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WO1999060056A1 - Copolymerisats de monoxyde de carbone ignifuges stables en fusion - Google Patents

Copolymerisats de monoxyde de carbone ignifuges stables en fusion Download PDF

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Publication number
WO1999060056A1
WO1999060056A1 PCT/EP1999/003198 EP9903198W WO9960056A1 WO 1999060056 A1 WO1999060056 A1 WO 1999060056A1 EP 9903198 W EP9903198 W EP 9903198W WO 9960056 A1 WO9960056 A1 WO 9960056A1
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Prior art keywords
carbon monoxide
copolymers
weight
monoxide copolymers
copolymers according
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German (de)
English (en)
Inventor
Joachim Queisser
Martin Klatt
Thomas Heitz
Peter Wolf
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BASF SE
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BASF SE
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Priority to EP99920862A priority Critical patent/EP1084180A1/fr
Priority to AU38282/99A priority patent/AU3828299A/en
Publication of WO1999060056A1 publication Critical patent/WO1999060056A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate

Definitions

  • the present invention relates to flame-retardant, melt-stable carbon monoxide copolymers containing
  • the invention further relates to a process for the production of flame-retardant carbon monoxide copolymers and their use for the production of moldings, fibers, films and coatings.
  • the class of compounds of carbon monoxide copolymers is that
  • alkaline earth metal carbonates are used as halogen-free flame retardants for carbon monoxide copolymers.
  • Calcium carbonate is preferred in amounts of 2 to 30% by weight, based on the total weight of the copolymer.
  • the present invention was therefore based on the object of finding flame retardants for carbon monoxide copolymers which do not have a disadvantageous effect on the melting behavior of carbon monoxide copolymers, at the same time enable very effective flame retardancy even in small amounts and do not falsify the mechanical properties of carbon monoxide copolymers.
  • Carbon monoxide copolymers are also to be understood here to mean any mixtures of the copolymers mentioned, i.e., for example Mixtures of statistical and linear alternating
  • the flame-retardant carbon monoxide copolymers according to the invention accordingly comprise both those carbon monoxide copolymers with thermoplastic and those with elastomeric properties.
  • Suitable carbon monoxide copolymers usually have a melting point in the range from 100 to 300, preferably in the range from 150 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 50 to 300, preferably from 100 to 250.
  • ⁇ -olefins are ethene and the C 3 - to C 2 -1-alkenes.
  • ⁇ -olefins 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 1 -C 2 ol 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 and even 500,000 g / mol can also be used. 5
  • the ⁇ -olefinic monomer units described for binary carbon monoxide copolymers can also be used for non-binary copolymer systems, in particular ternary carbon monoxide copolymers.
  • Such higher copolymers one of which 10 monomer component is selected preferably is selected from ethene, propene and 1-butene and the second monomer from the group of C 3 - to C 2 _ ol alkenes, in particular C 3 - to CIO 1- Alkenes.
  • olefinically unsaturated monomer components also conjugated or isolated C 5 - to C 0 -dienes, for example 1,4-hexadiene or 1, 5-hexadiene, cycloolefins such as norbornene or cyclopentadiene, ⁇ -olefinic monomers with ester , Ether or amide units such as -C ⁇ to C 3 alkyl (meth) acrylates, for example
  • vinyl ethers such as vinyl ethyl ether, aryl or methacrylamides and 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 partially crystalline thermoplastic terpolymers made of carbon monoxide / ethene / C - to C ⁇ o-1-alkenes and carbon monoxide / propene / C 4 - to C ⁇ _o-1-alkenes, especially terpolymers made of carbon monoxide, ethene and a C 3 - bis
  • elastomeric terpolymers can also be used.
  • 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.
  • M w average molecular weight
  • T g value less than 20 preferably less than -10 ° C.
  • the content of structural units in the carbon monoxide / propene / C 6 - to C 2 o-1-alkene terpolymers due to propene is generally in the range from 0.1 to 70 mol%, preferably in the range from 5 to
  • 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 6.0, but preferably assumes values less than 4.0.
