CN102311346B - Adamantane-containing resin as well as preparation method and application thereof - Google Patents
Adamantane-containing resin as well as preparation method and application thereof Download PDFInfo
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- CN102311346B CN102311346B CN201110166373.2A CN201110166373A CN102311346B CN 102311346 B CN102311346 B CN 102311346B CN 201110166373 A CN201110166373 A CN 201110166373A CN 102311346 B CN102311346 B CN 102311346B
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- CATPEQATFOZFNA-UHFFFAOYSA-N CC(C(OCC(COC(c(c(C(OCC1C2CC(C3)CC1CC3C2)=O)c1)cc(C(OCC2C3CC(C4)CC2CC4C3)=O)c1C(OCC(COC(C(C)=C)=O)O)=O)=O)O)=O)=C Chemical compound CC(C(OCC(COC(c(c(C(OCC1C2CC(C3)CC1CC3C2)=O)c1)cc(C(OCC2C3CC(C4)CC2CC4C3)=O)c1C(OCC(COC(C(C)=C)=O)O)=O)=O)O)=O)=C CATPEQATFOZFNA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an adamantane-containing resin, a preparation method and application thereof in dental restoration, belonging to the fields of a polymerized resin as well as a preparation method and application thereof and solving the problem that the service life of dental restoration is affected because overhigh shrinkage rate of resin causes a large curing shrinkage force. In the invention, through introducing a cage compound adamantane structure with high symmetry into a resin chain, multiple beneficial properties are brought in the resin, especially the curing shrinkage coefficient of the resin can be reduced; and on this basis, the preparation process and parameters of the adamantane-containing resin are determined, and the process parameters of the adamantane-containing resin in dental restoration are also determined. Experiments indicate that the resin has high reactive activity, good mechanical properties and low shrinkage rate in the aspect of dental restoration; moreover, the preparation process of the resin is simple, therefore, the resin is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of resin, particularly a kind of resin that contains adamantane group, the invention still further relates to the preparation method of this resin and the application in gear division is repaired thereof.
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 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, is combined and is formed Bis-GMA (dihydroxyphenyl propane glycidyl methacrylate) by two carbon chemical bond of two methacrylic acid groups with dihydroxyphenyl propane.Bis-GMA molecular weight is large, and volatility is low, and polymerization shrinkage is relatively little, and reaction is very fast, and the resinous substrates quality forming is solid, fine and close, thereby in performance, is better than methyl methacrylate.
Along with compound resin performance update and perfect, its intensity, hardness and wear resistance etc. can meet the needs that different zones, different tooth position are repaired completely.But all there is volume contraction change while solidifying in the compound resin using at present, in the time of clinical use, due to the bonding of resin and cavity wall, has limited the free shrink of resin, thereby caused the generation of string stress.The intensity of cohesive strength, resin and the tooth of this string stress to resin and tooth itself etc. all can produce obvious detrimentally affect.Studies show that, the curing shrinkage internal stress of resin can cause 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 in the time bearing snap-in force, the fracture of material easily appears in weak part.As can be seen here, the effect of compound resin to a great extent with the polymerization shrinkage of resin about. 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 covalent linkage distance, so in order to reduce or to avoid polymerization shrinkage, the structure of adjusting resin is main technique means, but for want of corresponding fundamental research, this resinoid rarely has report.
In prior art, gear division reparation is main mainly with double methyl methacrylate prepolymer (as glycidyl methacrylate Bis-GMA) with the compound resin of double methyl methacrylate reactive thinner (as TEGDMA TEGDMA) composition with resin matrix.For reducing its cure shrinkage, adjusting resin prepolymer and reactive thinner ratio, the content (denomination of invention: photo-curing compound resin used for dental repair take diatomite as filler and preparation method thereof, number of patent application is 201010132544) that increases mineral filler is Main Means.So the resin that research and development has high reaction activity, a low-shrinkage has the meaning of very important commercial applications and scientific research.
