WO1999060057A1

WO1999060057A1 - Thermoplastic nanocomposites

Info

Publication number: WO1999060057A1
Application number: PCT/EP1999/003004
Authority: WO
Inventors: Alexander Glück; Stefan Grutke; Joachim Queisser
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-05-14
Filing date: 1999-05-04
Publication date: 1999-11-25
Also published as: EP1086173A1; AU4137699A; DE19821477A1

Abstract

The invention relates to thermoplastic nanocomposites containing; A) 50 to 99.99 wt.% of carbon monoxide copolymer from carbon monoxide and at least one olefinic unsaturated compound formed as monomeric units, B) 0.01 to 50 wt.% of a delaminated layer silicate, C) 0 to 40 wt.% of fibrous fillers, D) 0 to 30 wt.% of additional additives, and E) 0 to 30 wt.% of a rubber-elastic polymerizate, whereby the sum of the weight percentages of the components A) to E) is equal to 100 % each time.

Description

Thermoplastic nanocomposites

description

The present invention relates to thermoplastic nanocomposites containing

A) 50 to 99.99% by weight of carbon monoxide copolymer composed of carbon monoxide and at least one olefinically unsaturated compound as monomer units,

B) 0.01 to 50% by weight of a delaminated layered silicate,

C) 0 to 40% by weight of fiber fillers,

D) 0 to 30 wt .-% of other additives and

E) 0 to 30% by weight of a rubber-elastic polymer, the sum of the parts by weight of components A) to E) giving in each case 100%.

Furthermore, the present invention relates to a method for producing the aforementioned thermoplastic nanocomposites, their use for the production of films, fibers, moldings or coatings, and such films, fibers, moldings or coatings.

Thermoplastic nanocomposites based on polyamides, polyesters or polystyrenes are known. These thermoplastic materials are characterized by with good rigidity and good toughness.

To improve the physicochemical properties of polymers, clay minerals were used early on as a reinforcing material (cf. HKG Theng in "Formation and Properties of Clay-Polymer Complexes", Elsevier, Amsterdam, 1979). The clay mineral was radically polymerized for compatibility in the presence of vinyl monomers. However, with this type of impregnation there is no effective penetration of the layer structure of the clay mineral with the polymer material, which is why the connection between the polymer and the inorganic filler material is unsatisfactory. Satisfactory results were only obtained in the polycondensation of caprolactam in the presence of clay mineral / aminolauric acid or clay mineral / amino caproic acid intercalates achieved (cf. Fukushima et al., Clay Miner. 1988, 23, p. 27).

To improve _U m _b ei polyamides the stiffness behavior without also sacrificing toughness of the resulting

Having to accept _M aterials, sat Giannelis EP (Adv. Mater. 1996, 8, pp 29-35) phyllosilicates, such as montmorillonite, pretreated with alkylammonium compounds, a. In this way, a reinforced polymer material with good heat resistance is obtained. Those described at Giannelis

_N anocomposite be obtained by LIKAT be pretreated Phyllosi- are together with the polymer and above the softening temperature of the polymer mixed together. The disadvantage here is that only those polymer materials can be used which have a softening temperature which is not too high and which are also stable at this temperature for a relatively long period of time, or at least for the duration of the processing. Another disadvantage is that the products obtained are generally characterized by poor flowability.

Furthermore, the German patent application DE-A 38 08 623 describes polyamides reinforced with layered silicates. The layered clay minerals used there are pretreated with a cation-active species as a so-called swelling agent in order to create a layer spacing that is suitable for the effective incorporation of the polymer chains. Organic compounds which have an onium and a functional group which can be incorporated into the polyamide chain are used as swelling agents. Only the carboxy group is mentioned as a suitable functional group in the aforementioned German patent application.

Starting from montmorillonite, Akelah and Moet (J. Mater. Sei., 1996, 31, pp. 3389-3396) arrive at a polystyrene linked to the mineral by means of grafting. For this purpose, in a first stage organic ammonium compounds, which advantageously have a terminal double bond, for example vinylbenzyltrimethylammonium chloride, are incorporated into the layers of montmorillonite by means of cation exchange. Then styrene is radically polymerized in the presence of the pretreated layered silicate. However, Akelah and Moet do not go into whether or to what extent the process they have found also relates to radical polymerizations with monomers other than styrene or possibly also to other polymerization methods such as polymerization condensation or transition metal-catalyzed Polymerization is transferable. No corresponding investigations were carried out.

In order to improve the mechanical property profile of carbon monoxide copolymers, for example with regard to tensile strength, reinforcement using ceramic or fiber fillers has always been used. According to EP-A 0 474 308 this requires e.g. in the fiberglass reinforcement of carbon monoxide copolymers, above all a suitable size, i.e. a transition between inorganic filler and organic polymer material, so that on the one hand the desired mechanical property improvements are produced and on the other hand no losses in processing behavior are recorded. Glass fiber reinforced carbon monoxide copolymers, in which the size material used is not matched to fiber and polymer, tend to crosslink under the conventional processing conditions. This is reflected in a reduced melt stability or an increased melt viscosity. In the European patent application mentioned, attempts were made to counter the problem described by using a special size, namely an aminosilane / polyurethane size.

According to US Pat. No. 5,114,992, the tensile strength of glass fiber-reinforced carbon monoxide copolymers can be improved with a special isocyanate size. In the patent applications mentioned, the fiber materials are preferably used in amounts of not less than 10% by weight, based on the reinforced copolymer. In addition to the quality of the connection, the surface available for glass fibers also limits the efficiency of the mechanical property improvement. Although large quantities of glass fiber material are desirable for mechanical reasons, the surface properties of the reinforced polymers (so-called glass fiber effect) regularly deteriorate, especially with high fiber contents.

In the light of the present state of the art, it would therefore be desirable to be able to produce reinforced carbon monoxide copolymer materials in a targeted manner, without having to rely on a size material that is matched to the particular glare problem.

