CN102276468B - Resin containing adamantanes, preparation method and application of resin - Google Patents
Resin containing adamantanes, preparation method and application of resin Download PDFInfo
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Abstract
The invention discloses resin containing adamantanes, a preparation method and application of the resin for dental restoration, belonging to a kind of polymer resin, a preparation method and application thereof for dental restoration. The general formula of the resin is shown as an equation in the specification, wherein m is 0-6, and n is 0-6. The preparation method comprises the following steps of: taking dihydroxyl adamantanes and a derivative thereof as raw materials; carrying out ring-opening reaction with a phthalic anhydride derivative to obtain a dicarboxyl product; and then carrying out ring-opening reaction with glycidyl acrylate to obtain dental restoration resin with photo-polymerization activity. The kind of resin has the structure of adamantane so that the resin has high reaction activity and a good mechanical performance.
Description
Technical field
The invention belongs to a Type of Collective resin, preparation method and in gear division reparation application, particularly contain resin, the preparation method of adamantane and apply in the gear division reparation.
Technical background
The resinous principle of dental compound resin is polymeric matrices.Polymkeric substance is repeatedly to link together formed by a large amount of monomers.Resin monomer is found in 1843 by Germany scientist J.Rcdtenbacher, and called after vinylformic acid.To 20th century, methacrylic acid and its some ester classes, comprise that methyl methacrylate is synthesized out, but its polymerization shrinkage is larger, and thermal expansivity is high, and variable color is remarkable, larger to the dental pulp infringement.Nineteen sixty-five, Bowen has synthesized brand-new monomer, and this monomer is similar to epoxy resin structural, and some functional group is replaced by methacrylic acid.This compound is synthetic by dihydroxyphenyl propane diglycidyl ether and methacrylic acid, by two carbon chemical bond of two methacrylic acid groups, is combined with dihydroxyphenyl propane and forms Bis-GMA (dihydroxyphenyl propane glycidyl methacrylate).The Bis-GMA molecular weight is large, and volatility is low, and polymerization shrinkage is little, and reaction is very fast, and the resinous substrates quality formed is solid, fine and close, thereby is better than methyl methacrylate on performance.Because the effect of compound resin is relevant with the polymerization shrinkage of resin to a great extent. and polymerization shrinkage is mainly to cause because of the Van der Waals distance between monomer molecule (vaIl der waals distances), and between the monomer molecule of monomer-polymer of the same race, be mainly to cause because of the covalent linkage distance, so in order to reduce or to avoid polymerization shrinkage
Along with the compound resin performance update and perfect, oneself can meet the needs that different zones, different tooth position are repaired fully its intensity, hardness and wear resistance etc.But all there is 1.5%～3% volumetric shrinkage variation in the compound resin used at present while solidifying, when clinical use, due to the bonding of resin and cavity wall, limited the free shrink of resin, thereby caused the generation of string stress.Claus-Peter Ernst etc. thinks: in clinical resin is repaired, cause that the failed major cause of bonding is not the size of volumetric shrinkage but the size of string stress.This string stress all can produce obvious detrimentally affect to intensity of cohesive strength, resin and the tooth itself of resin and tooth etc.Studies show that, the curing shrinkage internal stress of resin can cause the tack coat fracture, forms microfissure and then produces secondary caries: can cause the distortion of weak hole wall at the tooth of serious defect, even local jackknifing; The long-time existence of resin solidification string stress also makes the folding strength of resin itself reduce, and when bearing snap-in force, the fracture of material easily appears in weak part.Between the different sorts resin, between the one species different resins, all there is notable difference in its curing shrinkage internal stress, even between the different resins of equal volume shrinking percentage, its string stress also is not quite similar.Therefore research and develop the resin with high reaction activity, low-shrinkage and there is the meaning of very important commercial applications and scientific research.
