[go: up one dir, main page]

WO2011152251A1 - Composé alicyclique d'éther de monoallyle-éther de monoglycidyle - Google Patents

Composé alicyclique d'éther de monoallyle-éther de monoglycidyle Download PDF

Info

Publication number
WO2011152251A1
WO2011152251A1 PCT/JP2011/061898 JP2011061898W WO2011152251A1 WO 2011152251 A1 WO2011152251 A1 WO 2011152251A1 JP 2011061898 W JP2011061898 W JP 2011061898W WO 2011152251 A1 WO2011152251 A1 WO 2011152251A1
Authority
WO
WIPO (PCT)
Prior art keywords
alicyclic
compound
reaction
monoglycidyl ether
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/061898
Other languages
English (en)
Japanese (ja)
Inventor
博 内田
真尚 原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of WO2011152251A1 publication Critical patent/WO2011152251A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to an alicyclic monoallyl ether monoglycidyl ether compound, an alicyclic trialkoxysilyl monoglycidyl ether compound, and a curable resin composition containing the compound. More specifically, the present invention is excellent in optical properties, hardness, strength, and heat resistance, and particularly includes an alicyclic skeleton that is a raw material of a curable resin composition suitable for the field of electronic materials and light-emitting diode (LED) sealing.
  • the present invention relates to an alicyclic monoallyl ether monoglycidyl ether compound, an alicyclic trialkoxysilyl monoglycidyl ether compound derived therefrom, and a curable resin composition containing the compound.
  • Epoxy resins are excellent in electrical properties, adhesiveness, heat resistance, etc., and are used in many applications such as the paint field, civil engineering field, and electrical field.
  • aromatic epoxy resins such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are water resistant, adhesive, mechanical properties, heat resistant, and electrical insulating properties. It is widely used in combination with various curing agents because of its excellent economic efficiency.
  • Patent Document 1 discloses a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin, and an epoxy resin composition for electric / electronic materials containing a curing agent.
  • the following patent document 2 discloses an epoxy resin composition in which an alicyclic epoxy resin obtained by oxidizing a cyclic olefin or an epoxy resin having a nitrogen atom therein is blended.
  • the following Patent Document 3 discloses a resin composition using an epoxy resin having a silicone structure with excellent weather resistance in the main chain.
  • Patent Document 4 discloses a linear or cyclic siloxane bond and an alicyclic epoxy group (two adjacent carbon atoms forming an alicyclic skeleton and an oxygen atom, a three-membered ether (oxirane) A silicone hybrid epoxy resin having the structure)
  • Patent Document 5 discloses an epoxy silicone resin having a linear siloxane structure in the main chain and an isocyanuric group in the side chain or terminal.
  • Epoxy resin compositions are widely used in low-power white LED sealing applications because of the high hardness of the cured product and excellent handling properties and necessary durability.
  • high-power LEDs have the disadvantages that discoloration is likely to occur due to an increase in light emission and heat generation, and it is difficult to obtain a sufficient life.
  • an epoxy resin that exhibits a high glass transition temperature is used, but such an epoxy resin is highly elastic and has lower strength and deflection than a normal epoxy resin and is lit off. There is also a problem that the sealing material is easily cracked due to a sudden temperature change due to.
  • the sealing material is required to have high strength as well as further improvement in heat resistance and light resistance.
  • the compound represented by the formula (a) is an aliphatic glycidyl ether, the hardness is low and stickiness cannot be eliminated.
  • the compound represented by the formula (b) can improve the hardness and the like to some extent, but since it is a cyclohexene oxide skeleton epoxy resin, it has poor adhesion to the LED chip or package to be sealed. There is a problem.
  • the problem to be solved by the present invention is that the cured product has high hardness, has no stickiness on the surface, and has excellent transparency, heat resistance, UV resistance, and thermosetting for LED encapsulant.
