EP1913065A1 - Preparation saline organique solide, sa production et son utilisation - Google Patents

Preparation saline organique solide, sa production et son utilisation

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Publication number
EP1913065A1
EP1913065A1 EP06762428A EP06762428A EP1913065A1 EP 1913065 A1 EP1913065 A1 EP 1913065A1 EP 06762428 A EP06762428 A EP 06762428A EP 06762428 A EP06762428 A EP 06762428A EP 1913065 A1 EP1913065 A1 EP 1913065A1
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EP
European Patent Office
Prior art keywords
salt
mixture
halogen
salt preparation
solvent
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06762428A
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German (de)
English (en)
Inventor
Frank Reichwald
Stefan Fokken
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Baerlocher GmbH
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Baerlocher GmbH
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Publication date
Application filed by Baerlocher GmbH filed Critical Baerlocher GmbH
Publication of EP1913065A1 publication Critical patent/EP1913065A1/fr
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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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • the present invention relates to a solid salt preparation having improved handleability, which contains a mixture of an organic onium salt, a halogen-containing oxyacid and a solvent. Furthermore, the present invention relates to a process for preparing such salt preparations and their use, in particular in stabilizer compositions for halogen-containing polymers.
  • halogen-containing plastics tend to undergo undesired decomposition and degradation reactions during thermal stress during processing or in long-term use.
  • the degradation of halogenated polymers, especially in PVC, produces hydrochloric acid, which is eliminated from the polymer strand, resulting in a discolored, unsaturated plastic with colored polyene sequences.
  • the duration of use leads to changes in the color and the material properties, which can possibly progress to the unusability of the molded body.
  • compounds according to the invention are therefore suitable as onium perchlorates which have a positive charge due to protonation reactions. It is the same, however it is possible to use onium perchlorates in the context of the salt preparations or stabilizer compositions according to the invention which have a positive charge due to an alkylation or peralkylation reaction. Examples of such compounds are tetraalkylammonium, trialkylsulfonium or tetraalkylphosphonium perchlorates.
  • phosphonium perchlorates which are suitable for use, for example, in the salt preparations according to the invention are also suitable Derive tetracycloalkylphosphorus salts or Tetraarylphosphorsalzen. Suitable phosphonium perchlorates are therefore based, for example, on tetracycloalkyl or tetraarylphosphonium salts, such as tetracyclohexylphosphonium bromide or tetraphenylphosphonium bromide, and the like tetracycloalkyl or tetraarylphosphorus salts.
  • sulfonium perchlorates which are derived, for example, from tricycloalkylsulfonium salts or triarylsulfonium salts are also suitable for use in the context of the salt preparations according to the invention.
  • Suitable sulfonium perchlorates are therefore based, for example, on tricycloalkyl or triarylsulfonium salts such as tricyclohexylsulfonium bromide or triphenylsulfonium bromide and the like tricycloalkyl or triarylsulfonium salts.
  • ammonium perchlorates are in the context of the present invention, in principle, all compounds can be used, which lead by appropriate reaction of suitable reactants to an ammonium perchlorate.
  • ammonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of amines or amides, such as alkylmonoamines, alkylenediamines, alkylpolyamines, secondary or tertiary amines.
  • Suitable ammonium perchlorates are therefore derived, for example, from primary mono- or polyamino compounds having from 2 to about 40, for example from 6 to about 20, carbon atoms.
  • An organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids is "soluble" in the context of the present invention in a solvent or a mixture of two or more solvents, provided that it is present at 20 ° C. in an amount of at least 0.1 wt .-% or at least 0.5 wt .-% or at least 1.0 wt .-% or at least 3.0 wt .-% or at least 5.0 wt .-% or at least 10% by weight or at least 15% by weight or at least 20 wt .-%, each based on the solvent or the mixture of two or more solvents, dissolves.
  • the solubility is for example at least about 40% by weight or at least about 60% by weight or at least 80% by weight or even higher, for example at least about 100% by weight or at least about 120% by weight .-%, in each case based on the solvent or the mixture of two or more solvents.
  • a salt preparation according to the invention can be made exclusively from a solution, i. a mixture of organic onium salts of halogen-containing oxyacids and solvents which is essentially distributed in a molecularly dispersed manner.
