CN105837896A - Preparation method of ultra-high molecular weight polyethylene (UHMWPE) composite material - Google Patents
Preparation method of ultra-high molecular weight polyethylene (UHMWPE) composite material Download PDFInfo
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- CN105837896A CN105837896A CN201610247210.XA CN201610247210A CN105837896A CN 105837896 A CN105837896 A CN 105837896A CN 201610247210 A CN201610247210 A CN 201610247210A CN 105837896 A CN105837896 A CN 105837896A
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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Abstract
The invention relates to a preparation method of an ultra-high molecular weight polyethylene (UHMWPE) composite material, belonging to the technical field of high-polymer materials. The preparation method comprises the following steps: by using medical UHMWPE powder as a base material, compositely adding natural vitamin-E (VE) and single-layer graphene oxide (GO) to prepare mixed powder, adding the mixed powder into a mold, carrying out hot pressing to prepare a UHMWPE/GO-VE composite material; and carrying out gamma-ray irradiation crosslinking treatment to finally obtain the oxidation-resistant ultra-low-abrasion UHMWPE composite material. The gamma-ray irradiation crosslinking UHMWPE/GO-VE composite material has excellent wear resistance. The two-dimensional-structure GO with excellent mechanical properties and biocompatibility can lower the abrasion, thereby reducing the abrasive dust quantity and lowering the cell untoward effect degree caused by abrasive dust. The composite material has excellent oxidation resistance and aging resistance.
Description
Technical field
The present invention relates to the preparation method of a kind of ultra-high molecular weight polyethylene composite material, belong to technical field of polymer materials.
Background technology
Ultra High Molecular Weight Polyethylene Composites (abridge: UHMWPE) is the most widely used hip cotyle material by English name.At present, the ultra-high molecular weight polyethylene composite material being applied to clinic is mainly cross-linking radiation VE/UHMWPE composite, but, the addition of VE reduces the degree of cross linking of composite, thus reduces the performance of the abrasive wear resistance of composite.In addition the mechanical property of composite needs to be improved further compared to pure UHMWPE, improves its performance at mechanics Yu wear-resisting aspect the most further, has great meaning to medical applications.
Summary of the invention
It is an object of the invention to overcome above-mentioned weak point, it is provided that a kind of have excellent mechanical property, antioxidant ultra-low abrasion ultra-high molecular weight polyethylene composite.
The technical scheme provided according to the present invention, the preparation method of a kind of ultra-high molecular weight polyethylene composite material, by weight step be:
(1) preparation of mixed-powder: single-layer graphene oxide GO and Viamin E are joined after being sufficiently stirred in solvent disperseing through ultrasonically treated, add the dispersion of ultra-high molecular weight polyethylene UHMWPE powder magnetic agitation, the most ultrasonically treated, powder is obtained through ultrasonic stripping, then carry out ball milling mixing, form uniform three body mixed-powders；
(2) shaping: add in mould by step (1) gained mixed-powder, uses vulcanizing press in precompressed, is then incubated in incubator, then uses vulcanizing press to obtain sheet material in pressing mold process, is cooled to room temperature；
(3) irradiation: the composite 0.5-0.9MPa vacuum of step (3) gained sealed, the most at room temperature, uses gamma-radiation to carry out cross-linking radiation process, and irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co, finally give ultra-high molecular weight polyethylene composite material.
The purity of described vitamin E is VE > 98%, and particle diameter is less than 100 μm.
The particle size range of described ultra-high molecular weight polyethylene UHMWPE powder is 4.3-200 μm.
The preparation method of described ultra-high molecular weight polyethylene composite material, specifically comprises the following steps that
(1) preparation of mixed-powder: single-layer graphene oxide GO of 0.3-0.7 part and the Viamin E powder of 0.1-0.3 part are joined and is sufficiently stirred for dispersion in 500 parts of solvents, the most again with the ultrasonically treated 0.5-2h of 200-400W；The ultra-high molecular weight polyethylene powder UHMWPE of 99-99.6 part is joined in above-mentioned solution, by mixture 200-400W ultrasonic stripping 0.5-2h again after magnetic agitation 30-90min；Gained mixture is placed in grinding in ball grinder mixing 2-4h；
Mixture after grinding is placed in 60-80 DEG C of water-bath and is dried, and is incubated and is completely dried to it at 60-80 DEG C；It is again placed in grinding in ball grinder to pulverize, pulverizes 2-4h with the rotating speed of 300-600r/min；
(2) shaping: step (1) the gained mixed-powder of 100g is added in mould, use vulcanizing press precompressed 10-15min under 10-15MPa pressure, then 180-200 DEG C of insulation 2-3h in incubator, use vulcanizing press to process 15-20min at 15-20MPa pressure dip mold again and obtain composite board, be cooled to room temperature；
(3) irradiation: the composite vacuum of step (3) gained is sealed；The most at room temperature, using gamma-radiation to carry out cross-linking radiation process, exposure time is 9-12 days, finally gives product ultra-high molecular weight polyethylene composite material.
