Disclosure of Invention
The invention aims to provide a high-biocompatibility bio-based antibacterial dental restorative material which has the characteristics of long-acting antibacterial effect, high biocompatibility, low preparation process cost, stable quality, good mechanical property and the like.
In order to realize the aim, the invention provides a high-biocompatibility bio-based antibacterial dental prosthetic material and a preparation method thereof. The dental prosthetic material comprises a first monomer, a second monomer, a filler and a catalyst; the catalyst is prepared from a first monomer, a second monomer and a filler, wherein the first monomer is 5', 5-diallyl-2, 2' -biphenol, the second monomer is pentaerythritol tetramercapto acetate, the filler is tetraene silane, and the catalyst is 2-isopropyl thioxanthone.
As a further improvement of the invention, the mass part ratio of the first monomer, the second monomer, the filler and the catalyst is 38-45: 55-62: 20-40: 1-3.
A method for preparing the high-biocompatibility bio-based antibacterial dental restorative material, which comprises the following steps:
s1, stirring and mixing the 5', 5-diallyl-2, 2' -biphenol and the pentaerythritol tetramercapto acetate at 110 ℃ to completely dissolve the compounds;
s2, adding the 2-isopropyl thioxanthone into the mixed solution obtained in the step S1, and stirring until the 2-isopropyl thioxanthone is completely dissolved;
s3, adding the tetraene silane into the S2 mixed solution, and uniformly stirring to obtain a mixed solution;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
As a further improvement of the invention, the white or yellow viscous bio-based antibacterial dental restorative material with high biocompatibility needs to be subjected to photocuring treatment during application.
As a further improvement of the invention, the light curing treatment is to irradiate for 5-10 min by adopting a light source with the wavelength of 200-500 nm.
As a further improvement of the invention, the stirring speed is 200-400 r/min.
The invention has the beneficial effects that:
1. the invention provides a high-biocompatibility bio-based antibacterial dental restoration material and a preparation method thereof, the material is prepared by taking 5', 5-diallyl-2, 2' -biphenol and pentaerythritol tetramercaptoacetate as reactants, tetraene silane as a filler and 2-isopropyl thioxanthone as a catalyst through addition polymerization, and the material is applied by photocuring treatment under a light source. Wherein the 5', 5-diallyl-2, 2' -biphenol is plant extract, has pharmacological effects of resisting inflammation, bacteria, pathogenic microorganism, ulcer and oxidation, and can be used for treating acute enteritis, bacillary dysentery, amebic dysentery, chronic gastritis, etc. In the aspect of antibacterial action, the 5', 5-diallyl-2, 2' -biphenol has obvious antibacterial activity on gram-positive bacteria, acid-resistant bacteria and filamentous fungi, has more obvious antibacterial action on streptococcus mutans, and has the strongest inhibition effect on staphylococcus. In addition, the compound is thiol-ene click reaction, and phenolic hydroxyl does not participate in the reaction in the curing process, so that the dental material after curing still has antibacterial capability, and therefore, the bio-based antibacterial material prepared by using 5', 5-diallyl-2, 2' -biphenol has long-acting antibacterial and antibacterial effects when being used as a dental restoration material, the service life is prolonged, and beneficial effects on stomach diseases and oral diseases are achieved.
2. In the preparation process of the material, tetraene silane is added to replace the conventional silicon dioxide SiO2Inorganic filler, the vinyl on the tetraene silane can be polymerized with the mercapto on the pentaerythritol tetramercaptoacetate by addition, and the chemical connection effect is realized, so that the resin and the filler are bondedThe binding capacity is greatly increased. In addition, the addition of the tetraethylene silane can increase the hardness and the wear resistance of the teeth, so that the mechanical property is good, the quality is stable, the implanted teeth are easy to clean and brush, and the appearance of the teeth is bright and white.
