CN103417387A - Preparation method for hydrogel with X-ray developing function - Google Patents
Preparation method for hydrogel with X-ray developing function Download PDFInfo
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- CN103417387A CN103417387A CN2013103109302A CN201310310930A CN103417387A CN 103417387 A CN103417387 A CN 103417387A CN 2013103109302 A CN2013103109302 A CN 2013103109302A CN 201310310930 A CN201310310930 A CN 201310310930A CN 103417387 A CN103417387 A CN 103417387A
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Abstract
The invention relates to a preparation method for hydrogel with the X-ray developing function. The method comprises the following steps: (1), uniformly dispersing zircon salt, urea and surface active agent into deionized water, reacting for 6-18 hours at the temperature of 150-180 DEG C, after the reaction is completed, washing with a cleaning solution after cooling to the temperature of 20-40 DEG C, and then drying to obtain nanometer zirconia powder; (2), dispersing the nanometer zirconia powder obtained in the step (1), hydrophilic monomer, a cross-linking agent, an initiating agent and a catalyst into deionized water to obtain hydrogel liquid prepolymer, polymerizing the hydrogel liquid prepolymer at the temperature of 0-40 DEG C, so as to obtain the hydrogel with the X-ray developing function. The preparation method provided by the invention is simple and lower in cost; the hydrogel with the X ray developing function can be obtained through uniformly dispersing a small amount of zirconia nano particles into hydrogel, can avoid the coronal leakage while being used for root canal filling, and has an ideal clinical effect.
Description
Technical field
The invention belongs to the preparation field of functional aquagel, particularly a kind of preparation method with hydrogel of X ray developing function.
Background technology
In the adult more than 80%, all there is dental caries, health has been produced to great harm.By filler, the root pipe is carried out to complete filling, remove the interior pessimal stimulation to tip of a root surrounding tissue of root pipe, can cure dental pulp disease and periapical disease.The root cap filler is to affect the most key factor of root canal effect.With regard to root canal filling material, what the clinical practice kind was more at present is the combination filling system of gutta percha point and paste material, but there is no a kind of material, can reach desirable require (micro-seepage, biocompatibility, x-ray development etc.) fully.Find a kind of desirable filler, or formula and the placement method of root canal filling material at present commonly used improved, the material that obtains better filling effect and good X ray developing function is the emphasis direction of root canal.
The tradition root canal filling material is shown in paste and is formed by gutta-percha, because polymerization shrinkage makes between filler and root canal wall, the phenomenon of leaking hunting in hat side occurs, causes the root canal failure.The inorganic nano-particle that there is the X ray developing function by design in the hydrogel three-dimensional cross-linked network, preparation has " integrated " root-canal filling hydrogel of three-dimensional net structure and X ray developing function, is expected to thoroughly eliminate that leak hunting in hat side that the root canal filling material that uses at present exists and the defect of X ray developing function deficiency.
At present, a part by functional inorganic nano-particle as root canal filling material, Chinese patent CN1430947A discloses a kind of nano titanium oxide tooth root canal filling material, when titanium dioxide is made nanosized, nano titanium oxide shows stronger antibacterial action, can suppress the harmful bacteria in oral cavity, but this class hydrogel do not have the X ray developing property, is unfavorable for checking the root-canal filling situation; Chinese patent CN1535668A discloses and a kind of the aliphatic polyester series material has been adsorbed on to dental root canal filler prepared by hydroxyapatite surface, this class material hydroxyapatite consumption high (10-100%), and aliphatic polymer easily biological-degradable, after degraded, only have inorganic nano-particle residual, the problem that exists hat side to leak hunting; Chinese patent CN1899240A discloses a kind of nano zinc oxide clove oil root canal filling material, wherein ZrO
2The content of nanoparticle is higher, is 5-40%, and the problem that still exists hat side to leak hunting; Chinese patent CN101416923A discloses the root canal filling material of the mixture formed with thermoplastic polymer and barium salt (or strontium salt), but this class root canal filling material need to be under 140-250 ℃ of molten condition mixing 5-40 minute, although this material has X ray developing function, poor operability in actual use.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method with hydrogel of X ray developing function, the method technique is simple, cost is lower, a small amount of zirconium oxide nano-particle is dispersed in hydrogel can give hydrogel X ray developing function, this hydrogel root canal filling material has avoided traditional gutta percha point root canal filling material to have the defect of coronal leakage simultaneously, has higher using value.
