CN114230843A - Polyether-ether-ketone surface modification method - Google Patents
Polyether-ether-ketone surface modification method Download PDFInfo
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- CN114230843A CN114230843A CN202210026325.1A CN202210026325A CN114230843A CN 114230843 A CN114230843 A CN 114230843A CN 202210026325 A CN202210026325 A CN 202210026325A CN 114230843 A CN114230843 A CN 114230843A
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- polyether
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- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 185
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 184
- 238000002715 modification method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000003960 organic solvent Substances 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000010936 titanium Substances 0.000 claims description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 47
- 229910052719 titanium Inorganic materials 0.000 claims description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 38
- 239000004094 surface-active agent Substances 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000013877 carbamide Nutrition 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- 108010077895 Sarcosine Proteins 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 claims description 4
- 229960003964 deoxycholic acid Drugs 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 229940043230 sarcosine Drugs 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- -1 ether ether ketone Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims 2
- 229920000570 polyether Polymers 0.000 claims 2
- 229930194542 Keto Natural products 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims 1
- 125000000468 ketone group Chemical group 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- 239000007943 implant Substances 0.000 abstract description 5
- 210000000988 bone and bone Anatomy 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 3
- 238000005289 physical deposition Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 16
- 238000004506 ultrasonic cleaning Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000005498 polishing Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 210000001185 bone marrow Anatomy 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 5
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000975 bioactive effect Effects 0.000 description 4
- 238000004113 cell culture Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 3
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000010288 cold spraying Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a polyether-ether-ketone surface modification method, which comprises the following steps: hydroxylating the surface of polyether-ether-ketone by a wet chemical method to obtain hydroxylated polyether-ether-ketone; and depositing a titanium dioxide coating on the surface of the hydroxylated polyether-ether-ketone through hydrothermal treatment to obtain the surface modified polyether-ether-ketone. According to the surface modification method of the polyether-ether-ketone, provided by the invention, a surface modification strategy combining a wet chemical method and hydrothermal treatment is adopted, firstly, the surface of the polyether-ether-ketone is hydroxylated by the wet chemical method so as to improve the hydrophilicity of the surface of the polyether-ether-ketone, and then a titanium dioxide coating with bioactivity is deposited on the hydroxylated polyether-ether-ketone surface by the hydrothermal treatment, so that the bone integration capacity of the polyether-ether-ketone is improved; in addition, the surface modification method of the polyetheretherketone is simple, the requirements on instruments are simple, the use of complex and expensive equipment in the physical deposition process is avoided, and the treatment requirements of the implant with the complex shape are met.
Description
Technical Field
The invention relates to the technical field of surface modification of high polymer materials, in particular to a surface modification method of polyether-ether-ketone.
Background
The introduction of bioactive coating materials on the surface of Polyetheretherketone (PEEK) materials has become a major concern due to the significant improvement in the osteointegration capacity of PEEK. At present, there are many methods for depositing a bioactive coating on a PEEK substrate material, including plasma spraying, physical evaporation deposition, cold spraying, microwave-assisted deposition, wet chemical methods, and the like, but most of these methods require the use of relatively complex and expensive equipment, and the coating has poor binding force with the substrate material, is easy to fall off, is mostly limited by sight, and cannot be applied to the treatment of samples with complex shapes. The wet chemical method suitable for complex sample treatment deposits a polymer coating on the surface, and the coating structure on the surface is easily influenced by subsequent sterilization processes such as gamma rays, high temperature, moist heat and the like.
Disclosure of Invention
The invention mainly aims to provide a surface modification method of polyetheretherketone, aiming at providing a surface modification method of polyetheretherketone which can effectively improve the bioactivity of PEEK materials, avoid the use of complex and expensive equipment and meet the processing requirements of complex-shaped implants.
In order to achieve the purpose, the invention provides a polyether-ether-ketone surface modification method, which comprises the following steps:
hydroxylating the surface of polyether-ether-ketone by a wet chemical method to obtain hydroxylated polyether-ether-ketone;
and depositing a titanium dioxide coating on the surface of the hydroxylated polyether-ether-ketone through hydrothermal treatment to obtain the surface modified polyether-ether-ketone.
Optionally, the step of hydroxylating the surface of polyetheretherketone by wet chemical means to obtain hydroxylated polyetheretherketone comprises:
adding the washed and dried polyether-ether-ketone into the sodium borohydride-organic solvent mixed solution, heating and reducing for 0.5-24 h at 60-150 ℃ under the nitrogen atmosphere, separating out solids, washing and drying to obtain the hydroxylated polyether-ether-ketone.