Step (1) described solvent is absolute ethyl alcohol or acetone.
When using gamma-radiation to carry out cross-linking radiation process, irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co.
Beneficial effects of the present invention: the present invention selects material based on Ultra High Molecular Weight Polyethylene Composites UHMWPE powder, and to its compound interpolation vitamin VEAnd graphene oxide, take full advantage of the fine quality of Viamin E and graphene oxide, both non-oxidizability and the biocompatibility of UHMWPE had been added, the mechanical properties such as the wearability adding again UHMWPE, finally give and have excellent mechanical property, antioxidant ultra-low abrasion ultra-high molecular weight polyethylene composite；Chroman end in Viamin E molecular structure can be drawn and stabilized radical, forms phenoxyl radicals；Phenoxyl radicals can suffer steric hindrance, makes itself stable and is retained in polymer, stoping oxidizing process.
Detailed description of the invention
Hereinafter the present invention is described in further detail.
Ultra High Molecular Weight Polyethylene Composites powder UHMWPE, it is conventional commercial products, and particle size range is 4.3-200 μm.
Vitamin is conventional commercial products, and purity is more than 98%, is ground processing to it, and granularity is less than 100 μm.
Single-layer graphene oxide (GO), it it is a kind of derivative being prepared Graphene by redox reaction, it is to connect a large amount of oxygen-containing functional group on single-layer graphene two-dimensional structure, as completed base, carrying base, light base etc., has the mechanical properties such as higher elastic modelling quantity, tensile strength；Commercially available or prepare voluntarily.
The preparation method of single-layer graphene oxide GO involved by the following embodiment of the present invention is as follows:
(1) at a temperature of 40 DEG C, 5g Fine particle processing and 0.75g potassium permanganate is added in the concentrated sulfuric acid that 46g mass concentration is 98%, after continuously stirring 90min, product is washed with deionized water to neutrality, after vacuum drying, being incubated 50 seconds at 900 DEG C, the density obtaining the expanded graphite wherein concentrated sulfuric acid is calculated by 1.84g/mL, the corresponding 25mL concentrated sulfuric acid；
(2) under ice bath environment, to filling, the concentrated sulfuric acid that 42.3g mass concentration is 98% adds 0.5g sodium nitrate, 0.5g expanded graphite and 1.5g potassium permanganate, 30min is stirred at 35 DEG C, then heat temperature raising 98 DEG C, add 46g deionized water, stir 15min, observe that mixture is become golden yellow from black, with in the hydrogenperoxide steam generator that 30mL solubility is 30% and residual oxidizing agent, until the density that bubble-free generates the wherein concentrated sulfuric acid is calculated by 1.84g/mL, the corresponding 23mL concentrated sulfuric acid；
(3) dilute hydrochloric acid solution and deionized water with mass concentration is 5% wash repeatedly respectively, remove upper solution and obtain stable dispersion liquid, obtain described single-layer graphene oxide after vacuum drying.
Embodiment 1
(1) preparation technology of mixed-powder:
A, the Viamin E powder of the single-layer graphene oxide of 0.5 part and 0.1 part is joined 500 parts of solvents are sufficiently stirred for dispersion, the most again with the ultrasonically treated 1h of 200W；
B, the UHMWPE of 99.4 parts is joined in the solution that step a obtains, by mixture 200W ultrasonic stripping 1h again after magnetic agitation 30min；
It is that 400r/min grinding in ball grinder mixes 2h that c, mixture step b obtained are placed in rotating speed；
D, mixture step c obtained are placed in 60 DEG C of water-baths and are dried, and be incubated and be completely dried to it at 60 DEG C；
E, step d is processed after dried object be placed in grinding in ball grinder and pulverize, pulverize 2h with the rotating speed of 400r/min；
(2) moulding process: the above-mentioned mixed-powder of 100g is added in mould, use vulcanizing press precompressed 10min under 15MPa pressure, then 200 DEG C of insulation 2h in incubator, then use vulcanizing press to obtain sheet material at 20MPa pressure dip mold process 15min, it is cooled to room temperature；
(3) irradiation technique: composite 0.9MPa vacuum sealed the most at room temperature, uses gamma-radiation to carry out cross-linking radiation process, and irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co, irradiation 9 days, finally give and there is excellent mechanical property, antioxidant ultra-low abrasion ultra-high molecular weight polyethylene composite.
