CN112870448A - Ultrahigh molecular weight polyethylene plate and preparation method and application thereof - Google Patents
Ultrahigh molecular weight polyethylene plate and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an ultrahigh molecular weight polyethylene plate and a preparation method and application thereof. The invention provides a preparation method of an ultrahigh molecular weight polyethylene plate, which comprises the following steps: mixing an antioxidant and ultrahigh molecular weight polyethylene to obtain a plurality of mixed powder materials with different antioxidant contents; stacking the multiple mixed powder according to the content of the antioxidant, and then sequentially performing compression molding, irradiation crosslinking and annealing treatment to obtain the ultrahigh molecular weight polyethylene plate; the laminated rear layer materials are symmetrically arranged by taking the central layer as a center; the content of the antioxidant in each layer of the laminated material increases outwards on the basis of the central layer. According to the invention, the mixed powder with different antioxidant concentrations is laminated in a mode that the antioxidant concentrations are increased from inside to outside, so that the antioxidant content and the irradiation dose ratio of different sample depths are kept constant in the irradiation process, and the ultrahigh molecular weight polyethylene plate with uniform crosslinking density is obtained.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an ultrahigh molecular weight polyethylene plate and a preparation method and application thereof.
Background
Due to the excellent comprehensive performance of the ultra-high molecular weight polyethylene (the polyethylene with the molecular weight of more than 100 ten thousand), the ultra-high molecular weight polyethylene has the wear resistance, the corrosion resistance, the impact resistance and the self-lubricating property which are incomparable with other engineering plastics, is a novel thermoplastic engineering plastic and is widely used for artificial joint replacement. However, in the long-term in-vivo service process of the ultrahigh molecular weight polyethylene artificial joint, abrasion generated by friction with a matched material of the ultrahigh molecular weight polyethylene artificial joint is phagocytized by macrophages and cannot be absorbed and degraded, so that the macrophages die, and meanwhile, abrasion, action osteolysis, aseptic loosening, inflammation and the like are generated, and a secondary operation or a plurality of revision replacement operations are often required. In order to solve the above problems, ultra-high molecular weight polyethylene chemically cross-linked with silane was developed, but its yield was extremely low and clinical wear rate was extremely high (Kurtz s.uhmwpe Biomaterials Handbook [ J ] 2009,33-43), and the subsequent high energy electron beam and gamma ray irradiation cross-linking method improved wear resistance of the cross-linked ultra-high molecular weight polyethylene.
But the radiation penetration problem exists when the radiation crosslinking is carried out, the distribution of the radiation dose in the thick plate is not uniform, and the general trend is that the dose of the outer layer is large and the dose of the inner layer is small. Experiments show that the penetration depth of the 10MeV linear electron accelerator to the ultra-high molecular weight polyethylene is less than 50mm, and the irradiation doses of the inner layer and the outer layer of the plate are greatly different. The difference in irradiation dose directly results in uneven distribution of crosslink density. The cross-linking density and the distribution thereof are closely related to the distribution of the crystalline regions and the amorphous regions of the ultra-high molecular weight polyethylene plate and the strength, toughness and wearability of the cross-linked ultra-high molecular weight polyethylene plate product. Although the wear resistance is greatly improved by improving the crosslinking degree of the irradiation crosslinking, the residual free radicals in the crosslinking forming process can generate chain oxidation reaction with dissolved oxygen to form unstable peroxides, and the degradation of the peroxides causes the polymers to be embrittled through chain scission and recrystallization, so that the performance of the polymers is reduced, and finally, the problems of oxidative fragmentation, delamination and the like of the crosslinked ultrahigh molecular weight polyethylene material are shown. In order to solve the problems, a biocompatible antioxidant (such as vitamin E) is added into the ultra-high molecular weight polyethylene plate to eliminate residual free radicals and improve the oxidation stability of the ultra-high molecular weight polyethylene artificial joint.