  • Processes for producing linear alternating carbon monoxide copolymers are among others in EP-A-0 485 035 or EP-A-0 702 045.
  • EP-A 0 486 103 Elastomeric carbon monoxide copolymers, as described above, can according to the in DE-A-19 610 358 and the German patent application Az. 1 96 49 072 described processes can be obtained. These manufacturing methods are hereby expressly included in the present disclosure.
  • 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 which carry non- or poorly coordinating anions as counterions.
  • Linear alternating carbon monoxide copolymers can be obtained, for example, by copolymerizing carbon monoxide with ⁇ -olefinically unsaturated compounds in a virtually alcohol-free or water-free polymerization medium in the presence of a catalyst whose active composition is formed from a) a 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 an element from group VA of the periodic table of the elements, for example nitrogen, phosphorus, arsenic or antimony, preferably nitrogen or phosphorus, in particular phosphorus,
  • Z is 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 to R d substituents selected from the group consisting of C ⁇ ⁇ to C 2 o _ carbon-organic and C 3 - to C 3 o-organosilicon radicals, the radicals being a
  • L 1 , L 2 formally uncharged Lewis base ligands, for example a ine, nitriles such as aceto-, propio- or benzonitrile, ketones such as acetone or acetylacetone, ethers such as dimethyl ether, diethyl ether or tetrahydrofuran or water, in particular water ,
  • Lewis base ligands for example a ine, nitriles such as aceto-, propio- or benzonitrile, ketones such as acetone or acetylacetone, ethers such as dimethyl ether, diethyl ether or tetrahydrofuran or water, in particular water ,
  • T is a mono- or divalent anion, for example perchlorate, sulfate, phosphate, nitrate, carboxylate, organosulfonate or organoborate, r, s 1 or 2,
  • an activator component which contains a hydroxyl group in the molecule which, based on M in (I), is used in an amount of 0 to 1500 molar equivalents.
  • alternating carbon monoxide copolymers can be obtained by copolymerizing carbon monoxide and ⁇ -olefinically unsaturated compounds in the presence of a catalyst system whose active composition is formed from i) a metal complex of the general formula (II)
  • 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 an element from group VA of the periodic table of the elements, for example nitrogen, phosphorus, arsenic or antimony, preferably nitrogen or phosphorus, in particular phosphorus
  • Z is 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 C 2 o-Korganganganischen and C 3 - to C 3 o-organosilicon radicals, the radicals a
  • Element or more elements of groups IVA, VA, VIA and VIIA of the periodic table of the elements can contain L 1 , L 2 formally charged organic or inorganic ligands, for example C 3 - to C 20 _ aliphatic radicals, in particular methyl, ethyl, propyl , i-propyl, t-butyl or i-pentyl, C 3 - to 0 C ⁇ cycloaliphatic radicals, especially cyclohexyl, or cyclobutyl, C ⁇ - to C ⁇ -Arylre- ste, in particular phenyl, Ci to C 2 ⁇ "carboxylates, and in special acetate, trifluoroacetate, propionate, oxalate,
  • organic or inorganic ligands for example C 3 - to C 20 _ aliphatic radicals, in particular methyl, ethyl, propyl , i-propyl, t-butyl or
  • Citrate or benzoate salts of organic sulfonic acids, in particular methyl sulfonate, trifluoroethyl sulfonate or p-toluenesulfonate, and also halides, sulfates, hydrod, phosphates or nitrates, and ii) one or more Lewis or protonic acids or a mixture of Lewis and / or protonic acids.
  • 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 phosphinofunctionality (-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 methyl, ethyl, 1-propyl, l-propyl, 1-butyl, t-butyl, 1-hexyl, benzyl, phenyl, ortho-anisyl, cyclopropyl or cyclohexyl group are suitable.
  • the phenyl, cyclohexyl and t-butyl group are preferably used, particularly preferably the phenyl group.
  • Suitable protonic acids ii) are sulfuric acid, trifluoroacetic acid and p-toluenesulfonic acid, while Lewis acids ii) are particularly suitable as boron trifluoride, antimony pentafluoride and T ⁇ s (pentafluorophenyl) borane.
  • Particularly suitable metal complexes (II) are bis -1,3 (diphenylphoshmo) propane-palladium-bis-acetate, bis-1,3, [di (2-methoxyphenyl) phosph ⁇ no] propane-palladium-bis-ace- tat, bis (diphenylphosphinomethyl) phenyla in palladium bis acetate and bis (diphenylphosphinomethyl) t butylamine palladium bis acetate.
  • the flame-retardant carbon monoxide copolymers contain, as flame retardants B), mineral compounds i) and b 2 ), where
