CZ20002436A3 - Composite multilayer structure - Google Patents

Abstract

Thermoplastic bonding of multiple layers, which consists of bonding layer I of thermoplastic molding material and layer II of another thermoplastic molding compositions by means of a composition layer % of a cohesive composition comprising at least 5 wt. using a graft copolymer the following monomers: a) 0.5 to 25% by weight; based on the graft copolymer, polyamine with at least 4 nitrogen atoms and average molecular weight Mn at least 146 g / mol as well as b) the monomer-forming polyamide selected from lactams, n-aminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid.

Description

Technical field

BACKGROUND OF THE INVENTION The present invention relates to a cohesive agent for bonding a plurality of layers, as well as to a bundle of multiple layers comprising the cohesive agent.

BACKGROUND OF THE INVENTION

Individual polymers such as polyamides or polyesters per se are unsuitable as such for many applications. For example, polyamides are not resistant to atmospheric agents as they age in the light and gain air humidity. This leads to discoloration, deterioration of mechanical properties and deformation phenomena.

Although polyamides exhibit good mechanical properties, in particular good viscosity, they have poor blocking effects. In particular, polar substances can easily migrate through polyamides. This is extremely disadvantageous, for example, in fuel lines in which the propellant containing alcohol is conveyed.

Polyesters are generally well weather resistant and exhibit excellent blocking effect for both polar and non-polar media. However, they are generally not impact resistant; in particular notch toughness is often insufficient for polyesters. Therefore, polyesters alone cannot be used in many cases, and other properties such as excellent blocking ability, high heat resistance and good underdevelopment would be desirable.

Also, other polymers generally exhibit an unbalanced image.

properties and are therefore unsuitable for many applications. Thus, it would be desirable if a bond could be formed between different polymers, for example between polyamides and polyesters. Thereby, it would be possible to protect possible polyamide moldings from light and moisture by coating with polyester. Likewise, polyamide-coated polyester moldings could be protected from chemical and mechanical influences. Furthermore, it would be possible to provide fuel lines, which are usually made of polyamide (PA) such as PA 6, PA 11 or PA 12, with a blocking layer against the fuel, in particular against alcohol-containing substances. On the other hand, laminates of different layers having different functions are suitable as monolayers for food packaging.

Polyamide and polyester bundles are already known in principle. EA-A-0 336 806 describes the coextrusion of PA 12 α and polybutylene terephthalate (PBT) into one bilayer tube. DE-PS 38 27 092 discloses a multilayer pipe comprising inwardly outwards layers of polyamide, polyalcohol, polyamide and polyester. However, the skilled artisan will appreciate that most polymers are incompatible with each other, so that cohesion between the laminate layers is not achieved when preparing polymer laminates. However, a rigid connection between the individual polymer layers is absolutely necessary under normal technical conditions.

DE-OS 196 33 133 discloses a multilayer pipe of at least two well-connected layers, one layer being blocking and the thermoplastic of the other layer being provided with polyethyleneimine as a cohesive agent. However, when imitating DE-OS 196 33 133, the desired effect did not occur. Thus, it would be obvious, for example, to tie the polyester and polyamide layers with a cohesive agent consisting of a mixture of polyamide and polyester. However, such compositions which are conventionally prepared by melting the consistency which it contains Since the compositions present in the extruder are very friable. Appropriate coextrusion experiments with polyamide and polyester show cohesion to either polyamide or polyester, but never to both at the same time.

EP-A-0 509 211 discloses thermoplastic multilayer bonding in which one layer of polyamide mass and one layer of polyester mass is bonded by the polyamide / polyester bleaching agent, the problems discussed above, in a preferred embodiment, at least one part of the polyamide and a proportion of polyester as a block of polyamide and polyester. However, the preparation of a block polymer of this kind is not quite simple and requires the addition of excipients or catalysts. In addition, precise end-group control is required since the block polymers are prepared by linking suitable end-groups and there must be assurance that a sufficient concentration of suitable end-groups exists. Since commercial products do not meet these requirements, special types must be prepared which ultimately react to the block polymer. The production of such cohesion means is therefore associated with high costs. This applies even more to the block copolyester amides which have been used in the process according to EP-A-0 837 088 as a cohesion agent in a plurality of layers of polyamides and polyesters.

Also joining from other materials exists in the art; however, due to the intolerance of most polymer raw materials, there are usually special solutions with an individually suitable cohesive agent.

SUMMARY OF THE INVENTION • 999

SUMMARY OF THE INVENTION The object of the present invention is to provide an inexpensive, easy-to-prepare yet effective means of cohering a multilayer bundle. In such a multi-layer bundle, the coherence of the layers should also be maintained for a long time even when in contact with reagents such as propellants, solvents, oils or greases, as well as coherence at higher temperatures.

