Dental material based on chemically modified polyetherketoneketone, and preparation method and application thereof

Abstract

The invention is applicable to the field of biomedical materials, and provides a dental material based on chemically modified polyether ketone ketone as well as a preparation method and application thereof, and the preparation method of the dental material comprises the following steps: sequentially sulfonating polyether ketone ketone materials to obtain sulfonated polyether ketone ketone materials; carrying out chemical modification treatment of one or more of amination, hydroxylation and carboxylation on the sulfonated polyether ketone ketone material to obtain a chemically modified polyether ketone ketone material; and filling the surface of the chemically modified polyetherketoneketone material with dental resin to obtain the dental material. Amino, hydroxyl or carboxyl is grafted to the surface of the polyetherketoneketone material through a chemical method, the shear bonding strength between the polyetherketoneketone and dental resin can be remarkably improved, and the hydrophilicity of the material is improved.

Description

Technical Field

[0001] The present invention belongs to the field of biomedical materials, and in particular relates to a dental material based on chemically modified polyetherketoneketone, a preparation method and an application thereof. Background Art

[0002] Polyetherketoneketone (PEKK) is a high-performance polymer that has been introduced into dentistry due to its wide range of potential applications. PEKK has emerged as an alternative to metals and glass-ceramics due to its favorable stress distribution, high fracture resistance, and low wear on antagonist tooth enamel. Furthermore, due to its biocompatibility, it is commonly used as a bioimplant and has attracted attention as a replacement for titanium, long used in orthopedics. Within dentistry, PEKK is increasingly used as a temporary abutment for dental implants. It is also used as a clasp and framework for removable partial dental restorations. Furthermore, according to a limited analysis of a recent study, PEKK has great potential as a post and core material due to its favorable stress distribution. However, the gray or white color and low translucency of PAEK limit its use as anterior oral restorations. Therefore, an additional veneer is essential to achieve a satisfactory aesthetic outcome. Due to its low surface free energy and extremely low hydrophobicity, PEKK surfaces exhibit low bond strength when bonded to dental resins, making it difficult to form a strong and durable adhesion with the resin.

[0003] To improve the adhesion between PEKK and resin materials, researchers have used physical and chemical modifications to increase the surface roughness of PEKK, thereby enhancing adhesion. Physical modifications include sandblasting, plasma treatment, and filler modification, while chemical modifications currently primarily involve concentrated sulfuric acid etching. While existing modification methods can enhance the bond strength between PEEKK and dental resins, increasing the hydrophilicity of PEEKK and clinical application remains problematic, requiring further exploration. Summary of the Invention

[0004] The purpose of the embodiments of the present invention is to provide a method for preparing a dental material based on chemically modified polyetherketoneketone, aiming to solve the problems raised in the background technology.

[0005] The embodiment of the present invention is achieved by a method for preparing a dental material based on chemically modified polyetherketoneketone, comprising the following steps:

[0006] The polyetherketoneketone material is sequentially subjected to sulfonation treatment to obtain a sulfonated polyetherketoneketone material;

[0007] The sulfonated polyetherketoneketone material is subjected to chemical modification treatment by one or more of amination, hydroxylation and carboxylation to obtain a chemically modified polyetherketoneketone material;

[0008] The dental material is obtained by filling the surface of the chemically modified polyetherketoneketone material with dental resin.

[0009] Preferably, the dental resin is filled on the surface of the chemically modified polyetherketoneketone material coated with the binder to obtain the dental material.

[0010] Preferably, the method of sulfonation treatment comprises the following steps:

[0011] The surface of the polyetherketoneketone material is polished and ultrasonically cleaned with deionized water, acetone and anhydrous ethanol in sequence to obtain a pretreated polyetherketoneketone material;

[0012] The pretreated polyetherketoneketone material is immersed in concentrated sulfuric acid with a concentration of 95%-98% for modification treatment, and then ultrasonically cleaned with deionized water and acetone in sequence to remove residual sulfuric acid on the surface, and then vacuum dried to obtain the sulfonated polyetherketoneketone material.

