EP2475718A1

EP2475718A1 - Polymer materials comprising coupled components

Info

Publication number: EP2475718A1
Application number: EP10798248A
Authority: EP
Inventors: Felix Winkelmann
Original assignee: Individual
Current assignee: Individual
Priority date: 2009-09-09
Filing date: 2010-09-09
Publication date: 2012-07-18
Also published as: US20120238651A1; WO2011029433A1; US9458326B2

Abstract

Disclosed are intermediate products (semifinished products) for polymer materials, comprising surface-modified components, said polymer materials based on the intermediate products, a method for producing the intermediate products, and the use thereof.

Description

Polymeric materials with coupled components

The invention relates to intermediates (semi-finished products) for polymeric materials with surface-modified mineral components, the polymeric materials based on the intermediates, a process for their preparation of intermediates and their use in plastics technology, it is a common practice

Property profiles of the per se known polymers by admixture (compounding) of additives, such as fillers and additives to improve.

Important common fillers include chalk, sand, kieselguhr, glass fibers and spheres, zinc oxide, wood flour, wood fibers, cellulose fibers, textile fibers, starch, graphite, carbon black and talcum, mica (muscovite, phlogopite, sericite) aluminosilicates, clays (e.g. B. montmorillonite) carbon fibers, glass flakes, aluminum hydroxide (ATH), magnesium hydroxide (MDH), metal oxides such as Alumina, titanium dioxide, calcium carbonates (GCC, PCC, marble), gypsum, wollastonite, basalt fibers, rock wool fibers, quartz powder, fused silica, microsilica or feldspars. This is just an example list of possible components. From EP 1 340 788 A2, for example, the production of a compound based on a thermoplastic is known, for example. As described in this document, thermoplastics, e.g.

Polyvinyl chloride, with a crosslinking agent, a stabilizer, chalk as a filler and an alkylbenzophenone as radical initiator to a

processable compound processed. After shaping, here extrusion, the polymer is crosslinked by irradiation with UV light. The fillers are only physically stored in the thermoplastic and have a filling function.

The object of the present invention is the use of mineral

Components, as building blocks of synthetic plastics (compounds)

CONFIRMATION COPY Increase, for example, the mechanical stability, the tensile strength, the impact resistance, the scratch resistance or the modulus of elasticity.

There have been new intermediates for polymeric materials with mineral components, a radical starter and possibly others

Admixtures found, characterized in that the radical starter covers the surface of the surface-modified silicate component and the polymer chains on the surface of the modified silicate

Component are bound.

Compared to known polymer compounds in the new compounds based on the intermediates of the invention, the mineral components are chemically crosslinked with the polymer and not incorporated as a filler only physically. In contrast to other crosslinked thermoplastics, the networking is primarily with the mineral

Surface before, while the rest of the thermoplastic portion in the

Substantially remains uncrosslinked and thus a thermoplastic processing is accessible.

According to the present invention, the new compounds have increased chemical and mechanical stability such. As the strength or

Tear resistance or impact strength or Young's modulus compared to compounds with embedded mineral components or with

Bonding agents surface-modified mineral fillers on.

With the intermediates of the invention opens up a new class of polymeric composites (polymer compounds).

These mineral components are characterized by having surface hydroxyl groups that undergo a silanization reaction

are accessible.

Mineral components for the polymeric materials in the context of the present invention are silicate-containing materials or materials having silicate structures or metal oxides or oxide-containing structures comprising materials or metal hydroxides or hydroxidische structures having materials.

Mineral components in the context of the present invention may be, for example: silicates: natural and synthetic silicates, fumed and precipitated silicas, so-called island silicates, chain silicates, strip silicates, wetting silicates, layered silicates or aluminosilicates, quarternary quartz (quartz) minerals , Fused silica, cristobalite), zeolites, feldspars, calcium silicate phase minerals or calcium silicate hydrate phase minerals (eg.

Tobermorite or xonotlite) or metal oxides: natural or synthetic

Metal oxides such as alumina, silica, magnesia, calcia, titania, iron oxides, zinc oxide.

In particular, in the context of the present invention, the mineral component consists of silicate and / or aluminosilicate and / or silicon oxide and / or aluminum oxide materials or titanium dioxides

Examples which may be mentioned are the following siliceous materials: mica, talc, wollastonite, asbestos, quartz, fused silica, silicic acid, microsilica, kaolin, calcined kaolins, xonotlite, tobermorite, nepheline syenite,

Alumina, Titanium Dioxide In the context of the present invention, the mineral component may be present in granular form. In a preferred embodiment of

Present invention, the mineral component is present in finely divided form.

It is preferred here that the mineral component is present in a particle size of less than 4 mm

In particular, it is preferred here that the silicate component is present in a particle size of 5 nm to 250 μm.

The intermediates according to the invention are largely covered on the surface of the mineral component in a monomolecular layer, or at least in submonolayers. The radical generator is thereby attached to the organofunctional group remote from the surface. Subsequently, on the

Particle surface applied to the polymer, so that a quasi-multi-shell structure is built. Of course, a multilayer covering (multilayer) is also possible.

In the event that it is desired in the context of the invention that the mineral component is not completely linked to the polymer, it goes without saying that the covering can only be partially present (submonolayers). For the intermediates according to the invention, it is particularly preferred if as far as possible a reaction of bifunctional silanes with the free hydroxyl groups of the mineral component has taken place and as complete as possible coverage of the silane surface modified mineral component with the radical generator present.

Of course, the silane component can also be mixed with the

Radical formers present on the surface of the mineral component. Layered on the thermoplastic phase.

Free-radical generators in the context of the present invention are known per se

Free-radical generators in the context of the present invention can be:

Photoinitiators, photosensitizers or crosslinkers. They may also be functional silanes or siloxanes having functional groups which decompose into radicals upon energetic action and / or

Initiate crosslinking reaction

Preferred free-radical generators in the context of the present invention may be: photoinitiators: benzoin ethers, benzil, benzil ketals, alpha-splitters such as alpha, alpha-diethoxyacetophenone, alpha-hydroxyalkylphenones, alpha-aminoalkylphenones, aromatic ketone coinitiator systems: benzophenones and substituted benzophenones, Mischlers ketone, photosensitizers:

aromatic haloketones: phenacyl chloride, desyl chloride or 4- Chloromethylbenzophenone Crosslinking Agent: trimethylolpropane trimethacrylate, (TRIM) or triallyl cyanurate (TAC), triallyl isocyanurate (TAIC).

In the context of the present invention, polymers are attached to the surface of the mineral component modified with adhesion promoters and then crosslinked with it.

Polymers in the context of the present invention are unsaturated,

unbranched or branched, grafted or ungrafted thermoplastics and thermoplastic elastomers. They may be provided by addition reactions or by grafting with reactive groups. For example, the following polymers may be mentioned: polyethylene,

Polypropylene or blends of polyethylene and polypropylene (e.g., grafted and ungrafted), polyamide, polyurethane

Polyvinyl chloride, polycarbonate, PMMA, polyaryletherketones (e.g., PEEK), polyoxymethylene, polystyrenes, polyimides, thermoplastic elastomers and natural polymers. Of course, this is just a selection in principle

usable thermoplastics.

In the context of the present invention, it is possible that the

intermediates according to the invention further known per se

Contain admixtures. Examples of admixtures (additives) include: flame retardants such as aluminum trihydroxide (ATH) or magnesium hydroxides (MDH),

Stabilizers such as metal soaps or organotin compounds. Plasticizers such as substituted phthalates (e.g., dibutyl phthalate), lubricants such as paraffins or UV stabilizers, or fillers such as e.g. Marble flour or silicates. Bonding agents in the context of the present invention act as

Joining points between mineral surface and the polymer.

Adhesion agents are known per se. Examples of suitable silanes, such as H-silanes and siloxanes, such as bifunctional silanes or partially condensed silanes or called functional siloxanes, it can also be used other organo-metal alcoholates.

