SK56299A3 - Process for preparing compositions based on thermoplastic polymers and polyamides - Google Patents

Abstract

The invention concerns a process for preparing compositions containing at least one thermoplastic polymer A and at least one polyamide B by dissolving the thermoplastic polymer A in at least one lactam b and optionally further polyamide-forming monomers b, and subsequent polymerization of the monomers b. The monomers b are polymerized in the presence of between 0.001 and 5 wt % water, relative to the monomers b.

Description

The present invention relates to an improved process for preparing compositions comprising at least one thermoplastic polymer A and at least one polyamide B by dissolving thermoplastic polymer A in at least one lactam b and optionally other polyamide-forming monomers b and then polymerizing monomers b. The present invention further relates to compositions prepared by the method of the invention, their use and polymer blends, moldings, sheets or fibers containing the compositions.

BACKGROUND OF THE INVENTION

The polyamides can be prepared in various ways. One method of obtaining polyamides is the hydrolytic polymerization of ring cleaved lactams. A variant of this process, which can also be used in industrial mass production, is described, for example, in DE-A 43 21 683.

Mixtures of polyamides with amorphous plastics such as polyarylene ether sulfones or polyetherimides are known. The mechanical properties of the mixtures are always the better, the finer the amorphous polymers are dispersed in the polyamide.

U.S. Pat. No. 3,729,527 discloses, inter alia, that such mixtures can be prepared by polymerizing ε-caprolactam in the presence of polyarylene ether sulfone. German patent application DE-A 41 02 996 likewise proposes to polymerize lactams in the presence of amorphous polymers such as polysulfones, polyphenylene ethers, polyetherimides, polyamidoimides or styrene copolymers for the preparation of polymer alloys. Polymerization is initiated by strong bases.

When the components of the polymer blend are mixed in a melt, for example an extruder, compatibilizers are generally added thereto. According to EP-A 374 988, Mc Grath et al. Polym. Prepr. 14 (1973), 1032, or Corning et al., Makromol. Chem Macromol. Symp. 75 (1993), 159, suitable copolymers include copolymers comprising polyamide segments and polyarylene ether sulfone

-2segmenty; which are prepared by dissolving the polyarylene ether sulfone in a lactam melt and polymerizing the lactam in the presence of a strong base in the absence of water.

Anionic polymerization studies of lactams in the presence of polyetherimides or polysulfones in an extrusion press have also been reported, for example, by VanBuskirk et al., Polym. Prepr. 22 (1) (1988) 557.

Said methods present the disadvantage that the polymer chains of the thermoplastic polymers are degraded by the attack of the anions present in the reaction mixture. In addition, anionic polymerization requires specific technical measurements to control the degree of polymerization, since the reaction is essentially carried out very rapidly and there is a sharp increase in viscosity over a short period of time. Consequently, products with a defined structure can be obtained only with difficulty, i. chain length or viscosity, if at all possible. In addition, the products contain catalyst residues and degradation products or by-products that often cannot be removed. When the polymerization is carried out in an extruder, complete conversion is often not achieved and the final product therefore still contains residual monomers. Furthermore, generally only dark, for example brown, products are obtained.

Schnablegger et al., Acta Polym. 46 (1995), 307, describe the reaction of εcaprolactam with polyarylene ether sulfones containing terminal aminophenyl groups. The amino groups react with ε-caprolactam by ring cleavage and thus initiate a polymerization reaction. The reaction is carried out in the absence of water and phosphoric acid can be used as the catalyst. A disadvantage of this process is that polyarylene ether sulfones having two terminal aminophenyl groups per polymer chain can be prepared in pure form only by expensive process.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an improved process by which finely dispersed compositions can be obtained based on a wide range of thermoplastics and polyamides, and wherein the thermoplastic polymers are not degraded or degraded only to a very limited extent. The improved process should furthermore allow good viscosity control of the compositions to be prepared. Except for

By means of the improved process, it should be possible to obtain products which have good mechanical properties and are obtained either in pure form during preparation or can be easily purified.

We have found that this object can be achieved by a process for preparing compositions comprising at least one thermoplastic polymer A and at least one polyamide B by dissolving the thermoplastic polymer A in at least one lactam ba and optionally other polyamide-forming monomers b and subsequently polymerizing monomers b, wherein monomers b are polymerized in the presence of water in an amount of from 0.001 to 5% by weight, based on monomers b.

Suitable thermoplastic polymers A are all amorphous polymers which dissolve in lactams or mixtures thereof with other polyamide-forming monomers b and do not adversely affect their polymerization. According to the present invention, dissolution is understood to be the preparation of the melt, which appears transparent to the viewer, i. polymers A may be physically dissolved or present in finely dispersed form. Suitable amorphous polymers A include polyarylene ethers such as polyarylene ether sulfones or polyphenylene ethers, polyetherimides, polyamidoimides, polystyrene and styrene copolymers, such as styrene / acrylonitrile copolymers, styrene / diene copolymers, butene-like copolymers or acrylate copolymers, or acrylate-based copolymers (styrene), ASA (acrylonitrile / styrene / acrylate) or AES (acrylonitrile / ethylene / styrene), or other ethylene copolymers. Mixtures of different polymers A can also be dissolved.

Particularly suitable polyarylene ethers are the polyarylene ethers of formula (I)

wherein each of the variables taq in formula I may be 0, 1, 2 or 3. T, Q and Z, independently of each other, may be the same or different. They may represent a chemical bond or a group selected from -O-, -SO ₂ -, -S-, C = O, -N = N- and S = O. In addition, T, Q and Z may be a group of the formula

-4-R'C = CR ^b - or -CR ^e R ^d - in which R * and R ^b each represent a hydrogen atom or a C 1 -C 6 -alkyl and R ^c and R ^d each represent a hydrogen atom, C 1 -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, t-butyl or n-hexyl, C _r C ₁₀ -alkoxy, such as methoxy, ethoxy, n propoxy, isopropoxy or n-butoxy, or _{C6-C, s-} aryl, such as phenyl or naphthyl. R ^c and R ^d , together with the carbon atom to which they are attached, may also be joined to form a cycloalkyl ring containing from 4 to 7 carbon atoms. Of these, cyclopentyl and cyclohexyl are preferred. The cycloalkyl rings may be unsubstituted or substituted with one or more, preferably two or three, C 1 -C 6 alkyl groups. A preferred substituent for cycloalkyl rings is methyl. Particular preference is given to using polyarylene ethers in which T, Q and Z each represent -O-, -SO 2 -, C = O, a chemical bond or a group of the formula -CR'R ^d -. Preferred radicals R ^e and R ^d include hydrogen and methyl. Among the groups T, Q and Z, at least one is -SO 2 - or C = O. If taq admiration represent H, then Z is either -S0 ₂ - or C = 0, preferably -S0 ₂ -. Ar and Ar * each represent C ₆ -C ₁₈ aryl, such as 1,5-naphthyl, 1,6-naphthyl, 2,7-naphthyl, 1,5-anthryl, 9,10-anthryl, 2,6-anthryl , 2,7 anthryl or biphenyl, especially phenyl. These aryl groups are preferably unsubstituted. However, they may carry one or more, for example, two substituents. Suitable substituents are C 1 -C ₁₀ -alkyl such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or n-hexyl, C ₆ -C ₁₈ -aryl such as phenyl or naphthyl, C 1 -C 10 -alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy, and halogen. Particularly preferred substituents are methyl, phenyl, methoxy and chlorine.

Some suitable repeating units are listed below:

dl)

ds)

-7ο ο

ο

ο

(Ii?)

Polyarylene ethers which contain the repeating units (I '), (I') or (I _' ) are particularly preferred. These include, for example, polyarylene ethers containing from 0 to 100 mole percent repeat units (IJ) and from 0 to 100 mole percent repeat units (I ₂ ).

