WO2000031171A1 - Copolymeres de monoxyde de carbone stabilises - Google Patents

Copolymeres de monoxyde de carbone stabilises Download PDF

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Publication number
WO2000031171A1
WO2000031171A1 PCT/EP1999/008741 EP9908741W WO0031171A1 WO 2000031171 A1 WO2000031171 A1 WO 2000031171A1 EP 9908741 W EP9908741 W EP 9908741W WO 0031171 A1 WO0031171 A1 WO 0031171A1
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Prior art keywords
carbon monoxide
component
monoxide copolymers
weight
stabilized
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PCT/EP1999/008741
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German (de)
English (en)
Inventor
Joachim Queisser
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Basf Aktiengesellschaft
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Priority to AU12713/00A priority Critical patent/AU1271300A/en
Publication of WO2000031171A1 publication Critical patent/WO2000031171A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • 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
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine

Definitions

  • the present invention relates to stabilized carbon monoxide copolymers containing random or alternating carbon monoxide copolymers (A), one or more inorganic metal salt compounds (B), one or more chelating metal deactivators (C) and one or more unsubstituted or substituted lactone compounds (D) and optionally additives (E).
  • the invention further relates to a process for the preparation of the carbon monoxide copolymers according to the invention and their use for the production of fibers, films and moldings.
  • the invention relates to fibers, films and moldings containing the stabilized carbon monoxide copolymers mentioned.
  • the class of compounds of carbon monoxide copolymers is well known to the person skilled in the art. This includes both copolymers with a statistical distribution of the monomer units and those with a linear, alternating structure.
  • the former are regularly accessible by radical means, as described in US Pat. No. 2,495,286, the latter using transition metal catalysts (cf. EP-A 0 121 965 and Drent et al., Chem. Rev.,
  • Carbon monoxide copolymers are generally composed of carbon monoxide and olefinically unsaturated monomers. Depending on the olefinic monomer, polymer molding compositions with thermoplastic as well as with elastomeric basic properties can be obtained. The technical possible uses of, in particular, linear, alternating carbon monoxide copolymers are correspondingly diverse.
  • EP-A 0 489 517 describes the addition of a combination of an epoxy compound and a phenol substituted with sterically demanding groups. Instead of phenolic According to the document mentioned, compounds can also be used aluminum alkoxides.
  • EP-A 0 714 938 and WO 96/33237 mixtures of conventional UV stabilizers and antioxidants can also be used to (melt) stabilize carbon monoxide copolymers.
  • EP-A 0 714 938 stabilizes carbon monoxide copolymers with the aid of three-component mixtures of a sterically hindered amine or phenol, a phosphite or phosphonite and a metal salt.
  • a suitable metal salt compound that the discoloration and embrittlement due to the presence of phosphites or phosphonites in carbon monoxide copolymers is suppressed and improved stabilization is observed.
  • the present invention was therefore based on the object of making available carbon monoxide copolymers which are sufficiently stable under oxidative or radiation-intensive conditions and, above all, under thermal treatment, in particular in the melt, and moreover allow processing under conditions customary for thermoplastic or elastomeric polymer molding compositions . Accordingly, stabilized carbon monoxide copolymers containing random or alternating carbon monoxide copolymers (A), one or more inorganic metal salt compounds (B), one or more chelating metal deactivators (C) and one or more unsubstituted or substituted lactone compounds (D) and optionally additives (E), found.
  • A random or alternating carbon monoxide copolymers
  • B inorganic metal salt compounds
  • C chelating metal deactivators
  • D unsubstituted or substituted lactone compounds
  • E optionally additives
  • the stabilized carbon monoxide copolymers according to the invention contain 85.0 to 99.9985% by weight of linear, alternating carbon monoxide copolymers (component (A)), 0.0005 to 5.0% by weight of inorganic metal salt compound (co - component (B)),
  • lactone compound (component (D)) substituted with at least one sterically demanding group, in each case based on the sum of components A) to D).
  • The% by weight of components A) to D) always add up to 100%.
