DE10136286A1 - Thermoplastic block copolymers with poly(meth)acrylate and polyamide segments, used for production of fibres, film, mouldings and hot-melt adhesives or as coupling agents for polyamides and acrylics or polycarbonates - Google Patents

Abstract

Thermoplastic block copolymers with poly(meth)acrylate and polyamide segments, derived from: (I) poly(meth)acrylate-diols; (II) polyamide-dicarboxylic acids; and (III) other diols or diamines. Thermoplastic block copolymers of formula (A), containing the following segments (wt. %): (I) optionally imidated poly(meth)acrylate-diol(s) (HO-A-OH) of formula (1) (15-70); (II) polyamide-dicarboxylic acid(s) (HOOC-B-COOH) of formulas (IIA) or (IIB) (30-90); and (III) diol(s) or diamine(s) of formula (III) (1-20). p = 1-20; and q, r = 1-10 R<1>-(CH2-C(R<2>)(COOR<3>))z-R<4> (1), HO-(CO-(CH2)a-NH)b-CO-R<7>-COOH (IIA) HO-(CO-R<7>-CO-NH-R<8>-NH)b-CO-R<7>-COOH (IIB) HX-D-XH (III) z = 4-50; R<1> = -S-R<5>-OH, -C(C6H5)2-R<5>-OH or -SCS-N(C2H5)-C2H4-OH; R<2> = H or methyl; R<3> = optionally halogenated 1-12C alkyl; R<4> = R<5>OH, SCS-N(C2H5)-C2H4OH or CH2-CHR<2>-COOR<5>-OH; R<5> = optionally unsaturated 2-20C aliphatic hydrocarbylene, cycloaliphatic hydrocarbylene with up to 36 C atoms, 8-20C aliphatic-aromatic hydrocarbylene, a divalent aliphatic ether residue of formula R<6>-O-R<6>' or a divalent polyether residue of formula -(CnH2nO)m-CpH2p-; R<6>, R<6>' = groups with a total of 4-20C atoms; n, p = 2-4; m = at least 1; a = 5-11; b = 2-40; R<7> = hydrocarbylene groups as listed for R<5>; R<8> = 2-12C aliphatic hydrocarbylene, 6-20C cycloaliphatic hydrocarbylene, 8-20C aliphatic-aromatic hydrocarbylene, or -R<6>-O-R<6>'-; X = NH or O; D = optionally unsaturated 4-36C (cyclo)aliphatic hydrocarbylene, an optionally unsaturated aliphatic olefin polymer (mol. wt. 500-4000), a divalent polyether residue as in R<5> (mol. wt. 400-2500), a polyester residue of formula HO-R<9>-O-(CO-(CH2)a-O)n-H (4A) in which a = 5-11 and n = 5-30 or HO-R<9>-O-(CO-R<7>-CO-O-R<9>-O)n-H (4B) in which n = 3-20, or an organic polysiloxane residue with a mol. wt. of 500-3000; R<9> = 2-36C (cyclo)aliphatic hydrocarbylene Independent claims are also included for: (a) method for the production of (A) comprising: (i) production of (co)polyamide blocks with a number-average molecular weight (Mn) of 500-5000 (preferably 750-2500) and an amino end-group content of not more than 50 mmols/kg by polymerisation or polycondensation at 180-300 deg C and 1-30 bar (optionally with addition of component D if X = NH), followed by degassing to remove water for at least 0.5 hour at pressures down to 50 mbar; (ii) addition of alpha ,w-functionalized polyalkyl (meth)acrylate-diols (Mn = 600-5000, preferably 900-2500) in the form of solid, solution or melt, together with all or part of the diol component (III) (if X = O), or optional reaction of component (III) (X = O) with the PMMA-diol (I) in a parallel condensation step to give DMMP-polyester-diol; (iii) further polycondensation at 180-300 deg C under reduced pressure in presence of 0.05-0.2 wt% catalyst to give (A) and (iv) discharge from the reactor or further processing to molded products; (b) thermoplastic laminates comprising: (i) a layer based on (co)polyamide; (ii) layer(s) of thermoplastic molding material selected from polyalkyl (meth)acrylates (homo- or co-polymers in which up to 50 mol. % of the alkyl (meth)acrylate may be replaced by butyl (meth)acrylate, methacrylic acid, itaconic acid, styrene or maleic anhydride), polycarbonates, fluoropolymers and/or perfluorinated polymers; and (iii) at least one layer between (i) and (ii) based on a mixture of the polymers in (i) and (ii) with block copolymers (A); (c) optical leads with a fibre core and a fibre casing containing a plastic light guide with its protective sheath, in which the sheath consists of (co)polyamide with a melting point below 220 deg C and the fibre casing consists of polymers based on vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, tetrafluoropropyl, pentafluoropropyl, trifluoroethyl and/or heptadecafluorodecyl methacrylate(s), optionally with acrylic acid- or acrylate-modified polymers, or mixtures of these, with block copolymers (A) being used as the adhesive between fibre casing and protective layer.

Description

The present invention relates to novel thermo which can be produced by polycondensation plastic block copolymers consisting of poly (meth) acrylate and polyamide segments, the Manufacturing and their use. The block copolymers according to the invention show one unique combination of the properties of poly (meth) acrylates (PMMA) and polyamides, can be used as modifiers in both polyamide and poly (meth) acrylates , serve as a compatibility agent in blends or are tailor-made adhesion promoters in multi-layer systems, such as B. multilayer polymer tubes.

The polyamides are among the most important technical thermoplastics with a wide range of applications in various areas. This diversity results from the fact that Polyami de can be modified in many different ways and so tailor-made products are manufactured can. In addition to introducing reinforcing and filling materials, blending with other Ren polymer, the addition of various additives, the copolymer formation offers a important way to specifically influence the properties of the polyamides. Under the linear block In the literature, polymers are mainly known in addition to the polyamide segment Segments based on polyethers, polyester, polysiloxanes, polyimides and polycarbona ten (J. Stehlicek, J. Horsky, J. Roda, A. Moucha in "Lactam based Polyamides" Vol. 2, R. Puffr, V. Kubanek, Ed., CRC Press, Boca Raton 1991, 20 ff). However, there are only a few Examples of the combination of polyamide and vinyl monomer based segments. An exception to this are block copolymers consisting of polyamide-6 and polystyrene, Po ly (butadiene-co-acrylonitrile) (Colloid Polym. Sci. (1989), 267 (I), 9-15), poly (styrene-co-butadiene), Polybutadiene and polyisobutylene.

