WO2004048453A1 - Salz einer halogenhaltigen oxysäure geträgert auf einem trägermittel als stabilisierungszusammensetzung für halogenhaltige polymere - Google Patents
Salz einer halogenhaltigen oxysäure geträgert auf einem trägermittel als stabilisierungszusammensetzung für halogenhaltige polymere Download PDFInfo
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- the present invention relates to a stabilizer composition for halogen-containing polymers and polymer mixtures, comprising a carrier material of the general formula Ca x Al 2 (OH) 2 ( x + 2 ) HPO 3 "m H 2 O, where x is a number from 2 to 12 and m represents a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, where at least one salt of a halogen-containing oxyacid is present in finely divided form on the support material, a process for their preparation and their use ,
- Halogen-containing, thermoplastic resin compositions or molded parts made from them are broken down or decomposed by the action of heat or light.
- Stabilizers must therefore be added to these resins.
- articles such as profiles, plates or pipes, inorganic and / or organic compounds of toxic heavy metals such as lead, barium or cadmium are usually used for this.
- inorganic and / or organic compounds of toxic heavy metals such as lead, barium or cadmium are usually used for this.
- 2-basic lead phosphite 2-basic lead phosphite.
- DD-PS 61 095 mentions the use of basic lead phosphite as a stabilizer against the degradation of PVC by heat
- another use of the basic lead phosphite for PVC rigid foam mixtures is described in US Pat. No. 4,797,426.
- JP-PS 1 213 865 and in JP-OS 80 445/80 a hydrotalcite is proposed as a stabilizer. This substance is superior to mixtures of Ca / Zn metal soaps in terms of heat stability and transparency. However, using hydrotalcite does not solve the problem of resin discoloration during processing. According to JP-OS 80 444/82 it is proposed to use combinations of hydrotalcite and 1,3-diketone compounds to overcome this problem.
- EP 0 930 332 A2 relates to stabilizer combinations containing aminouracils and at least one further substance selected from a number of aluminum, lithium and calcium-aluminum compounds.
- this has the disadvantage that the stabilizers described do not meet all requirements with regard to heat stability and initial color.
- EP 0 506 831 B1 relates to basic calcium aluminum hydroxy phosphites and their use as stabilizers for halogen-containing polymers.
- the stabilizers described in the cited publication do not have the desired effect in all the areas required.
- DE 100 56 880 AI and DE 100 38 721 AI relate to stabilizer compounds for halogen-containing organic plastics.
- the stabilized products are each produced by homogenizing and plasticizing a PVC powder mixture and the recipe components mentioned in the documents for 5 minutes at 170 ° C.
- the proportion of sodium perchlorate resulting from the recipes described lies within a range which is not sufficiently effective.
- the invention was therefore based on the object of providing new stabilizer compositions and a process for their preparation which are particularly suitable as stabilizers for halogen-containing polymers without having the disadvantages of the known stabilizers mentioned above, and in particular are classified as non-toxic. Furthermore, it was an object of the invention to provide stabilizer compositions which extend the freedom of the user to formulate to such an extent that he can do without the additives required in the prior art, such as zinc salts or aminouracile, without achieving a significant deterioration in the result. In particular, the present invention was based on the object of new stabilizer compositions and to provide a process for their production, which are particularly suitable as stabilizers for soft PVC, PVC part, rigid PVC foam (free foam, Celuka foam).
- the present invention therefore relates to a stabilizer composition for halogen-containing polymers, comprising a carrier material of the general formula (I) Ca x Al 2 (OH) 2 ( X + 2 ) HPO 3 "m H 2 O (I), where x is for a Number from 2 to 12 and m is a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, at least one salt of a halogen-containing oxyacid being present in finely divided form on the support material.
- a carrier material of the general formula (I) Ca x Al 2 (OH) 2 ( X + 2 ) HPO 3 "m H 2 O (I), where x is for a Number from 2 to 12 and m is a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, at least one salt of a halogen-containing oxyacid being present in finely
- Stabilizer compositions according to the present invention have at least one carrier material, the carrier material being calcium aluminum hydroxyphosphite of the general formula I Ca x Al 2 (OH) 2 ( X + 2 ) HPO 3 "m H 2 O (I), in which x stands for a number from 2 to 8 and m stands for a number from 0 to 12.
- a “stabilizer composition” is understood to mean a composition which can be used to stabilize halogen-containing polymers.
- a stabilizer composition according to the invention is generally mixed with a halogen-containing polymer provided for stabilization and then processed.
- carrier material is understood to mean a material which, at least superficially, can have a compound that differs from the carrier material and is present in finely divided form on the carrier material.
- the term “on the carrier material” is to be interpreted in such a way that at least a predominant part the compound present on the carrier material adheres firmly to the carrier material through interactions between the carrier material and the compound.
- the interactions can be essentially arbitrary, for example ionic, electrostatic, covalent or Van der Waals forces or two or more of these interactions can simultaneously ensure adhesion to the carrier material.
- x preferably stands for a number from 3 to 6 and m preferably stands for a number from 2 to 4.
- compositions according to the invention with calcium aluminum hydrogen phosphites and salts of halogen-containing oxyacids give halogen-containing thermoplastic resins and the molded parts produced therefrom comparable heat stability to basic lead phosphites.
- the compounds according to the invention prevent discoloration in the production of e.g. Hard PVC molded parts, the color retention and the weathering stability of the molded parts stabilized with the compounds according to the invention are equivalent to the products stabilized with toxic heavy metal compounds.
- compositions according to the invention relate both to compositions which can contain such costabilizers and to compositions which are free from zinc salts or free from aminouracils or free from zinc salts and aminouracils.
- costabilizers such as zinc salts or aminouracils.
- the present invention therefore relates both to compositions which can contain such costabilizers and to compositions which are free from zinc salts or free from aminouracils or free from zinc salts and aminouracils.
- To produce the calcium aluminum hydroxy phosphites used according to the invention as supports for example, mixtures of calcium hydroxide and / or oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and / or oxide and sodium aluminate with phosphorous acid in amounts corresponding to the preparation of the desired compounds converts aqueous medium and the reaction product is separated and recovered in a manner known per se.
- the reaction product obtained directly from the reaction described above can be separated from the aqueous reaction medium by known processes, preferably by filtration.
- the separated reaction product is also worked up in a manner known per se, for example by washing the filter cake with water and drying the washed residue at temperatures of, for example, 60-130 ° C., preferably at 90-120 ° C.
- Both a finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium aluminate can be used for the reaction.
- Calcium can be used in the form of finely divided calcium oxide or hydroxide or mixtures thereof.
- the phosphorous acid can be used in different concentrations.
- the reaction temperatures are preferably between about 50 and 100 ° C, more preferably between about 60 and 85 ° C. No catalysts or accelerators are required.
- the water of crystallization can be removed in whole or in part by thermal treatment.
- the dried calcium aluminum hydroxyphosphites used according to the invention do not split off any water at the processing temperatures of 160-200 ° C. customary for hard PVC, for example, so that there are no troublesome blistering in the moldings.
- a stabilizer composition according to the invention has at least two components.
- a stabilizer composition according to the invention also contains at least one salt of a halogen-containing oxyacid.
- a stabilizer composition according to the invention preferably contains at least one inorganic or an organic salt of perchloric acid.
- Suitable inorganic perchlorates are those of the general formula M (ClO 4 ) k , where M is Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce.
