Preparation method of nano-zirconium dioxide composite resin

Abstract

The present application relates to a preparation method of nano ZrO2 composite resin, comprising the following steps: dispersing organic zirconium and resin monomer in an organic solvent with a boiling point higher than that of water to obtain a mixed solution; contacting water vapor with the mixed solution, and hydrolyzing the organic zirconium with the water vapor, wherein the hydrolysis reaction of the organic zirconium and the polymerization reaction of the resin monomer in the mixed solution occur simultaneously; centrifuging and separating the nano ZrO2 resin oligomer from the organic solution; and irradiating and curing the nano ZrO2 resin oligomer with light, and the nano ZrO2 resin oligomer is obtained. The present application solves the problems existing in the prior art, such as difficulty in effectively controlling the size of ZrO2 particles, uneven mixing of ZrO2 and resin, low bonding strength of ZrO2 and resin, and narrow range of ZrO2 and resin ratio, by simultaneously hydrolyzing the organic zirconium solution with water vapor and polymerizing the resin monomer, and can be used in the field of producing nano ZrO2 resin with wide ratio, strong bonding and controllable particle size.

Description

Technical Field

[0001] This invention relates to a method for preparing a composite resin, specifically a method for preparing a nano-ZrO2 composite resin. Background Technology

[0002] Resin is a widely used polymer material in the medical field. Zirconia is an inert material with good biocompatibility, exhibiting characteristics such as corrosion resistance, high hardness and strength, high wear resistance, and high fracture resistance. By combining the advantages of both materials, zirconia composite resin has gained significant attention in the field of medical devices, particularly in the manufacture of medical devices such as joint replacement and dental implants.

[0003] The common method for preparing nano-ZrO2 composite resins is to first roughen the surface of zirconium oxide, then apply a primer of MDP or phosphate monomer to the roughened surface, and finally bond it with a double or self-curing composite resin cement. To promote the bonding between nano-zirconia and the resin, five common surface roughening methods are used: alumina blasting, silicon film method, laser etching, low-temperature plasma method, and glass melting method. Among these, alumina blasting uses compressed air to create a high-speed jet that propels alumina (50–250 μm) onto the zirconium oxide surface. T., et al., Dental Materials (1999): 426-433. Silicon film methods can be divided into chemical friction methods, sol-gel methods, etc., with chemical friction methods being more commonly used. Zirconia is sandblasted after covering the surface of alumina particles with silica, embedding the silica particles into the zirconia surface (Hansson O., Moberg L., et al., Dental Research (1993): 101243–251). Laser etching uses lasers to etch the zirconia surface to generate localized high temperatures, causing the surface to melt and recrystallize, forming a rough surface. Low-temperature plasma methods involve placing the zirconia specimen center below the nozzle of an atmospheric pressure ejector-type low-temperature plasma generator, introducing a mixed gas of 98% He and 2% O2, and then connecting a DC power supply to generate ejector-type low-temperature plasma to treat the zirconia surface (Derand T., Molin M. and Kvam K., Dental Materials (2005): 1158–1162). The glass melting method involves fusing a layer of low-temperature glass ceramic onto the surface of zirconia using an enamel spraying technique, followed by acid etching of the zirconia surface with hydrofluoric acid to achieve surface roughening (Saied M., et al, Dental Materials (2011): 1011–1016).

[0004] In summary, existing technologies for preparing nano-zirconia composite resins are either redundant, require complex equipment, or are difficult to operate. The synthesized ZrO2 composite resins either have poor mechanical strength, weak adhesion between ZrO2 and the resin, or the ZrO2 nanoparticles are too large or have a disordered particle distribution. These factors significantly limit the development and application of nano-zirconia composite resins.

[0005] Therefore, developing a low-consumption and simple synthesis method to prepare nano-ZrO2 composite resins with a wide range of proportions, strong bonding, and controllable particle size has important scientific and economic significance, which is also the driving force for those skilled in the art. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a novel method for preparing nano-ZrO2 composite resin, solving issues such as difficulty in effectively controlling ZrO2 particle size, uneven mixing of ZrO2 and resin, low bonding strength between ZrO2 and resin, and narrow ZrO2-resin ratio range in existing methods. This method is simple, efficient, and yields a nano-ZrO2 composite resin with advantages including a wide ratio range, strong bonding, and controllable particle size.

[0007] This invention is achieved through the following technical solution: a method for preparing nano-ZrO2 composite resin, comprising the following steps:

[0008] Step 1: Disperse organozirconium and resin monomers in an organic solvent with a boiling point higher than that of water to obtain a mixture;

[0009] Step 2: Water vapor is brought into contact with the mixture, and the water vapor hydrolyzes the organozirconium. The hydrolysis reaction of the organozirconium in the mixture occurs simultaneously with the polymerization reaction of the resin monomer.

