CN111073004B - Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material - Google Patents
Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material Download PDFInfo
- Publication number
- CN111073004B CN111073004B CN201911293879.2A CN201911293879A CN111073004B CN 111073004 B CN111073004 B CN 111073004B CN 201911293879 A CN201911293879 A CN 201911293879A CN 111073004 B CN111073004 B CN 111073004B
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- weight polyethylene
- ultrahigh molecular
- joint material
- oxidation stability
- 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.)
- Active
Links
Images
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a method for improving irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material. The prepared artificial joint material consists of a plant phenolic acid antioxidant containing a double-bond structure and medical-grade ultrahigh molecular weight polyethylene, is prepared by compression molding and then irradiation crosslinking, and specifically comprises the following steps: the plant phenolic acid antioxidant containing a double-bond structure is doped with ultra-high molecular weight polyethylene; compression molding; and (4) performing irradiation crosslinking. The invention utilizes the double functional groups on the plant phenolic acid antioxidant containing the double bond structure, simultaneously improves the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material, and is expected to improve the in vivo service life and the in vitro storage stability of the ultrahigh molecular weight polyethylene joint material.
Description
Technical Field
The invention belongs to the field of high performance of biomedical high polymer materials, and particularly relates to a method for improving irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material.
Background
Ultra-high molecular weight polyethylene (UHMWPE) has good mechanical properties, impact resistance, fatigue resistance, self-lubricity and biocompatibility, and is the joint liner material of choice for replacing knee menisci and hip acetabular cartilage (Kurtz SM, J Biomech Eng,2006,1 (1), 107-123). However, UHMWPE is continuously worn to generate abrasive dust during long-term in vivo service, so that host immune stress is triggered, severe inflammatory erosion even tissue necrosis is caused, and timely revision surgery is required (Urban RM, J Bone Joint Surg Am 2000,82 (4), 457-476). Research shows that high-energy ray irradiation (such as X-ray and gamma ray) can enable UHMWPE to form a firm three-dimensional cross-linked network structure, reduce the plastic deformation capacity of the material and remarkably improve the wear resistance of the material (Muratoglu OK, biomaterials,2002,23 (3), 717-724). However, some of the radiation-induced free radicals are trapped in the crystalline region and undergo a chain oxidation reaction with dissolved oxygen during the service of the artificial prosthesis, which greatly degrades the wear resistance and mechanical properties of the material, eventually leading to failure of the prosthesis (Costa L, biomaterials,1998,19 (15), 1371-1385).
In order to eliminate residual free radicals, adding a biocompatible antioxidant is a simple and convenient solution. Vitamin E (VE, also known as alpha-tocopherol) has been clinically proven to be effective in improving radianceIn contrast to the oxidative stability of crosslinked ultra-high molecular weight polyethylene prosthetic joint materials (U.S. Pat. No. 6,153,483B 1, european patent EP0995450B 1). Vitamin E blended UHMWPE artificial joint materials, represented by the company Ticnona (Ticnona), were first commercialized in 2007 under the name of the first generation of products
(US patent US6277390B 1). In the same year, the full name (ASTM) promulgated the standard specification for vitamin E blended UHMWPE, indicating that it is widely accepted internationally (ASTM F2695-07). The mechanism of stabilizing UHMWPE by vitamin E is that phenolic hydroxyl groups on its molecular structure can provide proton hydrogen to quench free radicals, thereby blocking chain reaction (Bracco P, polym Degrad Stabil,2007,92 (12), 2155-62). However, since VE rapidly inactivates free radicals, the crosslinking reaction of the free radicals with each other is hindered, thus greatly reducing the efficiency of UHMWPE irradiation crosslinking. When the content of vitamin E is higher than 0.2wt%, the crosslinking density of the material cannot be increased with the increase of irradiation dose, and the mechanical properties are also significantly reduced by the increase of irradiation dose (Oral E, et al. Biomaterials 2008,29 (26), 3557-3560).