[0013] Preferably, the grinding and polishing process uses 400-800 grit sandpaper.

[0014] Preferably, the soaking time is 3-6 minutes.

[0015] Preferably, the chemical modification treatment method of amination is: using ethylenediamine as a modifier, through the Schiff base reaction of the amino group in ethylenediamine with the carbonyl group on the surface of the sulfonated polyetherketoneketone material, the amino group is grafted onto the polyetherketoneketone material to obtain a surface-aminated modified polyetherketoneketone material.

[0016] Preferably, the chemical modification treatment method of amination specifically comprises the following steps:

[0017] Ethylenediamine is heated to 120-130°C, and then the sulfonated polyetherketoneketone material is added to carry out a Schiff base reaction for 6-10 hours. Nitrogen is continuously introduced during the reaction as a protection. After the reaction is completed, ultrasonic cleaning is carried out with deionized water, isopropyl alcohol, and deionized water respectively to remove surface residues, and then drying is carried out to obtain a surface amino-modified polyetherketoneketone material.

[0018] Preferably, the chemical modification treatment method of hydroxylation is: using sodium borohydride as a modifier to reduce the carbonyl groups on the surface of the sulfonated polyetherketoneketone material to hydroxyl groups, thereby obtaining a surface hydroxylated polyetherketoneketone material.

[0019] Preferably, the chemical modification treatment method of hydroxylation specifically comprises the following steps:

[0020] 110-130 mg of sodium borohydride was dissolved in 60 mL of anhydrous dimethyl sulfoxide, and then the sulfonated polyetherketoneketone material was added. The temperature was raised to 115-125 ° C and the reaction was carried out for 3-9 hours. Nitrogen was continuously introduced during the reaction as a protection. After the reaction was completed, ultrasonic cleaning was carried out with anhydrous methanol, deionized water, dilute hydrochloric acid, deionized water, and anhydrous ethanol, respectively, and then drying was carried out to obtain a surface hydroxylation-modified polyetherketoneketone material.

[0021] Preferably, the chemical modification treatment method of carboxylation is: using acrylic acid as a modifier, grafting the carboxyl functional groups in the acrylic acid onto the surface of the sulfonated polyetherketoneketone material by ultraviolet light, to obtain a surface carboxyl-modified polyetherketoneketone material.

[0022] Preferably, the carboxylation chemical modification treatment method specifically comprises the following steps:

[0023] The sulfonated polyetherketoneketone material is added to an acrylic acid solution with a concentration of 0.5-1 mol / L, and irradiated with an ultraviolet lamp with a power of 400-600 W and a wavelength of 350±50 nm for 40-50 minutes (the distance between the material and the light is kept at 10-20 cm for irradiation) to carry out a UV grafting reaction. After the reaction is completed, it is washed with deionized water and anhydrous ethanol respectively to remove surface residues, and then dried to obtain a surface carboxyl-modified polyetherketoneketone material.

[0024] Another object of an embodiment of the present invention is to provide a dental material based on chemically modified polyetherketoneketone prepared by the above-mentioned preparation method.

[0025] Another object of an embodiment of the present invention is to provide a use of the above-mentioned dental material based on chemically modified polyetherketoneketone in the preparation of tooth restoration materials.