This object has been solved by thermoplastic bonding of a plurality of layers comprising a layer I of thermoplastic mass, layer II of another thermoplastic mass, and between them a layer of a cohesive agent comprising at least 5% by weight, preferably at least 10% by weight. % and particularly preferably at least 20 wt. a graft copolymer prepared using the following monomers:

a) 0.5 to 25 wt.%, preferably 1 to 20 wt. and particularly preferably 1.5 to 16% by weight, based on the graft copolymer, of a polyamine with at least 4, preferably at least 8 and particularly preferably with at least 11 nitrogen atoms and an average molecular weight M _{n of} at least 146 g / mol, preferably at least 500 g / mol and particularly preferably at least 800 g / mol;

(b) polyamide-forming monomers selected from lactams, ωaminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid.

In one preferred embodiment, the amino group concentration of the grafted polymer is in the range of 100 to 2500 mmol / kg.

For example, the following classes of compounds may be used as the polyamine:

- polyvinyl amines (Römpp Chemie Lexikon, 9th edition, vol. 6, p. 4921, Georg Thieme Verlag Stuttgart 1992) ·················· ·· · · · · · · · · · · · ·

- 5 - · · · · · · ····

polyamines prepared from alternating polyketones (DE-OS 196 54 058) dendrimers such as ((H ₂ N- (CH 2) 3) 2N- (CH 2) 3) 2 N (CH ₂ ) 2 -N (( CH ₂ ) ₂ -N ((CH ₂ ) 3 -NH ₂ ) ₂ ) 2 (DE-A-196 54 179) or tris (2-aminoethyl) amine, N, N-bis (2-aminoethyl) -Ν ', N 1'-bis [2- [bis (2-aminoethyl) amino] ethyl] 1,2-ethanediamine,

3,15-bis (2-aminoethyl) -6,12-bis [2- [bis (2-aminoethyl) amino] ethyl] -9- [2- [bis [2-bis (2-aminoethyl) amino] ethyl] amino] ethyl ] 3,6,9,12,15pentaazaheptadecane-1,17-diamine (JM Warakomski, Chem. Mat. 1992,4, 1000-1004);

linear polyethylenimines, which can be prepared by polymerizing 4,5-dihydro-1,3-oxazoles and subsequent hydrolysis (Houben-Weyl, Methoden der Organischen Chemie, Vol. E20, pp. 1482-1487, Georg Thieme Verlag, Stuttgart, 1987) );

branched polyethylenimines obtainable by the polymerization of aziridines (Houben-Weyl, Methoden der Organischen Chemie, Vol. E20, pp. 1482-1487, Georg Thieme Verlag, Stuttgart, 1987) and which generally contain the following amino group distributions:

up to 46% of primary amino groups, up to 45% of secondary amino groups, and 16 to 40% of tertiary amino groups.

Preferably, the polyamine has an average molecular weight

M _{n of at} most 20 000 g / mol, particularly preferably at most 10 000 g / mol and particularly preferably at most 5 000 g / mol. The lactams or ω-aminocarboxylic acids, which are used as polyamide-forming monomers, contain from 4 to 19, and in particular from 6 to 12, carbon atoms. 0000 0 # 0000 00 00 are particularly preferred

0 0 · 0000

0 0 00 0 0000 - 6 000 000 000 000

00 00 0 00 00 ε-caprolactam, ε-aminocaproic acid, caprylolactam, ω-aminocaprylic acid, lauric lactam, ω-aminododecanoic acid and / or ω-aminoundecanoic acid.

Combinations of diamine and dicarboxylic acid are, for example, hexamethylenediamine / adipic acid, hexamethylenediamine / dodecanedioic acid, octamethylenediamine / sebacic acid, decamethylenediamine / sebacic acid, decamethylenediamine / dodecanedicarboxylic acid, dodecamethylenediamine / dodecanedicarboxylic acid / dodecanedicarboxylic acid / dodecanedicarboxylic acid.

However, all other combinations such as decamethylenediamine / dodecanedicarboxylic acid / terephthalic acid, hexamethylenediamine / adipic acid / terephthalic acid, hexamethylenediamine / adipic acid / caprolactam, decamethylenediamine / dodecanoic acid / o-aminoundecanoic acid, decamethylenediamine / dodecanedicamine may also be used lauric acid, decamethylenediamine / terephthalic acid / lauric lactam or dodecamethylenediamine / 2,6-naphthalenedicarboxylic acid / lauric lactam.