- an "onium salt” is a compound which is an ammonium, sulfonium or phosphonium salt.
- An “onium salt” according to US is an organic onium salt. This means that the ammonium, sulfonium or phosphonium group of the onium salt carries at least one organic radical. Depending on the type of onium group, an onium salt can carry 1, 2, 3 or 4 organic residues.
- the organic radicals can be connected to the onium radical, for example via a C-X linkage, where X stands for S, N or P. However, it is also possible for the organic radicals to be connected to the onium radical via a further hetero atom, for example an O atom.
- An onium perchlorate which can be used in the context of the present invention has at least one positively charged N, P or S atom or two or more such positively charged N, P or S atoms or mixtures of two or more of the positively charged atom types mentioned on.
- compounds are used as onium perchlorates which contain at least one organic radical on the N, S or P atom and at most the maximum times possible number of organic residues. If an onium perchlorate which can be used according to the invention bears fewer organic residues than are necessary for the formation of a positively charged onium ion, the positive charge is generated in a conventional manner known to the person skilled in the art by protonation using a suitable acid, so that the corresponding onium perchlorate in this case in addition to a organic residue still bears at least one proton.
- a peralkylated onium perchlorate which can be used according to the invention has an aryl, alkaryl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl radical.
- an onium salt which can be used in the context of a stabilizer composition according to the invention has two or, if appropriate, more different types of substituents, for example an alkyl and a cycloalkyl radical or an alkyl and an aryl radical.
- an onium salt which can be used in the context of a stabilizer composition according to the invention has substituents which in turn are substituted by one or more functional groups.
- “Functional groups” are groups which improve the effects of the stabilizer composition or at least not or only insignificantly deteriorate them.
- Corresponding functional groups can be, for example, NH groups, NH 2 groups, OH groups, SH groups, ester groups, ether groups, thioether groups, isocyanurate groups or keto groups or mixtures of two or more thereof.
- all compounds which lead to a phosphonium perchlorate by appropriate reaction of suitable reactants can be used as phosphonium perchlorates in the context of the present invention.
- Phosphonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of tetraalkyl, tetracycloalkyl or tetraaryl phosphorus halides.
- Suitable phosphonium perchlorates are therefore derived, for example, from tetraalkylphosphorus salts such as tetra-n-ethylphosphonium bromide, tetra-n-propylphosphonium bromide, tetra-n-butylphosphomium bromide, tetra-n-isobutylphosphonium bromide, tetra-n-pentylphylbromidium, and the like Tetraalkyl phosphorus salts.
- phosphonium perchlorates which are derived, for example, from tetracycloalkyl phosphorus salts or tetraaryl phosphorus salts, are basically suitable for use in the context of the stabilizer compositions according to the invention. Suitable phosphonium perchlorates are therefore based, for example, on tetracycloalkyl or tetraaryl phosphorus salts such as tetracyclohexylphosphonium bromide or tetraphenylphosphonium bromide and the like tetracycloalkyl or tetraaryl phosphorus salts.
- the abovementioned compounds can be unsubstituted in the context of the present invention, but they can also have one or more of the abovementioned substituents, provided that these substituents have no adverse effects in the context of the stabilizer composition and do not adversely affect the intended use of the stabilizer composition.
- Organic phosphonium perchlorates which carry different types of organic substituents on a phosphorus atom, which can optionally be substituted differently, can also be used in the context of the present invention.
- tetra-n-butylphosphonium perchlorate or triphenylbenzylphosphonium perchlorate are used as phosphonium perchlorates.
- all compounds which lead to a sulfonium perchlorate through appropriate reaction of suitable reactants can be used as sulfonium perchlorates in the context of the present invention.
- Sulfonium perchlorates which can be used according to the invention can be obtained, for example, by appropriate reaction of sulfides such as alkyl monosulfides, alkyl disulfides, dialkyl sulfides or poly (alkyl sulfides).
- Suitable sulfonium perchlorates are therefore derived, for example, from dialkyl sulfides such as ethylbenzyl sulfide, allylbenzyl sulfide or alkyl disulfides such as hexane disulfide, heptane disulfide, octane disulfide and the like alkyl disulfides.
- dialkyl sulfides such as ethylbenzyl sulfide, allylbenzyl sulfide or alkyl disulfides such as hexane disulfide, heptane disulfide, octane disulfide and the like alkyl disulfides.
- sulfonium perchlorates which are derived, for example, from tricycloalkylsulfonium salts or triarylsulfonium salts are suitable in principle for use in the stabilizer compositions according to
- 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.
- Tricycloalkyl or triarylsulfonium salts such as tricyclohexylsulfonium bromide or triphenylsulfonium bromide and the like tricycloalkyl or triarylsulfonium salts.
- Trialkyl, triaryl or tricycloalkylsulfoxonium salts such as trimethylsulfoxonium perchlorate are also suitable.
- the abovementioned compounds can be unsubstituted in the context of the present invention, but they can also have one or more of the abovementioned substituents, provided that these substituents have no adverse effects in the context of the stabilizer composition and do not adversely affect the intended use of the stabilizer composition.
- Organic sulfonium perchlorates which have different types of organic substituents on a sulfur atom and which may be substituted differently can also be used in the context of the present invention.
- trimethylsulfoxonium perchlorate is used as the sulfonium perchlorate.
- ammonium perchlorates which by appropriate reaction of suitable reactants lead 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 2 to about 40, for example 6 to about 20, carbon atoms.
- these are ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, tert-butylamine, substituted amines with 2 to about 20 C atoms, such as 2- (N, N-dimethylamino) -l- aminoethane.
- Suitable diamines have, for example, two primary, two secondary, two tertiary or one primary and one secondary or one primary and one tertiary or one secondary and one tertiary amino group.
- Examples include diaminoethane, the isomeric diaminopropanes, the isomeric diaminobutanes, the isomeric diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane , 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as the diethylenetriamine or l, 8-diamino-4-aminomethyloctane or tertiary amines such as triethylamine, tributylamine, trihexylamine, triheptylamine, trioctylamine, dimethylethylamine, dimethylbenzylamine N-methyl-, N-cyclohexy
- aliphatic amino alcohols having 2 to about 40, preferably 6 to about 20, carbon atoms, for example triethanolamine, tripropanola in, triisopropanolamine, tributanolamine, tri-tert-butanolamine, tripentanolamine, l-amino-3 , 3-dimethyl-pentan-5-ol, 2-aminohexane-2 "-diethanolamine 2, 1-amino-2,5-dimethylcyclohexan-4-ol, 2-aminopropanol, 2-aminobutanol, 3-Aminopro ⁇ anol, l -Amino-2- ⁇ ropanol, 2-amino-2-methyl-l-propanol, 5-aminopentanol, 3-aminomethyl-3, 5,5-trimethylcyclohexanol, 1-amino-1-cyclopentane-methanol, 2-amino-2 -ethyl, 2-amino-2 -eth
- the perchlorates of heterocyclic compounds which have a cyclic ring system having amino groups are used as ammonium perchlorates.
- the perchlorates of heterocyclic amino alcohols are used which have at least 2, preferably at least 3 amino groups in the ring.
- the trimerization products of isocyanates are particularly suitable as the central ring component of the ammonium perchlorates which can be used according to the invention.
- hydroxyl-containing isocyanurates of the general formula II are suitable
- the groups Y and the indices m are each the same or different and m is an integer from 0 to 20 and Y is a hydrogen atom or a linear or branched, saturated or unsaturated alkyl group having 1 to about 10 carbon atoms.