The conventional antioxidant addition methods are mainly classified into two main groups, one is to mix the antioxidant into ultra-high molecular weight polyethylene powder before irradiation to form a preform, such as disclosed in patent publication nos. EP2291417B1 and CN 102089333A. However, the research shows that the antioxidant is added before the irradiation crosslinking to inhibit the crosslinking, and when the content of the antioxidant in the ultra-high molecular weight polyethylene is higher (such as the concentration of vitamin E is higher than 0.1wt percent), the antioxidant can react with free radicals generated by irradiation in the polyolefin, thereby hindering the crosslinking reaction between the free radicals in the polymer; the antioxidant not only inhibits the crosslinking reaction, but also accelerates the breakage of the molecular chain of the ultra-high molecular weight polyethylene, reduces the molecular weight, is not beneficial to improving the crosslinking degree, and influences the wear resistance and the comprehensive mechanical property; when the content of vitamin E is too low (e.g. the content of vitamin E is less than 0.01 wt%), the vitamin E loses antioxidant activity and loses antioxidant effect when irradiated by high-energy rays. The other way of adding the antioxidant is to immerse the irradiated and crosslinked ultrahigh molecular weight polyethylene into the antioxidant and diffuse the antioxidant to the surface of the ultrahigh molecular weight polyethylene plate at about 120 ℃. The plate was removed and kept at 120 ℃ for a while to allow the antioxidant to diffuse internally. Or the ultrahigh molecular weight polyethylene prosthesis blank is irradiated and crosslinked, and then is immersed into an antioxidant solution, and after being taken out, the ultrahigh molecular weight polyethylene prosthesis blank is further subjected to heat treatment to ensure that the antioxidant is internally diffused. However, the method of irradiation-soaking-diffusion is difficult to diffuse the antioxidant, the antioxidant is mainly distributed on the surface layer, the content of the antioxidant in the antioxidant is very little, and the internal and external concentrations are not uniform. Moreover, the heat treatment process is long, and the long-time heat treatment also causes the performance of the material to be reduced. And the content of the antioxidant with excessively low internal part can not play a role in eliminating free radicals, can not effectively eliminate the free radicals generated in the irradiation process and can play an anti-oxidation role in the subsequent use process.
Disclosure of Invention
In view of the above, the invention provides an ultrahigh molecular weight polyethylene plate, and a preparation method and an application thereof, and the invention increases the concentration of an antioxidant from inside to outside to ensure that the antioxidant content and the proportion of irradiation dose of different sample depths are kept constant in the irradiation process, thereby obtaining the ultrahigh molecular weight polyethylene plate with uniform crosslinking density.
In order to solve the technical problem, the invention provides a preparation method of an ultrahigh molecular weight polyethylene plate, which comprises the following steps:
mixing an antioxidant and ultrahigh molecular weight polyethylene to obtain a plurality of mixed powder materials with different antioxidant contents;
stacking the multiple mixed powder according to the content of the antioxidant, and then sequentially performing compression molding, irradiation crosslinking and annealing treatment to obtain the ultrahigh molecular weight polyethylene plate;
the laminated rear layer materials are symmetrically arranged by taking the central layer as a center;
the content of the antioxidant in each layer of the laminated material increases outwards on the basis of the central layer.
Preferably, the mass percentage of the antioxidant in the mixed powder is more than 0.01-1%.
Preferably, the number of the laminated layers is 3 to 9.
Preferably, the mass percentage of the antioxidant in the central layer is 0.01-0.3%; the mass percentage of the antioxidant in the surface layer of the ultra-high molecular weight polyethylene plate is 0.1-1%.
Preferably, the thickness of the ultra-high molecular weight polyethylene plate is 30 mm-100 mm.
Preferably, the compression molding includes: sequentially carrying out high-temperature compression molding and low-temperature compression molding;
the temperature of the high-temperature compression molding is 170-240 ℃, the pressure is 1-50 MPa, and the time is 0.5-10 h;
the low-temperature compression molding temperature is 110-130 ℃, the pressure is 1-50 MPa, and the time is 0.5-72 h.
Preferably, the irradiation dose of the irradiation crosslinking is 25-150 kGy, and the dose rate is 5-50 kGy/pass;
the annealing temperature is 110-130 ℃, and the heat preservation time is 0.5-72 h.
Preferably, the antioxidant comprises one or more of phosphite compounds, gallic acid, catechin, dodecyl gallic acid, propyl gallate, lauryl gallate, caffeic acid, hindered amine stabilizer TH-944, vitamin E, antioxidant 1076 and antioxidant 1010.
The invention also provides the ultra-high molecular weight polyethylene plate prepared by the preparation method in the technical scheme, wherein the difference value between the highest crosslinking density and the lowest crosslinking density in the ultra-high molecular weight polyethylene plate is 0-100 mol/m3。
The invention also provides application of the ultra-high molecular weight polyethylene plate in the technical scheme in preparation of artificial joints.
The invention provides a preparation method of an ultrahigh molecular weight polyethylene plate, which comprises the following steps: mixing an antioxidant and ultrahigh molecular weight polyethylene to obtain a plurality of mixed powder materials with different antioxidant contents; stacking the multiple mixed powder according to the content of the antioxidant, and then sequentially performing compression molding, irradiation crosslinking and annealing treatment to obtain the ultrahigh molecular weight polyethylene plate; the laminated rear layer materials are symmetrically arranged by taking the central layer as a center; the content of the antioxidant in each layer of the laminated material increases outwards on the basis of the central layer. According to the invention, the antioxidant is mixed with the ultrahigh molecular weight polyethylene according to a certain concentration sequence, and the mixed powder with different antioxidant concentrations is laminated in a mode that the antioxidant concentrations increase from inside to outside, so that the antioxidant contents and the irradiation dose proportion of different sample depths are kept constant in the irradiation process, and the ultrahigh molecular weight polyethylene plate with uniform crosslinking density is obtained. Meanwhile, the influence of the antioxidant on the inhibition effect of irradiation crosslinking is regulated and controlled by setting the concentration of the antioxidant in layers, so that the effective concentration of the antioxidant in the inner layer and the outer layer is ensured to be enough to eliminate residual free radicals, and the tensile strength, the elongation at break and the impact strength of the ultrahigh molecular weight polyethylene plate are improved.
