CN103340754A - Preparation method of zirconia nanotube reinforced denture powder - Google Patents
Preparation method of zirconia nanotube reinforced denture powder Download PDFInfo
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- CN103340754A CN103340754A CN201310221025XA CN201310221025A CN103340754A CN 103340754 A CN103340754 A CN 103340754A CN 201310221025X A CN201310221025X A CN 201310221025XA CN 201310221025 A CN201310221025 A CN 201310221025A CN 103340754 A CN103340754 A CN 103340754A
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Abstract
The invention belongs to the field of biomedical materials, and relates to a preparation method of a zirconia nanotube reinforced denture powder. The method comprises the steps: employing zirconia nanotubes prepared by an anodic oxidation method as a denture powder reinforcing material; firstly, impregnating the zirconia nanotubes with acetic acid aqueous solution, then carrying out a coupling reaction by adding the impregnated zirconia nanotubes into a anhydrous ethanol solution containing a silane coupling agent, so as to combine all coupling agent molecules with the surface of zirconia, and finally evenly grinding an ordinary denture powder and the zirconia nanotubes in a mortar. The preparation method has great adjustability and strong controllability. With the change of the amounts of the coupling agent and the zirconia nanotubes, the zirconia nanotube reinforced denture powder having different mechanical properties can be obtained.
Description
Technical field:
The invention belongs to the biomaterial for medical purpose field, particularly a kind of zirconium oxide nanotube strengthens the preparation method of dental base acrylic resin powder.
Background technology:
Dental base acrylic resin powder is the powder material of making basal seat area, mainly consists of polymethyl methacrylate, has a wide range of applications aspect stomatology.But problems such as polymethyl methacrylate has hardness and intensity is low, easy to wear, poor toughness.
In order to overcome the existing defective of polymethyl methacrylate, improve the intensity of basal seat area, people add suitable inorganic powder material in denture base resin.For example, " Medical University Of Tianjin's journal " (2006,1:94 – 96) reported a kind of nanometer SiO that uses
2Powder body improves the method for polymethyl methacrylate hardness and wearability, nanometer SiO wherein
2Powder body does not carry out surface treatment; " Chemical Engineer " (2004,4:61 – 62) reported a kind of nanometer SiO that uses
2Powder body improves the method for polymethyl methacrylate performance, nanometer SiO wherein
2Powder body carries out surface treatment with γ-(methacryloxy) propyl trimethoxy silicane, and processing method is with silane coupler and nanometer SiO
2Powder body directly carries out mechanical blending under 80 ℃ of conditions; " Shanghai stomatology " (2009,3:313 – 316) reported a kind of nanometer ZrO that uses
2Powder body improves the method for polymethyl methacrylate bending strength, nanometer ZrO wherein
2Powder body carries out surface treatment with γ-(methacryloxy) propyl trimethoxy silicane, and processing method is in acetone soln, with silane coupler to nanometer ZrO
2Powder body carries out finishing, carries out coupling reaction at 80 ℃.These reports all are to use nano-powder to strengthen, can not fine combinations between the powder body do not handled of surface and the polymethyl methacrylate, and it is inhomogeneous that simple mechanical blending causes coupling agent to disperse easily.When handling powder body with the organic solution of coupling agent, often there is the pollution problem of organic solvent.In addition, when using γ-(methacryloxy) propyl trimethoxy silicane, treatment temperature can not be too high, otherwise unsaturated bond wherein can mutual polymerization, and lower temperature is unfavorable for the reaction of coupling agent and powder surface hydroxyl.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of zirconium oxide nanotube to strengthen the preparation method of dental base acrylic resin powder, with load the zirconium oxide nanotube of silane coupler be reinforcing agent, to overcome the existing defective of polymethyl methacrylate, improve the intensity of basal seat area.
