EP2970661A1 - Flammhemmendes polycarbonat - Google Patents

Flammhemmendes polycarbonat

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Publication number
EP2970661A1
EP2970661A1 EP14779330.1A EP14779330A EP2970661A1 EP 2970661 A1 EP2970661 A1 EP 2970661A1 EP 14779330 A EP14779330 A EP 14779330A EP 2970661 A1 EP2970661 A1 EP 2970661A1
Authority
EP
European Patent Office
Prior art keywords
weight
phr
meth
aromatic
poly
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Withdrawn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
EP14779330.1A
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English (en)
French (fr)
Other versions
EP2970661A4 (de
Inventor
Xiangyang Li
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 LLC
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Covestro LLC
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Publication date
Priority claimed from US13/936,383 external-priority patent/US20140272375A1/en
Application filed by Covestro LLC filed Critical Covestro LLC
Publication of EP2970661A1 publication Critical patent/EP2970661A1/de
Publication of EP2970661A4 publication Critical patent/EP2970661A4/de
Withdrawn legal-status Critical Current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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds

Definitions

  • the present invention relates in general to polycarbonate compositions, more specifically, the invention relates to polycarbonate compositions having improved flanie-retardance.
  • U.S. Pat. No. 4,888,388, issued to Hongo et al. discloses a polycarbonate resin composition
  • a polycarbonate resin composition comprising a polycarbonate resin (A) or a mixture (A r ) of a polycarbonate resin with a saturated polyester resin and/or a polyester elastomer, and a compound rubber type grail copolymer (B) having at least one vinyl monomer graft-polymerized onto a compound rubber composed of from 10 to 90% by weight of a polyorganosiloxane rubber and from 10 to 90% by weight of a polyalkyl (meth)acrylate rubber in a total amount of 100% by weight in an inseparable interlocking fashion and having an average particle size of from 0.08 to 0.6 ⁇ , or a mixture ( ⁇ ') of such a compound rubber type graft copolymer (B) with a vinyl monomer, wherein component (B) or ( ⁇ ') is in an amount such that the compound mbber
  • Wittmann et al in U.S. Pat. No. 5,030,675, provide flame-resistant molding compounds . of polycarbonate, polyalkyl ene terephthalate, graft polymer, iluorinated polyolefine and phosphorus compound which can be worked up into molded products and which have a particularly advantageous combination of joint line strength, dimensional stability under heat and toughness.
  • U.S. Pat. No. 5,871,570 issued to Koyama et al, describes a flame retardant resin composition comprising the following components (A), (B), (C), (D), (E) and (F), wherein 1-10 parts by weight of (C).
  • thermoplastic resin composition comprising (R) a thermoplastic resin comprising (A) a polycarbonate resin and (B) an aromatic polyester resin in an (A)/(B) ratio of 99/1 to 50/50 by weight, and per 100 parts by weight of the thermoplastic resin (R), (C) 0.5 to 100 parts by weight of a silicate compound and (D) 0.5 to 30 parts by weight of an organic phosphorus based flame retarder,
  • the composition is said to exhibit excellent flame resistance and anti-drip property without containing a halogen atom and, moreover, have excellent properties such as heat resistance, mechanical strength, solvent resistance, surface property of moldings, and dimensional stability.
  • the composition comprises (A) 50 to 95 parts by weight of a polycarbonate resin and (B) 5 to 50 parts by weight of a thermoplastic polyester resin, contains (C) 0.1 to 5 parts by weight, per 100 parts by weight of the total, amount of (A) and (B), of coated stabilized red phosphorus and preferably contains (D) 0,1 to 100 parts by weight, per 100 parts by weight, of the total amount of (A) and (B). of a silicate compound.
  • thermoplastic molding composition characterized by its flame retardance and impact, strength.
  • the composition contains A) 70 to 99 parts by weight of aromatic poly(ester) carbonate B) 1 to 30 parts by weight of polyalkylene terephthalate, the total weight of A) and B) being 100 parts resin, and C) 1 to 20 parts per hundred parts resin (phr) of graft (co)polymer having a core-shell morphology, including a grafted shell that, contains polymerized alkyl(meth)acrylate and a composite rubber core that contains interpenetrated and inseparable polyorganosiioxane and poly(meth)alkyl acrylate components, D) 2 to 20 phr of a phosphorous-containing compound, and E) 0.1 to 2 part by weight of fluorinated polyolefin.
