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
  • 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
• • 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
  • 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
  • C08L69/005—Polyester-carbonates
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
  • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
  • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
  • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
  • H01M50/213—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for cells having curved cross-section, e.g. round or elliptic
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
  • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
  • H01M50/222—Inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
  • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
  • H01M50/227—Organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
  • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
  • H01M50/229—Composite material consisting of a mixture of organic and inorganic materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
  • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
  • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
  • H01M50/242—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries against vibrations, collision impact or swelling
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to flame retardant impact-modified polycarbonate-based battery cases containing, as a graft polymer, a silicone-acrylate composite rubber and a phosphorus-containing flame retardant which have high low-temperature impact strength, good flame resistance with thin wall thickness, and excellent chemical resistance. Furthermore, the present invention relates to the use of the polycarbonate compositions according to the invention for the production of battery housings.
• WO-A 2004/069914 discloses flame-retardant polycarbonate compositions containing polyalkyl (alkyl) acrylate and halogen-free oligophosphates which are free of polymers involved in the construction of butadiene, styrene or acrylonitrile.
• compositions are characterized by good Bindenahtfestmaschine, chemical resistance, heat resistance, elongation at break and flowability.
• the compositions of the present invention differ from the compositions according to WO-A 2004/069914 in that the compositions according to the invention contain no rubber-free polyalkyl (alkyl) acrylate.
• WO-A 2002/046305 discloses impact-modified, flame-retardant polycarbonate compositions containing polycarbonate, impact modifier, phosphorus-containing flame retardants. The compositions are characterized by an improved impact strength in the low temperature range. However, WO-A 2002/046305 does not disclose any compositions containing a sliding impact modifier with a graft base of silicone-acrylate composite rubber.
• EP-A 635547 discloses flame-retardant polycarbonate compositions containing polycarbonate, a copolymer gel, an acrylate or diene rubber based impact modifier, a flame retardant such as oligophosphate, and optionally an impact modifier having a diene rubber, acrylate rubber or EPDM rubber backbone. However, EP-A 635547 does not disclose any compositions containing a sliding impact modifier with a graft base of silicone-acrylate composite rubber.
• No. 4,623,766 discloses flame-retardant polycarbonate compositions having an impact modifier with a graft base of silicone-acrylate composite rubber, wherein the weight ratio of impact modifier to phosphorus from the phosphoric acid ester is between 2 and 15.
• the compositions have improved mechanical properties and Good Processing Behavior
• the compositions of the present invention differ from the compositions of US 6423766 in that the compositions of the present invention have a higher weight ratio of toughening modifier to phosphorus from the phosphoric acid ester.
• phosphorus compounds selected from the groups of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonateamines, phosphazenes and phosphinates, wherein also Mixtures of several components selected from one or more of these groups can be used as flame retardants.
• thermoplastic Vmyi (co) polymer E.I.
• / or polyalkylene terephthalate E.2
• the composition is free of thermoplastic vinyl (co) polymers (E.I.) and / or polyalkylene terephthalates (E.2), and
• compositions are preferably free of non-rubbery polyalkyl (aikyl) acrylate, and wherein all parts by weight in the present application are normalized such that the amounts of the parts by weight of components A + B + C in composition 100 give the desired profile of properties.
• 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 literature processes (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, z, B. DE-A 3 077 934) ,
• Heteroatom-containing rings may be condensed
• B is in each case C 1 to C 7 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
• x each independently 0, 1 or 2
• p 1 or 0
• R 7 and R 8 are individually selectable for each X 1 , independently of one another hydrogen or C 1 -C 4 -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 7 and R 8 are simultaneously aikyl.
• Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) C 1 -C 4 alkanes, bis (hydroxyphenyl) C 5 -C 6 cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) -sulfones and a, a-bis (hydroxyphenyl) -diisopropyl-benzenes and their comembromated and / or ring-chlorinated derivatives.
• diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1, Bis (4-hydroxyphene) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as, for example, 2,2-bis (3-chloro) 4-hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydrox'phenyl) -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
• Suitable chain terminators for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenoi or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (i, 3-tetramethyl-butyS) -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.
• the amount of chain terminators to be used is generally between 0.5 mol% mol% and 10 mol% mol%, based on the molar sum of the diphenols used in each case.
