DE10052646A1 - Production of functional polymers, e.g. for modification of products such as dyes and polymer additives, involves living polymerisation or post-polymerisation modification using species with specific functional properties - Google Patents

Abstract

Functional polymers or oligomers are produced as such (or as layer systems on solid surfaces) by living/controlled radical polymerisation of functional polymerizable species with other comonomers and/or by post-polymerisation modification of polymers with functional species obtained by living polymerisation.. A method for the production of functional polymers or oligomers by living/controlled radical polymerisation involves the following alternative stages or combinations of these: (a) living/controlled radical polymerisation of polymerizable species with certain specific functional properties which also appear in the resulting products which may be homopolymers, statistical copolymers, gradient copolymers, block copolymer or graft copolymers with conventional (co)monomers or macromonomers as used to make polymer materials or with (co)monomers or macromonomers which give the products additional specific functional properties and (b) modification of the polymer (without changing the degree of polymerisation) by attaching chemical species with specific functional properties at reactive centers in the polymer chain or at the chain ends, using oligomers or polymers (of the types as listed in a) obtained by living/controlled radical polymerisation (i.e. post-polymerisation modification), and also a similar method for the production of layers or layer systems of functional polymers or oligomers which are attached to any solid surface by main valency bonds using stages (c) and/or (d) corresponding to stages (a) and/or (b) above. Functional polymers in this context comprise polymers having chemical species with a specific functional property in the main chain, at the chain ends or as lateral groups. Specific functional properties are shown by chemically homo- or hetero-geneous species (functional materials), inorganic/organic hybrids and micro- or nano-particles which are used, e.g. as dyes, optical brighteners, pigments, piezoelectric materials, electrical conductors, semiconductors or insulators, antistatics, permeation modifiers, additives for improving material properties (hardness, wear resistance etc.), soil-repellent materials, radiopaque materials, light stabilisers, fire retardants, pharmaceutical vehicles etc. (50 applications listed). Independent claims are also included for (i) solid surfaces with layers of functional oligomer or polymer, obtained by the above method; (ii) materials produced by using functional oligomers or polymers (or layers/layer systems thereof), obtained by this method; (iii) polymer materials as described in (ii) above.

Description

The invention relates to a process for the production of functional polymers or oligomers on the one hand, and functional polymer or oligomer layers or layer systems on the other hand, which are bound to any solid surface via chemical main bond, using a "living" / controlled radical polymerization, as characterized by that either

• a) in the "living" / controlled radical polymerization such poly merizable chemical species as monomers or as macromonomers be used that be certain specific functional properties sit and these properties also the oligomer made from it or polymer, the resulting oligomers or polymers as well as those in oligomer or polymer layers or layer systems as Homopolymers or as statistical copolymers or as gradient copo polymers or as block copolymers or as graft copolymers that can, with conventional co- / monomers or macromonomers or mixtures of co- / monomers and macromonomers or from Mi additions of macromonomers that the oligomer or polymer coexists with additional specific functional properties, or
• b) which is produced via a "living" / controlled radical polymerization ten oligomers or polymers or oligomer or polymer layers subsequently modified in a polymer-analogous manner to obtain the polymer degree of chemical bonding of chemical species with speci fish functional properties, via reactive centers in the polymer chains or at the end of the polymer chains ("post-polymerization modification tion ").

In this document, polymers are referred to as functional polymers, which in the Polymer chain, at the end of the polymer chain, or as a side group / s chemical  Bear species that have a specific functional property and bind this property to the oligomer or polymer.

Specific functional properties are chemically homogeneous or heterogeneous rogene species ("functional substances"), also hybrids from inorganic and orga African components or even micro and nanoparticles, which act as color substances, fluorescent dyes, optical brighteners, photographic sensitizers gates, interference dyes, chromophores with nonlinear optical properties dyes with light-collecting properties, photochromic fabrics, Liquid crystals, substances used in the optical production of surface reliefs allow (active) pigments, chemiluminescent substances, electroluminescent fabrics, piezoelectric fabrics, ferroelectric fabrics, electrically conductive Fabrics, electrically semiconducting fabrics, electrically insulating fabrics, antistatic Substances, permeation-inhibiting substances, permeation-promoting substances, substances for Improvement of media resistance, slip-active substances, substances for control the material hardness, fabrics to improve the abrasion resistance, fabrics for ver Improvement of the slip resistance, fabrics for compatibility with the other environment (e.g. hydrophobization, hydrophilization, biocompatibility bilization, dispersibility, phase binding), substances with dirt repellency the effect, metal-binding substances, magnetic substances, light stabilizers, Anti-corrosion agents, anti-aging agents, radio-opaque substances, substances for Improvement of temperature resistance or heat resistance, Flame retardants, bactericides, antiseptics, antothrombogenic substances, fungicides de, pharmaceutical active ingredient carriers, pharmaceutical agent binders (e.g. for diagnostics), algicides, antifouling substances, etc. are known and use find.

If the method of the present invention functional polymers or ol gomere relates to the main chemical valences on solid surfaces are connected, the solid can be made of any material exist, be of massive or porous nature, in finely divided form are present, also nano-dimensioned, of natural or synthetic origin be or a heterogeneous surface structure or surfaces together have settlement. The physi Kalisch-mechanical properties of the solid used, such as. B.  Hardness, ductility, deformability, surface roughness, magnetism. Einzi The prerequisite is that the solid used on its surface already has chemical properties, or that chemical Let properties be created that connect chemical compounds permitted via principal valence bonds; is under the term "main valence bond "to understand the entire spectrum of chemical bonds, the covalent, ionic and metallic bond through the three borderline cases how the transition between the three borderline cases is given. Solids that already the suitable chemical nature for the connection of chemical There are connections on their surface, for example about hydroxyl groups. On the other hand, it is known that surfaces also non-polar substances, such as As poly (propene) or poly (tetrafluoroethene), without wide res with reactive groups, e.g. B. hydroxyl groups, z. B. on the way of plasma treatment.

