WO2003059993A1

WO2003059993A1 - An elastomeric composition, a method of preparing the composition, and a building block for an elastomeric composition

Info

Publication number: WO2003059993A1
Application number: PCT/DK2002/000907
Authority: WO
Inventors: Joachim KARTHÄUSER; Bjørn WINTHER-JENSEN
Original assignee: Nkt Research & Innovation A/S
Priority date: 2001-12-28
Filing date: 2002-12-23
Publication date: 2003-07-24
Also published as: AU2002367079A1

Abstract

The invention relates to an elastomeric composition comprising partly or totally coated solid particles, and primary polymer chains, wherein said particles being coated with one or more layers wherein the outermost comprises C atoms and/or Si atoms, and the coated particles are chemically linked via the outermost layer to said primary polymer chains and optionally to each other to thereby form a network, said chemically links preferably being covalent links such as C-C links or Si-C links. The coating on the solid particles may preferably be covalently linked to the particle. The invention also relates to a method of producing the elastomeric particles as will as an intermediate product therefore. The elastomeric composition has increased wear strength and is relatively cheap compared to comparable elastomers.

Description

An elastomeric composition, a method of preparing the composition, and a building block for an elastomeric composition

The present invention relates to a novel elastomeric composition, a method of preparing it as well as a building block for an elastomeric composition.

The term elastomeric composition includes elastomers, thermoplastics, and cross-linked polymers therefrom. Generally a large amount of different elastomer composition are known. Some of the most used compositions includes rubbers such as polybutadiene, ethylene- propylene rubber, polyisopren and natural rubber; thermoplastics such as polyethylene, polypropylene, polyvinyl, polystyrene and polycarbonate; ionomers such as poly (ethylene-co-methacrylic acid); block co-polymers such as SBS, SIS, SEBS and etc. Other examples of elastomeric compositions are described in EP 626 978, US 4,431,777, US 4,925894 and GB 1,056,247.

When selecting an elastomeric composition for a specific product a large number of properties normally should be fulfilled i.e. mechanical strength, elongation, stress strength modulus, resistance to acids and other chemicals, wearing qualities and many other properties. Generally it can be said that it is possible to find an optimal elastomeric polymer composition for any use. The problem in this connection is that in most situations this will be a too expensive polymer composition or it will be too expensive to use or shaping the material if it cannot be shaped using injection molding. Therefore the choice will often be a compromise between properties and cost . The objective of the present invention is to provide a novel elastomeric composition, which has relative good properties with respect to mechanical properties such as stress, strength, resistance to chemicals and wear resistance versus its cost compared to known polymeric compositions and thereby provide a further possibility to the constructors when selecting a polymer composition for a specific product.

This objective has been achieved by the elastomeric composition as it is defined in the claims. Further more the invention as defined in the claims includes a method of preparing it as well as a building block for the elastomeric composition.

It has surprisingly been found that it is possible to chemically bind solid particles in a polymeric matrix to thereby provide a novel elastomeric composition with a novel property matrix and/or to provide a novel elastomeric composition which is less expensive than comparable elastomeric compositions.

The elastomeric composition according to the invention has furthermore shown to be injection mouldable, which is a major advantage.

In the present contest the term elastomeric composition includes elastomers, thermoplastics, and cross-linked polymers therefrom which do still exhibit elastomeric properties. The elastomeric composition according to the invention should preferably have an elongation of at least 1%. The elastomeric composition should preferably have a Tg value above room temperature i.e. thermoplastic elastomers are preferred. Generally the Tg value of the elastomeric composition or in case it is a thermoplastic elastomer, blocks of the elastomeric composition comprising block copolymers should have a Tg value below

20 °C, preferably below 0 °C, such as around -85 °C (polybutadien or blocks of polybutadien) .

The elastomeric composition according to the invention comprises

i. partly or totally coated solid particles, and i. polymer chains, in the following denoted "^{^}primary polymer chains¹'.

The particles may in principle be any type of particles solid at room temperature. The particles may preferably solid at a temperature up to at least about 100 °C . The fillers mat thus, e.g. be in the form of inorganic material selected from the group consisting of glass, silica, silicon dioxide, ceramics, carbon, minerals and metal, such as bronze and mixtures thereof. The particles may also be in the form of organic material preferably a polymeric material such as polymers selected from the group consisting of olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof

In one embodiment the particles is of a thermoplastic material having a melt point above about 120 °C. In one embodiment it is desired that the particles is of an inorganic material, more preferably of glass or carbon.

The particles may have any shape, and it may be porous or nonporous. Preferably the solid particles is essentially non-porous. The particles may e.g. be in the form of fibres, beads and/or powder.

