CN115286508A - Resin monomer containing photoinitiator group, preparation method thereof and photopolymerisable composition - Google Patents

Resin monomer containing photoinitiator group, preparation method thereof and photopolymerisable composition Download PDF

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CN115286508A
CN115286508A CN202210987022.6A CN202210987022A CN115286508A CN 115286508 A CN115286508 A CN 115286508A CN 202210987022 A CN202210987022 A CN 202210987022A CN 115286508 A CN115286508 A CN 115286508A
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photoinitiator
resin monomer
resin
dental
monomer
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唐永强
饶日川
陈蕾
王方阔
杨森
许杏
李米绮
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Hefei Normal University
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Hefei Normal University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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
    • A61K6/80—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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    • C07—ORGANIC CHEMISTRY
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    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C08F222/1045—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate of aromatic tetraalcohols
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes

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Abstract

The invention discloses a resin monomer containing a photoinitiator group, which has a structural formula shown as a formula (1) or a formula (2); the preparation method comprises the step of carrying out epoxy ring-opening substitution reaction on a photoinitiator containing a dihydroxy functional group and glycidyl methacrylate in the presence of a catalyst and a polymerization inhibitor. The invention also discloses a dental photopolymerizable composition containing the resin monomer and a resin composite material obtained by polymerization of the composition initiated by illumination. The resin monomer contains the photoinitiator group segment, is applied to dental resin restoration, and can effectively prevent micro-leakage and bacterial breeding caused by the exudation of the small molecular initiator, thereby more effectively preventing the occurrence of dental caries.

Description

Resin monomer containing photoinitiator group, preparation method thereof and photopolymerisable composition
Technical Field
The invention relates to the technical field of photopolymerisable materials, in particular to a resin monomer containing a photoinitiator group, a preparation method thereof and a photopolymerisable composition.
Background
The photopolymerization technology originated in 1960, is a novel environment-friendly technology, has the function of curing liquid resin monomers under ultraviolet light or visible light, and has the advantages of high curing speed, energy conservation, environmental protection and the like. Photopolymerization is widely used in various fields of life such as repair of damaged teeth, architectural coatings, and ink printing in printing halls. The photopolymerization system mainly comprises an oligomer, a reactive diluent, a photoinitiator, an auxiliary agent and the like. Photoinitiators, although small in proportion to the photocurable system, play a very important role in polymerization.
The photoinitiator is one of the key technologies of the ultraviolet curing process, the development of the photoinitiator plays a significant role in the development of the ultraviolet technology, and with the progress of the technology, the development of the ultraviolet technology also provides a new standard for the development of the photoinitiator. The benzophenone and anthraquinone derivatives have excellent curing performance and good solubility, can keep objects in an unchanged yellow color for a long time, can prolong the storage time, and is widely applied to dye curing coatings, printing ink and adhesives.
However, conventional small molecular weight photoinitiators have several disadvantages, such as toxicity, low photoreactivity, high migration and poor storage stability, which adversely affect the cured material properties of the reaction product.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a resin monomer containing a photoinitiator group, a preparation method thereof and a photopolymerizable composition.
The invention provides a resin monomer containing a photoinitiator group, which has a structural formula shown as a formula (1) or a formula (2):
Figure BDA0003802235750000021
the invention also provides a preparation method of the resin monomer containing the photoinitiator group, which comprises the following steps: in the presence of a catalyst and a polymerization inhibitor, carrying out an epoxy ring-opening substitution reaction on a photoinitiator containing a dihydroxy functional group and glycidyl methacrylate to obtain the compound; the photoinitiator containing the dihydroxy functional group is 4,4' -dihydroxy benzophenone or 1,8-dihydroxy anthraquinone.
Preferably, the catalyst is a basic tertiary amine, preferably triethylamine, N-dimethyl-p-toluidine or a combination thereof; the polymerization inhibitor is at least one of resorcinol, hydroquinone and 2,5-di-tert-butyl hydroquinone.
Preferably, the molar ratio of the photoinitiator containing a dihydroxy functional group to glycidyl methacrylate is 1: (2-3), wherein the molar ratio of the photoinitiator containing the dihydroxy functional group to the catalyst is 1: (0.03-0.2), the molar ratio of the photoinitiator containing the dihydroxyl functional group to the polymerization inhibitor is 1: (0.1-0.5).
Preferably, the temperature of the epoxy ring-opening substitution reaction is 40-80 ℃ and the time is 8-16h.
