CN112980011A - Antioxidant gradient crosslinked polyethylene material and preparation method thereof - Google Patents
Antioxidant gradient crosslinked polyethylene material and preparation method thereof Download PDFInfo
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- CN112980011A CN112980011A CN202110316872.9A CN202110316872A CN112980011A CN 112980011 A CN112980011 A CN 112980011A CN 202110316872 A CN202110316872 A CN 202110316872A CN 112980011 A CN112980011 A CN 112980011A
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 36
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 33
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011812 mixed powder Substances 0.000 claims abstract description 166
- 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 74
- 239000004698 Polyethylene Substances 0.000 claims abstract description 63
- -1 polyethylene Polymers 0.000 claims abstract description 63
- 229920000573 polyethylene Polymers 0.000 claims abstract description 63
- 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 62
- 229930003427 Vitamin E Natural products 0.000 claims abstract description 37
- 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 37
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000011709 vitamin E Substances 0.000 claims abstract description 37
- 235000019165 vitamin E Nutrition 0.000 claims abstract description 37
- 229940046009 vitamin E Drugs 0.000 claims abstract description 37
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 35
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 31
- 229940074391 gallic acid Drugs 0.000 claims abstract description 31
- 238000010894 electron beam technology Methods 0.000 claims abstract description 30
- 238000011049 filling Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000007943 implant Substances 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 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
- 229920006037 cross link polymer Polymers 0.000 description 5
- 230000001678 irradiating effect 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
- 238000011161 development Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000446313 Lamella Species 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001590 oxidative effect 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
- 230000005855 radiation 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- 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
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- 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
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- 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
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an antioxidant gradient crosslinked polyethylene material and a preparation method thereof. The antioxidant gradient crosslinked polyethylene material provided by the invention is prepared by performing die filling, sintering, demoulding and electron beam irradiation on polyethylene mixture powder; the polyethylene mixture powder comprises a first mixed powder and a second mixed powder, wherein the first mixed powder is a mixed powder of polyethylene and vitamin E, and the second mixed powder is a mixed powder of polyethylene and gallic acid; and in the process of filling the mold, the first mixed powder and the second mixed powder are not blended. The invention controls the distribution condition of the two antioxidants in the polyethylene by utilizing the difference of the irradiation crosslinking inhibition degree of the vitamin E and the gallic acid on the polyethylene, obtains the polyethylene material with gradient crosslinking, and the material is very suitable for manufacturing the implant in the joint and prolongs the service life of the artificial joint.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antioxidant gradient crosslinked polyethylene material and a preparation method thereof.
Background
Due to excellent mechanical properties, good biocompatibility and wear resistance, ultra-high molecular weight polyethylene is used as a stress material for the inner lining of an artificial joint in the last 60 years. However, the ultra-high molecular weight polyethylene prosthesis products still generate a large amount of abrasive dust with the size of below several micrometers in the body after long-term friction and abrasion, and the abrasive dust is easy to cause the dissolution of the peripheral bone of the prosthesis, so that the aseptic loosening is caused, and the artificial joint fails.
In the last 90 s, radiation crosslinking technology was used to improve the abrasion resistance of ultra-high molecular weight polyethylene. However, the fatigue toughness and impact resistance of ultra-high molecular weight polyethylene after irradiation crosslinking are significantly reduced; in addition, free radicals generated by irradiation exist in ultra-high molecular weight polyethylene crystal lattices for a long time, and easily react with oxygen, so that the material is oxidized in a waterfall manner, molecular chains of the material are finally broken, the physical and mechanical properties are reduced, and the polyethylene prosthesis is finally fragile and fails.
Although the method of melt recrystallization after irradiation can eliminate residual free radicals generated by irradiation in the ultra-high molecular weight polyethylene and maintain oxidation stability, the melt recrystallization also reduces the crystallinity and the melting point of the polymer, the thickness of lamella is thinned, the tensile strength, the elongation at break, the fatigue toughness and the impact strength of the polymer are also reduced, and the method is not beneficial to the application of the polymer in artificial joints. The method of annealing and recrystallization after irradiation does not completely destroy the crystal structure, so that the mechanical properties of the crosslinked ultrahigh molecular weight polyethylene are well maintained, but because the annealing process does not completely destroy the crystal structure, the residual free radicals still existing in the material crystallization phase can cause the joint to be slowly oxidized in the long-term use process in vivo.
The U.S. Pat. No. 4, 2007/0059334, 1 discloses an ultra-high molecular weight polyethylene containing antioxidant vitamin E, wherein the Vitamin E (VE) molecules can capture and stabilize residual free radicals generated by irradiation after the polymer is irradiated and crosslinked, thereby remarkably improving the oxidative stability of the crosslinked polyethylene and avoiding the reduction of the mechanical properties of the material caused by the heat treatment process after irradiation.