Block copolymers from polyamide and poly (meth) acrylate segments are based on high molecular or oligomeric polyamides so far only on the way of radical poly merization of macromolecular initiators accessible. Either the synthesis takes place Initiators based on polyamide precondensates, usually equipped with amino end groups, by reaction with suitably functionalized, low-molecular azo or peroxo Initiators (Polymer Journal 31 (10), 864-871) or by nitrosation of a commercially available  Polyamides and subsequent photochemical rearrangement in the corresponding high molecular diazo esters (J. Polym. Sci., Polym. Chem. Ed. (1980), 18 (6), 2011-20; J. Polym. Sci., Polym. Chem. Ed. (1982), 20 (7), 1935-9). By radical mass or solution polymerization, thermally or photochemically induced, can be AB, ABA or on the Segmented multiblock copolymers can also be produced by way of nitrosation.

Biradi usually forms during the photochemically or thermally induced decay of the diazo esters kale, which give rise to ramifications and networking. Many of the products are therefore rubbery and insoluble. Due to the high transmission rate, the formation of graft unavoidable polymers. Furthermore, the properties of these copolymers are practical completely determined by the vinyl component. The yield of the reaction with MMA (Methyl methacrylate) is unsatisfactory. While for the reaction pair polyamide-6 / acrylonitrile or vinyl acetate sales are almost complete, sales are only for MMA 25%.

In the case of polyamide oligomers with azo end groups, only AB or ABA- Block copolymers accessible. The implementations must be carried out in solution. The In Itiator effectiveness is very low, so that inconsistent products are formed. Due to the necessary reactions are restrictions in the concentration, the segment length and the composition of the polyamide precondensates, as these parameters the dissolving behavior of the components involved and the resulting solution viscosi of the reaction mixture.

Y. Yamashita first describes polycondensation in Polymer Bulletin 5, 361-366 of a polymethacrylate macromonomer with polyamide-forming monomers for the production of Graft copolymers. The PMMA macromonomer was obtained by radical polymerization of MMA obtained in the presence of thiosuccinic acid as a chain transfer agent. The structure of the Polyamide backbone was made by catalyzed polycondensation with aromatic diamines and aliphatic dicarboxylic acids in solution.

Furthermore, Y. Chujo et al. in J. Polym. Sci., Part A: Polymer Chemistry 27, 2007-14 (1989) the use of 2-mercaptoethanol and 2-aminoethanethiol as chain transfer reagent for the functionalization of PMMA oligomers. The generated monofunctional PMMA oligomers are ent by subsequent reaction with trimellitic anhydride talking PMMA dicarboxylic acid converted. In turn, macromonomers stand for polycondensation is available. The copolymers obtained are graft copolymers with Polyamide main chain and PMMA side chains.  

The pre-formation of the PMMA macromers avoids the radical polymerization difficulties encountered, the structure of the polyamide chains described must also in Solution to be executed. However, the use of the α-bifunctionalized macromers enables only the synthesis of graft copolymers.

In US-A-4,501,861 thermoplastic polyamide blends consisting of polyamide-6 and anionically produced block polymers based on polyamide-6. The used oligomeric diols, including poly (alkyl acrylates), must be on both chain ends be implemented with an acyllactam unit so that an incorporation during the anionic Po Lymerisation of caprolactam is possible.

The anionic ring opening is limited to lactams and requires high purity components used, especially absolute freedom from water. The radio must also tionalization of the diols take place in full, since otherwise termination centers for the anioni chemical polymerization, resulting in a high residual lactam content and low Degrees of polymerization result. Reproducibility is therefore a major problem this process.

It is therefore an object of the present invention to provide new polyamide polyalkyl (meth) acrylate To provide block copolymers that overcome the above disadvantages of the prior art Avoid nik and can be produced by polycondensation.

The object is achieved in relation to the block copolymer by the features of claim 1, by the method of claim 7, with respect to the use of claims 8 to 10 solved.

The subclaims show advantageous embodiments of the invention.

The invention thus relates to polyamide-polyalkyl (meth) acrylate block copolymers composed of customary polyamide-forming monomers and 15-70 wt .-% poly-alkyl (meth) acrylates.

The block copolymers according to the invention are prepared in that in a first Po Lymerization or polycondensation step at temperatures from 180 to 300 ° C, a pressure from atmospheric pressure to 3 × 106 Pas (30 bar) polyamide or copolyamide blocks with one number-average molar mass in the range from 500 to 5000 g / mol, preferably in the range from two 750 to 2500 g / mol, with an amino end group concentration of at most  50 mmol / kg, optionally with the addition of component D if X = N in formula (III), be produced and to reduce the water content at least 0.5 hours at one Pressure from 50 mbar to atmospheric pressure is degassed, in a second step, α, ω-functio nalized poly-alkyl (meth) acrylate diols with a number-average molecular weight in the range between two between 600 and 5000 g / mol, preferably in the range between 900 and 2500 g / mol, as a solid substance, solution or melt together with all or part of the diol compo nente (III), in the case when X = O in formula (III) are added, or, if necessary, com component (III), in the case of X = O with the PMMA diol in a parallel condensation step is converted to the DMMP polyester diol, and the reaction mixture at a temperature of 180 to 300 ° C, in the presence of 0.05 to 0.2 wt .-% of one catalyst in another Polycondensation step under reduced pressure to form the high molecular weight block copolymer (A) fully condensed, discharged or processed into shaped bodies.

The invention also relates to thermoplastic multilayer composites consisting of minde at least one layer of a molding compound based on (co) polyamide, at least one layer from a molding compound made of a thermoplastic material, selected from the group, best Starting from poly-alkyl (meth) acrylates, polycarbonates and blends from polycarbonates with others Plastics, such as B. polyolefins, the poly-alkyl (meth) acrylates or homopolymers Are copolymers in which up to 50 mol% of the methyl (meth) acrylate is due to other monomers from the group consisting of butyl methacrylate, butyl acrylate, methacrylic acid, itaconic acid, styrene, malein Acid anhydride can be replaced, the fluoropolymers, or the perfused polymers or Ge mix the aforementioned compounds and at least one intermediate layer based on a Adhesion promoter molding compound from the thermoplastic block copolymers according to one or several of claims 1 to 6. As an adhesion-promoting intermediate layer between the layers (a) and (b) alternatively, according to the invention, there is also a blend of layers (a) and (b) building polymers into consideration, wherein at least part of the blend from the thermoplastic block copolymers (according to claims 1 to 6) can exist. In a special one Embodiment of the invention contains the physical mixture (blend) at least 8% by weight the thermoplastic block copolymers according to the invention. In another execution can form the intermediate layer based on an adhesion promoter molding compound from 100 wt .-% thermoplastic block copolymers according to one of claims 1 to 6.

The multilayer composites according to the invention are found in construction parts, above all in rich use of the automotive, electrical, mechanical engineering industries. In particular, they find Use for the production of fibers, films, moldings such. B. housings, housing parts of mobile phones and as a hot melt adhesive. Use as is particularly preferred Multi-layer pipe in the automotive sector.  