The term solid "surface" refers to this context not only on surfaces in common usage, but in general the interface between a solid and a gas or a liquid is understood. This also includes the inner surface of a porous one Material. In addition, using surface-modified Ma materials, the term surface refers generally to any Phase interfaces. So it can z. B. also about inner surface between two different components within one Trade composite material. Examples of this type are composite materials a polymer matrix and an inorganic enhancer, with dyes filled polymers or a polymer-metal composite, generally Ver composite materials made of a polymer matrix and a functional additive.

Another object of the invention are described in the present Oligomers manufactured using processes and equipped with functional substances Polymers and materials in which such functional oligomers or polymers re included.  

In the prior art, the desired physico-chemical property is inherent profile of a plastic material through physical mixing and / or the chemical dissolution of additives with specific functional Properties generated in the matrix polymer.

The scientific and patent literature describes in recent years increasingly examples in which copolymers with chemically incorporated functions ons tasks: A material property is accordingly not generated by an additive that disperses or dissolves in the matrix polymer , but the matrix polymer is produced as a copolymer by the Polymerization a comonomer is used, which the polymer with a specific functional property. It is common practice Lich the procedure of the classic, d. H. by radical formers in thermal or radical polymerisation carried out by radiation-chemical excitation on.

The classic radical polymerization allows, with appropriate reak activity of the comonomers used for the polymerization, the preparation of statistical copolymers with controllable content of the to be installed Comonomer.

According to the classic radical polymerisation mechanism, Ver many functional monomers with different physi properties have been homo- or copolymerized.

So z. B. H. Bartels et al. a photosensitizer homo- and copolyme rized [H. Bartels, M. L. Hallensleben, T. S. Wibowo, H. Wurm, "Photosensitive Polymer. I. Uni- and Copolymerization Behavior of 1,3-Bis (4-benzoyl-3- hydroxyphenoxy) -2-propyl methacrylate ", Polym. Bull. 21, 145 (1989)] and ge shows that when using classic radical initiation copolymers with different levels of photosensitizer with statistical distribution can be obtained along the polymer chain.

A. Costela et al. [A. Costela, I. Garcia-Moreno, J.M. Figuera, F. Amat-Guerri, R. Mallavia, M.D. Santa-Maria, R. Sastre, "Solid-state lasers based on modes fied Rhodamine 6G dyes copolymerized with methacrylic monomers ", J. Appl.  

Phys. 80, 3167 (1996)] have the dye rhodamine 6G with radical po polymerizable C-C double bonds and together with esters of Methacrylic acid as a comonomer, statistical copolymers prepared therefrom, which contain the function of the dye and are used for solid-state lasers can find.

In a U.S. patent, K.M. Sharma et al. [K. M. Sharma, L.I. Watson, "Stable waterborne polymeric colorant compositions having a dye co valently bonded in a polymer backbone and their preparation ", U.S. Pat. 5637637 A (1997)] the preparation and properties of a in water provided polymer with chemically covalently bound dye. Leave copolymers of N, N-dimethylacrylamide and 4-phenylazophenylacrylate reverts about the cis-trans isomerization of the azobenzene group by light switch sibel in their water solubility [R. Kröger, H. Menzel, M. L. Hallensle ben, "Light controlled solubility change of polymers: copolymers of N, N- dimethylacrylamide and 4-phenylazophenyl acrylate ", Macromol. Chem. Phys. 195, 2291 (1994)].

Azo dyes for use in nonlinear optics have been called Methacry late by M. Kato et al. in homopolymers and copolymers over classic radicals Polymerization built in [M. Kato, K. Kanda, T. Kimura, H. Matsuda, H. Naka nishi, "Synthesis of polymers bearing azo dye chromophore with photocrosslin cable moiety for nonlinear optics ", Polym. Bull. 36, 407 (1996)].

Two-dimensionally arranged pigment monolayers with an aliphatic ket built-in porphyrin dyes for use as light-collecting Structures made using the Langmuir-Blodgett technique are e.g. B. by B. W. Gregory et al. have been described [B. W. Gregory, D. Vaknin, J.D. Gray, B.M. Ocko, P. Stroeve, T. M. Cotton, W. S. Struve, "Two-dimensional pigment mo nolayer assemblies for light-harvesting applications: structural characterization at the air / water interface with X-ray specular reflectivity and on solid substrates by optical absorption spectroscopy ", J. Phys. Chem. B 101, 2006 (1997)].

Transparent photochromic polymer layers with a radi Kalische polymerization built-in dyes D. Henry et al. stove. Henry, J.J. Vial, "Novel transparent photochromic organic materials", PCT Appl. WO 97/03373 A1 (1997)]. These materials are said to be used in sun protection Find contact lenses and in glasses.  

As electroluminescent molecules such. B. grafted fluoropolymers with in containing electroluminescent comonomers described [T. Nishikawa, M. Ono, "Manufacture of grafting fluoropolymer composition high dielectrics and organic disperse electroluminescent devices ", JP Pat. Appl. 94- 28037 15 (1994)].

Many liquid crystalline polymers are used for a wide range of applications by copolymerizing appropriately liquid-crystalline monomers which the liquid crystal-forming residue as an ester grouping in acrylic acid or Contain methacrylic acid esters, made in copolymers [e.g. B. H. J. Haijema, G. O. R. Alberda von Ekenstein, Y. Y. Tan, "The liquid-crystalline monomer N- (p-methacryloyloxybenzylidene) -p-aminobenzoic acid: its synthesis, characte rization and polymerization ", Eur. Polym. J. 28, 1191 (1992)].

Are difficult or impossible to access using the classic radi Kalische polymerization sequenced copolymers, or block copolymers re with two, three or even more blocks or gradient copolyme re. This difficulty is due to the short-lived nature of classic radicals in vinyl polymerization, which does not allow the active growing chain nend to get during the polymerization process or even the active Chain end back after the workup and isolation of the polymer To have available.

This problem is due to the processes of "living" / controlled radicals polymerisation have been solved, in particular by the ATRP (atom transfer radical polymerization) mechanism, as described by K. Matyjaszewski et al. was introduced [K. Matyjaszewski, S. Coca, S. Gaynor, Y. Nakagawa, S. M. Jo, "Preparation of Novel Homo- and Copolymers Using Atom Transfer Ra dical Polymerization ", WO 98/01480 (Int. Publ. January 15, 1998)].