  • U.S. Pat. No. 8,217,101 issued to Li describes a thermoplastic molding composition characterized by its flame retardance.
  • the composition contains A) aromatic poly(ester) carbonate having a weight-average molecular weight of at least 25,000, B) (co)polyester and C) graft (co)polymer having a core-shell morphology, comprising a grafted shell that contains polymerized alkyl(meth)acrylate and a composite rubber core that contains interpenetrated and inseparable polyorganosiioxane and poly(meth)al.k l acrylate where the weight ratio of polyorganosiloxane/poly(meth)alkylacrylate/grafted shell is 70-90/5-15/5- 15, D) phosphorus-containing compound, E) fluorinated polyolefin and F) boron compound having average particle diameter of 2 to 10 ⁇ ,
  • WO 94/1 1429 in the name of Ogoe et al discloses a blended composition containing polycarbonate; polyester, an acrylate polymer, and/or a styrenic thermoplastic resin; poly(tetrafiuoroethylene); an acid acceptor; and a halogenated aryl phosphate; and optionally a halogenated aromatic carbonate oligomer, which cornposition possesses a desirable balance of ignition resistance, impact resistance and solvent resistance properties.
  • Urabe et al. in JP 04-345657, provide a flame retardant polycarbonate compound comprising 5-98 wt.% halogenated aromatic polycarbonate resin, 0-93 wt.% non-halogenated aromatic polycarbonate resin, 1-49 wt.% aromatic polyester resin, and 1 -20 wt.% graft rubber polymer composite obtained by grafting at least one vinyl monomer onto rubber particles having a mean particle size of 0.08-0.6 ⁇ and consisting of a polyorganosiloxane rubber and a polyalkyl (meth)acrylate rubber entangled with each other so as not to be separated from each other or 1-20 wt.% mixture of the graft rubber polymer composite with a vinyl polymer, and in which the sum of the two polycarbonate resins is 50-98 wt.% and the halogen content is 3-25 wt.%.
  • JP 06-239965 in the name of Urabe et al describes a resin composition composed of (A) 50-90 wt.% of an aromatic polycarbonate resin (preferably derived from bisphenol A). (B) 2-45 wt.% of an aromatic polyester resin (e.g. polyethylene terephthalate) and (C) 3-25 wt.% of a halogenated bisphenol epoxy resin of the formula
  • X is CI or Br
  • Y is alkylene, O, etc.
  • n is average polymerization degree and is 21-50.
  • the component C is said to be produced by condensing a halogenated bisphenol such as dibromobisphenol A with epichlorohydrin.
  • Ono et al. in JP 2001-031860, disclose a flame-retardant resin composition comprising 100 wt.% of the total of 86.7-35 wt.% of an aromatic polycarbonate resin (component (a)), 10-40 wt.% of polyalkyiene terephthalate resin (component b), 0.1 -1.0 wt.% of stabilized red phosphorus (component c), 1- 10 wt.% of a rubber-like polymer (component d), 0.1-1 wt.% of a polytetrafluoroethylene having fibril-forming ability (component e) and 0.1-35 wt.% of an inorganic compound consisting essentially of silicate (component, f).
  • An internal mechanism part of printing instrument can be molded from the flame- retardant thermoplastic resin composition.
  • JP 08-073692 in the name of Koyama et a!. provides a composition obtained by blending (A) 100 pts.wt. of a resin prepared by mixing (i) a PC resin having 16,000-29,000 viscosity-average molecular weight with (ii) a polyalkylene terephthalate resin in the weight ratio of the component (i)/(ii) of 75/25 to 90/10 with (B) 1-10 pts.wt.
  • Ri and R 2 are each a monofunctional aromatic group or aliphatic group
  • thermoplastic molding composition containing no halogen characterized by its flame retardance contains A) 60 to 99 parts by weight of aromatic poly(ester) carbonate and B) 1 to 20 parts per hundred parts resin (phr) of graft (co)polymer having a core-shell morphology, including a grafted shell that contains polymerized alkyl(meth)acrylate and a composite rubber core that contains interpenetrated and inseparable polyorganosiloxane and poly(meth)alkyl acrylate components, C) 2 to 20 phr of a phosphorous-containing compound, and D) 0.1 to 15 parts by weight of a boron compound having average particle diameter of 2 to 10 ⁇ .