- TEEIC tris (hydroxymethyl) isocyanurate
- ammonium perchlorates are, for example, compounds in which the amino group is bound to a substituted aromatic or heteroaromatic system, for example aminobenzoic acid, aminosalicylic acid or aminopyridinecarboxylic acid and their suitable derivatives.
- the ammonium perchlorates used are 2-ethylcarboxypyridinium perchlorate, formamidinium perchlorate, tetra-n-butylphosphonium perchlorate, trimethylsulfoxonium perchlorate, the perchlorate salt of trishydroxyethyl isocyanurate, the perchlorate salt of 2- (diethylamino-ethanolamine) tri-ethanolamine-tri-ethanolamethanol-ethanolamethanol-ethanolamethanol-ethanolamethanolamine , N- (2-hydroxyethyl) morpholinium perchlorate or trioctylammonium perchlorate or mixtures of two or more thereof.
- a stabilizer composition according to the invention can, for example, contain only one of the above-mentioned onium perchlorates.
- a stabilizer composition according to the invention contains a mixture of two or more of the above-mentioned onium perchlorates.
- onium perchlorates ie, for example, a mixture of ammonium perchlorates and sulfonium perchlorates or ammonium perchlorates and phosphonium perchlorates or sulfonium perchlorates and phosphonium perchlorates or ammonium perchlorates and sulfonium perchlorates and phosphonium perchlorates.
- a stabilizer composition according to the invention contains a mixture of two or more onium perchlorates of one type, ie a mixture of two or more ammonium perchlorates and a mixture of two or more sulfonium perchlorates and a mixture of two or more phosphonium perchlorates.
- a stabilizer composition according to the invention can contain only a salt of a halogen-containing oxy acid in the context of the present invention.
- a stabilizer composition according to the invention contains a mixture of two or more salts of halogen-containing oxyacids.
- a stabilizer composition according to the invention contains at least sodium perchlorate.
- the salt of a halogen-containing oxyacid or a mixture of two or more such salts is present in finely divided form on the support material.
- finely divided means the finding that discrete particles of the salt of a halogen-containing oxyacid or a mixture of two or more such salts present on the support material, provided such discrete particles are present or recognizable at all, have an average particle size of
- the term should preferably be interpreted in such a way that a total particle size of 10 ⁇ m, in particular a particle size of 5 ⁇ m or 1 ⁇ m is not exceeded, in particular for salt. Usual methods such as light or Electron microscopy can be used.
- the term “on the carrier material” is to be interpreted in such a way that at least a predominant part of the compound present on the carrier material adheres firmly to the carrier material due to interactions between the carrier material and the connection.
- the interactions can be essentially arbitrary, so For example, ionic, electrostatic, covalent or Van der Waals forces or two or more of these interactions can simultaneously adhere to the carrier material.
- a stabilizer composition according to the invention therefore contains a mixture of carrier material and salt of a halogen-containing oxyacid, in which at most 10% by weight of at least one salt a halogen-containing oxyacid can be separated from the carrier material by simple mechanical separation processes, for example by sieving.
- a “simple mechanical separation process” is understood to mean a separation process in which particles which are present separately or are only weakly adhering to one another are separated only before the separation process is carried out.
- a stabilizer composition according to the invention can also contain a salt of a halogen-containing oxyacid or a mixture of two or more such salts which are used in the sense of The above definition does not exist in a fine distribution on the carrier material.
- the salts of the halogen-containing oxyacid or the mixture of two or more such salts if the salts can be in crystal form, crystallites with a size of more than 30 ⁇ m or more than 20 ⁇ m or more than Have 10 ⁇ m. It follows that at least about 90% by weight of such salts have crystallites with a size of less than 30 ⁇ m or less than 20 ⁇ m or less than 10 ⁇ m.
- the average particle size is preferably within a range from approximately 0.5 to approximately 30 ⁇ m, for example approximately 1 to approximately 20 ⁇ m.
- the crystallite sizes of salts of halogen-containing oxyacids which are not present on a carrier material in the stabilizer composition according to the invention can, if these salts form crystallites, be determined in principle by any method for determining particle sizes.
- screening methods, sedimentation methods or methods based on the diffraction or refraction of electromagnetic waves, in particular light are basically suitable.
- electron Roscopic methods such as scanning electron microscopy or transmission electron microscopy.
- the total amount of salts of a halogen-containing oxyacid or a mixture of two or more halogen-containing oxyacids in the stabilizer composition according to the invention is about 0.1 to about 30% by weight, in particular about 0.5 to about 20% by weight.
- Examples of the contents of salts of a halogen-containing oxyacid or a mixture of two or more such salts are about 1 to about 15% by weight or about 2 to about 10% by weight.
- the ratio of salt or salts of a halogen-containing oxyacid to carrier material can essentially be designed as desired within the limits specified with regard to the desired stabilization result. If a stabilizer composition according to the invention is present exclusively on a carrier material, or such a mixture of two or more salts of a halogen-containing oxy acid, provided that the carrier material is to have the desired amount of salt or salts of a halogen-containing oxy acid in the sense of the above definition, the ratio should be designed in this way that the amount of salt or salts of a halogen-containing oxyacid can still be absorbed by the support material without the presence of salt or salts of a halogen-containing oxyacid separately from the support material.
- the ratio of salt or salts of a halogen-containing oxyacid to carrier material should be 1: 100 to 1: 1.
- the carrier material itself should be in particle form and should preferably not exceed an average particle size of 100 ⁇ m.
- the carrier material preferably has a particle size of 50 ⁇ m or less, in particular a particle size of 30 ⁇ m or less or of 10 ⁇ m or less.
- Fundamentally suitable for determining the particle size are, for example, sieving processes, sedimentation processes or processes based on the diffraction or refraction of electromagnetic waves, in particular light.
- the laser diffraction method is particularly suitable.
- Electron microscopic methods such as scanning electron microscopy or transmission electron microscopy are also suitable.
- a stabilizer composition according to the invention can also have one or more additives.
- blowing agents are, for example, organic azo and hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, salts of citric acid, for example ammonium citrate, and soda and sodium bicarbonate.
- ammonium citrate, azodicarbonamide or sodium bicarbonate or mixtures of two or more thereof are particularly suitable.
- physical blowing agents such as liquids which change to the gaseous state when the temperature rises accordingly or gases, for example water, CO 2 (supercritical), air or inert gases such as nitrogen, helium, argon and the like.
- a stabilizer composition according to the invention contains at least one blowing agent.
- the proportion of blowing agent in a stabilizer composition according to the invention is preferably about 0.01 to about 20% by weight, for example about 0.1 to about 10 or about 0.5 to about 5% by weight.
- suitable as additives in the context of the present invention are, for example, amino alcohols.
- Suitable amino alcohols in the context of the present invention are in principle all compounds which have at least one OH group and a primary, secondary or tertiary amino group or a combination of two or more of the amino groups mentioned.
- both solid and liquid amino alcohols are suitable as part of the stabilizer compositions according to the invention in the context of the present invention.
- the proportion of liquid amino alcohols is selected, for example, so that the entire stabilizer composition is essentially in solid form.
- amino alcohols which can be used in the context of the present invention have a melting point of more than about 30 ° C., in particular more than about 50 ° C.
- Suitable amino alcohols are, for example, mono- or polyhydroxy compounds which are based on linear or branched, saturated or unsaturated aliphatic mono- or polyamines.