[0026] An embodiment of the present invention provides a method for preparing a dental material based on chemically modified polyetherketoneketone. Through the Schiff base reaction between ethylenediamine and polyetherketoneketone, amino groups can be grafted onto the main chain of the polyetherketoneketone molecule; through the reducing property of sodium borohydride, the carbonyl groups on the polyetherketoneketone main chain can be reduced to hydroxyl groups; through ultraviolet grafting, the carboxyl groups in acrylic acid can be grafted onto the polyetherketoneketone main chain; and dental resin is then filled on the surface of the chemically modified polyetherketoneketone material, which can significantly improve the shear bond strength between the polyetherketoneketone and the dental resin and increase the hydrophilicity of the material.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows: the chemically modified polyetherketoneketone material obtained by the present invention can be grafted with amino groups, hydroxyl groups and carboxyl groups on its surface, which is conducive to the reaction between the chemical functional groups in the dental resin material and the chemical functional groups on the surface of the chemically modified polyetherketoneketone material, thereby improving the adhesion between the surface of the polyetherketoneketone material and the dental resin. In addition, the present invention can greatly improve the hydrophilicity of the polyetherketoneketone material by grafting chemical functional groups to the surface of the polyetherketoneketone material, which is conducive to the material adapting to the oral environment, and the modified material still maintains excellent mechanical properties and can meet the mechanical strength required as a dental application material. The preparation method provided by the present invention has a clear process, and compared with the currently common physical modification, it does not require high equipment and the required cost is reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Scanning electron micrographs of different polyetherketoneketone materials; a: PEKK; b: SP; c: SP-NH; d: SP-OH; e: SP-COOH.

[0029] Figure 2 This is the hydrophilicity test result diagram of different polyetherketoneketone materials;

[0030] Figure 3 This is a graph showing the bending strength test results of different polyetherketoneketone materials;

[0031] Figure 4 This is the shear bond strength test result of different polyetherketoneketone materials; DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0033] Example 1: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0034] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0035] S2. The pretreated polyetherketoneketone material was added to 98% concentrated sulfuric acid for sulfonation and stirred for 5 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid. The polyetherketoneketone sample was then placed in a vacuum oven at 60°C for 6 hours to obtain a sulfonated polyetherketoneketone material (denoted as SP).

[0036] S3. The sulfonated polyetherketoneketone material from S2 was added to a three-necked flask containing 60 mL of ethylenediamine. The temperature was raised to 120°C and heated for 8 hours. Nitrogen was continuously introduced during the reaction for protection. After the reaction, the material was ultrasonically cleaned in deionized water, isopropanol, and deionized water for 15 minutes each. The material was then dried in a vacuum oven to obtain a surface-amino-modified polyetherketoneketone material (denoted as SP-NH).

[0037] S4. Apply a layer of resin adhesive on the surface of the amino-modified polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 ) and observed for 160 seconds to obtain the dental material, and finally the shear bond strength test was performed using a universal testing machine.

[0038] The polyetherketoneketone material obtained in each step of Example 1 was subjected to scanning electron microscopy (SEM) testing, and the results were as follows: Figure 1 As shown in the figure, the surface of the PEEK material after grinding and polishing exhibits a highly regular and consistent morphology, with scratches on the surface caused by grinding. Within the field of view, there are no obvious surface undulations or granular protrusions. The surface of the PEEK material after sulfonation exhibits a complex and irregular porous microstructure. The pores vary in size and interconnect, forming a unique honeycomb structure. After being soaked in ethylenediamine, the surface of the PEEK material exhibits highly rough and complex morphological characteristics. The honeycomb structure caused by sulfonation disappears, and irregular protrusions and wrinkles form on the surface, reducing the pore size.

[0039] The hydrophilicity test of the polyetherketoneketone material surface obtained in each step of Example 1 was carried out, and the results were as follows: Figure 2 The polyetherketoneketone material modified by amino treatment has the lowest water contact angle, indicating that the material has the best hydrophilicity. The polyetherketoneketone material modified by sulfonation has a porous structure on the surface, which increases the relative specific surface area of ​​the material and reduces its hydrophilicity.

[0040] The mechanical strength test of the polyetherketoneketone material obtained in each step of Example 1 was carried out, and the results were as follows: Figure 3 As shown in the figure, the polished and ground PEEK material has the highest mechanical strength. The sulfonated material has a porous structure on its surface, which reduces the mechanical strength of the PEEK material. The long-term high-temperature immersion further weakens the mechanical strength of the amino-modified PEEK material.