In a preferred embodiment, the graft polymer is additionally prepared using an oligocarboxylic acid selected from 0.015 to about 3 mol% of dicarboxylic acid and 0.01 to about 1.2 mol% of tricarboxylic acid each based on the sum of excess polyamide-forming monomer. Under this condition, each of these monomers is considered individually with an equivalent combination of diamine and dicarboxylic acid. In this way, the polyamide-forming monomers contain a fairly slight excess of carboxyl groups. If an acid is used kyselina φ φ φ · · · • • φ φ • • • • • • • • • • • • • • • • • • • • dicarboxylic acid, preferably 0.03 to 2.2 mol%, particularly preferably 0.05 to 1.5 mol%, very particularly preferably 0.1 to 1 mol% and in particular 0, are added, 15 to 0.65 mol%; when a tricarboxylic acid is used, preferably 0.02 to 0.9 mol%, particularly preferably 0.025 to 0.6 mol%, very particularly preferably 0.03 to 0.4 mol% and in particular 0.04 to 0.6 mol% are taken. 0.25 mol%. The use of oligocarboxylic acids together greatly improves the resistance to dissolution and propellants, in particular the resistance to hydrolysis and alcoholysis and tear resistance, but also swelling and the associated dimensional stability, as well as the diffusion blocking effect.

Any dicarboxylic or tricarboxylic acid having from 6 to 24 catomas can be used as the oligocarboxylic acid, for example adipic acid, cork, azelaic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, cyclohexane-1,4 dicarboxylic acid, trimesic acid and / or trimellitic acid.

In addition, aliphatic, alicyclic, aromatic, aralkylic and / or alkylaryl-substituted monocarboxylic acids of 3 to 50 carbon atoms, such as lauric acid, unsaturated fatty acids, acrylic acid or benzoic acid, may also be used as regulators, if desired. With these regulators, the amino group concentration can be reduced without changing the shape of the molecule. Further, functional groups can be introduced in this way as double and triple bonds, respectively. However, it is desirable that the graft copolymer contain a substantial proportion of amino groups. Preferably, the amino group concentration of the graft copolymer is in the range from 150 to 1500 mmol / kg, particularly preferably in the range from 250 to 1300 mmol / kg and very particularly preferably in the range from 300 to 1100 mmol / kg. By amino groups here and in the following is meant not only terminal amino groups, but ····

I 4 4 «

• 4 4 4

4 4 4

4 4 4

4 4 4

44 also. also existing! secondary and tertiary amine functions, respectively, in the polyamine.

The graft copolymers of the invention can be prepared in various ways.

One possibility is to pre-assemble lactam or ω-aminocarboxylic acid and polymerize or polycondensate, respectively. The oligocarboxylic acid may be added either at the beginning or during the reaction.

However, a preferred process consists in carrying out in a two-step process first the lactam cleavage and prepolymerization in the presence of water (alternatively, the corresponding ω-aminocarboxylic acids, diamines and dicarboxylic acids, respectively, are directly introduced and prepolymerized); in the second step, the polyamine is added, while the oligocarboxylic acid used is also added before, during or after prepolymerization. It is then released at temperatures between 200 and 290 ° C and polycondensated in a stream of nitrogen or under vacuum.

Another preferred method consists in hydrolytically degrading the polyamide to a prepolymer and simultaneously or subsequently reacting with the polyamine. Preference is given to using polyamides in which the end group difference approaches zero or in which the carboxylic acid used together is already polycondensated. However, oligocarboxylic acid may also be added at the beginning or during the degradation reaction.

In this way, highly branched polyamides with an acid number of less than 40 mmol / kg, preferably less than 20 mmol / kg and particularly preferably less than 10 mmol / kg can be prepared. After a reaction time of one to five hours at temperatures from 200 to 290 ° C, approximately complete conversion is achieved.

If desired, the process can be connected to vacuum for several hours. This evacuation phase lasts at least hours, preferably at least 6 hours and particularly preferably

99

9 9 9 9 9

9 9 9 9 9 9 9 9 9 - 9— ···· · 9 9 9 9 9 9

99 99 9 99 99 • 9 99 9

9999 for at least 8 hours at 200 to 290 ° C. After an induction period of several hours, an increase in the melt viscosity is then observed, which could result in the reaction of the terminal amino groups taking place with the cleavage of ammonia and chain linking. As a result, the molecular weight is further increased, which is particularly advantageous for extrusion of the molding composition.

If the reaction is not to be carried out in the melt to the end, the highly branched polyamide can also be condensed in the solid state according to the prior art.

Most of the polymers or the molding compositions based thereon can be bonded together by this bonding agent. In general, all polymers which are physically compatible due to structural similarity to the graft copolymer used according to the invention, such as polyamides, are suitable. Equally suitable are all polymers that undergo a chemical coupling reaction of the amino groups of the graft copolymers or form at least hydrogen bridges such as polyester.

