JP2003246811A - Polymer-type material comprising silica particle, method for producing it and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer-type material, which can reduce a friction between joint parts of a joint implant or an artificial joint in a medical care engineering field and which at least partially overcomes problems of conventional technologies, and a production method therefor. <P>SOLUTION: The method for producing the polymer-type material comprising a polyolefin matrix and a silica particle as a filler, wherein the silica particle is compounded at least before completion of a polymerization process, is provided. The polymer-type material produced by the method is used for producing the joint implants, the artificial joints, sliding bearings, gears and other engineering parts. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer-based material containing a polyolefin matrix and silica particles as a filler, a method for producing the same, and an artificial joint or a joint implant using the polymer material.

[0002]

2. Description of the Prior Art For artificial joints or joint implants,
Various materials and combinations of materials are used, especially at different prices and durability. The combination of a suitable metal alloy with ultra high molecular weight polyethylene (sometimes referred to as UHMWPE) is one of the cheaper approaches to making the majority of such artificial joints or implants. Such a “metal-on-polymer” implant is described, for example, in US Pat.

[0003]

The drawback of the metal / UHMWPE combination is that the static friction existing between the metal and the plastic makes the plastic part prone to wear, and the UHMWPE
However, it is vulnerable to mounting errors and damage during mounting due to contamination with bone particles or bone cement, for example.

[0004]

SUMMARY OF THE INVENTION It is therefore an object of the present invention, at least in part, to overcome the disadvantages of the prior art by means of a material capable of reducing the friction between two joint parts in a joint implant or artificial joint. The present invention provides a polymer-based material that can be used, a method for producing the same, and joint implants, artificial joints or plain bearings, gears, and other industrial parts in the medical engineering field using the polymer-based material.

[0005]

The present invention which can achieve the above object can be specified by the following matters. (1) A method for producing a polymer material containing a polyolefin matrix and silica particles as a filler, wherein the silica particles are blended at least before the completion of a polymerization process. (2) The silica particles have an average diameter of 10 to 500 nm.
Polyethylene oxide functionalized monodisperse silica particles, wherein the monodisperse silica particles are used as a metallocene carrier, and the amount of metallocene immobilized on the monodisperse silica particles is 1 mass of the product silica content. % To 50% by weight, so that a sufficient amount of polyolefin is selected to be formed during the polymerization, the method for producing a polymer-based material according to (1) above. (3) The production of the polymer-based material as described in (1) or (2) above, wherein the silica particles are silica particles carrying a polymerization-active Ziegler-Natta catalyst species or Phillips catalyst species. Method. (4) One of the above (1) to (3), characterized in that the alkyl-functionalized monodisperse silica particles are further mixed with a catalyst in a sufficient amount and the mixture is used for the polymerization. A method for producing the polymer-based material as described. (5) The method for producing a polymer-based material according to any one of (1) to (3) above, wherein the olefin-functionalized monodisperse silica particles are mixed before polymerization. (6) The silica particles are a polymer-based material composed of a polyethylene matrix which is nano-dispersed and uniformly distributed, and the silica particles are functionalized with a non-acidic nucleophilic species. Polymer-based material. (7) The polymer material according to (6) above, wherein the silica particles are functionalized with a polyethylene oxide chain. (8) The polymer-based material according to (6) above, wherein alkyl-functionalized silica particles or olefin-functionalized silica particles are used. (9) A polymer-based material obtained by the method according to any one of (1) to (5) above. (10) Use of the polymer-based material according to any of (6) to (9) above, for producing a joint implant in the medical engineering field. (11) Use of the polymer-based material according to any of (6) to (9) above, for producing a plain bearing, a gear or other industrial parts. (12) At least a part of the joint component is a prosthetic joint of a prosthesis made of a metal material, a polymer material, or a ceramic material, and at least one joint component of the artificial joint has a silica particle content of 1% by mass to 50% by mass. An artificial joint comprising a polymer material manufactured from a polyolefin to which is added. (13) The artificial joint as described in (12) above, wherein the polymer material is a polyolefin containing 5% by mass to 30% by mass of silica particles. (14) The artificial joint as described in (12) or (13) above, wherein the polymer material is ultra-high molecular weight polyethylene. (15) An artificial joint based on the polymer material obtained by the method according to any one of (1) to (5) above. (16) The artificial joint according to any one of (12) to (15), characterized in that the artificial joint is an artificial hip joint or an artificial knee joint. (12) At least a part of the joint component is a prosthetic artificial joint made of a metal material, a polymer material, or a ceramic material, and at least one joint component of the artificial joint includes a polyolefin matrix and silica particles as a filler. An artificial joint comprising a polymer material having a silica content of 1% by mass to 50% by mass. (13) The artificial joint as described in (12) above, wherein the silica content is 5% by mass to 30% by mass. (14) The artificial joint as described in (12) or (13) above, wherein the polyolefin matrix is ultra-high molecular weight polyethylene. (15) An artificial joint based on the polymer material obtained by the method according to any one of (1) to (5) above. (16) The artificial joint according to any one of (12) to (15), characterized in that the artificial joint is an artificial hip joint or an artificial knee joint.

Suitable polyolefin matrices can include all types of polyolefins. However, polyethylene (sometimes referred to as PE) is preferred.

Molded articles such as joint implants, artificial joints, sliding bearings, gears, and other industrial parts used in the medical engineering field are preferably 3.9 × 10 ⁶ g.
UH having an extremely large number average molecular weight (sometimes referred to as Mn) from 1 / mol to 10.5 × 10 ⁶ g / mol
It is molded using MWPE.

Some of the technically important properties of such polyethylenes, such as wear resistance, notched impact strength, dimensional stability on heating and lubricity, improve with increasing number average molecular weight. On the other hand, the processability of the high molecular weight PE tends to be impaired. Therefore, the use of a polyolefin matrix having good processability, such as a PE matrix, in a composite having good properties similar to or better than those with conventional PE in the past. What is possible is a feature of the present invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In an artificial prosthesis using an artificial joint, the required compatibility with human tissue or animal tissue (so-called biocompatibility) and the large friction stress of joint parts are limited to a small number of materials. It means that it cannot be used.

Among the metallic materials, cobalt / chromium (CoCrMo), in particular, has proved successful. Titanium-based alloy or surface-modified titanium alloy (for example,
The application of titanium nitride) is still in the experimental stage. Among the plastics, UHMWPE, in particular, is used in the socket part of hip endoprostheses and as the sliding part of tibial components. Aluminum oxide and zirconium oxide are possible ceramic materials.

Also in the joint implant and artificial joint of the present invention, some parts may include joint parts formed of these known materials.

Wear in artificial joints of joint parts made of polymeric materials, for example PE, is minimized by incorporating solid, non-porous silica beads or particles into the polymeric material. However, usually
It is difficult to uniformly disperse silica beads and silica particles.

According to the invention, in order to achieve a nanodispersed and very homogeneous distribution of silica (sometimes referred to as silicon dioxide or SiO ₂ ) particles in a polyolefin matrix of the polymeric material of the invention, for example PE. The particles are blended at least before the end of the polymerization process. When silica particles are blended in this way, the catalyst is fragmented during the polymerization and the formed fragments are finely dispersed in the reaction product matrix, whereby the silica particles are uniformly dispersed in the matrix in the form of nanoparticles (nanoparticles). It may be referred to as dispersion).

UHMWPE is not normally extruded, but instead is processed by the hot pressing method. However, in this method, the subsequent mixing of the filler cannot be easily performed, and it is very difficult to obtain a filler in which the filler is uniformly dispersed.

In the method of making the polymeric material of the present invention, various methods (or combinations thereof) can be employed to incorporate silica particles with suitable functionalization into the polyolefin matrix, at least prior to the end of the polymerization process.