The size of the particles measured without coating may vary in dependence of the properties desired in the final elastomeric compositions. In one embodiment it is preferred that at least 90 % by weight of the particles have a size between 1 nm and 1000 μm, more preferably between 10 and 600 μm, and even more preferably between 1 and 100 μm measured using sieving.

In one preferred embodiment of the elastomeric compositions according to the invention the solid particles are in the form of glass beads, the size of the beads preferably being so that at least 90 % of the beads are in the interval 5-50 μm measured using sieving.

The particles is partly or totally coated with one or more layers i.e. up to for example 10 layers of a material as will be discussed in further detain below.

The innermost layer is designated a primary primer layer, the outermost layer is designated a secondary primer layer. In one embodiment is it is most preferred that the particles is totally coated with at least the outermost layer, and preferably with all layers if more than one layer. In one preferred embodiment the particles are coated with one primer layer only, i.e. this one primer layer constitutes both the innermost primer layer and the outermost primer layer.

In another preferred embodiment the particles is coated with two primer layers, wherein these two layers constitute, respectively, the innermost primer layer and the outermost primer layer.

The secondary primer layer should comprise C atoms and/or Si atoms. The amount of C atoms and/or Si atoms should preferably be at least 1 per 1000 atoms of the material, more preferably least 1 per 100 atoms of the material. These C atoms and/or Si atoms should preferably be evenly distributed in the material, to provide an essentially homogeneous surface of the outermost primer layer for bonding to the primary polymer chains. If there is more than one layer, the primary primer layer may preferably also comprise C atoms and/or Si atoms, and it is more preferred that the amount of C atoms and/or Si atoms should be at least 1 per 1000 atoms of the material, even more preferably least 1 per 100 atoms of the material.

In one preferred embodiment of the elastomeric compositions according to the invention the secondary primer layer is of a material comprising oxygen atoms and/or halogen atoms, preferably in the form of organic groups carrying electronegative group, more preferably selected from the group consisting of ester groups and halogen acid groups .

In one embodiment of the elastomeric composition according to the invention the particles is coated with two or more layers, where these two or more layers being chemically linked to each other, preferably in the form of covalent links.

In one embodiment the first primer layer and the secondary primer layer contain hydrogen atoms, and the first primer layer and the secondary primer layer, independently of each other, contain material selected from the group consisting of paraffin's, olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof.

The first primer layer and the secondary primer layer may furthermore, independently of each other, consist essentially of a polymeric material, whereby said polymeric material can be described as being built up from monomers having a boiling point of up to 80 °C measured at standard conditions (1 atm.) .

Generally it is preferred that the secondary primer layer being of a material which is initiable by contact with an anionic initiator to thereby form carbanions . In this context an anionic initiator should preferably be a chemical compound having a pH value above 10, such as an organo-metallic compound e.g. a group I and II organo- metallic compound such as alkali metal alkyl having 2-8 C atoms, alkaline earth metal alkyl having 2-8 C atoms, alkali metal alkene having 2-8 C atoms, alkaline earth metal alkene having 2-8 C atoms alkali metal aryl having 4-10 C atoms, alkaline earth metal aryl having 4-10 C atoms, wherein said alkene and/or said alkyl group (s) being linear or branched.

It is generally preferred that the first primer layer being chemically linked to the particles, to thereby provide an elastomeric composition with a high wearing quality. The chemically links may preferably being covalent links such as one or more of the links C-metal, Si-metal, C-mineral, Si-mineral and more preferably C-C and Si-C links. This chemically bonded layer may e.g. be provide using plasm as described further below.

The primary polymer chains may in principle have any length, but preferable the primary polymer chains should comprise at least 500 C atoms, more preferably between 2000 and 10 000 C atoms.

Generally it is preferred that the primary polymer chains should be polymerised using anionic polymerisation, more preferably said primary polymer chains being polymerised from monomers selected from the group consisting of dienes having 4-8 C atoms, linear or cyclic olefins having 2-8 C atoms and mixtures thereof.

In one preferred embodiment of the elastomeric compositions according to the invention the primary polymer chains is polymerised from monomers comprising and preferably essentially consisting of styrene and dienes having 4-8 C atoms, more preferably from styrene and butadiene and/or isoprene.

In another preferred embodiment is particularly preferred that the primary polymer chains comprises at least one and preferably two double bonds Examples of primary polymer chains include polybutadiene, polyisoprene, styrene-butadien or styrene copolymer, partly or fully halogenated or hydrogenated polydiene and mixtures thereof. Furthermore the primary polymer chains may be grafted with one or more units in the form of polar compounds, preferably selected from the group consisting of sulphur trioxide, oxides of nitrogen and other oxides .