Embodiments of the invention are, for example: a multilayer bundle comprising layers of different, less compatible or intolerable polyamide molding compositions which are bonded according to the invention by a cohesive means a multilayer bundle comprising layers of different co-incompatible polyamide molding compositions which are bonded according to the invention a multilayer bundle comprising one layer of a polyamide molding compound which according to the invention is bonded by a cohesive agent to a layer of another molding compound based on a polymer which is not a polyamide multilayer bundle comprising a single layer of polyester molding compound according to the invention joins the bonding agent with a layer of other molding material, - 10 - ···· 10 - ······ «· * ·· ** ·· ·· · «·· based polymer which is a polyester bundle multiple layers comprising the following layers:

I. layer 1 of polyamide molding compound;

II. layer II of polyester molding material;

between them a layer of the cohesion agent according to the invention.

Suitable polyamides are, in particular, aliphatic homopolycondensates and copolycondensates, for example PA 46, PA 66, PA 68, PA 612, PA 88, PA 810, PA 1010, PA 1012, PA 1212, PA 6, PA 7, PA 8 , PA 9, PA 10, PA 11 and PA 12. (The designation of polyamides corresponds to an international standard, the first digit indicating the number of C atoms of the starting diamine and the last digit indicating the number of C atoms of the dicarboxylic acid. that is based on α, ωaminocarboxylic acid and lactam derived therefrom, in reference to H. Domininghaus, Die Kunststoffe und ihre Eigenschaften, p. 272 nn., VDI - Verlag 1976).

If copolyamides are used, they may contain, for example, dipic acid, sebacic acid, corkic acid, isophthalic acid, terephthalic acid, naphthalene-6-dicarboxylic acid, etc. as the acids, respectively bis (4-aminocyclohexyl) methane, trimethylhexamethylenediamine, hexamethylenediamine or similar kodiamine. Lactams such as caprolactam or lauric lactam or aminocarboxylic acids such as ωaminoundecanoic can also be incorporated as co-components.

The preparation of these polyamides is known (for example, D. B. Jacobs, J. Zimmermann, Polymerization Processes, p. 424,467, Interscience Publishers, New York, 1977; DE-AS 21 · 52 194).

In addition, mixed polyamides are also suitable as polyamides

0 «· 000

0 • 0 »0 0« 00 00 »0 0 0 0 0 00 alpha-aromatic poles condensates as they are. described, for example, in US-PSS 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 as Kirk-Othmer, Encyclopedia of Chemical Technology, 3. ed., vol. 18, pp. 328 nn. and 462 nn., Wiley & Sons 1982. Other suitable polyamides are poles (etheresteramides) and poles (etheramides), respectively; these products have been described, for example, in DEOSS 25 23 991, 27 12 987 and 30 06 961.

The molding polyamide composition may comprise either one of these polyamides or multiple polyamides as a mixture. It may further comprise up to 40 wt. other thermoplastics insofar as they do not interfere with the bonding ability, in particular rubber-inducing toughness such as ethylene / propylene copolymers or ethylene / propylene / dienopolymers (EP-A-0 295 076), polypentenylene, polyoctenylene, statistically or block-built copolymers of alkenylaromatic compounds with aliphatic olefins dienes (EP-A-0 261 748) or coated rubber cores with an elastic core of methacrylate rubber, butadiene rubber or styrene / butadiene rubber having a glass transition temperature Tg <-10 ° C, the core being cross-linked and the shell constructed of styrene; and / or methyl methacrylate and / or other unsaturated monomers (DE-OSS 21 44 528, 37 28 685).

Conventional auxiliaries and additives such as flame retardants, stabilizers, plasticizers, processing aids, fillers, in particular to improve electrical conductivity, reinforcing fibers, pigments, etc. can be added to the polyamide molding composition. so that the required properties are not seriously compromised.

Linearly designed thermoplastic polyesters are suitable as polyesters. These are prepared by polycondensation of diols with dicarboxylic acid or its derivatives, respectively

Φ Φ «· · · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ jako φ Suitable diols have the formula HO-R-OH, wherein R represents a divalent, branched or unbranched aliphatic and / or cycloaliphatic radical having 2 to 40, preferably 2 to 12, C atoms. Suitable dicarboxylic acids have the formula HOOC-R'-COOH, where R 'is a divalent aromatic radical having 6 to 20, preferably 6 to 12 C-atoms.

Examples of diols are ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, and a C36-diol, called dimerdiol. The diols can be used alone or as a mixture of diols.

Up to 25 mol% of said diol can be replaced by the polyalkylene glycol of the following general formula

HO-f-R-O wherein R '' is a bivalent radical having 2 to 4 C atoms and x may have a value of from 2 to 50.