For example, the following adhesion promoters may be mentioned: organosilanes (for example AMEO®) or siloxanes Organo-Titanate, Organozirconate,

Maleic anhydride grafted polyethylene or other MSA, Ca stearates, fatty acids.

In particular, preferred adhesion promoters are: aminosilanes or

Amino functional silanes, vinyl silanes, acryl silanes,

Methacrylsilane, Octylsiiane or Epoxisilane. A process has also been found for the preparation of intermediates for polymeric materials with surface-modified mineral components, characterized in that the radical initiator is distributed over the surface-modified mineral component, the polymer is added and the crosslinking is started by energetic action

The radical starter can be mixed in a solid, finely divided, liquid state or in solution with the mineral component and distributed on the surface.

In general, it is preferred to evenly distribute the radical initiator on the mineral component.

For the process according to the invention, it is preferred to dissolve the radical initiator in a solvent and to disperse it on the mineral component.

Examples of suitable solvents for dissolving the radical initiators are: alcohols, organohalogenated solvents, silanes. Preferred solvents are, for example:

Methanol, methylene chloride, ethanol, isopropanol, acetone, organosilanes such as aminosilanes or Octylsiiane or other bi- or multi-functional silanes. Of course it is also possible mixtures of solvents

to use

A preferred embodiment of the method according to the invention is characterized in that the mineral component and the

Radical starter in a mass ratio less than 5%, preferably used in a ratio of less than 2%, based on the mass of the mineral component.

In a preferred embodiment of the method according to the invention, the mineral component is present in finely divided form. It is preferred here that the mineral component is present in a particle size of less than 4 mm.

In particular, it is preferred that the mineral component is present in a particle size of 5 nm to 250 μιτι.

In a preferred embodiment of the present invention, the thermoplastic is used in solution. , For the process according to the invention, it is preferable to dissolve the thermoplastic in a solvent and to bond it with adhesion promoters

surface-modified mineral component occupied by the radical starter.

Examples of suitable solvents for the solution of thermoplastics are: dichloromethane, butanone, tetrahydrofuran, chloroform, benzene. m-cresol, toluene, trichlorethylene, cyclohexanone, methyl ethyl ketone, acetone,

Dimethylformamide, ethyl acetate, methanol, ethanol or cyclohexane. The choice of solvent depends on the polymer to be dissolved.

Preferred solvents are, for example, polyamide: toluene, m-cresol, cyclohexanone, methyl ethyl ketone

In particular, toluene and m-cresol are preferred as the solvent for polyamide.

Of course, it is also possible to use mixtures of solvents. The concentration of the thermoplastic in the solvent is generally in the range of 1 to 80% by weight, preferably in the range of 10 to 60% by weight. The solution must be adjusted so low viscosity that it can be processed eg in a spray-coating process or can be distributed on the particle surface.

In the context of the process according to the invention, it is particularly preferable to use the thermoplastic as a dispersion or as a suspension in a solvent

In the context of the process according to the invention, it is particularly preferred to use the thermoplastic as the very finely ground powder, also dissolved or suspended in a solvent. It can also partially solved forms

find application

The relative amounts of the radical generator and the thermoplastic used can vary within wide limits and are determined by the desired degree of crosslinking.

Examples of suitable solvents for dissolving the free-radical initiators are: alcohols, halogenated organic solvents, silanes. Preferred solvents are, for example: methanol, methylene chloride, ethanol, isopropanol, acetone, organosilanes, e.g. Aminosilanes or octylsilanes or other bi- or multi-functional silanes.

In a preferred embodiment of the method according to the invention, a bonding agent is applied to the surface of the mineral component in a first layer. The radical starter is then applied in the following step. Adhesion promoters in the context of the present invention enhance the adhesion of the thermoplastic to the mineral component by acting as

Reactant enters the chemical bond with the thermoplastic, or reacts with the present reactants.

Adhesion agents are known per se. Examples of suitable silanes, such as H-silanes and siloxanes, such as bifunctional silanes or partially condensed silanes or called functional siloxanes, it could also be used other organo-metal alcoholates.

For example, the following adhesion promoters may be mentioned: organosilanes, or siloxanes (for example Ameo), organo-titanates, organo-zirconates,

Maleic anhydride grafted polyethylene or other MSA, Ca stearates, fatty acids.

In particular, preferred adhesion promoters are: aminosilanes, vinylsilanes, acrylsilanes, methacrylsilanes, octylsilanes, epoxysilanes or silanes containing amino groups For the process according to the invention, it is preferred to dissolve the adhesion promoter in a solvent and to distribute it on the mineral component and react with the surface ,

Examples of suitable solvents for solubilizing the adhesion promoters are: methanol, ethanol, propanol, isopropanol, or toluene. Of course it is also possible mixtures of solvents

to use or apply the bonding agents directly.

The concentration of the adhesion promoter in the solvent is in the

Generally in the range of 1% to 90% by weight. preferably in the range of 20 to 70% by weight. After the adhesion promoter reacts with the surface, the radical initiator is applied, the solvent is removed, then the thermoplastic solution is applied and the solvent is removed.

The reaction and thus the crosslinking of the coated mineral component with the thermoplastic in the context of the present invention is started by energetic action in a conventional manner.

In a preferred embodiment of the present invention, the reaction is initiated by energetic action in the form of ionizing radiation. The energetic influence can be caused by ionizing radiation or

electromagnetic radiation are introduced. In the present invention, beta radiation (electron beams) is in the range of 1 keV to 50 MeV, preferably in the range of 1 keV to 10 MeV, more preferably in the range of 3 keV to 8 MeV.

The dose in the context of the present invention is 0.1 to 500 kGy, preferably 1 to 100 kGy, particularly preferably 2 to 60 kGy

The irradiation time with the respective acting energy is in each case adapted to achieve the desired dose rate. The irradiation is carried out so that the individual particles are moved relative to the radiation source and thus the surfaces of the particles

be irradiated evenly. Preferably, this is the free-flowing

Bulk material circulated in a reactor.

In a particularly preferred form, the reaction is carried out under reduced pressures.

The process according to the invention for the preparation of the intermediates can be carried out, for example, as follows:

, The free-flowing powder of mineral nature is in the reactor

circulated.

2. The silane-solvent mixture is e.g. supplied by spraying and the particle surfaces with the mixture (spray coating).

3. The reaction of the silane coupling to the mineral surface is carried out with thermal support.

4. Any resulting and existing solvents are removed.

5. Steps 2 to 4 are repeated until the desired nominal coverage relative to the BET specific surface area is achieved. Typically, a monomolecular coating is used. Other degrees of coverage are possible. As an orientation, about 0.5% by weight of an aminosilane is applied to a mineral flour with about 8 m2 / g of specific surface area.

6. The radical starters are applied directly or in solution to the

Particle surfaces applied (typically: spray coating). For orientation, about 0.5 wt .-% of the radical generator

applied.

7. A polymer solution is added and the mixture becomes vigorous

mixed so that the surface of the mineral component is largely covered. It may be useful, a stronger mixing unit z. B. to use a kneader or a mortar mill or a Henschel mixer.

8. The solvent is removed while the mixing unit is working.

9. Vacuum is applied.

10. After removing the solvent components, the powder can be a

Irradiation be supplied with electron beams.

11. The irradiation is preferably carried out with constant stirring or continuous circulation of the free-flowing powder, so that all particle surfaces are uniformly crosslinked. The degree of crosslinking depends on the requirements in the end product and is adjusted by the irradiation energy and the irradiation time. The irradiation can be performed spatially elsewhere and is independent of the preparation of the coating. For this purpose commercial facilities are available. The irradiation dose is about 100 kGy, depending on the desired crosslinking strength.

12. The finished intermediate may be a further processing for

Compound are supplied, which is then available for thermoplastic processing for shaping the components available.

Based on the intermediates of the invention opens up a new class of polymeric materials in which the mineral component is crosslinked with the polymer. The present invention therefore also relates to novel polymeric materials based on thermoplastics and optionally other

Polymers, mineral components and optionally others

Admixtures and a radical initiator, characterized in that the radical initiator initiates a reaction, after which the surface of the mineral component with the thermoplastic polymer chains are chemically crosslinked.