Although the adoption of the vitamin E and the control of the distribution of the vitamin E in the block are effective means for improving the oxidation resistance and the mechanical property of the cross-linked ultrahigh molecular weight polyethylene, the vitamin E has a certain inhibiting effect on the irradiation cross-linking of the ultrahigh molecular weight polyethylene, so that the good consideration of the cross-linking degree, the oxidation resistance and the mechanical property of the material is difficult to realize.
Disclosure of Invention
In view of the above, the present invention provides an antioxidant gradient crosslinked polyethylene material and a preparation method thereof, and the polyethylene material provided by the present invention is in gradient crosslinking and has excellent antioxidant ability and high mechanical properties.
The invention provides an antioxidant gradient crosslinked polyethylene material, which is prepared by polyethylene mixture powder through die filling, sintering, demoulding and electron beam irradiation;
the polyethylene mixture powder comprises a first mixed powder and a second mixed powder, wherein the first mixed powder is a mixed powder of polyethylene and vitamin E, and the second mixed powder is a mixed powder of polyethylene and gallic acid;
in the process of die filling, the first mixed powder and the second mixed powder are not blended; and after the die filling is finished, 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.
Preferably, the number average molecular weight of the polyethylene is more than or equal to 1000 kDa.
Preferably, the mass ratio of the polyethylene to the vitamin E in the first mixed powder is (50-10000): 1;
the mass ratio of the polyethylene to the 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 a cambered surface.
The invention provides a preparation method of an antioxidant gradient crosslinked 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) respectively filling the first mixed powder and the second mixed powder into a mould, wherein the two mixed powders are not blended; after the filling is finished, 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 into the die, and then demoulding to obtain a blank to be irradiated;
d) and performing electron beam irradiation on the blank to be irradiated to obtain the antioxidant gradient crosslinked 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 into the die into blocks under the conditions of heating and pressurizing, maintaining pressure, annealing, cooling and demolding 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 energy of the electron beam irradiated by the electron beam 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 antioxidant gradient crosslinked polyethylene material and a preparation method thereof. The antioxidant gradient crosslinked polyethylene material provided by the invention is prepared by performing die filling, sintering, demoulding and electron beam irradiation on polyethylene mixture powder; the polyethylene mixture powder comprises a first mixed powder and a second mixed powder, wherein the first mixed powder is a mixed powder of polyethylene and vitamin E, and the second mixed powder is a mixed powder of polyethylene and gallic acid; in the process of die filling, the first mixed powder and the second mixed powder are not blended; and after the die filling is finished, 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 invention controls the distribution condition of the two antioxidants in the polyethylene by utilizing the difference of the irradiation crosslinking inhibition degree of the vitamin E and the gallic acid on the polyethylene, and obtains the polyethylene material with gradient crosslinking. The material has excellent oxidation resistance and higher mechanical property, can obtain high crosslinking on the friction surface of the material to improve the wear resistance, and can obtain low crosslinking in the material to improve the mechanical property, so that the material is 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 used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic flow chart of the preparation process of a horizontal plane layered oxidation-resistant gradient cross-linked polyethylene material provided by the embodiment of the invention;
FIG. 2 is a schematic flow chart of a process for preparing a horizontal cambered-surface layered antioxidant gradient crosslinked polyethylene material according to an embodiment of the present invention;
FIG. 3 is a schematic view of a process for preparing a vertical-plane layered oxidation-resistant gradient cross-linked polyethylene material according to an embodiment of the present invention;
fig. 4 is a schematic flow chart of a preparation process of a vertical cambered-surface layered antioxidant gradient cross-linked polyethylene material provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an antioxidant gradient crosslinked polyethylene material which is prepared by polyethylene mixture powder through die filling, sintering, demoulding and electron beam irradiation.