Suitable aromatic dicarboxylic acids are, for example, terephthalic acid, isophthalic acid, 1,4-, 1,5-, 2,6- and 2,7-naphthalenedicarboxylic acid, diphenoic acid, and diphenyl ether-4,4'-dicarboxylic acid. Up to 30 mol% of these dicarboxylic acids may be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid or cyclohexane-1,4-dicarboxylic acid.

Examples of suitable polyesters are polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene.

9 9 9 9 9 9

-13- 9999 999 9999

99 · <9 99 99

2,6-naphthalate, polypropylene-2,6-naphthalate and polybutylene-2,6-naphthalate.

The preparation of these polyesters belongs to the prior art (DEOSS 24 07 155, 24 07 156; Ullmanns Encyclopedia der technischen Chemie, 4th ed., Vol. 19, p. 65 nn., Verlag Chemie, Weinheim, 1980).

The polyester molding composition may comprise either one or more of the polyesters as a blend. In addition, other thermoplastics may be present up to 40% by weight as long as they do not interfere with the binding ability, in particular the toughness causing the rubbers, as mentioned above for polyamides. In addition, the polyester molding composition may contain conventional polyester auxiliaries and additives such as flame retardants, stabilizers, emollients, processing aids, fillers, in particular to improve electrical conductivity, reinforcing fibers, pigments, and the like. the required properties were not seriously compromised.

Typically, the polyamide molding composition comprises a continuous polyamide phase and the polyester molding composition comprises a continuous polyester phase.

If the bundle comprises a layer of polyamide molding material, in one preferred embodiment the bonding agent additionally to the graft copolymer comprises a polyamide, particularly preferably 10 to 90% by weight, based on the sum of the graft copolymer and the polyamide.

If the bundle comprises a layer of polyester molding material, it comprises - in one preferred embodiment - a cohesive agent in addition to the graft copolymer polyester, particularly preferably 10 to 90% by weight, based on the sum of the graft copolymer and polyester.

If the bundle comprises a layer I of polyamide molding compound and a layer II of polyester molding compound which bind • 4 »«

4 4 4 * 4 · 4 4 4 «44 44 444

44449 44444

43 4 4 43 4 44 4

44 44 * 44 · 4

4 ·· 4 together by means of cohesion. According to the invention, it is therefore preferred that the cohesive agent in addition to the graft copolymers contain both polyamide and polyester. Corresponding molding compositions are also an object of the invention.

In this embodiment, the cohesive agent preferably comprises the following composition:

I. 5 to 60 parts by weight of graft copolymers prepared using the following monomers:

a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine of at least 4, preferably at least 8 and particularly preferably of 11 nitrogen atoms and an average molecular weight Mn of at least 14 6 g / mol, preferably at least 500 g / mol and particularly preferably at least 800 g / mol as well as

b) polyamide-forming monomers selected from lactams, ωaminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid;

II. 10 to 85 parts by weight of polyamide;

III. 10 to 85 parts by weight of polyester;

wherein the sum of parts by weight of I., II. and III gives 100;

IV. a maximum of 40 parts by weight of additives selected from toughening rubber and / or conventional excipients or additives, respectively.

The polyamide of the cohesive agent should allow good compatibility with the polyamide of layer I and hence good cohesiveness. Suitable polyamide combinations are known to the person skilled in the art and can be readily ascertained by simple routine experimentation, for example by plate pressing. It is often sufficient that both polyamides have at least one monomeric monomer. 4 4 4 4 4 4 4 4 4 4 «···

4 4 4 4 4 4 4 4 4

The structural element is common or when both contain a corresponding monomeric structural element with the same number of C-atoms or the same length. Preferably, the polyamide should correspond as much as possible to the polyamide of layer I.

The same applies to the polyester of the cohesive agent which is to be well tolerated with the polyester of layer II. Here too, suitable combinations of polyesters are known to the person skilled in the art and can be readily ascertained by simple routine experiments, for example by plate pressing. It is often sufficient if both polyesters have at least one monomeric building block in common or when the corresponding monomeric building blocks are at least similar. Preferably, the polyester should correspond as much as possible to the polyester of layer II.

In addition to the grafted polymer as well as the polyamides and / or polyesters, the cohesion agent may also contain other components as additives, such as rubber impact strength and / or auxiliaries, as explained above as possible components of layers I and II . The amount of all additives is a total of at most 40 parts by weight, preferably at most 30 parts by weight and particularly preferably at most 20 parts by weight.

The multilayer bonding according to the invention is in one embodiment a pipe, a filler pipe or a container, in particular on a pipe or for the formation of liquid or gas storage reserves. This pipe may be straight or corrugated or only corrugated in certain sections. Corrugated pipes are known in the art (e.g., US 5,460,771) and therefore further clarification at this point is unnecessary. Important applications are for use as fuel lines, fuel fillers, vacuum lines (that is, pipelines through which fuel vapors, such as venting lines), are used.

stanice ,. as coolant lines, as air conditioning equipment lines or as fuel tanks.