Diamantane (Adamantane) is gained the name because the arrangement of carbon atom in its molecule is identical with the 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 large (1.07g/cm of density
3), the feature such as 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 in resin chain, can improve many performances of dental material as improved thermotolerance, oxidation-resistance and directional stability, improve resistance to solvent, water-fast, fast light radiation and resistance toheat, increase the intensity of polymkeric substance, and give dimensional stability, processing stability, the biocompatibility of polymkeric substance excellence, especially can reduce the cure shrinkage coefficient of resin.
Summary of the invention
The object of the present invention is to provide a kind of adamantane resin, this resin has high reactive behavior, good mechanical property, low shrinking percentage, be applied to gear division reparation aspect and can reduce the cure shrinkage power producing because resin shrinkage rate is too high, improve the work-ing life that tooth body is repaired.This resin preparation process is simple, is applicable to suitability for industrialized production.
A kind of adamantane resin of the present invention, its structure is as follows:
Wherein, m=0-6, R
1-R
4be selected from independently of one another 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 resinoid preparation method of diamantane of the present invention, comprises the following steps:
(1) R
3and R
4the pyromellitic acid anhydride and the R that replace
1and R
2the monohydroxy diamantane replacing mixes, and at 95-185 ℃ of stirring reaction 3-15 hour, obtains adamantane phthalic acid, and the mol ratio of wherein said pyromellitic acid anhydride and monohydroxy diamantane is 1: 2;
(2) the adamantane phthalic acid obtaining in (1) step is mixed with glycidyl methacrylate, add catalyzer and stopper, at 70-150 ℃ of reaction 2-18 hour, obtain adamantane resin of the present invention, the mol ratio of wherein said adamantane phthalic acid and glycidyl methacrylate is 1: 2.
The reaction formula relating in above-mentioned preparation method is as follows:
In above-mentioned preparation method, described in step (2), catalyzer is quaternary ammonium salt catalyzer, as 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, in molar weight, its consumption is the 0.1%-5% of adamantane phthalic acid.
Described in step (2), stopper is MEHQ, Resorcinol, phenothiazine or benzoquinones, and in molar weight, its consumption is the 0.1%-5% of adamantane phthalic acid.
The invention still further relates to the application of described adamantane resin aspect preparation gear division repair materials.
As nonrestrictive typical example: a kind of light-cured composite of repairing for gear division, comprise the resin matrix being formed by adamantane resin of the present invention and TEGDMA (TEGDMA), light trigger camphorquinone (CQ), aided initiating (dimethylamino)-ethyl benzoate (EDMAB), and silica filler.
This light-cured composite is that camphorquinone (CQ) and (dimethylamino)-ethyl benzoate (EDMAB) are dissolved in the resin matrix of adamantane resin and TEGDMA (TEGDMA) composition, then add silica filler, fully stir it is mixed, obtain light-cured composite.
In above-mentioned light-cured composite, each component proportion can be with reference to the routine data in this area.Preferably, based on the total mass of resin matrix and silica filler, the ratio of described resin matrix is 50-55%, and wherein adamantane resin accounts for the 73-76% of resin matrix total mass; The ratio of described silica filler is 45-50%.The amount of light trigger camphorquinone CQ and aided initiating (dimethylamino)-ethyl benzoate is respectively the 0.1-1% of resin matrix quality.
The mean particle size of described silica filler is 5-15 nanometer, and preferred filler is made up of two kinds of varigrained silicon-dioxide.
Adamantane resin of the present invention, is applied in gear division reparation and shows very high reactive behavior, and good mechanical property, and low shrinking percentage have guaranteed stablizing with long-acting in its use; And its preparation technology is simple, stable, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, but it should not be understood to limitation of the present invention.