Diamantane (Adamantane), because of the arrangement of carbon atom in its molecule and identical the gaining the name of elementary cell of diamond latticep, is the cage compound that a kind of symmetry is very high.The molecular structure of this uniqueness is given the physics and chemistry character of diamantane uniqueness.It,, as a kind of novel fine chemical material, is causing people's great attention.Diamantane has the characteristics such as density large (1.07g/cm3), calorific value high (combustion heat (6033 ± 3) kJ/mol).Its many nitros of derivative diamantane, many nitros of azepine diamantane etc. are the high Energy Density Materials of being praised highly most in recent years.
Adamantane structure is introduced to the resin medium chain, can improve many performances of dental material as improved thermotolerance, oxidation-resistance and directional stability, improve anti-solvent, water-fast, fast light radiation and resistance toheat, increase the intensity of polymkeric substance, reduce shrinkage coefficient and density, and give the dimensional stability of poly-platform thing excellence and the biocompatibility of processing stability and raising resin etc.
Summary of the invention
The invention discloses as shown in the formula a class containing the resin of adamantane, preparation method and the application of repairing in gear division thereof, the structure that this resinoid contains diamantane, give resin and have high reactive behavior, good mechanical property.
Resin containing adamantane of the present invention, the chemical structure of this resin is shown below:
Wherein, m=0-6, n=0-6;
Wherein said R=H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
2cH
3, C (CH
3)
3, F or Cl.
R wherein
1=H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
2cH
3, C (CH
3)
3, F or Cl.
R wherein
2=H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
2cH
3, C (CH
3)
3, F or Cl.
The reaction formula of the resin containing adamantane involved in the present invention is as follows:
The preparation method of the resin containing adamantane of the present invention, carry out according to following step:
(1) dihydroxyl diamantane and derivative thereof are mixed to intensification with o-benzoic acid acid anhydride and derivative thereof, mixture stirs 2-10 hour at 90-175 ℃, obtain containing adamantane phenylformic acid and derivative thereof, the mol ratio of wherein said dihydroxyl diamantane and derivative thereof and o-benzoic acid acid anhydride and derivative thereof is 1:2;
(2) will with glycidyl methacrylate, mix containing adamantane phenylformic acid and derivative thereof, add catalyzer and stopper, at 60-135 ℃ of reaction 1-12 hour, obtain the gear division resin for restoration containing adamantane, wherein adamantane phenylformic acid and derivative thereof: the mol ratio of glycidyl methacrylate is 1:2;
Catalyzer described in step of the present invention (2) is Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl bromide, four heptyl brometo de amonios, methyl triethyl brometo de amonio, benzyl triethyl ammonium bromide, benzyltrimethylammonium bromide, benzyl tributyl brometo de amonio, three normal-butyl amyl group brometo de amonios, three (octadecyl) methyl brometo de amonio, didodecyldimethylammbromide bromide, DDA, DHAB, two tetradecyl dimethyl brometo de amonios, four n-octyl bromination ammonium or dodecyl dimethyl benzyl ammonium bromides; Its consumption be adamantane phenylformic acid and derivative amount thereof in mole 0.1%-5%.
Stopper described in step of the present invention (2) is MEHQ, Resorcinol, phenothiazine or benzoquinones, its consumption be adamantane phenylformic acid and derivative amount thereof in mole 0.1%-5%.
The application of the resin containing adamantane of the present invention, can be applicable to the gear division reparation.
Advantage of the present invention: the invention belongs to a class and contain resin of adamantane and preparation method thereof, the preparation method is simple for this resinoid, and the structure that contains diamantane can be given resin and be had high reactive behavior, and good mechanical property, be applicable to the gear division reparation.
The accompanying drawing explanation
Accompanying drawing 1, the comparison diagram of the rate of polymerization of diamantane methacrylic resin and dihydroxyphenyl propane glycidyl methacrylate (Bis-GMA) resin, thinner is TEGDMA (TEGDMA), resin/TEGDMA=70/30 wt%, initiator arone (camphorquinone) is 1wt%, aided initiating 1wt%, light intensity is 20mW/cm
2.
Accompanying drawing 2, in unloaded situation, difference diamantane methacrylic resin and dihydroxyphenyl propane glycidyl methacrylate (Bis-GMA) resin, the comparison diagram of tan δ-T.Thinner used is TEGDMA (TEGDMA), resin/TEGDMA=70/30 wt%, initiator arone (camphorquinone) is 1wt%, aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) 1wt%, light intensity is 20mW/cm
2.