Wherein the epoxy ring-opening substitution reaction is carried out under an inert atmosphere.
Preferably, the preparation method further comprises a separation and purification post-treatment step, and specifically comprises the following steps:
after the reaction is finished, washing the reaction solution for 2-5 times by using a NaOH solution with the mass concentration of 5-10%, extracting for 2-3 times by using ethyl acetate, separating out an organic phase, evaporating to dryness the solvent by rotary evaporation, and purifying by column chromatography to obtain the compound.
Or:
after the reaction is finished, washing the reaction liquid for 1-2 times by using petroleum ether, washing the reaction liquid for 2-5 times by using a NaOH solution with the mass concentration of 5-10%, extracting the reaction liquid for 2-3 times by using ethyl acetate, separating an organic phase, evaporating the solvent by rotary evaporation and then purifying the solvent by column chromatography to obtain the catalyst.
The resin monomer in the formula (1) is marked as Bis-MDHBP, the monomer in the formula (2) is marked as Bis-MCHPAQ, and the synthetic route is as follows:
Figure BDA0003802235750000031
the invention also provides application of the resin monomer containing the photoinitiator group as a photoinitiator and a polymerization monomer in a photoinitiation polymerization system.
The invention also provides a dental photopolymerizable composition, which comprises the following components: the resin monomer containing photoinitiator groups, the acrylate resin monomer, the reactive diluent monomer, the tertiary amine co-initiator and the inorganic filler.
Preferably, the dental photopolymerizable composition comprises the following components in parts by mass: 10-30 parts of resin monomer containing photoinitiator groups, 20-60 parts of acrylate resin monomer, 20-60 parts of reactive diluent monomer, 20-40 parts of inorganic filler and 1-2 parts of tertiary amine co-initiator.
Preferably, in the photopolymerizable composition for dental use, the mass ratio of the resin monomer containing a photoinitiator group, the acrylate resin monomer, the reactive diluent monomer, the inorganic filler and the tertiary amine co-initiator is 1: (2-6): (1-6): (1.5-2): (0.05-0.1).
In the invention, the acrylate resin monomer, the reactive diluent monomer, the inorganic filler and the tertiary amine co-initiator are all common components in the field.
Preferably, the acrylate resin monomer is bisphenol A glycerol dimethacrylate, the reactive diluent monomer is triethylene glycol dimethacrylate, and the inorganic filler is silane coupling agent modified nano SiO 2 The tertiary amine co-initiator is dimethylamino ethyl methacrylate.
Preferably, the silane coupling agent is modified nano SiO 2 The preparation method comprises the following steps: mixing 2-8% of silane coupling agent in absolute ethyl alcohol solution with nano SiO 2 Mixing, stirring uniformly, heating to 40-60 ℃, stirring for reacting for 2-5h, and drying after the reaction is finished to obtain the catalyst; wherein the dosage of the silane coupling agent is nano SiO 2 1-10% of the mass.
The invention also provides a dental photopolymerisable resin composite material which is obtained by polymerizing the dental photopolymerisable composition under ultraviolet light or blue light irradiation initiation.
Preferably, the conditions for light-induced polymerization are: the optical density is 600-1000mW/cm 2 The wavelength is 280-500nm, and the illumination time is 20-160s.
The invention has the following beneficial effects:
the resin monomer containing the photoinitiator group is synthesized, and can be used as a photoinitiator and a polymerization monomer in a photoinitiation polymerization system. The resin monomer of the invention is used in a photo-initiated polymerization system, and the photopolymerization reaction can be carried out without adding a small-molecule photoinitiator.
The invention also discloses a dental photopolymerisable composition containing the resin monomer and a dental photopolymerisable resin composite material prepared from the dental photopolymerisable composition. In addition, the resin monomer containing the photoinitiator group has short photocuring time and high monomer conversion rate, so that the dental photopolymerization resin composite material using the resin monomer has excellent mechanical property and water resistance after being cured, and can meet the performance requirements of the industry standard as a dental filling material.
Drawings
FIG. 1 is a UV spectrum of a monomer resin in example 1-2.
FIG. 2 is a graph showing the relationship between the conversion of double bonds of the resin monomers in examples 1-2 as a function of curing time.
FIG. 3 shows the results of the flexural strength tests of the composite materials of examples 6 to 15.
