CN107754013B - High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof - Google Patents

High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof Download PDF

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CN107754013B
CN107754013B CN201711260076.8A CN201711260076A CN107754013B CN 107754013 B CN107754013 B CN 107754013B CN 201711260076 A CN201711260076 A CN 201711260076A CN 107754013 B CN107754013 B CN 107754013B
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molecular weight
antioxidant
weight polyethylene
ultrahigh molecular
joint material
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CN107754013A (en
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徐家壮
任悦
李忠明
徐玲
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Sichuan University
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    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Abstract

The invention discloses a high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and a preparation method thereof, wherein the artificial joint material is prepared by compression molding and irradiation crosslinking of polyphenol antioxidant epigallocatechin gallate or fat-soluble epigallocatechin gallate modified by palmitoyl chloride esterification doped with biocompatible ultrahigh molecular weight polyethylene, and specifically comprises the following steps: antioxidant-doped ultra-high molecular weight polyethylene; compression molding; and (4) performing irradiation crosslinking. The invention obviously improves the oxidation resistance of the irradiation cross-linked ultra-high molecular weight polyethylene under the condition of not reducing the cross-linking efficiency, and simultaneously, the addition of the polyphenol antioxidant does not influence the tensile property and the impact strength of the material, thereby improving the comprehensive use performance of the joint material and being beneficial to prolonging the service time of the joint material.

Description

High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical high polymer materials, and particularly relates to a high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and a preparation method thereof.
Background
The ultra-high molecular weight polyethylene (UHMWPE) becomes the first choice of the artificial joint replacement material by virtue of good wear resistance, mechanical property and biocompatibility. However, in the long-term use process, the UHMWPE joint material is continuously worn to generate abrasive dust, phagocytosis reaction of macrophages is easily triggered, osteolysis is triggered, prosthesis loosening and dislocation are caused, and secondary revision surgery is needed. Researches show that the wear resistance of UHMWPE can be improved by irradiation crosslinking, but partial irradiation-induced free radicals are trapped in a crystal region and combined with oxygen during the service period of the joint material to generate chain oxidation reaction, so that the joint material is oxidized and cracked, the mechanical property of the material is seriously reduced, and finally the prosthesis is failed.
To solve this problem, the antioxidant vitamin e (ve) is used to capture free radicals to improve the oxidative stability of UHMWPE. Compared to conventional highly crosslinked UHMWPE, vitamin e (ve) -stable highly crosslinked UHMWPE only undergoes a slight aging on the surface after 7 months of accelerated aging. This is because the phenolic hydroxyl group on the VE (alpha-tocopherol) molecule provides a hydrogen that can bind to a radical, avoiding oxidative chain scission caused by residual radicals. However, also for the above reasons, VE quenches the radiation-induced free radicals, inhibiting the formation of crosslinked structures. When the VE content is higher than 0.3 wt%, the crosslinking density and the wear rate of the material under high irradiation dose are obviously lower than those of a comparison sample without VE, and the excessively high irradiation dose can also increase the probability of chain fracture and is not beneficial to maintaining the mechanical property of the material; and too low amount of VE added makes it difficult to exert its antioxidant effect. At present, the VE content in commercial VE-stabilized crosslinked UHMWPE implant products does not exceed 0.2 wt% in order to balance the wear resistance and oxidation resistance of the material.
Therefore, the key to preparing high-performance artificial joint materials is to develop a novel antioxidant and achieve a better antioxidant effect on the premise of not blocking irradiation crosslinking.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the above mentioned technical problems.
The invention aims to provide a high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and a preparation method thereof.
The invention provides a preparation method of a high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material. Particularly, the adopted polyphenol antioxidant is preferably esterified by palmitoyl chloride, and a small molecular weight fatty chain is grafted to epigallocatechin gallate, so that the compatibility between the antioxidant and the ultrahigh molecular weight polyethylene matrix is improved, the oxidation resistance and the crosslinking density are greatly improved, and the mechanical property of the material is not adversely affected.
According to an embodiment of the preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, the preparation method specifically comprises the following steps:
A. the polyphenol antioxidant is doped with ultra-high molecular weight polyethylene: adding ultrahigh molecular weight polyethylene and a polyphenol antioxidant into isopropanol, continuously stirring, and drying the obtained mixture to obtain mixed powder particles;
B. compression molding: placing the mixed powder particles in a mould for compression molding, then slowly cooling to room temperature, and demoulding to obtain a compression molded blank;
C. irradiation crosslinking: and (3) carrying out high-energy ray irradiation on the mould pressing blank packaged in vacuum at room temperature to obtain the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material.