The invention also provides the ultra-high molecular weight polyethylene plate prepared by the preparation method in the technical scheme, wherein the difference value between the highest crosslinking density and the lowest crosslinking density in the ultra-high molecular weight polyethylene plate is 0-100 mol/m3. The ultra-high molecular weight polyethylene plate provided by the invention has uniform cross-linking density, so that the tensile strength and the toughness of the ultra-high molecular weight polyethylene plate are improved,Elongation at break and impact strength.
Drawings
Fig. 1 is a schematic structural diagram of an ultra-high molecular weight polyethylene plate prepared in example 2.
Detailed Description
The invention provides a preparation method of an ultrahigh molecular weight polyethylene plate, which comprises the following steps:
mixing an antioxidant and ultrahigh molecular weight polyethylene to obtain a plurality of mixed powder materials with different antioxidant contents;
stacking the multiple mixed powder according to the content of the antioxidant, and then sequentially performing compression molding, irradiation crosslinking and annealing treatment to obtain the ultrahigh molecular weight polyethylene plate;
the laminated rear layer materials are symmetrically arranged by taking the central layer as a center;
the content of the antioxidant in each layer of the laminated material increases outwards on the basis of the central layer.
The invention mixes the antioxidant and the ultra-high molecular weight polyethylene to obtain a plurality of mixed powder materials with different antioxidant contents. In the present invention, the antioxidant preferably includes one or more of phosphite compounds, gallic acid, catechin, dodecyl gallic acid, propyl gallate, lauryl gallate, caffeic acid, hindered amine stabilizer TH-944, vitamin E, antioxidant 1076 and antioxidant 1010, more preferably vitamin E; when the antioxidant comprises two or more of the above specific substances, the proportion of the specific substances is not particularly limited, and any proportion can be adopted. In the invention, the mass percentage content of the antioxidant in the multiple mixed powder materials is preferably 0.01-1%, more preferably 0.1-0.9%, and even more preferably 0.175-0.35%, so that the mixed powder materials with multiple oxidant contents are obtained. In the present invention, the average particle diameter of the powdery mixture is preferably 50 to 200. mu.m, and more preferably 80 to 130 μm. In the present invention, the mixing preferably includes any one of two mixing methods:
the first mixing means preferably comprises the steps of: mixing an antioxidant and ultrahigh molecular weight polyethylene and then carrying out ball milling; the rotation speed of the ball milling is preferably 30-800 r/min, and more preferably 100-400 r/min; the time is preferably 5 to 60min, and more preferably 10 to 30 min.
The second mixing means preferably comprises the steps of: dissolving an antioxidant in an organic solvent to obtain an antioxidant solution;
and mixing the antioxidant solution and the ultrahigh molecular weight polyethylene, and drying to obtain mixed powder.
The invention dissolves the antioxidant in the organic solvent to obtain the antioxidant solution. In the present invention, the organic solvent preferably includes acetone, n-butanol, ethanol, petroleum ether or cyclohexane, more preferably n-butanol or ethanol; the concentration of the antioxidant solution is preferably 20-300 g/L, and more preferably 80-200 g/L.
After the antioxidant solution is obtained, the antioxidant solution and the ultrahigh molecular weight polyethylene are mixed and dried to obtain mixed powder. The mixing method is not particularly limited, as long as the uniform mixing can be achieved. In the invention, the drying temperature is preferably 30-90 ℃, and more preferably 40-70 ℃; the time is preferably 3 to 15 days, and more preferably 6 to 10 days. The drying method is not particularly limited as long as the above temperature can be reached.
After a plurality of mixed powder materials with different antioxidant contents are obtained, the mixed powder materials are laminated according to the antioxidant contents and then subjected to compression molding, irradiation crosslinking and annealing treatment in sequence to obtain the ultrahigh molecular weight polyethylene plate; the laminated rear layer materials are symmetrically arranged by taking the central layer as a center; the content of the antioxidant in each layer of the laminated material increases outwards on the basis of the central layer. In the present invention, the number of stacked layers is preferably 3 to 9, and more preferably 5 to 7. In the present invention, two adjacent layers are considered to be one layer if the concentration of the antioxidant in the two adjacent layers is the same. In the invention, the blanks obtained after lamination are symmetrically arranged by taking the central layer as the center, the contents of the antioxidants in the two symmetrical layers are the same, and the thicknesses of the two symmetrical layers are also the same. The thickness of each symmetrical layer is not particularly limited in the present invention as long as the ratio of the antioxidant content to the irradiation dose can be kept constant with the change in the depth of the laminated material.
