CN111073004A - 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
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- CN111073004A CN111073004A CN201911293879.2A CN201911293879A CN111073004A CN 111073004 A CN111073004 A CN 111073004A CN 201911293879 A CN201911293879 A CN 201911293879A CN 111073004 A CN111073004 A CN 111073004A
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- 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
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- 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
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- 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 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 double-bond structure-containing plant phenolic acid antioxidant and medical ultra-high molecular weight polyethylene, is prepared by compression molding and then irradiation crosslinking, and specifically comprises the following steps: phenolic acid antioxidant doped ultra-high molecular weight polyethylene; compression molding; and (4) performing irradiation crosslinking. The invention utilizes the difunctional group on the double-bond-structure-containing plant phenolic acid antioxidant, 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 first choice joint spacer material for replacing knee meniscus and hip acetabular cartilage (Kurtz SM, J Biomech Eng,2006,1(1), 107-. However, in the long-term in vivo service process, UHMWPE is continuously worn to generate abrasive dust, so as to trigger host immune stress, severe inflammatory erosion even leads to tissue necrosis, and timely revision surgery is required (UrbanRM, J Bone Joint Surg Am2000,82 (4)), 457-. 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 crystal region and undergo a chain oxidation reaction with dissolved oxygen during the service of the artificial prosthesis, which greatly degrades both the wear resistance and the mechanical properties of the material, and finally leads to the failure of the prosthesis (Costa L, Biomaterials,1998,19(15), 1371-1385).
Vitamin E (VE, also called α -tocopherol) has been clinically verified to be effective in improving the oxidation stability of irradiation cross-linked ultra-high molecular weight polyethylene artificial joint materials (U.S. Pat. No. 6,483, 1, European patent EP0995450B1), represented by Ticnona, the first generation of product name, namely vitamin E blended UHMWPE artificial joint materials, was commercialized at the earliest in 2007
(U.S. Pat. No. 4, 6277390, 1). In the same year, the full name (ASTM) promulgated a standard specification for vitamin E blended UHMWPE, indicating that it is widely recognized internationally (ASTM F2695-07). The mechanism of vitamin E stabilizing UHMWPE is that the phenolic hydroxyl groups on its molecular structure can provide proton hydrogen to quench free radicals, thereby blocking chain reactions (Bracco P, polymdrawn stable, 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 0.2 wt%, 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 the ultrahigh molecular weight polyethylene free radical generated by irradiation induction to form a cross-linked network. Meanwhile, the phenolic hydroxyl on the 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.
The invention provides a method for improving irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material. The double bond structure-containing plant phenolic acid antioxidant is one of ferulic acid, hydroxycinnamic acid, caffeic acid, carnosic acid, rosmarinic acid or esterification-modified plant phenolic acid. Compared with vitamin E only having a monophenol functional group, the plant phenolic acid antioxidant containing 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 cross-linking network with the free radicals of the ultra-high molecular weight polyethylene, thereby obviously improving the cross-linking 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. phenolic acid antioxidant doped ultra-high molecular weight polyethylene: adding ultrahigh molecular weight polyethylene and phenolic acid antioxidant into isopropanol, stirring at high speed, and vacuum drying the obtained mixture to obtain antioxidant-doped powder;
B. compression molding: placing the mixed 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, caffeic acid, carnosic acid, rosmarinic acid or plant phenolic acid modified by esterification.
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 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 to 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 hours; 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 improving irradiation crosslinking density and 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, preferably electron beam rays; the irradiation dose is 50-150 kGy, and preferably 100-150 kGy.
Compared with the prior art, the invention has the following remarkable advantages:
(1) according to the invention, by introducing the double bond structure-containing plant phenolic acid antioxidant, 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 service stability of the artificial joint material in vivo.
Drawings
FIG. 1 shows the crosslink density of CAPE/UHMWPE and VE/UHMWPE at a radiation dose of 150 kGy.
Figure 2 shows the crosslink density of UHMWPE containing different types of antioxidants at 100 and 150kGy irradiation doses.
Figure 3 shows the oxidation induction times of UHMWPE containing different kinds of antioxidants 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 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 irradiation crosslinking density and 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 the obtained mixed powder is subjected to compression molding and then irradiation crosslinking to obtain the ultrahigh molecular weight polyethylene artificial joint material with high crosslinking degree and oxidation stability.
Namely, the invention adds the plant phenolic acid antioxidant containing double bond structure into the medical grade ultra-high molecular weight polyethylene, so as to obtain more excellent crosslinking density and oxidation resistance than the traditional irradiation crosslinking vitamin E stable ultra-high molecular weight polyethylene. The method improves the comprehensive use performance of the ultrahigh molecular weight polyethylene joint material, and is beneficial to 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: phenolic acid antioxidant doped ultra-high molecular weight polyethylene
Adding ultrahigh molecular weight polyethylene and phenolic acid antioxidant into isopropanol, stirring at high speed, and vacuum drying the obtained mixture to obtain antioxidant-doped powder; wherein the phenolic acid antioxidant accounts for 0.1-1.0% of the total mass of the ultrahigh molecular weight polyethylene and the phenolic acid 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 to 160 μm.
According to the invention, the selected plant phenolic acid antioxidant containing double bond structure is one or more of ferulic acid, hydroxycinnamic acid, caffeic acid, carnosic acid, rosmarinic acid or plant phenolic acid modified by esterification.
And B: compression molding
And D, placing the mixed powder prepared in the step A into a die for compression molding, slowly cooling to room temperature, and demolding to obtain a 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: 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 γ -ray, preferably an electron beam; the irradiation dose is 50-150 kGy, and preferably 100-150 kGy.
The method for improving the irradiation crosslinking density and the oxidation stability of the ultrahigh 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) phenolic acid antioxidant doped UHMWPE: adding UHMWPE and phenolic acid antioxidant into isopropanol, stirring at high speed (the phenolic acid type and the proportion of phenolic acid in the total mass of UHMWPE and phenolic acid are shown in Table 1, and the name and structure of antioxidant are shown in Table 2), and vacuum drying the obtained mixture to obtain phenolic acid doped powder.
(2) Compression molding: and (3) placing the obtained phenolic acid/UHMWPE mixed 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 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 antioxidant are shown in table 2) are added into isopropanol and stirred at high speed, and the obtained mixture is dried in vacuum to obtain VE doped powder.
(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 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 the antioxidants added in the 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 crosslink density of the comparative examples decreased significantly after the antioxidant content was greater than 0.2% as the antioxidant concentration 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, the crosslinking density of the examples is 350-400mol/m3Meanwhile, the antioxidant is hardly influenced by the change of the concentration of the antioxidant, and the phenolic acid antioxidant containing a double bond structure is proved to have the effect of promoting crosslinking (in table 2, the double bond counteracts 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 amount of added antioxidant, and increased with increasing irradiation dose (fig. 2). Different kinds of phenolic acid antioxidants have little influence on the crosslinking density, wherein the caffeic acid phenethyl ester obtained by esterifying and modifying caffeic acid has better effect.
The oxidation induction time of the material was tested by differential scanning calorimetry according to ISO11357-6: 2002. Under the same antioxidant content, the oxidation induction time of the material added with the non-fat-soluble 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 containing the double-bond structure has better oxidation resistance by the esterification modification method.
Combining the results of crosslink density and oxidation resistance, the use of the conventional antioxidant vitamin E antioxidant inhibits radiation crosslinking at high levels, which is detrimental to the wear resistance of the material. The 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 irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material. The phenolic acid antioxidant containing a double-bond structure is adopted to replace vitamin E, and the double bonds of the 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 skilled 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 (7)
1. A method for improving irradiation crosslinking density and oxidation stability of an ultrahigh molecular weight polyethylene joint material is characterized in that a 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. phenolic acid antioxidant doped ultra-high molecular weight polyethylene: adding ultrahigh molecular weight polyethylene and phenolic acid antioxidant into isopropanol, stirring at high speed, and vacuum drying the obtained mixture to obtain antioxidant-doped powder;
B. compression molding: placing the mixed 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 irradiation crosslinking density and oxidation stability of the ultrahigh molecular weight polyethylene joint material according to claim 1 or 2, wherein the double bond structure-containing plant phenolic acid antioxidant is one of ferulic acid, hydroxycinnamic acid, caffeic acid, carnosic acid, rosmarinic acid or plant phenolic acid modified by esterification.
4. 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 double bond structure-containing plant phenolic acid antioxidant accounts for 0.1-1.0% of the total mass of the ultrahigh molecular weight polyethylene and the phenolic acid antioxidant.
5. The method for improving irradiation crosslinking density and 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 to 160 μm.
6. 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; preferably, the temperature for molding is 200 ℃, the pressure is 10MPa, and the time is 4 h.
7. 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, preferably electron beam radiation; the irradiation dose is 50-150 kGy, and preferably 100-150 kGy.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN113980160A (en) * | 2021-11-08 | 2022-01-28 | 上海珀利医用材料有限公司 | Modified ultrahigh molecular weight polyethylene resin, preparation method thereof and heat-crosslinked plate |
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