The present invention was therefore based on the object of developing reinforced carbon monoxide copolymers which are not based on inorganic fiber materials and which, irrespective of the size material used - or entirely without it - are improved compared to unreinforced carbon monoxide copolymers show mechanical property profile and improved surface properties.

Accordingly, the reinforced carbon oxide copolymers described at the outset, also referred to herein as thermoplastic nanocomposites, were found. Furthermore, a process for the production of the aforementioned thermoplastic nanocomposites, their use for the production of films, fibers, moldings or coatings as well as such films, fibers, moldings or coatings have been found.

As component A), the molding compositions according to the invention contain 50 to 99.99% by weight, preferably 55 to 99.0% by weight and in particular 65 to 96% by weight of carbon monoxide copolymers.

Carbon monoxide copolymers for the purposes of the present invention include copolymers of carbon monoxide and olefinically unsaturated compounds. In particular, this includes linear, strictly alternating carbon monoxide copolymers of carbon monoxide and at least one olefinically unsaturated compound. In principle, all monomers of this class of compounds can be considered as olefinically unsaturated compounds. For example, substituted and unsubstituted alkenes can be used as well as cycloolefins or unsaturated aromatic monomers. Among the alkenes, preferred are monomers with a terminal double bond. 1-Alkenes of the formula H ₂ C = C (H) (R) with R in the meaning of, for example, hydrogen, alkyl, aryl, halogen, carboxy or heteroaryl are particularly preferred. In addition to ethylene, C ₃ - to C _IG -, in particular C to Cio-alkenes such as propene, 1-butene, 1-pentene, 1-hexene or 1-octene, are therefore also suitable. Ethylene and propene are preferred, and ethylene is particularly preferred. Of course, ethylene can also be used in a mixture with, for example, propene or 1-butene. Ethylene / propene mixtures are preferred. The radical R can furthermore be C ₁ -C ₄ -aryl-, in particular C 6- to Cio-aryl, for example phenyl. Accordingly, preferred aryl compounds with an olefinic radical are, for example, styrene or α-methylstyrene, preferably styrene. Also of importance as olefinically unsaturated monomer compounds are vinyl halides, for example vinyl chloride, vinyl esters such as vinyl acetate or vinyl propionate and vinyl heterocylenes such as N-vinylpyrrolidone. Also acrylic acid and methacrylic are of interest further understood acrylic acid and derivatives thereof, including in particular, the nitriles, amides and Ci to C alkyl esters _ß. Examples of the latter are ethyl acrylate, n-butyl acrylate, t-butyl acrylate or methyl methacrylate. Among the cycloolefins are especially C ₃ - to name -Cycloolefine ₀ to Cι, so for example, cyclopentene, cyclohexene, norbornene or norbornadiene.

5 Furthermore, di- or tri-substituted olefins can also be used.

Any mixtures of different olefinic monomers can of course also be used, the mixing ratio generally not being critical.

The preparation of the carbon monoxide can be used both by free-radical methods such as in US 2,495,286, described as ^■ * - also take place by means of transition metal catalysis ^{* ■ ••.} Carbon monoxide copolymers are preferably obtained catalyzed by transition metals, with generally linear, strictly alternating copolymers of carbon monoxide and at least one olefinically unsaturated compound being obtained. 20th

As a suitable catalyst for the transition metal catalyzed production process is a transition metal of Groups IB, II B or VIII B is generally a chelate complex comprising the Periodic Table of the Elements, so as palladium, ^{• *** ■■} - ^■ platinum, ruthenium, rhodium or iridium , and a bidentate ligand system, in question.

Suitable catalyst systems are, for example, metal complexes of the general type chelated with bidenate ligands

30 formula (I)

in which the substituents and indices have the following meaning:

45 G - (CR ^b ₂ ) r- or - (CR ^b ₂ ) _a -Si (R ^a ) ₂ - (CR ^b ₂ ) _t -, -A'-O-B'- or -A'-Z ( R ⁵ ) -B '- with R ^{5 is} hydrogen, linear or branched Cι ~ to C ₂ o ~ alkyl, C ₃ - to Cio-cycloalkyl, Cζ- to Cχ _5- aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted Cζ- bis

Ci ₅ ~ aryl, aralkyl with 1 to 10 carbon atoms in the alkyl radical and 6 to 15 carbon atoms in the aryl radical, heteroaryl, long-chain radicals with 5 to 30 carbon atoms in the chain, which have polar or charged end groups, -N (R ^b ) ₂ , Si (R ^c ) ₃ or a radical of the general

Formula II

R ^l R2

\ /

- El L ^l ⁽ II),

(C (R ^b ) 2> q- M, pf

B 'E ² L2

/ \ R3 R ⁴

in the

q denotes an integer from 0 to 20 and the further substituents in (II) have the same meaning as in (I),

A ', B' - (CR ₂ ) _r - or - (CR ^b ₂ ) _S -Si (R ^a ) ₂ - (CR ^b ₂ ) _t - or -N (R) -, an r'-, s - or t-atomic component of a ring system or together with Z a (r '+ l) -, (s + 1) - or (t + 1) -atomic component of a heterocycle,

R ^a independently linear or branched Ci to C ₂₀ alkyl, C ₃ - to Cio-cycloalkyl, Cξ- to Ci ₅ ~ aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des Periodic table substituted Cξ to cis aryl, aralkyl with 1 to 10 C atoms in the alkyl part and 6 to 15 C atoms in the aryl part,

R ^b as R ^a and additionally hydrogen and Si (R ^c ) ₃ ,

R ^c linear or branched Cχ ~ to C _2o alkyl, C ₃ - bis

Cio-cycloalkyl, C ₆ - to Cχ ₅ -aryl or aralkyl with 1 to 10 C-atoms in the alkyl part and 6 to 15 C-atoms in the aryl part, 1, 2, 3 or 4 and

1 or 2 ,

s, t 0, 1 or 2, where 1 <s + t <3

Z is an element from the VA group of the Periodic Table of the Elements

M is a metal selected from Groups VIIIB, IB or IIB of the Periodic Table of the Elements,

