DE19631563A1 - Pure or functionalised electroconductive polymer material - Google Patents

Abstract

Pure or functionalised or ferromagnetically functionalised, electroconductive material (I) in the form of dispersible solid particles consist mainly of: (a) particles of electroconductive polymer with a conjugated pi -system (II), based on 5-membered nitrogen or sulphur heterocyclic monomers and/or amino aromatic compounds, or (b) a core of functionalising material (III) and an outer coating of (II), or (c) a core of (II) and a coating of (III), and with anionic polymeric ionomers (IV) in each case, or (d) particles of (III) and ionomers (IV) and particles of (II) and ionomers (IV), or (e) particles with a ferromagnetic core (V) and a coating of (II) plus ionomers (IV), or (f) particles with a core of (II) and a coating of ferromagnetic functionalising material (VI), plus ionomers (IV), or (g) mixtures of ferromagnetic particles and ionomers (IV) and particles of (II) and ionomers (IV). Also claimed are: (i) a process for the production of (I); (ii) ferromagnetically functionalised liquids ("ferrofluids") based on (I); and (iii) a process for the production of physiologically compatible ferrofluids.

Description

The present invention relates to electronically conductive polymers, more particularly that Field of processable electronically conductive polymers, and especially that Field of functionalized processable electronically conductive polymers. Furthermore, the present invention relates to the field of nanosized ferromagnetic particles, more specifically the field of ferromagnetic functionalized liquids, so-called ferrofluids. Furthermore, the present describes Invention the field of polymeric ionomers, more specifically polymeric ionomers, that can be combined with electronically conductive polymers, d. H. as Counterions, and especially polymeric ionomers, with electronic conductive polymers can be combined (as counterions) and the are functionalized in such a way that they can be physically or chemically based paints, especially water-based acrylic paints, react can.  

Electronically conductive polymers are already extensive in terms of their Applicability for e.g. B. as antistatic coatings, electromagnetic shielding materials, conductive paints, electrode coatings u. a. have been examined, but with little commercial success (F. Lux, Doctoral thesis at the TU Berlin, 1993). Within the variety of electronic conductive polymers that have been studied for technical applications Polyaniline, polypyrrole and polythiophene are particularly promising as they are lightweight are to be produced, have good electrical conductivity and high Have stability against environmental influences. All three polymers can be chemically oxidatively or electrochemically (F. Lux, PhD thesis at the TU Berlin, 1993). The disadvantage is that the pure polymers are practically unprocessable, d. H. infusible and essentially insoluble, where polypyrrole is absolutely infusible and insoluble because it is a chemical has three-dimensionally linked microstructure (F. Lux, PhD thesis at the TU Berlin, 1993). In addition, interest in polyaniline is younger Past declined for environmental reasons as the emergence of the carcinogenic molecule benzidine in the course of the synthesis of polyaniline cannot be avoided.

To improve the processability of polyaniline, polythiophene and polypyrrole A variety of different methods have been used in the literature described, e.g. B. the introduction of long (flexible) side chains in the Monomer units, the polymerization of the electronically conductive polymer in the Presence of ordinary polymers and the preparation of stable ones colloidal dispersions of the electronically conductive polymers, the the latter dispersions by attaching long (bulky) Polymer molecules on the surfaces of the colloidal particles against coagulation (F. Lux, doctoral thesis at the TU Berlin, 1993 and E. Ruckenstein and L. Hong, Synth. Met., 66 (1994), pp. 249-256). Because of the lack commercial success that pure electronically conductive polymers have achieved the technical interest in these materials has shifted so that in the application the electronically conductive property is only one of several, which the applied material should have, d. H. to functionalized  processable electronically conductive polymers. An example of this is the Use of stable colloidal polyaniline dispersions for Corrosion protection purposes, which is based on the fact that the oxidation state of the individual polyaniline molecules can be easily changed and that the polyaniline is electronically conductive (information brochures from Zipperling, Kessler & Co., March 1996). However, the use of stable colloidal Polyaniline dispersions for corrosion protection purposes do not become a large-scale Use of the same materials cause only the anti-corrosion property for certain types of corrosion (i.e. pitting) others, commercially corrosion protection measures that are already widely used are superior.

Another disadvantage of ferromagnetic liquids, i. H. so-called. Ferrofluids, is that they are generally not physiologically compatible. Just in special cases where the nanosized ferromagnetic particles Molecules produced in the presence of dextran can be physiological compatible ferrofluids that have magnetic particles with diameters <10 nm [DE 41 31 846 and R.S. Molday and D. Mackenzie, J. Immunol. Meth., 52, (1982), Pp. 353-367].

In the current state of the art, the object of the invention underlying processable, functionalized and environmentally acceptable electronic To produce conductive polymer materials that are easy in large volume applications can be transferred. Electronically conductive polymers such as Polypyrrole, polyaniline and polythiophene with suitable nano-sized ones functionalizing particles, especially with nano-sized ferromagnetic Particles, d. H. Particles like those in ferromagnetic functionalized liquids, so-called ferrofluids can be used. The electronically conductive Polymer materials should u. a. be used in the microelectronics industry can help avoid static electricity and electromagnetic Interference, especially in the critical area of the near field electromagnetic spectrum.  

It is consequently the object of this invention to be environmentally acceptable, processable pure or functionalized electronically conductive polymers, such as Polypyrrole, polyaniline and polythiophene materials to avoid static Electricity, EMI shielding and other applications where the properties the pure or functionalized electronically conductive polypyrrole, polyaniline and Polythiophene materials can be used. More specific are environmentally acceptable, processable ferromagnetic functionalized electronically conductive polypyrrole, polyaniline and polythiophene materials that ferromagnetic particles, as functionalized in ferromagnetic Liquids, so-called ferrofluids, are contained and those to avoid static Electricity, EMI shielding and other applications where the properties the ferromagnetic functionalized electronically conductive polypyrrole, polyaniline and polythiophene materials of this invention can be used can manufacture. In particular, it is the task of environmentally acceptable processable ferromagnetic functionalized electronically conductive polymers such as Polypyrrole, polyaniline and polythiophene materials with large (particle diameter »20 nm), bare or partially with adequate anionic modified polymers or special, tailor-made polymeric ionomers covered, nano-sized particles of ferromagnetic materials, i. H. ferromagnetic particles that are in novel physiologically compatible Ferrofluids, are included, are functionalized and designed to avoid static Electricity, EMI shielding and other applications where the properties the ferromagnetic functionalized electronically conductive polypyrrole, polyaniline and polythiophene materials can be used, to manufacture.

Furthermore, it is an object of this invention methods of preparation of ready-to-market products consisting of ordinary polymers, in particular water-based acrylic paints, epoxy resins, silicone oils, rubber and Polyurethane resins, and processable, pure or functionalized or Ferromagnetic functionalized electronically conductive polypyrrole, polyaniline and To produce polythiophene materials.

But it is also a task of special, water-based polymeric ionomers, such functionalized to be active in two directions: 1) compatibilizing  between processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials and ordinary Polymers and 2) (when used as a compatibilizer in the final composite with the usual polymers) the formation of physical or chemical Cross-linking points with the ordinary polymers allow to develop. Another object is a method of making the aforementioned to develop polymeric ionomers.

Finally, it is also physiologically compatible ferromagnetic task functionalized liquids, so-called ferrofluids, the large (particle diameter »20 nm) nano-sized ferromagnetic particles and adequate Stabilization molecules contain and methods of producing such to develop physiologically compatible ferrofluids.

The object is achieved according to the invention by the production of the materials the characteristic features of the main claims and their others Design according to the other claims with its characteristic Features resolved.

To achieve the previously described and other goals and in Consistent with the purpose of this invention as set out in this transcript is detailed, it provides processable pure or functionalized electronically conductive polymer materials containing the following components: Nanosized (colloidal) particles of oxidized and polymerized amino substituted or thio-substituted aromatic or hetero-aromatic Monomers, a compatibilizing amount of anionically modified Polymers and / or copolymers and / or special, tailor-made polymeric or copolymeric ionomers (short: polymeric ionomers), Doping anions and (optionally) naked or partially with adequate polymers Ionomers covered nano-sized (colloidal) particles of a functionalizing Materials.

It has been shown that ferromagnetic processable by this invention Functionalized to produce electronically conductive polymer materials that  contain the following components: Nano-sized (colloidal) particles of oxidized and polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomers, a compatibilizing amount of anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), Doping anions and naked or partially with adequate polymeric ionomers covered nano-sized (colloidal) particles of ferromagnetic functionalizing Materials, d. H. ferromagnetic particles like those in ferromagnetic functionalized liquids, so-called ferrofluids, can be used.

Furthermore, the invention provides processable, functionalized electronically conductive polypyrrole, polyaniline or polythiophene materials, the following Components contain: Nano-sized (colloidal) hybrid particles consisting of bare or partially with adequately anionically modified polymers and / or Copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) covered core particles of a functionalizing Material, an electronically conductive coating of an oxidized and polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomer, a compatibilizing amount of polymeric ionomers and doping anions. The size of the hybrid particles lies in the colloidal area, d. H. between 15 and 1000 nm, preferably between 15 and 500 nm.

Another object of this invention provides processable, ferromagnetic Functionalized electronically conductive polypyrrole, polyaniline or polythiophene Materials that contain the following components: Nano-sized (colloidal) Hybrid particles consisting of bare or partially with adequate anionic modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) Core particles of a ferromagnetic functionalizing material, d. H. particle as used in ferromagnetic functionalized liquids, so-called ferrofluids be an electronically conductive coating of an oxidized and polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomer, a compatibilizing amount of  polymeric ionomers and doping anions. The size of the hybrid particles lies in the colloidal area, d. H. between 15 and 1000 nm, preferably between 15 and 500 nm.

The invention also provides processable, functionalized electronic conductive polypyrrole, polyaniline or polythiophene materials, the following Components contain: Nano-sized (colloidal) hybrid particles consisting of bare or partially with adequately anionically modified polymers and / or Copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) covered core particles of an oxidized and polymerized amino-substituted or thio-substituted aromatic or heteroaromatic Monomers, a coating of a functionalizing material, a compatibilizing amount of polymeric ionomers and Doping anions. The size of the hybrid particles is in the colloidal range, i. H. between 15 and 1000 nm, preferably between 15 and 500 nm.

The invention also provides processable, ferromagnetic functionalized electronically conductive polypyrrole, polyaniline or polythiophene materials that contain the following components: nano-sized (colloidal) hybrid particles, consisting of naked or partially with adequately anionically modified Polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) covered core particles of one oxidized and polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomer, a coating of a ferromagnetic functionalizing material, d. H. Particles like them in ferromagnetic functionalized liquids, so-called ferrofluids, are used, a compatibilizing amount of polymeric ionomers and Doping anions. The size of the hybrid particles is in the colloidal range, i. H. between 15 and 1000 nm, preferably between 15 and 500 nm.

The present invention further provides a method of manufacture processable, pure or functionalized electronically conductive Polymer materials that support oxidative polymerization (under mild conditions)  of amino-substituted or thio-substituted aromatic or heteroaromatic monomers in acidic or neutral or slightly alkaline Reaction media included. The reaction media contain (optional) Embossed, bare or partially with adequately anionically modified polymers and / or copolymers and / or special, tailor-made polymers Ionomers (short: polymeric ionomers) covered nanosized particles of one functionalizing material. In addition, the reaction media are either homogeneous phases or "emulsions" of two or more immiscible Liquids and:

• a) the homogeneous reaction media contain suitable oxidizing agents for the suspended or dissolved amino-substituted or thio-substituted aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• b) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers, a compatibilizing amount of polymeric ionomers dissolved or swollen by other phases of the "emulsion" and the amino-substituted or thio-substituted aromatic or heteroaromatic monomers dissolved in same and / or different phases.

As a result of the reaction, the polymeric ionomers partially cover the surfaces the generated conductive polymer particles or the <functionalizing Material / conductive polymer <core-shell particles, and thereby represent the Compatibility with ordinary polymers that are the same in nature as the non- have or have ionic portions of the polymeric ionomers that have been used are tolerated, sure.

The present invention further provides a method of manufacture processable, ferromagnetically functionalized electronically conductive Polymer materials that support oxidative polymerization (under mild conditions) of amino-substituted or thio-substituted aromatic or heteroaromatic monomers in acidic or neutral or slightly alkaline Reaction media included. The reaction media contain embossed, bare or partially with adequate anionically modified polymers and / or  Copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) covered nanosized particles of a ferromagnetic functionalizing material, d. H. Particles like those in ferromagnetic functionalized liquids, so-called ferrofluids, can be used. Also are the reaction media either homogeneous phases or "emulsions" of two or more immiscible liquids and:

• a) the homogeneous reaction media contain suitable oxidizing agents for the suspended or dissolved amino-substituted or thio-substituted aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• b) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers, a compatibilizing amount of polymeric ionomers dissolved or swollen by other phases of the "emulsion" and the amino-substituted or thio-substituted aromatic or heteroaromatic monomers dissolved in same and / or different phases.

As a result of the reaction, the polymeric ionomers partially cover the surfaces the <ferromagnetic functionalizing material / conductive polymer <core shell Particles, thereby ensuring compatibility with ordinary polymers that the same nature as the non-ionic parts of the polymeric ionomer used have been, have or are compatible with them.

The present invention further provides a method for producing processable functionalized electronically conductive polymer materials that includes the following steps:

• a) Production of the functionalizing material, consisting of nano-sized Particles of the functionalizing material and a partial covering with anionically modified ordinary polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers). The covering of the particles of the functionalizing material by the polymer Ionomers ensure compatibility with ordinary polymers, the nature of which corresponds to the non-ionic parts of the polymeric ionomers or with them are tolerated. The preparation is carried out in:  
• a1) homogeneous reaction media that the naked, embossed nano-sized Contain particles of the functionalizing material in suspension and in which the polymeric ionomers are dissolved or swollen or
• a2) "emulsion-like" reaction media consisting of immiscible liquids, which is the bare, embossed nano-sized particles of the functionalizing Material contained in suspension and in which the polymeric ionomers in some the immiscible liquids are dissolved or
• a3) suitable grinding machines.