The coated particles is chemically linked via the secondary primer layer to the polymer blocks and optionally to each other, wherein these chemically links e.g. are covalent links such as C-C links or Si-C links.

Generally it is preferred that the weight ratio between the coated particles and primary polymer chains should be between 10:90 and 95:5, preferably between 20:80 and 80:20, more preferably between 30:70 and 70:30.

Generally it is preferred that the elastomeric composition according to the invention is cross-linked either using a cross-linking agent or by vulcanising.

In one particularly preferred embodiment of the elastomeric composition according to the invention the composition comprises building blocks consisting of the coated particles linked to the primary polymer chains wherein, said building blocks being cross-linked to it self and/or to one or more polymeric cross-linkable units, preferably selected from the group consisting of elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof. The term ^{^}being cross-linked to it self'¹ means being cross-linked to it self or to other building blocks falling under the definition of the building blocks.

Even more preferred aspects of the above preferred embodiment will be described further below and with reference to the figures.

In one variation of the above described particular preferred embodiment of the elastomeric composition according to the invention the building blocks and said one or more polymeric cross-linkable units is vulcanised.

Generally the elastomeric composition according to the invention preferably should comprise one or more of the building blocks

coated particle [ polydiene ] _n (I)

wherein n represent an integer of at least 1, preferably between 10 and 1000, more preferably between 5 and 100;

coated particle [[polydiene ]_y [polystyrene] _n (II)

wherein n represent an integer of at least 1, preferably between 1 and 1000, more preferably between 5 and 100, and y and z represent an integer of preferably 1, and wherein y 0 z or z+1;

The elastomeric composition according to the invention may in principle comprise op to about 99 % by weight, such as up to about 75 % or 50 % by weight of other material than the building blocks composed of coated particles and primary chains . This material may in principle be any material provided that an elastomeric composition is formed, preferably an elastomeric composition having a Tg value below 20 °C. The composition may therefore comprising up to about 99 % by weight such as up to about 75 % or 50 % by weight of elastomeric polymers preferably selected from the group consisting of polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene , polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene , polypropylene, cellulose, nitrocellulose, natural rubber, butyl rubber, styrene butadiene rubber, bitumen, silicone rubber, polysilicates and mixtures thereof.

Furthermore, the composition may comprise up to about 50% by weight such as up to about 40 % or 25 % by weight of fillers preferably selected from the group consisting of carbon black, glass particles, mineral fibres, talcum, carbonates, mica, and silicates. It should be noted that the coated fibres chemically incorporated in the composition do not represent a filler material in this context .

The invention also relates to the building block as defined in the claims, wherein said building block preferably has the formula (I) or (II) as described above

The elastomeric composition may preferably be prepared according to the method defined in the claims. This method comprise the steps of i. providing solid particles of inorganic or organic material,

ii. coating said particles with one or more layers wherein the innermost layer is designated a primary primer layer, the outermost layer is designated a secondary primer layer, said secondary primer layer comprising C atoms and/or Si atoms,

iii. providing and chemically linking at least one primary polymer chain to said outermost primer layer.

The solid particles (type, size, shape etc.) and the one or more layers (type, combinations etc.), may be as described above when describing the elastomeric composition.

The one or more layers may be applied by any method as known in the art, e.g. as described in US 2448391, US 5798142 and US 5665424.

In one embodiment is, however, most preferred that at least one of said one or more layers being applied to said particles using a plasma process. Mostly it is preferred that all layers if more than one, are applied using a plasma method.

Method of applying coatings using plasma is generally known and further reference is made to patent application P200000446 DK, US 5876753, WO 97/21497 US 5290378, which is hereby incorporated by reference . Generally it is preferred using the method described in P200000446 DK is situations where the particles are of carbon or glass.

The method therefore preferably includes a step of activating the surfaces by generating radicals on the surfaces of the particles by subjecting the surfaces to a reducing gas plasma and forming a layer on the substrate surface using a plasma enhanced polymerisation process employing one or more monomers with a sufficient low molecular weight for them to be in their gaseous state in the gas plasma.

Prior to the step of activating the surfaces of the particles may preferably be cleaned by subjecting the surface to reducing gas plasma without monomers .

Most preferable at least the innermost primer layer should be applied to particles using a plasma process, thereby a covalent bonding between the particles and the primary polymer chains can be provided.

The monomers for the plasma treatment may preferably be selected from the group consisting of C^C^ alkanes, C₂- C₁₆ alkenes, C₂-C₁₆ alkynes, C₂-C₁₆ alkynes, styrene, aromatic monomers of styrene compounds, monomers of vinyl- and acrylate- compounds.

