CN102895126B - Method for preparing organic/inorganic hybrid filler for dental repair resin - Google Patents
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Abstract
The invention relates to a method for preparing an organic/inorganic hybrid filler for dental repair resin. The method comprises the following steps of: (1) preparing a carboxylated modified monomer C-BisGMA; (2) adding an inorganic material into cyclohexane, adding organic amine and a coupling reagent, and reacting to obtain a modified inorganic material of which the surface contains an amino group; and (3) dissolving the carboxylated modified monomer C-BisGMA into dichloromethane, sequentially adding a catalyst and a shrinkage agent, and adding the modified inorganic material of which the surface contains the amino group to obtain the organic/inorganic hybrid filler. The preparation method can be simply operated, is high in hybridization reaction efficiency and has a good resin mixing effect; and the surface of the prepared organic/inorganic hybrid filler contains an organic component and a polymerizable double-bond group which have relatively high content, and the organic component is applied to resin, so that the compatibility of the organic component and an organic matrix is strengthened, the interaction force of two-phase interfaces of the organic matrix and an inorganic filler is improved, and the physical and mechanical properties, the wear resistance, and the wet environment stability of composite resin are improved.
Description
Technical field
The invention belongs to the preparation field of gear division repair materials, particularly the preparation method of hybrid filler for a kind of gear division resin for restoration.
Background technology
Oral disease is commonly encountered diseases and frequently-occurring disease, have a strong impact on health, wherein the sickness rate of dental caries is up to 80%, and dental caries is classified as 21 century by World Health Organization (WHO) together with cardiovascular and cerebrovascular disease, tumor needs three large noninfectiouss of keypoint control, and the key for the treatment of is repair materials.Be applied to the composite resin that gear division is repaired, development rapidly, because its repair process is brief, attractive in appearance, mechanical property and the advantage such as biocompatibility is good, replaces conventional tooth dental repair material gradually nearly ten years, as silver amalgam etc.
Gear division repair materials needs to bear compared with large mastication power and the destruction that do not deform in long service, and this is even more important for oral cavity Molar repair.Adding of inorganic reinforcing filler, giving the physical and mechanical properties that material is stronger, as elastic modelling quantity, bending strength, compressive strength, wearability and hardness etc. simultaneously, reduced organic monomer constituent content, and then polymerization shrinkage while reducing resin solidification.Clinically mainly formed by organic resin matrix and surface-modified inorganic reinforcer with gear division resin for restoration, after organic monomer, inorganic reinforcing filler and initiator evenly mix, after radiation of visible light, form cured composite resin, wherein, inorganic reinforcing filler be generally do not process or simple surfaces modification after, mix and be applied to composite resin.But research shows (Hongquan Zhang, Biomedical Materials, 2010,5,) although inorganic enhancing can significantly improve the physical and mechanical properties of composite resin, the Shortcomings but dispersibility, the wellability of inorganic filler in composite remains unchanged, the biphase compatibility of inorganic filler and polymeric matrix is not good enough, a little less than the combination power of interface, be still cause that gear division repair composite material physical and mechanical properties is lower, one of stability and the poor major reason of water-fast adsorptivity (C.Santos, Biomaterials, 2002,23,1897-1904).
Therefore, by inorganic filler surface is modified, improve inorganic filler surface organic content and polymerizable groups quantity, Application and preparation is in the hybrid material of gear division repair composite material, for improving, improve the effect of composite multi phase interface, improve material combination property, significant (Maria M.Karabela, Dental Materials, 2008,24,1631-1639).
At present, in the research of gear division repair materials, more focus mostly in novel inorganic reinforcer and composite resin component proportion to aspects such as performance impacts, rarely have and improve composite resin interface problem aspect from hybrid filler and study, prepare to keep the each organic principle homology of composite resin and carry out hybrid filler taking gear division reparation monomer as organic principle, the method that improves hydridization filler and the biphase compatibility of organic matrix has no report.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of gear division resin for restoration hybrid filler, the hydridization reaction efficiency of the method is high, mixed with resin is effective, hydridization filler and resin matrix interface binding interactions power are strong, contribute to improve physical and mechanical properties, anti-wear performance, wet environment stability etc.