The polyarylene ethers may also be copolymers or block copolymers in which polyarylene ether segments and segments of other thermoplastic polymers such as polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides are present. The average molecular weight (average numerical value) of the blocks or grafts in the copolymers is usually from 1000 to 30,000 g / mol. The blocks of different structures may be arranged alternately or randomly. The proportion by weight of the polyarylene ethers in the copolymers or block copolymers is generally at least 10% by weight and can be up to 97% by weight. Copolymers or block copolymers containing up to 90% by weight of polyarylene ethers are preferred. Copolymers or block copolymers containing from 20 to 80% by weight of polyarylene ethers are particularly preferred.

Other suitable polyarylene ethers are those polyarylene ethers which are modified with monomers containing acidic or anhydride groups. Such polyarylene ethers can be prepared, for example, by starting from the corresponding monomers containing acidic and / or anhydride groups. These can also be obtained by cleaving these monomers into the polyarylene ether chain. Suitable acidic groups include carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. Polyarylene ether sulfones which contain acid groups distributed either sequentially or randomly through the polymer chain are particularly preferred, wherein the acid groups may be attached, for example, to arylene moieties or to alkylene members of intermediates. Suitable are, for example, polyarylene ether sulfones which are modified with fumaric acid, maleic acid, maleic anhydride or particularly preferably 4,4'-dihydroxyvaleric acid. Examples of such polyarylene ether sulfones are disclosed, for example, in EP-A 185 237.

Mixtures of two or more different polyarylene ether sulfones may also be used.

In general, polyarylene ethers have average molecular weights Mn of from 5,000 to 60,000 g / mol and relative viscosities of from 0.20 to 0.95 dl / g. Depending on the solubility of the polyarylene ethers, the relative viscosities are measured either in a 1% (w / w) solution of N-methylpyrrolidone, in mixtures of phenol and dichlorobenzene or in 96% sulfuric acid, in each case at temperatures of 20 ° C and 25 ° C.

The polyarylene ethers themselves containing the repeating units I themselves are known and can be prepared by known methods.

They are formed, for example, by condensation of aromatic bishalogen compounds and dialkali salts of aromatic bisphenols. They can also be prepared, for example, by self-condensation of alkali salts of aromatic halophenols in the presence of a catalyst. Polyarylene ethers containing carbonyl functions can also be obtained by electrophilic (Friedel-Crafts) polycondensation. In electrophilic polycondensation, carbonyl bridges are formed either by reacting dicarbonyl chlorides or phosgene with aromatic compounds containing two hydrogen atoms exchangeable for electrophilic substituents, or subjecting the aromatic carbonyl chloride containing both an acid chloride group and a replaceable hydrogen atom to autopolycondensation.

Preferred process conditions for the synthesis of polyarylene ethers are described, for example, in EP-A-113 112 and 135 130. Particularly suitable is the reaction of the monomers in aprotic solvents, in particular N-methylpyrrolidone, in the presence of

Anhydrous alkali metal carbonate, preferably potassium carbonate. Reacting monomers in the melt has proven advantageous in many cases.

The polyarylene ethers of the formula I can contain, for example, hydroxyl, chlorine, alkoxy, in particular of methoxy and phenoxy, amino or anhydride or mixtures of said terminal groups as terminal groups.

The thermoplastic polymers A may also be compounds based on substituted, in particular disubstituted, polyphenylene ethers, wherein the oxygen of the unit ether is bonded to the benzene core of the adjacent unit. Preference is given to using polyphenylene ethers substituted in the 2- and / or 6- position relative to the oxygen atom. Examples of substituents are halogen such as chlorine or bromine, long chain alkyl of up to 20 carbon atoms such as lauryl and stearyl, and short chain alkyl of 1 to 4 carbon atoms, which preferably does not contain an α-tertiary hydrogen atom such as methyl, ethyl, propyl or butyl. The alkyl chains may in turn be monosubstituted or polysubstituted by halogen, such as chlorine or bromine, or by a hydroxyl group. Further examples of possible substituents are alkoxy, preferably having 1 to 4 carbon atoms, or phenyl, which is unsubstituted or monosubstituted or polysubstituted with halogen and / or C 1 -C ₄ -alkyl as defined above. Also suitable are copolymers of various phenols, for example copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Mixtures of different polyphenylene ethers may, of course, also be used.

Examples of polyphenylene ethers. which can be used according to the invention are poly (2,6-diuryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2,6-dimethoxy-1, 4-phenylene ether), poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-thearyloxy-1) (4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether),

- 10poly (2,6-dibenzyl-1,4-phenylene ether), poly (2-ethoxy-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2,5-dibromo- l, 4-phenylene ether).

Preferred polyphenylene ethers are those polyphenylene ethers which are substituted with C1-C4 alkyl, for example.

poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether); γ (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether) and poly (2-ethyl-6-propyl-1,4-phenylene ether).

For purposes of the present invention, polyphenylene ethers are also to be understood as meaning those polyphenylene ethers that are modified with monomers such as fumaric acid, maleic acid or maleic anhydride.

Such polyphenylene ethers are described, inter alia, in WO 87/00540.

The polyphenylene ethers to be used in the compositions are in particular those polyphenylene ethers having an average molecular weight M _{w of} from about 8000 to 70,000, preferably from about 12,000 to 50,000, particularly preferably from about 20,000 to 49,000.

This corresponds to a boundary viscosity of from about 0.18 to 0.7, preferably from about 0.25 to 0.55, particularly preferably from about 0.30 to 0.50 dl / g, measured in chloroform at 25 ° C.

The molecular weights of the polyphenylene ethers are generally determined by gel permeation chromatography (0.8 x 50 cm Schodex separation columns of type A 803, A 804 and A 805 with tetrahydrofuran as the eluent at room temperature). Samples of polyphenylene ethers were dissolved in tetrahydrofuran at elevated atmospheric pressure at 110 ° C while injecting 0.16 mL of a 0.25% w / w solution.

Detection is generally performed using a UV detector. The columns are calibrated using samples of polyphenylene ethers whose absolute molecular weight distribution was determined by GPC / laser light scattering.

Other suitable thermoplastic polymers A are polyetherimides or mixtures of different polyetherimides.

In principle, either aliphatic or aromatic polyetherimides may be used. Polyetherimides containing both an aliphatic and an aromatic group in the backbone are also suitable. For example, polyetherimides may be used which contain repeating units of the formula II of ⁰

Λ Λ

-N Q'— O Z'— O Q 'N- R'- (II)

Where Q 'is selected from, for example

Z 'and R', independently of each other, may be the same or different. Z 'and R' can be, for example, C 1 -C ₃₀ -alkylene. The alkylene group can either be linear or branched or can be closed to form a ring. Examples are methylene, ethylene, n-propylene, isopropylene, cyclohexylene and n-decylene. However, Z 'and R' can also be C ₇ -C ₃₀ -alkylene. Such examples are diphenylene methane, diphenylene methane and 2,2-diphenylene propane. Z 'and R' may further be C ₆ -C ₁₈ -arylene, such as phenylene or biphenylene. Conversely, the above groups may be substituted by one or more substituents or may be interrupted by heteroatoms or heteroatom groups. Particularly preferred substituents are halogen, preferably chlorine or bromine, or a C _r C ₁₀ -alkyl, in particular methyl or ethyl. Preferred heteroatoms or heteroatom groups include -SO, -, -O- and -S-. Some suitable residues Z * and R 'are exemplified below:

wherein Q 'denotes -C _y H _2y _ -CO-, -SO ₂ -, -O- or -S-, q is 0 or 1, p is 0 or 1 and y is an integer of 1 to 5. R' may be C 1 -C ₁₀ -alkyl or C 1 -C ₁₀ -alkoxy may be zero or 1. In addition, the polyetherimides may contain other imide units in addition to the units of formula II. For example, units of formulas II and II ₂ or mixtures thereof are suitable:

(IIx)

(II ₂ )

Particularly preferred are polyetherimides which contain repeating units of formula III

(III) where Z 'and R' have the same meanings as Z 'and R'.

Particularly preferred polyetherimides contain repeating units in which Z 'is CH ₃

ch ₃ and R "is selected from

Particularly preferred polyetherimides contain repeating units of formula (IIIJ)

ch ₃ o

about

The polyetherimides generally have average molecular weights (MJ from 5000 to 50,000, preferably from 8000 to 40,000. They are known or can be obtained by known methods.