One, adamantane resin Preparation Example
Embodiment 1:
The pyromellitic acid anhydride of 0.1 mole (21.8g) mixes with the monohydroxy diamantane of 0.2 mole (30.4g), 100 ℃ of stirring reactions 3 hours, obtains adamantane phthalic acid.0.1 mole of (52.2g) adamantane phthalic acid is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer four heptyl brometo de amonio 5 mmoles (2.45g) and stopper MEHQ 5 mmoles (0.62g), 70 ℃ of reactions 2 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 1, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.00ppm (15H, 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), 8.92ppm (2H, phenyl ring).
Structural formula 1
Embodiment 2:
The pyromellitic acid anhydride of 0.1 mole (21.8g) mixes with the 1-hydroxy-3-methyl diamantane of 0.2 mole (33.2g), 185 ℃ of stirring reactions 15 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (55g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer tetraethylammonium bromide 1 mmole (0.165g) and hydroquinone of polymerization retarder 1 mmole (0.11g), 150 ℃ of reactions 18 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 2, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.00ppm (14H, diamantane), 1.06ppm (3H, the CH on diamantane
3), 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), 8.92ppm (2H, phenyl ring).
Structural formula 2
Embodiment 3:
The pyromellitic acid anhydride of 0.1 mole (21.8g) mixes with 1-hydroxyl-3-chlorine diamantane of 0.2 mole (37.3g), 135 ℃ of stirring reactions 5 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (59.1g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer Tetrabutyl amonium bromide 0.1 mmole (0.0322g) and hydroquinone of polymerization retarder 0.1 mmole (0.011g), 100 ℃ of reactions 9 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 3, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.00ppm (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), 8.92ppm (2H, phenyl ring).
Structural formula 3
Embodiment 4:
The pyromellitic acid anhydride of 0.1 mole (21.8g) mixes with 1-hydroxyl-3-isobutyl-diamantane of 0.2 mole (41.6g), 165 ℃ of stirring reactions 10 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (63.4g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer three (octadecyl) methyl brometo de amonio 1 mmole (0.869g) and stopper phenothiazine 2 mmoles (0.4g), 130 ℃ of reactions 7 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 4, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.00ppm (14H, diamantane), 1.06ppm (9H, C (CH
3)
3), 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), 8.92ppm (2H, phenyl ring).
Structural formula 4
Embodiment 5:
The methyl pyromellitic acid anhydride of 0.1 mole (23.2g) mixes with the monohydroxy diamantane of 0.2 mole (30.4g), 95 ℃ of stirring reactions 13 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (53.6g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer four heptyl brometo de amonio 0.5 mmoles (0.245g) and stopper MEHQ 5 mmoles (0.62g), 135 ℃ of reactions 13 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 5, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.00ppm (15H, diamantane), 1.93ppm (3H, CH
3), 2.35ppm (3H, Ar-CH
3), 4.30-4.41ppm (5H, CH
2cH (OH) CH
2) 5.58ppm (1H, two keys) 6.15ppm (1H, two keys), 8.73ppm (1H, phenyl ring).
Structural formula 5
Embodiment 6:
The methyl-isobutyl pyromellitic acid anhydride of 0.1 mole (28.8g) mixes with the monohydroxy diamantane of 0.2 mole (30.4g), 95 ℃ of stirring reactions 13 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (59.2g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer DDA 0.5 mmole (0.315g) and hydroquinone of polymerization retarder 1 mmole (0.11g), 135 ℃ of reactions 13 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 6, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.00ppm (15H, diamantane), 1.34ppm (9H, Ar-C (CH
3)
3), 1.93ppm (3H, CH
3), 2.35ppm (3H, Ar-CH
3), 4.30-4.41ppm (5H, CH
2cH (OH) CH
2) 5.58ppm (1H, two keys) 6.15ppm (1H, two keys).