3. The dental restorative material prepared from the natural biomass compound 5', 5-diallyl-2, 2' -biphenol used in the invention has excellent biocompatibility, is applied to the dental restorative material, has low manufacturing process cost, and solves the risk of toxicity caused by long-term retention of other chemical synthesis light-cured dental resin materials in human bodies.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the objects, advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
A high-biocompatibility bio-based antibacterial dental restorative material comprises a first monomer, a second monomer, a filler and a catalyst; wherein the first monomer is 5', 5-diallyl-2, 2' -biphenol, the second monomer is pentaerythritol tetramercaptoacetate, the filler is tetraethenylsilane, and the catalyst is 2-isopropyl thioxanthone. The mass part ratio of the first monomer to the second monomer to the filler to the catalyst is 38-45: 55-62: 20-40: 1-3.
Specifically, a network polymer obtained by photocuring a high-biocompatibility bio-based antibacterial dental restorative material under a lighting condition, wherein the molecular structural formula of the dental restorative material after curing is as follows:
the reaction equation of photocuring of a high-biocompatibility bio-based antibacterial dental restorative material is as follows:
a preparation method of a high-biocompatibility bio-based antibacterial dental prosthetic material comprises the following steps:
s1, stirring and mixing 5', 5-diallyl-2, 2' -biphenol and pentaerythritol tetramercapto acetate at 110 ℃, wherein the stirring speed is 200-400 r/min, so that the 5', 5-diallyl-2, 2' -biphenol and pentaerythritol tetramercapto acetate are completely dissolved, and the mass part ratio of the 5', 5-diallyl-2, 2' -biphenol to the pentaerythritol tetramercapto acetate is 38-45: 55-62;
s2, adding 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved, wherein the mass part ratio of the 2-Isopropyl Thioxanthone (ITX) to the S1 mixed solution is 1-3: 100;
s3, adding tetraene silane into the S2 mixed solution, wherein the mass part ratio of the tetraene silane to the S2 mixture is 20-40: 100;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restoration material;
wherein, the white or yellow viscous high-biocompatibility bio-based antibacterial dental restoration material needs to be subjected to photocuring treatment when in application; the light curing treatment is to irradiate for 5-10 min by adopting a light source with a wavelength of 200-500 nm.
In particular, the high-biocompatibility bio-based antibacterial material is used for preparing dental prosthetic materials, and 5', 5-diallyl-2, 2' -biphenol has pharmacological effects of anti-inflammation, antibiosis, pathogenic microorganism resistance, ulcer resistance, oxidation resistance and the like as a medicament, and is commonly used for treating acute enteritis, bacillary or amoebic dysentery, chronic gastritis and the like. In the aspect of antibacterial action, the 5', 5-diallyl-2, 2' -biphenol has obvious antibacterial activity on gram-positive bacteria, acid-resistant bacteria and filamentous fungi, has more obvious antibacterial action on streptococcus mutans, and has the strongest inhibition effect on staphylococcus. In addition, the compound is thiol-ene click reaction, and phenolic hydroxyl does not participate in the reaction in the curing process, so that the dental material after curing still has antibacterial capability, and therefore, the bio-based antibacterial material prepared by using 5', 5-diallyl-2, 2' -biphenol or derivatives thereof has long-acting antibacterial and antibacterial effects when being used as a dental restoration material, prolongs the service life, and has beneficial effects on stomach diseases and oral diseases.
Adding tetraene silane to replace conventional silicon dioxide SiO2Inorganic filler, vinyl on tetraene silane can carry out addition polymerization with the hydrosulfide group on pentaerythritol tetramercaptoacetate, and a chemical connection effect is achieved, so that the binding capacity of resin and filler is greatly increased. In addition, the addition of the tetraethylene silane can increase the hardness and the wear resistance of the teeth, so that the mechanical property is good, the quality is stable, the implanted teeth are easy to clean and brush, and the appearance of the teeth is bright and white.
The 5', 5-diallyl-2, 2' -biphenol used in the invention is a natural biomass compound, and the material prepared by using the 5', 5-diallyl-2, 2' -biphenol has excellent biocompatibility, and when the material is applied to a dental prosthetic material, the manufacturing process cost is low, and the risk that other chemical synthesis light-cured dental resin materials are retained in a human body for a long time to generate toxicity is solved.