According to an embodiment of the preparation method of the high antioxidant high crosslinking ultrahigh molecular weight polyethylene artificial joint material, the polyphenol antioxidant accounts for 0.05-0.20% of the total mass of the ultrahigh molecular weight polyethylene and the polyphenol antioxidant.
According to one embodiment of the preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, the ultrahigh molecular weight polyethylene is biomedical grade, and the relative molecular mass is 5 multiplied by 106～6×106g/mol, density of 0.93-0.98 g/cm3The particle diameter is 120 to 160 μm.
According to an embodiment of the preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, the polyphenol antioxidant is epigallocatechin gallate (EGCG) or fat-soluble epigallocatechin gallate (ls EGCG) modified by palmitoyl chloride esterification.
According to one embodiment of the preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, in the step A, the mixture is continuously stirred for 2-3 hours, and the obtained mixture is placed in a vacuum drying oven at the temperature of 50-70 ℃ to be dried for 5-7 days.
According to one embodiment of the preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, in the step B, the compression molding temperature is 180-220 ℃, the compression molding pressure is 5-50 MPa, and the compression molding time is 2-6 h; preferably, the temperature for molding is 200 ℃, the pressure is 10MPa, and the time is 4 h.
According to an embodiment of the method for preparing the high antioxidant high cross-linked ultrahigh molecular weight polyethylene artificial joint material, in the step C, the high energy radiation is electron beam or gamma radiation, preferably electron beam; the irradiation dose is 50-150 kGy, and preferably 100-150 kGy.
The invention also provides a high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material which is prepared by adopting the preparation method.
According to one embodiment of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, the oxidation induction time of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material is 10-30 min, and the crosslinking density is 250-400 mol/m3Tensile strength of 40 to 50MPa and impact strength of 70 to 120kJ/m2。
The beneficial effects of the invention include:
(1) according to the invention, a small amount of polyphenol antioxidant epigallocatechin gallate, especially fat-soluble epigallocatechin gallate is added, so that the antioxidant property of the ultrahigh molecular weight polyethylene is greatly improved, and the ultrahigh molecular weight polyethylene can still maintain strong antioxidant capacity after electron beam irradiation;
(2) the added epigallocatechin gallate polyphenol antioxidant, especially the fat-soluble epigallocatechin gallate has no adverse effect on the crosslinking density of the ultrahigh molecular weight polyethylene compared with the existing VE antioxidant;
(3) the mechanical property of the material prepared by the invention is not influenced by the antioxidant, and the use condition of the artificial joint is met.
Drawings
Fig. 1 shows the infrared spectra of EGCG and ls EGCG.
FIG. 2 shows the overall performance of the samples at a radiation dose of 100 kGy.
FIG. 3 shows the overall performance of the samples at a radiation dose of 150 kGy.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The high antioxidant and high crosslinking ultrahigh molecular weight polyethylene artificial joint material of the present invention and the preparation method thereof will be explained in detail below.
According to an exemplary embodiment of the present invention, the high antioxidant high cross-linked ultrahigh molecular weight polyethylene artificial joint material is prepared by mixing a polyphenol antioxidant with ultrahigh molecular weight polyethylene, molding the obtained mixed powder, and then performing irradiation cross-linking to obtain the high antioxidant high cross-linked ultrahigh molecular weight polyethylene artificial joint material.
That is, compared with the existing VE stabilizing system, the medical ultra-high molecular weight polyethylene composite material has the advantages that the antioxidant performance of the irradiation cross-linked ultra-high molecular weight polyethylene is obviously enhanced, the material has higher cross-linking density, the mechanical property is not influenced, the comprehensive use performance of the ultra-high molecular weight polyethylene composite material is improved, and the service time of the medical ultra-high molecular weight polyethylene composite material implanted into a body is prolonged.
Preferably, the polyphenol antioxidant accounts for 0.05-0.20% of the total mass of the ultra-high molecular weight polyethylene and the polyphenol antioxidant, and the proportion can ensure that the beneficial effects are shown at the same time to the maximum extent. If the proportion is too high, the antioxidant is easy to agglomerate, and the antioxidant efficiency is reduced; if the compounding ratio is too low, the antioxidant does not provide a satisfactory antioxidant effect.
Specifically, the production method of the present invention may include the following steps.