  • the inventive composition contains; A) 60 to 99 percent by weight (pbw), preferably 70 to 95 pbw, most preferably 70 to 85 pbw of aromatic poly(ester) carbonate having a weight-average molecular weight of at least 25,000 preferably at least 26,000 g/moL, B) 1 to 20 preferably 2 to 15, more preferably 5 to 12 most preferably 7 to 10 parts per 100 parts resin (herein phr) of a graft (co)polymer having a core-shell morphology, comprising a grafted shell that contains polymerized alkyl(meth)acr late and a composite rubber core that contains interpenetrated and inseparable polyorganosiloxane and poly(meth)alkyl acrylate components, where the weight ratio of polyorganosiloxane/ poly(meth)alkyl acrylate rigid shell is 70-90/5-15/5-15, C) 2 to 20, preferably 5 to 15, particularly preferably 7 to 15, most preferably
  • Suitable aromatic (co)polyearbonates and/or aromatic polyester carbonates are known.
  • (Co)polyearbonates may be prepared by known processes (see for instance SchneU's "Chemistry and Physics of Polycarbonates", Interscienee Publishers, 1964) and are widely available in commerce, for mstance from Bayer Material Science under the trademark MAKROLON.
  • Aromatic polycarbonates may be prepared by the known melt process or the phase boundary process.
  • Aromatic dihydroxy compounds suitable for the preparation of aromatic polycarbonates and/or aromatic polyester carbonates conform to formula (I)
  • A represents a single bond, Cj- to Cs-alkylene, Ci ⁇ to Cs-alkylidene, Cs ⁇ to C6-cycloalkylid.ene, -0 ⁇ , -SO-, -CO-, -S-, -SO?.-, Ce- to Cn-arylene, to which there may be condensed other aromatic rings optionally containing hetero atoms, or a radical conforming to formula ( ⁇ ) or (III)
  • substituents B independently one of the others denote Ci- to Csa-alkyl, preferably methyl,
  • x independently one of the others denote 0, 1 or 2
  • p 1 or 0
  • R? and R 6 are selected individually for each X' and each independently of the other denote hydrogen or Ci- to Ce-alkyl, preferably hydrogen, methyl or ethyl,
  • X 1 represents carbon
  • m represents an integer of 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 5 and R 6 are both alkyl groups.
  • Preferred aromatic dihydroxy compounds are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyI)-C i -Cs-alkanes, bis-(hydroxyphenyl)-Cs- Ce-cycioalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis- (hydroxyphenyl) ketones, bis-(hydroxyphenyl)-sulfones and ⁇ , ⁇ -bis- (hydroxyphenyl)-diisopropylbenzenes.
  • aromatic dihydroxy compounds are 4,4'-dihydrox.ydiphenyl, bisphenol A, 2,4-bis-(4-hydroxyphenyl)- 2-methylbutane, 1.1 -bis-(4-hydroxyphenyl)-cyclohexan.e, 1 , 1 -bis-(4- hydroxyphenyi) ⁇ 3,3,5-trirnethylcyclohexane 5 4 s 4'-dihydroxydiphenyl sulfide, 4,4 ! - dihydroxydiphenyl-sulfone.
  • 2,2-bis-(4-hydroxy- phenyl)-propane bisphenol A
  • These compounds may be used individually or in the form of any desired mixtures.
  • Chain terminators suitable for the preparation of thermoplastic aromatic polycarbonates include phenol, p-chlorophenol, p-tert.-butylphenol, as well as long-chained alkylphenols, such as 4-(l,3-tetramethylbutyl)-phenol or monoalkylphenols or dialkyiphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-hutylphenol, p-isooctylphenol, p-tert.- octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5- dimethylheptyl)-phenol.
  • alkylphenols such as 4-(l,3-tetramethylbutyl)-phenol or monoalkylphenols or dialkyiphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-d
  • the amount of chain terminators to be used is generally 0.5 to 10 % based on the total molar amount of the aromatic dihydroxy compounds used.
