Modified ceramic-based dental restoration resin and preparation method thereof

Abstract

The invention relates to the field of dental restoration materials, in particular to modified ceramic-based dental restoration resin and a preparation method thereof. Aiming at the problem of polymerization shrinkage of a current photocuring dental restoration material, photocurable acryloyl and an inorganic ceramic skeleton are combined, the material has the advantages of the two materials at the same time, the inorganic skeleton is utilized to limit molecular movement, and the photocurable acryloyl is combined to construct a high-density cross-linked network, so that the material has good biocompatibility. Curing shrinkage and internal stress and small gaps caused by curing shrinkage are reduced, it is guaranteed that the ceramic-based resin composite material can uniformly transfer stress when subjected to external force, the tensile strength and bending strength of the composite material after photocuring are improved, and moisture adsorption and monomer dissolution are reduced. On the other hand, the photocuring diluent containing a polyoxypropylene chain segment is prepared by reacting (methyl) isocyano ethyl acrylate with polyether amine, and the photocuring diluent is combined with triethylene glycol dimethacrylate to be used as the diluent, so that the hydrophilicity and the water absorption rate of the composite material can be reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of dental restoration materials, in particular to a modified ceramic base dental restoration resin and a preparation method thereof. BACKGROUND

[0002] The technical progress of dental composite materials has driven the innovation of the field of dental restoration, in which the composite materials mainly rely on the development of new organic monomers, the improvement of filler technology, the upgrading of light curing equipment and the development of high-efficiency photoinitiators, but there are still problems in the application of dental composite material technology, especially the problem of polymerization shrinkage of the current commercial bisphenol A glycidyl methacrylate (Bis-GMA-based) material in the light curing process. This shrinkage can generate significant stress at the interface between the dental tissue and the restoration, which destroys the close combination of the restoration and the tooth and can also cause microcracks in the tooth, ultimately leading to premature shedding of the restoration or secondary caries, and seriously shortening the service life of the restoration. In addition, the dental restoration needs to withstand the mechanical wear of oral mastication for a long time, and the Bis-GMA-based light-cured organic resin cannot uniformly transmit stress under external force, and the surface hardness is insufficient, so it is easy to appear surface wear and form collapse after long-term use, leading to the failure of the restoration function, causing occlusion discomfort, food impaction and other problems. The restoration also has the problem of easy water absorption and dissolution of incompletely cured monomers. Although the addition of inorganic fillers such as quartz can improve the wear resistance of the restoration, it does not significantly improve the organic-inorganic interfacial bonding force, and the dental composite material still has the problems of insufficient adhesion of inorganic fillers, high water absorption rate and high monomer dissolution rate.

[0003] On the other hand, there is a contradiction in the performance optimization of dental composite materials: increasing the content of inorganic fillers to improve strength will lead to increased viscosity and decreased flowability of the material, making it difficult to fill small cavities; increasing the diluent (such as TEGDMA) to improve the flowability of the material will exacerbate the problem of polymerization shrinkage. This contradiction in the performance optimization process further limits the clinical application scenarios of dental composite materials. SUMMARY

[0004] The purpose of the present application is to overcome the shortcomings of the prior art and to solve the problem of polymerization shrinkage in the light curing process. By combining the light-curable acryl monomer and the inorganic ceramic framework through the sol-gel method, the material can simultaneously possess the advantages of both types of materials. The inorganic framework limits molecular movement, reduces polymerization shrinkage during curing, improves the mechanical properties and hardness of the dental restoration resin, and improves the compatibility of the organic resin and the inorganic filler. The introduction of a diluent containing a polyoxypropylene segment reduces the hydrophilicity of the difunctional diluent, thereby reducing the water absorption and dissolution rates of the dental restoration resin.

[0005] To achieve the above technical purposes, the technical solutions adopted by the present application are as follows:

[0006] In a first aspect, a diacryloxy silane hybrid inorganic compound is prepared by first reacting glycidyl methacrylate with an amino silane coupling agent to obtain a diacryloxy silane, and then hybridizing the diacryloxy silane with an inorganic oxygen-containing compound or an inorganic oxide precursor.