  • the basic magnesium carbonates b 2 can be used in water-containing, ie containing water of crystallization or physisorbed water, and in anhydrous form.
  • the naturally occurring mineral hydromagnesite is particularly suitable.
  • the compounds bi) and b 2 ) generally have average grain sizes in the range from 0.01 to 50 ⁇ m. Average grain sizes of less than 20 ⁇ m are preferred, particularly preferably less than 5 ⁇ m.
  • the mineral compounds bi) and b 2 ) can either be untreated or pretreated with a suitable sizing material.
  • a suitable sizing material All conventional sizes suitable for glass fibers can be used as size materials. These are, for example, functionalized silane sizing or sizing based on starch.
  • silane sizes for example, amino, epoxy or vinyl silanes are used. Sizes made from multi-functionalized silanes such as aminosilanes with epoxy or urethane units are also possible. Sizes are also frequently used which also have polyurethane components.
  • Suitable silane compounds are those of the formula
  • f is an integer from 2 to 10
  • h is an integer from 1 to 5
  • preferably 1 to 2 g is an integer from 1 to 3, preferably 1
  • Preferred sizes are, for example, vinyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, beta-3, trimethoxysilane -Epoxycyclohexylethyl-, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -amino-propyltrimethoxysilane, aminobutyltrimethoxysilane, aminobutyltriethoxysilane Aminopropyltri- ethoxysilane, or also the corresponding glycidyl derivatives.
  • untreated mineral bi can be present in addition to untreated mineral b 2 ) or mineral treated bi) in addition to untreated mineral b 2 ).
  • the compounds bi) and b 2 ) can be added separately in any order or else premixed in the production of the carbon monoxide copolymers according to the invention.
  • the carbon monoxide copolymers according to the invention can contain 0 to 5, preferably 0.01 to 3.0 and particularly preferably 0.1 to 1.0% by weight of an antioxidant. These are usually phenols shielded with sterically demanding groups or secondary aliphatic amines, hydroquinones, pyrocatechols, aromatic amines or metal complexes. Dithiocarbamates, phosphonites or phosphites can also be used as antioxidants. Mixtures of the aforementioned compounds are also possible.
  • Suitable phenols shielded with sterically demanding groups are in principle all compounds with a phenolic structure which have at least one sterically demanding group, preferably at least two sterically demanding groups on the phenolic ring
  • At least one sterically demanding group should be in close proximity to the OH group, i.e. are in the ortho or meta position, preferably in the ortho position.
  • These antioxidants are described, for example, in DE-A 27 02 661 (US 4,360,617).
  • Suitable phenolic antioxidants mostly go back to alkylphenols, hydroxyphenylpropionates, aminophenols, bisphenols, alkylidene bisphenols or thiobisphenols.
  • Another group of suitable phenols is derived from substituted benzoecarboxylic acids, especially substituted benzoepropionic acids.
  • Examples of the compound class of sterically hindered phenols are 4-methyl-2, 6-di-tert-butylphenol (BHT), 4-methoxymethyl-2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl -4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4'-methylene- bis- (2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4,4-di-tert-butylphenyl ester, 2,2-bis- (4-hydroxypheny1 ) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 1, 6-hexanediol-bis-3- (3, 5-di-tert-buty
  • hydroquinone and its substituted derivatives for example 2,5-dihydroxy-1,4-di-tert-butylbenzene, 2,5-dihydroxy-1-tert-butylbenzene or tocopherol.
  • Aromatic amines are 4-isopropylamino-1-anilinobenzene, 1,4-dianilinobenzene,
  • a suitable sterically hindered aliphatic amine also abbreviated to HALS for example, is bis (2, 2, 6, 6-tetra-methyl-4-piperidyl) sebaceate.
  • a suitable metal complex is the copper (II) salt from
  • the preferred phosphorus-containing compounds used are phosphonites and phosphites.
  • phosphonites are particularly preferably used: bis - (2,4-di-tert-butylphenyl) -phenylphosphonite, tris (2, -dit-tert-butylphenyl) -phosphonite, tetrakis (2, 4-di-tert.
  • diphosphonites tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphonite, tetrakis - (2,4-di-tert-butylphenyl) -1,6 -hexylylene- are very particularly suitable.
  • Alkylaryl phosphites are also used as phosphorus-containing compounds. Both diarylmonoalkylphosphites such as bis- (p-tert-butylphenyl) octadecylphosphi, diphenylisodecylphosphite, diphenyldecylphosphite and 2-ethylhexyldiphenylphosphite as well as monoaryl dialkylphosphites such as diisodecylphitylphitylphitophyllite are suitable.
  • diarylmonoalkylphosphites such as bis- (p-tert-butylphenyl) octadecylphosphi, diphenylisodecylphosphite, diphenyldecylphosphite and 2-ethylhexyldiphenylphosphite
  • monoaryl dialkylphosphites such as di
  • Beson ⁇ ers oevorzu ⁇ t are with; high-quality groups suDstiiu erce pheno_ ⁇ scne antioxidants such as octadecyl 3- (3,5-d ⁇ - t butyl 4 nydroxy pnenyl) prcpanoat and mixtures of the above-mentioned compounds with at least one phosphorus-containing compound, msbeson ⁇ ere D stearyl-3, 5-d ⁇ -tert- butyl-4-hy ⁇ roxy-benzylphosphonate, 3, 5-B ⁇ s (tert-butyl) -4-hydroxyoenzylphospnonsau - rediethyl ester, tris- (nonylphenyl) phosphite, tris- (2, 4-d ⁇ e-t ⁇ rt-butylphenyl) phosphi and / or bis -stearyl-pentaeryth ⁇ tol- diphosphi.
  • alkaline earth phosphates in particular calcium phosphate (Ca 3 (P ⁇ 4 ) 2
  • Ca 3 (P ⁇ 4 ) 2 calcium phosphate
  • the flame-retardant carbon monoxide copolymers according to the invention contain 0 to 25, preferably 5 to 20 and particularly preferably 10 to 20% by weight of a rubber-elastic polymer (often also referred to as rubber or impact modifier).
  • Natural or synthetic rubbers can be used as component D).
  • the impact modifiers include polyoutadiene, polyisoprene, polyisooutylene or copolymers of butadiene and / or isoprene with styrene and other comonomers, the glass transition temperature, determined according to K.H. Illers and H. Breuer, Kolloidzeitsch ⁇ ft 190 (1), pp. 16-34 (1963), of about -100 bs 25 ° C, preferably below 10 ° C.
  • Correspondingly hydrogenated products can also be used.
  • Suitable rubber-elastic polymers gener for example back to graft rubbers with a crosslinked elastomeric core, which is preferably derived from butadiene, isoprene or alkyl acrylates, and a graft shell made from polystyrene.
  • Copolymers of ethene and acrylates or methacrylates as well as the so-called ethylene-propylene (EP) and ethylene-propylene-diene (EPDM) rubbers are also suitable, as are the EP or EPDM rubbers grafted with styrene.
  • Preferred impact modifiers are block copolymers of vinyl aromatics and dienes. Impact modifiers of this type are known. In DE-AS 1 932 234, DE-AS 2 000 118 and the DE-OS 2 255 930 describes differently constructed vinyl aromatic and diene blocks comprising elastomeric block copolymers. The use of corresponding hydrogenated block copolymers, optionally in a mixture with the non-hydrogenated precursor as an impact modifier, is described, for example, in DE-OS 2 750 515, DE-OS 2 434 848, DE-OS 3 038 551, EP-A-0 080 666 and WO 83/01254. Reference is hereby expressly made to the disclosure of the above publications.
  • the vinyl aromatic compounds mentioned are generally styrene, ⁇ -methylstyrene, vinyl toluene, vinyl or isopropenyl naphthalene. Styrene is preferred as the vinyl aromatic.
  • Particularly suitable dienes are, for example, butadiene, isoprene, 1,3-pentadiene or 2,3-dimethylbutadiene.
  • Preferred impact modifiers are further block copolymers of vinyl aromatics and dienes, which are characterized in that at ⁇ a pure diene rubber place a soft block of diene and vinyl aromatic is present, said diene and vinyl aromatics are distributed statistically in the soft block.
  • transitions between the blocks can be both sharp and smeared.
  • Mixtures of block copolymers of different structures e.g. Mixtures of two- and three-block copolymers or of hydrogenated and unhydrogenated block copolymers can also be used.
  • Suitable products are also commercially available, for example the ethylene-methacrylic acid copolymer "Nucrel ® 0910” from DuPont, the ethylene-acrylic acid ester-maleic anhydride terpolymer “Lotader ® 4720” from Elf Atoche or poly (ethylene-co-propylene) g-maleic anhydride) from Exxon Chemical (“Exxelor VA 1803).
  • Suitable block copolymers with at least one vinylaromatic and one elastomeric block are commercially available. Examples include the Carif1ex ® - R types (Shell), the Kraton ® types (Shell), the Finaprene (Fina) and the Europrene ® -SOL-TR types (Eniehern).
  • the carbon monoxide copolymers according to the invention can contain additives in proportions of 0 to 40% by weight, based on the total amount of carbon monoxide copolymer.
  • additives are understood to mean fibrous or particulate fillers, processing aids, stabilizers, dyes, pigments or antistatic agents.
  • the additives which are suitable according to the invention are essentially or completely halogen-free.
  • Processing aids and stabilizers are generally used in amounts of from 0.01 to 5, preferably from 0.1 to 1.0 and particularly preferably from 0.15 to 0.5% by weight, whereas reinforcing agents are generally used in amounts of 5 to 40, preferably from 5 to 30 and particularly preferably from 10 to 20% by weight, in each case based on the sum of components A) to E).
  • Carbon, aramid or glass fibers are particularly preferred as reinforcing agents E).
  • 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 as described for compounds of component B). 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.
  • Metal flakes, metal powder, metal fibers, metal-coated fillers (e.g. nickel-coated glass fibers) and other additives that shield electromagnetic waves are also mentioned.
  • metal flakes come into consideration for the latter purpose, furthermore the mixing of this mass with additional carbon stars, carbon black or nickel-coated carbon fibers.
  • Resorcins Rosorcins, salicylates, benzotriazoles or benzophenones can be used.
  • the flame-retardant carbon monoxide copolymers according to the invention can be produced by conventional mixing methods, for example by means of extrusion or kneading, from the constituents A) and B) and, if appropriate, C) to E).
  • the mixing process usually takes place at temperatures in the range from 180 to 250.degree.
  • the order in which the individual constituents A) to E) are added is generally not important.
  • the components bi) and b 2 > of component B) can also be added to the copolymer either separately or premixed.
  • the homogeneous is decisive Distribution of the flame retardant and optionally components C) to E) in the polymer matrix of the carbon monoxide copolymer.
  • components B) to E), in particular component C), are incorporated into the carbon monoxide copolymer during the preparation thereof, ie the carbon monoxide copolymerization takes place in the presence of components B), C), D) and / or E).
  • the flame-retardant carbon monoxide copolymers according to the invention can be processed in a known manner, for example by means of injection molding, to give moldings. Fibers, films and coatings made from the material according to the invention are also accessible.
  • the flame-retardant carbon monoxide copolymers according to the invention have good mechanical properties and, at the same time, very good flame retardancy.
  • the molding compositions according to the invention are extremely stable to melting, even with continued tempering, and can be processed without problems.
  • the viscosity, determined by means of a capillary or plate rheometer, of the carbon monoxide copolymers according to the invention at an annealing at 230 ° C. for 30 minutes is reproducibly below 900 Pas. With a tempering time of 1 hour, a value of 1300 Pas is not exceeded. Accordingly, the viscosity at tempering at 250 ° C still takes a value less than 1100 Pas after 30 minutes and less than 2500 Pas after 1 hour. Accordingly, the phenomenon of crosslinking, which is frequently observed in the technical processing of carbon monoxide copolymers, does not occur or only occurs to a minor extent under the conditions described in the carbon monoxide copolymers according to the invention.
  • Admission pressure set at 70 bar and the temperature brought to 90 ° C.
  • a final pressure of 100 bar was set for carbon monoxide.
  • the temperature and pressure were kept constant throughout the reaction.
  • the polymerization was stopped by cooling and relaxing the autoclave.
  • the product mixture was filtered, washed with methanol and dried at 80 ° C. in a high vacuum overnight (component Al). Yield: 643 g.
  • Viscosity number 150 ml / g (measured in ortho-dichlorobenzene / phenol (1/1) as 0.5% by weight solution),
  • Propene content 6.5 mol%, based on the total olefin content.
  • Irganox 1076 octadecyl-3 - (3,5-di-t-butyl-4-hydroxyphenyl) propanoate
  • Ciba-Geigy component C-la
  • Ca 3 ( P0) 2 calcium phosphate
  • the carbon monoxide copolymers provided with flame retardants were obtained on a kneader from Haake (Rheocord 90) at 250 ° C. and a kneading speed of 60 rpm, by first of all stabilizing the carbon monoxide copolymer over a period of 5 minutes. was melted and then the flame retardant was added.
  • homogeneous flame-retardant carbon monoxide copolymer was produced as described above - but at a temperature of 230 ° C. and then kneaded at this temperature for 20 minutes.
  • samples from the mixture described above were pressed into plates (100 x 10 x 1.6 mm). These panels were subjected to the UL94 (vertical) fire test.