  • the polycarbonates may be branched in a known manner, preferably by the incorporation of 0.05 to 2,0%, based on the sum of the molar amount of the aromatic dihydroxy compounds use, of compounds having a functionality of three or more, for example compounds having three or more phenolic groups.
  • Aromatic polyestercarbonates are known. Suitable such resins are disclosed in U.S. Pat. Nos. 4,334,053; 6,566,428 and in CA 1,173,998 all incorporated herein by reference.
  • Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates include diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxyiic acid and naphthalene-2,6-dicarboxyiic acid. Particularly preferred are mixtures of diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of from 1 :20 to 20: 1.
  • Branching agents may also be used in the preparation of suitable polyestercarbonates, for example, carboxylic acid chlorides having a functionality of three or more, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol,% (based on dicarboxylic acid dichlorides used), or phenols having a functionality of three or more, such as phloroglucinol, 4,6-dimethyl-2,4 ) 6-tri-(4-hydroxyphenyl)-heptene-2, 4,4- dimethyl ⁇ 2,4,6-trj-(4-hydroxyphenyi)-heptane, l ,3,5-tri-(4-hydroxyphenyl)-
  • Phenolic branching agents can be placed in the reaction vessel with the diphenols, acid chloride branching agents may be introduced together with the acid dichlorides.
  • the content of carbonate structural units in the thermoplastic aromatic polyester carbonates is preferably up to 100 mol.%, especially up to 80 mol.%, particularly preferably up to 50 mol.%. based on the sum of ester groups and carbonate groups. Both the esters and the carbonates contained in the aromatic polyester carbonates may be present in the polycondensation product in the form of blocks or in a randomly distributed manner,
  • thermoplastic aromatic poly(ester) carbonates have weight-average molecular weights (measured by gel permeation chromatography) of at least 25,000, preferably at least 26,000. Preferably, these have maximum weight- average molecular weights of 35,000, more preferably up to 32,000, particularly preferably up to 30,000 g/mol.
  • the thermoplastic aromatic poly(ester) carbonates may be used alone or in any desired mixture.
  • the graft (co)palymer suitable in the context of the invention has core/shell structure. It may be obtained by graft polymerizing alkyl(meth)aerylate and optionally a copolymerizable vinyl monomer onto a composite rubber core that includes interpenetrated and inseparable interpenetrating network (IPN) type polymer of polyorganosiloxane and alkyl(meth)acrylate. preferably polysiloxane and butylacrylate.
  • IPN interpenetrated and inseparable interpenetrating network
  • the shell is a polymeric rigid phase containing alkyl methacrylate, preferably methylmethacrylate.
  • the weight ratio of polysiloxane/alkyl(meth)acrylate/ rigid phase is 70-90/5-15/5-15, preferably 75- 85/7-12/7-12, most preferably 80/10/10.
  • the glass transition temperature of the rubber core is preferably below 0°C, preferably below -20°C, especially below -40°C.
  • the amount of component B present in the inventive composition is 1 to 20, advantageously 2 to 15, preferably 5 to 12, most preferably 7 to 10 phr.
  • the preferred rubber core has median particle size (dso value) of 0.05 to 5, more preferably 0.1 to 2 microns, especially 0.1 to 1 micron.
  • the median value may be determined by u!tracentrifuge measurement (W. SchoStan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).
  • the polyorganosiloxane component in the graft (co)polymer may be prepared by reacting an organosiloxane and a multifunctional crossUnking agent in an emulsion polymerization process. It is also possible to insert graft-active sites into the rubber by addition of suitable unsaturated organosiloxanes.
  • the organosiloxane is generally cyclic, the ring structures preferably containing from 3 to 6 Si atoms. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxaue, decamethylcyclopentasiloxane, dodecaraethyl- cyclohexasi ioxane, trimethyitriphenylcyclotrisiloxane, tetramethyltetra- phenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, which may be used alone or in a mixture of 2 or more such compounds.
  • the organosiloxane component is present in the silicone acrylate rubber in an amount of at least 70%, preferably at least 75%, based on weight of the graft (co)polymer,
  • Suitable crosslinking agents are tri- or tetra-functionai silane compounds.