The components of the materials consist of

A: mineral components that can carry hydroxyl groups on the surface

B: a bonding agent chemically bound on the surface of the mineral component

C: a radical initiator or mixtures of various, known as photoinitiators, crosslinking enhancers, photosensitizers D: thermoplastic polymers, oligomers or prepolymers or

Monomers (individual or mixtures (blends)) which are crosslinked to the surface of the mineral component, grafted or ungrafted.

E: a thermoplastic matrix polymer that may be identical to D, or different examples of each are:

A: natural or synthetic materials, with variable outer shape (eg fibers, platelets, particles, mixtures thereof), crystalline or amorphous structure, or mixtures thereof. The chemical nature of the mineral phase may be oxidic or silicate in nature, as are hydroxides and oxihydrates, as well as mixed oxides are relevant, as are pure metals and metal alloys. Examples are: aluminum oxide, titanium dioxide, calcium oxide, and their Oxihydrate and hydroxides. Examples of silicate components are: quartz, cristobalite, talc, kaolin, metakaolin, calcined kaolin, mica (muscovite, phlogopite, vermiculite), diatomaceous earth (Siliceous earth), Neuburg Siliceous Earth, glass spheres, hollow glass spheres, glass flakes, silica glass, feldspar plasorites, silicates, wollastonite, basalt, nepheline, nepheline syenite, perlite (expanded and unblooded), clays, calsium silicates (CS phase minerals) and calcium silicate hydrates (CSH) Phase minerals) eg

Tobermorite, xonotlite, glass fibers (E, A, C, D, R, AR), aluminosilicates

B: Metal alcoholates: silanes, titanates, aluminates, zirconates, (functional) siloxanes, silicone oils, MSA-grafted polymers, metal soaps, olefins. The metal alcoholates, especially the silanes, as bifunctional silanes are described in the form: Ri-Si-R (2-4) where R1 is a hydrolyzable alkoxy group (e.g., methoxy or

Ethoxy,) or simply hydroxy or chloro or hydrogen. R (2-4) are the same or different and represent organofunctional groups.

R2-R4 may be combinations of the following organofunctional groups:

Amino, e.g. B .: Dynasilan® AMEO: 3-AminoPropyltrietoxysilane z. For example: Dynasilan® DAMO, N- (2-aminoethyl, 3-aminopropyltrimethoxysilane, epoxi- (glycidyl), alkyl, octyl, eg: Dynasilan® OCTMO: trimethoxyoctylsilane, methyl, alkenyl, alkoxy , Carboxy-, acidahydride-, aryl-, phenyl-, vinyl-, eg: Dynasilan® VTMO: vinyltrimethoxysilane, acyl-, methacryl, for example: Dyansilan® MEMO: 3-methacrylpropyl-trimethoxysilane, nitrite-, Acrylonitrile, amido, photoinitiator, ureido, isocyanate, isocyanurate, sulfonido, mercapto, thio, sulfo, sulfino, alkylamino, dialkyl, amino, imino, nitro, nitroso, Oxo, formyl, chloro, bromo, fluoro, iodo, keto groups Likewise, partially condensed silanes derived from the above structure may be used.

C: radical formers are photoinitiators, crosslinking enhancers or

Photosensitizers and radical initiators. The photoinitiators are derived from the groups of benzophenones and its derivatives, dialkylbenzilketals and the a-diketone, the acylphosphine oxide of thionathone,

Aminocoinitiatorsysteme and aminoacrylates. These include:

the alkylbenzophenones: 2-methylbenzophenone, 4-methylbenzophenone, 2,4-dimethylbenzophenone, 3,4-dimethylbenzophenone, 4-isopropylbenzophenone, 4-dodecylbenzophenone, 2,4,6-trimethylbenzophenone , 3,3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, the dialkoxyacetophenonel Benziketale:, 4'-Bisdimethylaminobenzophenone ("Michlersketon"), 2,2 '

Dimethoxy-2-phenylacetophenone ("benzil dimethyl ketal"), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropanone-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one ("Doracur 1173®" ), (I-hydroxycyclohexyl) phenyl ketone,

the halobenzophenones: chloro derivatives, 2-chloro-benzophenone, 4-chloro-benzophenones, 2,2'-dichloro-benzophenones, the alkoxy-alkylthio-derivatives: 2, 3, 4-methoxy-benzophenone, 2, 4-methylthio Benzophenones, 2-ethoxy-benzophenones, 4-propoxy-benzophenones, 4-butoxy-benzophenones, 4-isopropoxy-benzophenones,

the carboxylic ester derivatives: 2-methoxycarbonyl-benzophenones, 3-ethoxycarbonyl-benzophenones, 2- or 4-ethoxycarbonyl-benzophenones, 2- or 4-isopropoxycarbonyl-benzophenones, 4-tert-butoxycarbonyl-benzophenones, 2-butoxycarbonyl-benzophenones, 2,2'- Diethoxycarbonylbenzophenones,

the dialkylbenzilketals / alpha-diketones: -aminoalkyphenones, benzoin ethers, benzoin butyl ether, benzoin isopropyl ether, phenylenediamine, 1-benzoylcyclohexanonol ("Irgacure 184 (©)"), 2 (dimethylaminoethyl acrylate),

Silyl benzyl ether, dodecylbenzophenone, benzil, the acylphosphine oxides:

Diethyl benzoylphosphinate, 2,4,6-trimethylbenzoylphosphine oxide

("TMDPO"), 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide ("TMPDO"), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, the thioanthones: 2- / 4-chlorothioxanthone, 2- / 4-isopropylthioxanthone, 2,4-Dimethylthioxanthone, the Aminocoinitiatorsysteme: N-methyldiethanolamine, triethanolamine, the

Amino acrylates: 2- (dimethylamino) ethyl acrylate, or the radical initiators: azo bis (isobutyronitrile) "Al BN" azobis (4-cyanovaleric acid), dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctate, tert-butyl perbenzoate, di (tert. butyl) peroxide, benzopinacol, 2,2'-di (C 1 -C 8 alkyl) benzpinacols, benzoin ethers,

Dialkylbenzilketal, dialkoxyacetophenone, acylphosphine oxide, 9.1 Phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil, 4,4'-dialkoxybenzil, camphorquinone, the photosensitizers: perylene,

Thioxanthone derivatives, anthracene derivatives, the crosslinking agents selected from the group of acrylates: trimethylolpropane trimethacrylate ("TRIM"),

Pentaerythriol triacrylate, pentaerythritol trimethacrylate, pentaerythritol pentaacrylate, dipentaerythrol pentamethacrylate, ditri methylol propane tereacrylate, Ditri methylol propantetramethacrylate, the group of cyanates / cyanurates: triallyl cyanurate ("TAG"), the group of isocyanates / isocyanurates: triallyisocyanurate (" TRAIC "), trimethallyl isocyanurate (" TMAIC "), others: polymethylene polyphenylene-N-maleimide, tris (4-vinyloxybutyl) trimellitate, bis (4-vinyloxybutyl) -isophthalate

D: the thermoplastics as polymers, oligomers, prepolymers and monomers

polyolefins

CSM Chlorosulfonated polyethylene

EEA ethylene-ethyl acrylate copoplymer

EPDM ethylene-propylene terpolymer

EPM ethylene-propylene elastomer

EVA ethylene vinyl acetate

PE polyethylene (PE-LD, PE-HD, PE-LLD)

PE-C Chlorinated polyethylene

PEO polyethylene oxide

PP Polypropylene PA Polyamide 6, PA 6.6, PA 11, PA 12, cast polyamide and the like. Polyamides PVAL polyvinyl alcohol

Halogenated polymers:

CSM Chlorosulfonated polyethylene

ETFE ethylene tetrafluoroethylene

PEP Polyfluoroethylenepropylene

FPM fluoroelastomer PE-C Chlorinated polyethylene

PVC polyvinyl chloride

PVDF polyvinylidene fluoride

PVF polyvinyl fluoride

Thermoplastic elastomers:

FPM fluoroelastomer (thermoplastic)

TPE-E Polyetherester Copolymers TPE-0 based on polyolefin

TPE-S based on styrene

TPE-U polyurethane

TPE-V polyolefin with vulcanized blocks

E: represents building blocks such as D as a thermoplastic polymeric matrix.