In addition, the publication by D. M. Haddleton et al. [D. M. Haddleton, M.C. Crossman, K.H. Hunt, C. Topping, C. Waterson, K.G. Suddaby, "Iden tifying the Nature of the Active Species in the Polymerization of Methacrylates: Inhibition of Methyl Methacrylate Homopolymerizations and Reactivity Ratios for Copolymerization of Methyl Methacrylate / n-Butyl Methacrylate in Classical Anionic, Alkyllithium / Trialkylaluminum-Initiated, Group Transfer Polymerization,  Atom Transfer Radical Polymerization, Catalytic Chain Transfer, and Classical Free Radical Polymerization ", Macromolecules 30, 3992, (1997)] proves that the relative reactivity of Comono when using the ATRP mechanism mer is almost the same as when using a classic bottom Free radicalization mechanism so that those known from the literature Copolymerization parameters (also called r parameters) are practically unchanged also apply to the ATRP mechanism. This gives the ATRP Mechanism according to K. Matyjaszewski et al. of great practical importance in the production of statistical copolymers. The ATRP mechanism however, it also allows block copolymers and, when using Macromonomers, graft copolymers with a targeted sequence after a radical to produce chemical polymerization mechanism.

For example, H. Böttcher et al. shown that in a heterophasic process Poly (styrene) grafted onto silica by the ATRP mechanism, itself after working up and storing the reaction product in air for a long time, the chain ends of the graft branches almost completely reactivated can be used to block a second generation of poly (styrene) on them to grow up [H. Böttcher, M. L. Hallensleben, S. Nuß, H. Wurm, "ATRP grafting from silica surface to create first and second generation of grafts ", Polym. Bull. 44, 223 (2000)].

A larger number of works is known in which a mono-, bi- or Hö her functional, polymeric ATRP initiator for the production of block copo lymeren is used.

Jankova et al. [K. Jankova, J.H. Trueselsen, X. Chen, J. Kops, W. Batsberg, "Controlled /" living "atom transfer radical polymerization of styrene in the synthesis sis of amphiphilic diblock copolymers from a poly (ethylene glycol) macroinitia tor ", Polym. Bull. 42, 153 (1999)] used a water-soluble Po ly (ethylene glycol monomethyl ether), the free OH group of which is Chloropropionyl chloride to a monofunctional polymeric ATRP initiator converted to initiate styrene to form a two-block copolymer ren.

K. Jankova et al. [K. Jankova, J. Kops, X. Chen, B. Gao, W. Batsberg, "Synthesis of poly (styrene-b-isobutylene-b-styrene)  triblock copolymer by ATRP ", Polym. Bull. 41, 639 (1998)] by using a central block made of isobutylene bifunctionally as a polymeric ATRP initiator and then used to initiate styrene.

K. Matyjaszewski et al. [M. H. Acar, K. Matyjaszewski, "Block copolymers by transformation of living anionic polymerization into controlled / "living" atom transfer radical polymerization ", Macromol. Chem. Phys. 200, 1094 (1999)] converted a monofunctional carbon ionic "living" poly (styrene) with 2- Bromisobutyryl bromide in the corresponding polymeric ATRP initiator and thus initiated block formation by polymerizing methacrylate, n- Butyl acrylate, methyl methacrylate and from acrylonitrile to two-block copolymers.

The synthesis of block copolymers always has the goal of two or more Polymer chains with different chemical and / or physical egg to link properties to a single macromolecule. So you can by means of ATRP, for example, to obtain a two-block copolymer which was a little different water soluble (hydrophilic) and a water insoluble (hydrophobic) part li near chemically linked contains [X. Zhang, K. Matyjaszewski, "Synthesis of hydrophilic-hydrophobic AB and ABA block copolymers by atom transfer radical polymerization ", ACS Polym. Div., Polym. Prepr. 39, 560 (1998)].

The direct copolymerization of two comonomers under ATRP Conditions for block copolymers are known. This is how K. Matyjaszewski reports et al. on a simple synthesis of block copolymers as a one-pot reaction using ATRP [K. Matyjaszewski, D.A. Shipp, G.P. McMurty, S. G. Gaynor, T. Pakula, "Simple and Effective One-Pot Synthesis of (Meth) Acrylic Block Copolymers Through Atom Transfer Radical Polymerization ", J. Polym. Sci., Part A, Polym. Chem. 38, 2023 (2000)].

But also simply end-functionalized polymers are available via the ATRP Mechanism accessible. Because of the "living" character of these radicals polymerisation, the growing end groups remain during the Growth process always chemically identical and survive an up working and isolation of the polymer chains, p. in addition the publication by H. Bottcher et al. [H. Böttcher, M. L. Hallensleben, S. Nuß, H. Wurm, "ATRP graf ting from silica surface to create first and second generation of grafts ", polym.  Bull. 44, 223 (2000)]. A final functionalization according to the ATRP mechanism mus is also possible by, before working up the polymer, still during the polymerization after consumption of the polymerized Monomers, another functional end group (D. M. Haddleton, C. Waterton, P.J. Derrick, C.B. Jasieczek, A.J. Shooter, "Monohydroxy terminally functionalized poly (methyl methacrylate) from atom transfer radical polymeriza tion ", Chem. Commun. 1997, 683].

The diversity of the molecular weights and molecular ares possible with ATRP Architectures in block copolymers are expressed in the writing by K. Matyjaszewski et al. [K. A. Davis, B. Charleux, K. Matyjaszewski, "Preparation of Block Copolymers of Polystyrene and Poly (t-butyl acrylate) of Various Mo lecular Weights and Architectures by Atom Transfer Radical Polymerization ", J. Polym. Sci., Part A, Polym. Chem. 38, 2274 (2000)], in which about linear and star-shaped block copolymers are reported.