  • Preferred examples include trimethoxymethyl silane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysi lane, tetra-n-propoxysilane, tetrabutoxysilane.
  • Graft-active sites may be included into the polyorganosiloxane component of the silicone acrylate rubber by incorporating a compound conforming to any of the following structures:
  • CH2 CH-SiR 5 nO 3 . j ,)/2 (Gi-3) Hs --- CH 7 S;R ;: nG ;3 ., tV2
  • R 5 denotes methyl, ethyl, propyl or phenyl
  • R 6 denotes hydrogen or methyl
  • n denotes 0, 1 or 2
  • p denotes 1 to 6.
  • (Meth)acryloyloxysilane is a preferred compound for forming the structure (GI-1).
  • Preferred (meth)acryloyloxysilanes include ⁇ -meihacryloyloxyethyl- dimethoxy-methyl-silane, ⁇ -methacryloyl-oxy-propylmethoxy-dimethyl-silane, ⁇ - methacryloyloxypiOpyl-dimethoxy-methyl-silane, y-methacry!oyloxypropyl-tri- methoxy-silane, y-methacryloyloxy-propyl-ethoxy-diethyl-silane, y-methacryloyl- oxypropyl-diethoxy-methyl-silane, y-methacryloyloxy-butyl-diethoxy-methyl- silane.
  • Vinylsiloxanes especially tetramethyl-tetmvinyl-cyclotetrasiloxane, are suitable for forming the structure GI-2,
  • p-Vinylphenyl-dimethoxy-methylsilane for example, is suitable for forming structure GI-3.
  • y-Mercaptopropyidimethoxy-methylsilane, y-rnercaptopropylmethoxy-dimethylsilan.e, y-mercaptopropyl- diethoxymethylsilane, etc. are suitable for forming structure Gi-4.
  • the amount of these compounds is up to 10%, preferably 0.5 to 5.0% (based on the weight of polyorganosiloxane).
  • the acrylate component in the silicone acrylate composite rubber may be prepared from alkyl (meth)actylates, crosslinkers and graft-active monomer units.
  • alkyl (meth)acrylates examples include alkyl acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and alkyl methacrylates, such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-laury! methacrylate, n-butyl acrylate is particularly preferred.
  • Multifunctional compounds may be used as crosslinkers. Examples include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3- butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate,
  • allyl methacrylate triallyl cyanurate, triallyl isocyanurate.
  • allyl methacrylate may also act as crosslinker.
  • These compounds may be used in amounts of 0.1 to 20%, based on the weight of acrylate rubber component.
  • the graft polymerization onto the graft base may be carried out in suspension, dispersion or emulsion. Continuous or discontinuous emulsion polymerization is preferred.
  • the graft polymerization is carried out with free- radical initiators (e.g. peroxides, azo compounds, hydroperoxides, persulfates, perphosphates) and optionally using anionic emulsifiers, e.g. carboxonium salts, sulfonic acid salts or organic sulfates.
  • the graft shell (B.2) may be formed of a mixture of
  • B.2.1 0 to 80%, preferably 0 to 50%, especially 0 to 25% (based on the weight of the graft shell), of vinyl aromatic compounds or ring-substituted vinyl aromatic compounds (e.g. styrene, a-methylstyrene, p-methylstyrene), vinyl cyanides (e.g. acrylonitrile and methacrylonitrile), and
  • the preferred graft shell includes one or more (meth)acrylic acid (Cs-Cs)- alkyl esters, especially methyl methacrylate.
  • Phosphorus-containing compounds suitable in the context of the invention include oligomeric organic phosphoric or phosphonic acid esters conforming structurally to formula (IV)
  • R ! , R 2 , R 3 and R 4 independently one of the others, each represents IV to Cg-alkyl, or Cs-6-cycloalkyl, C 6 -20-aryl or C7-j?. ⁇ aralkyl each optionally substituted by alkyl, preferably by d-4-alkyl,
  • n independently one of the others denotes 0 or 1 , preferably 1 ,
  • q denotes 0,5 to 30, preferably 0.8 to 15, particularly preferably 1 to 5, especially 1 to 2, and
  • X is a mono- or poly-nuclear aromatic radical having from 6 to 30 carbon atoms, or an aliphatic radical having from 2 to 30 carbon atoms, which may be OH-substituted and may contain up to 8 ether bonds.