A kind of preparation method with hydrogel of X ray developing function of the present invention comprises:
(1) zirconates, carbamide, surfactant are evenly spread in deionized water to reaction 6-18 hour under 150-180 ℃ of condition; Reaction finishes, be cooled to 20-40 ℃ after with the cleaning mixture washing, obtain nano zirconium oxide powder after drying; Wherein in reaction system, the mass fraction of zirconates is 1-5%, and the mass fraction of carbamide is 5-20%, and the mass fraction of surfactant is 0.5-5%, and all the other are deionized water;
(2) nano zirconium oxide powder, hydrophilic monomer, cross-linking agent, initiator, the catalyst of step (1) gained are evenly spread in deionized water and obtain hydrogel pre-polymerization liquid; By above-mentioned hydrogel pre-polymerization liquid, 0-40 ℃ of lower polymerization, polymerization time is 1 minute-12 hours, must have the hydrogel of X ray developing function; Wherein in hydrogel pre-polymerization liquid, the mass fraction of nano zircite is 1-10%, the mass fraction of hydrophilic monomer is 10-50%, and the mass fraction of cross-linking agent is 0.01-1%, and the mass fraction of initiator is 0.01-1%, the mass fraction of catalyst is 0.01-1%, and all the other are deionized water.
Described step (1) zirconates is Zr (NO
3)
45H
2O, Zr (CH
3COO)
4, ZrCl
4, ZrOCl
28H
2One or more in O.
In described step (1), surfactant is one or more in polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone.
In described step (1), cleaning mixture is one or more in deionized water, ethylene glycol, dehydrated alcohol.
The particle diameter of the nano zirconium oxide powder obtained in described step (1) is 5-100nm.
In described step (2), hydrophilic monomer is one or more in NIPA, acrylamide, acrylic acid, methacrylic acid.
In described step (2), cross-linking agent is polyethylene glycol dimethacrylate, polyethyleneglycol diacrylate, TEGDMA, N, one or more in N '-methylene-bisacrylamide.
In described step (2), initiator is one or more in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
In described step (2), catalyst is triethanolamine, N, N, N ', one or more in N '-tetramethylethylenediamine, sodium thiosulfate.
The hydrogel with X ray developing function obtained in described step (2) is for the preparation of tooth root canal filling material.
The X ray developing performance of the hydrogel with X ray developing function obtained in described step (2) is equivalent to the aluminium sheet that 1-5mm is thick.
The ZrO prepared by step (1)
2Uniform particle diameter, good dispersion in water, have specific crystal structure, has higher X ray developing function.And the ZrO that step (1) is prepared
2For the preparation of gel, play the physical crosslinking effect, also have method simple, the advantage such as preparation time is short simultaneously.
Beneficial effect
(1) preparation method of the present invention is simple, and the material choice scope is large, and cost is low, applicable to batch production, has very high using value.
(2) hydrogel with X ray developing function that prepared by the present invention, due to the distinctive swellability of hydrogel and good biocompatibility, can solve microgap and coronal leakage defect that traditional root tube material causes due to polymerization shrinkage; Simultaneously, this class hydrogel has significant X ray developing function, is convenient to check, has excellent stability and good military service behavior.
The accompanying drawing explanation
The stereoscan photograph that Fig. 1 is zirconium oxide nano-particle.
Fig. 2 has the stereoscan photograph of the hydrogel of X ray developing function.
