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EP1725274A2 - Materiaux composites a base d'acide polysilicique et leur procede de production - Google Patents

Materiaux composites a base d'acide polysilicique et leur procede de production

Info

Publication number
EP1725274A2
EP1725274A2 EP05716942A EP05716942A EP1725274A2 EP 1725274 A2 EP1725274 A2 EP 1725274A2 EP 05716942 A EP05716942 A EP 05716942A EP 05716942 A EP05716942 A EP 05716942A EP 1725274 A2 EP1725274 A2 EP 1725274A2
Authority
EP
European Patent Office
Prior art keywords
composite materials
materials according
polysilicic acid
composite
calcium phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP05716942A
Other languages
German (de)
English (en)
Inventor
Marianne Teller
Hans-Georg Neumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DOT GmbH
Original Assignee
DOT GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DOT GmbH filed Critical DOT GmbH
Publication of EP1725274A2 publication Critical patent/EP1725274A2/fr
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the invention relates to composite materials based on polysilicic acid, which contain as further constituents an organic polymer, at least one calcium phosphate phase and optionally application-specific additives and can be in the form of dispersions, pastes, powders, granules, layers or compact moldings.
  • the composite materials known in this connection consist either of polysilicic acid and at least one calcium phosphate phase or at least one calcium phosphate phase and an organic polymer.
  • DE10003824A1 claims a bone replacement material that, among other things, porous silicon dioxide-calcium phosphate composites, which are formed into threads via nozzles.
  • DE4132331C2 describes a calcium phosphate cement powder that contains a water-soluble polymer in addition to calcium phosphate phases.
  • the combination of calcium phosphate powders with a polysaccharide is carried out in DE69809158T2.
  • a bone replacement material - that in addition to a calcium phosphate phase, a hardening matrix, e.g. contains in the form of poly (g ⁇ ycol-co-lactic acid) and other organic components and living cells is disclosed in DE19956503 AI.
  • the bone substitute material produced is provided in a multiple syringe consisting of several syringes that are combined or a complete syringe with several chambers.
  • a 3-component osteosynthesis composite material is described in WO9911296.
  • the components consist of a bioceramic or a bioglass, a biodegradable polymer and a biodegradable polymer matrix.
  • Zhao et al in Biomaterials 2002, 23 (15), 3227-34 describe the production of a three-dimensional organic network in which hydroxyapatite granules are distributed in a chitosan-gelatin mixture.
  • phosphate and calcium-containing solutions and sodium hydroxide are dripped into an acidic solution of collagen, and the product is separated off by grinding at the end of the procedure and ground.
  • the order is modified in CN1337271.
  • a solution of calcium ions is placed in an acidic collagen solution, then drop by drop a phosphate solution is added and then the pH is adjusted with sodium hydroxide.
  • the product Collagraft Strip on the market from NeuColl is based on a composition of hydroxylapatite (65%) and tricalcium phosphate (35%) as well as high-purity collagen type.
  • the material described is compared with autogenous bone and evaluated positively (company publications at http://www.neucoll.com).
  • Bonfield et al describe a phase diagram for calcium phosphate collagen systems, taking temperature and pH into account (Bioceramics, Vol. 16, ed. MA Barbosa et al, Trans Tech Publications Ltd., Uetikon-Zurich, 2003, p 593-596).
  • WO02059395A2 claims electrochemical deposition of the components calcium phosphate and chitosan from electrolytes which contain corresponding components and precursors.
  • bioactive glasses have been converted into polymer suspensions for the purpose of injectability (WO0030561).
  • Composite materials that can be used can only be generated from two base materials, either silicon dioxide in combination with calcium phosphate (or other constituents in bio glasses) or calcium phosphate with physiologically compatible polymers.
  • the mechanical properties of the composites are determined by the main components. In the combination of silicon dioxide and calcium phosphate, there is almost no elastic behavior of the composite. Rather, the materials produced at low temperatures are brittle or the materials produced at high temperatures are characterized by high hardness.