The invention therefore also relates to multi-layer, polymer hose or pipelines that oppose can also be corrugated in at least one partial area, consisting of an interior layer made of fluoropolymers, an outer layer made of polyamide, with polyamide being a special Polyamide-12 or polyamide-12 derivatives are preferred, and an intermediate one Adhesion promoter layer based on the thermoplastic block copolymers according to one of the An Proverbs 1 to 6. However, a physical mixture can also be used as an adhesion promoter layer the polymers forming the inner and outer layers may be present, at least some of which be replaced by the thermoplastic block copolymers according to one of claims 1 to 6 can. This physical mixture advantageously contains at least 8% by weight of the inventin thermoplastic block copolymers according to the invention. But the intermediate layer can also 100 wt .-% consist of the thermoplastic copolymers.

The for the inner layer of the multilayer polymer hose or tube according to the invention Fluropolymers used in lines are selected from fluoropolymers based on Te trafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene fluoride (VDF) and fluorine polymers based on tetrafluoroethylene (TFE), perfluoromethyl vinyl ether (PMVE) and viny lidenefluoride (VDF). According to the invention, a terpolymer made from tetra is particularly preferred fluoroethylene, hexafluoropropylene, vinylidene fluoride (trade name THV 500 G, from 3M). An inner layer made of PVDF is also particularly preferred.

Polyamide part

In principle, all customary lactams, amino carboxylic acids, dicarboxylic acids and diamine pairs can be used as the polyamide-forming monomers. According to the invention, therefore, monomer building blocks which are selected from the group of the lactams with 6-12 C atoms, such as laurolactam or which correspond to the α, ω-aminocarboxylic acids with 6-12 C atoms, are suitable for the polyamide segments , such as B. ω-aminolauric acid or the combination of aliphatic diamines with 2-12 C atoms and dicarboxylic acids with 2-44 C atoms and aliphatic and cycloaliphatic diamines with 2-18 C atoms such as for example dodecanediamine / dodecanedioic acid or dodecanediamine / Sebacic acid or dodecane diamine / C36-dimer acid and, on the other hand, other monomers such as are used for partially aromatic polyamides. However, the polyamide component of the block copolymers according to the invention is preferably based on:

• 1. aliphatic homopolyamides such as PA 46, PA 6, PA 66, PA 69, PA 610, PA 612, PA 636, PA 810, PA 1010, PA 1012, PA 11, PA 12, PA 1212, or partially aromatic polyamides such as PA 61 , PA 6T, PA 6I6T, PA 9T, PA 12T as well as copolyamides and multipolyamides, based on the dicarboxylic acids C ₂ -C ₃₆ and diamines C ₂ -C ₂₄ as well as lactam-6, lactam-12, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid. The polyamide component can also be obtained by polycondensation of the corresponding salts of diamine and dicarboxylic acid.
• 2. amorphous polyamides or copolyamides, which consist of branched or unbranched alipha table diamines with 6-18 carbon atoms, such as B. 1,6-hexamethylene diamine, 2,2,4- or 2,4,4- Trimethylhexamethylene diamine, cycloaliphatic diamines, such as. B. 4,4'-diamino dicyclo-hexyl methane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane, isophorone diamine or aromatic diamines with 6-12 C atoms, such as. B. m- and p-xylylenediamine and aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 6-12 C atoms are built up.
• 3. However, transparent copolyamides also come as additional polyamide-forming polymers a glass temperature of 30-130 ° C, which are made up of 90-45 parts by weight Laurin lactam, which can be replaced by ω-aminocarboxylic acids with 9-12 C atoms or through aliphatic diamines with 9-12 C atoms in combination with aliphatic dicarbon acids with 9-12 carbon atoms, and 55-10 parts by weight of other monomers for partial aroma table polyamides, consisting of an aliphatic diamine with 2-12 C atoms in almost equimolar ratio to the diamine and at least one aromatic dicarboxylic acid, by a maximum of 15 mol% of another aliphatic dicarboxylic acid with 9-36 C atoms can be replaced. Such transparent copolyamides are described in EP 603 813 B1.

The polyamide segments according to the invention have number-average molar masses in the range from 500 to 5000 g / mol, preferably in the range between 750-2500 g / mol.

PMMA part

The polyalkyl (meth) acrylate segment for the fiction accessible by polycondensation block copolymers in the form of an α, ω-functionalized polyalkyl (meth) acrylate introduced, which carries condensable end groups. As such, the offer after the so-called "Iniferter technique" (C.P. Reghunadhan Nair et al. in J. Polymer Sci., Part A: Polymer Chemistry 27, 1795 (1989)) or according to DE-A-43 14 111 or US-A- 5,900,464 accessible α, ω-poly (meth) acrylatediols or those described in EP-A-0 708 115 α, ω-poly (meth) acrylate dicarboxylic acids.

The α, ω-functionalized polyalkyl (meth) acrylates used have number-average moles masses in the range between 600 and 5000 g / mol, preferably in the range between 900 and 2500 g / mol. The bifunctionality is at least 90%. The glass transition temperature is  between -50 and + 170 ° C.

Component D

A further component of the block copolymers is a diol or diamine of the formula (III)

HX-D-XH (III), with X = NH or O

used, D being selected from the group consisting of (1), (2), (3), (4), (5):

• 1. a divalent aliphatic, optionally cycloaliphatic hydrocarbon radical 4-36 carbon atoms, optionally unsaturated,
• 2. an aliphatic olefin polymer with a molecular weight of 500-4000 g / mol, if appropriate unsaturated,
• 3. a divalent polyether radical of the general formula - (C _n H _2n O) _m -C _p H _2p , where n = 2-4, p = 2-4 and the molar mass is 400-2500 g / mol,
• 4. a polyester radical of the general formula (IVa) or (IVb):
  where n = an integer from 3 to 20
  respectively.
  where a = an integer from 5 to 11 and n = an integer from 5 to 30,
  wherein R ^{9 is} an aliphatic or cycloaliphatic hydrocarbon radical with 2-36 carbon atoms and
  R ^{7 is} a divalent aliphatic, optionally unsaturated hydrocarbon radical with 2-20 carbon atoms, a cycloaliphatic hydrocarbon with up to 36 C atoms
  or is an aliphatic-aromatic hydrocarbon radical with 8-20 C atoms;
• 5. an organic polysiloxane residue with a molecular weight of 500-3000 g / mol.

Examples include: butanediol, hexanediol, cyclohexanedimethanol, dodecanediol, dimer diol, hexamethylene diamine, dodecane diamine, 2,2,4- and 2,4,4-trimethylhexa-methylene diamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclo-hexylmethane, polyethylene lenglycol diol, polypropylene glycol diol, polytetramethylene diols, polyethylene glycol diamine, Polypropylene glycol diamines, polytetramethylene diamines, polybutadiene diols and poly (butadiene co-ethylene) diols, optionally hydrogenated, polycaprolactone diols, polyester diols based of aliphatic or aromatic dicarboxylic acids and aliphatic or cycloaliphatic C2-C36 diols or aromatic C6-C18 diols.

The following may be mentioned as further examples of the group of substances (III) HX-D-XH:

The first 3 products have a pure C chain, while the last 3 examples Copoly are ester diols. Tegomer H-Si 2311 is a polysiloxane diol.