Step A: polyphenol antioxidant doped ultra-high molecular weight polyethylene
Ultra High Molecular Weight Polyethylene (UHMWPE) and a polyphenolic antioxidant are added to isopropanol with constant stirring, and the resulting mixture is dried to give mixed powder. Wherein the polyphenol antioxidant accounts for 0.05-0.20% of the total mass of the ultra-high molecular weight polyethylene and the polyphenol antioxidant. Preferably, the polyphenolic antioxidant constitutes 0.20% of the total mass of the ultra high molecular weight polyethylene and the polyphenolic antioxidant.
According to the invention, the selected ultra-high molecular weight polyethylene is biomedical grade, and the relative molecular mass is 5 multiplied by 106～6×106g/mol, density of 0.93-0.98 g/cm3The particle diameter is 120 to 160 μm. The selected polyphenol antioxidant is epigallocatechin gallate (EGCG) or fat-soluble epigallocatechin gallate (ls EGCG) modified by palmitoyl chloride esterification. The two have a plurality of antioxidant active centers, compared with the traditional antioxidant VE, the antioxidant VE has stronger antioxidant capacity, particularly ls EGCG is prepared by esterification reaction of EGCG and palmitoyl chloride, the compatibility with UHMWPE is improved by grafting long carbon chain acyl, and the antioxidant VE shows better antioxidant effect, and is the preferable antioxidant.
In the step, the mixture is continuously stirred for 2-3 hours to ensure that the antioxidant is uniformly dispersed in UHMWPE, and the obtained mixture is placed in a vacuum drying oven with the temperature of 50-70 ℃ to be dried for 5-7 days to completely remove isopropanol, so that mixed powder particles of the ultrahigh molecular weight polyethylene and the antioxidant are finally obtained.
And B: compression molding
And D, placing the mixed powder particles prepared in the step A into a mold for compression molding, slowly cooling to room temperature, and demolding to obtain a compression molded blank.
In the step, the mould pressing temperature is controlled to be 180-220 ℃, the mould pressing pressure is controlled to be 5-50 MPa, and the mould pressing time is 2-6 h, so that a better pressing effect is ensured. Preferably, the molding temperature is 200 ℃, the molding pressure is 10MPa, and the molding time is 4 h.
And C: crosslinking by irradiation
And (3) performing high-energy ray irradiation on the mould pressing blank packaged in vacuum at room temperature to obtain the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material.
In this step, the high-energy radiation is an electron beam or a γ -ray, preferably an electron beam; the irradiation dose is 50-150 kGy, and preferably 100-150 kGy.
The high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material is prepared by adopting the preparation method. According to the invention, the oxidation induction time of the obtained high-oxidation-resistance high-crosslinking ultrahigh molecular weight polyethylene artificial joint material is 10-30 min, and the crosslinking density is 250-400 mol/m3Tensile strength of 40 to 50MPa and impact strength of 70 to 120kJ/m2。
The high antioxidant and high crosslinking ultrahigh molecular weight polyethylene artificial joint material and the preparation method thereof according to the present invention will be further described with reference to specific examples and comparative examples.
Example 1:
(1) EGCG-doped UHMWPE: adding UHMWPE and EGCG (wherein the EGCG accounts for 0.20 percent of the total mass of the UHMWPE and the EGCG) into isopropanol, and continuously stirring for 3 hours to ensure that the EGCG is fully and uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and placing the obtained EGCG/UHMWPE mixed powder into a mould, carrying out compression molding on the EGCG/UHMWPE mixed powder at the temperature of 200 ℃ and under the pressure of 10MPa, then slowly cooling to room temperature, and demoulding to obtain a blank.
Example 2:
(1) EGCG-doped UHMWPE: adding UHMWPE and EGCG (wherein the EGCG accounts for 0.20 percent of the total mass of the UHMWPE and the EGCG) into isopropanol, and continuously stirring for 3 hours to ensure that the EGCG is fully and uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and placing the obtained EGCG/UHMWPE mixed powder into a mould, carrying out compression molding on the EGCG/UHMWPE mixed powder at the temperature of 200 ℃ and under the pressure of 10MPa, then slowly cooling to room temperature, and demoulding to obtain a blank.
(3) Irradiation crosslinking: the vacuum packed EGCG/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 100 kGy.