Wherein the polyethylene mixture powder comprises a first mixed powder and a second mixed powder, the first mixed powder is a mixed powder of polyethylene and Vitamin E (VE), and the second mixed powder is a 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 specifically 10000-13000 kDa; the mass ratio of the polyethylene to the vitamin E in the first mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may be specifically 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 the polyethylene to the gallic acid in the second mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may be specifically 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 (0.5-2): 1, specifically 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 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 that vitamin E and an organic solvent are uniformly mixed and then are mixed with polyethylene; the drying temperature is preferably 40-80 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5-14 days, and specifically may be 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 that the gallic acid and the organic solvent are uniformly mixed and then are mixed with the polyethylene; the drying temperature is preferably 40-80 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5-14 days, and specifically may be 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 first mixed powder and the second mixed powder are not blended in the process of filling the mould with the polyethylene mixture powder; after the die filling is finished, 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 present invention, the specific process of sintering preferably includes: sintering the mixed powder filled into the die into blocks under the conditions of heating and pressurizing, maintaining the pressure, annealing and cooling. Wherein the heating temperature is preferably 180-250 deg.C, and specifically 180 deg.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 specifically can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h; the pressurizing pressure is preferably 1-50 MPa, and specifically can be 1MPa, 5MPa, 10MPa, 15MPa, 20MPa, 25MPa, 30MPa, 35MPa, 40MPa, 45MPa or 50 MPa; the temperature of the pressure maintaining annealing is preferably 110-130 ℃, and specifically can be 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃; the pressure maintaining annealing time is preferably 0.5-72 h, more preferably 0.5-5 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h; the temperature after cooling is preferably room temperature.
In the invention, the electron beam energy of the electron beam irradiation is preferably 3-10 MeV, and specifically can be 3MeV, 3.5MeV, 4MeV, 4.5MeV, 5MeV, 5.5MeV, 6MeV, 6.5MeV, 7MeV, 7.5MeV, 8MeV, 8.5MeV, 9MeV, 9.5MeV or 10 MeV; the single irradiation measurement 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 5 Mrad; the total irradiation dose of the electron beam irradiation is preferably 2.5-25 Mrad, and specifically may be 2.5Mrad, 3Mrad, 4Mrad, 5Mrad, 6Mrad, 7Mrad, 8Mrad, 9Mrad, 10Mrad, 12Mrad, 15Mrad, 17Mrad, 20Mrad, or 25 Mrad.
The invention also provides a preparation method of the antioxidant gradient crosslinked 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) respectively filling the first mixed powder and the second mixed powder into a mould, wherein the two mixed powders are not blended; after the filling is finished, 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 into the die, and then demoulding to obtain a blank to be irradiated;
d) and performing electron beam irradiation on the blank to be irradiated to obtain the antioxidant gradient crosslinked 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 specifically 10000-13000 kDa; the mass ratio of the polyethylene to the vitamin E in the first mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): 1 may be specifically 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 the polyethylene to the gallic acid in the second mixed powder is preferably (50-10000): 1, more preferably (500 to 3000): specifically, 1 may 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 present 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 that vitamin E and an organic solvent are uniformly mixed and then are mixed with polyethylene; the drying temperature is preferably 40-80 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5-14 days, and specifically may be 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 that the gallic acid and the organic solvent are uniformly mixed and then are mixed with the polyethylene; the drying temperature is preferably 40-80 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃; the drying time is preferably 5-14 days, and specifically may be 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 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 the filling is finished, 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 the mixed powder is filled, the mixed powder filled in the die is sintered, and then the die is removed, so that the blank to be irradiated is obtained. The specific steps preferably comprise: sintering the mixed powder filled into the die into blocks under the conditions of heating and pressurizing, maintaining pressure, annealing, cooling and demolding to obtain the blank to be irradiated. Wherein the heating temperature is preferably 180-250 deg.C, and specifically 180 deg.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 specifically can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h; the pressurizing pressure is preferably 1-50 MPa, and specifically can be 1MPa, 5MPa, 10MPa, 15MPa, 20MPa, 25MPa, 30MPa, 35MPa, 40MPa, 45MPa or 50 MPa; the temperature of the pressure maintaining annealing is preferably 110-130 ℃, and specifically can be 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃; the pressure maintaining annealing time is preferably 0.5-72 h, more preferably 0.5-5 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h; 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. The electron beam energy of the electron beam irradiation is preferably 3-10 MeV, and specifically can be 3MeV, 3.5MeV, 4MeV, 4.5MeV, 5MeV, 5.5MeV, 6MeV, 6.5MeV, 7MeV, 7.5MeV, 8MeV, 8.5MeV, 9MeV, 9.5MeV or 10 MeV; the single irradiation measurement 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 5 Mrad; the total irradiation dose of the electron beam irradiation is preferably 2.5-25 Mrad, and specifically may be 2.5Mrad, 3Mrad, 4Mrad, 5Mrad, 6Mrad, 7Mrad, 8Mrad, 9Mrad, 10Mrad, 12Mrad, 15Mrad, 17Mrad, 20Mrad, or 25 Mrad. And after the electron beam irradiation is finished, obtaining the antioxidant gradient crosslinked polyethylene material.