The present invention is also a process for the preparation of polymeric materials based on thermoplastics and optionally other polymers, surface-modified mineral components and optionally other admixtures and a radical initiator, characterized in that the radical initiator initiates a chemical reaction, after which the surface of the mineral component with the

thermoplastic polymer phase are chemically crosslinked.

The energetic action is effected by means of ionizing radiation, which acts in the form of electron beams, UV rays or X-rays on the particles.

The present invention is also the use of polymeric materials based on thermoplastics and optionally other polymers, mineral components and optionally other admixtures and a free radical initiator, wherein the radical initiator the

Surface of the mineral component covered and the polymer chains are bonded to the surface of the mineral component, as

thermoplastic semi-finished in common thermoplastic

Forming process (so-called primary forming, joining and machining). Examples include the extrusion process or injection molding process, or the blow molding process, as intake pipes in vehicles, fuel tanks vehicles, support plates in electrical and electronic applications, plain bearings, slide conveyors, cutlery, tubes, profiles, tubes, plates,

Cable jackets, shoe soles, fibers, bristles, housings, gears, screws, gaskets, fans, rods, fasteners and mountings in the automobile, in particular under the bonnet, bobbins, blow molded parts, polymer concrete.

The polymeric materials of the invention are characterized by increased chemical and mechanical properties compared to materials in which the mineral component is not crosslinked with the polymer.

With the materials according to the invention can be, for example, increased by at least 10% tensile strength, increased by at least 10% modulus, increased by more than 15 K heat resistance and increased by at least 15% impact resistance with and without notch compared to comparable obtained per se known materials.

^• k ~ k ~ k ~ k ~ k

The invention relates to intermediates (semifinished products) for polymers

Composite materials with coupled mineral and / or polymeric

Components, the polymeric materials based on the intermediates, a process for their preparation of the intermediates and their use.

In plastics technology, it is a common practice that

Property profiles of the polymers known per se by admixture

(Compounding) of additives, such as fillers and additives, or by mixing different types of plastic (blends) to change so that they meet the specific requirements.

Polymeric composites usually consist of at least two different phases, where one of the two phases usually consists of an inorganic material. The inorganic phase is surrounded by an organic phase. This organic phase is also referred to as binder or resin. Composite materials in the context of this invention are two-substance systems or multi-substance systems with an organic phase which forms the matrix and various other phases which occur during the

Processing or use are not completely miscible with the organic phase. The individual phases can be modified with an interphase and these phase boundaries can be made compatible with one another via adhesion promoters

The crosslinking is initiated via a radical generator which is deposited within the phases. The radical form of the radical generator itself is caused by energetic action z. B. formed in the form of ionizing radiation. From EP 1 340 788 A2, for example, the preparation of a compound based on a thermoplastic is known. Like in this one

Document is described, thermoplastics, z. As polyvinyl chloride, processed with a crosslinking agent, a stabilizer, chalk as a filler and an alkylbenzophenone as a radical starter to a workable compound. After shaping, here extrusion, the polymer is crosslinked by irradiation with UV light. The fillers are merely

physically stored in the thermoplastic and have only one filling function. After crosslinking, the phase has largely lost its thermoplastic character. Object of the present invention is the use of filler components, as components in polymer compounds based on synthetic plastics or plastics based on renewable raw materials to increase, for example, the mechanical stability, the tensile strength, the

Impact resistance, scratch resistance, modulus of elasticity, chemical

Durability etc.

There have been new intermediates for polymeric materials with components which may optionally be surface-modified, a radical generator, a matrix polymer and optionally other admixtures found, characterized in that the polymer chains are chemically crosslinked with the surface of a filler components According to the invention, the crosslinking may also be given or in proportions on the primer or the radical generator

Compared to known polymer compounds are in the new compounds based on the intermediates of the invention the

Filler components chemically crosslinked with the matrix polymer and not only physically incorporated as a "blend". In contrast to other crosslinked thermoplastics, the crosslinking is predominantly on the inner surface, while the remainder of the thermoplastic portion is substantially further uncrosslinked and thus accessible to thermoplastic processing. According to the present invention, the new compounds have increased chemical and mechanical stability such. As the strength or

Tear strength or impact strength or modulus of elasticity compared to compounds with incorporated filler components or with adhesion promoters surface-modified filler components. With the intermediates of the invention opens up a new class of polymeric composites (polymer compounds).

The filler components can be divided into two groups: a) inorganic components for the polymeric materials in the context of the present invention are e.g. B. silicates containing materials or

Silikatische structures having materials or metal oxides or oxidic structures having materials or metal hydroxides or hydrous structures having materials, carbides or carbonaceous materials such as carbon black, carbon fibers, carbon nanotubes of various structure, fullerenes, or nitrides or nitrogen-containing components, carbonates, sulfates or oxides or Oxihydrate or mixtures thereof b) Organic components are preferably those which do not form a substantial mixture with the matrix polymer in processing or use conditions: thermosets, thermoplastics, elastomers or thermoplastic elastomers (as polymers, prepolymers or oligomers), all in particulate form (e.g. Particles, fiber or platelets), or natural raw materials such as natural fibers such. Hemp, sisal, etc

Mineral components in the context of the present invention may be

Silicates: natural and synthetic silicates, pyrogenic and precipitated

Silicas, so-called island silicates, chain silicates, strip silicates,

Silicates, phyllosilicates or aluminosilicates, minerals of the group of

Quartz (quartz, fused silica, cristobalite), zeolites, feldspars, caleiumsilicate phase minerals or caciulphate hydrate phase minerals (eg tobermorite or xonotlite) or

Metal oxides: natural or synthetic metal oxides such as aluminum oxide,

Silica, magnesia, calcia, titania, iron oxides, zinc oxide. Of course this is just an example list of possible components.

In a particularly preferred embodiment of the present invention, the filler component consists of organic components immiscible with the matrix polymer or inorganic components which carry hydroxyl groups on the surfaces, such as hydrosilicate and / or aluminosilicate and / or silicon oxide and / or aluminum oxide materials or

Titanium dioxides. Likewise, carbon or glass or rockwool fibers, as well as carbon nanotubes may be used. For example, the following mineral materials may be mentioned:

Mica, talc, wollastonite, asbestos, quartz, fused silica, silicic acid,

Microsilica, kaolin, calcined kaolins, xonotlite, tobermorite, nepheline syenite, alumina, titanium dioxide

In the context of the present invention, the filler component may be present in granular form. In a preferred embodiment of

present invention, the filler component is present in finely divided form, isolated or as a dispersion or suspension

It is hereby preferred that the filler component in a

Grain size distribution of less than 4 mm is present.

In particular, it is preferred that the filler component is present in a particle size distribution of 5 nm to 250 μι ^η .

The intermediates of the invention are at the surface of

Filler component largely in a monomolecular layer of

Matrix polymer, but at least covered in sub-monolayers.

The radical generator is incorporated into the inner boundary surface of the phases, so that a quasi-multi-layered structure is built up.

Of course, a multi-layered covering is also possible.

In the event that it is desired within the scope of the invention that the mineral component is not completely linked to the matrix polymer, the coverage may, of course, be only partially present

(Submonolayers).

Free-radical generators in the context of the present invention are known per se.

Free-radical generators in the context of the present invention can be:

Photoinitiators, photosensitizers or crosslinkers. It may also be functional silanes or siloxanes having functional groups which decompose into radicals under energetic action and / or a

Initiate crosslinking reaction.