[0007] wherein the amino silane coupling agent contains at least one primary amino group and at least one hydrolysable Si-OR group, R being selected from a hydrocarbon group of 1 to 4 carbon atoms;

[0008] Preferably, the amino silane coupling agent is selected from any one or more of 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3- aminopropylmethoxydimethylsilane, 3-aminopropylethoxydimethylsilane, N- aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and N-aminoethyl-3- aminopropylmethyldiethoxysilane.

[0009] The inorganic compound of the diacryloxy silane hybrid inorganic compound is selected from any one of silicon, aluminum, calcium, or titanium.

[0010] The inorganic oxygen-containing compound is selected from any one of an inorganic oxide or an inorganic hydroxide.

[0011] The inorganic oxide precursor is capable of hydrolyzing to form the corresponding inorganic oxide by reacting with water.

[0012] In a second aspect, a method for preparing the diacryloxy silane hybrid inorganic compound described above is provided, comprising: first reacting glycidyl methacrylate with an amino silane coupling agent to obtain a diacryloxy silane, and then hybridizing the diacryloxy silane with an inorganic oxygen-containing compound or an inorganic oxide precursor to obtain the diacryloxy silane hybrid inorganic compound.

[0013] wherein the molar ratio of glycidyl methacrylate to the amino silane coupling agent is (2-2.2): 1;

[0014] The reaction temperature of glycidyl methacrylate and the amino silane coupling agent is 60-100°C.

[0015] The molar ratio of the inorganic oxygen-containing compound or the inorganic oxide precursor to the diacryloxy silane is (0.5-2): 1.

[0016] After the hybridization reaction is completed, the diacryloxy silane hybrid inorganic compound is obtained by drying.

[0017] Preferably, after the hybridization reaction is completed, the diacryloxy silane hybrid inorganic compound is obtained by vacuum drying.

[0018] Preferably, the temperature of the vacuum drying is 40-60℃.

[0019] In a third aspect, a bifunctional reactive diluent is obtained by reacting isocyanatoethyl (meth)acrylate with a polyether amine, and includes unsaturated double bonds at both ends of the molecular chain and a chain segment wherein n is a positive integer greater than or equal to 1.

[0020] In a fourth aspect, a method for preparing the bifunctional reactive diluent described above includes reacting isocyanatoethyl (meth)acrylate with a polyether amine at room temperature to 60℃.

[0021] Preferably, the polyether amine is a polyether amine terminated with primary amino groups at both ends;

[0022] Preferably, the average molecular weight of the polyether amine is 200-500 g / mol;

[0023] More preferably, the average molecular weight of the polyether amine is 230 g / mol.

[0024] Preferably, the molar ratio of isocyanatoethyl (meth)acrylate to polyether amine is (2-2.2):1.

[0025] In a fifth aspect, the use of the bisacryloxy silane hybrid inorganic material and the bifunctional reactive diluent described above in the preparation of a dental restorative material.

[0026] In a sixth aspect, a ceramic-based dental restorative resin composition includes the bisacryloxy silane hybrid inorganic material, the reactive diluent, the filler, and the auxiliary agent described above.

[0027] Preferably, the bisacryloxy silane hybrid inorganic material is selected from a bisacryloxy silane hybrid silicon, a bisacryloxy silane hybrid aluminum, a bisacryloxy silane hybrid calcium, and a bisacryloxy silane hybrid titanium.

[0028] Preferably, the bisacryloxy silane hybrid inorganic material is selected from a bisacryloxy silane hybrid silicon, a bisacryloxy silane hybrid aluminum, a bisacryloxy silane hybrid calcium, and a bisacryloxy silane hybrid titanium.

[0029] More preferably, the bisacryloxy silane hybrid inorganic material is selected from a bisacryloxy silane hybrid silicon, a bisacryloxy silane hybrid aluminum, a bisacryloxy silane hybrid calcium, and a bisacryloxy silane hybrid titanium.

[0030] Preferably, the reactive diluent is selected from any one of the bifunctional reactive diluent described above or triethylene glycol dimethacrylate or a combination of both;

[0031] Preferably, the reactive diluent is selected from the group consisting of the above-mentioned bifunctional reactive diluent and triethylene glycol dimethacrylate.

[0032] The filler is selected from the group consisting of glass powder and white carbon black, wherein the glass powder is a powder formed by melting inorganic oxides including SiO2, B2O3, Al2O3, BaO, SrO, Na2O, etc. at high temperature to form a uniform glass liquid, then rapidly cooling and grinding; and the white carbon black is an extremely fine amorphous silica powder synthesized by a gas phase method or a precipitation method.