Example 1
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 1 of the invention comprises the following steps:
s1, stirring and mixing 3.8g of 5', 5-diallyl-2, 2' -biphenol and 6.2g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 100mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the ITX is completely dissolved;
s3, adding 2g of tetraene silane into the mixed solution obtained in the step S2 and uniformly stirring;
s4, removing bubbles in the mixed solution obtained in the step S3 in vacuum at 110 ℃ to obtain the white or yellow viscous bio-based antibacterial dental restorative material with high biocompatibility.
The dental restorative material obtained in example 1 was coated on a teflon plate and exposed to ultraviolet light having a wavelength of 365nm for 10min to cure the dental material, and then the cured dental restorative material was characterized as follows.
Referring to FIGS. 1-2, FIG. 2 is an infrared spectrum of the bio-based antibacterial dental restorative material prepared in example 1, from which it can be seen that 1635cm after polymerization of the reactants
-1Of
Characteristic peak sum 2571cm
-1Of
The characteristic peak disappeared at 1134.71cm
-1Appear
Characteristic peaks prove the successful synthesis of the bio-based antibacterial material. The structural formula of the material after curing is shown as figure 1:
FIG. 4 is a graph showing the results of CCK-8 assay on the activity of L929 cells in examples 1 and 2 and a blank control group according to the present invention. The relative cell survival rate of 24h in example 1 is 98.65%, which proves that the bio-based antibacterial material of the invention has very excellent cell compatibility and can be applied to dental prosthetic materials.
Example 2
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 2 of the invention comprises the following steps:
s1, stirring and mixing 4.5g of 5', 5-diallyl-2, 2' -biphenol and 5.5g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 300mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved;
s3, adding 4g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
The dental restorative material obtained in example 2 was coated on a teflon plate and exposed to ultraviolet light having a wavelength of 365nm for 10min to cure the dental material, and then the cured dental restorative material was characterized as follows.
Referring to FIG. 3, FIG. 3 is a chart showing an infrared spectrum of the bio-based antibacterial material prepared in example 2, from which it can be seen that 1635cm after polymerization of reactants
-1Of
Characteristic peak sum 2571cm
-1Of
The characteristic peak disappeared at 1134.99cm
-1Appear
Characteristic peaks prove the successful synthesis of the bio-based antibacterial material.
FIG. 4 is a graph showing the results of CCK-8 assay on the activity of L929 cells in examples 1 and 2 and a blank control group according to the present invention. The relative cell survival rate of 24h in example 2 is 99.16%, which proves that the bio-based antibacterial material of the invention has excellent cell compatibility and can be well applied to dental restorative materials.
Comparative example 1
Comparative example 1 is a blank control group, which is a pure bacterial solution cultured at 37 ℃ for 24 hours and the absorbance thereof was measured by ultraviolet-visible spectrophotometry.
Comparative example 2
Comparative example 2 is a glass ionomer cement group, which is a commercially available glass ionomer cement dental material and pure bacterial liquid cultured at 37 ℃ for 24 hours, and the absorbance thereof was measured by uv-vis spectrophotometry.