As the silica particles that can be used in the present invention, those having an average particle diameter (sometimes referred to as an average particle diameter) of 10 to 500 nm are preferably used. Specific examples of preferable silica particles include, for example,
Mention may be made of monodisperse silica particles. The monodisperse silica particles are commercially available monospheres (Mon
ospheres (registered trademark)) 100 (manufactured by Merck,
Spherical silica particles, average diameter 100 nm, standard deviation of average diameter <5%), monospheres (Monospheres)
(Registered trademark)) 150 (manufactured by Merck, spherical silica particles,
The average diameter is 150 nm, and the standard deviation of the average diameter is <5%).

The silica particles used in the present invention are, for example,
It can be added to the polyolefin matrix by adding it with the metallocene and then using it for polymerization. The metallocene can be replaced by a polymerization active Ziegler-Natta catalyst species (eg TiCl ₄ ) or Phillips catalyst species. When silica particles are added in the above manner to polymerize ethene, PE is formed around the silica particles in this polymerization process, which may result in, for example, more than mixing during the extrusion process. A good uniform distribution of silica particles is achieved.

Based on the total mass of the mixture, silica is 1
It is preferred in this case to choose the addition in such a way that it is present in the polyolefin matrix in an amount of between 50% and 50% by weight. More preferably, the amount is 5% by mass to 30% by mass. High silica content (eg,
> 55% by mass), the polymer-based material tends to be brittle and fragile, so that the silica content is preferably adjusted according to the purpose.

Direct functionalization of compounds (primarily metallocene-like compounds) that can be activated with methylaluminoxane (MAO) by functionalizing silica particles with nucleophilic non-acidic compounds (eg polyethers). Will be possible. Silica particles functionalized with nucleophilic non-acidic compounds are sometimes referred to as carriers or nanoparticulate materials. The functionalized silica particles have a MA
A gel can be formed with O, thus the metallocene binds to the support via MAO. A homogeneous distribution of support and polymerization active species (sometimes referred to as catalyst species) is achieved in this process. After drying, the carrier supporting the catalyst species (sometimes referred to as a catalyst) is directly
It can be used as a catalyst for polymerization.

In the case of supporting the Ziegler-Natta catalyst species, the polymerization-active compound can be directly supported (for example, as TiCl ₄ vapor) on the silica particles and supported by a generally known method.

The polymerization can be carried out continuously or discontinuously by a known method in a solution state, a suspension state or a gas phase, but gas phase polymerization and suspension polymerization are particularly preferable. Typical temperatures in the polymerization are in the range 0 ° C to 200 ° C, preferably in the range 20 ° C to 140 ° C.

The addition of metallocene and activation of the catalyst is
It is selected in such a way that a catalyst productivity of 2 to 10 (gPE) / (g catalyst) is achieved. This corresponds to a silica content of 10% by weight to 50% by weight.

Catalysts commonly used for the production of polyolefins and aimed at high productivity are likewise prepared by "diluting" the correspondingly treated silica particles with the polymer-based material of the invention. It can be used in a manufacturing method. It is preferred in this case to use olefin-functionalized particles which no longer have reactive groups on their surface. Deactivation can be carried out first by olefin functionalization and by further treatment with an alkylaluminum compound (eg diisobutylaluminium hydride).

Alternatively, it is possible to immobilize the silica particles within a polyolefin matrix such as PE by alkyl or olefin functionalization of the silica particles. The functional groups introduced by such functionalization are included as copolymers in the polyolefin matrix, eg PE, in order to achieve particularly good fixation.

The compounds used for the above functionalization of the silica particles are, for example:

[0026]

[Chemical 1] In the formula, A is an alkoxy group, preferably an ethoxy group or a methoxy group, B is an alkoxy group or an alkyl group of the same type, preferably a methyl group, and D is
A hydrocarbon group having at least one terminal alkyl functional group, preferably a linear alkyl group having a terminal double bond.

X is a direct bond or (CH ₂ ) _n --O
Is any heteroatom-containing bond, such as-wherein n is 1 to 5.

For alkyl functionalization, for example, the following compounds are used:

[0029]

[Chemical 2] In the formula, A is an alkoxy group, preferably an ethoxy group or a methoxy group, B is an alkoxy group or an alkyl group of the same type, preferably a methyl group, and C is
It is an alkyl group having a length of 1 to 25 (preferably 10 to 20).

X is a direct bond or (CH ₂ ) _n --O
Is any heteroatom-containing bond, such as-wherein n is 1 to 5.

In the medical engineering field of the present invention, joint implants, artificial joints, joint parts used for manufacturing the artificial joints of the present invention, and methods for manufacturing sliding bearings, gears and other industrial parts are particularly limited. Not something. Considering various conditions such as the shape of the desired product, the required performance, the characteristics of the polymer-based material of the present invention used for the production of the product, an appropriate method is selected from the known production methods in the technical field. And use it. Further, additives such as an antioxidant, an ultraviolet absorber, a lubricant, a pigment and a filler, which are generally used in the art, can be added to the polymer material of the present invention.

The following examples and figures serve to explain the invention in more detail.

FIG. 1 shows a transmission electron micrograph of a polymer-based material of the present invention containing 8% by mass of silica and having PE as a matrix. This transmission electron micrograph is P
It was recorded at an accelerating voltage of 200 kV using a transmission electron microscope CM20 (trade name) manufactured by Philips.

Samples were prepared by the ultramicrotome technique. The polymeric material was prepared with the aid of metallocene-supported silica particles. The catalyst productivity was 11 g polyethylene / g catalyst. The distribution of silica particles can be clearly seen.

10 monodisperse silica particles functionalized with a non-acidic nucleophile such as a polyether, preferably PEO.
having an average diameter of nm to 500 nm, preferably about 1
It has an average diameter of 00 nm. The amount of metallocene immobilized on the silica particles is to maintain the silica content of the resulting polymeric material between preferably 1% by weight and 50% by weight (more preferably 5% by weight to 30% by weight). ,
It is selected in such a way that sufficient polyolefin (preferably UHMWPE) is formed during the polymerization.

The silica particles which can be used in the present invention, a method for preparing silica particles functionalized with a nucleophilic non-acidic compound, and further embodiments of the present invention include those described below. it can.

