WO1999060056A1 - Flameproof, melt-stable carbon monoxide copolymers - Google Patents

Abstract

The invention relates to flameproof, melt-stable carbon monoxide copolymers containing carbon monoxide copolymers, magnesium-calcium carbonate MgxCay(CO3)x+y.m(H2O) and basic magnesium-carbonate Mgn(CO3)v(OH)2n-2v.w(H2O) at a ratio of between 10:1 and 1:10, as well as possibly an antioxidant, a rubber-elastic polymer or additives.

Description

Flame-retardant, melt-stable carbon monoxide copolymers

description

The present invention relates to flame-retardant, melt-stable carbon monoxide copolymers containing

A) copolymers of carbon monoxide and α-olefinically unsaturated compounds as monomer units, also called carbon monoxide copolymers for short, and

B) mineral compounds bi) and b ₂ ), where

bi) a magnesium calcium carbonate of the general formula Mg _x Ca _y (C0 ₃ ) _{x +} ym (H ₂ 0) with x, y as integers from 1 to 5, x / y> 1 and m> 0

and

b) a basic magnesium carbonate of the general formula Mg _n (CO ₃ ) v (OH) 2n-2v - (H ₂ 0) with n as an integer from 1 to 6, v as an integer from 1 to 5, n / represent v> 1 and w> 0

and in a ratio of 10: 1 to 1:10 in the flame-retardant carbon monoxide copolymer.

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

Known specialist. This includes both copolymers with a statistical distribution of the monomer units and those with a linear alternating structure. The former are accessible by radical means, as described in US Pat. No. 2,495,286, the latter with the aid of transition metal catalysts (cf. EP-A 0 121 965 and Drent et al., Chem. Rev., 1996, 96, p. 663). Linear alternating carbon monoxide copolymers can have a thermoplastic or an elastomeric property profile, depending on the molecular weight and the olefinic monomer building blocks. The technical applications of carbon monoxide copolymers are correspondingly diverse. These are, for example, in Automotive and household goods sector as well as in the electrical and electronics sector.

Since must be met for many technical applications in increasingly stringent requirements particularly with regard to adequate fire protection ^¬, also arises for Kohlenmonoxidcopo ^¬ mers the question of an effective flame retardant. Is that it influences the basic properties of the polymeric material and / or the behavior during processing does not adversely ^¬ be essential in the selection of a flame retardant ^¬ means. The requirement to be able to provide halogen-free flame-retardant polymer materials is also becoming increasingly important.

In US Pat. No. 4,761,449, 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.

As the patent specification US 4,885,328 can be seen, the ge ^¬ Mäss US 4,761,449 are flame retardant carbon monoxide obtained for many technical applications not sufficient, which is (oxygen index LOI Limiting) in an LOI value of less than 30 is reflected. With alkaline earth metal hydroxides, in particular with magnesium hydroxide as flame retardant, optionally also with the addition of alkaline earth metal carbonates, LOI values greater than 30 can be achieved in accordance with US Pat. No. 4,885,328. However, this is often only possible with a proportion of 40% by weight of flame retardant, based on the total amount of flame retardant copolymer.

According to US 4,921,897, carbon monoxide copolymers with additions of zinc or barium borates can be effectively flame-retarded. However, these compounds also require an amount of flame retardant in the order of 40% by weight in order to obtain effective flame retardancy.

As is known, carbon monoxide copolymers, in the presence of small amounts of base, acid or a transition metal compound, in particular under thermal stress, tend to undergo intra- and intermolecular crosslinking reactions due to structural conditions. This often leads to a deterioration in the melt stability and thus to inadequate processing behavior. For this reason, strongly basic flame retardants such as magnesium or barium hydroxide are problematic, especially in large-scale applications with a copolymer that is not particularly melt-stable due to its molecular structure. Ξrd- Alkaline carbonates or borates are less basic, but their flame retardant effect is insufficient.

It would therefore be desirable to be able to provide carbon monoxide copolymers with effective flame retardancy without impairing melt stability or processing behavior at the same time.

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.