E ¹ , E ² a non-metallic element from group VA of the periodic table of the elements,

R ¹ to R ⁴ branched C ~ to C ₂ o ~ alkyl, C ₃ - to Cirj-cycloalkyl, Cζ- to cis-aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted Ce * - to cis-aryl, aralkyl with 1 to 10 carbon atoms in the alkyl radical and 6 to 15

Carbon atoms in the aryl radical or heteroaryl,

L ¹ , L ² formally charged or neutral ligands,

X formally mono- or polyvalent anions,

0, 1, 2, 3 or 4,

m, n 0, 1, 2, 3 or 4,

where p = m x n,

or a compound of the general formula (III)

wherein

R ^d , R ^e , R ^f , R9 independently of one another for hydrogen, straight-chain or branched Ci to C ₆ alkyl or

R ^e and R ^f together represent a five- or six-membered carbo- or heterocycle and

the other substituents and indices assume the meaning given under formula (I).

Suitable metals of the metal complexes according to the invention are the metals from groups VIIIB, IB and IIB of the Periodic Table of the Elements, that is to say, in addition to copper, silver or zinc, also iron, cobalt and nickel, and the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum, Palladium is very particularly preferred.

The elements E ¹ and E ^{2 of} the chelating ligands are the non-metallic elements of the 5th main group of the periodic table of the elements, for example nitrogen, phosphorus or arsenic. Nitrogen or phosphorus, in particular phosphorus, are particularly suitable. The chelating ligands can contain different elements E ¹ and E ² , for example nitrogen and phosphorus.

The structural unit G in the metal complex (I) is a mono- or multi-atom bridging structural unit. A bridging structural unit is basically understood to mean a grouping which connects the elements E ¹ and E ² in (I) to one another.

Among the mono-atomic structural units are those with a bridging atom from group IVA of the periodic table of the elements such as -C (R ^b ) ₂ - or -Si (R ^a ) ₂ -, wherein R ^a independently of one another in particular for linear or branched Cι ~ to Cio-alkyl, for example methyl, ethyl, i-propyl or t-butyl, C - to C _δ- cycloalkyl, such as cyclopropyl or cyclohexyl, Cζ- to Cio-aryl, such as phenyl or naphthyl, with functional groups based on non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted Cg- to Cio-aryl, for example tolyl, (trifluoromethyl) phenyl, dimethylamino-phenyl, p-methoxyphenyl or partially or perhalogenated phenyl, aralkyl with 1 to 6 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, and R ^b in particular represents hydrogen and also represents the meanings given above for R ^a , preferred. R ^a represents in particular a methyl group, R ^{b represents} in particular hydrogen. Among the multi-atom bridged systems, the two- and three-atom bridged structural units should be emphasized, the latter generally being preferred.

In general, compounds of the general formula (III) are also suitable as complexes with diatomically bridged structural units

wherein

R ^d, R ^e, R ^f, R 9 independently of one another represent hydrogen, straight-chain or branched Ci- to C _ß alkyl such as methyl, ethyl or i - propyl, or

the other substituents and indices can assume the general and preferred meaning given under formula (I).

Chelate ligands such as 1, 10-phenanthroline, 2, 2 '-bipyridine or 4,4'-dimethylbipyridine or their substituted derivatives can be traced back to diatomically bridged structural units.

Suitable three-atom bridged structural units are generally based on a chain of carbon atoms, that is to say

Example propylene (-CH ₂ CH ₂ CH-), or on a bridge unit with a hetero atom from group IVA, VA or VIA of the periodic table of the elements, such as silicon, nitrogen, phosphorus or oxygen in the chain structure.

In the case of bridges built entirely from carbon atoms, the free valences can be substituted by C * to Cς alkyl, such as methyl, ethyl or t-butyl, Cς to Cio aryl, such as phenyl, or by functional groups such as triorganosilyl, dialkylamino or halogen. be acted upon. Suitable substituted propylene bridges are for Example those with a methyl, phenyl or methoxy group in the 2-position.

Among the tri-atomic structural units with a heteroatom in the chain skeleton, compounds are advantageously used in which Z is nitrogen (see formula (I) above). The radical R ⁵ in Z may particularly represent: hydrogen, linear or branched Cι ~ to C o alkyl, such as methyl, ethyl, i-propyl or t-butyl, C ₃ - to C _ß cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ - to Cio-aryl, for example phenyl, substituted by functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, C ₁ to C 10 -alkyl or C ₆ - to Cio-aryl, such as trifluoromethyl, 2, 2,2-trifluoroethyl, nitromethyl, 2-nitroethyl and tolyl, mesityl or 2, 4-difluorophenyl, aralkyl with 1 to 6 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical, pyridyl, long-chain radicals with 12 up to 22 carbon atoms in the chain which have polar or charged end groups, such as -S0 ₃ ^" , -C0 ₂ ^" , -C0 ₂ R, -CONR ₂ , halogen, in particular F, CI, Br or I, hydroxy, -OR, tosyl, -NR ₂ or -NR ₃ ⁺ , -NH ₂ (R very generally stands for an aryl or alkyl radical or for hydrogen), dialkylamino, for example dimethyl, dibenz yl- or diphenylamino, triorganosilyl, such as trimethyl, triphenyl, triethyl or t-butyldiphenylsilyl or a radical of the general formula II

R ¹ R ²

\ /

A El ^ ^ Ll (II),

(C (R ^b ) ₂ ) q M ^

"^" L

BE ² ^

/ \

R3 R ⁴

in which the substituents and indices have the following meaning:

q an integer from 1 to 20,

A ', B' - (CR ^b ₂ ) r _' - or - (CR ^b ₂ ) _S -Si (R ^a ) ₂ - (CR ^b ₂ ) _t - or -N (R ^b ) -, an r'- , s or t atomic component of a ring system or together with Z a (r '+ l) -, (s + 1) - or (t + 1) - atomic component of a heterocycle,