Described solvent is absolute ethyl alcohol.
Embodiment 2
(1) preparation technology of mixed-powder:
A, the Viamin E powder of the single-layer graphene oxide of 0.6 part and 0.2 part is joined 500 parts of solvents are sufficiently stirred for dispersion, the most again with the ultrasonically treated 1.5h of 400W；
B, the UHMWPE of 99.2 parts is joined in the solution that step a obtains, by mixture 300W ultrasonic stripping 1.5h again after magnetic agitation 60min；
It is that 400r/min grinding in ball grinder mixes 2h that c, mixture step b obtained are placed in rotating speed；
D, mixture step c obtained are placed in 70 DEG C of water-baths and are dried, and be incubated and be completely dried to it at 70 DEG C；
E, step d is processed after dried object be placed in grinding in ball grinder and pulverize, pulverize 3 hours with the rotating speed of 400r/min；
(2) moulding process: the above-mentioned mixed-powder of 100g is added in mould, use vulcanizing press precompressed 15min under 10MPa pressure, then 180 DEG C of insulation 3h in incubator, then use vulcanizing press to obtain sheet material at 15MPa pressure dip mold process 20min, it is cooled to room temperature；
(3) irradiation technique: composite 0.9MPa vacuum sealed the most at room temperature, uses gamma-radiation to carry out cross-linking radiation process, and irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co, irradiation 9 days, finally give and there is excellent mechanical property, antioxidant ultra-low abrasion ultra-high molecular weight polyethylene composite.
Described solvent is acetone.
Embodiment 3
(1) preparation technology of mixed-powder:
A, the Viamin E powder of the single-layer graphene oxide of 0.7 part and 0.3 part is joined 500 parts of solvents are sufficiently stirred for dispersion, the most again with the ultrasonically treated 1h of 400W；
B, the UHMWPE of 99 parts is joined in the solution that step a obtains, by mixture 400W ultrasonic stripping 2h again after magnetic agitation 90 minutes；
It is that 400r/min grinding in ball grinder mixes 4h that c, mixture step b obtained are placed in rotating speed；
D, mixture step c obtained are placed in 80 DEG C of water-baths and are dried, and be incubated and be completely dried to it at 80 DEG C；
E, step d is processed after dried object be placed in grinding in ball grinder and pulverize, pulverize 3 hours with the rotating speed of 600r/min；
(2) moulding process: the above-mentioned mixed-powder of 100g is added in mould, use vulcanizing press precompressed 12min under 13MPa pressure, then 190 DEG C of insulation 2.5h in incubator, then use vulcanizing press to obtain sheet material at 18MPa pressure dip mold process 18min, it is cooled to room temperature；
(3) irradiation technique: composite 0.9MPa vacuum sealed the most at room temperature, uses gamma-radiation to carry out cross-linking radiation process, and irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co, irradiation 9 days, finally give and there is excellent mechanical property, antioxidant ultra-low abrasion ultra-high molecular weight polyethylene composite.
Described solvent is absolute ethyl alcohol.
Claims (6)
1. a preparation method for ultra-high molecular weight polyethylene composite material, is characterized in that step is by weight:
(1) preparation of mixed-powder: single-layer graphene oxide GO and Viamin E are joined after being sufficiently stirred in solvent disperseing through ultrasonically treated, add the dispersion of ultra-high molecular weight polyethylene UHMWPE powder magnetic agitation, the most ultrasonically treated, powder is obtained through ultrasonic stripping, then carry out ball milling mixing, form uniform three body mixed-powders；
(2) shaping: add in mould by step (1) gained mixed-powder, uses vulcanizing press in precompressed, is then incubated in incubator, then uses vulcanizing press to obtain sheet material in pressing mold process, is cooled to room temperature；
(3) irradiation: the composite 0.5-0.9MPa vacuum of step (3) gained sealed, the most at room temperature, uses gamma-radiation to carry out cross-linking radiation process, and irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co, finally give ultra-high molecular weight polyethylene composite material.