Structural formula 6
Embodiment 7:
The pyromellitic acid anhydride of 0.1 mole (21.8g) mixes with the monomethylol diamantane of 0.2 mole (33.2g), 105 ℃ of stirring reactions 12 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (55g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer four heptyl brometo de amonio 5 mmoles (2.45g) and stopper benzoquinones 0.7 mmole (0.0756g), 145 ℃ of reactions 4 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 7, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.01ppm (15H, diamantane), 1.93ppm (3H, CH
3), 4.21ppm (2H ,-CH
2-), 4.30-4.41ppm (5H, CH
2cH (OH) CH
2) 5.58ppm (1H, two keys) 6.15ppm (1H, two keys), 8.90ppm (2H, phenyl ring).
Structural formula 7
Embodiment 8:
The pyromellitic acid anhydride of 0.1 mole (21.8g) mixes with single hydroxyl hexyl diamantane of 0.2 mole (47.2g), 95 ℃ of stirring reactions 13 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (69g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer Tetrabutyl amonium bromide 0.1 mmole (0.0322g) and stopper benzoquinones 0.7 mmole (0.0756g), 105 ℃ of reactions 15 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 8, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.01ppm (15H, diamantane), 1.93ppm (3H, CH
3), 4.21ppm (2H ,-CH
2-), 4.30-4.41ppm (5H, CH
2cH (OH) CH
2) 5.58ppm (1H, two keys) 6.15ppm (1H, two keys), 8.90ppm (2H, phenyl ring).
Structural formula 8
Embodiment 9:
The n-hexyl chlorine pyromellitic acid anhydride of 0.1 mole (33.6g) mixes with single hydroxyl hexyl diamantane of 0.2 mole (47.2g), 95 ℃ of stirring reactions 13 hours, obtains adamantane phthalic acid.The adamantane phthalic acid of 0.1 mole (80.8g) is mixed with the glycidyl methacrylate of 0.2 mole (28.4g), add catalyzer dodecyl dimethyl benzyl ammonium bromide 0.3 mmole (0.115g) and hydroquinone of polymerization retarder 0.1 mmole (0.011g), 105 ℃ of reactions 15 hours, obtain the low-shrinkage adamantane resin of gear division reparation use.
Product structure is as shown in structural formula 9, and characterization data is as follows:
1h NMR (250MHz) in CDCl
3: δ 1.18-2.01ppm (15H, diamantane), 0.96-2.55ppm (13H, hexyl), 1.93ppm (3H, CH
3), 4.21ppm (2H ,-CH
2-), 4.30-4.41ppm (5H, CH
2cH (OH) CH
2) 5.58ppm (1H, two keys) 6.15ppm (1H, two keys).
Structural formula 9
Two, Application Example
Dissolve 0.05g light trigger camphorquinone (CQ) and 0.05g aided initiating (dimethylamino)-ethyl benzoate (EDMAB) in 2.5g TEGDMA (TEGDMA), again with 7.5g adamantane mixed with resin of the present invention, fully stir system is mixed, then be that aerosil filler AEROSIL R711 (the German DEGUSSA company) 7.34g of 12 nanometers and mean particle size are aerosil filler AEROSILR202 (the German DEGUSSA company) 0.92g of 7 nanometers to adding mean particle size in this system, fully stir it is mixed, obtain compound resin system.In darkroom, this compound resin system is left standstill to the polyfluortetraethylene plate that injects 8mm (diameter) × 1mm (thickness) after 12 hours, upper and lower surface clamps by glass slide, leaves standstill when without bubble to be tested.Under room temperature, in air atmosphere, by testing sample light intensity 200mW/cm
2visible lamp irradiate 300 seconds, obtain the oyster white cured film of visible-light curing filled composite resin, with infrared instrument tracking monitor under near infrared condition, calculate final double bond conversion rate.
Successively the adamantane resin making in Preparation Example 1-9 is applied in above-mentioned Application Example, experimental result sees the following form 1.
The double bond conversion rate result of the each Application Example of table 1
Three, application performance comparison
The object of this experiment is adamantane resin of the present invention to compare in the performance aspect gear division reparation and prior art.
For outstanding resin property difference, in system, do not add mineral filler.System to be measured composed as follows: the resin matrix being formed according to the weight ratio of 70: 30 by prepolymer resin and TEGDMA, the 0.5wt% light trigger camphorquinone CQ based on resin matrix weight, the 1wt% aided initiating EDMAB based on resin matrix weight; Wherein prepolymer resin is adamantane resin shown in structural formula 1 or dihydroxyphenyl propane glycidyl methacrylate (Bis-GMA), and Bis-GMA is prior art.
These two groups of gear divisions are repaired to compound resin and carry out volumetric shrinkage, solvability and absorptive test, experimental result is as shown in table 2.
Adamantane resin shown in table 2 structural formula 1 and Bis-GMA contrast
Note: double bond conversion rate adopts REAL TIME INFRARED THERMAL IMAGE to test;
Measure volumetric shrinkage by pycnometric method;
According to water-absorbent and the solvability of material after ISO4049 canonical measure photocuring.
Claims (7)
1. an adamantane resin, is characterized in that, the structural formula of this resin is:
Wherein, m=0-6; R
1, R
2, R
3, R
4be selected from independently of one another 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 resinoid preparation method of diamantane claimed in claim 1, is characterized in that, comprises the following steps:
(1) R
3and R
4the pyromellitic acid anhydride and the R that replace
1and R
2the monohydroxy diamantane replacing mixes, and at 95-185 ℃ of stirring reaction 3-15 hour, obtains adamantane phthalic acid, and the mol ratio of wherein said pyromellitic acid anhydride and monohydroxy diamantane is 1:2;
(2) the adamantane phthalic acid obtaining in (1) step is mixed with glycidyl methacrylate, add catalyzer and stopper, at 70-150 ℃ of reaction 2-18 hour, obtain adamantane resin, the mol ratio of wherein said adamantane phthalic acid and glycidyl methacrylate is 1:2;
The reaction formula relating in preparation method is as follows:
Described catalyzer is quaternary ammonium salt catalyzer, and in molar weight, its consumption is the 0.1%-5% of adamantane phthalic acid;
Described stopper is MEHQ, Resorcinol, phenothiazine or benzoquinones, and in molar weight, its consumption is the 0.1%-5% of adamantane phthalic acid.
3. the application of adamantane resin aspect preparation gear division repair materials described in claim 1.
4. a light-cured composite of repairing for gear division, comprise the resin matrix being formed by adamantane resin claimed in claim 1 and TEGDMA (TEGDMA), light trigger camphorquinone (CQ), aided initiating (dimethylamino)-ethyl benzoate (EDMAB), and silica filler.
5. light-cured composite according to claim 4, is characterized in that, based on the total mass of resin matrix and silica filler, the ratio of described resin matrix is 50-55%, and wherein adamantane resin accounts for the 73-76% of resin matrix total mass; The ratio of described silica filler is 45-50%; The amount of light trigger camphorquinone and aided initiating (dimethylamino)-ethyl benzoate is respectively the 0.1-1% of resin matrix quality.
6. light-cured composite according to claim 4, is characterized in that, the mean particle size of described silica filler is 5-15 nanometer.
7. light-cured composite according to claim 4, is characterized in that, described silica filler is made up of two kinds of varigrained silicon-dioxide.
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| CN101547885A (en) * | 2006-11-29 | 2009-09-30 | 出光兴产株式会社 | Adamantane derivative, process for producing the same, and resin composition containing adamantane derivative |
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| CN101547885A (en) * | 2006-11-29 | 2009-09-30 | 出光兴产株式会社 | Adamantane derivative, process for producing the same, and resin composition containing adamantane derivative |
Non-Patent Citations (2)
| Title |
|---|
| 含金刚烷结构新型环氧树脂的合成;孟运东等;《热固性树脂》;20100131;第25卷(第01期);26－29 * |
| 孟运东等.含金刚烷结构新型环氧树脂的合成.《热固性树脂》.2010,第25卷(第01期), |
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