  • a compound useful as a raw material of a resin composition, and a curable resin composition containing a derivative of the compound is a compound useful as a raw material of a resin composition, and a curable resin composition containing a derivative of the compound.
  • a curable resin composition containing a reaction product of a compound having a glycidyl ether structure and a silicone compound having a hydrosilyl group is suitable for LED sealing applications, and other electronic material applications such as semiconductor sealing materials and printed wiring boards. It was also found useful, and the present invention was completed.
  • R represents an alicyclic monoallyl ether monoglycidyl ether compound according to the above [1] having a C 4-8 cycloalkane skeleton.
  • R represents a divalent hydrocarbon group containing an alicyclic hydrocarbon having 4 to 20 carbon atoms
  • R ' represents a hydrocarbon group having 1 to 4 carbon atoms.
  • the curable resin composition containing the alicyclic trialkoxysilyl monoglycidyl ether compound obtained by reacting the alicyclic monoallyl ether monoglycidyl ether compound and trialkoxysilane of the present invention has a hardened cured product. , There is little cure shrinkage, no stickiness on the surface of the cured product, excellent strength and transparency, excellent heat resistance and light resistance. Therefore, the curable resin composition of the present invention is useful in the fields of electronic materials such as paints, coating agents, printing inks, resist inks, adhesives, semiconductor encapsulants, molding materials, casting materials, and electrical insulating materials. It is.
  • the curable resin composition of the present invention is particularly useful in the LED field, and is excellent as a thermosetting resin composition for LED sealing.
  • FIG. 1 is a diagram showing a general change over time of an epoxidation reaction in which diallyl ether is oxidized using an oxidizing agent.
  • FIG. 2 shows the 1 H-NMR measurement results of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 1.
  • FIG. 3 shows the results of 13 C-NMR measurement of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 1.
  • FIG. 4 shows the 1 H-NMR measurement results of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 2.
  • FIG. 5 shows the results of 13 C-NMR measurement of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 2.
  • FIG. 1 is a diagram showing a general change over time of an epoxidation reaction in which diallyl ether is oxidized using an oxidizing agent.
  • FIG. 2 shows the 1 H-NMR measurement results of the
  • FIG. 6 shows the 1 H-NMR measurement results of the epoxysilicone compound obtained in Example 3.
  • FIG. 7 shows the results of 13 C-NMR measurement of the epoxysilicone compound obtained in Example 3.
  • FIG. 8 shows the 1 H-NMR measurement results of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 4.
  • FIG. 9 shows the results of 13 C-NMR measurement of the alicyclic monoallyl ether monoglycidyl ether compound obtained in Example 4.
  • FIG. 10 shows the 1 H-NMR measurement results of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 5.
  • FIG. 11 shows the results of 13 C-NMR measurement of the alicyclic trialkoxysilyl monoglycidyl ether compound obtained in Example 5.
  • FIG. 12 shows the 1 H-NMR measurement results of the epoxysilicone compound obtained in Example 6.
  • FIG. 13 shows the results of 13 C-NMR measurement of the epoxysilicone compound obtained in Example 6.
  • the alicyclic monoallyl ether monoglycidyl ether compound according to the present invention has the following general formula (1): ⁇ Wherein R represents a C 4-20 divalent hydrocarbon group containing an alicyclic skeleton. ⁇ .
  • Such alicyclic monoallyl ether monoglycidyl ether compounds include, for example: (1) A method of partially epoxidizing the corresponding diallyl ether with hydrogen peroxide, peracid or the like, or (2) a method of etherifying the corresponding diol with allyl chloride and further glycidyl ether using epichlorohydrin, However, it is more preferable to use the method (1) in which no chlorine compound is mixed as an impurity.
