CN113173868A - Low-surface-energy hydrophobic dental resin and preparation method thereof - Google Patents

Low-surface-energy hydrophobic dental resin and preparation method thereof Download PDF

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CN113173868A
CN113173868A CN202110464606.0A CN202110464606A CN113173868A CN 113173868 A CN113173868 A CN 113173868A CN 202110464606 A CN202110464606 A CN 202110464606A CN 113173868 A CN113173868 A CN 113173868A
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何经纬
刘芳
童辉
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South China University of Technology SCUT
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Abstract

The invention discloses a dental resin with low surface energy hydrophobicity and a preparation method thereof. The invention prepares fluorine-containing (methyl) acrylate prepolymer by two-step reaction of fluorine dihydric alcohol, diisocyanate and (methyl) acrylic acid isocyanatoethyl ester, and then prepares the low surface energy hydrophobic dental resin by photo-initiation polymerization of the fluorine-containing (methyl) acrylate prepolymer, low viscosity (methyl) acrylate reactive diluent, photoinitiator and accelerator. Compared with the existing commercially used dental resin matrix, the dental resin matrix has lower surface energy and larger hydrophobicity, can effectively reduce micro leakage and adhesion of bacteria on the surface of the dental resin matrix, and achieves the purpose of reducing the incidence rate of secondary caries.

Description

Low-surface-energy hydrophobic dental resin and preparation method thereof
Technical Field
The invention belongs to the field of dental restoration materials, and particularly relates to a fluorine-containing (methyl) acrylate prepolymer, a preparation method and application thereof, a low-surface-energy hydrophobic dental resin prepared from the fluorine-containing (methyl) acrylate prepolymer and a preparation method thereof.
Background
Caries is a chronic progressive disease which occurs in hard tooth tissues under the influence of various factors mainly including bacteria, can cause the color, the shape, the texture and the function of the tooth to be damaged, and seriously influences the oral cavity and the whole body health of human beings. Caries is classified by WHO as a non-infectious disease of human focus. Once caries causes substantial defects in tooth tissue, it is necessary to surgically remove the carious region, prepare a cavity, select an appropriate filling material to repair the defective region, and stop the development of the caries.
The composite resin has the characteristics of excellent physical and chemical properties, simulated aesthetic effect, simple and convenient operation performance and the like, and gradually replaces silver-mercury alloy as a filling material for repairing carious tissues. The prepolymer containing the methacrylate structure is an indispensable organic component of the composite resin. Currently, commonly used methacrylic acid esters in commercially available dental composite resins include Bis-GMA (bisphenol A glycidyl dimethacrylate), UDMA (diurethane dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), and the like.
However, when the dental composite resin is cured by light, the methacrylate resin matrix in the composite resin is converted from van der waals force to covalent bonding force due to intermolecular interaction force, so that the intermolecular distance is decreased, and the composite resin undergoes large volume shrinkage and large shrinkage stress. When the shrinkage stress is greater than the adhesive force between the composite resin and the tooth body, micro-cracks are generated, and oral saliva containing bacteria permeates into the micro-cracks due to capillary phenomenon, resulting in a high incidence rate of secondary caries. On the other hand, compared with repair materials such as silver-mercury alloy, glass ions and the like, the composite resin has no antibacterial property, bacteria are easy to accumulate on the surface of the composite resin, and the secondary caries incidence is high. Research has shown that secondary caries is the major cause of failure of clinical repair of complex resins.
Studies have shown that oral cariogenic bacteria such as streptococcus mutans are high surface energy bacteria that do not readily adhere to low surface energy surfaces. In addition, if the surface of the composite resin is more hydrophobic, the permeability of saliva in microcracks due to polymerization shrinkage is reduced. Therefore, the surface hydrophobicity of the composite resin is improved by reducing the surface energy of the composite resin, and the incidence rate of secondary caries can be effectively reduced. The performance of the composite resin depends on the performance of a resin matrix to a great extent, so that the development of the hydrophobic resin with low surface energy has practical significance for improving the clinical repair success rate of the composite resin. Patent CN105018083B discloses a Bis (meth) acrylate monomer with a fluorine-containing structure, which can replace Bis-GMA as a host resin and can reduce the volume shrinkage of a dental resin system to some extent. However, the monomer has a low fluorine content, cannot achieve the purposes of reducing surface energy and improving hydrophobicity, and still has a certain volume shrinkage problem, so that the problem of secondary caries of the dental composite resin cannot be solved.
Disclosure of Invention
Aiming at the problem of high secondary caries incidence of the existing dental composite resin, the invention aims to provide a fluorine-containing (methyl) acrylate prepolymer and a preparation method thereof.
The invention also aims to provide application of the fluorine-containing (methyl) acrylate prepolymer in preparation of the low-surface-energy hydrophobic dental resin.
It is still another object of the present invention to provide a low surface energy hydrophobic dental resin prepared from the above fluorine-containing (meth) acrylate prepolymer, and a method for preparing the same.
The purpose of the invention is realized by the following technical scheme:
a fluorine-containing (methyl) acrylate prepolymer has a structural formula as follows:
Figure BDA0003043259810000021
Figure BDA0003043259810000031
m in the structural formula can be any one of A-I:
Figure BDA0003043259810000032
wherein n is 1-10, R is methyl (CH)3) Or hydrogen (H).
The preparation method of the fluorine-containing (methyl) acrylate prepolymer comprises the following steps:
(1) taking a solvent as a reaction medium, and reacting fluorine-containing dihydric alcohol and diisocyanate at the temperature of 40-80 ℃ for 8-24 hours under the action of a catalyst to obtain a hydroxyl-terminated fluorine-containing chain prepolymer;
(2) taking a solvent as a reaction medium, reacting the hydroxyl-terminated fluorine-containing chain prepolymer with (methyl) acrylic acid isocyanatoethyl ester at 40-80 ℃ for 8-24 hours under the condition of containing a polymerization inhibitor, and purifying to obtain the fluorine-containing (methyl) acrylic ester prepolymer.
Preferably, the solvent in steps (1) and (2) is at least one of acetone, butanone, dichloromethane, chloroform, cyclohexanone and tetrahydrofuran.
Preferably, the fluorine-containing diol prepared in the step (1) is a solution with a concentration of 0.2-0.4mol/L, the diisocyanate is a solution with a concentration of 0.2mol/L, and the diisocyanate solution is dropwise added into the fluorine-containing diol solution within 2-3 hours to perform a heating reaction.
Preferably, the fluorine-containing diol obtained in the step (1) has a structural formula of
Figure BDA0003043259810000041
Wherein n is 1-10. The fluorine-containing diol is more preferably at least one of octafluoro-1, 6-hexanediol and 1H,1H,10H, 10H-perfluoro-1, 10-decanediol.
Preferably, the diisocyanate of step (1) is at least one of the following structural formulas:
Figure BDA0003043259810000042
the diisocyanate in the step (1) is more preferably isophorone diisocyanate.
Preferably, the molar ratio of the fluorine-containing diol to the diisocyanate in the step (1) is 1.1-2: 1. more preferably 2: 1.
preferably, the catalyst in step (1) is at least one of triethylamine, triethylenediamine, tetramethylbutanediamine, N-dimethylbenzylamine, dibutyltin dilaurate and stannous octoate.
Preferably, the catalyst used in the step (1) accounts for 0.1-0.5% of the total weight of the reactants; more preferably 0.1 to 0.25%.
Preferably, the reaction temperature in the step (1) is 50-60 ℃ and the reaction time is 12-13 hours. The reaction temperature in the step (2) is 50-60 ℃, and the reaction time is 16-24 hours.
Preferably, the molar ratio of the hydroxyl-terminated fluorine-containing chain prepolymer in the step (2) to the isocyanatoethyl (meth) acrylate is 1: 0.2-2. More preferably 1: 2.
preferably, the polymerization inhibitor in the step (2) is at least one of hydroquinone, p-benzoquinone, p-hydroxyanisole, methylhydroquinone and 2-tert-butylhydroquinone.
Preferably, the amount of the polymerization inhibitor used in the step (2) is 0.1-0.5% of the total weight of the reactants; more preferably 0.1 to 0.2%.
Preferably, a hydroxyl-terminated fluorine-containing chain prepolymer solution is obtained after the reaction in the step (1), and isocyanatoethyl (meth) acrylate and a polymerization inhibitor are directly added into the hydroxyl-terminated fluorine-containing chain prepolymer solution and are subjected to a heating reaction.
And (3) the polymerization inhibitor in the step (2) is used for protecting double bonds in the isocyanatoethyl (meth) acrylate so as to prevent polymerization reaction caused by overhigh temperature in the reaction process.
The chemical reaction equation of the above steps (taking octafluoro-1, 6-hexanediol, isophorone diisocyanate, and isocyanatoethyl methacrylate as examples) is as follows:
Figure BDA0003043259810000051
the application of the fluorine-containing (methyl) acrylate prepolymer in preparing the low-surface-energy hydrophobic dental resin.
The low surface energy hydrophobic dental resin is prepared with the prepolymer containing fluoro (methyl) acrylate in 49-80 weight portions, low viscosity reactive (methyl) acrylate diluent in 20-50 weight portions, light initiator in 0.2-1.0 weight portions and promoter in 0.2-1.0 weight portions and through light initiating polymerization.
Preferably, the low surface energy hydrophobic dental resin is prepared by photo-initiated polymerization of 49-59.16 parts by weight of the fluorine-containing (meth) acrylate prepolymer, 39.44-49 parts by weight of low viscosity (meth) acrylate reactive diluent, 0.7-1.0 part by weight of photoinitiator and 0.7-1.0 part by weight of accelerator.
Preferably, the low viscosity (meth) acrylate reactive diluent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.02,6] decane dimethanol acrylate, (perfluorocyclohexyl) methacrylate, 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, dodecafluoroheptyl methacrylate, perfluorooctyl methacrylate, 1H-perfluoro-n-decyl methacrylate, 2,3,3,4,4, 4-heptafluorobutyl methacrylate, hexafluorobutyl methacrylate and 1H methacrylate, 1H, 5H-octafluoropentyl ester.
More preferably, the low viscosity (meth) acrylate reactive diluent is at least one of hexafluorobutyl methacrylate and triethylene glycol dimethacrylate, and most preferably, the mass ratio of hexafluorobutyl methacrylate to triethylene glycol dimethacrylate is 1: 3-3: 1.
Preferably, the photoinitiator is at least one of camphorquinone, benzophenone, and 1-phenyl-1, 2-propanedione. More preferably camphorquinone.
Preferably, the accelerator is at least one of ethyl dimethylaminobenzoate, N-dimethylaminoethyl methacrylate and dimethylaminoethyl methacrylate. More preferably dimethylaminoethyl methacrylate.
The preparation method of the low-surface-energy hydrophobic dental resin comprises the following specific steps:
the fluorine-containing (methyl) acrylate prepolymer, the low-viscosity (methyl) acrylate reactive diluent, the photoinitiator and the accelerator are mixed and stirred uniformly according to a proportion, and then the mixture is polymerized for 20 to 60 seconds under the irradiation of light to obtain the low-surface-energy hydrophobic dental resin.
Preferably, the light is at least one of blue light and ultraviolet light; the light intensity range is 500-2000mW/cm2
Compared with the prior art, the invention has the following advantages and beneficial effects:
compared with the existing commercially used dental resin matrix, the dental resin matrix prepared by the invention has lower surface energy and larger hydrophobicity, so that the resin-based dental material prepared by the resin can reduce micro-leakage and adhesion of bacteria on the surface of the resin matrix, and the aim of reducing the incidence rate of secondary caries is fulfilled. In addition, compared with the existing fluorine-containing dental resin (such as CN105017083B), the fluorine-containing (methyl) acrylate prepolymer prepared by the invention is used for preparing the dental resin, has lower surface energy, larger hydrophobicity and smaller volume shrinkage, and thus more effectively solves the problem of secondary caries rate of the existing dental composite resin.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
AF4CH3Synthesis of (2)
5.24g of octafluoro-1, 6-hexanediol, 50mL of tetrahydrofuran and 0.01g of dibutyltin dilaurate were placed in a round-bottomed flask equipped with magnetons, and after mixing to homogeneity the temperature was raised to 60 ℃. Dissolving 2.22g of isophorone diisocyanate in 50mL of tetrahydrofuran, dropwise adding into a round-bottom flask through a constant-pressure dropping funnel for 2 hours, and reacting at 60 ℃ for 10 hours after the dropwise adding is finished until isocyanate groups in the system are completely reacted. 3.10g of isocyanatoethyl methacrylate and 0.01g of p-hydroxyanisole are weighed and added into a reaction system, the reaction is continued for 16 hours at 60 ℃ until isocyanate groups in the system are completely reacted, and after the reaction is cooled to room temperature, the reactant is purified to obtain AF4CH3
Example 2
AF8CH3Synthesis of (2)
9.24g of 1H,1H,10H, 10H-perfluoro-1, 10-decanediol, 100mL of tetrahydrofuran and 0.028g of dibutyltin dilaurate were placed in a round-bottomed flask containing magnetite and, after mixing homogeneously, the temperature was raised to 50 ℃. Dissolving 2.22g of isophorone diisocyanate in 50mL of tetrahydrofuran, dropwise adding into a round-bottom flask through a constant-pressure dropping funnel for 3 hours, and reacting at 50 ℃ for 10 hours after the dropwise adding is finished until isocyanate groups in the system are completely reacted. 3.10g of isocyanatoethyl methacrylate and 0.03g of p-hydroxyanisole are weighed and added into a reaction system, the reaction is continued for 24 hours at 50 ℃ until isocyanate groups in the system are completely reacted, and after the reaction system is cooled to room temperature, the reactant is purified to obtain AF8CH3
Comparative example 1
59.16% of bisphenol A glycidyl dimethacrylate, 39.44% of dimethylpropeneTriethylene glycol ester, 0.7% camphorquinone, and 0.7% dimethylaminoethyl methacrylate. Weighing the components in parts by mass, uniformly mixing the components in a dark place, and then uniformly mixing the components at the concentration of 1000mW/cm2The blue light of (2) was irradiated for 40 seconds to obtain comparative example 1.
Example 3
A low surface energy hydrophobic dental resin comprises the following components in percentage by mass: 59.16% AF4CH329.58% hexafluorobutyl methacrylate, 9.86% triethylene glycol dimethacrylate, 0.7% camphorquinone and 0.7% dimethylaminoethyl methacrylate. Weighing the components in parts by mass, uniformly mixing the components in a dark place, and then uniformly mixing the components at the concentration of 1000mW/cm2For 40 seconds, example 3 was obtained.
TABLE 1 surface energy, contact angle and polymerization shrinkage of the resins obtained in example 3 and comparative example 1 by photocuring
Figure BDA0003043259810000081
Comparative example 2
49% of bisphenol A glycidyl dimethacrylate, 49% of triethylene glycol dimethacrylate, 1.0% of camphorquinone and 1.0% of dimethylaminoethyl methacrylate. Weighing the components in parts by mass, uniformly mixing the components in a dark place, and then uniformly mixing the components at the concentration of 1000mW/cm2The blue light of (2) was irradiated for 40 seconds to obtain comparative example 1.
Example 4
A low surface energy hydrophobic dental resin comprises the following components in percentage by mass: 49% AF8CH349% triethylene glycol dimethacrylate, 1.0% camphorquinone and 1.0% dimethylaminoethyl methacrylate. Weighing the components in parts by mass, uniformly mixing the components in a dark place, and then uniformly mixing the components at the concentration of 1000mW/cm2For 40 seconds to example 4.
TABLE 2 surface energy, contact angle and polymerization shrinkage of the resins obtained in example 4 and comparative example 2 by photocuring
Figure BDA0003043259810000082
Figure BDA0003043259810000091
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A fluorine-containing (methyl) acrylate prepolymer is characterized in that the structural formula is as follows:
Figure FDA0003043259800000011
in the structural formula, M can be any one of the following structures:
Figure FDA0003043259800000012
n is 1-10, and R is methyl or hydrogen.
2. The method for preparing a fluorine-containing (meth) acrylate prepolymer according to claim 1, comprising the steps of:
(1) taking a solvent as a reaction medium, and reacting fluorine-containing dihydric alcohol and diisocyanate at the temperature of 40-80 ℃ for 8-24 hours under the action of a catalyst to obtain a hydroxyl-terminated fluorine-containing chain prepolymer;
(2) taking a solvent as a reaction medium, reacting the hydroxyl-terminated fluorine-containing chain prepolymer with (methyl) acrylic acid isocyanatoethyl ester at 40-80 ℃ for 8-24 hours under the condition of containing a polymerization inhibitor, and purifying to obtain the fluorine-containing (methyl) acrylic ester prepolymer.
3. According to claim 2The preparation method of the fluorine-containing (methyl) acrylate prepolymer is characterized in that the structural formula of the fluorine-containing dihydric alcohol in the step (1) is shown in the specification
Figure FDA0003043259800000021
N is 1-10 in the structural formula;
or the fluorine-containing dihydric alcohol in the step (1) is at least one of octafluoro-1, 6-hexanediol and 1H,1H,10H, 10H-perfluoro-1, 10-decanediol;
the diisocyanate in the step (1) is at least one of the following structural formulas:
Figure FDA0003043259800000022
the molar ratio of the fluorine-containing diol to the diisocyanate in the step (1) is 1.1-2: 1;
the mol ratio of the hydroxyl-terminated fluorine-containing chain prepolymer in the step (2) to the isocyanatoethyl (meth) acrylate is 1: 0.2-2.
4. The method according to claim 2, wherein the catalyst in the step (1) is at least one selected from the group consisting of triethylamine, triethylenediamine, tetramethylbutanediamine, N-dimethylbenzylamine, dibutyltin dilaurate, and stannous octoate;
the dosage of the catalyst in the step (1) accounts for 0.1-0.5% or 0.1-0.25% of the total weight of the reactants;
the polymerization inhibitor in the step (2) is at least one of hydroquinone, p-benzoquinone, p-hydroxyanisole, methyl hydroquinone and 2-tert-butyl hydroquinone;
the amount of the polymerization inhibitor in the step (2) accounts for 0.1-0.5% or 0.1-0.2% of the total weight of the reactants;
the solvent in the steps (1) and (2) is at least one of acetone, butanone, dichloromethane, trichloromethane, cyclohexanone and tetrahydrofuran.
5. The method for preparing the fluorine-containing (meth) acrylate prepolymer according to claim 2, wherein the reaction temperature in the step (1) is 50 to 60 ℃ and the reaction time is 12 to 13 hours;
preparing a solution with the concentration of 0.2-0.4mol/L by using the fluorine-containing dihydric alcohol in the step (1), preparing a solution with the concentration of 0.2mol/L by using diisocyanate, and dropwise adding the diisocyanate solution into the fluorine-containing dihydric alcohol solution within 2-3 hours to carry out heating reaction;
after the reaction in the step (1) is finished, obtaining a hydroxyl-terminated fluorine-containing chain prepolymer solution, directly adding (methyl) acrylic acid isocyanatoethyl ester and a polymerization inhibitor into the hydroxyl-terminated fluorine-containing chain prepolymer solution, and heating for reaction;
the reaction temperature in the step (2) is 50-60 ℃, and the reaction time is 16-24 hours.
6. Use of a fluorine-containing (meth) acrylate prepolymer according to claim 1 for preparing a low surface energy hydrophobic dental resin.
7. A low surface energy hydrophobic dental resin, which is characterized in that the resin is prepared by 49-80 parts by weight of the fluorine-containing (methyl) acrylate prepolymer of claim 1, 20-50 parts by weight of low viscosity (methyl) acrylate reactive diluent, 0.2-1.0 part by weight of photoinitiator and 0.2-1.0 part by weight of accelerator through photoinitiated polymerization.
8. The hydrophobic dental resin with low surface energy as claimed in claim 7, which is prepared by photo-initiated polymerization of 49-59.16 parts by weight of the fluorine-containing (meth) acrylate prepolymer of claim 1, 39.44-49 parts by weight of low viscosity (meth) acrylate reactive diluent, 0.7-1.0 part by weight of photoinitiator and 0.7-1.0 part by weight of accelerator.
9. The low surface energy hydrophobic dental resin of claim 7, wherein the low viscosity (meth) acrylate reactive diluent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.02,6] decane dimethanol acrylate, (perfluorocyclohexyl) methacrylate, 1, 6-bis (acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, dodecafluoroheptyl methacrylate, perfluorooctyl methacrylate, 1H-perfluoro-n-decyl methacrylate, 2,3,3,4,4, at least one of 4-heptafluorobutyl methacrylate, hexafluorobutyl methacrylate and 1H,1H, 5H-octafluoropentyl methacrylate;
or, the low-viscosity (methyl) acrylate reactive diluent is at least one of hexafluorobutyl methacrylate and triethylene glycol dimethacrylate;
or the low-viscosity (methyl) acrylate reactive diluent is hexafluorobutyl methacrylate and triethylene glycol dimethacrylate according to the mass ratio of 3: 1;
the photoinitiator is at least one of camphorquinone, benzophenone and 1-phenyl-1, 2-propanedione;
the accelerant is at least one of ethyl dimethylaminobenzoate, N-dimethylaminoethyl methacrylate.
10. The method for preparing the dental resin with low surface energy and hydrophobicity according to any one of claims 7 to 9, wherein the fluorine-containing (meth) acrylate prepolymer according to claim 1, the low-viscosity (meth) acrylate reactive diluent, the photoinitiator and the accelerator are mixed and stirred uniformly in proportion, and then polymerized for 20 to 60 seconds under the irradiation of light to obtain the dental resin with low surface energy and hydrophobicity;
the light is at least one of blue light and ultraviolet light; the light intensity range is 500-2000mW/cm2
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