Accordingly, the flame-retardant carbon monoxide copolymers described at the outset were found. Furthermore, a process for the production of these copolymers and their use for the production of moldings, films, fibers and coatings have been found.

Flame retardant carbon monoxide copolymers are preferred

A) 20 to 99% by weight of a linear alternating copolymer of carbon monoxide and at least one α-olefinically unsaturated compound as monomer units,

B) 1 to 80% by weight of mineral compounds bi) and b ₂ ), where

bi) a magnesium calcium carbonate of the general formula Mg _x Ca _y (C0 ₃ ) _{x +} ym (H ₂ 0) with x, y as integers from 1 to 5, x / y> 1 and> 0 and b ₂ ) a basic magnesium carbonate of the general formula Mg _n (CO ₃ ) _v (OH) _2n - _2v - (H ₂ 0) with n as an integer from 1 to 6, v as an integer from 1 to 5, n / v> 1 and w represent> 0 and are in a ratio of 10: 1 to 1:10,

C) 0 to 5% by weight of an antioxidant,

D) 0 to 25% by weight of a rubber-elastic polymer and

E) 0 to 40 wt .-% additives

included, the proportions of components A) to E) always adding up to 100% by weight. In principle, all 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 synthesized in a radical manner, as described in US Pat. No. 2,495,286. Linear alternating carbon monoxide copolymers are preferably used. These are obtained from transition metal-catalyzed carbon monoxide and α-olefinically unsaturated compounds. Linear alternating carbon monoxide copolymers can exist as binary, ternary or higher copolymer systems.

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

Copolymers, mixtures of different binary or ternary carbon monoxide copolymers or mixtures of binary, ternary and / or higher copolymers. 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.

In principle, all monomers of this class of compounds come into consideration as α-olefins. Particularly suitable as α-olefins are ethene and the C ₃ - to C ₂ -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. For 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. However, copolymers with a molecular weight M _w of 70,000, 100,000 and even 500,000 g / mol can also be used. 5

The α-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.

In addition to the α-olefins mentioned, they are suitable for binary, ternary

15 as well as higher systems as 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, α-olefinic monomers with ester , Ether or amide units such as -C ~ to C ₃ alkyl (meth) acrylates, for example

20 methyl methacrylate, vinyl ethers such as vinyl ethyl ether, aryl or methacrylamides and vinyl aromatic monomers. Suitable vinyl aromatic monomers are, for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene or m-isopropylstyrene, in particular styrene.

25

Preferred ternary copolymer systems are partially crystalline thermoplastic terpolymers made of carbon monoxide / ethene / C - to Cιo-1-alkenes and carbon monoxide / propene / C ₄ - to Cι_o-1-alkenes, especially terpolymers made of carbon monoxide, ethene and a C ₃ - bis

30 Ca-l alkene. Carbon monoxide / ethene / propene terpolymers with a melting point in the range from 180 to 250 ° C. are very particularly preferred.

In addition, elastomeric terpolymers can also be used.

35 These are essentially carbon monoxide / propene / - or carbon monoxide / 1-butene / Cs to C ₂ o ~ l 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

40 can also be used with average molecular weights M _w greater than 70,000, 170,000, 500,000 or 1,000,000 g / mol. 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

45 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 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. For the production of carbon monoxide copolymers containing vinyl aromatic monomer units, reference is hereby expressly made to 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 α-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)

2 ©

R * R ^D

E ^l

IΛ

M [T ^« ©] (I)

E2 L2

R Rd

in which the substituents and indices have the following meaning: 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 Cι ~ to C ₂ o ^_ carbon-organic and C ₃ - to C ₃ o-organosilicon radicals, the radicals being a

May contain one or more elements from groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements,

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 ,

T is a mono- or divalent anion, for example perchlorate, sulfate, phosphate, nitrate, carboxylate, organosulfonate or organoborate, r, s 1 or 2,

where r x s = 2, and

b) 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.

