CN112980011B - Antioxidant gradient cross-linked polyethylene material and preparation method thereof - Google Patents
Antioxidant gradient cross-linked polyethylene material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 31
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011812 mixed powder Substances 0.000 claims abstract description 168
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims abstract description 80
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004698 Polyethylene Substances 0.000 claims abstract description 65
- -1 polyethylene Polymers 0.000 claims abstract description 65
- 229920000573 polyethylene Polymers 0.000 claims abstract description 65
- 229930003427 Vitamin E Natural products 0.000 claims abstract description 40
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011709 vitamin E Substances 0.000 claims abstract description 40
- 235000019165 vitamin E Nutrition 0.000 claims abstract description 40
- 229940046009 vitamin E Drugs 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 37
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 34
- 229940074391 gallic acid Drugs 0.000 claims abstract description 34
- 238000010894 electron beam technology Methods 0.000 claims abstract description 30
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000011049 filling Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000005429 filling process Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 4
- 230000003064 anti-oxidating effect Effects 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 21
- 230000001678 irradiating effect Effects 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000007943 implant Substances 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 13
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 13
- 229920013716 polyethylene resin Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 238000003892 spreading Methods 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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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
-
- 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
- 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
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an antioxidant gradient cross-linked polyethylene material and a preparation method thereof. The antioxidant gradient cross-linked polyethylene material provided by the invention is prepared by filling polyethylene mixture powder into a mold, sintering, demolding and irradiating with electron beams; the polyethylene mixture powder comprises first mixed powder and second mixed powder, wherein the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid; the first mixed powder and the second mixed powder are not blended during the mold filling process. According to the invention, the distribution of the two antioxidants in the polyethylene is controlled by utilizing the difference of the inhibition degree of vitamin E and gallic acid on the irradiation crosslinking of the polyethylene, so that the gradient crosslinking polyethylene material is obtained, and the material is very suitable for manufacturing intra-articular implants, and the service life of artificial joints is prolonged.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antioxidant gradient cross-linked polyethylene material and a preparation method thereof.
Background
Ultra-high molecular weight polyethylene has been used as an artificial joint lining stress material in the last 60 th century due to its excellent mechanical properties, good biocompatibility and wear resistance. However, the long-term frictional wear of ultra-high molecular weight polyethylene prosthetic articles in the body still produces large amounts of wear debris below several microns in size, which can easily cause dissolution of the peripheral bone of the prosthesis, thereby causing aseptic loosening and failure of the prosthetic joint.
In the 90 s of the last century, irradiation crosslinking technology was employed to improve the abrasion resistance of ultra-high molecular weight polyethylene. However, the ultra-high molecular weight polyethylene after irradiation crosslinking has significantly decreased fatigue toughness and impact resistance; in addition, free radicals generated by irradiation exist in ultra-high molecular weight polyethylene crystal lattices for a long time, and are easy to react with oxygen, so that the material is oxidized in a waterfall manner, and finally, the molecular chains of the material are broken, the physical and mechanical properties are reduced, and the polyethylene prosthesis is finally fragile and fails.
Although the method of melting and recrystallization after irradiation can eliminate residual free radicals generated by irradiation in ultra-high molecular weight polyethylene and maintain oxidation stability, the melting and recrystallization also reduces the crystallinity and melting point of the polymer, the thickness of the platelet is thinned, and the tensile strength, elongation at break, fatigue toughness and impact strength of the polymer are reduced, which is not beneficial to the application of the polymer in artificial joints. The annealing recrystallization method after irradiation does not completely destroy the crystal structure, so that the mechanical property of the cross-linked ultra-high molecular weight polyethylene is well reserved, but the residual free radicals still existing in the material crystal phase can cause slow oxidation of the joint in the long-term use process in vivo because the annealing process does not completely destroy the crystal structure.
U.S. patent No. 2007/0059334 A1 discloses an ultra-high molecular weight polyethylene containing antioxidant vitamin E, wherein after the polymer is irradiated and crosslinked, vitamin E (VE) molecules therein can capture and stabilize residual free radicals generated by irradiation, thereby remarkably improving the oxidation stability of the crosslinked polyethylene, and simultaneously avoiding the reduction of mechanical properties of the material caused by the heat treatment process after irradiation.