(1) A microparticle material comprising a nanoparticle core of an inorganic material having an oligomeric or polymer structure containing a non-acidic nucleophilic group on its surface, the core being a non-acidic nucleophilic group A microparticulate material which has been agglomerated by the interaction of a functional group with at least one further component containing an electrophilic group. (2) A microparticulate material for a catalyst formed from a carrier, at least one catalytically active species and optionally at least one cocatalyst, characterized in that the carrier comprises a core of inorganic material. The microparticle material according to (1). (3) The microparticle material according to (1) or (2), wherein the further component containing an electrophilic group is at least one catalytically active species or at least one cocatalyst. (4) A nanoparticle material including a core of an inorganic material,
A nanoparticulate material in which an oligomeric or polymeric structure containing non-acidic nucleophilic groups is present on the surface of its core. (5) The inorganic material of the core is preferably an oxide of an element of main group 3 or 4 or subgroup 3 to 8 of the periodic table, particularly preferably aluminum oxide, silicon oxide, boron oxide, germanium oxide, titanium oxide. The microparticle material according to any one of (1) to (3), wherein the microparticle material is an oxide material selected from the group consisting of oxides, zirconium oxide, iron oxide, mixed oxides, and oxide mixtures of the compounds. Alternatively, the nanoparticle material according to (4). (6) The oligomer or polymer structure containing a non-acidic nucleophilic group on the core surface is a polymer, preferably a linear polymer grafted on the surface, and the non-acidic nucleophilic group is Any one of (1) to (3), which may be present directly in the main chain, or may be in the form of a functional group or a small molecule as a side chain. The microparticle material according to (5) or the nanoparticle material according to any one of (4) or (5). (7) The polymer containing a non-acidic nucleophilic group is particularly a polyether such as polyethylene oxide, polypropylene oxide or a mixed polymer of ethylene oxide and propylene oxide, or polyvinyl alcohol, a polysaccharide or a polycyclodextrin. Microparticle material or nanoparticle material as described in (6) characterized by the above-mentioned. (8) The surface of the core is a functional group having a chemical functional group at the terminal of the active molecular chain that enables grafting of a polymer serving as a shell, preferably a terminal double bond, a halogen functional group, an epoxy group or a polycondensable group. The microparticle material or the nanoparticle material according to any one of (1) to (7), which is formed. (9) The component containing an electrophilic group is the main group 3 of the periodic table.
Or an organometallic compound of (semi) metal of 4, preferably
Any one of (1) to (3) or (5) to (8), which is a compound of each element of boron, aluminum, tin, or silicon, particularly preferably methylaluminoxane. Microparticle material according to paragraph. (10) The polymer containing a non-acidic nucleophilic group is polyethylene oxide (PEO), and the other component containing an electrophilic group is methylaluminoxane (MAO).
The microparticle material according to any one of (1) to (3) or (5) to (9). (11) The microparticulate material has a ratio of 1.5: 1 to 1: 1 in all cases with an average of all three mutually perpendicular diameters.
It consists of spherical particles in the range of 1.5, and the average particle size of the material is in the range of 1 to 150 μm, preferably 3
To 75 μm, the microparticle material according to any one of (1) to (3) or (5) to (10). (12) A heterogeneous catalyst, comprising: a) at least one nanoparticulate material according to any one of (4) to (8), and b) at least one periodic table subgroup 3 to 8 A compound of any transition metal, and c) at least one main group 3 or 4 (semi) of the periodic table
Compounds b) and c) including organometallic compounds of metals
Heterogeneous catalysts in which are bound to the nanoparticulate material a) and together form a catalytically active species. (13) The microparticle material according to any one of (1) to (3) or (5) to (11), wherein the component a) and the component b) or c) are combined. The heterogeneous catalyst according to (12), characterized in that (14) The compound of the transition metal of subgroup 3 to 8 of the periodic table is a complex compound, and particularly preferably, the central metal is
Preference is given to metallocene compounds preferably selected from the elements titanium, zirconium, hafnium, vanadium, palladium, nickel, cobalt, iron and chromium, particularly preferred central metals being titanium or especially zirconium (12 ) Or (13) a heterogeneous catalyst. (15) A method for producing a nanoparticulate material, which comprises applying an oligomeric or polymeric structure containing a non-acidic nucleophilic group to the surface of a core of an inorganic material. (16) It is characterized in that a functional group is introduced on the surface of the core before applying the oligomer or polymer structure (1
The method according to 5). (17) A method for producing a microparticle material, comprising a nanoparticle core of an inorganic material having on its surface an oligomeric or polymer structure containing a non-acidic nucleophilic group and at least one further comprising an electrophilic group. A method comprising agglomerating with other components. (18) A method for producing a heterogeneous catalyst, comprising: a) at least one nanoparticle material according to any one of (4) to (8) or (15) or (1).
6) reacting the nanoparticulate material produced by the process described with at least one organometallic compound of a main group 3 or 4 (semi) metal of the periodic table, and b) at least one subgroup 3 of the periodic table To a compound of a transition metal of any one of 8 to 8 to produce a heterogeneous catalyst. (19) Use of the heterogeneous catalyst according to any one of (12) to (14) or the heterogeneous catalyst produced by the method according to (18), which is used for producing a polyolefin. . (20) A method for producing a polyolefin, comprising:
A heterogeneous catalyst according to any one of (12) to (14) or a heterogeneous catalyst produced by the method according to (18), and the formula R ¹ CH═CHR ² (provided that R ¹ and R ² may be the same or different and is selected from the group consisting of hydrogen and cyclic and acyclic alkyl groups having 1 to 20 carbon atoms). (21) The method for producing a polyolefin according to (20), wherein the polymerization is carried out by gas phase polymerization or suspension polymerization. (22) Use of the heterogeneous catalyst according to any one of (12) or (14) or the heterogeneous catalyst produced by the method according to (18), wherein a polyolefin having a spherical particle structure is used. Use for manufacturing. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to micro and nanoparticulate materials, catalysts made from these materials, methods of making these materials or catalysts, and olefins of the catalysts. The present invention relates to a use for polymerization and a method of polymerizing using the catalyst.

PRIOR ART Metallocene-catalyzed polymerization has made significant progress since the early 1980s. Originally thought of as a model system for the Ziegler-Natta catalyst, it gradually evolved into an independent process with very great potential for (co) polymerizing ethene and higher molecular weight 1-olefins. . In addition to using a cocatalyst, methylaluminoxane, which increases the activity instead of just a trialkyl compound, the crucial factor for rapid development is the activity due to the systematic understanding of the structure / activity relationship of the catalyst. And continuous improvement of stereoselectivity (G.
G. Hlatky, Coord. Chem. Rev. 1
999, 181, 243; Mulhaupt, Na
chr. Chem. Tech. Lab. 1993, 4
1,1341).

However, homogeneous catalysts have only a limited suitability for large-scale industrial applications where gas phase or suspension polymerization processes are usually used. Agglomeration of catalytically active centers often occurs, resulting in caking on the walls of the reactor or otherwise known as "reactor fouling." As a result, supported catalysts have been developed for that purpose. The loading of the catalyst is intended to avoid the above problems.

Carrier materials commonly described herein include silicon oxide (eg, US Pat. No. 4,808,561).
U.S. Pat. No. 5,939,347, International Publication No. 96
/ 34898) or aluminum oxide (eg,
M. Kaminaka, K .; Soga, Macromo
l. Rapid Commun. 1991, 12, 36
7) or phyllosilicates (eg US Pat.
830,820, German Patent Publication No. 197 27 2
57, European Patent Publication No. 849 288), zeolites (eg, LK Van Looveren,
D. E. De Vos, K .; A. Vercruyss
e, D. F. Geysen. B. Janssen, P .;
A. Jacobs, Cat. Lett. 1998, 56
(1), 53) or the like, or cyclodextrin (D.-H. Lee, K.-B. Yoon, Ma.
cromol. Rapid Commun. 1994,
15, 841; Lee, K .; Yoon, Macro
mol. Symp. 1995, 97, 185) or polysiloxane derivatives (K. Soga, T. Arai,
B. T. Hoang, T .; Uozumi, Macrom
ol. Rapid Commun. 1995, 16, 9
05) and other model systems.

A new problem that arises with the use of carriers is that the activity and selectivity of the catalyst are reduced compared to homogeneous polymerization.

[Problems to be Solved by the Invention] Therefore, there has been a demand for a material which prevents the disadvantages of the prior art which are generated by using a heterogeneous catalyst.

[Means for Solving the Problem] Surprisingly, it is now possible that the nanoparticle agglomerates having a core of an inorganic substance described below can be advantageously used for this type of catalyst. Was found.

The present invention firstly comprises a nanoparticle core of an inorganic material which is a microparticulate material having an oligomeric or polymeric structure containing nonacidic nucleophilic groups on its surface, the core being nonacidic. Of nucleophilic groups and a further component containing at least one electrophilic group that is aggregated by interaction.

The microparticulate material is preferably a catalyst formed from a support and at least one catalytically active species and optionally at least one cocatalyst, which support has non-acidic nucleophilic groups on its surface. Comprising a core of an inorganic material having an oligomeric or polymeric structure containing
The core is characterized in that it is aggregated by the interaction of a non-acidic nucleophilic group with a further component containing at least one electrophilic group.

DETAILED DESCRIPTION OF THE INVENTION The term “nanoparticles” as used herein refers to an average particle size of about 1 nm to 1000 nm.
Applies to all particles in the range below. Correspondingly, the term “microparticle” means that the average particle size is from 1 μm to 10 μm.
Applies to all particles in the range of less than 00 μm.

The further component containing an electrophilic group is preferably at least one catalytically active species or at least one cocatalyst.

The present invention further relates to nanoparticulate materials comprising a core of inorganic material, the surface of which has an oligomeric or polymeric structure containing non-acidic nucleophilic groups.