Preparation of nanosized particles from at least one electronically conductive Polymer, partially covered by polymeric ionomers, by oxidative Polymerization under mild conditions of polymerizable amino substituted or thio-substituted aromatic or heteroaromatic monomers in acidic, neutral or basic reaction media. The covering the nanosized electronically conductive polymer particles through the polymers Ionomers represents compatibility with ordinary polymers or Copolymers whose nature matches that of the non-ionic parts of the polymers Ionomers agree or are compatible with them, for sure. The Reaction media are either homogeneous phases or "emulsions" of immiscible liquids and:

• b1) the homogeneous reaction media contain a suitable oxidizing agent for the suspended or dissolved amino-substituted or thio-substituted aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• b2) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers and a compatibilizing amount of polymeric ionomers dissolved or swollen by other phases and the amino-substituted or thio- substituted aromatic or heteroaromatic monomers dissolved in the same and / or other phases or
• b3) preparation of nanosized particles of electronically conductive polymers, partially covered with polymeric ionomers, in suitable grinding machines.
• c) Thoroughly mixing the materials resulting from steps a) and b).

The present invention further provides a method for producing processable ferromagnetic functionalized electronically conductive Polymer materials that include the following steps:

• a) Production of the ferromagnetic functionalizing material, consisting of nano-sized particles of the ferromagnetic functionalizing material, d. H. Particles like those in ferromagnetic functionalized liquids, so-called Ferrofluids, are used, and partially covered with anionic modified ordinary polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers). The Covering the particles of the ferromagnetic functionalizing material the polymeric ionomer ensures compatibility with ordinary polymers, whose nature corresponds to that of the non-ionic parts of the polymeric ionomers or who are compatible with them. The preparation is carried out in:
• a1) homogeneous reaction media that the naked, embossed nano-sized Contain particles of the ferromagnetic functionalizing material in suspension and in which the polymeric ionomers are dissolved or swollen, or
• a2) "emulsion-like" reaction media consisting of immiscible liquids, which are the bare, embossed nano-sized particles of ferromagnetic Functionalizing material contained in suspension and in which the polymer Ionomers are dissolved in some of the immiscible liquids or
• a3) suitable grinding machines.

Preparation of nanosized particles from at least one electronically conductive Polymer, partially covered by polymeric ionomers, by oxidative Polymerization under mild conditions of polymerizable amino substituted or thio-substituted aromatic or heteroaromatic Monomers in acidic, neutral or basic reaction media. The covering the nanosized electronically conductive polymer particles through the polymers Ionomers represents compatibility with ordinary polymers or copolymers, their nature with that of the non-ionic parts of the polymeric monomers matches or which are compatible with them, for sure. The reaction media are either homogeneous phases or "emulsions" of immiscible liquids and:

• b1) the homogeneous reaction media contain a suitable oxidizing agent for the suspended or dissolved amino-substituted or thio-substituted  aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• b2) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers and a compatibilizing amount of polymeric ionomers dissolved or swollen by other phases and the amino-substituted or thio- substituted aromatic or heteroaromatic monomers dissolved in the same and / or other phases or
• b3) preparation of nanosized particles of electronically conductive polymers, partially covered with polymeric ionomers, in suitable grinding machines.
• c) Thoroughly mixing the materials resulting from steps a) and b).

The present invention further provides a method of manufacture processable, functionalized electronically conductive polymer materials that includes the following steps:

• a) Synthesis of nanosized particles of at least one electronically conductive polymer, which are partially covered with anionically modified Polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), by oxidative polymerization under mild conditions of polymerizable amino-substituted or thio- substituted aromatic or heteroaromatic monomers in acidic, neutral or basic reaction media. The covering of the nano-sized particles of the electronically conductive polymer through the polymeric ionomers represents the Compatibility with ordinary polymers sure, the nature of which is the same as those of the non-ionic parts of the polymeric ionomers or those compatible with them are. The reaction media are either homogeneous phases or "emulsions" of at least two insoluble liquids and:
• a1) the homogeneous reaction media contain a suitable oxidizing agent for the suspended or dissolved amino-substituted orthio-substituted ones aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• a2) the "emulsion-like reaction media" contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio-  substituted aromatic or heteroaromatic monomers and a compatibilizing amount of polymeric ionomers dissolved in or swollen by other phases and the amino-substituted or thio- substituted aromatic or heteroaromatic monomers dissolved in the same and / or other phases or
• a3) preparation of nanosized particles of electronically conductive polymers, partially covered with polymeric ionomers using suitable grinding machines.
• b) Production of nano-sized particles of functionalizing materials within of parts of the reaction mixtures of a).
• c) (optional) addition of certain amounts of polymeric ionomers for resulting reaction mixture of b).

The present invention further provides a method of manufacture processable, ferromagnetically functionalized electronically conductive Polymer materials that include the following steps:

• a) Synthesis of nanosized particles of at least one electronically conductive polymer, which are partially covered with anionically modified Polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), by oxidative polymerization under mild conditions of polymerizable amino-substituted or thio- substituted aromatic or heteroaromatic monomers in acidic, neutral or basic reaction media. The covering of the nano-sized particles of the electronically conductive polymer through the polymeric ionomers represents the Compatibility with ordinary polymers sure, the nature of which is the same as those of the non-ionic parts of the polymeric ionomers or those compatible with them are. The reaction media are either homogeneous phases or "emulsions" of at least two insoluble liquids and:
• a1) the homogeneous reaction media contain a suitable oxidizing agent for the suspended or dissolved amino-substituted or thio-substituted ones aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• a2) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers and a  compatibilizing amount of polymeric ionomers dissolved in or swollen by other phases and the amino-substituted or thio- substituted aromatic or heteroaromatic monomers dissolved in the same and / or other phases or
• a3) preparation of nanosized particles of electronically conductive polymers, partially covered with polymeric ionomers using suitable grinding machines.
• b) Production of nanosized particles of ferromagnetic functionalizing Materials within parts of the reaction mixtures of a).
• c) (optional) addition of certain amounts of polymeric ionomers for resulting reaction mixture of b).

Another object of this invention provides processable ferromagnetic functionalized electronically conductive polymer materials, the following Components contain: Nano-sized (colloidal) particles of oxidized and polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomers, a compatibilizing amount of anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), Doping anions and large (particle diameter »20 nm), bare or nano-sized (colloidal) partially covered with adequate polymeric ionomers Particles of ferromagnetic functionalizing materials, i. H. ferromagnetic Particles such as those used in new, physiologically compatible ferrofluids will.

The invention also provides processable, ferromagnetically functionalized ones electronically conductive polypyrrole, polyaniline or polythiophene materials that contain the following components: nano-sized (colloidal) hybrid particles, consisting of large (particle diameter »20 nm), bare or partially with adequate anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomer covered particles of a ferromagnetic functionalizing core material, d. H. Particles like them in novel physiologically compatible ferrofluids are used, one  electronically conductive sheath of an oxidized and polymerized amino substituted or thio-substituted aromatic or heteroaromatic Monomers, a compatibilizing amount of polymeric ionomers and Doping anions. The size of the hybrid particles is in the colloidal range, i. H. between 15 and 1000 nm, preferably between 15 and 500 nm.

Yet another object of this invention provides processable, ferromagnetic Functionalized electronically conductive polypyrrole, polyaniline or polythiophene Materials that contain the following components: Nano-sized (colloidal) Hybrid particles consisting of bare or partially with adequate anionic modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) Particles of an oxidized and polymerized amino-substituted or thio- substituted aromatic or heteroaromatic monomer, an envelope a ferromagnetic functionalizing material, d. H. huge (Particle diameter »20 nm) nano-sized particles like those in new types physiologically compatible ferrofluids are used, a compatibilizing effective amount of polymeric ionomers and doping anions. The size of the Hybrid particle is in the colloidal area, i. H. between 15 and 1000 nm, preferably between 15 and 500 nm.

The present invention further provides a method of manufacture processable, ferromagnetically functionalized electronically conductive Polymer materials that support oxidative polymerization (under mild conditions) of amino-substituted or thio-substituted aromatic or heteroaromatic monomers in acidic or neutral or slightly alkaline Reaction media included. The reaction media contain embossed, large ones (Particle diameter »20 nm), bare or partially with adequate anionic modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) nano-sized particles of a ferromagnetic functionalizing material, d. H. Particles such as those used in new, physiologically compatible ferrofluids will. In addition, the reaction media are either homogeneous phases or "Emulsions" of two or more immiscible liquids and:

• a) the homogeneous reaction media contain suitable oxidizing agents for the suspended or dissolved amino-substituted or thio-substituted aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• b) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers, a compatibilizing amount of polymeric ionomers dissolved or swollen by other phases of the "emulsion" and the amino-substituted or thio-substituted aromatic or heteroaromatic monomers dissolved in same and / or different phases.

As a result of the reaction, the polymeric ionomers partially cover the surfaces the <ferromagnetic functionalizing material / conductive polymer <core shell Particles, thereby ensuring compatibility with ordinary polymers that the same nature as the non-ionic parts of the polymeric ionomer used have been, have or are compatible with them.

The present invention further provides a method for producing processable ferromagnetic functionalized electronically conductive Polymer materials that include the following steps:

• a) Production of the ferromagnetic functionalizing material, consisting of large (particle diameter »20 nm) nanosized particles of ferromagnetic functionalizing material, d. H. Particles like those in novel physiologically compatible ferrofluids are used, and a partial Covering made from anionically modified ordinary polymers and / or Copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers). Covering the particles of the ferromagnetic functionalizing material by the polymeric ionomers secures the Compatibility with ordinary polymers, the nature of which is that of non-ionic Parts of the polymeric ionomers correspond or are compatible with them. The Preparation is carried out in:
• a1) homogeneous reaction media that the naked, embossed nano-sized Contain particles of the ferromagnetic functionalizing material in suspension and in which the polymeric ionomers are dissolved or swollen, or  
• a2) "emulsion-like reaction media" consisting of immiscible liquids, which are the bare, embossed nano-sized particles of ferromagnetic Functionalizing material contained in suspension and in which the polymer Ionomers are dissolved in some of the immiscible liquids or
• a3) suitable grinding machines.

Preparation of nanosized particles from at least one electronically conductive Polymer, partially covered by polymeric ionomers, by oxidative Polymerization under mild conditions of polymerizable amino substituted or thio-substituted aromatic or heteroaromatic u-ionomers in acidic, neutral or basic reaction media. The covering the nanosized electronically conductive polymer particles through the polymers Ionomers represents compatibility with ordinary polymers or copolymers, their nature with that of the non-ionic parts of the polymeric ionomers matches or which are compatible with them, for sure. The reaction media are either homogeneous phases or "emulsions" of immiscible liquids and:

• b1) the homogeneous reaction media contain a suitable oxidizing agent for the suspended or dissolved amino-substituted or thio-substituted aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• b2) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers and a compatibilizing amount of polymeric ionomers dissolved or swollen by other phases and the amino-substituted or thio- Substituted aromatic or heteroaromatic monomers dissolved in the same and / or other phases or
• b3) preparation of nanosized particles of electronically conductive polymers, partially covered with polymeric ionomers, in suitable grinding machines.
• c1) Thoroughly mix the materials resulting from steps a) and b).

The present invention further provides a method of manufacture processable ferromagnetic functionalized electronically conductive Polymer materials that include the following steps:

• a) Synthesis of nanosized particles of at least one electronically conductive Polymer that are partially covered with anionically modified polymers and / or Copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), by oxidative polymerization under mild conditions of polymerizable amino-substituted or thio-substituted aromatic or heteroaromatic monomers in acidic, neutral or basic Reaction media. Covering the nanosized particles of the electronically conductive polymer through the polymeric ionomers provides compatibility with ordinary polymers, the nature of which is the same as that of the non- ionic parts of the polymeric ionomers or which are compatible with them. The Reaction media are either homogeneous phases or "emulsions" of at least two insoluble liquids and:
• a1) the homogeneous reaction media contain a suitable oxidizing agent for the suspended or dissolved amino-substituted or thio-substituted ones aromatic or heteroaromatic monomers and polymeric ionomers dissolved or swollen from the reaction media or
• a2) the "emulsion-like" reaction media contain dissolved in at least one Phase a suitable oxidizing agent for the amino-substituted or thio- substituted aromatic or heteroaromatic monomers and a compatibilizing amount of polymeric ionomers dissolved in or swollen by other phases and the amino-substituted or thio- substituted aromatic or heteroaromatic monomers dissolved in the same and / or other phases or
• a3) preparation of nanosized particles of electronically conductive polymers, partially covered with polymeric ionomers using suitable grinding machines.
• b) Production of large (particle diameter »20 nm) nano-sized particles ferromagnetic functionalizing materials, d. H. Particles like those in novel physiologically acceptable ferrofluids are used within parts of the Reaction mixtures from a).
• c) (optional) addition of certain amounts of polymeric ionomers for resulting reaction mixture of b).

In addition, methods of preparing composites and are ready for the market Materials of the aforementioned processable, pure or functionalized or  Ferromagnetic functionalized electronically conductive polymer materials (short: processable conductive polymer materials) with ordinary polymers, whose nature is identical to that of the non-ionic parts of the polymer Ionomers used in processable, conductive polymer materials were shown, or which are compatible with them. These methods include simplest stirring and kneading techniques and all other typical polymer Processing techniques used in the prior art of polymer processing are included, in particular such methods for producing composites and marketable products consisting of processable, conductive Polymer materials and water-based acrylic paints, epoxy resins, unsaturated polyesters, silicone oils, rubber and polyurethane resins.

Yet another object of this invention are novel physiological compatible ferrofluids, the large (particle diameter »20 nm) nano-sized Particles of ferromagnetic material contain, and thereby the Magnetization / viscosity behavior of physiologically compatible ferrofluids strong improve.

Yet another object of this invention is a method of manufacture novel ferrofluids, the large (particle diameter »20 nm) nano-sized Particles of ferromagnetic materials contain the following substances includes:

• a) adequate reaction media,
• b) adequate salts or compounds of ferromagnetic elements,
• c) (optional) adequate precipitation or reduction substances and
• d) adequate stabilizing substances.

