CN110327219B - High-strength dental repair resin filled with organic/inorganic hybrid filler - Google Patents

High-strength dental repair resin filled with organic/inorganic hybrid filler Download PDF

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CN110327219B
CN110327219B CN201910513463.0A CN201910513463A CN110327219B CN 110327219 B CN110327219 B CN 110327219B CN 201910513463 A CN201910513463 A CN 201910513463A CN 110327219 B CN110327219 B CN 110327219B
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朱美芳
陈红艳
王瑞莉
卫施琦
刘红梅
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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
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/62—Photochemical radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/76—Fillers comprising silicon-containing compounds
    • 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
    • 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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon

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Abstract

The invention relates to an organic/inorganic hybrid filler filled high-strength dental repair resin, which comprises the following components in percentage by weight: hybrid filler P-SiO2Resin monomers and photoinitiators. The hybrid filler is simple and convenient in preparation method and good in mixing property with a resin matrix, is rough and has high-content functional groups capable of polymerizing with the resin matrix, and improves the interface binding force between the filler and the resin, so that the physical and mechanical properties of the dental composite resin are improved, and the hybrid filler has a good application prospect.

Description

High-strength dental repair resin filled with organic/inorganic hybrid filler
Technical Field
The invention belongs to the field of dental restoration materials, and particularly relates to high-strength dental restoration resin filled with organic/inorganic hybrid filler.
Background
Caries is a chronic, progressive, destructive disease of hard tissue areas of the teeth, which is caused by the combined action of a number of factors, mainly bacteria. The incidence rate of the children is high, the incidence range is wide, and the result of the fourth national oral health epidemiological survey in 2017 shows that the caries rate of the children is on the rising trend, wherein the constant caries rate of the children aged 12 and 5 is 34.5 percent and 70.9 percent respectively, and is 7.8 percent and 5.8 percent respectively higher than that of the children aged ten years ago. The world health organization has classified caries as one of three major non-infectious diseases that need significant control next to cardiovascular disease and cancer in the 21 st century. Therefore, the treatment of caries is a hot research issue in the oral community. Compared with the silver-mercury alloy used in the early stage, the dental composite resin is gradually favored by doctors and patients in clinical application by virtue of the advantages of higher aesthetic degree, good adhesion with teeth, less toxicity irritation and the like. However, the materials still face the problems of unmatched mechanical properties with tooth bodies, high polymerization shrinkage rate and the like in the long-term service process, and further cause secondary dental caries and repair fracture, so that treatment failure is caused.
Dental composite resinThe composite material mainly comprises an organic monomer, inorganic filler and an initiator, wherein the inorganic filler is used as a disperse phase and plays an important role in the performances of mechanical property, glossiness, viscosity, biocompatibility and the like of the material. The inorganic filler generally used is mixed with the organic resin without treatment or simple surface treatment to prepare a composite resin. The filler in the composite resin can not be well soaked in a resin matrix, the interface compatibility between the filler and the resin matrix is poor, and the mechanical property and the service property of the composite resin are poor. Studies have shown that the compatibility of organic/inorganic interfaces in composite resins plays a decisive role in their mechanical properties (h.y.chen et al. macromolecular materials and engineering,2018,1800264). Therefore, modifying the surface of the filler to improve the interfacial bonding force between the filler and the resin matrix has received much attention from researchers. For example, Miao et al selected from silanized and modified submicron SiO2As an inorganic filler, a reinforced dental composite resin having a flexural strength of up to 115.0. + -. 7.6MPa (X.L. Miao et al. materials Science and Engineering C,2012,32, 2115-. The method improves the bending strength and the wear resistance of the composite resin by optimizing the surface composition of the filler, but the silanization reagent can be hydrolyzed in the special complex environment of the Oral cavity (T.Nihei.journal of Oral Science,2016,58,151-155.), thereby weakening the interface bonding property of the organic-inorganic phase and reducing the physical-mechanical properties of the composite resin. In addition, Wang et al select mesoporous SiO2The mesoporous silicon dioxide is used as a filler, and the interface bonding force of the filler and resin is improved through the micro-mechanical interlocking effect between the mesoporous silicon dioxide of the filler and the resin. The results show that the mechanical properties, hydrolytic stability and other properties of the prepared composite resin are improved (R.L. Wang, et al. Dental Materials,2017,33,1139-1148.), but the filling amount of the filler is low, and the mechanical properties still can not meet the requirements of patients.