The core of the inorganic material preferably consists of a metal or metalloid or metal salt, particularly preferably a metal chalcogenide or metal pnictide. The term "chalcogenide" as used for the purposes of the present invention applies to compounds in which an element of group 16 of the periodic table is an electronegative binding partner, the term "pnictid"
The term "e)" applies to those elements of group 15 of the periodic table which are electronegative binding partners.

The preferred core is a metal chalcogenide, preferably a metal oxide, or a metal pnictide, preferably a nitride or phosphide. A "metal" as used for these terms is an element that can all be expressed as electropositive partners compared to counterions, such as classical subgroup metals or first and second main group members. Main group metals as well as all elements of the third main group as well as silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth and the like. Preferred metal chalcogenides and metal pnictides include in particular silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide, gallium nitride, boron nitride, aluminum nitride, silicon nitride, phosphorus nitride and the like.

For the purposes of the present invention, the core inorganic material is preferably an oxide of an element of main groups 3 and 4 of the periodic table and subgroups 3 to 8, particularly preferably aluminum oxide, oxides. In particular, a microparticle or nanoparticle material characterized in that it is an oxide material selected from silicon, boron oxide, germanium oxide, titanium oxide, zirconium oxide, or iron oxide, or a mixed oxide or an oxide mixture of the above compounds. preferable.

In one variant of the invention, the starting materials employed for the production of the core / shell type particles according to the invention are:
Preferably, it comprises a monodisperse core of silicon dioxide, which should be obtainable, for example, by the method described in US Pat. No. 4,911,903. Here, the core is produced by hydrolyzing tetraalkoxysilane in an aqueous medium containing ammonia to polycondense,
There, first, a sol of primary particles was produced, and the obtained Si
The O ₂ particles are then converted to the desired particle size by the subsequent metered addition of tetraalkoxysilane. This method allows the production of monodisperse SiO ₂ cores with a standard deviation of 5% average particle size.

Further preferred starting materials are, for example, T
It includes a SiO ₂ core coated with a (semi) metal or non-absorbing metal oxide such as iO ₂ , ZrO ₂ , ZnO ₂ , SnO ₂ , or Al ₂ O ₃ . SiO ₂ coated with metal oxide
For manufacturing cores, see, for example, US Pat.
6,310, German Patent 198 42 134 and German Patent 199 29 109 are described in more detail.

With additional starting materials that can be used
Then TiO₂, ZrO₂, ZnO ₂, SnO₂, Or
Al₂O₃Or a single metal oxide such as a mixture of metal oxides.
A distributed core is included. For their manufacture, even
For example, as described in European Patent No. 0,644,914.
It Furthermore, monodisperse SnO₂European patent for manufacturing cores
The method of No. 0,216,278 can be easily applied to other oxides.
Should give similar results.
It Tetraethoxysilane, tetrabutoxytitanium, te
Trapropoxy zirconium, or a mixture of
Exactly 30 to 4 using a thermostat
Alcohol, water and ammonia adjusted to 0 ° C
The resulting mixture was added to the mixture with vigorous stirring.
Stir vigorously for another 20 seconds to reach the nanometer range
A suspension of monodisperse cores of After reaction for 1 to 2 hours
After a period of time, the core is removed in the usual way, for example by centrifugation.
Separated, washed and dried.

The oligomeric or polymeric structure containing non-acidic nucleophilic groups on the core surface is preferably a polymer grafted or polymerized onto the surface, ie surface-synthesized (wherein the term "oligomer" refers to From here on, it will be basically included under the term of polymer). The polymer may be branched or unbranched, but in a preferred embodiment the polymer has a linear structure. The non-acidic nucleophilic groups here may be present directly in the main chain or may be in the form of functional groups or small molecules as side chains. The polymer may optionally be grafted or polymerized directly onto the functionalized surface, ie synthesized on the surface or attached to the surface by means of spacers. In a preferred embodiment of the invention, the spacer is an inert polymer such as polyethylene, polypropylene or polystyrene or a cyclic or acyclic low molecular weight hydrocarbon compound, particularly preferably an alkyl chain having 1 to 20 carbon atoms. . The polymers containing non-acidic nucleophilic groups are preferably polyethers such as polyethylene oxide, polypropylene oxide or mixed polymers of ethylene oxide and propylene oxide, or polyvinyl alcohols, polysaccharides or polycyclodextrins, among others.

According to the invention, these oligomeric or polymeric structures are applied to the inorganic core after it has been formed. Accordingly, the invention further relates to a method of producing a nanoparticulate material, characterized in that an oligomeric or polymeric structure containing non-acidic nucleophilic groups is applied to the core surface of an inorganic material.

To apply the oligomeric or polymeric structure to the core surface, it may be advantageous to introduce functional groups on the core surface, as already mentioned above. Therefore, for the purpose of the present invention, a method of introducing a functional group onto the core surface before applying the oligomer or polymer structure is preferred. Here, it is particularly preferable to apply a chemical function that allows a polymer as a shell to be grafted onto the surface as an active molecular chain end. Examples which may be mentioned here are, inter alia, terminal double bonds, halogen functional groups, epoxy groups and polycondensable groups. The introduction of the functional group at this point can be carried out directly during the production of the particles. In a preferred embodiment, functionalized silicon dioxide particles are prepared by the method described in EP 216 278 using a trialkoxysilane which already has the desired groups for surface functionalization. obtain. Modification of surfaces with hydroxyl groups is disclosed, for example, in EP-A-337 144. Further methods of modifying the surface of the particles are known to those skilled in the art, especially those involved in the production of chromatographic materials.
Well-known and various textbooks, such as Unge
r, K. K. , Porous Silica, Else
vier Scientific Publicshin
g Company (1979) and the like.

The components containing electrophilic groups are preferably organometallic compounds of (semi) metals of main group 3 or 4 of the periodic table, which are also referred to below as "cocatalysts". They are particularly preferably compounds of elements such as boron, aluminum, tin or silicon, preferably compounds of boron or aluminum. Compounds free of halides are preferred. The organic radical of the compound is preferably alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy,
Selected from the group consisting of alkaryloxy, aralkoxy radicals and fluorine-substituted derivatives.

Preferred compounds are trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and the like.

Aluminoxanes containing an alkyl group on aluminum, such as methyl-, ethyl-, propyl-, isobutyl-, phenyl-, or benzylaluminoxane, are particularly preferred, especially the methylaluminoxane well known by the abbreviation of MAO. Is particularly preferable.

The selection of components containing electrophilic groups such that the microparticle material is produced through interaction with the nanoparticle core is fundamental here. The person skilled in the art has no difficulty in choosing the nucleophilic and electrophilic groups which interact in a corresponding manner.

The microparticulate material is preferably gradually formed from the nanoparticulate core by the cores being held together through the interaction of the non-acidic nucleophilic groups on the core with the electrophilic groups of other components. Manufacturing this type of microparticulate material in which a nanoparticle core of an inorganic material having on its surface an oligomeric or polymeric structure containing non-acidic nucleophilic groups is agglomerated with at least one further constituent containing electrophilic groups The method of doing is likewise the subject of the invention.

In a particularly preferred embodiment of the invention,
The polymer containing non-acidic nucleophilic groups is polyethylene oxide (PEO) and the further component containing electrophilic groups is methylaluminoxane (MAO). In this case, it is assumed that agglomerates are formed and the polymer chains of PEO are stabilized by coordination with the metal center of MAO. According to this concept, the microparticulate material is in the form of a MAO network including a core having a PEO-modified surface.

The material according to the invention has the following advantages over the prior art when used as or as a catalyst. -The catalytically active compound is evenly distributed on the carrier. -The catalyst is uniformly subdivided during the reaction. -The formed fragments are fine and evenly distributed in the reaction product. -The material properties of the polymers produced by the catalysts according to the invention are minimally or not at all affected by evenly distributed catalyst fragments in small amounts. The uniform distribution of the catalyst on the support, together with the uniform fragments, leads to a uniform progression of the catalytic reaction. -This catalyst can be advantageously used, especially in a reaction such as a polymerization reaction in which control of reaction heat poses a technical problem, because an exothermic peak is avoided by the progress of a uniform reaction.