Although vitamin E is adopted and the distribution of vitamin E in the block is controlled to be an effective means for improving the oxidation resistance and mechanical property of the crosslinked ultra-high molecular weight polyethylene, the vitamin E has a certain inhibition effect on the irradiation crosslinking of the ultra-high molecular weight polyethylene, so that the good compromise of the crosslinking degree, oxidation resistance and mechanical property of the material is difficult to realize.
Disclosure of Invention
In view of the above, the invention aims to provide an antioxidant gradient cross-linked polyethylene material and a preparation method thereof.
The invention provides an antioxidant gradient cross-linked polyethylene material, which is prepared by filling polyethylene mixture powder into a mold, sintering, demolding and irradiating with electron beams;
the polyethylene mixture powder comprises first mixed powder and second mixed powder, wherein the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid;
in the die filling process, the first mixed powder and the second mixed powder are not mixed; after the die filling is finished, a first mixed powder layer and a second mixed powder layer are formed in the die, and an interface is formed between the two mixed powder layers.
Preferably, the number average molecular weight of the polyethylene is more than or equal to 1000kDa.
Preferably, the mass ratio of the polyethylene to the vitamin E in the first mixed powder is (50-10000): 1, a step of;
the mass ratio of polyethylene to gallic acid in the second mixed powder is (50-10000): 1.
preferably, the volume ratio of the first mixed powder to the second mixed powder is (0.5-2): 1.
preferably, the interface is a plane or an arc.
The invention provides a preparation method of an antioxidant gradient cross-linked polyethylene material, which comprises the following steps:
a) Preparing a first mixed powder and a second mixed powder; the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid;
b) Filling the first mixed powder and the second mixed powder into a mold respectively, wherein the two mixed powders are not mixed; after filling, forming a first mixed powder layer and a second mixed powder layer in the die, wherein an interface is formed between the two mixed powder layers;
c) Sintering the mixed powder filled in the mould, and demoulding to obtain a blank to be irradiated;
d) And carrying out electron beam irradiation on the blank to be irradiated to obtain the oxidation-resistant gradient cross-linked polyethylene material.
Preferably, the first mixed powder is prepared according to the following steps: mixing polyethylene, vitamin E and an organic solvent, and drying to obtain first mixed powder;
the second mixed powder is prepared according to the following steps: mixing polyethylene, gallic acid and organic solvent, and drying to obtain second mixed powder.
Preferably, step c) specifically comprises:
sintering the mixed powder filled in the die into blocks under the conditions of heating and pressurizing, carrying out pressure maintaining annealing, cooling and demoulding to obtain the blank to be irradiated.
Preferably, the heating temperature is 180-250 ℃; the pressurizing pressure is 1-50 MPa; the temperature of the pressure maintaining annealing is 110-130 ℃, and the time of the pressure maintaining annealing is 0.5-72 h.
Preferably, the electron beam energy of the electron beam irradiation is 3-10 MeV; the single irradiation measurement of the electron beam irradiation is 0.1-5 Mrad, and the total irradiation measurement is 2.5-25 Mrad.
Compared with the prior art, the invention provides an oxidation-resistant gradient cross-linked polyethylene material and a preparation method thereof. The antioxidant gradient cross-linked polyethylene material provided by the invention is prepared by filling polyethylene mixture powder into a mold, sintering, demolding and irradiating with electron beams; the polyethylene mixture powder comprises first mixed powder and second mixed powder, wherein the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid; in the die filling process, the first mixed powder and the second mixed powder are not mixed; after the die filling is finished, a first mixed powder layer and a second mixed powder layer are formed in the die, and an interface is formed between the two mixed powder layers. According to the invention, the distribution condition of the two antioxidants in the polyethylene is controlled by utilizing the difference of the inhibition degree of vitamin E and gallic acid on the irradiation crosslinking of the polyethylene, so that the gradient crosslinking polyethylene material is obtained. The material has excellent oxidation resistance and higher mechanical property, can obtain high crosslinking on the rubbed surface of the material to improve wear resistance, and can obtain low crosslinking in the material to improve mechanical property, thereby being very suitable for manufacturing intra-articular implants and prolonging the service life of artificial joints.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a preparation flow of an antioxidant gradient cross-linked polyethylene material layered on a horizontal plane, which is provided by the embodiment of the invention;
FIG. 2 is a schematic diagram of a preparation flow of an antioxidant gradient cross-linked polyethylene material with a layered horizontal cambered surface provided by the embodiment of the invention;
FIG. 3 is a schematic illustration of a preparation flow of a vertical plane layered oxidation resistant gradient cross-linked polyethylene material according to an embodiment of the present invention;
fig. 4 is a schematic diagram of a preparation flow of an antioxidant gradient cross-linked polyethylene material layered by a vertical cambered surface according to an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an antioxidant gradient cross-linked polyethylene material, which is prepared by filling polyethylene mixture powder into a mold, sintering, demolding and irradiating with electron beams.