2. the preparation method of ultra-high molecular weight polyethylene composite material as claimed in claim 1, is characterized in that: the purity of described vitamin E is VE >
98%, particle diameter is less than 100 μm.
3. the preparation method of ultra-high molecular weight polyethylene composite material as claimed in claim 1, is characterized in that: the particle size range of described ultra-high molecular weight polyethylene UHMWPE powder is 4.3-200 μm.
4. the preparation method of ultra-high molecular weight polyethylene composite material as claimed in claim 1, is characterized in that specifically comprising the following steps that
(1) preparation of mixed-powder: single-layer graphene oxide GO of 0.3-0.7 part and the Viamin E powder of 0.1-0.3 part are joined and is sufficiently stirred for dispersion in 500 parts of solvents, the most again with the ultrasonically treated 0.5-2h of 200-400W；The ultra-high molecular weight polyethylene powder UHMWPE of 99-99.6 part is joined in above-mentioned solution, by mixture 200-400W ultrasonic stripping 0.5-2h again after magnetic agitation 30-90min；Gained mixture is placed in grinding in ball grinder mixing 2-4h；
Mixture after grinding is placed in 60-80 DEG C of water-bath and is dried, and is incubated and is completely dried to it at 60-80 DEG C；It is again placed in grinding in ball grinder to pulverize, pulverizes 2-4h with the rotating speed of 300-600r/min；
(2) shaping: step (1) the gained mixed-powder of 100g is added in mould, use vulcanizing press precompressed 10-15min under 10-15MPa pressure, then 180-200 DEG C of insulation 2-3h in incubator, use vulcanizing press to process 15-20min at 15-20MPa pressure dip mold again and obtain composite board, be cooled to room temperature；
(3) irradiation: the composite vacuum of step (3) gained is sealed；The most at room temperature, using gamma-radiation to carry out cross-linking radiation process, exposure time is 9-12 days, finally gives product ultra-high molecular weight polyethylene composite material.
5. the preparation method of ultra-high molecular weight polyethylene composite material as claimed in claim 2, is characterized in that: step (1) described solvent is absolute ethyl alcohol or acetone.
6. the preparation method of ultra-high molecular weight polyethylene composite material as claimed in claim 2, is characterized in that: when using gamma-radiation to carry out cross-linking radiation process, irradiation is 100kGy, and the close rate of irradiation is 5kGyh-1, gamma-radiation former material 60Co.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210070960A1 (en) * | 2019-09-06 | 2021-03-11 | Jiangnan University | Method for preparing ultra high molecular weight polyethylene composite materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277390B1 (en) * | 1998-10-21 | 2001-08-21 | Sulzer Orthopaedie Ag | UHMW polyethylene for implants |
| CN101998974A (en) * | 2007-09-04 | 2011-03-30 | 史密夫和内修整形外科股份公司 | Ultra high molecular weight polyethylene for bearing surfaces |
| CN104327357A (en) * | 2014-11-08 | 2015-02-04 | 江南大学 | Preparation method of composite material and composite material |
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2016
- 2016-04-20 CN CN201610247210.XA patent/CN105837896A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277390B1 (en) * | 1998-10-21 | 2001-08-21 | Sulzer Orthopaedie Ag | UHMW polyethylene for implants |
| CN101998974A (en) * | 2007-09-04 | 2011-03-30 | 史密夫和内修整形外科股份公司 | Ultra high molecular weight polyethylene for bearing surfaces |
| CN104327357A (en) * | 2014-11-08 | 2015-02-04 | 江南大学 | Preparation method of composite material and composite material |
Non-Patent Citations (2)
| Title |
|---|
| JUAN C. BAENA等: "Wear Performance of UHMWPE and Reinforced UHMWPE", 《LUBRICANTS》 * |
| 齐贵亮: "《塑料挤出成型实用技术》", 31 July 2012, 北京：机械工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210070960A1 (en) * | 2019-09-06 | 2021-03-11 | Jiangnan University | Method for preparing ultra high molecular weight polyethylene composite materials |
| US11597812B2 (en) * | 2019-09-06 | 2023-03-07 | Jiangnan University | Method for preparing ultra high molecular weight polyethylene composite materials |
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