The advantages mentioned above can be achieved in a particularly pronounced manner in the polymerization reaction. The catalyst according to the invention is therefore preferably a polymerization catalyst or it is particularly preferred to use the catalyst according to the invention for a polymerization reaction. In particular, it has been surprisingly found that the polymers obtained in this way have improved material properties compared to those of the prior art. In particular, there are advantages in terms of polymer transparency, polymer tear strength, and polymer appearance due to reduced inhomogeneity due to catalyst fragments.

In a preferred embodiment of the invention spherical particles are obtained. Here, spherical means that the particles give a spherical shape in a scanning electron micrograph. "Spherical" can be quantified in the sense that the average difference between the three mutually perpendicular diameters of the particles is at most 50% of the length of each other. This means that the ratio of all three mutually perpendicular diameters is in each case in the range 1.5: 1 to 1: 1.5. The ratio of the three average diameters is
Preferably all are in the range 1.3: 1 to 1: 1.3, ie the difference in diameter from each other is at most 30%.

The materials according to the invention are usually 1 to 150
It has an average particle size in the range of μm, preferably in the range of 3 to 75 μm. The particle size distribution here should be controllable by classification, for example by air classification. Surface area of particles-BET method (S. Brunnauer, PH Em.
mett, E .; Teller, J .; Am. Chem. S
oc. 1938, 60, 309) -is usually 50 to 500 m ² / g, but 150 to 45
A surface area in the range of 0 m ² / g is preferred. The pore volume is similarly measured by the BET method, but generally 0.5 to 4.
It is in the range of 5 ml / g and the preferred pore volume is 0.8
greater than ml / g, particularly preferably 1.5 to 4.
It is in the range of 0 ml / g.

The materials according to the invention are suitable as supports for a very wide variety of catalysts. In principle, all homogeneous catalysts can be immobilized with the aid of such materials.

In a particularly important embodiment of the invention,
The material is used as a carrier for an olefin polymerization catalyst.

Conventional catalyst systems for the polymerization of olefins include compounds of the transition metals of any of subgroups 3 to 8 of the Periodic Table,
It usually consists of a cocatalyst which is an organometallic compound of a (semi) metal of main group 3 or 4 of the periodic table.

The present invention therefore further comprises at least one nanoparticulate material as described above, at least one compound of a transition metal of any of subgroups 3 to 8 of the Periodic Table, and at least one main group 3 of the Periodic Table or And a transition metal component and an organometallic component bonded to the nanoparticle material, and together form a catalytically active species.

Here, it is particularly preferred for both the nanoparticulate material and the transition metal or organometallic component to form a microparticulate material, as described above.

The compound of the transition metal of any one of subgroups 3 to 8 of the periodic table, which will be referred to as a "catalyst" in the following, is preferably a complex compound, and particularly preferably a metallocene compound. In principle this can be any metallocene. Bridged (ansa) or unbridged metallocene complexes containing (substituted) π ligands such as cyclopentadienyl, indenyl or fluorenyl ligands are considered here and are symmetric with central metal groups 3-8. Or it gives an asymmetric complex. The central metal employed is preferably the metal titanium, zirconium, hafnium, vanadium, palladium, nickel, cobalt, iron or chromium, with titanium and especially zirconium being particularly preferred.

Suitable zirconium compounds include, for example, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl).
Zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis (cyclopentadienyl) cyclohexyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, Bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride monohydride, bis (indenyl) zirconium monochloride monohydride, bis (cyclo Pentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconi Mumonokurorido, bis (cyclopentadienyl) ethyl zirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride,
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium Dichloride, bis (cyclopentylcyclopentadienyl)
Zirconium dichloride, bis (octadecylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) dimethylzirconium, bis (4,5,6,7-tetrahydro-1)
-Indenyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) methoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium chloride, bis (Cyclopentadienyl) butoxyzirconium chloride, bis (cyclopentadienyl) -2-ethylhexyloxyzirconium chloride (bis (cyclope
ntadienyl) -2-ethylhexoxyzirconium chloride), bis (cyclopentadienyl) methyl zirconium ethoxide, bis (cyclopentadienyl) methyl zirconium butoxide, bis (cyclopentadienyl) ethyl zirconium ethoxide, bis (cyclopentadienyl) ) Phenylzirconium ethoxide, bis (cyclopentadienyl) benzylzirconium ethoxide, bis (methylcyclopentadienyl) ethoxyzirconium chloride, bis (indenyl) ethoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium, bis ( Cyclopentadienyl) butoxyzirconium, bis (cyclopentadienyl) -2-ethylhexyloxyzirconium (bis (cyclopentadienyl) -2-ethyl
hexoxyzirconium), bis (cyclopentadienyl) phenoxyzirconium monochloride, bis (cyclopentadienyl) cyclohexyloxyzirconium chloride
(bis (cyclopentadienyl) cyclohexoxyzirconium chlorid
e), bis (cyclopentadienyl) phenylmethoxyzirconium chloride, bis (cyclopentadienyl) methylzirconium phenylmethoxide, bis (cyclopentadiphenyl) trimethylsiloxyzirconium chloride, bis (cyclopentadienyl) triphenylsiloxyzirconium Chloride, bis (cyclopentadienyl) thiophenylzirconium chloride, bis (cyclopentadienyl) neoethylzirconium chloride, bis (cyclopentadienyl) bis (dimethylamido) zirconium, bis (cyclopentadienyl) diethylamide zirconium chloride , Dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, dimethylsilylenebis (4,
5,6,7-Tetrahydro-1-indenyl) dimethyl zirconium, dimethylsilylene bis (2-methyl-)
4,5-benzoindenyl) zirconium dichloride,
Dimethylsilylenebis (4-t-butyl-2-methylcyclopentadienyl) zirconium chloride, dimethylsilylenebis (4-t-butyl-2-methylcyclopentadienyl) dimethylzirconium, ethylenebis (indenyl) ethoxyzirconium chloride , Ethylene bis (4,5,6,7-tetrahydro-1-indenyl)
Ethoxyzirconium chloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) dibenzylzirconium, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis ( Indenyl) ethyl zirconium monochloride, ethylenebis (indenyl) benzylzirconium monochloride, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5) , 6,7-Tetrahydro-1-indenyl) dimethyl zirconium, ethylene bis (4,5,6) 7-tetrahydro-1-indenyl) methyl zirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7
-Tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1)
-Indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,4)
7-dimethoxy-1-indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethoxide, ethylenebis (indenyl) zirconium diethoxide, ethylenebis (indenyl) methoxyzirconium chloride, ethylenebis (indenyl) ethoxyzirconium chloride, ethylenebis (Indenyl) methylzirconium ethoxide, ethylenebis (4,5,
6,7-Tetrahydro-1-indenyl) zirconium dimethoxide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium diethoxide,
Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) methoxyzirconium chloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl)
Ethoxyzirconium chloride, ethylenebis (4,
5,6,7-Tetrahydro-1-indenyl) methyl zirconium ethoxide, ethylene bis (4,5,6,7
-Tetrahydro-1-indenyl) dimethylzirconium, isopropylene (cyclopentadienyl) (1-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (1-fluorenyl) zirconium dichloride.

