WO2005092938A1

WO2005092938A1 - Radically coupled perfluoropolymer-polymer materials and method for producing the same

Info

Publication number: WO2005092938A1
Application number: PCT/EP2005/051376
Authority: WO
Inventors: Dieter Lehmann; Bernd KLÜPFEL
Original assignee: Leibniz-Institut Für Polymerforschung Dresden E.V.
Priority date: 2004-03-29
Filing date: 2005-03-24
Publication date: 2005-10-06
Also published as: DE102004016873B4; DE102004016873A1

Abstract

The invention relates to the field of chemistry and specifically to radically coupled perfluoropolymer-polymer materials which can for example be used in tribomaterials. The aim of the invention is to provide perfluoropolymer-polymer materials which have improved wearing properties for comparable lubricating properties. For this purpose, the radically coupled perfluoropolymer-polymer materials consist of perfluoropolymer to the perfluoropolymer chains of which olefinically unsaturated monomers and/or macromers and/or oligomers and/or polymers are chemically-radically coupled by way of reactive conversion in a molten-state reaction. The radicals required for the radical coupling in the perfluoropolymer are persistent active or reactivated perfluoroalkyl(peroxy) radicals and/or radicals stemming from thermal decomposition groups that do not stem from a radiation process and/or plasma modification. The invention also relates to a method for producing radically coupled perfluoropolymer-polymer materials. According to the inventive method, perfluoropolymers are reacted in dispersion with persistent active or reactivated perfluoroalkyl(peroxy) radicals and/or radicals stemming from thermal decomposition groups that do not stem from a radiation process and/or plasma modification in a molten-state reaction while adding olefinically unsaturated polymers.

Description

Radically coupled perfluoropolymer polymer materials and processes for their manufacture

The invention relates to the field of chemistry and relates to free-radically coupled perfluoropolymer polymer materials, which can be used, for example, as tribo materials, and to a process for their production.

... Unsintered and uncompressed PTFE emulsion and suspension polymers are fibrous and felty. A transmission z. B. the anti-adhesive and sliding properties of PTFE on other media by incorporation in aqueous or organic dispersions, polymers, paints, varnishes, resins or lubricants is not possible because this PTFE can not be homogenized, but tends to form lumps, agglomerates, floats or settles.

Because of the insolubility of the PTFE and its degradation products (with the exception of the very low molecular weight products), the usual methods of determining the molar mass cannot be used. Molecular weight determination must be done indirectly. "[A. Heger et al., Technology of Radiation Chemistry on Polymers, Akademie-Verlag Berlin 1990] The incompatibility with other materials often has a disadvantageous effect. A modification can be achieved by chemically activating PTFE by the known processes with (1.) sodium amide in liquid ammonia and (2.) alkali alkyl and alkali aromatic compounds in aprotic inert solvents. These modifications can be used to achieve improved interface interactions, either reactively or only via adsorptive forces.

The PTFE degradation products are used in a wide range of applications - including as an additive to plastics for the purpose of achieving sliding or non-stick properties. The fine powder substances are more or less finely dispersed as filler components in a matrix [Ferse et al., Plaste et al. Kautschuk, 29 (1982), 458; Ferse et al. DD-PS 146 716 (1979)]. When the matrix component is dissolved, the PTFE fine powder can be eliminated or is retained unchanged.

Although the properties of PTFE fine powder improve the properties compared to the commercial fluorocarbon-free additives, the incompatibility, the insolubility, the storage and also inhomogeneous distribution are disadvantageous for many areas of application.

Grafted fluorine-containing plastics (US Pat. No. 5,576,106), which consist of fluorine-containing plastic particles, to whose surface a non-homopolymerized ethylenically unsaturated compound is grafted are also known. The non-homopolymerized ethylenically unsaturated compounds can be acids, esters or anhydrides.

These grafted fluorine-containing plastics are produced by exposing the fluorine-containing plastic powder to a source of ionizing radiation in the presence of the ethylenically unsaturated compound. The ethylenically unsaturated compounds are bound to the surface of the fluorine-containing plastic particles.

The object of the invention is to provide perfluoropolymer-polymer materials which, with comparable sliding properties, have improved wear resistance and thereby the service life of the components made from these materials is extended, and continue to provide a simple and powerful process for producing such materials.