- Suitable for this purpose are, for example, derivatives of primary mono- or polyamino compounds containing OH groups with 2 to about 40, for example 6 to about 20, carbon atoms.
- these are corresponding OH group-bearing derivatives of ethylamine, n-propylamine, i-propylamine, n-propylamine, sec-propylamine, tert-butylamine, 1-aminoisobutane, substituted amines with two to about 20 C atoms, such as 2 - (N, N-Dimethylamino) -l-aminoethane.
- Suitable OH group-bearing derivatives of diamines are, for example, those based on diamines with a molecular weight of 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.
- Examples include diaminoethane, the isomeric diaminopropanes, the isomeric diaminobutanes, the isomeric diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane , 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as the diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
- Aliphatic amino alcohols with 2 to about 40, preferably 6 to about 20 C atoms, for example l-amino-3,3-dimethyl-pentan-5-ol, 2-aminohexane-2 ', 2 "-diethanolamine, l are particularly suitable -Amino-2,5-dimethylcyclohexan-4-ol- 2-aminopropanol, 2-aminobutanol, 3-aminopropanol, l-amino-2-propanol, 2-amino-2-methyl-l-propanol, 5-aminopentanol, 3 - Aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-l-cyclopentane-methanol, 2-amino-2-ethyl-l, 3-propanediol, 2- (dimethylaminoethoxy) ethanol, aromatic-aliphatic or aromatic cycloaliphatic amino alcohols having 6 to about 20
- the amino alcohols used are heterocyclic compounds which have a cyclic ring system containing amino groups, the OH groups being connected to the ring either directly or preferably via spacers.
- heterocyclic amino alcohols which have at least 2, preferably at least 3, amino groups in the ring.
- trimerization products of isocyanates are particularly suitable as the central ring component of the amino alcohols which can be used according to the invention. Isocyanurates of the general formula II already mentioned above are particularly preferred.
- TBEIC tris (hydroxymethyl) isocyanurate
- a stabilizer composition according to the invention can, for example, contain only one amino alcohol. However, it is also provided in the context of the present invention that a stabilizer composition according to the invention contains a mixture of two or more different amino alcohols.
- n for a number from 1 to 100,000, the radicals R 4 , R 5 , R 1 and R 2 each independently of one another for hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical having 1 to 44 C atoms, one optionally substituted saturated or unsaturated cycloalkyl radical having 6 to 44 C atoms or an optionally substituted aryl radical having 6 to 44 C atoms or an optionally substituted aralkyl radical having 7 to 44 C atoms or the radical R 1 is an optionally substituted acyl radical with 2 to 44 carbon atoms or the radicals R 1 and R 2 are linked to form an aromatic or heterocyclic system and wherein the radical R 3 is hydrogen, an optionally substituted, linear or branched, saturated or unsaturated aliphatic alkyl or alkylene radical or oxyalkyl or oxyalkylene radical or mercaptoalkyl or mercaptoalkylene radical or aminoalkyl or aminoalkylene
- a compound based on a, ⁇ -unsaturated ⁇ -aminocarboxylic acid in particular a compound based on ⁇ -aminocrotonic acid, is used as the compound of the general formula III.
- the esters or thioesters of the corresponding aminocarboxylic acids with monohydric or polyhydric alcohols or mercaptans are particularly suitable here, where X in the cases mentioned is in each case O or S.
- radical R 3 together with X represents an alcohol or mercaptan radical
- a radical can be composed, for example, of methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, isooctanol, isononanol, decanol, lauryl alcohol, myristyl alcohol, palmityl alcohol , Stearyl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, thio-diethanol, trimethylolpropane, glycerin, tris (2-hydroxymethyl) isocyanurate , Triethanolamine, pentaerythritol, di-trimethylolpropane, diglycerol, sorbitol, mannitol, xylitol
- a compound of general formula III is used in which R 1 for a linear alkyl radical having 1 to 4 carbon atoms, R 2 for hydrogen and R 3 for a linear or branched, saturated , mono- to hexavalent 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 III 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-ß-aminocrotonic acid ester Dipentaeiythritol-hexa- ⁇ -aminocrotonic acid ester and the like.
- 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 IV are also suitable in the context of the present invention as compounds of the general formula IV.
- R 8 in which the radicals R 6 and R 7 each independently represent hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl radical having 1 to 44 C atoms, an optionally substituted saturated or unsaturated cycloalkyl radical having 6 to 44 C atoms or an optionally substituted aryl radical with 6 to 44 C atoms or an optionally substituted aralkyl radical with 7 to 44 C atoms and the radical R 8 is hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to 44 carbon atoms, an optionally substituted saturated or unsaturated cycloa- lipatic hydrocarbon radical having 6 to 44 carbon atoms or an optionally substituted aromatic hydrocarbon radical having 6 to 44 carbon atoms.
- the compound according to formula IV thus falls under the compounds according to formula III, where n in the general formula III for 1 and the radicals R 1 and R 3 according to the general formula IV to form the structural element of the general formula V.
- R 9 are linked, where X is S or O.
- R 1 thus represents NR 9
- R 6 and R 8 are a linear or branched alkyl radical having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl , Pentyl or hexyl, a linear or branched alkyl radical with 1 to 6 C atoms substituted by OH groups, for example hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl or hydroxyhexyl, an aralkyl radical with 7 to 9 C atoms, for example benzyl, pheny - Methyl, phenylpropyl, dimethylbenzyl or phenylisopropyl, where the aralkyl radicals mentioned can be substituted, for example, with halogen, hydroxy or methoxy or an alkenyl radical with 3 to 6 carbon atoms,
- compounds of the general formula V are used in the stabilizer compositions according to the invention, in which R 6 and R 8 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-, i-, sec- or t- Stand butyl.
- compounds of the general formula III are, for example, compounds in which the radicals R and R are linked to form an aromatic or heteroaromatic system, for example aminobenzoic acid, aminosalicylic acid or aminopyridinecarboxylic acid and their suitable derivatives.
- a stabilizer composition according to the invention contains a compound of the general formula III or a mixture of two or more compounds of the general formula III, for example a compound of the general formula III, in an amount of from about 0.1 to about 99 , 5% by weight, in particular about 5 to about 50% by weight or about 5 to about 25% by weight.
- Suitable further additives in the context of the present invention are, for example, compounds which have at least one mercapto-functional, sp 2 -hybridized carbon atom.
- Z stands for an atom or a structural element which allows the formation of corresponding tautomeric structures, for example N or C.
- the sp 2 -hybridized C atom can be part of an optionally substituted aliphatic compound or part of an aromatic system.
- Suitable types of compounds are, for example, thiocarbamic acid derivatives, thiocarbamates, thiocarboxylic acids, thiobenzoic acid derivatives, thioacetone derivatives or thiourea or thiourea derivatives.
- Suitable compounds with at least one mercapto-functional, sp 2 -hybridized carbon atom are for example in the unpublished German patent application with the file number 101 09 366.7.
- thiourea or a thiourea derivative is used as the compound having at least one mercapto-functional, sp 2 -hybridized carbon atom.
- additives for the stabilizer compositions according to the invention are, for example, carbazole or carbazole derivatives or mixtures of two or more thereof.
- additives are, for example, 2,4-pyrrolidinedione or its derivatives, as mentioned, for example, in the unpublished German patent application with the file number 101 09 366.7.
- Epoxy compounds are also suitable as additives.