[0041] The shear bond strength test of the polyetherketoneketone material obtained in each step of Example 1 was carried out, and the results are as follows: Figure 4 As shown, the load was applied at a crosshead speed of 1 mm / min with the bonded surfaces parallel to the loading piston. The maximum load was measured before debonding occurred. Shear bond strength values ​​were calculated using the formula = F / A, where is the shear bond strength (MPa), F is the breaking load (N), and A is the bond area (mm 2 ).

[0042] Example 2: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0043] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0044] S2. The pretreated polyetherketoneketone material was added to 98% concentrated sulfuric acid for sulfonation and stirred for 5 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid. The polyetherketoneketone sample was then placed in a vacuum oven at 60°C for 6 hours to obtain a sulfonated polyetherketoneketone material (denoted as SP).

[0045] S3. Dissolve 130 mg of sodium borohydride in 60 mL of anhydrous dimethyl sulfoxide and transfer it to a three-necked flask. Then add the polyetherketoneketone material after sulfonation in S2 to the flask. The reaction temperature is 120 ° C. Nitrogen is continuously introduced during the reaction for protection. The reaction time is 7 hours. After the reaction is completed, the polyetherketoneketone material is ultrasonically cleaned with anhydrous methanol, deionized water, dilute hydrochloric acid, deionized water, and anhydrous ethanol for 10 minutes each. The polyetherketoneketone material is then placed in a vacuum oven for drying to obtain a surface hydroxylated polyetherketoneketone material (denoted as SP-OH).

[0046] S4. Apply a layer of resin adhesive on the surface of the surface hydroxylated polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 ) and observed for 160 seconds to obtain the dental material, and finally the shear bond strength test was performed using a universal testing machine.

[0047] The polyetherketoneketone material obtained in each step of Example 2 was subjected to scanning electron microscopy (SEM) testing, and the results were as follows: Figure 1 The electron micrograph of the polished and sulfonated polyetherketoneketone sample is the same as that in Example 1. The surface of the polyetherketoneketone material reduced with sodium borohydride becomes rougher, the grooves on the surface of the material deepen, and the pore structure size becomes larger.

[0048] The hydrophilicity test of the polyetherketoneketone material surface obtained in each step of Example 2 was carried out, and the results were as follows: Figure 2 As shown in Figure 2, the hydrophilicity of the polyetherketoneketone material is greatly improved after sodium borohydride reduction.

[0049] The mechanical strength test of the polyetherketoneketone material obtained in each step of Example 2 was carried out, and the results were as follows: Figure 3 The mechanical strength of the polyetherketoneketone material after sodium borohydride reduction is lower than that of the polished polyetherketoneketone sample.

[0050] The shear bond strength test of the polyetherketoneketone material obtained in each step of Example 2 was carried out, and the results are as follows: Figure 4 As shown, the load was applied at a crosshead speed of 1 mm / min with the bonded surfaces parallel to the loading piston. The maximum load was measured before debonding occurred. Shear bond strength values ​​were calculated using the formula = F / A, where is the shear bond strength (MPa), F is the breaking load (N), and A is the bond area (mm 2 ).

[0051] Example 3: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0052] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0053] S2. The pretreated polyetherketoneketone material was added to 98% concentrated sulfuric acid for sulfonation and stirred for 5 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid. The polyetherketoneketone sample was then placed in a vacuum oven at 60°C for 6 hours to obtain a sulfonated polyetherketoneketone material (denoted as SP).

[0054] S3: Prepare a 1 mol / L acrylic acid solution with deionized water. Add the sulfonated polyetherketoneketone material from S2 to the acrylic acid solution. Use a 500W UV lamp with a wavelength of 350±50nm for UV grafting. Keep the sample at a distance of 15cm from the light for 45 minutes. After the reaction, wash the sample several times with deionized water and anhydrous ethanol to remove surface residues. Then, dry the sample in a vacuum oven to obtain a surface-carboxylated polyetherketoneketone material (denoted as SP-COOH).

[0055] S4. Apply a layer of resin adhesive on the surface of the surface carboxyl modified polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 ) and observed for 160 seconds to obtain the dental material, and finally the shear bond strength test was performed using a universal testing machine.