The radically coupled perfluoropolymer-polymer materials according to the invention consist of perfluoropolymer, on the perfluoropolymer chains of which polymers in the melt are chemically radically coupled via a reactive reaction, the radicals necessary for the radical coupling being persistent active or reactivatable perfluoroalkyl (peroxy) radicals and / or radicals from thermally decayed groups that do not originate from an irradiation process and / or a plasma modification.

The persistent reactive and / or reactivatable perfluoroalkyl (peroxy) radicals and / or the radicals from thermally decomposed groups advantageously come from a polymerization process.

The binding point of the polymers with the perfluoropolymer chain on the polymer chain is advantageously statistically distributed.

Polymers which have olefinically unsaturated groups in the main chain and / or in the side chain are advantageously radically coupled as polymers.

Such advantageous polymers are radically coupled SBS, ABS, SBR, NBR, NR and other butadiene and / or isoprene and / or chloroprene homo-, co- or ter polymers.

It is also advantageous if the perfluoropolymers are PTFE and / or FEP.

In the process according to the invention for producing free-radically coupled perfluoropolymer polymer materials, perfluoropolymer with persistent active or reactivatable perfluoroalkyl (peroxy) radicals and / or radicals from thermally decomposed groups which do not originate from an irradiation process and / or from a plasma treatment, reacted in the melt with the addition of olefinically unsaturated polymers. It is advantageous if the perfluoropolymer is used as a micropowder.

It is also advantageous if PTFE and / or FEP are used as the perfluoropolymer.

It is also advantageous if the reaction is carried out in the melt in a melt mixer, preferably in an extruder.

Polymers which have olefinically unsaturated groups in the main chain and / or in the side chain are also advantageously used as polymers.

SBS, ABS, SBR, NBR, NR and other butadiene and / or isoprene and / or chloroprene homo-, co- or ter-polymers are used as such advantageous polymers.

The radical coupling according to the invention of perfluoropolymer with olefinically unsaturated polymers via a (melt) modification reaction leads to compatibility and tight integration in a matrix, which can advantageously be used for tribo materials. For example, special thermoplastics, elastomers and special duromers with perfluoropolymer can be modified in the form via reactive conversion / extrusion in such a way that, in addition to improved sliding friction, increased wear resistance is achieved compared to the pure starting materials and the physical mixtures with perfluoropolymer.

In the production of perfluoropolymer that has not been modified by an irradiation process and / or a plasma modification, persistent active or reactivatable perfluoroalkyl (peroxy) radicals and / or radicals are formed from thermally decomposed groups, which surprisingly can be coupled with olefinically unsaturated polymers are capable of reactive implementation. The coupling takes place via radical reactions and the olefinically unsaturated polymers used are present as polymers which can also have olefinically unsaturated double bonds even after the radical coupling. The perfluoropolymers are advantageously produced in a polymerization process. It was particularly surprising that the persistent active or reactivatable perfluoroalkyl (peroxy) radicals and / or radicals from thermally decomposed groups are suitable for coupling with olefinically unsaturated polymers in a reactive reaction.

After the melt modification in the laboratory kneader, for example for SBS, ABS and also olefinically unsaturated elastomers such as SBR, NBR, NR, polybutadiene with a perfluoropolymer not originating from an irradiation process and / or a plasma modification and after separation of the unbound matrix, a chemical was used by IR spectroscopy Coupling proven. The olefinically unsaturated polymers could no longer be separated from this perfluoropolymer by extraction (for example Zonyl MP 1600 and TF 9207). In comparison to physical blends of thermally degraded perfluoropolymer (for example TF 9205), in which the perfluoropolymer could still be separated quantitatively.

In a further variant of the invention, after the production of the perfluoropolymer, which has not been modified by an irradiation process and / or a plasma modification, a radiation-chemical and / or a radiation-chemical and / or a concentration for perfluoroalkyl (peroxy) radicals can be increased and / or adjusted for the respective application. or plasma treatment. However, this radiation chemical and / or plasma treatment is used exclusively to optimize the radical coupling of the perfluoropolymer-polymer material according to the invention. The effect according to the invention that such a coupling can be achieved at all between a perfluoropolymer, which has not been modified by an irradiation process and / or a plasma modification, and olefinically unsaturated polymers, is also achieved without a radiation chemical and / or plasma treatment. Be prepared according to the invention the free-radically coupled perfluoropolymer polymer materials, for example by a PTFE polymer (Zonyl ^® MP1600 or TF 9207) is used. This PTFE polymer has been produced in a polymerization process. Persistent active or reactivatable perfluoroalkyl (Peroxy) radical centers and / or groups which decompose thermally to form radicals, which form a radical coupling with the olefinically unsaturated polymers in the subsequent melt modification process.