The invention further relates to the use of the block copolymers for the production of sern, foils and moldings z. B. of mono or multilayer pipes and as a hot melt adhesive for textile and technical applications.

Furthermore, it is also possible to use the block copolymers according to the invention as an adhesive extension of housing parts such. B. use housings for mobile phones. So far it is usual to manufacture displays of mobile phones from PMMA, while the housing from Po lycarbonate (polycarbonate resins are due to their excellent heat resistance, their  excellent impact resistance and good shape retention) or ABS best hen. Both parts are then with the help of adhesives such. B. ver ver polyurethanes sticks. Due to increased requirements, however, there is a need for housing made of Po lyamide materials such as B. Grilamid TR90. So far there has been no possibility Such a housing part made of Grilamid TR90 or polycarbonate with a display To glue PMMA. With the aid of the new block copolymers according to the invention, however, this is the case possible for the first time. It can splash water PMMA display with a housing made of Grilamid TR90 be tightly glued.

The invention relates u. a. thermoplastic multilayer composites made of polyamides and Polyalkyl (meth) acrylates and polycarbonates or fluoropolymers as well as copolymers and Blends based on the substance groups mentioned.

The thermoplastic multilayer composite according to the invention consists of

• 1. A: at least one layer of (co) polyamide and
• 2. B: at least one layer of a thermoplastic material selected from the Group of polyalkyl (meth) acrylates, polycarbonates, fluoropolymers or per fluorinated polymers;
• 3. C: at least one adhesion promoter adjacent to layers A and B, the Layers are non-positively connected and the Blockco as an adhesion promoter polymer according to one of claims 1 to 6 is used.

Preferred embodiments according to the invention:

1. multilayer composite, produced by injection molding or extrusion, in which the layers A and B Polyamide-12 and PMMA are.

2. multilayer composite, produced by injection molding, extrusion, calendering or welding, in which layers (a) and (b) are transparent polyamide and PMMA or PMMA Are copolymer or polycarbonate. The transparent polyamides used have a Light transmission in the wavelength range of visible light of at least 80%. Amorphous polyamides of terephthalic acid and the isomer are particularly preferred Mixture of 2,2,4- and 2,4,4-trimethylhexamethylene diamine, the copolyamide from isophthal acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam and the polyamide  1,12-dodecanedicarboxylic acid and 4,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'- diaminodicyclohexylmethane.

The layer C lying between the layers A and B can via the adhesion-promoting Wir have additional functions. By introducing UV, for example absorbing, photochromic, polarizing or thermotropic substances in layer C the multilayer composite can be used as a functional unit in optical applications. It would also be conceivable to use such a functionalized layer as an external layer outer or inner layer. Depending on the requirements, the block copolymer can pass through Setting the segment density ratio rather the typical properties of the underlying polyamides - or P (M) MA.

The scratch resistance of a construction part made of transparent polyamide (PA) can be increased by bring a PMMA outer layer can be improved. Conversely, gives an outer layer made of transparent polyamide the multi-layer composite a good stress cracking and chemical enbeständigkeit. In both cases, due to the incompatibility of the polyamide and P (M) MA Layers a force-transmitting, adhesion-promoting layer are used. Through commitment of polymethacrylimide (PMI) instead of PMMA, applications can be realized that allow a significantly higher continuous use temperature. Through partial or complete imi The (meth) acrylate component in the block copolymer is also temperature-adjusted Continuity increased and the compatibility with PMI significantly improved.

Layer B in embodiments 1) and 2) is in particular made of polyalkyl (meth) acrylates with 1-12 C atoms in the carbon chain of the alkyl radical, which, if appropriate is partially or fully fluorinated. The polyalkyl (meth) acrylates are more common have a melt flow index of 0.5 to 30 g / 10 min, measured at 230 ° C with a Bela capacity of 3.8 kg. Polymethyl methacrylate and polybutyl methacrylate are particularly preferred. However, copolymers of polyalkyl (meth) acrylates can also be used. It can up to 50 mol% of the methyl methacrylate through other monomers such as butyl methacrylate, buty Acrylate, methacrylic acid, itaconic acid, styrene, maleic anhydride can be replaced. Polymers for Layer B can be used, stabilizers, processing aids, Impact modifiers, fillers and other conventional additives or additives in the usual quantities included.

3. Multi-layer composite, produced by injection molding or extrusion, in which the layers A and B Polyamide-12 and PVDF are. Due to the good barrier properties of the PVDF compared to ver  Different fuels can be a three-layer pipe with an inner layer made of PVDF, a medium Ren layer of the block copolymer of the invention and an outer protective layer Polyamide-12 can be used as a fuel-carrying line in automobiles. The inside Layer of the polymer or hose line according to the invention is to be transported rendering medium inert; the outer layer is resistant to pressure and mechanical influences constantly. The layer thickness of the hose and pipeline according to the invention is not critical. before outer layers in the range of 0.2-0.8 mm are added, adhesive layers in the range of 0.05 to 0.3 mm and inner layers in the range of 0.01-0.7 mm. As stated above, it is also possible that the wall of the hose or pipe with an annular or spiral gene is curved, the inner layers antistatic with z. B. carbon black or carbon fibrils equip and the outer layers with plasticizers or other modifiers after the Modify prior art. By adding glass fibers, length stability can be achieved can be achieved.

The multilayer polymer lines according to the invention can be corrugated in a line part be, and the rings formed by the waves run around the pipe axis, the Waves at least partially in an oval shape or in the form of an ellipse or in the form of an one side flattened circle can be formed. Such geometries, i. H. Training the Shafts of pipes are described for example in DE-A-44 32 584.

The polymer line according to the invention can be obtained by coextrusion of a polymer tube and if necessary, subsequent formation of the shafts including any flattening be made by suction or blow molding. The polymer line according to the invention can but also with extrusion blow molding, coextrusion blow molding, sequential blow molding and be manufactured without tube manipulation.

4. multilayer composite, produced by extrusion, in which a non-positive bond between the cladding of a polymer optical fiber and the adjacent protective cover becomes. The protective sheath of the plastic consisting of at least one layer Optical fiber (KLWL) is based on polyamide 12 or polyamide elastomers or polyamide 12 copolymers or blends based on polyamide-12 or thermoplastic polyurethane hanen, which can also be flame-retardant.