  • the temperatures (500-1200 ° C.) used in the production or aftertreatment of the composites which are absolutely necessary for the physicochemical structuring of the materials, do not allow direct integration of organic, in particular bioorganic, polymers. Disclosure of the Invention Technical Problem
  • the structuring of the composite materials should be largely variable and include both fluid, pasty and solid forms. Bone replacement materials, bone regeneration materials and Bone cements can be realized with the composite materials. [026] The composite materials should also be able to be used for coating implant surfaces regardless of their material compositions and surface structures.
  • This object of producing composite materials based on polysilicic acid as a surface layer on human or veterinary implants or as bone substitute materials or bone regeneration materials with improved mechanical properties is achieved according to the invention in that the composite materials polysilicic acid, an organic polymer, at least one Calcium phosphate phase and optionally an application-specific additive in certain proportions. It has been found that contents of calcium phosphate materials of more than 15% by mass bring about a substantial increase in the physicochemical stability of the composite. Depending on its chemical structure and the properties associated with it in relation to the other composite components and the application requirements, the organic polymer should be in the range from 0.01 to 20% by mass.
  • the polysilicic acid can be generated from various sources, which can be used alone or in combination.
  • condensation from inorganic silicates which is usually carried out under acidic or neutral pH conditions, is possible, where the polysilicic acid matrix can contain a proportion of further metal oxides, such as titanium dioxide and aluminum oxide or their precursors.
  • Tetraalkoxysilanes or organoal oxysilanes can also be used as starting materials for the formation of polysilicic acid and corresponding derivatives.
  • Another source can be tapped from solid spherical or amorphous nano- or micro-silicate particles, whereby the chemical functionality necessary for the formation of the composite is produced via the properties of the particle surface.
  • the particle diameter used is preferably between 10 nm and 10 ⁇ m.
  • Natural, synthetic or semi-synthetic polymers can function as the organic polymer. They are used in the form of homo- or copolymers or also as polymer blends, which can have natural or synthetically inserted reactive and functional groups, sequences or substructures.
  • biopolymers as a com- positive component to a preferred role.
  • proteins and polysaccharides, their fragments and derivatives such as cellulose, laminaran, starch or their components amylose and amylopectin, glycogen, dextrins, dextran, pullulan, inulin, chitosan, xanthan, alginic acid and their salts and esters, rubber arabic, chondroitin, heparin and keratan as well as sulfates, hyaluronic acid and teichoic acids derived from them, as well as esters, collagen and gelatin derived therefrom in native or modified form.
  • synthetic polymers that have sufficient compatibility with all media involved can also be used. This applies to their sole use as well as the combination with biopolymers.
  • Such synthetic polymers originate in particular from the compound classes polyamines and imines, polyols and their ethers and esters, polycarboxylic acids including the derivatives derived therefrom, such as esters and amides.
  • other polyvinyl compounds, polyethers, polyesters, polyketones or polysulfones can also be considered as a composite component.
  • the solubility in water or the chosen reaction medium, the swellability or dispersibility of the organic polymers determine the percentage in the composite material (0.01% and 20% (w / w)).
  • the main constituent of the composite material is generally at least one calcium phosphate phase.
  • This calcium phosphate phase can be supplied prefabricated in crystalline or amorphous form to the reaction medium, or it can be prepared in situ by combining components containing calcium and phosphate under neutral or basic conditions.
  • the calcium phosphate phase maintains its morphology during the further manufacturing process, so that the end product is given a corresponding porosity.
  • Hydroxyapatite, a- or b -tricalcium phosphate, discalcium phosphate, dicalcium phosphate dihydrate, octacalcium pentaphosphate or corresponding mixed phases or mixtures can be used as calcium phosphate phases.