FIG. 4 is the equilibrium water absorption for the composites of examples 6-15.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
In the following examples, silane coupling agent modified nano SiO 2 The preparation method comprises the following steps:
mixing 3% anhydrous alcohol solution of silane coupling agent KH-550 with nanometer SiO 2 Mixing, stirring, heating to 55 deg.C, stirring, reacting for 3 hr, and drying at 45 deg.C for 6 hr; wherein the dosage of the silane coupling agent KH-550 is nano SiO 2 2% by mass.
Example 1
Adding 0.1-0.5 part of resorcinol and 1.0 part of 4,4' -dihydroxy benzophenone into a three-neck flask under the protection of nitrogen by mol parts, adding 2.0-3.0 parts of glycidyl methacrylate and 0.03-0.2 part of triethylamine (Et) 3 N), heating to 40-80 ℃, and stirring for reaction for 8-16h. After the reaction is finished, transferring the reaction solution to a separating funnel, washing the reaction solution for 2 to 5 times by using a NaOH solution with the mass concentration of 5 to 10 percent, extracting the reaction solution for 1 to 2 times by using ethyl acetate, separating an organic phase, evaporating the solvent by using a rotary evaporator, and purifying the solvent by using column chromatography to obtain a Bis-MDHBP resin monomer (the structural formula is shown in the formula (1)).
The resin monomer is processed by a Nicolet IR 200 type infrared spectrometer (KBr tablet); bruker AV-400 nuclear magnetic resonance apparatus (TMS is internal standard, deuterated DMSO is solvent) tests and characteristics, and the results are as follows: IR, v (cm) -1 ):3432(-O-H stretching)， 1 H NMR(400MHz,C 2 D 6 SO),δ(TMS,ppm):1.97(s，6H)，3.22-3.61(m，8H)，4.02(d，2H)，5.70(s，2H)，6.17(d，2H)，6.55(d，2H)，7.05(d，4H)，7.47(m，4H)。
Example 2
Putting 0.1-0.5 part of resorcinol and 1.0 part of 1,8-dihydroxy anthraquinone into a three-neck flask under the protection of nitrogen by mol parts, adding 2.0-3.0 parts of glycidyl methacrylate, 0.03-0.2 part of N, N-dimethyl-p-toluidine (DMPT), heating to 40-80 ℃, and stirring for reacting for 8-16h. After the reaction is finished, transferring the reaction liquid to a separating funnel, washing the product 1-2 times by using petroleum ether, washing the product 2-5 times by using a NaOH solution with the mass concentration of 5-10%, extracting the product 1-2 times by using ethyl acetate, separating an organic phase, evaporating the solvent by using a rotary evaporator, and purifying by using column chromatography to obtain a Bis-MCHPAQ resin monomer (the structural formula is shown as the formula (2)).
The resin monomer is processed by a Nicolet IR 200 type infrared spectrometer (KBr tablet); bruker AV-400 nuclear magnetic resonance apparatus (TMS as internal standard, CDCl) 3 As solvent) test characterization, the results are as follows: IR, v (cm) -1 ):3340(-O-H stretching)， 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):2.04(s，6H)，4.12-4.35(m，8H)，4.85(d，2H)，5.60(s，2H)，6.12(d，2H)，6.50(d，2H)，7.47(d，2H)，7.95(m，4H)。
Example 3
A dental photopolymerizable composition comprises the following components in parts by mass: 10 parts of Bis-MDHBP resin monomer, 20 parts of bisphenol A glycerol dimethacrylate, 20 parts of triethylene glycol dimethacrylate and silane coupling agent modified nano SiO 2 20 parts of dimethylaminoethyl methacrylate and 1 part of dimethylaminoethyl methacrylate.
Example 4
A dental photopolymerizable composition comprises the following components in parts by mass: 30 parts of Bis-MCHPAQ resin monomer, 60 parts of bisphenol A glycerol dimethacrylate, 60 parts of triethylene glycol dimethacrylate and silane coupling agent modified nano SiO 2 40 parts of dimethylaminoethyl methacrylate and 2 parts of dimethylaminoethyl methacrylate.
Example 5
A dental photopolymerizable composition comprises the following components in parts by mass: bis-MDHBP resin sheet20 parts of body, 40 parts of bisphenol A glycerol dimethacrylate, 40 parts of triethylene glycol dimethacrylate and silane coupling agent modified nano SiO 2 30 parts of dimethylaminoethyl methacrylate and 1.5 parts of dimethylaminoethyl methacrylate.