To achieve a good overall performance of the coated plastic optical fiber (KLWL) the core and cladding of the KLWL must not be used during the coating process soften. Any uncontrolled deformation or violation of the KLWL or cladding  inevitably increases the attenuation, so that the signal range becomes insufficient. migrating Components from the layers adjacent to the KLWL, which are the refractive index of the Clad change things must be avoided, because this way the total reflection and so that the signal transmission is negatively affected. The block copolymer according to claim 1 ent holds only a very low concentration of residual monomer and no plasticizer. That's sticky mediating block copolymer according to claim 1 can be adjusted so that despite the relatively low processing temperature, good flow behavior results, resulting in a smooth, thin and even layer that adheres well to the KLWL. Thanks to its unique cha characteristic, is with the adhesion promoter according to the invention on almost all commercially available KLWLs, which are different in terms of their chemical composition sit (PVDF, fluorine copolymers, partially fluorinated P (M) MAs or (M) MA copolymers, epoxy dated polymers), good to very good adhesion values achieved. Because of the variable composition In the polyamide component there is also very good adhesion. a. to different polyamides, PA elastomers and copolymers, PA olefin blends or polyurethane as outer or middle layer reached.

Optical wires of the type described above and the materials used are in the WO 00/60382 to which reference is made here in this connection.

The polyamides used according to the invention can also stabilizers, processing auxiliaries, customary impact modifiers, plasticizers and other common additives and Contains additives in the usual quantities.

The block copolymers according to claim 1 or produced therefrom are used as adhesive agents Molding compounds used in the manufacture of multilayer composites (extrusion, injection molding, Sealing) result in a frictional connection with the adjacent layers. With more suitable Selection of the polyamide component does not or does the transparency of the multilayer composite only slightly reduced.

The thermoplastic multilayer composites can be produced in one or more stages consequences.

The invention is explained in more detail below by means of several examples, without going into it limit.

example 1

308.45 g of aminododecanoic acid, 62.0 g of a polypropylene glycol diamine with a number average molecular weight of 380 g / mol. and 82.25 g of adipic acid are condensed at temperatures up to 260 ° C. to form a prepolymer with acid end groups. Then the temperature is reduced to 220 ° C. and 409.09 g of PMMA diol with M _n = 900 g / mol and 1.00 g of monobutyltinic acid are added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After 3.5 hours, the esterification is terminated by breaking the vacuum and the block polymer is discharged.

Example 2

375.55 g of aminododecanoic acid, 44.50 g of a polytetrahydrofuran diamine (M _n = 950 g / mol) and 57.43 g of adipic acid are condensed at temperatures up to 260 ° C. to form a polyether amide prepolymer. The temperature is then reduced to 220 ° C. and 355.26 g of PMMA diol with M _n = 900 g / mol and 1.00 g of monobutyltinic acid are added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After 3.5 hours, the esterification is terminated by breaking the vacuum and the block polymer is discharged.

Example 3

4.00 kg of laurolactam are added with the addition of 1.14 kg of terephthalic acid and 2.05 kg of water Temperatures up to 300 ° C and a pressure of 20 bar in a polyamide 12 precondensate transferred a number average molecular weight of 750 g / mol. After the temperature of the pre condensate melt was reduced to 230 ° C, 3.09 kg of a PMMA diol with a number average molecular weight of 900 g / mol, 1.88 kg of dimer diol and 14 g of monobutyltinic acid given. Immediately afterwards, the reactor is closed and the pressure is below 10 mbar reduced. After reaching the specified torque of 30 Nm, the esterification ended by breaking the vacuum and discharged the block polymer.

Example 4

5.00 kg of laurolactam are polymerized with the addition of 1.00 kg of terephthalic acid and 2.40 kg of water (pressure phase: 280-300 ° C, 17-23 bar, 3 h; relaxation and degassing at 260 ° C). Then the temperature is reduced to 230 ° C. and 2.70 kg of PMMA diol with M _n = 900 g / mol, 1.65 kg of dimer diol and 17 g of tetra-n-propyl zirconate are added as a 65% solution in n-propanol , Immediately afterwards, the reactor is closed and the pressure is reduced (<10 bar). After reaching the desired torque, the esterification is terminated by breaking the vacuum, the block polymer is discharged and granulated.

Example 5

6.00 kg of laurolactam are polymerized with the addition of 0.75 kg of terephthalic acid and 2.70 kg of water (pressure phase: 280-300 ° C and 17-23 bar, relaxation and degassing at 260 ° C). The temperature is then reduced to 240 ° C. and 2.03 kg of PMMA diol with M _n = 900 g / mol, 1.24 kg of dimer diol and 12 g of metatin S26 (monobutyltinic acid) are added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After reaching the desired torque, the esterification is terminated by breaking the vacuum and the block polymer is discharged.

Example 6

3.78 kg of laurolactam are polymerized with the addition of 1.07 kg of terephthalic acid and 1.90 kg of water (pressure phase: 270-310 ° C. and 17-23 bar, relaxation and degassing at 260 ° C.). The temperature is then reduced to 230 ° C. and 4.66 kg PMMA diol with M _n = 900 g / mol, 0.89 kg dimer diol and 17 g tetra-n-butyl zirconate dissolved in n-butane are added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After reaching the desired torque, the esterification is ended by breaking the vacuum, the block polymer is discharged and granulated.

Example 7

4.00 kg of laurolactam are polymerized with the addition of 1.14 kg of terephthalic acid and 2.05 kg of water (pressure phase: 270-300 ° C and 17-20 bar, relaxation and degassing at 260 ° C). The temperature is then reduced to 225 ° C. and 4.94 kg of PMMA diol with M _n = 900 g / mol, 0.94 kg of dimer diol and 18 g of tetra-n-propyl zirconate dissolved in n-propanol are added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After reaching the desired torque, the esterification is ended by breaking the vacuum, the block polymer is discharged and granulated.

Example 8

3.60 kg of laurolactam are polymerized with the addition of 1.02 kg of terephthalic acid (pressure phase: 300 ° C and 20 bar, relaxation and degassing at 260 ° C). The temperature is then reduced to 230 ° C. and 3.89 kg of PMMA diol with M _n = 900 g / mol, 1.85 kg of polybutyl methacrylate diol with M _n = 1000 g / mol, 0.17 kg of dimer diol and 12 g of tin dioctoate are added , Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After reaching the desired torque, the esterification is terminated by breaking the vacuum and the block polymer is discharged.

Example 9

4.00 kg of laurolactam are polymerized with the addition of 1.14 kg of terephthalic acid and 2.05 kg of water (pressure phase: 300 ° C. and 20 bar, relaxation and degassing at 260 ° C.). Then the temperature is lowered to 230 ° C. and 3.39 kg of PMMA diol with M _n = 900 g / mol, 1.88 kg of di-mer diol and 17 g of n-butylpolytitanate are added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After the desired torque has been reached, the esterification is terminated by breaking the vacuum, the block polymer is discharged and granulated.

Example 10

389.49 g of aminododecanoic acid and 52.46 g of adipic acid are condensed to a PA-12 precondensate at temperatures up to 260 ° C. The temperature is then reduced to 220 ° C. and 296.76 g of PMMA diol with M _n = 900 g / mol, 83.45 g of a polytetrahydrofuran diol with M _n = 1000 g / mol and 1.36 g of tetra-n-propyl zirconate dissolved in n-propanol added. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After 3.5 hours, the esterification is terminated by breaking the vacuum and the block polymer is discharged.