[0056] The polyetherketoneketone material obtained in each step of Example 3 was subjected to scanning electron microscopy (SEM) testing, and the results were as follows: Figure 1 The electron micrograph of the polished and sulfonated polyetherketoneketone sample is the same as that in Example 1. The polyetherketoneketone material grafted with acrylic acid retains the three-dimensional porous structure produced by sulfonation and forms a dense graft layer on the surface of the material.

[0057] The hydrophilicity test of the polyetherketoneketone material surface obtained in each step of Example 3 was carried out, and the results were as follows: Figure 2As shown in the figure, the polyetherketoneketone material grafted with acrylic acid has the lowest water contact angle compared to amino and hydroxylation modifications due to the extremely strong hydrophilicity of the carboxyl group.

[0058] The mechanical strength test of the polyetherketoneketone material obtained in each step of Example 3 was carried out, and the results were as follows: Figure 3 The mechanical strength of the polyetherketoneketone material after acrylic acid UV grafting is slightly reduced compared with the polishing and grinding treatment.

[0059] The polyetherketoneketone material obtained in each step of Example 3 was subjected to shear bond strength test, and the results are as follows: Figure 4 As shown, the load was applied at a crosshead speed of 1 mm / min with the bonded surfaces parallel to the loading piston. The maximum load was measured before debonding occurred. Shear bond strength values ​​were calculated using the formula = F / A, where is the shear bond strength (MPa), F is the breaking load (N), and A is the bond area (mm 2 ).

[0060] Example 4: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0061] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0062] S2. The pretreated polyetherketoneketone material was added to 95% concentrated sulfuric acid for sulfonation and stirred for 3 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid. The polyetherketoneketone sample was then placed in a vacuum oven at 60° C. for 6 hours to obtain the sulfonated polyetherketoneketone material.

[0063] S3. Add the sulfonated polyetherketoneketone (PEK) material from S2 to a three-necked flask containing 60 mL of ethylenediamine. Heat to 130°C for 8 hours, continuously introducing nitrogen for protection during the reaction. After the reaction, ultrasonically clean the material in deionized water, isopropyl alcohol, and deionized water for 15 minutes each. The material is then dried in a vacuum oven to obtain a surface-amino-modified PEEK material.

[0064] S4. Apply a layer of resin adhesive on the surface of the amino-modified polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 )Observe for 160 seconds and obtain dental materials.

[0065] Example 5: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0066] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0067] S2. The pretreated polyetherketoneketone material was added to 95% concentrated sulfuric acid for sulfonation and stirred for 6 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid on the sample. The polyetherketoneketone sample was then placed in a vacuum oven at 60° C. for 6 hours to obtain the sulfonated polyetherketoneketone material.

[0068] S3. Dissolve 110 mg of sodium borohydride in 60 mL of anhydrous dimethyl sulfoxide and transfer the mixture to a three-necked flask. Then, add the sulfonated polyetherketoneketone material from S2 to the flask. The reaction temperature is 125°C. Nitrogen is continuously introduced for protection during the reaction. The reaction time is 9 hours. After the reaction, the polyetherketoneketone material is ultrasonically cleaned with anhydrous methanol, deionized water, dilute hydrochloric acid, deionized water, and anhydrous ethanol for 10 minutes each. The polyetherketoneketone material is then placed in a vacuum oven for drying to obtain a surface-hydroxylated polyetherketoneketone material.

[0069] S4. Apply a layer of resin adhesive on the surface of the surface hydroxylated polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 )Observe for 160 seconds and obtain dental materials.

[0070] Example 6: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0071] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0072] S2. The pretreated polyetherketoneketone material was added to 98% concentrated sulfuric acid for sulfonation and stirred for 3 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid. The polyetherketoneketone sample was then placed in a vacuum oven at 60° C. for 6 hours to obtain the sulfonated polyetherketoneketone material.