  • the method of (1) is the following general formula (5): ⁇ In the formula, R represents a divalent hydrocarbon group having 4 to 20 carbon atoms including an alicyclic skeleton having 4 to 20 carbon atoms. ⁇ A method of oxidizing an alicyclic diallyl ether compound corresponding to the alicyclic monoallyl ether monoglycidyl ether compound represented by the above general formula (1), specifically, : (A) a method of epoxidation with hydrogen peroxide in an acetonitrile-alcohol solvent, (B) a method of epoxidation with a tungstic acid catalyst, or (C) a method of epoxidation with peracetic acid, However, in the method (C), a peracid that tends to explode is used, and in the method (B), the epoxy group may be hydrolyzed. Therefore, the method (A) is more preferable.
  • acetonitrile 0.5 to 10-fold mol of acetonitrile is used with respect to the corresponding diallyl ether compound, an alcohol solvent is added to a concentration of 10 to 80% by mass, and the pH is adjusted with alkali. While controlling in the range of 7.5 to 13, by dropping 0.5 to 2 times mole hydrogen peroxide to the diallyl ether compound at a temperature of 0 to 80 ° C., the desired alicyclic ring A formula monoallyl ether monoglycidyl ether compound can be obtained.
  • the alicyclic monoallyl ether monoglycidyl ether compound preferably has at least a cycloalkane skeleton composed of a 4- to 8-membered ring, more preferably a 5- to 6-membered ring, in order to ensure adhesion to an LED chip or a package. Contains one.
  • the molecular weight of the alicyclic monoallyl ether monoglycidyl ether compound is preferably 400 or less, more preferably 350 or less.
  • the molecular weight is preferably 150 or more, more preferably 220 or more.
  • Examples of such alicyclic monoallyl ether monoglycidyl ether compounds include the following formula (2): Formula (3): Or formula (4): And a compound having a structure represented by:
  • the amount of acetonitrile used is preferably 0.5 to 10-fold mol, and more preferably 1 to 6-fold mol based on the corresponding diallyl ether compound.
  • Acetonitrile reacts with hydrogen peroxide to produce a peroxide, which is said to oxidize allyl ether to give glycidyl ether, and at that time, equimolar acetamide is by-produced. . Therefore, it is necessary to remove acetamide after completion of the reaction, but this can be removed, for example, by adding a solvent such as toluene to the reaction solution and washing with water.
  • the epoxidation can be carried out with a solvent of acetonitrile alone, but the presence of alcohol is preferable because the selectivity of epoxidation is increased.
  • the alcohol is preferably a saturated alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and isobutanol. In consideration of solubility in water, methanol, ethanol N-propanol and isopropanol are preferable, and methanol is particularly preferable in consideration of azeotropy with acetonitrile.
  • the amount of the alcohol solvent used is preferably 10 to 80% by mass, more preferably 20 to 70% by mass with respect to the concentration of the reaction solution before hydrogen peroxide is added (dropped as an aqueous hydrogen peroxide solution). .
  • the hydrogen peroxide is preferably used in an amount of 0.5 to 2 moles, more preferably 0.75 to 1.5 or 1.75 moles per mole of the diallyl ether compound.
  • hydrogen peroxide although depending on the pH of the reaction solution described later, there is a concern that when the required amount is charged into the reaction system from the beginning, the reaction rate is high and the reaction may run out of control.
  • a method of dropping the reaction solution as a hydrogen oxide aqueous solution is desirable.
  • the hydrogen peroxide concentration of the reaction solution should be controlled to be 10% by mass or more, preferably 5% by mass or more.
  • the concentration of the aqueous hydrogen peroxide solution used is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 45% by mass because the higher the concentration, the higher the productivity, but the greater the safety risk. % Range.
  • the pH of the reaction solution is preferably 7.5 to 13, more preferably 8 to 12. Further, as the aqueous hydrogen peroxide solution is dropped, the pH moves to the neutral side, so it is more preferable to add an alkali compound and keep it constant. More preferably, the pH range is controlled within 10 to 11 from the start to the end of the reaction.
  • alkali compound for adjusting the pH examples include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, and organic amine compounds.
