CN102973416B - Preparation method of dental restoring resin taking silicon dioxide and cluster of silicon dioxide as stuffing - Google Patents
Preparation method of dental restoring resin taking silicon dioxide and cluster of silicon dioxide as stuffing Download PDFInfo
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- CN102973416B CN102973416B CN201210525631.6A CN201210525631A CN102973416B CN 102973416 B CN102973416 B CN 102973416B CN 201210525631 A CN201210525631 A CN 201210525631A CN 102973416 B CN102973416 B CN 102973416B
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Abstract
The invention relates to a preparation method of dental restoring resin taking silicon dioxide and cluster of the silicon dioxide as stuffing. The method comprises the following steps: (1) preparing the cluster of the silicon dioxide by using the reaction between bonded groups on the surface of silicon dioxide; (2) adding the silicon dioxide, the cluster of the silicon dioxide, an amine catalyst, and a double-bond-containing silane coupling agent in a cyclohexane solvent, thus obtaining surface-functionalized inorganic general stuffing after reaction; and (3) uniformly mixing the surface-functionalized inorganic general stuffing and an organic resin matrix with a light initiator and finally carrying out photo-curing for 40-120s, thus obtaining the dental restoring resin. The method is simple in preparation technology, easy to operate and suitable to industrial production; the raw materials are cheap in price; and the obtained dental restoring composite resin has a low polymerization-shrinkage ratio and excellent wear-resistant performance and is expected to be used clinically.
Description
Technical field
The invention belongs to the gear division preparation field of repair materials, particularly a kind of preparation method taking silicon dioxide and cluster thereof as the gear division resin for restoration of filler.
Background technology
Composite resin is since coming out as teeth repairing material mid-term nineteen sixties, rely on its unique aesthetic beauty, good biocompatibility, excellent physical-mechanical property and the performance such as operating handle and being widely used in labial teeth and Molar repair treatment easily, and substitute gradually traditional silver amalgam, become the teeth repairing material that welcome by doctor and patient.But such material still comes with some shortcomings at present, the problem such as higher in polymerization shrinkage, mechanical property is not mated with tooth body and anti-wear performance is poor in life-time service process, these deficiencies have limited such material and have applied more widely.
Gear division is repaired composite resin and is mainly made up of organic matrix, inorganic filler and photoinitiator system, and wherein the factor such as the composition of organic matrix and the kind of inorganic filler, particle diameter, loading is the deciding factor that affects composite resin material performance.Along with the development of organic synthesis technology, people are by adopting novel organic matrix to make the polymerization shrinkage of composite resin be reduced to 2% left and right, but the synthetic method of such monomer is comparatively complicated, required reagent is expensive, be unfavorable for large-scale production, therefore the research and development of inorganic filler have caused that people pay close attention to more widely.Inorganic filler is as the decentralized photo of composite resin, be mainly used in strengthening the physical-mechanical property of composite resin, develop into the conventional micro-filler of mixing at present from early stage bulky grain filler, this development is greatly improved the performance of composite resin, but the micron order filler in this filler can come off gradually in life-time service process, thereby form pit at material surface, have a strong impact on the performance attractive in appearance of resin.In recent years, along with the development of nanosecond science and technology in dental material field, the nanocluster of being constructed by small-particle and the application in resin for restoration thereof have obtained paying close attention to widely, and the introducing of this nanocluster structure is expected to give the combination property of material excellence.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method taking silicon dioxide and cluster thereof as the gear division resin for restoration of filler, and this preparation method is simple, is suitable for suitability for industrialized production, organic and the inorganic component compatibility is good in the gear division resin for restoration obtaining.
Of the present invention a kind of taking silicon dioxide and cluster thereof as the preparation method of the gear division resin for restoration of filler, comprising:
(1) preparation of Silica clusters
The preparation of a, functionalized SiO 2
In ethanol, add silicon dioxide and contain amino coupling agent, then under 60 ± 5 ° of C, mechanical agitation is spent the night, and reaction finishes rear centrifugal, uses respectively ethanol and deionized water wash, then in 40 ~ 60 ° of C vacuum drying 14 ~ 18h, obtains the silicon dioxide of amino functional;
In ethanol, add silicon dioxide and carboxylic coupling agent, then under 60 ± 5 ° of C, mechanical agitation is spent the night, and reaction finishes rear centrifugal, uses respectively ethanol and deionized water wash, then in 40 ~ 60 ° of C vacuum drying 14 ~ 18h, obtains the silicon dioxide of carboxyl-functional;
In ethanol, add silicon dioxide and the coupling agent containing epoxy radicals, then under 60 ± 5 ° of C, mechanical agitation is spent the night, and reaction finishes rear centrifugal, uses respectively ethanol and deionized water wash, in 40 ~ 60 ° of C vacuum drying 14 ~ 18h, obtain the silicon dioxide of epoxy radicals functionalization again;
The preparation of b, silica nanometer cluster body
Two kinds in the silicon dioxide of the silicon dioxide of the silicon dioxide of above-mentioned amino functional, carboxyl-functional, epoxy radicals functionalization are dissolved in respectively in dehydrated alcohol, obtain respectively the dispersion liquid of the two; Then the dispersion liquid of the two is mixed, mechanical agitation, at 20 ~ 60 ° of C reaction 24 ~ 32h, in 50 ~ 80 ° of C vacuum drying 12 ~ 24h, obtains Silica clusters after centrifuge washing;
(2) the surface-functionalized inorganic preparation of filler altogether
Silicon dioxide and cluster, amines catalyst (n-propylamine) and double bond containing silane coupler (γ-methacryloxypropyl trimethoxy silane) are added in cyclohexane solvent, room temperature reaction 20 ~ 60min, stir 30-40min in 60 ± 5 ° of C again, after removal solvent, in 60 ± 5 ° of C vacuum drying 18-24h, obtain surface-functionalized inorganic filler altogether; The mass ratio of wherein said silicon dioxide and cluster thereof, amines catalyst and double bond containing silane coupler is 5:0.1-0.2:0.5-0.8, the mass ratio 5:1-1:1 of nano silicon and its cluster body in described nano silicon and cluster thereof;
(3) preparation of light-cured composite
By even to surface-functionalized inorganic filler, organic resin matrix and light trigger blend altogether, after last photocuring 40 ~ 120s, obtain light-cured composite (gear division resin for restoration).
The particle diameter of the silicon dioxide described in step (1) a is 20 ~ 100nm.
The amino coupling agent that contains described in step (1) a is specially gamma-aminopropyl-triethoxy-silane, carboxylic coupling agent is specially 3-(3-carboxyl acrylyl amido) propyl-triethoxysilicane, is specially γ-glycidyl ether oxygen propyl trimethoxy silicane containing the coupling agent of epoxy radicals.
Described in step (1) a containing amino coupling agent, carboxylic coupling agent, be respectively 0.5 ~ 5.0mL:5g, 0.5 ~ 5.0mL:5g, 0.5 ~ 5.0mL:5g containing the coupling agent of epoxy radicals and the amount ratio of silicon dioxide.
The consumption of two kinds in the silicon dioxide of the silicon dioxide of the amino functional described in step (1) b, the silicon dioxide of carboxyl-functional, epoxy radicals functionalization is respectively 0.5 ~ 3.0g, and the consumption of dehydrated alcohol is 10 ~ 50mL.
The particle diameter of the Silica clusters obtaining in step (1) b is 0.04 ~ 3.60 μ m.
Light-cured composite described in step (3) comprises organic resin matrix and the surface-functionalized inorganic filler altogether of 40 ~ 80wt% of 20 ~ 60wt%.
Organic resin matrix described in step (3) is taking bisphenol-A-glycidyl methacrylate (Bis-GMA) as main monomer, add one or more the composite uses in TEGDMA (TEGDMA), two ethyoxyl bisphenol-A dimethylacrylates (EBPADMA), carbamate double methyl methacrylate (UDMA), wherein the mass percent of bisphenol-A-glycidyl methacrylate and other acrylic monomers (or monomer sum) is 70:30 ~ 40:60.
Light trigger described in step (3) is the mixed system of main initiator and aided initiating, and wherein main initiator is camphorquinone (CQ), 2, the one in 3-diacetyl (2,3-Butanedione); Aided initiating is the one in (dimethylamino)-ethyl benzoate (4-EDMAB), DMA (N, N-dimethylaniline), and the mass ratio of main initiator and aided initiating is 1:3-5.
In the present invention the concrete preparation method of light-cured composite be by the organic matrix of different component, through the inorganic filler of modification and light trigger after manual premix, put it into again mix homogeneously in three-roll grinder, obtain uncured gear division reparation composite resin; After photocuring 40 ~ 120s, just obtain light-cured composite.
First the present invention prepares Silica clusters body by the reaction between silica surface functional group; Respectively these two kinds of inorganic fillers are carried out to surface modification treatment afterwards, obtain the inorganic filler that reactive group is contained on surface; Finally using these two kinds of fillers as common filler for the preparation of photo-curing compound resin used for dental repair.
The present invention adopts silicon dioxide and cluster thereof to prepare photo-curing compound resin used for dental repair as inorganic filler altogether, there is cavity structure in the cluster inside that its advantage is made up of silicon dioxide, adding of nano-sized filler can be filled up the cavity in cluster body gradually, improve the bulk density of inorganic filler, and then ensureing outside the mechanical performance that material is good, also can reduce the polymerization shrinkage of composite resin, improve the anti-wear performance of material simultaneously.
The prepared composite resin of the present invention is compared with commercialization composite resin Esthet-X, and the minima of polymerization shrinkage is 2.6%, and the polymerization shrinkage of Esthet-X is up to 3.3%.In addition, the volume attrition value of the prepared composite resin of the present invention after 10,000 wearing and tearing is lower than 100 × 10
-3mm
3, and the volume attrition value of commercialization Esthet-X is up to 126 × 10
-3mm
3, therefore the prepared composite resin of the present invention shows good combination property.
Beneficial effect:
(1) preparation method of the present invention is simple, and cost of material is cheap, is suitable for suitability for industrialized production;
(2) composite resin of the present invention shows good combination property, and polymerization shrinkage is lower, and wearability is good.
Brief description of the drawings
Fig. 1 is the SEM figure of the Silica clusters that obtains of embodiment 1;
The polymerization shrinkage figure of Fig. 2 composite resin;
The anti-wear performance figure of Fig. 3 composite resin;
Fig. 4 is the SEM figure of the composite resin cross-section morphology that obtains of embodiment 1.
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.
Embodiment 1
The component of table 1 composite resin and the content of each component
| Component | Mass fraction (wt%) |
| Bis-GMA | 14.85 |
| TEGDMA | 14.85 |
| CQ | 0.06 |
| 4-EDMAB | 0.24 |
| Silanized silica | 35 |
| Silanized silica cluster | 35 |
(1) preparation of silica nanometer cluster body
The preparation of a functionalized nano silicon dioxide
Two parts of 5.0g nano silicons (particle diameter is 20 ~ 100nm) are dispersed to respectively in ethanol, add respectively 0.5mL to contain the coupling agent (3-(3-carboxyl acrylyl amido) propyl-triethoxysilicane) that amino coupling agent (gamma-aminopropyl-triethoxy-silane) and 0.5mL contain carboxyl and carry out functionalized modification, under 65 ° of C, mechanical agitation is spent the night, it is centrifugal that reaction finishes rear difference, use again ethanol and deionized water wash, 60 ° of C vacuum drying 16h, obtain respectively the silicon dioxide of amino functional and the silicon dioxide of carboxyl-functional.
The preparation of b Silica clusters
Take respectively the silicon dioxide of amino functional and the each 1g of the silicon dioxide of carboxyl-functional, the silicon dioxide of two kinds of functionalization is dissolved in respectively and in 20mL dehydrated alcohol, is made into corresponding dispersion liquid, afterwards the silica dispersions of carboxyl-functional is dropwise added in the silica dispersions of amino functional, at room temperature mechanical agitation 32h, after centrifuge washing in 60 ° of C vacuum drying 20h, obtain Silica clusters, particle diameter is 0.04 ~ 3.60um.
(2) the surface-modified inorganic preparation of filler altogether
5.0g nano silicon and cluster body (the two mass ratio is 1:1), 0.2g amines catalyst (n-propylamine) and the double bond containing silane coupler of 0.8g (γ-methacryloxypropyl trimethoxy silane) are added in 100mL cyclohexane solvent, room temperature reaction 40min, stir 40min in 60 ° of C again, remove after solvent, dry 24h in 60 ° of C vacuum drying ovens, obtains the inorganic filler altogether through silane coupler surface modification.
(3) the concrete preparation process of light-cured composite
According to the ratio in table 1 formula, Bis-GMA, TEGDMA, CQ and 4-EDMAB are pressed to corresponding proportion to be mixed, to be mixedly add inorganic filler (silicon dioxide of silane modified processing and cluster thereof) altogether after evenly, manual premix is to inorganic filler during fully by resin matrix moistening, putting it into three-roll grinder secondary mixes, to obtain the uncured composite resin cream of mix homogeneously, after processing finally by photocuring, make photo-curing compound resin used for dental repair.
Inorganic filler and the light-cured composite sample of preparation carry out dependence test as described below, utilize FE-SEM to observe prepared Silica clusters bodily form looks, as shown in Figure 1; Adopt density balance to evaluate composite resin polymerization shrinkage, result as shown in Figure 2; Adopt biphase sliding friction instrument to evaluate the anti-wear performance of composite resin, result as shown in Figure 3; Adopt FE-SEM to observe composite resin cross-section morphology, result as shown in Figure 4.
Embodiment 2
The component of table 2 composite resin and the content of each component
| Component | Mass fraction (wt%) |
| Bis-GMA | 14.85 |
| EBPADMA | 14.85 |
| 2,3-diacetyl | 0.06 |
| DMA | 0.24 |
| Silanized silica | 40 |
| Silanized silica cluster | 30 |
(1) preparation of silica nanometer cluster body
The preparation of a functionalized nano silicon dioxide
Two parts of 5.0g nano silicons (particle diameter is 20 ~ 100nm) are dispersed to respectively in ethanol, add respectively 0.5mL to contain the coupling agent (3-(3-carboxyl acrylyl amido) propyl-triethoxysilicane) that amino coupling agent (gamma-aminopropyl-triethoxy-silane) and 0.5mL contain carboxyl and carry out functionalized modification, under 65 ° of C, mechanical agitation is spent the night, it is centrifugal that reaction finishes rear difference, use again ethanol and deionized water wash, 60 ° of C vacuum drying 16h, obtain respectively the silicon dioxide of amino functional and the silicon dioxide of carboxyl-functional.
The preparation of b Silica clusters
Take respectively the silicon dioxide of amino functional and the each 1g of the silicon dioxide of carboxyl-functional, the silicon dioxide of two kinds of functionalization is dissolved in respectively and in 20mL dehydrated alcohol, is made into corresponding dispersion liquid, afterwards the silica dispersions of carboxyl-functional is dropwise added in the silica dispersions of amino functional, at room temperature mechanical agitation 32h, after centrifuge washing in 60 ° of C vacuum drying 20h, obtain Silica clusters, particle diameter is 0.04 ~ 3.60um.
(2) the surface-modified inorganic preparation of filler altogether
5.0g nano silicon and cluster body (the two mass ratio is 4:3), 0.2g amines catalyst (n-propylamine) and the double bond containing silane coupler of 0.8g (γ-methacryloxypropyl trimethoxy silane) are added in 100mL cyclohexane solvent, room temperature reaction 40min, stir 40min in 60 ° of C again, remove after solvent, dry 24h in 60 ° of C vacuum drying ovens, obtains the inorganic filler altogether through silane coupler surface modification.
(3) the concrete preparation process of light-cured composite
According to the ratio in table 2 formula, by Bis-GMA, EBPADMA, 2,3-diacetyl and N, accelerine is pressed corresponding proportion and is mixed, to be mixedly add inorganic filler (silicon dioxide of silane modified processing and cluster thereof) altogether after evenly, manual premix, puts it into three-roll grinder secondary and mixes during fully by resin matrix moistening to inorganic filler, to obtain the uncured composite resin cream of mix homogeneously, after processing finally by photocuring, make photo-curing compound resin used for dental repair.
Select commercialization resin Esthet-X to describe as a control group.The method of testing of the light-cured composite of embodiment 2 is identical with embodiment 1, and commercialization resin is tested equally.The polymerization shrinkage recording and anti-wear performance are shown in respectively Fig. 2 and Fig. 3.
Embodiment 3
The component of table 3 composite resin and the content of each component
| Component | Mass fraction (wt%) |
| Bis-GMA | 14.85 |
| UDMA | 14.85 |
| CQ | 0.06 |
| N, methylphenylamine | 0.24 |
| Silanized silica | 50 |
| Silanized silica cluster | 20 |
(1) preparation of silica nanometer cluster body
The preparation of a functionalized nano silicon dioxide
Two parts of 5.0g nano silicons (particle diameter is 20 ~ 100nm) are dispersed to respectively in ethanol, add respectively 0.5mL to contain amino coupling agent (gamma-aminopropyl-triethoxy-silane) and 0.5mL and carry out functionalized modification containing the coupling agent (γ-glycidyl ether oxygen propyl trimethoxy silicane) of epoxy radicals, under 65 ° of C, mechanical agitation is spent the night, it is centrifugal that reaction finishes rear difference, use again ethanol and deionized water wash, 60 ° of C vacuum drying 16h, obtain respectively the silicon dioxide of amino functional and the silicon dioxide of epoxy radicals functionalization.
The preparation of b Silica clusters
Take respectively the silicon dioxide of amino functional and the each 1g of silicon dioxide of epoxy radicals functionalization, the silicon dioxide of two kinds of functionalization is dissolved in respectively and in 20mL dehydrated alcohol, is made into corresponding dispersion liquid, afterwards the silica dispersions of epoxy radicals functionalization is dropwise added in the silica dispersions of amino functional, at room temperature mechanical agitation 32h, after centrifuge washing in 60 ° of C vacuum drying 20h, obtain Silica clusters, particle diameter is 0.04 ~ 3.60um.
(2) the surface-modified inorganic preparation of filler altogether
5.0g nano silicon and cluster body (the two mass ratio is 5:2), 0.2g amines catalyst (n-propylamine) and the double bond containing silane coupler of 0.8g (γ-methacryloxypropyl trimethoxy silane) are added in 100mL cyclohexane solvent, room temperature reaction 40min, stir 40min in 60 ° of C again, remove after solvent, dry 24h in 60 ° of C vacuum drying ovens, obtains the inorganic filler altogether through silane coupler surface modification.
(3) the concrete preparation process of light-cured composite
According to the ratio in table 3 formula, by Bis-GMA, UDMA, CQ and N, accelerine is pressed corresponding proportion and is mixed, to be mixedly add inorganic filler (silicon dioxide of silane modified processing and cluster thereof) altogether after evenly, manual premix is to inorganic filler during fully by resin matrix moistening, put it into three-roll grinder secondary and mix, to obtain the uncured composite resin cream of mix homogeneously, after processing finally by photocuring, make photo-curing compound resin used for dental repair.
Select commercialization resin Esthet-X to describe as a control group.The method of testing of the light-cured composite of embodiment 3 is identical with embodiment 1, and commercialization resin is tested equally.The polymerization shrinkage recording and anti-wear performance are shown in respectively Fig. 2 and Fig. 3.
Claims (7)
1. taking silicon dioxide and cluster thereof as a preparation method for the gear division resin for restoration of filler, comprising:
(1) a, in ethanol, add silicon dioxide and containing amino coupling agent, then at 60 ± 5 DEG C, mechanical agitation is spent the night, and reaction finishes rear centrifugal, uses respectively ethanol and deionized water wash, in 40～60 DEG C of vacuum drying 14～18h, obtain the silicon dioxide of amino functional again;
In ethanol, add silicon dioxide and carboxylic coupling agent, then at 60 ± 5 DEG C, mechanical agitation is spent the night, and reaction finishes rear centrifugal, uses respectively ethanol and deionized water wash, then in 40～60 DEG C of vacuum drying 14～18h, obtains the silicon dioxide of carboxyl-functional;
In ethanol, add silicon dioxide and the coupling agent containing epoxy radicals, then at 60 ± 5 DEG C, mechanical agitation is spent the night, and reaction finishes rear centrifugal, uses respectively ethanol and deionized water wash, in 40～60 DEG C of vacuum drying 14～18h, obtain the silicon dioxide of epoxy radicals functionalization again;
B, two kinds in the silicon dioxide of the silicon dioxide of the silicon dioxide of above-mentioned amino functional, carboxyl-functional, epoxy radicals functionalization are dissolved in respectively in dehydrated alcohol, obtain respectively the dispersion liquid of the two; Then the dispersion liquid of the two is mixed, mechanical agitation, at 20～60 DEG C of reaction 24～32h, in 50～80 DEG C of vacuum drying 12～24h, obtains Silica clusters after centrifuge washing;
(2) silicon dioxide and cluster, amines catalyst and double bond containing silane coupler are added in cyclohexane solvent, room temperature reaction 20～60min, stir 30-40min in 60 ± 5 DEG C again, after removal solvent, in 60 ± 5 DEG C of vacuum drying 18-24h, obtain surface-functionalized inorganic filler altogether; The mass ratio of wherein said silicon dioxide and cluster thereof, amines catalyst and double bond containing silane coupler is 5:0.1-0.2:0.5-0.8, the mass ratio 5:1-1:1 of silicon dioxide and its cluster body in described silicon dioxide and cluster thereof;
(3) by even to surface-functionalized inorganic filler, organic resin matrix and light trigger blend altogether, after last photocuring 40～120s, obtain light-cured composite;
The amino coupling agent that contains described in step (1) a is specially gamma-aminopropyl-triethoxy-silane, carboxylic coupling agent is specially 3-(3-carboxyl acrylyl amido) propyl-triethoxysilicane, is specially γ-glycidyl ether oxygen propyl trimethoxy silicane containing the coupling agent of epoxy radicals;
Described in step (1) a containing amino coupling agent, carboxylic coupling agent, be respectively 0.5～5.0mL:5g, 0.5～5.0mL:5g, 0.5～5.0mL:5g containing the coupling agent of epoxy radicals and the amount ratio of silicon dioxide;
Amines catalyst described in step (2) is n-propylamine, and double bond containing silane coupler is γ-methacryloxypropyl trimethoxy silane.
2. according to claim 1 a kind of taking silicon dioxide and cluster thereof as the preparation method of the gear division resin for restoration of filler, it is characterized in that: the particle diameter of the silicon dioxide described in step (1) a is 20～100nm.
3. a kind of preparation method taking silicon dioxide and cluster thereof as the gear division resin for restoration of filler according to claim 1, it is characterized in that: the consumption of two kinds in the silicon dioxide of the silicon dioxide of the amino functional described in step (1) b, the silicon dioxide of carboxyl-functional, epoxy radicals functionalization is respectively 0.5～3.0g, and the consumption of dehydrated alcohol is 10～50mL.
4. according to claim 1 a kind of taking silicon dioxide and cluster thereof as the preparation method of the gear division resin for restoration of filler, it is characterized in that: the particle diameter of the Silica clusters obtaining in step (1) b is 0.04～3.60 μ m.
5. according to claim 1 a kind of taking silicon dioxide and cluster thereof as the preparation method of the gear division resin for restoration of filler, it is characterized in that: the light-cured composite described in step (3) comprises organic resin matrix and the surface-functionalized inorganic filler altogether of 40～80wt% of 20～60wt%.
6. a kind of preparation method taking silicon dioxide and cluster thereof as the gear division resin for restoration of filler according to claim 1, it is characterized in that: the organic resin matrix described in step (3) is taking bisphenol-A-glycidyl methacrylate as main monomer, add one or more the composite uses in TEGDMA, two ethyoxyl bisphenol-A dimethylacrylate, carbamate double methyl methacrylate, wherein the mass percent of bisphenol-A-glycidyl methacrylate and other acrylic monomers or monomer sum is 70:30～40:60.
7. a kind of preparation method taking silicon dioxide and cluster thereof as the gear division resin for restoration of filler according to claim 1, it is characterized in that: the light trigger described in step (3) is the mixed system of main initiator and aided initiating, wherein main initiator is camphorquinone, 2, the one in 3-diacetyl; Aided initiating is the one in (dimethylamino)-ethyl benzoate, DMA, and the mass ratio of main initiator and aided initiating is 1:3-5.
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| CN103211711B (en) * | 2013-04-02 | 2014-10-15 | 东华大学 | Highly wear-resisting composite resin with high modulus for dental repair and preparation method thereof |
| CN109199873B (en) * | 2017-07-06 | 2020-07-24 | 北京化工大学 | Inorganic nanoparticle cluster for dental repair resin and preparation method thereof |
| CN109481317A (en) * | 2017-09-11 | 2019-03-19 | 北京化工大学 | A kind of gear division reparation nanocomposite and preparation method thereof |
| CN108852858A (en) * | 2018-07-12 | 2018-11-23 | 东华大学 | A kind of rambutan shape SiO2Base gear division compound resin and preparation method thereof |
| CN114539813A (en) * | 2020-11-18 | 2022-05-27 | 华为技术有限公司 | Non-spherical silica particles, preparation method thereof and polishing solution |
| CN113081859B (en) * | 2021-03-15 | 2022-06-03 | 山东沪鸽口腔材料股份有限公司 | Anti-staining hard resin denture and preparation method thereof |
| CN113943519B (en) * | 2021-12-22 | 2022-03-25 | 北京结力能源科技有限公司 | High-durability heavy-duty anticorrosion powder spraying modified resin and preparation method thereof |
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