Furthermore, alternating carbon monoxide copolymers can be obtained by copolymerizing carbon monoxide and α-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)

R * Rb

E ^l

L ^l

", z M (II)

E ^{2 ■ L} ~ R ^c R ^d

in which the substituents and indices have the following meaning:

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 Cι ~ 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 Cι cycloaliphatic radicals, especially cyclohexyl, or cyclobutyl, Cς - to Cι -Arylre- ste, in particular phenyl, Ci to C _2θ "carboxylates, and in special acetate, trifluoroacetate, propionate, oxalate,

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.

Suitable bridging structural units Z are those with one, two, three or four elements from Group IVA of the Periodic Table of the Elements, such as methylene (-CH ₂ -), 1,2-ethylene (-CH ₂ -CH ₂ -), 1, 3-propylene (- (CH ₂ ) ₃ -), ethylidene (CH ₃ (H) C =) or disilapropylene (- (R) ₂ S -CH ₂ -Si (R) ₂ - with R = C_- to Cι ₀ -Alkyl or C _ß -bis Cio-aryl). 1,3-Propylene is particularly suitable as a bridging unit Z. Furthermore, 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.

Examples of 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 Tπs (pentafluorophenyl) borane.

Particularly suitable metal complexes (I) include (bis-1, 3 (diphenylphosphmo) propane-palladium-dι-acetone-trιl) bis - (tetrafluoroborate) (^ [Pd (dppp) (NCCH ₃ ) ₂ 1 (BF ₄ ) ₂ , dppp = 1,3 (diphenylphosphino) propane), (bis-1,3 (diphenylphosphmo) propane-palladium-di-aquo) bis (tetrafluoroborate), bis-1,3 (diphenylphosphino) propane-palladium- bis (3-hydroxypropiomtrile) bis (tetrafluoroborate), (bis -1, 4 (dιphenylphosphino) butane-palladium-dι- acetonitrile) bis (tetrafluoroborate) and (Bιs-1, 4 - (diphenyl-phosphιno) butane-palladium-dι -aquo) bis (tetrafluoroborate).

Particularly suitable metal complexes (II) are bis -1,3 (diphenylphoshmo) propane-palladium-bis-acetate, bis-1,3, [di (2-methoxyphenyl) phosphιno] propane-palladium-bis-ace- tat, bis (diphenylphosphinomethyl) phenyla in palladium bis acetate and bis (diphenylphosphinomethyl) t butylamine palladium bis acetate.

According to the invention, the flame-retardant carbon monoxide copolymers contain, as flame retardants B), mineral compounds i) and b ₂ ), where

bi) a magnesium calcium carbonate of the general formula

Mg _x Ca _y (C0 ₃ ) _{x + y} - m (H ₂ 0) with x, y as integers from 1 to 5, x / y> 1 and m> o and b ₂ ) a basic magnesium carbonate of the general formula

Represent Mg _n (C0 ₃ ) _v (OH) _2n - _2v -w (H ₂ 0) with n as an integer from 1 to 6, v as an integer from 1 to 5, n / v> 1 and w> 0

and in a ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, particularly preferably 1: 1 to 3: 1 and in particular 1: 1 to 2: 1 in the carbon monoxide copolymer according to the invention.

Mixtures of the compounds bi) and b ₂ ) in an amount of from 1 to 80, particularly preferably from 5 to 40 and in particular from 10 to 30% by weight, based on the total amount of flame-retardant carbon monoxide copolymer, are preferred in this copolymer. merisat included.

The magnesium-calcium carbonates bi) are preferably present in anhydrous form in the flame-retardant carbon monoxide copolymers according to the invention. This means that the compounds bi) show no water of crystallization (m = 0) in the elemental analysis and contain a maximum of 1% by weight of residual water and / or physisorbed water, preferably no residual water and physisorbed water. Particularly preferred minerals bi) are dolomite and huntite, especially huntite.

The basic magnesium carbonates b ₂ ) can be used in water-containing, ie containing water of crystallization or physisorbed water, and in anhydrous form. In addition to synthetic magnesium carbonates, 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 μm. Average grain sizes of less than 20 μm are preferred, particularly preferably less than 5 μm.

The mineral compounds bi) and b ₂ ) can either be untreated or pretreated with 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. Among the 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

(X- (CH ₂ ) f) _g -Si- (0-C _h H _2h + l) 2-g

in which the substituents have the following meaning:

X NH ₂ -, CH ₂ -CH-, HO-,

\ / 0

f is an integer from 2 to 10, preferably 3 to 4 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, γ-methacryloxypropyltrimethoxysilane, beta-3, trimethoxysilane -Epoxycyclohexylethyl-, γ-glycidyloxypropyltrimethoxysilane, γ-amino-propyltrimethoxysilane, aminobutyltrimethoxysilane, aminobutyltriethoxysilane Aminopropyltri- ethoxysilane, or also the corresponding glycidyl derivatives.

Of course, not only both compounds bi) and b ₂ ) can be present in the copolymer according to the invention, but also 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. As a further component (component C)), 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, also called sterically hindered phenols, 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

Have molecule. 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-butyl-4-hydroxyphenyl) propionate), octadecyl 3- (3,5-bis (tert-butyl) -4-hydroxyphenyl) propionate, pentaerythritol tetrakis (3- ( 3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 3, 5-di- tert-butyl-4-hydroxyphenyl-3, 5-distearyl-thiotriazylamine, 2, 4-bis (n-oc-tylthio) -6- (4-hydroxy-3, 5-di-tert-butyla nilino) -1, 3, 5-triazine, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole, 3, 5-di-tert-butyl-4-hydroxybenzyldimethylamine, 2,6,6-trioxy-l-phosphabicyclo- (2.2.2) oct-4-yl-methyl-3,5-di-tert- butyl-4-hydroxyhydrocinnamic acid ester and N, N '-hexamethylene-bis-3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide.

Also suitable as an antioxidant is 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,

4-bis (butyl- (2) -amino) benzene (DBPPD) or 2-anilinonaphthalene in question. 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

Called 1,2-bis (2-hydroxybenzylindenamino) ethane.

The preferred phosphorus-containing compounds used are phosphonites and phosphites.

The following phosphonites are particularly preferably used: bis - (2,4-di-tert-butylphenyl) -phenylphosphonite, tris (2, -dit-tert-butylphenyl) -phosphonite, tetrakis (2, 4-di-tert. bu ^¬ tyl - 6 -methylphenyl) -4,4'-biphenylylene-di-phosphonite, tetrakis (2, 4-di -tert.butylphenyl) -4,4'-biphenylylene-diphosphonite, tetrakis (2, 4- di-methylphenyl) -1,4 -phenylylene-diphosphonite, tetrakis- (2, 4-di-tert-butylphenyl) -1, 6 -hexylylene-diphosphonite and / or tetrakis- (3, 5 -di-methyl -4 - hydroxy-phenyl) -4, 4'-biphenylylene diphosphonite, tetrakis - (3, 5-di-tert-butyl -4 -hydroxy-phe ^¬ nyl) -4,4'-biphenylylene diphosphonite.

The diphosphonites tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphonite, tetrakis - (2,4-di-tert-butylphenyl) -1,6 -hexylylene- are very particularly suitable. diphosphonite, tetrakis (3, 5-dimethyl-4-hydroxyphenyl) -4,4 '-biphenylylene-diphosphonite and tetrakis - (3, 5-di-tert-butyl -4-hydroxyphenyl) -4,4' -bipheny - Lylene-diphosphonite and tetrakis - (2, 4 -di - tert .butyl) - 1, 4-phenylene-diphosphonite, with the diphosphonite in particular tetrakis (3, 5 -dimethyl -4 -hydroxyphenyl) - 4,4'-biphenylylene diphosphonite and tetrakis - (3, 5-di-tert-butyl -4-hydroxylphenyl) -4, 4-biphenylylene diphosphonite is preferred.

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. Besonαers oevorzuαt are with; high-quality groups suDstiiu erce pheno_ιscne antioxidants such as octadecyl 3- (3,5-dι- t butyl 4 nydroxy pnenyl) prcpanoat and mixtures of the above-mentioned compounds with at least one phosphorus-containing compound, msbesonαere D stearyl-3, 5-dι-tert- butyl-4-hyαroxy-benzylphosphonate, 3, 5-Bιs (tert-butyl) -4-hydroxyoenzylphospnonsau - rediethyl ester, tris- (nonylphenyl) phosphite, tris- (2, 4-dιe-tεrt-butylphenyl) phosphi and / or bis -stearyl-pentaerythπtol- diphosphi.

Furthermore, it has proven to be advantageous to add small amounts of alkaline earth phosphates, in particular calcium phosphate (Ca ₃ (Pθ ₄ ) ₂ ), to the antioxidants (C). A proportion in the range from 0.1 to 1.0, preferably from 0.15 to 0.6 and particularly preferably from 0.2 to 0.5% by weight, based on the amount of carbon monoxide copolymer, is generally sufficient, to sustainably increase the effect of antioxidants.

As component D), 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). In addition to natural rubber, 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, Kolloidzeitschπft 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, α-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. For further information on this embodiment, reference is hereby expressly made to the German application DE-A 44 20 952.

The 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).

Furthermore, a large number of 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).

As a further component (component E)), 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. According to the invention, 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 µm. 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.

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. In particular, aluminum 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.

Various substituted UV stabilizers can be used

Resorcins, 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. In a further embodiment, 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. In addition, 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.

The present invention is illustrated by the following examples.

Examples:

Component A)

a) Preparation of the carbon monoxide copolymer

In a 9, 0-1 autoclave, 1, 3-bis (diphenylphosphino) propane-palladium-bis-acetate (25.4 mg), p-toluenesulfonate (133.5 mg), methanol (4 1) and Propene (440 g) introduced. A mixture of ethene and carbon monoxide (1: 1) was used

Admission pressure set at 70 bar and the temperature brought to 90 ° C. By further adding the gas mixture of ethene and A final pressure of 100 bar was set for carbon monoxide. The temperature and pressure were kept constant throughout the reaction. After 7 hours, 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),

Melting point: 227 ° C,

Propene content: 6.5 mol%, based on the total olefin content.

Component B)

A 2: 1 mixture of the compounds bi) and b ₂ ) treated with an aminosilane size was used, where bi) Mg ₃ Ca (C0 ₃ ) ₄ (huntite) and b ₂ ) Mg ₅ (C0 ₃ ) ₄ (OH) -4H ₂ 0 (hydromagnesite). This mixture was the commercially available product Securoc C from Ince in (component B1).

For comparison purposes, flame retardants were used

i) Magnesium hydroxide from Martinsried (Magnifin SE 465) treated with an aminosilane size (component B-VI), ii) untreated magnesium hydroxide (from Merck) (component B-V2), iii) huntite (CaMg ₃ (C0 ₃ ) ₄ ) (Component B-V3) and iv) hydromagnesite (Mg ₅ (C0 ₃ ) (0H) ₂ -4H ₂ O) (component B-V4).

Component C)

A mixture of Irganox 1076 (octadecyl-3 - (3,5-di-t-butyl-4-hydroxyphenyl) propanoate) from Ciba-Geigy (component C-la) and calcium phosphate (Ca ₃ ( P0) ₂₎ (Comp ^¬ component C-lb) used. These compounds were already added during the production of component A) and were in this in proportions of 0.2% by weight (Irganox 1076) and 0.5% by weight (Ca ₃ (P0) 2) / based on the total amount of carbon monoxide copolymer obtained.

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.

The tendency to cross-link and the fire behavior were examined using the following methods:

The time course of the torque during kneading as a measure of the increasing crosslinking was followed at 250 ° C. The values determined are given in the unit [gm] analogously to EP-A 0 489 517.

In addition, 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.

The melt stability of samples of the mixtures obtained was determined using a plate rheometer (Rheometrics Dynamic Spectrometer; plates: d = 25 mm, h = 1 mm) at 230 and at 250 ° C. at a shear rate ω of 1 rad / sec.

Furthermore, 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.