Until recently, the compound was only available for soluble or liquid phase reaction described the "living" / controlled radical Polymerization according to the ATRP mechanism (homogeneous reaction) was carried out by H. Böttcher et al. transferred to a heterogeneous process [H. Böttcher, M. L. Hallensleben, H. Wurm, "Process for the chemical modification of feast fabric surfaces by "living" / controlled radical reactions ", DE 198 38 241 A1 (Offen. 24/02/2000); H. Böttcher, M. L. Hallensleben, H. Wurm, "Process for the production of defined layers or layer systems", WO 00/11043 (Int. Publ. 02. 03. 2000); H. Böttcher, M. L. Hallensleben, S. Nuß, H. Wurm, "ATRP grafting from silica surface to create first and second genera tion of grafts ", Polym. Bull. 44, 223 (2000)]. In this process ATRP- Initiators chemically bound to surfaces of any solid and there assuming a "living" / controlled radical polymerization defined layers or layer systems made of polymers or oligomers with controlled structure, the layers over chemical Hauptva bound to the solid surface. H. Böttcher et al. have in the cited literature DE 198 38 241 A1 and WO 00/11043 stated that on the one hand the polymerizations with radically polymerizable monomers  or macromonomers or with monomer or macromonomer mixtures or carried out with mixtures of monomers and macromonomers can and that on the other hand in steps that follow a polymerization gene, the polymer layers can be modified polymer-analog. I.e. on functional groups of the oligomer or Polymer chains can undergo chemical transformations with suitable reactants be carried out while maintaining the degree of polymerization. The functional groups can be given by each individual monomer unit or but by the "living" end group. With the appropriate reactants, it can they are low or high molecular weight, also heterogeneous.

Furthermore, it is stated that the solid polymer Layer systems through cross-linking reactions in three-dimensional polymer materials trizes can be chemically integrated.

As another important aspect, the authors point out that solids particles from which the "living" / controlled radical polymerization is triggered during the polymerization and also after the polymerization individual solid particles remain.

The selection of works for the production of statistical reproduced here Copolymers or end-functionalized polymers or gradient copolymers or block copolymers or graft copolymers or polymer analog modifi graced polymers demonstrates the state of knowledge and technology of the Possibilities for the targeted production of oligomers or polymers and solid-bound layers of oligomers or polymers with ge desired and defined structure using the "living" / control gated radical polymerization, especially the ATRP mechanism according to the teaching of K. Matyjaszewski et al. in publication WO 98/01480.

The methods of the prior art have the following disadvantages: Is a material property generated by a functional material as "Additive" in the broadest sense is merely dispersed in the matrix polymer the distribution of the functional substance in the matrix polymer is often a difficult task gift, e.g. B. due to hydrophilic / hydrophobic interactions or higher Surface energy of mixture components. Functional fabrics can be  At best, only distribute evenly in a mixture approach, not specifically position. Dispersed substances are not firmly anchored in the matrix polymer, may have an adverse effect on mechanical material properties, dif base u. U. from the material, especially at elevated temperatures and Swelling of the material and can be removed from it with suitable solvents Lich and extractable. This not only worsens that caused by the Functional material-related material property, but the environment of the Material is also by u. U. contaminated toxic functional substances. This Aspect deserves Be with toxic additives (including dyes) attention, because a finite concentration of the Substance is present. Functional substances soluble in the matrix polymer can be distribute better homogeneously, but otherwise the above applies to them. Disadvantage.

Become Copo according to the classic radical polymerization mechanism polymers with chemically built-in functional tasks by the Polymerization a comonomer is used, which the polymer with a specific functional property, this way, with the corresponding reactivity of the Comono which comes to the polymerization meren, statistical copolymers with a controllable content of that accessible to the comonomer, in which a "post-polymerization Modification "is possible, so as to species with specific functional properties anchored to the polymer by means of a chemical bond. About the Process of classical radical polymerisation accessible polymers always have a wide chain length distribution and the chains lengths can only be controlled insufficiently. Difficult or not at all Sequenced copolymers or block copolymers with two, three or more blocks or gradient copolymers or single polymers functionalized at the chain end. Neither does it exist for a material composition significant possibility on solid surfaces to produce bonded polymer layers via main chemical valences, without simultaneously and to a greater extent also unbound polymer produce.

A disadvantage of classic radika that severely limits its applicability Polymerization is also their sensitivity to functional groups  in functional substances (e.g. the azobenzene group), which the polymer on disturb or even inhibit.

Compared to classic radical polymerization, the "living" / controlled radical polymerization, especially after the ATRP Mechanism not related to the former weaknesses on. Using the method of "living" / controlled radicals polymerisation functional polymers or layers of functional polymers ren on solid surfaces in which species with specific functional properties that differ significantly in their chemistry from standard Distinguish monomers that are chemically bound by major valences So far not described in the literature and therefore not state of knowledge and technology.

The technical problem to be solved is a manufacturing process on the one hand functional polymers or oligomers and on the other hand radio tion polymer or oligomer layers or layer systems to any t on solid surfaces via main chemical bond are to be made available, which at the same time opens up the possibility of Architecture of the polymers and the polymer layers, especially with regard to them Lich the incorporation of species with specific functional properties in a homopolymer or in copolymers with random, block-like or block well-branched structure or gradient structure largely as desired to design or such functionality only as an end group in one Install homo- or copolymer.

Specific functional properties are chemically homogeneous or heterogeneous rogene species, also hybrids from inorganic and organic compo or micro and nanoparticles that are used as dyes, fluorescent zenzfarben, optical brighteners, photographic sensitizers, Interfe reference dyes, chromophores with non-linear optical properties, color substances with light-collecting properties, photochromic substances, liquid crystals, Substances that allow the optical production of surface reliefs, (active) pigments, chemiluminescent substances, electroluminescent substances, piezo electrical substances, ferroelectric substances, electrically conductive substances, electrical semiconducting substances, electrically insulating substances, antistatic substances, permeation-inhibiting substances  Substances, permeation-promoting substances, substances for improvement media resistance, slip-active substances, substances for controlling the material hardness, fabrics to improve abrasion resistance, fabrics to improve the slip resistance, materials for compatibility with the surrounding environment (e.g. hydrophobization, hydrophilization, biocompatibility, the spillability, phase binding), substances with a dirt-repellent effect, metal-binding substances, magnetic substances, light stabilizers, corrosion protective agents, anti-aging agents, radio-opaque substances, substances for improvement tion of temperature resistance or heat resistance, flame protective agents, bactericides, antiseptics, antothrombogenic substances, fungicides, pharmaceutical active substance carriers, pharmaceutical agent binders (e.g. for Diagnostics), algicides, antifouling substances, etc. are known and use Find.