  • copolymers of this class of compounds come into consideration as carbon monoxide copolymers.
  • Suitable copolymers exist either as statistical copolymers or in the form of linear alternating copolymers.
  • Statistical copolymers are generally synthesized in a radical manner, as described in US Pat. No. 2,495,286.
  • Linear alternating carbon monoxide copolymers are preferably used. These are usually obtained from carbon monoxide and ⁇ -olefinically unsaturated compounds catalyzed by transition metals.
  • Linear, alternating carbon monoxide copolymers can exist as binary, ternary or higher copolymer systems.
  • Carbon monoxide copolymers (A) are also understood here to mean any mixtures of the copolymers mentioned, that is to say, for example, mixtures of statistical and linear, alternating copolymers, mixtures of different binary or ternary carbon monoxide copolymers or mixtures of binary, ternary and / or higher copolymers.
  • the coal Accordingly, monoxide copolymers comprise both those carbon monoxide copolymers with thermoplastic and those with more elastomeric properties.
  • Suitable thermoplastic carbon monoxide copolymers usually have a melting point in the range from 50 to 300, preferably in the range from 100 to 250 ° C., and a viscosity number VZ (reduced viscosity), measured in o-dichlorobenzene / phenol (1: 1) as 0.5 % solution, in the range from 30 to 300, preferably from 50 to 250.
  • VZ reduced viscosity
  • ⁇ -olefins for the production of the carbon monoxide copolymers.
  • Particularly suitable as ⁇ -olefins are ethene and the C 3 - to C 4 -1-alkenes. Examples include ethene, propene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1-eicosen.
  • binary carbon monoxide copolymers preference is given to using ethene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene, in particular ethene and propene.
  • Suitable binary systems include carbon monoxide / ethene, carbon monoxide / propene, carbon monoxide / 1-butene, carbon monoxide / 1-pentene and carbon monoxide / 1-hexene copolymers.
  • the average molecular weight M n of carbon monoxide / ethene copolymers is usually above 10,000, preferably above 20,000 g / mol, that of carbon monoxide / propene copolymers generally above 5,000, preferably above 10,000 g / mol .
  • Binary carbon monoxide copolymers with C - to C nl ⁇ alkenes as described in German Patent Application No. 1 96 49 072, can also be used.
  • These elastomeric copolymers preferably have an average molecular weight M w greater than 15,000, preferably greater than 40,000 g / mol and a glass transition temperature (T g value) less than -20 ° C.
  • T g value glass transition temperature
  • copolymers with a molecular weight M w of 70,000, 100,000, 150,000, 200,000 and even 500,000 g / mol can also be used.
  • ⁇ -olefinic monomer units described for binary carbon monoxide copolymers are also suitable for non-binary copolymer systems, in particular ternary carbon monoxide copolymers.
  • Preferred higher copolymers are those whose one monomer component is selected from ethene, propene and 1-butene and whose second monomer component is selected from the group of the C 3 - to C rj-1-alkenes, in particular the C 3 - to C ⁇ n-1- Alkenes.
  • cycloolefins are also suitable for binary, ternary and also higher systems as olefinically unsaturated monomer components how Norbornene, cyclopentene or cyclopentadiene, ⁇ -olefinic monomers with ester, epoxy, ether and / or amide units such as C 1 -C 6 -alkyl (meth) acrylates, for example methyl methacrylate, or glycidyl methacrylate, vinyl ethers such as vinyl ethyl ether, acrylic or methacrylamides as well as vinyl aromatic monomers.
  • C 1 -C 6 -alkyl (meth) acrylates for example methyl methacrylate, or glycidyl methacrylate
  • vinyl ethers such as vinyl ethyl ether, acrylic or methacrylamides as well as vinyl aromatic monomers.
  • Suitable vinyl aromatic monomers are, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene or m-isopropylstyrene, in particular styrene.
  • Preferred ternary copolymer systems are terpolymers of carbon monoxide / ethene / C 3 -C 1 -C 1 -alkenes and carbon monoxide / propene / C or Cs-1-alkenes, in particular terpolymers of carbon monoxide, ethene and a C 3 - up to C ⁇ -1 alkene.
  • Carbon monoxide / ethene / propene terpolymers with a melting point in the range from 180 to 250 ° C. are very particularly preferred.
  • elastomeric terpolymers can also be used. These are essentially carbon monoxide / propene / or carbon monoxide / 1-butene / Cg to C 2 o-1 alkene terpolymers. These terpolymers generally have an average molecular weight M w greater than 40,000 g / mol and a T g value less than 20, preferably less than -10 ° C. Of course, these terpolymers can also be used with average molecular weights M w greater than 70,000, 150,000, 200,000, 500,000 or 1,000,000 g / mol.