Example 3:
(1) EGCG-doped UHMWPE: adding UHMWPE and EGCG (wherein the EGCG accounts for 0.20 percent of the total mass of the UHMWPE and the EGCG) into isopropanol, and continuously stirring for 3h to ensure that the EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and placing the obtained EGCG/UHMWPE mixed powder into a mould, carrying out compression molding on the EGCG/UHMWPE mixed powder at the temperature of 200 ℃ and under the pressure of 10MPa, then slowly cooling to room temperature, and demoulding to obtain a blank.
(3) Irradiation crosslinking: the vacuum packed EGCG/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Example 4:
(1) EGCG-doped UHMWPE: adding UHMWPE and EGCG (wherein the EGCG accounts for 0.05 percent of the total mass of the UHMWPE and the EGCG) into isopropanol, and continuously stirring for 3h to ensure that the EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and placing the obtained EGCG/UHMWPE mixed powder into a mould, carrying out compression molding on the EGCG/UHMWPE mixed powder at the temperature of 200 ℃ and under the pressure of 10MPa, then slowly cooling to room temperature, and demoulding to obtain a blank.
(3) Irradiation crosslinking: the vacuum packed EGCG/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Example 5:
(1) EGCG-doped UHMWPE: adding UHMWPE and EGCG (wherein the EGCG accounts for 0.10 percent of the total mass of the UHMWPE and the EGCG) into isopropanol, and continuously stirring for 3h to ensure that the EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and placing the obtained EGCG/UHMWPE mixed powder into a mould, carrying out compression molding on the EGCG/UHMWPE mixed powder at the temperature of 200 ℃ and under the pressure of 10MPa, then slowly cooling to room temperature, and demoulding to obtain a blank.
(3) Irradiation crosslinking: the vacuum packed EGCG/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Example 6:
(1) ls EGCG doped UHMWPE: UHMWPE and ls EGCG (wherein the ls EGCG accounts for 0.20 percent of the total mass of the UHMWPE and the ls EGCG) are added into isopropanol, and stirring is continued for 3 hours to ensure that the ls EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol. Wherein ls EGCG is fat-soluble epigallocatechin gallate modified by palmitoyl chloride esterification.
(2) Compression molding: the ls EGCG/UHMWPE mixed powder obtained was placed in a mold and compression molded at a temperature of 200 ℃ and a pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
Example 7:
(1) ls EGCG doped UHMWPE: UHMWPE and ls EGCG (wherein the ls EGCG accounts for 0.20 percent of the total mass of the UHMWPE and the ls EGCG) are added into isopropanol, and stirring is continued for 3 hours to ensure that the ls EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: the ls EGCG/UHMWPE mixed powder obtained was placed in a mold and compression molded at a temperature of 200 ℃ and a pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed ls EGCG/UHMWPE compression moulded blanks were irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 100 kGy.
Example 8:
(1) ls EGCG doped UHMWPE: UHMWPE and ls EGCG (wherein the ls EGCG accounts for 0.20 percent of the total mass of the UHMWPE and the ls EGCG) are added into isopropanol, and stirring is continued for 3 hours to ensure that the ls EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: the ls EGCG/UHMWPE mixed powder obtained was placed in a mold and compression molded at a temperature of 200 ℃ and a pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed ls EGCG/UHMWPE compression moulded blanks were irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Example 9:
(1) ls EGCG doped UHMWPE: UHMWPE and ls EGCG (wherein the ls EGCG accounts for 0.05 percent of the total mass of the UHMWPE and the ls EGCG) are added into isopropanol, and stirring is continued for 3 hours to ensure that the ls EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: the ls EGCG/UHMWPE mixed powder obtained was placed in a mold and compression molded at a temperature of 200 ℃ and a pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed ls EGCG/UHMWPE compression moulded blanks were irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Example 10:
(1) ls EGCG doped UHMWPE: UHMWPE and ls EGCG (wherein the ls EGCG accounts for 0.10 percent of the total mass of the UHMWPE and the ls EGCG) are added into isopropanol, and stirring is continued for 3 hours to ensure that the ls EGCG is uniformly dispersed in the UHMWPE. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: the ls EGCG/UHMWPE mixed powder obtained was placed in a mold and compression molded at a temperature of 200 ℃ and a pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed ls EGCG/UHMWPE compression moulded blanks were irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Comparative example 1:
(1) VE-doped UHMWPE: UHMWPE and VE (wherein VE accounts for 0.20% of the total mass of UHMWPE and VE) are added into isopropanol, and stirring is continued for 3h, so that uniform dispersion of VE in UHMWPE is ensured. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and (2) placing the mixed VE/UHMWPE powder into a die, and carrying out compression molding on the VE-doped UHMWPE powder at the temperature of 200 ℃ and the pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
Comparative example 2:
(1) blending VE with UHMWPE powder: UHMWPE and VE (wherein VE accounts for 0.20% of the total mass of UHMWPE and VE) are added into isopropanol, and stirring is continued for 3h, so that uniform dispersion of VE in UHMWPE is ensured. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and (2) placing the mixed VE/UHMWPE powder into a die, and carrying out compression molding on the VE-doped UHMWPE powder at the temperature of 200 ℃ and the pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed VE/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 100 kGy.