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Abstract

L'invention concerne des copolymérisats de monoxyde de carbone ignifugés stables en fusion, qui contiennent des copolymères de monoxyde de carbone, du carbonate de magnésium et de calcium MgxCay(CO3)x+y.m(H2O) et du carbonate de magnésium basique Mgn(CO3)v(OH)2n-2v.w(H2O), selon un rapport de 10:1 à 1:10, et éventuellement un antioxydant, un polymérisat ayant l'élasticité du caoutchouc ou des adjuvants.
PCT/EP1999/003198 1998-05-18 1999-05-10 Copolymerisats de monoxyde de carbone ignifuges stables en fusion Ceased WO1999060056A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99920862A EP1084180A1 (fr) 1998-05-18 1999-05-10 Copolymerisats de monoxyde de carbone ignifuges stables en fusion
AU38282/99A AU3828299A (en) 1998-05-18 1999-05-10 Flameproof, melt-stable carbon monoxide copolymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19822208.4 1998-05-18
DE19822208A DE19822208A1 (de) 1998-05-18 1998-05-18 Flammgeschützte, schmelzestabile Kohlenmonoxidcopolymerisate

Publications (1)

Publication Number Publication Date
WO1999060056A1 true WO1999060056A1 (fr) 1999-11-25

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/003198 Ceased WO1999060056A1 (fr) 1998-05-18 1999-05-10 Copolymerisats de monoxyde de carbone ignifuges stables en fusion

Country Status (4)

Country Link
EP (1) EP1084180A1 (fr)
AU (1) AU3828299A (fr)
DE (1) DE19822208A1 (fr)
WO (1) WO1999060056A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4921897A (en) * 1989-03-31 1990-05-01 Shell Oil Company Flame retardant composition containing zinc borate
WO1997014743A1 (fr) * 1995-10-16 1997-04-24 Shell Internationale Research Maatschappij B.V. Melange polymere polycetonique ignifuge
US5684117A (en) * 1995-10-16 1997-11-04 Shell Oil Company Flame retardant polyketone polymer blend

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4921897A (en) * 1989-03-31 1990-05-01 Shell Oil Company Flame retardant composition containing zinc borate
WO1997014743A1 (fr) * 1995-10-16 1997-04-24 Shell Internationale Research Maatschappij B.V. Melange polymere polycetonique ignifuge
US5684117A (en) * 1995-10-16 1997-11-04 Shell Oil Company Flame retardant polyketone polymer blend

Also Published As

Publication number Publication date
AU3828299A (en) 1999-12-06
DE19822208A1 (de) 1999-11-25
EP1084180A1 (fr) 2001-03-21

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