Suitable titanium compounds include, for example,
Bis (cyclopentadienyl) titanium monochloride monohydride, bis (cyclopentadienyl) methyl titanium hydride, bis (cyclopentadienyl) phenyl titanium chloride, bis (cyclopentadienyl) benzyl titanium chloride, bis (cyclopenta Dienyl) titanium dichloride, bis (cyclopentadienyl) dibenzyl titanium, bis (cyclopentadienyl) ethoxy titanium chloride, bis (cyclopentadienyl) butoxy titanium chloride, bis (cyclopentadienyl) methyl titanium ethoxide , Bis (cyclopentadienyl) phenoxytitanium chloride, bis (cyclopentadienyl) trimethylsiloxytitanium chloride, bis (cyclopentadienyl) thiophenyltitanium chloride, bis (cyclopentadienyl) bis Dimethylamido) titanium, bis (cyclopentadienyl) ethoxytitanium, bis (n-butylcyclopentadienyl) titanium dichloride, bis (cyclopentylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, ethylenebis (indenyl) ) Titanium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride.

Suitable hafnium compounds include, for example, bis (cyclopentadienyl) hafnium monochloride monohydride, bis (cyclopentadienyl) ethylhafnium hydride, bis (cyclopentadienyl).
Phenylhafnium chloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) benzyl hafnium, bis (cyclopentadienyl) ethoxyhafnium chloride, bis (cyclopentadienyl) butoxyhafnium chloride, bis (cyclopenta) Dienyl) methylhafnium ethoxide, bis (cyclopentadienyl) phenoxyhafnium chloride, bis (cyclopentadienyl) thiophenylhafnium chloride, bis (cyclopentadienyl) bis (diethylamido) hafnium, ethylenebis (indenyl) hafnium Dichloride, ethylene bis (4,5,
6,7-Tetrahydro-1-indenyl) hafnium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) hafnium dichloride and the like.

Suitable iron compounds include, for example, 2,
6- [1- (2,6-diisopropylphenylimino)]
Ethyl] pyridine iron dichloride, 2,6- [1- (2,
6-dimethylphenylimino) ethyl] pyridine iron dichloride.

Suitable nickel compounds include, for example, (2,3-bis (2,6-diisopropylphenylimino) butane) nickel dibromide and 1,4-bis (2,6-diisopropylphenyl) acenaphthenediimino. There are nickel dichloride, 1,4-bis (2,6-diisopropylphenyl) acenaphthene diimino nickel dibromide.

Suitable palladium compounds include, for example, (2,3-bis (2,6-diisopropylphenylimino) butane) palladium dichloride and (2,3-bis (2,6-diisopropylphenylimino) butane).
There is dimethyl palladium.

It is particularly preferable to use a zirconium compound here, and examples of such a compound include bis (cyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, ethylenebis (4,4). 5,6,7-Tetrahydro-1-indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride are particularly preferred.

However, according to the invention, compounds of the transition metals of any of the subgroups 3 to 8 can also be traditional Ziegler-Natta compounds, for example titanium tetrachloride, tetraalkoxytitanium, alkoxytitanium chloride. , Vanadium halides, vanadium halide oxides, alkoxy vanadium compounds and the like (wherein the alkyl group has 1 to 20 carbon atoms).

According to the invention, it is possible to use both pure transition metal compounds and mixtures of various transition metal compounds, mixtures of metallocene or Ziegler-Natta compounds and metallocene and Ziegler-.
Both mixtures with Natta compounds can be advantageous.

The average particle size of the catalyst particles is usually 1 to 150.
It is in the range of μm, preferably in the range of 3 to 75 μm.

In a preferred embodiment of the present invention, the heterogeneous catalyst according to the present invention enables the production in which the particle size and shape of the polymer particles can be controlled. Here, the particle size can be set in the range of about 50 μm to about 3 mm. The preferred particle shape is spherical and, as noted above, it can be produced by spherical carrier particles which are particularly uniformly coated with the catalyst.

The invention further relates to a process for preparing the heterogeneous catalysts according to the invention, in which a) at least one nanoparticulate material as described above is added to at least one main group 3 or 4 of the periodic table. And (b) at least one transition metal compound of any of subgroups 3 to 8 of the Periodic Table to produce a heterogeneous catalyst.

The production of heterogeneous catalysts using the nanoparticulate materials according to the invention can be carried out in various ways, with particular consideration of the continuous reaction between the components.

In one preferred method, the organometallic compound of a (semi) metal of main group 3 or 4 of the periodic table (hereinafter referred to as the cocatalyst) is first absorbed on a nanoparticulate material (hereinafter also referred to as the carrier), A compound of a transition metal of any of subgroups 3 to 8 of the Periodic Table (hereinafter also referred to as a catalyst) is added thereafter. Alternatively, as in the preferred method, the mixture of catalyst and cocatalyst is reacted with a support. In some cases, the catalyst may be first immobilized on the support and then reacted with the cocatalyst. In a preferred variant of this method, the microparticulate material according to the invention is produced by reacting the nanoparticulate material with a cocatalyst or a first component of the catalyst. Alternatively, for example, the cocatalyst methylaluminoxane can be generated in situ by reacting with a support material containing trimethylaluminum and water. Direct chemical bonding of metallocene catalysts to nanoparticulate materials with the aid of spacers or anchor groups is also a possible step in the preparation of heterogeneous catalysts.

The nanoparticulate material is usually suspended in an inert solvent and the catalyst and cocatalyst are added as a solution or suspension. After the individual reaction steps, washing with a suitable solvent can be carried out for purification.

All catalyst preparation process steps are preferably carried out under a protective gas such as argon or nitrogen.

Suitable inert solvents include, for example, pentane, isopentane, hexane, heptane, octane, nonane, cyclopentane, cyclohexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene and the like.

In a particularly preferred variant of the process according to the invention, the nanoparticulate material is reacted with an aluminoxane, preferably the commercially available methylaluminoxane. In this case, the nanoparticulate material is suspended, for example, in toluene and then with the aluminum component and 0 ° C. and 140 ° C.
React for about 30 minutes at a temperature between 0 ° C. This gives the heterogenized methylaluminoxane as a microparticulate material. The cocatalyst thus supported is then contacted with a metallocene, preferably dicyclopentadienylzirconium dichloride, in a catalyst / cocatalyst ratio of between 1 and 1: 100000. The mixing time is 5 minutes to 48 hours, preferably 5 minutes to 60 minutes.

The actual catalytically active centers of the heterogeneous catalyst according to the present invention are not formed part way through the reaction of the nanoparticulate material with the catalyst and cocatalyst components.

According to the invention, heterogeneous catalysts are preferably used for producing polyolefins.

The invention therefore also relates to the use of heterogeneous catalysts for producing polyolefins as described above.

The term "polyolefin" is taken very broadly here and has at least 1 in the monomer molecule.
It means a polymer compound obtained by polymerization of a substituted or unsubstituted hydrocarbon compound having one double bond.

The olefin monomer is preferably a compound of the formula R ¹ CH═CHR ² where R ¹ and R ² can be the same or different and can be hydrogen and 1 to 2
Cyclic and acyclic alkyl groups having 0 carbon atoms,
Selected from the group consisting of aryl groups and alkylaryl groups).

The olefins that can be adopted are, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-hexadecene,
Mono-olefins such as 1-octadecene, 3-methyl-1-butene, 4-methyl-1-pentene, 4-methyl-1-hexene, for example 1,3-butadiene, 1,4-
Diolefins such as hexadiene, 1,5-hexadiene, 1,6-hexadiene, 1,6-octadiene, 1,4-dodecadiene, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p
Aromatic olefins such as -t-butylstyrene, m-chlorostyrene, p-chlorostyrene, indene, vinylanthracene, vinylpyrene, 4-vinylbiphenyl, dimethanooctahydronaphthalene, acenaphthalene, vinylfluorene and vinylchrysene, for example, Cyclopentene, 3-vinylcyclohexene, dicyclopentadiene, norbornene, 5-vinyl-2-norbornene, t
-Ethylidene-2-norbornene, 7-octenyl-9
Cyclic olefins and diolefins, such as borabicyclo [3.3.1] nonane, 4-vinylbenzocyclobutane, tetracyclododecene, and also, for example, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylonitrile, Examples thereof include 2-ethylhexyl acrylate, methacrylonitrile, maleimide, N-phenylmaleimide, vinylsilane, trimethylallylsilane, vinyl chloride, vinylidene chloride and isobutylene.