The preparation method of hybrid filler for a kind of gear division resin for restoration of the present invention, comprising:
(1) bisphenol-A-glycidyl Methacrylate (BisGMA) is carboxylated
Anhydride is added in pyridine, after dissolving, obtain the pyridine solution of anhydride; Dilute BisGMA with pyridine, obtain the pyridine solution of BisGMA, then the pyridine solution of BisGMA is dropped in the pyridine solution of above-mentioned anhydride, react 18-30 hour at 20-25 DEG C, obtain modified monomer solution, finally by processing and obtain carboxylated modified monomer C-BisGMA later; Wherein the mol ratio of anhydride and BisGMA is 2-2.5:1;
(2) surface-modified inorganic filler preparation
In cyclohexane extraction, add inorganic material, mechanical agitation 30-60 minute, ultrasonic dispersion 30-60 minute, add again organic amine and coupling agent, in 20-25 DEG C of reaction 30-60 minute, then react 30-90 minute at 55-65 DEG C, obtain surface containing amino modified inorganic material; Wherein the weight ratio of inorganic material, coupling agent, organic amine is 2-5:0.5-1:0.1-0.4;
(3) hybrid filler preparation
The carboxylated modified monomer C-BisGMA that step (1) is obtained is dissolved in dichloromethane, obtain the dichloromethane solution of C-BisGMA, then drip successively the dichloromethane solution that contains catalyst and the dichloromethane solution that contains dehydrating agent, add again the surface that step (2) obtains to contain amino modified inorganic material, mechanical agitation after ultrasonic being uniformly dispersed, at 20-30 DEG C, react 20-25h, obtain hybrid filler reactant liquor, then filtration washing, finally obtain hybrid filler in 35-45 DEG C of vacuum drying 18-24 hour; Wherein, C-BisGMA is 0.1-0.5:1 with surface containing the mass ratio of amino modified inorganic material, and the mol ratio of C-BisGMA, dehydrating agent, catalyst is 1:1-1.5:0.01-0.5.
Anhydride described in step (1) is saturated or unsaturated dicarboxylic anhydride, is specially the one in succinic anhydride, maleic anhydride, glutaric anhydride etc.
In the pyridine solution of BisGMA described in step (1), the mass volume ratio of BisGMA and pyridine is 5-10g:5-15mL.
In the pyridine solution of the BisGMA described in step (1) and anhydride, the mass volume ratio of pyridine is 5g:100-150mL.
Post processing concrete operations described in step (1) are: by the modified monomer solution obtaining at 35-50 DEG C, distilling under reduced pressure obtains viscous liquid, then add dichloromethane to dissolve, use again after 10-20wt% dilute hydrochloric acid cyclic washing 1-5 time, get dichloromethane layer, after dry, filter, finally in 35-50 DEG C of distilling under reduced pressure and in 35-50 DEG C of vacuum drying.
Described in step (1), BisGMA monomer reacts with dicarboxylic anhydride, and site is hydroxyl, and products therefrom contains carboxylic group, as shown in Figure 1.
Inorganic material described in step (2) is the one in preparing spherical SiO 2, hydroapatite particles, hydroxyapatite crystal whisker, zirconium oxide, ceramics.
Coupling agent described in step (2) is containing the one in the silane coupler of amino structure, as gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane etc.; Described organic amine is n-propylamine.
In the dichloromethane solution of C-BisGMA described in step (3), the mass volume ratio of C-BisGMA and dichloromethane is 0.2g:100mL-200mL.
Catalyst described in step (3) is the one in N-hydroxy-succinamide, DMAP, I-hydroxybenzotriazole, and dehydrating agent is the one in dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
In the dichloromethane that contains catalyst described in step (3), the mass volume ratio of catalyst and dichloromethane is 0.04-0.06g:10-15mL; In the dichloromethane solution that contains dehydrating agent, the mass volume ratio of dehydrating agent and dichloromethane is 0.01-0.035g:10-15mL.