Example 11

Amorphous polyamide oligomer with a number average molecular weight of 2000 g / mol and one Amino end group concentration = 50 mmol / kg: 1.27 kg 3,3'-dimethyl-4,4'-diaminodi-cyclo hexylmethane, 1.23 kg dodecanedioic acid and 0.21 kg isophthalic acid are at temperatures of 270 ° C condensed to an amorphous PA precondensate. After the condensation has ended the condensate is discharged and crushed using a crusher. The amorphous PA precondensate has a solution viscosity of 1.15 (0.5% in m-cresol) and a glass transition temperature of 120 ° C.

Example 12

460.00 g of amorphous PA precondensate from Example 11 are mixed with 195.90 g of PMMA diol with M _n = 900 g / mol, 33.30 g of polytetramethylene glycol with a number-average molecular weight of 980 g / mol and 1.20 g of a tetra- Polymerized n-propyl zirconate dissolved in n-propanol under reduced pressure (<10 mbar). After reaching the desired torque, the esterification is terminated by breaking the vacuum and the block polymer is discharged.

Example 13

2.63 kg of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2.54 kg of dodecanedioic acid and 0.95 kg of isophthalic acid are converted to an amorphous PA precondensate at temperatures of 250-280 ° C. The temperature is then reduced to 230 ° C. and the precondensate is added to a melt mixture of 2.58 kg PMMA diol with M _n = 900 g / mol, 1.57 kg dimer diol and 24 g of an esterification catalyst preheated to 200 ° C. Immediately after the components have been combined, the reactor is closed and the pressure is reduced to 5-20 mbar. After 2 hours in a vacuum, the desired torque of 30 Nm is reached and the esterification is ended by breaking the vacuum, and the block polymer is discharged and granulated.

Example 14

2.54 kg of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2.46 kg of dodecanedioic acid and 0.42 kg of isophthalic acid become an amorphous polyamide (PA) precondensate at temperatures between 230 and 280 ° C and normal pressure a number average molecular weight of 1000 g / mol implemented. Before the precondensate is combined with a melt of 1.70 kg PMMA diol with M _n = 900 g / mol, 0.35 kg dimer diol and 24 g of an esterification catalyst, the temperature of the precondensate melt must be reduced to 230 ° C. Immediately afterwards, the reactor is closed and the polymer structure is initiated by reducing the pressure. After approx. 2 h at a pressure of 5-10 mbar, a torque of 25 Nm is reached and the esterification is ended by breaking the vacuum. The block polymer is then discharged and granulated.

Example 15

An amorphous polyamide oligomer is prepared by reacting 3.05 kg of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 3.67 kg of dodecanedioic acid at temperatures of 230-270 ° C under normal pressure. After the pre-condensate melt had been cooled to 230 ° C., a mixture of 2.06 kg of PMMA diol with M _n = 900 g / mol, 0.43 kg of dimer diol and 20 g of tetra-n-butyl zirconate was dissolved in at 230 ° C. metered in n-butanol. Immediately afterwards, the reactor is closed and the pressure is reduced (<10 mbar). After reaching the desired torque, the esterification is ended by breaking the vacuum, the block polymer is discharged and granulated.

Table 1

Composition and analysis results of the polyamide-polymethyl methacrylate copolymers

Examples 1 to 10 and 12 to 15

Example 16

To check the adhesion, two-piece DIN tension rods were used on an Arburg All rounder 350-210-750 manufactured and subjected to a tensile test.

First, inserts were made from the block polyester amides according to the invention which the corresponding homopolymers were sprayed on. The processing temperatures were chosen so that a partial melting of the inserts at the common con tact area was possible. Table 2 summarizes the tensile strength determined in the tensile test according to DIN 53455 together.  

Table 2

Bonding between polyamide-polymethyl methacrylate copolymers and various polymers

Tensile strength of the two-part tension rods in [MPa]

Grilamid L16 is a low-viscosity and Grilamid L20 is a medium-viscosity polyamide-12 from the company EMS CHEMIE. Grilamid L16 LM is a special PA-12 type for cable sheathing.
Grilamid ELY 60 is a copolyamide from EMS CHEMIE based on lactam-12, polyether diamine and dimerized fatty acid with a melting point of approx. 160 ° C.
Solef 1008 is a polyvinylidene fluoride from Solvay with an MVI of 8 g / 10 min measured at 230 ° C and a load of 5 kg.
Riaglas 09000ST is a PMMA injection molding grade with an MVR of 2.3 measured at 230 ° C and 3.80 kg overlay.
Grilamid TR55 and Grilamid TR70 are amorphous copolyamides based on lactam-12, isophthalic acid and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane with a glass transition temperature of around 160 ° C and 190 ° C.
Grilamid TR90 is an amorphous polyamide based on dodecanedioic acid and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane with a glass transition temperature of 155 ° C.

Example 17

To check the adhesion, two-piece DIN tension rods were used on an Arburg All rounder 350-210-750 manufactured and subjected to a tensile test.  

First, inserts were made from the block polyester amides according to the invention which Lexan 101, a polycarbonate from GE Plastics Europe with an MVI of 6, ge measure at 300 ° C and 1.20 kg overlay, was sprayed on. The processing temperature were chosen so that a partial melting of the inserts on the common Contact area was possible.

The tensile strength determined in the tensile test according to DIN 53455 is 18 Mpa.

Surprisingly, according to the invention, the block polymers were able to adhere very well Polycarbonate can be found.

Example 18

On a ZSK-25 at a melt temperature between 200 and 240 ° C and a speed in the range of 150 to 300 RPM and a throughput of 5-10 kg / h

• a) Grilamid L16 A (amine-terminated, low-viscosity PA-12) and Plexiglas 6 N (PMMA from Röhm) without further addition in a ratio of 1: 2 and
• b) 1 part of Grilamid L16 A and 2 parts of Plexiglas 6 N become one with the addition of 10% Block polyester amide extruded from Examples 6-9.

While the extrusion under a) resulted in a non-granulable, strongly pulsating strand or even the compound in the form of elongated drops fell off the discharge nozzle and thus could not be withdrawn, a homogeneous, not pulsie formed during extrusion b) render strand with a smooth surface that was easy to granulate. Looking at the Pha Sen distribution via SEM, it can be seen that the disperse polyamide phase in case a) as spheres or deformed cylinders with a diameter of 2 to 10 µm, in case b) clearly homogeneous distributed; with domain sizes significantly smaller than 0.5 µm. This result shows in a clearly the tolerance-promoting effect of the block copoly according to the invention mere in polyamide-PMMA blends.

Example 19

A PMMA-based plastic fiber optic cable from Toray (Toray PFU FB 1000 L) with the following structure was coated on a pilot plant for cable sheathing:
Inner layer: adhesion promoter from example 6
Outer layer: Grilamid L16 LM.

