CN110003407B - Resin material for dental prosthesis - Google Patents
Resin material for dental prosthesis Download PDFInfo
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- CN110003407B CN110003407B CN201910230402.3A CN201910230402A CN110003407B CN 110003407 B CN110003407 B CN 110003407B CN 201910230402 A CN201910230402 A CN 201910230402A CN 110003407 B CN110003407 B CN 110003407B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- Chemical & Material Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plastic & Reconstructive Surgery (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to the technical field of biomedical materials, and particularly relates to a resin material for dental filling, which is prepared by copolymerizing bridged acrylic acid polysiloxane and methyl methacrylate, is used as a component of a dental filling repair material, has excellent wear resistance and small volume shrinkage, does not contain heavy metal, and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a resin material for dental filling.
Background
Dental caries, also known as caries or decayed tooth, is a bacterial disease, and can be secondary to pulpitis and periapical periodontitis, and even alveolar bone and jaw inflammation in severe cases. If not treated in time, the lesion continues to develop, forming a cavity, eventually the crown is completely destroyed and disappears, the end result of which is the loss of teeth. Untreated caries cavities do not heal on their own.
The method for treating dental caries mainly comprises removing caries tissue, making into a certain hole shape, cleaning, sterilizing, filling with dental prosthetic material, and recovering tooth defect shape, wherein the filling material mainly comprises silver amalgam or composite filling resin. The silver-mercury alloy is a special alloy, the silver-mercury alloy is an amalgam compound formed by interaction of mercury and silver-tin alloy powder at normal temperature, and the silver-mercury alloy is the most common dental restoration material. The silver-tin alloy powder contains various metals such as silver, tin, copper and zinc, etc. and is prepared according to a proper proportion, so that the defects of other metals can be compensated by the advantages of one metal, and the silver-mercury alloy has excellent performances such as proper expansion, enough strength and hardness, small creep deformation, proper hard setting time, etc. However, the silver-mercury alloy contains mercury which is harmful to the environment, so the silver-mercury alloy is gradually eliminated; compared with traditional repair materials such as silver amalgam and the like, the composite filling resin has excellent biological, mechanical and aesthetic properties, and becomes the most important mode for repairing various tooth tissue defects at present. However, the dental resin material has a limited service life because of the volume shrinkage during the polymerization of the dental resin, the incidence of secondary caries of patients and the limited wear resistance and mechanical strength of the polymer resin, and the clinical service life of the resin bonded prosthesis is less than 6 years at present.
Therefore, it is very important to develop a novel tooth filling material with high wear resistance, high mechanical strength and small volume shrinkage.
Disclosure of Invention
The invention aims to provide a resin material for dental filling, which is used as a component of a dental filling restoration material, has excellent wear resistance and small volume shrinkage, does not contain heavy metal, and is environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resin material for dental use is prepared by copolymerizing bridged acrylic polysiloxane ester and methyl methacrylate, wherein the bridged acrylic polysiloxane ester has a structural formula shown in formula I, and m is 500-1000,
according to the invention, the bridged cyclic olefine acid polysiloxane is prepared by alpha, omega-dihydroxy polydimethylsiloxane and (Z) -4-isopropyl-4-azatricyclo [5.3.1.1 ] under the protection of nitrogen and the action of an acid-binding agent2,6]Dodecane-12- (1-alkene) acetyl chloride is used as a raw material and is obtained by reacting in an organic solvent, the acid-binding agent is selected from triethylamine, sodium carbonate, sodium hydroxide and potassium hydroxide, and the alpha, omega-dihydroxy polydimethylsiloxane and (Z) -4-isopropyl-4-azatricyclo [5.3.1.1 ]2,6]The mol ratio of dodecane-12- (1-ene) acetyl chloride is 1: 2-4, and the organic solvent is selected from toluene, chloroform and dichloromethane; preferably, the bridged cyclic olefine acid polysiloxane is prepared by reacting alpha, omega-dihydroxy polydimethylsiloxane and (Z) -4-isopropyl-4-azatricyclo [5.3.1.1 ] under the protection of nitrogen and the action of triethylamine2,6]Dodecane-12- (1-ene) acetyl chloride as a raw material is obtained by reacting the raw material in toluene, wherein the alpha, omega-dihydroxy polydimethylsiloxane and the (Z) -4-isopropyl-4-azatricyclo [5.3.1.12,6]The molar ratio of dodecane-12- (1-ene) acetyl chloride was 1: 2.