The present invention solves this technical problem the technical scheme that adopts:
A kind of zirconium oxide nanotube strengthens the preparation method of dental base acrylic resin powder, may further comprise the steps:
Glycerol: Methanamide=1:1 mixes glycerol and Methanamide by volume, adds ammonium fluoride and water again, obtains containing the electrolyte of 1% ammonium fluoride and 1% water; Electrolyte is added in the reaction vessel, and the zirconium sheet is made anode, and platinized platinum is made negative electrode, and anodic oxidation is 3 hours under room temperature, 50V condition; Reaction is peeled off the nanotube that makes after finishing from the zirconium sheet, 2% hydrochloric acid solution supersound process 30min is put in washing, washes then, dries, and 500 ℃ of calcining 2h get the zirconium oxide nanotube;
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with the 0.1-1.0% aqueous acetic acid; Add silane coupler in dehydrated alcohol, after the dissolving evenly, add the zirconium oxide nanotube through the aqueous acetic acid impregnation process again, stir 10min, slow heating makes ethanol evaporation under stirring condition then; After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent; Wherein the quality proportioning is dehydrated alcohol: silane coupler: through the zirconium oxide nanotube=2:0.05-0.2:10 of aqueous acetic acid impregnation process;
In the common dental base acrylic resin powder of 100g, add the zirconium oxide nanotube of 2-6g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
In the above-mentioned preparation method, described percentage is mass percent,
Described silane coupler is vinyltrimethoxy silane or VTES.
The invention has the beneficial effects as follows:
(1) outstanding feature of the present invention is, the zirconium oxide nanotube that adopts anodizing to prepare is made the reinforcing material of dental base acrylic resin powder.Zirconium oxide is a kind of bio-inert material, has hardness height, good toughness, advantages such as corrosion-resistant, wear-resistant, low heat conduction, chemical stability and good biocompatibility, in technical field of biological material important application is arranged.The draw ratio of zirconium oxide nanotube is big, this can strengthen the winding between it and the macromolecular chain, the pore structure of nanotube can enter wherein macromolecular chain, therefore, compare with powder body, have stronger adhesion between zirconium oxide nanotube and the macromolecular chain, this is conducive to improve the comprehensive mechanical property of basal seat area.In addition, the pore structure of zirconium oxide nanotube can also reduce the thermal conductivity of basal seat area.
(2) distinguishing feature of the present invention is, with aqueous acetic acid impregnation process zirconium oxide nanotube, carries out the coupling reaction in the ethanol solution with its adding silane coupler then earlier.With aqueous acetic acid impregnation process zirconium oxide nanotube, can form acid adsorbed water environment in zirconium surface, be conducive to ethyoxyl in the coupling agent or the hydroxyl reaction of methoxyl group and zirconium surface, acetic acid in the aqueous solution can also reduce interfacial tension, is conducive to aqueous solution to the infiltration of zirconium oxide nanotube.Silane coupler is dissolved in the dehydrated alcohol, is in order to improve coupling agent in the nanotube surface dispersed uniform, simultaneously, can also to stop the cross-linking reaction between the coupling agent, and ethanol is also harmless substantially to environment.Heat-treating at 120 ℃, is in order to promote carrying out fully of coupling reaction, to make coupling agent molecule can both be combined in zirconium surface.
(3) distinguishing feature of the present invention is, used silane coupler is a kind of in VTES and the vinyltrimethoxy silane.Vinyl in these two kinds of coupling agents is difficult for homopolymerization, can carry out the coupling reaction at higher temperature, is conducive to the combination of coupling agent and zirconium oxide nanotube.
(4) distinguishing feature of the present invention is, common dental base acrylic resin powder and zirconium oxide nanotube is ground evenly get final product in mortar, need not loaded down with trivial details ball-milling technology.
Adjustability of the present invention is big, controllability is strong, and by changing the consumption of coupling agent and zirconium oxide nanotube, the zirconium oxide nanotube that can obtain different mechanical properties strengthens dental base acrylic resin powder.
Description of drawings
Fig. 1 is the bending strength that the embodiment of the invention 1 prepared zirconium oxide nanotube strengthens dental base acrylic resin powder and common dental base acrylic resin powder curing post polymerization thing.