The polyethylene mixture powder comprises first mixed powder and second mixed powder, wherein the first mixed powder is mixed powder of polyethylene and Vitamin E (VE), and the second mixed powder is mixed powder of polyethylene and Gallic Acid (GA); the number average molecular weight of the polyethylene is preferably more than or equal to 1000kDa, more preferably 5000-20000 kDa, and particularly 10000-13000 kDa; the mass ratio of polyethylene to vitamin E in the first mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may specifically be 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1700:1, 1800:1, 1900:1, 2000:1, 2100:1, 2200:1, 2300:1, 2400:1, 2500:1, 2600:1, 2700:1, 2800:1, 2900:1, or 3000:1; the mass ratio of polyethylene to gallic acid in the second mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may specifically be 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1700:1, 1800:1, 1900:1, 2000:1, 2100:1, 2200:1, 2300:1, 2400:1, 2500:1, 2600:1, 2700:1, 2800:1, 2900:1, or 3000:1; the volume ratio of the first mixed powder to the second mixed powder is preferably (0.5 to 2): 1, specifically may be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1.
In the present invention, the first mixed powder is preferably prepared by the steps of: mixing polyethylene, vitamin E and an organic solvent, and drying to obtain first mixed powder; wherein the organic solvent includes, but is not limited to, acetone; the mixing mode is preferably to uniformly mix vitamin E and an organic solvent and then mix the vitamin E and the organic solvent with polyethylene; the drying temperature is preferably 40-80 ℃, and can be specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5 to 14 days, and may be specifically 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days or 14 days. The second mixed powder is prepared according to the following steps: mixing polyethylene, gallic acid and an organic solvent, and drying to obtain second mixed powder; wherein the organic solvent includes, but is not limited to, acetone; the mixing mode is preferably to uniformly mix gallic acid and an organic solvent and then mix the gallic acid and the organic solvent with polyethylene; the drying temperature is preferably 40-80 ℃, and can be specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5 to 14 days, and may be specifically 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days or 14 days.
In the invention, the polyethylene mixture powder is not blended with the first mixed powder and the second mixed powder in the process of die filling; after die filling is finished, a first mixed powder layer and a second mixed powder layer are formed in the die, and an interface is formed between the two mixed powder layers; the interface can be a plane or an arc surface.
In the present invention, the specific process of sintering preferably includes: sintering the mixed powder filled in the die into blocks under the conditions of heating and pressurizing, carrying out pressure maintaining annealing and cooling. Wherein the heating temperature is preferably 180-250deg.C, specifically 180deg.C, 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C, 210 deg.C, 215 deg.C, 220 deg.C, 225 deg.C, 230 deg.C, 235 deg.C, 240 deg.C, 245 deg.C or 250 deg.C; the heating time is preferably 1-5 h, and can be specifically 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h; the pressure of the pressurization is preferably 1-50 MPa, and can be specifically 1MPa, 5MPa, 10MPa, 15MPa, 20MPa, 25MPa, 30MPa, 35MPa, 40MPa, 45MPa or 50MPa; the temperature of the pressure maintaining annealing is preferably 110-130 ℃, and can be specifically 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃; the pressure maintaining annealing time is preferably 0.5-72 h, more preferably 0.5-5 h, and can be specifically 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h; the temperature after cooling is preferably room temperature.