Preferred free radical generators in the context of the present invention may be: photoinitiators:

Benzoin ethers, benzil, benzil ketals, alpha-splitters such as alpha, alpha-diethoxyacetophenone, alpha-hydroxyalkylphenones, alpha-aminoalkylphenones, aromatic ketone coinitiator systems: benzophenones and substituted ones

Benzophenones, Mischlers ketone,

Sensitizers: aromatic haloketones: phenacyl chloride, desyl chloride or 4-chloromethylbenzophenone

Crosslinking agent: trimethylolpropane trimethacrylate, (TRIM) or

Triallyl cyanurate (TAC), triallyl isocyanurate (TAIC).

In the context of the present invention, matrix polymers are added to the

Surface of the adhesion promoter-modified filler component attached and then crosslinked with her.

Matrix polymers in the context of the present invention are unsaturated, unbranched or branched, grafted or ungrafted thermoplastics and thermoplastic elastomers. They may be provided by addition reactions or by grafting with reactive groups.

Examples which may be mentioned are the following matrix polymers: polyethylene, polypropylene or mixtures of polyethylenes and polypropylenes (for example grafted and ungrafted), polyamide, polyurethane, polyvinyl chloride,

Polycarbonate, PMMA, polyaryletherketones (eg PEEK), polyoxymethylene, polystyrenes, polyimides, thermoplastic elastomers and natural polymers. Of course, this is just a selection of thermoplastics that can be used in principle.

In the context of the present invention, it is possible that the

intermediates according to the invention further known per se

Stabilizers such as metal soaps or organotin compounds. Plasticizers such as substituted phthalates (eg dibutyl phthalate), lubricants such as paraffins or UV stabilizers or fillers such. B. marble flour or silicates adhesion promoter in the context of the present invention act as

Wetting aids and can be linking points between the

Surface of the filler component and the matrix polymer component

Adhesion agents are known per se. For example, silanes, such as H-silanes and siloxanes, such as. B. bifunctional silanes or partially condensed silanes or functional siloxanes, functional polysiloxanes, silicone oils, other organo-metal alcoholates or maleic anhydride (MSA) grafted polymeric metal soaps, low molecular weight olefins, fats, waxes or oils may also be used. For example, the following adhesion promoters may be mentioned: Organo-silanes (e.g. AMEO®) or Siloxane Organo-Titanate, Organozirconate,

Maleic anhydride grafted polyethylene or other MSA, Ca stearates, fatty acids.

In particular, preferred adhesion promoters are aminosilanes or

Amino-containing bifunctional silanes, vinylsilanes, acrylsilanes, methacrylsilanes, octylsilanes or epoxysilanes.

A process has also been found for preparing the intermediates for polymeric materials with components, characterized in that the radical initiator is concentrated on the surface of the component, the matrix polymer is added, and the crosslinking is initiated by energetic action.

The free radical initiator may be mixed in a solid, finely divided, liquid state or in solution with the filler component and distributed on the surface. In general, it is preferred that the radical initiator be uniform on the

Distribute filler component.

For the process according to the invention, it is preferred to dissolve the radical initiator in a solvent and to distribute it on the filler component.

Examples of suitable solvents for dissolving the radical initiators include: alcohols, organohalogen solvents, silanes, alkanes and alkene, and ionic liquids.

Preferred solvents are, for example: methanol, methylene chloride, ethanol, isopropanol, acetone, organosilanes such as. As aminosilanes or octylsilanes or other bi- or multi-functional silanes and ionic liquids Of course it is also possible mixtures of solvents

use.

A preferred embodiment of the method according to the invention is characterized in that the filler component and the radical initiator in a mass ratio of less than 5%, preferably in the ratio of less than 2%

are used, based on the mass of the filler component.

In a preferred embodiment of the method according to the invention, the filler component is present in finely divided form.

It is preferred here that the filler component is present in a particle size of less than 4 mm.

In particular, is preferred here that the filler ^η in a grain size of 5 nm to 250 μ π present

The thermoplastic and the interphase may be added as a dissolved matrix polymer, as an oligomer or prepolymer, as a monomer, in gaseous or finely divided form or in solution or as a low molecular weight polymer to the filler component with the radical initiator. Of course, it is also possible to use mixtures of different polymers

In a preferred embodiment of the present invention, the thermoplastic is used in solution. For the process according to the invention, it is preferred to dissolve the thermoplastic in a solvent and that with adhesive agents

surface-modified mineral filler component associated with the

Radical starter is busy to distribute

Dimethylformamide, ethyl acetate, methanol, ethanol or cyclohexane. The choice of solvent depends on the matrix polymer to be dissolved and the filler component. Preferred solvents are, for example, polyamide: toluene, m-cresol, cyclohexanone, methyl ethyl ketone

In particular, toluene and m-cresol are preferred as the solvent for polyamide.

Of course, it is also possible to use mixtures of solvents. The concentration of the thermoplastic in the solvent is in the

Generally in the range of 1% to 80% by mass, preferably in the range of 10 to 60% by mass. The solution should be adjusted so low viscosity that z. B. is to process in a spray-coating process or can be distributed on the particle surface. In the context of the process according to the invention, it is particularly preferable to use the thermoplastic as a dispersion or as a suspension in a solvent.

Find application.

The relative amounts of the radical generator and the thermoplastic used can vary within wide limits and are determined by the desired degree of crosslinking. In a preferred embodiment of the method according to the invention, the surface of the filler component is incorporated in a first layer

Applied adhesion promoter. The radical starter is then applied in the following step.

Adhesion promoters in the context of the present invention enhance the adhesion of the matrix polymer to the filler component by promoting, as a surfactant, wetting with the matrix polymer

Adhesion agents are known per se. For example, silanes, such as H-silanes and siloxanes, such as. B. bifunctional silanes or partially condensed silanes or called functional siloxanes, it could also be used other organo-metal alcoholates.

For example, the following adhesion promoters may be mentioned: organosilanes, or siloxanes (for example Ameo®), organotitanates, organozirconates,

Maleic anhydride grafted polyethylene or other MSA, Ca stearates, fatty acids.

In particular, preferred adhesion promoters are: aminosilanes, vinylsilanes, acrylsilanes, methacrylsilanes, octylsilanes, epoxysilanes or silanes containing amino groups. For the process according to the invention, it is preferred to dissolve the adhesion promoter in a solvent and to distribute it on the filler component and, in the case of a mineral filler, to react with the surface

Examples of solvents used to dissolve the adhesion promoters include:

Methanol, ethanol, propanol, isopropanol, or toluene. Of course it is also possible mixtures of solvents

to use or apply the bonding agents directly.

The concentration of the coupling agent in the solvent is generally in the range of 1% to 90% by weight. preferably in the range of 20 to

70% by weight. After action and optionally reaction of the coupling agent with the

Surface of the radical initiator is applied, the solvent removed, then applied the thermoplastic solution and the solvent removed. In the case of applying an interphase is proceeding successively

The reaction and thus the crosslinking of the filler component with the thermoplastic in the context of the present invention is started by energetic action in a conventional manner.

In a preferred embodiment of the present invention, the reaction is by energetic action in the form of ionizing radiation initiated.

The energetic influence can be caused by ionizing radiation or

The irradiation time with each acting energy is adjusted to achieve the desired dose rate each.

The irradiation is carried out so that the individual particles are moved relative to the radiation source and thus the surfaces of the particles are uniformly irradiated. Preferably, the free-flowing bulk material is circulated in a reactor. In a particularly preferred form, the reaction is carried out under reduced pressures.

1. The free-flowing powder z. B. mineral nature we in the reactor

circulated.