[0033] Preferably, the white carbon black is a fumed white carbon black.

[0034] Preferably, the glass powder is selected from the group consisting of barium glass powder, strontium glass powder, strontium boron aluminum silicate glass, and barium aluminum silicate glass, alone or in combination.

[0035] The auxiliary agent includes one or more combinations of an initiator, a co-initiator, a polymerization inhibitor, a heat stabilizer, and a UV stabilizer.

[0036] The initiator is selected from the group consisting of camphorquinone, 1-phenyl-1,2-propanedione, and benzophenone-1,3-dioxane, alone or in combination.

[0037] The co-initiator is selected from the group consisting of 4-(dimethylamino)phenethyl alcohol, 1,3-benzodioxolane, piperonyl alcohol, and N-phenyl glycine, alone or in combination.

[0038] The polymerization inhibitor is selected from the group consisting of 4-methoxyphenol, hydroquinone, and tert-butyl hydroquinone, alone or in combination.

[0039] The heat stabilizer is selected from the group consisting of hindered phenol heat stabilizers.

[0040] Preferably, the hindered phenol heat stabilizer is 2,6-di-tert-butyl-4-methylphenol.

[0041] The UV stabilizer is selected from the group consisting of benzophenone UV stabilizers.

[0042] Preferably, the benzophenone UV stabilizer is 2-hydroxy-4-methoxybenzophenone.

[0043] Further, the ceramic-based dental restoration resin composition includes, by weight parts, 40-60 parts of the above-mentioned bisacryloxy silane hybrid inorganic substance, 30-50 parts of a reactive diluent, 240-300 parts of a filler, and 0.2-1.0 parts of an auxiliary agent.

[0044] When the filler content is less than 240 parts, the mechanical strength and hardness of the cured repair resin are obviously insufficient; when the filler content is more than 300 parts, the content of the active diluent is relatively insufficient, the viscosity of the resin system is too high, and the photocuring is difficult to perform, and the completion of photocuring time is more than 180s. Therefore, when the filler content is 240-300 parts, the balance of the comprehensive performance of the cured repair resin can be achieved.

[0045] Preferably, the filler includes glass powder 220-250 parts and white carbon black 20-40 parts;

[0046] Preferably, the auxiliary agent includes initiator 0.2-0.4 parts, co-initiator 0.1-0.3 parts, polymerization inhibitor 0.005-0.02 parts, heat stabilizer 0.005-0.02 parts and UV stabilizer 0.005-0.02 parts;

[0047] Preferably, the bis-acryloxy silane hybrid inorganic substance includes bis-acryloxy silane hybrid silicon 15-45 parts, bis-acryloxy silane hybrid aluminum 5-15 parts, bis-acryloxy silane hybrid calcium 5-15 parts and bis-acryloxy silane hybrid titanium 5-15 parts.

[0048] In a seventh aspect, a ceramic-based dental repair resin cured product is obtained by uniformly mixing the above-mentioned ceramic-based dental repair resin composition and performing photocuring using an LED light source.

[0049] Preferably, the light intensity of the LED light source is not less than 300mW / cm 2 ;

[0050] Preferably, the photocuring time is 60-300s.

[0051] More preferably, the photocuring time is 60-180s.

[0052] Still more preferably, the photocuring time is 90-180s.

[0053] In an eighth aspect, the above-mentioned ceramic-based dental repair resin cured product is applied in the preparation of dental adhesive, dental restoration and pit and fissure sealant.

[0054] The beneficial effects of the technical solutions proposed in the present application are: in view of the problem of polymerization shrinkage of the current photocured dental repair material, the photocurable acryl group is combined with the inorganic framework through the sol-gel method, wherein the bis-acryloxy silane hybrid silicon is the core of the organic-inorganic hybrid network, and the rest of the bis-acryloxy silane hybrid aluminum, bis-acryloxy silane hybrid calcium and bis-acryloxy silane hybrid titanium are optional, which are used to further adjust the specific performance of the dental repair material.