Specific implementation method:
Following embodiment describes the present invention in detail, but does not limit the scope of the invention.
Embodiment 1:
Mole 0.1 (16.8g) 1,3-dihydroxyl diamantane mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 5 hours at 135 ℃, obtains 1,3-dihydroxyl diamantane benzoic ether o-benzoic acid.Mole 0.1 (36.4g) 1,3-dihydroxyl diamantane benzoic ether o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer tetraethylammonium bromide 1 mmole (0.165) and hydroquinone of polymerization retarder 1 mmole (0.11g), 95 ℃ of reactions 4 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxyl diamantane benzoic ether o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 1.
1h NMR (250 MHz) in CDCl
3: δ 1.41-2.34ppm (14H, diamantane), 1.93ppm (3H, CH
3), 4.18-4.53ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Structural formula 1
Embodiment 2:
0.1 the 1-hydroxyl-3 methylol diamantane of mole (18.2g) mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 3 hours at 80 ℃, obtains 1-hydroxyl-3 methylol diamantane benzoic ether o-benzoic acid.0.1 the 1-hydroxyl-3 methylol diamantane benzoic ether o-benzoic acid of mole (47.8g) mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer Tetrabutyl amonium bromide 0.1 mmole (0.0322g) and hydroquinone of polymerization retarder 0.1 mmole (0.011g), 135 ℃ of reactions 1 hour, obtain opening glycidyl methacrylate containing the gear division resin for restoration 1-hydroxyl-3 methylol diamantane benzoic ether o-benzoic acid of adamantane, structure is as shown in structural formula 2.
1h NMR (250 MHz) in CDCl
3: δ 1.07-1.78ppm (14H, diamantane), 1.93ppm (3H, CH
3), 4.17ppm (2H, CH
2oOC), 4.18-4.53ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.58-8.08ppm(4H, phenyl ring).
Structural formula 2
Embodiment 3:
Mole 0.1 (18.2g) 1,3-dihydroxyl-5-methyl adamantane mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 12 hours at 150 ℃, obtains 1,3-dihydroxyl-5-methyl adamantane benzoic ether o-benzoic acid.Mole 0.1 (47.8g) 1,3-dihydroxyl-5-methyl adamantane benzoic ether o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer four heptyl brometo de amonio 5 mmoles (2.45) and stopper MEHQ 5 mmoles (0.62g), 60 ℃ of reactions 8 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxyl-5-methyl adamantane benzoic ether o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 3.
1h NMR (250 MHz) in CDCl
3: δ 1.06ppm (3H, CH
3), 1.41-2.34ppm (13H, diamantane), 1.93ppm (3H, CH
3), 4.30-4.41ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Embodiment 4:
Mole 0.1 (22.4g) 1,3-dihydroxyl-5-isobutyl-diamantane mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 7 hours at 110 ℃, obtains 1,3-dihydroxyl-5-isobutyl-diamantane benzoic ether o-benzoic acid.Mole 0.1 (52g) 1,3-dihydroxyl-5-isobutyl-diamantane benzoic ether o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer four heptyl brometo de amonio 0.5 mmoles (0.245) and stopper MEHQ 5 mmoles (0.62g), 100 ℃ of reactions 6 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxyl-5-isobutyl-diamantane benzoic ether o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 4.
1h NMR (250 MHz) in CDCl
3: δ 1.06ppm (9H, C (CH
3)
3), 1.41-2.34ppm (13H, diamantane), 1.93ppm (3H, CH
3), 4.30-4.41ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Structural formula 4
Embodiment 5:
Mole 0.1 (30.8g) 1,3-dihydroxyl-5-isobutyl--5 ˊ-n-hexyl-diamantane mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 6 hours at 95 ℃, obtains 1,3-dihydroxyl-5-isobutyl--5 ˊ-n-hexyl-diamantane benzoic ether o-benzoic acid.Mole 0.1 (59.6g) 1,3-dihydroxyl-5-isobutyl--5 ˊ-n-hexyl-diamantane benzoic ether o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer three (octadecyl) methyl brometo de amonio 1 mmole (0.869) and stopper phenothiazine 2 mmoles (0.4g), 87 ℃ of reactions 4 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxyl-5-isobutyl--5 ˊ-n-hexyl-diamantane benzoic ether o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 5.