Particularly preferred are ethylene, propylene and generally also 1-olefins, which are either homopolymerized or alternatively copolymerized in a mixture with other monomers. .

Accordingly, the present invention further comprises the above heterogeneous catalysts and the formula R ¹ CH═CHR ² where R ¹ and R ² may be the same or different and may be hydrogen and 1 to 20 Olefins selected from the group consisting of cyclic and non-cyclic alkyl groups having carbon atoms, aryl groups and alkylaryl groups).

The polymerization is carried out continuously or discontinuously by a known method such as solution polymerization, suspension polymerization or gas phase polymerization, and gas phase polymerization and suspension polymerization are particularly preferable. Typical temperatures during polymerization range from 0 ° C to 200 ° C, preferably 20 ° C.
To 140 ° C.

The polymerization is preferably carried out in a high pressure autoclave. If necessary, hydrogen may be added as a molecular weight modifier during the polymerization.

The heterogeneous catalysts used according to the invention are:
Allows the production of homopolymers, copolymers and block copolymers.

As mentioned above, substantially spherical polymeric particles having a controllable particle size can be obtained by appropriate choice of carrier.

The invention therefore also relates to the use of the heterogeneous catalysts according to the invention or of the heterogeneous catalysts prepared according to the invention for the production of polyolefins having a spherical particle structure.

[0105]

EXAMPLES The following abbreviations may be used: MAO methylaluminoxane PEO polyethylene oxide Monospher® xxx Monodisperse silica particles with a mean particle size xxx nm, standard deviation of mean particle size <5% (Merck KGaA , Darmstadt) (Example 1) Preparation of catalyst a) Introduction of functional groups into nanoparticles (Monospheres)
(Registered trademark) 100 (manufactured by Merck)) Monospheres (registered trademark) 100 (manufactured by Merck, spherical silica particles, average diameter 100 nm, standard deviation of average diameter <5%) (60 g corresponds to 1 mol of silica)
In the form of a 10% by weight ethanol solution,
Stir vigorously at 70 ° C. with 4.93 g (20 mmol) of (3,4-epoxycyclohexyl) ethylmethoxysilane to mix. The dispersion is refluxed for 24 hours. The dispersion is then evaporated to dryness and the powder is dried under reduced pressure at 70 ° C. overnight, 10 μmol /
Give a surface coverage density of m ² .

B) Grafting of polyethylene oxide chain Polyethylene oxide 350 (M = 350 g / mol)
50 ml of 5.25 g of with 100 mg of sodium
Stir in tetrahydrofuran until the generation of gas subsides. The solution is added with a dropper to a suspension of Monosphere® 100 treated according to Example 1a) in 5 g of tetrahydrofuran. 1
After stirring for 2 hours, add 2 ml of water and add Monosph
er is centrifuged, washed with tetrahydrofuran three times, and then dried.

C) Immobilization of metallocene Monosph with PEO functional group introduced in Example 1b).
20 g of a solution of methylaluminoxane (MAO) in toluene (c (Al) = 1.5 mol / l)
Suspended in. After stirring for 1 hour, 0.31 mmo of dicyclopentadienylzirconium in 11 ml of a toluene solution of MAO (c (Al) = 1.5 mol / l).
1 ml of solution 3 ml was added and the mixture was stirred for 30 minutes,
Remove the solvent under reduced pressure.

The catalyst obtained was 0.028 m of metallocene.
It has a coating of mol / g catalyst (total mass including metallocene and cocatalyst) and an Al / Zr ratio 410. The scanning electron micrograph shows a particle size of the catalyst particles of about 50 μm.

(Example 2) Preparation of catalyst a) Introduction of functional groups into nanoparticles (Monospheres)
(Registered trademark) 150 (manufactured by Merck)) 16.1 g of Monospheres (registered trademark) 150 (manufactured by Merck, spherical silica particles, average diameter 150 nm, standard deviation <5% of average diameter) are suspended in 300 ml of water. 2.44 g of trimethoxychloropropylsilane
A solution of (12.34 mmol) in 25 ml of ethanol is slowly added dropwise under reflux. 2 the dispersion
Reflux for 4 hours. Monosph with this functional group introduced
Eres is then separated by centrifugation. Purification
This is done by suspending in ethanol three times and then centrifuging. The powder obtained is dried under reduced pressure.

B) Grafting of polyethylene oxide chain Polyethylene oxide 350 (M = 350 g / mol)
2.68 g of is slowly added at 0 ° C. to 221 mg of sodium hydride in 50 ml of tetrahydrofuran.
The mixture is then stirred for another 30 minutes at 0 ° C. and another 30 minutes at room temperature. The solution is Monosphere
5 g of (registered trademark) 150 (from Example 2a)
Is added to the suspension of in tetrahydrofuran using a dropper. After stirring for 12 hours, the solvent is removed and the residue is washed 3 times with ethanol.

C) Immobilization of metallocene Monosph with PEO functional group introduced in Example 2b).
20 g of a solution of methylaluminoxane (MAO) in toluene (c (Al) = 1.5 mol / l)
Suspended in. After stirring for 1 hour, 0.10 of dicyclopentadienyl zirconium dichloride in 11 ml of a solution of MAO in toluene (c (Al) = 1.5 mol / l).
3 ml of a 31 mmol solution is added, the mixture is stirred for 30 minutes and the solvent is removed under reduced pressure.

Example 3 A hexane solution of polymerized triisobutylaluminum (c (A
5 ml of l) = 1 mol / l) was introduced into a 1 liter steel autoclave. Fill the autoclave with 400 ml of isobutane and heat to 70 ° C. and add 3 parts of ethene.
A pressure of 6 bar was introduced. 70 mg of the catalyst of Example 1
Was introduced through a pressure lock with excess pressure of argon. The reactor pressure was kept constant at 40 bar during the polymerization by ethene passing through a press flow controller. After a polymerization time of 1 hour, the reaction is released by releasing the pressure. Isobutane evaporates during the process, leaving polyethene as fine granules that flow steadily. Yield: 48.6 g, Productivity: PE 700 g / g catalyst. Example 4 Preparation of Polyethylene Oxide Functionalized Monodisperse Silica Particles Monospheres (registered trademark) 100
(Merck, spherical silica particles, average diameter: 100n
m, standard deviation of average diameter <5%, 60 g is 1 of SiO ₂
60 g (corresponding to mol) in the form of a 10% by weight ethanol dispersion are mixed with 4.93 g (20 mmol) of 2- (3,4-epoxycyclohexyl) ethylmethoxysilane by vigorous stirring at 70 ° C. 2 of that dispersion
Reflux for 4 hours. The dispersion is then evaporated to dryness and the powder is dried under vacuum at 70 ° C. overnight.
Silane-treated monodisperse silica particles were obtained at a surface coverage density of 0 μmol / m ² .

Polyethylene oxide 350 (M = 350
5.25 g (g / mol) with 100 mg sodium are stirred in 50 ml tetrahydrofuran until gas evolution subsides. The solution is added with a dropper to a tetrahydrofuran suspension of 5 g of the silanized monodisperse silica particles. After stirring for 1 hour, 2 ml
Water was added, the silica particles were centrifuged, washed with tetrahydrofuran three times, and then dried to obtain polyethylene oxide-functionalized monodisperse silica particles.

[Use as Microparticulate Material for Metallocene] 2 g of the above polyethylene oxide-functionalized monodisperse silica particles were stirred for 2 hours with 4 ml of a toluene solution of methylaluminoxane (w (MAO) = 5%).
Solution of dicyclopentadienylzirconium dichloride in the above MAO solution (c (Zr) = 0.05 mol /
0.2 ml of l) was added. After stirring was continued for another 30 minutes, the solvent was removed under reduced pressure, leaving a yellow free flowing powder. This was directly used for the polymerization (support amount: 2.3 μmol of Zr per 1 g of catalyst, Al / Zr = 630).