In the present invention, the electron beam energy of the electron beam irradiation is preferably 3 to 10MeV, and may be specifically 3MeV, 3.5MeV, 4MeV, 4.5MeV, 5MeV, 5.5MeV, 6MeV, 6.5MeV, 7MeV, 7.5MeV, 8MeV, 8.5MeV, 9MeV, 9.5MeV or 10MeV; the single irradiation dose of the electron beam irradiation is preferably 0.1-5 Mrad, and specifically can be 0.1Mrad, 0.5Mrad, 1Mrad, 1.5Mrad, 2Mrad, 2.5Mrad, 3Mrad, 3.5Mrad, 4Mrad, 4.5Mrad or 5Mrad; the total dose of the electron beam irradiation is preferably 2.5 to 25Mrad, and may specifically be 2.5Mrad, 3Mrad, 4Mrad, 5Mrad, 6Mrad, 7Mrad, 8Mrad, 9Mrad, 10Mrad, 12Mrad, 15Mrad, 17Mrad, 20Mrad or 25Mrad.
The invention also provides a preparation method of the antioxidant gradient cross-linked polyethylene material, which comprises the following steps:
a) Preparing a first mixed powder and a second mixed powder; the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid;
b) Filling the first mixed powder and the second mixed powder into a mold respectively, wherein the two mixed powders are not mixed; after filling, forming a first mixed powder layer and a second mixed powder layer in the die, wherein an interface is formed between the two mixed powder layers;
c) Sintering the mixed powder filled in the mould, and demoulding to obtain a blank to be irradiated;
d) And carrying out electron beam irradiation on the blank to be irradiated to obtain the oxidation-resistant gradient cross-linked polyethylene material.
In the preparation method provided by the invention, first mixed powder and second mixed powder are prepared, wherein the first mixed powder is mixed powder of polyethylene and Vitamin E (VE), and the second mixed powder is mixed powder of polyethylene and Gallic Acid (GA); the number average molecular weight of the polyethylene is preferably more than or equal to 1000kDa, more preferably 5000-20000 kDa, and particularly 10000-13000 kDa; the mass ratio of polyethylene to vitamin E in the first mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may specifically be 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1700:1, 1800:1, 1900:1, 2000:1, 2100:1, 2200:1, 2300:1, 2400:1, 2500:1, 2600:1, 2700:1, 2800:1, 2900:1, or 3000:1; the mass ratio of polyethylene to gallic acid in the second mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may specifically be 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1700:1, 1800:1, 1900:1, 2000:1, 2100:1, 2200:1, 2300:1, 2400:1, 2500:1, 2600:1, 2700:1, 2800:1, 2900:1, or 3000:1.
In the preparation method provided by the invention, the first mixed powder is preferably prepared according to the following steps: mixing polyethylene, vitamin E and an organic solvent, and drying to obtain first mixed powder; wherein the organic solvent includes, but is not limited to, acetone; the mixing mode is preferably to uniformly mix vitamin E and an organic solvent and then mix the vitamin E and the organic solvent with polyethylene; the drying temperature is preferably 40-80 ℃, and can be specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5 to 14 days, and may be specifically 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days or 14 days. The second mixed powder is prepared according to the following steps: mixing polyethylene, gallic acid and an organic solvent, and drying to obtain second mixed powder; wherein the organic solvent includes, but is not limited to, acetone; the mixing mode is preferably to uniformly mix gallic acid and an organic solvent and then mix the gallic acid and the organic solvent with polyethylene; the drying temperature is preferably 40-80 ℃, and can be specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5 to 14 days, and may be specifically 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days or 14 days.
In the preparation method provided by the invention, after the first mixed powder and the second mixed powder are obtained, the first mixed powder and the second mixed powder are respectively filled into a die. Wherein the volume ratio of the first mixed powder to the second mixed powder is preferably (0.5-2): 1, specifically may be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1. In the filling process, the two mixed powders are not mixed; after filling, forming a first mixed powder layer and a second mixed powder layer in the die, wherein an interface is formed between the two mixed powder layers; the interface can be a plane or an arc surface.