In the present invention, taking fig. 1-4 as an example, the preparation processes of 4 antioxidant gradient crosslinked polyethylene materials with different structures are provided. Fig. 1 shows a preparation process of a horizontal plane layered antioxidant gradient crosslinked polyethylene material, fig. 2 shows a preparation process of a horizontal arc layered antioxidant gradient crosslinked polyethylene material, fig. 3 shows a preparation process of a vertical plane layered antioxidant gradient crosslinked polyethylene material, and fig. 4 shows a schematic diagram of a preparation process of a vertical arc layered antioxidant gradient crosslinked polyethylene material.
The technical scheme provided by the invention controls the distribution condition of the two antioxidants in the polyethylene by utilizing the difference of the irradiation crosslinking inhibition degree of the vitamin E and the gallic acid on the polyethylene, so as to obtain the gradient crosslinked polyethylene material. The material has excellent oxidation resistance and higher mechanical property, can obtain high crosslinking on the friction surface of the material to improve the wear resistance, and can obtain low crosslinking in the material to improve the mechanical property, so that the material is very suitable for manufacturing intra-articular implants and prolonging the service life of artificial joints.
For the sake of clarity, the following examples are given in detail.
In the following examples provided by the present invention, the polyethylene resin powder used is 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 1L 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 1L of acetone solvent, mixing uniformly, adding 100 kg of polyethylene resin powder, mixing fully, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): spreading the first mixed powder in a mold to compact, wherein the powder adding amount is about 1/3 of the volume of the mold, and spreading a second mixed powder with the same volume on the upper layer of the first mixed powder;
and (3): placing the mould containing the powder on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, keeping the temperature and the pressure unchanged for 2 hours, and sintering 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;
and (4): irradiating the block blank under a 10MeV high-energy electron beam at room temperature to obtain 3Mrad of irradiation dose each time, wherein the total irradiation dose is 9Mrad, and the irradiation dose is measured by a standard irradiation color development film; and (3) vertically irradiating the surface of the sample by using an electron beam during irradiation to ensure that the irradiation on each part of the sample is uniform, and obtaining the antioxidant gradient cross-linked polymer after irradiation, wherein the antioxidant gradient cross-linked polymer is marked as a sample A.
Example 2
Step (1): adding 100 g of vitamin E into 1L 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 1L of acetone solvent, mixing uniformly, adding 100 kg of polyethylene resin powder, mixing fully, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): spreading the first mixed powder in a mold to compact, wherein the powder adding amount is about 1/3 of the volume of the mold, and spreading a second mixed powder with the same volume on the upper layer of the first mixed powder;
and (3): placing the mould containing the powder on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, keeping the temperature and the pressure unchanged for 2 hours, and sintering 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;
and (4): irradiating the block blank under a 10MeV high-energy electron beam at room temperature to obtain 3Mrad of irradiation dose each time, wherein the total irradiation dose is 6Mrad, and the irradiation dose is measured by a standard irradiation color development film; and when in irradiation, the electron beam is vertically irradiated to the surface of the sample, so that the sample is uniformly irradiated, and the antioxidant gradient cross-linked polymer is obtained after irradiation and is marked as a sample A1.
Example 3
Step (1): adding 100 g of vitamin E into 1L 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 1L of acetone solvent, mixing uniformly, adding 100 kg of polyethylene resin powder, mixing fully, and drying at 60 ℃ for 14 days to obtain second mixed powder;
step (2): spreading the first mixed powder in a mold to compact, wherein the powder adding amount is about 1/3 of the volume of the mold, and spreading a second mixed powder with the same volume on the upper layer of the first mixed powder;
and (3): placing the mould containing the powder on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, keeping the temperature and the pressure unchanged for 2 hours, and sintering the mixture powder into blocks; then the temperature is reduced to 120 ℃, the pressure is kept unchanged for 1.5 hours, then the temperature is reduced to room temperature, and a block-shaped blank is obtained after demoulding and is marked as a sample A2.
Example 4
Step (1): adding 50 g of vitamin E into 1L 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 1L of ethanol solvent, mixing uniformly, adding 100 kg of polyethylene resin powder, mixing fully, 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 volume ratio of 1:1 in a mold separated by a flat sheet in the middle, separating the two mixtures from each other, and drawing out the flat sheet for separation after compaction, wherein the total powder addition amount is about 2/3 of the volume of the mold;
and (3): placing the mould containing the powder on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, keeping the temperature and the pressure unchanged for 2 hours, and sintering 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;
and (4): irradiating the block blank under a 10MeV high-energy electron beam at room temperature to obtain 3Mrad of irradiation dose each time, wherein the total irradiation dose is 9Mrad, and the irradiation dose is measured by a standard irradiation color development film; after irradiation, an antioxidant gradient crosslinked polymer was obtained and recorded as sample B.