The multilayer bonding according to the invention may exist as a flat bundle, for example as a foil, for example as a food wrapping foil, as a composite body with a coating to improve UV resistance or as extruded multilayer boards.

When using a bundle of multiple bonded layers according to the invention for pipes or reservoirs of flammable liquids, gases or powders such as fuels or vapors thereof, it is recommended to provide one of the layers belonging to the bundle or an additional inner layer electrically conductive. This can be accomplished by association with an electrically conductive additive according to all prior art methods. As conductive additive, for example, conductive carbon black, metal sequins, metal powders, metalized glass beads, metalized glass fibers, metal fibers (e.g. stainless steel), metalized whiskers, carbon fibers (also metalized), internally conductive polymers or graphite flanges. Mixtures of various conductive additives may also be used.

Preferably, the electrically conductive layer is in direct contact with the environment guided or stored therein and has a surface resistance of maximálně ⁹ Ω cm at most.

When the multilayer bundle according to the invention is designed as a tube, it may still be coated with another layer of elastomer. Both cross-linked rubber materials and thermoplastic elastomers are suitable for sheathing. The sheathing of the tubes can be carried out both with and without the additional cohesion means, for example by extrusion through a cross-injection head or by extending the preformed elastomeric hose over the finished extruded multilayer tube.

The multi-layer bundle can be produced in one stage •

Or multistage, for example by means of a single-stage process by multi-component injection molding, coextrusion or coextrusion blow molding, or by a multi-stage process, as described, for example, in US 5 554 425.

In its simplest embodiment, the multilayer bundle may consist of a layer I, a cohesive agent and a layer II; however, for example, the following layer configurations may exist using additional layers:

rubber (layer I) / cohesive agent / layer II; layer I / bonding agent / layer II / electrically conductive layer II;

layer I / cohesive agent / layer II / cohesive agent / layer I;

layer 1 / bonding agent / layer II / bonding agent / electrically conductive layer

AND;

rubber (layer 1) cohesive agent / layer II / cohesive agent / layer I / electrically conductive layer I;

layer II / bonding agent / layer I / electrically conductive layer I.

The results shown in the experiments were determined using the following measurement methods.

To determine the carboxyl end groups, 1 g of graft copolymers was dissolved in 50 ml of benzyl alcohol under nitrogen at 165 ° C. The dissolution time was a maximum of 20 min. The solution was titrated to phenolphthalein with a solution of KOH in ethylene glycol (0.05 mol KOH / L) until color change.

For the determination of amino groups, 1 g of graft copolymers was dissolved in 50 ml of m-cresol at 25 ° C. The solution was titrated potentiometrically with perchloric acid.

• • • • • • • • • 9 9 9

Determination of the viscosity of the solution rjrei (relative viscosity) was carried out using 0.5 wt. m-cresol solution at 25 ° C according to DIN 53727 / ISO 307.

DETAILED DESCRIPTION OF THE INVENTION

The following components were used in the experiments:

Graft copolymer 1:

29.7 kg of lauric acid lactam were melted in a heated boiler at 180 ° C to 210 ° C and transferred to a pressure-resistant polycondensation boiler; then 1.5 kg of water and 1.71 g of phosphoric acid were added. The cleavage of lauric acid lactam was performed at 280 ° C under its own pressure which was set; then 3 bar was released to a residual water vapor pressure over 3 hours and 300 g of polyethyleneimine (LUPASO1 G 100 OD BASF AG, Ludwigshafen) was added.

The polyethyleneimine was processed at its set self-pressure; then the pressure was released to atmospheric pressure and then nitrogen was passed through the melt for 2 hours at 280 ° C. The clear melt was discharged as a fiber by means of a melt pump, cooled in a water bath and finally granulated.

T rel: 1.68

Melting point T _m : 175 ° C

Concentration of amino groups: 225 mmol / kg

End carboxyl group concentration: <10 mmol / kg

Graft polymer 2:

9.5 kg of lauric acid lactam were melted in a heated boiler at 180 ° C to 210 ° C and transferred to a pressure-resistant polycondensation boiler; then 475 g of water and 0.54 g of phosphoric acid were added. Cleavage • · • ·· · • ·

lauric acid lactam was performed at 280 ° C under self-pressure that was set; 5 g of polyethyleneimine (LUPASOL G 100 from BASF AG, Ludwigshafen) as well as 15 g of dodecanedioic acid were added to the residual water vapor pressure over 3 hours. Both components were processed at their established self-pressure; then the pressure was released to atmospheric pressure and then nitrogen was passed through the melt for 2 hours at 280 ° C. The clear melt was discharged as a fiber by means of a melt pump, cooled in a water bath and finally granulated.