In the invention, the mass percentage of the antioxidant in the center layer material of the ultra-high molecular weight polyethylene plate is preferably 0.01-0.3%, and more preferably 0.05-0.1%; the surface layer material of the ultra-high molecular weight polyethylene plate preferably contains 0.1-1% of antioxidant by mass, and more preferably contains 0.3-0.9% of antioxidant by mass. In the invention, the content of the antioxidant in each layer of material after lamination increases outwards by taking the central layer as a reference; the present invention does not specifically limit the magnitude of the increase, as long as the ratio of the antioxidant content to the irradiation dose can be kept constant with the change in the depth of the laminated material.
In the invention, the number of laminated layers of the ultra-high molecular weight polyethylene plate is specifically 3, 5, 7 or 9. When the number of the layers is 3, the mass percentage content of the antioxidant in the central layer is 0.1 percent; the mass percentage of the antioxidant in the surface layer is 0.3 percent. When the number of the layers is 5, the mass percentage content of the antioxidant in the central layer is 0.1 percent; the mass percentage content of the antioxidant in the adjacent layer of the central layer is 0.2 percent; the mass percentage of the antioxidant in the surface layer is 0.3 percent. When the number of the layers is 5, the mass percentage content of the antioxidant in the central layer is 0.3%; the mass percentage of the antioxidant in the adjacent layer of the central layer is 0.6 percent; the mass percentage of the antioxidant in the surface layer is 0.9 percent. When the number of the layers is 7, the mass percentage content of the antioxidant in the central layer is 0.1 percent; the mass percentage content of the antioxidant in the adjacent layer of the central layer is 0.15 percent; the mass percentage content of the antioxidant in the adjacent layer of the surface layer is 0.25 percent; the mass percentage of the antioxidant in the surface layer is 0.3 percent. When the number of the layers is 7, the mass percentage content of the antioxidant in the central layer is 0.05 percent; the mass percentage content of the antioxidant in the adjacent layer of the central layer is 0.15 percent; the mass percentage content of the antioxidant in the adjacent layer of the surface layer is 0.2 percent; the mass percentage of the antioxidant in the surface layer is 0.3 percent. When the number of the layers is 9, the mass percentage content of the antioxidant in the central layer is 0.05 percent; the mass percentage of the antioxidant in the adjacent layer of the central layer is 0.075%; the mass percentage of the antioxidant in the third layer from the surface layer is 0.175 percent; the mass percentage content of the antioxidant in the adjacent layer of the surface layer is 0.27 percent; the mass percentage of the antioxidant in the surface layer is 0.35%.
In the present invention, the lamination is preferably performed in a die, and the shape of the die is not particularly limited, and may be set according to the shape required for the ultra-high molecular weight polyethylene sheet material.
The apparatus for press molding is not particularly limited, and in the examples of the present invention, the press molding is performed in a press vulcanizer. The method also preferably comprises the step of carrying out preliminary compression molding on the laminated product before compression molding, wherein the pressure of the preliminary compression molding is preferably 5-15 MPa, and more preferably 8-10 MPa; the time is preferably 0.8 to 1.2 hours, and more preferably 1 hour. The invention can compact the mixed powder by carrying out preliminary compression molding, and is beneficial to carrying out subsequent compression molding. In the present invention, the press molding preferably includes: sequentially carrying out high-temperature compression molding and low-temperature compression molding; the temperature of the high-temperature compression molding is preferably 170-240 ℃, and more preferably 200-220 ℃; the pressure is preferably 1-50 MPa, and more preferably 3-20 MPa; the time is preferably 0.5 to 10 hours, and more preferably 3 to 6 hours. The temperature of the low-temperature compression molding is preferably 110-130 ℃, and more preferably 120-125 ℃; the pressure is preferably 1-50 MPa, and more preferably 10-20 MPa; the time is preferably 0.5 to 72 hours, and more preferably 2.5 to 10 hours. In the invention, the temperature for low-temperature compression molding is preferably obtained by cooling on the basis of the temperature for high-temperature compression molding, and the invention has no special requirement on the cooling rate as long as the temperature can be cooled to the required temperature. In the present invention, the preliminary press molding and press molding are preferably performed under vacuum conditions, and the degree of vacuum of the vacuum conditions is not particularly limited as long as air in the press molding environment can be removed.
In the present invention, the post-press molding preferably further comprises cooling and demolding the press molded product. In the present invention, the temperature after the temperature reduction is preferably room temperature. The cooling method is not particularly limited, and the cooling method can be realized by adopting a method known by a person skilled in the art.
The compression-molded product is preferably subjected to vacuum packaging before irradiation crosslinking, and the material for vacuum packaging is preferably an aluminum plastic bag. In the present invention, the irradiation crosslinking preferably includes high energy electron beam irradiation crosslinking, gamma ray irradiation crosslinking formed by decay of a cobalt source, or X-ray irradiation crosslinking, and more preferably, high energy electron beam irradiation crosslinking. In the invention, the electron beam energy for irradiation and crosslinking of the high-energy electron beam is preferably 1-20 MeV, and more preferably 10-15 MeV. In the invention, the irradiation dose of irradiation crosslinking is preferably 25-150 kGy, and more preferably 75-100 kGy; the dosage rate is 5-50 kGy/pass, more preferably 20-40 kGy/pass, and still more preferably 25-35 kGy/pass.