Referring to FIG. 5, FIG. 5 is a graph showing the results of measuring the absorbance of the co-cultured bacterial suspension by UV-visible spectrophotometry in examples 1-2 and comparative examples 1-2. The bacteria used for testing is staphylococcus aureus, and the mass ratio of the tested bacterial liquid to the dental restoration material is 200: 1. The experimental method comprises the following steps: the bio-based antibacterial material prepared in the above example 1-2 was co-cultured with staphylococcus aureus liquid for 24 hours at 37 ℃, and the absorbance of the solution at 600nm wavelength, i.e., the cell density OD600 of the cells, was measured by uv-vis spectrophotometry, and the bacteriostatic rate was calculated. In the figure, comparative example 1 is a blank control group, which is a pure bacterial solution cultured at 37 ℃ for 24 hours, and the OD600 value is measured by an ultraviolet-visible spectrophotometry method; comparative example 2 OD600 value after 24h of coculture of the dental restorative material of glass ion cement and pure bacteria solution in the group of glass ion cement; in the figure, data of examples 1-2 are OD600 values measured by UV-Vis spectrophotometry after coculture of the dental restorative materials prepared in examples 1 and 2 above with a pure bacterial solution at 37 ℃ for 24 hours. The results were: the OD value of comparative example 1 was 0.693; comparative example 2 had an OD of 0.657; the OD value of the sample 1 is 0.053, and compared with a blank control group, the bacteriostasis rate is 92.35%; the OD value of the example 2 is 0.043, and compared with the blank control group, the bacteriostasis rate is 93.80%. The antibacterial and bacteriostatic effects of the bio-based antibacterial material are very good, and when the bio-based antibacterial material is applied to a dental restoration material, the long-acting antibacterial property can be endowed.
Example 3
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 3 of the invention comprises the following steps:
s1, stirring and mixing 3.8g of 5', 5-diallyl-2, 2' -biphenol and 6.2g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 200mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved;
s3, adding 3g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
Example 4
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 4 of the invention comprises the following steps:
s1, stirring and mixing 3.8g of 5', 5-diallyl-2, 2' -biphenol and 6.2g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 300mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved;
s3, adding 4g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
Example 5
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 5 of the invention comprises the following steps:
s1, stirring and mixing 4.0g of 5', 5-diallyl-2, 2' -biphenol and 6.0g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 100mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the ITX is completely dissolved;
s3, adding 2g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
Example 6
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 6 of the invention comprises the following steps:
s1, stirring and mixing 4.0g of 5', 5-diallyl-2, 2' -biphenol and 6.0g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 200mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved;
s3, adding 3g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
Example 7
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 7 of the invention comprises the following steps:
s1, stirring and mixing 4.0g of 5', 5-diallyl-2, 2' -biphenol and 6.0g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 300mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved;
s3, adding 4g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
Example 8
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 8 of the invention comprises the following steps:
s1, stirring and mixing 4.5g of 5', 5-diallyl-2, 2' -biphenol and 5.5g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 100mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the ITX is completely dissolved;
s3, adding 2g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
Example 9
The preparation method of the bio-based antibacterial material applied to the dental prosthetic material in the embodiment 9 of the invention comprises the following steps:
s1, stirring and mixing 4.5g of 5', 5-diallyl-2, 2' -biphenol and 5.5g of pentaerythritol tetramercaptoacetate at 110 ℃, wherein the stirring speed is 200r/min, so that the components are completely dissolved;
s2, adding 200mg of 2-Isopropyl Thioxanthone (ITX) into the mixed solution obtained in the step S1, and stirring until the mixture is completely dissolved;
s3, adding 3g of tetraene silane into the S2 mixed solution and uniformly stirring;
s4, performing vacuum defoaming treatment on the mixed solution obtained in the step S3 at 110 ℃ to obtain a white or yellow viscous high-biocompatibility bio-based antibacterial dental restorative material.
In conclusion, the high-biocompatibility bio-based antibacterial dental restoration material and the preparation method thereof are prepared by performing addition polymerization by using 5', 5-diallyl-2, 2' -biphenol and pentaerythritol tetrathioglycolate as reactants, tetraene silane as a filler and 2-isopropyl thioxanthone as a catalyst; the material can be cured and applied under the irradiation of a light source. The filler is combined with the organic thermosetting resin in a chemical bond mode, so that the hardness and the wear resistance of the material can be improved, and the material has good mechanical property and stable quality. In addition, the bio-based antibacterial material prepared by using the 5', 5-diallyl-2, 2' -biphenol or the derivatives thereof can play a long-acting antibacterial and bacteriostatic role when being applied to a dental restoration material, and the service life is prolonged; and the material has excellent biocompatibility, not only has low manufacturing process cost, but also solves the toxicity risk that other chemical synthesis photo-curing dental resin materials are retained in a human body for a long time.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.