ou différent et représente respectivement un reste amine qui est le cas échéant halogéné, de préférence halogéné au fluor, un alkyle en C1 à C8, de préférence méthyle, éthyle, propyle ou butyle, un alcoxy en C1 à C8, de préférence méthoxy, éthoxy, propoxy ou butoxy, qui est le cas échéant substitué par un alkyle, de préférence un alkyle en C1 à C4, et/ou par un halogène, de préférence le chlore et/ou le brome, un cycloalkyle en C5 à C6, qui est le cas échéant substitué par un alkyle, de préférence un alkyle en C1 à C4, et/ou par un halogène, de préférence le chlore et/ou le brome, et/ou par un hydroxyle, un aryloxy en C6 à C20, de préférence phénoxy, naphtyloxy, qui est le cas échéant substitué par un alkyle, de préférence un alkyle en C1 à C4, et/ou par un halogène, de préférence le chlore et/ou le brome, un aralkyle en C7 à C12 substitué, de préférence un phénylalkyle en C1 à C4, ou un reste halogène, de préférence le chlore, ou un reste OH,D) 0 à 15,0 parties en poids de (co)polymère de vinyle dépourvu de caoutchouc ou de polytéréphtalate d'alkylène, E) 0 à 15,0 parties en poids d'additifs, F) 0,05 à 5,0 parties en poids d'agent anti-gouttage ; toutes les indications de parties en poids étant normées de telle façon que la somme des parties en poids de l'ensemble des composants A+B+C+D+E+F de la composition soit égale à 100. La présente invention concerne en outre l'utilisation des compositions pour fabriquer des articles façonnés, ainsi que les articles façonnés fabriqués à partir de ces compositions.
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KR102135991B1 (ko) 2020-07-20
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US20150315381A1 (en) 2015-11-05

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