Comparative example 3:
(1) blending VE with UHMWPE powder: UHMWPE and VE (wherein VE accounts for 0.20% of the total mass of UHMWPE and VE) are added into isopropanol, and stirring is continued for 3h, so that uniform dispersion of VE in UHMWPE is ensured. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: the obtained VE/UHMWPE mixed powder was placed in a mold and compression molded at a temperature of 200 ℃ and a pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed VE/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Comparative example 4:
(1) blending VE with UHMWPE powder: UHMWPE and VE (wherein VE accounts for 0.05% of the total mass of UHMWPE and VE) are added into isopropanol, and stirring is continued for 3h, so that uniform dispersion of VE in UHMWPE is ensured. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and (2) placing the mixed VE/UHMWPE powder into a die, and carrying out compression molding on the VE-doped UHMWPE powder at the temperature of 200 ℃ and the pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed VE/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Comparative example 5:
(1) blending VE with UHMWPE powder: UHMWPE and VE (wherein VE accounts for 0.10% of the total mass of UHMWPE and VE) are added into isopropanol, and stirring is continued for 3h, so that uniform dispersion of VE in UHMWPE is ensured. The above mixture was dried in a vacuum oven at 60 ℃ for 7 days to completely remove isopropanol.
(2) Compression molding: and (2) placing the mixed VE/UHMWPE powder into a die, and carrying out compression molding on the VE-doped UHMWPE powder at the temperature of 200 ℃ and the pressure of 10 MPa. Then slowly cooling to room temperature, and demoulding to obtain the blank.
(3) Irradiation crosslinking: the vacuum packed VE/UHMWPE moulded blank was irradiated with a 10MeV electron beam at room temperature with an irradiation dose of 150 kGy.
Wherein, the characteristic group of ls EGCG prepared by esterification reaction of palmitoyl chloride is researched by Fourier transform infrared spectroscopy, and the result is shown in figure 1. Ls EGCG was at 1735cm except for the characteristic peak of EGCG-1Having a non-conjugated saturated lipidFatty ester vc＝oAnd at 2924cm-1And 2853cm-1Respectively has two strong long-chain alkanesasV and vsCharacteristic absorption peak of (a), indicating that the long carbon chain acyl group was successfully grafted on EGCG.
The oxidation induction times of the materials obtained in the examples and comparative examples were tested according to ISO11357-6:2002 using a differential scanning calorimeter. As can be seen from Table 1, the antioxidant properties of EGCG-doped and ls-EGCG-doped ultra-high molecular weight polyethylene are superior to those of VE-doped polyethylene, and especially the addition of ls-EGCG brings about more obvious antioxidant enhancement effect. Meanwhile, the polyphenol antioxidants EGCG and ls EGCG can still keep longer oxidation induction time after irradiation quenching, while the traditional antioxidant VE is greatly influenced by irradiation and cannot keep high antioxidant activity.
To investigate the effect of the polyphenolic antioxidant on the crosslink density, the crosslink density of the material was tested according to ASTM F2214 and the results are shown in Table 1. The crosslinking density of the sample added with the EGCG and the ls EGCG polyphenol antioxidant is higher than that of the sample added with the VE under the same irradiation dose, and the crosslinking density of the sample added with the ls EGCG is slightly higher than that of the sample added with the EGCG, even reaches 400mol/m3Above, it was proved that the polyphenol antioxidant does not inhibit the irradiation crosslinking, and also has a crosslinking promoting effect to some extent, thereby contributing to the improvement of the abrasion resistance of the joint material.
In order to examine the mechanical properties of the prepared high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, the tensile property test is carried out according to ASTM-D638, and the impact property test is carried out according to ASTM-F648. As shown in table 1, the tensile and impact properties of the added natural polyphenols at each irradiation dose were substantially equivalent to those of the VE samples, with no significant difference.