  • a salt preparation according to the invention it is also possible for a salt preparation according to the invention to contain essentially any desired amount of undissolved salt constituents, for example up to about 90% by weight or less, for example up to about 80, 70, 60, 50, 40, 30, 20, 10 or 5% by weight or less, based in each case on the total salt preparation, of undissolved organic onium salts of a halogen-containing oxyacid.
  • the mixing ratio between an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or the mixture of two or more solvents in a mixture can be adjusted so that the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids in the solvent or in the mixture of two or more solvents substantially completely dissolves and forms a solid solution at 5 0 C.
  • the subject of a specific embodiment of the present invention is therefore for example a salt preparation, characterized in that the organic onium salt of a halogen-containing oxyacid or at least one organic onium salt of a halogen-containing oxyacid of a mixture of two or more organic onium salts of halogenated oxyacids at 80 ° C is liquid.
  • the subject of the present invention therefore also forms salt preparation, characterized in that the salt preparation at the melting point of the organic onium salt of a halogen-containing oxyacid or at the melting point of the lowest-melting organic onium salt of a mixture of two or more organic onium salts of halogen-containing oxy acids is solid.
  • Suitable solvents in the context of a salt preparation according to the invention are both inorganic and organic solvents and mixtures thereof. In a preferred embodiment, organic solvents are used.
  • polyols which can be used as polar organic solvents are polyols.
  • polyols refers to organic compounds which have two or more OH groups per molecule.
  • suitable polyols are pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimetalolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcycloheptanol , Glycerin, diglycerin,
  • aliphatic amino alcohols for example amino monoalcohols or amino polyols having 2 to about 40, preferably 2 to about 20 C atoms, for example ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tri-n-propanolamine, tributanolamine, tripentanolamine, Amino-3,3-dimethylpentan-5-ol, 2-aminohexane-2 ', 2 "-diethanolamine, 1-amino-2,5-dimethylcyclohexan-4-ol, 2-aminopropanol, 2-aminobutanol, 3 Aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentan-methanol, 2- Amino-2
  • At least one solvent which has a beneficial effect on the stabilization of halogen-containing polymers is used as constituent of the salt preparation according to the invention.
  • an organic onium salt of a halogen-containing oxyacid or a mixture of two or more organic onium salts of halogenated oxyacids and a solvent or a mixture of two or more solvents is carried out according to the invention in such a way that the solvent or the mixture of two or more solvents during mixing is used in liquid form. It is also provided according to the invention that the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts contains halogen Oxyklaren is used in liquid form.
  • the mixing is carried out in such a way that both the solvent or the mixture of two or more solvents, and the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids are used in liquid form.
  • the preparation of a solid salt preparation according to the present invention succeeds in principle by any method known to those skilled in mixing different solid and liquid substances, for example by simply mixing the organic onium salt of a halogenated oxyacid or the mixture of two or more organic onium salts of halogenated oxyacids and the solvent or of the mixture of two or more solvents.
  • the solvent or the mixture of two or more solvents may be initially charged and the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids added.
  • the organic onium salt of a halogen-containing oxyacid or the mixture of two or more organic onium salts of halogen-containing oxyacids are initially charged and then the solvent or the mixture of two or more solvents is added.
  • suitable amines or mercaptans or sulfides or phosphines or mixtures of two or more of these compounds may be used together with an acid or a mixture of at least two acids instead of the organic onium salts become.
  • Inorganic acids suitable according to the invention include, for example, mineral acids such as HCl, HClO 2 , HClO 3 , HClO 4 , HBr, HBrO 3 , HBrO 4 , HI, HIO 3 , HIO 4 , H 2 SO 4 , H 2 N-SO 2 -OH, HNO 3 , H 3 PO 3 , H 3 PO 4 .
  • Inorganic acids suitable in accordance with the invention include, in particular, acidic zeolites.