R ^a independently of one another hydrogen, linear or branched C 1 to C 10 alkyl, such as methyl, ethyl, i-propyl or t-butyl, C ₃ to C 6 cycloalkyl, for example cyclo- hexyl, C ₆ ~ to Cio-aryl, for example phenyl, C ₆ - to Cio-aryl, such as tolyl, trifluoromethylphenyl, aminophenyl, substituted with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, Hydroxyphenyl, anisyl or mono- or dichlorophenyl, aralkyl with 1 to 6 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl,

R ^b as R ^a and additionally hydrogen and Si (R ^c ) ₃ with

R ° linear or branched Cι ~ to Cio-alkyl, such as methyl or ethyl, C ₃ - to Cβ-cycloalkyl, for example cyclohexyl, C ₆ - to Cio-aryl, for example phenyl or aralkyl with 1 to 6 carbon atoms in Alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, with which, for example, trimethyl, triethyl, triphenyl or t-butyldiphenylsilyl fall under the formula Si (R ^c ) ₃ .

Among those chelated with monatomic ligands

Metal complexes (I) are preferred, for example, in which M is present as divalent positively charged palladium, the elements E ¹ and E ^{2 are} phosphorus and the bridging structural unit G is methylene, ethylidene, 2-propylidene, dimethylsilylene or diphenylsilylene, in particular methylene. The monatomically bridged metal complexes advantageously have radicals R ¹ to R ⁴ , at least one of which is a non-aromatic radical. Among the aromatic radicals, phenyl and tolyl are particularly noteworthy, among the aliphatic radicals these are those with bulky groups, for example t-butyl, i-propyl, s-butyl, cyclohexyl or menthyl.

Metal complexes (I) which have a three-atom bridge are particularly preferred. This includes, for example, compounds in which the elements E ¹ and E ^{2 are} connected by a propylene unit (-CH ₂ CHCH -).

Examples of preferred propylene-bridged metal complexes are

(1,3-bis (diphenylphosphino) propane-palladium-bis-acetate,

1,3-bis (di - 2-methoxyphenylphosphino) propane palladium bis - acetate, 1,3 - bis (diphenylphosphino) propane palladium dichloride, 1,3 - bis (di -2 - methoxyphenylphosphino) propane palladium dichloride and (1,3 - bis (diphenylphosphino) propane-palladium-bis-acetonitrile) - bis (perchlorate),

(1,3-bis (diphenylphosphino) ropan-palladium-bis-acetonitrile) - bis (tetrakis (3,5-bis (trifluoromethyl) phenyDborate), (1,3-bis (di-2-methoxyphenylphosphino) propane-palladium-bis-aceto-nitride (perchlorate), and

(1,3-bis (di -2-methoxyphenylphosphino) propane-palladium-bis-aceto-nitride (tetrakis (3,5-bis (trifluoromethyl) phenyl) borate) and the corresponding complexes in which the bis-acetonitrile unit is replaced by a Bistetrahydrofuran unit is replaced.

Among the three-atom bridged metal complexes (I), those with a bridging structural unit -A '-N (R ⁵ ) -B' - are also preferred.

Examples of these particularly preferred metal complexes (I) are

(Bis (diphenylphosphinomethyl) phenylamine-palladium-bis-aceto-nitrile) bis (perchlorate), (bis (diphenylphosphinomethyl) phenylamine-palladium-bis-aceto-nitride) (trifluoroacetate),

(Bis (diphenylphosphinomethyl) phenylamine-palladium-bis-aceto-nitride (tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate),

(Bis (diphenylphosphinomethyl) -t-butylamine-palladium-bis-aceto-nitrile) bis (perchlorate),

(Bis (diphenylphosphinomethyl) -t-butylamine-palladium-bis-aceto-nitride (trifluoroacetate),

(Bis (diphenylphosphinomethyl) -t-butylamine-palladium-bis-aceto-nitride (tetrakis (3,5-bis (trifluoromethyl) henyl) borate) as well

(Bis (diphenylphosphinomethyl) phenylamine-palladiu -chloride-aceto-nitrile) (perchlorate),

(Bis (diphenylphosphinomethyl) phenylamine-palladium chloride-acetonitrile) (trifluoroacetate), (bis (diphenylphosphinomethyl) phenylamine-palladium chloride-aceto-nitrile) (tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),

(Bis (diphenylphosphinomethyl) t-butylamine-palladium chloride-acetonitrile) (perchlorate),

(Bis (diphenylphosphinomethyl) -t-butylamine-palladium chloride-acetonitrile) (trifluoroacetate),

(Bis (diphenylphosphinomethyl) t-butylamine-palladium chloride-acetonitrile) (tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate),

(Bis (diphenylphosphinomethyl) phenylamine palladium chloride acetate,

(Bis (diphenylphosphinomethyl) t-butylamine palladium chloride acetate and the corresponding complexes in which the acetonitrile units are replaced by tetrahydrofuran units.

Of course, the aforementioned metal complexes (I) can also be used in the form of the corresponding palladium-bis-acetate or palladium dichloride compounds, ie without new tralligands such as acetonitrile or tetrahydrofuran. Examples include bis (diphenylphosphinomethyl) phenylamine-palladium-bis -palladium dichloride and

Bis (diphenylphosphinomethyl) t-butylamine palladium bis acetate or palladium dichloride. The palladium (II) acetate complexes (I) are preferably used.

With regard to the preparation of the metal complexes of the general formula (I), reference is hereby expressly made to the processes described in German patent application 19651685.4.

The transition metal catalysts can be added to the reaction mixture in a defined form or as individual components - in a mixture or successively. They can also be used in supported form, it being possible for the catalyst to be applied to the support in a defined form or in the form of its individual components.

The transition metal-catalyzed copolymerization processes for the production of carbon monoxide copolymers can be carried out batchwise or continuously.

Suitable reaction parameters for the production of copolymers from carbon monoxide and olefinically unsaturated compounds are pressures of 100 to 500,000 kPa, preferably 500 to 350,000 kPa and in particular 1000 to 10,000 kPa, temperatures of -50 to 400 ° C, preferably 10 to 250 ° C and in particular 20 to 150 ° C proved to be suitable.