T rel: 1.52

Melting point T _m : 169 ° C

Amino group concentration: 810 mmol / kg of terminal carboxyl group concentration; <10 mmol / kg

PA 1: PA 12 molding compound with η _Γβ ι. = 2.1 and extrusion end _capping carboxyl groups

PA 2: PA 12 molding compound with Tirei = 2.1 and extrusion-end-excess amino groups

PES 1; VESTODUR 1000, homopolybutylene terephthalate DegussaHils AG with dissolution viscosity J, measured in phenol / o-ortodichlorobenzene (1: 1), 107 cm / g

PES 2: VESTODUR 3000, homopolybutylene terephthalate Degussao

Hils AG with a dissolution viscosity J of 165 cm / g

EXXELOR VA 1803: EPM rubber from Exxon Chemical, Kolín, functionalized with approx. 1% maleic anhydride

Polyamide of layer I:

PA 3; Extrusion-capable, plasticized, modified to stiffness PA 12 _{s r} ei. = 2.1 and end-capping carboxyl groups

4

Polyester layer II:

PES 3: VESTODUR 2000, homopolybutylene terephthalate DegussaHUls AG with dissolution viscosity J 145 cm ³ / g

Example 1

At 250 [deg.] C. and a pressure time of 30 s, a three layer stack of pressed sheets of PA 3, graft copolymer 1 as a bonding agent, and PES 3 was prepared.

Example 2

As Example 1, but with graft copolymer 2 as a cohesive agent. Here, too, an inseparable cohesion was obtained for both the polyester layer and the polyamide layer.

Comparative Example 1

As in Example 1, a pack of PA 3 and PES 3 molded plates was prepared. Instead of graft copolymer 1, LUPASOL G 100 in an anhydrous form was applied in a very thin layer to the top of the PA 3 plate to be bonded to PES 3.

After pressing and cooling, the plate was removed and tested. It turned out that there was no cohesion.

Comparative Example 2

Four different blends of PA 2 and polyethyleneimine (LUPASOL G 100 in anhydrous form, BASF AG, Ludwigshafen) were prepared in a Haake laboratory kneader according to Table 1.

· · Fcfc ·· • fc fcfcfcfc · · fc • fcfc • fcfc · · · • fcfc · fc fcfc · • fcfc · • fcfc · • fc fcfc

Table 1

A mixture of polyamide and polyethyleneimine

Composite component Weight fraction PA 2 99 95 90 80 Polyethylenimine 1 5 10 20 May Mixing was performed for 8 minutes at: ≥ 80 ° C and 64 rpm

minute.

The mixtures were finally comminuted and applied to the PES 1 spray plate which was in the compression mold. Then, it was pressed as described in Example 1.

In all four cases, when checking the consistency of the layers, it became apparent that the interface connection could be separated by hand.

Means causing cohesion - mixtures:

HV 1 (not according to the invention):

12.6 kg of PA 1 and 22.82 kg of PES 1 were blended into a melt, compressed into a fiber and granulated in a Bergstorff ZE 25 33D twin screw kneader at 270 ° C and 200 rpm as well as at a throughput of 10 kg / h.

HV 2 (according to the invention):

12.6 kg of PA 1 and 22.82 kg of PES 1 and 5.0 kg of graft copolymers 2 were in a ZE 25 33D twin-screw kneader

Bergstorff at 270 ° C and 150 rpm as well as at a throughput of 10 kg / h was blended to melt, compressed into fiber, and granulated.

HV 3 (according to the invention):

12.6 kg PA 2 and 22.82 kg PES 2 and 5.0 kg grafted ·· ··················· · 4 of the copolymer 2 were in a ZE 25 33D twin-screw kneader

Bergstorff at 270 ° C and 150 rpm as well as at a throughput of 10 kg / h was blended to melt, compressed into fiber, and granulated.

HV 4 (according to the invention):

As HV 3, but with additional use of 4.0 kg EXXELOR VA 1803.