2. The silane solvent mixture is z. B. supplied by spraying and the particle surfaces with the mixture occupied (spray coating)

4. Any resulting and existing solvents are removed.

5. Repeat steps 2 to 4 until the desired one

Nominal coverage relative to the specific surface, determined by BET, is reached. Typically, a monomolecular coating is used. Other degrees of coverage are possible. When

Orientation is applied about 0.5 M% of an aminosilane to a mineral flour with about 8 m ² / g of specific surface area. The radical starters are applied directly or in solution to the

Particle surfaces applied (typically: spray coating). to

Orientation about 0.5 M% of the radical generator are applied. A matrix polymer solution is added and the mixture vigorously mixed so that the surface of the mineral component is largely covered. It may be useful, a stronger mixing unit z. B. to use a kneader or a mortar mill or a Henschel mixer. The solvent is removed while the mixing unit is working. It is created vacuum. After removing the solvent portions, the powder can be supplied to an electron beam irradiation. The irradiation is preferably carried out with constant stirring or

continuous circulation of the free-flowing powder is carried out so that all particle surfaces are evenly crosslinked. The degree of

Crosslinking depends on the requirements in the end product and is adjusted via the irradiation energy and the irradiation time. The irradiation can be performed spatially elsewhere and is independent of the preparation of the coating. For this purpose commercial facilities are available. The irradiation dose is about 100 kGy, depending on the desired crosslinking strength. The finished intermediate product can be used for further processing

Compound are fed, which subsequently to

thermoplastic processing for shaping the components is available. On the basis of the intermediates according to the invention, a new class of polymeric materials opens up in which the filler component is crosslinked with the matrix polymer.

The present invention therefore also relates to novel polymers

Materials based on thermoplastics and possibly other

Polymers, mineral components and optionally others

Admixtures and a free radical initiator characterized in that the free radical initiator initiates a reaction whereby the surface of the filler component is chemically crosslinked directly or indirectly with the thermoplastic matrix polymer chains.

The components of the materials can consist of:

Components which, relative to the matrix polymer during processing or

Operating temperature is not or reduced mixable bar, about fixed during processing and use. But not limited to that. · One applied to the surface of the filler component

bonding agent

A free radical initiator or mixtures of various known as photoinitiators, crosslinking enhancers, photosensitizers

Thermoplastic polymers, oligomers or prepolymers or monomers (individual or mixtures (blends)), which are compatible with the

Surface of the mineral component are crosslinked, grafted or ungrafted.

• one on the modified surface of the filler component

applied adhesion promoter, optionally with a radical generator · a thermoplastic matrix polymer

Examples of the individual components are: natural or synthetic materials, with variable outer shape (eg.

Fibers, platelets, particles, mixtures thereof), crystalline or amorphous structure, or mixtures thereof. The chemical nature of phase F can be organic. These include thermosets, thermoplastics, elastomers or thermoplastic elastomers or polymers based on renewable raw materials. Likewise, the chemical nature of the phase F may be inorganic nature: These include in particular metals (pure and alloys) and their metal oxides, metal hydroxides and Oxihydrate. Likewise hydroxides and

Oxihydrate, as well as mixed oxides are relevant. Examples are: alumina, titania, Caiciumoxid, and their Oxihydrate and hydroxides. Similarly, the phase F may consist of mineral components, such as. Examples of silicate components are: quartz, cristobalite, talc, kaolin, metakaolin, calcined kaolin, mica (muscovite, phlogopite, vermiculite), diatomaceous earth

(Siliceous earth), Neuburg Siliceous Earth, glass balls, hollow glass spheres,

Glass flakes, fused silica, feldspar, plasorites, silicates, wollastonite, basalt, nepheline, nepheline syenite, perlite (expanded and unblooded), clays, calsium silicates (CS phase minerals) and calcium silicate hydrates (CSH phase minerals), e.g. B. Tobemorite, xonotlite, glass fibers (E, A, C, D, R, AR), aluminosilicates. This also includes mixtures of the components.

Metal alcoholates: silanes, titanates, aluminates, zirconates, (functional) siloxanes, silicone oils, MSA grafted polymers, metal soaps, olefins. The metal alcoholates, especially the silanes, as bifunctional silanes are described in the form, and mixtures thereof R-i-Si-R ^), wherein

R1 is a hydrolyzable alkoxy group (eg, methoxy or ethoxy,) or

Hydroxy or chloro or hydrogen.

R (2-4) represent organofunctional groups.

R2-R4 can be combinations of: Amino, e.g. B .: Dynasilan® AMEO: 3-AminoPropyltrietoxysilane z. For example, Dynasilan® DAMO, N- (2-aminoethyl, 3-aminopropyl-trimethoxysilane, epoxi- (glycidyl), alkyl, octyl, e.g., Dynasilan® OCTMO: trimethoxyoctylsilane, methyl, alkenyl, Alkoxy, carboxy, acidahydride, aryl, phenyl, vinyl, eg: Dynasilan® VTMO: vinyltrimethoxysilane, acyl, methacryl, for example: Dyansilan® MEMO: 3-methacrylpropyl-trimethoxysilane, nitrile , Acrylonitrile, amido, photoinitiator, ureido, isocyanate, isocyanurate, sulfonido, mercapto, thio, sulfo, sulfino, alkylamino, dialkylamino, imino, nitro, nitroso, Oxo, formyl, chloro, bromo, fluoro, iodo, keto groups Likewise, partially condensed silanes derived from the above structure can be used or mixtures thereof.

Free radical generators may be photoinitiators, crosslinkers or

Be photosensitizers and radical initiators.

The photoinitiators are derived from the groups of benzophenones and their derivatives, the dialkylbenzilketals and the a-diketones, the acylphosphine oxides of the thionathones, aminocoinitiator systems and the aminoacrylates. These include the

Alkylbenzophenones: 2-methylbenzophenone, 4-methylbenzophenone, 2,4-dimethylbenzophenone, 3,4-dimehtylbenzophenone, 4-isopropylbenzophenone, 4-dodecylbenzophenone, 2,4,6-trimethyl- Benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, the dialkoxyacetophenone, benziketals:, 4'-bisdimethylaminobenzophenone ("Michlersketon"), 2,2'-dimethoxy-2-phenylacetophenone ("benzil dimethyl ketal") , 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one ("Doracur 1173®"), (I-hydroxycyclohexyl) - Phenyl ketone, the halobenzophenones: chloro derivatives, 2-chloro-benzophenone, 4-chloro

Benzophenones, 2,2'-dichloro-benzophenones, the alkoxy-alkylthio-derivatives: 2-, 3-, 4-methoxy-benzophenone, 2-, 4-methylthio-benzophenones, 2-ethoxy-benzophenones, 4-propoxy-benzophenones, 4 Butoxy Benzophenones, 4-Isopropoxy Benzophenones,

the carboxylic ester derivatives: 2-methoxycarbonylbenzophenones, 3 Methoxycarbonylbenzophenones, 2- or 4-ethoxycarbonyl-benzophenones, 2- or 4-isopropoxycarbonyl-benzophenones, 4-tert-butoxycarbonyl-benzophenones, 2-butoxycarbonyl-benzophenones, 2,2-diethoxycarbonyl-benzophenones, the dialkylbenzilketals alpha-diketones: α -Aminoalkyphenones, benzoin ethers, benzoin butyl ether, benzoin isopropyl ether, 1-Q-phenanthrenequinone, 1-benzoylcyclohexanonol ("Irgacure 184 (®)"), 2 (dimethylamino-ethylacrylate),

Silylbenzyl ether, dodecylbenzophenone, benzil, the acylphosphine oxides: diethyl benzoylphosphinate, 2,4,6-trimethylbenzoylphosphine oxide ("TMDPO"), 2,4,6-

Trimethylbenzoylethoxyphenylphosphine oxide ("TMPDO"), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, the thioanthones: 2- / 4-chlorothioxanthone, 2- / 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, the aminocoinitiator systems: N-methyldiethanolamine, triethanolamine, the aminoacrylates: 2- (dimethylamino) ethyl acrylate, or the free radical generators: azo-bis (isobutyronitrile) "AIBN" azobis (4-cyanovaleric acid), dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctate, tert-butyl perbenzoate , Di- (tert-butyl) peroxide, benzopinacol, 2,2'-di (C 1 -C 8 -alkyl) benzpinacols, benzoin ethers, dialkylbenzilketal, dialkoxyacetophenone,

Acylphosphine oxide, 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil, 4,4'-dialkoxybenzil, camphorquinone, the photosensitizers: perylene, thioxanthone derivatives, anthracene derivatives, the crosslinking agents from the group of acrylates Trimethyloporontrimethacrylate ("TRIM"), pentaerythriol triacrylate, pentaerythritol trimethacrylate, pentaerythritol pentaacrylate, di pentaerythrol pentamethacrylate, ditri methylol propane tetratacrylate, di-methylol propane tetramethacrylate, the group of cyanates / cyanurates: TriallylCyanurat ("TAG"), the group of

Isocyanates / isocyanurates: triallyisocyanurate ("TRAIC"), trimethallyl isocyanurate ("TMAIC"), others: polymethylene polyphenylene-N-maleimide, tris (4-vinyloxybutyl) trimellitate, bis (4-vinyloxybutyl) -isophthalate. These include metal alcoholates (eg, silanes) which are the one above as an organofunctional group contained groups.

