CN102973416B - Preparation method of dental restoring resin taking silicon dioxide and cluster of silicon dioxide as stuffing - Google Patents

Abstract

The invention relates to a preparation method of a dental restorative resin using silica and its clusters as fillers, comprising: (1) preparing silica clusters by utilizing the reaction between bonding groups on the silica surface; 2) Add silica and its clusters, amine catalysts and silane coupling agents containing double bonds into cyclohexane solvent to react to obtain surface-functionalized inorganic co-fillers; (3) surface-functionalized inorganic co-fillers Filler, organic resin matrix and photoinitiator are blended evenly, and finally photocured for 40~120s. The preparation process of the invention is simple, easy to operate, and the price of raw materials is cheap, which is suitable for industrial production. The obtained composite resin for dental restoration has low polymerization shrinkage and excellent wear resistance, and is expected to be used clinically.

Description

Preparation method of dental restorative resin using silica and its clusters as filler

technical field

The invention belongs to the field of preparation of dental restoration materials, in particular to a preparation method of dental restoration resin using silicon dioxide and its clusters as fillers.

Background technique

Since the advent of composite resin as a dental restoration material in the mid-1960s, it has been widely used due to its unique aesthetics, good biocompatibility, excellent physical-mechanical properties, and convenient handling. In the treatment of anterior and posterior teeth, it gradually replaces the traditional silver amalgam and becomes a dental restoration material that is widely welcomed by doctors and patients. However, there are still some deficiencies in this type of material, such as high polymerization shrinkage, mismatch between mechanical properties and teeth, and poor wear resistance during long-term use. These deficiencies limit the wider application of this type of material. .

Dental restoration composite resin is mainly composed of organic matrix, inorganic filler and photoinitiator system, among which the composition of organic matrix and the type, particle size and filling amount of inorganic filler are the decisive factors affecting the performance of composite resin materials. With the development of organic synthesis technology, people have reduced the polymerization shrinkage of the composite resin to about 2% by using a new type of organic matrix, but the synthesis method of this type of monomer is relatively complicated, and the reagents required are expensive, which is not conducive to large-scale production , so the research and development of inorganic fillers has aroused more widespread attention. Inorganic fillers, as the dispersed phase of composite resins, are mainly used to enhance the physical-mechanical properties of composite resins. From the early stage of large-particle fillers to the commonly used mixed micro-fillers, this development has greatly improved the performance of composite resins, but The micron-sized filler in the filler will gradually fall off during long-term use, thereby forming pits on the surface of the material, which seriously affects the aesthetic performance of the resin. In recent years, with the development of nanotechnology in the field of dental materials, nanoclusters constructed of small particles and their application in restoration resins have received extensive attention. The introduction of this nanocluster structure is expected to endow the material with excellent Comprehensive performance.

Contents of the invention

The technical problem to be solved by the present invention is to provide a preparation method of dental restoration resin using silica and its clusters as filler. The preparation method is simple and suitable for industrial production. The obtained dental restoration resin contains organic and inorganic compounds. The machine components have good compatibility.

A preparation method of a dental restorative resin using silica and its clusters as a filler of the present invention, comprising:

(1) Preparation of silica clusters

a. Preparation of functionalized silica

Add silicon dioxide and an amino-containing coupling agent to ethanol, then mechanically stir overnight at 60±5°C, centrifuge after the reaction, wash with ethanol and deionized water, and then vacuum-dry at 40~60°C 14~18h, to obtain amino-functionalized silica;

Add silica and carboxyl-containing coupling agent to ethanol, then mechanically stir overnight at 60±5°C, centrifuge after the reaction, wash with ethanol and deionized water, and then vacuum dry at 40~60°C 14~18h, get carboxyl functionalized silica;

Add silicon dioxide and an epoxy-containing coupling agent to ethanol, then mechanically stir overnight at 60±5°C, centrifuge after the reaction, wash with ethanol and deionized water, and then place at 40~60°C Vacuum drying for 14-18 hours to obtain epoxy-functionalized silica;

b. Preparation of silica nanoclusters

Two kinds of the above-mentioned amino-functionalized silicon dioxide, carboxyl-functionalized silicon dioxide, and epoxy-functionalized silicon dioxide were respectively dissolved in absolute ethanol to obtain dispersions of the two respectively; and then the two Mix the dispersion liquid of the former, stir mechanically, react at 20~60°C for 24~32h, centrifuge and wash, and dry in vacuum at 50~80°C for 12~24h to obtain silica clusters;

(2) Preparation of surface functionalized inorganic co-fillers

Add silica and its clusters, amine catalyst (n-propylamine) and double bond-containing silane coupling agent (γ-methacryloxypropyltrimethoxysilane) into cyclohexane solvent and react at room temperature 20~60min, then stir at 60±5°C for 30-40min, remove the solvent and then dry in vacuum at 60±5°C for 18-24h to obtain the surface functionalized inorganic co-filler; the silica and its The mass ratio of clusters, amine catalysts and silane coupling agents containing double bonds is 5:0.1-0.2:0.5-0.8, the nano-silica and its clusters in the described nano-silica and its clusters Mass ratio 5:1-1:1;

(3) Preparation of light-cured composite resin

The surface-functionalized inorganic co-filler, organic resin matrix and photoinitiator are evenly blended, and finally photocured for 40-120s to obtain a photocurable composite resin (dental restoration resin).

The particle size of the silicon dioxide in step (1)a is 20-100nm.

The amino group-containing coupling agent described in step (1) a is specifically γ-aminopropyltriethoxysilane, and the carboxyl-containing coupling agent is specifically 3-(3-carboxyacrylamide)propyl triethoxysilane Ethoxysilane, the epoxy group-containing coupling agent is specifically γ-glycidyl etheroxypropyltrimethoxysilane.

The dosage ratios of the amino group-containing coupling agent, carboxyl-containing coupling agent, epoxy-containing coupling agent and silica described in step (1) a are 0.5~5.0mL:5g, 0.5~5.0 mL: 5g, 0.5~5.0mL: 5g.

The dosages of two of the amino-functionalized silica, carboxyl-functionalized silica, and epoxy-functionalized silica described in step (1) b are 0.5-3.0 g respectively, and absolute ethanol The dosage is 10~50mL.

The particle size of the silica clusters obtained in step (1)b is 0.04-3.60 μm.

The photocurable composite resin described in step (3) includes 20-60wt% organic resin matrix and 40-80wt% surface-functionalized inorganic co-filler.

The organic resin matrix described in step (3) is based on bisphenol A-glycidyl methacrylate (Bis-GMA), and triethylene glycol dimethacrylate (TEGDMA), bisethoxy One or more of bisphenol-A dimethacrylate (EBPADMA) and urethane dimethacrylate (UDMA) are used in combination, in which bisphenol A-glycidyl methacrylate is combined with other acrylic acid The mass percentage of quasi-monomers (or the sum of monomers) is 70:30~40:60.

The photoinitiator described in the step (3) is a mixed system of a main initiator and a co-initiator, wherein the main initiator is camphorquinone (CQ), 2,3-butanedione (2,3-Butanedione) One; co-initiator is one of ethyl p-dimethylaminobenzoate (4-EDMAB) and N,N-dimethylaniline (N,N-dimethylaniline), the quality of main initiator and co-initiator The ratio is 1:3-5.

The specific preparation method of the photocurable composite resin in the present invention is to manually premix the organic matrix of different components, the modified inorganic filler and the photoinitiator, and then put it into a three-roll mill and mix it evenly to obtain Uncured composite resin for dental restoration; light-cured composite resin can be obtained after 40~120s of light curing.

In the present invention, silica clusters are firstly prepared through the reaction between functional groups on the surface of silica; then the two kinds of inorganic fillers are subjected to surface modification treatment to obtain inorganic fillers with reactive groups on the surface; finally, the two The fillers are used as co-fillers in the preparation of photocurable composite resins for dental restorations.

In the present invention, silica and its clusters are used as inorganic co-fillers to prepare photocurable composite resin for dental restoration. Filling the cavities in the cluster increases the bulk density of the inorganic fillers, thereby not only ensuring the good mechanical properties of the material, but also reducing the polymerization shrinkage of the composite resin and improving the wear resistance of the material.

Compared with the commercial composite resin Esthet-X, the composite resin prepared by the present invention has a minimum polymerization shrinkage of 2.6%, while the polymerization shrinkage of Esthet-X is as high as 3.3%. In addition, the volume wear value of the composite resin prepared by the present invention is lower than 100×10 ^-3 mm ³ after 10,000 times of wear, while the volume wear value of the commercialized Esthet-X is as high as 126×10 ^-3 mm ³ , so the present invention The prepared composite resin exhibits good comprehensive properties.

Beneficial effect:

(1) The preparation method of the present invention is simple, the raw material is cheap, and is suitable for industrial production;

(2) The composite resin of the present invention exhibits good comprehensive properties, low polymerization shrinkage and good wear resistance.

Description of drawings

Fig. 1 is the SEM picture of the silica cluster that embodiment 1 obtains;

The polymerization shrinkage figure of Fig. 2 composite resin;

The wear resistance diagram of Fig. 3 composite resin;

Fig. 4 is the SEM image of the cross-sectional morphology of the composite resin obtained in Example 1.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

Table 1 Composite resin components and the content of each component

components Mass fraction (wt%) Bis-GMA 14.85 TEGDMA 14.85 CQ 0.06 4-EDMAB 0.24 Silanized silica 35 Silanized silica clusters 35

(1) Preparation of silica nanoclusters

a Preparation of functionalized nano-silica

Disperse two parts of 5.0g nano-silica (particle size: 20~100nm) into ethanol respectively, add 0.5mL coupling agent containing amino group (γ-aminopropyltriethoxysilane) and 0.5mL containing carboxyl group Coupling agent (3-(3-carboxyacrylamido)propyltriethoxysilane) for functional modification, mechanically stirred overnight at 65°C, centrifuged separately after the reaction, and then ethanol and deionized water Washing and vacuum drying at 60° C. for 16 h to obtain amino-functionalized silica and carboxyl-functionalized silica respectively.

b Preparation of silica clusters

Weigh 1 g of amino-functionalized silica and carboxy-functionalized silica, respectively, dissolve the two functionalized silicas in 20 mL of absolute ethanol to prepare corresponding dispersions, and then dissolve the carboxyl-functionalized silica The silica dispersion liquid was added dropwise to the amino-functionalized silica dispersion liquid, mechanically stirred at room temperature for 32 hours, centrifuged and washed, and then vacuum-dried at 60°C for 20 hours to obtain silica clusters with a particle size of 0.04~ 3.60um.

(2) Preparation of surface modified inorganic co-fillers

5.0g of nano-silica and its clusters (the mass ratio of the two is 1:1), 0.2g of amine catalyst (n-propylamine) and 0.8g of double bond-containing silane coupling agent (γ-methacryloyl Oxypropyltrimethoxysilane) was added to 100mL cyclohexane solvent, reacted at room temperature for 40min, then stirred at 60°C for 40min, after removing the solvent, dried in a vacuum oven at 60°C for 24h to obtain the silane coupling agent Surface-modified inorganic co-fillers.

(3) Specific preparation steps of light-cured composite resin

According to the ratio in the formula in Table 1, mix Bis-GMA, TEGDMA, CQ and 4-EDMAB according to the corresponding ratio. After mixing evenly, add inorganic co-filler (silica and its clusters modified by silane), and manually Pre-mix until the inorganic filler is fully wetted by the resin matrix, put it into a three-roll mill for secondary mixing, so as to obtain a uniformly mixed uncured composite resin paste, and finally obtain a dental restoration after photocuring Cured composite resin.

The prepared inorganic filler and light-cured composite resin samples were subjected to the relevant tests described below, and the morphology of the prepared silica clusters was observed by FE-SEM, as shown in Figure 1; Evaluation is carried out, and the results are shown in Figure 2; the wear resistance of the composite resin is evaluated by a two-phase sliding friction instrument, and the results are shown in Figure 3; the cross-sectional morphology of the composite resin is observed by FE-SEM, and the results are shown in Figure 4 .

Example 2

Table 2 Composite resin components and the content of each component

components Mass fraction (wt%) Bis-GMA 14.85 EBPADMA 14.85 2,3-Butanedione 0.06 N,N-Dimethylaniline 0.24 Silanized silica 40 Silanized silica clusters 30

(1) Preparation of silica nanoclusters

a Preparation of functionalized nano-silica

Disperse two parts of 5.0g nano-silica (particle size: 20~100nm) into ethanol respectively, add 0.5mL coupling agent containing amino group (γ-aminopropyltriethoxysilane) and 0.5mL containing carboxyl group Coupling agent (3-(3-carboxyacrylamido)propyltriethoxysilane) for functional modification, mechanically stirred overnight at 65°C, centrifuged separately after the reaction, and then ethanol and deionized water Washing and vacuum drying at 60° C. for 16 h to obtain amino-functionalized silica and carboxyl-functionalized silica respectively.

b Preparation of silica clusters

Weigh 1 g of amino-functionalized silica and carboxy-functionalized silica, respectively, dissolve the two functionalized silicas in 20 mL of absolute ethanol to prepare corresponding dispersions, and then dissolve the carboxyl-functionalized silica The silica dispersion liquid was added dropwise to the amino-functionalized silica dispersion liquid, mechanically stirred at room temperature for 32 hours, centrifuged and washed, and then vacuum-dried at 60°C for 20 hours to obtain silica clusters with a particle size of 0.04~ 3.60um.

(2) Preparation of surface modified inorganic co-fillers

5.0g of nano-silica and its clusters (the mass ratio of the two is 4:3), 0.2g of amine catalyst (n-propylamine) and 0.8g of double bond-containing silane coupling agent (γ-methacryloyl Oxypropyltrimethoxysilane) was added to 100mL cyclohexane solvent, reacted at room temperature for 40min, then stirred at 60°C for 40min, after removing the solvent, dried in a vacuum oven at 60°C for 24h to obtain the silane coupling agent Surface-modified inorganic co-fillers.

(3) Specific preparation steps of light-cured composite resin

According to the ratio in the formula in Table 2, mix Bis-GMA, EBPADMA, 2,3-butanedione and N,N-dimethylaniline according to the corresponding ratio, and add inorganic co-filler (modified by silane) Silica and its clusters), manually premixed until the inorganic filler is fully wetted by the resin matrix, put it into a three-roll mill for secondary mixing, in order to obtain a uniformly mixed uncured composite resin paste, and finally pass After photocuring treatment, a photocurable composite resin for dental restoration is prepared.

The commercial resin Esthet-X was selected as the control group for illustration. The test method of the photocurable composite resin in Example 2 is the same as in Example 1, and the commercial resin is tested in the same way. The measured polymerization shrinkage and wear resistance are shown in Figure 2 and Figure 3, respectively.

Example 3

Table 3 Composite resin components and the content of each component

components Mass fraction (wt%) Bis-GMA 14.85 UDMA 14.85 CQ 0.06 N,N-Methylaniline 0.24 Silanized silica 50 Silanized silica clusters 20

(1) Preparation of silica nanoclusters

a Preparation of functionalized nano-silica

Disperse two parts of 5.0g nano-silica (with a particle size of 20-100nm) into ethanol respectively, add 0.5mL of amino-containing coupling agent (γ-aminopropyltriethoxysilane) and 0.5mL of ring-containing Oxygen coupling agent (γ-glycidyl ether oxypropyltrimethoxysilane) for functional modification, mechanically stirred overnight at 65°C, centrifuged after the reaction, washed with ethanol and deionized water, 60°C C was dried in vacuum for 16 hours to obtain amino-functionalized silica and epoxy-functionalized silica, respectively.

b Preparation of silica clusters

Weigh 1 g of amino-functionalized silica and epoxy-functionalized silica, respectively, dissolve the two functionalized silicas in 20 mL of absolute ethanol to prepare corresponding dispersions, and then mix epoxy The amino-functionalized silica dispersion was added dropwise into the amino-functionalized silica dispersion, stirred mechanically at room temperature for 32 hours, and vacuum-dried at 60°C for 20 hours after centrifugal washing to obtain silica clusters, particles The diameter is 0.04~3.60um.

(2) Preparation of surface modified inorganic co-fillers

5.0g of nano-silica and its clusters (the mass ratio of the two is 5:2), 0.2g of amine catalyst (n-propylamine) and 0.8g of double bond-containing silane coupling agent (γ-methacryloyl Oxypropyltrimethoxysilane) was added to 100mL cyclohexane solvent, reacted at room temperature for 40min, then stirred at 60°C for 40min, after removing the solvent, dried in a vacuum oven at 60°C for 24h to obtain the silane coupling agent Surface-modified inorganic co-fillers.

(3) Specific preparation steps of light-cured composite resin

According to the ratio in the formula in Table 3, Bis-GMA, UDMA, CQ and N,N-dimethylaniline were mixed according to the corresponding ratio, and the inorganic co-filler (silane modified by silane and its Clusters), manually premixed until the inorganic filler is fully wetted by the resin matrix, put it into a three-roll mill for secondary mixing, in order to obtain a uniformly mixed uncured composite resin paste, and finally obtain it after photocuring Light-curing composite resins for dental restorations.

The commercial resin Esthet-X was selected as the control group for illustration. The test method of the photocurable composite resin in Example 3 is the same as in Example 1, and the commercial resin is tested in the same way. The measured polymerization shrinkage and wear resistance are shown in Figure 2 and Figure 3, respectively.

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.