CN 109481317A discloses a nano composite resin for dental restoration and a preparation method thereof, wherein a silane coupling agent used for modifying silicon dioxide has fewer functional groups which are the same as organic matrixes, so that the improvement of organic/inorganic interface compatibility is limited to a certain extent. The organic-inorganic hybrid POSS used in the invention not only contains more functional groups similar to organic matrixes and increases interface compatibility, but also has excellent mechanical strength and biocompatibility.
Disclosure of Invention
The invention aims to solve the technical problem of providing high-strength dental repair resin filled with organic/inorganic hybrid filler, overcoming the technical defects of silanized filler and low filling amount of mesoporous filler in the prior art, and solving the technical problems of silanized filler and low filling amount of mesoporous filler by applying the method to SiO2Surface modification, preparing organic/inorganic hybrid filler. The filler has rough surface and contains functional groups capable of being polymerized with organic resin, so that the interface bonding force between the filler and the resin can be improved, and finally the physical-mechanical properties, especially the bending strength, of the composite resin are improved.
The invention relates to an organic/inorganic hybrid filler for dental repair resin, which is characterized in that the filler is spherical silicon dioxide P-SiO modified by organic/inorganic hybrid POSS molecules2The structure is a small ball with a plurality of bulges on the surface of the silicon dioxide ball.
The organic-inorganic hybrid POSS is one of MA-POSS, ME-POSS, VI-POSS and MI-POSS; P-SiO2The particle diameter of (A) is 0.1 to 2 μm.
The invention relates to a preparation method of an organic/inorganic hybrid filler for dental repair resin, which comprises the following steps:
(1) adding tetraethyl orthosilicate TEOS into a mixed solution of ethanol, deionized water and an alkaline catalyst under the action of magnetic stirring, stirring the obtained solution at 20-80 ℃ for reaction for 1-2h, centrifuging and washing to obtain spherical SiO2；
(2) Spherical SiO2Ultrasonically dispersing in solvent, adding (3-mercaptopropyl) triethoxysilane MPTES and n-propylamine under magnetic stirring until the solution is clarified, reacting at 90 ℃ for 0.5-2h, drying by rotary evaporation, and vacuum drying for 10-18h to obtain sulfhydryl modified SiO2(s-SiO2)；
(3)s-SiO2Dissolving in solvent to obtain s-SiO2Adding organic-inorganic hybrid POSS, pentaerythritol tetra (3-mercaptopropionate) PETMP and photoinitiator into the solution2In the solution, the solution is added with a solvent,sealing and illuminating for 0.5-2h, centrifuging, washing, and vacuum drying to obtain P-SiO2And (4) filling.
In the step (1), the mass ratio of the ethanol to the deionized water to the alkaline catalyst is (0.1-8) to 1 (0.1-1); the alkaline catalyst is one of ammonia water, sodium hydroxide and urea.
SiO in the step (2)2The mass ratio of the solvent, the MPTES and the n-propylamine is (10-60) to (200-400) to (2-8): 1; wherein the solvent is cyclohexane.
s-SiO in the step (3)2The mass ratio of the solvent, the organic-inorganic hybrid POSS, the PETMP and the photoinitiator is (5-50) to (1000-6000): (10-40):(5-20): 1; wherein the solvent is dichloroethane; the photoinitiator is one of benzoin dimethyl ether, 2-hydroxy-methyl phenyl propane-1-ketone and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide.
The invention relates to an organic/inorganic hybrid filler filled high-strength dental repair resin, which comprises the hybrid filler P-SiO in claim 12The dental composite resin comprises a resin monomer and a photoinitiator, wherein the hybrid filler accounts for 40-70% of the total mass of the dental composite resin, and the resin monomer accounts for 30-60% of the total mass of the dental composite resin; the photoinitiator accounts for 1-3% of the mass of the organic monomer.
The resin monomer consists of a main monomer and a diluent monomer, wherein the mass ratio of the main monomer to the diluent monomer is 1-4: 1; the photoinitiator consists of a main initiator and an auxiliary initiator, wherein the mass ratio of the main initiator to the auxiliary initiator is 1: 1-5.