According to the invention, the copolymerization reaction of the bridged acrylic acid polysiloxane and the methyl methacrylate is carried out in an inert organic solvent under the protection of nitrogen, and the bridged acrylic acid polysiloxane and the methyl methacrylate react under the action of an initiator.
According to the invention, the inert organic solvent is selected from one or more of toluene, acetonitrile, chloroform and 2-butanone; preferably, the inert organic solvent is toluene.
According to the invention, the initiator is selected from the group consisting of benzoyl peroxide, tributyl hydroperoxide, lauryl peroxide, azobis (isobutyronitrile), azobis (2, 4-dimethylvaleronitrile) and azobis (2-methylbutyronitrile).
According to the invention, the mol ratio of the bridged ring olefine acid polysiloxane to the methyl methacrylate is 1: 2-6; preferably, the mol ratio of the bridged ring olefine acid polysiloxane to the methyl methacrylate is 1: 2-3.
According to the invention, the amount of the initiator is 0.1-1% of the total mass of the bridged ring olefine acid polysiloxane and the methyl methacrylate, and preferably, the amount of the initiator is 0.1% of the total mass of the bridged ring olefine acid polysiloxane and the methyl methacrylate.
In a specific embodiment, the copolymerization reaction of the bridged ring olefine acid polysiloxane and the methyl methacrylate is carried out under the protection of nitrogen, the bridged ring olefine acid polysiloxane and the methyl methacrylate are polymerized for 5-8 hours at 55-60 ℃ in toluene and under the action of an initiator, the temperature is raised to 70-80 ℃ and the polymerization is carried out for 2-3 hours, and the usage amount of the initiator is 0.1 percent of the total mass of the bridged ring olefine acid polysiloxane and the methyl methacrylate.
The resin material for tooth filling takes the bridged acrylic acid polysiloxane and the methyl methacrylate as polymerization monomers, and introduces the tricyclic and the polysiloxane groups into the structure, so that the shrinkage rate of polymerization reaction can be reduced, and simultaneously, the strength and the wear resistance of the resin material are enhanced.
Detailed Description
Example 14-benzyl-4-azatricyclo [5.3.1.12,6]Preparation of Dodecan-12-ones
Weighing 1mmoL benzylamine, 100mL hydrochloric acid, 1mmoL bicyclo [3.3.1] nonan-3-one, 235mL 37% formaldehyde water solution and 1800mL acetic acid in a reaction bottle, heating to 80 ℃ under the protection of nitrogen, reacting for 2h, stopping the reaction, cooling to room temperature, concentrating under reduced pressure, adding water and diethyl ether into the residue, washing the water layer with diethyl ether, adding sodium carbonate solid into the water layer to adjust the pH value to 8, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, adding 280mL ethanol and 94mL acetic anhydride into the residue, stirring for 2h at room temperature, adding 100mL concentrated hydrochloric acid, continuing stirring for 2h, concentrating, adding water, extracting with ethyl acetate for 3 times, combining organic phases, drying with anhydrous sodium sulfate, concentrating, and purifying by column chromatography to obtain the title compound.