Furthermore, the invention provides special, tailor-made water-based at least two-component polymeric ionomers, which when used in processable, pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials (short: processable, conductive polymer materials) the production of marketable processable, conductive polymer materials based on commercial water-based Allow colors, especially of water-based acrylic colors. This  tailor-made polymeric ionomers consist of anionic, polymerizable monomer units, water-soluble, non-ionic, polymerizable monomer units that (during their polymerization) too water-soluble polymers, and (in the case of at least three- component polymeric ionomers) water-soluble, non-ionic, polymerizable monomer units which, during polymerization, become water-insoluble Polymers.

The present invention further provides a method for the synthesis of special bespoke and water-based at least two-component polymeric ionomers which, when used in processable, pure or functionalized or ferromagnetic functionalized electronically conductive Polymer materials (short: processable, conductive polymer materials) die Generation of marketable, processable, conductive polymer materials on the Basis of commercial water-based paints, especially water based acrylic paints. This method includes the graft Copolymerization of suitable non-ionic, water-soluble monomers water-soluble polymers or oligomers containing anionic groups Use of suitable oxidizing agents in aqueous reaction media.

The particular advantages of the invention are detailed in the following Description of the invention shown.

The present invention includes processable, pure or functionalized or Ferromagnetic functionalized electronically conductive polymer materials (short processable, conductive polymer materials). Oxidative polymerization will thereby for the preparation of the electronically conductive component of the invention applied. Such reactions can be oxidative with a variety polymerizable monomers are carried out. Suitable, oxidative polymerizable monomers include amino-substituted or thio-substituted aromatic or heteroaromatic monomers, such as pyrrole, aniline and thiophene and substituted pyrroles, anilines and thiophenes. Without the present To want to limit the invention in its scope come from  substituted pyrroles, anilines and thiophenes suitable substituents from the Range of alkyl, aryl, aralkyl, alkaryl, hydroxy, methoxy, chloro, bromo and Nitro groups. The appropriate substituents are in accordance with the desired polymerization conditions and properties of the resulting processable, conductive polymer materials selected. Pyrrole, aniline and Thiophene are the particularly preferred amino-substituted or thio- substituted aromatic or heteroaromatic monomers of the present Invention.

The term "functionalized" means in connection with the present Invention that the amino-substituted or thio-substituted aromatic or heteroaromatic monomers during their polymerization on the surfaces of nano-sized, bare or partially with suitable anionically modified Polymers and / or copolymers and / or special, tailor-made polymeric ionomers covered particles of functionalizing materials, which are suspended in the reaction medium, are precipitated and thereby Core-shell particles that have a core of functionalizing material and one Form iron cover of electronically conductive material. Furthermore the term functionalization implies that the electronically conductive Polymer through the incorporation of the functionalizing component new, Desired material properties can be inserted in the pure electronic conductive polymers either not at all or only to a very great extent small extent can be determined. The functionalization is therefore limited not on the change in material density (i.e. inert functionalizing 023023Additives) and the fact that the nanosized particles of functionalizing materials in the first moment of their storage as Precipitation sites for the growing molecules of the electronically conductive Polymers work.

Alternatively, the functionalization can also be achieved as follows:

• 1) Preparation of pure compositions of the functionalizing material nano-sized particles of the functionalizing material and compatibilizing effective amounts of anionically modified polymers and / or copolymers  and / or special, tailor-made polymeric ionomers (short: polymer Ionomers) included.
• 2) Preparation of pure compositions of the electronically conductive material that nano-sized particles of polymerized amino-substituted or thio-substituted aromatic or hetero-aromatic monomers and compatibilizing contain effective amounts of polymeric ionomers.

The nature of the polymeric ionomers is generally the same in steps 1) and 2), can also be different as long as these materials are compatible with each other are.

• 3) Thoroughly mix the materials resulting from steps 1) and 2), to a functionalized mixture of the electronically conductive polymers receive.

Another method to achieve functionalization includes:

• 4) the preparation of pure compositions from electronically conductive Materials containing nanosized particles of polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomers and compatibilizing amounts of anionically modified polymers and / or copolymers and / or special, tailor-made polymers Contain ionomers (polymeric ionomers for short),
• 5) the production of nanosized particles of the functionalizing material in the presence of the electronically conductive polymer materials, which in step 4 were generated
• 6) (Optional) adding an extra amount of polymeric ionomers to the Hydride material resulting from step 5). The nature of the polymeric ionomers used in steps 4) and 6) is generally the same, but can be different as long as this Materials are compatible with each other.

The term "ferromagnetic functionalized" means in connection with the present invention that the amino-substituted or thio-substituted aromatic or heteroaromatic monomers during their polymerization the surfaces of nano-sized, bare or partially with suitable anionic modified polymers and / or copolymers and / or special, tailor-made polymeric ionomer covered particles of ferromagnetic  functionalizing materials, d. H. Particles like those in ferromagnetic Functionalized liquids, so-called ferrofluids, are used, which in the Reaction medium are suspended, put down and thereby Core-shell particles that have a core made of ferromagnetic functionalizing Have material and a shell made of electronically conductive material.

Alternatively, the ferromagnetic functionalization can also be as follows can be achieved:

• 1) Preparation of pure compositions of the ferromagnetic functionalizing Material that nanosized particles of the ferromagnetic functionalizing Materials, i.e. H. Particles like those in ferromagnetic functionalized liquids, So - called ferrofluids are used, and amounts of anionically modified polymers and / or copolymers and / or special, contain customized polymeric ionomers (short: polymeric ionomers).
• 2) Preparation of pure compositions of the electronically conductive material that nano-sized particles of polymerized amino-substituted or thio-substituted aromatic or hetero-aromatic monomers and compatibilizing contain effective amounts of polymeric ionomers.

The nature of the polymeric ionomers is generally the same in steps 1) and 2), can also be different as long as these materials are compatible with each other are.

• 3) Thoroughly mix the materials resulting from steps 1) and 2), to a functionalized mixture of the electronically conductive polymers receive.

Yet another method of achieving ferromagnetic Functionalization includes:

• 4) the preparation of pure compositions from electronically conductive Materials containing nanosized particles of polymerized amino-substituted or thio-substituted aromatic or heteroaromatic monomers and compatibilizing amounts of anionically modified polymers and / or copolymers and / or special, tailor-made polymers Contain ionomers (short: polymeric iononiers),  
• 5) the production of nano-sized particles of ferromagnetic functionalizing material, d. H. Particles like those in ferromagnetic functionalized liquids, so-called ferrofluids, are used in the Presence of the electronically conductive polymer materials generated in stage 4) were
• 6) (Optional) adding an extra amount of polymeric ionomers to the Hydride material resulting from step 5).

The nature of the polymeric ionomers used in steps 4) and 6) is generally the same, but can be different as long as this Materials are compatible with each other.

The production of new, physiologically compatible ferrofluids is described in Reaction mixtures containing the following components are achieved:

• 7) polar and / or non-polar liquids,
• 8) suitable salts or compounds of ferromagnetic elements,
• 9) (optional) suitable precipitants or reducing agents,
• 10) suitable polymeric stabilizing substances.

The production of new, physiologically compatible ferrofluids in is preferred Reaction mixtures carried out, which contain the following components:

• 11) water,
• 12) Iron (II) and iron (III) salts, the total molarity of the iron salts in the Reaction solution is <0.2 M and the proportion of divalent iron is greater than that of trivalent iron,
• 13) ammonia, NaOH or KOH
• 14) Polystyrene-4-sulfonate, sodium salt, M.W. = 70,000 and 500,000, Polyacrylic acid, M.W. = 450,000 or polyacrylamide-co-acrylic acid, M.W. = 200,000 (90/10 wt%).

The production of new types of physiology is very particularly preferred compatible ferrofluids carried out in reaction mixtures that the contain the following components:

• 15) water,  
• 16) Iron (II) chloride and iron (III) chloride, the total molarity of Iron salts in the reaction solution is <0.2 M and the proportion of dihydric iron is larger than that of trivalent iron,
• 17) ammonia or NaOH,
• 18) poly (oligo) styrene-4-sulfonate graft acrylamide, sulfonated dextran, Polymethyl vinyl ether co-maleic acid or a 1: 1 weight mix of  Poly (oligo) styrene-4-sulfonate graft acrylamide and sulfonated dextran.

The term "processable" as used in connection with the processable, pure or functionalized or ferromagnetic functionalized electrically conductive Polymer materials (short: processable, conductive polymer materials) this Invention is used that the processable, conductive Polymer materials easily into liquefied polymers, solutions, or melts Polymers and / or copolymers and those of more than one polymer or Copolymer (short: ordinary polymers) as long as the polymers and / or Copolymers are compatible with one another, can be mixed. With "easy" what is meant here is that the mixing process is already too relative by means of hand stirring homogeneous mixtures, although achieving higher levels of homogeneity may require the use of mixing methods known in the prior art polymer processing are included. In the latter context, it depends most suitable mixing process from the specific combination of processable, conductive polymer material and the usual used Polymers. It is also important that the blends and ready for the market Materials that are processable, conductive polymer materials and ordinary Contain polymer materials, not necessarily long-term stable mixtures and are marketable materials, d. H. with stabilities of more than a week. Rather, the stability of such mixtures and marketable materials is only so good that in the application case (during the drying or hardening process) no phase separation of the processable, conductive polymer materials from the ordinary polymers.

The processable, pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials (short: processable, conductive polymer materials) of the present invention  compatibilizing amounts of anionically modified polymers and / or copolymers and / or special, tailor-made polymers Ionomers (short: polymeric ionomers). Without being tied to a specific theory it is believed that the polymeric ionomers are quite similar to Steric stabilizer molecules act as they do in long-term stable colloidal Dispersions of any kind of material are used, i. H. the polymers Ionomers are on the outer surfaces of the nano-sized <(ferromagnetic) Functionalizing material / electronically conductive polymer <core-shell particles or the nano-sized particles made of (ferromagnetic) functionalizing material and / or the nanosized particles of electronically conductive polymer physical or chemical bonds attached so that (if at all) only loosely connected aggregates of several of the relevant nano-sized ones Particles during the respective syntheses of the processable, conductive Can form polymer materials.

With a view to the anionically modified polymers and / or copolymers and / or the special, tailor-made polymeric ionomers (short: polymeric ionomers), as used in the present invention for compatibility of the processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials with ordinary polymers and / or copolymers and / or mixtures of different compatible polymers and / or Copolymers are used, it is clear that these polymeric ionomers on very different types with the nano-sized <(ferro-magnetic) functionalizing Material / electronically conductive polymer <hybrid particles, the pure nano-sized Particles made of (ferromagnetic) functionalizing material and / or the pure nanosize particles made of electronically conductive polymer interact Depending on the specific composition of the polymeric ionomers, e.g. B. on interactions of the aforementioned nano-sized particles with amino, Hydroxy, diglycidyl, carbonyl and. a. Groups in the polymeric ionomers available. However, due to the presence of anionic Groups in all of these polymeric ionomers, and in accordance with that Know about the interactions between nano-sized particles ferromagnetic materials, d. H. Particles like those in ferromagnetic functionalized liquids, so-called ferrofluids, are used, and nano-sized  Particles made of electronically conductive polymer with anionic groups Molecules, (and without the scope of the present invention want to restrict) assumed that the polymeric ionomers over ionic Interactions with the nano-sized particles in the materials of this Invention are connected.

The amount of anionic groups containing monomers within the anionic modified polymers and / or copolymers and / or more specific, tailor-made polymeric ionomer (short: polymeric ionomer) is in the generally small, d. H. <10 mol%, although larger amounts of this type of Monomers also possible or through the preparation route of the polymer Monomers are conditional. There is no restriction regarding the ordinary polymers or copolymers that may be used to synthesize anionically modified polymers or copolymers in the sense of the present Invention can be used. Rather, the availability of certain it only anionically modifies polymers or copolymers through problems be limited in the course of the manufacturing process of anionic modified polymers or copolymers occur. The anionically modified Polymers or copolymers generally result from polymer analogs Reactions of ordinary polymers or copolymers with smoking Sulfuric acid, sulfur trioxide or chlorosulfonic acid. That way e.g. B. the synthesis of sulfonated polystyrenes, sulfonated epoxy resins, sulfonated polyesters, sulfonated silicone oils and sulfonated polyurethane resins possible. In addition, it has been shown to contain anionic groups polymeric ionomers also through special copolymerization experiments that anionic and non-ionic monomers, e.g. B. copolymers of acrylic acid and Acrylic acid derivatives, can be generated. Even more special polymers Ionomers are generated on even more special macromolecular synthetic routes.

The present invention also relates to special, tailor-made water based graft-copolymer-like polymeric ionomers with at least two various monomeric repeating units which, when used in processable, pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials (short: processable,  conductive polymer materials) the production of marketable processable, conductive polymer materials (blended into commercial, water-based Allow colors, especially water-based acrylic paints). Some can these tailor-made polymeric ionomers also for the production of new types physiologically compatible ferrofluids can be used.

Oxidative graft copolymerizations are used to make the custom-made, water-based polymeric ionomers. Of the The synthetic route involves a two-stage polymerization reaction. Step 1, the Synthesis of adequate oligomeric or short chain polymers or copolymers (M.W. <10,000) contains molecules, is carried out with the following ingredients:

• 19) Suitable polar and / or non-polar liquids,
• 20) suitable anionic and (optionally) non-ionic, polymerizable Monomers and
• 21) suitable initiators / oxidizing agents.

Step 2 involves the graft copolymerization of suitable, polymerizable Monomers on the oligomeric or short chain polymeric molecules that are made up Step 1 result. The reaction includes the following components:

• 22) Suitable polar and / or non-polar liquids,
• 23) suitable non-ionic, water-soluble and (optionally) water-insoluble, polymerizable monomers,
• 24) the oligomeric or polymeric molecules from step 1 and
• 25) suitable initiators / oxidizing agents.

A particularly preferred method of producing customized, water-based graft copolymers for use as compatibilizers in processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials and in novel In step 1, physiologically compatible ferrofluids include:

• 26) As a polar liquid, water,
• 27) as an anionic, polymerizable monomer styrene-4-sulfonate, sodium salt and
• 28) as initiator / oxidizing agent ammonium peroxodisulfate and in step 2:
• 29) water as polar liquid,  
• 30) as non-ionic, water-soluble monomer acrylamide,
• 31) the oligomeric or polymeric styrene-4-sulfonate, sodium salt chains Step 1 and
• 32) as initiator / oxidizing agent ammonium cerium (IV) nitrate.