Example 6
Preparing a dental photopolymerisable resin composite material:
weighing 0.3g of Bis-MDHBP resin monomer, 1.8g of bisphenol A glycerol dimethacrylate and 0.6g of triethylene glycol dimethacrylate, adding the components into a beaker which is shielded from light by tin foil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.6g, stirring uniformly, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED light curing lamp (800 mw/cm) with the wavelength of 300nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 7
Preparing a dental photopolymerizable resin composite material:
weighing 0.3g of Bis-MDHBP resin monomer, 1.2g of bisphenol A glycerol dimethacrylate and 1.2g of triethylene glycol dimethacrylate, adding the weighed materials into a beaker which is shielded from light by tin foil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.6g, stirring uniformly, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED light curing lamp (800 mw/cm) with the wavelength of 300nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 8
Preparing a dental photopolymerisable resin composite material:
weighing 0.3g of Bis-MDHBP resin monomer, 0.6g of bisphenol A glycerol dimethacrylate and 1.8g of triethylene glycol dimethacrylate, adding the weighed materials into a beaker which is shielded from light by tin foil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.6g, evenly stirred and ultrasonically dispersed for 45 minutes, and then vacuum drying is carried outVacuumizing a drying box for 2h, drying, adding into a polytetrafluoroethylene mold, uniformly coating, flatly removing bubbles, and curing with an LED (light-emitting diode) light curing lamp (800 mw/cm) with the wavelength of 300nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 9
Preparing a dental photopolymerizable resin composite material:
weighing 0.6g of Bis-MDHBP resin monomer, 1.8g of bisphenol A glycerol dimethacrylate and 0.6g of triethylene glycol dimethacrylate, adding the weighed materials into a beaker which is shielded from light by tin foil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.9g, stirring uniformly, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED light curing lamp (800 mw/cm) with the wavelength of 300nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 10
Preparing a dental photopolymerisable resin composite material:
weighing 0.6g of Bis-MDHBP resin monomer, 1.8g of bisphenol A glycerol dimethacrylate and 0.6g of triethylene glycol dimethacrylate, adding the mixture into a lightproof beaker made of tinfoil paper, and then adding 0.06g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 1.2g, uniformly stirring, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED (light-emitting diode) light curing lamp (800 mw/cm) with the wavelength of 300nm 2 ) And (4) demolding after irradiating for 100s to obtain the resin composite material.
Example 11
Preparing a dental photopolymerizable resin composite material:
weighing 0.3g of Bis-MCHPAQ resin monomer, 1.8g of bisphenol A glycerol dimethacrylate and 0.6g of triethylene glycol dimethacrylate, adding the materials into a beaker which is shielded from light by tin foil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.6g, stirred evenly and dispersed by ultrasonic for 45 minutes, and then putVacuum-pumping in a vacuum drying oven for 2h, drying, adding into a polytetrafluoroethylene mold, uniformly coating, removing bubbles, and curing with LED light curing lamp (800 mw/cm) with wavelength of 420nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 12
Preparing a dental photopolymerizable resin composite material:
weighing 0.3g of Bis-MCHPAQ resin monomer, 1.2g of bisphenol A glycerol dimethacrylate and 1.2g of triethylene glycol dimethacrylate, adding the materials into a beaker which is shielded from light by tin foil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.6g, stirring uniformly, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED light curing lamp (800 mw/cm) with the wavelength of 420nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 13
Preparing a dental photopolymerisable resin composite material:
weighing 0.3g of Bis-MCHPAQ resin monomer, 0.6g of bisphenol A glycerol dimethacrylate and 1.8g of triethylene glycol dimethacrylate, adding the mixture into a lightproof beaker made of tinfoil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.6g, stirring uniformly, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED light curing lamp (800 mw/cm) with the wavelength of 420nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Example 14
Preparing a dental photopolymerisable resin composite material:
weighing 0.6g of Bis-MCHPAQ resin monomer, 1.8g of bisphenol A glycerol dimethacrylate and 0.6g of triethylene glycol dimethacrylate, adding the mixture into a lightproof beaker made of tinfoil paper, and then adding 0.03g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 0.9g, stirred evenly and dispersed by ultrasound 4After 5 minutes, the mixture is placed into a vacuum drying oven for vacuumizing and exhausting for 2 hours, the dried mixture is added into a polytetrafluoroethylene mold, air bubbles are evenly coated and discharged, and an LED light curing lamp (800 mw/cm) with the wavelength of 420nm is used 2 ) And (4) demolding after irradiating for 100s to obtain the resin composite material.