The composition of the tested samples and the results of the tests described are summarized in Table 1 below.

Table 1 :

a) Vergleichsversuch b) n.k. nicht klassifizierbar, d.h. UL 94 -Kriterien werden in keiner Weise erfüllt.

a) Comparison test b) nk not classifiable, ie UL 94 criteria are not met in any way.

Claims

claims 1. Containing flame-retardant, melt-stable carbon monoxide copolymers A) Copolymers of carbon monoxide and α-olefinically unsaturated compounds as monomer units and B) mineral compounds b ^) and b ₂ ), where bi) a magnesium calcium carbonate of the general formula Mg _x Ca _y (C0 ₃ ) _{x + y} -m (H ₂ 0) with x, y as integers from 1 to 5, x / y> 1 and m> 0 and b) a basic magnesium carbonate of the general For ^¬ mel Mg _n (C0 _{3) v} (OH) _2n - ₂ v - (H ₂ 0) with n as a whole number from 1 to 6, v is an integer 1-5 , n / a> 1 and w> 0 and in the ratio of 10: 1 to 1:10 in the flame-retardant coal lenmonoxidcopolymerisat present, and, optionally, an antioxidant (C), a rubber-elastic polymer ^¬ (D) or an additive (E). 2. Carbon monoxide copolymers according to claim 1, containing A) 20 to 99 wt .-% of a linear alternating Copolymers of carbon monoxide and at least one α-olefinically unsaturated compound as monomer units, B) 1 to 80% by weight of mineral compounds bi) and b ₂ ), where bi) a magnesium calcium carbonate of the general formula Mg _x Ca _y (C0 ₃ ) _{x + y} -m (H ₂ 0) with x, y as integers from 1 to 5, x / y> 1 and m> 0 and b ₂ ) a basic magnesium carbonate of the general formula Mg _n (C0 ₃ ) _v (0H) _2n _. ₂ v - (H ₂ 0) with n as an integer from 1 to 6, v as an integer from 1 to 5, represent n / a> 1 and w> 0 and in a ratio of 10: 1 to 1:10, C) 0 to 5% by weight of an antioxidant, D) 0 to 25% by weight of a rubber-elastic polymer and E) 0 to 40% by weight of additives, the proportions of components A) to E) always add up to 100% by weight. 3. Carbon monoxide copolymers according to claims 1 or 2, characterized in that as the mineral compound bi) a magnesium calcium carbonate of the general formula Mg _x Ca _y (C0) _{x + y} 0 (H ₂ 0) with x, y as integers from 1 to 5 and x / y> 1 is used. 4. Carbon monoxide copolymers according to claims 1 to 3, characterized in that binary carbon monoxide / ethene, Carbon monoxide / propene, carbon monoxide / 1-butene, carbon monoxide / 1-pentene or carbon monoxide / 1-hexene copolymers (A) use. 5. Carbon monoxide copolymers according to claims 1 to 4, characterized in that one uses ternary carbon monoxide / ethene / C ₃ - to CQ - alk-1-ene copolymers. 6. Carbon monoxide copolymers according to claims 1 to 5, thereby geκennzeιchnet that one uses as compound bi) huntite and as compound b ₂ ) hydromagnesite. 7. Carbon monoxide copolymers according to claims 1 to 6, characterized in that phenols, phosphonites, phosphites or mixtures of the aforementioned compounds are used as the antioxidant (C) with sterically demanding groups. 8. Carbon monoxide copolymers according to claims 1 to 7, characterized in that the antioxidant in an amount in Range from 0.01 to 3.0% by weight, based on the amount of carbon monoxide copolymer, is present and has calcium phosphate as a constituent. 9. A process for the preparation of the flame-retardant carbon monoxide copolymers according to claims 1 to 8, characterized in that components (A) and (B) and, if appropriate, if necessary, (C) to (E) are mixed at a temperature in the range from 180 to 250 ° C. to form a homogeneous molding compound. 10. Use of the carbon monoxide copolymers according to claims 1 to 8 for the production of moldings, films, fibers or coatings.