Very particularly preferred methods of producing customized, water based graft copolymer for use as compatibilizers in processable, pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials include in step 1:

• 33) As a polar liquid, water,
• 34) as an anionic, polymerizable monomer styrene-4-sulfonate, sodium salt and
• 35) as initiator / oxidizing agent ammonium peroxodisulfate and in step 2:
• 36) water as a polar liquid,
• 37) as non-ionic, water-soluble, polymerizable monomers acrylamide and 2- Hydroxyethyl methacrylate or acrylamide and N-hydroxymethylacrylamide,
• 38) the oligomeric or polymeric styrene-4-sulfonate, sodium salt chains Step 1 and
• 39) as initiator / oxidizing agent ammonium cerium (IV) nitrate.

Furthermore, the present invention relates to methods for the production of processable, pure or functionalized electronically conductive Polymer materials (short: processable, conductive polymer materials). A Method for achieving the preparation involves the polymerization of amino-substituted or thio-substituted aromatic or heteroaromatic Monomers in mixtures that have the following ingredients:

• 40) polar liquids,
• 41) (depending on the specific case), embossed, bare or partially with suitable anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) covered nanosized particles of a functionalizing material,
• 42) polymeric ionomers,
• 43) (depending on the specific case) non-polar liquids and  
• 44) suitable initiators / oxidizing agents.

Other substances, e.g. B. polymerization regulators and Additive, in this method of manufacturing processable, conductive Polymer materials are used.

Another method of making processable, functionalized Electronically conductive polymer materials include a 3-step process:

• 1) production of nano-sized particles of the functionalizing material, partially covered with anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymer Ionomers) in mixtures with the following components:
• 45) embossed bare, nano-sized particles of the functionalizing material and
• 46) polymeric ionomers.
• 2) Polymerization of amino-substituted or thio-substituted aromatic or heteroaromatic monomers to produce nano-sized particles electronically conductive polymer in blends containing the following components contain:
• 47) polar liquids,
• 48) polymeric ionomers,
• 49) (depending on the specific case) non-polar liquids and
• 50) suitable initiators / oxidizing agents.

Other substances, e.g. B. polymerization regulators and additives, can also be used in steps 1) and 2).

• 3) Thoroughly mix the materials resulting from steps 1) and 2) to to produce a homogeneous material.

Yet another method of making processable, functionalized ones electronically conductive polymer materials includes another 3 step Process:

• 1) Preparation of nanosized particles of polymers which contain amino-substituted or thio-substituted aromatic or heteroaromatic monomeric building blocks from mixtures which contain the following constituents:
  032
• 51) polar liquids  
• 52) anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers),
• 53) (depending on the specific case) non-polar liquids and
• 54) suitable initiators / oxidizing agents.
• 2) Preparation of nanosized particles of a functionalizing material in Divide the final reaction mixture from 1).
• 3) (Optional) adding an amount of polymeric ionomers to the final one Reaction mixture from step 2).

Other substances, e.g. B. polymerization regulators and additives, can also be used in steps 1) -3).

Furthermore, the present invention relates to methods for the production of processable, ferromagnetic functionalized electronically conductive polymer materials (in short: processable, conductive polymer materials). A method for achieving the preparation involves the polymerisation of amino substituted or thio-substituted aromatic or heteroaromatic Monomers in mixtures that have the following ingredients:

• 55) polar liquids,
• 56) embossed, bare or partially with suitable anionically modified Polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymer ionomers) covered nanosized particles a ferromagnetic functionalizing material, d. H. Particles like them in ferromagnetic functionalized liquids, so-called ferrofluids, are used,
• 57) polymeric ionomers,
• 58) (depending on the specific case) non-polar liquids and
• 59) suitable initiators / oxidizing agents.

Other substances, e.g. B. polymerization regulators and Additive, in this method of manufacturing processable, conductive Polymer materials are used.

Another method of manufacturing processable, ferromagnetic functionalized electronically conductive polymer materials includes a 3- Step process:

• 1) Production of nanosized particles of the ferromagnetic functionalizing Materials, i.e. H. Particles like those in ferromagnetic functionalized liquids, So-called ferrofluids are used, partially covered with anionically modified Polymers and / or copolymers (i.e. polymeric ionomers) and / or special, tailor-made polymeric ionomers (short: polymeric ionomers) in mixtures with the following components:
• 60) embossed bare, nano-sized particles of the functionalizing material and
• 61) polymeric ionomers.
• 2) Polymerization of amino-substituted or thio-substituted aromatic or heteroaromatic monomers to produce nano-sized particles electronically conductive polymer in blends containing the following components contain:
• 62) polar liquids,
• 63) polymeric ionomers,
• 64) (depending on the specific case) non-polar liquids and
• 65) suitable initiators / oxidizing agents.

Other substances, e.g. B. polymerization regulators and additives, can also be used in steps 1) and 2).

• 3) Thoroughly mix the materials that result from steps 1) and 2) to produce a homogeneous material.

Yet another method of manufacturing processable, ferromagnetic functionalized electronically conductive polymer materials includes one another 3-step process:

Other substances, e.g. B. polymerization regulators and additives, can also be used in steps 1) -3).

The present invention also relates to the manufacturing process of composites and / or marketable materials that are processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials and ordinary polymers or copolymers or mixtures of different compatible, contain polymer or copolymer. These procedures include in generally simple hand mixing or mixing in one Laboratory mortar aimed at relatively homogeneous composite materials or ready for the market Get materials. However, it can be in the case of marketable products the mixing process may be necessary under more strictly defined conditions perform, d. H. applying all typical polymer Processing methods used in the prior art of polymer processing may be necessary. Optionally, in all of these Preparation methods also add additives to the resulting materials confer further special properties or the specific, desired chemical and / or cause physical reactions in the resulting materials, to be used.

The ratio of the anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomer (short: polymer Ionomers) to the nano-sized <(ferromagnetic) functionalizing Material / electronically conductive polymer material <core-shell particles or the nano-sized particles of the (ferromagnetic) functionalizing material and / or the nano-sized particles of the electronically conductive material can in vary in a wide range from 1:99 to 99: 1 parts by weight. The exact Ratio in a special case of a processable, pure or  functionalized or ferromagnetic functionalized electronically conductive Polymer material (short: processable, conductive polymer material) is, however determined by two conditions:

• 72) The polymeric ionomers are said to be compatible with the processable, conductive Polymer materials with ordinary polymers and / or copolymers or Mixtures of different compatible polymers and / or copolymers (short: ordinary polymers) ensure. I.e. a certain minimum amount polymeric ionomers must be in the processable, conductive polymer materials to be available.
• 73) The processable, conductive polymer materials should not necessarily be stable colloidal dispersions when in liquid ordinary polymers are redispersed. I.e. the surface coverage of the nano-sized particles of <(ferromagnetic) functionalizing Material / electronically conductive polymer material <or (ferromagnetic) functionalizing material and / or electronically conductive material with polymeric ionomers are generally not intended to be complete.

In any case, the amount of anionically modified polymer and / or Copolymer and / or special, tailor-made polymeric ionomer (short: polymeric ionomers), which is most suitable in individual cases, based on the Diameter of the nano-sized particles in the processable, pure or functionalized or ferromagnetic functionalized electronically conductive Polymer materials (in short: processable, conductive polymer materials) available are, the average surface area of a molecule of the polymeric ionomers is shielded when it is coated with the nano-sized particles in the processable conductive polymer materials are present, interact, the density of the nano-sized particles contained in the processable, conductive polymer materials are present, the molecular weights of the polymeric ionomers and the Parts by weight of the nano-sized particles from <(ferromagnetic) functionalizing material / electronically conductive material <or (ferromagnetic) functionalizing material and / or electronically conductive Estimated polymer material in the processable, conductive polymer materials will.  

The amounts of anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers used in the polymerization reaction mixtures of the amino-substituted or thio-substituted aromatic or heteroaromatic monomers, and / or the reaction mixtures in which the nano-sized particles of the (ferromagnetic) functionalizing materials are manufactured in such a way that the resulting processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials compatible with ordinary polymers and / or Copolymers or mixtures of compatible polymers and / or copolymers are (see above).

The initiators / oxidizing agents used for the oxidative polymerization of the amino substituted or thio-substituted aromatic or heteroaromatic, polymerizable monomers of the present invention must be used compatible with the anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymer Ionomers) and capable of oxidative polymerization of the amino-substituted or thio-substituted aromatic or heteroaromatic monomers. With "Compatible" means that the combination of Initiators / oxidizing agents with the polymeric ionomers not for training significant amounts of insoluble precipitate in the reaction media, in where the polymerization reactions are carried out. With "significant" is meant that any amount of insoluble precipitate that possibly arises, can be easily filtered off and not a drastic one Reduction of the amount of processable, pure or functionalized or leads ferromagnetic functionalized electronically conductive polymer material. In addition, the initiators / oxidizers must be relatively mild Initiators / oxidizers, d. H. the initiators / oxidizing agents may amino-substituted or thio-substituted aromatic or heteroaromatic Do not polymerize monomers at such a rate that the resulting electronically conductive polymer regardless of presence precipitating polymeric ionomers. Ammonium peroxodisulfate and azoisobutyronitrile are the preferred Initiators / oxidizers for the combination of pyrrole, aniline and thiophene  with polymeric ionomers containing SO3 groups. More usable Initiators / oxidizers for use in the present invention Iron (III) chloride and benzoyl peroxide, depending on the tolerance with the special polymeric ionomers that are compatible with ordinary polymers and / or copolymers and / or mixtures more compatible Polymer and / or copolymer can be used.

The molar ratio between the amino-substituted or thio-substituted aromatic or heteroaromatic polymerizable monomers and the Initiators / oxidizers depend on the extent of oxidation that is necessary to polymerize the amino-substituted or thio-substituted to achieve aromatic or heteroaromatic monomers and for the Defined overoxidation of the resulting polymers so that they are the maximum have electronic conductivity is necessary. In the case of polymerization of pyrrole with ammonium peroxodisulfate is the molar monomer / oxidizer Ratio 1: 1. 17 (8) since each pyrrole monomer has to be oxidized twice to be polymerized and a further oxidation step every three Pyrrole monomer units is necessary to convert the polypyrrole into the electrical to transfer the most conductive state. In the case of the polymerization of thiophene using azoisobutyronitrile, is the molar monomer / oxidant ratio also 1: 1. 17 (8). In the case of the polymerization of aniline with Ammonium peroxodisulfate is the molar monomer / oxidizing agent ratio 1: 1. The concentration of the initiators / oxidizing agents in the reaction media can vary. Generally the initiator / oxidant concentration is between 0.001 and 1 M. Preferred molar initiator / oxidizer concentrations are between 0.03 and 0.1 M.

The pH of the reaction media for manufacturing processable, pure or Functionalized or ferromagnetic functionalized electronically conductive Polymer materials (in short: processable, conductive polymer materials) depend on special case from:

• 1) In the case of the preparation of processable conductive polymer materials over the production of nano-sized core-shell particles, the core in essentially from embossed nano-sized particles of (ferromagnetic)  functionalizing material, the pH is usually neutral or light angry. However, due to the polymerization of the amino-substituted or thio- substituted aromatic or heteroaromatic monomers a considerable Decrease in pH, which is sometimes due to the addition of adequate alkaline solutions must be balanced.
• 2) In the case of the preparation of processable, conductive polymer materials over the mixing of embossed materials consisting of nano-sized particles of (ferro-magnetic) functionalizing materials and compatibilizing effective amounts of anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymer Ionomers), and nanosized particles of electronically conductive Polymer materials and compatibilizing amounts of polymer Ionomers, the pH values of the individual preparation steps are not critical, as long as both components of the resulting processable, conductive Polymer material chemically stable and / or electronically conductive in the common pH, which results when mixing the individual components.
• 3) In the case of the preparation of processable, conductive polymer materials over the precipitation of nano-sized particles of (ferromagnetic) functionalizing materials on the surfaces of embossed [(optional) partially covered with polymeric ionomers] nanosize particles of Electronically conductive polymers depend on the pH values of the reaction media again the physical stability of the electronically conductive state of the electronically conductive polymer and the chemical stability of the nanosized Particles of the (ferromagnetic) functionalizing material.
• 4) In the case of the preparation of pure processable, conductive Polymer materials, the nano-sized particles of electronically conductive polymers and contain compatibilizing amounts of polymeric ionomers the pH of the individual preparation steps is not critical as long as that processable, conductive polymer material at the end of production in electronic is conductive state.

The reaction media can also be suitable non-polar / non-polar organic Contain liquids. The nature of these organic liquids depends on the Nature of the non-water soluble parts of the anionically modified polymers  and / or copolymers and / or special, tailor-made polymeric ionomers from. In connection with "suitable" is meant that these organic Liquids are insensitive to oxidation, i. H. they don't affect them Amount of resulting processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer material (short processable, conductive polymer material) and are not involved in the Polymerization reaction of the amino-substituted or thio-substituted aromatic or heteroaromatic monomers, making the electronic Conductivities of the resulting conductive polymer materials can be reduced would and do not hinder the formation of the nano-sized particles (ferromagnetic) functionalizing material, making the functionalizing Properties of the functionalizing materials in the processable, conductive Polymer materials would be affected. Suitable non-polar / non-polar organic liquids are toluene, ethyl acetate and chloroform.

The methods for the preparation of processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials and anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers are occasionally used in so-called "Emulsions" carried out the polar and non-polar / non-polar liquids contain. With "emulsion" are generally mixtures of immiscible Liquids are meant that are quasi-emulsified by very strong stirring. The Terms "non-polar / non-polar" as used in this invention relate to liquids and gel-like materials, their dielectric constant is less than 2.

The temperature of the various reaction media is in general Room temperature, d. H. approx. 25 ° C, if the reactions are the same even at higher or lower temperatures can be performed if desired or is appropriate. The choice of reaction temperature can also depend on the solubility the reactants and the products depend at a certain temperature.