1h NMR (250 MHz) in CDCl
3: δ 0.96-1.29ppm (13H, CH
2cH
2cH
2cH
2cH
2cH
3), 1.06ppm (9H, C (CH
3)
3), 1.41-2.34ppm (12H, diamantane), 1.93ppm (3H, CH
3), 4.30-4.41ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Structural formula 5
Embodiment 6:
Mole 0.1 (20.3g) 1,3-dihydroxyl-5-chlorine diamantane mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 12 hours at 150 ℃, obtains 1,3-dihydroxyl-5-methyl adamantane benzoic ether o-benzoic acid.Mole 0.1 (49.9g) 1,3-dihydroxyl-5-chlorine diamantane benzoic ether o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer four heptyl brometo de amonio 5 mmoles (2.45) and stopper benzoquinones 0.7 mmole (0.0756g), 95 ℃ of reactions 7 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxyl-5-chlorine diamantane benzoic ether o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 6.
1h NMR (250 MHz) in CDCl
3: δ 1.41-2.94ppm (13H, diamantane), 1.93ppm (3H, CH
3), 4.30-4.41ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Structural formula 6
Embodiment 7:
Mole 0.1 (20.3g) 1,3-dihydroxyl diamantane mixes intensification with 0.2 mole of (32.4g) 1-methyl o-benzoic acid acid anhydride, mixture stirs 5 hours at 105 ℃, obtains 1,3-dihydroxy diamantane benzoic ether methyl o-benzoic acid.1 mole (52.7g) 1,3-dihydroxy diamantane benzoic ether methyl o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer DDA 0.5 mmole (0.315) and hydroquinone of polymerization retarder 1 mmole (0.11g), 105 ℃ of reactions 3 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxy diamantane benzoic ether methyl o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 7.
1h NMR (250 MHz) in CDCl
3: δ 1.41-2.94ppm (14H, diamantane), 1.93ppm (3H, CH
3), 2.35ppm (6H, C
6h
4cH
3) 4.30-4.41ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Embodiment 8:
Mole 0.1 (20.3g) 1,3-dihydroxyl diamantane mixes intensification with 0.2 mole of (33.2g) 1-fluorine o-benzoic acid acid anhydride, mixture stirs 3 hours at 145 ℃, obtains 1,3-dihydroxy diamantane benzoic ether fluorine o-benzoic acid.1 mole (53.5g) 1,3-dihydroxy diamantane benzoic ether fluorine o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer dodecyl dimethyl benzyl ammonium bromide 0.3 mmole (0.115) and stopper benzoquinones 0.7 mmole (0.0756g), 115 ℃ of reactions 6 hours, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxy diamantane benzoic ether fluorine o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 8.
1h NMR (250 MHz) in CDCl
3: δ 1.41-2.34ppm (14H, diamantane), 1.93ppm (3H, CH
3), 2.35ppm (6H, C
6h
4cH
3) 4.30-4.41ppm(5H, CH
2cH (OH) CH
2) 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.29-7.85ppm(3H, phenyl ring).
Structural formula 8
Embodiment 9:
0.1 the 1-hydroxyl-3 hydroxyl hexyl diamantane of mole (25.2g) mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 3 hours at 80 ℃, obtains 1,3-diamantane benzoic ether o-benzoic acid.0.1 the 1-hydroxyl-3 hydroxyl hexyl diamantane benzoic ether o-benzoic acid of mole (54.8g) mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer Tetrabutyl amonium bromide 0.1 mmole (0.0322g) and stopper benzoquinones 0.7 mmole (0.0756g), 125 ℃ of reactions 4 hours, obtain opening glycidyl methacrylate containing the gear division resin for restoration 1-hydroxyl-3 hydroxyl hexyl diamantane benzoic ether o-benzoic acid of adamantane, structure is as shown in structural formula 1.