[0055] The inorganic framework restricts the movement of the photocurable monomer molecules, reduces the curing shrinkage and the internal stress and small voids caused by the curing shrinkage, ensures that the ceramic matrix resin composite can uniformly transmit stress when subjected to external force, improves the tensile strength and bending strength of the composite after photocuring, and reduces water absorption and monomer dissolution.

[0056] On the other hand, in order to solve the problem of high hydrophilicity of the photocuring diluent containing a polyoxyethylene segment, a photocuring diluent containing a polyoxypropylene segment is prepared by reacting isocyanatoethyl (meth)acrylate with a polyether amine, and the photocuring diluent combined with triethylene glycol dimethacrylate as a diluent can reduce the hydrophilicity and water absorption of the composite. BRIEF DESCRIPTION OF DRAWINGS

[0057] In order to more clearly illustrate the technical solutions in the embodiments of the present application, more completely understand the present application and its beneficial effects, the drawings needed to be used in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0058] Figure 1 Infrared spectrum of the bisacryloyloxy silane hybrid inorganic material prepared in Example 2-5. DETAILED DESCRIPTION

[0059] The technical solutions in the embodiments will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application. It should be noted that the terms used herein are only for describing the specific embodiments, and are not intended to limit the exemplary embodiments according to the present application. As used herein, the singular form is intended to include the plural form unless the context clearly indicates otherwise, and it should be understood that when the terms "comprise" and / or "include" are used in the specification, there is a feature, step, operation, device, component and / or combination thereof.

[0060] If the specific conditions of the experiments are not specified in the embodiments, they are usually in accordance with the conventional conditions in the art, or in accordance with the conditions recommended by the reagent company; the materials, reagents and the like used in the embodiments can be obtained by commercial means, unless otherwise specified.

[0061] Unless otherwise stated or contradictory, the terms or phrases used in this text have the following meanings:

[0062] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

[0063] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0064] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0065] In this application, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions containing the listed features.

[0066] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the aforementioned numerical intervals are considered continuous and include the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In this document, this is equivalent to directly listing every integer. For example, if t is an integer selected from 1 to 10, it means that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0067] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0068] In this application, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass-volume percentage.

[0069] All references to documents mentioned in this application are incorporated herein by reference as if each document were individually incorporated herein by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, all cited documents are incorporated herein by reference in their entirety and for all purposes. When citing documents in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When citing documents in this application, examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.

[0070] Example 1

[0071] Synthesis and characterization of bisacryloyloxysilane. Using γ-aminopropyltriethoxysilane (KH550) and glycidyl methacrylate (GMA) as starting materials, 55.34 g (0.25 mol) of KH550 and 74.0 g (0.52 mol) of GMA were added to a four-necked flask, followed by the addition of 0.01 g of methoxyphenol as a polymerization inhibitor. The mixture was heated to 60 °C and stirred for 2 hours under nitrogen protection, then heated to 80 °C and stirred for another 3 hours. The reaction endpoint was determined by trifluoroethanol-hydrochloric acid potentiometric titration, where the amino content in the reaction mixture was below 0.2 mg KOH / g.

[0072] Structural characterization of the reaction products 1 H-NMR(CDCl3): δ0.98-1.09(2H,m),1.32(9H,m),1.70-1.91(8H,m),2.06-2.21(4H,m),2.84(2H,dd,J=2.67,2.67Hz),3.39(6 H,q,J=6.91Hz), 4.28(4H,dd,J=7.11,7.11Hz), 4.47(2H,dd,J=2.67,2.67Hz), 5.55(2H,d,J=3.86Hz), 6.05(2H,d,J=3.86Hz).

[0073] 13 C-NMR(CDCl3): δ9.0,18.5(5C),29.4,33.1(2C),52.8,58.4(3C),63.7(2C),111.6(2C),125.6(2C),136.1(2C),167.3(2C).

[0074] Therefore, the chemical structural formula of bisacryloyloxysilane is confirmed as follows:

[0075] Example 2

[0076] Synthesis of bisacryloyloxysilane hybrid silicon. 50.6 g (0.1 mol) of the bisacryloyloxysilane prepared in Example 1, 0.3 mol of deionized water, and 12 mL of 5 mol / L hydrochloric acid were added to a beaker and stirred at room temperature for 12 hours. After aging and standing for 24 hours, the pH of the system was adjusted to 7.5-8.0 using ammonia. Then, 6 g of hydrophilic 200 hydrophilic fumed silica (Shanghai Aladdin) was added, and the mixture was stirred at room temperature for another 4 hours. Finally, it was vacuum dried at 45°C for 6 hours to obtain a white solid.