Resulting from the oxidation of the amino-substituted or thio-substituted aromatic or heteroaromatic monomers, e.g. B. pyrrole, aniline or  Thiophene leading to electronically conductive polypyrrole, polyaniline and polythiophene leads, doping anions, which result from the oxidation reactions, e.g. B. HSO₄⁻ anions in the case that ammonium peroxodisulfate as Initiator / oxidizing agent is used, or already present in the reaction medium are (e.g. chloride ions in the case of chloride-containing reaction mixtures or the anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers) in the nano-sized particles of Polypyrrole, polyaniline or polythiophene or on the surfaces thereof nano-sized particles embedded.

At the end of the various synthesis reactions, the resulting ones nano-sized core-shell particles made of <(ferromagnetic) functionalizing Material / electronically conductive polymer <or the nano-sized particles of (ferromagnetic) functionalizing material, both partially covered with adequately anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), and / or the nanosized particles made of electronically conductive polymers, likewise partially covered with adequate polymeric ionomers, from the respective Reaction mixtures by sedimentation and decanting the supernatants Liquid phases or failures with adequate liquids and collecting in funnels severed. After the resulting powdery materials with adequate Liquids (in the funnel) can be washed with the intended ones Liquids or liquid polymers and / or copolymers or mixtures of various compatible polymers and / or copolymers or Polymer solutions are mixed. The latter is advantageously done by stirring by hand or by kneading in a laboratory mortar, but it can also more reproducible mixing processes, as used in the prior art Polymer processing are included, used to make materials with higher To obtain degrees of homogeneity. It was found that after selecting the correct polymeric ionomer no more problems occur when that manufactured processable, pure or functionalized or ferromagnetic functionalized electronically conductive polymer into the intended ordinary Polymer material is incorporated.  

The terms "adequate precipitation liquids" and "adequate washing liquids" involve the liquids used to precipitate and wash the synthesized nano-sized core-shell particles from <(ferromagnetic) functionalizing material / electronically conductive polymer <or the nano-sized particles made of (ferromagnetic) functionalizing material, both partially covered with adequately anoinically modified polymers and / or Copolymers and / or special, tailor-made polymeric ionomers (short: polymeric ionomers), and / or the nanosized particles of electronically conductive Polymers, also partially covered with adequate polymeric ionomers, are used precipitate or wash them whole, d. H. without major parts of the compatibilizing polymeric ionomers of the nano-sized particles, those in the various types of processable, pure or functionalized or Ferromagnetic functionalized electronically conductive polymer materials (in short: processable, conductive polymer materials) are available, separate / wash off. The precipitation liquids used may also be used and washing liquids the ingredients of the processable, conductive Do not destroy polymer materials by chemical or physical attacks, d. H. damage their material properties. In addition, the used Wash liquids will be able to by-products of the synthesis reactions and the used initiators / oxidizing agents from the synthesized processable, wash out conductive polymer materials.

Powder compacts made from the processable, pure or functionalized or ferromagnetically functionalized electronically conductive polymer materials have solid direct current conductivities between 0.01 and 20 Siemens per centimeter (S / cm), these values regardless of the presence of the compatibilizing amounts of anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers. The mixing of the processable, pure or functionalized or ferromagnetically functionalized electronically conductive polymer materials with ordinary polymers and / or copolymers and / or mixtures of different compatible polymers and / or copolymers generally means that the resulting materials have lower DC conductivities, ie values between 10 ^-8 and 5 S / cm, depending on the specific case and the mixing technique that was used.

The amount of nanosized particles of (ferromagnetic) functionalizing Material in the processable, functionalized or ferromagnetic Functionalized electronically conductive polymer materials (short: processable, conductive polymer materials) can range from 1 to 90 Weight percent of the total mixture. It is limited by the Need that the electronically conductive polymer must be able to three-dimensional conductive network in pure, dried materials to be able to produce and that this property also in the final composites and marketable products, which also contain common polymer materials, can be transferred. Another limitation results from the fact that the processable, conductive polymer materials compatible with ordinary Polymers and / or copolymers or mixtures of different compatible polymers and / or copolymers must be in the most preferred processable conductive polymer materials is the proportion of (ferromagnetic) functionalizing material between 5 and 60 Percent by weight.

In the most preferred preparation methods for processable, pure or functionalized or ferromagnetic functionalized electronically conductive Polymer materials (short: processable, conductive polymer materials) of In the present invention, the amino-substituted or thio-substituted ones aromatic or heteroaromatic monomers to the following Reaction mixtures added:

• 74) An organic-based emulsion that contains the anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers (short polymer ionomers) and contains a small part of water, or
• 75) a suitable aqueous solution or a suitable organic solution or a suitable organic-based or water-based suspension, which covered the embossed bare or partially with polymeric ionomers nano-sized particles of the (ferro-magnetic) functionalizing material contain.

The initiators / oxidizing agents are added to:

• 76) A suitable aqueous solution or a suitable organic solution or a suitable organic-based or water-based suspension, which covered the embossed bare or partially with polymeric ionomers nano-sized particles of the (ferro-magnetic) functionalizing material included, or
• 77) a water-based "emulsion" or solution or suspension containing the contain polymeric ionomers.

The resulting mixtures 74) 76) and 75) 7f) are at room temperature, i.e. H. approx. 25 ° C, stirred for a reasonably long period of time Polymerization reactions of the amino-substituted or thio-substituted ones terminate aromatic or heteroaromatic monomers. In addition to the The aforementioned ingredients of the mixtures 74) 76) and 75) 77) can still be used contain other (optional) ingredients that are dissolved or only suspended. The nature of such optional additives varies widely and includes all the materials that are known to those who deal with fillers know about polymer particles. The total proportion of these other materials can up to 98 percent by weight of the total mixture. Usually become for commercially interesting products additional ingredients in the range of 2-90 Weight percent (of the end product) used. At the end of the different Synthesis reactions are the resulting processable, conductive Polymer materials are separated from their synthesis mixtures and cleaned in each case with agents similar to those in the field of colloidal dispersions know, are known.

The present invention is detailed in the examples below described. However, the examples are only to be understood as illustrative and not as Limitations of the invention to be considered because of a variety of modifications and Variations will be obvious to those who are familiar with the matter.  

Example A Manufacture of anionically modified epoxy resin

30 g of a commercial epoxy resin (Rütapox 0164 type; Bakelite) was dissolved in 300 ml of chloroform. Subsequently, pre-dried nitrogen enriched with chlorosulfonic acid gas was passed through the epoxy resin solution, the solution being magnetically stirred (100 min ^-1 ). The reaction took place at room temperature, ie at about 25 ° C, the reaction time was 24 h. At the end of the chlorosulfonic acid treatment, the reaction solution was diluted with an additional 200 ml of chloroform and contacted with 100 ml of distilled water (over 2 days). The resulting chlorosulfonic acid-treated epoxy resin was used immediately after its synthesis to produce processable, ferromagnetically functionalized, electronically conductive polymer materials.

Example B

Example A was repeated, but using unsaturated Polyester (supplied by NESTE Oy, Finland).

Example C

Example A was repeated, but using commercial available silicone oil (polydimethylsiloxane, hydroxy-terminated, viscosity 20,000 cSt at 25 ° C; Aldrich Chemicals).

Example D

Example A was repeated, but using commercial Polybutadiene (M.W. = 400,000 type; Aldrich Chemicals). Indeed only 10 g of the polybutadiene were dissolved in 300 ml of chloroform because of the solubility of polybutadiene in chloroform did not allow higher polybutadiene contents.

Example E

Example A was repeated, but using commercial polypropylene glycol bis-2-aminopropyl ether (M _η = 4,000 type, Aldrich Chemicals).

Example F Manufacture of anionically modified polystyrene

10 g of commercial polystyrene (PS 158 K type; BASF) were suspended in 100 ml of concentrated sulfuric acid using a magnetic stirrer (100 min ^-1 ). The suspension was heated to 70 ° C. and the sulfonation was carried out for 3 hours. The sulfuric acid was then decanted and the polystyrene balls were dissolved in a mixture of 300 ml of toluene and 100 ml of distilled water. Finally, the pH of the prepared emulsion was increased to 7 by adding 6 N NaOH. The sulfuric acid-treated polystyrene was used immediately after its production for the synthesis of processable, ferromagnetically functionalized, electrically conductive polymer material.

Example G Manufacture of anionically modified dextran

10 g of commercially available dextran (M.W. = 77,000 type; SIGMA) were added 60 ° C dissolved in 300 ml of N, N-dimethylformamide. To the magnetically stirred 0.465 g of sulfur trioxide were added to the suspension. The sulfonation was over 24 hours. The suspension was then brought to room temperature, i.e. H. approx. 25 ° C, cooled and precipitated with an excess of acetone (51). After this the sulfonated dextran was collected in a funnel, it was finally added to 70 ° C dried for 24 h in a vacuum drying cabinet.

Example H

Manufacture of nanosized ferromagnetic particles, d. H. Particles as they functionalized in (physiologically compatible) ferromagnetic Liquids, so-called ferrofluids, are used.

0.28 mol FeCl³ * 6H₂O and 0.165 mol FECl₂ * 4H₂O were dissolved in one liter of distilled water at room temperature, ie approx. 25 ° C. While the resulting solution was magnetically stirred (500 min ^-1 ), its pH was raised to pH 10-11 by the dropwise addition of 4 N NaOH. After the production of the nano-sized, colloidal particles had been achieved, the pH of the suspension was reduced again to pH = 7, which was achieved by decanting and diluting with distilled water.

example 1

Production of nanosized ferromagnetic particles, such as those used in novel physiologically compatible ferrofluids and in most processable, ferromagnetically functionalized electronically conductive polymer materials of the present invention. 0.166 mol FeCl₃ * 6H₂O and 0.333 mol FeCl₂ * 4H₂O were dissolved in 2.5 liters of distilled water. While the resulting solution was stirred using a mechanical stirrer (520 min ^-1) , the pH of the solution was increased to between 10 and 11 by dropwise addition of 6 N NaOH at room temperature, ie at about 25 ° C. At the beginning the NaOH addition rate was 0.2 ml / min, which was maintained for one hour, after which it was gradually increased to values between 1-3 ml / min, and the total amount of NaOH solution required was added over 2.5 hours After the NaOH addition, the resulting iron oxide suspension was stirred for a further 2 hours, and finally the pH of the suspension was lowered again to a neutral value, which was done by decanting and diluting with distilled water.

It should be noted that the addition conditions, i. H. the addition speeds u. a., have a great influence on the properties of the resulting precipitation.

Example 2

Preparation of a custom polymeric ionomer that styrene-4-sulfonate and ayrylamide contains repeat units.

Step 1 Synthesis of oligomeric or short-chain polymeric styrene-4-sulfonate Molecules

25 g of styrene-4-sulfonate were dissolved in 400 ml of distilled water at room temperature, ie approx. 25 ° C. Then 3.1 g of ammonium peroxodisulfate were dissolved in 100 ml of distilled water and then poured into the styrene-4-sulfonate solution. The resulting reaction mixture was stirred vigorously (300 min ^-1 ) and its temperature increased to 60-70 ° C. The polymerization was carried out over 24 hours. Finally, the reaction product is precipitated with an excess of acetone, collected in a funnel and dried at ambient temperature for 4 weeks.

step 2 Graft copolymerization of acrylamide onto the styrene-4-sulfonate Molecules from step 1

5 g of the oligomeric or short-chain polyelectrolyte, which was synthesized in step 1, and 17.5 g of acrylamide were dissolved in 500 ml of distilled water. 4.99 g of ammonium cerium (IV) nitrate were then dissolved in 250 ml of distilled water and then poured into the magnetically stirred (300 min ^-1 ) solution of the acrylamide and the styrene-4-sulfonate molecules. Then the reaction temperature was raised to 60-70 ° C and the polymerization reaction was carried out for three hours. The graft copolymer produced (polyacrylamide chains were grafted onto the styrene-4-sulfonate molecules) was precipitated with an excess of methanol, collected in a funnel and finally dried in a vacuum drying cabinet at 70 ° C. for 24 hours.

Example 3

Preparation of a tailor-made polymeric ionomer containing styrene-4-sulfonate, acrylamide and 2-hydroxyethyl methacrylate as repeat units 10 g of the oligomeric or short chain polymeric polyelectrolyte produced in step 1 of Example 2 of this invention, 29.4 g of acrylamide and 3.2 g of 2- Hydroxy-ethyl methacrylates were dissolved in 500 ml of distilled water. 9.98 g of ammonium cerium (IV) nitrate were then dissolved in 250 ml of distilled water and poured into the magnetically stirred (300 min ^-1 ) solution of the polyelectrolyte from step 1 of Example 2 of this invention, the acrylamide and the 2-hydroxyethyl methacrylate. The resulting reaction mixture was then raised to 60-70 ° C. and the polymerization was carried out for three hours. At the end of this time, the resulting graft copolymer was precipitated with an excess of methanol, collected in a funnel and finally dried in a vacuum drying cabinet at 70 ° C. for 24 hours.

Example 4

Example 3 was repeated, but using 10 g of styrene-4-sulfonate Molecules as resulting from step 1 of Example 2 of this invention, 31.1 g Acrylamide and 11.51 ml of a 48 weight percent solution of N-hydroxymethyl acrylamide in water.

Example 5

Production of a processable, ferromagnetically functionalized, electronically conductive polymer material, with nanosized ferromagnetic particles, polypyrrole and sulfonated epoxy resin as ingredients . Sulfonated epoxy resin was made according to the methodology of Example A of the present invention. Following the production of the nanosized ferromagnetic particles, the volume of the neutralized reaction phase was reduced to 1.5 l. The remaining suspension was stirred vigorously with a mechanical stirrer (300 min ^-1 ) and 38.6 g of ammonium peroxodisulfate, dissolved in 200 ml of distilled water, were poured into this suspension. Then 10 ml of pyrrole was poured into the solution of the sulfonated epoxy resin. Subsequently, the water-based suspension containing the oxidizing agent and the organic solution containing the pyrrole were contacted, ie the latter was poured into the former, with vigorous stirring (520 min ^-1 ). After the two reaction components had been contacted, the polymerization of the pyrrole started immediately and proceeded rapidly, ie it was almost completely complete after about 15 minutes. The decrease in pH due to the pyrrole polymerization was counteracted by adding about 40 ml of 6N NaOH dropwise to the polymerization mixture. The polymerization was carried out at room temperature, ie about 25 ° C., for 6 h. At the end of the polymerization, the reaction product was allowed to settle at the bottom of the reaction vessel (2 h). The supernatant was then removed with a pipette and the remaining gel-like reaction product was precipitated with an excess of methanol. The precipitated reaction product was then collected in a funnel and washed with an additional liter of methanol. Finally, the resulting ferromagnetic functionalized polypyrrole material, which still contained a little methanol, was transferred to a glass bottle. The DC conductivity of the dried material (measured on a powder compact) was 2.5 S / cm.