  • the aliphatic radical may be linear or branched.
  • R ! , R 2 , R 3 and R 4 each independently of the others represent tV 4-a!kyL phenyl, naphthyl or phenyl-d-4-alkyl.
  • R 3 ⁇ 4 , R 2 , R 3 and R 4 may be substituted by alkyl groups, preferably by Ci-4-alkyl.
  • Particularly preferred aryl radicals are cresy!, phenyl, xylenyl, propylphenyl or butylphenyl.
  • X represents a mono- or poly-nuclear aromatic radical having from 6 to 30 carbon atoms, it is preferably derived from any of the aromatic dihydroxy compounds of formula (I).
  • X particularly preferably represents at least one member selected from the group consisting of
  • X may be derived from resorcinoi, hydroquinone, bisphenol A or diphenylphenol and particularly preferably from bisphenol A.
  • R', R 2 , R 3 , R 4 , n and q are as defined for formula (IV),
  • n independently one of the others represents 0, 1 , 2, 3 or 4,
  • R 3 and R 6 independently one of the others represents Ci-4-alkyi, preferably methyl or ethyl
  • Y represents Ci- to Cy-alkylidene, Ci-7-alkylene, Cs-12-cycioalkylene, C5-12- cycloalkylidene, -0-, -S-, -SO2 or --CO-, preferably isopropylidene or methylene,
  • Such phosphorus compounds are known (see, for example, U.S. Pat. Nos. 5,204,394 and 5,672,645, both incorporated herein by reference) or may be prepared by known methods (e.g. Ullmanns Enzyklopadie der ischen Chemie, Vol. 18, p. 301 et seq, 1979; Houben-Weyl, Methoden der organischen Chemie, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
  • Component C is present in the inventive composition in amount of 2 to 20, preferably 5 to 15, particularly preferably 7 to 15 most preferably 10 to 15 pl r.
  • the boron compound suitable in the context of the present invention is not particularly limited so long as it is a compound having a boron atom.
  • Examples include boric acid, boron oxide and borates.
  • the borates include zinc borates such as zinc tetraborate, zinc metaborate and basic zinc borate, barium borates such as barium orthoborate, barium metaborate, barium diborate and barium tetraborate, lead borate, cadmium borate and magnesium borate.
  • Such boron compounds may be used alone or in combination as a mixture of two or more of them.
  • the preferred boron compound is zinc borate.
  • the preferred zinc borate has the general chemical formula mZn(>nB2(3 ⁇ 4*xH20 where the ratio of x/m/n is around 0-7/1-5/2-6. This borate is well known and commercially available.
  • the average particle diameter is between 2 and 0 ⁇ , advantageously 4 to 6 ⁇ , alternatively 8-10 ⁇ . Particle size and particle diameter always means the average particle diameter.
  • the inventive composition may further include additives that are known for their function in the context of thermoplastic molding compositions that contain poly(ester)carbonates.
  • lubricants include any one or more of lubricants, mold release agents, for example pentaerythritol tetrastearate, nucleating agents, antistatic agents, thermal stabilizers, light stabilizers, hydrolyticai stabilizers, fillers and reinforcing agents, colorants or pigments, as well as further (non- halogen containing) flame retarding agents or a flame retarding synergists.
  • mold release agents for example pentaerythritol tetrastearate
  • nucleating agents for example pentaerythritol tetrastearate
  • antistatic agents for example pentaerythritol tetrastearate
  • thermal stabilizers for example light stabilizers, hydrolyticai stabilizers, fillers and reinforcing agents, colorants or pigments, as well as further (non- halogen containing) flame retarding agents or a flame retarding synergists.
  • thermal stabilizers for example
  • inventive compositions may be prepared conventionally using conventional equipment and following conventional procedures.
  • the inventive composition may be used to produce moldings of any kind by thermoplastic processes such as injection molding, extrusion and blow molding methods.
  • PC a bisphenol-A based homopolycarbonate having melt flow rate of about 4 g/10 min (at 300°C, 1 .2 g) per ASTM D
  • MMA methyl methaerylate
  • BA siloxane(Si)-butyl acrylate
  • P-COMPOUND conforms to the following structure:
  • Cone peak hea release rate was determined in accordance with ASTM E662 on 1.5 mm plaques with heat flux of 35 kW/rn 2 .