  • the content of structural units in the carbon monoxide / propene / C 6 - to Co-1-alkene terpolymers based on propene is generally in the range from 0.1 to 70 mol%, preferably in the range from 5 to 60 mol% % and in particular in the range from 10 to 50 mol%, based on the total amount of terpolymer.
  • the molecular weight distribution M w / M n (weight average / number average) of the elastomeric binary and ternary carbon monoxide copolymers, determined by means of gel permeation chromatography (GPC) at 25 ° C. with Microstyragel (Waters) as column material and chloroform as solvent against polystyrene standard, is generally in the range from 1.2 to 10.0, but preferably assumes values less than 4.0.
  • Component (A) in the carbon monoxide copolymers according to the invention is generally in amounts in the range from 85 to 99.9985, preferably from 91 to 99.985 and particularly preferably from 94 to 99.97% by weight, based on the total weight of the components A) to D).
  • EP-A-0 485 035 or EP-A-0 702 containing vinyl aromatic monomer units reference is hereby expressly made to EP-A 0 486 103.
  • Elastomeric carbon monoxide copolymers, as described above, can be obtained by the processes described in DE-A-19 610 358 and German patent application No. 1 96 49 072. These manufacturing methods are hereby expressly included in the present disclosure.
  • Carbon monoxide copolymers can be produced in solution, suspension or in the gas phase.
  • the synthesis of carbon monoxide copolymers takes place most suitably with cationic transition metal catalysts based on the elements of group VIIIB of the periodic table, which have at least one bidentate chelate ligand with coordinating atoms of groups VA or VIA of the periodic table of the elements and as counterions not bad or not coordinating anions.
  • Linear alternating carbon monoxide copolymers can be obtained, for example, by copolymerizing carbon monoxide with ⁇ -olefinically unsaturated compounds in the presence of a catalyst system whose active composition is formed from a) a defined metal complex of the general formula (I)
  • M is a metal from group VIIIB of the periodic table of the elements, for example iron, cobalt, nickel, ruthenium, rhodium, osmium, iridium, platinum or palladium, in particular palladium
  • E 1 , E 2 is a non-metallic element from group VA of the periodic table of the elements , for example nitrogen, phosphorus or arsenic, preferably nitrogen or phosphorus, in particular phosphorus, a bridging structural unit, the elements connecting the units E 1 and E 2 being selected from groups IVA, VA and VIA of the Periodic Table of the Elements, R a to R d substituents selected from the group consisting of C ⁇ ⁇ to Cr_-Korgan-organic and C 3 - to C 3 o-organosilicon radicals, the radicals being one or more elements from groups IVA, VA, VIA and VIIA of the periodic table of the elements can contain L 1 , L 2 formally uncharged Lewis base ligands, for example amines
  • Ci to C r . -aliphatic radicals in particular methyl, ethyl, propyl, i-propyl, t-butyl or i-pentyl, C 3 - to cyclocaliphatic radicals, in particular cyclohexyl or cyclobutyl, C 6 - to C 4 -aryl radicals, in particular phenyl , Ci to C rj carboxylates, especially acetate, trifluoroacetate, propionate, oxalate, citrate or benzoate, salts of organic sulfonic acids, especially methyl sulfonate, trifluoromethyl sulfonate or p-toluenesulfonate, as well as halides, sulfates, hydride, phosphates or nitrates, and T a
  • 1,3-Propylene is particularly suitable as a bridging unit Z.
  • alkylene-bonded structural units Z can also be used in which an alkylene unit is replaced by an amino or phosphino functionality (-N (R ') - or -P (R') -).
  • Chelate ligands with nitrogen or phosphorus atoms in the bridge and catalyst systems for carbon monoxide copolymerization based on these ligand systems can be found in German patent applications DE-A 19651685 and DE-A 19651786. Reference is hereby expressly made to their disclosure.
  • Suitable carbon-organic radicals R a to R d are aliphatic, cycloaliphatic or aromatic radicals with 1 to 20 carbon atoms.
  • the phenyl, cyclohexyl and t-butyl group are preferably used, particularly preferably the phenyl group.
  • Suitable protonic acids b) are sulfuric acid, trifluoroacetic acid and p-toluenesulfonic acid; boron trifluoride, antimony pentafluoride and tris (pentafluorophenyl) borane are particularly suitable as Lewis acids b).
  • Suitable stabilizer components (B) are inorganic metal salt compounds such as metal oxides, for example zinc oxide, hydroxides, for example aluminum hydroxide, carbonates, sulfides, for example zinc sulfide, sulfates, phosphates, for example lanthanum phosphate or silicates.