  • the calcium phosphate phase also contains a proportion of alkylene bisphosphonate calcium salts.
  • the calcium phosphate phase can also act as a calcium precursor for complex formation with the polymer component of the composite. This complex formation is additionally increased by the proportionate addition of alkylene bisphosphonate calcium salts.
  • other metal cations such as sodium, potassium, silver, magnesium, zinc or lithium, and fluoride, chloride, sulfate, carbonate or silicate as anions can be present in the calcium phosphate phase.
  • the composite material for the basic constituents polysilicic acid, polymer and calcium phosphate component can have an application-specific one Additive can be added.
  • This additive can be used as a chemically or morphologically modified polysilicic acid compound, organic polymer or calcium phosphate phase. It is also possible to add an additive in the form of solid nano or micro particles or capsules.
  • bioactive substances such as antibiotics, tumor statics, hormones or growth factors or a combination of these classes of substances, the bioactive substances can also be used encapsulated. As is known, a controlled release of the active substances can be achieved via the type of encapsulation.
  • the process-technical implementation of the production of the composite material begins with the addition of an organic polymer, at least one calcium phosphate phase and optionally an application-specific additive to a gel made from silica sol.
  • the preparation of a gel from a silica sol has been extensively described in the literature (H. Schmidt: "Chemistry of Material Preparation by Sol-Gel Process” in J. Non-Cryst. Solids 100, 51 (1988); J: DF Ramsay : “Sol-Gel Processing” in Controlled Particle, Droplett and Bubble Formation, Ed .: DJ Wedlock, Butterwoth-Heinemann Ltd., Oxford, 1994, p.1-36).
  • the individual components of the composite material are combined in succession or in combination depending on their chemical and physical properties. Once all the components have been combined, the mixture is homogenized depending on the viscosity of the mass using various stirring techniques (stirrers, dispersers). The subsequent shaping is also determined via the viscosity.
  • the still moist composite material can be e.g. pour, squeeze, spray or spray. Improved adhesive strength on surfaces can be achieved by depositing the composite material in a damp state with reduced pressure. In addition, the composite material can be applied to surfaces by dipping or spraying. The application is not only limited to static surfaces, but can also be expanded to rotating substrates.
  • Metallic, natural and synthetic or ceramic surfaces are suitable for coating with the composite material, regardless of their roughness, pretreatment or precoating.
  • Electrochemical (cathodic) deposition offers a completely different possibility for coating with the composite material. There are basically two options here. On the one hand, the finished component mixture is used or the components are deposited electrochemically one after the other.
  • the combination of polysilicic acid derivatives with suitable calcium phosphates and polymers with the alternative of adding application-specific ones Additives make it possible to use the composite material in conjunction with medical devices or directly as a medical device.
  • the composite material can be used directly as a base material, as a filler, depot material or as a coating.
  • the composite material can be used in the form of dispersions, pastes, powders, granules, layers or as compact moldings.
  • the composite material itself can contain an application-specific additive, this can be used directly as a medicament or in combination with medicinal products.
  • the material made according to the invention is implantable or injectable.
  • the composition of the composite material with the resulting properties makes it possible to use the composite material for bone substitution and / or for bone regeneration. This material can also be used for wound healing purposes.
  • Example 1 Production of a composite material based on polysilicic acid, polymer and a calcium phosphate phase:
  • Example 2 Production of a composite material based on polysilicic acid, polymer and two calcium phosphate phases:
  • Example 04 Production of a composite material based on polysilicic acid, polylactic acid and hydroxylapatite - 10% polymer content (w / w):
  • 13.8 ml of tetraethoxysilane are mixed with 4 ml of 0.1M hydrochloric acid and 5.5 ml of ethanol and 4 ml of water are added.