In the present invention, the annealing treatment is preferably performed under a protective atmosphere, which preferably includes an argon atmosphere or a nitrogen atmosphere, more preferably an argon atmosphere. In the invention, the annealing treatment temperature is preferably 110-130 ℃, and more preferably 115-120 ℃; the heat preservation time is preferably 0.5-72 h, and more preferably 6-15 h. In the invention, the annealing treatment can enable the antioxidant to fully react with free radicals and eliminate redundant free radicals.
The invention can relate to the thickness of the ultra-high molecular weight polyethylene plate according to actual needs, and in the invention, the thickness of the ultra-high molecular weight polyethylene plate is preferably 30-100 mm, and more preferably 70-90 mm.
The invention also provides the ultra-high molecular weight polyethylene plate prepared by the preparation method in the technical scheme, wherein the difference value between the highest crosslinking density and the lowest crosslinking density in the ultra-high molecular weight polyethylene plate is 0-100 mol/m3. In the invention, the ultra-high molecular weight polyethylene plate has uniform cross-linking density, thereby improving the tensile strength, the elongation at break and the impact strength of the ultra-high molecular weight polyethylene plate.
The invention also provides application of the ultra-high molecular weight polyethylene plate in the technical scheme in preparation of artificial joints. In the present invention, the artificial joint preferably includes an artificial hip joint or an artificial knee joint.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Ball-milling 1.8g of vitamin E and 1800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 50min at the rotating speed of 100r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.1 percent;
ball-milling 5.4g of vitamin E and 1800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 50min at the rotating speed of 100r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.3 percent;
spreading 900g of mixed powder with the vitamin E content of 0.3 percent by mass in a film cavity (the size is 250mm x 125mm) of a mold to form a 1 st layer; laying 1800g of mixed powder with the vitamin E content of 0.1 percent by mass on the surface of the layer 1 as a layer 2; laying 900g of mixed powder with the vitamin E content of 0.3 percent by mass on the surface of the 2 nd layer to be used as the 3 rd layer;
placing the laminated product in a vulcanizing press, vacuumizing, and performing primary compression molding for 1h at 80 ℃ and 10 MPa; heating to 200 ℃ after preliminary compression molding, and carrying out high-temperature compression molding for 6h under the pressure of 6 MPa; cooling to 125 deg.C, performing low temperature compression molding under 10MPa for 2.5h, cooling the product, and demolding at room temperature;
carrying out vacuum packaging on the product after demoulding in an aluminum-plastic bag, and carrying out irradiation crosslinking by using a high-energy electron beam (with the energy of 10MeV), wherein the irradiation dose rate is 25kGy/pass, and the total dose is 75 kGy;
and annealing the product after irradiation crosslinking for 10 hours at 110 ℃ in an argon atmosphere to obtain the ultrahigh molecular weight polyethylene plate.
Example 2
Ball-milling 1.2g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 40min at the rotating speed of 200r/min to obtain mixed powder with the vitamin E content of 0.1 percent by mass;
ball-milling 2.4g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 40min at the rotating speed of 200r/min to obtain mixed powder with the vitamin E content of 0.2 percent by mass;
ball-milling 3.6g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 40min at the rotating speed of 200r/min to obtain mixed powder with the vitamin E content of 0.3 percent by mass;
spreading 600g of mixed powder with vitamin E content of 0.3% in mass in a film cavity (size of 250mm x 125mm) of a mold to form a layer 1; laying 600g of mixed powder with the vitamin E content of 0.2 percent by mass on the surface of the layer 1 to serve as a layer 2; laying 1200g of mixed powder with the vitamin E content of 0.1 percent by mass on the surface of the layer 2 to serve as a layer 3; laying 600g of mixed powder with the vitamin E content of 0.2 percent by mass on the surface of the No. 3 layer to be used as a No. 4 layer; laying 600g of mixed powder with the vitamin E content of 0.3 percent by mass on the surface of the 4 th layer as a 5 th layer;
placing the laminated product in a vulcanizing press, vacuumizing, and performing primary compression molding for 1h at 80 ℃ and 10 MPa; heating to 210 ℃ after preliminary compression molding, and carrying out high-temperature compression molding for 4h under the pressure of 6 MPa; cooling to 125 deg.C, performing low temperature compression molding under 10MPa for 2.5h, cooling the product, and demolding at room temperature;
carrying out vacuum packaging on the product after demoulding in an aluminum-plastic bag, and carrying out irradiation crosslinking by using a high-energy electron beam (with the energy of 10MeV), wherein the irradiation dose rate is 25kGy/pass, and the total dose is 75 kGy;
and annealing the product after irradiation crosslinking for 10 hours at 110 ℃ in an argon atmosphere to obtain the ultrahigh molecular weight polyethylene plate.