Fig. 3 hydrogel is the X ray developing performance after filling in root canal.The aluminium sheet that the left side is different-thickness (1-12mm), the X ray development photo that centre is circular hydrogel.The right is for being filled to hydrogel in the X ray development photo after the tooth root pipe.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
By 1.28g eight water zirconium oxychlorides, 7.5g carbamide, it is even that the 0.5g polyvinyl pyrrolidone evenly spreads to the 50g deionized water for stirring, under 150 ℃, reaction is 10 hours, and reaction is cooled to 25 ℃ after finishing, use the deionized water wash drying, obtain nano zirconium oxide powder.By the 0.05g nano zirconium oxide powder, the 4g acrylamide, 0.04gN, N '-methylene-bisacrylamide, 0.02g potassium peroxydisulfate, 0.04g N, N, N ', it is even that N '-tetramethylethylenediamine joins the 10g deionized water for stirring, obtain hydrogel pre-polymerization liquid, hydrogel pre-polymerization liquid is expelled in disk mould or root canal, under 25 ℃, reaction obtains having the hydrogel of X ray developing function in 1 hour.
Embodiment 2
By 2.32 eight water zirconium oxychlorides, 7.5g carbamide, it is even that the 1g polyvinyl alcohol evenly spreads to the 50g deionized water for stirring, and under 180 ℃, reaction is 8 hours, and reaction is cooled to 30 ℃ after finishing, and uses the deionized water wash drying, obtains nano zirconium oxide powder.By the 0.03g nano zirconium oxide powder, 3.5g methacrylic acid, 0.03gN, N '-methylene-bisacrylamide, 0.03g potassium peroxydisulfate, 0.03g N, N, N ', it is even that N '-tetramethylethylenediamine joins the 10g deionized water for stirring, obtain hydrogel pre-polymerization liquid, hydrogel pre-polymerization liquid is expelled in disk mould or root canal, under 25 ℃, reaction obtains having the hydrogel of X ray developing function in 30 minutes.
Embodiment 3
By the 0.85g zirconium chloride, 5.4g carbamide, it is even that the 1.5g Polyethylene Glycol evenly spreads to the 50g deionized water for stirring, and under 150 ℃, reaction is 18 hours, and reaction is cooled to 25 ℃ after finishing, and uses the absolute ethanol washing drying, obtains nano zirconium oxide powder.By the 0.02g nano zirconium oxide powder, the 4g acrylamide, 0.04g polyethylene glycol dimethacrylate, 0.02g Ammonium persulfate., 0.04g it is even that triethylamine joins the 10g deionized water for stirring, obtain hydrogel pre-polymerization liquid, hydrogel pre-polymerization liquid is expelled in disk mould or root canal, under 5 ℃, reaction obtains having the hydrogel of X ray developing function in 5 hours.
Embodiment 4
By 1.56g five water zirconium nitrates, 8.2 carbamide, it is even that the 2g polyvinyl pyrrolidone evenly spreads to the 50g deionized water for stirring, and under 150 ℃, reaction is 12 hours, and reaction is cooled to 30 ℃ after finishing, and uses the absolute ethanol washing drying, obtains nano zirconium oxide powder.By the 0.5g nano zirconium oxide powder, the 2g acrylamide, 0.08g TEGDMA, 0.05g Ammonium persulfate., 0.03g it is even that triethanolamine joins the 10g deionized water for stirring, obtain hydrogel pre-polymerization liquid, hydrogel pre-polymerization liquid is expelled in disk mould or root canal, under 25 ℃, reaction obtains having the hydrogel of X ray developing function in 5 minutes.
Embodiment 5
By the 1.6g zirconium acetate, 7.5g carbamide, it is even that the 1.5g polyvinyl alcohol evenly spreads to the 50g deionized water for stirring, and under 180 ℃, reaction is 8 hours, and reaction is cooled to 20 ℃ after finishing, and the spent glycol washing is dry, obtains nano zirconium oxide powder.By the 0.5g nano zirconium oxide powder, the 2gN-N-isopropylacrylamide, 0.04g polyethyleneglycol diacrylate, 0.05g sodium peroxydisulfate, 0.03g it is even that sodium thiosulfate joins the 10g deionized water for stirring, obtain hydrogel pre-polymerization liquid, hydrogel pre-polymerization liquid is expelled in disk mould or root canal, under 37 ℃, reaction obtains having the hydrogel of X ray developing function in 2 minutes.