Example 15
Preparing a dental photopolymerisable resin composite material:
weighing 0.6g of Bis-MCHPAQ resin monomer, 1.8g of bisphenol A glycerol dimethacrylate and 0.6g of triethylene glycol dimethacrylate, adding the weighed materials into a beaker which is shielded from light by tin foil paper, and then adding 0.06g of dimethylamino ethyl methacrylate and silane coupling agent modified nano SiO 2 1.2g, uniformly stirring, ultrasonically dispersing for 45 minutes, putting into a vacuum drying oven, vacuumizing and exhausting for 2 hours, drying, adding into a polytetrafluoroethylene mold, uniformly coating and horizontally exhausting bubbles, and using an LED (light-emitting diode) light curing lamp (800 mw/cm) with the wavelength of 420nm 2 ) And (4) demolding after the irradiation for 100s to obtain the resin composite material.
Test examples
The UV spectrums of the resin monomers of examples 1-2 were measured, and the results are shown in FIG. 1. As can be seen from FIG. 1, the Bis-MDHBP and the Bis-MCHPAQ resin monomers have distinct characteristic absorption peaks at 298nm and 410nm, respectively, so that the photo-initiation effect can be achieved under a light source with a specific wavelength to induce the photo-polymerization reaction of the acrylate monomers.
The resin monomers of examples 1-2 were tested for double bond conversion as a function of curing time, and the results are shown in FIG. 2. In the initial stage of photocuring (0-40 s), the double bond conversion rate of the composite resin is low, and the growth rate is slow. When the curing time is more than 40s, the conversion rate of double bonds is greatly increased, the growth rate is high, and most of resin monomers participate in the polymerization reaction. The increase in double bond conversion gradually flattens out until the curing time reaches 80 s. When the curing time reaches 120s, the double bond conversion rates of the Bis-MDHBP and the Bis-MCHPAQ resin reach 63.1 percent and 60.9 percent respectively.
Resin composite test pieces having the dimensions of 25mm × 2mm × 2mm were prepared and tested for flexural resistance according to the methods of examples 6-15, as follows:
a three-point bending loading method is adopted in a universal material testing machine, and a sample is loaded at a loading speed of 1mm/min until the sample reaches a yield point or reaches a fracture point if no yield point exists. The maximum load applied when the specimen reaches the yield or breaking point is recorded.
Flexural strength (σ/MPa):
Figure BDA0003802235750000111
f-maximum load value (N); b-is the test piece width measured immediately; l-the distance of the fulcrum of the lower loading platform; h-is the specimen height measured immediately.
The bending resistance results are shown in FIG. 3. In FIG. 3, the left side of the group A of abscissas is example 6 and the right side is example 11; group B left is example 7 and right is example 12; group C left example 8 and right example 13; group D left is example 9 and right is example 14; group E has example 10 on the left and example 15 on the right. As can be seen from fig. 3, the bending strength macroscopically exhibited becomes larger as the monomer content of the resin increases. Under the same conditions, the content of the modified filler becomes larger, and the bending strength also shows an increasing trend. After 100s of light irradiation, the bending strength of the composite resin of example 6 was 82.4MPa, and the bending strength of the composite resin of example 11 was 81.9MPa.
Resin composite disc samples having a diameter of 25mm and a height of 1mm were prepared according to the methods of examples 6-15 and were subjected to a balanced water absorption test as follows:
the sample was immersed in distilled water (37 st 1) deg.C for 7 days. Using an isolation frame to ensure that the samples are vertically placed and the gaps among the samples are at least 3mm, taking out the samples after soaking each sample in water with the volume of at least 10ml and 7d, washing with water, sucking water on the surfaces of the samples, and shaking in the air for 15s. The sample is taken out of the water for 1min and weighed, and is recorded as m 1 . After weighing, putting the sample into a dryer to reach the constant mass, and recording as m 0 。
The water absorption Wsp of the sample was calculated by the following equation.