[0077] Example 3

[0078] Synthesis of bisacryloyloxysilane hybrid aluminum. Using bisacryloyloxysilane prepared in Example 1 as raw material, the initial hydrolysis process was the same as in Example 2. After aging and standing for 24 hours, the pH of the system was adjusted to 8.0-8.5 with ammonia water, and then 7.8 g of aluminum hydroxide was added. After stirring at room temperature for 4 hours, the mixture was dried under vacuum at 50°C for 8 hours to obtain a white solid.

[0079] Example 4

[0080] Synthesis of bisacryloyloxysilane hybrid calcium. Using bisacryloyloxysilane prepared in Example 1 as raw material, the initial hydrolysis process was the same as in Example 2. After aging and standing for 24 hours, the pH of the system was adjusted to 8.0-8.5 with sodium hydroxide, and then 7.4 g of calcium hydroxide was added. After stirring at room temperature for 4 hours, the mixture was dried under vacuum at 50°C for 8 hours to obtain a white solid.

[0081] Example 5

[0082] Synthesis of bisacryloyloxysilane hybrid titanium. Using bisacryloyloxysilane prepared in Example 1 as raw material, the initial hydrolysis process was the same as in Example 2. After aging and standing for 24 hours, the pH of the system was adjusted to 8.0-8.5 with sodium hydroxide, and then 17g of tetrabutyl titanate was added. After stirring at room temperature for 4 hours, the mixture was dried under vacuum at 60°C for 8 hours to obtain a white solid.

[0083] Example 6

[0084] Synthesis of bisacryloyloxy polyetheramine diluent. 62 g (0.4 mol) of isocyanate methacrylate and 46 g of polyetheramine D230 (BASF). EC 301) was reacted at 40°C for 3 hours. The reaction ended when the characteristic peak of the reaction mixture at 2250-2260 cm⁻¹ disappeared, as determined by infrared spectroscopy. The structure of the product was characterized as follows, which proves that the isocyanate group NCO reacts with the amino group NH₂ to introduce polyoxypropylene segments and polymerizable acryloyloxy groups into the molecule.

[0085] 1H-NMR(CDCl3): δ1.08-1.30(9H,m),1.80-1.99(10H,m),3.10-3.25(4H,m),3.43( 2H,d,J=6.17Hz), 3.50(2H,d,J=7.13Hz), 3.60(2H,d,J=3.01Hz), 3.68(1H,qdd,J= 6.17,6.17,6.17Hz),3.76(1H,qdd,J=6.17,3.01,3.01Hz),4.05(1H,ddq,J=7.13, 7.13, 6.63Hz), 4.25-4.41 (4H, m), 5.55 (2H, d, J = 3.87Hz), 6.05 (2H, d, J = 3.87Hz).

[0086] Preparation of ceramic-based dental restorative resins

[0087] The raw materials for the ceramic-based dental restorative resins of Examples 7-14 and Comparative Examples 1-2, by weight, are specifically listed in Table 1. The proportions of the initiator camphorquinone, co-initiator 4-(dimethylamino)phenylethanol, polymerization inhibitor 4-methoxyphenol, UV stabilizer 2-hydroxy-4-methoxybenzophenone, heat stabilizer 2,6-di-tert-butyl-4-methylphenol, filler barium aluminum silicate glass powder, and filler silica were kept constant at 0.25, 0.15, 0.01, 0.01, 0.01, 240, and 30 parts by weight, respectively. The fillers selected were barium aluminum silicate glass powder GM31684 (Schott) and fumed silica (Zhejiang Fujit).

[0088] Table 1

[0089]

[0090] The specific preparation method and curing process include: adding relevant initiators, co-initiators, inhibitors, ultraviolet stabilizers and heat stabilizers to 50 parts of the hybrid bisacryloyloxysilane prepared in Examples 2-5 and the difunctional photocurable diluent TEGDMA and / or the polyether amine diluent prepared in Example 6, and mixing them evenly to obtain a resin mixture. Then, the resin mixture is ground and mixed with barium aluminum silicate glass powder and fumed silica in a mortar to obtain a paste.