Optionally, in the sodium borohydride-organic solvent mixed solution, the organic solvent includes at least one of tetrahydrofuran, methanol, ethanol, and dimethyl sulfoxide.
Optionally, in the sodium borohydride-organic solvent mixed solution, the concentration of sodium borohydride is 0.1-6 g/L.
Optionally, the step of depositing a titanium dioxide coating on the surface of the hydroxylated polyetheretherketone by hydrothermal treatment to obtain a surface-modified polyetheretherketone comprises:
and (2) soaking the hydroxylated polyether-ether-ketone in a titanium precursor-organic solvent mixed solution, carrying out hydrothermal synthesis reaction at 60-150 ℃ for 0.5-24 h, adding a surfactant aqueous solution for hydrothermal treatment, separating out solids, cleaning and drying to obtain the surface-modified polyether-ether-ketone.
Optionally, in the titanium precursor-organic solvent mixed solution, the titanium precursor includes at least one of titanium tetrachloride, tetraethyl titanate, tetrabutyl titanate, and titanyl sulfate; and/or the presence of a gas in the gas,
in the titanium precursor-organic solvent mixed solution, the organic solvent includes at least one of ethanol, ethylene glycol, isopropanol, methanol and glycerol.
Optionally, in the aqueous surfactant solution, the surfactant comprises sodium dodecylbenzene sulfonate, methyl alpha-sulfoester sulfonate, carboxymethyl cellulose, sodium deoxycholate, sodium dodecylsulfonate, cetyltrimethylammonium chloride, sodium cholate, sarcosine, tween-20, tween-80, or urea.
Optionally, the pH of the surfactant aqueous solution is 2-7; and/or the presence of a gas in the gas,
the concentration of the surfactant in the surfactant aqueous solution is 1 x 10-5~0.01 mol/L。
Optionally, the temperature of the hydrothermal treatment is 25-100 ℃; and/or the presence of a gas in the gas,
the hydrothermal treatment time is 0.5-12 h.
Optionally, the hydroxylated polyether ether ketone is soaked in a titanium precursor-organic solvent mixed solution, hydrothermal synthesis reaction is carried out for 0.5-24 h at 60-150 ℃, then a surfactant aqueous solution is added for hydrothermal treatment, then a solid is separated, and the dried product is washed and dried to obtain the surface modified polyether ether ketone, wherein the drying temperature is 45-120 ℃.
According to the technical scheme, a surface modification strategy combining a wet chemical method and hydrothermal treatment is adopted, firstly, the surface of the polyether-ether-ketone is hydroxylated by the wet chemical method to improve the hydrophilicity of the surface of the polyether-ether-ketone, and then a titanium dioxide coating with bioactivity is deposited on the hydroxylated polyether-ether-ketone surface by the hydrothermal treatment, so that the bone integration capacity of the polyether-ether-ketone is improved; in addition, the surface modification method of the polyetheretherketone is simple, the requirements on instruments are simple, the use of complex and expensive equipment in the physical deposition process is avoided, and the treatment requirements of the implant with the complex shape are met.
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 some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a method for modifying a surface of polyetheretherketone according to the present invention;
FIG. 2 is a schematic flow chart of another embodiment of a PEEK surface modification method proposed by the present invention;
FIG. 3 is a scanning electron microscope image of a surface modified PEEK and a PEEK sheet prepared in accordance with example 1 of the present invention;
FIG. 4 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) tests performed on surface-modified PEEK and PEEK sheets prepared in example 1 of the present invention;
FIG. 5 is a diagram showing the cell activity of the surface-modified PEEK prepared in example 1 of the present invention during a cell culture test;
FIG. 6 is a graph showing the detection of alkaline phosphatase activity of surface-modified polyetheretherketone prepared in example 1 of the present invention during a cell culture assay.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. 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 introduction of bioactive coating materials on the surface of Polyetheretherketone (PEEK) materials has become a major concern due to the significant improvement in the osteointegration capacity of PEEK. At present, there are many methods for depositing a bioactive coating on a PEEK substrate material, including plasma spraying, physical evaporation deposition, cold spraying, microwave-assisted deposition, wet chemical methods, and the like, but most of these methods require the use of relatively complex and expensive equipment, and the coating has poor binding force with the substrate material, is easy to fall off, is mostly limited by sight, and cannot be applied to the treatment of samples with complex shapes. The wet chemical method suitable for complex sample treatment deposits a polymer coating on the surface, and the coating structure on the surface is easily influenced by subsequent sterilization processes such as gamma rays, high temperature, moist heat and the like.