  • alkali metal or alkaline earth metal hydroxides examples include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, and organic amine compounds.
  • the reaction is preferably performed at 0 to 80 ° C., more preferably 20 to 60 ° C.
  • the treatment can be performed by an industrially practiced treatment method.
  • a solvent such as toluene or cyclohexane is added to separate an aqueous layer and an organic layer to separate excess hydrogen peroxide.
  • the organic layer is treated with a reducing agent such as sulfite, bisulfite, and thiosulfate, and further if necessary.
  • the crude product can be obtained by washing with water and distilling off the solvent.
  • the time course of the epoxidation reaction generally follows the course as shown in FIG.
  • Monoallyl ether monoglycidyl ether can be obtained by purifying and separating the obtained crude product by a method such as column chromatography. Further, it is possible to carry out the hydrosilylation reaction described later as it is, using a crude reaction solution containing 10% by mass or more, preferably 20% by mass or more of monoallyl ether monoglycidyl ether, and industrially. Rather, it may be preferable because it saves the labor of separation.
  • the alicyclic trialkoxysilyl monoglycidyl ether compound according to the present invention has the following general formula (6): ⁇ In the formula, R represents a divalent hydrocarbon group containing an alicyclic hydrocarbon having 4 to 20 carbon atoms, and R 'represents a hydrocarbon group having 1 to 4 carbon atoms. ⁇ .
  • the alicyclic trialkoxysilyl monoglycidyl ether compound represented by the general formula (6) is obtained by replacing the alicyclic monoallyl ether monoglycidyl ether compound represented by the general formula (1) with trialkoxysilane and hydrosilyl. It can be obtained by a chemical reaction. Specifically, a trialkoxysilane such as trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-tert-butoxysilane, or the like is used as the above crude product solution.
  • a trialkoxysilane such as trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-tert-butoxysilane, or the like is used as the above crude product solution.
  • the reaction is carried out with the isolated monoallyl ether monoglycidyl ether or the crude product liquid as it is in the presence of a noble metal catalyst.
  • the amount of trialkoxysilane used is preferably 1 to 5 times mol and more preferably 1.5 to 4 times mol based on the alicyclic monoallyl ether monoglycidyl ether compound.
  • the catalyst various known noble metals or complex compounds thereof can be used.
  • the noble metal catalyst examples include platinum, rhodium, palladium, ruthenium, iridium and the like.
  • the noble metal catalyst is not limited to these, and two or more of them may be used as necessary.
  • noble metal complex compounds include platinum halogen compounds (PtCl 4 , H 2 PtCl 6 ⁇ 6H 2 O, Na 2 PtCl 6 ⁇ 4H 2 O, etc.), platinum-olefin complexes, platinum-alcohol complexes, platinum-alcolate complexes, platinum -Ether complexes, platinum-carbonyl complexes, platinum-ketone complexes, platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis ( ⁇ -picoline) -platinum Dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis (alkynyl) bis (triphenylphosphine) platinum complex, bis (alkynyl) bis
  • the above precious metal catalysts may be dissolved alone or in advance in a solvent to be dissolved, and then charged into the reaction system.
  • the use ratio of the noble metal catalyst is not particularly limited, but is in the range of 0.1 ppm to 100,000 ppm, preferably in the range of 1 ppm to 10,000 ppm, based on the mass of the isolated monoallyl ether monoglycidyl ether or crude product liquid usually used in the reaction. .
  • the hydrosilylation reaction can proceed without a solvent, but the reaction system may be diluted with an organic solvent if necessary, and the organic solvent to be used is not particularly limited as long as it does not adversely affect the reaction.
  • the organic solvent used as necessary include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane, and fats such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone.
  • Aromatic ketones such as benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene and dichlorobenzene, ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, esters such as ethyl acetate and n-butyl acetate Kind. Two or more of these organic solvents may be selected and used as a mixed solvent.