- examples of such 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 attached directly to a carbon, oxygen, nitrogen or sulfur atom.
- Glycidyl or methyl glycidyl esters can be obtained by reacting a compound with 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 for example, can be used as compounds having at least one carboxyl group in the molecule.
- carboxylic acids examples include 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 rest of this text mentioned mono- or polycarboxylic acids.
- cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid or 4-methylhexahydrophthalic acid.
- Aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid are also suitable.
- Glycidyl ether or methyl glycidyl ether can be obtained by reacting a compound with 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-1,2-diol or poly (oxypropylene) glycols, butane-1,4-diol, poly (oxytetramethylene) ) glycols, pentane-l, 5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerin, 1,1,1-trimethylolpropane, bis-trimethylolpropane, pentaerythritol,. Sorbitol and polyepichlorohydrins. Butanol, amyl alcohol, pentanol and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol or technical alcohol mixtures, for example technical fatty alcohol mixtures.
- 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-en 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-en 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 they are based on multinuclear 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- nylsulfones or on condensation products of phenol with formaldehyde obtained under acidic conditions, for example phenol novolaks.
- mononuclear phenols for example from phenol, resorcinol or hydroquinone
- multinuclear 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- nylsulfones or on condensation products of
- Further terminal epoxides which are suitable as additives in the context of the present invention are, for example, glycidyl-1-naphthyl ether, glycidyl-2-phenylphenyl ether, 2-diphenylglycidyl ether, N- (2,3-epoxypropyl) phthalimide or 2,3-epoxypropyl-4 - methoxyphenyl ether.
- N-glycidyl compounds such as those obtainable by dehydrochlorination of the editorial products of epichlorohydrin with amines which contain at least one amino hydrogen atom.
- amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.
- S-glycidyl compounds for example di-S-glycidyl ether derivatives which are derived from dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether, are also suitable.
- 1,3-dicarbonyl compounds in particular the ⁇ -diketones and ⁇ -keto esters.
- dicarbonyl compounds of the general formula RC (O) CHR -C (O) R as described, for example, on page 5 of EP-1 046 668, to which, in particular with regard to the radicals R ′, R "and R '" is expressly referred to and their disclosure as part of the disclosure of the present text is looked at.
- 1, 3 -Diketo compounds can be contained in an inventive stabilizer composition in an amount of up to about 20% by weight, for example up to about 10% by weight.
- Polyols are also suitable as additives in the context of the stabilizer composition according to the invention.
- Suitable polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, Bistrimetylolethan, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxymethyl) isocyanurate, palatinite, tetramethylolcyclohexanol, Tetramethylolcyclopenta - nol, tetramethylolcycloheptanol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1- O- ⁇ -D-glycopyranosyl-D
- Suitable as additives are, for example, sterically hindered amines as mentioned on pages 7 to 27 of EP-A 1 046 668. Reference is expressly made to the sterically hindered amines disclosed therein, the compounds mentioned there are considered to be part of the disclosure of the present text.
- the sterically hindered amines suitable as additives can be present in an inventive stabilizer composition in an amount of up to about 30% by weight, for example up to about 10% by weight.
- hydrotalcites are also suitable as additives in the stabilizer compositions according to the invention.
- Suitable hydrotalcites, zeolites and alkali alumocarbonates are, for example, in EP-A 1 046 668 on pages 27 to 29, EP-A 256 872 on pages 3, 5 and 7, and DE-C 41 06 411 on pages 2 and 3 or DE-C 41 06 404 on page 2 and 3.
- hydrotalcites, zeolites and alkali alumocarbonates suitable as additives can be contained in an inventive stabilizer composition in an amount of up to about 50% by weight, for example up to about 30% by weight.
- Hydrocalumites of the general formula VI, for example, are also suitable as additives in the context of the stabilizer compositions according to the invention
- M stands for calcium, magnesium or zinc or mixtures of two or more thereof
- A for a j-valued inorganic or organic acid anion, j for 1, 2 or 3
- B for a different inorganic or organic acid anion
- r for one integer> 1 and, if r> 1, indicates the degree of polymerization of the acid anion and 1 stands for 1, 2, 3 or 4 and indicates the valence of the acid anion
- rl indicates the valency of the polyanion and the following rules for the parameters x, y, a, b, r, z, and j be valid:
- compounds of the general formula VI are used as additives, where M is calcium, which may optionally be present in a mixture with magnesium or zinc or magnesium and zinc.
- A stands for an r-valent inorganic or organic acid anion, where r stands for 1, 2 or 3.
- acid anions present in the context of hydrocalumites which can be used according to the invention are halide ions, SO 3 2 " , 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, in which the alkyl groups may be the same or different, straight-chain, branched or cyclic and preferably have 1 to about 20 C atoms.
- acid anions A suitable are the anions of optionally functionalized di-, tri- or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesinate, pyromellitate, maleate, tartrate, frante and anions of the isomeric forms of hydroxyphthalic acid or hydroxymesic acid.
- A stands for an inorganic acid anion, in particular a halide ion, for example F " , C ⁇ or Bf, preferably for Cl " .
- B represents an acid anion that is different from A.
- letter B stands for a 1-valent, inorganic or organic acid anion, where 1 stands for the number 2, 3 or 4. Examples of compounds of the general which can be used according to the invention
- Formula V acid anions B present are, for example, O “ , SO 3 “ , SO 4 “ , SO 3 “ , S 2 O 4 “ , HPO 2” , PO 4 3 “ , CO 3 2” , alkyl and dialkyl phosphates, alkyl mercaptides and alkyl sulfonates , in which the alkyl groups, the same or different, can be straight-chain or branched or cyclic and preferably have 1 to about 20 C atoms.
- acid anions A are also suitable as acid anions A are the anions of optionally functionalized di-, tri- or tetracarboxylic acids such as maleate, phthalate, aconitate, trimesmat, pyromellitate, maleate, tartrate, frante and anions of the isomeric forms of hydroxyphthalic acid or hydroxymesic acid.
- B preferably represents a borate or an anion of an optionally functionalized di-, tri- or tetracarboxylic acid.
- Carboxylic acid anions and anions of hydroxycarboxylic acids with at least two carboxyl groups are particularly preferred, citrates being very particularly preferred.
- r in the general formula VI stands for a number of more than 1
- the term [B r ] rl stands for an inorganic or organic polyanion with the degree of polymerization r and the value 1 of the individual monomer units of the polyanion with the total value - keit rl, where 1 is equal to or greater than 1.
- suitable polyanions [B r ] " are polyacrylates, polycarboxylates, polyborates, polysilicates, polyphosphates or polyphosphonates.
- the acid anions A and B can be present in any ratio a / b in the compounds of the general formula VI.
- the compounds of the general formula VI are not layered compounds of the hydrotalcite or hydrocalumite type, but a physical mixture of M 2+ / aluminum oxide hydrates with salts of divalent metals.
- X-ray diffractograms of the compounds of the general formula VI used in the composition according to the invention clearly show that it is not a matter of discrete crystalline compounds of a known type but of X-ray amorphous mixtures.
- the reaction products can be mixed directly with the surface treatment agent, the product separated from the mother liquor by filtration and dried at suitable temperatures between 100 and 250 ° C.
- the amount of surface treatment agent added is, for example, about 1 to about 20% by weight.
- a stabilizer composition according to the invention contains at least one basic calcium salt.
- Suitable basic calcium salts are, for example, calcium oxide, calcium carbonate or, unless it is already a mandatory component of the stabilizer compositions according to the invention, calcium hydroxide.