[0010] Step 3: Centrifuge the organic solution obtained in Step 2 to obtain nano-ZrO2 resin oligomers;

[0011] Step four: Irradiate and cure the nano-ZrO2 resin oligomer with light to obtain nano-ZrO2 composite resin.

[0012] Preferably, the volume ratio of the organozirconium to the resin is 0.1 to 10:1, and more preferably, the volume ratio of the organozirconium to the resin is 0.5:1.

[0013] Preferably, the volume ratio of the total volume of the organozirconium and the resin to the volume of the organic solvent is 0.1 to 10:1; more preferably, the volume ratio of the total volume of the organozirconium and the resin to the volume of the organic solvent is 1:2.

[0014] Preferably, the organozirconium is selected from at least one of zirconium alkoxides and zirconium esters, and more preferably, zirconium ethanol.

[0015] Preferably, the resin monomer is selected from at least one of methacrylic resins, chitosan resins, lactic acid resins, carbonate resins, phenolic resins, and corresponding modified resins.

[0016] Preferably, the organic solvent is at least one of the following: ester organic solvents, aromatic hydrocarbon organic solvents, halogenated hydrocarbon organic solvents, and high carbon number alkane organic solvents that are poorly soluble in water.

[0017] Preferably, in step two, the pressure is 0.1–5 MPa and the temperature is 100–280 °C.

[0018] Preferably, in step four, the wavelength of the light is one of 365nm, 385nm, and 495nm, and the irradiation curing time is 1 to 100 seconds.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] In this invention, nano-ZrO2 composite resin is prepared in a reactor by using steam hydrolysis of organic solution. Before hydrolysis, organozirconium molecules and resin monomers are uniformly dispersed in the organic solvent at the molecular level and fully contacted, so that the hydrolysis reaction and polymerization reaction can occur simultaneously. The prepared ultrafine nano-ZrO2 and resin oligomers are fully connected at the nanoscale, which greatly increases the interaction between the two. Then, the ultrafine nano-ZrO2 and resin oligomers are fully bonded by photocuring to obtain a strongly bonded nano-ZrO2 composite resin.

[0021] The solubility of organozirconium and resin monomers in organic solutions can be effectively adjusted to obtain nano-ZrO2 composite resins with a wide range of proportions. By adjusting the hydrolysis temperature and time, the particle size of nano-ZrO2 can be effectively controlled, resulting in nano-ZrO2 composite resins with controllable particle size.

[0022] The method provided by this invention is simple, efficient, and greatly reduces costs, achieving excellent technical results. Attached Figure Description

[0023] Figure 1 The image shows the X-ray diffraction pattern of the nano-ZrO2 composite resin prepared at 160℃ according to the present invention.

[0024] Figure 2 This is a low-magnification transmission electron microscope (TEM) image of the nano-ZrO2 composite resin prepared at 160℃ according to the present invention.

[0025] Figure 3 This is a high-magnification transmission electron microscope (TEM) image of the nano-ZrO2 composite resin prepared at 160℃ according to the present invention.

[0026] Figure 4 The comparison diagram provided by this invention shows the simultaneous occurrence of steam hydrolysis of organozirconium solution and resin monomer polymerization before and after. Figure 4 In the image, the left side shows the area before hydrolysis and polymerization, and the right side shows the area after hydrolysis and polymerization. Detailed Implementation

[0027] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0028] Example 1: Preparation method of nano ZrO2 composite resin

[0029] A method for preparing nano-ZrO2 composite resin includes the following steps: Step 1, dispersing zirconium ethoxide and methyl methacrylate monomers in toluene (above the boiling point of water) to obtain a mixture, wherein the volume ratio of organozirconium to resin in the mixture is 0.5:1, and the volume ratio of the total volume of organozirconium and resin to the volume of organic solvent is 1:2; Step 2, hydrolyzing at a pressure of 2 MPa and a temperature of 160 °C for 15 h, allowing water vapor to contact the mixture, causing the zirconium ethoxide in the mixture to hydrolyze into ZrO2 and undergo oligomerization with ethanol and methyl methacrylate to generate ZrO2 methyl methacrylate oligomers; Step 3, centrifuging to separate the nano-ZrO2 methyl methacrylate oligomers from the toluene; Step 4, irradiating and curing the nano-ZrO2 methyl methacrylate oligomers with ultraviolet light at a wavelength of 365 nm for 18 seconds to obtain nano-ZrO2 composite methyl methacrylate resin. Its fracture toughness was measured to be 3.61 MPa·m. 1 / 2 The bending strength is 151 MPa.