Accordingly, the corresponding dianhydrides can be reacted with suitable diamines to form polyetherimides. This reaction is usually carried out in the absence of a solvent or in an inert solvent at temperatures from 100 to 250 ° C. Particularly suitable solvents are o-dichlorobenzene and m-cresol. Polyetherimides can also be prepared in the melt at temperatures from 200 to 400 ° C, preferably from 230 to 300 ° C. For the preparation of polyetherimides, the dianhydrides are basically reacted with diamines in equimolar ratios. However, it is also possible to use a certain molar excess, for example from 0.1 to 5 mol% of dianhydride or diamine.

According to the present invention, polystyrenes can also be used as polymers A. Particularly preferred monomers are styrene as well as core or side chain alkylated styrenes. Examples are chlorostyrene, α-methylstyrene, styrene, p-methylstyrene, vinyltoluene and p-tert-butylstyrene. However, the use of styrene alone is preferred.

Homopolymers are generally prepared by known sequential, solution or suspension methods (cf. Ullmanns Enzyklopädie der technischen Chemie, Volume 19, pp. 265-272, Verlag Chemie, Weinheim 1980). Homopolymers may have average molecular weights M _{w of} from 100 to 300,000, which may be determined using conventional methods.

In addition, thermoplastic polymers A may be styrene-based copolymers, which according to the present invention also include copolymers based on other vinylaromatic monomers, such as α-methylstyrene or other substituted styrenes, for example C 1 -C 10 -alkylstyrenes such as methylstyrene, or mixtures of various vinylaromatic monomers. Preferred are, for example, styrene-containing copolymers

- from 50 to 95% by weight, preferably from 60 to 80% by weight of styrene, methylstyrene or substituted styrenes, N-phenylmaleimide or mixtures thereof and from 5 to 50% by weight, preferably from 20 to 40% by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof.

The styrene copolymers are resin-like, thermoplastic and rubber-free. Particularly preferred styrene copolymers are copolymers of styrene with acrylonitrile and, optionally, methyl methacrylate, α-methylstyrene with acrylonitrile and, if appropriate, methyl methacrylate and styrene and α-methylstyrene with acrylonitrile and, optionally, methyl methacrylate and styrene methacrylate. Several of the styrene copolymers described may also be used at the same time.

These styrene copolymers themselves are known and can be prepared by free radical polymerization, in particular emulsion, suspension, solution and sequential polymerization. Usually, they have viscosity numbers of from about 40 to 160, corresponding to average molecular weights of from about 40,000 to 2,000,000.

Styrene copolymers of vinyl aromatic monomers, for example styrene or α-methylstyrene and conjugated dienes, can also be used in the process of the invention. A particularly suitable vinylaromatic monomer is styrene. As conjugated dienes, butadiene or isoprene may be used, butadiene is preferably used. Also copolymers can be used as styrene copolymers which are obtained by first polymerizing the vinylaromatic monomers with conjugated dienes and then subjecting the product to a hydrogenation reaction.

Such styrene copolymers can be obtained primarily by anionic polymerization of vinylaromatic monomers and conjugated dienes. In this case, predominantly block copolymers of these comonomers are obtained. Methods for preparing such styrene copolymers are generally known (US-A 3,595,942).

The styrene copolymers used can be of any structure, particularly preferred are block copolymers having a tri-block structure as well as branched, i. star structures with multiblock structure. Synthesis of starfish

16-block copolymers of vinylaromatic adiene monomer monomers are the subject of German patent application DOS 1,959,922 and the synthesis of star-initiated multiple-initiation block copolymers is the subject of DE 25 50 226 and US-A 3,639,517.

Suitable monomers and initiators are similarly described in the aforementioned documents. Block copolymers based on styrene as vinylaromatic monomer and butadiene and / or isoprene as conjugated diene monomers are particularly preferred. The proportion of vinylaromatic monomer in the styrene copolymer used is essentially from 25 to 95, preferably from 40 to 90% by weight.

Furthermore, graft copolymers may be used as thermoplastic polymers A, preferably consisting of ai) from about 40 to 80, preferably from about 50 to 70% by weight of a graft base comprising an elastomeric polymer having a glass transition temperature of less than 0 ° C, and a ₂ ) from about 20 to 60, preferably from about 30 to 50% by weight of a graft layer consisting of ₂₁ ) from about 50 to 95, preferably from about 60 to 80% by weight of styrene or substituted styrenes of the above formula III or methyl methacrylate or a mixture thereof; ₂₂ ) from about 5 to 50, preferably from about 20 to 40% by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof.

Polymers suitable for the grafting base are also those whose glass transition temperature is less than 10 ° C, preferably less than 0 ° C, most preferably less than -20 ° C. Such as natural rubber, synthetic rubber based on conjugated dienes or mixtures thereof with other copolymers based aelastomérmi C _r C ₈ -alkyl esters of acrylic acid, which may contain further comonomers.

Preferred cleavage bases a,) are polybutadiene and copolymers of butadiene and styrene.

Preference is further given to such cleavage bases a,) which comprise from 70 to 99.9, preferably 99% by weight, of at least one alkyl acrylate, the alkyl radical having 1 to 8 carbon atoms, preferably n-butyl acrylate and / or 2- ethylhexyl acrylate, particularly preferably n-butyl acrylate as the only alkyl acrylate, and _,; from 0 to 30, preferably from 20 to 30% by weight of another copolymerizable, monoethylenically unsaturated monomer such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate and / or vinyl methyl ether; and ₁₅ ) from 0.1 to 5, preferably from 1 to 4 % by weight of a copolyincrizable, polyfunctional, preferably bifunctional or trifunctional, monomer which affects the crosslinking.

Suitable bifunctional or polyfunctional crosslinking monomers a, ₃ ) of this type are monomers which preferably contain two, optionally also three or more, ethylene double bonds which are capable of copolymerization and are not conjugated at 1,3 positions. Examples of suitable crosslinking monomers are divinylbenzene, dialyl maleate, dialyl fumarate. dialyl phthalate, trialyl cyanurate and trialyl isocyanurate. The acrylic acid tricyclodecenyl alcohol ester has proven to be a particularly preferred crosslinking monomer (cf. DE-A-12 60 135).

Splitting bases of this type are also commonly known and are described in the literature.

Preferred cleavage layers i) are those in which a _2I ) is styrene or α-methylstyrene. Preferred monomer mixtures are in particular styrene and acrylonitrile, α-methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate, styrene, N-phenylmaleimide and maleic anhydride. The grafted layers can be obtained by copolymerizing the components a ₎ and i) and ₂₂ ).

If the graft copolymers contain a graft base α,), which consists of polybutadiene polymers, the term ABS rubber is used.

As is well known, the graft copolymerization can be carried out in solution, suspension or, preferably, in an emulsion. The soft phase of the graft copolymer preferably has an average particle diameter (d _{J 0} value of the integral mass distribution) of 0.08 pm in the preparation of ABS rubber and the grafting in emulsion. By increasing the particle size, for example, by agglomeration or emulsion recovery using a cleavage latex method, the d value _is shifted to a range of 0.2 to 0.5 µm. Such graft copolymerization involves at least partially chemical bonding of the polymerized monomers to the polymerized rubber, which bond is likely to occur on the double bonds contained in the rubber. Thus, at least a portion of the monomers are cleaved to the rubber, i.e., by covalent bonding to linear rubber molecules.

The cleavage can also be carried out in several stages, first by cleavage to a portion of the monomers constituting the cleavage shell and then the remainder.

If the grafting base and the graft copolymer is composed of _n components a), and optionally ₁₂₎ and on _i3), used the term ASA rubber. Its preparation is known per se or can be carried out by conventional methods.

The grafted layers of the graft copolymers may be synthesized in one step or in two steps.

In the case of a single-step graft synthesis, the mixture of monomers ₂₁ ) and ₂₂ ) in the desired weight ratio of from 95: 5 to 50:50, preferably from 90:10 to 65:35, is polymerized in the presence of an elastomer and in a conventional manner, preferably in an emulsion.