  • Organic acids suitable according to the invention include, for example, abietic acid, adipic acid, malic acid, formic acid, arachic acid, behenic acid, benzoic acid, succinic acid, butyric acid, capric acid, caproic acid, caprylic acid, acetic acid, erucic acid, fumaric acid, uric acid, icosenoic acid, lauric acid, lignoceric acid, margaric acid, maleic acid, malonic acid, Methanesulfonic, lactic, myristic, nervonic, nonadecanoic, oleic, ennomanic, oxalic, palmitic, palmitoleic, pelargonic, pentadecanoic, propionic, stearic, trichloroacetic, tridecanoic, undecanoic, valeric, tartaric, citric acids.
  • suitable inorganic salts of halogen-containing oxy acids include for example ACLO, ACLO 2, ACLO 3, ACLO 4, ⁇ bro, ⁇ bro 2, ⁇ bro 3, ⁇ bro 4, AIO, AIO 3, AlO 4, E (ClO) 2, E (Cloz) 2, e (C1O 3) 2, e (C1O 4) 2, e (BrO) 2, e (2 BrO) ,, e (BrO 3) 2, e (BrO 4) 2, e (IO) 2, e (IO 3) 2, e (IO 4) 2, G (ClO) 3, G (C1O 2) 3, G (C1O 3) 3, G (C1O 4) 3, G (BrO) 3, G (BrO 2) 3 , G (BrO 3 ) 3 , G (BrO 4 ) 3 , G (IO) 3 , G (IO 3 ) 3 , G (IO 4 ) 3 , where A is an NH 4 , Li, Na or K
  • cerium such as Ce (ClO) 2 , Ce (C10 2 ) 2 , Ce (ClO 3 ) 4 , Ce (C10 4 ) 4 , Ce (BrO) 4 , Ce (BrO 2 ) 4 , Ce (BrO 3 ) 4 , Ce (BrO 4 ) 4 , Ce (IO) 4 , Ce (IO 2 ) 4 , Ce (IO 3 ) 4 , Ce (IO 4 ) 4 .
  • an amine or mercaptan or sulfide or phosphine is used together with an inorganic salt of a halogen-containing oxyacid to prepare a salt preparation according to the invention
  • the inorganic cation of the inorganic salt of a halogen-containing oxyacid can be exchanged for protons of an ion exchanger, whereby the amine or mercaptan suitable according to the invention or sulfide or phosphine protonated and the corresponding organic onium salt of a halogen-containing oxyacid is prepared.
  • the present invention therefore also provides processes for preparing salt preparations according to the invention.
  • the present invention thus also relates to processes for preparing salt preparations according to the invention, characterized by the mixing of
  • the solvent or the mixture of two or more solvents is preferably used in liquid form.
  • solvents which are liquid at room temperature are suitable. It is also provided according to the invention to use solvents, for example, above 80 ° C or at 80 0 C or at 70 0 C or at 60 0 C or at 50 ° C or at 40 ° C or at 30 ° C or at room temperature are firm.
  • a suitable temperature is understood to mean a temperature at which the mixing of an organic onium salt of a halogen-containing oxy acid or a mixture of two or more organic onium salts of halogen-containing oxyacids and a solvent or a mixture of two or more solvents ensures the preparation of a salt preparation according to the invention.
  • a purification step of the present invention is any process step that is suitable for removing from a mixture of substances, for example a salt preparation according to the present invention, substances and / or compounds or separating a mixture of substances.
  • the present invention therefore provides a process for preparing a salt preparation according to the invention, characterized in that the salt preparation is formulated directly after the ion exchange.
  • packing means providing, for example, a salt preparation in a form suitable, for example, for transport or storage.
  • forms are, for example, granules, lozenges, flakes and other physical forms known to those skilled in the art.
  • a salt preparation according to the present invention can be used, for example, as a stabilizer composition or as a constituent of a stabilizer composition for stabilizing halogen-containing polymers.
  • Suitable OH-bearing derivatives of diamines are, for example, those which are based on diamines having a molecular weight of from about 32 to about 200 g / mol, the corresponding diamines having at least two primary, two secondary or one primary and one secondary amino group.
  • Hydroxyl-containing isocyanurates of the general formula I are particularly preferred
  • the compound of general formula II used is a compound in which R 1 is a linear alkyl radical having 1 to 4 C atoms, R 2 is hydrogen and R 3 is a linear or branched, saturated , mono- to hexahydric alkyl or alkylene radical having 2 to 12 carbon atoms or a linear, branched or cyclic 2- to 6-valent ether alcohol radical or thioether alcohol radical.