The polymerization reactions can be carried out in the gas phase in a fluidized bed or stirred, in suspension, in liquid and in supercritical monomers and in solvents which are inert under the polymerization conditions.

Particularly suitable solvents or suspending agents for the processes according to the invention are those which are protic or which contain a protic component in portions. For example, low molecular weight alcohols such as methanol, ethanol, i-, n-propanol or water come into question; methanol is preferably used as the solvent / suspending agent or as the solvent / suspending agent component.

The polymerization reactions can also be carried out in a virtually alcohol-free or water-free polymerization medium. This means that the reaction mixture of monomers, catalyst and possibly inert solvent or suspending agent, except optionally the ligand L ¹ or L ² , contains no further alcohol or water components.

Suitable inert solvents and suspending agents are those which do not contain any hydroxyl group in the molecule, i.e. ethers such as diethyl ether, tetrahydrofuran, aromatic solvents such as benzene, toluene, ethylbenzene, chlorobenzene, aliphatic hydrocarbons such as i-butane or chlorinated aliphatic hydrocarbons such as dichloromethane, 1, 1 , 1-trichloromethane or mixtures of the compounds mentioned.

One method for producing the carbon monoxide copolymers is to initially charge the catalyst in an inert solvent and, after the monomers have been added, to carry out the polymerization at a temperature in the range from 20 to 150 ° C. and a pressure in the range from 1000 to 10,000 kPa.

It has proven to be advantageous to initially introduce the monomers and then to start the copolymerization by adding the catalyst under the conditions mentioned.

The copolymerization processes described can also be carried out in the presence of an oxidizing agent such as benzoquinone or naphthoquinone and / or with the addition of hydrogen.

By means of transition metal catalysis, for example, binary linear alternating carbon monoxide / ethene copolymers or ternary carbon monoxide / ethene / propene or carbon monoxide / ethene / 1-butene copolymers can be produced. The molecular weights of the linearly alternating copolymers are generally in the range from 5000 to 500,000 g / mol.

Suitable carbon monoxide copolymers are also to be understood in the present case as copolymers obtained by free radical means, it being possible to use the starting monomers already described in the transition metal-catalyzed copolymerization. The polymerization can be started either by means of radical initiators such as peroxides, hydroperoxides or oxygen or with the aid of high-energy radiation, for example γ-radiation. As a rule, temperatures in the range from 120 to 165 ° C. and pressures up to approximately 1000 bar are required in order to obtain suitable carbon monoxide copolymers. The radical copolymerization of carbon monoxide and olefinically unsaturated compounds can be found, for example, in US Pat. No. 2,495,286. As component B), the molding compositions according to the invention contain 0.01 to 50, preferably 0.5 to 15 and in particular 2 to 10% by weight of a delaminated layered silicate (phyllosilicate).

Under a layer silicate is generally understood silicates, in which the Si0 ₄ tetrahedra are connected etzwerken in two-dimensional infinite _N. (The empirical formula for the anion is (Si ₂ θ ₅ ² ") _n ). The individual layers are connected to each other by the cations between them, mostly as cations Na, K, Mg, Al or / and Ca in the natural occurring layered silicates.

As examples of synthetic and natural phyllosilicates _(P hyllosilikate) are montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, fluorine hectorite, saponite, beidellite, talc, nontronite, stevensite, bentonite, mica, vermiculite, Fluoromiculite, halloysite and fluorine-containing synthetic mica types called.

A delaminated layered silicate within the meaning of the invention is to be understood as meaning layered silicates in which the layer spacings are initially increased and a similar polarity is achieved by reaction with so-called hydrophobizing agents (before the molding compositions according to the invention are produced).

By subsequent mixing e.g. the hydrophobicized swollen layered silicate is made up with carbon monoxide copolymers, and the layers are widened again, before the shaped body preferably leads to a layer spacing of at least 30 Å, preferably at least 40 Å. Alternatively, to produce the thermoplastic nanocomposites according to the invention, the copolymerization of carbon monoxide and olefinically unsaturated compounds can be carried out in the presence of hydrophobic layered silicate.

Suitable as water repellents are e.g. Onium ions or onium salts.

The cations of the layered silicates are replaced by these organic hydrophobizing agents, it being possible for the nature of the organic residue to set the desired layer spacings, which depend on the type of the particular monomer or polymer in which the layered silicate is to be incorporated. The metal ions can be exchanged completely or partially. A complete exchange of the metal ions is preferred. The amount of exchangeable metal ions is usually given in milliequivalents (meq) per 100 g layered silicate and is referred to as the ion exchange capacity.

Layered silicates with a cation exchange capacity of at least 50, preferably 80 to 130 meq / 100 g are preferred.

Suitable organic water repellents are derived from

Oxonium, ammonium, phosphonium and sulfonium ions, which can carry one or more organic radicals.

Suitable hydrophobicizing agents are those of the general formula IV and / or IV:

IV IV where the substituents have the following meaning:

R ⁶ , R ⁷ , R ⁸ , R ^9, independently of one another, are hydrogen, a straight-chain or branched, saturated or unsaturated hydrocarbon radical having 1 to 40, preferably 1 to 20, carbon atoms or 2 of the radicals, in particular to form a heterocyclic radical Radical having 5 to 10 carbon atoms, preferably at least one radical R ⁶ to R ⁹ having a terminal unsubstituted olefinic double bond,

Q phosphorus or nitrogen,

Oxygen or sulfur,

V an anion.

Suitable anions (V) are derived from proton-providing acids, in particular mineral acids, halides such as chloride, bromide, fluoride or iodide and sulfate, sulfonate, phosphate, phosphonate, phosphite and carboxylate and in particular acetate being preferred as anions. _As alkylammonium ions, for example laurylammonium, myristylammonium, palmitylammonium, stearylammonium, pyridinium, octadecylammonium, monomethyloctadecylammonium and dimethyloctadecylammonium ions are preferred.