[0091] A cylindrical mold with a diameter of 6 mm and a thickness of 3 mm was used to fill the above-mentioned paste into the mold, followed by a light intensity of 320 mW / cm². 2 The LED light source illuminates both sides of the sample for 90 seconds to complete the curing process.

[0092] Using a 25mm×2mm×2mm rectangular mold, fill the mold with the above paste, and then use a light intensity of 320mW / cm². 2The LED light source illuminates both sides of the sample for 180 seconds to complete the curing process.

[0093] Using a cylindrical mold with a diameter of 10 mm and a thickness of 2 mm, the above-mentioned paste was filled into the mold, and then light intensity of 320 mW / cm was applied. 2 The LED light source illuminates both sides of the sample for 90 seconds to complete the curing process.

[0094] Test section

[0095] Tensile strength testing was performed by stretching cylindrical molds with a diameter of 6 mm and a thickness of 3 mm prepared in different embodiments using a universal testing machine. The relevant fracture load P (N) was recorded, and the tensile strength was calculated based on the fracture load P. The crosshead speed during the stretching process was 10 mm / min.

[0096] The formula for calculating tensile strength TS is:

[0097]

[0098] The parameters in the formula are defined as follows: P is the fracture load (N), D is the sample diameter (mm), and L0 is the sample thickness (mm).

[0099] Bending strength testing was performed using a universal testing machine to determine the bending strength of cured 25mm×2mm×2mm strip-shaped molds prepared in different embodiments, with the crosshead speed set to 1mm / min. The specimen was placed horizontally on an aluminum platform plate, with two 2mm diameter metal support rods underneath, 20mm apart at their centers. The bending load was applied at the midpoint of the specimen. The fracture load F(N) at which the specimen broke was recorded, and the bending strength (FS) was calculated from the fracture load F(N) using the following formula:

[0100]

[0101] The parameters in the formula are defined as follows: F = fracture load (N), L = span between the two support rods on the base plate (mm), b = specimen width (mm), d = specimen height (mm).

[0102] The hardness test of the cured product was used to measure the Vickers hardness of both sides of the cured product of a cylindrical mold with a diameter of 6 mm and a thickness of 3 mm prepared in different embodiments. Before the hardness test, the sample surface was polished with 800-grit silicon carbide sandpaper.

[0103] Water absorption and dissolution rate tests were conducted on cured cylindrical molds with a diameter of 10 mm and a thickness of 2 mm prepared in different embodiments. Before testing, the sample surface was polished with 800-mesh silicon carbide sandpaper and dried in a vacuum desiccator at 37°C until constant weight, recorded as W1. The sample was then immersed in distilled water at 37°C for 168 hours. After immersion, the surface moisture was wiped off and the sample was weighed, recorded as W2. The sample was then dried in a vacuum desiccator at 37°C until constant weight, recorded as W3. The water absorption rate (WS, μg / mm3) and dissolution rate (S, μg / mm3) were calculated using the following formulas:

[0104]

[0105] The parameters in the formula are defined as follows: W1: initial dry weight (μg), W2: weight after soaking in distilled water (μg), W3: final dry weight (μg), V: sample volume (mm²). 3 ).

[0106] The test results are listed in Table 2.

[0107] Table 2

[0108] Test performance Tensile strength (MPa) Flexural strength (MPa) Vickers hardness (kg / mm 2 ) Water absorption (μg / mm 3 )]]> Dissolution rate (pg / mm 3 )]]> Example 7 37.4 60.2 67.3 34.0 6.5 Example 8 35.7 61.6 68.5 31.6 6.3 Example 9 35.2 62.3 69.7 28.4 6.3 Example 10 34.9 62.5 63.0 36.5 7.7 Example 11 34.3 61.8 68.2 33.9 7.2 Example 12 35.8 61.1 64.6 34.5 8.5 Example 13 36.0 59.7 65.1 32.7 6.0 Example 14 33.6 58.9 64.2 35.8 8.9 Comparative Example 1 28.1 57.4 56.9 42.4 11.4 Comparative Example 2 25.6 54.3 50.2 46.5 12.2