  • Suitable compounds of the general formula II include, for example, ⁇ -aminocrotonic acid stearyl ester, 1,4-butanediol-di ( ⁇ -aminocrotonic acid) ester, thio-diethanol- ⁇ -aminocrotonic acid ester, trimethylolpropane tri- ⁇ -aminocrotonic acid ester, pentaerythritol tetra-n-butylester.
  • the compounds mentioned can each be contained in a stabilizer composition according to the invention alone or as a mixture of two or more thereof.
  • aminouracil compounds of the general formula III are aminouracil compounds of the general formula III
  • compounds of general formula III are used in the stabilizer compositions of the invention wherein R and R are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-, i-, sec- or t-butyl ,
  • Suitable additives are, for example, epoxy compounds.
  • epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized cottonseed oil and glycidyl compounds.
  • Glycidyl compounds contain a glycidyl group bonded directly to a carbon, oxygen, nitrogen or sulfur atom.
  • Glycidyl or methyl glycidyl esters are obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or methyl epichlorohydrin. The reaction is conveniently carried out in the presence of bases.
  • aliphatic carboxylic acids can be used as compounds having at least one carboxyl group in the molecule.
  • these carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic acid, methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid or pelargonic acid, and the mono- or tri-acid mentioned in the further course of this text polycarboxylic acids.
  • cycloaliphatic carboxylic acids such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.
  • Glycidyl ethers or methyl glycidyl ethers can be obtained by reacting a compound having at least one free alcoholic OH group or a phenolic OH group and a suitably substituted epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst and subsequent alkali treatment.
  • Ethers of this type are derived for example from acyclic alcohols such as ethylene glycol, diethylene glycol or higher poly (oxyethylene) glycols, propane-l, 2-diol or poly (oxypropylene) glycols, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane -1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bis-trimethylolpropane, pentaerythritol, sorbitol and of polyepichlorohydrins, butanol, amyl alcohol, Pentanol and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol or technical alcohol mixtures, such as technical fatty alcohol mixtures from.
  • acyclic alcohols
  • Suitable ethers are also derived from cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1,1-bis (hydroxymethyl ) cyclohexan-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline.
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1,1-bis (hydroxymethyl ) cyclohexan-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline.
  • Suitable epoxy compounds can also be derived from mononuclear phenols, for example from phenol, resorcinol or hydroquinone, or based on polynuclear phenols, such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 4,4'-Dihydroxydiphe- nylsulfonen or obtained under acidic conditions condensation products of phenol with formaldehyde, such as phenol novolacs.
  • mononuclear phenols for example from phenol, resorcinol or hydroquinone
  • polynuclear phenols such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 4,4'-Dihydroxydiphe- nylsulfonen or obtained under acidic conditions condensation products of
  • terminal epoxides suitable as additives in the context of the present invention are, for example, glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-diphenyl glycidyl ether, N- (2,3-epoxypropyl) phthalimide or 2,3-epoxypropyl-4-methoxyphenyl ether ,
  • S-glycidyl compounds for example di-S-glycidyl ether derivatives which are derived from dithiols such as ethane-l, 2-dithiol or bis (4-mercaptomethylphenyl) ether.
  • 1,3-dicarbonyl compounds are also suitable as additives in the context of the present invention.
  • Dicarbonyl compounds of the general formula R - C (O) CHR - C (O) R are suitable for the purposes of the present invention.
  • R "and R '" and the disclosure of which is considered to be part of the disclosure of the present text.
  • 1, 3 -Diketo compounds may be present in a stabilizer composition according to the invention in an amount of up to about 20 wt .-%, for example up to about 10 wt .-%.
  • polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimetylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, tetramethylolcyclohexanol, tetramethylolcyclopentanole , Tetramethylolcycloheptanol, glycerin, diglycerin, polyglycerol, thiodiglycerin or 1-O- ⁇ -D-glycopyranosyl-D
  • the polyols suitable as additives may be present in a stabilizer composition according to the invention in an amount of up to about 30% by weight, for example up to about 10% by weight.