_W hen appropriate phosphonium include for example thylphosphonium Dicosyltrime-, Hexatriacontyltricyclohexylphosphonium, octadecyl cyltriethylphosphonium, Dicosyltriisobutylphosphonium, nonylphosphonium methyltri-, Ethyltrihexadecylphosphonium, Dimethyldidecyl - phosphonium, Diethyldioctadecylphosphonium, lylphosphonium Octadecyldiethylal-, Trioctylvinylbenzylphosphonium, hydroxyethylphosphonium Dioctadecylethyl-, Docosyldiethyldichlorbenzylphosphoniu, Octylnonyldecylpropargylphosphonium, Triisobutylperfluordecyl - phosphonium, Eicosyltrihydroxymethylphosphonium, Triacontyltriscyanethylphosphonium and bis-trioctylethylene diphosphonium called.

Other suitable water repellents include in WO 93/4118, WO 93/4117, EP-A 398 551 and DE-A 36 32 865.

Compounds which, in addition to an onium group, also have a group which is capable of reacting in the production of polyketone are preferably used as hydrophobizing agents for carbon monoxide copolymers. These are, for example, alkylammonium ions with vinyl functionality. Preferred alkylammonium ions are obtained by reacting suitable amino-1-lenes, e.g. of ω-amino-1-alkenes, such as ω-amino-1-dodecene, ω-amino-1-undecene or ω-amino-1-hexene, or of allylamines such as allyl-n-hexylamine with conventional mineral acids, for example

Hydrochloric acid, sulfuric acid, phosphoric acid or methylating agents such as methyl iodide. The amino group can be a primary, secondary or tertiary amino group. The amino group can be both in the allylic position to the terminal double bond and in a more distant position to this, such as in the 5-amino-1-octene.

The layered silicates used as starting materials are generally implemented in the form of a suspension. The preferred suspending agent is water, optionally in a mixture with alcohols, especially lower alcohols with 1 to 3 carbon atoms. It can be advantageous to use a hydrocarbon, for example heptane, together with the aqueous medium, since the hydrophobized phyllosilicates are usually more compatible with hydrocarbons than with water. Other suitable examples of suspending agents are ketones and hydrocarbons. A water-miscible solvent is usually preferred. When the hydrophobizing agent is added to the layered silicate, an ion exchange takes place, as a result of which the layered silicate usually becomes more hydrophobic and precipitates out of the solution. The metal salt formed as a by-product of the ion exchange is preferably water-soluble, so that the hydrophobicized layered silicate can be separated off as a crystalline solid by, for example, filtering off.

The ion exchange is largely independent of the reaction temperature. The temperature is preferably above the crystallization point of the medium and below its boiling point. In aqueous systems, the temperature is between 0 and 100 ° C, preferably between room temperature (about 20 ° C) and 80 ° C.

After the hydrophobization, the layered silicates have a layer spacing of 5 to 100 Å, preferably 5 to 50 Å and in particular 8 to 40 Å. The layer spacing usually means the distance from the lower layer edge of the upper layer to the upper layer edge of the lower layer. The length of the leaflets is usually up to 2000 Å, preferably up to 1500 Å.

The layered silicate hydrophobicized in the above manner can then be mixed in suspension or as a solid with the monomers or prepolymers and the polymerization can be carried out in the customary manner as described above for the carbon monoxide copolymerization.

Furthermore, it is possible not to introduce the hydrophobization step separately from the carbon monoxide copolymerization, but rather to carry it out in a reaction container simultaneously or almost simultaneously with the copolymerization. For example, as soon as the layered silicates and the hydrophobizing agent are in suspension, in particular in methanolic suspension, the carbon monoxide copolymerization can be started by adding the monomers and the catalyst under the process conditions already described. The hydrophobicizing agents used suitably have an olefinically unsaturated group capable of being incorporated into the copolymer chain.

In a further embodiment, the thermoplastic nanocomposites according to the invention can be obtained by carbon monoxide copolymers with delaminated layered silicate by generally known methods, for example by means of extrusion, at a temperature assemblies in the range of 160 to 260 ° C, preferably from 180 to 250 ° C.

In addition to component B), the thermoplastic nanocomposites according to the invention may also contain, as component C), 0 to 40, preferably 0.5 to 30 and in particular 2 to 25% by weight of a fibrous or particulate filler.

Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers, in particular E-glass, being particularly preferred. These can be used as rovings or cut glass in the commercially available forms.

The fibrous fillers can be pretreated with a size for better compatibility with the thermoplastic. Suitable sizes are based, for example, on organic compounds with a silane, (poly) urethane or epoxy functionality. Among the silane sizes, aminosilane sizes are preferred. Mixtures of silane, (poly) urethane and / or epoxy compounds can also be used as the sizing material. It is also possible for suitable sizing materials to be based on polyfunctional compounds, for example on aminosilanes with (poly) urethane or epoxy functionality. Preferred silane sizes are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as a substituent.

The silane compounds are generally used in amounts of

0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to

1 wt .-%, based on C), used for surface coating.

The molding compositions of the invention contain, as component D), from 0 to 30% by weight, preferably from 0 to 15% by weight, of further additives. These include, for example, heat and light stabilizers, antioxidants, lubricants and mold release agents, colorants such as dyes and pigments. Preferred antioxidants are phenols shielded with sterically demanding groups, in particular those with substituents in the ortho-position to the OH group. These antioxidants are described, for example, in DE-A 27 02 661 (US 4,360,617). Examples include 4-methyl -2, 6-di-tert-butylphenol and octadecyl -3 - (3, 5-di-butyl-4-hydroxyphenyl) propanoate. It has also proven to be advantageous to add small amounts of alkaline earth metal carbonates, in particular calcium carbonate, or calcium phosphate (Ca ₃ (P0 ₄ ) ₂ ) to the antioxidants. A proportion in the range of 0.1 to 1.0% by weight, based on the amount of carbon monoxide copolymer, is in general already sufficient to increase the action of the antioxidants.