Thermoplastics may be polymers, oligomers, prepolymers and monomers, such as:

polyolefins

CS Chlorosulfonated polyethylene

EEA ethylene-ethyl acrylate copoplymer

EPOM ethylene-propylene terpolymer

EPM ethylene-propylene elastomer

EVA ethylene vinyl acetate

PE polyethylene (PE-LO, PE-HO, PE-LLO)

PE-C Chlorinated polyethylene

PEO polyethylene oxide

PE polypropylene

PA Polyamide 6, PA 6.6 PA 11, PA 12 and others. Polyamides, cast polyamide

PVAL polyvinyl alcohol

Halogenated polymers

CSM Chlorosulfonated polyethylene

ETFE ethylene tetrafluoroethylene

PEP Polyfluoroethylenepropylene

FPM fluoroelastomer

PE-C Chlorinated polyethylene

PVC polyvinyl chloride

PVOF polyvinylidene fluoride

PVF polyvinyl fluoride

Thermoplastic elastomers:

FPM fluoroelastomer (thermoplastic) TPE-E Polyetherester Copolymers

Polyolefin-based TPE-O

TPE-S based on styrene

TPE-U polyurethane

TPE-V polyolefin with vulcanized blocks

which may additionally all be provided with functional groups or mixtures thereof

The present invention is also a process for the preparation of polymeric materials based on thermoplastics and optionally other polymers, surface-modified mineral components and optionally other admixtures and a radical initiator, characterized in that the free-radical initiator initiates a chemical reaction, after which the surface of the filler component with the thermoplastic polymer phase is chemically crosslinked.

The energetic action is effected by means of ionizing radiation, in the form of electron beams, UV rays or X-rays on the

Systems acts

The present invention also relates to the use of

polymeric materials based on thermoplastics and optionally other polymers, mineral components and optionally other admixtures and a free radical initiator, wherein the radical starter the

Cover surface of the filler component and the polymer chains are bonded to the surface of the mineral component, as

thermoplastic semi-finished in common thermoplastic

Cable jackets, soles, fibers, bristles, housings, gears, Screws, gaskets, fans, rods, fasteners and brackets in automobiles, in particular under the bonnet, bobbins, blow-molded parts, polymer concrete

The polymeric materials of the invention are characterized by increased chemical and mechanical properties compared to materials in which the mineral component is not crosslinked with the polymer

They have, for example, a tensile strength which is increased by at least 10%, an E modulus increased by at least 10%, an increased heat resistance by more than 15 K and an increase of at least 5%

Impact resistance with and without notch on.

Claims

1. Intermediates for polymeric materials with mineral

Components, a radical starter and possibly others

Admixtures, characterized in that the radical initiator covers the surface of the surface-modified mineral component and the polymer chains are bonded to the surface of the modified silicate component.

2. Intermediates according to claim 1, that the mineral component consists largely of silicate minerals, oxide, or hydroxide minerals.

3. Intermediate product according to one of claims 1 or 2, characterized

characterized in that the mineral component is present in a particle size of less than 4mm.

4. Intermediate product according to one of claims 1 to 3, characterized

characterized in that the mineral component is present in a particle size of 5 nm to 250 pm

5. Intermediate product according to one of claims 1 to 4, characterized

characterized in that the radical starter the surface of the

mineral component largely in at least one

covered monomolecular layer

6. Intermediate product according to one of claims 1 to 5, characterized

characterized in that as radical initiator photoinitiators or

Crosslinking enhancers or photosensitizers or mixtures thereof may be used

7. Intermediate product according to one of claims 1 to 6, characterized

in that thermoplastic polymers, oligomers or prepolymers or mixtures thereof with the surface of the

mineral component chemically covalently connected.

8. Intermediate product according to one of claims 1 to 7, characterized

in that additives and auxiliaries which are typical in thermoplastic processing are used as admixtures:

Lubricants, antiblocking agents, release agents, antistatic agents, flame retardants, colorants, flexibilizers and plasticizers, adhesion promoters, blowing agents, nucleating agents, antibacterial agents, fungicides, conductive agents

9. Intermediate product according to one of claims 1 to 8, characterized

characterized in that the surface of the mineral component contains a bonding agent.

10. Intermediate product according to one of claims 1 to 9, characterized

in that the surface of the mineral component contains as adhesion promoter a bifunctional silane.

1 . Intermediate product according to one of claims 1 to 9, characterized

in that the surface of the mineral component contains as adhesion promoter a functional polysiloxane. 2. Intermediate product according to one of claims 1 to 11, characterized

characterized in that it is in finely divided and solid state.

13. Intermediate product according to one of claims 1 to 12, that it is present with an average grain size in the range of 5 nm to 250 pm.

14. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components, characterized in that the radical initiator is distributed on the mineral component, the thermoplastic polymer is added and the crosslinking is started by energetic action. 5. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to claim 14, characterized in that the radical starter in solution or as finely divided suspension on the mineral

Component is distributed.

16. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to any one of claims 14 or 15, characterized in that the radical initiator dissolved in a solvent and on the

mineral component is distributed.

17. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 16, characterized in that the mineral component is present in finely divided state.

18. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to any one of claims 14 to 17, characterized in that the mineral component is present with an average grain size in the range of 5 nm to 250 pm. 9. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to any one of claims 14 to 18, characterized in that the thermoplastic polymer is added in solution to the mineral component with the radical initiator.

20. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 19, characterized in that the thermoplastic polymer is used as a solution or as a suspension or as a dispersion or is applied in the form of a very finely divided powder.

21.A process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 20, characterized in that the adhesion promoter and the radical initiator in a molar ratio of 100: 1 to 1: 100 is used.

22. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to any one of claims 14 to 21, characterized in that the mineral component is covered with a primer and then the radical starter is distributed.

23. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 22, characterized in that a silane is used as the adhesion promoter. 24. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 22, characterized in that a functional polysiloxane is used as the adhesion promoter.

25. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components

26. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 24, characterized in that the polymerization is started with electron beams. 27. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to one of claims 14 to 24, characterized in that the polymerization is started with UV or X-rays.

28. Process for the preparation of intermediates for polymers

Materials with surface-modified mineral components according to any one of claims 14 to 24, characterized in that the polymerization with a mixture of electron beams,

X-rays and UV rays are started.

29. Polymeric materials based on thermoplastic polymers and optionally other polymers, mineral components and optionally other admixtures, adhesion promoters and

Free radical generators, characterized in that the adhesion promoter covers the surface of the mineral component, the free radical initiator initiates a reaction, after which thermoplastic polymer chains are chemically covalently bound to the surface of the mineral component.

30. Process for the preparation of polymeric materials based on

thermoplastic polymers and optionally other polymers, surface modified mineral components and

optionally other admixtures, adhesion promoters and a radical starter, characterized in that the coupling reaction is initiated by energetic action.

31. The method according to claim 30, characterized in that the

energetic action in the form of ionizing radiation

is carried out.

32. learn according to claim 30, characterized in that the

energetic action in the form of high-energy

Electron beams is performed.

