Biomedicine material composition, method for production thereof and biomedicine material

FIELD: composite polymer biomedicine materials containing polymer binder, biocompatible filler and carbon reinforcing filler.

SUBSTANCE: claimed composition contains polymer binder, namely mixture of polymethylmethacrylate or methylmethacrylate copolymer with methylacrylate and monomer methylmethacrylate in ratio of polymer part to monomer from 1:0.3 to 1:0.5 mass pts (50-72 mass pts); peroxide initiator (0.05-0.5 mass pts): carbon continuous fibers of 200-1000 filaments made of hydratcellulose fiber of polyacrylonitrile fiber (2-10 mass pts); and hydroxyapatite as filler (25-40 mass pts). Method for production of material from claimed composition useful in manufacturing of jowl implants also is disclosed.

EFFECT: polymer material having natural bone-like properties.

3 cl, 10 ex, 1 tbl

 

The invention relates to the field of composite polymeric materials for biomedical application containing polymer binder, biocompatible filler and carbon reinforcing filler. These compositions are intended for the manufacture of reinforced polymer materials for implants used in surgery for hip replacement.

Known polymer compound for biomedical application (patent RU 2197509 C1; application 200111591/04 Krasnov A.P., Afonicheva O.V., Popov A.B., Cossacks M.E. Ter-Minassian, Rashkovan I.A., Volozhin A.I., Popov V.K., Ulyanov S.A. "Polymer compound for biomedical application"), consisting of a polymeric binder, which is used as the polyamide-12, as a biocompatible filler - hydroxyapatite and carbon fiber in the form of fine powder.

The main disadvantage of the material obtained from this composition, is the impossibility of obtaining from her implants complex profile, as, for example, jaw implants, as the processing composition is analog only possible through the melt by the method of injection molding or injection molding at a temperature of 240°and With the pressure.

Other shortcomings of the composition are reduced strength in thin-walled implants and low (˜100-120 MPa) hardness of surface layers, significantly octopuse the indicator of natural bone.

Known composite material for surgical implants, obtained from a polymer composition consisting of a polymeric binder (polyethylene), filler (hydroxyapatite) and discrete oriented high modulus polyethylene fibers (Ward, Ian Macmilean, Ladizesky, Noe Huqo) (Compacted biomaterials) G.B. Pat 96 - 800960115.

The disadvantage of this reinforced biostable material lies in the impossibility of obtaining from it the product of a complex type simple process by casting in a plaster form, obtained by melting the wax model. In addition, low hardness polyethylene (˜20 MPa) reduces its structural features when used to replace bones of the maxillofacial skeleton.

Known composition (N.H.Ladizesky, E.M.Pirhonen, D.B.Appleyarol, I.M.Ward, W.Bonfield) (Fibre reinforcement of ceramic/polymer composites for a major load - bearing bone Substitute materials. Composites Science and Technology 58 (1998), 419-434), consisting of layers of oriented continuous polyethylene fibers, hydroxyapatite and polyethylene.

This material is similar process or by extrusion or injection moulding with the manufacture of blanks for further products by means of mechanical processing. Its disadvantage is the impossibility of processing simple "filling" technology by the method of "investment model". It makes available the receipt of the his in the processing of products with complex profile, which are almost all bone implants.

Products obtained from the latest materials analogues, have low hardness (about 20 MPa) and high wetting angle that differs markedly from those of natural bone.

Known composition, selected as a prototype, including methacrylic copolymer and methyl methacrylate (Thetubes, Aijalon Hyper-Dev, Aphrase, Vscope, VII // osteointegration properties of polymethylmethacrylate, chemically related synthetic hydroxyapatite. Sat. "Biomedical technology" RAMS, "VILAR", 2002, p.54-62), which is a mixture of powdered polymethyl methacrylate, monomer - methyl acrylate in a ratio of 3:1 and the initiator benzoyl peroxide in the amount of 0.2% of the polymeric binder. To the resulting mixture add the hydroxyapatite powder filler. From a song by her fill at room temperature to form a complex profile, followed by polymerization at a temperature of 100°To receive the workpiece implants of complex configuration. Implants of this material is currently used in surgery for hip replacement.

The material obtained from the composition of the prototype is biostable, non-toxic, however, significant constraints is receiving for its wider use is insufficient impact strength (˜ the 2.4 kJ/m2), especially in the fabrication of implants in maxillofacial surgery, when applied finishing mechanical finishing of workpieces with getting on their surface through holes for germination of bone tissue, which significantly reduces the resistance of the target product with ˜ and 2.4 kJ/m2to value ˜1,5 kJ/m2.

The objective of this invention to provide a polymeric composition for biomedical application, able to be processed by pouring the polymer-monomer mass with fillers in the form of a complex configuration, to obtain a polymeric material having biocompatibility, biostability, hardness, high toughness as in the original molding product, and after drilling through holes, that is, for complex properties approaching those of natural bone.