The step of providing and chemically linking at least one primary polymer chain to said outermost primer layer may in principle be carried out using two different sub- methods . In the first sub-method the step of providing and chemically linking at least one primary polymer chain to said outermost primer layer includes the sub-steps

a) subjecting the outermost primer layer to an anionic initiator, and

b) polymerisation of monomer or prepolymer onto said outermost primer layer via anionic polymerisation to thereby linking said at least one primary chain to said outermost primer layer.

Thereby the surface of the outermost primer layer is initiated by the contact with the anionic initiator and C^" and/or Si^" ions exposed on the surface, onto these ions the monomers are directly polymerised using anionic polymerisation to finally provide at least one primary chain linked to said outermost primer layer.

In the second sub-method of providing and chemically linking at least one primary polymer chain to said outermost primer layer, the secondary primer layer should preferably further comprise organic groups carrying electronegative group, preferably selected from the group consisting of ester groups and halogen acid groups, the second sub-method includes the sub-steps

a ' ) providing primary polymer chains by mixing monomers and an anionic initiator,

b ') combining and chemically reacting said coated particles and polymer chains with each other to thereby chemically linking said at least one primary chain to said outermost primer layer. Thereby the primary polymer chain (s) are polymerised using an anionic initiator, where after the coated particles are added and due to the anionic polymerisation the primary polymer chains will still be activated i.e. comprising C^" and/or Si^" ions, which ions will react with electronegative group exposed on the surface of the outermost primer layer to thereby link the primary polymer chain (s) to the coated particles and to finally provide at least one primary chain linked to the outermost primer layer.

The primary polymer chain may in length, type, composition and other be as described above when describing the elastomeric composition.

The anionic initiator may be any type of anionic initiator. Preferably the anionic initiator includes a chemical compound having a pH value above 10, more preferably an organo-metallic compound even more preferably group I and II organo-metallic compounds such as alkali metal alkyl having 2-8 C atoms, alkaline earth metal alkyl having 2-8 C atoms, alkali metal alkene having 2-8 C atoms, alkaline earth metal alkene having 2- 8 C atoms alkali metal aryl having 4-10 C atoms, alkaline earth metal aryl having 4-10 C atoms, wherein said alkene and/or said alkyl group (s) being linear or branched.

The most used and preferred anionic initiator is organo- lithium, preferably selected from the group consisting of alkyl-lithium and phenyl-lithium. This initiator is thus both effective and not too expensive. The anionic initiator may preferably be brought into contact with the outermost primer layer when using the first sub-method or may be mixed with said monomers when using the second sub-method in the form of a solution or dispersion in an solvent . The skilled person will easily be able to find a suitable solvent. Preferably the solvent is a paraffinic solvents including linear and cyclic C4-C8 compounds, more preferably selected from the group consisting of hexane, cyclohexane, pentane and cyclopentane . During the anionic polymerisation the solution wherein the polymerisation takes place, should preferably be free of water or other anion-terminating component, as this may reduce or terminate the polymerisation .

The weight ratio between the coated particles and primary polymer chains may be as described above when describing the elastomeric composition.

The method further includes the step of cross-linking the elastomeric composition either using a cross-linking agent or by vulcanising.

The method of cross-link may be carried out using any conventional process.

' In one particularly preferred embodiment of method according to the invention wherein the composition comprising building blocks consisting of the coated particles linked to the primary polymer chains, the method includes the step of cross-linking the building blocks to it self and/or to one or more polymeric cross- linkable units, preferably selected from the group consisting of elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof .

The building blocks may preferably be as described above when describing the elastomeric composition.

As mentioned above more preferred aspects of the above preferred embodiment will be described further below and with reference to the figures.

The method according to the invention may further comprise the step of mixing the elastomeric material with other materials to obtain an elastomeric composition comprising at least 1 % by weight of the coated particles linked to primary chains. The additional material may be as described above when describing the elastomeric composition.

The invention also relates to an elastomeric composition obtainable according to the method as defined in the claims as well as an elastomeric composition comprising a building block as defined in the claims.

The elastomeric composition may be used in almost any materials, such as for preparing and modifying asphalt as used in road construction, roofing and waterproofing membranes, for preparing and modifying heavy duty-rubber products such as tires, carrier belts, drive belts, for preparing and modifying adhesives, sealant and coatings, and for preparing and modifying polymer formulations and compounds useful for injection moulding, extrusion and calendering of elastic items. FIGURES

Figure 1 is a schematic illustration of the process of linking polymer chains to a solid bead.

Figure 2 illustrate a building block comprising solid particle with isoprene/butadien and styrene blocks.

Figure 3 illustrates an elastomer with soft and hard domains, where some of the hard domains are made from solid particles.