The radical coupling of the perfluoropolymer according to the invention and the resulting integration / compatibility into a matrix leads to an improvement in the material and sliding friction properties and to an increase in wear resistance compared to the unmodified starting materials and the physical mixtures with perfluoropolymer. To improve wear resistance, it is also advantageous to use the chemically coupled perfluoropolymer particles at the same time as a storage medium for the PFPE additive (PFPE = perfluoropolyether), which is incompatible with the polymer matrix and contributes to lowering the coefficient of friction while increasing wear resistance.

Due to the chemical coupling, these products have improved mechanical and tribological properties. These products are of particular interest for sliding friction processes. The radical modification / compatibility of the perfluoropolymer particle with the matrix material results in a good connection and an improvement in wear resistance, since the perfluoropolymer grain cannot be rubbed out of the matrix material by mechanical stress.

Since the perfluoropolymer grain interacts directly with the matrix, improved material properties are observed depending on the degree of attachment compared to the physical mixtures.

With the chemical coupling of the perfluoropolymer in the matrix, new materials are obtained which, with comparable sliding friction coefficients, have improved wear resistance, ie an increased service life in the applications. Furthermore, by adding PFPE, a further reduction in the sliding friction coefficients and a noticeable improvement in wear resistance is achieved, the chemically coupled perfluoropolymer additionally functioning as a storage medium. Perfluoropolymers include the following substances: - polytetrafluoroethylene [PTFE], - poly (tetrafluoroethylene-co-hexafluoropropylene) [FEP], - poly (tetrafluoroethylene-co-perfluoropropyl vinyl ether) [PFA], - poly (tetrafluoroethylene-co-perfluoro-2 , 2-dimethyldioxol) as well as the - poly (chlorotrifluoroethylene) [PCTFE].

The invention is explained in more detail below using several exemplary embodiments.

Comparative Example 1: Melt modification of SBS with PTFE micropowder,

40 g SBS (Cariflex TR 1102 S, stabilized) is melted at 160 ° C in a laboratory kneader at 60 rpm. After 3 minutes, 20 g of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) are metered in. 5 minutes after the addition of PTFE, the experiment is stopped and the material is removed from the kneading chamber. The SBS matrix material is separated from the PTFE solid product by dissolving in methylene chloride and centrifuging. The solid product / residue is reslurried with methylene chloride. The dissolving / extracting and centrifuging were repeated 4 times, then the PTFE solid product was separated and dried.

The IR spectroscopic examination of the separated, purified PTFE micropowder revealed no chemically coupled PTFE-SBS material. No SBS absorptions are found in the IR spectrum. This physical PTFE-SBS mixture serves as the standard for measuring the coefficient of sliding friction and wear resistance in the context of tribological investigations.

Example 1: Melt modification of SBS with PTFE micropowder TF 9207 (Dyneon)

The experiment was carried out and the polymer matrix was separated off as in Comparative Example 1, but 20 g of PTFE emulsion polymer TF 9207 (Dyneon) were used instead of the thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated). The IR spectroscopic examination of the separated and cleaned PTFE micropowder showed a detectable SBS absorption in addition to that of the PTFE as evidence for chemically coupled PTFE-SBS material. In comparative example 1 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations showed that the chemically coupled PTFE-SBS material has a comparable sliding friction coefficient to the physical mixture, but that an increased wear resistance can be observed. The wear in the block / ring test with the chemically coupled material shows a reduction to 65% in comparison to the physical mixture (comparative example 1).

Example 2: Melt modification of SBS with PTFE micropowder Zonyl ^® MP 1600 (DuPont)

Experimental procedure and separation of the polymer matrix was carried out similarly to Comparative Example 1, there are, however, 20 g Zonyl ^® PTFE MP 1600 (DuPont) instead of the thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) is used.