In conclusion, the antioxidant VE, although improving the oxidation resistance of UHMWPE, hinders the crosslinking reaction of the radiation-induced free radicals, limiting the crosslinking density of the material. The acquisition of the ultrahigh molecular weight polyethylene artificial joint material with high irradiation crosslinking and high oxidation resistance becomes a key and difficult point of research and development.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for improving irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material. The plant phenolic acid antioxidant with a double-bond structure is adopted, and the double bond of the plant phenolic acid antioxidant reacts with ultra-high molecular weight polyethylene free radicals generated by irradiation induction to form a cross-linked network. Meanwhile, the phenolic hydroxyl on the plant phenolic acid is used for supplying hydrogen to eliminate residual free radicals, so that the material is endowed with excellent oxidation stability. The prepared material has the dual characteristics of high crosslinking and high antioxidation, and is favorable for prolonging the long-term service life of the ultrahigh molecular weight polyethylene artificial joint implant.
According to the method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material, provided by the invention, the plant phenolic acid antioxidant containing a double-bond structure is doped in the ultrahigh molecular weight polyethylene powder, so that the irradiation crosslinked material after compression molding has high crosslinking density and oxidation stability. The double-bond structure-containing plant phenolic acid antioxidant is one of ferulic acid, hydroxycinnamic acid, rosmarinic acid or caffeic acid phenethyl ester. Compared with vitamin E only with a monophenol functional group, the plant phenolic acid antioxidant with a double-bond structure can not only eliminate free radicals through the supply of hydrogen by phenolic hydroxyl groups to play an antioxidation function, but also can excite the activity of double bonds by utilizing irradiation energy to form a crosslinking network with the free radicals of the ultra-high molecular weight polyethylene, thereby obviously improving the crosslinking density of the material.
According to one embodiment of the method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material, the preparation method of the material specifically comprises the following steps:
A. the plant phenolic acid antioxidant containing double bond structure is doped with ultra-high molecular weight polyethylene: adding ultrahigh molecular weight polyethylene and a plant phenolic acid antioxidant containing a double bond structure into isopropanol, stirring at a high speed, and vacuum drying the obtained mixture to obtain antioxidant-doped powder;
B. compression molding: placing the antioxidant doped powder in a die for compression molding, then slowly cooling to room temperature, and demolding to obtain a 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 ultrahigh molecular weight polyethylene joint material.
According to an embodiment of the method for improving irradiation crosslinking density and oxidation stability of the ultrahigh molecular weight polyethylene joint material, the double-bond-structure-containing plant phenolic acid antioxidant is one of ferulic acid, hydroxycinnamic acid, rosmarinic acid or caffeic acid phenethyl ester.
According to one embodiment of the method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material, the plant phenolic acid antioxidant containing the double bond structure accounts for 0.1-1.0% of the total mass of the ultrahigh molecular weight polyethylene and the plant phenolic acid antioxidant.
According to one embodiment of the method for improving irradiation crosslinking density and oxidation stability of the ultrahigh molecular weight polyethylene 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 90-160 μm.
According to one embodiment of the method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene 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 2-8 h.
According to one embodiment of the method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material, in the step C, the high-energy rays are electron beam rays or gamma rays, and the irradiation dose is 50-150 kGy.
Compared with the prior art, the invention has the remarkable advantages that:
(1) According to the invention, the double bond-containing plant phenolic acid antioxidant is introduced, and the double bond of the plant phenolic acid antioxidant and the ultrahigh molecular weight polyethylene molecular chain are subjected to a crosslinking reaction on the premise of not adding other crosslinking agents, so that the crosslinking density of the material is improved;
(2) The selected part of the plant phenolic acid antioxidant has a plurality of phenolic hydroxyl groups, and can provide more antioxidant active sites compared with vitamin E containing monophenol hydroxyl groups, so that the oxidation stability of the material is further improved;
(3) The ultrahigh molecular weight polyethylene artificial joint material prepared by the invention has the dual advantages of high crosslinking and high antioxidation, and can greatly improve the stability of the artificial joint material in service in vivo.
Drawings
FIG. 1 shows the crosslink density of CAPE/UHMWPE and VE/UHMWPE at a radiation dose of 150kGy.
Figure 2 shows the crosslink density of UHMWPE containing different classes of antioxidant at radiation doses of 100 and 150kGy.