The specific embodiment:
The present invention is further described below in conjunction with drawings and Examples, and the materials such as raw material that embodiment relates to only are used for describing the present invention in detail, are not considered as the restriction to claim protection domain of the present invention.
Embodiment 1
(1) preparation of zirconium oxide nanotube
With glycerol and Methanamide 1:1 mixing by volume, contain the electrolyte of 1% ammonium fluoride and 1% water with this mixed solvent preparation.Electrolyte is added in the reaction vessel, and the zirconium sheet is made anode, and platinized platinum is made negative electrode, and anodic oxidation is 3 hours under room temperature, 50V condition.Reaction is peeled off the nanotube that makes after finishing from the zirconium sheet, 2% hydrochloric acid solution supersound process 30min is put in washing, washes then, dries, and 500 ℃ of calcining 2h get the zirconium oxide nanotube.
(2) the zirconium oxide nanotube strengthens the preparation of dental base acrylic resin powder
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 0.5% aqueous acetic acid.Adding 0.1g VTES in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g I type denture base resin, add the zirconium oxide nanotube of 4g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
Prepared zirconium oxide nanotube strengthens the bending strength of dental base acrylic resin powder and common dental base acrylic resin powder (I type denture base resin) curing post polymerization thing and sees Fig. 1, the former bending displacement, fracture strength, bending modulus, bending strength are respectively 3.5mm, 209.6N, 3515.78MPa, 98.23MPa, and the latter's bending displacement, fracture strength, bending modulus, bending strength are respectively 2.7mm, 152.8N, 3080.98MPa, 71.62MPa.The result shows that the prepared zirconium oxide nanotube of the present invention strengthens toughness and the intensity that dental base acrylic resin powder can significantly improve denture base polymer.
Embodiment 2
By embodiment 1(1) step prepares the zirconium oxide nanotube.
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 0.1% aqueous acetic acid.Adding 0.05g VTES in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g I type denture base resin, add the zirconium oxide nanotube of 3g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
Embodiment 3
By embodiment 1(1) step prepares the zirconium oxide nanotube.
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 1.0% aqueous acetic acid.Adding 0.2g VTES in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g I type denture base resin, add the zirconium oxide nanotube of 2g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
Embodiment 4
By embodiment 1(1) step prepares the zirconium oxide nanotube.
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 0.3% aqueous acetic acid.Adding 0.08g VTES in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g I type denture base resin, add the zirconium oxide nanotube of 6g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
Embodiment 5
By embodiment 1(1) step prepares the zirconium oxide nanotube.
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 0.8% aqueous acetic acid.Adding 0.15g VTES in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g I type denture base resin, add the zirconium oxide nanotube of 5g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
Embodiment 6
By embodiment 1(1) step prepares the zirconium oxide nanotube.
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 0.6% aqueous acetic acid.Adding 0.12g vinyltrimethoxy silane in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g II type denture base resin, add the zirconium oxide nanotube of 5g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
Embodiment 7
By embodiment 1(1) step prepares the zirconium oxide nanotube.
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with 0.2% aqueous acetic acid.Adding 0.08g vinyltrimethoxy silane in the 2g dehydrated alcohol after the dissolving evenly, adds 10g through the zirconium oxide nanotube of aqueous acetic acid impregnation process, stirs 10min, and slow heating makes ethanol evaporation under stirring condition then.After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent.
In 100g II type denture base resin, add the zirconium oxide nanotube of 3g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder.
The present invention does not address part and is applicable to prior art.