The IR spectroscopic examination of the separated and cleaned PTFE micropowder revealed a detectable SBS absorption in addition to that of the PTFE as evidence for chemically coupled PTFE-SBS material. In comparative example 1 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations showed that the chemically coupled PTFE-SBS material has a comparable sliding friction coefficient to the physical mixture, but that an increased wear resistance can be observed. The wear in the block / ring test with the chemically coupled material shows a reduction to 68% compared to the physical mixture (comparative example 1).

Comparative Example 2: Melt modification of SBR with PTFE micropowder

40 g of SBR elastomer are plasticized into small pieces at 140 ° C in a laboratory kneader at 60 rpm. After 2 minutes, 20 g of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) metered in. 5 minutes after the addition of PTFE, the experiment is stopped and the material is removed from the kneading chamber. The SBR matrix material is separated from the solid PTFE product by dissolving in methylene chloride and centrifuging. The solid product / residue is reslurried with methylene chloride. The dissolving / extracting and centrifuging was repeated 4 times, then the PTFE solid product was separated and dried. The IR-spectroscopic examination of the separated, purified PTFE micropowder revealed no chemically coupled PTFE-SBR material. No SBR absorptions are found in the IR spectrum. After vulcanization, this physical PTFE-SBR mixture serves as the standard for measuring the coefficient of sliding friction and wear resistance in the context of tribological investigations.

Example 3: Melt modification of SBR with PTFE micropowder

The experiment and the separation of the polymer matrix were carried out analogously to Comparative Example 2, but 20 g of PTFE emulsion polymer TF 9207 (Dyneon) were used instead of the thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated).

The IR spectroscopic examination of the separated and cleaned PTFE micropowder revealed detectable SBR absorptions in addition to that of the PTFE as evidence for chemically coupled PTFE-SBR material. In comparative example 2 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations were carried out on vulcanized test specimens - the tests showed that the chemically coupled PTFE-SBR material has a comparable sliding friction coefficient to the physical mixture (comparative example 2), but that an increased wear resistance can be observed. The wear on the block / ring test showed a reduction to 70%.

As a further tribological investigation, 0.5 mass% of PFPE (perfluoropolyether, DuPont) was added shortly before the laboratory kneader experiment was terminated, which showed that the vulcanized test specimens had a sliding friction coefficient of around 30% compared to the physical mixture (comparative example 2) has lower value and that an increase in wear resistance watch is. The wear on the block / ring test showed a reduction to 25%.

Example 4: Melt modification of SBR with PTFE micropowder

Experimental procedure and separation of the polymer matrix was carried out similarly to Comparative Example 2, there are, however, 20 g Zonyl ^® PTFE MP 1600 (DuPont) instead of the thermally degraded PTFE polymer used TF 9205 (Dyneon, unirradiated).

The IR spectroscopic examination of the separated and cleaned PTFE micropowder revealed detectable SBR absorptions in addition to that of the PTFE as evidence for chemically coupled PTFE-SBR material. In comparative example 2 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations were carried out on vulcanized test specimens - the tests showed that the chemically coupled PTFE-SBR material has a comparable sliding friction coefficient to the physical mixture (comparative example 2), but that a significantly increased wear resistance can be observed. The wear on the block / ring test showed a reduction of 20%.

As a further tribological investigation, 0.5 mass% of PFPE (perfluoropolyether, DuPont) was added shortly before the laboratory kneader experiment was terminated, which showed that the vulcanized test specimens had a sliding friction coefficient of around 30% compared to the physical mixture (comparative example 2) has a lower value and that an increase in wear resistance can be observed. The wear on the block / ring test showed a reduction to 60%.

Comparative Example 3: Melt Modification of ABS with PTFE Micropowder,

40 g ABS are melted at 160 ° C in a laboratory mixer at 60 rpm. After 3 minutes, 20 g of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) are metered in. 5 minutes after the addition of PTFE, the experiment is stopped and the material is removed from the kneading chamber. The ABS matrix material is separated from the PTFE by dissolving in methylene chloride and centrifuging Solid product separated. The solid product of the residue is slurried again with methylene chloride. The dissolving / extracting and centrifuging was repeated 4 times, then the PTFE solid product was separated and dried. The IR spectroscopic examination of the separated and cleaned PTFE micropowder showed no chemically coupled PTFE-ABS material. ABS absorptions are not found in the IR spectrum. This physical PTFE-ABS mixture serves as the standard for measuring the coefficient of sliding friction and wear resistance in the context of tribological investigations.