5 Other additives are reinforcing agents such as gypsum fibers, synthetic calcium silicates, kaolin, calcined kaolin, wollastonite, talc and chalk. For example, polyethylene waxes can be considered as lubricants. Carbon blacks or titanium oxide can be used as pigments, for example. When using

10 Ti0 ₂ , the average particle size is generally in the range from 50 to 400 nm, in particular from 150 to 240 nm. Industrial uses include rutile and anatase, which are optionally coated with metal oxides, for example aluminum oxides, silicon oxides, oxides of zinc, or siloxanes are. Under soot, micro-

15 crystalline, finely divided carbons can be understood (see. Kunststofflexikon, 7th ed., 1980). Oven blacks, acetylene blacks, gas blacks and the thermal blacks obtainable by thermal production may be mentioned as suitable. The particle sizes are preferably in the range from 0.01 to 0.1 μm and the surfaces in

20 Range from 10 ² to 10 ⁴ m ² / g (BET / ASTM D 3037) with DBP absorption from 10 ² to 10 ³ ml / 100 g (ASTM D 2414).

As component E), the thermoplastic nanocomposites according to the invention contain 0 to 30, preferably 0 to 25 and particularly 25 preferably 0 to 20% by weight of a rubber-elastic polymer (often also referred to as an elastomer or impact modifier).

Natural or synthetic rubbers can be used as component E). In addition to natural rubber,

30 modifiers e.g. polybutadiene, polyisoprene, polyisobutylene or

Copolymers of butadiene and / or isoprene with styrene and other comonomers are suitable which have a glass transition temperature, determined according to K.H. Illers and H. Breuer, Kolloidzeitschrift 190 (1), pp. 16-34 (1963), from about -100 to 25 ° C, preferably below

35 10 ° C. Correspondingly hydrogenated products can also be used.

Suitable rubber-elastic polymers are based, for example, on graft rubbers with a crosslinked elastomer

40 core, which is preferably derived from butadiene, isoprene or alkyl acrylates, and a graft shell made of polystyrene. Also suitable are copolymers of ethene and acrylates or methacrylates, as well as the so-called ethylene-propylene (EP) and ethylene-propylene-diene (EPDM) rubbers, as well as those grafted with styrene.

45th EP or EPDM rubbers. Preferred impact modifiers are block copolymers of vinyl aromatics and dienes. Impact modifiers of this type are known. DE-AS 1 932 234, DE-AS 2 000 118 and DE-OS 2 255 930 describe 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. On the revelation above

Reference is hereby expressly made. 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 services are e.g. Butadiene, isoprene, 1, 3 -pentadiene or 2, 3-dimethylbutadiene.

Preferred impact modifiers are also block copolymers of vinyl aromatics and dienes, which are distinguished by the fact that instead of a pure diene rubber, a soft block of diene and vinyl aromatics is present, with diene and vinyl aromatics being statistically distributed 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, such as the ethylene lenmethacrylsäurecopolymer "Nucrel ^® 0910" from. DuPont

Ethylene-acrylic acid ester-maleic anhydride terpolymer "Lotader ^®

4720 "from. Elf Atochem, or poly (ethylene-co-propylene-g-maleic anhydride.) Made by 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 Cariflex ^® TR types (Shell), the Kraton ^® types (Shell), the Finaprene (Fina) and the

Europrene ^® -SOL- R types (Enichem) called.

The thermoplastic nanocomposites according to the invention are expediently produced by mixing the components at temperatures in the range from 220 to 260 ° C. in conventional mixing Devices such as kneaders, Banburyisers and single-screw extruders, preferably twin-screw extruders. Intensive mixing is necessary to obtain the most homogeneous molding compound possible. The order of mixing the components can be varied, two or optionally three components can be premixed or all components can also be mixed together, components A) to E) being able to be homogenized both as solids and in suspension. Components A) and B) of the molding compositions according to the invention are preferably mixed in such a way that, in the course of the copolymerization of carbon monoxide with olefinically unsaturated compounds, the hydrophobizing agent and delaminated or undelaminated layered silicate are added or introduced.

The molding compositions according to the invention are notable for very good heat resistance, measured, for example, via the forestry temperature HDT / B according to ISO 75-2, and very good rigidity with high strength at the same time. In addition, a lower mold shrinkage in the case of injection molded parts made from the molding compositions according to the invention compared to those made from non-reinforced materials can be determined. Particularly in comparison with glass fiber reinforced polyketone material, an improved surface behavior and comparable mechanical properties are observed with a significantly lower filler content. In addition, the thermoplastic nanocomposites according to the invention are distinguished by very good melting behavior, i.e. very good flowability. A melt index greater than 60, measured according to ISO 1133, is generally readily possible. Melt index values greater than 70 and also greater than 85 can also be obtained reproducibly. Accordingly, the molding compositions according to the invention are suitable for the production of fibers, foils, moldings or coatings of any kind, applications in the electrical and electronics sector being just as possible as those in the automotive sector.

The invention is explained in more detail below with the aid of examples.

Examples

I. separate production of components A) and B)

a) Preparation of the carbon monoxide copolymer A) A CO / ethene (1: 1) gas mixture was injected to a total pressure of 70 bar in a 9.0 liter pressure vessel onto a mixture of propene (440 g) in methanol (4 liters). At a temperature of 90 ° C., 1,3-bis (diphenylphosphino) propane-palladium (II) acetate (0.025 g) and p-toluenesulfonic acid (0.14 g) in methanol (50 ml) were added with stirring. The total pressure was adjusted to 100 bar by adding the CO / Ethe (1: 1) gas mixture and kept at the temperature and pressure mentioned for 7 h. After cooling to room temperature, the reaction vessel was let down, the polymer product was filtered off, washed with methanol and acetone and dried in vacuo at 80.degree. The yield was 636 g.

b) Preparation of component B)

In a reaction kettle, 1 kg of purified montmorillonite as 2 wt. -% aqueous solution with an ion exchange capacity of 120 meq / 100 g with 2.5 mol of allyl-n-hexylamine and 1 1 3 molar aqueous HC1 at room temperature over a period of 30 minutes. The suspension was then filtered, the precipitate was cleaned with water and spray-dried. The layer spacing was 29.2 Å (determined by wide-angle X-ray scattering: λ = 0.15 418 nm).

c) Assembling components A) and B) into a thermoplastic nanocomposite

Example 1:

The components obtained according to Ia) and Ib) were processed at a weight ratio of 93: 7 using a twin-screw extruder (ZSK 40) at 240 ° C. to give the molding composition according to the invention.