[0030] exist Figure 1 The XRD peaks are significantly broadened, indicating that the prepared ZrO2 is nanocrystal. According to the Scherer formula, the particle size is less than 10 nm. The methyl methacrylate resin has no obvious X-ray diffraction peaks.

[0031] exist Figure 2 In the middle section, low-magnification transmission electron microscopy revealed that the nano-ZrO2 composite resin exhibited composite characteristics of inorganic polymer materials.

[0032] exist Figure 3 In the study, high-magnification transmission electron microscopy revealed the nanoscale properties of ZrO2, with an average particle size of approximately 6 nm.

[0033] exist Figure 4 The image shows a comparison of the results before and after the simultaneous hydrolysis of the organozirconium solution by steam and the polymerization of the resin monomers. The left side shows the result before hydrolysis and polymerization, and the right side shows the result after hydrolysis and polymerization.

[0034] Example 2-8: Preparation method of ZrO2 composite resin (nanometers)

[0035] Following the method in Example 1, hydrolysis was carried out at 160°C for 15 hours. By changing the hydrolysis temperature, hydrolysis time, type of organozirconium, type of resin monomer, ratio of different organozirconium and resin monomer, irradiation wavelength and curing time, a series of nano ZrO2 composite resins with different properties can be obtained.

[0036] Table 1. Performance test results of nano-ZrO2 composite resins obtained in Examples 1-8

[0037]

[0038] Preparation method of nano-ZrO2 composite resin in Examples 9-13

[0039] Following the method in Example 1, a series of nano-ZrO2 composite resins with different particle sizes can be obtained by simply changing the hydrolysis temperature and hydrolysis time.

[0040] Table 2. Particle size results of nano-ZrO2 composite resins obtained in Examples 9-13

[0041]

[0042] As shown in Table 1, in the embodiments of the present invention, nano-ZrO2 composite resin was prepared by hydrolyzing an organozirconium solution with water vapor and polymerizing it with resin monomers at a certain temperature. Under the same conditions, only the type of organozirconium source was changed in the experiments. The nano-ZrO2 composite resin obtained by zirconium ethoxide / methyl methacrylate monomer showed the best performance, and zirconium ethoxide / methyl methacrylate monomer was selected for subsequent examples. Under the same conditions, adjusting the ratio of zirconium ethoxide to resin monomers yielded a series of nano-ZrO2 composite resins with different properties. Among them, the nano-ZrO2 composite resin with the ratio of zirconium ethoxide to resin was the best, and the zirconium ethoxide to resin ratio of 0.5:1 was selected for subsequent examples. Under the same conditions, adjusting the irradiation wavelength and irradiation time, the nano-ZrO2 composite resin obtained by irradiating with a wavelength of 365 nm for 18 s exhibited the best fracture toughness and flexural strength.

[0043] As shown in Table 2, by keeping other variables constant and adjusting the hydrolysis temperature and time, nano-zirconia particles of different sizes can be obtained.

[0044] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing nano-ZrO2 composite resin, characterized in that, Includes the following steps: Step 1: Disperse organozirconium and resin monomer in toluene to obtain a mixture, wherein the volume ratio of organozirconium to resin monomer is 0.1 to 10:1, and the volume ratio of the total volume of organozirconium and resin monomer to toluene is 0.1 to 10:

1. The organozirconium is selected from zirconium ethoxide and tetrabutyl zirconate, and the resin monomer is selected from methyl methacrylate. Step 2: Water vapor is brought into contact with the mixture, and the water vapor hydrolyzes the organozirconium. The hydrolysis reaction of the organozirconium in the mixture occurs simultaneously with the polymerization reaction of the resin monomer. Step 3: Centrifuge the organic solution obtained in Step 2 to obtain nano-ZrO2 resin oligomers; Step four: Irradiate and cure the nano-ZrO2 resin oligomer with light to obtain nano-ZrO2 composite resin.

2. The method for preparing the nano-ZrO2 composite resin according to claim 1, characterized in that, The volume ratio of the organozirconium to the resin monomer is 0.5:

1.

3. The method for preparing the nano-ZrO2 composite resin according to claim 1, characterized in that, The total volume ratio of the organozirconium and the resin monomer to toluene is 1:

2.

4. The method for preparing the nano-ZrO2 composite resin according to claim 1, characterized in that, In step two, the pressure for steam hydrolysis of organozirconium is 0.1–5 MPa, and the temperature is 100–280 °C.

5. The method for preparing the nano-ZrO2 composite resin according to claim 1, characterized in that, In step four, the wavelength of the light is one of 365nm, 385nm, and 495nm, and the irradiation curing time is 1 to 100 seconds.

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