This technical problem is solved according to the invention by a process for producing functional polymers or oligomers on the one hand and functional polymer or oligomer layers or layer systems on the other hand, which are bonded to any solid surface via chemical main valence bonds, using a "living" / controlled radi cal Polymerization and alternatively the procedure is as follows:

• a) Co- / polymers, co- / oligomers or co- / polymer or co- / oligomer layers produced via a “living” / controlled radical polymerization, in particular according to the ATRP mechanism, are polymer-analogously modified while maintaining the degree of polymerization by chemical Connection of chemical species with specific functional properties, via reactive centers in the polymer chains or at the end of the polymer chains ("post-polymerization modification").
  The species with specific functional properties can also be mixtures of different species. In addition, the polymer-analogous reaction can be carried out in steps, each after a polymerization step, in which different monomers or comonomers or macromonomers can also be used.
• b) In the "living" / controlled radical polymerization, in particular according to the ATRP mechanism, those polymerizable chemical species are used which have certain specific functional properties and also impart these properties to the oligomer or polymer produced therefrom. These oligomers or polymers can be prepared as homopolymers or as random copolymers or as gradient copolymers or as block copolymers or as graft copolymers, with conventional co- / monomers or macromonomers from which polymer materials are produced, or with such polymerizable species as co- / monomers or macromonomers that provide the oligomer or polymer with additional specific functional properties.
  The "living" / controlled radical polymerization can also be carried out in steps to produce a second or further polymer chain segment with a different chemical composition and thus a different specific chemical or physical property implemented therein.

The advantage of the method according to the invention is that after a polymer / material based on an extremely broadly applicable basic principle architecture, also a very complex one, with functional materials integrated into it - also several at the same time with different functions - can be built specifically. Functional fabrics can be selectively used in the chain segments of the Oli incorporate gomers or polymers, e.g. B. near the ends of polymer Concentrate Pfröpflingen: On the one hand, the material properties remain the unmodified polymer or the surrounding polymer layers unbe stirs, on the other hand it comes to the efficient effect of the functional substances u. U. on the fact that they are in the surface layer of the material (e.g. for dyes, flame retardants, carriers, etc.).

With (possibly valuable) functional fabrics can be used very sparingly, because the substances in the layer structure can be specifically bound.

With the process of "living" / controlled radical polymerization starting from solid surfaces, one can use chemical main valence bonds bound, adjustable in density and thickness laying the solid surface with functional materials, if necessary can be protected by another polymer layer.  

Are they equipped with functional substances according to the described procedure oligomers or polymers via chemical main bond to solid bound to the body, so the oligomers or polymers with the inte Free functional fabrics largely independent of the surrounding media um (exception: ionic bond) permanently attached to the solid. Functional substances bound in polymers do not diffuse out of the material and cannot be washed out of the material. This doesn't just stay the quality of the process described using functional substances prepared materials, but the environment of the materials also not contaminated by leaking functional substances. So stay with for example, possibly toxic properties of functional substances on the carrier tied to material.

The only requirement for the usability of chemical species with specific functional properties ("functional substances") in the invent The method according to the invention is the availability of suitable reactive Zen occur at these species in order to incorporate them into the functional polymers and To be able to make functional oligomers. These reactive centers can already exist in functional materials known from the literature or in Modification of these functional substances through chemical derivatization / function nalization are introduced.

A large number of functional groups can be considered as suitable reactive centers. The following functional groups are mentioned as examples:

Functional substances that easily ver in the "post-polymerization modification" turn, have, for example, hydroxyl groups. on the other hand it is known that surfaces are also non-polar solids, such as. B. Po ly (propene) or poly (tetrafluoroethene), easily with reactive group pen, e.g. B. hydroxyl groups, z. B. on the way of plasma treatment.

In the "post-polymerization modification" the links with the Polymer generated by substitution, addition or condensation reactions become.

If the functional substances in the process according to the invention as co- / Monomers or macromonomers, i.e. polymerizable species, are used these functional substances - if necessary via the aforementioned, Possibly also subsequently created reactive centers - in a chemical deriva tization with polymerizable C-C double bonds. Such polymerizable C-C double bonds are preferred as styryl Rest or introduced as an acrylic or methacrylic residue, since such groups are suitable for carrying out the ATRP.

Also functional fabrics with functional groups, which the classic radical disrupt or inhibit chemical polymerization (e.g. azobenzene groups) polymerized according to the ATRP mechanism.  

Solid particles, from which the "living" / controlled radical Po Lymerisation is triggered remain during the polymerization and also after individual solid particles during the polymerization.

The functional polymers and solid-state polymer layer systems produced can be networked afterwards.

The applicability of the method according to the invention extends to all Areas in which physico-chemical property profiles of Po polymer materials by physical mixing and / or chemical Dissolving additives with specific functional properties in the measure trixpolymer were generated and especially in those areas in which already have copolymers with other chemical methods built functional tasks were produced. In addition, the Ver drive new areas of application in the field of polymer materials as well as more complex Polymer composite materials, since functional polymers or oligomers as well any solid, chemically bound functional polymer or oligo merschichten or layer systems can be produced, which with specifi functional properties and a combination of both Properties can be equipped.