The main monomer is one or more of bisphenol A-glycidyl methacrylate Bis-GMA and carbamate dimethacrylate UDMA; the diluent monomer is one or more of bisethoxybisphenol-A dimethacrylate EBPADMA, triethylene glycol dimethacrylate TEGDMA, 1, 6-hexanediol diacrylate, 4-hydroxybutyl acrylate and methyl methacrylate MMA; the main initiator is one or more of camphorquinone CQ, benzophenone and diphenylethanone; the auxiliary initiator is one or more of ethyl p-dimethylaminobenzoate 4-EDMAB, trimethyl benzoyl phenyl ethyl phosphonate and methyl benzoylformate.
The invention discloses a preparation method of high-strength dental repair resin filled with organic/inorganic hybrid filler, which comprises the following steps:
adding P-SiO2The resin monomer and the photoinitiator are premixed and then put into a three-roll grinder for further mixing, and the infiltration of the organic monomer in the mesoporous gaps is promoted through vacuum negative pressure treatment to obtain uncured composite resin paste; finally, curing by visible light (460-.
The invention relates to application of high-strength dental repair resin filled with organic/inorganic hybrid filler.
Advantageous effects
(1) The preparation method is simple, the hybridization efficiency is high, and the resin mixing effect is good;
(2) the hybrid filler is organic/inorganic hybrid POSS modified spherical SiO2Compared with unmodified SiO2The particles have rough surface structure and functional groups capable of polymerizing with a resin matrix, so that the bonding performance of a two-phase interface is improved, the falling of the filler from the matrix is effectively reduced, and the mechanical strength of the composite resin is improved.
Drawings
FIG. 1 shows organic/inorganic hybrid POSS modified spherical SiO2SEM picture of (a);
FIG. 2 is organic/inorganic hybrid POSS modified spherical SiO2The FI-IR picture of (1);
FIG. 3 shows the flexural strengths of the composite resins obtained in examples 1 to 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Wherein tetraethyl orthosilicate, ethanol, sodium hydroxide, cyclohexane and dichloroethane are purchased from national medicine group, and other medicines are purchased from Sigma company and are prepared by deionized water laboratories.
Example 1
(1)P-SiO2Preparation of the filler:
a:SiO2the preparation of (1): 15mL tetraethyl orthosilicate (TEOS) was added to a solvent of ethanol (150mL), deionized water (50mL), and sodium hydroxide (3g) with magnetic stirring, and the resulting solution was stirred at 60 ℃ for 2 h. After centrifugation and washing, the spherical SiO is obtained2；
b：P-SiO2Preparation of the filler: 5g of SiO2Ultrasonic dispersing in 100mL cyclohexane solution, adding 0.7mL (3-mercaptopropyl) triethoxysilane (MPTES) and 0.6mL n-propylamine, magnetically stirring until the solution is clear, reacting at 90 deg.C for 1h, rotary steaming, drying under vacuum for 18h to obtain solid powder (s-SiO)2). Subsequently 5g s-SiO2Ultrasonically dispersing in 400mL dichloroethane solution, adding 9g of MA-POSS, 3g of pentaerythritol tetra (3-mercaptopropionic acid) ester (PETMP) and 0.6g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide into the solution, sealing and illuminating for 1h, centrifuging, washing and drying in vacuum to obtain P-SiO2And (4) filling.
(2) Preparation of composite resin
The above P-SiO was premixed by hand according to the formulation shown in Table 12Mixing the particles, the organic monomer and the photoinitiator, putting the mixture into a three-roll grinder (EXAKT 80E, Germany) for secondary mixing when the filler is fully wetted by the resin matrix, and carrying out vacuum negative pressure treatment to obtain the uncured composite resin paste. Then curing the mixture for 60 seconds by visible light (460-.
TABLE 1 Components of composite resin and contents of the components
Figure BDA0002094242790000041
(3) Characterization of the composite resin
The flexural strength of the dental composite resin was measured by a universal testing machine (Instron 5900, USA) according to International Standard ISO 4049-2009, and the result was 115.2. + -. 3.5 MPa.