In the case of two-stage synthesis of the graft layer and _2), the first stage is generally from 20 to 70, preferably 25 to 50% by weight based on a _2). Preferably, only monoethylenically unsaturated aromatic hydrocarbons (a ₂₁ ) are used for this preparation.

The second stage of the graft layer generally accounts for from 30 to 80, in particular 50 to 75% by weight, based in each case on a _2). Mixtures of the above monoethylenically unsaturated aromatic hydrocarbons are used for the preparation

₂₁ ) and monoethylene unsaturated monomers; and ₂₂ ) in a weight ratio of ₂₁ ) / and ₂₂ ) in general from 90:10 to 60:40, in particular from 80:20 to 70:30.

The conditions of the graft copolymerization are preferably chosen so that the final size of the particles was 50-700 nm _(the d value of the integral mass distribution). Suitable measures are known.

The coarse-particle rubber dispersion can be prepared directly using the latex cleavage method.

In order to obtain very tough products, it is often advantageous to use a mixture of at least two graft copolymers having different particle sizes.

To achieve this, the particle size of the rubber is increased in a known manner, for example by agglomeration, such that the latex is incorporated bimodally (for example from 50 to 180 nm and from 200 to 700 nm).

Other examples of thermoplastic polymers A are α-olefin copolymers. and olefins are usually C 2 to C 8 monomers, preferably ethylene and propylene. Alkyl acrylates or alkyl methacrylates derived from C1-C8 alcohols, preferably ethanol, butanol or ethylhexanol, and reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (meth) acrylate and furthermore vinyl esters, especially vinyl acetate, have proven to be advantageous as comonomers. Mixtures of different comonomers may also be used. Ethylene copolymers with ethyl or butyl acrylate and acrylic acid and / or maleic anhydride as comonomers have proven to be particularly suitable.

The copolymers can be prepared by a high pressure process at a pressure of from 400 to 4500 bar or by cleavage of comonomers to a poly-α-olefin. The amount of α-olefin in the copolymer is generally from 99.95 to 55% by weight.

As lactam b, for example, ε-caprolactam, enantholactam, capryllactam and laurolactam and mixtures thereof, preferably ε-caprolactam, can be used.

As other polyamide-forming monomers, for example, dicarboxylic acids, such as alkanedicarboxylic acids having 6 to 12 carbon atoms, preferably 6 to 10, carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, and terephthalic acid and isophthalic acid, diamines such as C ₄ -C ₁₂ -alkyldiamines, in particular of 4 to 8 carbon atoms such as hexamethylenediamine, tetramethylenediamine or octamethylenediamine, and also m-xylylenediamine, bis- (4-aminophenyl) methane, 2 , 2-bis (4-aminophenyl) propane or bis (4-aminocyclohexyl) methane, and mixtures of dicarboxylic acids and diamines, in any combination of proportions with each other, but preferably in proportions equivalent to each other, such as hexamethylenediammonium adipate, hexamethylenediammonium tetramate tetramethylate. preferably hexamethylenediammonium adipate and hexamethylenediammonium terephthalate. In particular, polycaprolactam and polyamides synthesized from caprolactam, hexamethylenediamine and adipic acid, isophthalic acid and / or terephthalic acid are of industrial importance.

In a preferred embodiment, ε-caprolactam and hexamethylenediammonium adipate (AH salt) are used.

In general, from 30 to 100, preferably from 35 to 100% by weight of the lactams, based on the total amount of monomers b, and from 0 to 70, preferably from 0 to 65%, based on the total amount of monomers b, are used. . The AH salt is usually used in the form of an aqueous solution, the concentration of which is generally from 30 to 75, preferably from 35 to 70% by weight, based on the aqueous solution. The weight ratio of lactam to AH salt is usually selected in the range from 4: 1 to 20: 1, preferably from 5: 1 to 15: 1.

According to the present invention, the polyamide-forming monomers b in which the polymers A are dissolved are polymerized in the presence of from 0.001 to 5% by weight, based on the monomer b, of water. The polymerization is preferably carried out in the presence of more than 0.005, for example from 0.01 to 5% by weight of water. Particularly preferred are amounts of water in the range of from 0.1 to 4.5, preferably from 0.5 to 4% by weight, based on monomers b. Under these conditions the speed is

Surprisingly, the polymerization is sufficiently high and the thermoplastic polymers A surprisingly remain in solution or finely dispersed.

Water may be added to a solution of thermoplastic polymer A in polyamide-forming monomer b. If these solutions already contain water, for example because the AH salt is used in the form of an aqueous solution, either no additional water is added or the water is added only in an amount such that the total amount of water, based on monomers b, is in the range of invention.

In general, thermoplastic polymers A are added to the polyamide-forming monomers b. However, it is also possible for polymers A to be presented and polyamide-forming monomers b added thereto. The amount of thermoplastic polymers A in the solution is usually from 1 to 75% by weight. Correspondingly, the amount of polyamide-forming monomers is from 25 to 99% by weight. The solution preferably contains from 2 to 75, in particular from 3 to 70% by weight of thermoplastic polymers A and from 25 to 98, in particular from 30 to 97% by weight of polyamide-forming monomers b.

Depending on the melting point of the polyamide-forming monomers b, polymers A are dissolved in monomers b at a temperature of from 50 to 300 ° C, preferably from 80 to 290 ° C. In order to mix the components of the solution as thoroughly as possible, mixture A and b are preferably mixed. For example, boilers with agitators are suitable for this purpose. The water is then essentially added at once, in portions or continuously. The temperature of the solution is raised either simultaneously or subsequently, usually to a temperature of 180 to 33 ° C, preferably to 220 to 310 ° C. The solution may either remain in the apparatus in which it is prepared, or it may be transferred to another reaction vessel, before or after the temperature increase, or before or after the addition of water.

Various embodiments may be used to prepare the compositions of the invention. For example, according to EP-A 129 195 and 129 196, the polymerization can be carried out in tubes at elevated atmospheric pressure up to a certain conversion to form a prepolymer, which is then subjected to postcondensation. A two-step process that is also suitable for preparing the compositions of the invention is disclosed in US 2,241,322. Suitable postcondensation conditions are described, for example, in EP-A 38 094.

The preferred process is usually carried out in such a way that the water-containing solution which is preheated to 75 to 90 ° C is introduced into the reaction vessel, the reaction mixture is heated to 220 to 310 ° C, preferably to 240 to 290 ° C.

Preferably, the reaction vessel comprises partition walls, either as arranged mixing elements (e.g., a so-called Sulzer filler) or disordered mixing elements such as cartridges (e.g., Raschig rings, beads or Pall rings), so as to advantageously ensure the melt residence time of the monomers is as short as possible. to achieve a high conversion) and also to avoid as far as possible zones in which there is no or minimal transport of the melt (dead zones) and to prevent back-mixing.

The reaction pressure is basically chosen such that the reaction mixture is present in a simple liquid phase. This is advantageous because the formation of gas bubbles generally causes flow pulsation which could result in back-mixing and uneven polymerization. In our case, the pressure is usually from 5 to 30, preferably from 8 to 18 bar (absolute).

The residence time, which depends essentially on the temperature, pressure and water content of the reaction mixture, is usually chosen in the range from 2 to 4, preferably from 2 to 2.5 hours. For reaction times of less than 2 hours and a water content of less than 1% by weight, a conversion of less than 86% is generally achieved. Reaction times in excess of 4 hours essentially result in poor space-time yields, which is moreover associated with larger and more technically complicated reactors.

When caprolactam is used, usually after the first reaction zone, a composition is obtained which comprises polycaprolactam having a molecular weight of from 3000 to 9000, preferably from 5000 to 6700 g / mol. The total concentration of the terminal groups is essentially in the range from 220 to 670, preferably from 300 to 400 mmol / kg and viscosity

The melt represents a value in the range of from 100 to 10,000, preferably from 200 to 4000 mPa · s (at 270 ° C).