According to the schematic illustration shown in figure 1, the elastomeric building blocks according to the invention may be produced by selecting a solid particle e.g. a glass bead 1, and coating it with a monomer using plasma as described above, to thereby provide a polymer coating 2 which is chemically linked to the surface of the bead. Thereafter the polymer coating it treated with organo-metallic compound in the presence of diene monomer whereby an anionic polymerisation is initiated to provide primary polymer chains 3 linked to the polymer coating 3. The building block may be further modified by adding styrene monomer and re-initiate by adding further BuLi.

Figure illustrates a similar building block. In this illustration, the size of the different components is indicated. The solid particle 12 which may e.g. be a glass fibre comprise several primary chains composed of soft domains (isoprene and/or butadiene) and hard domains (styrene) . The soft blocks may e.g. have a length of 100- 300 n and the styrene blocks may e.g. have a length of around 100 nm. Figure 3 is an illustration of an elastomer comprising solid particles in the form of glass beads 20. The glass beads are coated as described above and broad into contact with monomers including styrene and diene and an initiator for providing a net-work of diene blocks 22, and styrene blocks 21.

EXAMPLES

Example 1 :

Glass fibers made of E-glass, and with typical dimensions: average length 75 μm and average diameter 15 μm are subjected to a plasma coating process according to patent application P200000446 DK.

In an experimental series (a) - (c) , a primary primer coating is of paraffinic nature whilst a secondary primer coating is a plasma coating, which is different from serie to serie, and consists of (a) epoxy groups, (b) chlorine groups and (c) ester groups.

The plasma coatings on the fibers treated in this way cannot be extracted from the fibers or removed by solvents, indicating that strong (covalent) chemical links is formed between the fibers and the coatings. The total weight of the plasma coating (all layers) is 0.2 % of the weight of the fibers.

After the plasma process, the fibers are transferred to a vessel suitable for chemical syntheses under exclusion of moisture. The fibers are dried at elevated temperature and high vacuum (150-200 °C, < 1 μbar) for 8 hours. After drying, the fibers are not acting as agents preventing anionic polymerisation reactions, indicating both full coverage of the glass fiber surfaces, and absence of any residual water and residual hydroxyl groups from the glass fiber surfaces.

To a quantity of glass fibers, a solution containing

''living polymer'' composed of lithium salts of diblock copolymers consisting of (a) polyisoprene and (b) polyisoprene coupled to polystyrene is added. The living polymer being prepared from styrene or styrene/isoprene and an anionic initiator BuLi as it is generally known in the art. The weight ratio between glass fibers and living polymer being 20:80.

After completion of the coupling reaction, the elastomeric composition formed is analysed for mol weight distribution. Based on the results, the reactivity of plasma coatings in coupling reactions with bulky anions can be ranked as follows:

Epoxy > halogene (chlorine) >> ester.

After having removed the lithium salts by washing and after removal of the solvent (cyclohexane) , it was not possible to remove the glass beads from the polymer matrix.

Example 2 :

Glass fibers made of E-glass, and with typical dimensions: average length 75 μm and average diameter 15 μm are subjected to a plasma coating process as in example 1.

In an experimental series (a) - (c) , a primary primer coating is of paraffinic nature whilst secondary primer coating is varied and consists of (a) vinyl double bonds, (b) other, partly conjugated double bonds on the basis of acetylene or diolefins and (c) ester and carbonyl groups.

The plasma coatings on the fibers treated in this way cannot be extracted from the fibers or removed by solvents, indicating that strong (covalent) chemical links are formed between the fibers and the coatings. The total weight of the plasma coating (all layers) is 0.2 % of the weight of the fibers.

To a quantity of glass fibers treated in the manner described above, a paraffinic solvent (cyclopentane) is added, and a quantity of strong base (lithiumbutyl) sufficient to abstract acidic protons from the plasma coating. Thereafter, isoprene is fed into the reactor, leading to polymerisation starting from the glass beads, however, in a competitive reaction also from the dissolved feedstock monomer.

After completion of the polymerisation, the polymer formed is analysed for mol weight distribution. Based on those results, the suitability of plasma coatings for maximum polymerisation starting from the glass beads can be ranked as follows:

vinyl > diolefins > carbonyl containing >> acetylene. Irrespective of the monomer used for the plasma coating, usage of a very low energy level during plasma polymerisation is recommended. This way cross-linking of the plasma coating is minimized, effecting possibly a higher yield of abstractable protons and better stereochemical accessibility of the reactive sites.