ES：M/Z 270[M+H]+。
Example 24-isopropyl-4-azatricyclo [5.3.1.12,6]Preparation of Dodecan-12-ones
0.5mmoL of the 4-benzyl-4-azatricyclo [5.3.1.1 ] product obtained in example 1 was weighed2,6]Adding 50mL of methanol and 0.1g of 10% palladium-carbon into a reaction bottle, reacting for 5h at normal temperature in a hydrogen atmosphere, filtering with kieselguhr, concentrating, adding 20mL of toluene and K into the residue2CO30.2g, KOH0.15g and 0.5mmoL isopropyl bromide, stirring to dissolve, adding 0.2mmoL tetra-n-butylammonium bromide, heating to 80 ℃ to react for 4h, stopping the reaction, cooling to room temperature, adding 50mL ice water, extracting with ethyl acetate, combining organic layers, washing with a saturated sodium chloride solution, drying with anhydrous sodium sulfate, filtering, and purifying by column chromatography to obtain the title compound.
ES：M/Z 222[M+H]+。
Example 3 (Z) -4-isopropyl-4-azatricyclo [5.3.1.12,6]Preparation of methyl dodecane-12- (1-ene) acetate
50mmoL of sodium hydrogen is weighed into a reaction bottle, 50mL of DMF is added, 25mmoL of trimethylphosphonoacetate is slowly dripped at 0 ℃, the stirring is continued for 1 hour at 0 ℃, 20mL of 4-isopropyl-4-azatricyclo [5.3.1.1 ] dissolved with 20mmoL of the product obtained in the example 2 is slowly dripped2,6]And (3) after dripping the DMF solution of dodecane-12-ketone, continuously stirring at 0 ℃ for 2h, slowly heating to room temperature, continuously stirring for 1h, stopping the reaction, adding a 1N hydrochloric acid solution to quench the reaction, adding ethyl acetate to extract, combining several layers, washing with saturated saline, drying with anhydrous sodium sulfate, filtering, concentrating, and carrying out column chromatography to obtain the title compound.
ES：M/Z 278[M+H]+。
1H NMR(600MHz,CDCl3)(δ,ppm):5.56(s,1H),3.77(s,3H),2.70～2.72(m,1H),2.33～2.36(m,4H),1.71～1.75(m,4H),1.39～1.41(m,5H),1.20～1.22(m,1H),1.08～1.10(m,7H).
EXAMPLE 4 preparation of bridged cycloalkenoic acid polysiloxane esters
(Z) -4-isopropyl-4-azatricyclo [5.3.1.1 ] obtained in example 3 was weighed2,6]10mmoL of dodecane-12- (1-ene) methyl acetate, 1g of sodium hydroxide, 50mL of methanol and 20mL of water, stirring for 1h at 45 ℃, concentrating under reduced pressure, adding 30mL of water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, evaporating to remove the solvent, adding DMF2mL, slowly dropwise adding 5mL of thionyl chloride at 0-5 ℃, continuously stirring for 1h at 0-5 ℃, and spin-drying for later use.
Weighing 370g of alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 1000 in a reaction bottle, adding 1000mL of toluene, 14mL of triethylamine and the acyl chloride, introducing nitrogen for protection, reacting at 0-5 ℃ for 1.5h, heating to room temperature, continuing stirring for 1h, stopping reaction, filtering, decompressing, evaporating to remove the solvent, and drying in vacuum to obtain the bridged acrylic acid polysiloxane.
EXAMPLE 5 preparation of bridged cycloalkenoic acid polysiloxane esters
Weighing 10mmoL of (Z) -4-isopropyl-4-azatricyclo [5.3.1.12,6] dodecane-12- (1-ene) methyl acetate obtained in example 3, 1g of sodium hydroxide, 50mL of methanol, 20mL of water, stirring for 1h at 45 ℃, concentrating under reduced pressure, adding 30mL of water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, evaporating to remove the solvent, adding DMF2mL, slowly dropwise adding 5mL of thionyl chloride at 0-5 ℃, continuously stirring for 1h at 0-5 ℃, and spin-drying for later use.