The structural schematic diagram of the ultra-high molecular weight polyethylene plate prepared in example 2 is shown in fig. 1.
Example 3
Ball-milling 2.7g of vitamin E and 900g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 30min at the rotating speed of 300r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.3 percent;
ball-milling 2.25g of vitamin E and 900g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 30min at the rotating speed of 300r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.25 percent;
ball-milling 1.35g of vitamin E and 900g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 30min at the rotating speed of 300r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.15 percent;
ball-milling 0.9g of vitamin E and 900g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 30min at the rotating speed of 300r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.1 percent;
paving 450g of mixed powder with the vitamin E content of 0.15 percent by mass in a film cavity (the size is 250mm x 125mm) of a mold to form a 1 st layer; paving 450g of mixed powder with the vitamin E content of 0.25 percent by mass on the surface of the layer 1 to serve as a layer 2; paving 450g of mixed powder with the vitamin E content of 0.15 percent by mass on the surface of the layer 2 to serve as a layer 3; laying 900g of mixed powder with the vitamin E content of 0.1 percent by mass on the surface of the No. 3 layer to be used as a No. 4 layer; paving 450g of mixed powder with the vitamin E content of 0.15 percent by mass on the surface of the 4 th layer to serve as a 5 th layer; paving 450g of mixed powder with the vitamin E content of 0.25 percent by mass on the surface of the 5 th layer to serve as a 6 th layer; paving 450g of mixed powder with the vitamin E content of 0.3 percent by mass on the surface of the 6 th layer to serve as a 7 th layer;
placing the laminated product in a vulcanizing press, vacuumizing, and performing primary compression molding for 1h at 80 ℃ and 10 MPa; after preliminary compression molding, heating to 230 ℃, and carrying out high-temperature compression molding for 2h under the pressure of 6 MPa; cooling to 120 ℃, carrying out low-temperature compression molding for 2.5h under the pressure of 15MPa, and cooling the product of low-temperature compression molding to remove the film at room temperature;
carrying out vacuum packaging on the product after demoulding in an aluminum-plastic bag, and carrying out irradiation crosslinking by using a high-energy electron beam (with the energy of 10MeV), wherein the irradiation dose rate is 20kGy/pass, and the total dose is 80 kGy;
and annealing the product after irradiation crosslinking for 10 hours at 110 ℃ in an argon atmosphere to obtain the ultrahigh molecular weight polyethylene plate.
Example 4
Ball-milling 2.8g of vitamin E and 800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 20min at the rotating speed of 400r/min to obtain mixed powder with the vitamin E content of 0.35 percent by mass;
ball-milling 2.2g of vitamin E and 800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 20min at the rotating speed of 400r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.275 percent;
ball-milling 1.4g of vitamin E and 800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 20min at the rotating speed of 400r/min to obtain mixed powder with the vitamin E content of 0.175 percent by mass;
ball-milling 0.6g of vitamin E and 800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 20min at the rotating speed of 400r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.075 percent;
ball-milling 0.2g of vitamin E and 400g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 20min at the rotating speed of 400r/min to obtain mixed powder with the vitamin E content of 0.05 percent by mass
Spreading 400g of mixed powder with the vitamin E content of 0.35 percent by mass in a film cavity (the size is 250mm x 125mm) of a mold to form a 1 st layer; spreading 400g of mixed powder with the vitamin E content of 0.275 percent by mass on the surface of the layer 1 to serve as a layer 2; spreading 400g of mixed powder with the vitamin E content of 0.175 percent by mass on the surface of the layer 2 to form a layer 3; 400g of mixed powder with the vitamin E content of 0.075 percent in mass is flatly paved on the surface of the No. 3 layer to be used as a No. 4 layer; spreading 400g of mixed powder with the vitamin E content of 0.05 percent by mass on the surface of the 4 th layer to be used as a 5 th layer; 400g of mixed powder with the vitamin E content of 0.075 percent in mass is flatly paved on the surface of the 5 th layer to be used as a 6 th layer; spreading 400g of mixed powder with the vitamin E content of 0.175 percent by mass on the surface of the 6 th layer to be used as a 7 th layer; spreading 400g of mixed powder with the vitamin E content of 0.275 percent by mass on the surface of the 7 th layer to be used as an 8 th layer; spreading 400g of mixed powder with the vitamin E content of 0.35 percent by mass on the surface of the 8 th layer to be used as a 9 th layer;
placing the laminated product in a vulcanizing press, vacuumizing, and performing primary compression molding for 1h at 80 ℃ and 10 MPa; heating to 190 ℃ after preliminary compression molding, and carrying out high-temperature compression molding for 8h under the pressure of 10 MPa; cooling to 125 deg.C, performing low temperature compression molding under 10MPa for 2.5h, cooling the product, and demolding at room temperature;
carrying out vacuum packaging on the product after demoulding in an aluminum-plastic bag, and carrying out irradiation crosslinking by using a high-energy electron beam (with the energy of 10MeV), wherein the irradiation dose rate is 30kGy/pass, and the total dose is 90 kGy;
and annealing the product after irradiation crosslinking for 72 hours at 110 ℃ in an argon atmosphere to obtain the ultrahigh molecular weight polyethylene plate.