1h NMR (250 MHz) in CDCl
3: δ 1.21-4.25ppm ((CH
2)
5cH
2oOC), 1.41-2.34ppm (14H, diamantane), 1.93ppm (3H, CH
3), 4.30-4.41ppm(5H, CH
2cH (OH) CH
2), 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Structural formula 9
Embodiment 10:
Mole 0.1 (33.6g) 1,3-dihydroxy hexyl diamantane mixes intensification with 0.2 mole of (29.6g) o-benzoic acid acid anhydride, mixture stirs 3 hours at 80 ℃, obtains 1,3-dihydroxy hexyl diamantane benzoic ether o-benzoic acid.Mole 0.1 (47.8g) 1,3-dihydroxy hexyl diamantane benzoic ether o-benzoic acid mixes with the glycidyl methacrylate of 2 moles (28.4g), add catalyzer dodecyl dimethyl benzyl ammonium bromide 0.3 mmole (0.115) and hydroquinone of polymerization retarder 0.1 mmole (0.011g), 135 ℃ of reactions 1 hour, obtain the gear division resin for restoration 1 containing adamantane, 3-dihydroxy hexyl diamantane benzoic ether o-benzoic acid is opened glycidyl methacrylate, and structure is as shown in structural formula 1.
1h NMR (250 MHz) in CDCl
3: δ 1.21-4.25ppm (12H, (CH
2)
5cH
2oOC) 1.41-2.34ppm (14H, diamantane), 1.93ppm (3H, CH
3), 4.30-4.41ppm(5H, CH
2cH (OH) CH
2), 5.58ppm(1H, two keys) 6.15ppm(1H, two keys), 7.57-8.10ppm(4H, phenyl ring).
Structural formula 10
Application Example
Application Example 1
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 1, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 78.7%, curing depth is 3mm, material flexural strength 88.3MPa.
Application Example 2
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 2, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 67.8%, curing depth is 2.8mm, material flexural strength 89.3MPa.
Application Example 3
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 3, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 72.5%, curing depth is 3.1mm, material flexural strength 87.3MPa.
Application Example 4
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 4, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 69.4%, curing depth is 2.6mm, material flexural strength 88.6MPa.
Application Example 5
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 5, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 75.2%, curing depth is 3.5mm, material flexural strength 90.5MPa.
Application Example 6
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 6, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 76.1%, curing depth is 3.6mm, material flexural strength 86.3MPa.
Application Example 7
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 7, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 70.7%, curing depth is 2.7mm, material flexural strength 91.5MPa.
Application Example 8
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 8, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 73.3%, curing depth is 3.4mm, material flexural strength 95.6MPa.
Application Example 9
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 9, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 75.4%, curing depth is 3.3mm, material flexural strength 91.8MPa.
Application Example 10
Dissolve 0.05g light trigger virtue diketone (CQ) and 0.05g aided initiating 4-N, N-dimethylaminobenzoic acid ethyl ester (EDMAB) is in 2.5g TEGDMA (TEGDMA), prepare the proportioning 75wt%:25wt% of diamantane resin/TEGDMA with the diamantane mixed with resin of 7.5g embodiment 10, the content of CQ is 0.5 wt%, the organic resin system that the content of EDMAB is 0.5 wt%, fully stir system is mixed, then to add the aerosil filler AEROSIL R711 that mean particle size is 12 nanometers (German DEGUSSA company) 7.34g(mass content in this system be amount of the mixture 40%) and the mean particle size aerosil filler AEROSIL R202 that is 7 nanometers (German DEGUSSA company) 0.92g(mass content be amount of the mixture 5%), fully stir it is mixed, obtain the composite system that organic resin system and mineral filler mass ratio are 55:45.In darkroom, this composite system is injected to the 8mm(diameter after standing 12 hours) * 1mm(thickness) polyfluortetraethylene plate, after upper and lower surface clamps by glass slide, standing to be tested to without bubble the time.Under room temperature, in air atmosphere, by testing sample light intensity 100mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite materials, with infrared instrument tracking monitor under the near infrared condition, calculating final double bond conversion rate is 71.3%, curing depth is 3.4mm, material flexural strength 87.9MPa.