Example 6

Example 5 was repeated, but using the nano size ferromagnetic particles in Example 1 of the present invention were manufactured. The DC conductivity of the dried material was determined to be 1.5 S / cm.

Example 7

Example 6 was repeated, but using the unsaturated Polyester resin made in Example B of the present invention. The DC conductivity of the dried material was determined to be 10 S / cm.

Example 8

Example 6 was repeated, but using sulfonated silicone oil, which was prepared according to Example C of the present invention.

Example 9

Example 6 was repeated, but using sulfonated Polybutadiene made according to Example D of the present invention has been. The DC conductivity of the dried material became 0.5 S / cm certainly.

Example 10

Example 6 was repeated, but using sulfonated polystyrene, as prepared in Example F of the present invention, and under Use of toluene instead of chloroform for the dissolution of the sulfonated Polystyrene. At the end of the synthesis reaction, the reaction product with Precipitated n-hexane, collected in a funnel and finally at 70 ° C in Vacuum drying cabinet dried for 2 h. The reaction product was a  Powdery, processable, ferromagnetic functionalized polypyrrole Received material. The DC conductivity of the material became 6.8 S / cm certainly.

Example 11

Example 6 was repeated, but using sulfonated Polypropylene glycol bis-2-aminopropyl ether as described in Example E of the present Invention was made. At the end of the synthesis reaction it became the Reaction product allows itself to collect at the bottom of the reaction vessel (2nd Days). Then most of the supernatant was removed with a Pipette removed. Then the reaction product became excess Methanol is precipitated and collected in a funnel. Then the collected precipitate washed with a liter of 1,3-propanediol. On it following the washed precipitate was again in 300 ml of chloroform redispersed and by azeotropic drying of water still present exempted. Finally, the reaction product was again in a funnel collected; there was a powder-like processable, ferromagnetic Functionalized polypyrrole material that still contained a little chloroform. The DC conductivity of the dried material was determined to be 5 S / cm.

Example 12

Preparation of Processable, Ferromagnetically Functionalized, Electronically Conductive Polymer Material Containing Nanosized Ferromagnetic Particles, Polythiophene, and Sulfonated Polypropylene Glycol bis-2-aminopropyl Ether Nano-sized ferromagnetic particles were made according to Example 1 of the present invention. After the ferromagnetic particles had settled on the bottom of the reaction vessel (after one day), the excess liquid, which had already been neutralized, was reduced to a volume of 400 ml. One liter of chloroform was then poured into the resulting suspension with vigorous stirring (300 min ^-1 ). Then 24.02 g of azoisobutyronitrile, dissolved in 600 ml of chloroform, were also poured into the suspension. Then 10 ml of thiophene was poured into the emulsion of sulfonated polypropylene glycol bis-2-aminopropyl ether as resulting from Example E of the present invention. The thiophene mixture was then poured into the suspension of the ferromagnetic particles with vigorous stirring (520 min ^-1 using a mechanical stirrer). As a result of contacting the two mixtures, the polymerization of the thiophene began, which was accompanied by a sharp decrease in the pH of the aqueous component of the reaction medium. This lowering of the pH was neutralized by the dropwise addition of about 40 ml of 6N NaOH. The polymerization reaction was carried out at 35 ° C for 24 hours. The resulting ferromagnetic functionalized polythiophene material was then separated from the reaction mixture using the procedure of Example 11 of the present invention. The dried material had a direct current conductivity (powder compact) of 15 S / cm.

Example 13

Example 12 was repeated, but using the sulfonated Epoxy resin as shown in Example A of the present invention, and using the workup scheme as described in Examples 5-9 of present invention was used. The DC conductivity of the dried material (powder compact) was determined to be 8 S / cm.

Example 14

Manufacture of a water-based processable, ferromagnetic functionalized electronically conductive polymer material, the nano-sized ferromagnetic particles, polypyrrole and the tailor-made polymeric ionomers as shown in Example 3 of the present invention contains.

Nano-sized ferromagnetic particles were made according to Example 1 of the present invention. After the resulting ferromagnetic material was neutralized, he was allowed to settle at the bottom of the reaction vessel (1 day), the volume of the supernatant was reduced to 1 liter. 30 g of the tailored polymeric ionomer as prepared in Example 3 of the present invention was dispersed in 1.3 liters of distilled water. In addition, 38.6 g of ammonium peroxodisulfate were dissolved in 200 ml of distilled water. Then 10 ml of pyrrole were poured into the strongly stirred suspension (300 min ^-1 with a mechanical stirrer) of the ferromagnetic particles. The peroxide solution was then poured into the dispersion of the tailor-made polymeric ionomer, with vigorous stirring using a magnetic stirrer (200 min ^-1 ). The dispersion of the tailor-made polymeric ionomer was then poured into the suspension of the ferromagnetic particles. The stirring speed for the resulting suspension was increased to 500 min ^-1 . As a result of the contacting of the dispersion containing the oxidizing agent and the suspension containing the pyrrole monomer, the polymerization of the pyrrole started immediately. The latter led to a sharp decrease in the pH of the reaction medium, which was neutralized by the dropwise addition of about 40 ml of 6N NaOH. The polymerization reaction was carried out at room temperature, ie about 25 ° C. for 24 hours. At the end of the polypyrrole synthesis, the reaction product was precipitated with an excess of methanol, collected in a funnel and washed again with an excess of methanol (2 l). The resulting processable, ferromagnetically functionalized polypyrrole material, still containing a little methanol, was redispersed in 190 ml of distilled water. The direct current conductivity of the dried material (powder compact) was determined to be 1.2 S / cm.

Example 15

Example 14 was repeated, but using the bespoke one polymeric ionomers as shown in Example 2 of the present invention. The DC conductivity of the dried material became 0.8 S / cm certainly.

Example 16

Example 14 was repeated, but using the bespoke one polymeric ionomers resulting from Example 4 of the present invention. The DC conductivity of the dried material became 4.3 S / cm certainly.

Example 17

Manufacture of a processable, ferromagnetically functionalized electronic conductive polymer material, the nano-sized ferromagnetic particles,  the with anionically modified polymer, as is apparent from Example C of present invention, are compatible, and nanosized particles of electronically conductive polyaniline, also compatible with the same anionically modified polymer.

Step 1 Production of the compatibilized ferromagnetic particles

Nano-sized ferromagnetic particles were made according to Example of the present invention. After their synthesis and neutralization of the reaction medium, the latter was reduced to a volume of 1.5 l. Then 20 g of the anionically modified silicone oil, prepared in accordance with Example C of the present invention (dissolved in 900 ml of chloroform and contacted with 100 ml of distilled water), were slowly added to the strongly mechanically stirred (520 min ^-1 ) suspension of the within 1.5 h cast nanosized ferromagnetic particles. The reaction mixture was then stirred for a further 2 h. The reaction product was then allowed to settle at the bottom of the reaction vessel, the supernatant liquid was removed with a pipette, the reaction product was precipitated, collected in the funnel and washed, using methanol (5 l) as the precipitation and washing liquid. Finally, the reaction product, which still contained a little methanol, was poured into a glass bottle.

step 2 Preparation of compatibilized electronically conductive polyaniline

10 ml of aniline was dissolved in a mixture of 1.4 l of distilled water, 900 ml of chloroform, 20 g of anionically modified silicone oil, which was prepared in accordance with Example C of this invention, and 120 g of ± camphor-10-sulfonic acid, to this mixture, which was mechanically strong was stirred (520 min ^-1 ), 25.15 g of ammonium peroxodisulfate, dissolved in 200 ml of distilled water, were poured. The polymerization of the aniline was carried out over 3 h at room temperature, ie approx. 25 ° C. The reaction product was then precipitated, collected in the funnel and washed, using methanol (51) as the precipitation and washing liquid. Finally, the reaction product (which still contained a little methanol) was added to the ferromagnetic material made in step 1. The direct current conductivity of the homogenized, dried material (powder compact) was determined to be 6.7 S / cm.

Example 18

Manufacture of a water-based processable, ferromagnetic functionalized electronically conductive polymer material that is ferromagnetic reactive particles, compatible with the tailor-made polymer Ionomer as can be seen in Example 3 of the present invention, and nano-sized electronically conductive polypyrrole particles, also with the same tailor-made polymeric ionomers.

Step 1 Production of compatibilized ferromagnetic particles

Nano-sized ferromagnetic particles were made according to Example of the present invention. After their synthesis and neutralization, the volume of the reaction medium was reduced to one liter. Then 29 g of the tailor-made polymeric ionomer, which was prepared in accordance with Example 3 of the present invention, were dispersed in 1.5 l of distilled water and then slowly poured into the suspension of the ferromagnetic particles over the course of 2 hours, the suspension being stirred mechanically vigorously (520 min ^-1 ) was. After the addition of the tailored polymeric ionomer was complete, the resulting reaction mixture was stirred for a further 22 h. The reaction product was then precipitated, collected in the funnel and washed, using methanol (51) as the precipitation and washing liquid. Finally, the reaction product (which still contained a little methanol) was redispersed in 50 ml of distilled water.

step 2 Manufacture of compatible electronically conductive polypyrrole

10 ml of pyrrole was mechanically emulsified in 1.1 l of distilled water. 38.6 g of ammonium peroxodisulfate were dissolved in 200 ml of distilled water. The peroxide solution was then poured into 1.2 liters of distilled water which additionally contained 20 g of the tailored polymeric ionomer from Example 3 of the present invention. Then the pyrrole emulsion was contacted with the oxidant solution, the latter being poured into the former. The mixing process was carried out with vigorous mechanical stirring (520 min ^-1 ). The pyrrole polymerization was carried out for 24 h at room temperature, ie about 25 ° C. The reaction product was then precipitated, collected in the funnel and washed, using methanol (51) as the precipitation and washing liquid. Finally, the resulting polypyrrole / polymeric ionomer complex was mixed with the ferromagnetic material from step 1, with an additional 50 ml of distilled water being added. The direct current conductivity of the resulting material (powder compact) was found to be 3 S / cm.

Example 19

Manufacture of processable, ferromagnetically functionalized, electronically conductive polymer material, the core-shell particle, consisting of an electronically conductive core material, which is partially covered with customized polymeric ionomers, as is evident from Example 3 of the present invention, and a ferromagnetically reactive shell -Material made according to Example 1 of the present invention contains Electronically conductive polypyrrole was made according to Step 2 of Example 18 of the present invention. At the end of the synthesis, the reaction product was allowed to settle on the bottom of the reaction vessel (2 days). The supernatant was then removed several times until a neutral pH had been established. The final volume of this dilution process was 21. 0.166 mol FeCl₃ * 6H₂O and 0.333 mol FeCl₂ * 4H₂O, dissolved in 0.5 l distilled water, were poured into the resulting dispersion. During vigorous mechanical stirring (520 min ^-1 ), the pH of this dispersion was slowly raised to a value between 9 and 10, which was done using 6 N NaOH. The addition rates of the alkaline solution were the same as described in Example 1 of this invention, except that a dropping rate of about 1 ml / min was used at the start of the addition. After the addition of the sodium hydroxide solution had ended, the dispersion was stirred for a further 2 h at room temperature, ie about 25 ° C. The reaction product was then allowed to settle at the bottom of the reaction vessel, followed by repeated replacement of the supernatant with distilled water until a neutral pH was reached. Following this, the reaction volume was concentrated to 1.3 l and 10 g of the polymeric ionomer, which was prepared in Example 3 of the present invention and was dispersed in 1 l of distilled water, in several portions within 1 h to the mechanically strongly stirred (520 min ^-1 ) Residual dispersion cast from electronically conductive polypyrrole / iron oxide hybrid particles. The dispersion was then stirred at room temperature for a further 22 h. The reaction product was then precipitated, collected in the funnel and washed, using methanol (5 l) as the precipitation and washing liquid. Finally, the filter cookie was redispersed in 100 ml of distilled water. The direct current conductivity of the dried material (powder compact) was determined to be 0.2 S / cm.

Example 20

Manufacture of marketable materials that are processable, ferromagnetic it functionalizes electronically conductive polypyrrole, compatible with sulfonated epoxy resin, commercial epoxy resin, hardener and accelerator contain.

1.5 g of the processable, ferromagnetically functionalized, electronically conductive polypyrrole material resulting from Example 5 of the present invention was mixed with 0.5 g epoxy resin (MW = 374 type; Aldrich Chemicals) and 0.5 g CAPCURE 3-800 (HENKEL) in a laboratory mortar. After the mixture had been thoroughly homogenized, 0.25 g of accelerator (DMP 30; Bakelite) was mixed in. The hardening compound was then poured into a square (10 mm edge length, 3 mm deep) casting mold and spread on glass plates. After the hardening reaction, (black) molded parts and coatings made of cross-linked epoxy resin were produced that were clearly ferromagnetic (tested with a permanent portable laboratory magnet). The direct current conductivity of the materials was found in the antistatic range between 5 * 10 ^-8 and 5 * 10 ^-6 S / cm.

Example 21

Example 20 was repeated, but using the processable ferromagnetic functionalized electronically conductive polymer material made from Example 7 of the present invention results, and using commercial unsaturated polyester, d. H. a solution of unsaturated  Polyester in styrene (60/40 weight percent), as made by NESTE Oy, Finland is sold as K330 Type. About 4 g of the workable, ferromagnetic functionalized electronically conductive polypyrrole material and 20 ml of Mixture of unsaturated polyester and styrene were in a glass bottle homogenized by hand stirring. No attempts have been made To achieve hardening of the resulting material.