Composition for the manufacture of material for biomedical application containing polymer binder and biocompatible powder filler - hydroxyapatite, characterized in that the binder comprises a mixture of a powder of polymethyl methacrylate or a copolymer of methyl methacrylate and methyl acrylate and the monomer is methyl methacrylate in a ratio of polymer to monomer is from 1:0.3 to 1:0.5, the peroxide initiator, the composition additionally contains the inhabitants of carbon fibrous filler in the form of carbon continuous yarns on 200-1000 filament of the hydrated cellulose fibers or polyacrylonitrile fibers in the following ratio of components in mass parts:

Binder50-72
Hydroxyapatite25-40
Carbon filament2-10
Peroxide initiator0,05-0,5

The method of obtaining the polymer material of the composition is that powdered methacrylate polymer or copolymer is mixed with hydroxyapatite with a further introduction to the obtained powdery mass of liquid monomer is methyl methacrylate, the initiator, in a mass ratio of binder 50-72 parts by weight, hydroxyapatite 25-40 parts by weight, the initiator of 0.05-0.5 parts by weight and the subsequent laying of continuous carbon fibers in a weight ratio of 2-10 parts by weight in the swollen polymer mass necessary for the product direction with the distance between the threads of 1-4 mm and a subsequent heat treatment of the composition in a closed mold at a temperature of 80-120°for 45-120 minutes.

The polymeric material is a partially vzaimopronikayut mesh polymeric binder (50-72 parts by weight) containing insoluble in the binder in the amount of 18-35 wt. -%, filled with a powdery filler - hydroxyapatite in the amount of 25-40 parts by weight and reinforced with continuous carbon fibers from natural hydrate cellulose fibers or polyacrylonitrile fiber is in the amount of 2-10 parts by weight, with the indicator toughness on Distate 3,2-4,8 kJ/m2.

As the polymer binder offers a mixture consisting of powderedmethacrylicpolymerormethacrylic copolymer in a mixture with methyl methacrylate, taken in the mass. the ratio of polymer - monomerfrom 1:0.3 to 1:0.5 and when the content of the polymerization initiator (benzoyl peroxide) from 0.05 to 0.5 mass in composition.

Fillers are powdered hydroxyapatite (1-10 μm) and continuous biocompatible carbon filament containing 200-1000 filament, obtained from natural hydrate cellulose or acrylic fiber with the distance between the threads 1-4 mm

After mixing the binder with the mixture of fillers, heat treatment is carried out at 80-120°in which process is the polymerization of the Monomeric component of the binder with the creation of patterns vzaimopronikayut grid.

The essence of the invention lies in the fact that the proposed polymer composition for biomedical application is obtained by mixing a polymeric binder, which represents the viscous mass of swollen powdered acrylic polymer in the monomer (methyl methacrylate), which is injected powder of hydroxyapatite. Then in a viscous polymer-monomer weight stack continuous reinforcing the s carbon filament. To produce the polymer material from which the finished product (billet implants), are Samoobrona composition at a temperature of 80-120°within 40-120 minutes, during which undergoes polymerization of Monomeric part of the binder in the presence of fillers. Thus obtained, the workpiece is subjected to the required finish machining.

It turned out that in contrast to the composition of the prototype and material on its basis a significant advantage of the proposed composition is a sharp increase in toughness due to the reinforced anisotropic structure of the material obtained, in spite of the small amount of carbon fibrous filler. In the claimed composition of the fibers used in the form of continuous filaments, containing 200-1000 individual fibers (filament), which are located at a distance from each other, 1-4 mm, which determines the obtained anisotropic material and sharp (40% or more compared to the unreinforced counterpart) increase toughness, despite the relatively low number of input carbon fiber (2-10 wt.%). Feature the introduction of the carbon fibers is the different nature of their location: along the longest side, or transverse, combined, ring stacking, etc. In all cases otlicials the th feature of the material is the distance between threads, which should be in the range of 1-4 mm

As a binder used:

poly (methyl methacrylate)- (CH2-(CH3)-SN(SOON3))-nthe density of 1.19 g/cm3in mixture with the monomer methyl methacrylate, benzoyl peroxide or peroxide Dicumyl, a copolymer of methyl methacrylate and methyl acrylate, a density of 1.14 g/cm3.

All of these polymers were investigated biocompatibility and used as a binder materials, currently used as implants for maxillofacial surgery. The advantage of the chosen binder in comparison with polymer-analogues is that they are mixed with the monomer are swollen viscous mass, which when added in small amounts (0.05 to 0.5 M.Ch.) standard initiators, which, as a rule, are peroxides (benzoyl peroxide, peroxide Dicumyl), the process of polymerization at relatively low temperatures without the application of pressure, allowing you to carry out this process in closed form very complex profile, made from materials such as plaster, rubber, polymers, etc. This is a decisive advantage for the use of the selected binders for create filled reinforced materials used in surgery. As a filler to obtain the inventive polymer compositions the AI uses a powder standard hydroxyapatite, a powder with a particle size of from 1 to 10 μm with a ratio C/F≈1,67.

Hydroxyapatite [CA10(PO4)6(OH)2] is widely used in surgery and dentistry product as a biocompatible filler.

As the reinforcing filler of the claimed composition used carbon fiber, which results in a sharp increase in toughness of the developed material. Used fiber is of two types: derived from polyacrylonitrile fiber (Chis) and the hydrated cellulose fibers (UVIS). Used fibrous fillers along with biocompatibility have high physical and mechanical properties. Carbon fiber from the hydrated cellulose fiber - modulus 100-120 GPA, a density of 1.6 g/cm3the strength of 1000-1500 MPa, ⊘ 4,9-5 μm; carbon fiber from polyacrylonitrile fiber - modulus of elasticity - 200-250 HPa, the density of 1,72 to 1.76 g/cm3the strength of 2500-4000 MPa, ⊘ 7-7,5 ám.

A specific example of production of the material is given below.

Material components: powdered methacrylic polymer in a quantity of 50 parts by weight is mixed with 30 parts by weight of hydroxyapatite, the calculation amount of the initiator, benzoyl peroxide and 0.15 parts by weight and add 20 parts by weight of the monomer is methyl methacrylate. In the resulting viscous mass stack thread containing 800 carbon filament in the fibre Chis, derived from polyacrylonitrile, in the amount of 8 parts by weight, in 1.5 mm between threads.

A lot utverjdayut in the form of gypsum without pressure at a temperature of 100°C for 1 hour.

Test results: bending strength 60,0 MPa impact strength of 4.1 kJ/m2; the hardness of 210 MPa.

The advantages of the proposed polymer composition for biomedical application are the simplicity of the technological process of manufacture. The workpiece can be obtained during the heat treatment directly in the required form, including in view of the part corresponding to the implant complex configuration, or in blocks, plates, cylinders, which can easily be machined. Moreover, an advantage of the claimed composition is the ability to change the location of the reinforcing threads in any direction. In addition, the impact strength of the polymer material obtained from the proposed composition, closer to those of natural bone than that of the material obtained from the composition of the prototype.

Additional advantage of the composition should include the availability of components, of which it is composed.

The claimed material far exceeds the prototype for toughness (3,2-4,8 instead of 2.4 kJ/m2) and bending strength (60 instead of 50 MPa) and is blizek to those of natural bone.

When the number of reinforcing fibers and powdered filler material affects manufacturability, and by reducing the amount of hydroxyapatite deteriorating biocompatibility, while reducing the reinforcing fibers decreases the impact strength of the material, which was confirmed by the table of examples.

Thus, for a number of defining properties to create the necessary surgical implant with the desired performance of the inventive composition is superior to the properties of the composition of the prototype, first of all, in terms of impact strength of the material.

The combination of the polymeric material derived from the claimed composition, high technology, contributing to the possibility of obtaining products of complex profile with high strength properties coming on indicators to natural bone, ensures its successful use, primarily in the field of maxillofacial surgery, especially for making implants jaw experiencing along with static and shock loads.

Table of specific examples of the composition of the claimed composition and properties of the obtained material
The COMPOSITION, the composition in wt. the frequent.Polymeric material and blanks
Ingred.PolymerHydroxyCarbonImpact strengthImpact strengthDistance
№ p/pbinderApatitethreadmonolithic samplesample with holes ⊘ 1.5 mmbetween threads
1722623,21,74
25040103,42,01
3553783,42,41,2
4503084,42,81,5
5603553,62,72,8
6643064,83,51,4
7722533,31,83,2
84245131,00,60,6
9 6520152,51,25
107030-2,41,3-

1. Composition to obtain material for biomedical application, containing a polymeric binder, initiator is benzoyl peroxide and biocompatible powder filler - hydroxyapatite, characterized in that it contains as a binder a mixture of polymethyl methacrylate or a copolymer of methyl methacrylate and methyl acrylate and the monomer is methyl methacrylate in a ratio of polymer to monomer is from 1:0.3 to parts by weight of 1:0.5 to parts by weight and the peroxide initiator further comprises a carbon fiber filler, which is used graphite continuous filament on 200-1000 filament of the hydrated cellulose fibers or polyacrylonitrile fibers in the following ratio of components, parts by weight:

Binder50-72
Hydroxyapatite25-40
Carbon filament2-10
Benzoyl peroxide0,05-0,5

2. The method of obtaining the polymer material of the composition according to claim 1, consisting in that the powdery copolymer matilla is relata mixed with hydroxyapatite with a further introduction to the obtained powdery mass of liquid monomer - methyl methacrylate and initiator, followed by the laying of continuous carbon fibers in the swollen polymer mass necessary for the product direction with the distance between the threads of 1-4 mm and a subsequent heat treatment of the composition in the closed form at temperatures of 80-120°for 45-120 minutes

3. The polymeric material obtained by the method according to claim 2 and which is partially vzaimopronikayut mesh polymeric binder content insoluble in the binder in the amount of 18-35 wt.%, filled with a powdery filler - reinforced hydroxyapatite and continuous carbon graphite filaments from natural hydrate cellulose fibers or polyacrylonitrile fibers having an index of toughness on Distate 3,2-4,8 kJ/m2.



 

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