In view of the above, the invention provides a surface modification method of polyetheretherketone, which can effectively improve the bioactivity of a PEEK material, avoid the use of complex and expensive equipment, and meet the treatment requirements of implants with complex shapes.
In an embodiment of the present invention, a method for modifying a surface of polyetheretherketone is provided, referring to fig. 1, including the following steps:
and step S10, hydroxylating the surface of the polyether-ether-ketone by a wet chemical method to obtain hydroxylated polyether-ether-ketone.
And S20, depositing a titanium dioxide coating on the surface of the hydroxylated polyether-ether-ketone through hydrothermal treatment to obtain the surface modified polyether-ether-ketone.
According to the technical scheme, a surface modification strategy combining a wet chemical method and hydrothermal treatment is adopted, firstly, the surface of the polyether-ether-ketone is hydroxylated by the wet chemical method to improve the hydrophilicity of the surface of the polyether-ether-ketone, and then a titanium dioxide coating with bioactivity is deposited on the hydroxylated polyether-ether-ketone surface by the hydrothermal treatment, so that the bone integration capacity of the polyether-ether-ketone is improved; in addition, the surface modification method of the polyetheretherketone is simple, the requirements on instruments are simple, the use of complex and expensive equipment in the physical deposition process is avoided, and the treatment requirements of the implant with the complex shape are met.
Further, referring to fig. 2, step S10 includes:
and S11, adding the cleaned and dried polyether-ether-ketone into the sodium borohydride-organic solvent mixed solution, heating and reducing for 0.5-24 h at 60-150 ℃ under the nitrogen atmosphere, separating out solids, cleaning and drying to obtain the hydroxylated polyether-ether-ketone.
Through the step S11, carbonyl on the PEEK main chain can be reduced to obtain a hydroxylated surface structure, so that the hydrophilicity of the PEEK material surface is improved, and the subsequent deposition of titanium dioxide on the surface and the increase of the bonding force between the PEEK base material and the titanium dioxide coating are facilitated.
It should be noted that the sodium borohydride-organic solvent mixed solution is prepared by dissolving sodium borohydride in an organic solvent, and in order to ensure the reduction effect of sodium borohydride on the carbonyl group on the PEEK main chain, the organic solvent in the sodium borohydride-organic solvent mixed solution includes at least one of tetrahydrofuran, methanol, ethanol, and dimethyl sulfoxide. That is, the organic solvent may be tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, a mixed solvent of any two of tetrahydrofuran, methanol, ethanol, and dimethyl sulfoxide, a mixed solvent of any three of tetrahydrofuran, methanol, ethanol, and dimethyl sulfoxide, or a mixed solvent of tetrahydrofuran, methanol, ethanol, and dimethyl sulfoxide.
Further, in the sodium borohydride-organic solvent mixed solution, the concentration of sodium borohydride is 0.1-6 g/L, such as 0.1g/L, 1g/L, 3g/L, 4g/L, 5g/L, 6g/L, and the like.
With continued reference to fig. 2, step S20 includes:
step S21, soaking the hydroxylated polyether-ether-ketone in a titanium precursor-organic solvent mixed solution, carrying out hydrothermal synthesis reaction at 60-150 ℃ for 0.5-24 h, adding a surfactant aqueous solution for hydrothermal treatment, separating out solids, cleaning, and drying to obtain the surface-modified polyether-ether-ketone.
The hydroxylated PEEK surface is favorable for the adhesion of a titanium dioxide precursor on the PEEK surface, and the precursor is continuously hydrolyzed to generate titanium dioxide along with the sol-gel process of the titanium dioxide precursor in a hydrothermal system, and is chemically bonded with hydroxyl on the PEEK surface to construct a titanium dioxide coating on the PEEK material surface.
The titanium precursor-organic solvent mixed solution is prepared by dissolving a titanium precursor in an organic solvent, wherein in the titanium precursor-organic solvent mixed solution, the titanium precursor comprises at least one of titanium tetrachloride, tetraethyl titanate, tetrabutyl titanate and titanyl sulfate, and the titanium precursor is used for being converted into titanium dioxide during hydrothermal treatment so as to obtain a titanium dioxide coating. The titanium precursor can be at least one of titanium tetrachloride, tetraethyl titanate, tetrabutyl titanate and titanyl sulfate, and the titanium dioxide coating formed by using the compound as the titanium precursor has good effect. Of course, in some other embodiments, the titanium precursor may also be a compound that can be hydrothermally treated to obtain titanium dioxide, and the invention is not limited thereto.