The pulling force is measured on a semi-stripped fiber in a tensile-stretching experiment sen. A force of 50-60 N must be applied on average around the fiber from the jacket move on. So there is a very good adhesion between the fiber and the jacket.

Comparative Example 1

A plastic optical waveguide from Toray (Toray PFU FB 1000 L) with the following structure was coated by coextrusion:
Inner layer: Grilamid L16 A as an adhesion promoter
Outer layer: Grilamid L16 LM.

The pulling force is measured on the semi-stripped fiber in a tensile-stretching experiment sen. A force of 10 N must be applied to pull the fiber out of the jacket. The adhesion between fiber and sheath is insufficient.

Comparative Example 2

A plastic optical waveguide from Toray (Toray PFU FB 1000 L) with the following structure was coated by coextrusion:
Inner layer: Lotader AX 8900 (Atofina, copolymer of ethylene, methyl acrylate and glycidyl acrylate) as an adhesion promoter
Outer layer: Grilamid L16 LM.

The pulling force is measured on the semi-stripped fiber in a tensile-stretching experiment sen. A force of 25 N must be applied to pull the fiber out of the jacket. The adhesion between the fiber and the sheath is thus significantly worse than in Example 18 and ge does not meet the requirements, adhesive seat greater than or equal to 50 N.

Claims (20)

1. Thermoplastic block copolymers of the general formula (A):
in which mean:
p = an integer from 1 to 20,
q = an integer from 1 to 10, and
r = an integer from 1 to 10,
containing the following segments (I), (II) and (III):

• A) 15-70% by weight of at least one poly (meth) acrylate diol (HO-A-OH) of the formula (1):
  in which mean:
  z = an integer from 4 to 50 and
  R ¹ = -SR ⁵ -OH or -C (C ₆ H ₅ ) ₂ -R ⁵ -OH, -SC (S) -N (C ₂ H ₅ ) C ₂ H ₄ -OH,
  R ² = H, CH ₃ ,
  R ³ = an alkyl radical with 1-12 C atoms, which can optionally be halogenated,
  R ⁴ = a radical from the group from (1), (2), (3):
  • 1. -R ⁵ -OH,
  • 2. -SC (S) -N (C ₂ H ₅ ) C ₂ H ₄ -OH,
  • 3. -CH ₂ -CHR ² -CO-OR ⁵ -OH
  in which mean:
  R ⁵ = a radical from the group from (1), (2), (3):
• B) a divalent aliphatic, optionally unsaturated hydrocarbon residue with 2 to 20 C atoms, a cycloaliphatic hydrocarbon residue with up to 36 C atoms or an aliphatic-aromatic hydrocarbon residue with 8 to 20 C atoms,
• C) a divalent, aliphatic ether radical -R ⁶ -OR ^{6 '} , the radicals -R ⁶ and R ^6' together having 4-20 C atoms,
• D) a divalent polyether radical of the general formula - (C _n H _2n O) _m -C _p H _2p , in which n = 2-4, m ≧ 1 and p = 2-4,

and the poly (meth) acrylate (II) is optionally partially or completely imidized,

• A) 30-90% by weight of at least one polyamide dicarboxylic acid (HOOC-B-COOH) of the general formula (IIa) or (IIb):
  in which mean:
  a = an integer from 5 to 11 and b = an integer from 2 to 50, or
  in which mean:
  b = an integer from 2 to 40,
  where in the formulas (IIa) or (IIb) R ^{7 is} a divalent aliphatic, optionally unsaturated hydrocarbon radical with 2-20 carbon atoms, a cyclo-aliphatic hydrocarbon with up to 36 carbon atoms or an aliphatic-aromatic hydrocarbon radical with 8-20 C-atoms,
  R ^{8 is} a bifunctional aliphatic hydrocarbon radical with 2-12 C atoms, a cycloaliphatic hydrocarbon radical with 6-20 C atoms, an aliphatic-aromatic hydrocarbon radical with 8-20 C atoms or a divalent, aliphatic ether radical -R ⁶ -OR ^{6 '} - whose residues R ⁶ and R ^{6 '} together have 4-20 C atoms,
• B) 1-20% by weight of at least one diol or diamine of the formula (III):
  HX-D-XH (III)
  where X = NH or O,
  and wherein D is selected from the group consisting of (1), (2), (3), (4), (5):
  • 1. a divalent aliphatic, optionally cycloaliphatic carbon hydrogen test with 4-36 C atoms, which may be unsaturated,
  • 2. an aliphatic olefin polymer having a molecular weight of 500-4000 g / mol, optionally unsaturated,
  • 3. a divalent polyether radical of the general formula - (C _n H _2n O) _m -C _p H _2p -, where n = an integer from 2-4, p = an integer from 2-4 and the molar mass of the polyether radical Is 400-2500 g / mol,
  • 4. a polyester radical of the general formula (IVa) or (IVb):
    where a = an integer from 5 to 11 and
    n = an integer from 5 to 30,
    or
    where n = an integer from 3 to 20,
    wherein in the formulas (IVa) or (IVb) R ⁹ = an aliphatic or cycloaliphatic hydrocarbon radical having 2-36 carbon atoms, and
    R ^{7 is} a divalent aliphatic, optionally unsaturated hydrocarbon radical with 2-20 carbon atoms, a cycloaliphatic hydrocarbon with up to 36 C atoms or an aliphatic-aromatic hydrocarbon radical with 8-20 C atoms;
  • 5. an organic polysiloxane residue with a molecular weight of 500-3000 g / mol.

and wherein the components (I), (II) and (III) add up to 100% by weight. 2. Thermoplastic block copolymers according to claim 1, characterized in that they

• 30 to 60% by weight of at least one poly (meth) acrylate diol (HO-A-OH) of the formula (I),
• - 40 to 60 wt .-% of at least one polyamide dicarboxylic acid (HOOC-B-COOH) of the general formula (IIa) or (IIb) and
• 1 to 10% by weight of at least one diol or diamine of the formula (III)

included, the sum of components (I), (II) and (III) to 100% by weight. 3. Thermoplastic block copolymers according to claims 1 or 2, characterized in net that the polyamide segments number average molecular weights in the range of 500 to 5000 g / mol, preferably in the range between 750 to 2500 g / mol. 4. Thermoplastic block copolymers according to one of claims 1 to 3, characterized records that the polyamide segments are composed of monomers selected from the Group of the lactams with 6 to 12 carbon atoms, the α, ω-aminocarboxylic acids with 6 to 12 carbon atoms, the aliphatic diamines with 2 to 10 carbon atoms and di  carboxylic acids with 2 to 44 carbon atoms and aliphatic or cycloaliphatic Diamines with 2 to 18 carbon atoms. 5. Thermoplastic block copolymers according to claim 1, characterized in that the Polyalcyl (meth) acrylates (I) are α, ω-functionalized polyalkyl (meth) acrylates and numbers average molar masses in the range between 600 and 5000 g / mol, preferably in the range between 900 and 2500 g / mol. 6. Thermoplastic block copolymers according to claim 1, characterized in that as diol or diamine of formula (III) at least one is selected from the group consisting of butanediol, hexanediol, cyclohexanedimethanol, dodecanediol, dimerdiol, hexamethylene diamine, dodecanediamine, 2.2, 4- and 2,4,4-trimethylhexamethylene diamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, polyethylene glycol diol, polypropylene glycol diol, polytetramethylene diols, polyethylene glycol diamine, polypropylene glycol diamine, polytetramethylene diamine, polytetramethylene diamine Po ly (butadiene-co-ethylene) diols, optionally hydrogenated, polycaprolactone diols, polyester diols based on aliphatic or aromatic dicarboxylic acids and aliphatic or cycloaliphatic C ₂ -C ₃₆ diols or aromatic C ₆ -C ₁₈ diols. 7. A process for the preparation of thermoplastic block copolymers according to one or more of claims 1 to 6, characterized in that