Claims

1. An elastomeric composition comprising

iii. partly or totally coated solid particles, and iv. primary polymer chains,

wherein said particles being coated with one or more layers wherein the innermost layer is designated a primary primer layer, the outermost layer is designated a secondary primer layer, said secondary primer layer comprising C atoms and/or Si atoms, and

said coated particles being chemically linked via said secondary primer layer to said primary polymer chains and optionally to each other to thereby form a network, said chemically links preferably being covalent links such as C-C links or Si-C links.

2. An elastomeric composition according to claim 1 wherein said primary polymer chains comprising at least 500 C atoms, more preferably comprising between 2000 and 10 000 C atoms,

3. An elastomeric composition according to any one of the claims 1 and 2 wherein said primary polymer chains being polymerised using anionic polymerisation, preferably said primary polymer chains being polymerised from monomers selected from the group consisting of dienes having 4-8 C atoms, linear or cyclic olefins having 2-8 C atoms and mixtures thereof .

4. An elastomeric composition according to claim 3 wherein said primary polymer chains being polymerised from monomers comprising styrene and dienes having 4-8 C atoms, more preferably from styrene and butadiene and/or isoprene.

5. An elastomeric composition according to any one of the preceding claims wherein said primary polymer chains comprises at least one and preferably two double bonds, said primary polymer chains preferably being selected from the group consisting of polybutadiene, polyisoprene, styrene-butadien or styrene copolymer, partly or fully halogenated or hydrogenated polydiene and mixtures thereof, said primary polymer chains optionally being grafted with one or more units in the form of polar compounds, preferably selected from the group consisting of sulphur trioxide and oxides of nitrogen.

6. An elastomeric composition according to any one of the preceding claims wherein said secondary primer layer is of a material comprising oxygen atoms and/or halogen atoms .

7. An elastomeric composition according to any one of the preceding claims wherein said particles being coated with one single layer constituting both the primary and the secondary primer layer, said layer preferably being covalently linked to the particles.

8. An elastomeric composition according to any one of the preceding claims 1-6 wherein said particles being coated with two or more layers, said two or more layers being chemically linked to each other, preferably in the form of covalent links, more preferably said primary primer layer being covalently linked to the particles.

9. An elastomeric composition according to any one of the preceding claims wherein said first primer layer and said secondary primer layer contain hydrogen atoms, and said first primer layer and said secondary primer layer independently of each other contain material selected from the group consisting of paraffin's, olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof.

10. An elastomeric composition according to any one of the preceding claims wherein said first primer layer and said secondary primer layer independently of each other consist essentially of a polymeric material, whereby said polymeric material can be described as being built up from monomers having a boiling point of up to 80 °C.

11. An elastomeric composition according to any one of the preceding claims wherein said first primer layer being chemically linked to said particles, said chemically links preferably being covalent links such one or more of the links C-metal, Si-metal, C-mineral, Si- mineral and more preferably C-C and Si-C links.

12. An elastomeric composition according to any one of the preceding claims wherein said secondary primer layer being of a material which is initiable by contact with an anionic initiator to thereby form carbanions, wherein said anionic initiator preferably being selected from the group consisting of chemical compound having a pH value above 10, preferably an organo-metallic compound more preferably group I and II organo-metallic compound such as alkali metal alkyl having 2-8 C atoms, alkaline earth metal alkyl having 2-8 C atoms, alkali metal alkene having 2-8 C atoms, alkaline earth metal alkene having 2- 8 C atoms alkali metal aryl having 4-10 C atoms, alkaline earth metal aryl having 4-10 C atoms, wherein said alkene and/or said alkyl group (s) being linear or branched.

13. An elastomeric composition according to any one of the preceding claims wherein said particles being of an inorganic material selected from the group consisting of glass, silicon dioxide, ceramics, carbon, minerals and metal such as bronze and mixtures thereof.

14. An elastomeric composition according to any one of the preceding claims wherein said particles being of an organic material preferably a polymeric material such as polymers selected from . the group consisting of olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof said, particles more preferably being of a thermoplastic material having a melt point above about 120 °C

15. An elastomeric composition according to any one of the preceding claims wherein said particles being in the form of fibres, beads and/or powder.

16. An elastomeric composition according to any one of the preceding claims wherein at least 90 % by weight of the particles having a size between 1 nm and 1000 μm, preferably between 10 and 600 μm, and even more preferably between 1 and 100 μm measured using sieving.

17. An elastomeric composition according to any one of the preceding claims wherein the weight ratio between the coated particles and primary polymer chains being between 10:90 and 95:5, preferably between 20:80 and 80:20, more preferably between 30:70 and 70:30.

18. An elastomeric composition according to any one of the preceding claims wherein building blocks consisting of said coated particles linked to said primary polymer chains, said building blocks being cross-linked to it self and/or to one or more polymeric cross-linkable units, preferably selected from the group consisting of elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof .

19. An elastomeric composition according to claim 18 wherein said building blocks and said one or more polymeric cross-linkable units being vulcanised.

20. An elastomeric composition according to any one of the preceding claims 18-19 wherein the composition comprise the building block

coated particle [ polydiene ] _n (I )

21. An elastomeric composition according to any one of the preceding claims 1-18 wherein the composition comprise the building block

coated particle [[polydiene ]_y [polystyrene] _n (II)

22. An elastomeric composition according to any one of the preceding claims further comprising up to about 99 % by weight of elastomeric polymers preferably selected from the group consisting of polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile , polymethylmethacrylate, polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, natural rubber, butyl rubber, styrene butadiene rubber, bitumen, silicone rubber, polysilicates and mixtures thereof .

23. An elastomeric composition according to any one of the preceding claims wherein the composition further comprise up to about 50% of fillers preferably selected from the group consisting of carbon black, glass particles, mineral fibres, talcum, carbonates, mica, and silicates .

24. A building block for an elastomeric composition consisting essentially of

i. partly or totally coated solid particles, and i. polymer chains designated primary polymer chains,

wherein said particles being coated with one or more layers wherein the innermost layer is designated a primary primer layer, the outermost layer is designated a secondary primer layer, said secondary primer layer comprising C atoms and/or Si atoms,

said coated particles being chemically linked via said secondary primer layer to said polymer blocks, said chemically links preferably being covalent links such as C-C links or Si-C links.

25. A building block according to claim 24 having the formula

coated particle [polydiene ]_n (I)

26. A building block according to claim 24 having the formula

coated particle [[polydiene ] [polystyrene] _z] _n (II)

27. A method of preparing an elastomeric composition comprising the steps of

iv. providing solid particles of inorganic or organic material

v. coating said particles with one or more layers wherein the innermost layer is designated a primary primer layer, the outermost layer is designated a secondary primer layer, said secondary primer layer comprising C atoms and/or Si atoms,

i . providing and chemically linking at least one primary polymer chain to said outermost primer layer.

28. A method according to claim 27 said step of providing and chemically linking at least one primary polymer chain to said outermost primer layer includes the sub-step

c) subjecting the outermost primer layer to an anionic initiator, and

d) polymerisation of monomer or prepolymer onto said outermost primer layer via anionic polymerisation to thereby linking said at least one primary chain to said outermost primer layer.

29. A method according to claim 27 said step of providing and chemically linking at least one primary polymer chain to said outermost primer layer wherein said secondary primer layer further comprises organic groups carrying electronegative group, preferably selected from the group consisting of ester groups and halogen acid groups, said method includes the sub-steps

b ' ) combining and chemically reacting said particles and polymers with each to thereby chemically linking said at least one primary chain to said outermost primer layer.

30. A method according to any one of the preceding claims 27-29 wherein said primary polymer chains comprising at least 500 C atoms, more preferably at least 1000 C atoms.

31. A method according to any one of the preceding claims 27-31 wherein said primary polymer chains being polymerised from monomers selected from the group consisting of dienes having 4-8 C atoms, linear or cyclic olefins having 2-8 C atoms and mixtures thereof.

32. A method according to claim 31 wherein said primary polymer chains being polymerised from monomers comprising styrene and dienes having 4-8 C atoms more preferably from styrene and butadiene .

33. A method according to any one of the preceding claims 27-32 wherein said particles being coated with one single layer constituting both the primary and the secondary primer layer.

34. A method according to any one of the preceding claims 27-32 wherein said particles being coated with two or more layers, said two or more layers being chemically linked to each other, preferably in the form of covalent links .

35. A method according to any one of the preceding claims 27-34 wherein at least one of said one or more layers being applied to said particles using a plasma process.

36. A method according to claim 35 wherein the plasma treatment comprises the step of activating the surfaces by generating radicals on the surfaces of the particles by subjecting the surfaces to a reducing gas plasma and forming a layer on the substrate surface using a plasma enhanced polymerization process employing one or more monomers comprising monomers with a sufficient low molecular weight for them to be in their gaseous state in the gas plasma.

37. A method according to any one of the preceding claims 35 and 36 wherein at least the innermost primer layer being applied to said particles using a plasma process, said innermost primer layer preferably also constitute the outermost primer layer.

38. A method according to any one of the preceding claims 35 - 37 wherein the monomers for the plasma treatment being selected from the group consisting of C_X-C_1S alkanes, C₂-C₁₆ alkenes, C₂-C₁₆ alkynes, C₂-C₁₆ alkynes, styrene, aromatic monomers of styrene compounds, monomers of vinyl- and acrylate- compounds, preferably said surfaces of the particles being cleaned prior to the step of activating by subjecting the surface to a reducing gas plasma.