Comparative Example 3 as well as Examples 3 to 5:

A bundle coextrusion molding tool with an output width of 30 mm was used to prepare the multilayer bundle, and the combining of the various layers in the tool was performed shortly before the melt exited the tool. The tool was fed by three Storck 25 extruders. After exiting the tool, the bundle of three bonded layers was placed on a cooling roller and pulled off (Chill-Roll method). The results are again shown in the following table; the signs of cohesion referred to therein mean:

no coherence slight coherence a little coherence; good cohesion can be separated with little effort; detachable only with great effort and also by means of tools inseparable • «» • · · · · · · · · · · · · · ·

Table 2: Preparation of trilayer bundles

Example (B) or comparative Layer AND Means causing cohesion Layer II Cohesion Interface: layer 1 / means causing cohesion Interface: layer 11 / means causing cohesion example (IN) V 3 BYE 3 HV 1 DOG 1 0 4 B 3 BYE 3 HV 2 DOG 1 4 4 B 4 BYE 3 HV 3 DOG 3 4 4 B 5 BYE 3 HV 4 DOG 1 4 4

In addition, Examples 4 and 5 of the invention were repeated in a modified form in which a three-layer pipe with the corresponding layer configuration (with PA 3 as the outer layer) was prepared. The results coincide (in all cases the coherence sign 4).

In all the cases examined, the long-term resistance of the multilayer bundle in contact with the propellant containing alcohol as well as at 40 ° C and at 60 ° C was excellent.

PI / 6 & 00

Claims (22)

PATENT CLAIM 1. Thermoplastic multilayer bonding comprising the following steps: I. layer I of thermoplastic molding material; II. a second thermoplastic molding material layer II; between them a layer of a cohesion agent consisting of at least 5% by weight of graft copolymers prepared using the following monomers: (a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine of at least 4 nitrogen atoms and an average molecular weight M _{n of} at least 146 g / mol; and b) polyamide-forming monomers selected from lactams, ωaminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid. Multilayer thermoplastic bonding according to claim 1 1, characterized in that at least one of the layers I and II consists of a polyamide molding compound or a polyester molding compound. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the layer I consists of a polyamide molding material and 9 9999. 25 99 99 * 9 • 9 9 9 9 9 9 9 99 · 9 · 999 99 · 9 99 9 9,999,999 The layer II consists of a polyester molding material. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the polyamine contains at least 8 nitrogen atoms. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the polyamine contains at least 11 nitrogen atoms Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the polyamine comprises an average molecular weight M _{n of} at least 500 g / mol. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the polyamine has an average molecular weight M _{n of} at least 800 g / mol. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the amino group concentration of the graft copolymers is in the range from 100 to 2500 mmol / kg. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the graft copolymer is prepared using the following added monomer: c) an oligocarboxylic acid selected from 0.015 to about 3 mol% of the dicarboxylic acid and 0.01 to about 1.2 mol% of the tricarboxylic acid, each based on the sum 0 0 • 000 0 0 0 0 0 0 0 0 0 »0000 0 0 0 0 0 0 0 0 0 0 · 0 0 0 The remaining polyamide-forming monomer Multilayer thermoplastic bonding according to claim 2 and 3, characterized in that the bonding agent comprises in addition to the graft copolymers a polyamide and / or a polyester. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the bundle comprises more than one layer I and / or more than one layer II. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that one of the layers is electrically conductive. Thermoplastic multilayer bonding according to claims 1 to 11, characterized in that a further electrically conductive layer is bonded to the inner layer. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that the bundle is a tube. 15. The multilayer thermoplastic bonding of claim 14, wherein the bundle is corrugated wholly or partially. Multilayer thermoplastic bonding according to claims 14 and 15, characterized in that a rubber layer is attached to the outer layer. The thermoplastic multilayer bonding of claim 44 »» 3 4 • 4 4 4 4 4 4 4 4 4 * 4 999 8 44 * • k »4 4 4 4 4 4 4 4 4 4 4 · 4 · 4 4 4 4 4 4 44 14 and 16, characterized in that it is a fuel line, a brake fluid line, a coolant line, a hydraulic line, a service station line, an air conditioning unit line or a vacuum line. Multilayer thermoplastic bonding according to claims 1 to 13, characterized in that the bundle is a hollow body. Multilayer thermoplastic coupling according to claims 1 to 13 as well as 18, characterized in that the bundle is a container, in particular a fuel container, or filling nozzles, in particular refueling fillers. Multilayer thermoplastic bonding according to claims 1 to 13, characterized in that it is a foil or a multilayer board. Multilayer thermoplastic bonding according to any one of the preceding claims, characterized in that it is prepared by injecting multiple components, by coextrusion or by coextrusion blow molding. 22. A molding composition comprising the following components: I. 5 to 60 parts by weight of a graft copolymer prepared using the following monomers: (a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine of at least 4 nitrogen atoms and an average molecular weight M _{n of} at least 146 g / mol; and b) polyamide-forming monomers selected from lactams, ωaminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid; 44 4 * 4 · 4 · * 4 II. 10 to 85 parts by weight of polyamide; III. 10 to 85 parts by weight of polyester; wherein the sum of parts by weight of I., II. and III. gives 100; IV. a maximum of 40 parts by weight of additives selected from stiffening rubber and / or conventional excipients or additives, respectively.