Further, in the titanium precursor-organic solvent mixed solution, the organic solvent includes at least one of ethanol, ethylene glycol, isopropanol, methanol and glycerol, and the organic solvent is used for dissolving the titanium precursor, and the alcohols are used as the solvent to ensure the sol-gel process of the titanium precursor in the hydrothermal system.
In the surfactant aqueous solution, the surfactant comprises sodium dodecyl benzene sulfonate, alpha-sulfo ester methyl sulfonate, carboxymethyl cellulose, sodium deoxycholate, sodium dodecyl sulfonate, hexadecyl trimethyl ammonium chloride, sodium cholate, sarcosine, tween-20, tween-80 or urea. Sodium dodecyl benzene sulfonate, alpha-sulfo ester methyl sulfonate, carboxymethyl cellulose, sodium deoxycholate, sodium dodecyl sulfate, hexadecyl trimethyl ammonium chloride, sodium cholate, sarcosine, tween-20, tween-80 or urea are used as surfactants, which is beneficial to improving the quality of the titanium dioxide coating. In addition, in the embodiment of the invention, the pH of the surfactant aqueous solution is preferably 2-7, for example, the pH is 2, the pH is 3, the pH is 4, the pH is 5, the pH is 6, and the pH is 7; the concentration of the surfactant in the surfactant aqueous solution is 1 x 10-50.01mol/L, e.g., 1X 10-5 mol/L、9.1×10-4 mol/L、1×10-3mol/L, 0.01mol/L, and the like.
In addition, the temperature during the hydrothermal treatment is suitable to ensure that the titanium precursor is converted into the titanium dioxide coating more effectively, and the temperature of the hydrothermal treatment is 25 ℃ to 100 ℃, such as 25 ℃, 30 ℃, 50 ℃, 70 ℃, 90 ℃, 100 ℃ and the like.
The time for the hydrothermal treatment is also suitable to ensure that the titanium precursor is converted into the titanium dioxide coating more fully, and the time for the hydrothermal treatment is 0.5-12 h, such as 0.5h, 2h, 4h, 8h, 10h, 12h and the like.
Further, in step S21, the drying temperature is 45 to 120 ℃, such as 45 ℃, 60 ℃, 90 ℃, 110 ℃, 120 ℃ and the like. At the above temperature, the obtained surface-modified polyetheretherketone does not have impurities such as moisture left on the surface.
An embodiment of the method for modifying a surface of polyetheretherketone according to the present invention is given below:
(1) grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding the cleaned and dried PEEK slices into 0.1-6 g/L sodium borohydride-organic solvent mixed solution, and adding the PEEK slices into N2Heating and reducing at 60-150 ℃ for 0.5-24 h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) And (2) soaking the hydroxylated polyether-ether-ketone in 40ml of titanium precursor-organic solvent mixed solution containing 1-5 ml of titanium precursor, transferring all the solutions into a reaction kettle, and placing the reaction kettle in an oven to perform hydrothermal synthesis reaction at the temperature of 60-150 ℃ for 0.5-24 h. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 1X 10) was added-50.01mol/L, and the pH value of the surfactant aqueous solution is 2-7). And placing the reaction kettle in an oven at room temperature to 100 ℃ again for reaction for 0.5 to 12 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in an oven at the temperature of 45-120 ℃ to obtain the surface modified polyether-ether-ketone.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding cleaned and dried PEEK sheet into 6g/L sodium borohydride-organic solvent mixed solution (the organic solvent is dimethyl sulfoxide), and adding into N2Heating and reducing at 120 ℃ for 6h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) The hydroxylated polyether-ether-ketone is soaked in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is ethanol, and the titanium precursor is tetrabutyl titanate) containing 1ml of titanium precursor, all the solutions are transferred to a reaction kettle and placed in an oven for hydrothermal synthesis reaction at the temperature of 100 ℃, and the reaction time is 4 hours. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 9.1X 10) was added-4mol/L, pH 6.5, surfactant sodium dodecyl sulfate). And (4) putting the reaction kettle into a 70 ℃ oven again for reaction for 4 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in a 60 ℃ drying oven to obtain the surface modified polyether-ether-ketone.