[0073] S3: Prepare a 0.5 mol / L acrylic acid solution with deionized water. Add the sulfonated polyetherketoneketone (PEK) material from S2 to the acrylic acid solution. UV grafting is performed using a 400W UV lamp with a wavelength of 350±50nm. The sample is kept 10 cm from the light and illuminated for 40 minutes. After the reaction, the sample is washed several times with deionized water and anhydrous ethanol to remove surface residues. The sample is then dried in a vacuum oven to obtain a surface-carboxylated PEEK material.

[0074] S4. Apply a layer of resin adhesive on the surface of the surface carboxyl modified polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 )Observe for 160 seconds and obtain dental materials.

[0075] Example 7: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0076] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0077] S2. The pretreated polyetherketoneketone material was added to 95% concentrated sulfuric acid for sulfonation and stirred for 4 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid on the sample. The polyetherketoneketone sample was then placed in a vacuum oven at 60° C. for 6 hours to obtain the sulfonated polyetherketoneketone material.

[0078] S3. Dissolve 120 mg of sodium borohydride in 60 mL of anhydrous dimethyl sulfoxide and transfer the mixture to a three-necked flask. Then, add the sulfonated polyetherketoneketone material from S2 to the flask. The reaction temperature is 115°C. Nitrogen is continuously introduced for protection during the reaction. The reaction time is 5 hours. After the reaction, the polyetherketoneketone material is ultrasonically cleaned with anhydrous methanol, deionized water, dilute hydrochloric acid, deionized water, and anhydrous ethanol for 10 minutes each. The polyetherketoneketone material is then placed in a vacuum oven for drying to obtain a surface-hydroxylated polyetherketoneketone material.

[0079] S4. Apply a layer of resin adhesive on the surface of the surface hydroxylated polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 )Observe for 160 seconds and obtain dental materials.

[0080] Example 8: This example provides a method for preparing a dental material based on chemically modified polyetherketoneketone, which specifically comprises the following steps:

[0081] S1. Cut polyetherketone ketone (PEK) into samples with a diameter of 8 mm and a thickness of 2 mm. Polish the samples with 600-grit sandpaper. Ultrasonic clean the polished samples with acetone, anhydrous ethanol, and deionized water, sequentially for 15 minutes each. Place the cleaned samples in a vacuum oven at 50°C for 6 hours to obtain pretreated PKK material.

[0082] S2. The pretreated polyetherketoneketone material was added to 98% concentrated sulfuric acid for sulfonation and stirred for 5 minutes. After the reaction, the sulfonated polyetherketoneketone material was ultrasonically cleaned with deionized water and acetone for 10 minutes each to remove residual concentrated sulfuric acid. The polyetherketoneketone sample was then placed in a vacuum oven at 60° C. for 6 hours to obtain the sulfonated polyetherketoneketone material.

[0083] S3: Prepare a 0.8 mol / L acrylic acid solution with deionized water. Add the sulfonated polyetherketoneketone (PEK) material from S2 to the acrylic acid solution. UV grafting is performed using a 600W UV lamp with a wavelength of 350±50 nm. The sample is illuminated at a distance of 20 cm from the lamp for 50 minutes. After the reaction, the sample is washed several times with deionized water and anhydrous ethanol to remove surface residues. The sample is then dried in a vacuum oven to obtain a surface-carboxylated PKK material.

[0084] S4. Apply a layer of resin adhesive on the surface of the surface carboxyl modified polyetherketoneketone material and blow it with water-free and oil-free air until the adhesive stops flowing. Then use a light curing lamp (500mW / cm 2 ) for 10 seconds. Subsequently, a polytetrafluoroethylene (PTFE) mold with an inner diameter of 2.5 mm, a height of 2 mm, and a thickness of 1 mm was fixed on the PEKK bonding coating. To avoid bubbles in the bonding resin, dental resin was injected into the mold with a needle and then cured with a light curing lamp (500 mW / cm 2 )Observe for 160 seconds and obtain dental materials.