II. In situ production of the thermoplastic nanocomposite

Example 2:

A suspension of montmorillonite (29 g), allyl-n-hexylamine (7.1 g) and p-toluenesulfonic acid (9.3 g) in methanol (4 l) was placed in a 9.0 liter pressure vessel for 6 hours at 75 ° C stirred intensively. After cooling to room temperature, propene (440 g) was added, a total pressure of 70 bar was set with a 1: 1 CO / ethene gas mixture and the temperature was brought to 90 ° C. with stirring (500 rpm). 1,3-bis (diphenylphosphino) propane-palladium (II) acetate (0.025 g) and p-toluenesulfonic acid (0.14 g) in methanol (50 ml) were added, the total pressure was adjusted to 100 bar and the reaction held for 7 h under the conditions mentioned. After cooling to room temperature, the reaction vessel relaxed, the polymer product filtered off, washed with methanol and acetone and dried in vacuo at 80 ° C. The yield was 640 g.

III. Comparative Examples

Example 3:

The carbon monoxide copolymer produced according to Ia) was made up with glass fibers from PPG (PPG 22517) in a weight ratio of 70:30 on a twin-screw extruder (ZSK 40) at 240 ° C. The glass fibers used had a 1 / d ratio of 20 to 23 in the injection molded part.

Example 4:

The carbon monoxide copolymer prepared according to Ia) was made up with talc (2.4 Moh) in a weight ratio of 70:30 on a twin-screw extruder (ZSK 40) at 240 ° C.

Example 5:

The production of the reinforced molding compound was carried out in accordance with GB 2217720. The glass fibers used had a 1 / d ratio of 28 to 32.

The measurement results summarized in Table 1 below were carried out on standard small rods.

Table 1:

^a > Comparative ^example t in ^b 'determined according to ISO 527-2 ^c »determined according to ISO 1133 ^d > determined according to ISO 179/1 eU e> determined according to ISO 75-2 ^f > determined according to ISO DIN 67 530

Claims

claims

1. Thermoplastic nanocomposites containing

B) 0.01 to 50% by weight of a delaminated layered silicate,

C) 0 to 40% by weight of fiber fillers,

) 0 to 30 wt .-% of other additives and

E) 0 to 30% by weight of a rubber-elastic polymer, the sum of the parts by weight of components A) to E) giving 100% in each case.

Thermoplastic nanocomposites according to claim 1, characterized in that they

A) 55 to 99.0 wt .-% of carbon monoxide copolymer from carbon

monoxide and at least one olefinically unsaturated compound as monomer units,

B) 0.5 to 15% by weight of a delaminated layered silicate,

C) 0.5 to 30% by weight of fiber fillers,

D) 0 to 15 wt .-% of other additives and

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

5. A process for the preparation of thermoplastic nanocomposites according to claims 1 to 3, characterized in that components A) and B) and optionally C), D) and E) are assembled at temperatures in the range from 160 to 260 ° C.

6. Use of the thermoplastic nanocomposites according to claims 1 to 3 for the production of films, fibers, moldings or coatings.

Films, fibers, moldings or coatings, consisting essentially of thermoplastic nanocomposites according to claims 1 to 3.

CHANGED REQUIREMENTS

[Received at the International Office on October 26, 1999 (October 26, 1999); original claims 6 and 7 deleted; original claims 1 and 2 amended; added new claim 3; original claims 3-5 changed and renumbered as claims 4-6 (2 pages)]

1. Thermoplastic nanocomposites containing

5

B) 0.01 to 50% by weight of a delaminated layered silicate which is obtained by reacting a layered silicate with a hydrophobizing agent which, in addition to an onium group, has a group capable of reacting in the production of polyketone, 5

C) 0 to 40% by weight of fiber fillers,

D) 0 to 30 wt .-% of other additives and

0 E) 0 to 30% by weight of a rubber-elastic polymer, the sum of the parts by weight of components A) to E) giving 100% in each case.

2. Thermoplastic nanocomposites according to claim 1, characterized 5 indicates that they

A) 55 to 99.0% by weight of carbon monoxide copolymer composed of carbon monoxide and at least one olefinically unsaturated compound as monomer units, 0

B) 0.5 to 15% by weight of a delaminated layered silicate which is obtained by reacting a layered silicate with a hydrophobizing agent which, in addition to an onium group, has a group which is capable of reacting in the production of polyketone,

C) 0.5 to 30% by weight of fiber fillers,

D) 0 to 15% by weight of further additives and 0

E) contain 0 to 25% by weight of a rubber-elastic polymer, the sum of the parts by weight of components A) to E) giving in each case 100%.

5 3. Thermoplastic nanocomposites according to claims 1 or 2, characterized in that the delaminated layered silicate B) by reacting a layered silicate with a hydropho- Bating agent, which alkylammonium ions with vinyl

_F contains UNCTIONALITY is obtained.

4. _T thermoplastic nanocomposites according to claims 1 to 3, characterized in that binary or ternary linear, strictly alternating copolymers of carbon monoxide and ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene as carbon monoxide copolymers or styrene can be used.

5. A process for the preparation of thermoplastic nanocomposites according to claims 1 to 4, characterized in that the preparation of component A) is carried out in the presence of delaminated layered silicate B).

6. A process for the preparation of thermoplastic nanocomposites according to claims 1 to 4, characterized in that components A) and B) and optionally C), D) and E) are assembled at temperatures in the range from 160 to 260 ° C.