Example 5
Step (1): adding 300 g of vitamin E into 1L 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 1L of isopropanol solvent, mixing uniformly, adding 100 kg of polyethylene resin powder, mixing fully, 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 volume ratio of 1:1 in a die with the middle separated by a cambered sheet to separate the two mixtures from left and right, and drawing out the cambered sheet for separation after compaction, wherein the total powder adding amount is about 2/3 of the volume of the die;
and (3): placing the mould containing the powder on a hot plate of a flat vulcanizing machine, heating to 240 ℃, pressurizing to 20MPa, keeping the temperature and the pressure unchanged for 2 hours, and sintering 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;
and (4): irradiating the block blank under a 10MeV high-energy electron beam at room temperature to obtain 3Mrad of irradiation dose each time, wherein the total irradiation dose is 9Mrad, and the irradiation dose is measured by a standard irradiation color development film; after irradiation, an antioxidant gradient crosslinked polymer was obtained and recorded as sample C.
Performance comparison
The results of the tests performed on the products prepared in examples 1 to 5 are shown in the following table:
as can be seen from the above table test results, the ultrahigh 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 body, the side close to gallic acid has high crosslinking degree under the same irradiation dose, and the side close to vitamin E has low crosslinking degree; 2) higher tensile strength; 3) higher impact strength. Therefore, by utilizing the technology of the invention, the gradient cross-linked 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, so that the purposes of obtaining high cross-linking on the friction surface of the material to improve the wear resistance and obtaining low cross-linking inside the material to improve the mechanical property are achieved, and the material can be used for manufacturing implants in joints and prolonging the service life of artificial joints.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An antioxidant gradient cross-linked polyethylene material is prepared by molding polyethylene mixture powder, sintering, demolding and electron beam irradiation;
the polyethylene mixture powder comprises a first mixed powder and a second mixed powder, wherein the first mixed powder is a mixed powder of polyethylene and vitamin E, and the second mixed powder is a mixed powder of polyethylene and gallic acid;
in the process of die filling, the first mixed powder and the second mixed powder are not blended; and after the die filling is finished, 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.
2. The oxidation resistant gradient crosslinked polyethylene material of claim 1, wherein the polyethylene has a number average molecular weight of 1000kDa or more.
3. The oxidation-resistant gradient cross-linked polyethylene material as claimed in claim 1, wherein the mass ratio of the polyethylene to the vitamin E in the first mixed powder is (50-10000): 1;
the mass ratio of the polyethylene to the gallic acid in the second mixed powder is (50-10000): 1.
4. the oxidation-resistant gradient cross-linked polyethylene material as claimed in claim 1, wherein the volume ratio of the first mixed powder to the second mixed powder is (0.5-2): 1.
5. the oxidation resistant gradient crosslinked polyethylene material of claim 1, wherein the interface is a flat or curved surface.
6. A preparation method of an 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;
b) respectively filling the first mixed powder and the second mixed powder into a mould, wherein the two mixed powders are not blended; after the filling is finished, 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 into the die, and then demoulding to obtain a blank to be irradiated;
d) and performing electron beam irradiation on the blank to be irradiated to obtain the antioxidant gradient crosslinked polyethylene material.
7. The method according to claim 6, wherein the first mixed powder is prepared by the steps of: 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.
8. The method according to claim 6, wherein step c) comprises in particular:
sintering the mixed powder filled into the die into blocks under the conditions of heating and pressurizing, maintaining pressure, annealing, cooling and demolding to obtain the blank to be irradiated.
9. The method according to claim 8, wherein the heating temperature is 180 to 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.
10. The method according to claim 6, wherein the electron beam irradiation has an electron beam energy of 3 to 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.
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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 |
| CN105713217A (en) * | 2016-04-20 | 2016-06-29 | 江南大学 | Method for preparing anti-oxidation anti-wear ultrahigh molecular weight polyethylene composite material |
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Effective date of registration: 20240123 Address after: 201201 Room 101, floor 1, building 21, No. 315, Qingda Road, Pudong New Area, Shanghai Patentee after: Shanghai perli medical materials Co.,Ltd. Country or region after: China Address before: Room 304, 3 / F, No.2 Lane 720, Cailun Road, China (Shanghai) pilot Free Trade Zone, Pudong New Area, Shanghai, 201203 Patentee before: Shanghai Weigao Medical Technology Development Co.,Ltd. Country or region before: China |