• A) in a first polymerization or polycondensation step at temperatures from 180 to 300 ° C., a pressure from atmospheric pressure to 3 × 10 ⁶ Pas (30 bar) polyamide or copolyamide blocks with a number-average molar mass in the range from 500 to 5000 g / mol, preferably in the range from 750 to 2500 g / mol, with an amino end group concentration of at most 50 mmol / kg, optionally with the addition of component D, if X = N in formula (III), and for reducing the water content at least 0 , Degassed for 5 hours at a pressure of 50 mbar to atmospheric pressure, in a second step,
• B) α, ω-functionalized poly-alkyl (meth) acrylate diols with a number average molecular weight in the range between 600 and 5000 g / mol, preferably in the range between 900 and 2500 g / mol, as a solid substance, solution or melt together with the all or part of the diol component (III), in the case when X = O in formula III, are added, or optionally component (III), in the case when X = O in formula (III), with the polymethacrylate diol (PMMA diol) of the formula (I) is converted to DMMP polyester diol in a parallel condensation step and
• C) the reaction mixture at a temperature of 180 to 300 ° C, in the presence of 0.05 to 0.2 wt .-% of a catalyst, condensed in a further polycondensation step under reduced pressure to give the high molecular weight block copolymer (A),
• D) is discharged or processed into moldings.

8. Use of the thermoplastic block copolymers according to one or more of the above going claims 1 to 6 for the production of fibers, films, moldings and enamel Glue. 9. Use of the thermoplastic block copolymers according to one of claims 1 to 6 as an adhesion or tolerance enhancer in coextrudates based on (co) polyamide and poly-alkyl (meth) acrylate. 10. Use of the thermoplastic block copolymers according to one of claims 1 to 6 as an adhesion or tolerance promoter in coextrudates based on (co) polyamide and polycarbonate. 11. Thermoplastic multilayer composite consisting of

• a) at least one layer of a molding compound based on (co) polyamide,
• b) at least one layer of a molding compound made of a thermoplastic material, selected from the group consisting of poly-alkyl (meth) acrylates and polycarbonates, the poly-alkyl (meth) acrylates being homopolymers or copolymers, in which up to 50 mol% of the alkyl (meth) acrylate can be replaced by other monomers from the group consisting of butyl methacrylate, butyl acrylate, methacrylic acid, itaconic acid, styrene, maleic anhydride, the fluoropolymers, or the perfluorinated polymers or mixtures of the aforementioned compounds and
• c) at least one layer lying between (a) and (b) based on a mixture of the polymers which form the layers (a) and (b), at least part of the mixture or the entire mixture of the thermoplastic block copolymers according to one or more of claims 1 to 6 can exist.

12. Thermoplastic multilayer composite according to claim 11, characterized in that the at least one layer of a molding composition based on (co) polyamide (a) Layer of a molding compound based on polyamide-12, of polyamide-12 copolymers, based on a polyamide-12 polymer alloy, or a layer of one is amorphous polyamide or a polymer alloy based on an amorphous polyamide. 13. Multi-layer composite according to claim 11 or 12, characterized in that the mind  at least one layer of a molding compound based on (co) polyamide an amorphous polya mid from the monomer building blocks terephthalic acid and the isomer mixture from 2,2,4- and 2,4,4-trimethylhexamethylene diamine, the copolyamide from isophthalic acid, 3,3'-dimethyl-4,4'- diaminodicyclohexylmethane and laurolactam and the polyamide from 1,12- Dodecanedicarboxylic acid and 4,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'- is diaminodicyclohexylmethane. 14. Thermoplastic multilayer composite according to claim 11, characterized in that the poly-alkyl (meth) acrylate of layer (b) is a polyalkyl methacrylate with 1 to 12 carbons atoms in the carbon chain of the alkyl radical, which is partially or completely is fluorinated, with polymethyl methacrylate and polybutyl methacrylate being preferred. 15. Thermoplastic multilayer composite according to claims 1 to 14, characterized records that it is a housing or housing part of a mobile radio telephone. 16. Thermoplastic multilayer composite according to one or more of claims 1 to 14, characterized in that it is a multi-layer polymer hose or pipe, the if necessary, is curled in at least one partial area. 17. Multi-layer hose or pipe according to claim 16, characterized in that they consist of at least one inner layer made of thermoplastically processable fluoropolymers, an outer layer made of polyamide, with polyamide-12 or polyamide-12 derivatives are particularly preferred, and an intermediate adhesive layer based on the thermoplastic block copolymers according to one of claims 1 to 6. 18. Multi-layer hose or pipe according to claim 16, characterized in that the fluoropolymers are selected from polyvinylidene fluoride (PVDF) or from fluoropoly mers based on tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene flu orid (VDF) or fluoropolymers based on tetrafluoroethylene (TFE), perfluoromethyl vinyl ether (PMVE) and vinylidene fluoride (VDF), whereby PVDF or a terpolymer of Te trafluoroethylene, hexafluoropropylene, vinylidene fluoride is preferred. 19. Multi-layer composite according to one of claims 11 to 17, characterized in that it by injection molding extrusion, calendering or welding. 20. Optical core with a fiber core and a single or multi-layer fiber sheathed plastic optical fiber (K-LWL) and at least one den  K-LWL enclosing protective cover, the fiber jacket or at least its outer Layer made of a fluorine-containing plastic and the protective cover made of polyamide because characterized in that the protective cover made of polyamides or copolyamides or their Mixtures with a melting point below 220 ° C and the fiber jacket consists of Vinylidene fluoride, tetrafluoroethylene, hexafluoropropene, methacrylic acid tetrafluoropropyl ester, Pentafluoropropyl methacrylic acid, trifluoroethyl methacrylic acid ester, methacrylic acid heptadecafluorodecyl ester and mixtures or copolymers of the substances mentioned, optionally also from acrylic acid and acrylate modified polymers, copolymers or Polymer mixtures exist and the adhesion between the fiber jacket and the protective layer through the thermoplastic block copolymers is produced according to one of claims 1 to 6.