FIGS. 2 and 3 summarize the oxidation induction time, crosslink density, elongation at break, and impact strength of materials doped with different antioxidants in each example after irradiation at 100kGy and 150kGy, respectively. According to the graphs in FIGS. 2 and 3 and from the comprehensive properties, ls EGCG not only greatly improves the oxidation stability and the crosslinking density of the material, but also has no influence on the mechanical properties of the material, and shows the best effect.
TABLE 1 comparison of antioxidant, crosslink density and mechanical Properties of examples 1-10 and comparative examples 1-5
Figure GDA0001551874600000111
In conclusion, the invention provides a method for improving the oxidation resistance and the crosslinking density of the crosslinked UHMWPE, and simultaneously, the mechanical property of the material is not reduced, and the prepared artificial joint material has excellent comprehensive performance.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those of ordinary skill in the art that various modifications and variations can be made to the above-described embodiments without departing from the spirit and scope of the claims.

Claims (11)

1. A preparation method of a high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material is characterized in that a polyphenol antioxidant is doped with ultrahigh molecular weight polyethylene, the obtained mixed powder is subjected to compression molding, and irradiation crosslinking is carried out to prepare the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material, wherein the polyphenol antioxidant is epigallocatechin gallate or fat-soluble epigallocatechin gallate modified through palmitoyl chloride esterification, the fat-soluble epigallocatechin gallate is prepared by esterification reaction of epigallocatechin gallate and palmitoyl chloride, and the compatibility of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and the ultrahigh molecular weight polyethylene is improved by grafting long carbon chain acyl; the specific method for doping the polyphenol antioxidant with the ultra-high molecular weight polyethylene comprises the following steps: ultra high molecular weight polyethylene and a polyphenolic antioxidant are added to the isopropanol and stirred continuously.
2. The preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material as claimed in claim 1, wherein the preparation method specifically comprises the following steps:
A. the polyphenol antioxidant is doped with ultra-high molecular weight polyethylene: adding ultrahigh molecular weight polyethylene and a polyphenol antioxidant into isopropanol, continuously stirring, and drying the obtained mixture to obtain mixed powder particles;
B. compression molding: placing the mixed powder particles in a mould for compression molding, then slowly cooling to room temperature, and demoulding to obtain a compression molded blank;
C. irradiation crosslinking: and (3) carrying out high-energy ray irradiation on the mould pressing blank packaged in vacuum at room temperature to obtain the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material.
3. The preparation method of the high antioxidant high crosslinking ultrahigh molecular weight polyethylene artificial joint material as claimed in claim 1 or 2, wherein the polyphenol antioxidant accounts for 0.05-0.20% of the total mass of the ultrahigh molecular weight polyethylene and the polyphenol antioxidant.
4. The method for preparing the high antioxidant high cross-linked ultrahigh molecular weight polyethylene artificial joint material according to claim 1 or 2, wherein the ultrahigh molecular weight polyethylene is biomedical grade, and the relative molecular mass is 5 x 106~6×106g/mol, density of 0.93-0.98 g/cm3The particle diameter is 120 to 160 μm.
5. The preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material as claimed in claim 2, wherein in the step A, the mixture is continuously stirred for 2-3 h, and the obtained mixture is dried in a vacuum drying oven at 50-70 ℃ for 5-7 days.
6. The preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material as claimed in claim 2, wherein in the step B, the temperature for compression molding is 180-220 ℃, the pressure for compression molding is 5-50 MPa, and the time for compression molding is 2-6 h.
7. The method for preparing the high antioxidant high crosslinking ultrahigh molecular weight polyethylene artificial joint material according to claim 2, wherein in step C, the high energy ray is an electron beam or a gamma ray; the irradiation dose is 50-150 kGy.
8. The preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material as claimed in claim 6, wherein in the step B, the temperature for compression molding is 200 ℃, the pressure for compression molding is 10MPa, and the time for compression molding is 4 h.
9. The preparation method of the high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material according to claim 7, wherein in the step C, the irradiation dose is 100-150 kGy.
10. The high-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material is characterized by being prepared by the preparation method of any one of claims 1 to 9.
11. The high antioxidant high crosslinked ultrahigh molecular weight polyethylene artificial joint material as claimed in claim 10, wherein the oxidation induction time of the high antioxidant high crosslinked ultrahigh molecular weight polyethylene artificial joint material is 10-30 min, and the crosslinking density is 250-400 mol/m3Tensile strength of 40 to 50MPa and impact strength of 70 to 120kJ/m2。
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