Example 2
(1) Grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding cleaned and dried PEEK sheet into 6g/L sodium borohydride-organic solvent mixed solution (the organic solvent is dimethyl sulfoxide), and adding into N2Heating and reducing at 120 ℃ for 6h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) Soaking the hydroxylated polyether-ether-ketone in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is ethanol, and the titanium precursor is tetrabutyl titanate) containing 1ml of titanium precursor, transferring all the solutions into a reaction kettle, placing the reaction kettle in an oven for hydrothermal synthesis reaction at the temperature of 70 ℃,the reaction time is 1 h. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 9.1X 10) was added-4mol/L, pH 6.5, surfactant sodium dodecyl sulfate). And (4) putting the reaction kettle into a 70 ℃ oven again for reaction for 4 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in a 60 ℃ drying oven to obtain the surface modified polyether-ether-ketone.
Example 3
(1) Grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding cleaned and dried PEEK sheet into 6g/L sodium borohydride-organic solvent mixed solution (the organic solvent is dimethyl sulfoxide), and adding into N2Heating and reducing at 120 ℃ for 24h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) The hydroxylated polyether-ether-ketone is soaked in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is ethanol, and the titanium precursor is tetrabutyl titanate) containing 5ml of titanium precursor, all the solutions are transferred to a reaction kettle and placed in an oven for hydrothermal synthesis reaction at the temperature of 100 ℃, and the reaction time is 4 hours. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 9.1X 10) was added-4mol/L, pH 2, surfactant sodium dodecyl sulfate). And (4) putting the reaction kettle into a 70 ℃ oven again for reaction for 4 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in a 60 ℃ drying oven to obtain the surface modified polyether-ether-ketone.
Example 4
(1) Grinding and polishing a PEEK sheet with the thickness of 10mm multiplied by 1mm,sequentially placing in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying in an oven at 80 deg.C. Adding cleaned and dried PEEK sheet into 6g/L sodium borohydride-organic solvent mixed solution (the organic solvent is dimethyl sulfoxide), and adding into N2Heating and reducing at 120 ℃ for 24h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) The hydroxylated polyether-ether-ketone is soaked in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is ethanol, and the titanium precursor is tetrabutyl titanate) containing 5ml of titanium precursor, all the solutions are transferred to a reaction kettle and placed in an oven for hydrothermal synthesis reaction at the temperature of 70 ℃, and the reaction time is 1 h. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 9.1X 10) was added-4mol/L, pH 2, surfactant sodium dodecyl sulfate). And (4) putting the reaction kettle into a 70 ℃ oven again for reaction for 4 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in a 60 ℃ drying oven to obtain the surface modified polyether-ether-ketone.
Example 5
(1) Grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding the cleaned and dried PEEK sheet into 0.1g/L sodium borohydride-organic solvent mixed solution (the organic solvent is methanol), and adding into N2Heating and reducing at 60 ℃ for 12h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) Impregnating the hydroxylated polyether-ether-ketoneSoaking in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is ethylene glycol, and the titanium precursor is titanium tetrachloride) containing 3ml of titanium precursor, transferring all the solutions into a reaction kettle, and placing the reaction kettle in an oven to perform hydrothermal synthesis reaction at the temperature of 60 ℃ for 24 h. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 1X 10) was added-5mol/L, pH 7, surfactant sodium dodecyl benzene sulfonate). And (4) placing the reaction kettle in the oven again for reaction at room temperature for 12 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in an oven at the temperature of 80 ℃ to obtain the surface modified polyether-ether-ketone.
Example 6
(1) Grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding the cleaned and dried PEEK sheet into 3g/L sodium borohydride-organic solvent mixed solution (the organic solvent is a mixed solvent of methanol and dimethyl sulfoxide according to the mass ratio of 1: 1), and adding the PEEK sheet into N2Heating and reducing at 100 ℃ for 0.5h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning with hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) The hydroxylated polyether-ether-ketone is soaked in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is methanol, and the titanium precursor is a mixture of tetraethyl titanate and tetrabutyl titanate according to the volume ratio of 1: 1) containing 3ml of a titanium precursor, all the solutions are transferred into a reaction kettle and placed in an oven for hydrothermal synthesis reaction, the temperature of the hydrothermal synthesis reaction is 150 ℃, and the reaction time is 0.5 h. After the hydrothermal reaction, the reaction kettle was cooled at room temperature, and then an aqueous surfactant solution (concentration 1X 10) was added-3mol/L, pH 5, surfactant sodium cholate). The reaction kettle is placed at 100 ℃ again for dryingThe reaction is carried out in the box for 0.5h, solid is separated after the reaction is finished, and the reaction product is cooled to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in a 120 ℃ oven to obtain the surface modified polyether-ether-ketone.