Claims (2)
1. a zirconium oxide nanotube strengthens the preparation method of dental base acrylic resin powder, it is characterized by may further comprise the steps:
Glycerol: Methanamide=1:1 mixes glycerol and Methanamide by volume, adds ammonium fluoride and water again, obtains containing the electrolyte of 1% ammonium fluoride and 1% water; Electrolyte is added in the reaction vessel, and the zirconium sheet is made anode, and platinized platinum is made negative electrode, and anodic oxidation is 3 hours under room temperature, 50V condition; Reaction is peeled off the nanotube that makes after finishing from the zirconium sheet, 2% hydrochloric acid solution supersound process 30min is put in washing, washes then, dries, and 500 ℃ of calcining 2h get the zirconium oxide nanotube;
Zirconium oxide nanotube after the calcining is flooded 60min, 100 ℃ of oven dry then with the 0.1-1.0% aqueous acetic acid; Add silane coupler in dehydrated alcohol, after the dissolving evenly, add the zirconium oxide nanotube through the aqueous acetic acid impregnation process again, stir 10min, slow heating makes ethanol evaporation under stirring condition then; After ethanol evaporates substantially fully, sample at 120 ℃ of heating 120min, is got the zirconium oxide nanotube of load coupling agent; Wherein the quality proportioning is dehydrated alcohol: silane coupler: through the zirconium oxide nanotube=2:0.05-0.2:10 of aqueous acetic acid impregnation process;
In the common dental base acrylic resin powder of 100g, add the zirconium oxide nanotube of 2-6g load coupling agent, grind evenly with mortar, namely get the zirconium oxide nanotube and strengthen dental base acrylic resin powder;
In the above-mentioned preparation method, described percentage is mass percent.
2. zirconium oxide nanotube as claimed in claim 1 strengthens the preparation method of dental base acrylic resin powder, and it is characterized by described silane coupler is vinyltrimethoxy silane or VTES.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017185473A1 (en) * | 2016-04-29 | 2017-11-02 | 成都贝施美医疗设备有限公司 | Denture material composition |
| CN109485459A (en) * | 2018-12-12 | 2019-03-19 | 中国人民解放军总医院第八医学中心 | A kind of Nano tube of zirconium dioxide film coating of zirconia ceramics coating surface and the preparation method and application thereof |
| CN111377735A (en) * | 2018-12-27 | 2020-07-07 | 上海元颉新材料科技有限公司 | Surface-modified nano zirconia ceramic powder and preparation method and application thereof |
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| CN101049964A (en) * | 2007-05-23 | 2007-10-10 | 河北工业大学 | Method for preparing Nano tube of zirconium dioxide |
| US20100015576A1 (en) * | 2007-01-16 | 2010-01-21 | Rejuvedent Llc | Method and apparatus for diagnostic and treatment using hard tissue or material microperforation |
| CN101690696A (en) * | 2009-09-25 | 2010-04-07 | 李榕生 | Method for preparing anti-secondary caries cavity repairing material |
| EP2275076A1 (en) * | 2008-04-28 | 2011-01-19 | Kuraray Medical Inc. | Dental composition and composite resin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100015576A1 (en) * | 2007-01-16 | 2010-01-21 | Rejuvedent Llc | Method and apparatus for diagnostic and treatment using hard tissue or material microperforation |
| CN101049964A (en) * | 2007-05-23 | 2007-10-10 | 河北工业大学 | Method for preparing Nano tube of zirconium dioxide |
| EP2275076A1 (en) * | 2008-04-28 | 2011-01-19 | Kuraray Medical Inc. | Dental composition and composite resin |
| CN101690696A (en) * | 2009-09-25 | 2010-04-07 | 李榕生 | Method for preparing anti-secondary caries cavity repairing material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017185473A1 (en) * | 2016-04-29 | 2017-11-02 | 成都贝施美医疗设备有限公司 | Denture material composition |
| CN109485459A (en) * | 2018-12-12 | 2019-03-19 | 中国人民解放军总医院第八医学中心 | A kind of Nano tube of zirconium dioxide film coating of zirconia ceramics coating surface and the preparation method and application thereof |
| CN109485459B (en) * | 2018-12-12 | 2023-09-05 | 中国人民解放军总医院第八医学中心 | Zirconium dioxide nanotube film coating plated on surface of zirconium oxide ceramic, and preparation method and application thereof |
| CN111377735A (en) * | 2018-12-27 | 2020-07-07 | 上海元颉新材料科技有限公司 | Surface-modified nano zirconia ceramic powder and preparation method and application thereof |
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