In the preparation method provided by the invention, after filling of the mixed powder is completed, the mixed powder filled in a die is sintered, and then the die is removed to obtain a blank to be irradiated. The specific steps preferably comprise: sintering the mixed powder filled in the die into blocks under the conditions of heating and pressurizing, carrying out pressure maintaining annealing, cooling and demoulding to obtain the blank to be irradiated. Wherein the heating temperature is preferably 180-250deg.C, specifically 180deg.C, 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C, 210 deg.C, 215 deg.C, 220 deg.C, 225 deg.C, 230 deg.C, 235 deg.C, 240 deg.C, 245 deg.C or 250 deg.C; the heating time is preferably 1-5 h, and can be specifically 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h; the pressure of the pressurization is preferably 1-50 MPa, and can be specifically 1MPa, 5MPa, 10MPa, 15MPa, 20MPa, 25MPa, 30MPa, 35MPa, 40MPa, 45MPa or 50MPa; the temperature of the pressure maintaining annealing is preferably 110-130 ℃, and can be specifically 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃; the pressure maintaining annealing time is preferably 0.5-72 h, more preferably 0.5-5 h, and can be specifically 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h; the temperature after cooling is preferably room temperature.
In the preparation method provided by the invention, after the blank to be irradiated is obtained, the blank to be irradiated is subjected to electron beam irradiation. Wherein, the electron beam energy of the electron beam irradiation is preferably 3-10 MeV, and can be 3MeV, 3.5MeV, 4MeV, 4.5MeV, 5MeV, 5.5MeV, 6MeV, 6.5MeV, 7MeV, 7.5MeV, 8MeV, 8.5MeV, 9MeV, 9.5MeV or 10MeV; the single irradiation dose of the electron beam irradiation is preferably 0.1-5 Mrad, and specifically can be 0.1Mrad, 0.5Mrad, 1Mrad, 1.5Mrad, 2Mrad, 2.5Mrad, 3Mrad, 3.5Mrad, 4Mrad, 4.5Mrad or 5Mrad; the total dose of the electron beam irradiation is preferably 2.5 to 25Mrad, and may specifically be 2.5Mrad, 3Mrad, 4Mrad, 5Mrad, 6Mrad, 7Mrad, 8Mrad, 9Mrad, 10Mrad, 12Mrad, 15Mrad, 17Mrad, 20Mrad or 25Mrad. And after the electron beam irradiation is finished, the antioxidation gradient cross-linked polyethylene material is obtained.
In the invention, taking figures 1-4 as examples, the preparation flow of the antioxidant gradient cross-linked polyethylene materials with 4 different structures is provided respectively. Wherein, fig. 1 shows a preparation flow of an antioxidant gradient cross-linked polyethylene material layered on a horizontal plane, fig. 2 shows a preparation flow of an antioxidant gradient cross-linked polyethylene material layered on a horizontal cambered surface, fig. 3 shows a preparation flow of an antioxidant gradient cross-linked polyethylene material layered on a vertical plane, and fig. 4 shows a schematic diagram of a preparation flow of an antioxidant gradient cross-linked polyethylene material layered on a vertical cambered surface.
According to the technical scheme provided by the invention, the distribution condition of the two antioxidants in the polyethylene is controlled by utilizing the difference of the inhibition degree of vitamin E and gallic acid on the irradiation crosslinking of the polyethylene, so that the gradient crosslinking polyethylene material is obtained. The material has excellent oxidation resistance and higher mechanical property, can obtain high crosslinking on the rubbed surface of the material to improve wear resistance, and can obtain low crosslinking in the material to improve mechanical property, thereby being very suitable for manufacturing intra-articular implants and prolonging the service life of artificial joints.
For clarity, the following examples are provided in detail.
In the examples provided below, the polyethylene resin powder used was a polyethylene resin having a number average molecular weight of 1000 to 1300 kilodaltons.
Example 1
Step (1): adding 100 g of vitamin E into 1 liter of acetone solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain first mixed powder; adding 100 g of gallic acid into 1 liter of acetone solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): spreading the first mixed powder in a mould for compaction, wherein the powder addition amount is about 1/3 of the volume of the mould, and spreading the second mixed powder with the same volume on the upper layer of the first mixed powder;
step (3): placing the powder-containing mold on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, and keeping the temperature and pressure unchanged for 2 hours to sinter the mixture powder into blocks; then cooling to 120 ℃, keeping the pressure unchanged for 1.5 hours, cooling to room temperature, and demoulding to obtain a block blank;
step (4): irradiating the block blank under 10MeV high-energy electron beam at room temperature, obtaining 3Mrad irradiation dose each time, wherein the total irradiation dose is 9Mrad, and measuring the irradiation dose by a standard irradiation chromogenic film; and (3) when the electron beam irradiates the surface of the sample vertically during irradiation, so that the irradiation on the sample is uniform, and an antioxidant gradient cross-linked polymer is obtained after the irradiation and is marked as a sample A.