Example 2
(1)P-SiO2Preparation of the filler:
a:SiO2the preparation of (1): 30mL of tetraethyl orthosilicate (TEOS) was added to a solvent of ethanol (350mL), deionized water (70mL), and urea (10g) with magnetic stirring, and the resulting solution was stirred at 60 ℃ for 2 h. After centrifugation and washing, the spherical SiO is obtained2；b：P-SiO2Preparation of the filler: 5g of SiO2Ultrasonic dispersing in 100mL cyclohexane solution, adding 0.3mL (3-mercaptopropyl) triethoxysilane (MPTES) and 0.1mL n-propylamine, magnetically stirring until the solution is clear, reacting at 90 deg.C for 2h, rotary steaming, drying under vacuum for 18h to obtain solid powder (s-SiO)2). Subsequently 5g s-SiO2Ultrasonically dispersing in 250mL dichloroethane solution, adding 3g of MA-POSS, 1g of pentaerythritol tetra (3-mercaptopropionic acid) ester (PETMP) and 0.1g of 2-hydroxy-methyl phenyl propane-1-ketone into the solution, sealing and illuminating for 2h, centrifuging, washing, and vacuum drying to obtain P-SiO2And (4) filling.
(2) Preparation of composite resin
The above P-SiO was premixed by hand according to the formulation shown in Table 22Mixing the particles, the organic monomer and the photoinitiator, putting the mixture into a three-roll grinder (EXAKT 80E, Germany) for secondary mixing when the filler is fully wetted by the resin matrix, and carrying out vacuum negative pressure treatment to obtain the uncured composite resin paste. Then curing the mixture for 60 seconds by visible light (460-.
TABLE 2 Components of composite resin and contents of the components
Figure BDA0002094242790000051
(3) Characterization of the composite resin
The composite resin obtained in example 2 was characterized in the same manner as in example 1, and the flexural strength of the composite resin was measured to be 136.3. + -. 3.9 MPa.
Example 3
(1)P-SiO2Preparation of the filler:
a:SiO2the preparation of (1): 17mL tetraethyl orthosilicate (TEOS) was added to a solvent of ethanol (225mL), deionized water (30mL), and ammonia (150mL) with magnetic stirring, and the resulting solution was stirred at 60 ℃ for 2 h. After centrifugation and washing, the spherical SiO is obtained2；b：P-SiO2Preparation of the filler: 3.7g of SiO2Ultrasonic dispersing in 80mL cyclohexane solution, adding 0.4mL (3-mercaptopropyl) triethoxysilane (MPTES) and 0.1mL n-propylamine, magnetically stirring until the solution is clear, reacting at 90 deg.C for 1h, rotary steaming, drying under vacuum for 18h to obtain solid powder (s-SiO)2). Subsequently 2g s-SiO2Ultrasonically dispersing in 115mL dichloroethane solution, adding 2g of MA-POSS, 0.8g of pentaerythritol tetra (3-mercaptopropionic acid) ester (PETMP) and 0.08g of benzoin dimethyl ether into the solution, sealing and illuminating for 1h, centrifuging, washing, and drying in vacuum to obtain P-SiO2And (4) filling.
(2) Preparation of composite resin
The above P-SiO was premixed by hand according to the formulation shown in Table 32Mixing the particles, the organic monomer and the photoinitiator, putting the mixture into a three-roll grinder (EXAKT 80E, Germany) for secondary mixing when the filler is fully wetted by the resin matrix, and carrying out vacuum negative pressure treatment to obtain the uncured composite resin paste. Then curing the mixture for 60 seconds by visible light (460-.
TABLE 3 Components of composite resin and contents of the components
Figure BDA0002094242790000061
Further, smooth spherical SiO having the same average particle diameter was prepared by a sol-gel method2Particles, the organic monomers and photoinitiators shown in table 3 were selected to prepare dental composite resins, which were used as a control.
(3) Characterization of the composite resin
The composite resin obtained in example 3 was characterized in the same manner as in example 1. The flexural strength of the composite resin obtained in example 3 was found to be 179.6. + -. 6.5MPa, and that of the control group was found to be 78.3. + -. 4.3 MPa.
The bending strength of the composite resin was found to be equivalent to that of spherical SiO as shown in FIG. 32Compared with the composite resin (comparison group) prepared by the filler, the performance of the composite resin prepared by the 3 embodiments of the invention is better than that of the comparison group, namely P-SiO2The particles are advantageous for improving the bending strength of the dental composite resin. This is mainly because of the P-SiO2The surface structure is rough and contains polymerizable functional groups with the resin matrix, so that the interface bonding performance between the filler and the matrix is improved, the material fracture caused by relative slippage between the fillers is reduced, and the mechanical property and the wear resistance of the composite resin are improved; in addition, the inorganic part in the POSS molecule presents a cage-shaped structure and has good mechanical strength.