33. The method according to claim 30, characterized in that the

energetic action in the form of UV radiation is performed.

34. The method according to claim 30, characterized in that the

energetic action in the form of X-rays is performed.

35. The method according to claim 30, characterized in that the

energetic action in the form of a combination of

Electron radiation, UV radiation and / or X-radiation is performed.

36. The method according to claim 30 to 35, characterized in that the action of the ionizing radiation is carried out statistically uniformly on the particle surfaces by the radiation source and the particles of the bulk material are moved relative to each other during the action.

37. Use of polymeric materials based on

thermoplastic polymers and optionally other polymers, surface-modified mineral components and

optionally other admixtures and a free radical generator, wherein the free radical initiator initiates a reaction, after which the

thermoplastic polymer chains covered the surface of the mineral component and the polymer chains are chemically covalently bonded to the surface of the mineral component, as a thermoplastic semi-finished in thermoplastic

Forming procedure

^• k ~ k ~ k - ~ k

38. Intermediates for polymeric materials with components the

optionally surface-modified, a radical generator, a matrix polymer and optionally other admixtures found, characterized in that the polymer chains are chemically crosslinked with the surface of a filler components. 39. Intermediates according to claim 38, characterized in that the filler component consists of organic or inorganic components which showed no or only a slight mixture in processing or use conditions with the matrix phase

40. Intermediate product according to one of claims 38 or 39, characterized

characterized in that the filler component is present in a particle size of less than 4 mm

41. Intermediate product according to one of claims 38 to 40, characterized

in that the mineral component is present in a particle size of 5 nm to 250 μm. 42. Intermediate product according to one of Claims 38 to 41, characterized characterized in that the radical starter covers the surface of the mineral component largely in at least one monomolecular layer.

43. Intermediate product according to one of claims 38 to 42, characterized

characterized in that as radical initiator photoinitiators or

Crosslinking enhancers or photosensitizers or mixtures thereof may be used.

44. Intermediate product according to one of claims 38 to 43, characterized

in that thermoplastic polymers, oligomers or prepolymers or mixtures thereof are chemically covalently bonded to the surface of the filler component.

45. Intermediate product according to one of claims 38 to 44, characterized

characterized in that as admixtures lubricants, antiblocking agents,

Release agents, antistatic agents, flame retardants, colorants, fillers fibers, flexibilizers and plasticizers, adhesion promoters, blowing agents,

Nucleating agents, antibacterial agents, fungicides, conductivity and UV stabilizers can be used.

46. Intermediate product according to one of claims 38 to 45, characterized

in that the surface of the filler component contains adhesion promoters. 47. Intermediate product according to one of claims 38 to 46, characterized

in that the surface of the mineral component contains as adhesion promoter a bifunctional silane

48. Intermediate product according to one of claims 38 to 46, characterized

in that the surface of the mineral component contains as adhesion promoter a functional polysiloxane.

49. Intermediate product according to one of claims 38 to 48, characterized

characterized in that it is in finely divided and solid state.

50. Intermediate according to one of claims 38 to 49, that it is present with an average particle size in the range of 5 nm to 250 μηη, as a dispersion or solid powder.

51. A process for the preparation of intermediates for polymeric materials with filler components of organic or inorganic components is that the radical initiator is distributed on the mineral component, the thermoplastic polymer is added and the crosslinking is started by energetic action.

52. Process for the preparation of intermediates for polymeric materials with surface-modified optionally mineral

Filler components according to claim 51, characterized in that the free radical initiator is distributed in solution or as finely divided suspension or dispersion on the mineral component.

53. Process for the preparation of intermediates for polymeric materials with surface-modified optionally mineral

Filler components according to one of claims 51 or 52, characterized in that the radical initiator is dissolved in a solvent and distributed on the filler component

54. A process for the preparation of intermediates for polymeric materials with filler components according to any one of claims 51 to 53, characterized in that the filler components is in finely divided state

55. Process for the preparation of intermediates for polymeric materials with surface-modified optionally mineral

Filler components according to any one of claims 51 to 54, characterized

characterized in that the filler components are present with an average grain size in the range of 5 nm to 250 pm

56. A process for the preparation of intermediates for polymeric materials with optionally surface-modified filler components according to any one of claims 51 to 55, characterized in that the thermoplastic polymer is added in solution to the mineral component with the radical initiator

57. A process for the preparation of intermediates for polymeric materials with surface-modified and / or unmodified components according to one of claims 51 to 56, characterized in that the thermoplastic polymer is used as a solution, or as a suspension or as a dispersion or is applied in the form of a very finely divided powder.

58. Process for the preparation of intermediates for polymeric materials with optionally surface-modified mineral

Filler component according to any one of claims 51 to 57, characterized

in that the adhesion promoter and the radical initiator are used in a molar ratio of 100: 1 to 1: 100

59. A process for the preparation of intermediates for polymeric materials with surface-modified mineral components according to one of claims 51 to 58, characterized in that the mineral

Component is covered with a primer and then the radical starter is distributed

60. Process for the preparation of intermediates for polymeric materials with optionally surface-modified mineral

Filler component according to one of claims 51 to 59, characterized

in that, as adhesion promoter, a b ^{'ifunktlonelles} silane is used

61. Process for the preparation of intermediates for polymeric materials with optionally surface-modified mineral

Filler component according to one of claims 51 to 59, characterized

in that a functional polysiloxane is used as adhesion promoter.

62. Process for the preparation of intermediates for polymeric materials with optionally surface-modified mineral

Filler component according to one of claims 51 to 61, characterized

characterized in that the polymerization is started with ionizing radiation.

63. Process for the preparation of intermediates for polymeric materials with optionally surface-modified mineral

Filler component according to one of claims 51 to 61, characterized

characterized in that the polymerization is started with electron beams

64. A process for the preparation of intermediates for polymeric materials with surface-modified and / or unmodified filler component according to any one of claims 51 to 61, characterized in that the polymerization is started with UV or X-rays. 65. Process for the preparation of intermediates for polymeric materials with optionally surface-modified mineral

Filler component according to one of claims 51 to 61, characterized

characterized in that the polymerization with a mixture of

E-beams, X-rays and UV rays are started. 66. Polymeric materials based on thermoplastic polymers and optionally other polymers, mineral components and

optionally other admixtures, adhesion promoters and radical formers, characterized in that the adhesion promoter the surface of the

Filler component covered, thereon is a polymer matrix and the free radical initiator initiates a reaction, after which the thermoplastic

Polymer chains of the polymer matrix either directly or the polymer chains are chemically covalently bonded to the surface of the filler component directly or indirectly via the primer or the radical generator.

67. Process for the preparation of polymeric materials based on thermoplastic polymers and optionally other polymers,

Surface modified and / or unmodified filler components and optionally other admixtures, adhesion promoters and a

Radical starter, characterized in that the coupling reaction is initiated by energetic action. 68. The method according to claim 67, characterized in that the

energetic action in the form of ionizing radiation is performed

69. The method according to claim 67, characterized in that the

energetic action is carried out in the form of high-energy electron beams 70. The method according to claim 67, characterized in that the

energetic action in the form of UV radiation is performed

71. The method according to claim 67, characterized in that the

energetic action in the form of X-rays is performed

72. The method according to claim 67, characterized in that the

energetic action in the form of a combination of electron radiation, UV radiation and / or X-radiation is performed

73. The method according to claim 67, characterized in that the effect of the ionizing radiation on the particle surfaces is carried out statistically uniformly by the radiation source and the particles of the bulk material being moved relative to one another during the action. 74. The use of polymeric materials based on thermoplastic polymers and optionally other polymers, surface-modified mineral components and optionally other admixtures and a free radical generator, wherein the radical initiator initiates a reaction after which the thermoplastic polymer chains the surface of the mineral

Component covered and the polymer chains on the surface of

mineral component chemically covalently bound, as

thermoplastic semi-finished in common thermoplastic

molding process

~ k ~ k - ~ k ^~ k