- the basic calcium salts can optionally be surface-modified.
- the metal oxides, metal hydroxides or metal soaps 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 within the scope of a preferred embodiment of the present invention the stabilizer compositions according to the invention are free of zinc.
- carboxylic acid anions include anions of monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, lauric acid, palmitic acid, palmitic acid 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, tolylic acid, dimethylbenzoic acid,
- metal soaps are used as additives, the anions of which are derived from saturated or unsaturated carboxylic acids or hydroxycarboxylic acids having from about 8 to about 20 carbon atoms. Stearates, oleates, laurates, palmitates, behenates, versatates, hydroxystates, dihydroxystearates, p-tert-butylbenzoates or (iso) octanoates of calcium or zinc or mixtures of two or more thereof are particularly preferred.
- a stabilizer composition according to the invention can contain the metal oxides, metal hydroxides or metal soaps mentioned 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 can furthermore contain an organotin compound or a mixture of two or more organotin compounds as a thermostabilizer component.
- Suitable organotin compounds are, for example, methyltin tris (isooctyl thioglycolate), methyltin tris (isooctyl 3-mercaptopropionate), methyltin tris (isodecyl thioglycolate), dimethyltin bis (isooctyl thioglycolate), di- butyltin bis (isooctyl thioglycolate), monobutyltin tris (isooctyl thioglycolate), dioctyltin bis (isooctyl thioglycolate), monooctyltin tris (isooctyl thioglycolate) 2-ethylethylhex-bis- mercap
- organotin compounds mentioned in EP-A 0 742 259 on pages 18 to 29 and described in their preparation can be used in the context of the stabilizer compositions according to the invention. Reference is expressly made to the above-mentioned disclosure, the compounds mentioned there and their preparation being understood as part of the disclosure of the present text.
- a stabilizer composition according to the invention can contain the organotin compounds described in an amount of 0 to about 20% by weight, in particular 0 to about 10% by weight.
- a stabilizer composition according to the invention can contain organic phosphite esters with 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 carbon atoms, optionally substituted alkyl radicals having 6 to 20 carbon atoms or optionally substituted aralkyl radicals having 7 to 20 carbon atoms.
- organic phosphite esters are tris (nonylphenyl), trilauryl, tributyl, trioctyl, tridecyl, tridodecyl, triphenyl, octyldiphenyl, dioctylphenyl, tri (octyl ⁇ henyl), tribenzyl, butyl dikresyl -, octyl-di (octylphenyl) -, tris- (2-ethylhexyl) - 5 tritolyl-, tris- (2-cyclohexyl-phenyl) -, tri- -naphthyl-, tris- (phenylphenyl) -, tris- (2nd phenylethyl), tris (dimethylphenyl), tricresyl or tris (p-nonylphenyl) phosphite or tristearyl
- a stabilizer composition according to the invention can contain the phosphite compounds described in an amount of 0 to about 30% by weight, in particular 0 to about 10% by weight.
- a stabilizer composition according to the invention may also contain blocked mercaptans as additives, as are mentioned on pages 4 to 18 of EP-A 0 742 259. Reference is expressly made to the disclosure in the document given, it is understood to be part of the disclosure of the present text.
- a stabilizer composition according to the invention can contain the blocked mercaptans described in an amount of 0 to about 30% by weight, in particular 0 to about 10% by weight.
- a stabilizer composition according to the invention can also contain 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, chlorinated paraffins, glycerol esters or alkaline earth metal soaps.
- Lubricants that can also be used are also described in "Kunststoffadditive", R. Gumbleter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pp. 478-488.
- lubricants are, for example, fatty ketones as described in DE 4,204,887 and silicone-based lubricants as described for example in EP-A 0 259 783, or combinations thereof as described in EP-A 0 259 783.
- Lubricants from the Baerolub® product range from Baerlocher GmbH (Schschleissheim, Germany) are particularly suitable in the context of the present invention.
- a stabilizer composition according to the invention can contain the described lubricants in an amount of from 0 to about 70% by weight, in particular up to about 40% by weight.
- Organic plasticizers are also suitable as additives for stabilizer compositions according to the present invention.
- 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 and di-iso -nonyl, di-iso-decyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl or diphenylphthalate and mixtures of phthalates, for example mixtures of alkyl phthalates with 7 to 9 or 9 to 11 carbon atoms in Ester alcohol or mixtures of alkyl phthalates with 6 to 10 and 8 to 10 carbon atoms in the ester alcohol.
- Particularly suitable for the purposes of the present invention are dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl, di-iso-decyl, Di-iso-tridecyl and benzyl butyl phthalate and the mixtures of alkyl phthalates mentioned.
- 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 are di-2-ethylhexyl adipate, di-isooctyl adipate, di-iso-nonyl adipate, di-iso-decyl adipate, benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-iso-decylseb.
- preference is given to di-2-ethylhexyl acetate and di-iso-octyl adipate.
- Trimellitic acid esters such as tri-2-ethylhexyl trimellithate, tri-iso-tridecyl trimellithate, tri-iso-octyl trimellithate and trimellitic acid esters with 6 to 8, 6 to 10, 7 to 9 or 9 to 11 carbon atoms in the ester group are also suitable as plasticizers or mixtures of two or more of the compounds mentioned.
- 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”, WV Titow, 4th edition, Elsevier Publishers, 1984, pages 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 acid 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 can contain the plasticizers described in an amount of from 0 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 contain.
- the lower limit for the plasticizers described as part of the stabilizer compositions according to the invention is about 0.1% by weight or more, for example about 0.5% by weight, 1% by weight, 2% by weight. -% or 5% by weight.
- 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, 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 anthaquinone pigments.
- a stabilizer composition according to the invention can also contain fillers as described in the "Handbook of PVC Formulating", EJ Wickson, John Wiley & Sons, Inc., 1993, pages 393-449 or reinforcing agents as described in the "Taschenbuch der Kunststoffadditive", 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.
- a stabilizer composition according to the invention contains chalk.
- the stabilizer compositions according to the invention can contain antioxidants, UV absorbers and light stabilizers or propellants. Suitable antioxidants are described, for example, on pages 33 to 35 of EP-A 1 046 668.
- the products of the Irganox® series (manufacturer: Ciba Specialty Chemicals), for example rrganox® 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 on pages 35 and 36 of EP-A 1 046 668. Both disclosures are expressly referred to here, the disclosures being considered part of the present text.
- a stabilizer composition according to the invention can also contain impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, flame retardants and antifogging compounds.
- Suitable compounds of these classes of compounds are described, for example, in "Kunststoff Additive”, R. Kessler / H. Müller, Carl Hanser Verlag, 3rd edition, 1989 and in the "Handbook of PVC Formulating", EJ. Wilson, J. Wiley & Sons, 1993.
- the stabilizer compositions according to the invention can in principle be in their simplest form by mixing a carrier material of the general formula I Ca x Al 2 (OH) 2 (x + 2 ) HPO "m H 2 O (I), where x is a number from 2 - 12 and m represents a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, wherein when mixed at least one salt of a halogen-containing oxyacid is present in dissolved form.
- a carrier material of the general formula I Ca x Al 2 (OH) 2 (x + 2 ) HPO "m H 2 O (I), where x is a number from 2 - 12 and m represents a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, wherein when mixed at least one salt of a halogen-containing oxyacid is present in dissolved form.