Compared with the product disclosed in CN 109481317A, the filler prepared by the invention has better interface bonding force with organic resin, and the bending strength of the composite resin is obviously improved.

Claims (8)

1. The high-strength dental repair resin filled with organic/inorganic hybrid filler is characterized by comprising hybrid filler P-SiO2The dental composite resin comprises a resin monomer and a photoinitiator, wherein the hybrid filler accounts for 40-70% of the total mass of the dental composite resin, and the resin monomer accounts for 30-60% of the total mass of the dental composite resin; the photoinitiator accounts for 1 to 3 percent of the mass of the organic monomer;
wherein the hybrid filler is spherical silicon dioxide P-SiO modified by organic and inorganic hybrid POSS molecules2(ii) a The organic-inorganic hybrid POSS is one of MA-POSS, ME-POSS, VI-POSS and MI-POSS;
the hybrid filler P-SiO2Prepared by the following method:
(1) adding tetraethyl orthosilicate TEOS into a mixed solution of ethanol, deionized water and an alkaline catalyst under the action of magnetic stirring, stirring the obtained solution at 20-80 ℃ for reaction for 1-2h, and centrifuging and washing to obtain spherical SiO2；
(2) Spherical SiO2Ultrasonically dispersing in solvent, adding (3-mercaptopropyl) triethoxysilane MPTES and n-propylamine under magnetic stirring until the solution is clear, reacting at 90 ℃ for 0.5-2h, rotary steaming, drying, and vacuum drying to obtain sulfhydryl modified SiO2(s-SiO2)；
(3)s-SiO2Dissolving in solvent to obtain s-SiO2Adding organic-inorganic hybrid POSS, pentaerythritol tetra (3-mercaptopropionate) PETMP and photoinitiator into the solution2In the solution, the solution is sealed and irradiated for 0.5 to 2 hours, and P-SiO is obtained after centrifugation, washing and vacuum drying2And (4) filling.
2. The dental restoration resin according to claim 1, wherein the P-SiO is2The particle diameter of (A) is 0.1 to 2 μm.
3. The dental restoration resin according to claim 1, wherein SiO in step (2)2The mass ratio of the solvent, the MPTES and the n-propylamine is (10-60) to (200-400) to (2-8): 1; wherein the solvent is cyclohexane.
4. The dental restoration resin according to claim 1, wherein the s-SiO in step (3)2The mass ratio of the solvent, the organic-inorganic hybrid POSS, the PETMP and the photoinitiator is (5-50) to (1000-6000): (10-40):(5-20): 1; wherein the solvent is dichloroethane; the photoinitiator is one of benzoin dimethyl ether, 2-hydroxy-methyl phenyl propane-1-ketone and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide.
5. The dental restoration resin according to claim 1, wherein the resin monomer is composed of a main monomer and a diluent monomer, wherein the mass ratio of the main monomer to the diluent monomer is 1-4: 1; the photoinitiator consists of a main initiator and an auxiliary initiator, wherein the mass ratio of the main initiator to the auxiliary initiator is 1: 1-5.
6. The dental restoration resin according to claim 5, wherein the main monomer is one or more of bisphenol A-glycidyl methacrylate Bis-GMA and urethane dimethacrylate UDMA; the diluent monomer is one or more of bisethoxybisphenol-A dimethacrylate EBPADMA, triethylene glycol dimethacrylate TEGDMA, 1, 6-hexanediol diacrylate, 4-hydroxybutyl acrylate and methyl methacrylate MMA; the main initiator is one or more of camphorquinone CQ, benzophenone and diphenylethanone; the auxiliary initiator is one or more of ethyl p-dimethylaminobenzoate 4-EDMAB, trimethyl benzoyl phenyl ethyl phosphonate and methyl benzoylformate.
7. A method for preparing the organic/inorganic hybrid filler-filled high-strength dental restorative resin of claim 1, comprising:
adding P-SiO2Premixing the resin monomer and the photoinitiator, putting the mixture into a three-roll grinder for further mixing, and performing vacuum negative pressure treatment to obtain uncured composite resin paste; finally, the dental repair resin is obtained through visible light curing.
8. Use of the organic/inorganic hybrid filler-filled high strength dental restorative resin of claim 1.
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