• thermoplastic aromatic polycarbonates have weight average molecular weights (M w , measured, for example, by GPC, ultracentrifuge or scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, more preferably 24,000 to 32,000 g / mol.
• thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those containing three and more phenolic groups.
• 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 Pat. No. 3,419,634) and can be prepared by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
• Preferred polycarbonates are, in addition to the bisphenol A homopolycarbonates, the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums of diphenols, of other than preferred or particularly preferred diphenols, in particular 2,2-bis (3,5 dibromo-4-hydroxyphenyl) -propane.
• Aromatic dicarboxylic acid dihalides 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.
• 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 terminators.
• the aromatic polyester carbonates may also contain aromatic flydroxycarboxylic acids incorporated.
• the aromatic Polvestercarbonate can be both linear and branched in a known manner (see DE-A 2 940 024 and DE-A 3,007,934).
• Suitable branching agents are, for example, trihydric 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 tri or more functional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-one 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri- (4 -hydroxyphenyl) ethane, tri
• arom ates Po lye carbo onates can be varied as much as possible to carbonate structural units.
• 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 content of the aromatic polyester carbonates may be in the form of blocks or randomly distributed in the. Polycondensate present.
• the graft polymers B are prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization.
• Suitable monomers B 1 are vinyl monomers such as vinyl aromatics and / or ring-substituted vinylaromatics (such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene), methacrylic acid (C 1 -C 6) -alkyl esters (such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, Allyl methacrylate), acrylic acid (C] -Cg) alkyl esters (such as methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate), organic acids (such as acrylic acid, methacrylic acid) and / or vinyl cyanides (such as acrylonitrile and methacrylonitrile) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example, male
• Preferred monomers B 1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene, methyl methacrylate, n-butyl acrylate and acrylonitrile. Particular preference is given to using B.l. methyl methacrylate as the monomer.
• the glass transition temperature of the graft B.2 is ⁇ 10 ° C, preferably ⁇ 0 ° C, more preferably ⁇ -20 ° C.
• the graft base B.2 generally has an average particle size (d 5 o ⁇ value) of 0.05 to 10 ⁇ , preferably 0.06 to 5 ⁇ , particularly preferably 0.08 to 1 ⁇ .
• the glass transition temperatures are determined by dynamic differential thermal analysis (DSC) according to the DIN EN 61006 standard at a heating rate of 10 K / min with definition of the T "as center temperature (tangent method).
• the average particle size d 50 is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by ultracentrifuge measurement (W. Schortau, H. Lange, Kolloid-Z and Z. Polymere 250 (1972), 782-796).
• silicone-acrylate composite rubber is used as Pfropfgrundiage B.2 according to the invention. These silicone acrylate composite rubbers are preferably composite rubbers having grafting sites containing 10 to 90% by weight, preferably 30 to 85% by weight, of silicone rubber content and 90 to 10% by weight, preferably 70 to 15% by weight. % Polyalkyl (meth) acrylate rubber content, wherein the two mentioned rubber components penetrate each other in the composite rubber so that they can not be substantially separated from one another.
• the finished resin compositions have disadvantageous surface properties and degraded colorability.
• the proportion of the polyalkyl (meth) acrylate rubber component in the composite rubber is too high, the impact resistance of the finished resin composition is adversely affected).
• Silicone acrylate composite rubbers are known and described, for example, in US Pat. No. 5,807,914, EP 430134 and US Pat. No. 4,888,388.
• Suitable silicone rubber components B.2.1 of the silicone-acrylate composite rubbers according to B.2 are silicone rubbers having graft-active sites whose preparation method is described, for example, in US Pat. No. 2,891,920, US Pat. No. 3,294,425, DE-OS 3 631 540, EP 249964, EP 430134 and US Pat ,
• the silicone rubber according to B.2.1 is preferably prepared by emulsion polymerization, in which siloxane monomer building blocks, crosslinking or branching agents (IV) and optionally grafting agents (V) are used.
• siloxane monomer building blocks are dimethylsiloxane or cyclic organosiloxanes having at least 3 ring members, preferably 3 to 6 ring members, such as, for example and preferably, hexamethylcyclo-trisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiioxane, dodecamethyicylohexasioxane, trimethyltriphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane used.
• the organosiloxane monomers may be used alone or in the form of mixtures with 2 or more monomers.