  • melt flow rates (MVR) of the compositions were determined in accordance with ASTM D-1238 at 300°C, 1.2kg load.
  • VOC AT Vicat temperature
  • Heat Deflection Temperature was determined according to ASTM D 648 at 0.455MPa, 120°C/h (HDT1) and at 1.82MPa, 120°C/h (HDT2).
  • Notched Izod impact energy was detemiined according to ASTM D 256 at 23 °C on 1/8" samples.
  • thermoplastic molding composition comprising: A) 60 to 99 percent by weight (pbw) aromatic poly(ester) carbonate having a weight- average molecular weighi of at least 25,000; B) 1 to 20 parts per 100 parts resin (phr) graft (co)polymer having a core-shell morphology, comprising a grafted shell that coniains polymerized alkyl(meth)acrylate and a composite rubber core that contains interpenetrated and inseparable polyorganosiloxane and po!y(meth)aik.yi acrylate where the weight ratio of polyorganosiloxane/ poiy(meth)alkylacrylate/ grafted shell is 70-90/5-15/5-15; C) 2 to 20 phr phosphorus-containing compound; D) 0.1 to 15 pin * boron compound having average particle diameter of 2 to 10 microns.
  • composition according to clause 1, wherein said phosphorous compound is a member selected from the group consisting of phosphoric acid ester and phosphonic acid ester.
  • Ri, R 3 ⁇ 4 R 3 and R4 independently one of the others, each represents Ci- to Cg-alkyl, or Cs-e-cycloalkyl.
  • q denotes 0.5 to 30, and
  • X is a mono- or poly-nuclear aromatic radical having from 6 to 30 carbon atoms, or an aliphatic radical having from 2 to 30 carbon atoms.
  • composition according to clause 1 further containing at least one member selected from the group consisting of lubricant, mold-release agent, nucleating agent, antistatic, thermal stabilizer, hydrolyticai stabilizer, light stabilizer, colorant, pigment, filler, reinforcing agent, flame proofing agent other than component C), and flame proofing synergist.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP14779330.1A 2013-03-11 2014-03-05 Flammhemmendes polycarbonat Withdrawn EP2970661A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201361775806P 2013-03-11 2013-03-11
US13/936,383 US20140272375A1 (en) 2013-03-15 2013-07-08 Electrically conductive and dissipative polyurethane foams
PCT/US2014/020515 WO2014164096A1 (en) 2013-03-11 2014-03-05 Flame retardant polycarbonate

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EP2970661A4 EP2970661A4 (de) 2016-10-12

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69223550T2 (de) * 1991-05-28 1998-04-16 Denki Kagaku Kogyo Kk Flammhemmende Harzzusammensetzung
JP3202259B2 (ja) * 1991-05-28 2001-08-27 電気化学工業株式会社 難燃性の組成物
JP3926938B2 (ja) * 1998-12-03 2007-06-06 三菱エンジニアリングプラスチックス株式会社 難燃性ポリカーボネート樹脂組成物
DE10234420A1 (de) * 2002-07-29 2004-02-12 Bayer Ag Schlagzähmodifizierte Polycarbonat Blends
JP5168812B2 (ja) * 2006-04-13 2013-03-27 三菱エンジニアリングプラスチックス株式会社 熱可塑性樹脂組成物および樹脂成形品
US8217101B2 (en) * 2007-03-02 2012-07-10 Bayer Materialscience Llc Flame retardant thermoplastic molding composition
US7977415B2 (en) * 2007-11-30 2011-07-12 Bayer Materialscience Llc Impact resistant, flame retardant thermoplastic molding composition
JP5609644B2 (ja) * 2009-07-17 2014-10-22 東レ株式会社 難燃性熱可塑性樹脂組成物および成形品
DE102010041387A1 (de) * 2010-09-24 2012-03-29 Bayer Materialscience Aktiengesellschaft Flammgeschützte schlagzähmodifizierte Batteriegehäuse auf Polycarbonatbasis I

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KR20150126848A (ko) 2015-11-13
EP2970661A4 (de) 2016-10-12
WO2014164096A1 (en) 2014-10-09

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