Specific functional properties are chemically homogeneous or heterogeneous rogene species, also hybrids from inorganic and organic compo or micro and nanoparticles that are used as dyes, fluorescent zenzfarben, optical brighteners, photographic sensitizers, Interfe reference dyes, chromophores with non-linear optical properties, color substances with light-collecting properties, photochromic substances, liquid crystals, Substances that allow the optical production of surface reliefs, (active) pigments, chemiluminescent substances, electroluminescent substances, piezo electrical substances, ferroelectric substances, electrically conductive substances, electrical semiconducting substances, electrically insulating substances, antistatic substances, permeati onsinhibiting substances, permeation-promoting substances, substances for improvement media resistance, slip-active substances, substances for controlling the material hardness, fabrics to improve abrasion resistance, fabrics to improve the slip resistance, materials for compatibility with the surrounding environment (for example hydrophobization, hydrophilization, biocompatibility, dispersibility,  Phase connection), substances with dirt-repellent effect, metal-binding substances, magnetic substances, light stabilizers, corrosion protective agents, anti-aging agents, radio-opaque substances, substances for improvement tion of temperature resistance or heat resistance, flame protective agents, bactericides, antiseptics, antothrombogenic substances, fungicides, pharmaceutical active substance carriers, pharmaceutical agent binders (e.g. for Diagnostics), algicides, antifouling substances, etc. are known and use Find.

Radio produced by the method according to the invention are used tion polymers and layers of functional polymers u. a. in areas of application, in which it is important that functional substances are largely independent are inseparably connected to the solid from the surrounding medium or in Functional materials bound to polymers do not diffuse out of the material and are not washable out of the material or functional substances specifically in the polymer and material architecture are to be built in or with (possibly valuable) functional materials should be used sparingly.

Examples

1st example

Synthesis of compound 1

Tetrahydrofuran (THF) is dried by refluxing it over sodium wire and refluxing it. It is distilled off directly before use. Triethylamine is dried over CaH ₂ and fractionally distilled. 2-bromo-2-methylpropionic acid bromide is fractionally distilled in vacuo. Petroleum ether is fractionally distilled, using the fraction with the boiling range between 40 ° C and 65 ° C. Diethyl ether and ethyl acetate are distilled. 11-bromundecan-1-ol is used without further purification.

5 g (19.9 mmol) 11-bromundecan-1-ol are dissolved in 100 mL dry THF. 2.80 mL (20.1 mmol) of triethylamine are added to the solution and the solution solution cooled to 0 ° C in an ice bath. A solution is then added dropwise 2.70 mL (21.8 mmol) 2-bromo-2-methylpropionic acid bromide in 25 mL dry given a THF. When the addition is complete, the mixture is stirred at 0 ° C. for 2 h, then warmed to room temperature and excluded for a further 6 h stirred by moisture.

The mixture is filtered and the solvent is removed in vacuo. The residue is taken up in diethyl ether and the organic phase with 0.5 N HCl, sat. Washed NaHCO ₃ and water. The organic phase is dried over Na ₂ SO ₄ and the solvent is removed in vacuo. After purification by column chromatography on SiO ₂ using petroleum ether / ethyl acetate (10/1 v / v) as the eluent, compound 1 is obtained.
Yield: 5.81 g of compound 1
Investigations: ¹ H-NMR

Fig. 1, ¹ H-NMR spectrum of the compound 1

Admission requirement: Solution of compound 1 in CDCl ₃ with TMS as internal standard.

2nd example

Synthesis of initiator 2

Diethyl ether is distilled. A solution of trimethylamine in abs. ethanol (4.2 M) is used without further pretreatment. The pretreatment of others Chemicals and solvents are in the above. Example 1 described.

1.2 g (3 mmol) of compound 1 in 5 ml of dry THF are placed in a round-bottomed flask. 10 mL (42 mmol) of a solution of trimethyl amine in abs. Ethanol (4.2 M) added. The reaction mixture is stirred at room temperature in the absence of light and moisture.

For working up, volatile constituents are removed in vacuo. The white solid is suspended in 20 mL diethyl ether, the suspension centrifuged and the supernatant solution decanted. This process is repeated twice. The initiator 2 is dried in vacuo at room temperature.
Yield: 1.17 g of compound 2
Investigations: ¹ H-NMR

Fig. 2 shows the ¹ H-NMR spectrum of Compound 2

Condition for admission: Solution of compound 2 in CDCl ₃ with TMS as internal standard.

3rd example Initiator 2 bound to montmorillonite

P ₂ O ₅ and Na ⁺ montmorillonite (Süd-Chemie AG) are used without further purification.

With vigorous stirring, 0.5 g Na ⁺ montmorillonite in 250 mL dist. Water suspended. After 30 min, a solution of 230 mg (0.5 mmol) of initiator 2 in 25 mL dist. Water added. The reaction mixture is stirred at room temperature for 4 h and left to stand for a further 12 h without stirring. The product is filtered off, with 0.5 L dist. Washed water and dried in vacuo over P ₂ O ₅ .
Yield: 0.64 g of montmorillonite coated with initiator 2 corresponds to 0.75 mmol of initiator 2 per g of montmorillonite
Investigation: FT-IR, TGA

Fig. 3 shows the FT-IR spectrum of montmorillonite with initiator 2 attached to the surface.

Recording technology: transmission spectrum of a KBr compact

FIG. 4 shows the diagram of the thermogravimetric analysis of the montmorillo nit with the initiator 2 attached to the surface.

analysis conditions

Heating in a nitrogen atmosphere from 30 ° C to 550 ° C, then in an air atmosphere from 550 ° C to 750 ° C, heating rate = 20 ° C / min. because at the weight loss of the sample is detected.  

4th example Polymerization of methyl methacrylate at 60 ° C with initiator 2 attached to montmo rillanit

Methyl methacrylate is dried over CaH ₂ , distilled under reduced pressure, flushed with argon and stored at -20 ° C. Acetone is dried over P ₂ O ₅ , distilled at normal pressure, flushed with argon and stored at 0 ° C. CuBr is used with conc. Washed acetic acid, water and ethanol. Methanol is distilled. 1,1,7,9,10,10-hexamethylenetriethylene tetramine (HMTETA) is used without further purification.

100 mg of montmorillonite with attached initiator 2 are placed in a Schlenk flask, then degassed three times in vacuo and aerated with nitrogen. 0.5 mL abs. Acetone added and the reaction vessel sealed with a septum. The suspension is stirred for 30 minutes at room temperature. 3 mL (28 mmol) methyl methacrylate, 1.5 mL abs. Acetone, 9.6 mg (0.067 mmol) CuBr and 18 µL (0.067 mmol) HMTETA added, then degassed three times in vacuo and each vented with nitrogen. This homogeneous solution is taken up in a nitrogen-flushed syringe and through the septum to the suspension of Montmoril lonite with attached initiator 2 in abs. Given acetone. The reaction mixture is quickly heated in an oil bath preheated to 60 ° C. and held at this temperature for 4 h.

After this time, the poly (methyl methacrylate) grafted montmorillonite is precipitated in methanol. The product is filtered off and dried in vacuo at 40 ° C.
Yield: 1.6 g of poly (methyl methacrylate) grafted montmorillonite
Investigation: FT-IR, TGA

Fig. 5 shows the FT-IR spectrum of the poly (methyl methacrylate) grafted mont morillonite

Recording technology: transmission spectrum of a KBr compact

Figure 6 shows the thermogravimetric analysis diagram of the poly (methyl methacrylate) grafted montmorillonite

analysis conditions

Heating in a nitrogen atmosphere from 30 ° C to 550 ° C, then in an air atmosphere from 550 ° C to 750 ° C, heating rate = 20 ° C / min. because at the weight loss of the sample is detected.

5th example

Synthesis of compound 3

6- (4- (4-Ethylphenylazo) phenoxy) hexanol is prepared according to known literature [Weichart, B .; Dissertation, University of Hanover (1994); H. Menzel, B. Weichart, M. L. Hallensieben, "Langmuir-Blodgett-films of photochromic polyglutamates. II. Synthesis and spreading behavior of photochromic polyglutamates with alkyl spacers and -tails of different length ", Polym. Bull. 27, 637 (1992)]. Methacryloyl chloride is used without further purification. The pretreatment of others Chemicals and solvents are mentioned in the above. Examples 1 and 2 described.

2 g (6.1 mmol) of 6- (4- (4-ethylphenylazo) phenoxy) hexanol are dissolved in 50 ml of dry THF, 0.94 ml (12.2 mmol) of triethylamine are added and the mixture is cooled to 0 ° C. in an ice bath , Then 1.2 mL (12.4 mmol) methacryloyl chloride in 20 mL dry THF are added dropwise. It is stirred for 2 h at 0 ° C and 12 h at room temperature in the absence of light and moisture. The mixture is filtered and the solvent is removed in vacuo. The residue is taken up in diethyl ether and the organic phase with 0.5 N HCl, sat. NaHCO ₃ , sat. Washed NaCl and water. The organic phase is dried over Na ₂ SO ₄ and the solvent is removed in vacuo. After purification by column chromatography on SiO ₂ using petroleum ether / diethyl ether (5/1 v / v) as the eluent, the compound 3 is obtained.
Yield: 2.04 g of compound 3
Investigations: ¹ H-NMR

Fig. 7 shows the ¹ H-NMR spectrum of Compound 3

Admission requirement: Solution of compound 3 in CDCl ₃ with TMS as internal standard.

6th example Copolymerization of compound 3 with methyl methacrylate in solution at 60 ° C

Toluene is dried by refluxing over sodium wire Boiling is heated. It is distilled off directly before use. THF is distilled. Ethyl 2-bromo-2-methylpropionate is used without further purification det. The pretreatment of other chemicals and solvents is described above. Example 4 described.

1 mL (9.3 mmol) of methyl methacrylate, 370 mg (0.94 mmol) of compound 3 , 1 mL of dry toluene, 13.5 mg (94 µmol) of CuBr and 25 µL (92 µmol) of HMTETA are placed in a Schlenk flask, then degassed three times in vacuo and vented with nitrogen. The reaction vessel is closed with a septum. 14 µL (95 µmol) of ethyl 2-bromo-2-methylpropionate are added to the polymerization solution through the septum using a syringe. The reaction mixture was rapidly heated in an oil bath preheated to 60 ° C. and held at this temperature for 12 h.

After 12 h the copolymer is filtered through a small column filled with aluminum oxide (neutral). Dest serves as eluent. THF. After concentrating the solution in vacuo, the copolymer is distilled. Petroleum ether failed. The copolymer is purified by repeated precipitation from THF in petroleum ether. The product is dried in vacuo at 60 ° C.
Yield: 1.12 g of poly (methyl methacrylate-stat- 3 )
Investigation: GPC, ¹ H-NMR

Fig. 8 shows the GPC chromatogram of the poly (methyl methacrylate-stat- 3 ) s.

Chromatography conditions: eluent: THF, detection: UV and RI, calibration: Poly (styrene) standards

From UV: M _W = 11468, M _n = 8357, U = 0.37; from RI: M _W = 11191, M _n = 8579, U = 0.30.

Fig. 9 shows the ¹ H-NMR spectrum of the poly (methyl methacrylate-stat- 3 ) s.

Admission requirement: Solution of compound 3 in CDCl ₃ with TMS as internal standard.

Claims (17)

1. Process for the production of functional polymers or oligomers using a "living" / controlled radical polymerization by the following alternative steps or their combination:

• a) Carrying out a "living" / controlled radical polymerization, characterized in that those polymerizable chemical species are used which have certain specific functional properties and also impart these properties to the oligomer or polymer produced therefrom, the resulting oligomers or polymers can be prepared as homopolymers or as statistical copolymers or as gradient copolymers or as block copolymers or as graft copolymers, with conventional co- / monomers or macromonomers from which polymer materials are produced, or with such polymerizable species as co- / monomers or macromonomers which provide the oligomer or polymer with additional specific functional properties.
• b) carrying out a polymer-analogous modification while maintaining the degree of polymerization, characterized by the connection of chemical species with specific functional properties, via reactive centers in the polymer chains or at the end of the polymer chains, starting from oligomers or polymers which are used as homopolymers or as statistical Copolymers or as gradient copolymers or as block copolymers or as graft copolymers via a "living" / controlled radical polymerization were produced ("post-polymerization modification").

and a - based on the same principles - process for the production of layers or layer systems from functional polymers or oligomers, which are bonded to any solid surface via chemical main valence bonds, using a "living" / controlled radical polymerization, by the following alternative steps or their combination:

• a) Carrying out a "living" / controlled radical polymerisation on the basis of suitable initiators which are bound to any solid surface by chemical main valence bonds, characterized in that those polymerizable chemical species are used which have certain functional properties and these properties as well impart to the oligomer or polymer produced therefrom or the oligomer or polymer layers or layer systems, the resulting oligomers or polymers being able to be prepared as homopolymers or as statistical copolymers or as gradient copolymers or as block copolymers or as graft copolymers, with conventional copolymers / monomers or macromonomers from which polymer materials are produced, or with those polymerizable species as co- / monomers or macromonomers which provide the oligomer or polymer with additional specific functional properties n.
• b) carrying out a polymer-analogous modification while maintaining the degree of polymerization, characterized by the connection of chemical species with specific functional properties, via reactive centers in the polymer chains or at the end of the polymer chains, starting from oligomers or polymers in oligomer or polymer layers or -Layer systems which were produced as homopolymers or as statistical copolymers or as gradient copolymers or as block copolymers or as graft copolymers via a "living" / controlled radical polymerization and are bonded to any solid surface via chemical main bond ("post-polymerization modification."").

In this context, functional polymers are referred to as polymers which carry chemical species in the polymer chain, at the end of the polymer chain, or as side groups, which have a specific functional property and bind this property to the oligomer or polymer.
Specific functional properties have chemically homogeneous or heterogeneous species (“functional substances”), including hybrids composed of inorganic and organic components or also microparticles and nanoparticles, which are used as dyes, fluorescent dyes, optical brighteners, photographic sensitizers, interference dyes, chromophores with non-linear optical properties , Dyes with light-collecting properties, photo chrome substances, liquid crystals, substances that allow the optical production of surface reliefs, (active) pigments, chemiluminescent substances, electroluminescent substances, piezoelectric substances, ferroelectric substances, electrically conductive substances, electrically semiconducting substances, electrically insulating substances, antistatic substances, permeation-inhibiting substances, permeation-promoting substances, substances to improve media resistance, slip-active substances, substances to control material hardness, substances to improve abrasion resistance, Fabrics to improve slip resistance, fabrics to make them compatible with the surrounding environment (e.g. hydrophobization, hydrophilization, biocompatibility, dispersibility, phase binding), fabrics with a dirt-repellent effect, metal-binding materials, magnetic fabrics, light stabilizers, corrosion inhibitors, anti-aging agents, radio-opaque fabrics, fabrics to improve the temperature resistance or heat resistance, flame retardants, bactericides, antiseptics, antothrombogenic substances, fungicides, pharmaceutical agent carriers, pharmaceutical agent binders (z. B. for Diagno stika), algicides, antifouling substances, etc. are known and use the fin. 2. The method according to claim 1, characterized in that after the step a) step a) and / or step b) is carried out several times under Use of "living" / controlled radical polymerization. The repetition of step a) and / or step b) Issued polymer or oligomer chain segments are from the from the first step a) produced "living" polymer or oligomer chains initiated. The repetition of step a) and / or step b)  can with other monomer or macromonomer species or a Mi be made of monomers and macromonomers that Repetition of step a) with other polymerizable functions onsstoffe as co- / monomers. 3. The method according to claim 1, characterized in that after the step b) step a) and / or step b) is carried out several times under Use of "living" / controlled radical polymerization. The repetition of step a) and / or step b) Issued polymer or oligomer chain segments are from the from the first step b) produced "living" polymer or oligomer chains initiated. The repetition of step a) and / or step b) can with other monomer or macromonomer species or a Mi be made of monomers and macromonomers that Repetition of step a) with other polymerizable functions onsstoffe as co- / monomers. 4. The method according to claim 1, characterized in that after the step c) step c) and / or step d) is carried out several times under Use of "living" / controlled radical polymerization. The repetition of step c) and / or step d) Issued polymer or oligomer chain segments are from the from the first step c) produced "living" polymer or oligomer chains initiated. The repetition of step c) and / or step d) can with other monomer or macromonomer species or a Mi be made of monomers and macromonomers that Repetition of step a) with other polymerizable functions onsstoffe as co- / monomers. 5. The method according to claim 1, characterized in that after the step d) step c) and / or step d) is carried out several times under Use of "living" / controlled radical polymerization. The repetition of step c) and / or step d) Issued polymer or oligomer chain segments are from the from the  first step d) produced "living" polymer or oligomer chains initiated. The repetition of step c) and / or step d) can with other monomer or macromonomer species or a Mi be made of monomers and macromonomers that Repetition of step a) with other polymerizable functions onsstoffe as co- / monomers. 6. The method according to claims 1 to 5, characterized in that the "living" / controlled radical polymerization preferred after the ATRP mechanism is performed. 7. The method according to claim 1, characterized in that in the poly mer-analogous modification of the oligomers or polymers or oligomer or polymer layers or layer systems, the chemical linkage of the chemical species with specific functional properties is preferably carried out via a reactive group from the following list:
The link between the functional species and the oligo mer or polymer can be carried out by condensation, substitution or addition reactions. 8. The method according to claims 1 to 7, characterized in that the Functional oligomers or polymers produced are chemically crosslinked. 9. The method according to claims 1 to 7, characterized in that the manufactured functional oligomer or polymer layers or layer systems me be chemically cross-linked. 10. The method according to claims 1 to 7 and 9, characterized in that the solid is of natural or synthetic origin. 11. The method according to claims 1 to 7, 9 and 10, characterized in net that the solid can consist of any material. 12. The method according to claims 1 to 7 and 9 to 11, characterized records that the solid in massive, porous or finely divided form is present. 13. The method according to claims 1 to 7 and 9 to 12, characterized records that the surface structure of the solid be heterogeneous can.   14. The method according to claims 1 to 7 and 9 to 13, characterized records that the surface composition of the solid hetero can be. 15. Solid surface with functional oligomer or polymer layers or -layer systems, produced by the method according to the claims 1 to 7 and 9 to 14. 16. Materials made using functional oligomers or polymers or layers or layer systems of functional oligomers or polymers, produced by the method according to the claims 1 to 15. 17. Polymer materials made using functional oligomers or polymers or layers or layer systems of functional olives gomers or polymers, prepared by the method according to An sayings 1 to 16.