Example 22

Example 20 was repeated, but using the processable ferromagnetic functionalized electronically conductive polypyrrole material that resulting from Example 8 of the present invention, and using commercial silicone oil (DOW 245; DOW CORNING). About 20 g of the processable, ferromagnetic functionalized polypyrrole / sulfonated silicone oil Materials were placed in 50 ml of the commercial silicone oil with a glass rod stirred in. The resulting material is an electronically conductive silicone oil. The intrinsic ferromagnetic and electrical characteristics of this material have not been determined, however, in a qualitative experiment, in whose electro-rheological behavior was examined, clearly showed that this composite material is electrically conductive under the conditions used was.

Example 23

Example 22 was repeated, but using the processable ferromagnetic functionalized, electronically conductive polyaniline material that is apparent from Example 17 of the present invention.

Example 24

Example 20 was repeated, but using the processable, ferromagnetic, functionalized, electronically conductive polymeric material resulting from Example 9 of the present invention and using a 60 g / l solution of commercial polybutadiene (MW = 400,000 type; Aldrich Chemicals) in chloroform. About 15 g of the processable ferromagnetic functionalized material was redispersed in 50 ml of the polybutadiene solution by hand. The resulting material could be used to produce ferromagnetic coatings on glass plates with direct current conductivities between 10 ^-4 -10 ^-3 S / cm. In addition, the coatings obtained in this way can be crosslinked by exposure to a 2-4% by volume solution of disulfide dichloid in gasoline.

Example 25

Example 20 was repeated, but using the processable ferromagnetic functionalized electronically conductive polymer material made from Example 11 of the present invention, and using a commercial polyethylene glycol (M.W. = 400 type; Aldrich Chemicals). About 20 g of the processable ferromagnetic functionalized, electronic conductive polymer material were in a laboratory mortar in 50 ml Polyethylene glycol mixed in. The resulting material can be used to manufacture electrically conductive and ferromagnetic reacting lumps of polyurethane are used when they are used with Desmodur R (Bayer), a typical Cross-linking reagent for polyurethane resins. This way and 20 g of the above mixture were mixed with 12 g Desmodur R in a laboratory mortar mixed and hardened. When measuring the electrical resistance with a portable ohm meter, the resulting polyurethane lumps showed one Resistance of 5-10 M.

Example 26

Example 25 was repeated, but using the processable ferromagnetic functionalized electronically conductive polythiophene material, resulting from Example 12 of the present invention.

Example 27

Example 20 was repeated, but using the processable ferromagnetic functionalized polypyrrole material resulting from Example 14 of the present invention and water-soluble acrylic paint (DULUX living room paint, ICI). About 2 g of the ferromagnetic functionalized polypyrrole was mixed into 20 ml of the DULUX color by hand stirring. The application of the resulting mixture on glass plates with a brush results in medium to dark gray electrically conductive and ferromagnetic reactive and (after drying) water-insoluble coatings. The DC conductivities of the coatings were found to be between 10 ^-4 -10 ^-3 S / cm.

Example 28

Example 27 was repeated, but using a different water based acrylic wall paint ("painting with" acrylic facade paint, FHG Münster). The direct current conductivity of the resulting coatings was identical to that found in Example 27.

Example 29

Example 27 was repeated, but using the processable ferromagnetic functionalized polypyrrole material derived from Example 15 of the present invention. 1.2 g of the processable ferromagnetic functionalized polypyrrole material were mixed to approx. 30 ml of the color. The DC conductivity of resulting paints was found in the range of 10 ^-6 -10 ^-5 S / cm.

Example 30

Example 27 was repeated, but using the processable ferromagnetic functionalized electronically conductive polypyrrole material derived from Example 16 of the present invention. About 1.5 g of the processable ferromagnetic functionalized polypyrrole material was added to about 25 ml of the acrylic paint. The DC conductivity of resulting paints was found at 10 ^-4 S / cm.

Example 31

Example 28 was repeated, but using the processable, ferromagnetically functionalized, electronically conductive polypyrrole material derived from Example 16 of the present invention. The DC conductivity of the resulting coatings was between 10 ^-4 and 10 ^-3 S / cm.

Example 32

Example 28 was repeated, but using the processable ferromagnetic functionalized electronically conductive polymer material made from Example 18 of the present invention emerged. The resulting materials were just as electrically conductive as those from Example 28.

Example 33

Example 32 was repeated, but using the processable ferromagnetic functionalized electronically conductive polymer material made from Example 19 of the present invention emerged. The resulting composite Materials were as conductive as those in Example 28.

Example 34

Preparation of Pure Processable Electronically Conductive Polypyrrole Material Step 2 of Example 18 of the present invention was repeated to obtain the desired processable electronically conductive polypyrrole material. However, some minor variations were made in the reaction mixture. 10 ml of pyrrole were emulsified in 0.75 l of distilled water. 38.6 g of ammonium peroxodisulfate were dissolved in 200 ml of distilled water. The peroxide solution was then poured into a dispersion of 30 g of custom polymeric ionomer made as described in Example 3 of the present invention in 1.5 liters of distilled water. Then the pyrrole emulsion was contacted with the dispersion containing the oxidizing agent, ie the latter was poured into the former. The mixing process took place with strong mechanical stirring (520 min ^-1 ). The pyrrole polymerization was carried out for 24 h at room temperature, ie about 25 ° C. The reaction product was then precipitated, collected in a funnel and washed, using methanol (5 l) as the precipitation and washing liquid. Finally, the resulting polypyrrole / polymeric ionomer complex was redispersed in 100 ml of distilled water. The direct current conductivity of the dried material (powder compact) was determined to be 5.5 S / cm.

Example 35

Example 28 was repeated, but using the processable electronically conductive polypyrrole material derived from Example 34 of the present invention. The direct current conductivity of resulting coatings on glass plates was found at 10 ^-5 S / cm.

Example 36

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention emerge, and polystyrene-4-sulfonate, sodium salt as homopolymer Stabilizer, contains.

The ferromagnetic colloidal particles were prepared according to Example 1 of the present invention using a total reaction volume of the initial iron salt solution of 500 ml. After the neutralization of the resulting iron oxide suspension, 25 g of polystyrene-4-sulfonate, sodium salt (MW = 70,000 type; Aldrich Chemicals), dissolved in 250 ml of distilled water, became strong within 2 hours at room temperature, ie about 25 ° C. stirred (520 min ^-1 ) iron oxide suspension added dropwise. After complete addition of the stabilizer, the resulting suspension was stirred for a further 2 hours. The suspension was then allowed to settle at the bottom of the reaction vessel and the supernatant was diluted several times until the colloidal stability began to be visible, ie the smallest iron oxide particles covered with polystyrene-4-sulfonate no longer failed. The iron oxide suspension was then filled into centrifuge bottles and then freed from further amounts of positive ions in 6-10 centrifugation / dilution cycles. The centrifugal speed was set so that a centrifugal acceleration of 14,000 g was effective. Finally, the centrifuge biscuit was redispersed in 20 ml of distilled water, which could be achieved by ultrasound treatment for 1 h. The resulting ferrofluid is 80% stable and physiologically compatible.

Example 37

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention  emerge, and polystyrene-4-sulfonate, sodium salt as homopolymer Stabilizer, contains.

Example 36 was repeated, but using polystyrene-4-sulfonate, Sodium salt, which has a molecular weight of M.W. = 500,000 (M.W. = 500,000 type; Polysciences Europe GmbH). The resulting iron oxide colloid is 100% stable (for at least half a year) and physiologically compatible.

Example 38

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention emerge, and contains polyacrylic acid as a homopolymeric stabilizer.

Example 36 was repeated, but using polyacrylic acid (M.W. = 450,000 type; Aldrich Chemicals). The resulting colloidal dispersion is 100 % stable and physiologically compatible.

Example 39

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention emerge, and contains polyacrylamide-co-acrylic acid as a copolymeric stabilizer.

Example 36 was repeated, but using polyacrylamide-co acrylic acid (M.W. = 200,000 type, 90 wt .-% acrylamide; Polysciences Europe GmbH). This steric stabilizer was placed in 625 ml of distilled water dissolved and added dropwise to the iron oxide suspension within 5 h. The resulting one colloidal dispersion is 100% stable and physiologically compatible.

Example 40

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention emerge, and the tailor-made polymeric ionomer, which from Example 2 of the present invention emerges contains.

Example 36 was repeated, but using the bespoke one polymeric ionomer obtained from Example 2 of the present invention as Graft copolymers steric stabilizer. The steric stabilizer was developed in 625 ml of distilled water dissolved and within 5 hours to the iron oxide suspension  dripped. The resulting centrifugal biscuit was filled into dialysis tubes and dialyzed against 20 * 1 l of distilled water, with the aim of residual toxic Acrylamide, which may still have been present in the stabilizer, wash out. The resulting colloidal dispersion is 90% stable and physiologically compatible.

Example 41

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention emerge, and polymethyl vinyl ether-co-maleic acid as a copolymeric stabilizer contains.

Example 36 was repeated, but using polymethyl vinyl ether co-maleic acid (M.W. = 67,000 type; Aldrich Chemicals) as copolymers steric stabilizer. The stabilizer was dissolved in 1 liter of distilled water was added dropwise to the iron oxide dispersion within 8 hours. The resulting Iron oxide colloid is 80% stable and physiologically compatible.

Example 42

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention emerge, and the anionically modified dextran, which from Example G der present invention emerges contains.

Example 36 was repeated, but using the anionically modified Dextrans as seen in Example G of the present invention as copolymeric steric stabilizer. The resulting centrifuge biscuit was dialyzed against 20 * 1 l of distilled water to remove residues of the toxic N, N- Dimethylformamide, which may still be present in the sulfonated dextran was to wash out. The resulting iron oxide colloid is physiologically acceptable and 80% stable.

Example 43

Production of a physiologically compatible ferrofluid that ferromagnetic particles obtained from Example 1 of the present invention  emerge, and the polymeric ionomers, as shown in Examples G and 2 of the present invention emerge contains.

Example 36 was repeated, but using a 50/50 Mixture by weight of the polymeric ionomers as obtained from Examples G and 2 of the present invention emerged as copolymeric steric stabilizers. The resulting centrifugal biscuit was against 20 * 1 l of distilled water dialyzed for residues of the toxic molecules acrylamide and N, N-dimethylformamide, which may still be in the sulfonated dextran or in the poly / oligostyrene graft acrylamide were present to wash out. The resulting iron oxide colloid is physiologically compatible and 90% stable.

Although the present invention has detailed examples it is not intended to be the details shown as To view limitations of the scope of the invention.

Claims (45)