Example 2
Step (1): adding 100 g of vitamin E into 1 liter of acetone solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain first mixed powder; adding 100 g of gallic acid into 1 liter of acetone solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): spreading the first mixed powder in a mould for compaction, wherein the powder addition amount is about 1/3 of the volume of the mould, and spreading the second mixed powder with the same volume on the upper layer of the first mixed powder;
step (3): placing the powder-containing mold on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, and keeping the temperature and pressure unchanged for 2 hours to sinter the mixture powder into blocks; then cooling to 120 ℃, keeping the pressure unchanged for 1.5 hours, cooling to room temperature, and demoulding to obtain a block blank;
step (4): irradiating the block blank under 10MeV high-energy electron beam at room temperature, obtaining 3Mrad irradiation dose each time, wherein the total irradiation dose is 6Mrad, and measuring the irradiation dose by a standard irradiation chromogenic film; and (3) when the electron beam irradiates the surface of the sample vertically during irradiation, so that the irradiation on the sample is uniform, and an antioxidant gradient cross-linked polymer is obtained after the irradiation and is marked as a sample A1.
Example 3
Step (1): adding 100 g of vitamin E into 1 liter of acetone solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain first mixed powder; adding 100 g of gallic acid into 1 liter of acetone solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): spreading the first mixed powder in a mould for compaction, wherein the powder addition amount is about 1/3 of the volume of the mould, and spreading the second mixed powder with the same volume on the upper layer of the first mixed powder;
step (3): placing the powder-containing mold on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, and keeping the temperature and pressure unchanged for 2 hours to sinter the mixture powder into blocks; then cooling to 120 ℃, keeping the pressure unchanged for 1.5 hours, cooling to room temperature, demoulding to obtain a block blank, and marking the block blank as a sample A2.
Example 4
Step (1): adding 50 g of vitamin E into 1 liter of ethanol solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain first mixed powder; adding 100 g of gallic acid into 1 liter of ethanol solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): simultaneously placing the first mixed powder and the second mixed powder in a mould with the middle separated by a plane sheet according to the volume ratio of 1:1, separating the two mixtures left and right, compacting, and then extracting the separated plane sheet, wherein the total powder addition amount is about 2/3 of the volume of the mould;
step (3): placing the powder-containing mold on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, and keeping the temperature and pressure unchanged for 2 hours to sinter the mixture powder into blocks; then cooling to 120 ℃, keeping the pressure unchanged for 1.5 hours, cooling to room temperature, and demoulding to obtain a block blank;
step (4): irradiating the block blank under 10MeV high-energy electron beam at room temperature, obtaining 3Mrad irradiation dose each time, wherein the total irradiation dose is 9Mrad, and measuring the irradiation dose by a standard irradiation chromogenic film; the oxidation-resistant gradient cross-linked polymer was obtained after irradiation and was designated as sample B.
Example 5
Step (1): adding 300 g of vitamin E into 1 liter of isopropanol solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain first mixed powder; adding 100 g of gallic acid into 1 liter of isopropanol solvent, uniformly mixing, adding 100 kg of polyethylene resin powder, fully mixing, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): simultaneously placing the first mixed powder and the second mixed powder in a mould with the middle separated by an arc-surface sheet according to the volume ratio of 1:1, separating the two mixtures left and right, compacting, and then extracting the separated arc-surface sheet, wherein the total powder addition amount is about 2/3 of the volume of the mould;
step (3): placing the powder-containing mold on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, and keeping the temperature and pressure unchanged for 2 hours to sinter the mixture powder into blocks; then cooling to 120 ℃, keeping the pressure unchanged for 1.5 hours, cooling to room temperature, and demoulding to obtain a block blank;
step (4): irradiating the block blank under 10MeV high-energy electron beam at room temperature, obtaining 3Mrad irradiation dose each time, wherein the total irradiation dose is 9Mrad, and measuring the irradiation dose by a standard irradiation chromogenic film; the oxidation-resistant gradient cross-linked polymer was obtained after irradiation and was designated as sample C.