[0109] Analysis of the data in Table 2 shows that the modified ceramic-based dental restorative resins prepared by light curing in Examples 7-14 have better mechanical strength, higher surface hardness, and lower water absorption and dissolution rates. Specifically, the bisacryloyloxysilane hybrid silicon prepared in Example 2 organically combines curable acryloyl groups and Si-OR groups. The Si-OR groups act as an interfacial compatibilizer, coupling with the inorganic filler through hydrolysis-condensation, thereby tightly binding the inorganic components of the modified ceramic-based dental restorative resin with the light-curable organic components, restricting molecular chain slippage. Simultaneously, it reduces curing shrinkage and the internal stress and fine voids caused by curing shrinkage, ensuring that the resin material can uniformly transmit stress when subjected to external forces, thus improving the tensile and flexural strength of the resin after light curing and reducing water adsorption and monomer dissolution.

[0110] In addition, the bifunctional polyether amine diluent prepared in Example 6 was introduced to partially replace the bifunctional TEGDMA diluent. Hydrophobic side methyl groups were added to the hydrophilic ether bond (-O-), thereby disrupting the regularity of the molecular chain and shielding the ability of the ether bond to form hydrogen bonds with water molecules, thereby reducing the overall hydrophilicity and water absorption of the repair resin after curing.

[0111] Comparing the test results of Examples 7-14 in Table 2, it can be seen that the bisacryloyloxysilane hybrid silicon prepared in Example 2, as the core of the organic-inorganic hybrid network, plays a leading role in improving mechanical properties and reducing water absorption. Based on this, further introduction of bisacryloyloxysilane hybrid aluminum, calcium, or titanium further regulates and optimizes the mechanical properties, hardness, water absorption, and dissolution rate of the cured repair resin. Notably, Example 14 did not use the hybrid bisacryloyloxysilane prepared in Examples 3-5 at all; it used only the bisacryloyloxysilane hybrid silicon prepared in Example 2, and the corresponding effect was lower compared to Examples 7-13.

[0112] Comparative Example 1 uses Bis-GMA instead of the bisacryloyloxysilane hybrid silicon prepared in Example 2, and uses the hybrid bisacryloyloxysilane prepared in Examples 3-5. Comparative Example 2 uses Bis-GMA instead of the bisacryloyloxysilane hybrid silicon prepared in Example 2 and the hybrid bisacryloyloxysilane prepared in Examples 3-5. The mechanical properties and Vickers hardness of the modified ceramic-based dental restorative resins corresponding to Comparative Examples 2-3 are significantly reduced compared with Examples 7-14, while the water absorption and dissolution rates are significantly increased.

[0113] Finally, it should be noted that the above-described embodiments are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be pointed out that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. Furthermore, it should be understood that after reading the above teachings of this application, those skilled in the art can make various alterations or modifications to this application, and the equivalent forms obtained also fall within the scope of protection of this application. It should also be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A bis-acryloyloxy silane hybrid inorganic material, characterized by, The glycidyl (meth)acrylate is first reacted with an amino silane coupling agent to obtain a bis-acryloyloxy silane, and then the bis-acryloyloxy silane is hybridized with an inorganic oxygen-containing compound or an inorganic oxide precursor to obtain a bis-acryloyloxy silane hybrid inorganic compound; The amino silane coupling agent contains at least one primary amino group and at least one hydrolysable Si-OR group, and R is selected from a hydrocarbon group with 1 to 4 carbon atoms; The inorganic compound of the bis-acryloyloxy silane hybrid inorganic compound is selected from any one of silicon, aluminum, calcium or titanium; The inorganic oxygen-containing compound is selected from any one of inorganic oxide or inorganic hydroxide; The inorganic oxide precursor can be hydrolyzed to form the corresponding inorganic oxide by reacting with water.

2. A method for preparing the bisacryloyloxysilane hybrid inorganic compound according to claim 1, characterized by, The glycidyl (meth)acrylate is first reacted with an amino silane coupling agent to obtain a bis-acryloyloxy silane, and then the bis-acryloyloxy silane is hybridized with an inorganic oxygen-containing compound or an inorganic oxide precursor to obtain a bis-acryloyloxy silane hybrid inorganic compound; The molar ratio of the glycidyl (meth)acrylate to the amino silane coupling agent is (2-2.2):1; The reaction temperature of the glycidyl (meth)acrylate and the amino silane coupling agent is 60-100℃; The molar ratio of the inorganic oxygen-containing compound or the inorganic oxide precursor to the bis-acryloyloxy silane is (0.5-2):1; After the hybridization reaction is completed, the bis-acryloyloxy silane hybrid inorganic compound is obtained after drying.