Example 5
Ball-milling 3.6g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 10min at the rotating speed of 500r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.3 percent;
ball-milling 7.2g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 10min at the rotating speed of 500r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.6 percent;
ball-milling 10.8g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 10min at the rotating speed of 500r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.9 percent;
spreading 600g of mixed powder with vitamin E content of 0.9% in mass in a film cavity (size of 250mm x 125mm) of a mold to form a layer 1; laying 600g of mixed powder with the vitamin E content of 0.6 percent by mass on the surface of the layer 1 to serve as a layer 2; laying 600g of mixed powder with the vitamin E content of 0.3 percent by mass on the surface of the layer 2 to serve as a layer 3; laying 600g of mixed powder with the vitamin E content of 0.6 percent by mass on the surface of the No. 3 layer to be used as a No. 4 layer; laying 600g of mixed powder with the vitamin E content of 0.9 percent by mass on the surface of the 4 th layer as a 5 th layer;
placing the laminated product in a vulcanizing press, vacuumizing, and performing primary compression molding for 1h at 80 ℃ and 10 MPa; heating to 200 ℃ after preliminary compression molding, and carrying out high-temperature compression molding for 6h under the pressure of 6 MPa; cooling to 115 ℃, carrying out low-temperature compression molding for 4h under the pressure of 30MPa, and cooling the product subjected to low-temperature compression molding to remove the film at room temperature;
carrying out vacuum packaging on the product after demoulding in an aluminum-plastic bag, and carrying out irradiation crosslinking by using a high-energy electron beam (the energy is 10MeV), wherein the irradiation dose rate is 40kGy/pass, and the total dose is 80 kGy;
and annealing the product after irradiation crosslinking for 0.5h at 130 ℃ in an argon atmosphere to obtain the ultrahigh molecular weight polyethylene plate.
Example 6
Ball-milling 3.6g of vitamin E and 1200g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 50min at the rotating speed of 50r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.3 percent;
ball-milling 2.0g of vitamin E and 1000g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 50min at the rotating speed of 50r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.2 percent;
ball-milling 1.2g of vitamin E and 800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 50min at the rotating speed of 50r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.15 percent;
ball-milling 0.4g of vitamin E and 800g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m for 50min at the rotating speed of 50r/min to obtain mixed powder with the mass percentage content of the vitamin E of 0.05 percent;
spreading 600g of mixed powder with vitamin E content of 0.3% in mass in a film cavity (size of 250mm x 125mm) of a mold to form a layer 1; spreading 500g of mixed powder with the vitamin E content of 0.2 percent by mass on the surface of the layer 1 to serve as a layer 2; spreading 400g of mixed powder with the vitamin E content of 0.15 percent by mass on the surface of the layer 2 to form a layer 3; laying 800g of mixed powder with the vitamin E content of 0.05 percent by mass on the surface of the No. 3 layer to be used as a No. 4 layer; spreading 400g of mixed powder with the vitamin E content of 0.15 percent by mass on the surface of the 4 th layer to be used as a 5 th layer; spreading 500g of mixed powder with the vitamin E content of 0.2 percent by mass on the surface of the 5 th layer to be used as a 6 th layer; laying 600g of mixed powder with the vitamin E content of 0.3 percent by mass on the surface of the 6 th layer as a 7 th layer;
placing the laminated product in a vulcanizing press, vacuumizing, and performing primary compression molding for 1h at 80 ℃ and 10 MPa; heating to 200 ℃ after preliminary compression molding, and carrying out high-temperature compression molding for 6h under the pressure of 6 MPa; cooling to 125 deg.C, performing low temperature compression molding under 10MPa for 2.5h, cooling the product, and demolding at room temperature;
carrying out vacuum packaging on the product after demoulding in an aluminum-plastic bag, and carrying out irradiation crosslinking by using a high-energy electron beam (with the energy of 10MeV), wherein the irradiation dose rate is 25kGy/pass, and the total dose is 75 kGy;
and annealing the product after irradiation crosslinking for 10 hours at 110 ℃ in an argon atmosphere to obtain the ultrahigh molecular weight polyethylene plate.
Comparative example 1
Ball-milling 7.2g of vitamin E and 3600g of ultra-high molecular weight polyethylene with the molecular weight of 300 ten thousand and the average particle size of 90-120 mu m to obtain mixed powder with the mass percentage content of the vitamin E of 0.2 percent;
and (3) flatly spreading the mixed powder in a film cavity, and sequentially carrying out primary die pressing, irradiation crosslinking and annealing treatment on a flatly spread product according to the method in the embodiment 1 to obtain the ultrahigh molecular weight polyethylene plate.