Performance comparison
The products prepared in examples 1 to 5 were tested and the results are shown in the following table:
from the above table, it can be seen that the ultra-high molecular weight polyethylene containing gallic acid and vitamin E has several advantages after irradiation crosslinking: 1) The crosslinking degree is distributed in a gradient manner in the block, and has high crosslinking degree near the gallic acid side and low crosslinking degree near the vitamin E side under the same irradiation dose; 2) Higher tensile strength; 3) Higher impact strength. Therefore, by utilizing the technology of the invention, gradient crosslinking ultra-high molecular weight polyethylene materials with different thicknesses can be designed and obtained by controlling the distribution of two antioxidants in the ultra-high molecular weight polyethylene, the purposes of obtaining high crosslinking on the friction surface of the material, improving the wear resistance and obtaining low crosslinking in the material to improve the mechanical property are achieved, and the material can be used for manufacturing intra-articular implants and prolonging the service life of artificial joints.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. An antioxidizing gradient cross-linked polyethylene material is prepared from the mixture of polyethylene powder through die loading, fusion, demoulding and electron beam irradiation;
the polyethylene mixture powder comprises first mixed powder and second mixed powder, wherein the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid; the mass ratio of polyethylene to vitamin E in the first mixed powder is (50-10000): 1, wherein the mass ratio of polyethylene to gallic acid in the second mixed powder is (50-10000): 1, a step of;
in the die filling process, the first mixed powder and the second mixed powder are not mixed; after the die filling is finished, a first mixed powder layer and a second mixed powder layer are formed in the die, and an interface is formed between the two mixed powder layers.
2. The oxidation resistant gradient cross-linked polyethylene material according to claim 1, wherein the polyethylene has a number average molecular weight of not less than 1000kDa.
3. The antioxidant gradient cross-linked polyethylene material according to claim 1, wherein the volume ratio of the first mixed powder to the second mixed powder is (0.5-2): 1.
4. the oxidation resistant gradient cross-linked polyethylene material according to claim 1, wherein the interface is a planar or cambered surface.
5. The preparation method of the antioxidant gradient cross-linked polyethylene material comprises the following steps:
a) Preparing a first mixed powder and a second mixed powder; the first mixed powder is mixed powder of polyethylene and vitamin E, and the second mixed powder is mixed powder of polyethylene and gallic acid; the mass ratio of polyethylene to vitamin E in the first mixed powder is (50-10000): 1, wherein the mass ratio of polyethylene to gallic acid in the second mixed powder is (50-10000): 1, a step of;
b) Filling the first mixed powder and the second mixed powder into a mold respectively, wherein the two mixed powders are not mixed; after filling, forming a first mixed powder layer and a second mixed powder layer in the die, wherein an interface is formed between the two mixed powder layers;
c) Sintering the mixed powder filled in the mould, and demoulding to obtain a blank to be irradiated;
d) And carrying out electron beam irradiation on the blank to be irradiated to obtain the oxidation-resistant gradient cross-linked polyethylene material.
6. The method of claim 5, wherein the first mixed powder is prepared by: mixing polyethylene, vitamin E and an organic solvent, and drying to obtain first mixed powder;
the second mixed powder is prepared according to the following steps: mixing polyethylene, gallic acid and organic solvent, and drying to obtain second mixed powder.
7. The method according to claim 5, wherein step c) comprises:
sintering the mixed powder filled in the die into blocks under the conditions of heating and pressurizing, carrying out pressure maintaining annealing, cooling and demoulding to obtain the blank to be irradiated.
8. The method of claim 7, wherein the heating is at a temperature of 180-250 ℃; the pressurizing pressure is 1-50 MPa; the temperature of the pressure maintaining annealing is 110-130 ℃, and the time of the pressure maintaining annealing is 0.5-72 h.
9. The method according to claim 5, wherein the electron beam energy of the electron beam irradiation is 3 to 10MeV; the single irradiation measurement of the electron beam irradiation is 0.1-5 Mrad, and the total irradiation measurement is 2.5-25 Mrad.
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