Claims (5)
1. containing the resin of adamantane, it is characterized in that the chemical structure of this resin is shown below:
Wherein, m=0-6, n=0-6;
R=H wherein, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
2cH
3, C (CH
3)
3, F or Cl;
R wherein
1=H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
2cH
3, C (CH
3)
3, F or Cl;
R wherein
2=H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
3, CH
2cH
2cH
2cH
2cH
2cH
3, C (CH
3)
3, F or Cl.
2. the preparation method of the resin containing adamantane according to claim 1 is characterized in that carrying out according to following step:
(1) dihydroxyl diamantane and derivative thereof are mixed to intensification with Tetra hydro Phthalic anhydride and derivative thereof, mixture stirs 2-10 hour at 90-175 ℃, obtain containing adamantane phenylformic acid and derivative thereof, the mol ratio of wherein said dihydroxyl diamantane and derivative thereof and o-benzoic acid acid anhydride and derivative thereof is 1: 2;
(2) will with glycidyl methacrylate, mix containing adamantane phenylformic acid and derivative thereof, add catalyzer and stopper, at 60-135 ℃ of reaction 1-12 hour, obtain the gear division resin for restoration containing adamantane, wherein the mol ratio containing adamantane phenylformic acid and derivative and glycidyl methacrylate is 1: 2.
3. the preparation method of the resin containing adamantane according to claim 2, it is characterized in that wherein the catalyzer described in step (2) is Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl bromide, four heptyl brometo de amonios, methyl triethyl brometo de amonio, benzyl triethyl ammonium bromide, benzyltrimethylammonium bromide, benzyl tributyl brometo de amonio, three normal-butyl amyl group brometo de amonios, three (octadecyl) methyl brometo de amonio, didodecyldimethylammbromide bromide, DDA, DHAB, two tetradecyl dimethyl brometo de amonios, four n-octyl bromination ammonium or dodecyl dimethyl benzyl ammonium bromides, its consumption for containing adamantane phenylformic acid and derivative amount thereof in mole 0.1%-5%.
4. the preparation method of the resin containing adamantane according to claim 2, it is characterized in that wherein the stopper described in step (2) is MEHQ, Resorcinol, phenothiazine or benzoquinones, its consumption for containing adamantane phenylformic acid and derivative amount thereof in mole 0.1%-5%.
5. the application of the resin containing adamantane described in claim 1, is characterized in that being applied to the gear division reparation.
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| US20190300472A1 (en) * | 2014-08-26 | 2019-10-03 | Tokuyama Dental Corporation | Polymerizable monomer, method of producing polymerizable monomer, curable composition and resin member |
| CN104910354B (en) * | 2015-05-30 | 2017-05-31 | 吴爱群 | A kind of adamantyl resin combination and its manufacture method |
| CN104910123A (en) * | 2015-05-30 | 2015-09-16 | 吴爱群 | Adamantyl resin monomer mixture and manufacturing method thereof |
| JP6629089B2 (en) * | 2016-02-12 | 2020-01-15 | 株式会社トクヤマデンタル | Dental curable composition |
| JP6629088B2 (en) * | 2016-02-12 | 2020-01-15 | 株式会社トクヤマデンタル | Dental mucosal conditioner |
| JP6629090B2 (en) * | 2016-02-12 | 2020-01-15 | 株式会社トクヤマデンタル | Powder-liquid type dental hardening material |
| JP6614996B2 (en) * | 2016-02-18 | 2019-12-04 | 株式会社トクヤマデンタル | Method for producing polymerizable monomer |
| CN116368118A (en) * | 2020-10-09 | 2023-06-30 | 保土谷化学工业株式会社 | Adamantane compound, organic electroluminescent element, and electronic device |
| CN117186361B (en) * | 2023-08-08 | 2024-05-17 | 广东炎墨方案科技有限公司 | Adamantane modified high-heat-resistance photo-curing solder resist ink and preparation method thereof |
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