3. A dual functionality reactive diluent characterized in that, obtained by reacting isocyanatoethyl (meth)acrylate with a polyether amine, including unsaturated double bonds at both ends of the molecular chain and a chain segment including wherein n is a positive integer greater than or equal to 1.

4. A method for preparing the bifunctional reactive diluent according to claim 3, comprising reacting isocyanatoethyl (meth)acrylate with a polyether amine at room temperature to 60℃.

5. Use, characterized in that, The bis-acryloyloxy silane hybrid inorganic compound according to claim 1 and the bifunctional reactive diluent according to claim 3 are used in the preparation of a dental restorative material.

6. A ceramic dental restorative resin composition, characterized by, The composition comprises the bis-acryloyloxy silane hybrid inorganic compound according to claim 1, a reactive diluent, a filler and an auxiliary agent; The bis-acryloyloxy silane hybrid inorganic compound is selected from a bis-acryloyloxy silane hybrid silicon; The reactive diluent is selected from any one or both of the bifunctional reactive diluent according to claim 3 or triethylene glycol dimethacrylate; The filler is selected from glass powder and white carbon black; The auxiliary agent comprises one or more of an initiator, a co-initiator, a polymerization inhibitor, a thermal stabilizer and a UV stabilizer; Further, the ceramic-based dental restorative resin composition comprises, in parts by weight, 40-60 parts of the bis-acryloyloxy silane hybrid inorganic compound, 30-50 parts of the reactive diluent, 240-300 parts of the filler and 0.2-1.0 parts of the auxiliary agent.

7. The ceramic core dental restorative resin composition according to claim 6, wherein The bis-acryloyloxy silane hybrid inorganic compound is selected from any one or more combinations of a bis-acryloyloxy silane hybrid silicon, a bis-acryloyloxy silane hybrid aluminum, a bis-acryloyloxy silane hybrid calcium and a bis-acryloyloxy silane hybrid titanium; The reactive diluent is selected from any one or both of the bifunctional reactive diluent and triethylene glycol dimethacrylate; The initiator is selected from any one or more combinations of camphorquinone, 1-phenyl-1,2-propanedione and benzophenone p-1,3-dioxane. And / or, the co-initiator is selected from one or more of 4-(dimethylamino)benzyl alcohol, 1,3-benzodioxolane, piperonyl alcohol and N-phenylglycine; And / or, the polymerization inhibitor is selected from one or more of 4-methoxyphenol, hydroquinone and tert-butyl hydroquinone; And / or, the heat stabilizer is selected from hindered phenolic heat stabilizers; And / or, the UV stabilizer is selected from benzophenone UV stabilizers.

8. The ceramic core dental restorative resin composition according to claim 6, wherein The filler includes glass powder 220-250 parts and white carbon black 20-40 parts; And / or, the auxiliary agent includes initiator 0.2-0.4 parts, co-initiator 0.1-0.3 parts, polymerization inhibitor 0.005-0.02 parts, heat stabilizer 0.005-0.02 parts and UV stabilizer 0.005-0.02 parts; And / or, the bis-acryloxy silane hybrid inorganic material includes bis-acryloxy silane hybrid silicon 15-45 parts, bis-acryloxy silane hybrid aluminum 5-15 parts, bis-acryloxy silane hybrid calcium 5-15 parts and bis-acryloxy silane hybrid titanium 5-15 parts.

9. A ceramic dental restoration resin cure characterized by, The ceramic dental restoration resin composition according to any one of claims 6-8 is mixed uniformly and then light cured using an LED light source to obtain; The light intensity of the LED light source is not less than 300 mW / cm 2 ; The light curing time is 60-300 seconds.

10. Use, characterized in that, The use of the ceramic dental restoration resin cured product according to claim 9 in the preparation of dental adhesives, dental restoratives and pit and fissure sealants. The use of the ceramic dental restoration resin cured product according to claim 9 in the preparation of dental adhesives, dental restoratives and pit and fissure sealants.

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