• the silicone rubber preferably contains not less than 50% by weight and more preferably not less than 60% by weight of organosiloxane, based on the total weight of the silicone rubber component.
• crosslinking or branching agent (IV) it is preferred to use silane-based crosslinking agents having a functionality of 3 or 4, more preferably 4. Examples which may be mentioned are: trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetrabutoxysilane.
• the crosslinking agent may be used alone or in a mixture of two or more. Particularly preferred is tetraethoxysilane,
• the crosslinking agent is used in an amount range of between 0.1 and 40.0% by weight, based on the total weight of the silicone rubber component.
• the amount of crosslinking agent is chosen so that the degree of swelling of the silicone rubber, measured in toluene, is between 3 and 30, preferably between 3 and 25, and more preferably between 3 and 15.
• the degree of swelling is defined as the weight ratio between the amount Toluene which is absorbed by the silicone rubber when saturated with toluene at 25 ° C and the amount of silicone rubber in the dried state.
• the determination of the degree of swelling is described in detail in EP 249964. When the degree of swelling is less than 3, that is, when the content of crosslinking agent is too high, the silicone rubber does not show sufficient rubber elasticity. If the swelling index is greater than 30, the silicone rubber can not form a domain structure in the matrix polymer and therefore can not improve impact resistance, the effect would then be similar to simple addition of polydimethylsiloxane.
• Tetrafunctional crosslinkers are preferred over irifunctional because then the degree of swelling is easier to control within the limits described above.
• Suitable as the grafting agent (V) are compounds capable of forming structures of the following formulas:
• CH 2 C (R 9 ) -COO- (CH 2 ) p -SiR 10 n O (3 ⁇ ) / 2 (VI)
• CH 2 CH-SiR 1 ° n O (3 _n ) / 2 (V-) 2) or
• C j -C / j -A! kyl preferably methyl, ethyl or propyl, or phenyl
• p is an integer from 1 to 6.
• Acryloyi- or methacryloyloxysilanes are particularly suitable, the o.g. Structure (V-l) to form, and have a high grafting efficiency. This ensures effective formation of the graft chains and thus favors the impact resistance of the resulting resin composition.
• Exemplary and preferred are: ⁇ ⁇ methacr'loyloxy-ethyidimethoxymethyl ⁇ silane, y-methacryloyloxy-propylmemoxydimethyl-silane, y-methacryloyloxy-propyldimethoxymethyl-silane, y-methacryloxy-propyltrimethoxy-sian, ⁇ -methacryloyloxy-propylethoxydiethyl-silane, y- Methacryloyloxy-propyldiethoxymethyl-silane, ⁇ -methaciyloyl-oxy-butyldiethoxymethyl-silanes or mixtures thereof. Preference is given to using from 0 to 20% by weight of grafting agent, based on the total weight of the silicone rubber.
• the silicone rubber can be prepared by emulsion polymerization, as described, for example, in US Pat. No. 2,892,920 and US Pat. No. 3,294,725.
• the silicone rubber falls in the form of a aqueous latex.
• a mixture comprising organosiloxane, crosslinking agent and, if appropriate, grafting agent is shear mixed with water, for example by means of a honeycomb, in the presence of an electrolyte solution on silica gel b as is wi ez.
• B. Aikyibenzolsulfonklad or alkyl sulfonic acid, wherein the mixture polymerized to the silicone rubber latex.
• aikyibenzenesulfonic acid since it acts not only as an emulsifier but also as a polymerization initiator.
• a combination of the sulfonic acid with a metal salt of aikyibenzenesulfonic acid or with a metal salt is favorable for an alkylsulfuric acid, thereby stabilizing the polymer during the late graft polymerization.
• Suitable polyalkyl (meth) acrylate rubber components B.2.2 of the silicone acrylate composite rubbers according to B.2 can be prepared from alkyl methacrylates and / or alkyl acrylates, a crosslinking agent (IV) and a grafting agent (V).
• alkyl methacrylates and / or alkyl acrylates are the C 1 to C 6 alkyl esters, for example methyl, eihylene, n-butyl, t-butyl, n-propyl, n-hexyi, n-octyl, n Lauryl and 2-ethylhexyesters: haloalkyl esters, preferably halogen-Cj-Cg-alkyl esters, such as chloroethyl acrylate and mixtures of these monomers. Particularly preferred is n-butyl acrylate.
• crosslinking agent (IV) for the polyalkylene (meth) acrylate rubber component of the silicone acrylate rubber monomers having more than one polymerizable double bond can be used.
• Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate , 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate.
• the crosslinkers may be used alone or in mixtures of at least two crosslinkers.
• Exemplary and preferred grafting agents (V) are ailyimethacrylate, triallyl cyanurate, triallyl isocyanurate, or mixtures thereof.
• Ailyimethacrylate can also be used as a crosslinking agent (IV).
• the grafting agents may be used alone or in mixtures of at least two grafting agents.
• the amount of crosslinking agent (IV) and grafting agent (V) is 0.1 to 20% by weight based on the total weight of the polyalkyl (meth) acrylate rubber component of the silicone acrylate rubber.
• the silicone acrylate composite rubber is prepared by first preparing the silicone rubber according to B.2.1 as an aqueous latex.
• This latex is then enriched with the methacrylic acid esters and / or alkyl acylates, the crosslinking agent (IV) and the grafting agent (V) to be used, and polymerization is carried out.
• a free-radically initiated emulsion polymerization for example by a peroxide, an azo or redox initiator.
• a redox initiator system especially a sulfoxylate initiator system prepared by combining iron sulfate, disodium ethylenediaminetetraacetate, Rongalit and hydroperoxide.
• the grafting agent (V) used in the production of the silicone rubber causes the polyalkyl (meth) acrylate rubber portion to be covalently attached to the silicone rubber portion.
• the two rubber components penetrate each other and thus form the composite rubber, which can no longer be separated after the polymerization in its components of silicone rubber component and polyalkyl (meth) acrylate rubber component.
• the monomers B.I are grafted onto the rubber base B.2.
• the graft polymerization is carried out according to the following polymerization method:
• the desired vinyl monomers B.sub.1 are grafted onto the graft base, which is in the form of an aqueous latex.
• the grafting efficiency should be as high as possible and is preferably greater than or equal to 10%.
• the grafting efficiency depends largely on the grafting agent (V) used.
• the silicone (acrylate) graft rubber After polymerization to the silicone (acrylate) graft rubber, the aqueous latex is placed in hot water in which metal salts have been previously dissolved, such as calcium chloride or magnesium sulfate. The silicone coats (acrylate) graft rubber and can then be separated.
• the ais component B) Methacryl Acid Chimethacryl Acid alkyl ester Pfropikautschuke are commercially available. Examples include: Metablen® SX 005, Metablen® S-2030 and Metablen® SRK 200 from Mitsubishi Rayon Co. Ltd. Component C
• compositions of the invention also contain flame retardants, these being preferably selected from the group comprising the phosphorus-containing flame retardants and halogenated flame retardants.
• phosphorus-containing flame retardants are selected from the groups of mono- and oligomeric phosphoric and phosphonic, Phosphonatamine, phosphazenes and phosphinic, wherein mixtures of a plurality of components selected from one or more of these groups can be used as flame retardants .
• Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.
• Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (VI)
• R 1, R 2, R 3 and R 4 are each independently optionally halogenated C 1 to C 8 alkyl, in each case optionally substituted by alkyl, preferably C 1 to C 4 alkyl, and / or halogen, preferably chlorine, bromine, substituted C 5 to C 6 cycloalkyl, C 6 to C20-aryl or C7 to C12-aralkyl,
• n independently, 0 or 1
• X is a mononuclear or polynuclear aromatic radical having 6 to 30 C atoms, or a linear or branched aliphatic radical having 2 to 30 C atoms, which may be OH-substituted and may contain up to eight ether bonds.
• R 1, R 2, R 3 and R 4 independently of one another are Cl to C 4 -alkyl, phenyl, naphthyl or phenyl-C 1 -C 4 -alkyl.
• the aromatic groups R 1, R 2, R 3 and R 4 may in turn be substituted by halogen and / or alkyl groups, preferably chlorine, bromine and / or C 1 to C 4 alkyl.
• Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
• X in the formula (VI) is preferably a mono- or polynuclear aromatic radical with
• n in the formula (VI) may independently be 0 or 1, preferably n is the same
• q (also in formula VII) stands for integer values of 0 to 30, preferably 0 to 20, particularly preferably 0 to 10, in the case of mixtures for average values of 0.8 to 5.0, preferably 1.0 to 3.0 , more preferably. 1.05 to 2.00, and more preferably from 1.08 to 1.60.