Figure 3 shows the oxidation induction time of UHMWPE containing different kinds of antioxidants at a radiation dose of 150kGy.
Detailed Description
All of the features disclosed in this specification, or all of the steps of 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 an equivalent or similar purpose, 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 method for improving the irradiation crosslinking density and oxidation stability of the ultrahigh molecular weight polyethylene joint material according to the present invention will be described in detail below.
According to an exemplary embodiment of the invention, the method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material is to dope the double bond structure-containing plant phenolic acid antioxidant with the ultrahigh molecular weight polyethylene, and perform compression molding on the obtained antioxidant-doped powder and then perform irradiation crosslinking to obtain the ultrahigh molecular weight polyethylene artificial joint material with high crosslinking degree and oxidation stability.
Namely, the plant phenolic acid antioxidant containing a double bond structure is added into the medical ultra-high molecular weight polyethylene, so that the vitamin E-stabilized ultra-high molecular weight polyethylene obtained by the invention has more excellent crosslinking density and oxidation resistance than the traditional irradiation crosslinking vitamin E-stabilized ultra-high molecular weight polyethylene. The method improves the comprehensive use performance of the ultrahigh molecular weight polyethylene joint material, and is favorable for prolonging the service time of the ultrahigh molecular weight polyethylene joint material implanted into a body.
Specifically, the production method of the present invention may include the following steps.
Step A: double-bond structure-containing plant phenolic acid antioxidant doped ultra-high molecular weight polyethylene
Adding ultrahigh molecular weight polyethylene and a double-bond structure-containing plant phenolic acid antioxidant into isopropanol, stirring at a high speed, and vacuum drying the obtained mixture to obtain antioxidant-doped powder; wherein, the plant phenolic acid antioxidant containing double bond structure accounts for 0.1 to 1.0 percent of the total mass of the ultrahigh molecular weight polyethylene and the 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 90-160 μm.
According to the invention, the double-bond-structure-containing plant phenolic acid antioxidant is one or a combination of ferulic acid, hydroxycinnamic acid, rosmarinic acid or caffeic acid phenethyl ester.
And B: compression molding
And D, placing the antioxidant doped powder prepared in the step A into a die for compression molding, then 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.
Step C: compression molding
And (3) performing radiation crosslinking on the mould pressing blank packaged in vacuum by using high-energy rays to prepare the ultrahigh molecular weight polyethylene artificial joint material with high crosslinking degree and oxidation stability.
In this step, the high-energy radiation is an electron beam or a gamma ray, and the irradiation dose is 50 to 150kGy.
The method for increasing the irradiation crosslinking density and oxidation stability of the ultra-high molecular weight polyethylene joint material according to the present invention will be further described with reference to specific examples and comparative examples.
Examples 1 to 12:
(1) The plant phenolic acid antioxidant containing the double bond structure is doped with UHMWPE: adding UHMWPE and double bond structure-containing plant phenolic acid antioxidant into isopropanol, stirring at high speed (the double bond structure-containing plant phenolic acid type and the proportion of the double bond structure-containing plant phenolic acid in the total mass are shown in Table 1, and the antioxidant name and structure are shown in Table 2), and vacuum drying the obtained mixture to obtain plant phenolic acid doped powder.
(2) Compression molding: and (3) putting the obtained plant phenolic acid/UHMWPE powder into a mould, carrying out compression molding at the temperature of 200 ℃ and the pressure of 10MPa, then slowly cooling to room temperature, and demoulding to obtain the required material.
(3) Irradiation crosslinking: the vacuum packed plant phenolic acid/UHMWPE moulded blanks were irradiated with a 10MeV electron beam at room temperature with the irradiation dose given in table 1.
Comparative examples 1 to 6:
(1) VE-doped UHMWPE: UHMWPE and VE (the ratio of VE to the total mass of UHMWPE and VE is shown in table 1, and the name and structure of the antioxidant are shown in table 2) are added into isopropanol and stirred at high speed, and the obtained mixture is subjected to vacuum drying to obtain VE doped powder.