For the polymerization, 960 mg of the above catalyst,
Filled with 400 ml of isobutane, 36 ba with ethene
It was introduced into a 1 l steel reactor pressurized to r at 70 ° C. via a lock with a pressure higher than that of argon. After 10 minutes, the polymerization was stopped by releasing the pressure. Yield: 8.6 g of colorless free-flowing powder (productivity:
7.6 g PE / g catalyst, silica content: 11%).

The product exhibits increased abrasion resistance in the ASTM G99 abrasion test compared to conventional PE. Example 5 Use as Reactor Additive Preparation of C ₁₈ Silane Treated Monodisperse Silica Particles 132 g Monospheres (registered trademark) dispersion and 150 g ethanol in a 500 ml three neck flask. To introduce. The mixture is heated to 70 ° C. and, with vigorous stirring, 12.7 g of the ethanolic trimethoxyoctadecylsilane solution are added dropwise via a dropping funnel over 20 minutes. During the addition, it must be ensured that the silane solution is introduced at the rim of the container, but not in contact with the wall of the container.

The mixture is then refluxed for 20 hours. Transfer the suspension with the nodule form of solids to a beaker. The solid is washed 5 times with deionized water by decantation. After the addition of toluene, the water is removed azeotropically from the mixture by means of a water separator.

Mass measurement by gravimetric analysis shows that the SiO ₂ concentration of the dispersion is 19.4% by weight.

[Use as Reactor Additive] 400 m
10 g of the C ₁₈ silane-treated monodisperse silica particles prepared above with 1 l of isobutane are introduced into a 1 l steel reactor. Heat the reactor to 70 ° C. and add 3 with ethene.
Pressurize to 6 bar. 80 mg of silica-supported dicyclopentadienylzirconium dichloride are introduced via a lock with a pressure higher than that of argon. After 60 minutes, the polymerization is stopped by releasing the pressure. yield:
78 g of colorless granules (0.5 mm to 1 mm particle diameter). Catalyst productivity: 850 g PE / g catalyst, silica content: 12.8% by mass. The product is ASTM compared to PE prepared by the same method without additives.
It shows increased wear resistance in the G99 wear test.

EFFECTS OF THE INVENTION The micro and nanoparticulate materials of the present invention, catalysts made from these materials, methods of making these materials or catalysts, uses of this catalyst for olefin polymerization, using this catalyst. The polymerization method can provide a catalyst in which the catalytic active sites are evenly distributed on the support and the catalyst fragments are uniformly distributed in the reaction product, as compared with the prior art. Further, the polyolefin produced according to the present invention has less heterogeneity due to catalyst fragments,
It is possible to provide a polyolefin having excellent material properties such as transparency and tear strength.

Summary [Problems] Micro and nanoparticulate materials, catalysts made from these materials, methods of making these materials or catalysts, their use in olefin polymerization, and their use. And a method of polymerizing.

[Solution] A nanoparticle core of a microparticle material, which has an oligomeric or polymeric structure containing a non-acidic nucleophilic group on its surface, is included,
The core agglomerates by the interaction of a non-acidic nucleophilic group with at least one further component containing an electrophilic group.

[0123]

INDUSTRIAL APPLICABILITY The polymer-based material of the present invention has a very uniform dispersion of silica particles as a filler, which makes it possible to obtain excellent wear resistance, joint implants and artificial implants in the medical engineering field of the present invention. Joints, artificial joint parts, plain bearings, gears, and other industrial parts can be provided.

[Brief description of drawings]

FIG. 1: 8 wt% recorded using a Philips CM20 transmission electron microscope (accelerating voltage: 200 kV).
3 is a transmission electron micrograph of PE containing silica. Samples were prepared by ultramicrotome technology.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 23/00 ZNM C08L 23/00 ZNM 4J015 F16C 33/20 F16C 33/20 A 4J128 F16H 55/06 F16H 55 / 06 (71) Applicant 591032596 Frankfurter Str. 250, D-64293 Darmstadt, Federal Republish of Germany (72) Inventor Beer Tort Nice, Germany 64407 Frenkisch-Kulmbach Bahnhofstraße 27 (72) Inventor, Matthias Koch, Federal Republic of Germany 65183, Wiesberth 72 65 ) Inventor Holger Winkla-Germany 64291 Darmstadt Remerstraße 63 Art F-Term (reference) 3J011 QA05 SC01 SD03 3J030 AC10 BC01 BC10 CA10 4C081 AB05 BB08 CA021 CF132 DA11 DC12 EA02 EA05 4J002 BB001 BB031 BB011BB1 BB041 BB011BB1 BC081 BC111 BD031 BD101 BG011 BG041 BG061 BG101 BH021 BK001 BL011 BL021 BQ001 DJ016 FA086 FB266 FD016 GB02 GM02 GM05 4J011 PA13 PB06 PB15 PB19 ACB AC AD AC45 AC05 AC48 AC48 AC58 AC02 AC02 AB02 AC02 AB02 AC02 AB02 AC02 AB02 AC02 AB02 AB02 AC02 AB02 AB02 BA00B BA01A BA01B BB00A BB00B BB01A BB01B BC15B BC25A CA28A CA28B CB28C EA01 EB02 EB04 EB05 EB06 EB07 EB08 EB09 EB10 EB12 EB13 EB16 EB17 EB18 EB21 EB22 EB25 EB26 EC01 EC02 FA02 EC01 EC02 FA02

Claims (16)

[Claims] 1. A method for producing a polymer-based material containing a polyolefin matrix and silica particles as a filler, wherein the silica particles are blended at least before the completion of a polymerization process. . 2. The silica particles have an average diameter of 10 to 50.
0 nm polyethylene oxide functionalized monodisperse silica particles, wherein the monodisperse silica particles are used as a metallocene carrier, wherein the amount of metallocene immobilized on the monodisperse silica particles results in a silica content of the product of 1 5% by mass
In order to keep it between 0% by weight, sufficient polyolefin is selected such that it is formed during polymerization.
The method for producing the polymer-based material according to claim 1. 3. The method for producing a polymer-based material according to claim 1, wherein the silica particles are silica particles carrying a polymerization-active Ziegler-Natta catalyst species or Phillips catalyst species. . 4. Alkyl-functionalized monodisperse silica particles are further admixed with the catalyst in a sufficient amount, and the mixture is used for the polymerization. The method for producing a polymer-based material. 5. The olefin-functionalized monodisperse silica particles are:
The method for producing a polymer-based material according to any one of claims 1 to 3, wherein the polymer-based material is mixed before the polymerization. 6. A silica-based polymer material comprising a nano-dispersed and homogeneously distributed polyethylene matrix, wherein the silica particles are functionalized with a non-acidic nucleophilic species. And polymer materials. 7. Polymeric material according to claim 6, characterized in that the silica particles are functionalized with polyethylene oxide chains. 8. Alkyl-functionalized or olefin-functionalized silica particles are used,
The polymer-based material according to claim 6. 9. A polymer-based material obtained by the method according to claim 1. 10. Use of the polymeric material according to any of claims 6 to 9 for manufacturing joint implants in the medical engineering area. 11. Use of a polymer-based material according to any of claims 6 to 9 for the production of plain bearings, gears or other industrial parts. 12. A prosthesis artificial joint, at least some of which are made of a metal material, a polymer material or a ceramic material, at least one of which is a polyolefin matrix and silica as filler. An artificial joint comprising a polymer material containing particles, the polymer content of which is 1 to 50% by mass of silica. 13. The artificial joint according to claim 12, wherein the silica content is 5% by mass to 30% by mass. 14. The polyolefin matrix is ultra-high molecular weight polyethylene.
The artificial joint according to 2 or 13. 15. An artificial joint based on a polymer-based material obtained by the method according to any one of claims 1 to 5. 16. The artificial joint according to claim 12, wherein the artificial joint is an artificial hip joint or an artificial knee joint.