  • metal oxides for example zinc oxide
  • hydroxides for example aluminum hydroxide
  • carbonates sulfides, for example zinc sulfide, sulfates, phosphates, for example lanthanum phosphate or silicates.
  • Preferred metal cations can be found in the groups of the alkali and alkaline earth metals, in particular the alkaline earth metals. Calcium and magnesium, in particular calcium, are particularly preferred.
  • the anionic counterions are sulfate, carbonate and especially phosphate and hydroxyphosphate.
  • the metal salt compounds are the alkali metal phosphates and, in particular, the alkaline earth metal phosphates and hydroxyl phosphates.
  • Calcium phosphate (Ca 3 (P0 4 )) and natural or synthetic hydroxyapatite (Ca ⁇ o (P0) 6 (OH)) are preferably used, calcium phosphate being particularly preferred.
  • Self-confidence Any mixtures of metal salt compounds (B) can of course be used.
  • the metal salt compounds (B) mentioned are sufficiently known to the person skilled in the art.
  • Component (B) in the carbon monoxide copolymers according to the invention is generally in amounts in the range from 0.0005 to 5.0, preferably from 0.005 to 3.0 and particularly preferably from 0.01 to 2.0% by weight, based on the total weight of components (A) to (D).
  • Chelating metal deactivators are used as stabilizer component (C).
  • organic compounds with a 1,3-diketone unit such as stearoylbenzoylmethane or dibenzoylmethane and compounds of hydrazine, e.g.
  • N N'- bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine and 2,2'-oxalyldiamidodi- (ethyl-3- (3,5-di-tert -butyl-4-hydroxyphenyDpropionat) are for example under the name Irganox ® 1024 MD (Ciba Specialty Chemicals) or Naugard ® XL-1 (Uniroyal) available.
  • Component (C) in the carbon monoxide copolymers according to the invention is generally in amounts in the range from 0.0005 to 5.0, preferably from 0.005 to 3.0 and particularly preferably from 0.01 to 2.0% by weight, based on the total weight of components A) to D).
  • the stabilizer component (D) is an unsubstituted or substituted lactone compound.
  • ⁇ -, ⁇ - or ⁇ -lactones and in particular ⁇ -lactones are suitable.
  • Lactones which are derived from phenolic or naphtholic compounds which are substituted ortho-permanently to the phenolic or naphtholic hydroxyl group with a radical carrying a carboxylic acid functionality are preferred. This particularly includes compounds from the class of benzofuran-2-ones.
  • lactones mentioned preference is again given to those which are in the vicinity of the alkoxy unit and / or in the vicinity of the carbonyl group, i.e. have a sterically demanding substituent in the ⁇ or ⁇ position, preferably in the ⁇ position.
  • lactone compounds are covered, for example, by formula II
  • R 1 is unsubstituted or with Ci to Cin-alkyl, in particular Ci to C ß -alkyl, ⁇ to C ⁇ _-alkoxy, in particular Ci to C6 alkoxy, Ce ⁇ to C ⁇ aryl, with functional-group on the base of the elements of groups IVA, VA, VIA or VIIA of the periodic table of the elements substituted C 6 - to C ⁇ -aryl, hydroxy, halogen, amino, C - to Cirj-alkylamino, in particular Ci- bi ⁇ C -alkylamino, phenylamino or di - (C] _- to C ⁇ o ⁇ alkyl) amino.
  • di- (C ⁇ - to C -alkyl) amino substituted phenyl, naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetra- hydro-1-naphthyl, thienyl, benzo [b] thienyl, naphthol [2, 3 -b] thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl Indolyl,
  • Indazolyl purinyl, quinolizinyl, isoquinolyl, quinoline, phthalazinyl, naphthyridinyl, quinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, ß-carbolineyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolothiazyl, phenolyl, phenazylyl, phenazylyl, phenazylyl, phenazylyl
  • R 2 to R 5 independently of one another are hydrogen, chlorine, hydroxy, C 1 -C 25 -alkyl, C 7 -Cg -phenylalkyl, phenyl which is unsubstituted or substituted by C 1 -C 4 -alkyl, in particular C 1 -C 4 -alkyl, unsubstituted or by C ⁇ "C ⁇ o- alkyl particular Ci to C alkyl, substituted C 5 -C 6 cycloalkyl, C ⁇ -C ⁇ 8 -alkoxy, C ⁇ 8 alkylthio, C ⁇ -C 4 alkylamino, di- (C ⁇ -C 4 -alkyl) amino,
  • Ci-C5 alkanoyloxy, Ci -C 25 alkanoylamino, C 3 -C 5 alkenoyloxy, by oxygen, sulfur or> NR '(R' Ci to C 6 alkyl or C 6 - to C 10 -aryl ) represent interrupted C 3 -C 25 alkanoyloxy, C 6 -C 9 cycloalkylcarbonyloxy, benzoyloxy or benzoyloxy substituted by C 1 -C 4 alkyl, or furthermore the radicals R 2 and R 3 or the radicals R 3 and R 4 and R 5 together with the carbon atoms to which they are attached form a benzene ring, R 4 additionally represents (CH 2 ) p -C0R 'or - (CH) q 0H,
  • R 6 is hydrogen or unsubstituted or substituted by functional groups based on the elements of groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements Ci to Cio alkyl, C to Cirj cycloalkyl, C 6 to C ⁇ 4 aryl.