  • the temperature conditions for the hydrosilylation reaction are not particularly limited, but are usually 0 ° C. to 200 ° C., preferably 30 ° C. to 180 ° C. If it is less than 0 ° C., it takes time for the reaction to proceed and it is not economical. On the other hand, if it exceeds 200 ° C., the addition reaction between the epoxy group and the hydrosilyl moiety proceeds, making it difficult to control the reaction.
  • hydrosilylation reaction is performed by using at least one carbon-carbon double bond and another compound containing an epoxy group in one molecule.
  • the obtained resin may be used as a curable resin composition.
  • examples of other compounds containing at least one carbon-carbon double bond and an epoxy group in one molecule include allyl glycidyl ether, 4-vinylcyclohexene oxide, limonene oxide, and the like. Two or more kinds may be used in combination.
  • this compound is not specifically limited, From a viewpoint of function expression of the curable resin composition which concerns on this invention, with respect to 100 mass parts of isolated monoallyl ether monoglycidyl ether or crude product liquid used for reaction. 50 parts by mass or less is preferable.
  • the hydrosilylation product thus obtained that is, the alicyclic trialkoxysilyl monoglycidyl ether compound according to the present invention is subjected to a sol-gelation reaction by a known method, whereby another aspect of the present invention is achieved.
  • a curable resin composition containing an epoxy silicone compound can be obtained.
  • As a general sol-gel reaction a method of hydrolytic condensation in the presence of an acidic catalyst or a basic catalyst is used.
  • the hydrolysis condensation catalyst used in the sol-gelation reaction is not particularly limited, and a known acidic catalyst or basic catalyst can be used.
  • the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, toluenesulfonic acid, acetic acid, phosphoric acid, oxalic acid, and citric acid.
  • the basic catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.
  • the amount of the catalyst added is not particularly limited, but is represented by the general formula (6) in order to have sufficient reactivity and to keep the ring opening and gelation of the epoxy ring low.
  • the range of 0.001 to 0.2 mol is preferable and the range of 0.005 to 0.1 mol is more preferable with respect to a total of 1 mol of hydrolyzable groups in the hydrosilylation product.
  • the reaction temperature in the sol-gelation reaction is not particularly limited because it varies depending on the reactivity of the hydrosilylation product represented by the general formula (6) as a raw material, the solvent used, etc., but the reaction rate becomes sufficiently high, and In order to suppress undesired side reactions, the range of 0 ° C. to 100 ° C. is preferable, and the range of 10 ° C. to 80 ° C. is more preferable. If the reaction temperature is too low, the reaction does not proceed efficiently, and if it is too high, side reactions such as opening of the epoxy ring may proceed.
  • the solvent to be used is not particularly limited as long as the raw material alkoxysilane and water are uniformly dissolved.
  • alcohols such as methanol, ethanol, 2-propanol, n-butanol, isobutanol, and t-butanol are used.
  • the solvent include ketone solvents such as acetone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.
  • the reaction time of the sol-gelation reaction is not particularly limited because it varies depending on the reactivity, reaction temperature, etc. of the hydrosilylation product represented by the general formula (6) as a raw material, but in order to sufficiently increase the molecular weight of the product Is preferably in the range of 1 to 40 hours.
  • the reaction time is less than 1 hour, unreacted raw materials and low molecular weight oligomers may remain.
  • the condensation reaction often does not proceed further.
  • Example 1 Synthesis of alicyclic monoallyl ether monoglycidyl ether compound
  • 1,4-cyclohexanedimethanol diallyl ether as a raw material was synthesized as follows based on Williamson synthesis.
  • 144.2 g (1.00 mol) of 1,4-cyclohexanedimethanol manufactured by Shin Nippon Rika Co., Ltd. was added, and the inside of the reactor system was purged with nitrogen, and hydroxylated.
  • the resulting reaction mixture was purified by column chromatography using silica gel (developing solvent: hexane and ethyl acetate 4: 1 (volume ratio) mixed solution) to obtain monoallyl ether monoglycidyl ether.
  • the 1 H-NMR and 13 C-NMR of the purified product are shown in FIGS. 2 and 3, respectively.
  • Example 2 Synthesis of alicyclic trialkoxysilyl monoglycidyl ether compound
  • Example 3 Synthesis of epoxy silicone compound
  • a 100 mL eggplant flask equipped with a dropping funnel was charged with 10 g of 2-propanol, 1.87 g of distilled water, and 0.19 g of a 25% aqueous solution of tetramethylammonium hydroxide (manufactured by Showa Denko KK) and mixed uniformly. The temperature rose.
  • the dropping funnel was charged with 7 g of the mixture containing the trialkoxysilyl monoglycidyl ether compound obtained in Example 2 as the main component and 10 g of 2-propanol, and dropped into the eggplant flask at 50 ° C. over 10 minutes. After completion of dropping, the mixture was further stirred at 50 ° C.
  • Example 4 Synthesis of tricyclodecane dimethanol monoallyl monoglycidyl ether
  • 100.0 g (0.36 mol) of tricyclodecane dimethanol diallyl ether (Asahi Chemical Industry Co., Ltd.)
  • 92.3 g (2.88 mol) of methanol manufactured by Junsei Chemical Co., Ltd.
  • Example 5 Synthesis of trialkoxysilyl monoglycidyl ether compound of tricyclodecane dimethanol] 8.4 g (51 mmol) of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 15 g of toluene were placed in a 200 mL three-necked flask equipped with a dropping funnel, a reflux tube and a ball stopper, and the inside of the three-necked flask was purged with nitrogen.
  • triethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd.
  • Example 6 Synthesis of epoxy silicone compound
  • a 100 mL eggplant flask equipped with a dropping funnel was charged with 5 g of 2-propanol, 0.20 g of distilled water, and 0.08 g of a 25% aqueous solution of tetramethylammonium hydroxide (manufactured by Showa Denko KK) and mixed uniformly. The temperature rose.
  • the dropping funnel was charged with 1 g of a mixture containing the trialkoxysilyl monoglycidyl ether compound obtained in Example 5 as a main component and 5 g of 2-propanol, and dropped into the eggplant flask at 50 ° C. over 10 minutes. After completion of dropping, the mixture was further stirred at 50 ° C. for 5 hours.
  • the curable resin composition containing the alicyclic trialkoxysilyl monoglycidyl ether compound obtained by reacting the alicyclic monoallyl ether monoglycidyl ether compound and trialkoxysilane according to the present invention has a hardened product.
  • the curable resin composition according to the present invention is used in the fields of electronic materials such as paints, coating agents, printing inks, resist inks, adhesives, semiconductor encapsulants, molding materials, casting materials, and electrical insulating materials.
  • the curable resin composition of the present invention is particularly useful in the LED field, and is excellent as a thermosetting resin composition for LED sealing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un composé utile en tant que matière première pour une composition de résine thermodurcissable destinée à l'encapsulation de DEL, ledit composé étant une substance durcie présentant une résistance élevée, ne collant pas à la surface et affichant une excellente transparence, résistance à la chaleur, résistance aux UV et force. Le composé est un composé alicyclique d'éther de monoallyle-éther de monoglycidyle représenté par la formule générale (1) ci-dessous {dans la formule, R représente un groupe hydrocarbure bivalent de 4 à 20 carbones contenant une structure alicyclique}. L'invention concerne également une composition de résine thermodurcissable contenant : un composé alicyclique d'éther de trialcoxysilyl-monoglycidyle obtenu en forçant le composé alicyclique d'éther de monoallyle-éther de monoglycidyle de subir une réaction d'hydrosilylation avec un trialcoxysilane ; et un composé de silicone époxy obtenu en appliquant le procédé sol-gel au dit composé d'éther de trialcoxysilyl-monoglycidyle.
PCT/JP2011/061898 2010-06-03 2011-05-24 Composé alicyclique d'éther de monoallyle-éther de monoglycidyle Ceased WO2011152251A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-127857 2010-06-03
JP2010127857A JP2014024753A (ja) 2010-06-03 2010-06-03 脂環式モノアリルエーテルモノグリシジルエーテル化合物

Publications (1)

Publication Number Publication Date
WO2011152251A1 true WO2011152251A1 (fr) 2011-12-08

Family

ID=45066628

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/061898 Ceased WO2011152251A1 (fr) 2010-06-03 2011-05-24 Composé alicyclique d'éther de monoallyle-éther de monoglycidyle

Country Status (3)

Country Link
JP (1) JP2014024753A (fr)
TW (1) TWI444372B (fr)
WO (1) WO2011152251A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787452A (en) * 1971-06-29 1974-01-22 Ciba Geigy Corp Epoxysilanes
DE4003621C1 (en) * 1990-02-07 1990-12-20 Th. Goldschmidt Ag, 4300 Essen, De Silane poly:oxy:alkylene glycidyl ether - for improving e.g. epoxy] resins and inorganic materials e.g. glass fibres
EP0741134A1 (fr) * 1995-05-05 1996-11-06 ENICHEM S.p.A. Esters de glycidyle insaturés et leur utilisation dans la modification de polyoléfines
WO1998012186A1 (fr) * 1996-09-18 1998-03-26 Daiso Co., Ltd. Procede de preparation d'ethers glycidyliques
KR20090072379A (ko) * 2007-12-28 2009-07-02 주식회사 동진쎄미켐 폴리이미드 전구체용 반응성 단량체 및 이를 이용한폴리이미드 전구체
JP2010106009A (ja) * 2008-09-30 2010-05-13 Sanyo Chem Ind Ltd エポキシ化合物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787452A (en) * 1971-06-29 1974-01-22 Ciba Geigy Corp Epoxysilanes
DE4003621C1 (en) * 1990-02-07 1990-12-20 Th. Goldschmidt Ag, 4300 Essen, De Silane poly:oxy:alkylene glycidyl ether - for improving e.g. epoxy] resins and inorganic materials e.g. glass fibres
EP0741134A1 (fr) * 1995-05-05 1996-11-06 ENICHEM S.p.A. Esters de glycidyle insaturés et leur utilisation dans la modification de polyoléfines
WO1998012186A1 (fr) * 1996-09-18 1998-03-26 Daiso Co., Ltd. Procede de preparation d'ethers glycidyliques
KR20090072379A (ko) * 2007-12-28 2009-07-02 주식회사 동진쎄미켐 폴리이미드 전구체용 반응성 단량체 및 이를 이용한폴리이미드 전구체
JP2010106009A (ja) * 2008-09-30 2010-05-13 Sanyo Chem Ind Ltd エポキシ化合物の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KITAORI, K. ET AL.: "CsF in organic synthesis. Regioselective nucleophilic reactions of phenols with oxiranes leading to enantiopure P-blockers", TETRAHEDRON, vol. 55, no. 50, 1999, pages 14381 - 14390 *
KITAORI, K. ET AL.: "CsF in organic synthesis. The first and convenient synthesis of enantiopure bisoprolol by use of glycidyl nosylate", TETRAHEDRON LETTERS, vol. 39, no. 20, 1998, pages 3173 - 3176 *

Also Published As

Publication number Publication date
TWI444372B (zh) 2014-07-11
TW201202211A (en) 2012-01-16
JP2014024753A (ja) 2014-02-06

Similar Documents

Publication Publication Date Title
CN101484434B (zh) 脂环族二环氧化合物、环氧树脂组合物及固化物
JP5037385B2 (ja) エポキシシリコーン樹脂を含む硬化性樹脂組成物
US9777107B2 (en) Silicone-modified epoxy resin and composition and cured article thereof
TW202104199A (zh) 脂環式環氧化合物製品
KR101415113B1 (ko) 글리시딜에테르 화합물의 제조 방법 및 모노알릴모노글리시딜에테르 화합물
WO2019138988A1 (fr) Produit composé époxy alicyclique
JP6238699B2 (ja) 多価グリシジル化合物の製造方法
WO2011152251A1 (fr) Composé alicyclique d'éther de monoallyle-éther de monoglycidyle
JP5139857B2 (ja) エポキシシリコーン樹脂を含む硬化性樹脂組成物
JP5141499B2 (ja) 熱硬化性樹脂組成物
JP2014240377A (ja) 多価グリシジル化合物の製造方法
JP6514685B2 (ja) シリコーン変性エポキシ樹脂および該エポキシ樹脂を含む組成物並びにその硬化物
CN102666519B (zh) 环氧化合物的制造方法
US20090137774A1 (en) Adamantane derivative, resin composition containing same, and optoelectronic component using same
JP4899818B2 (ja) 脂環式ジエポキシ化合物、脂環式ジエポキシ化合物の製造方法、硬化用組成物および硬化物
JP6521943B2 (ja) シリコーン変性エポキシ樹脂および該エポキシ樹脂を含む組成物並びにその硬化物
JP5449802B2 (ja) 脂環構造を有するエポキシシリコーン樹脂、及び硬化性樹脂組成物
JP4966014B2 (ja) 硬化性ジアマンタン化合物
JP5473636B2 (ja) イソシアヌレート化合物
JP6849971B2 (ja) シリコーン変性エポキシ樹脂およびその組成物と硬化物
KR20150047298A (ko) 실란 화합물의 신규한 합성방법
JP2016117837A (ja) 硬化性樹脂組成物、その硬化物および硬化剤

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11789660

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11789660

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP