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WO2009092494A1 - Polymères de coordination absorbant les uv - Google Patents

Polymères de coordination absorbant les uv Download PDF

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Publication number
WO2009092494A1
WO2009092494A1 PCT/EP2008/067128 EP2008067128W WO2009092494A1 WO 2009092494 A1 WO2009092494 A1 WO 2009092494A1 EP 2008067128 W EP2008067128 W EP 2008067128W WO 2009092494 A1 WO2009092494 A1 WO 2009092494A1
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Prior art keywords
tert
acid
butyl
bis
hydroxy
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German (de)
English (en)
Inventor
Richard Riggs
Monica Fernandez Gonzalez
Christoph Kiener
Markus Schubert
Norbert Stock
Denis Sorokin
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to compositions comprising at least one polymer and a light-stabilizing additive component distributed in solid form in the polymer and to the use of organometallic frameworks as light-screening additive.
  • the synthetic materials may be, for example, polymers, such as synthetic plastics, in which aging due to solar radiation may occur, so that they are often mixed with light protection additives. This can be done for example by means of extruders.
  • compositions containing such sunscreen additive components It is therefore an object of the present invention to provide compositions containing such sunscreen additive components.
  • composition comprising at least one polymer and a light-stabilizing additive component which is distributed in solid form in the polymer and contains an organometallic framework, wherein the organometallic framework contains at least one at least one bidentate organic aromatic compound coordinated to at least one metal ion.
  • organometallic frameworks which contain metal ions and coordinately bound aromatic compounds have one purpose have improved behavior as a sunscreen additive compared to the aromatic compounds as such.
  • Organometallic frameworks typically have pores. Such porous organometallic frameworks are described as such in the art.
  • the porous organometallic framework material contains at least one at least one metal ion coordinated at least bidentate organic compound.
  • This organometallic framework is described, for example, in US Pat. No. 5,648,508, EP-A 0 790 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000), 3-20; Li, H., et al., Nature 402 (1999), 276; M. Eddaoudi et al., Topics in Catalysis 9 (1999), 105-11; Chen et al., Science 291 (2001), 1021-1023 and DE-A 101 1 1 230.
  • MOF organometallic framework
  • the organometallic frameworks according to the present invention usually contain pores, in particular micropores and / or mesopores.
  • Micropores are defined as those with a diameter of 2 nm or smaller and mesopores are defined by a diameter in the range of 2 to 50 nm, each according to the definition as described by Pure & Applied Chem. 57 (1985), 603- 619 is indicated in particular on page 606.
  • the presence of micro- and / or mesopores can be checked by means of sorption measurements, these measurements determining the uptake capacity of the MOF for nitrogen at 77 Kelvin according to DIN 66131 and / or DIN 66134.
  • the specific surface area - calculated according to the Langmuir model according to DIN 66135 (DIN 66131, 66134) for a MOF in powder form is more than 5 m 2 / g, more preferably more than 10 m 2 / g, more preferably more than 50 m 2 / g, more preferably more than 500 m 2 / g, even more preferably more than 1000 m 2 / g and particularly preferably more than 1500 m 2 / g.
  • the organometallic framework material may also have no pores or have such small pores that a determination of the specific surfaces with nitrogen is not possible. The presence of pores is not required in the present invention.
  • the metal component in the framework material is preferably selected from groups Ia, IIa, IIIa, IVa to Villa and Ib to VIb. Particularly preferred are Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni , Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi. More preferred are Zn, Al, Mg, Ca, Cu, Ni, Fe, Pd, Pt, Ru, Rh and Co.
  • Zn, Al, Ni, Cu, Mg, Ca, Fe are particularly preferred.
  • the term "at least bidentate organic aromatic compound” refers to an organic compound containing at least one functional group capable of having at least two coordinative bonds to a given metal ion and / or two or more, preferably two, metal atoms each having a coordinative bond
  • the organic aromatic compound preferably has at least two functional groups, each of which groups coordinately binds to different metals, so that an organometallic skeleton can be built up
  • the main body contains at least one mononuclear or polynuclear aromatic ring, wherein a ring carbon atom or several carbon atoms may be replaced by nitrogen.
  • Examples of functional groups which can be used to form the abovementioned coordinative bonds are, for example, the following functional groups: -CO 2 H, -CS 2 H, -NO 2 , PO 2 H, PO (OH) 2 , -B ( OH) 2 , -SO 3 H, -Si (OH) 3 , -Ge (OH) 3 , Sn (OH) 3 , -Si (SH) 4 , -Ge (SH) 4 , -Sn (SH) 3 , -PO 3 H, -AsO 3 H, -AsO 4 H, -P (SH) 3 , -As (SH) 3 , CH (RSH) 2 , -C (RSH) 3 , -CH (RNH 2 ) 2 , -C (RNH 2 ) 3 , -CH (ROH) 2 , -C (ROH) 3 , -CH (RCN) 2 , C (RCN) 3 where
  • functional groups are to be mentioned in which the abovementioned radical R is absent.
  • -CH (SH) 2 , -C (SH) 3 -CH (NH 2 ) 2 , -C (NH) 3 , -CH (OH) 2 , -C (OH) 3 , -CH ( CN) 2 or -C (CN) 3 ZU call.
  • the at least two functional groups can in principle be bound to any suitable organic compound, as long as it is ensured that the organic compound containing these functional groups to form the coordinate bond and is capable of producing the framework material and is at least partially aromatic.
  • the aromatic compound may thus also have an aromatic part and an aliphatic part and may have one or more cores, for example two, three, four or five cores, the cores being separate from one another and / or at least two cores being in condensed form can.
  • the aromatic compound or the aromatic moiety of the both aliphatic and aromatic compounds has one, two or three nuclei, with one or two nuclei being particularly preferred.
  • each nucleus of the named compound may contain at least one heteroatom, such as, for example, N, O, S, B, P, Si, Al, preferably N, O and / or S.
  • the aromatic compound or the aromatic moiety of the both aromatic and aliphatic compounds contains one or two C 6 cores, the two being either separately or in condensed form.
  • benzene, naphthalene and / or biphenyl and / or bipyridyl and / or pyridyl may be mentioned as aromatic compounds.
  • Aromatic in the context of the present invention are five-membered and six-membered rings which can have the maximum possible number of conjugated double bonds. Examples which may be mentioned are cyclopentadiene, pyrrole, furan, thiofuran, imidazole, pyrrazole, triazole, benzene, pyridine, pyrimidine, pyrimidazine, pyrazine, triazine or pyran.
  • the at least one aromatic organic compound has one, two, three or four aromatic rings.
  • the at least one at least bidentate organic aromatic compound is derived from an aromatic di-, tri- or tetracarboxylic acid.
  • the term "derive" in the context of the present invention means that the di-, tri- or tetracarboxylic acid can be present in the framework material in a partially deprotonated or completely deprotonated form contain a substituent or independently of each other a plurality of substituents.
  • substituents are -OH, -NH 2 , -OCH 3 , -CH 3 , -NH (CH 3 ), -N (CH 3 ) 2 , -CN and halides.
  • the at least bidentate organic compound is derived from a dicarboxylic acid such as 4-oxo-pyran-2,6-dicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3 dicarboxylic acid, 1,4-benzenedicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-dicarboxylic acid.
  • a dicarboxylic acid such as 4-oxo-pyran-2,6-dicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3 dicarboxylic acid, 1,4
  • the at least bidentate organic compound is one of the above-exemplified dicarboxylic acid as such.
  • the at least bidentate organic compound may be derived from a tricarboxylic acid, such as
  • the at least bidentate organic compound is one of the above-exemplified tricarboxylic acids as such.
  • 1, 1-Dioxidperylo [1, 12-BCD] thiophene-3,4,9,10-tetracarboxylic acid perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfone-3, 4,9,10-tetracarboxylic acid, 1, 2,4,5-benzene tetracarboxylic acid, 1, 4,5,8-naphthalenetetracarboxylic acid, benzophenone tetracarboxylic acid or 3,3 ', 4,4'-benzo-phenontetracarboxylic acid,
  • the at least bidentate organic compound is one of the above exemplified tetracarboxylic acids as such.
  • each of the cores can contain at least one heteroatom, where two or more nuclei have identical or different heteroatoms may contain.
  • monocarboxylic dicarboxylic acids preference is given to monocarboxylic dicarboxylic acids, monocarboxylic tricarboxylic acids, monocarboxylic tetracarboxylic acids, dicercaric dicarboxylic acids, dicercaric tricarboxylic acids, dicerated tetracarboxylic acids, tricarboxylic dicarboxylic acids, tricarboxylic tricarboxylic acids, tricarboxylic tetracarboxylic acids. acids, tetracyclic dicarboxylic acids, tetracyclic tricarboxylic acids and / or tetracyclic tetracarboxylic acids.
  • Suitable heteroatoms are, for example, N, O, S, B, P.
  • Preferred heteroatoms here are N, S and / or O.
  • a suitable substituent in this regard is, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group ,
  • the at least one at least bidentate organic aromatic compound is derived from one of the following compounds.
  • Me is methyl and R is H or Ci -4 alkyl.
  • Ci -4 alkyl means methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl.
  • the organometallic framework material may also comprise one or more monodentate ligands and / or one or more at least bidentate ligands which are not derived from a di-, tri- or tetracarboxylic acid.
  • the organometallic framework can also comprise one or more monodentate ligands.
  • organometallic framework material in which Zn, Mg, Ca, Fe, Al, Ni or Cu metal ion and the at least bidentate organic compound are terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid or 1,3,5-benzenetricarboxylic acid.
  • MOFs produced in this way have particularly good properties in connection with the adsorption and desorption of chemical substances, in particular of gases. They thus differ from those produced conventionally, even if they are formed from the same organic and metal ion components.
  • electrochemically produced MOFs are particularly preferred.
  • the electrochemical preparation relates to a crystalline organometallic framework material comprising at least one at least one metal ion coordinatively bound, at least bidentate organic compound which in a reaction medium containing the at least one bidentate organic compound and the at least one metal ion, which by oxidation of at least one the corresponding metal-containing anode is produced is obtained.
  • electrochemical preparation refers to a production process in which the formation of at least one reaction product is associated with the migration of electrical charges or the occurrence of electrical potentials.
  • at least one metal ion as used in connection with the electrochemical preparation refers to embodiments according to which at least one ion of a metal or at least one ion of a first metal and at least one ion of at least one second metal different from the first metal by anodic Oxidation be provided.
  • the electrochemical preparation comprises embodiments in which at least one ion of at least one metal is provided by anodic oxidation and at least one ion of at least one metal via a metal salt, the at least one metal in the metal salt and the at least one metal that is anodic Oxidation can be provided as a metal ion, the same or different from each other.
  • the present invention encompasses an embodiment according to which the reaction medium contains one or more different salts of a metal and additionally contains the metal ion contained in this salt or salts by anodic oxidation of at least one metal containing said metal Anode is provided.
  • the reaction medium may contain one or more different salts of at least one metal and at least one metal other than these metals may be provided via anodic oxidation as the metal ion in the reaction medium.
  • the at least one metal ion is provided by a-node oxidation of at least one of said at least one metal-containing A-node, wherein no further metal is provided via a metal salt.
  • metal as used in the context of the present invention in connection with the electrochemical preparation of organometallic frameworks includes all elements of the periodic table which can be provided via anodic oxidation by electrochemical means in a reaction medium and having at least one at least bidentate organic compounds are capable of forming at least one organometallic framework.
  • the organometallic framework materials accumulate in powder form. These can have particle sizes of up to 100 ⁇ m.
  • the organometallic framework material preferably has a particle size (d 5 o) of less than 2 ⁇ m, more preferably less than 1 ⁇ m and particularly preferably less than 0.1 ⁇ m.
  • the d 50 value can help with The laser diffractometry can be determined, a device for performing such a measurement, for example, the spectrometer Master Sizer S from Malvern.
  • the particle size results directly from the preparation by selection of suitable starting materials, terminating reagents and condition during preparation and precipitation.
  • the desired particle size can be obtained by grinding.
  • Suitable mills are hammer mills and jet mills. Especially for particles in the sub-micrometer range, so nanoparticles, grinding in a liquid suspension is advantageous.
  • the organometallic framework material is dispersed in a polymer in solid form as part of a photoprotective additive component in a polymer.
  • the framework material may also form the sunscreen additive component. This can be introduced into the polymer by simple addition and coextrusion.
  • polymer is also used in a simplified manner for polymer mixtures.
  • frame material is also used.
  • the polymer can be of different nature.
  • the polymer or monomers forming the polymer contain double bonds, more particularly conjugated double bonds, and especially aromatic rings and / or functional groups such as ether, sulfide, amine, ester, amide, sulfamide, carbonate, urethane groups ,
  • the polymer is preferably an aromatic polymer and / or a polyamide and / or a polyester and / or a polyether and / or a polyacetal and / or a polycarbonate and / or a polyacrylate. Particularly preferred are polyesters. However, it is also possible to use simple polyolefins, such as polyethylene, which is preferred. Generally, polyolefins which are optionally halogenated, PMMA, polystyrenes, ABS and polycarbonates are preferred. Preferred monomers that can form the polymer are vinyl analogues, especially vinyl compounds, in which a conjugation of the vinylic double bond with other conjugated double bonds of the monomer compound is present.
  • Suitable monomers are styrene and also styrene derivatives, acrylates, butadiene, isoprene, acrylamide, acrylonitrile, vinyl acetate, vinyl ethers, esters of acrylic and / or methacrylic acid with alkanols having 1 to 12 C atoms, vinyl alcohols, vinyl halides, vinylpyrrolidone, vinylcarbazole , Divinylformal or vinyl ester and unsaturated, optionally halogenated hydrocarbons, such as isobutylene, butadiene, ethylene, propylene, tetrafluoroethylene. Likewise, cyclic or linear acetals can be used.
  • the monomers can be used for the preparation of homopolymers or copolymers.
  • epoxides can be used as monomers such as ethylene oxide, propylene oxide or butylene oxide.
  • the monomers so that they can undergo a polycondensation condensation.
  • a reaction can be carried out, for example, starting from diols and diacids or diamines and diacids.
  • polyols and polyacids in particular polycarboxylic acids.
  • Lactams and lactones, such as caprolactam or caprolactone can also be used as polycondensating monomers, if appropriate in combination with other suitable bifunctional compounds.
  • the polymer is a styrene-based polymer.
  • a styrene-based polymer is present when at least one monomer involved in the formation of the polymer is styrene or a styrene derivative.
  • polycarbonates can be used.
  • Polycarbonates can be obtained by polycondensation of carbonic acid with diols or polyols. Suitable di- or polyols have already been listed above.
  • polyoxymethylene copolymers can be used.
  • the polyoxymethylene homo- or copolymers (POM) are known as such and are commercially available. They are usually prepared by polymerization of formaldehyde or, preferably, trioxane; in the Preparation of copolymers also comonomers are used.
  • the monomers are preferably selected from trioxane and other cyclic or linear formals or other sources of formaldehyde.
  • such POM polymers have at least 50 mole percent of recurring units -CH 2 O- in the polymer backbone.
  • Suitable polyoxymethylene copolymers are in particular those which, in addition to the repeating units -CH 2 O-, also contain up to 50, preferably 0.01 to 20, in particular 0.1 to 10 mol% and very particularly preferably 0.5 to 6 mol. % of recurring units
  • R 1 to R 4 independently of one another denote a hydrogen atom, a C 1 - to C 4 -alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 denotes a --CH 2 -, -CH 2 O-, a to C 4 alkyl or C 1 to C 4 haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3.
  • these groups can be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n have the abovementioned meaning.
  • R 1 to R 5 and n have the abovementioned meaning.
  • 1, 3-dioxolane and 1, 3-dioxepane are particularly preferred comonomers.
  • Oxymethylenterpolymerisate for example, by reacting trioxane, one of the cyclic ethers described above with a third monomer, preferably bifunctional compounds of the formula
  • Z is a chemical bond
  • -O-, -ORO- R is d- to Cs-alkylene or C3- to Cs-cycloalkylene
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in the molar ratio 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms such as the diglycidyl ethers of ethylene glycol , 1, 4-butanediol, 1, 3-butanediol, cyclobutane-1, 3-diol, 1, 2-propanediol and cyclohexane-1, 4-diol, to name just a few examples.
  • polyesters based on aromatic or aliphatic or both an aliphatic and an aromatic moiety having dicarboxylic acids and an aliphatic or aromatic or both an aliphatic and an aromatic part having dihydroxy compound can be used.
  • polyesters and polyalcohols are usable.
  • monocarboxylic acids and monools can be used.
  • hydroxycarboxylic acids are useful.
  • acids as a monomer and their derivatives such as esters, anhydrides or halides can be used.
  • di- or polyols examples include ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, dipropylene, triethylene, tripropylene, tetraethylene glycol, 1,2- and / or 1,4-butanediol , 1, 3-Butylethylpropandiol, 1, 3-methylpropanediol, 1, 5-pentanediol, bisphenol A, B, C, F, norbornene glycol, 1, 4-benzyldimethanol and / or -ethanol, 2, 4-dimethyl-2 -ethylhexane-1,3-diol, cyclohexanedimethanol, dicidol, hexanediol, neopentyl glycol, trimethylolpropane, trimethylolethane, 1, 2,6-trihydroxyhexaerythritol, glycerol, trishydroxyethyl isocyanurate, pen
  • di-, tri- and tetracarboxylic acids have already been described in connection with the structure of the framework.
  • 2-ethylhexanoic acid 2-ethylhexanoic acid.
  • polyesters As a first group of preferred polyesters, mention may be made of polyalkylene terephthalates which in particular have 2 to 10 C atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for. B. by halogen such as chlorine and bromine or by dC 4 alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.
  • These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof.
  • Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.
  • Further preferred polyesters are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms.
  • polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred.
  • PET and / or PBT which contain up to 1 wt .-%, preferably up to 0.75 wt .-% 1, 6-hexanediol and / or 2-methyl-1, 5-pentanediol as further monomer units.
  • aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to using mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures of these two acids.
  • the aromatic dihydroxy compounds preferably have the general formula
  • Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m is the value 0 to 2 has.
  • the compounds can also carry dC 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • Suitable parent compounds of these compounds are dihydroxydiphenyl, di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) nyl) sulfoxide, alpha, alpha'-di- (hydroxyphenyl) -dialkylbenzene, di (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone and their ring-alkylated or ring-halogenated derivatives.
  • polyalkylene terephthalates and wholly aromatic polyesters and / or polycarbonates are preferred.
  • mixtures of polyalkylene terephthalates and wholly aromatic polyesters and / or polycarbonates generally contain from 20 to 98% by weight, preferably from 80 to 96% by weight, of the polyalkylene terephthalate and from 2 to 80% by weight, preferably from 4 to 50% by weight, of the wholly aromatic polyester and / or of the polycarbonate.
  • Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula
  • Q is a single bond, a Ci-Cs-alkylene, a C 2 -C 3 -alkylidene, C 3 -C 6 - cycloalkylidene group, a C6-Ci2 arylene group and -O-, -S- or - SO 2 - and m is an integer from 0 to 2.
  • the diphenols may also have substituents on the phenylene radicals, such as C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy.
  • diphenols examples include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis - (4-hydroxyphenyl) cyclohexane.
  • Particular preference is given to 2,2-bis- (4-hydroxyphenyl) -propane and 1,1-bis (4-hydroxyphenyl) -cyclohexane, and also 1,1-bis- (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane.
  • Both homopolycarbonates and copolycarbonates may be suitable; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable 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 at least trifunctional compounds, for example those containing three or more three phenolic OH groups.
  • the diphenols of the general formula are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators.
  • phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process)
  • Suitable chain terminators are, for example, phenol, pt-butylphenol, but also long-chain alkylphenols, such as 4- (1,3-dimethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenol, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- ( 3,5-dimethylheptyl) -phenol.
  • alkylphenols such as 4- (1,3-dimethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms the alkyl substituents according to DE-A 35 06 47
  • Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the preparation of the polycarbonates with phosgene by the interfacial process, is not to be regarded as halide-containing in the context of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.
  • amorphous polyester carbonates wherein phosgene has been replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
  • bisphenol A can be replaced by bisphenol TMC.
  • vinyl aromatic polymers are also suitable.
  • vinyl aromatic polymers of styrene, chlorostyrene, alpha-methylstyrene and p-methylstyrene called;
  • comonomers such as (meth) acrylonitrile or (meth) acrylic esters may be involved in the construction.
  • Particularly preferred vinyl aromatic polymers are polystyrene and impact modified polystyrene. It is understood that mixtures of these polymers can be used. The preparation is preferably carried out according to the method described in EP-A-302 485.
  • Preferred ASA polymers are composed of a soft or rubber phase of a graft polymer of:
  • the main monomers A 11 ) used are esters of acrylic acid having 2 to 10 C atoms, in particular 4 to 8 C atoms.
  • Particularly preferred monomers which may be mentioned here are tert-butyl, isobutyl and n-butyl acrylate and also 2-ethylhexyl acrylate, of which the latter two are particularly preferred.
  • esters of acrylic acid are used from 0.1 to 5, in particular 1 to 4 wt .-%, based on the total weight of A 11 + A 12 of a polyfunctional monomer having at least two olefinic, non-conjugated double bonds.
  • difunctional compounds ie having two non-conjugated double bonds
  • difunctional compounds ie having two non-conjugated double bonds
  • examples which may be mentioned here are divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate, of which the last two are particularly preferred.
  • the exact polymerization conditions, in particular the type, dosage and amount of the emulsifier are preferably chosen so that the latex of the acrylic acid ester which is at least partially crosslinked, an average particle size (weight average d 5 o) in the range of about 200 to 700, in particular from 250 to 600 nm.
  • the proportion of the graft to the graft polymer A 1 A 1 + A 2 is 50 to 90, preferably 55 to 85 and in particular 60 to 80 wt .-%, based on the total weight of A 1 + A2.
  • a graft A 2 is grafted by copolymerization of
  • R represents alkyl radicals having 1 to 8 C atoms, hydrogen atoms or halogen atoms and R 1 represents alkyl radicals having 1 to 8 C atoms or halogen atoms and n is 0, 1, 2 or 3, and
  • a 22 10 to 80 preferably 10 to 70 and in particular 20 to 70 wt .-% of acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof is available.
  • substituted styrenes are alpha-methylstyrene, p-methylstyrene, p-chlorostyrene and p-chloro-alpha-methylstyrene, of which styrene and alpha-methylstyrene are preferred.
  • Preferred acrylic or methacrylic acid esters are those whose homopolymers or copolymers with the other monomers of component A 22 ) have glass transition temperatures of more than 20 ° C .; In principle, however, it is also possible to use other acrylic acid esters, preferably in amounts such that a total T g of glass transition temperature above 20 ° C. results for component A 2 .
  • esters of acrylic or methacrylic acid with CrC 8 -alcohols and epoxy-containing esters such as glycidyl acrylate or glycidyl methacrylate.
  • epoxy-containing esters such as glycidyl acrylate or glycidyl methacrylate.
  • methyl methacrylate, t-butyl methacrylate, glycidyl methacrylate and n-butyl acrylate called, the latter due to its property to form polymers with very low Tg, is preferably used in not too high proportion.
  • the graft shell A 2 may be in one or more, z. B. two or three, process steps are made, the gross composition remains unaffected.
  • the graft shell is prepared in emulsion, as described, for. B. in DE-PS 12 60 135, DE-OS 32 27 555, DE-OS 31 49 357 and DE-OS 34 14 1 18 is described.
  • the graft copolymer A 1 + A 2 generally has an average particle size of from 100 to 1000 nm, in particular from 200 to 700 nm, (d50 weight average).
  • the conditions in the preparation of the elastomer D 1 ) and in the grafting therefore become preferably chosen such that particle sizes result in this range. Measures are known and z. For example, in DE-PS 12 60 135 and DE-OS 28 26 925 and in Journal of Applied Polymer Science, Vol. 9 (1965), p 2929-2938 described.
  • the particle size increase of the latex of the elastomer may, for. B. be accomplished by means of agglomeration.
  • the graft polymer (A 1 + A 2 ) also includes the free, non-grafted homopolymers and copolymers which are formed in the graft copolymerization to prepare component A 2 ).
  • component A3 may, for. Example, be prepared according to the method described in DE-AS 10 01 001 and DE-AS 10 03 436.
  • ABS polymers have the same structure as described above for ASA polymers.
  • conjugated dienes are usually used, so that the following composition is preferably obtained for the graft base A4: A 41 70 to 100 wt .-% of a conjugated diene and
  • Grafting A 2 and the hard matrix of the SAN copolymer A 3 remain unchanged in the composition.
  • Such products are commercially available. The production methods are known to the person skilled in the art, so that further information is unnecessary.
  • the weight ratio of (A 4 + A 2 ): A 3 is in the range of 3: 1 to 1: 3, preferably 2: 1 to 1: 2.
  • compositions of components (A) comprise a mixture of:
  • a 2 0 to 40 wt .-% of a polyester, preferably polybutylene terephthalate,
  • a 3 1 to 40 wt .-% of an ASA or ABS polymers or mixtures thereof.
  • polyamides may be suitable.
  • Examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.
  • alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
  • adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned as acids.
  • Suitable diamines are, in particular, alkanediamines having 6 to 12, in particular 6 to 8, carbon atoms and also m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, 2,2-di (4- aminophenyl) -propane or 2,2-di (4-aminocyclohexyl) propane.
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also copolyamides 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.
  • polyamides are also mentioned, the z. B. by condensation of 1, 4 diaminobutane with adipic acid at elevated temperature are available (polyamide-4,6). Manufacturing process for polyamides of this structure are z. As described in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary.
  • the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
  • polyphenylene ethers which are known per se and are preferably prepared by oxidative coupling of phenols which are disubstituted in the o-position.
  • substituents are halogen atoms such as chlorine or bromine and alkyl radicals having 1 to 4 carbon atoms, which preferably have no alpha-tertiary tertiary hydrogen atom, for.
  • halogen atoms such as chlorine or bromine
  • alkyl radicals having 1 to 4 carbon atoms which preferably have no alpha-tertiary tertiary hydrogen atom, for.
  • methyl, ethyl, propyl or butyl radicals may in turn be substituted by halogen atoms such as chlorine or bromine or by a hydroxyl group.
  • alkoxy radicals preferably having up to 4 carbon atoms or phenyl radicals optionally substituted by halogen atoms and / or alkyl groups.
  • copolymers of various phenols such.
  • Copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are also known.
  • mixtures of different polyphenylene ethers can be used.
  • the polyphenylene ethers used may optionally contain process-related defects, which are described, for example, in White et al., Macromolecules 23, 1318-1329 (1990).
  • polyphenylene ethers are used which are compatible with vinyl aromatic polymers, i. H. completely or largely soluble in these polymers (see A. Noshay, Block Copolymers, pp. 8-10, Academic Press, 1977 and O. Olabisi, Polymer Polymer Miscibility, 1979, pp. 117-189).
  • polyphenylene ethers examples include poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl-1, 4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-diethoxy-1, 4-phenylene) ether, poly (2-methoxy-6-ethoxy-1, 4-phenylene) ether, poly (2-ethyl-6-stearyloxy-1, 4- phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1, 4- phenylene) ether, poly (2-ethoxy-1, 4-phenylene) ether, poly (2-chloro-1, 4-phenylene) ether, poly (2,5-dibromo-1, 4-phenylene) ether.
  • Polyphenylene ethers are preferably used in which the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1, 4-phenylene) ether, poly (2,6-diethyl-1, 4-phenylene) ether, Poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether and poly (2-ethyl-6-propyl-1,4-phenylene) ether.
  • the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1, 4-phenylene) ether, poly (2,6-diethyl-1, 4-phenylene) ether, Poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene)
  • graft copolymers of polyphenylene ether and vinyl aromatic polymers such as styrene, alpha-methylstyrene, vinyltoluene and chlorostyrene are suitable.
  • Functionalized or modified polyphenylene ethers are known per se, for. WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 1 16 and EP-A-254 048 and are preferably used for mixtures with PA or polyester.
  • an unmodified polyphenylene ether is prepared by incorporation of at least one carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam, or halobenzyl group modified, so that a sufficient compatibility z. B. is ensured with the polyamide.
  • the modification is generally carried out by reacting an unmodified polyphenylene ether with a modifier which contains at least one of the abovementioned groups and at least one C-C double or C-C triple bond in solution (WO-A 86/2086), in aqueous dispersion, in a gas-phase process (EP-A-25 200) or in the melt, if appropriate in the presence of suitable vinylaromatic polymers or impact modifiers, optionally radical initiators may be present.
  • Suitable modifiers are, for example, maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, eg. B. of d- and C 2 -C 8 alkanols, the mono- or diamides of these acids such as N-phenylmaleimide, maleic hydrazide.
  • a 2 0 to 25, preferably 0 to 20 wt .-% of a vinyl aromatic polymer
  • a 3 0.05 to 5, preferably 0.05 to 2.5 wt .-% of at least one compound from the group formed from a 3 i) an alpha, beta-unsaturated dicarbonyl compound,
  • weight percentages refer to the sum of ai) to a 4 ), in the course of
  • the vinylaromatic polymer a 2 should preferably be compatible with the polyphenylene nether used, as described above under 2.
  • Examples of preferred vinyl aromatic polymers compatible with polyphenylene ethers can be found in the abovementioned monograph of Olabisi, pages 224 to 230 and 245.
  • Radical starters a4) may be mentioned:
  • Ri to Re represent alkyl groups having 1 to 8 C atoms, alkoxy groups having 1 to 8 C atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles with an electron system and nitrogen, oxygen or sulfur as heteroatoms.
  • the substituents R 1 to R 6 may in turn contain functional groups as substituents, such as carboxyl, carboxyl, hydroxyl, amino, thiol or epoxy groups. Examples are 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and 2,2,3,3-tetraphenylbutane.
  • polyphenylene ethers are obtained by modification with maleic acid, maleic anhydride and fumaric acid.
  • Such polyphenylene ethers preferably have an acid number of from 1.8 to 3.2, in particular from 2.0 to 3.0.
  • thermoplastics include thermoplastic polyurethanes (TPU), as described, for example, in EP-A 1 15 846 and EP-A 1 15 847 and EP-A 1 17 664.
  • suitable polymers include polyolefins such as polyethylene and / or polypropylene homopolymers or copolymers, and also polyketones, polyarylene ethers (so-called HT thermoplastics), in particular polyether sulfones, polyvinyl chlorides, poly (meth) acrylates and mixtures (blends) of all the thermoplastics listed above called.
  • elastomers can be used, such as, for example, the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1 , 5-diene, 2,5-dimethylhexa-1, 5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene 2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) - 3,8-decadiene or mixtures thereof.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
  • EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives are z.
  • glycidyl (meth) acrylate, and called maleic anhydride are examples.
  • Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
  • the rubbers may still dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, eg. As esters and anhydrides, and / or containing epoxy groups monomers.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture
  • R 1 C (COOR 2 ) C (COOR 3 )
  • R 1 to R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 0 to 5.
  • the radicals R 1 to R 9 preferably denote hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy groups-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.
  • the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.
  • Preferred elastomers are also emulsion polymers whose preparation z. As described in Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.
  • homogeneously constructed elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
  • E- elastomeric elastomers such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof called.
  • monomers can with other monomers such.
  • styrene, acrylonitrile, vinyl ethers and other Acrv laten or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
  • the soft or rubber phase (with a glass transition temperature of below 0 ° C.) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers having more than two-shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
  • one or more hard components (with glass transition temperatures of more than 20 0 C) to the structure of the elastomer, so these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, alpha-methylstyrene, p-methylstyrene, Acrylklareestern and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers.
  • methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers.
  • smaller proportions of other comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are for. B. epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups, by the concomitant use of monomers of the general formula
  • R 10 is hydrogen or a C 1 -C 4 -alkyl group
  • R 11 is hydrogen, a C 1 -C 8 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a Ci-Cio-alkyl, a C6-Ci2 aryl group, or -OR 13
  • R 13 is a Ci-C 8 -alkyl or C 6 -C 2 aryl group which may be substituted by O- or N-containing groups,
  • X is a chemical bond, a CrClio-alkylene or or
  • Y OZ or NH-Z and Z is a Ci-Cio-alkylene or C 6 -C 2 arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-diethylamino) ethyl acrylate called.
  • the particles of the rubber phase can also be crosslinked.
  • monomers acting as crosslinking agents are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and also the compounds described in EP-A 50 265.
  • graftlinking monomers can also be used, i. H. Monomers having two or more polymerizable double bonds, which react at different rates in the polymerization. Preferably, those compounds are used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) z. B. polymerized much slower (polymerize). The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, ie. H. the grafted phase is at least partially linked via chemical bonds to the graft base.
  • graft-crosslinking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoally
  • the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
  • some preferred emulsion polymers are listed.
  • graft polymers having a core and at least one outer shell which have the following structure:
  • graft polymers with a multi-shell structure can also homogeneous, d.
  • H. single-shell elastomers of buta-1, 3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above mentioned copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the elastomers described can also be prepared by other conventional methods, for. B. by suspension polymerization. Silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred.
  • fillers and additives can also be used in the polymer formation.
  • Suitable additives are known in the art. Examples of this are described in Hans Zweifel, Plastics Additives Handbook, 5th edition 2001, Carl Hanser Verlag. Suitable fillers are known to the person skilled in the art. Examples are in Katz, Harry S .; Milewski, John V. [Ed.], Handbook of Fillers for Plastics, 1987, Kluwer Academic Publishers Group.
  • polyolefin encompasses all polymers which are built up from olefins without further functionality, such as low or high density polyethylene, polypropylene, linear polybutene-1 or polyisobutylene or polybutadiene and also copolymers of monoolefins or diolefins.
  • Preferred polyolefins are the homopolymers and copolymers of ethylene and the homopolymers and copolymers of propylene.
  • Suitable polyethylene (PE) homopolymers are, for example:
  • LD -PE-LD (LD - low density), obtainable for example by the high pressure process (ICI) at 1000 to 3000 bar and 150 to 300 0 C with oxygen or peroxides as catalysts in autoclaves or tubular reactors.
  • LLD linear low density
  • HD high density
  • chromium oxide as a catalyst
  • titanium halides, titanium esters or aluminum alkyls as catalysts, molecular weight about 200 000 bis 400 000 g / mol.
  • HMW high molecular weight
  • Ziegler, Phillips or gas phase method high density and high molecular weight
  • polyethylene which is produced in a gas-phase fluidized-bed process using (normally supported) catalysts, for example Lupo len ® (Basell).
  • polyethylene produced using metallocene catalysts.
  • polyethylene eg ® as Luflexen (Basell) are commercially available.
  • Suitable ethylene copolymers all commercially available ethylene copolymers are suitable, for example, Luflexen ® grades (Basell), Nordel ® and Engage ® (Dow, DuPont).
  • Suitable comonomers are, for example, ⁇ -olefins having from 3 to 10 carbon atoms, in particular propylene, but-1-ene, hex-1-ene and oct-1-ene, and also alkyl acrylates and methacrylates having from 1 to 20 carbon atoms. Atoms in the alkyl radical, in particular butyl acrylate.
  • Other suitable comonomers are dienes such as butadiene, isoprene and octadiene.
  • Other suitable comonomers are cycloolefins, such as cyclopentene, norbornene and dicyclopentadiene.
  • the ethylene copolymers are usually random copolymers or block or impact copolymers.
  • Suitable block or impact copolymers of ethylene and comonomers are, for example, polymers in which in the first stage
  • Homopolymer of the comonomer or a random copolymer of the comonomer, for example, with up to 15 wt .-% ethylene produces and then in the second stage
  • the polymerization for the preparation of the ethylene-comonomer copolymers can be carried out by means of a Ziegler-Natta catalyst system. However, it is also possible to use catalyst systems based on metallocene compounds or on the basis of polymerization-active metal complexes.
  • Propylene polymers :
  • polypropylene is to be understood as meaning both homo- and copolymers of propylene.
  • Copolymers of propylene contain subordinate amounts of monomers copolymerizable with propylene, for example O 2 -Cs-Al k-1-enes such as ethylene, but-1-ene, pent-1-ene or hex-1-ene. Two or more different comonomers can also be used.
  • Suitable polypropylenes are i.a. Homopolymers of propylene or copolymers of propylene with up to 50 wt .-% of copolymerized other alk-1-enes having up to 8 carbon atoms.
  • the copolymers of propylene are random copolymers or block or impact copolymers. If the copolymers d of propylene are of random structure, they generally contain up to 15% by weight, preferably up to 6% by weight, of other alk-1-enes having up to 8 carbon atoms, in particular ethylene, butylene. 1-ene or a mixture of ethylene and but-1-ene.
  • Suitable block or impact copolymers of propylene are, for example, polymers in which, in the first stage, a propylene homopolymer or a random copolymer of propylene with up to 15% by weight, preferably up to 6% by weight, of other alk-1 ene with up to 8 carbon atoms and then in the second stage, a propylene-ethylene copolymer having ethylene contents of 15 to 80 wt .-%, wherein the propylene-ethylene copolymer additionally further C 4 -C 8 -Alk- I -ene may contain, polymerized. In general, so much of the propylene-ethylene copolymer is polymerized that the copolymer produced in the second stage in the final product has a content of 3 to 60 wt .-%.
  • the polymerization for the production of polypropylene can be carried out by means of a Ziegler-Natta catalyst system. Particular preference is given to using those catalyst systems which, in addition to a titanium-containing solid component a), also have co-catalysts in the form of organic aluminum compounds b) and electron donor compounds c).
  • the preparation of the polypropylenes is usually carried out by polymerization in at least one, often also in two or more successive reaction zones (reactor cascade), in the gas phase, in a suspension or in a liquid phase (Bulk phase). It is possible to use the customary reactors used for the polymerization of O 2 -Cs-AIk-1-enes. Suitable reactors include continuously operated stirred tanks, loop reactors, powder bed reactors or fluidized bed reactors.
  • the polymerization for the preparation of the polypropylene used is carried out under conventional reaction conditions at temperatures of 40 to 120 0 C, in particular from 50 to 100 0 C and pressures of 10 to 100 bar, in particular from 20 to 50 bar.
  • Suitable polypropylenes generally have a melt flow rate (MFR), according to ISO 1 133, of 0.1 to 200 g / 10 min., In particular from 0.2 to 100 g / 10 min., At 230 0 C and under a weight of 2.16 kg.
  • MFR melt flow rate
  • the plastic contains at least one polyolefin.
  • Preferred polyolefins contain at least one copolymerized monomer selected from among ethylene, propylene, but-1-ene, isobutylene, 4-methyl-1-pentene, butadiene, isoprene and mixtures thereof.
  • Homopolymers, copolymers of the stated olefin monomers and copolymers of at least one of said olefins as main monomer and other monomers (such as, for example, vinylaromatics) as comonomers are suitable.
  • Preferred polyolefins are low density polyethylene homopolymers (PE-LD) and polypropylene homopolymers and polypropylene copolymers.
  • Preferred polypropylenes are, for example, biaxially oriented polypropylene (BOPP) and crystallized polypropylene.
  • composition according to the invention may contain further additives.
  • composition according to the invention additionally contains at least one further light stabilizer and / or further (co) stabilizers.
  • Suitable light stabilizers or UV absorbers and further (co) stabilizers are selected, for example, from groups a) to s):
  • the group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula (aa)
  • the compounds are known from EP-A-916 335.
  • the substituents R 10 and / or R 11 is preferably -C 8 alkyl and C 5 -C 8 cycloalkyl.
  • the group b) of cinnamic acid esters include, for example, 4-methoxycinnamic acid 2-isoamyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, methyl ⁇ -methoxycarbonyl cinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate and methyl- ⁇ -methoxycarbonyl-p-methoxycinnamate.
  • the group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl) 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-
  • the group d) of the hydroxybenzophenones include, for example, 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 , 2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy-4- (n-octyloxy ) benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 2,2'-dihydroxy-4,4 ' - dimethoxybenzophenone-5,5'-bisulfonic acid
  • the group e) of the diphenylcyanoacrylates includes, for example, ethyl-2-cyano-3,3-diphenylacrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate, which is commercially available, for example, as Uvinul® 3039 from BASF AG, Ludwigshafen, and 1, 3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2 bis ⁇ [2'-cyano-3 ', 3'-diphenyl-acryloyl) oxy] methyl ⁇ propane, which is available, for example, commercially under the name Uvinul® 3030 Fa. BASF AG, Ludwigshafen.
  • the group f) of the oxamides includes, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5 , 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides.
  • Group g) of 2-phenyl-1,3,5-triazines includes, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) - 1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl)
  • the group h) of the antioxidants includes, for example:
  • alkylated monophenols such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6- dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-
  • 2,6-di-nonyl-4-methylphenol 2,4-dimethyl-6- (1-methyl-undecyl) 1 -yl) -phenol
  • 2,4-dimethyl-6- (1-methylheptadec-1-yl) -phenol 2,4-dimethyl-6- (1-methyltridec-1-yl) -phenol and mixtures see from that.
  • alkylthiomethylphenols such as, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-
  • hydroquinones and alkylated hydroquinones such as, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6- Diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butylhydroquinone tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-a
  • tocopherols such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers such as, for example, 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio bis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3 : 6-di-sec -amylphenol), 4,4'-
  • alkylidene bisphenols for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl-6- ( ⁇ -methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-
  • Benzyl compounds for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tri-decyl-4-hydroxy -3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, 1, 3,5-tri- (3,5-di-tert-butyl-4-) hydroxybenzyl) -2,4,6-trimethylbenzene, di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy 5-methylbenzyl) malonate, di-dodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
  • hydroxybenzyl aromatics such as, for example, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -
  • triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6 bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-) hydroxyphenoxy) - 1, 3,5-tolazine, 2,4 !
  • benzylphosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ((3,5-bis (1,1-bis)) -dimethylethyl) -4-hydroxyphenyl) methyl) lphosphonklarediethylester), diocta decyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, calcium salt of the 3rd 5-Di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
  • acylaminophenols such as 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine and octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate.
  • esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols such.
  • mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol,
  • esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols such as.
  • mono- or polyhydric alcohols such as.
  • mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol,
  • Diethylene glycol triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6, 7-trioxabicyclo [2.2.2] octane.
  • esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols such as.
  • amides of ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl ] - propionyloxy) ethyl] -oxamide (eg Naugard® XL-1 from Uniroyal). h.18) ascorbic acid (vitamin C)
  • Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl ) -p-phenylenediamine, N, N'- Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p - phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N'-phen
  • Toluenesulfamoyl) diphenylamine N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4 tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-
  • group i) of the nickel compounds include nickel complexes of 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol] such as the 1: 1 or 1: 2 complex. optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonklamonoalkylester such. As the methyl or ethyl esters, nickel complexes of ketoximes such. From 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel Complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel
  • the group j) of the hindered amines include, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy 2,2,6,6-tetramethylpiperidine, bis (2 : 2,6,6-tetramethyl-4-piperidyl) sebacate !
  • the group k) of the metal deactivators includes, for example, N, N'-diphenyloxalic diamide, N-salicylal-N'-salicyloyl-hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipic dihydrazide, N, N'- Bis (salicyloyl) oxalic acid dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazi
  • the group I) of the phosphites and phosphonites include, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2 , 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythrito
  • the group m) of the hydroxylamines include, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine , N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine and N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.
  • the n) group of nitrones includes, for example, N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ -tricyclodnitrone , N-hexadecyl- ⁇ -pentadecylnitrone, N-octadecyl- ⁇ -heptadecylnitrone, N-hexadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ -pentadecylnitrone, N-heptadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ -hexadecylnitrone, N Methyl ⁇ -heptadecyl
  • the group o) of the amine oxides includes, for example, amine oxide derivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide and trihexadecylamine oxide.
  • the group p) of the benzofuranones and indolinones include, for example, those disclosed in U.S. Patents 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; in DE-A 4 316 61 1; in DE-A 4 316 622; in DE-A 4 316 876; in EP-A 0 589 839 or EP-A 0 591 102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di tert-butyl 3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-
  • the group r) of the peroxide-destroying compounds include, for example, esters of .beta.-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis (ß-dodecylmercapto) propionate.
  • esters of .beta.-thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester
  • mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyldithiocarbamate
  • dioctadecyldisulfide pentaerythritol
  • the group s) of the basic costabilizers include, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony catecholate or zinc catechinate.
  • composition of the invention may contain other additives and additives.
  • Suitable additives of group t) are the customary additives, such as.
  • Suitable pigments are inorganic pigments, for example titanium dioxide in its three modifications rutile, anatase or brookite, ultramarine blue, iron oxides, bismuth vanadates or carbon black and the class of organic pigments, for example compounds from the class of phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrolopyrols, Quinacridone, dioxazine, indanthrone.
  • inorganic pigments for example titanium dioxide in its three modifications rutile, anatase or brookite, ultramarine blue, iron oxides, bismuth vanadates or carbon black
  • class of organic pigments for example compounds from the class of phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrolopyrols, Quinacridone, dioxazine, indanthrone.
  • Dyes are to be understood as meaning all colorants which dissolve completely in the plastic used or are present in a molecularly disperse distribution and can thus be used for the highly transparent, non-scattering coloring of polymers.
  • E- b Phase Change dyes
  • organic compounds are to be regarded, which have a fluorescence in the visible part of the electromagnetic spectrum as fluorescent dyes.
  • Suitable nucleating agents include, for example, inorganic substances, for example talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts such. For example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers ("ionomers").
  • Suitable fillers or reinforcing agents include, for example, calcium carbonate, silicates, talc, mica, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • fibrous or powdery fillers are also carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads and wollstonite into consideration. The incorporation of glass fibers can take place both in the form of short glass fibers and in the form of continuous fibers (rovings).
  • Suitable antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or -alkyleneamines, polyethylene glycol esters and ethers, ethoxylated carboxylic esters and amides and glycerol mono- and distearates, and mixtures thereof.
  • the incorporation of the additives and optional further components into the polymer is carried out by known methods, such as dry mixing in the form of a powder or wet mixing in the form of solutions, dispersions or suspensions, for example in an inert solvent, water or oil.
  • the additives according to the invention and optional further additives can be incorporated, for example, before or after molding or else by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or of the suspension / dispersing agent.
  • the incorporation can be carried out in any heatable container equipped with a stirrer, for example in a closed apparatus, such as a kneader, mixer or stirred vessel.
  • a closed apparatus such as a kneader, mixer or stirred vessel.
  • the incorporation is preferably carried out in an extruder or in a kneader. It does not matter if processing takes place in an inert atmosphere or in the presence of oxygen.
  • the addition of the additive or additive mixture to the polymer can be carried out in all conventional mixing machines wherein the polymer is melted and mixed with the additives. Suitable machines are known to the person skilled in the art. They are predominantly mixers, kneaders and extruders.
  • the process is preferably carried out in an extruder by introducing the additive during processing.
  • Particularly preferred processing machines are single-screw extruders, co-rotating and counter-rotating twin-screw extruders, planetary gear extruders, ring extruders or co-kneaders. It is also possible to use processing machines that are equipped with at least one gas removal chamber to which vacuum can be applied.
  • Suitable extruders and kneaders are described, for example, in the Handbook of Plastic Extrusion, Volume 1 Fundamentals, Editors F. Hensen, W. Knappe, H. Potente, 1989, pages 3-7, ISBN: 3-446-14339-4 (Volume 2 Extrusion Plants 1986, ISBN 3-446-14329-7).
  • the screw length is 1-60 screw diameter, preferably 35-48 screw diameter.
  • the speed of rotation of the screw is preferably 10-600 revolutions per minute (rpm), more preferably 25-300 rpm.
  • the maximum throughput depends on the screw diameter, the rotational speed and the driving force.
  • the method of the present invention may also be practiced at a level below the maximum throughput by varying the mentioned parameters or using weighing devices that deliver the dosage amounts.
  • incorporation may take place before or during a molding operation or by applying the dissolved or dispersed compound to the polymer with or without subsequent evaporation of the solvent.
  • elastomers these can also be stabilized as latexes.
  • a further possibility for incorporating the additives according to the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or before crosslinking.
  • composition of the present invention as described herein can be used in the manufacture of molds, rotational molded articles, injection molded articles, blow molded articles, films, tapes, monofilaments, fibers, nonwovens, profiles, adhesives or putties, surface coatings, and the like.
  • thermoplastic olefins polypropylene molded articles
  • polyethylene film polyethylene film
  • agricultural mulch film polyethylene molded articles
  • Flame retardants wire filled with lubricant and cable insulation; Laminations over plastic substrates, polyolefin tanks or containers containing chemicals, nonwoven polypropylene fabric for agricultural applications, for example blinds, polyolefin films with an antistatic agent, polyprolylene tape or slip film, polyethylene nonwoven fabrics, flame resistant polypropylene fiber, flame retardant polyethylene film automotive coatings, two-component -Acrylic urethane
  • Coatings pigmented motor vehicle OEM coatings, white polyester / melamine based on oil-free alkyd coil coatings, aromatic urethane paints, medium oil alkyd enamel, abrasion resistant coating compositions, chromogenic photographic coatings, oil modified urethane alkyds for wood applications, polyolefin in contact with chlorinated water
  • polyethylene or polypropylene pressure tubes optionally containing acid scavengers and / or benzofuranones, spreadable thermoplastic olefins, polypropylene fiber, polyethylene film for greenhouse, polypropylene fiber with brominated flame retardants, shaped thermoplastic olefin with brominated flame retardants, thermoplastic elastomers with other costabilizers, ⁇ -irradiated polyolefins
  • Polycarbonate blends for example PC / ABS, PC / PA, polyethylene gas pipes, polyolefin films with antifoggants, polyolefin films with thermal IR fillers,
  • compositions for coatings, for example as paints.
  • the invention therefore also relates to those compositions in which the polymer is a film-forming binder for coatings.
  • the binder may, in principle, be any binder customary in the industry, for example that described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages 368 to 426, VCH, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples include alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof. Cold-hardenable or heat-curable binders are possible.
  • the addition of a curing catalyst may be advantageous. Suitable catalysts which accelerate the curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, page 469, VCH Verlagsgesellschaft, Weinheim, 1991.
  • the binder comprises a functional acrylate resin and a crosslinking agent.
  • coating compositions containing special binders are:
  • polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during sintering, if desired, with the addition of a melamine resin;
  • One-component polyurethane paints based on aliphatic or aromatic urethanes or polyurethanes and hydroxyl-containing acrylate, polyester or polyether resins;
  • thermoplastic polyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;
  • paint systems in particular for clearcoats based on malonate-blocked isocyanates with melamine resins (for example hexamethoxymethylmelamine) as crosslinker (acid-catalyzed),
  • UV-curable systems based on oligomeric urethane acrylates and / or acrylates, if desired, in combination with other oligomers or monomers;
  • the fraction of the organometallic framework material is preferably from 0.001 to 5% by weight, based on the total weight of the compositions.
  • the organometallic framework material serves as a light stabilizer additive in the composition and can thus protect the polymer in particular from the effects of UV irradiation.
  • another object of the present invention is the use of an organometallic framework as a light stabilizer additive, wherein the organometallic framework contains at least one at least one metal ion coordinatively bound, at least bidentate organic aromatic compound.
  • organometallic framework material can thus serve in the form of a composition according to the invention for the protection of a polymer.
  • the organometallic skeleton material can also be used as a light-shielding additive in sunscreens such as sunscreens or the like.
  • the low Impact is colorless after warming up the reaction mixture.
  • the reaction mixture is cooled to RT and the product is filtered off, washed with water and ethanol and dried at 60 0 C for 30 h.
  • Example 4 SSyynidine theses of an organometallic framework of Mg and 2,6-naphthalenedicarboxylic acid (Mg-ndc)
  • Solution 2 is added to solution 2 with stirring within about 1 min. added. There is a colorless precipitate.
  • the reaction mixture is heated at 110 ° C for 1.5 h.
  • the reaction mixture is cooled to RT and the product filtered off, washed with water and ethanolamine nol and at 5O 0 C for 20 h dried.
  • a colorless colloidal precipitate is formed, which is filtered off with the aid of a blue-band filter and washed with ethanol and dried in air.
  • organometallic frameworks from Examples 1, 3 * , 4 and 5 are incorporated in polyethylene by extrusion. Thin (-0.1 mm thick) films are obtained which are exposed to artificial sunlight.
  • FIG. 1 organometallic framework material Zn-ndc according to Example 1
  • FIG. 2 naphthalene-2,6-dicarboxylic acid dimethyl ester
  • the organometallic framework material has a higher stability.

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Abstract

L'invention se rapporte à une composition contenant au moins un polymère et un composant additif photoprotecteur dispersé sous forme solide dans le polymère et qui contient un squelette organométallique, le squelette organométallique contenant au moins une liaison aromatique organique au moins bidentée fixée de manière coordonnée à au moins un ion métallique. La présente invention concerne en outre l'utilisation d'un squelette organométallique en tant qu'additif photoprotecteur, le squelette organométallique contenant au moins une liaison aromatique organique au moins bidentée fixée de manière coordonnée à au moins un ion métallique.
PCT/EP2008/067128 2007-12-14 2008-12-09 Polymères de coordination absorbant les uv Ceased WO2009092494A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8530717B2 (en) 2008-07-21 2013-09-10 Basf Se Process for the industrial isolation of propene
WO2014166865A1 (fr) * 2013-04-09 2014-10-16 Basf Se Stabilisation de polyamide avec des structures organométalliques à base de cuivre

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DE1568884A1 (de) * 1965-10-21 1970-11-26 Ici Ltd Stabilisatoren fuer Polymerisate
US4122033A (en) * 1976-11-26 1978-10-24 Black James F Oxidation inhibitor and compositions containing the same
DE2849346A1 (de) * 1977-11-15 1979-05-17 Fuji Photo Film Co Ltd Verfahren zum stabilisieren organischer substrate einschliesslich photographischer farbbilder gegen licht
US4248594A (en) * 1980-02-04 1981-02-03 American Cyanamid Company Nickel salt-ester stabilizing compositions
EP1770121A1 (fr) * 2005-09-21 2007-04-04 The Goodyear Tire & Rubber Company Pneumatique comprenant un component de caoutchouc contenant un materiau structural à base d'organo-zinc
WO2008020218A1 (fr) * 2006-08-17 2008-02-21 The University Court Of The University Of St Andrews Adsorption et libération d'oxyde nitrique dans des milieux organométalliques

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Publication number Priority date Publication date Assignee Title
DE1568884A1 (de) * 1965-10-21 1970-11-26 Ici Ltd Stabilisatoren fuer Polymerisate
US4122033A (en) * 1976-11-26 1978-10-24 Black James F Oxidation inhibitor and compositions containing the same
DE2849346A1 (de) * 1977-11-15 1979-05-17 Fuji Photo Film Co Ltd Verfahren zum stabilisieren organischer substrate einschliesslich photographischer farbbilder gegen licht
US4248594A (en) * 1980-02-04 1981-02-03 American Cyanamid Company Nickel salt-ester stabilizing compositions
EP1770121A1 (fr) * 2005-09-21 2007-04-04 The Goodyear Tire & Rubber Company Pneumatique comprenant un component de caoutchouc contenant un materiau structural à base d'organo-zinc
WO2008020218A1 (fr) * 2006-08-17 2008-02-21 The University Court Of The University Of St Andrews Adsorption et libération d'oxyde nitrique dans des milieux organométalliques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8530717B2 (en) 2008-07-21 2013-09-10 Basf Se Process for the industrial isolation of propene
WO2014166865A1 (fr) * 2013-04-09 2014-10-16 Basf Se Stabilisation de polyamide avec des structures organométalliques à base de cuivre
CN105102523A (zh) * 2013-04-09 2015-11-25 巴斯夫欧洲公司 铜基金属有机骨架对聚酰胺的稳定化

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