  • Example 4 Production of a composite material based on polysilicic acid, polylactic acid and hydroxylapatite - 20% polymer content (w / w):
  • 13.8 ml of tetraethoxysilane are mixed with 4 ml of 0.1M hydrochloric acid and 5.5 ml of ethanol and 4 ml of water.
  • Example 5 Production of a composite material based on polysilicic acid, active ingredient-containing polylactic acid microparticles and hydroxyapatite:
  • 14 ml of tetraethoxysilane are mixed with 4 ml of 0.1M hydrochloric acid and 5.5 ml of ethanol and 4 ml of water.
  • Example 8 Production of a composite material using epoxy-functionalized pol silica particles:
  • a polysilicic acid sol is produced from 9 ml of tetraethoxysilane, 3 ml of 0.1M hydrochloric acid and 3 ml of ethanol water.
  • 3 ml l, 5% chitosan solution are added dropwise.
  • 10 ml of the polysilicic acid sol-chitosan solution are reacted with 15.6 g of dicalcium phosphate dihydrate via a mixing cannula.
  • the composite material produced in this way does not dissolve when sprayed into SBF buffer and has pressure-elastic properties.
  • Example 10 Production of composite materials by successive electrochemical deposition of the components:
  • chitosan is electrochemically deposited from a 1.5% chitosan solution at pH 5.0. The excess gel-like chitosan film is rinsed off. Then a silicate surface is created on it by using a 0.1M sodium silicate solution as the polysilicic acid precursor. With the addition of 0.1M calcium chloride solution and 1M hydrochloric acid, the calcium-containing polysilicic acid layer is generated on the calcium phosphate-chitosan coating at a voltage between 5 and 8V.
  • 27 ml of tetraethosysilane are mixed with 8 ml of 0.1 M hydrochloric acid and 10 ml of ethanol.
  • the polysilicic acid solution in 7.5 ml collagen solution (in 10% lactic acid) added dropwise.
  • 27 g of hydroxyapatite and 18 g of ⁇ -tricalcium phosphate are introduced into the solution with stirring.
  • 2.25 g of gentamicin sulfate are dissolved in 4 ml of water and stirred into the composite material. After 30 minutes the product is poured into molds and dried at 130 ° C.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Transplantation (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne des matériaux composites à base d'acide polysilicique contenant de nouvelles compositions à propriétés améliorées et pouvant se présenter sous forme de dispersions, pâtes, poudres, granulés, couches ou corps moulés compacts. L'invention a pour but de produire des matériaux composites à base d'acide polysilicique, dotés de propriétés mécaniques améliorées et, à cet effet, est caractérisée en ce que les matériaux composites à base d'acide polysilicique renferment un polymère organique, à raison de 0,01 à 20 % en masse, au moins une phase phosphate de calcium, à raison de plus de 15 % en masse et, éventuellement, un additif spécifique pour l'utilisation. Le matériau fabriqué conformément à l'invention est implantable ou injectable. La composition du matériau composite doté des propriétés qui en résultent permet l'utilisation de celui-ci pour la substitution osseuse et/ou la régénération osseuse dans des applications en médecine humaine et vétérinaire. En outre, ce matériau peut être utilisé pour la guérison de blessures.
EP05716942A 2004-03-13 2005-03-07 Materiaux composites a base d'acide polysilicique et leur procede de production Ceased EP1725274A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004012411A DE102004012411A1 (de) 2004-03-13 2004-03-13 Kompositmaterialien auf der Basis von Polykieselsäuren und Verfahren zu deren Herstellung
PCT/EP2005/051012 WO2005087284A2 (fr) 2004-03-13 2005-03-07 Materiaux composites a base d'acide polysilicique et leur procede de production

Publications (1)

Publication Number Publication Date
EP1725274A2 true EP1725274A2 (fr) 2006-11-29

Family

ID=34895362

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05716942A Ceased EP1725274A2 (fr) 2004-03-13 2005-03-07 Materiaux composites a base d'acide polysilicique et leur procede de production

Country Status (8)

Country Link
US (1) US20070196419A1 (fr)
EP (1) EP1725274A2 (fr)
JP (1) JP2007529253A (fr)
CN (1) CN1929881A (fr)
AU (1) AU2005221333A1 (fr)
CA (1) CA2555166A1 (fr)
DE (1) DE102004012411A1 (fr)
WO (1) WO2005087284A2 (fr)

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JP2007529253A (ja) 2007-10-25
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AU2005221333A1 (en) 2005-09-22
DE102004012411A1 (de) 2005-09-29
WO2005087284A3 (fr) 2006-05-11
US20070196419A1 (en) 2007-08-23
WO2005087284A2 (fr) 2005-09-22

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