The conversion (calculated from the extract content, where the conversion = 100 - extract content) according to the invention represents at least 85%, preferably greater than or equal to 87%, particularly preferably greater than or equal to 89%.

Generally, the reaction mixture is allowed to expand adiabatically at elevated atmospheric pressure, i.e., the pressure is allowed to drop in the second reaction zone in a manner in which the heat required for evaporation is not supplied from the outside, the pressure in the second reaction zone usually being in the range 0. 1 to 1.1 bar, preferably from 500 to 1050 mbar. In general, during this method, the reaction mixture from the first reaction zone is cooled to 215 to 300 ° C, preferably to 235 to 265 ° C.

In addition, volatile components such as lactam and other monomer units as well as their volatile oligomers are preferably removed by steam in the second reaction zone. In a further preferred embodiment, the volatile components are quantitatively recycled continuously into the process, i.e. preferably into the first reaction zone.

The retention time in the second reaction zone is generally chosen in the range of from 2 to 60, preferably from 3 to 30 minutes.

If caprolactam is used, the preferred process will usually provide, after the second reaction to the reaction, a composition comprising caprolactam having a molecular weight of from 3000 to 14,000, preferably from 6000 to 12,000 g / mol. The total concentration of the terminal groups is generally from 140 to 670, preferably from 170 to 330 mmol / kg and the melt viscosity is from 100 to 10,000, preferably from 200 to 4000 mPa.s (at 270 ° C).

The compositions prepared by the process of the present invention comprise at least one thermoplastic polymer A in addition to polyamide B obtained from b or a mixture of different polyamides B. In addition, the compositions thus prepared comprise compounds derived from reactions of polymers A with monomers b or polymers B or with them mixtures. Polymers A do not decompose or decompose only slightly, so that the chain length of the A polymers remains essentially preserved.

After the second reaction zone, a composition is usually obtained which can be shot by conventional methods, for example in which the composition is in the form of fused profiles, which are then passed through a water bath and cooled and then granulated.

The composition prepared by the process of the present invention can be extracted by conventional methods. The polyamide B contained in the composition can be converted, sequentially or simultaneously, into a higher molecular weight polyamide B or a high molecular weight polyamide B.

For example, the composition can be extracted with water using a countercurrent method (cf. DD-A 206999). The desired viscosity number of the end product, which is usually from 80 to 350 ml / g, can be adjusted in a known manner by drying or polycondensation of the solid phase at elevated temperatures.

Another possibility of further processing is the extraction of the gas phase (cf. EP-A 284968) with simultaneous increase in molecular weight, in which the extraction and heating can be carried out simultaneously by superheated steam. The desired viscosity number of the end product is generally also from 80 to 350 ml / g.

The compositions may contain additives. The additives are usually added before granulation and / or before, during or after, preferably after polymerization of the monomers b.

The compositions may contain, as additives, from 0 to 40, preferably from 1 to 30% by weight, based on the total composition, of one or more impact rubber modifiers.

For example, conventional impact modifiers suitable for polyamides and / or polymers A may be used.

Rubbers that increase the toughness of polyamides generally have two characteristics: they contain an elastomeric fraction having a glass transition temperature of less than -10 ° C, preferably less than -30 ° C, and contain at least one functional group that can interact with each other polyamide. Suitable functional groups are, for example, groups such as carboxyl, carboxylic anhydride, carboxylic ester, carboxamido, carboximido, amino, hydroxy, cpoxide, urethane and oxazoline.

Examples of rubbers that increase the toughness of the compositions are as follows:

EP and EPDM rubbers that cleave into the above functional groups. Suitable cleaving agents are, for example, maleic anhydride, itaconic acid, acrylic acid glycidyl acrylate and glycidyl methacrylate.

These monomers can be cleaved to the polymer in the melt or in solution, in the presence or absence of a free radical initiator such as cumyl hydroxy peroxide.

The α-olefin copolymers described for polymers A, among them in particular ethylene copolymers, can also be used as rubbers instead of as polymers A and as such can be admixed with the compositions of the present invention.

Another class of suitable elastomers include a core-sheath that cleaves rubbers. Thus, the grafted rubbers are prepared in an emulsion and comprise at least one hard and one soft component. A hard component is usually a polymer having a glass transition temperature of at least 25 ° C, and a soft component is a polymer having a glass transition temperature of no more than 0 ° C. These products have a structure comprising a core and at least one shell, the structure being determined by the sequence of addition of the monomers. The soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally other monomers. Suitable siloxane cores can be prepared, for example, starting from the cyclic oligomeric octamethyltetrasiloxane or from tetravinyltetramethyltetrasiloxane. These can be reacted, for example, with γ-26-mercaptopropylmethyldimethoxysilane by ring-opening carton polymerization, preferably in the presence of sulfonic acids, to obtain soft siloxane cores. The siloxanes can also be crosslinked, for example, by carrying out a polymerization reaction in the presence of silanes containing hydrolyzable groups such as halogen or alkoxy, for example tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane. Examples of suitable comonomers are styrene, acrylonitrile and crosslinked or grafted active monomers having more than one polymerizable double bond, such as dialyl phthalate, divinylbenzene, butanediol diacrylate, or triallyl (iso) cyanurate. The hard components are generally derived from styrene, amethylstyrene and copolymers thereof, with acrylonitrile, methacrylonitrile and methyl methacrylate being preferred as comonomers.

Preferred core-shredded rubbers comprise a soft core and a hard shell or hard core, one soft shell and at least one other hard shell. The incorporation of functional groups such as carbonyl, carboxyl, anhydride, amido, imido, carboxylic ester, amino, hydroxy, epoxy, oxazoline, urethane, urea, lactam or halobenzyl is preferably accomplished herein by addition of suitable functionalized monomers during polymerization of the final coating. Examples of suitable functionalized monomers are maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline. The amount of monomers having functional groups is generally from 0.1 to 25, preferably from 0.25 to 15% by weight, based on the total weight of the core-shredded rubber. The weight ratio of the soft and hard components is essentially from 1: 9 to 9: 1, preferably from 3: 7 to 8: 2.

Such rubbers which increase the toughness of polyamides are well known and are described, for example, in EP-A 208 187.

Another group of suitable impact modifiers include thermoplastic polyester elastomers. By polyester-elastomers is meant segmented copolyetheresters containing long-chain segments, which are usually derived from poly (alkylene) ether glycols, and short-chain segments, which are derived from lower molecular weight diols and di-carboxylic acids. Such products are well known and described in the literature, for example in US-A 3,651.

-η014. Corresponding products are also commercially available under the names Hytrel ® (Du Pont), Arnitel ® (Akzo) and Pelprene ® (Toyobo Co. Ltd.).

Of course, it is also possible to use mixtures of different rubbers.

The compositions may further comprise fillers or reinforcing agents, usually in amounts of from 0 to 40% by weight based on the total weight of the compositions.

Examples of fibrous fillers or reinforcing agents are carbon fibers, potassium titanate whiskers, aramid fibers and particularly preferably glass fibers. If glass fibers are used, they can be adjusted in size and adhesion improvement to achieve better compatibility with the matrix of the base material. Generally, the carbon and glass fibers used have a diameter of from 6 to 20 gm.

The glass fibers may be incorporated either in the form of short glass fibers or in the form of roving. In the finished injection part, the average length of the glass fiber is preferably from 0.08 to 0.5 mm.

The carbon and glass fibers may also be used in the form of fabrics, mats or glass skeins.

Particularly suitable fillers are amorphous silica, carbonates such as magnesium carbonate (chalk), powdered silica, mica, various silicates such as clays, muscovite, biotite, suzoite, cimaletite, talc, chlorite, phlogofite, feldspar, and silicates such as wollastonite or kaolin, in particular calcined kaolin.

In a particularly preferred embodiment, particles comprising fillers are used, of which at least 95, preferably at least 98% by weight of the particles have a diameter (maximum dimension) determined on the final product of less than 45 gm, preferably less than 40 gm, and whose so-called ratio the length to diameter is from 1 to 25, preferably from 2 to 20, determined on the final product.