[0085] In summary, the embodiments of the present invention graft amino, hydroxyl or carboxyl groups onto the surface of the polyetherketoneketone material by chemical methods, which can significantly improve the shear bond strength between the polyetherketoneketone and the dental resin and increase the hydrophilicity of the material.

[0086] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing a dental material based on chemically modified polyetherketoneketone, characterized in that: The following steps are involved: The polyetherketoneketone material is sequentially subjected to sulfonation treatment to obtain a sulfonated polyetherketoneketone material; The sulfonated polyetherketoneketone material is subjected to chemical modification treatment by one or more of amination, hydroxylation and carboxylation to obtain a chemically modified polyetherketoneketone material; The dental material is obtained by filling the surface of the chemically modified polyetherketoneketone material with dental resin.

2. The method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 1, characterized in that: The method for sulfonation treatment comprises the following steps: The surface of the polyetherketoneketone material is polished and ultrasonically cleaned with deionized water, acetone and anhydrous ethanol in sequence to obtain a pretreated polyetherketoneketone material; The pretreated polyetherketoneketone material is immersed in concentrated sulfuric acid with a concentration of 95%-98% for modification treatment, and then ultrasonically cleaned with deionized water and acetone in sequence, and then vacuum dried to obtain the sulfonated polyetherketoneketone material.

3. A method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 1 or 2, characterized in that: The chemical modification treatment method of amination is: ethylenediamine is selected as a modifier, the amino group in ethylenediamine is reacted with the carbonyl group on the surface of the sulfonated polyetherketoneketone material to undergo a Schiff base reaction, the amino group is grafted onto the polyetherketoneketone material, and a surface-aminated polyetherketoneketone material is obtained.

4. The method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 3, characterized in that: The chemical modification treatment method of amination specifically comprises the following steps: Ethylenediamine is heated to 120-130° C., and then the sulfonated polyetherketoneketone material is added to carry out a Schiff base reaction. After the reaction is completed, ultrasonic cleaning is carried out with deionized water, isopropyl alcohol, and deionized water respectively, and then drying is carried out to obtain a surface-amino-modified polyetherketoneketone material.

5. The method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 1 or 2, characterized in that: The chemical modification treatment method of hydroxylation is: sodium borohydride is selected as a modifier to reduce the carbonyl groups on the surface of the sulfonated polyetherketoneketone material to hydroxyl groups, thereby obtaining a surface hydroxylated polyetherketoneketone material.

6. The method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 5, characterized in that: The chemical modification treatment method of hydroxylation specifically comprises the following steps: Sodium borohydride is dissolved in anhydrous dimethyl sulfoxide, and then the sulfonated polyetherketoneketone material is added and the temperature is raised to 115-125°C for reaction. After the reaction is completed, ultrasonic cleaning is carried out with anhydrous methanol, deionized water, dilute hydrochloric acid, deionized water, and anhydrous ethanol respectively, and then drying is carried out to obtain a surface hydroxylated modified polyetherketoneketone material.

7. A method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 1 or 2, characterized in that: The chemical modification treatment method of carboxylation is as follows: acrylic acid is selected as a modifier, and the carboxyl functional groups in the acrylic acid are grafted onto the surface of the sulfonated polyetherketoneketone material through ultraviolet light to obtain a surface carboxyl-modified polyetherketoneketone material.

8. The method for preparing a dental material based on chemically modified polyetherketoneketone according to claim 7, characterized in that: The carboxylation chemical modification treatment method specifically comprises the following steps: The sulfonated polyetherketoneketone material is added to an acrylic acid solution with a concentration of 0.5-1 mol / L, and is irradiated with an ultraviolet lamp with a power of 400-600 W and a wavelength of 350±50 nm to carry out an ultraviolet grafting reaction. After the reaction is completed, it is washed with deionized water and anhydrous ethanol respectively, and then dried to obtain a surface carboxyl-modified polyetherketoneketone material.

9. A dental material based on chemically modified polyetherketoneketone prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the chemically modified polyetherketoneketone-based dental material according to claim 9 in the preparation of tooth restoration materials.

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