Example 5: Melt modification of ABS with PTFE micropowder

The experiment and the polymer matrix were carried out analogously to Comparative Example 3, but 20 g of PTFE TF 9207 (Dyneon) were used instead of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated).

The IR spectroscopic examination of the separated and cleaned PTFE micropowder showed detectable ABS absorptions in addition to those of the PTFE as evidence for chemically coupled PTFE-ABS material. In comparative example 3 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations showed that the chemically coupled PTFE-ABS material has a comparable sliding friction coefficient to the physical mixture, but that increased wear resistance can be observed. The wear in the block / ring test with the chemically coupled material shows a reduction to 70% compared to the physical mixture (comparative example 3).

Example 6: Melt modification of ABS with PTFE micropowder

Experimental procedure and separation of the polymer matrix was carried out similarly to Comparative Example 3, there are, however, 20 g Zonyl ^® PTFE MP 1600 (DuPont) instead of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) is used.

The IR spectroscopic examination of the separated and cleaned PTFE micropowder revealed detectable ABS absorptions in addition to those of the PTFE as Proof of chemically coupled PTFE-ABS material. In comparative example 3 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations showed that the chemically coupled PTFE-ABS material has a comparable sliding friction coefficient to the physical mixture, but that a significantly increased wear resistance can be observed. The wear in the block / ring test with the chemically coupled material shows a reduction to 75% compared to the physical mixture (comparative example 3).

Comparative Example 4: Melt Modification of NBR with PTFE Micropowder,

40 g of NBR elastomer are plasticized into small pieces at 80 ° C in a laboratory kneader at 50 rpm. After 2 minutes, 20 g of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) are added. The test is stopped 5 minutes after the addition of PTFE and the material is removed from the kneading chamber. The NBR matrix material is separated from the solid PTFE product by dissolving in methylene chloride and centrifuging. The solid product / residue is reslurried with methylene chloride. The dissolving / extracting and centrifuging was repeated 4 times, then the PTFE solid product was separated and dried. The IR spectroscopic examination of the separated, purified PTFE micropowder revealed no chemically coupled PTFE-NBR material. No NBR absorptions are found in the IR spectrum. After vulcanization, this physical PTFE-NBR mixture serves as the standard for measuring the coefficient of sliding friction and wear resistance as part of the tribological tests.

Example 7: Melt modification of NBR with PTFE micropowder

The experiment and the separation of the polymer matrix were carried out analogously

Comparative Example 4, but 20 g of PTFE TF 9207 (Dyneon) are used instead of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated).

The IR spectroscopic examination of the separated and cleaned PTFE

Micropowder gave detectable NBR absorptions in addition to that of PTFE Proof of chemically coupled PTFE-NBR material. In comparative example 4 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological tests were carried out on vulcanized test specimens - the tests showed that the chemically coupled PTFE-NBR material has a comparable sliding friction coefficient to the physical mixture (comparative example 4), but that increased wear resistance can be observed. The wear on the block / ring test showed a reduction to 65%.

As a further tribological investigation, 0.5 mass% of PFPE (perfluoropolyether, DuPont) was added shortly before the laboratory kneader experiment was terminated, which showed that the vulcanized test specimens had a sliding friction coefficient of around 30% compared to the physical mixture (comparative example 4) has a lower value and that an increase in wear resistance can be observed. The wear on the block / ring test showed a reduction to 65%.

Example 8: Melt modification of NBR with PTFE micropowder

Experimental procedure and separation of the polymer matrix was carried out similarly to Comparative Example 4, it will, however, 20 g Zonyl ^® PTFE MP 1600 (DuPont) instead of thermally degraded PTFE polymer TF 9205 (Dyneon, unirradiated) is used.

The IR spectroscopic examination of the separated and cleaned PTFE micropowder revealed detectable NBR absorptions in addition to those of the PTFE as evidence for chemically coupled PTFE-NBR material. In comparative example 4 (physical mixture), only pure PTFE was detectable in the IR spectrum. The tribological investigations were carried out on vulcanized test specimens - the tests showed that the chemically coupled PTFE-NBR material has a comparable sliding friction coefficient to the physical mixture (comparative example 4), but that a significantly increased wear resistance can be observed. The wear on the block / ring test showed a reduction to 72%.