Step (3) is obtained to hybrid filler and mix monomer (bisphenol-A-glycidyl Methacrylate BisGMA, double methyl methacrylate triethylene glycol ester TEGDMA), composite initiator (camphorquinone, 4-N, N-dimethylaminobenzoic acid ethyl ester) after manual premix, again by ultra-fine three-roll grinder mix homogeneously, obtain uncured resin cream, obtain gear division resin for restoration finally by visible-light curing; Wherein, to account for the percetage by weight of gear division resin for restoration be 50%-85% to hybrid filler; The weight ratio of mix monomer and composite initiator is 1:0.01; The weight ratio of bisphenol-A-glycidyl Methacrylate and double methyl methacrylate triethylene glycol ester is 4-7:6-3, camphorquinone and 4-N, and the weight ratio of N-dimethylaminobenzoic acid ethyl ester is 1:3-4.
The present invention, first by methodology of organic synthesis, by main monomer BisGMA modification for gear division reparation, makes molecule carboxyl group; Adopt again the organic solvent modified system containing amino coupling agent, inorganic material surface is processed, obtain surface containing amino modified inorganic material; Finally, in organic solvent, the novel organic/inorganic hybridization material of preparation is reacted to containing amino inorganic material in surface with modified monomer, can be used for gear division resin for restoration.
Beneficial effect:
(1) preparation method of the present invention is simple to operate, and reaction efficiency is high, and mixed with resin is effective, can specific aim be applied to gear division resin for restoration field;
(2) the obtained novel hybrid filler of the present invention, compare the inorganic filler of traditional gear division resin for restoration, the organic component that high level is contained on surface and polymerizable double bond group, surface organic component and composite resin preparation monomer holding structure homology, be applied in gear division resin for restoration, strengthen itself and the organic matrix compatibility, improve and improve organic matrix and inorganic filler two-phase interface interaction force, and then contribute to increase Inorganic Fillers Filled amount, improve the physical and mechanical properties, anti-wear performance, wet environment stability of composite resin etc.
Brief description of the drawings
Fig. 1 is organic monomer modification route map of the present invention;
Fig. 2 is the FT-IR figure of organic monomer of the present invention/inorganic (silicon dioxide) hydridization filler;
Fig. 3 is the thermogravimetric curve figure of organic monomer of the present invention/inorganic (silicon dioxide) hydridization filler.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
(1) bisphenol-A-glycidyl Methacrylate is carboxylated
2.1489g succinic anhydride is added in 100mL pyridine solvent, stirring and dissolving, with after 10mL pyridine dilution 5.0000gBisGMA, drop in above-mentioned anhydride pyridine solution, under room temperature, react 24 hours, obtain modified monomer solution, then at 45 DEG C, distilling under reduced pressure to non-pyridine is isolated, add 100mL dichloromethane to dissolve and pour separatory funnel into, clarify to supernatant liquid for several times with 10wt% dilute hydrochloric acid cyclic washing, get dichloromethane layer, add desiccant to spend the night after processing, filter, 45 DEG C of distilling under reduced pressure in 45 DEG C of vacuum drying oven processing, obtain modified monomer C-BisGMA.
(2) surface modification silica dioxide granule preparation
In 100mL cyclohexane extraction, add 5.0000g preparing spherical SiO 2 granule, mechanical agitation 45 minutes, ultrasonic dispersion 45 minutes, add again 0.1000g n-propylamine and 0.5000g gamma-aminopropyl-triethoxy-silane, in 25 DEG C of reactions 30 minutes, then at 60 DEG C, react 60 minutes, distilling under reduced pressure is except desolventizing and escaping gas, be placed in 90 DEG C of vacuum drying ovens and dry 18 hours, obtain surface containing amino modified silica particles.
(3) C-BisGMA/ SiO 2 hybrid filler preparation
0.2000g C-BisGMA is dissolved in 100mL dichloromethane, dissolve 0.0500g4-dimethylamino naphthyridine and 0.0100g dicyclohexylcarbodiimide with 10mL dichloromethane respectively, successively drop in above-mentioned solution, add again 1.0000g surface modification silica dioxide granule, after ultrasonic being uniformly dispersed, mechanical agitation, at 25 DEG C of room temperatures, react 24h, obtain hydridization filler reactant liquor, then use washed with dichloromethane, filter cake is taken off to dissolve in dichloromethane and disperse rear filtration, after repeating for several times, being placed in 40 DEG C of vacuum drying ovens processes 24 hours, must can be applicable to the C-BisGMA/ SiO 2 hybrid filler of gear division resin for restoration.
Embodiment 2
The preparation of C-BisGMA/ SiO 2 hybrid filler potting resin
The 7.0000g C-BisGMA/ SiO 2 hybrid filler that embodiment 1 is obtained and 1.5000g BisGMA, 1.5000gTEGDMA, 0.0060g camphorquinone, 0.0240g 4-N, N-dimethylaminobenzoic acid ethyl ester, through ultra-fine three roller mixer mix homogeneously, make the composite resin cream containing hydridization filler, then make gear division resin for restoration through visible-light curing.
The C-BisGMA/ silicon dioxide hybrid materials of preparation utilizes Fourier infrared spectrograph analysis, the compound C-BisGMA of surface success; Adopting the resistance to thermal gravimetric analyzer of speeding of Germany to record hybrid material surface C-BisGMA content is 9.2.wt%.
Embodiment 3
(1) bisphenol-A-glycidyl Methacrylate is carboxylated
4.7279g maleic anhydride is added in 240mL pyridine solvent, stirring and dissolving, with after 15mL pyridine dilution 10.0000g BisGMA, drop in above-mentioned anhydride pyridine solution, under room temperature, react 24 hours, obtain modified monomer solution, then at 45 DEG C, distilling under reduced pressure to non-pyridine is isolated, add 150mL dichloromethane to dissolve and pour separatory funnel into, clarify to supernatant liquid for several times with 10wt% dilute hydrochloric acid cyclic washing, get dichloromethane layer, add desiccant to spend the night after processing, filter, 45 DEG C of distilling under reduced pressure in 45 DEG C of vacuum drying oven processing, obtain modified monomer C-BisGMA.
(2) surface modification hydroxyapatite crystal whisker preparation
In 100mL cyclohexane extraction, add 5g hydroxyapatite crystal whisker, mechanical agitation 45 minutes, ultrasonic dispersion 45 minutes, add again 0.2000g n-propylamine and 0.6000g gamma-aminopropyl-triethoxy-silane, in 25 DEG C of reactions 30 minutes, then at 60 DEG C, react 60 minutes, distilling under reduced pressure is except desolventizing and escaping gas, be placed in 90 DEG C of vacuum drying ovens and dry 18 hours, obtain surface containing amino modified hydroxylapatite whisker.
(3) C-BisGMA/ hydroxyapatite crystal whisker hydridization filler preparation
0.2000g C-BisGMA is dissolved in 150mL dichloromethane, dissolve 0.0480g4-dimethylamino naphthyridine and 0.0150g dicyclohexylcarbodiimide with 10mL dichloromethane respectively, successively drop in above-mentioned solution, add again 1.0000g surface modification hydroxyapatite whisker, after ultrasonic being uniformly dispersed, mechanical agitation, at 25 DEG C of room temperatures, react 24h, obtain hydridization filler reactant liquor, then use washed with dichloromethane, filter cake is taken off to dissolve in dichloromethane and disperse rear filtration, after repeating for several times, being placed in 40 DEG C of vacuum drying ovens processes 24 hours, must can be applicable to the C-BisGMA/ hydroxyapatite crystal whisker hydridization filler of gear division resin for restoration.
Embodiment 4
The preparation of C-BisGMA/ hydroxyapatite crystal whisker hydridization filler potting resin
The 7.5000g C-BisGMA/ hydroxyapatite crystal whisker hydridization filler that embodiment 3 is obtained and 1.0000g BisGMA, 1.5000g TEGDMA, 0.0050g camphorquinone, 0.0200g 4-N, N-dimethylaminobenzoic acid ethyl ester, through ultra-fine three roller mixer mix homogeneously, make the composite resin cream containing hydridization filler, then after visible-light curing, make gear division resin for restoration.
Embodiment 5
(1) bisphenol-A-glycidyl Methacrylate is carboxylated
2.3820g succinic anhydride is added in 150mL pyridine solvent, stirring and dissolving, with after 15mL pyridine dilution 5.0000gBisGMA, drop in above-mentioned anhydride pyridine solution, under room temperature, react 24 hours, obtain modified monomer solution, then at 45 DEG C, distilling under reduced pressure to non-pyridine is isolated, add 100mL dichloromethane to dissolve and pour separatory funnel into, clarify to supernatant liquid for several times with 10wt% dilute hydrochloric acid cyclic washing, get dichloromethane layer, add desiccant to spend the night after processing, filter, 45 DEG C of distilling under reduced pressure in 45 DEG C of vacuum drying oven processing, obtain modified monomer C-BisGMA.
(2) surface modification hydroapatite particles preparation
In 100mL cyclohexane extraction, add 5.0000g hydroapatite particles, mechanical agitation 45 minutes, ultrasonic dispersion 45 minutes, add again 0.1500g n-propylamine and 0.7000g γ-aminopropyltrimethoxysilane, in 25 DEG C of reactions 30 minutes, then at 60 DEG C, react 60 minutes, distilling under reduced pressure is except desolventizing and escaping gas, be placed in 90 DEG C of vacuum drying ovens and dry 18 hours, obtain surface containing amino modified hydroxylapatite granule.
(3) the hydroxyapatite hybridized filler preparation of C-BisGMA/
0.2000g C-BisGMA is dissolved in 100mL dichloromethane, dissolve 0.0600g4-dimethylamino naphthyridine and 0.03200g dicyclohexylcarbodiimide with 10mL dichloromethane respectively, successively drop in above-mentioned solution, add again 1.0000g surface modification hydroapatite particles, after ultrasonic being uniformly dispersed, mechanical agitation, at 25 DEG C of room temperatures, react 24h, obtain hydridization filler reactant liquor, then use washed with dichloromethane, filter cake is taken off to dissolve in dichloromethane and disperse rear filtration, after repeating for several times, being placed in 40 DEG C of vacuum drying ovens processes 24 hours, must can be applicable to the hydroxyapatite hybridized filler of C-BisGMA/ of gear division resin for restoration.
Embodiment 6
The preparation of C-BisGMA/ hydroapatite particles hydridization filler potting resin
The hydroxyapatite hybridized filler of 6.0000g C-BisGMA/ that embodiment 5 is obtained and 2.4000g BisGMA, 1.6000g TEGDMA, 0.0080g camphorquinone, 0.0320g 4-N, N-dimethylaminobenzoic acid ethyl ester, through ultra-fine three roller mixer mix homogeneously, make the composite resin cream containing hydridization filler, then make gear division resin for restoration through visible-light curing.
Claims (3)
1. a preparation method for hybrid filler for gear division resin for restoration, comprising:
(1) anhydride is added in pyridine, after dissolving, obtain the pyridine solution of anhydride; Dilute BisGMA with pyridine, obtain the pyridine solution of BisGMA, then the pyridine solution of BisGMA is dropped in the pyridine solution of above-mentioned anhydride, react 18-30 hour at 20-25 DEG C, obtain modified monomer solution, finally by processing and obtain carboxylated modified monomer C-BisGMA later; Wherein the mol ratio of anhydride and BisGMA is 2-2.5:1;
(2) in cyclohexane extraction, add inorganic material, mechanical agitation 30-60 minute, ultrasonic dispersion 30-60 minute, add again organic amine and coupling agent, in 20-25 DEG C of reaction 30-60 minute, then react 30-90 minute at 55-65 DEG C, obtain surface containing amino modified inorganic material; Wherein the weight ratio of inorganic material, coupling agent, organic amine is 2-5:0.5-1:0.1-0.4;
(3) carboxylated modified monomer C-BisGMA step (1) being obtained is dissolved in dichloromethane, obtain the dichloromethane solution of C-BisGMA, then drip successively the dichloromethane solution that contains catalyst and the dichloromethane solution that contains dehydrating agent, add again the surface that step (2) obtains to contain amino modified inorganic material, mechanical agitation after ultrasonic being uniformly dispersed, at 20-30 DEG C, react 20-25h, obtain hybrid filler reactant liquor, then filtration washing, finally obtain gear division resin for restoration hybrid filler in 35-45 DEG C of vacuum drying 18-24 hour, wherein, C-BisGMA is 0.1-0.5:1 with surface containing the mass ratio of amino modified inorganic material, and the mol ratio of C-BisGMA, dehydrating agent, catalyst is 1:1-1.5:0.01-0.5,
Anhydride described in step (1) is the one in succinic anhydride, maleic anhydride, glutaric anhydride;
Post processing concrete operations described in step (1) are: by the modified monomer solution obtaining at 35-50 DEG C, distilling under reduced pressure obtains viscous liquid, then add dichloromethane to dissolve, use again after 10-20wt% dilute hydrochloric acid cyclic washing 1-5 time, get dichloromethane layer, after dry, filter, finally in 35-50 DEG C of distilling under reduced pressure and in 35-50 DEG C of vacuum drying;
Inorganic material described in step (2) is the one in preparing spherical SiO 2, hydroapatite particles, hydroxyapatite crystal whisker, zirconium oxide, ceramics;
Described coupling agent is gamma-aminopropyl-triethoxy-silane or γ-aminopropyltrimethoxysilane; Described organic amine is n-propylamine;
In the dichloromethane solution of C-BisGMA described in step (3), the mass volume ratio of C-BisGMA and dichloromethane is 0.2g:100mL-200mL; Described catalyst is the one in N-hydroxy-succinamide, DMAP, I-hydroxybenzotriazole, and dehydrating agent is the one in dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
2. the preparation method of hybrid filler for a kind of gear division resin for restoration according to claim 1, is characterized in that: in the pyridine solution of the BisGMA described in step (1), the mass volume ratio of BisGMA and pyridine is 5-10g:5-15mL; In described BisGMA and the pyridine solution of anhydride, the mass volume ratio of pyridine is 5g:100-150mL.
3. the preparation method of hybrid filler for a kind of gear division resin for restoration according to claim 1, it is characterized in that: after the gear division resin for restoration that step (3) is obtained hybrid filler and mix monomer, the manual premix of composite initiator, again by ultra-fine three-roll grinder mix homogeneously, obtain uncured resin cream, obtain gear division resin for restoration finally by visible-light curing; Wherein, to account for the percetage by weight of gear division resin for restoration be 50%-85% to hybrid filler; The weight ratio of mix monomer and composite initiator is 1:0.01; Described mix monomer is bisphenol-A-glycidyl Methacrylate and double methyl methacrylate triethylene glycol ester, and wherein the weight ratio of bisphenol-A-glycidyl Methacrylate and double methyl methacrylate triethylene glycol ester is 4-7:6-3; Described composite initiator is camphorquinone and 4-N, N-dimethylaminobenzoic acid ethyl ester, and wherein camphorquinone and 4-N, the weight ratio of N-dimethylaminobenzoic acid ethyl ester is 1:3-4.
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| CN103211712B (en) * | 2013-04-02 | 2015-08-12 | 东华大学 | A kind of gear division reparation low shrinkage nano composite resin and preparation method thereof |
| BR102013028247A2 (en) * | 2013-11-01 | 2015-09-22 | Univ Fed De Santa Catarina Ufsc | process for increasing adhesion of an inorganic reinforcement material to a polymer matrix, inorganic reinforcement material, process for obtaining a thermoplastic composite material, thermoplastic composite material and thermoplastic composite article |
| CN103637919B (en) * | 2013-12-04 | 2016-01-06 | 东华大学 | A kind of preparation method of sea urchin type hydroxyapatite-reinfdental dental repair resin |
| US10898415B2 (en) | 2019-01-02 | 2021-01-26 | Kerr Corporation | Fillers for dental restorative materials |
| CN109730935B (en) * | 2019-01-17 | 2021-12-21 | 东华大学 | High-strength dental composite resin and preparation method thereof |
| CN113174020B (en) * | 2021-03-19 | 2022-08-16 | 东华大学 | Preparation of high-performance low-shrinkage hyperbranched polyamine-ester composite resin for dental repair |
| CN114795975B (en) * | 2022-04-22 | 2024-07-26 | 佛山(华南)新材料研究院 | Dental material and preparation method thereof |
| CN115160908B (en) * | 2022-07-06 | 2023-07-07 | 海利得新材料研究(上海)有限公司 | Solvent-free UV matte coating and preparation method thereof |
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Application publication date: 20130130 Assignee: YANTAI ZHENGHAI BIO-TECH CO., LTD. Assignor: Donghua University Contract record no.: 2018310000028 Denomination of invention: Method for preparing organic/inorganic hybrid filler for dental repair resin Granted publication date: 20140702 License type: Exclusive License Record date: 20180611 |