The particle diameter can be determined, for example, by recording with an electron micrograph of a thin section of the polymer blend and using at least 25, preferably at least 50, filler particles for recovery. Determination of the particle diameter can also be performed by sedimentation analysis, according to the Transactions of

ASAE, p. 491 (1983). The filler mass fraction, which is less than 40 * μιη, can also be measured by sieve analysis. The length to diameter ratio is the ratio of the diameter of the particles to the thickness (maximum dimension to minimum dimension).

Particularly preferred filler particles are talc, kaolin, such as calcined kaolin, or wollastonite or mixtures of two or all of these fillers. Among these, talc having a proportion of at least 95% by weight of particles having a diameter of less than 40 gm and a length to diameter ratio of from 1.5 to 25, determined in each case on the finished product, is particularly preferred. The kaolin preferably has a proportion of at least 95% by weight of particles having a diameter of less than 20 gm and a length to diameter ratio of from 1.2 to 20, determined in each case on the finished product.

Examples of other additives are processing aids, stabilizers and antioxidants, heat stabilizers, UV stabilizers, lubricants and mold release agents, flame retardants, dyes and pigments and plasticizers. The amount thereof is generally up to 40%, preferably up to 15% by weight, based on the total weight of the composition.

The pigments and dyes are generally present in amounts of from 0 to 4, preferably from 0.5 to 3.5, particularly preferably from 0.5 to 3% by weight.

Pigments for dyeing thermoplastics are commonly known, for example, R. Gächter and H. Miiller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, p. 494-510. A first preferred group of pigments includes white pigments such as zinc oxide, zinc sulfide, lead white (2 PbCO 3 .beta.OH), zinc white, antimony white, and titanium dioxide. Of the two most commonly used crystalline modifications (types of ruthenium and anatase) of titanium dioxide, the form of ruthenium is primarily used to improve the whiteness of the molding compositions of the invention.

-29Black pigments that can be used according to the present invention are ferric black (Fe ₃ O ₄ ), spinel black (Cu (Cr, Fe), O ₄ ), manganese black (a mixture of manganese dioxide, silica and iron oxide), cobalt black and antimony black, and particularly preferably carbon black, which is generally used in the form of lamp black or gas black (for this see G. Benzing, Pigmente für Anstrichmittel, Expert-Verlag (1988), p. 78 et seq. ).

Naturally, inorganic color pigments such as chrome green or organic color pigments such as azo pigments and phthalocyanines can naturally also be used according to the present invention to achieve certain color shades. Such pigments are commercially available.

Furthermore, it may also be advantageous if said pigments or dyes are used in a mixture, for example carbon black with copper phthalocyanines, which generally facilitates the dispersion of the color in thermoplastics.

Antioxidants and heat stabilizers which may be added to the thermoplastic materials of the invention are, for example, Group I metal halides of the periodic table, for example sodium, potassium and lithium halides, optionally in combination with copper (I) halides, for example chlorides, bromides or iodides copper halides may also contain electron-rich π-ligands. Examples of such copper complexes are copper halide complexes with, for example, triphenylphosphine. Zinc fluoride and zinc chloride may also be used. Furthermore, sterically hindered phenols, hydroquinones, representatives of this group containing substituents, secondary aromatic ainines, optionally in combination with phosphorus-containing acids or salts thereof, and mixtures of these compounds, preferably in concentrations up to 1% by weight, based on the weight of the mixture, can be used.

Examples of UV stabilizers are various substituted resorcinols, saicylates, benzotriazoles and benzophenones, which are generally used in amounts up to 2% by weight.

Lubricants and mold release agents that are added to thermoplastic materials generally in amounts up to 1% by weight are stearic acid, stearyl alcohol, stearic acid alkyl esters and stearic amides, as well as pentaerythritol esters of long chain fatty acids. Stearic acid calcium, zinc or aluminum salts as well as dialkyl ketones such as distearyl ketone can also be used.

The advantages of the process according to the invention compared to the known processes are, inter alia, that the chain length of the thermoplastic polymers A does not shorten or shortens very little and the polymers A are present in the composition in the form of a very fine dispersion, which results in very good mechanical properties. In particular, they are characterized by very good strength, good flowability and excellent toughness.

Another advantage is the clear natural coloring of the compositions which can be achieved by the method of the present invention.

Since the compositions obtainable by the process of the present invention comprise polymers A and polyamides B in particular in finely divided form, they are suitable as compatibilizers in polymer blends whose components are incompatible with each other but are compatible with either polymer A or polyamide B composition.

Examples of suitable components and such polymer blends that are compatible with polymers of the compositions are those described under A. Component and may include a polymer or a mixture of two or more polymers. Component a may be selected to correspond to the polymer or polymers of the composition. However, component a may not be identical to A. Thus, a may be a polyphenylene ether and A may be a styrene polymer, or a may be a polyarylene ether having a defined structure, while A is a polyarylene ether of a different composition. Polymers A and a can also be distinguished, for example, by having different molecular weights or different molecular weight distributions. In general, component a is present in the polymer blends in amounts of from 1 to 97, preferably from 5 to 90% by weight, based on the total weight of the polymer blends.

As mentioned above, suitable polymers β are all polymers that are compatible with the polyamides B of the composition. Polymer β or a mixture of two or more different polymers β may be used. Particularly preferably, thermoplastic polyamides are used. Such polyamides are commonly known and include semi-crystalline and amorphous resins having molecular weights (mean weight) of at least 5000 g / mol, commonly referred to as nylon. Such polyamides are described, for example, in U.S. Pat.

Polyamides b can be prepared, for example, by condensing equimolar amounts of a saturated or aromatic dicarboxylic acid having 4 to 12 carbon atoms, with a saturated or aromatic diamine containing 14 carbon atoms, or by condensation of ω-aminocarboxylic acids or by polyaddition of the corresponding lactams.

I

Examples of such polyamides are polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylenesebacic acid amide (nylon 610), polyhexamethylenedodecanedicarboxylic acid amide (nylon 612), polyamide, and poly-11-aminoundecanoic acid and polyamide obtained from di (p-aminocyclohexyl) methane and dodecanedicarboxylic acid.

It is also possible to use as component β polyamides which have been prepared by copolycondensation of two or more of the abovementioned polymers or components thereof, for example copolymers of adipic acid, isophthalic acid or terephthalic acid and hexamethylenediamine or copolymers of caprolactam of terephthalic acid and hexamethylenediamine. Such partially aromatic copolyamides usually contain from 40 to 90% by weight of units derived from terephthalic acid and hexamethylenediamine. A small amount of terephthalic acid, preferably not more than 10% by weight of the total amount of aromatic dicarboxylic acids used, can be replaced by isophthalic acid or other aromatic dicarbo-32-xylic acids, preferably those in which the carboxyl groups are in para position.

Other suitable monomers for the preparation of polyamides β are cyclic diamines such as those of formula IV

nh ₂ (IV) in which

R ¹ represents a hydrogen atom or C 1 -C ₄ -alkyl,

R ² and R ³ each represent C 1 -C 4 alkyl or a hydrogen atom.

Particularly preferred diamines of formula IV are bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane or

2,2-bis (4-amino-3-methylcyclohexyl) propane.

Examples of other diamines of formula IV are 1,3- and 1,4-cyclohexanediamine or isophorone diamine.

In addition to the units derived from terephthalic acid and hexamethylenediamine, the partially aromatic copolyamides comprise units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine.

The amount of units derived from ε-caprolactam is up to 50, preferably from 20 to 50, particularly preferably from 25 to 40% by weight, while the amount of units derived from adipic acid and hexamethylenediamine is up to 60, preferably from 30 to 60, particularly preferably from 35 to 55% by weight.

The copolyamides may also contain both units, ε-caprolactam units and units of adipic acid and hexamethylenediamine; in this case, it must be ensured that the proportion of units which do not contain aromatic groups is at least 10, preferably at least 20% by weight. The ratio of units derived from ε-caprolactam to units derived from adipic acid and hexamethylenediamine is not subject to any restrictions.