(2) Compression molding: the VE/UHMWPE powder was placed in a mold and the VE doped UHMWPE powder was 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 blanks were irradiated with a 10MeV electron beam at room temperature with the irradiation dose given in Table 1.
TABLE 1 formulations and irradiation conditions for examples 1-12 and comparative examples 1-5
TABLE 2 full name, abbreviation, structural formula and structural characteristics of antioxidant added in examples and comparative examples
The crosslinking densities of the examples and comparative examples were tested according to ASTM F2214. As shown in FIG. 1, the crosslinking density of the comparative examples was significantly decreased after the antioxidant content was more than 0.2% as the concentration of the antioxidant was increased. When the antioxidant mass fraction was 1.0%, the crosslink density of the examples was only 100mol/m3Indicating that VE significantly inhibits radiation crosslinking at high concentrations. In sharp contrast thereto, of the examplesThe crosslinking density is 350-400mol/m3Meanwhile, the antioxidant is hardly influenced by the change of the concentration of the antioxidant, and the double bond structure-containing plant phenolic acid antioxidant is proved to have the function of promoting crosslinking (the double bonds counteract the influence of partial phenolic hydroxyl groups on scavenging free radicals to inhibit crosslinking); the crosslinking density of the examples was higher than that of the comparative examples at different irradiation doses with the same added amount of the antioxidant, and increased as the irradiation dose increased (fig. 2). The different kinds of plant phenolic acid antioxidants have little influence on the crosslinking density, wherein the caffeic acid phenethyl ester obtained by esterification modification of caffeic acid has better effect.
The oxidation induction time of the material was tested by differential scanning calorimetry according to ISO 11357-6. Under the same antioxidant content, the oxidation induction time of the material added with the non-fat-soluble plant phenolic acid is equivalent to that of the comparative example, while the material added with the caffeic acid phenethyl ester (example 2) has better oxidation induction time which is nearly 2 times that of other samples. Proves that the plant phenolic acid with double bond structure has better oxidation resistance by the esterification modification method.
The result of the combination of crosslinking density and oxidation resistance is that the traditional antioxidant vitamin E antioxidant is adopted to inhibit irradiation crosslinking at high content, which is not favorable for the wear resistance of the material. The plant phenolic acid antioxidant containing the double-bond structure not only has a group capable of providing an antioxidant function, but also has double bonds for promoting a crosslinking reaction, so that the oxidation resistance of the material is ensured, and the wear resistance of the material is greatly improved.
In conclusion, the invention provides a method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material. The plant phenolic acid antioxidant containing a double-bond structure is adopted to replace vitamin E, and the double bonds of the plant phenolic acid antioxidant and the ultra-high molecular weight polyethylene free radicals are subjected to crosslinking reaction, so that the crosslinking density of the material is greatly improved. Meanwhile, the phenolic hydroxyl group serving as an antioxidant active group can still eliminate residual free radicals, and the stability of the material in the in-vivo use and storage processes is maintained.
Although the present invention has been described in connection with the 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 (5)
1. A method for improving irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material is characterized in that 0.1-1.0% of ferulic acid, hydroxycinnamic acid, rosmarinic acid or caffeic acid phenethyl ester plant phenolic acid antioxidant containing a double bond structure is doped in ultrahigh molecular weight polyethylene powder, and after compression molding and irradiation crosslinking, the composite material has high crosslinking density and high oxidation stability.
2. The method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material according to claim 1, wherein the preparation method of the material specifically comprises the following steps:
A. the plant phenolic acid antioxidant containing a double-bond structure is doped with ultra-high molecular weight polyethylene: adding ultrahigh molecular weight polyethylene and a double-bond structure-containing plant phenolic acid antioxidant into isopropanol, stirring at a high speed, and vacuum drying the obtained mixture to obtain antioxidant-doped powder;
B. compression molding: placing the antioxidant doped powder in a die for compression molding, then slowly cooling to room temperature, and demolding to obtain a 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 ultrahigh molecular weight polyethylene joint material.
3. The method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material according to claim 1 or 2, wherein the ultrahigh molecular weight polyethylene is biomedical grade and has a relative molecular mass of 5 x 106～6×106g/mol, density of 0.93-0.98 g/cm3The particle diameter is 90-160 μm.