• X is particularly preferred for
• X is derived from resorcinol, hydroquinone, bisphenol A or diphenyiphenol.
• X is particularly preferably derived from bisphenol A.
• Phosphorus compounds of the formula (VI) are in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri (isopropyiphenyl) phosphate, resorcinol bridged oligophosphate and bisphenol A bridged oligophosphate.
• the use of oligomeric phosphoric acid esters of the formula (VI) derived from bisphenol A is particularly preferred.
• component C is bisphenol A-based oligophosphate of the formula (Via)
• component C is resorcinol-based qligophosphate according to formula (VIb)
• the phosphorus compounds according to component C are known (cf., for example, EP-A 0 363 608, EP-A 0 640 655) or can be prepared by known methods in an analogous manner (eg Ullmanns Enzyklopadie der ischen Chemie, Vol ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein, Vol. 6, p. 177).
• component C it is also possible to use mixtures of phosphates with different chemical structure and / or with the same chemical structure and different molecular weight.
• the mean q value can be determined by determining the composition of the phosphorus compound (molecular weight distribution) by means of a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and from this the mean values for q are calculated.
• a suitable method gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)
• phosphonatoms and phosphazenes as described in WO 00/00541 and WO 01/18105, can be used as flame retardants.
• the flame retardants can be used alone or in any mixture with each other or in mixture with other flame retardants.
• Further preferred flame retardants in the sense of the invention are salts of a phosphinic acid with any desired metal cations. It is also possible to use mixtures of salts which differ in their metal cation.
• the metal cations are the cations of metals of main group 1 (alkali metals, preferably Li +, Na ', K +), the 2nd Hauptgrappe (alkaline earth metals, preferably Mg 2+, Ca 2+, Sr 2+, Ba 2 + , more preferably Ca 2+ ) or the 3rd main group (elements of the boron group, preferably Al ' + ) and / or the 2nd, 7th or 8th subgroup (preferably ⁇ 2 ⁇ , Mn 2+ , Fe 2 " , Fe 3+ ) of the periodic table.
• alkali metals preferably Li +, Na ', K +
• the 2nd Hauptgrappe alkaline earth metals, preferably Mg 2+, Ca 2+, Sr 2+, Ba 2 + , more preferably Ca 2+
• the 3rd main group elements of the boron group, preferably Al ' +
• the 2nd, 7th or 8th subgroup preferably ⁇ 2 ⁇ , Mn
• a salt or a mixture of salts of a phosphinic acid of the formula (IX) is used,
• the average particle size d 50 of the Phosphinklasaizes (component C) is less than 80 ⁇ , preferably less than 60 ⁇ , more preferably d 5 o is between 10 ⁇ and 55 ⁇ .
• the average particle size d 50 is the diameter, above and below which each 50 wt .-% of the particles are. It is also possible to use mixtures of salts which differ in their mean particle size d 50 .
• the phosphinic acid salt can be used either alone or in combination with other phosphorus-containing flame retardants.
• compositions according to the invention may preferably contain fluorinated polyolefins D.
• Fluorinated polyolefins are generally known (cf., for example, EP-A 640 655).
• a commercially available product is, for example, Teflon® 30 N from DuPont.
• the fluorinated polyolefins may also be used in the form of a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of the graft polymers B) or an emulsion of a copolymer E.I) preferably based on styrene / acrylonitrile or polymethyl methacrylate, wherein the fluorinated polyolefin as emulsion is mixed with an emulsion of the graft polymer or (co) polymer and then coagulated.
• the fluorinated polyolefins can be used as a precompound with the graft polymer B) or a copolymer E.I) preferably based on styrene / acrylonitrile or polymethyl methacrylate.
• the fluorinated polyolefins are mixed as powder with a powder or granules of the graft polymer or copolymer and compounded in the melt generally at temperatures of 200 to 330 ° C in conventional units such as internal mixers, extruders or twin-screw.
• the fluorinated polyolefins may also be used in the form of a masterbatch prepared by emulsion polymerizing at least one monoethylenically unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin.
• Preferred monomer components are styrene, acrylonitrile, polymethylmethacrylate and mixtures thereof.
• the polymer is used after acid precipitation and subsequent drying as a free-flowing powder.
• the coagulates, pre-compounds or masterbatches usually have solids contents of fluorinated polyolefin of 5 to 95 wt .-%, preferably 7 to 60 wt .-%.
• Component E comprises one or more thermoplastic vinyl (co) polymers E.I. and / or poly (ethylene terephthalates) E.2.
• Suitable as vinyl (co) polymers E. l polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co) polymers of
• E.1.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and / or unsaturated carboxylic acids (such as may acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example Maleic anhydride and N-phenylmaleimide).
• vinyl cyanides unsaturated nitriles, such as acrylonitrile and methacrylonitrile
• carboxylic acids such as may acid
• derivatives such as anhydrides and imides
• unsaturated carboxylic acids for example Maleic anhydride and N-phenylmaleimide
• the Vinyi (co) polymers E.I are resinous, thermoplastic and rubber free.
• the copolymer of E.1.1 Styroi and E.1.2 acrylonitrile is particularly preferred.
• the (co) polymers according to E.1 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 Mw (weight average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
• the Poiyaikylenterephthaiate of component E.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, and mixtures of these reaction products.
• Preferred polyisocyanate terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90% by mole, based on the diol component of ethylene glycol and / or butanediol , 4-residues.
• the preferred polyisocyanate terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as for example Remains of phthalic acid, Is ophtha! acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
• other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as for example Remains of phthalic acid, Is ophtha! acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldica
• the preferred polyalkylene terephthalates in addition to ethylene glycol or butanediol-l, 4-radicals up to 20% by mole, preferably up to 10% by mole, other aliphatic Dioie having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 C Contain atoms, for example residues of 1,3-propanediol, 2-ethylpropanediol-1, 3, neopentyl glycol, pentanediol-1, 5, hexanediol-1, 6, cyclohexane-dimethanol-1, 4, 3-ethylpentanediol-2,4, 2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3-hexanediol
• the polyalkylene terephthalates may be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US Pat. No. 3,692,744.
• preferred branching agents are trime sinic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
• polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
• Mixtures of polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate.
• the polyalkylene terephthalates which are preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in the Ubbelohde viscometer.
• the polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973).
• the molding compositions according to the invention may contain at least one of the usual additives, e.g. Lubricants and mold release agents, Nukieiermittei, antistatic agents, stabilizers, dyes and pigments and fillers and reinforcing materials.
• Lubricants and mold release agents e.g., Lubricants and mold release agents, Nukieiermittei, antistatic agents, stabilizers, dyes and pigments and fillers and reinforcing materials.
• the component F also comprises very finely divided inorganic compounds which are distinguished by an average particle diameter of less than or equal to 200 nm, preferably less than or equal to 150 nm, in particular from 1 to 100 nm.
• Suitable finely divided inorganic compounds preferably consist of at least one polar compound of one or more metals of the 1st to 5th main group or 1st to 8th subgroup of the Periodic Table, preferably the 2nd to 5th main group or 4th to 8th subgroup, especially preferably the 3rd to 5th main group or 4th to 8th subgroup, or compounds of these metals with at least one element selected from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.
• Examples of preferred compounds are oxides, hydroxides, hydrous oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.
• the finely divided inorganic compounds of oxides, phosphates, hydroxides preferably (from Ti0 2, Si0 2, Sn0 2, ZnO, ZnS, boehmite, Zr0 2, A1 2 0 3, aluminum phosphates, iron oxides, further TiN, WC, AlO OH ), Fe 2 O 3 iron oxides, NaSO 4 , vanadium oxides, cadmium borate, silicates such as Al Siiikate, Mg silicates, one-, two-, three-dimensional silicates and talc. Mixtures and doped compounds are also useful.
• these very finely divided inorganic compounds can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be produced. Particularly preferred are hydrated aluminas (eg boehmite) or TiO 2 .
• Particle size and particle diameter of the inorganic particles means the average particle diameter d 50 , determined by sedimentation measurements on the settling velocity of the particles, for example in a Sedigraph.
• the inorganic compounds may be present as powders, pastes, brine dispersions or suspensions. By precipitation, powders can be obtained from dispersions, sols or suspensions.
• the inorganic compounds can be incorporated into the thermoplastic molding compositions by conventional methods, for example by direct kneading or extrusion of molding compositions and the very finely divided inorganic compounds.
• Preferred methods provide the Preparation of a masterbatch, for example in flameproofing additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-extrusion of a thermoplastic component and the very finely divided inorganic compounds, eg. by co-precipitation of an aqueous emulsion and the very finely divided inorganic compounds, optionally in the form of dispersions, suspensions, pastes or sols of the very finely divided inorganic materials.
• compositions according to the present invention are prepared by subjecting the respective constituents in a known manner and melt-compounding and melt-extruding at temperatures of 200 ° C to 300 ° C in conventional aggregates such as internal mixers, extruders and twin-screw screws.
• the mixing of the individual constituents can be carried out in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
• the thermoplastic compositions and molding compositions according to the present invention are due to their excellent balance of high impact strength at low temperatures, good flame retardancy with thin walls and excellent chemical resistance for the production of inventive battery housings.
• the invention also provides methods for producing the battery housing and the use of the molding compositions for the production of battery housings.
• the molding compounds can be processed by injection molding to battery housings.
• Another object of the invention is the production of battery cases by thermoforming of previously prepared plates or films.
• the battery cases are suitable for the following applications: vehicle battery and accumulators, battery cases for automobiles, buses, trucks, campers, rail vehicles, aircraft, watercraft or other vehicles, stationary batteries, e.g. in buildings for the emergency power supply, Speicherang of solar power from photovoltaic systems.
• the battery cases preferably meet the requirements of the UN 3480 transport test.
• FIGS. 1 and 2 Examples of battery housing according to the invention are shown in FIGS. 1 and 2.
• FIG. 1A shows a battery housing for flat battery cells, which has a spacing between the insertion slots for the flat cells, in which a coolant can be arranged or in which a coolant circulates.
• Figure 1B shows a plan view of the battery housing for flat battery lines.
• Figure IC shows a sectional view (section AA) through the battery case for flat battery cells.
• Figure 2A shows a battery case for cylindrical battery cells, which has a distance between the insertion slots for the cylindrical cells, in which a coolant may be arranged or in which a coolant circulates.
• FIG. 2B shows a plan view of the battery housing for cylindrical battery lines.
• Figure 2C shows a sectional view (section DD) through the battery housing for cylindrical
• the battery housing channels for cooling the individual cells preferably a water / Gkykol- or air cooling on.
• the battery housing consists of an outer housing and an inner insert for receiving the individual cells, the outer housing optionally comprising insulation, e.g. by a double wall, may have.
• the outer housing and the receptacle of the cells (insertion slots) are preferably made of a material and, more preferably, of a component (in one piece).
• a plurality of battery housings can be modulatively extended to larger units.
• the battery housing contains a receptacle for control electronics.
• Silicone acrylate composite rubber having the following composition:
• Silicone acrylate composite rubber having the following composition:
• F-2 phosphite stabilizer, phosphite stabilizer, Irganox® B900 (mixture of 80% Irgafos® 168 and 20% Irganox® 1076; BASF AG; Ludwigshafen / Irgafos® 168 (tris (2,4-di-tert-butyl-phenyl) - phosphite) / Irganox® 1076 (2,6-di-tert-butyl-4- (octadecanoxycarbonylethyl) phenol).
• Irganox® B900 mixture of 80% Irgafos® 168 and 20% Irganox® 1076; BASF AG; Ludwigshafen / Irgafos® 168 (tris (2,4-di-tert-butyl-phenyl) - phosphite) / Irganox® 1076 (2,6-di-tert-butyl
• the feedstocks listed in Table 1 are compounded at a speed of 225 rpm and a throughput of 20 kg / h at a machine temperature of 260 ° C and granulated.
• 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 flowability was determined according to ISO 11443 (melt viscosity).
• the notch toughness ak was measured in accordance with ISO 1 80 / 1A on a single-sided sprayed test rod of dimension 80 ⁇ 10 ⁇ 4 mm at the indicated measuring temperatures.
• the heat resistance was measured in accordance with DIN ISO 306 (Vicat softening temperature, method B with 50 N load and a heating rate of 120 K / h) on a single-side molded test rod of dimension 80x10x4 mm.
• the fire behavior is measured according to UL 94V on rods measuring 127 x 12.7 x 1.5 mm.
• the elongation at break and tensile modulus of elasticity were measured according to DIN EN ISO 527 on rods measuring 170.0 ⁇ 10.0 ⁇ 4.0 mm.

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