Polyamides β having from 50 to 80, in particular from 60 to 75% by weight units derived from terephthalic acid and hexamethylenediamine and from 20 to 50, preferably from 25 to 40% by weight units derived from ε-caprolactam are have proven to be particularly advantageous for many purposes of use.

The partially aromatic β-copolyamides can be prepared, for example, as described in EP-A-129 195 and EP 129 196.

Particularly preferred partially aromatic polyamides β are those containing less than 0.5% by weight of triamine units, especially dihexamethylenetriamine units. Partially aromatic polyamides β having a triamine content of 0.3% by weight or less are particularly preferred.

Linear polyamides having a melting point above 200 ° C are particularly preferred as component β.

Preferred polyamides β are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam as well as polyamide 6 / 6T and polyamide 66 / 6T and polyamides containing cyclic diamines as comonomers. Polyamides generally have a relative viscosity of from 2.0 to 5, determined in a 1% (w / w) solution in 96% sulfuric acid at 23 ° C, which corresponds to an average molecular weight of from about 15,000 to 45,000. Particularly preferred are polyamides having a relative viscosity of from 2.4 to 3.5, in particular from 2.5 to 3.4.

Other examples of component β are polyamides which can be obtained, for example, by condensing 1,4-diaminobutane with adipic acid at elevated temperatures (polyamide 4,6). Methods for preparing polyamides having the indicated structure are described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524.

The amount of component β in the polymer blend may be from 1 to 97, preferably from 5 to 90 wt%, based on the total weight of the polymer blend.

The compositions used according to the present invention as compatibilizing agents γ in polymer blends can be used either alone or in the form of additives already added. The composition itself is preferably used as component γ. Usually the polymer blends contain from 2 to 80, preferably from 5 to 70% by weight of the component γ, based on the total weight of the polymer blend.

In addition, the polymer blends may comprise as an additional component δ, an impact rubber modifier or a mixture of two or more impact rubber modifiers. Suitable ingredients δ are those described above as ingredients for compositions. This component γ comprises an impact rubber modifier, which may be the same or different from the impact rubber modifier additionally contained as component δ in the polymer blends. The polymer blends generally comprise from 0 to 40, for example from 0 to 30, preferably from 0 to 25% by weight of the component δ, based on the total weight of the polymer blend.

In a preferred embodiment, the polymer blends comprise fillers or reinforcing agents. Examples of suitable fillers or reinforcing agents are those described above for compositions.

The polymer blends may contain from 0 to 60, for example from 0 to 40, preferably from 0.5 to 20% by weight of component ε.

In addition, the polymer blends may contain additives such as processing aids, stabilizers, antioxidants, heat stabilizers, light stabilizers, lubricants or mold release agents, flame retardants, dyes, pigments or plasticizers. Naturally, the polymer blends may

Also include mixtures of two or more ingredients. Suitable additives that can be used in the polymer blends are those listed as additives for the compositions. The component χ may differ in the ingredients used in the component. Generally, the amount of component χ in the polymer blend is from 0 to 30, preferably from 0 to 20 wt%, based on the total weight of the polymer blends.

Polymer blends can be prepared, for example, by mixing the ingredients in conventional mixing equipment such as a mixer, mixer, extruder, for example a screw extruder, preferably a twin screw extruder, or a mill such as a Banbury or Brabender mill, and then extruding the blends.

After extrusion, the extruded product is usually cooled and expanded.

The sequence with which the ingredients are mixed may be varied, for example two or optionally three ingredients may be prepared as a masterbatch, but it is also possible to mix all the ingredients together.

Intensive mixing is preferred to obtain particularly homogeneous molding compositions. For this purpose, average mixing times of from 0.2 to 30 minutes at temperatures from 280 to 380 ° C are generally required.

In particular, the polymer blends are characterized by their good toughness. Both the composition and the polymer blends are suitable for the production of moldings, films or fibers. The area in which these materials can be used readily is the automotive industry.

DETAILED DESCRIPTION OF THE INVENTION

Testing of usage characteristics:

The proportion of units containing acidic groups in polyarylene ether sulfone A2 was determined by ’H-NMR measurements according to Parsons et al., Polymer 34 (1994), 2836.

The viscosity number of the polyarylene ether sulfones was determined using a 1% (w / w) solution in N-methylpyrrolidone at 25 ° C.

The molecular weight of the polyphenylene ether was determined by gel permeation chromatography (under the conditions described in the description).

The dried granules of the compositions were processed to obtain standard small bars, round disks and pull test bars. The dried granules of the polymer blends were processed to obtain ISO bars and round disks. The treatment was carried out at a melt temperature of 280 ° C and a mold temperature of 80 ° C.

The melt volume index (MVI) was determined at a temperature of 275 ° C and a load of 5 kg.

The modulus of elasticity [N / mm ² ] was determined according to DIN 53 457 from the slope of the tangent at the original tensile stress curve at a test speed of 1 mm per minute on pull test bars (average of 10 tests).

Notch toughness (a _k [kJ / m ² ]) was determined using standard small bars according to DIN 53 453 by subjecting loosely supported standard small bars to a sudden impact, determining the energy to break the bars (10 individual tests).

Impact resistance (a "[kJ / m ² ]) was measured using non-serrated ISO bars according to ISO 179, Part I.

Total penetration energies (W _m N / m) were determined using round discs according to DIN 53 443, by penetrating a fixed clamped round disc with a penetration element at a constant speed (4.5 m / s). Total penetration energy was determined from a force-strain curve (5 individual measurements).

The color of the composition was evaluated visually. The color range ranged from very bright (1) through beige (2) and brown (3) to brown (4) and dark brown (5).

Amorphous polymers A1 to A4

-37Al: Polyarylene ether sulfone containing repeating units of formula I ₂ , characterized by a viscosity number of 48 ml / g, for example Ultrason ® S 1010 from BASF.

A2: Acid-containing polyarylene ether sulfone

5.742 kg of dichlorodiphenylsulfone, 4.374 kg of bisphenol A and 112 g of 4,4 ' dihydroxyvaleric acid were dissolved in 29 kg of N-methylpyrrolidone under nitrogen and 2.820 kg of anhydrous potassium carbonate was added.

The reaction mixture was initially heated at 180 ° C for one hour at 300 mbar, with constant distillation of the reaction water and N-methylpyrrolidone, and then the reaction was continued for 6 hours at 190 ° C.

After addition of 40 kg of N-methylpyrrolidone, the inorganic components were filtered off. The basic groups were neutralized by the addition of 50 ml of glacial acetic acid and subsequently the polymer was isolated by precipitation in water. After extraction with water, the product was dried under reduced pressure at 140 ° C. A white powder was obtained.

The amount of acid-containing units was determined by HNMR as 1.4% by weight and the viscosity number of the product was 38.1 ml / g.

A3: Polyphenylene ether, characterized by an average molecular weight of 40,000 g / mol, as determined by gel permeation chromatography using chloroform as solvent.

A4: Poly (styrene-co-acrylonitrile), characterized by an acrylonitrile content of 25% by weight and a viscosity number of 80 ml / g (measured using a 0.5% solution (w / w) in dimethylformamide at 25 ° C, for example Luran®) 358 N from BASF).

ingredients:

Cl: Glass fibers with a fiber thickness of 10 mm and polyurethane sizing material.

-38C2: Talc with an average particle size of 1.5 µm.

D: Ethylene / propylene rubber modified with 0.7% by weight of maleic acid / maleic anhydride, characterized by an MFI of 3 g / 10 minutes (measured under a load of 2.16 kg and at 230 ° C).

Preparation of Composition 1 and Comparative Tests V6 and V7 kg of polymer A1 were dissolved in 24 kg of caprolactam. After addition of 1000 g of water, the mixture was heated to 235 ° C in a stirrer boiler with an internal pressure of 7.5 bar. After pre-condensation for 2 hours, the vessel was allowed to expand for a period of 1.5 hours, followed by postcondensation for 2.5 hours at 235 ° C.

The melt was then discharged from the boiler and granulated. The obtained granules were extracted with hot water.

The results obtained in characterizing this product are shown in Table 1.

Compositions 2-5, V6 and V7 were prepared similarly. The amounts used and the results of the performance characteristics testing are shown in Table 1.

Comparative experiments

For comparison, polyarylene ether A1 was mixed at 280 ° C with polyamide 6, characterized by a viscosity number of 146 ml / g, measured using a 0.5% (w / w) solution in 96% (w / w) sulfuric acid (m / m). for example, Ultramide B from BASF) in an extruder (ZSK 30 from Werner and Pfleiderer), and the mixture is then granulated. The obtained granules were dried at 80 ° C under reduced pressure for six hours. The results are shown in Table 1 (V8).

Molding materials V9 to Vil were also prepared similarly, except that the processing of molding material Vil was carried out at a melt temperature of 250 ° C.

-39Tabuľkal

compositions 1 2 3 4 5 V6 V7 V8 V9 V10 Vil ε- caprolactam [Kg] 24 1 27 24 24 24 24 24 A1 [kg] 8 3 7 - - - - 1.5 1.31 - - A2 [kg] - - 1 - - - - - 0.19 - - A3 [kg] - - - 8 - - - - - 1.5 - A4 [kg] - - - - 8 - - - - 1.5 Water [kg] 1 1 1 1 1 0 5.5 - - - - Polyamide 6 [kg] - - - - - - 4.5 4.5 4.5 4.5 Method of preparation WITH with with WITH with WITH WITH E E E E features and "[kJ / m ² ] 345 404 410 376 319 a) 103 78 210 67 120 [Nm] 33.4 46.6 43.2 29.1 34.2 - 1.1 1.2 3.2 0.9 U MVI [ml / 10 ’] 178 234 246. 231 248 - > 25 0 145 149 178 201 Color 1 1 1 1 1 - 2 2 2 3 2

S: Boiler with stirrer

E: Extruder

(a) without polymerisation

The granular compositions 1, 2 and 5 were mixed with either glass fibers C or rubbers D in the extruder at a melt temperature of 280 ° C. The mixtures were then granulated and processed to give test samples.

For comparison purposes, the granulated molding materials of polymers A1 or A4 and polyamide 6 were mixed with glass fibers C in an extrusion mold in a similar manner (cf. Comparative Examples V15 and V16). The compositions and mechanical properties of these products are shown in Table 2.

-40Table 2

Examples 12 13 14 V15 V16 17 18 19 V20 Ingredients [% by weight]: Composition 1 70 80 67.5 Composition 2 - 70 - - - - - - Composition 5 - - 70 - - - 80 - Al - - - 17.5 - - - 16.8 A4 - - - - 17.5 - - - Polyamide 6 - - - 52.5 52.5 - - 50.7 Cl 30 30 30 30 30 - - - - C2 - - - - - - - 12.5 12.5 D - - - - - 20 20 20 20 features: [kJ / m ² ] 80 67 59 55 32 - - 347 97 and _k [kJ / m ² ] - - - - - 56 49 17 5 Elasticity modulus [N / mm ² ] 9200 9550 10100 9200 9700 2000 2150 2800 2900 W ', [Nm] - - - - - 78 69 78 2 MVI *) [mI / 10 ’] 88 105 108 68 87 76 165 20 17

*) at 275 ° C and under a load of 5 kg

Polymer blends:

component a,: polyarylene ether Al component a ₂ : polystyrene-co-acrylonitrile A 4 component cc ₃ : polyphenylene ether A component βρ polycaprolactam (polyamide 6, for example Ultramid® B3 from BASF), characterized by viscosity number 150 ml / g (determined according to DIN 53 727 in a 0.5% (w / w) solution in 96% (w / w) sulfuric acid) component γ: composition 1 component γ ₂ : composition 3 component y ₃ : composition 4

-41 component 5 _l : rubber D

Preparation of polymer blends

The ingredients were blended in a twin screw extruder (ZSK 30 from Werner and Pfleiderer) at a temperature ranging from 270 to 320 ° C with a capacity of 10 kg / hour for 250 minutes, extruded and then granulated. After drying, the granules were injection molded to give test samples. The weight composition of the polymer blends and the results of the mechanical tests are shown in Table 3.

Table 3

30 27 1 1 m within 01 1 1 - 324 about M * 24.1 OJ ΓΊ > 30 1 1 70 1 1 1 126 m Γ4 H * CM V28 σι 1 1 within r ~ 1 1 1 15 301 12.5 24.1 27 1 1 51 T m 1 1 15 404 H m 57.0 within η > 1 within about r-i 89.4 1 1 1 167 n N · » m ²⁵ 1 1 1 09 1 40 361 ΓΊ X 22.4 V24 1 10.6 1 89.4 1 1 T 138 <I < H H CM ²³ 1 1 1 09 1 1 40 1 324 <n n H r- CM V22 10.6 1 89.4 1 1 1 214 M ¹ M 11.2 21 1 1 09 40 1 1 1 356 n 35, 1 Example component [% by weight] D and N and <1 and D WHAT. D ? - n >> n D (ABOUT features: r-i b b rt * " b b * a * - m «£ s

Table 3

30 r * O1 1 1 63 10 1 1 1 324 ABOUT pH with ^ 1 ' fM V29 30 1 1 70 1 1 1 1 126 m The OJ 2.1 V28 cn 1 1 within Γ 1 1 15 301 12.5 24.1 27 1 1 1 51 m 1 15 404 34.1 57.0 V26 • 10.6 89.4 1 1 1 167 % OJ CH n 25 1 1 09 1 1 40 1 pH VO m OJ M * 22.4 V24 1 10.6 89.4 1 1 1 1 138 H 2.1 23 1 1 09 1 40 Ό ¹ OJ ΓΊ 3.9 • j OJ V22 10.6 1 89.4 1 - 1 1 214 2.4 CM pH pH 21 1 1 1 09 about 1 1 1 356 WHAT M * 35.1 Example component [% by weight] ä n ä ï H WHAT. > - N > · n > - rl WHAT features: e b c -M io N E \ Ό * M (0 - *) s S

Claims (13)

A process for the preparation of a composition comprising at least one thermoplastic polymer A and at least one polyamide B by dissolving thermoplastic polymer A in at least one lactam ba and optionally other polyamide-forming monomers b and subsequently polymerizing monomers b, characterized in that monomers b are polymerized in the presence of 0.001 to 5% by weight of water, based on monomers b. Method according to claim 1, characterized in that the polymer A used is a polyetherimide, a polyarylene ether, a polyphenylene ether, a polystyrene, a styrene copolymer or an ethylene copolymer. Method according to claim 1 or 2, characterized in that ε-caprolactam is used as lactam b. Method according to any one of the preceding claims, characterized in that in the next step the molecular weight is increased. Method according to claim 4, characterized in that the increase in molecular weight is achieved by extraction or heating or a combination of these measures. A composition obtainable by a process according to any one of claims 1 to 4. A composition according to claim 6, characterized in that it comprises at least one rubber, filler or reinforcing agent or other additives or a mixture of two or more thereof. Use of a composition according to claim 6 as a compatibilizer in polymer blends. 9. A polymer blend comprising the composition of claim 6. Polymeric composition according to claim 9, characterized in that it contains fillers or reinforcing agents. -4511. Polymeric composition according to claim 9, characterized in that it contains talc as a filler or reinforcing agent. Polymeric composition according to any one of claims 8 to 10, characterized in that it comprises (a) from 1 to 97% by weight of at least one polymer compatible with polymer A (b) from 1 to 97% by weight of at least one polyamide B compatible polymer γ) from 2 to 80% by weight of the composition according to claim 6 δ) from 0 to 40% by weight of impact rubber modifier ε) from 0 to 60% by weight of filler or reinforcing agent or mixture thereof χ) from 0 to 30% by weight of additives the percentages are based on the total weight of the polymer blend. Use of a composition according to claim 6 or a polymer blend according to any one of claims 7 to 11, for the production of moldings, films or fibers. Molding, film or fiber, comprising a composition according to claim 6.