Claims (10)
1. the preparation method with hydrogel of X ray developing function comprises:
(1) zirconates, carbamide, surfactant are evenly spread in deionized water to reaction 6-18 hour under 150-180 ℃ of condition; Reaction finishes, be cooled to 20-40 ℃ after with the cleaning mixture washing, obtain nano zirconium oxide powder after drying; Wherein in reaction system, the mass fraction of zirconates is 1-5%, and the mass fraction of carbamide is 5-20%, and the mass fraction of surfactant is 0.5-5%, and all the other are deionized water;
(2) nano zirconium oxide powder, hydrophilic monomer, cross-linking agent, initiator, the catalyst of step (1) gained are evenly spread in deionized water and obtain hydrogel pre-polymerization liquid; By above-mentioned hydrogel pre-polymerization liquid, 0-40 ℃ of lower polymerization, polymerization time is 1 minute-12 hours, must have the hydrogel of X ray developing function; Wherein in hydrogel pre-polymerization liquid, the mass fraction of nano zircite is 1-10%, the mass fraction of hydrophilic monomer is 10-50%, and the mass fraction of cross-linking agent is 0.01-1%, and the mass fraction of initiator is 0.01-1%, the mass fraction of catalyst is 0.01-1%, and all the other are deionized water.
2. a kind of preparation method with hydrogel of X ray developing function according to claim 1, it is characterized in that: described step (1) zirconates is Zr (NO
3)
45H
2O, Zr (CH
3COO)
4, ZrCl
4, ZrOCl
28H
2One or more in O.
3. a kind of preparation method with hydrogel of X ray developing function according to claim 1 is characterized in that: in described step (1), surfactant is one or more in polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone.
4. a kind of preparation method with hydrogel of X ray developing function according to claim 1 is characterized in that: in described step (1), cleaning mixture is one or more in deionized water, ethylene glycol, dehydrated alcohol.
5. a kind of preparation method with hydrogel of X ray developing function according to claim 1, it is characterized in that: the particle diameter of the nano zirconium oxide powder obtained in described step (1) is 5-100nm.
6. a kind of preparation method with hydrogel of X ray developing function according to claim 1 is characterized in that: in described step (2), hydrophilic monomer is one or more in NIPA, acrylamide, acrylic acid, methacrylic acid.
7. a kind of preparation method with hydrogel of X ray developing function according to claim 1, it is characterized in that: in described step (2), cross-linking agent is polyethylene glycol dimethacrylate, polyethyleneglycol diacrylate, TEGDMA, N, one or more in N '-methylene-bisacrylamide.
8. a kind of preparation method with hydrogel of X ray developing function according to claim 1 is characterized in that: in described step (2), initiator is one or more in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate; Catalyst is triethanolamine, N, N, N ', one or more in N '-tetramethylethylenediamine, sodium thiosulfate.
9. a kind of preparation method with hydrogel of X ray developing function according to claim 1, it is characterized in that: the hydrogel with X ray developing function obtained in described step (2) is for the preparation of tooth root canal filling material.
10. a kind of preparation method with hydrogel of X ray developing function according to claim 1, it is characterized in that: the X ray developing performance of the hydrogel with X ray developing function obtained in described step (2) is equivalent to the aluminium sheet that 1-5mm is thick.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101647756A (en) * | 2009-09-10 | 2010-02-17 | 东华大学 | Organic/inorganic nano hybridized hydrogel for tooth root canal filling material |
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|---|---|---|---|---|
| CN101647756A (en) * | 2009-09-10 | 2010-02-17 | 东华大学 | Organic/inorganic nano hybridized hydrogel for tooth root canal filling material |
Non-Patent Citations (1)
| Title |
|---|
| 温圣达: "纳米氧化锆制备新工艺研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 4, 15 April 2011 (2011-04-15) * |
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