  • the sterically hindered amines suitable as additives may be present in a stabilizer composition according to the invention in an amount of up to about 30% by weight, for example up to about 10% by weight.
  • hydrotalcites zeolites and alkali metal aluminocarbonates.
  • Suitable hydrotalcites, zeolites and alkali metal aluminocarbonates are described, for example, in EP-A 1 046 668 on pages 27 to 29, EP-A 256 872 on pages 3, 5 and 7, of DE-C 41 06 411 on pages 2 and 3 or DE-C 41 06 404 described on pages 2 and 3.
  • EP-A 1 046 668 on pages 27 to 29, EP-A 256 872 on pages 3, 5 and 7, of DE-C 41 06 411 on pages 2 and 3 or DE-C 41 06 404 described on pages 2 and 3.
  • hydrotalcites, zeolites and alkali metal aluminates suitable as additives may be present in a stabilizer composition according to the invention in an amount of up to about 50% by weight, for example up to about 30% by weight.
  • hydrocalumites of the general formula V are, for example, hydrocalumites of the general formula V
  • compounds of general formula V wherein M is calcium, which may optionally be present in admixture with magnesium or zinc or magnesium and zinc.
  • A is an R-valent inorganic or organic acid anion, where r is 1, 2 or 3.
  • acid anions present within the scope of inventive hydrocalumites are halide ions, SO 3 " , SO 4 2" , S 2 O 3 2 " , S 2 O 4 2” , HPO 3 2 " , PO 4 3” , CO 3 2 " , Alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates, wherein the alkyl groups may be identical or different, straight-chain, branched or cyclic and preferably have from 1 to about 20 C.
  • acid anions A are the anions of optionally functionalized di-, tri or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesinate, pyromellitate, maleate, tartrate, citrate and anions of the isomeric forms of hydroxyphthalic acid or of hydroxymesinic acid
  • A represents an inorganic acid anion, in particular a halide ion, for example F “ , Cl “ or Br " , preferably for Cl " .
  • B represents an acid anion other than A.
  • letter B stands for a 1-, inorganic or organic acid anion, where 1 is the number 2, 3 or 4.
  • acid anions B present in the context of compounds of general formula V that can be used according to the invention are, for example, O “ , SO 3 " , SO 4 " , S 2 O 3 “ , S 2 O 4 “ , HPO 3 2” , PO 4 3 “ , CO 3 2 " , alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates in which the alkyl groups, identical or different, may be straight-chain or branched or cyclic and preferably have 1 to about 20 C atoms.
  • the acid anions A and B may be present in any ratio a / b in the compounds of general formula V.
  • the compounds of general formula V are not layered compounds of the hydrotalcite or hydrocalumite type, but a physical mixture of M 2+ / alumina hydrates with salts of divalent metals.
  • X-ray diffractograms of the compounds of the general formula V used in the stabilizer composition according to the invention clearly show that they are not discrete crystalline compounds of a known type but X-ray amorphous mixtures.
  • Compounds of general formula V can be used in the context of the stabilizer compositions according to the invention in an amount of up to about 50 wt .-%, for example up to about 30 or up to about 15 wt .-%.
  • a stabilizer composition according to the invention comprises at least one basic calcium salt.
  • Suitable basic calcium salts are, for example, calcium oxide, calcium carbonate or, if it is not already a mandatory constituent of the stabilizer compositions according to the invention, calcium hydroxide.
  • the basic calcium salts may optionally be surface-modified.
  • the metal oxides, metal hydroxides or metal soaps which are suitable as additives preferably have a divalent cation, the cations of calcium or zinc or lead or mixtures of two or more thereof are particularly suitable, but in a preferred embodiment of the present invention the stabilizer compositions according to the invention are free from zinc.
  • carboxylic acid anions include anions of monovalent carboxylic acids such as acetic, propionic, butyric, valeric, hexanoic, enanthic, octanoic, neodecanoic, 2-ethylhexanoic, pelargonic, decanoic, undecanoic, dodecanoic, tridecanoic, myristic, palmitic, lauric, isostearic, stearic, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4- hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid,
  • metal soaps are used as additives whose anions are derived from saturated or unsaturated carboxylic acids or hydroxycarboxylic acids having about 8 to about 20 C atoms. Particular preference is given here to stearates, oleates, laurates, palmitates, behenates, versatates, hydroxystearates, dihydroxystearates, p-tert-butylbenzoates or (iso) octanoates of calcium or zinc or mixtures of two or more thereof.
  • a stabilizer composition according to the invention comprises calcium stearate or zinc stearate or a mixture thereof.
  • a stabilizer composition according to the invention may contain said metal oxides, metal hydroxides or metal soaps or a mixture of two or more thereof in an amount of up to about 50% by weight, for example in an amount of up to about 30% by weight.
  • a stabilizer composition according to the invention may furthermore furthermore contain, as thermostabilizer component, an organotin compound or a mixture of two or more organotin compounds.
  • organotin compounds are methyltin tris (isooctyl thioglycolate), methyltin tris (isooctyl) 3-mercaptopropionate, methyltin tris (isodecyl thioglycolate), dimethylzimi bis (isooctyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), monobutyltin tris (isooctyl thioglycolate), diocryltin bis (isooctyl thioglycolate), monooctyltin tris (isooctyl tioglycolate) or dimethyl tin bis (2-ethylhexyl -bet
  • a stabilizer composition according to the invention may contain organic phosphite esters having 1 to 3 identical, pairwise identical or different organic radicals.
  • Suitable organic radicals are, for example, linear or branched, saturated or unsaturated alkyl radicals having 1 to 24 C atoms, optionally substituted alkyl radicals having 6 to 20 C atoms or optionally substituted aralkyl radicals having 7 to 20 C atoms.
  • a stabilizer composition according to the invention may contain the described phosphite compounds in an amount of up to about 30% by weight, in particular up to about 10% by weight.
  • a stabilizer composition according to the invention may furthermore comprise, as additives, mercaptans blocked, as are mentioned in EP-A 0 742 259 on pages 4 to 18.
  • the disclosure in the indicated specification is expressly incorporated, it is understood as part of the disclosure of the present text.
  • a stabilizer composition according to the invention may contain the described blocked mercaptans in an amount of up to about 30% by weight, in particular up to about 10% by weight.
  • a stabilizer composition according to the invention may further comprise lubricants such as paraffin waxes, polyethylene waxes, polypropylene waxes, montan waxes, ester lubricants such as fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps.
  • lubricants such as paraffin waxes, polyethylene waxes, polypropylene waxes, montan waxes, ester lubricants such as fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps.
  • Useful lubricants are also in "plastic additives", R. Gumbleter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, p. 478-488.
  • lubricants are, for example, fatty ketones as described in DE 4,204,887 and silicone-based lubricants, as mentioned, for example, in EP-A 0 259 783, or combinations thereof, as mentioned in EP-A 0 259 783.
  • the documents cited are hereby incorporated by reference, the disclosure of which relates to lubricants being considered part of the disclosure of the present text.
  • lubricants of the product series Baerolub® from Baerlocher GmbH (Schschleissheim, Germany) are particularly suitable.
  • a stabilizer composition according to the invention may contain the lubricants described in an amount of up to about 70% by weight, in particular up to about 40% by weight.
  • additives for stabilizer compositions according to the present invention are organic plasticizers.
  • Suitable plasticizers are, for example, compounds from the group of phthalic acid esters such as dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl -, di-iso-decyl, dicyclohexyl, di-methylcyclohexyl-, dimethyl glycol, dibutyl glycol, benzyl butyl or diphenyl phthalate and mixtures of phthalates, for example mixtures of alkyl phthalates having 7 to 9 or 9 to 11 C atoms in the ester alcohol or Mixtures of alkyl phthalates having 6 to 10 and 8 to 10 C atoms in the ester alcohol.
  • phthalic acid esters such as dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-oc
  • plasticizers are the esters of aliphatic dicarboxylic acids, in particular the esters of adipic, azelaic or sebacic acid or mixtures of two or more thereof.
  • plasticizers examples include di-2-ethylhexyl adipate, diisooctyl adipate, diiso-nonyl adipate, diisodecyl adipate, benzyl butyl adipate, benzyloctyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate.
  • preference is given to di-2-ethylhexyl acetate and diisoctyl adipate.
  • trimellitic esters such as tri-2-ethylhexyl trimellitate, triiso-tridecyl trimellitate, triisoctyl trimellitate and trimellitic esters having 6 to 8, 6 to 10, 7 to 9 or 9 to 11 C atoms in the ester group or mixtures of two or more of said compounds.
  • plasticizers are, for example, polymer plasticizers, as described in "Kunststoffadditive”, R. Gumbleter / H. Müller, Carl Hanser Verlag, 3rd Edition, 1989, Chapter 5.9.6, pages 412-415, or "PVC Technology”, W.V. Titov, 4th Edition, Elsevier Publishers, 1984, pp. 165-170.
  • polyester plasticizers are, for example, dicarboxylic acids such as adipic, phthalic, azelaic or sebacic acid and diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or diethylene glycol or mixtures of two or more thereof.
  • dicarboxylic acids such as adipic, phthalic, azelaic or sebacic acid
  • diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or diethylene glycol or mixtures of two or more thereof.
  • phosphoric esters are also suitable as plasticizers.
  • suitable phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, triphenyl phosphate, tricresyl phosphate or trixylenyl phosphate, or mixtures of two or more thereof.
  • plasticizers are chlorinated hydrocarbons (paraffins) or hydrocarbons as described in "Kunststoffadditive", R. Gumbleter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, chapter 5.9.14.2, pp. 422-425 and chapter 5.9.14.1, p. 422.
  • a stabilizer composition according to the invention may contain the plasticizers described in an amount of up to about 99.5% by weight, in particular up to about 30% by weight, up to about 20% by weight or up to about 10% by weight ,
  • the lower limit for the described plasticizers as part of the stabilizer compositions according to the invention about 0.1 wt .-% or more, for example about 0.5 wt .-%, 1 wt .-%, 2 wt. -% or 5%, -%.
  • pigments are also suitable as a constituent of the stabilizer compositions according to the invention.
  • suitable inorganic pigments are titanium dioxide, carbon black, Fe 2 O 3 , Sb 2 O 3 , (Ba, Sb) O 2 , Cr 2 O 3 , spinels such as cobalt blue and cobalt green, Cd (S, Se) or ultramarine blue.
  • Suitable organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments or anthraquinone pigments.
  • a stabilizer composition according to the invention may further comprise fillers as described in the Handbook of PVC Forming, EJ Wickson, John Wiley & Sons, Inc., 1993, pages 393-449, or reinforcing agents as described in the "Plastic Adhesive Handbook". , R. Gumbleter / H. Müller, Carl Hanser Verlag, 1990, pages 549-615.
  • Particularly suitable fillers or reinforcing agents are, for example, calcium carbonate (chalk), dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibers, talc, kaolin, chalk, carbon black or graphite, wood flour or other renewable raw materials.
  • Stabilizer composition according to the invention Cretaceous is one preferred embodiment of the present invention.
  • the stabilizer compositions according to the invention may contain antioxidants, UV absorbers and light stabilizers or blowing agents. Suitable antioxidants are described, for example, in EP-A 1 046 668 on pages 33 to 35.
  • the products of the Irganox® series (manufacturer: Ciba Specialty Chemicals), for example Irganox® 1010 or 1076 or products of the Lowinox series from Great Lakes, are preferably used as antioxidants.
  • Suitable UV absorbers and light stabilizers are mentioned in EP-A 1 046 668 on pages 35 and 36. Both disclosures are hereby incorporated by reference, the disclosures being considered as part of this text.
  • the present invention therefore also relates to a process for the preparation of a stabilizer composition, characterized in that a salt preparation according to the invention or a salt preparation prepared according to the invention and at least one further additive are mixed.
  • graft polymers of PVC with EVA, ABS or MBS are also suitable for stabilization with the stabilizer compositions according to the invention.
  • Preferred substrates for such graft copolymers are also the abovementioned homopolymers and copolymers, in particular mixtures of vinyl chloride homopolymers with other thermoplastic or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PAA (polyalkyl acrylate), PAMA (polyalkyl methacrylate), EPDM, polyamides or polylactones.
  • a polymer composition according to the invention contains the stabilizer composition according to the invention in an amount of 0.1 to 20 phr, in particular about 0.5 to about 15 phr or about 1 to about 12 phr.
  • the unit phr stands for "per hundred resin” and thus relates to parts by weight per 100 parts by weight of polymer.
  • a polymer composition according to the invention as a halogenated polymer at least partially contains PVC, wherein the PVC content is in particular at least about 20, preferably at least about 50 wt .-%, for example at least about 80 or at least about 90 wt .-%.
  • the present invention also relates to a process for stabilizing halogen-containing polymers, in which a halogen-containing polymer or a mixture of two or more halogen-containing polymers or a mixture of one or more halogen-containing polymers and one or more halogen-free polymers is mixed with a stabilizer composition according to the invention.
  • the present invention therefore also provides a process for stabilizing halogen-containing polymers, in which a halogen-containing polymer or a mixture of two or more halogen-containing polymers or a mixture of one or more halogen-containing polymers and one or more halogen-free polymers with a salt preparation according to the invention or one according to the invention prepared salt preparation or a stabilizer composition according to the invention or a stabilizer composition according to the invention is mixed.
  • the term “shaped body” basically encompasses all three-dimensional structures that can be produced from a polymer composition according to the invention.
  • the term “shaped body” in the context of the present invention for example, wire sheaths, automotive components, such as automotive components such as those used in the interior of the car, in the engine compartment or on the outer surfaces, cable insulation, decorative films, agricultural films, hoses, sealing profiles, Office films, hollowware (bottles), packaging films (thermoformed films), blown films, tubes, foams, heavy profiles (window frames), lightwall profiles, building profiles, sidings, fittings, sheets, foam sheets, recycled core coextrudates or housings for electrical equipment or machines, such as computers or Domestic appliances.
  • moldings which can be produced from a polymer composition according to the invention are artificial leather, floor coverings, textile coatings, wallpaper, coil coatings or underbody protection for motor vehicles.
  • Table 1 Zeolites of Examples EB 1-7 according to the invention
  • Test recipe S-PVC (K value 65) 100.00
  • the thermal stability is improved by the stabilizers according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne une préparation saline solide à facilité d'utilisation améliorée, qui contient un mélange comprenant un sel d'onium organique d'un oxacide halogéné et un solvant. L'invention concerne également un procédé servant à produire de telles préparations salines, ainsi que leur utilisation, notamment dans des compositions stabilisantes pour polymères halogénés.
EP06762428A 2005-07-06 2006-07-05 Preparation saline organique solide, sa production et son utilisation Withdrawn EP1913065A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510031623 DE102005031623A1 (de) 2005-07-06 2005-07-06 Feste organische Salzzubereitung, deren Herstellung und Verwendung
PCT/EP2006/006571 WO2007003433A2 (fr) 2005-07-06 2006-07-05 Preparation saline organique solide, sa production et son utilisation

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EP1913065A1 true EP1913065A1 (fr) 2008-04-23

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DE102007037795A1 (de) * 2007-08-10 2009-02-12 Nabaltec Ag Stabilisatorsysteme für halogenhaltige Polymere
DE202015000838U1 (de) 2015-02-05 2015-03-20 Peter Würz Thermostabilitätsverbesserer von transparenten PVC-haltigen Materialien

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DE10118179A1 (de) * 2001-04-11 2002-10-24 Baerlocher Gmbh Stabilisatorkombination für halogenhaltige Polymere und deren Verwendung
ITMI20011020A1 (it) * 2001-05-17 2002-11-17 Reagens Spa Stabilizzanti per pvc
DE10160662A1 (de) * 2001-12-11 2003-06-18 Baerlocher Gmbh Stabilisatorzusammensetzung, deren Herstellung und Verwendung
DE10214152A1 (de) * 2002-03-28 2003-10-09 Baerlocher Gmbh Feste Stabilisatorzusammensetzung, deren Herstellung und Verwendung
DE10255155B4 (de) * 2002-11-26 2006-02-23 Baerlocher Gmbh Stabilisierungszusammensetzung für halogenhaltige Polymere, Verfahren zu deren Herstellung und deren Verwendung

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WO2007003433A2 (fr) 2007-01-11
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