  • Preferred compounds (II) are those in which the radical R 1 is phenyl or naphthyl, in particular phenyl, or phenyl or naphthyl, in particular phenyl, substituted one or more times with C 1-6 alkyl groups.
  • Particularly preferred as radical R 1 is phenyl substituted in the ortho and meta or in the meta and para position with methyl, ethyl, i-propyl or tert-butyl, preferably methyl.
  • radicals R 2 and R 4 also mean i-propyl, tert-butyl or cyclohexyl, in particular tert-butyl, and the radicals R 3 , R 5 and R 6 are hydrogen or Methyl, especially hydrogen. It is also preferred
  • any mixtures of the compounds of component (D) described can also be used.
  • Component (D) in the carbon monoxide copolymers according to the invention is generally in amounts in the range from 0.0005 to 5.0, preferably from 0.005 to 3.0 and particularly preferably from 0.01 to 2.0% by weight, based on the total weight of components (A) to (D).
  • Compounds (D) e.g. of the type of benzofuran-2-ones as described above, which are preferably used as component (D), are known to the person skilled in the art and can be obtained, for example, according to the regulations according to US 4,325,863, US 5,175,312, US 5,488,117 or US 5,516,920.
  • An isomer mixture of 3 - (2, 3 -di-methyl-phenyl) - and 3 - (3, 4 -di-methyl-phenyl) -5, 7-di-tert-butyl-benzofuran-2-one is e.g. commercially available under the name HP 136 (Ciba Specialty Chemicals).
  • Preferred stabilizer mixtures for the carbon monoxide copolymers according to the invention are those based exclusively on components (B), (C) and (D).
  • Particularly advantageous stabilizer mixtures contain calcium phosphate or hydroxyphosphate as component (B), N, N 'bis (3 - (3, 5-di-tert-butyl-4-hydroxyphenyDpropionyl) hydrazine as component (C) and as component ( D) one or more benzofuran-2 -ones of the formula (II) in which R 1 is phenyl or with methyl, ethyl, 1-propyl or t-butyl, in particular methyl, one or two, in particular two, preferably in 2- and 3- or 3- and 4-position, substituted phenyl, R 2 and R 4 are methyl, ethyl, i-propyl or 2-butyl, in particular t-butyl, and R 3 , R 5 and R 6 are hydrogen.
  • the stabilized carbon monoxide copolymers according to the invention can be obtained by customary processes.
  • components (B) to (D) can be mixed into the carbon monoxide copolymer (A) in the form of a powder or granules, preferably as a powder, in the dry state.
  • the stabilizer constituents can also be used with the carbon monoxide copolymer which has not yet been completely freed from solvent residues, as in generally arises in the transition metal-catalyzed copolymerization.
  • the stabilizer components are advantageously added before component (A) begins to be thermally stressed.
  • components (B) to (D) are added is not critical as long as a homogeneous distribution of the stabilizer components (B) to (D) in the carbon monoxide copolymer (A) is ensured.
  • Components (B) to (D) forming the stabilizer system can be added individually or together, ie premixed, dry or in the form of a solution or suspension to component (A).
  • the solvent or suspension medium is usually removed, for example by applying a vacuum. Small amounts of solvent or suspending agent are tolerated during further processing without there being any subsequent or decomposition reactions.
  • Suitable solvents or suspending agents include low molecular weight alcohols such as methanol or ethanol, aromatic hydrocarbons such as toluene or xylene, ketones such as acetone or methyl ethyl ketone, ethers such as diethyl ether or tetrahydrofuran or halogenated hydrocarbons such as dichloromethane or chloroform.
  • the process of mixing components (A) to (D) can also be carried out under a protective gas atmosphere, e.g. in the presence of argon or nitrogen.
  • the mixture of components (A) to (D) obtainable according to the above process can be used in the melt in a conventional manner, e.g. Stabilized carbon monoxide copolymers can be produced by means of presses or plate presses, kneading, extrusion or blow molding. Temperatures in the range from 230 to 290 ° C. are generally sufficient for the assembly of the mixture from components (A) to (D). For large-scale extrusion applications, it is advisable to introduce the homogeneous mixture of components (A) to (D) into the extruder in an upstream feed unit, e.g. a so-called stuffing screw. If appropriate, the stabilized carbon monoxide copolymers can also be prepared in the presence of a protective gas atmosphere, for example under argon or nitrogen.
  • a protective gas atmosphere for example under argon or nitrogen.
  • additives can also be added to the carbon monoxide copolymers according to the invention.
  • additives are understood to mean fibrous or particulate fillers, processing aids, light stabilizers, dyes, pigments or antistatic agents.
  • Processing aids, light stabilizers, dyes, pigments and antistatic agents are generally used in amounts of 0 to 5, preferably 0.1 to 3.0 and particularly preferably 0.15 to 1.0% by weight, but fillers are generally used in amounts from 0 to 50, preferably from 3 to 40 and particularly preferably from 5 to 30% by weight, in each case based on the sum of additive and stabilized carbon monoxide copolymer.
  • Carbon, aramid or glass fibers are particularly preferred as reinforcing agents.
  • the glass fibers used can be made of E, A or C glass and are preferably with a size, e.g. based on epoxy resin or polyurethane and an adhesion promoter based on functionalized silanes, e.g. Aminosilanes, equipped. Their diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used.
  • Fillers or reinforcing materials such as carbon black, graphite, glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder or wollastonite can also be added.
  • Resorcins Rosorcins, salicylates, benzotriazoles or benzophenones can be used.
  • the carbon monoxide copolymers according to the invention can be prepared in a known manner, e.g. by means of injection molding or extrusion, to form fibers, films and moldings and behave sufficiently melt-stable under the customary conditions used in the assembly. Temperatures in the range from 230 to 290 ° C., even over a period of 20 to 60 minutes, do not lead to noticeable decomposition or crosslinking reactions which disrupt further processing. Accordingly, little or no molecular weight degradation and little or no discoloration of the melt is observed.
  • the structure of the carbon monoxide copolymers was determined by means of ⁇ H NMR and 13 C NMR spectroscopy on a device from the Bruker company.
  • the viscosity numbers were at 0.5 wt. % polymer solutions in a capillary viscometer from Schott, type: 53720/11 at room temperature in an equimolar mixture of ortho-dichlorobenzene and phenol.
  • the melt stabilities were determined using a Rheica Cord 90 kneader from Fima Haake at 250 ° C. and 60 rpm.
  • the change in torque over time at constant speed served as a measure of the melt stability.
  • the torque was registered by a measuring unit integrated in the kneader and the torque curve recorded directly via a recorder connected to the kneader.
  • Irganox ® 1024 MD N, N '-bis (3 - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine (0.2 wt .-%) (component C )),
  • Irganox ® 1024 MD (0.2 wt .-%)
  • Irganox ® 1076 (0ctadecyl-3 - (3, 5-di- tert-butyl-4-hydroxy phenyl) propionate) (0.2 wt .-%);
  • Irganox ® 245 triethylene glycol bis - [3 - (5 - tert-butyl -4 - hydroxy-m-tolyl) propionate] (0.2 wt .-%);
  • Calcium phosphate (0.5 wt .-%), Irganox ® 1076 (0.2 wt .-%), Irgafos ® 168 (0.2 wt .-%);
  • Calcium phosphate (0.5 wt .-%), Irganox ® 245 (0.05 wt .-%), Irgafos ® 168 (0.05 wt .-%);
  • the stabilizers listed with the names Irganox ® , Irgafos ® , HP 136 and HP 2225 FF are products of Ciba Specialty Chemicals.
  • VZ viscosity number
  • the stabilizer compounds (for amounts and components of the mixtures used, see under I.) were mixed dry into the carbon monoxide copolymer (55 g) and homogenized for several hours using a wheelchair as a mixing device.
  • the measuring kneader Rheocord 90 was operated under an argon atmosphere at 20 250 ° C. and a speed of 60 rpm. For easier handling, the according to III. The mixtures obtained are pressed into tablets at room temperature and metered into the measuring kneader under argon. After a short melting phase, the torque curve was recorded over a period of 25 minutes. The viscosity number was determined from samples taken from the kneader at regular intervals.
  • Table 2 shows the viscosity numbers of melt samples of the carbon monoxide copolymers stabilized with the mixtures Ml to M5 as a function of the kneading time.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne des copolymères de monoxyde de carbone stabilisés contenant des copolymères de monoxyde de carbone (A) statiques ou alternants, au moins un composé sel métallique inorganique (B), au moins un désactivateur métallique (C) d'action de chélation et au moins un composé lactone (D) substitué ou non substitué et éventuellement d'autres additifs (E).
PCT/EP1999/008741 1998-11-20 1999-11-12 Copolymeres de monoxyde de carbone stabilises WO2000031171A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU12713/00A AU1271300A (en) 1998-11-20 1999-11-12 Stabilised carbon monoxide copolymerizates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853707A DE19853707A1 (de) 1998-11-20 1998-11-20 Stabilisierte Kohlenmonoxidcopolymerisate
DE19853707.7 1998-11-20

Publications (1)

Publication Number Publication Date
WO2000031171A1 true WO2000031171A1 (fr) 2000-06-02

Family

ID=7888524

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/008741 WO2000031171A1 (fr) 1998-11-20 1999-11-12 Copolymeres de monoxyde de carbone stabilises

Country Status (3)

Country Link
AU (1) AU1271300A (fr)
DE (1) DE19853707A1 (fr)
WO (1) WO2000031171A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202017002839U1 (de) 2017-05-30 2018-08-31 Perlon Nextrusion Monofil GmbH Polyketonfasern, deren Herstellung und Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010524A1 (fr) * 1990-12-05 1992-06-25 Dsm N.V. Composition de copolymere ethylene-monoxyde de carbone
US5175312A (en) * 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
EP0714938A2 (fr) * 1994-11-29 1996-06-05 Shell Internationale Researchmaatschappij B.V. Stabilisation de polycétones
DE19808938A1 (de) * 1997-03-06 1998-10-08 Ciba Geigy Ag Stabilisierung von Polycarbonaten, Polyester und Polyketonen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5175312A (en) * 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
WO1992010524A1 (fr) * 1990-12-05 1992-06-25 Dsm N.V. Composition de copolymere ethylene-monoxyde de carbone
EP0714938A2 (fr) * 1994-11-29 1996-06-05 Shell Internationale Researchmaatschappij B.V. Stabilisation de polycétones
DE19808938A1 (de) * 1997-03-06 1998-10-08 Ciba Geigy Ag Stabilisierung von Polycarbonaten, Polyester und Polyketonen

Also Published As

Publication number Publication date
AU1271300A (en) 2000-06-13
DE19853707A1 (de) 2000-05-25

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