1. Pure or functionalized or ferromagnetically functionalized, electronically conductive polymer materials, characterized in that they are in the form of dispersible solid particles, consisting essentially either of particles of electronically conductive polymer, with a conjugated π-electron system, the monomeric compounds from the class of 5- membered heterocyclic compounds containing nitrogen or sulfur as a hetero atom and / or the amino aromatic compounds or mixtures of these compounds, or a core of functionalizing material and a covering of an electronically conductive polymer, with a conjugated π-electron system, the monomers Compounds from the class of 5-membered heterocyclic compounds which contain nitrogen or sulfur as the hetero atom or of the amino aromatic compounds or mixtures of these compounds and / or a core from an e electronically conductive polymer with a conjugated π-electron system, the monomeric compounds from the class of 5-membered heterocyclic compounds containing nitrogen or sulfur as a heteroatom or the aminoaromatic compounds or mixtures of these compounds and a covering of a functionalizing material, and each anionic polymeric ionomers or that it contains dispersible solid particles, consisting of functionalizing particles and anionic polymeric ionomers and particles of electronically conductive polymers, with a conjugated π-electron system, the monomeric compounds from the class of 5-membered heterocyclic compounds containing nitrogen or sulfur contained as a hetero atom, or of the amino aromatic compounds or mixtures of these compounds, and anionic polymeric ionomers or
that they are in the form of dispersible solid particles, consisting essentially of either a ferromagnetic core and a covering of an electronically conductive polymer, with a conjugated π-electron system, the monomeric compounds from the class of 5-membered heterocyclic compounds, the nitrogen or sulfur contain as a hetero atom or the amino aromatic compounds or mixtures of these compounds, or a core of an electronically conductive polymer with a conjugated π-electron system, the monomeric compounds from the class of 5-membered heterocyclic compounds containing nitrogen or sulfur as a hetero atom or of the amino aromatic compounds or mixtures of these compounds, and a covering of a ferromagnetic functionalizing material, and in each case anionic polymeric ionomers or
that it contains dispersible solid particles, consisting of ferromagnetic particles and anionic polymeric ionomers and particles of electronically conductive polymers, with a conjugated π-electron system, the monomeric compounds from the class of 5-membered heterocyclic compounds containing nitrogen or sulfur as a hetero atom or of the amino aromatic compounds or mixtures of these compounds, and anionic polymeric ionomers. 2. Pure or functionalized or ferromagnetic functionalized electrical conductive polymer materials according to claim 1, characterized in that the particle diameter of each solid particles present between 15 and 1000 nm, preferably between 15 and 500 nm. 3. Pure or functionalized or ferromagnetic functionalized electrical conductive polymer materials according to claims 1 and 2, characterized in that the anionically modified polymers anionically modified homopolymers and / or copolymers, d. H. anionic polymeric and / or copolymeric ionomers, and / or special, tailor-made are polymeric ionomers.   4. Pure or functionalized or ferromagnetic functionalized electrical conductive polymer materials according to claims 1 and 2, characterized in that the ratio of anionic modified polymers and / or copolymers and / or the special, tailor-made polymeric ionomers to either the nano-sized hybrid < (ferromagnetic) functionalizing materials / electronically conductive Polymers <core / shell and / or shell / core particles or the nano-sized Particles of the (ferromagnetic) functionalizing materials and / or the nano-sized electronically conductive polymer particles from 1 to 99 to 99 to 1 from Weight ago. 5. Pure or functionalized or ferromagnetic functionalized electrical conductive polymer materials according to claims 1 and 2, characterized in that the nanosized particles contained therein of at least one electronically conductive polymer, some with anionic modified polymers and / or copolymers and / or special, custom polymeric ionomers can be encased by oxidative Polymerization under gentle conditions of polymerizable, amino substituted or thio-substituted aromatic or heteroaromatic Monomers are produced. 6. Pure or functionalized or ferromagnetic functionalized electrical conductive polymer materials according to claims 1 and 2, characterized in that by covering either the nano-sized hybrid <(ferromagnetic) functionalizing Materials / electronically conductive polymer <core / shell and / or Sheath / core particles or the nano-sized particles of (ferromagnetic) functionalized materials and / or the nano-sized electronically conductive Polymer particles each by the anionically modified polymers and / or Copolymers and / or the special, tailor-made polymeric ionomers Compatibility with ordinary polymers and / or copolymers or Mixtures of compatible polymers and / or copolymers or Prepolymers or monomers is guaranteed.   7. Pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials according to claims 1 and 2, characterized in that the amount contained (ferromagnetic) functionalizing material between 1 and 99, preferably is between 5 and 60 percent by weight. 8. Pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials according to claims 1 and 2, characterized in that it consists of the nano-sized particles ferromagnetic material is such particles, which are usually in ferromagnetic functionalized liquids, d. H. so-called ferrofluids, Find application. 9. Pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials according to claims 1 and 2, characterized in that it consists of the nano-sized particles ferromagnetic material around very large particles (particle diameter »20 nm) deals with a physiological tolerance and a high Magnetization / viscosity behavior. 10. Pure or functionalized or ferromagnetic functionalized, electronic conductive polymer materials according to claim 1, characterized in that the amine-modified polymers special, tailor-made water-based graft copolymers (polymers Ionomers) with several types of monomeric repeat units are on oligomeric or short-chain polymeric molecules that contain anionic groups, non-ionic water-soluble polymer chains that are grafted physically or chemically with water-soluble paints and varnishes, especially water-soluble Acrylic paints, can react.   11. Pure or functionalized or ferromagnetic functionalized, electronic conductive polymer materials according to claim 10, characterized in that the special, tailor-made water-based graft copolymers (polymeric ionomers) with several types monomeric repeating units the grafted nonionic water soluble Polymer chains a smaller part of non-water-soluble blocks than co- Contain components that have an improved physical anchor in dried water-based paints and inks, especially water-soluble Acrylic paints, and / or improved chemical reactivity with water-soluble paints and colors, especially water-soluble acrylic paints. 12. Pure or functionalized or ferromagnetic functionalized, electronic conductive polymer materials according to claims 10 and 11, characterized in that the special, tailor-made water-based graft copolymers (polymeric ionomers) with several types monomeric repeat units on oligomeric or short-chain polymers Styrene-4-sulfonate chains are grafted onto polyacrylamide chains. 13. Pure or functionalized or ferromagnetic functionalized, electronic conductive polymer materials according to claims 10 and 11, characterized in that the special, tailor-made water-based graft copolymers (polymeric ionomers) with several types monomeric repeat units on oligomeric or short-chain polymers Styrene-4-sulfonate chains polyacrylamide-co-2-hydroxyethyl methacrylate and / or Polyacrylamide-co-N-hydroxymethyl-acrylamide chains are grafted on. 14. Pure or functionalized or ferromagnetic functionalized, electronic conductive polymer materials according to claims 10-13, characterized in that the special, tailor-made water-based graft copolymers (polymeric ionomers) with several types monomeric repeating units, the oligomeric or short-chain polymers Styrene-4-sulfonate chains by oxidative polymerization of styrene-4-sulfonate with Ammonium peroxodisulfate are formed.   15. Pure or functionalized or ferromagnetic functionalized, electronic conductive polymer materials according to claims 10-13, characterized in that for the special, customized water-based graft copolymers (polymeric ionomers) with several types of monomeric repeating units ammonium cerium (IV) nitrate as an oxidizing agent for the grafting of polyacrylamide and polyacrylamide copolymers based on the oligomeric or short-chain polymeric styrene-4- sulfonate chains used. 16. Pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials according to claim 1, characterized in that the pure or functionalized obtained Polymer material has an electrical direct current conductivity (four-point method) between 0.001 and 20 Siemens per centimeter (S / cm). 17. A process for the preparation of pure or functionalized or ferromagnetically functionalized electronically conductive polymer materials, characterized in that the polymerization of the electronically conductive polymers takes place either in a homogeneous reaction medium in which dissolved or swollen anionic polymeric ionomers are present and the (optionally) suspended functionalizing or contains ferromagnetic functionalizing nano-sized particles or is carried out in an "emulsion-like" reaction medium from at least two immiscible liquids, in which the anionic polymeric ionomers are each dissolved and / or swollen in at least one liquid and the (optionally) suspended, functionalizing or ferromagnetic functionalizing contains nanosized particles or that

• 1) nano-sized particles of a (ferromagnetic) functionalizing material are produced, which are covered with anionic polymeric ionomers, the preparation either in a homogeneous reaction medium, that prefabricated, bare nano-sized particles of the (ferromagnetic) functionalizing material and anionic polymeric ionomers (dissolved or swollen) ) contains, is carried out or takes place in an "emulsion-like" reaction medium, consisting of immiscible liquids in which the bare prefabricated nanosized particles of the (ferromagnetic) functionalizing material are suspended and the anionic polymeric ionomers, dissolved and / or swollen in one or contain several of the immiscible liquids, or the nano-sized particles are produced from (ferro-magnetic) functionalizing material in suitable grinding machines,
• 2) nano-sized particles of electronically conductive polymers are produced, some of which are covered with anionic polymers, the polymerization taking place under mild conditions and the reaction medium is either a homogeneous phase which contains anionic polymeric ionomers, dissolved and / or swollen, or a " emulsion-like "mixture of two immiscible liquids, the" emulsion-like "reaction medium containing anionic polymeric ionomers dissolved and / or swollen in some liquids or the production of nanosized particles of electronically conductive polymers in suitable grinding machines,
• 3) by carefully mixing the nanosized particles of (ferromagnetic) functionalizing material [1)] and the nanosized particles of the electronically conductive polymers, [2)] or that
• 1) nano-sized particles of electronically conductive polymers are produced, which can be partially covered with anionic polymeric ionomers, under mild polymerization conditions, the reaction medium being either a homogeneous phase, with polymeric ionomers, dissolved and / or swollen or an "emulsion-like" mixture of two immiscible liquids with anionic polymeric ionomers dissolved and / or swollen in some liquids or the production of nanosized particles of electronically conductive polymers takes place in suitable grinding machines.
• 2) the production of nano-sized particles from (ferromagnetic) functionalizing materials in parts of the reaction mixtures and, optionally, the addition of anionic polymeric ionomers into the resulting mixture of [2)].

18. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the reaction medium oxidizing agent for amino-substituted and / or thio-substituted aromatic and / or contains heteroaromatic monomers. 19. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the oxidizable polymerizable Monomeric amino-substituted and / or thio-substituted aromatic and / or heteroaromatic compounds, preferably pyrrole, aniline and thiophene or their substituted compounds are. 20. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the oxidative polymerization in one acidic, neutral or basic reaction medium. 21. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17 and 19, characterized in that the substituting groups in particular alkyl, aryl, aralkyl, hydroxy, methoxy, chloro, bromo or Are nitro groups. 22. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the anionically modified polymers and / or copolymers by adding fuming sulfuric acid, Sulfur trioxide, chlorosulfonic acid or gas streams, the sulfur trioxide or Contain chlorosulfonic acid, are produced.   23. Process for the production of pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials Claims 1, 10-15 and 17, characterized in that for Manufacture of special, tailor-made water-based graft copolymers (polymeric ionomer) with several types of monomeric repeating units that Synthesis the graft copolymerization of non-ionic, water-soluble Monomers on prepolymerized blocks of (anionic groups) containing includes water-soluble short-chain polymers or oligomers and with suitable oxidizing agents in predominantly aqueous reaction media takes place. 24. Process for the production of pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials Claims 1, 10-15 and 17, characterized in that for Manufacture of special, tailor-made water-based graft copolymers (polymeric ionomer) with several types of monomeric repeating units, the preparation of the special, tailor-made polymeric ionomers in one first stage of prepolymerization of anionic and / or non-ionic water-soluble and / or non-water-soluble polymerizable monomers in predominantly aqueous phases with suitable initiators and the second stage of Graft polymerization of non-ionic, water-soluble and / or non- water-soluble monomers on the oligomers formed or short-chain Polymers from stage 1 in a predominantly aqueous phase with suitable initiators he follows. 25. Process for the production of pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials Claim 1, 10-15, 17 and 23, characterized in that for Manufacture of special, tailor-made water-based graft copolymers (polymeric ionomer) with several types of monomeric repeat units in the first stage the reaction medium is water and the molar styrene-4- sulfonate / ammonium peroxodisulfate ratio between 0.000 1 and 1, preferred between 0.05 and 0.5.   26. Process for the production of pure or functionalized or ferromagnetic functionalized electronically conductive polymer materials Claim 1, 10-15, 17 and 23, characterized in that for Manufacture of special, tailor-made water-based graft copolymers (polymeric ionomer) with several types of monomeric repeating units in the second step the reaction medium is water and the molar styrene-4- sulfonate / ammonium cerium (IV) nitrate ratio between 1: 1 and 100: 1, preferred 3: 1. 27. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that polymerization mediators and / or Additives are added. 28. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the polymerization of pyrrole under Use of ammonium peroxodisulfate, preferably with a molar Monomer / oxidizing agent ratio of 1: 1.17 (8). 29. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the polymerization of thiophene under Use of azoisobutyronitrile, preferably with a molar Monomer / oxidizing agent ratio of 1: 1.17 (8). 30. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the polymerization of aniline under Use of ammonium peroxodisulfate, preferably with a molar Monomer / oxidizing agent ratio of 1: 1.   31. Process for the production of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 17, characterized in that the concentration of Initiators / oxidizing agents in the reaction medium 0.001 to 1 molar, preferred is between 0.03 and 0.1 molar. 32. Use of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer materials according to claim 1-7 and 17-21, characterized in that the polymer systems with non-conductive polymers and / or copolymers and / or mixtures compatible polymers and / or copolymers and / or prepolymers and / or monomers from which a matrix polymer is produced are mixed will. 33. Pure or functionalized or ferromagnetically functionalized electroconductive polymer systems according to claims 1-7, 17-21 and 32, characterized in that the compounds obtained from non-conductive polymer and pure or (ferromagnetically) functionalized electrically conductive polymer material have a direct current conductivity of 10 ^-8 to 5 S / cm. 34. Use of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer systems according to claim 1-7, 17- 21 and 32, characterized in that the non-conductive Polymers and / or copolymers and / or mixtures of compatible polymers and / or copolymers and / or prepolymers and / or monomers which a matrix polymer is produced, preferably water-based paints, especially acrylic paints, epoxy resins, unsaturated polyesters, rubber, silicone oils and are polyurethane resins. 35. Use of pure or functionalized or ferromagnetic Functionalized electronically conductive polymer systems according to claims 32-34, characterized in that processing aids and / or additives are added.   36. Use of pure or functionalized or ferromagnetically functionalized electronically conductive polymer systems according to claims 1-7, 17-21, 32 and 34, characterized in that molded articles or paints in particular

• - as protection against antistatic charges,
• - for shielding against electromagnetic waves (EMI shielding) and / or
• - For tasks in which the properties of the polymer compounds equipped with pure or (ferromagnetic) functionalized electronically conductive polymer materials can be advantageously used.

37. Ferromagnetically functionalized liquids, so-called ferrofluids, characterized in that they consist essentially of very large ferromagnetic particles (particle diameter »20 nm) and polyelectrolytes and / or anionically modified polymers and / or copolymers and / or special, tailor-made polymeric ionomers exist and physiologically are compatible and have a high magnetization / viscosity behavior of have physiologically compatible ferrofluids. 38. Process for the production of physiologically compatible ferromagnetic Functionalized liquids, characterized in that the nano-sized ferromagnetic particles in liquid reaction media, preferred Water, with ferromagnetic compounds and / or elements, especially iron (III) chloride and iron (II) chloride and (optional) adequate Precipitation, reduction or formation reagents are preferred Ammonia solution, KOH or NaOH are formed and then with Stabilization polymers are contacted and the rate of precipitation is chosen so that the entire, for the formation of nano-sized ferromagnetic particles necessary, amount of precipitation reagent within of at least two hours is added slowly and the addition rate on The beginning of the addition is significantly less than the end.   39. Process for the production of physiologically compatible ferromagnetic functionalized liquids according to claim 38, characterized in that the concentration of iron salts is lower 0.2 molar, preferably 0.1 molar, and the molar iron (III) chloride too Iron (II) chloride ratio is 1/1000: 999/1000, preferably 0.033: 0.066. 40. Process for the production of physiologically compatible ferromagnetic functionalized liquids according to claim 38, characterized in that concentrated ammonia solution is used and the KOH or NaOH is preferably a normality of 6 having. 41. Process for the production of physiologically compatible ferromagnetic functionalized liquids according to claim 38, characterized in that the initial addition rate is 0.2 Is milliliters per minute (ml / min) and the final addition rate is 1 to 3 ml / min and the increase in the addition rate from the initial value to the final value begins after, 1 hour and the total amount of precipitation reagent is in two Hours added. 42. Process for the production of physiologically compatible ferromagnetic functionalized liquids according to claims 38 and 41, characterized in that after the addition of the total amount Precipitation reagent the suspension of nanosized ferromagnetic reacting Particles is moved for at least another 2 hours. 43. Process for the production of physiologically compatible ferromagnetic functionalized liquids according to claim 38, 41 and 42, characterized in that the total amount of necessary Precipitation reagent is given in that the final pH of the resulting iron oxide suspension between 9 and 11, preferably between 9 and 10.   44. Process for the production of physiologically compatible ferromagnetic functionalized liquids according to claim 38, characterized in that the stabilizing polymers polystyrene-4- sulfonates, polyacrylic acid, polyvinyl methyl ether-co-maleic acid, poly (oligo) styrene 4-sulfonate graft polyacrylamide, polyacrylic acid-co-acrylamide, or sulfonated Is dextran. 45. Use of physiologically compatible ferromagnetic functionalized Liquids according to claim 1, 11, 17, 37-44, characterized in that the application in human or animal body.