Figure BDA0003802235750000121
In the formula:
m l mass in milligrams (mg) after the sample is soaked in water for 7 days; m is 0 Constant mass in milligrams (mg) oven-dried after the sample has been soaked in water for 7 days; v-sample volume in cubic millimeters (mm) 3 )。
The results of the equilibrium water absorption test are shown in fig. 4. In FIG. 4, the left side of the group A of abscissas is example 6 and the right side is example 11; group B left is example 7 and right is example 12; the left side of group C is example 8, and the right side is example 13; group D left example 9 and right example 14; group E has example 10 on the left and example 15 on the right. It can be seen that the swelling is not easily expanded because the crosslinked network structure which can be formed after the resin monomer is cured restricts the volume increase upon water absorption. However, as the amounts of the reactive diluent and the inorganic filler are increased, the gaps of the network structure are increased, and the equilibrium water absorption rate is increased. The highest balance water absorption value of the composite resin in each embodiment is 2.86% (including Bis-MDHBP) and 2.94% (including Bis-MCHPAQ), and the highest balance water absorption value is converted into a water absorption value, namely 37.1 mu g/mm 3 And 38.2. Mu.g/mm 3 。
According to the national industry standard YY1042-2011 dental science polymer-based filling, repairing and cementing material, the resin composite material is a class II material according to the classification standard, namely a non-occlusal surface filling repairing material (type II) and a filling repairing material which is solidified by external energy, blue light or heat energy. According to the parameters given by the standard, the bending strength is required to be more than 50MPa, and the water absorption value is less than 40 mu g/mm 3 . The performance result of the resin composite material meets the parameter value defined by the standard, and meets the condition of being used as a dental filling material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. A resin monomer containing a photoinitiator group is characterized in that the structural formula is shown as formula (1) or formula (2):
Figure FDA0003802235740000011
2. the method for preparing the resin monomer containing the photoinitiator group according to claim 1, wherein the resin monomer is obtained by performing an epoxy ring-opening substitution reaction of the photoinitiator containing a dihydroxy functional group and glycidyl methacrylate in the presence of a catalyst and a polymerization inhibitor; the photoinitiator containing the dihydroxy functional group is 4,4' -dihydroxybenzophenone or 1,8-dihydroxyanthraquinone.
3. The method of claim 2, wherein the catalyst is a basic tertiary amine, preferably triethylamine, N-dimethyl-p-toluidine or a combination thereof; the polymerization inhibitor is at least one of resorcinol, hydroquinone and 2,5-di-tert-butyl hydroquinone.
4. The method of claim 2, wherein the molar ratio of the dihydroxy functional group-containing photoinitiator to glycidyl methacrylate is 1: (2-3), wherein the molar ratio of the photoinitiator containing the dihydroxy functional group to the catalyst is 1: (0.03-0.2), the molar ratio of the photoinitiator containing the dihydroxyl functional group to the polymerization inhibitor is 1: (0.1-0.5);
preferably, the temperature of the epoxy ring-opening substitution reaction is 40-80 ℃ and the time is 8-16h.
5. Use of the resin monomer containing a photoinitiator group according to claim 1 as a photoinitiator and as a polymerization monomer in a photoinitiated polymerization system.
6. A photopolymerizable composition for dental use, comprising the following components: the resin monomer containing photoinitiator groups, the acrylate resin monomer, the reactive diluent monomer, the tertiary amine co-initiator and the inorganic filler of claim 1.
7. A photopolymerizable composition for dental use according to claim 6 characterized by comprising the following components in parts by mass: 10-30 parts of resin monomer containing photoinitiator groups, 20-60 parts of acrylate resin monomer, 20-60 parts of reactive diluent monomer, 20-40 parts of inorganic filler and 1-2 parts of tertiary amine auxiliary initiator according to claim 1.
8. The photopolymerizable composition for dental use according to claim 6 or 7, wherein the acrylate resin monomer is bisphenol A glycerol dimethacrylate, the reactive diluent monomer is triethylene glycol dimethacrylate, and the inorganic filler is silane coupling agent modified nano SiO 2 The tertiary amine co-initiator is dimethylamino ethyl methacrylate.
9. A dental photopolymerizable resin composite material, which is obtained by polymerizing the dental photopolymerizable composition according to any one of claims 6 to 8 under ultraviolet light or blue light irradiation.
10. A dental photopolymerizable resin composite according to claim 9, wherein the condition for the light-induced polymerization is: the optical density is 600-1000mW/cm 2 The wavelength is 280-500nm, and the illumination time is 20-160s.
CN202210987022.6A 2022-08-17 2022-08-17 Resin monomer containing photoinitiator group, preparation method thereof and photopolymerisable composition Pending CN115286508A (en)

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