Test example
Sampling the ultra-high molecular weight polyethylene plates prepared in the examples 1-6 and the comparative example 1 by using high-precision engraving and milling equipment, wherein the sampling positions are the surface layer, the central layer (at the depth of 1/2) and the depth of 1/4 of the ultra-high molecular weight polyethylene plate; the resulting samples were tested for tensile properties according to ASTM D638, for impact properties according to ASTM F648, and for crosslink density according to ASTM F2214, the results of which are given in Table 1.
Table 1 properties of the ultra high molecular weight polyethylene sheets of examples 1 to 6 and comparative example 1.
As can be seen from the data in Table 1, the uniformity of the distribution of the crosslinking density at different positions of the crosslinked panel is improved after the antioxidant is added in layers, and in example 6, the total amount of each layer of the mixed powder from the center to the two sides is different, i.e., the thickness of each layer is different, but the concentration of the antioxidant is kept to decrease gradually from the two sides to the center layer by layer, so that the effect of uniform distribution of the crosslinking density is also achieved. The ultrahigh molecular weight polyethylene plate prepared in the comparative example 1 has uniform distribution of the concentration of the antioxidant, the high concentration of the antioxidant at the center, low irradiation intensity and inhibition of crosslinking reaction, the irradiation intensity of the surface layer is higher than that of the central layer, the crosslinking density is high, and the overall crosslinking density is not uniform.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A preparation method of an ultra-high molecular weight polyethylene plate comprises the following steps:
mixing an antioxidant and ultrahigh molecular weight polyethylene to obtain a plurality of mixed powder materials with different antioxidant contents;
stacking the multiple mixed powder according to the content of the antioxidant, and then sequentially performing compression molding, irradiation crosslinking and annealing treatment to obtain the ultrahigh molecular weight polyethylene plate;
the laminated rear layer materials are symmetrically arranged by taking the central layer as a center;
the content of the antioxidant in each layer of the laminated material increases outwards on the basis of the central layer.
2. The preparation method according to claim 1, wherein the antioxidant is contained in the mixed powder in an amount of 0.01 to 1% by mass.
3. The method according to claim 1, wherein the number of layers stacked is 3 to 9.
4. The preparation method according to claim 3, wherein the mass percentage of the antioxidant in the central layer is 0.01-0.3%; the mass percentage of the antioxidant in the surface layer of the ultra-high molecular weight polyethylene plate is 0.1-1%.
5. The method of claim 1, wherein the ultra-high molecular weight polyethylene sheet has a thickness of 30mm to 100 mm.
6. The production method according to claim 1, wherein the press molding includes: sequentially carrying out high-temperature compression molding and low-temperature compression molding;
the temperature of the high-temperature compression molding is 170-240 ℃, the pressure is 1-50 MPa, and the time is 0.5-10 h;
the low-temperature compression molding temperature is 110-130 ℃, the pressure is 1-50 MPa, and the time is 0.5-72 h.
7. The preparation method according to claim 1, 3 or 4, wherein the irradiation dose of the irradiation crosslinking is 25-150 kGy, and the dose rate is 5-50 kGy/pass;
the annealing temperature is 110-130 ℃, and the heat preservation time is 0.5-72 h.
8. The method of claim 1, wherein the antioxidant comprises one or more of a phosphite compound, gallic acid, catechin, dodecyl gallic acid, propyl gallate, lauryl gallate, caffeic acid, hindered amine stabilizer TH-944, vitamin E, antioxidant 1076, and antioxidant 1010.
9. The ultra-high molecular weight polyethylene plate prepared by the preparation method of any one of claims 1 to 8, wherein the difference between the highest crosslinking density and the lowest crosslinking density in the ultra-high molecular weight polyethylene plate is 0 to 100mol/m3。
10. Use of the ultra high molecular weight polyethylene sheet according to claim 9 for the preparation of an artificial joint.
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| CN113995886A (en) * | 2021-10-28 | 2022-02-01 | 苏州微创关节医疗科技有限公司 | Artificial joint component, preparation method thereof and friction pair |
| CN114344568A (en) * | 2021-12-13 | 2022-04-15 | 苏州微创关节医疗科技有限公司 | Joint prosthesis with surface cross-linked layer, preparation method thereof and mould pressing assembly |
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| US20120041094A1 (en) * | 2009-02-20 | 2012-02-16 | Ebru Oral | High temperature melting |
| CN102604188A (en) * | 2012-03-02 | 2012-07-25 | 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120041094A1 (en) * | 2009-02-20 | 2012-02-16 | Ebru Oral | High temperature melting |
| CN102604188A (en) * | 2012-03-02 | 2012-07-25 | 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113995886A (en) * | 2021-10-28 | 2022-02-01 | 苏州微创关节医疗科技有限公司 | Artificial joint component, preparation method thereof and friction pair |
| CN114344568A (en) * | 2021-12-13 | 2022-04-15 | 苏州微创关节医疗科技有限公司 | Joint prosthesis with surface cross-linked layer, preparation method thereof and mould pressing assembly |
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