- the present invention therefore also provides a stabilizer composition which can be prepared by mixing together a carrier material of the general formula I Ca x Al 2 (OH) 2 (x + 2) HPO 3 'm H 2 O (I) wherein x is a number from 2-12 and m represents a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, wherein at least one salt of a halogen-containing oxyacid is present in dissolved form when mixed.
- a carrier material of the general formula I Ca x Al 2 (OH) 2 (x + 2) HPO 3 'm H 2 O (I) wherein x is a number from 2-12 and m represents a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, wherein at least one salt of a halogen-containing oxyacid is present in dissolved form when mixed.
- Suitable solvents for the salts of a halogen-containing oxyacid or a mixture of two or more such salts are in principle all solvents which, on the one hand, dissolve the salt of a halogen-containing oxyacid or the mixture of two or more such salts in sufficient quantity and, on the other hand, after mixing with the powder Carrier material can be removed if necessary by heating the mixture or by applying a reduced pressure or by a combination of both measures, so that a mixture of carrier material and supported salt of a halogen-containing oxyacid or a mixture of two or more of such salts is formed.
- the amount of dissolved salt of a halogen-containing oxyacid or the mixture of two or more such salts can be added as desired within the limits already mentioned above in the text.
- the salt of a halogen-containing oxyacid or the mixture of two or more such salts is added in an amount of 1 to 50% by weight, based on the halogen-containing oxyacid and carrier material.
- “mixing” is also understood to mean a process in which a corresponding salt of a halogen-containing oxyacid is precipitated from a solution in the presence of the carrier material.
- Such a stabilizer composition can also, as already described above, contain one or more additives.
- the present invention furthermore relates to a process for the preparation of a stabilizer composition according to the invention, in which a carrier material of the general formula Ca x Al 2 (OH) 2 ( x + 2 ) HPO 3 "m H 2 O, where x is a number of 2 - 12 and m stands for a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts is mixed, wherein at least one salt of a halogen-containing oxyacid is in solution in the mixing.
- the reaction of the powdered carrier material with the aqueous solution can in principle be done in any way, provided that sufficient mixing of powder and aqueous solution is ensured.
- conventional mixing devices such as broom mixers or ploughshare mixers are suitable for carrying out the method according to the invention.
- processes which lead to a particularly fine distribution of the compounds which react with one another are particularly suitable, for example fluidized bed processes, spray tower processes or jet-jet processes.
- the process according to the invention can also be carried out, for example, as a combination of mixing and grinding processes.
- an aqueous solution of a salt of a halogen-containing oxyacid or a mixture of two or more such salts can be fed in during the grinding process.
- a stabilizer composition according to the invention is to contain one or more additives in addition to the two main components, these additives can be added before, during or after the mixing of the carrier material with the solution of the salt of a halogen-containing oxyacid or the mixture of two or more such salts.
- additives should only be added before or during mixing if the additives are inert to the compounds involved in the mixing. In the other case, namely if the additives are not inert, they are only added after the reaction, provided the stabilizer composition according to the invention is to contain such additives.
- the stabilizer compositions according to the invention are suitable for stabilizing halogen-containing polymers.
- the present invention therefore also relates to a polymer composition comprising a halogen-containing polymer or a mixture of two or more halogen-containing polymers and a stabilizer composition according to the invention.
- halogen-containing polymers are polymers of vinyl chloride, vinyl resins which contain vinyl chloride units in the polymer backbone, copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid or acrylonitrile or mixtures of two or more thereof, copolymers of Vinyl chloride with diene compounds or unsaturated dicarboxylic acids or their anhydrides, for example copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and other compounds such as vinyl, methol methylene ether, crotonaldehyde Vinyl isobutyl ether and the like, polymers and copolymers of vinylidene chloride with vinyl chloride and other
- the 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 homo- and copolymers mentioned above, 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, especially PMMA - polymethyl methacrylate), EPDM, polyamides or polylactones.
- halogenated and non-halogenated polymers for example mixtures of the above-mentioned non-halogenated polymers with PVC, in particular mixtures of polyurethanes and PVC, are also suitable for stabilization with the stabilizer compositions according to the invention.
- recycled chlorine-containing polymers can also be stabilized with the stabilizer compositions according to the invention, with basically all recycled materials of the above-mentioned halogenated polymers being suitable for this.
- PVC recyclate for example, is suitable in the context of the present invention.
- 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 approximately 0.5 to approximately 15 phr or approximately 1 up 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 preferably contains PVC as a halogenated polymer at least in part, the PVC content being in particular at least about 20, preferably at least about 50% by weight, for example at least about 80 or at least about 90% by weight.
- the present invention also relates to a method 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 mixing of polymers or polymers and the stabilizer composition according to the invention can in principle take place at any time before or during the processing of the polymer.
- the stabilizer composition can be mixed with the polymer in powder or granule form before processing.
- a polymer composition according to the invention can be brought into a desired shape in a known manner. Suitable processes are, for example, calendering, extruding, injection molding, sintering, extrusion blowing or the plastisol process. A polymer composition according to the invention can also be used, for example, for the production of foams. In principle, the poly- mer compositions for the production of hard or soft PVC, in particular for the production of PVC foams.
- a polymer composition according to the invention can be processed into moldings.
- the present invention therefore also relates to moldings containing at least one stabilizer composition according to the invention or a polymer composition according to the invention.
- the term “molded body” basically comprises all three-dimensional structures that can be produced from a polymer composition according to the invention.
- the term “molded body” encompasses, for example, wire jackets, automotive components, for example automotive components such as are used in the interior of the automobile, in the engine compartment or on the outer surfaces, cable insulation, decorative foils, agricultural foils, hoses, sealing profiles, office foils, hollow bodies (bottles) , Packaging films (thermoformed films), blown films, pipes, foams, heavy profiles (window frames), light wall profiles, building profiles, sidings, fittings, plates, foam plates, coextrudates with recycled core or housing for electrical equipment or machines, for example computers or household appliances.
- moldings which can be produced from a polymer composition according to the invention are synthetic leather, floor coverings, textile coatings, wallpapers, coil coatings or underbody protection for motor vehicles.
- Another object of the present invention is the use of a mixture of a carrier material of the general formula Ca x Al 2 (OH) 2 (x + 2 ) HPO 3 "m H 2 O, where x is a number from 2 to 12 and m is is a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, at least one salt of a halogen-containing oxyacid being present in finely divided form on the support material, for stabilizing halogen-containing polymers.
- a carrier material of the general formula Ca x Al 2 (OH) 2 (x + 2 ) HPO 3 "m H 2 O, where x is a number from 2 to 12 and m is is a number from 0 to 12, and a salt of a halogen-containing oxyacid or a mixture of two or more such salts, at least one salt of a halogen-containing oxyacid being present in finely divided form on the support material, for stabilizing
- Three differently stabilized PVC samples (formulations 1 to 3) were each checked for their rate of decomposition using a dynamic stability test in a plastic order.
- the dynamic stability test was carried out at 190 ° C./60 g at 30 rpm.
- the state of discoloration of the three PVC samples was determined every five minutes.
- the time at which the PVC samples were completely decomposed was also determined.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003288166A AU2003288166A1 (en) | 2002-11-26 | 2003-11-25 | Salt of a halogen-containing oxyacid carried by a carrier as a stabilisation composition for halogen-containing polymers |
DE50307041T DE50307041D1 (de) | 2002-11-26 | 2003-11-25 | Salz einer halogenhaltigen oxysäure geträgert auf einem trägermittel als stabilisierungszusammensetzung für halogenhaltige polymere |
EP03780053A EP1565517B1 (de) | 2002-11-26 | 2003-11-25 | Salz einer halogenhaltigen oxysäure geträgert auf einem trägermittel als stabilisierungszusammensetzung für halogenhaltige polymere |
US11/140,395 US7179400B2 (en) | 2002-11-26 | 2005-05-26 | Stabilization composition for halogen-containing polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10255155A DE10255155B4 (de) | 2002-11-26 | 2002-11-26 | Stabilisierungszusammensetzung für halogenhaltige Polymere, Verfahren zu deren Herstellung und deren Verwendung |
DE10255155.3 | 2002-11-26 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/140,395 Continuation US7179400B2 (en) | 2002-11-26 | 2005-05-26 | Stabilization composition for halogen-containing polymers |
Publications (1)
Publication Number | Publication Date |
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WO2004048453A1 true WO2004048453A1 (de) | 2004-06-10 |
Family
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Family Applications (1)
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---|---|---|---|
PCT/EP2003/013256 WO2004048453A1 (de) | 2002-11-26 | 2003-11-25 | Salz einer halogenhaltigen oxysäure geträgert auf einem trägermittel als stabilisierungszusammensetzung für halogenhaltige polymere |
Country Status (9)
Country | Link |
---|---|
US (1) | US7179400B2 (de) |
EP (1) | EP1565517B1 (de) |
CN (1) | CN100519639C (de) |
AT (1) | ATE359318T1 (de) |
AU (1) | AU2003288166A1 (de) |
DE (2) | DE10255155B4 (de) |
ES (1) | ES2285219T3 (de) |
RU (1) | RU2309166C2 (de) |
WO (1) | WO2004048453A1 (de) |
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US7179400B2 (en) | 2002-11-26 | 2007-02-20 | Baerlocher Gmbh | Stabilization composition for halogen-containing polymers |
WO2011045168A1 (de) * | 2009-10-14 | 2011-04-21 | Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg | Stabilisator-kombinationen für halogenhaltige polymere |
WO2013083249A1 (de) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Alkali-aluminium-mischphosphite, verfahren zur ihrer herstellung sowie deren verwendung |
CN104114485A (zh) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | 亚磷酸氢铝与铝盐的混合物、其制备方法及其用途 |
CN104114486A (zh) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | 亚磷酸铝与难溶性铝盐和杂质离子的混合物、其制备方法及其用途 |
US9481831B2 (en) | 2011-12-05 | 2016-11-01 | Clariant International Ltd. | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
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DE10255154A1 (de) * | 2002-11-26 | 2004-06-09 | Baerlocher Gmbh | Stabilisatorzusammensetzung für halogenhaltige Polymere |
DE10359318A1 (de) † | 2003-12-17 | 2005-07-14 | Baerlocher Gmbh | Stabilisatorzusammensetzung für halogenierte Polymere |
FR2873380B1 (fr) * | 2004-07-20 | 2006-11-03 | Arkema Sa | Poudres de polyamides ignifuges et leur utilisation dans un procede d'agglomeration par fusion |
DE102004050480A1 (de) | 2004-10-15 | 2006-04-27 | Chemische Fabrik Budenheim Kg | Pigment für laserbeschriftbare Kunststoffe und dessen Verwendung |
DE102004050479A1 (de) | 2004-10-15 | 2006-04-27 | Chemische Fabrik Budenheim Kg | Formmasse für die Herstellung schwer entflammbarer Gegenstände, Pigment hierfür und dessen Verwendung |
KR100772793B1 (ko) | 2006-12-29 | 2007-11-01 | 주식회사 효성 | 내염소성 폴리우레탄 탄성섬유 |
DE102007037795A1 (de) * | 2007-08-10 | 2009-02-12 | Nabaltec Ag | Stabilisatorsysteme für halogenhaltige Polymere |
DE102007050428A1 (de) | 2007-10-22 | 2009-04-23 | Catena Additives Gmbh & Co. Kg | Verfahren zur Herstellung eines Granulates ausgehend von Triethanlamin und einem Alkali- bzw. Erdalkaliperchlorat |
KR20130008580A (ko) * | 2010-03-09 | 2013-01-22 | 교와 가가꾸고교 가부시키가이샤 | 합성 수지용 충전제, 합성 수지 조성물, 그 제조 방법, 및 그 성형품 |
JP2016053133A (ja) * | 2014-09-04 | 2016-04-14 | 株式会社Adeka | 塩化ビニル系樹脂用安定剤組成物、該安定剤組成物を用いた塩化ビニル系樹脂組成物及び該樹脂組成物から得られる成形品 |
EP3145937B1 (de) * | 2015-06-05 | 2018-06-06 | Galata Chemicals LLC | Stabilisatoren enthaltend hochreine mono-octylzinn und di-methylzinn verbindungen |
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- 2003-11-25 AT AT03780053T patent/ATE359318T1/de active
- 2003-11-25 RU RU2005119997/04A patent/RU2309166C2/ru not_active IP Right Cessation
- 2003-11-25 ES ES03780053T patent/ES2285219T3/es not_active Expired - Lifetime
- 2003-11-25 WO PCT/EP2003/013256 patent/WO2004048453A1/de active IP Right Grant
- 2003-11-25 CN CNB2003801042232A patent/CN100519639C/zh not_active Expired - Fee Related
- 2003-11-25 AU AU2003288166A patent/AU2003288166A1/en not_active Abandoned
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US7179400B2 (en) | 2002-11-26 | 2007-02-20 | Baerlocher Gmbh | Stabilization composition for halogen-containing polymers |
WO2007003433A2 (de) * | 2005-07-06 | 2007-01-11 | Baerlocher Gmbh | Feste organische salzzubereitung, deren herstellung und verwendung |
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CN104114485A (zh) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | 亚磷酸氢铝与铝盐的混合物、其制备方法及其用途 |
CN104114486A (zh) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | 亚磷酸铝与难溶性铝盐和杂质离子的混合物、其制备方法及其用途 |
CN104114484A (zh) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | 碱金属-铝-混合亚磷酸盐、其制备方法及其用途 |
US9481831B2 (en) | 2011-12-05 | 2016-11-01 | Clariant International Ltd. | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
US10202549B2 (en) | 2011-12-05 | 2019-02-12 | Clariant International Ltd. | Mixtures of aluminum phosphite with sparingly soluble aluminum salts and foreign ions, process for the production thereof and the use thereof |
US10421909B2 (en) | 2011-12-05 | 2019-09-24 | Clariant International Ltd. | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
Also Published As
Publication number | Publication date |
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CN1717442A (zh) | 2006-01-04 |
AU2003288166A1 (en) | 2004-06-18 |
DE10255155A1 (de) | 2004-06-09 |
ATE359318T1 (de) | 2007-05-15 |
RU2309166C2 (ru) | 2007-10-27 |
ES2285219T3 (es) | 2007-11-16 |
US20050288414A1 (en) | 2005-12-29 |
EP1565517B1 (de) | 2007-04-11 |
DE50307041D1 (de) | 2007-05-24 |
DE10255155B4 (de) | 2006-02-23 |
US7179400B2 (en) | 2007-02-20 |
CN100519639C (zh) | 2009-07-29 |
EP1565517A1 (de) | 2005-08-24 |
RU2005119997A (ru) | 2006-01-20 |
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