39. A method according to any one of the preceding claims 27-38 wherein said anionic initiator being selected from the group consisting of chemical compound having a pH value above 10, preferably an organo-metallic compound more preferably group I and II organo-metallic compound such as alkali metal alkyl having 2-8 C atoms, alkaline earth metal alkyl having 2-8 C atoms, alkali metal alkene having 2-8 C atoms, alkaline earth metal alkene having 2- 8 C atoms alkali metal aryl having 4-10 C atoms, alkaline earth metal aryl having 4-10 C atoms, wherein said alkene and/or said alkyl group (s) being linear or branched.

40. A method according to claim 39 wherein said anionic initiator being organo-lithium, preferably selected from the group consisting of alkyl-lithium and phenyl-lithium.

41. A method according to any one of the preceding claims 27-40 wherein said anionic initiator being brought into contact with said outermost primer layer or being mixed with said monomers in the form of a solution or dispersion in an solvent preferably a paraffinic solvents including linear and cyclic C4-C8 compounds, more preferably selected hexane, cyclohexane, pentane and cyclopentane .

42. A method according to any one of the preceding claims 27-41 wherein said particles being of an inorganic material selected from the group consisting of glass, silicon dioxide, ceramics, carbon, minerals and metal such as bronze and mixtures thereof .

43. A method according to any one of the preceding claims 27-42 wherein said particles being of an organic material organic material preferably a polymeric material such as polymers selected from the group consisting of olefins polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber, silicates, polysilicates and mixtures thereof, said particles more preferably being of a thermoplastic material having a melt point above about 120 °C.

44. A method according to any one of the preceding claims 27-43 wherein said particles being in the form of fibres, beads, powder.

45. A method according to any one of the preceding claims 27-44 wherein at least 90 % by weight of the particles having a size between 1 nm and 1000 μm, preferably between 10 and 600 μm, and even more preferably between 1 and 100 μm measured using sieving.

46. A method according to claim 45 wherein the weight ratio between the coated particles and primary polymer chains being between 10:90 and 95:5, preferably between 20:80 and 80:20, more preferably between 30:70 and 70:30.

47. A method according to any one of the preceding claims 27-46 further comprising the step of cross-linking building blocks consisting of said coated particles linked to said primary polymer chains to it self and/or to one or more polymeric cross-linkable units, preferably selected from the group consisting of elastomers such as polyolefin, polybutadiene, polyisoprene, styrene-butadien copolymer, partly or fully halogenated polydiene and mixtures thereof .

48. A method according to claim 47 wherein said building blocks and said one or more polymeric cross-linkable units being vulcanised.

49. A method according to any one of the preceding claims 47-48 wherein the building block has the formula (I)

coated particle [ polydiene ] _n (I)

50. A method according to any one of the preceding claims 27-46 wherein monomer or prepolymer of dienes and styrene groups are polymerised onto said secondary primer layer preferably to form a the building block (II) , said building block constitute or being part of the composition coated particle [[polydiene ]_n styrene]_m (II)

51. A method according to any one of the preceding claims 27-50 further comprising the step of mixing the building blocks comprising coated particles linked to primary chains with up to about 99 %, by weight of elastomeric polymers preferably selected from the group consisting of polyolefines such as polyethylene; polystyrene, polivinylacetate, polyviylchloride, polyvinylpyrrolidene, polyacrylonitrile , polymethylmethacrylate , polytetrafluoroethylene, polypropylene, cellulose, nitrocellulose, natural rubber, butyl rubber, styrene butadiene rubber, bitumen, silicone rubber, polysilicates and mixtures thereof .

52. A method according to any one of the preceding claims 27-51 further comprising the step of mixing the building blocks comprising coated particles linked to primary chains with up to about 50% of fillers preferably selected from the group consisting of carbon black, glass particles, and mineral fibres.

53. An elastomeric composition obtainable according to any one of the claims 27-52.

54. An elastomeric composition comprising a building block as defined in any one of the claims 24-26.

55. Use of an elastomeric composition as defined in anyone of the claims 1-23 for preparing and modifying asphalt as used in road construction, roofing and waterproofing membranes.

56. Use of an elastomeric composition as defined in anyone of the claims 1-23 for preparing and modifying heavy duty-rubber products such as tires, carrier belts, drive belts.

57. Use of an elastomeric composition as defined in anyone of the claims 1-23 for preparing and modifying adhesives, sealant and coatings.

58. Use of an elastomeric composition as defined in anyone of the claims 1-23 for preparing and modifying polymer formulations and compounds useful for injection moulding, extrusion and calendering of elastic items.