4. The method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh molecular weight polyethylene joint material according to claim 2, wherein 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 2-8 h.
5. The method for improving irradiation crosslinking density and oxidation stability of the ultrahigh molecular weight polyethylene joint material according to claim 2, wherein in step C, the high energy radiation is electron beam radiation or gamma radiation, and the irradiation dose is 50-150 kGy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911293879.2A CN111073004B (en) | 2019-12-16 | 2019-12-16 | Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911293879.2A CN111073004B (en) | 2019-12-16 | 2019-12-16 | Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111073004A CN111073004A (en) | 2020-04-28 |
| CN111073004B true CN111073004B (en) | 2022-11-01 |
Family
ID=70315170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911293879.2A Active CN111073004B (en) | 2019-12-16 | 2019-12-16 | Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111073004B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620971A (en) * | 2020-05-31 | 2020-09-04 | 上海化工研究院有限公司 | Antioxidant ultrahigh molecular weight polyethylene resin and preparation method and application thereof |
| CN113980160B (en) * | 2021-11-08 | 2023-06-16 | 上海珀利医用材料有限公司 | Modified ultra-high molecular weight polyethylene resin, preparation method thereof and thermal crosslinking plate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1966293A1 (en) * | 2005-10-27 | 2008-09-10 | Polnox Corporation | Stabilized polyolefin compositions |
| CN102604188B (en) * | 2012-03-02 | 2014-02-05 | 中国科学院宁波材料技术与工程研究所 | Antioxidant cross-linked polymer and preparation method thereof |
| CN104098790B (en) * | 2014-08-05 | 2017-09-26 | 四川大学 | The method for improving the polymeric material anti-oxidant efficiency of antioxidant |
| WO2016153925A1 (en) * | 2015-03-25 | 2016-09-29 | Zimmer, Inc. | Melt-stabilized ultra high molecular weight polyethylene |
| CN107754013B (en) * | 2017-12-04 | 2020-11-10 | 四川大学 | High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof |
-
2019
- 2019-12-16 CN CN201911293879.2A patent/CN111073004B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111073004A (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5314423B2 (en) | Ultra high molecular weight polyethylene article and method of forming ultra high molecular weight polyethylene article | |
| CN111073004B (en) | Method for improving irradiation crosslinking density and oxidation stability of ultrahigh molecular weight polyethylene joint material | |
| JP4256096B2 (en) | Oxidation-resistant and wear-resistant polyethylene for artificial joints and method for producing the polyethylene | |
| CN107754013B (en) | High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof | |
| EP1891987B1 (en) | Medical implant bearing material | |
| JP5735443B2 (en) | Ultra high molecular weight polyethylene article and method of forming ultra high molecular weight polyethylene article | |
| JP5969637B2 (en) | Ultra high molecular weight polyethylene article and method of forming ultra high molecular weight polyethylene article | |
| CN110448723B (en) | Synergistic antioxidant type high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof | |
| AU2012203503B2 (en) | Ultra high molecular weight polyethylene articles and methods of forming ultra high molecular weight polyethylene articles | |
| CN111135343B (en) | High-crosslinking high-antioxidant-doped artificial joint prosthesis material and preparation method thereof | |
| CN114058102B (en) | Wear-resistant and oxidation-resistant ultrahigh molecular weight polyethylene material and preparation method and application thereof | |
| CN110075350B (en) | Wear-resistant and oxidation-resistant biological material for artificial joints | |
| KR100307799B1 (en) | Abrasion Resistance Improvement Method of Ultra-high Molecular Weight Polyethylene for Artificial Joints | |
| CA2788687C (en) | Ultra high molecular weight polyethylene articles and methods of forming ultra high molecular weight polyethylene articles | |
| CN113980160A (en) | Modified ultrahigh molecular weight polyethylene resin, preparation method thereof and heat-crosslinked plate | |
| Bellare et al. | The polyethylene history | |
| AU2014201581B2 (en) | Ultra high molecular weight polyethylene articles and methods of forming ultra high molecular weight polyethylene articles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |