Dental restoration composite resin with long-acting antibacterial property and preparation method thereof

Abstract

The application discloses a kind of MXene reinforced composite resin with long-acting antibacterial for dental restoration and a preparation method thereof.The composite resin is composed of MXene antibacterial agent, inorganic filler reinforced phase, photocured resin matrix phase and initiator.The preparation method comprises the following steps: using liquid phase stripping method, MXene nanosheet is obtained by etching MAX phase material;in the presence of initiator, the resin matrix of doped MXene nanosheet and inorganic filler is cured by photocuring method, and the reinforced composite resin for dental restoration is obtained.The reinforced composite resin prepared by the application utilizes the slow release of antibacterial components of MXene material to endow the resin with long-acting antibacterial performance;and with the help of the interface mechanical interlocking of inorganic filler, the mechanical strength of the composite resin is improved.Compared with traditional resin, the reinforced composite resin prepared by the application has excellent long-acting antibacterial ability, mechanical strength and friction and wear performance, and also has good biocompatibility and biological safety, so it has wide application prospect.

Description

Technical Field

[0001] The present invention relates to a method for preparing a MXene-reinforced composite resin for dental restoration with long-lasting antibacterial properties, and belongs to the technical field of dental restoration material preparation. Background Art

[0002] Resin-based materials are widely used in dental restorations due to their excellent physical, chemical, and aesthetic properties. However, current commercially available resin-based materials also suffer from shortcomings such as poor mechanical strength and susceptibility to bacterial biofilm adhesion, significantly shortening their service life. To address these issues, researchers have conducted extensive research. In terms of improving the antibacterial ability of resin-based materials, researchers have demonstrated that materials such as zinc-doped mesoporous silica spheres (CN201911376709.0), expanded pore mesoporous silica grafted with long-chain alkyl quaternary ammonium salts (CN202210877057.4), methacryloyloxydodecylpyridinium bromide (CN201310618301.6), zinc oxide mesocrystals (CN201811287088.4), lamellar flower-shaped zinc oxide (CN202211030026.1), zinc-containing nanoclusters (CN202111668649.7), silver ions (CN201910044744.6), and betulin (CN202011231572.2) can improve the antibacterial properties of composite resins to a certain extent. However, there are also problems such as excessive release rate and low biocompatibility, making it difficult to achieve long-term antibacterial properties of composite resins. In terms of improving the mechanical strength of resins, researchers have demonstrated that the doping of inorganic mesoporous materials can improve the mechanical strength of composite resins to a certain extent.

[0003] In recent years, the potential applications of two-dimensional MXene materials in nanomaterial technology have been widely explored due to their excellent antibacterial properties and unique photothermal antibacterial capabilities. However, research on MXene materials in dental restoration resins has not yet been reported. This invention utilizes the antibacterial properties and two-dimensional layered structure of MXene materials, combined with the filler-reinforcing properties of inorganic nanoparticles, to prepare a dental restoration composite resin synergistically reinforced with MXene and inorganic fillers. This composite resin also achieves long-term antibacterial properties, which has great market value and application prospects in the field of dental restoration. Summary of the Invention

[0004] The purpose of the present invention is to provide a MXene-reinforced composite resin for dental restoration with long-lasting antibacterial properties and a preparation method thereof.

[0005] 1. Synthesis of few-layer MXene two-dimensional materials by hydrofluoric acid etching

[0006] The MAX phase raw material was slowly added to the hydrofluoric acid solution and reacted with magnetic stirring at 30-50°C for 12-72 hours. The reaction solution was centrifuged at 3000-5000 rpm for 15-35 minutes. The precipitate after centrifugation was then collected and redispersed in deionized water. After filtration, vacuum drying was performed to obtain the etched multilayer MXene powder. The multilayer MXene powder obtained in the above steps was prepared into a concentration of 1-5 mg mL -1 The aqueous solution was centrifuged at 5000-8000 rpm for 20-35 min; the supernatant after centrifugation was taken and centrifuged at 15000-20000 rpm for 20-40 min, the precipitate after centrifugation was collected and vacuum dried at 40-60 ° C overnight to obtain a few-layer MXene powder.

[0007] The MAX phase raw material is one or more of Ti3AlC2, Ti2AlC, Ti3AlCN, V2AlC, V3AlC2, V3AlCN, Nb3AlC2, Nb2AlC, Nb3AlCN, Mo2AlC, Cr2AlC, and Hf2AlC, and its concentration in the hydrofluoric acid solution is 0.05-0.5 g mL -1 .

[0008] 2. Preparation of MXene-reinforced composite antibacterial resin

[0009] The main monomer and diluent monomer in the resin matrix are mixed evenly, and a certain amount of few-layer MXene powder and inorganic filler are added. Under the action of the main initiator and co-initiator, the above mixture is photocured for 30 to 180 seconds (3W, 420 to 480nm) to obtain a MXene-reinforced composite resin with long-lasting antibacterial effect.

[0010] Among them, MXene antibacterial agent is Ti3C2T x Nanosheets, Ti2CT x Nanosheets, Ti3CNT x Nanosheets, V2CT x Nanosheets, V3C2T x Nanosheets, V3CNT x Nanosheets, Nb3C2T x Nanosheets, Nb2CT x Nanosheets, Nb3CNT x Nanosheets, Mo2CT x Nanosheets, Cr2CT x Nanosheets, Hf2CT x The mass fraction of one or more of the nanosheets and the MXene antimicrobial agent is 0 to 20 wt % of the resin matrix.

[0011] The inorganic filler reinforcement phase is one or more of mesoporous silica, mesoporous titania, mesoporous alumina, mesoporous zirconia, mesoporous zinc oxide, silane-modified silica, silane-modified zinc oxide, silane-modified titania, silane-modified alumina, and silane-modified zirconia, and the mass fraction of the inorganic filler reinforcement phase is 40 to 85 wt % of the resin matrix.

[0012] In the photocurable resin matrix, the main monomer is one or two of bisphenol A-glycidyl methacrylate (Bis-GMA) and urethane dimethacrylate (UDMA); the diluent monomer is one or more of bisethoxybisphenol-A dimethacrylate (EBPADMA), triethylene glycol dimethacrylate (TEGDMA), 1,6-hexanediol diacrylate, 4-hydroxybutyl acrylate, and methyl methacrylate (MMA), and the mass ratio of the main monomer to the diluent monomer is 1:1 to 5:1.

[0013] The initiator consists of a main initiator and a co-initiator. The main initiator is one or more of camphorquinone, benzophenone and diphenylacetophenone; the co-initiator is one or more of ethyl p-dimethylaminobenzoate 4-EDMAB, ethyl trimethylbenzoylphenylphosphonate, methyl benzoylformate, N,N-dimethylaminoethyl methacrylate (DMAEMA) and 4-ethane-N,N-dimethylaminobenzoic acid vinyl. The mass fraction of the main initiator is 0.5-5wt% of the resin matrix, and the mass fraction of the co-initiator is 1-5 times that of the main initiator.

[0014] In summary, the method for preparing the MXene-reinforced composite resin for dental restoration with long-lasting antibacterial properties prepared by the present invention has the following advantages over the prior art:

[0015] 1. The MXene composite resin for dental restoration prepared in this invention exhibits sustained, long-lasting antibacterial activity. On one hand, the two-dimensional MXene material itself possesses excellent antibacterial properties, enabling the composite resin prepared in this invention to achieve controlled release of MXene and long-term stability. Furthermore, due to the unique photothermal properties of MXene, the composite resin prepared in this invention significantly enhances its antibacterial properties under illumination.

[0016] 2. The MXene-reinforced composite resin for dental restoration prepared in this invention exhibits excellent mechanical stability and anti-friction properties. Due to the synergistic effect of the inorganic filler reinforcement phase and the two-dimensional MXene nanosheets, the interfacial bonding strength between the composite resin matrix and the additive is greatly enhanced, significantly reducing the interfacial microstress generated during tensile and friction wear of the composite resin, thereby improving the mechanical and friction and wear properties of the composite resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 (a) shows different Ti3C2T x The wear volume of the composite resin prepared at the concentration of .

[0018] Figure 1 (b) shows different Ti3C2T x The antibacterial effect of the composite resin prepared at the concentration against Streptococcus mutans. DETAILED DESCRIPTION

[0019] The preparation method and properties of the MXene-reinforced composite resin for dental restoration with long-lasting antibacterial properties of the present invention are further described below through specific examples.

[0020] Example 1

[0021] Ti3AlC2 was slowly added to the hydrofluoric acid solution at a concentration of 0.1 g mL -1 , after magnetic stirring at 30 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer Ti3C2T x Powder; Take the multilayer Ti3C2T obtained in the above steps x Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and dried in vacuum at 40 ° C overnight to obtain a few-layer Ti3C2T x powder.

[0022] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 1 wt% Ti3C2T x The powder and 70 wt% of silane-modified silica were photocured for 180 s (3 W, 420-480 nm) in the presence of 1 wt% camphorquinone and 2 wt% DMAEMA to obtain Ti3C2T x Reinforced composite resin.

[0023] Example 2

[0024] Ti3AlC2 was slowly added to the hydrofluoric acid solution at a concentration of 0.1 g mL -1 , after magnetic stirring at 30 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer Ti3C2T x Powder; Take the multilayer Ti3C2T obtained in the above stepsx Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and dried in vacuum at 40 ° C overnight to obtain a few-layer Ti3C2T x powder.

[0025] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 2 wt% Ti3C2T x The powder and 70 wt% of silane-modified silica were photocured for 180 s (3 W, 420-480 nm) in the presence of 1 wt% camphorquinone and 2 wt% DMAEMA to obtain Ti3C2T x Reinforced composite resin.

[0026] Example 3

[0027] Ti3AlC2 was slowly added to the hydrofluoric acid solution at a concentration of 0.1 g mL -1 , after magnetic stirring at 30 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer Ti3C2T x Powder; Take the multilayer Ti3C2T obtained in the above steps x Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and dried in vacuum at 40 ° C overnight to obtain a few-layer Ti3C2T x powder.

[0028] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 0.5 wt% Ti3C2T x The powder and 70 wt% of silane-modified silica were photocured for 180 s (3 W, 420-480 nm) in the presence of 1 wt% camphorquinone and 2 wt% DMAEMA to obtain Ti3C2T x Reinforced composite resin.

[0029] Example 4

[0030] Ti2AlC was slowly added to the hydrofluoric acid solution at a concentration of 0.1 g mL -1, after magnetic stirring at 30 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer Ti2CT x Powder; Take the multilayer Ti2CT obtained in the above steps x Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and dried in vacuum at 40 ° C overnight to obtain a few-layer Ti2CT x powder.

[0031] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 1 wt% Ti2CT x The powder and 70 wt% of silane-modified silica were photocured for 180 s (3 W, 420-480 nm) in the presence of 1 wt% camphorquinone and 2 wt% DMAEMA to obtain Ti2CT x Reinforced composite resin.

[0032] Example 5

[0033] Ti3AlC2 was slowly added to the hydrofluoric acid solution at a concentration of 0.1 g mL -1 , after magnetic stirring at 50 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer Ti3C2T x Powder; Take the multilayer Ti3C2T obtained in the above steps x Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and dried in vacuum at 60 ° C overnight to obtain a few-layer Ti3C2T x powder.

[0034] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 0.5 wt% Ti3C2T x The powder and 70 wt% of silane-modified silica were photocured for 180 s (3 W, 420-480 nm) in the presence of 1 wt% camphorquinone and 2 wt% DMAEMA to obtain Ti3C2T x Reinforced composite resin.

[0035] Example 6

[0036] Slowly add V3AlC2 into the hydrofluoric acid solution to a concentration of 0.1 g mL -1 , after magnetic stirring at 30 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer V3C2T x Powder; Take the multilayer V3C2T obtained in the above steps x Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and vacuum dried at 40 ° C overnight to obtain a few-layer V3C2T x powder.

[0037] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 0.5 wt% of V3C2T was added. x Powder and 70wt% silane-modified silica were prepared. The mixture was photocured for 180s (3W, 420-480nm) in the presence of 1wt% camphorquinone and 2wt% DMAEMA to obtain V3C2T x Reinforced composite resin.

[0038] Example 7

[0039] Slowly add V3AlC2 into the hydrofluoric acid solution to a concentration of 0.1 g mL -1 , after magnetic stirring at 30 ° C for 12 hours; the reaction solution was centrifuged at 3500 rpm for 20 minutes; the precipitate after centrifugation was collected, redispersed in deionized water, filtered and vacuum dried to obtain the etched multilayer V3C2T x Powder; Take the multilayer V3C2T obtained in the above steps x Powder, prepared to a concentration of 2 mg mL -1 The aqueous solution was centrifuged at 8000 rpm for 30 min; the supernatant after centrifugation was taken and centrifuged at 18000 rpm for 30 min. The precipitate after centrifugation was collected and vacuum dried at 40 ° C overnight to obtain a few-layer V3C2T x powder.

[0040] Bis-GMA and TEGDMA monomers were mixed uniformly at a mass ratio of 7:3, and 0.5 wt% of V3C2T was added. xPowder and 70wt% silane-modified zinc oxide were prepared. The mixture was photocured for 180s (3W, 420-480nm) in the presence of 1wt% camphorquinone and 2wt% DMAEMA to obtain V3C2T x Reinforced composite resin.

[0041] The Ti3C2T prepared in Examples 1-3 x Reinforced composite resin for performance evaluation:

[0042] 1. Ti3C2T x Evaluation of wear properties of reinforced composite resin

[0043] Test Method: A pin-on-disc testing machine was used to conduct a rotational friction test on the composite resin. The composite resin sample size was 30.0 mm × 7.0 mm × 4.0 mm (length × width × height), the load was 5.0 N, and the test temperature was room temperature.

[0044] Figure 1 a is the different Ti3C2T prepared in Examples 1-3 x The wear amount of composite resin with different concentrations can be seen from the figure. x With the increase of concentration, the wear amount of the composite resin gradually decreased, proving that the Ti3C2T prepared in Examples 1-3 x The reinforced composite resin has excellent anti-wear properties and with the addition of Ti3C2T x With the increase of concentration, the anti-wear performance of the composite resin is significantly enhanced. This is due to the two-dimensional Ti3C2T x The introduction of nanosheets forms a synergistic effect with inorganic fillers, reducing the generation of microstress at the composite resin interface and improving the mechanical strength of the composite resin.

[0045] 2. Ti3C2T x Evaluation of antibacterial properties of reinforced composite resin

[0046] Test method: 1) Take 1mL 10 7 CFU mL -1 The concentration of mutans streptococcus culture solution was added to the sterilized Ti3C2T x 1) 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12) 13) 14) 15) 16) 17) 18) 19) 20) 21) 22) 23) 24) 25) 26) 27) 28) 29) 30) 31) 32) 33) 34) 35) 36) 37) 38) 39) 40) 41) 42) 43) 44) 45) 46) 47) 48) 49) 50) 51) 52) 53) 54) 55) 56) 57) 58) 59) 60) 61) 62) 63) 64) 65)

[0047] Figure 1 b are different Ti3C2T prepared in Examples 1-3 xThe antibacterial effect of the composite resin on Streptococcus mutans can be seen from the figure. x With the continuous increase of concentration, the survival rate of Streptococcus mutans on the composite resin surface gradually decreased, proving that the Ti3C2T prepared in Examples 1-3 x The reinforced composite resin has excellent antibacterial ability, and the antibacterial ability increases with the increase of Ti3C2T x The increase in concentration was significantly enhanced.

Claims

1. Application of a MXene-reinforced composite resin with long-lasting antibacterial properties in dental restoration, characterized in that: The composite resin consists of a MXene antibacterial agent, an inorganic filler reinforcement phase, a light-curable resin matrix phase and an initiator; The MXene antibacterial agent is Ti3C2T x Nanosheets, Ti2CT x Nanosheets, Ti3CNT x Nanosheets, V2CT x Nanosheets, V3C2T x Nanosheets, V3CNT x Nanosheets, Nb3C2T x Nanosheets, Nb2CT x Nanosheets, Nb3CNT x Nanosheets, Mo2CT x Nanosheets, Cr2CT x Nanosheets, Hf2CT x One or more of the nanosheets; The inorganic filler reinforcement phase is one or more of mesoporous silica, mesoporous titania, mesoporous alumina, mesoporous zirconia, mesoporous zinc oxide, silane-modified silica, silane-modified zinc oxide, silane-modified titania, silane-modified alumina, and silane-modified zirconia.

2. The use according to claim 1, characterized in that In the photocurable resin matrix phase, the main monomer is one or two of bisphenol A-glycidyl methacrylate and urethane dimethacrylate; the diluent monomer is one or more of bisethoxybisphenol-A dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 4-hydroxybutyl acrylate, and methyl methacrylate.

3. The use according to claim 1, characterized in that The initiator consists of a main initiator and a co-initiator, wherein the main initiator is one or more of camphorquinone, benzophenone, and diphenylacetophenone, and the co-initiator is one or more of ethyl p-dimethylaminobenzoate 4-EDMAB, ethyl trimethylbenzoylphenylphosphonate, methyl benzoylformate, N,N-dimethylaminoethyl methacrylate, and 4-ethane-N,N-dimethylaminobenzoic acid vinyl.

4. The use according to claim 1, wherein The preparation method of MXene-reinforced composite resin for dental restoration with long-lasting antibacterial properties comprises the following steps: (1) Add the MAX phase raw material to the hydrofluoric acid solution and react with magnetic stirring at 30-50 °C for 12-72 h; centrifuge the solution at 3000-5000 rpm for 15-35 min; then collect the precipitate after centrifugation, redisperse it in deionized water, filter it, and vacuum dry it to obtain the etched multilayer MXene powder; take the multilayer MXene powder obtained in the above steps and prepare it into a concentration of 1-5 mg mL -1 The aqueous solution was centrifuged at 5000-8000 rpm for 20-35 min; the supernatant after centrifugation was taken and centrifuged at 15000-20000 rpm for 20-40 min, the precipitate after centrifugation was collected and vacuum dried at 40-60 ° C overnight to obtain a few-layer MXene antibacterial agent; (2) The main monomer and diluent monomer in the resin matrix are mixed evenly, and a certain amount of MXene antibacterial agent and inorganic filler reinforcement phase are added. Under the action of the main initiator and co-initiator, light curing is carried out for 30 to 180 seconds to obtain a MXene-reinforced composite resin with long-lasting antibacterial effect.

5. The use according to claim 4, characterized in that In step (1), the MAX phase raw material is one or more of Ti3AlC2, Ti2AlC, Ti3AlCN, V2AlC, V3AlC2, V3AlCN, Nb3AlC2, Nb2AlC, Nb3AlCN, Mo2AlC, Cr2AlC, and Hf2AlC, with a concentration of 0.05 to 0.5 g mL -1 .

6. The use according to claim 4, characterized in that In step (2), the mass fraction of the MXene antibacterial agent is 0.5 to 2 wt% of the resin matrix; the mass fraction of the inorganic filler reinforcement phase is 40 to 85 wt% of the resin matrix.

7. The use according to claim 4, characterized in that In step (2), the mass ratio of the main monomer to the diluent monomer is 1:1 to 5:

1.

8. The use according to claim 4, characterized in that In step (2), the mass fraction of the main initiator is 0.5 to 5 wt % of the resin matrix, and the mass fraction of the co-initiator is 1 to 5 times that of the main initiator.

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