Example 7
(1) Grinding and polishing a 10mm multiplied by 1mm PEEK sheet, sequentially placing the PEEK sheet in acetone, alcohol and deionized water for ultrasonic cleaning for 15 min each time, and drying the PEEK sheet in an oven at 80 ℃. Adding the cleaned and dried PEEK slices into a 4g/L sodium borohydride-organic solvent mixed solution (the organic solvent is tetrahydrofuran), and adding the PEEK slices into N2Heating and reducing at 150 ℃ for 5h under the protection of atmosphere, taking out the PEEK sheet, carrying out ultrasonic cleaning by using hydrochloric acid (0.5 mol/L), distilled water and absolute ethyl alcohol in sequence for 10min each time, and then drying in an oven at 60 ℃ for 3h to obtain the hydroxylated polyether ether ketone.
(2) The hydroxylated polyether-ether-ketone is soaked in 40ml of titanium precursor-organic solvent mixed solution (the organic solvent is a mixed solvent formed by mixing methanol and glycerol according to the mass ratio of 1:1, and the titanium precursor is tetraethyl titanate) containing 2ml of titanium precursor, all the solutions are transferred into a reaction kettle and placed in an oven for hydrothermal synthesis reaction, the temperature of the hydrothermal synthesis reaction is 60 ℃, and the reaction time is 0.5 h. After the hydrothermal reaction, the reaction kettle is cooled at room temperature, and then a surfactant aqueous solution (the concentration is 0.01mol/L, the pH is 4.5, and the surfactant is urea) is added. And (3) putting the reaction kettle into a 60 ℃ oven again for reaction for 6 hours, separating out solids after the reaction is finished, and cooling to room temperature. And ultrasonically cleaning the substrate for 10min by using distilled water and absolute ethyl alcohol in sequence, and then drying the substrate for at least 24h in a drying oven at the temperature of 45 ℃ to obtain the surface modified polyether-ether-ketone.
The surface-modified polyether ether ketone obtained in example 1 will be described as an example.
Scanning electron micrographs of the surface-modified PEEK sheet prepared in example 1 and the PEEK sheet without surface modification are obtained as shown in fig. 3, where fig. 3(a) is the scanning electron micrograph of the PEEK sheet without surface modification, and fig. 3(b) is the scanning electron micrograph of the surface-modified PEEK sheet prepared in example 1.
The results of X-ray photoelectron spectroscopy (XPS) tests of the surface-modified PEEK film obtained in example 1 and the non-surface-modified PEEK film are shown in fig. 4, in which fig. 4(a) is an XPS chart of the non-surface-modified PEEK film and fig. 4(b) is an XPS chart of the surface-modified PEEK film obtained in example 1.
The surface modified PEEK prepared in example 1 was used to perform a rat bone marrow mesenchymal stem cell culture test, and the cell activities of the rat bone marrow mesenchymal stem cells after 1 day, 4 days, and 7 days were measured using an Alarm Blue kit during the culture process, and the measurement results are shown in fig. 5, where unmodified PEEK represents the PEEK sheet without surface modification, and modified PEEK represents the surface modified PEEK prepared in example 1.
The surface modified polyetheretherketone prepared in example 1 was used to perform a rat bone marrow mesenchymal stem cell culture test, and the alkaline phosphatase activity of the rat bone marrow mesenchymal stem cells was measured 7 days and 14 days after the culture, and the measurement results are shown in fig. 6, in which PEEK represents PEEK flakes without surface modification, PEEK @ TiO2Represents the surface-modified polyetheretherketone prepared in example 1.
As can be seen from fig. 3 and 4, the modified PEEK material has a significantly increased Ti content on the surface, and most of the surface is covered by the titanium dioxide coating.
As can be seen from fig. 5 and 6, the proliferation rate of the surface-modified polyetheretherketone-surface rat bone marrow mesenchymal stem cells prepared in example 1 was increased after 4 days of culture, and the alkaline phosphatase activity was improved after 14 days of culture.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
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| CN118290929A (en) * | 2024-06-03 | 2024-07-05 | 南通丰盛纺织品有限公司 | Fatigue-resistant low-density flame-retardant sponge and preparation method thereof |
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