Polymer antifriction composition for biomedical purposes

FIELD: chemistry.

SUBSTANCE: present invention pertains to compositions, with low coefficient of friction for use in friction units of living organisms. Proposal is given of an antifriction composition, containing, as polymer binding mixture (with ratio of components in the binder): methyl methacrylate monomer (27-36 mass units), polymethyl methacrylate polymer powder (72-64 mass units), initiator - benzoyl peroxide 1 mass units (polymer binder A); or a mixture (with ratio of components in the binder): methyl methacrylate (27-36 mass units), copolymer powder (72-64 mass units) with the following content of components: methyl methacrylate - 89 mass units, ethyl methacrylate - 8 mass units, methyl methacrylate - 2 mass units, as well as initiator-benzoyl peroxide - 0.6-1.5 mass units (polymer, binder B) and ultrahigh-molecular polyethylene with 1·106 - 12·106 dalton molecular weight, in powder form (2-15 mass units per 85-98 mass units of polymer binder). Compared to the prototype, the value of coefficient of friction decreases by 2-4 times.

EFFECT: design of a composition, which reduces friction in the maxillotemporal joint of a polymer implant.

3 cl, 4 tbl

 

The invention relates to compositions having low coefficient of friction for use in friction units of living organisms. The most appropriate use of the invention in the friction nodes of the skeleton of a man, namely in the lower jaw, the friction TMJ.

Known selected as the analogue for the appointment of a 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, Hugo Noe) (Compacted biomaterials) Pat. GB./ 96-800 960115.

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.

The most similar in composition and method of use of the claimed composition is a composition for biomedical material, is known from the patent RU 2281300 C1 from 03.03.2005, the Composition obtained in the same binder and in the same way as the claimed composition is me. Additionally it contains to enhance the effect of biocompatibility powdered hydroxyapatite and to improve the impact strength of reinforcing carbon yarn, obtained from polyacrylonitrile and the hydrated cellulose fibers in a ratio (mass parts):

Binder50-72
Hydroxyapatite25-40
Carbon filament2-10
Peroxide initiator0,06-0,5

Get the prototype material with high biocompatibility and impact strength designed for use in arthroplasty.

The disadvantage of the material obtained is not satisfactory lubricating properties when used for the manufacture of the head joint of the lower jaw, especially the deteriorating with the introduction hydroxyapatite (table 1).

Based on the composition of the entire lower jaw, including the head of the mandible, is a monolithic mass, consisting of polymethylmethacrylate (PMMA) and copolymers containing as filler reinforced hydroxyapatite and carbon fibers. Our research surface of the head of the lower jaw of the prototype showed that surface as a result of technological operations is when receiving is almost only the polymer, and hydroxyapatite and carbon filaments are absent. This is due to the fact that in the formation of any of the compositions of the most polar components are located inside the composition, and less polar outside. Upon receipt of the composition of the prototype polymer coats the filler and is located in the outer layers of the surface, which answered to the authors.

However, the surface composition head polymers, representing PMMA, or its copolymers, are not antifriction materials in tribological classifications and have studied in conditions of high coefficient of friction (>0,7).

The essence of the invention.

The invention consists in reducing friction in the temporomandibular joint polymer of the implant, which in the composition of the implant head, the lower jaw impose additional powdery ultrahigh molecular weight polyethylene in an amount of 2-15 parts by weight of

Powdery ultrahigh molecular weight polyethylene (UHMWPE) is introduced into the composition, representing the initial monomer - methyl methacrylate (MMA), powdered PMMA or copolymer of MMA with other acrylic monomers: ethyl methacrylate and methyl acrylate, and a known polymerization initiator, which is usually benzoyl peroxide in an amount of 0.6 to 1.5 parts by weight of the Composition mixed to obtain homogeneous the mass and then placed in the form, where the polymerization process. The polymerization is carried out with an alternating temperature regime: first, within 30-60 minutes, the polymerization is carried out at a temperature of 55-65°and then for 1 hour at a temperature of 95-100°C.

After polymerization the product is recovered from the mold and determine its tribological and mechanical properties.

Evaluation of anti-friction properties developed composition in comparison with the prototype were carried out on the machine end of the friction type And-47 at specific load of 0.1 MPa, the sliding speed of 0.5 m/s in terms of friction without lubricant, duration - 6 hours. The counterbody was a titanium alloy (TiAl). Evaluation of antifrictional was performed according to the temperature value generated in the friction zone (temperature heating above room temperature) and the coefficient of friction of the material of the polymer composition.

Table 1
№№ p/pTrackIndicators
The increase of frictional heating temperature with respect to room, °The coefficient of friction
1.Binder "And" - PMMA+60,5
2.Binder "And" + gap (30 mA is C) +100,7
3.Binder "And" + 5 parts by weight of UHMWPE+50,4
4.Binder "And" + 5 parts by weight of UHMWPE radiation modified+40,4
5.Binder "And" + 5 parts by weight of UHMWPE modified in the environment SC CO2+30,3
6.Binder "B" + 5 parts by weight of UHMWPE+50,38
7.Binder "B" + 5 parts by weight of UHMWPE modified in the environment SC CO2+30,25

Note:

Binder "A" in the examples is a mixture (ratio of the components in the binder): monomer methyl methacrylate (36 parts by weight), powdered polymer (methyl methacrylate) (64 parts by weight) and the initiator benzoyl peroxide (1 parts by weight) binder and "B" represents the mixture ratio of the components in the binder): methyl methacrylate (36 parts by weight), powdery copolymer (64 parts by weight) [content components: methyl methacrylate (89 parts by weight), ethyl methacrylate (8 parts by weight) of methyl acrylate (2 parts by weight)] and the initiator benzoyl peroxide (1 parts by weight).

It turned out that significant improvements in antifrictional can be achieved by introducing a relatively small quantity of powdered UHMWPE, the OS is especially when its modifications in the environment of supercritical CO 2(IC CO2and radiation-chemical method.

It is known that the UHMWPE has a good sliding performance, but his introduction to polymer compositions leads to a sharp decrease of physico-mechanical characteristics. It was found that the introduction of relatively small (2-15 parts by weight) amounts of ultra-high molecular weight polyethylene in the monomer - polymer composition lowers the physico-mechanical properties of only a relatively small amount. Especially in the pre-treatment ultra-high molecular weight polyethylene in the medium of supercritical carbon dioxide or by radiation-chemical processing.

In terms of friction coefficient and wear the composition of the prototype is significantly inferior to the claimed composition. The material results of comparative tests carried out on the machine end of the friction type And-47 without lubrication, are shown in table 2. Note that the tests were carried out under severe conditions of dry friction without lubrication the friction, the coefficient of mutual overlap, equal to the unit.

Table 2
The results of the comparative material testing of developed composition and prototype (P UD=0.1 MPa, V=0.5 m/s, friction without lubrication, the counterbody - alloy is Ethan TiAl)
№№ p/pSample typeThe coefficient of frictionThe increase of frictional heating temperature with respect to room, °
1.The placeholder>0,7+10
2.The claimed composition0,3-0,4+3-5

The determination of physical and mechanical properties is required, as it is well known that the introduction of the filler, and the more non-polar polymer filler, such as UHMWPE, dramatically affects the physical and mechanical properties of any polymer composition. Table 3 presents data illustrating the effect of the number of UHMWPE on the physico-mechanical properties of the polyacrylate composition.

Table 3
CompositionPhysico-mechanical properties
Polyacrylic composition (in parts by weight)UHMWPE (in parts by weight)Impact strength, kJ/m2Flexural strength, σtechnology,MPa
100 "B"-6,5-7,091
99,5 "B"0,56,589
99 "B"16,287
97 "B"35,182
95 "B"5*6,379
95 "B"5**5,589
95 "A"5*5,676
95 "A"5**5,285
90 "B"10a 4.9
*UHMWPE modified radiation;
**UHMWPE modified in the environment SC CO2

Binder "A" in the examples is a mixture (ratio of the components in the binder): monomer methyl methacrylate (36 parts by weight), powdered polymer (methyl methacrylate) (64 parts by weight) and the initiator benzoyl peroxide (1 parts by weight) binder and "B" represents the mixture ratio of the components in the binder): methyl methacrylate (36 parts by weight), powdery copolymer (64 parts by weight) [content components: methyl methacrylate (89 parts by weight), ethyl methacrylate (8 parts by weight) of methyl acrylate (2 parts by weight)] and the initiator benzoyl peroxide (1 parts by weight).

The table shows that the introduction of UHMWPE above 15 parts by weight dramatically reduces physical and mechanical properties of poly (acrylic composition that is not optimim during operation antifriction endoprosthesis, with constant alternating loads.

Even more high physical-mechanical indicators have compositions with the introduction of the modified UHMWPE. Modification of UHMWPE is held in one of two ways. The first method consists in processing powder of UHMWPE in the medium of supercritical carbon dioxide (SC CO2in the face of pressure from 70 to 600 atmospheres and a temperature of from 38 to 110°C for from 1 hour to 8 hours. The second method consists in processing powder of UHMWPE γ irradiation to a dose of 2 to 30 Mrad and subsequent surgery neutralize free radicals.

As a result of modifications happen restructuring and the changing composition of the surface layers, which is probably a positive effect on the adhesion-strength properties of the composition.

Ultra-high molecular weight polyethylene is a powdery product with a particle size of from 1 to 200 microns, with a molecular weight of from 1·106up to 12·106daltons.

Essential components of the claimed composition is that of polymer drag reducing composition comprises polyacrylic binder, in which the polymeric binder contains a mixture (ratio of the components in the binder): monomer methyl methacrylate (27-36 parts by weight), powdered polymer (methyl methacrylate) (72-64 parts by weight), the initiator re the IRS benzoyl 1 parts by weight(polymer binder "A"); or a mixture (ratio of the components in the binder): methyl methacrylate (27-36 parts by weight), powdery copolymer (72-64 parts by weight) containing components: methyl methacrylate - 89 parts by weight, ethyl methacrylate, and 8 parts by weight, of methyl acrylate to 2 parts by weight, and contains the initiator is benzoyl peroxide 1 parts by weight (polymer binder "B") and, optionally, contains ultra-high molecular weight polyethylene with a molecular Massai 1·106up to 12·106Dalton in the powdered state in the following ratio of components in the amount, parts by weight: polymer binder is 85-98 and ultra-high molecular weight polyethylene in original or modified form - 2-15,

All of these claimed composition ingredients are produced, characterized and approved for use in medical purposes. As for the modified UHMWPE in the environment SC CO2this type of modification does not introduce significant changes in the composition of the polymer.

Below are examples of specific compounds of the claimed composition and properties of the obtained materials.

Table 4
№№ p/pThe composition, parts by weightProperties of composition
Physico-mechanical properties Tribological properties
Polyacrylic binder component "B"UHMWPEImpact strength, kJ/m2Flexural strength, σtechnology, MPaThe coefficient of frictionThe temperature increase of frictional heating, °
1100-6,5-7910,5+6
295,50,56,5890,49+3
39555,5740,4+5
49010a 4.9710,37+3
585153,5650,38+3
682182,7600,42+5
7955*6,3790,4+4
8955**5,5890,3+3
995***55,072 0,42+5
* radiation-modified UHMWPE
** - UHMWPE modified in the environment SC CO2.
*** in example 9 used polyacrylic binder.

1. Polymer drag reducing composition for biomedical application, containing a polymeric binder and a peroxide initiator type, characterized in that it contains a polymeric binder mixture with the ratio of components in the binder): monomer methyl methacrylate (27-36 M.Ch.), powdered polymer (methyl methacrylate) (72-64 M.Ch.), the initiator is benzoyl peroxide 1 M.Ch. (polymeric binder; or a mixture (ratio of the components in the binder): methyl methacrylate (27-36 M.Ch.), powdery copolymer (72-64 M.Ch.) containing components: methyl methacrylate - 89 M.Ch., methacrylate - 8 M.Ch., methyl methacrylate - 2 machine hours, and also contains the initiator is benzoyl peroxide 0.6 to 1.5 M.Ch. (polymeric binder "B") and, optionally, contains ultra-high molecular weight polyethylene with a molecular weight of from 1·106up to 12·106Yes in the powdered state in the following ratio of components:

polymer binder85-98 parts by weight
servicecompany polyethylene 2-15 parts by weight

2. Polymer drag reducing composition biomedical applications according to claim 1, in which the powdery ultrahigh molecular weight polyethylene prior to use in the composition is processed in the environment of supercritical carbon dioxide under conditions of: pressure 70-600 ATM, temperature 38-110°and duration of 1-8 hours

3. Polymer drag reducing composition biomedical applications according to claim 1, in which the powdery ultrahigh molecular weight polyethylene undergoes radiation and chemical processing from 2 to 30 Mrad.



 

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17 cl, 8 tbl

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

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3 cl, 10 ex, 1 tbl

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1 cl, 2 tbl, 7 ex

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1 cl, 1 ex, 1 tbl

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4 cl, 2 dwg, 3 tbl

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1 tbl

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2 cl, 1 dwg, 2 tbl, 6 ex

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1 cl, 1 tbl, 4 ex

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EFFECT: providion of availability on a surface added to binding calcium and phosphorus.

20 cl, 1 ex

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