740g of alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 2000 is weighed into a reaction bottle, 2000mL of toluene, 14mL of triethylamine and the acyl chloride are added, nitrogen is introduced for protection, the reaction is carried out for 1.5h at the temperature of 0-5 ℃, the temperature is raised to room temperature, the stirring is continued for 1h, the reaction is stopped, the filtration is carried out, the solvent is removed by reduced pressure evaporation, and the bridged acrylic acid polysiloxane is obtained by vacuum drying.
EXAMPLE 6 preparation of bridged cycloalkenoic acid polysiloxane esters
Weighing 10mmoL of (Z) -4-isopropyl-4-azatricyclo [5.3.1.12,6] dodecane-12- (1-ene) methyl acetate obtained in example 3, 1g of sodium hydroxide, 50mL of methanol, 20mL of water, stirring for 1h at 45 ℃, concentrating under reduced pressure, adding 30mL of water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, evaporating to remove the solvent, adding DMF2mL, slowly dropwise adding 5mL of thionyl chloride at 0-5 ℃, continuously stirring for 1h at 0-5 ℃, and spin-drying for later use.
Weighing 555g of alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 1500 into a reaction bottle, adding 2000mL of toluene, 14mL of triethylamine and the acyl chloride, introducing nitrogen for protection, reacting at 0-5 ℃ for 1.5h, heating to room temperature, continuing stirring for 1h, stopping reaction, filtering, decompressing, evaporating to remove the solvent, and drying in vacuum to obtain the bridged acrylic acid polysiloxane.
Example 7 dental resin Material of the present invention
Under the protection of nitrogen, adding the bridged ring olefine acid polysiloxane and methyl methacrylate obtained in the example 4 into a reaction bottle according to the molar ratio of 1:3, adding toluene and benzoyl peroxide, carrying out polymerization reaction for 8 hours at the temperature of 55-60 ℃, and heating to about 80 ℃ for polymerization reaction for 2 hours to obtain the product.
EXAMPLE 8 dental resin Material according to the present invention
Under the protection of nitrogen, adding the bridged ring olefine acid polysiloxane and the methyl methacrylate obtained in the example 5 into a reaction bottle according to the molar ratio of 1:2, adding toluene and azobis (isobutyronitrile), carrying out polymerization reaction for 6 hours at the temperature of 55-60 ℃, and heating to about 70 ℃ for polymerization reaction for 3 hours to obtain the product.
Example 9 dental resin Material of the present invention
Under the protection of nitrogen, adding the bridged ring olefine acid polysiloxane and the methyl methacrylate obtained in the embodiment 6 into a reaction bottle according to the molar ratio of 1:3, adding toluene and azobis (2, 4-dimethylvaleronitrile), carrying out polymerization reaction for 6 hours at the temperature of 55 ℃ to 60 ℃, and heating to about 70 ℃ for polymerization reaction for 3 hours to obtain the bridged ring olefine acid polysiloxane and methyl methacrylate.
Adding 20g of chitin, 20g of calcium phosphate and 10g of silicon dioxide into a ball mill, stirring, grinding and mixing, stirring and grinding to obtain a mixture, crushing the obtained mixture by using ultrasonic waves for 1.5 hours, placing the mixture into a crucible, stirring and mixing, adding 50g of the dental resin material prepared in the embodiment 7-9, heating to 65 ℃, preserving heat for 20 hours, introducing the melt into a mold, cooling for 5 minutes at a speed of 5 ℃/min, and then cooling to room temperature at a speed of 10 ℃/min to obtain the dental material. The dental filling material obtained is tested, the average Rockwell hardness value is 105, the average compressive strength is 200.32MPa, and the average polymerization shrinkage rate is 1.2% by adopting a video-controlled procedure.