As a further tribological investigation, 0.5 mass% of PFPE (perfluoropolyether, DuPont) was added shortly before the laboratory kneader experiment was terminated. which showed that the vulcanized test specimens have a coefficient of sliding friction which is about 30% lower than that of the physical mixture (comparative example 4) and that an increase in wear resistance can be observed. The wear on the block / ring test showed a reduction to 48%.

Comparative Example 5: Melt modification of SBS with FEP

40 g SBS (Cariflex TR 1102 S, stabilized) is melted at 160 ° C in a laboratory kneader at 60 rpm. After 3 minutes, 20 g of FEP polymer (thermally degraded and aftertreated, unirradiated) are metered in. 5 minutes after the FEP addition, the experiment is stopped and the material is removed from the kneading chamber. The SBS matrix material is separated from the FEP solid product by dissolving in methylene chloride and centrifuging. The solid product / residue is reslurried with methylene chloride. The dissolving / extracting and centrifuging was repeated 4 times, then the FEP solid product was separated and dried.

The IR-spectroscopic examination of the separated, purified FEP revealed pure FEP and no chemically coupled FEP-SBS material. No SBS absorptions are found in the IR spectrum. This physical FEP-SBS mixture serves as a standard for measuring the coefficient of sliding friction and wear resistance in the context of tribological investigations.

Example 9: Melt modification of SBS with FEP

Comparative Example 1, but 20 g of FEP polymer were used instead of the thermally degraded FEP polymer (unirradiated).

The IR spectroscopic examination of the separated and purified FEP revealed a detectable SBS absorption in addition to that of the FEP as evidence for chemically coupled FEP-SBS material.

In comparative example 1 (physical mixture), only pure FEP was detectable in the IR spectrum. The tribological investigations showed that the chemically coupled FEP-SBS material has a comparable sliding friction coefficient to the physical mixture, but that increased wear resistance can be observed. The wear in the block / ring test with the chemically coupled material shows a reduction to 76% compared to the physical mixture (comparative example 1).

Claims

claims

1. Radically coupled perfluoropolymer polymer materials, consisting of perfluoropolymer, on the perfluoropolymer chains of which polymers in the melt are chemically radically coupled via a reactive reaction, the radicals necessary for radical coupling in the perfluoropolymer being persistent or reactivatable perfluoroalkyl (peroxy) radicals and / or are radicals from thermally decayed groups that do not originate from an irradiation process and / or a plasma modification.

2. Radically coupled perfluoropolymer polymer materials according to claim 1, in which the persistent reactive and / or reactivatable perfluoroalkyl (peroxy) radicals and / or the radicals come from thermally decomposed groups from a polymerization process.

3. Radically coupled perfluoropolymer-polymer materials according to claim 1, in which the binding site of the polymers with the perfluoropolymer chain is randomly distributed on the polymer chain.

4. Radically coupled perfluoropolymer polymer materials according to claim 1, wherein the polymers have olefinically unsaturated groups in the main chain and / or in the side chain.

5. Radically coupled perfluoropolymer polymer materials according to claim 1, in which the polymers are SBS, ABS, SBR, NBR, NR and other butadiene and / or isoprene and / or chloroprene homo-, co- or ter- Polymers are radically coupled.

6. Radically coupled perfluoropolymer polymer materials according to claim 1, wherein the perfluoropolymers are PTFE and / or FEP.

7. Process for the production of radically coupled perfluoropolymer polymer materials, in which the perfluoropolymer with persistent active or reactivable perfluoroalkyl (peroxy) radicals and / or radicals from thermally decomposed Groups that do not originate from an irradiation process and / or a plasma modification are reacted in the melt with the addition of olefinically unsaturated polymers.

8. The method according to claim 7, in which PTFE or FEP are used as the perfluoropolymer.

9. The method according to claim 7, wherein the perfluoropolymer is used as a micropowder.

10. The method according to claim 7, wherein the reaction is carried out in the melt in a melt mixer.

11. The method according to claim 7, wherein the reaction is carried out in a melt in an extruder.

12. The method according to claim 7, are used in the polymers with olefinically unsaturated groups in the main chain and / or in the side chain.

13. The method according to claim 7, in which the polymers SBS, ABS, SBR, NBR, NR and other butadiene and / or isoprene and / or chloroprene homo-, co- or ter polymers are added.