Claims (9)
1. A resin material for dental use is prepared by copolymerizing bridged acrylic polysiloxane ester and methyl methacrylate, wherein the bridged acrylic polysiloxane ester has a structural formula shown in formula I, and m is 500-1000,
2. the dental resin material as set forth in claim 1, wherein: under the protection of nitrogen and the action of acid-binding agent, the said bridged olefine acid polysiloxane is prepared from alpha, omega-dihydroxy polydimethyl siloxane and (Z) -4-isopropyl-4-azatricyclo [5.3.1.12,6]Dodecane-12- (1-alkene) acetyl chloride is used as a raw material and is obtained by reacting in an organic solvent, the acid-binding agent is selected from triethylamine, sodium carbonate, sodium hydroxide and potassium hydroxide, and the alpha, omega-dihydroxy polydimethylsiloxane and (Z) -4-isopropyl-4-azatricyclo [5.3.1.1 ]2,6]The mole ratio of the dodecane-12- (1-ene) acetyl chloride is 1: 2-4, and the organic solvent is selected from toluene, chloroform and dichloromethane.
3. The dental resin material as set forth in claim 1, wherein: under the protection of nitrogen and the action of triethylamine, the bridged cyclic olefine acid polysiloxane is prepared from alpha, omega-dihydroxy polydimethylsiloxane and (Z) -4-isopropyl-4-azatricyclo [5.3.1.1 ]2,6]Dodecane-12- (1-ene) acetyl chloride as a raw material is obtained by reacting the raw material in toluene, wherein the alpha, omega-dihydroxy polydimethylsiloxane and the (Z) -4-isopropyl-4-azatricyclo [5.3.1.12,6]The molar ratio of dodecane-12- (1-ene) acetyl chloride was 1: 2.
4. The dental resin material as set forth in claim 1, wherein: the copolymerization reaction of the bridged acrylic polysiloxane ester and the methyl methacrylate comprises the following steps: under the protection of nitrogen, the bridged acrylic acid polysiloxane and the methyl methacrylate react in an inert organic solvent under the action of an initiator to obtain the epoxy acrylate modified epoxy resin.
5. The dental resin material as set forth in claim 4, wherein: the inert organic solvent is selected from one or more of toluene, acetonitrile, chloroform and 2-butanone.
6. The dental resin material as set forth in claim 4, wherein: the initiator is selected from benzoyl peroxide, lauryl peroxide, azo-bis (isobutyronitrile), azo-bis (2, 4-dimethylvaleronitrile) and azo-bis (2-methylbutyronitrile).
7. The dental resin material as set forth in claim 4, wherein: the mol ratio of the bridged acrylic acid polysiloxane to the methyl methacrylate is 1: 2-6.
8. The dental resin material as set forth in claim 4, wherein: the usage amount of the initiator is 0.1 to 1 percent of the total mass of the bridged acrylic acid polysiloxane and the methyl methacrylate.
9. The dental resin material as set forth in claim 4, wherein: the amount of the initiator used is 0.1% of the total mass of the bridged acrylic polysiloxane ester and the methyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910230402.3A CN110003407B (en) | 2019-03-26 | 2019-03-26 | Resin material for dental prosthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910230402.3A CN110003407B (en) | 2019-03-26 | 2019-03-26 | Resin material for dental prosthesis |
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| Publication Number | Publication Date |
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| CN110003407A CN110003407A (en) | 2019-07-12 |
| CN110003407B true CN110003407B (en) | 2021-04-23 |
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| CN201910230402.3A Active CN110003407B (en) | 2019-03-26 | 2019-03-26 | Resin material for dental prosthesis |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2571207C (en) * | 2004-06-15 | 2014-08-05 | Dentsply International Inc. | Low shrinkage and low stress dental compositions |
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Non-Patent Citations (2)
| Title |
|---|
| Update on Dental Nanocomposites;M.-H. Chen;《Journal of Dental Research》;20100630;第89卷(第6期);第549-560页 * |
| 聚硅氧烷丙烯酸酯的合成及其应用的研究;李东辉;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120115(第1期);B016-64页 * |
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