CN102234256B - Novel diepoxide - Google Patents
Novel diepoxide Download PDFInfo
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- CN102234256B CN102234256B CN201110107121.2A CN201110107121A CN102234256B CN 102234256 B CN102234256 B CN 102234256B CN 201110107121 A CN201110107121 A CN 201110107121A CN 102234256 B CN102234256 B CN 102234256B
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- 0 C*(C)(C)CC(C)(C=C(*C(C=C1c2ccccc2)=CC(C)(C)C=C1OC(*)C1(*)*C1)C=C1c2ccccc2)C=C1OCC1(*)OC1 Chemical compound C*(C)(C)CC(C)(C=C(*C(C=C1c2ccccc2)=CC(C)(C)C=C1OC(*)C1(*)*C1)C=C1c2ccccc2)C=C1OCC1(*)OC1 0.000 description 2
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Abstract
The invention provides a novel diepoxide, which has good heat resistance and flame retardation and low moisture absorption, and low melting point and good solvent dissolution. The diepoxide is expressed by a formula (1), wherein R1 represents a hydrogen atom or methyl; R2 and R3 respectively and independently represent alkyl having 1-8 carbon atoms, alkoxy having 1-8 carbon atoms or phenyl; a and b respectively and independently represent 0 or an integer from 1 to 4, but a and b cannot be 0 at the same time; at least one of substituent groups represented by R2 and R3 is phenyl; A is a divalent group expressed by the following formula (2) or formula (3). In the formula (2), R4 represents alkyl having 1-8 carbon atoms, alkoxy having 1-8 carbon atoms or phenyl; a represents 0 or an integer from 1 to 4. In the formula (3), R5 represents alkyl having 1-8 carbon atoms, alkoxy having 1-8 carbon atoms or phenyl; d represents 0 or an integer from 1 to 4.
Description
Technical field
The present invention relates to a kind of Novel diepoxide.
Background technology
Epoxy resin is widely used in as the multiple fields of tackiness agent, coating, general industry structured material and electronics/electric installation assembly or material.In recent years, along with expansion and the development of the application to these epoxy resin, be there is to strong demand in operability and the further improvement of the various performances that comprise thermotolerance, moistureproofness, chemical resistant properties, electrical characteristic and mechanical characteristics.Therefore, need exploitation to be adapted to the new epoxy compound of such demand.
Till now, the diepoxides being derived from many multinuclear bis-phenols is known as the starting material for having good stable on heating epoxy resin, or as the diepoxides with low melting point.For example, 4, 4'-[1, two (1-methyl ethylidene) two (the phenylene Oxymethylene oxyethane) of 4-phenylene] (4, 4'-[1, 4-phenylenebis (1-methylethylidene) bis (phenylene oxymethylene oxirane)]) (Japanese kokai publication hei 07-206837 patent documentation), 4, 4'-two (2, 3, 6-trimethylammonium hydroxyphenyl)-1, diglycidyl ether (the diglycidyl ether of 4 of 1'-biphenyl, 4'-bis (2, 3, 6-trimethyl hydroxyphenyl)-1, 1'-biphenyl) (TOHKEMY 2005-314499 patent documentation), 1, two (4'-propylene oxide phenoxy group)-1-(1''-the biphenyl)-1-cyclohexyl-methanes (1 of 1-, 1-bis (4'-epoxypropanyloxyphenyl)-1-(1''-biphenyl)-1-cyclohexylmethane) diglycidyl ether (diglycidyl ether of 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl) benzene) of (No. 2005/092826 patent documentation of international publication) or 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl) benzene, wherein p-terphenyl skeleton is by alkyl, the diglycidyl ether replacement (TOHKEMY 2005-206814 patent documentation) of 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene etc. is all known.
But, these diepoxidess commonly known in the art need to improve, because when as cured resin, they are still unsatisfactory aspect thermotolerance, flame retardant resistance and agent of low hygroscopicity, and they are being added to man-hour, and they are also unsatisfactory aspect low melting point and solvent solubility.
The present invention is exactly in order to meet foregoing demand.The object of this invention is to provide a kind of Novel diepoxide, when as cured resin, this compound has good thermotolerance and flame retardant resistance and agent of low hygroscopicity, when being added, it there is low melting point and good solvent solubility man-hour, this compound not only can be advantageously used in the performance of the tackiness agent, coating and the common industrial structured material that improve the epoxy resin that adopts prior art, can also be used for wishing in recent years to have electronics/electric installation assembly of better performance and better function etc.
Summary of the invention
The present inventor, to provide the epoxy compounds of said feature above to carry out scrutiny simultaneously, has therefore completed the present invention.Particularly, the invention provides a kind of diepoxides being represented by general formula (1):
Wherein R
1represent hydrogen atom or methyl, R
2and R
3represent to have independently of one another 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, a and b represent 0 or from 1 to 4 integer independently of one another, but a and b can not be 0 simultaneously, by R
2and R
3at least one in the substituting group representing is phenyl, and when a and b be 2 or when above independently of one another, R
2and R
3separately can be identical or different, and A is the divalent group being represented by following general formula (2) or general formula (3):
General formula (2):
Wherein R
4represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, c represents 0 or from 1 to 4 integer, and when c be 2 or when above, R
4can be identical or different; Or
General formula (3):
Wherein R
5represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, d represents 0 or from 1 to 4 integer, and when d be 2 or when above, R
5can be identical or different.
Because diepoxides of the present invention has 1, two (4-phenoxy group) benzene (1 of 4-, 4-bis (4-oxyphenyl) benzene) or 1, two (4-the phenoxy group)-1-tetrahydrobenzene (1 of 4-, 4-bis (4-oxyphenyl)-1-cyclohexene) skeleton, wherein at least one of the 4-phenoxy group at the two ends of frame center is substituted by phenyl, so, with there is identical skeleton, wherein the 4-phenoxy group at two ends is not substituted or the diepoxides that replaced by alkyl is compared, it has lower fusing point and higher solvent solubility.In addition, it shows good aspect thermotolerance, flame retardant resistance and water absorbability, because it has for example such rigid backbone of p-terphenyl.Therefore, in the time that diepoxides of the present invention is used as resin raw material, can carry out industrial treatment to it more easily, because when it is added to man-hour, it shows good and solidifies at a lower temperature aspect solution solubleness, and it also has good flame retardant resistance and thermotolerance and agent of low hygroscopicity and base material sticking power when as cured resin.Not only can be advantageously used in tackiness agent, coating and the common industrial structured material of the epoxy resin that adopts prior art according to such Novel diepoxide of the present invention, can also be used for electronics/electric installation assembly, the requirement that for example miniaturization, pinpoint accuracy, high-resolution and the high-density of electronics/electric installation assembly are sealed improves in recent years.
Embodiment
Diepoxides of the present invention is represented by following structural formula (1):
Wherein R
1represent hydrogen atom or methyl, R
2and R
3represent to have independently of one another 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, a and b represent 0 or from 1 to 4 integer independently of one another, but a and b can not be 0 simultaneously, by R
2and R
3at least one in the substituting group representing is phenyl, and when a and b be 2 or when above independently of one another, R
2and R
3separately can be identical or different, and A is the divalent group being represented by following general formula (2) or general formula (3):
General formula (2):
Wherein R
4represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, c represents 0 or from 1 to 4 integer, and when c be 2 or when above, R
4can be identical or different; Or
General formula (3):
Wherein R
5represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, d represents 0 or from 1 to 4 integer, and when d be 2 or when above, R
5can be identical or different,
R
1hydrogen atom or methyl, preferably hydrogen atom.In addition, for by R
2and R
3the alkyl with 1 to 8 carbon atom representing, it can be straight chain, side chain or ring-type, and for chain, it preferably has the alkyl of 1 to 4 carbon atom, and for ring-type, it preferably has the cycloalkyl of 5 to 8 carbon atoms.
In addition, such alkyl can be replaced by phenyl or alkoxyl group.
Particularly, for example, alkyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, also has cyclohexyl, cyclopentyl etc.Among them, preferably alkyl straight chain or side chain, first-selection is methyl or ethyl.For the alkoxyl group with 1 to 8 carbon atom, it can be alkoxyl group straight chain, side chain or ring-type, and such alkoxyl group also can be replaced by phenyl or alkoxyl group.Particularly, for example, alkoxyl group comprises methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy, cyclopentyloxy (cyclopentyloxy) etc.Among alkyl and alkoxyl group, preferably alkyl.
In addition the alkoxyl group that, phenyl can for example be had 1 to 3 alkyl of 1 to 4 carbon atom and/or have 1 to 4 carbon atom replaces.Such substituting group is preferably as the alkyl of methyl.But it is first-selected there is no substituent phenyl.
In general formula (1), preferably 1 to 3 of the sum of phenyl, first-selected 1 or 2.
In addition, in this general formula, a and b represent 0 or from 1 to 4 integer independently of one another, and a is 0 when different with b, they preferably 0 or 1 to 2, first-selected a be 1 or 2 and b be 0.
In addition, in the diepoxides being represented by general formula of the present invention (1), by R
2and R
3at least one in the substituting group representing is phenyl.Preferably such compound of diepoxides: by R
2and R
3any one in the substituting group representing is phenyl, or, a and b be all 1 or when above by R
2the substituting group representing neutralizes by R
3in the substituting group representing, respectively there is one to be phenyl, and first-selected such compound: by R
2and R
3any one in the substituting group representing is phenyl.
In addition R,
2and R
3the position of substitution be preferably in the ortho position of ether on benzene nucleus, and be first-selectedly substituted in the ortho position of ether on benzene nucleus for phenyl.
In addition, in general formula, divalent group A represents by general formula (2) or general formula (3), in above-mentioned general formula, and R
4or R
5the alkyl with 1 to 8 carbon atom, alkoxyl group or the phenyl with 1 to 8 carbon atom, and they and by R
2or R
3the alkyl with 1 to 8 carbon atom representing, alkoxyl group or the phenyl with 1 to 8 carbon atom are identical.In addition, in above-mentioned general formula, c or d represent 0 or from 1 to 4 integer, they preferably 0 or 1 to 2, and first-selection is 0.When d is 1 or when above, R
5the position of substitution be preferably in the position except the 4-position of 1-tetrahydrobenzene skeleton, and when d be 2 or when above, R
5preferably not with substituting group on same carbon atom.
Therefore, in general formula (1), by R
2and R
3any one in the substituting group representing is phenyl, and in the time that divalent group A is represented by general formula (2), and the c in general formula preferably 0, or in the time that divalent group A is represented by general formula (3), the d in general formula preferably 0.
Therefore the of the present invention preferred diepoxides, being represented by general formula (1) is represented by following general formula (4) or general formula (5):
General formula (4):
Wherein R
1with the R in general formula (1)
1identical, R'
2and R'
3represent to have the alkyl of 1 to 8 carbon atom or have the alkoxyl group of 1 to 8 carbon atom, a-1 is that a in general formula (1) subtracts 1 integer obtaining, wherein a be 1 or more than, and b is identical with the b in general formula (1),
Wherein by R'
2and R'
3the alkyl with 1 to 8 carbon atom representing or there is the alkoxyl group of 1 to 8 carbon atom and the alkyl with 1 to 8 carbon atom of general formula (1) or to have the alkoxyl group of 1 to 8 carbon atom identical; Or
General formula (5):
Wherein R
1, R'
2and R'
3and R in a-1 and aforementioned formula (4)
1, R'
2and R'
3and a-1 is identical, and b-1 is that b in general formula (1) subtracts 1 integer obtaining, wherein b be 1 or more than.
In addition, if the divalent group A in general formula (1) by general formula (2) represent, general formula (1) is represented by following general formula (6) so:
Wherein R
1, R
2and R
3and R in a and b and general formula (1)
1, R
2and R
3and a is identical with b, and R
4with the R in c and general formula (2)
4identical with c.
Preferably such diepoxides of the compound of general formula (6): wherein c is 0; And by R
2and R
3any one in the substituting group representing is phenyl (general formula (7)), or by R
2the substituting group representing neutralizes by R
3in the substituting group representing, respectively there is one to be phenyl (general formula (8)).
General formula (7):
Wherein R
1, R'
2and R'
3and R in a-1 and b and general formula (4)
1, R'
2and R'
3and a-1 is identical with b.
General formula (8):
Wherein R
1, R'
2and R'
3and R in a-1 and b-1 and general formula (5)
1, R'
2and R'
3and a-1 is identical with b-1.
In addition, if the divalent group A in general formula (1) by general formula (3) represent, general formula (1) is represented by following general formula (9) so:
Wherein R
1, R
2and R
3and R in a and b and general formula (1)
1, R
2and R
3and a is identical with b, and R
5with the R in d and general formula (3)
5identical with d.Preferably such diepoxides of the compound of general formula (9): wherein d is 0; And by R
2and R
3any one in the substituting group representing is phenyl (general formula (10)), or by R
2the substituting group representing neutralizes by R
3in the substituting group representing, respectively there is one to be phenyl (general formula (11)).
General formula (10):
Wherein R
1, R'
2and R'
3and R in a-1 and b and general formula (4)
1, R'
2and R'
3and a-1 is identical with b.
General formula (11):
Wherein R
1, R'
2and R'
3and R in a-1 and b-1 and general formula (5)
1, R'
2and R'
3and a-1 is identical with b-1.
The such diepoxides being represented by general formula (1) for example specifically comprises:
1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene):
1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene):
1, two (4-the is oxidized glycidol-3-phenyl) benzene (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl) benzene), 1,4-is two, and (4-is oxidized glycidol-3,5-diphenyl phenyl) benzene (1,4-bis (4-glycidyloxy-3,5-diphenylphenyl) benzene), 1-(4-is oxidized glycidol-5-methyl-3-phenyl)-4-(4-oxidation glycidol phenyl) benzene (1-(4-glycidyloxy-5-methyl-3-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene), 1-(4-is oxidized glycidol-2-methyl-5-phenyl)-4-(4-oxidation glycidol phenyl) benzene (1-(4-glycidyloxy-2-methyl-5-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene), 1-(4-is oxidized glycidol-2-phenyl)-4-(4-oxidation glycidol phenyl) benzene (1-(4-glycidyloxy-2-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene), 1-(4-is oxidized glycidol-5-methyl-2-phenyl)-4-(4-oxidation glycidol phenyl) benzene (1-(4-glycidyloxy-5-methyl-2-phenylphenyl)-4-(4-glycidyloxyphenyl) benzen e), (4-is oxidized glycidol-3 to 1-, 5-diphenyl phenyl)-4-(4-oxidation glycidol phenyl) benzene (1-(4-glycidyloxy-3,5-diphenylphenyl)-4-(4-glycidyloxyphenyl) benzene), 1-(4-is oxidized glycidol-3-phenyl)-4-(4-is oxidized glycidol-3-tolyl)-2-toluene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxy-3-methylphenyl)-2-methylbenzene),1-(4-is oxidized glycidol-3-phenyl)-4-(4-oxidation glycidol phenyl)-3-biphenyl (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-3-phenylbenzene), 1-(4-is oxidized glycidol-3-phenyl)-4-(4-is oxidized glycidol-3-tolyl)-3-biphenyl (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxy-3-methylphenyl)-3-phenylbenzene), 1, two (4-is oxidized glycidol-3-phenyl)-2-biphenyl (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl)-2-phenylbenzene), 1, two (4-is oxidized glycidol-3-phenyl)-1-cyclohexene (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl)-1-cyclohexene), 1,4-is two, and (4-is oxidized glycidol-3,5-diphenyl phenyl)-1-cyclohexene (1,4-bis (4-glycidyloxy-3,5-diphenylphenyl)-1-cyclohexene), 1-(4-is oxidized glycidol-5-methyl-3-phenyl)-4-(4-oxidation glycidol phenyl)-1-cyclohexene (1-(4-glycidyloxy-5-methyl-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene), 1-(4-is oxidized glycidol-2-phenyl)-4-(4-oxidation glycidol phenyl)-1-cyclohexene (1-(4-glycidyloxy-2-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene), 1-(4-is oxidized glycidol-5-methyl-2-phenyl)-4-(4-oxidation glycidol phenyl)-1-cyclohexene (1-(4-glycidyloxy-5-methyl-2-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene), 1-(4-is oxidized glycidol-3-methyl-2-phenyl)-4-(4-oxidation glycidol phenyl)-1-cyclohexene (1-(4-glycidyloxy-3-methyl-2-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene),(4-is oxidized glycidol-3 to 1-, 5-diphenyl phenyl)-4-(4-oxidation glycidol phenyl)-1-cyclohexene (1-(4-glycidyloxy-3,5-diphenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexe ne), 1-(4-is oxidized glycidol-3-phenyl)-4-(4-is oxidized glycidol-3-tolyl)-2-methyl isophthalic acid-cyclohexene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxy-3-methylphenyl)-2-methyl-1-cyclohexene), 1-(4-oxidation glycidol phenyl)-4-(4-is oxidized glycidol-3-phenyl)-2-phenyl-1-cyclohexene (1-(4-glycidyloxyphenyl)-4-(4-glycidyloxy-3-phenylphenyl)-2-phenyl-1-cyclohexene), 1-(4-oxidation glycidol-3-tolyl-4-(4-is oxidized glycidol-3-phenyl)-2-phenyl-1-cyclohexene (1-(4-glycidyloxy-3-methylphenyl)-4-(4-glycidyloxy-3-phenylphenyl)-2-phenyl-1-cyclohexene), 1, two (4-is oxidized glycidol-3-phenyl)-2-phenyl-1-cyclohexene (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl)-2-phenyl-1-cyclohexene) etc.
Although be not particularly limited according to the preparation method of the diepoxides being represented by general formula (1) of the present invention, but routine several method described as follows etc. is all known: the 1) method of the epoxidation reaction of phenolic compound, it is by being dissolved in raw material phenolic compound in epoxyhalopropane and using the quaternary ammonium salt as tetramethyl ammonium chloride and trimethyl benzyl ammonia chloride as catalyzer, they to be reacted, add afterwards the basic cpd as alkali metal hydroxide and/or add the aqueous solution of the basic cpd as alkali metal hydroxide so that reaction product can cyclisation, 2) phenolic compound is dissolved in the epoxyhalopropane as epoxy chloropropane, add the polar solvent as methyl alcohol and ethanol, after the solid base metal hydroxides adding as sodium hydroxide and potassium hydroxide or add the method that in the process of the solid base metal hydroxides as sodium hydroxide and potassium hydroxide, mixture is reacted, 3) method of the aqueous solution of use alkali metal hydroxide, in reactive system, add continuously alkali metal hydroxide, simultaneously therefrom continuous still battery water outlet and epoxyhalopropane under decompression or normal pressure, thereby and this mixture separation is removed to water and epoxyhalopropane is turned back in reactive system continuously, 4) phenolic compound and the vinyl halide as propenyl chloride and allyl bromide 98 react in the situation that there is alkali in solvent, then after reaction completes, the oxygenant as metachloroperbenzoic acid etc. that allows to the carbon-to-carbon double bond to be oxidized to epoxy group(ing) reacts to the reaction mixture forming, or for example, after mixing with water at reaction soln and removing reaction product, oxygenant is reacted to reaction product, afterwards, for example, if needed, make remaining oxygenant degraded, then thereby concentration response product obtains method of epoxy compounds etc.Any method in these methods can be used for obtaining epoxy compounds of the present invention.
For the diepoxides that obtains being represented by general formula (1) according to of the present invention, utilize corresponding to the diphenol compound being represented by following general formula (12) of the structure of diepoxides and as the epoxyhalopropane being represented by following general formula (13) of raw material with regard to enough (reaction formula (1)).
Reaction formula (1):
In the raw material diphenol compound being represented by above-mentioned general formula (12), R
2and R
3, R in a, b and A and general formula (1)
2and R
3, a, b be identical with A.Therefore,, for the diphenol compound being represented by above-mentioned general formula (12), in the time that A is represented by general formula (2), diphenol compound is represented by following general formula (14):
Wherein R
2and R
3and R in a and b and general formula (1)
2and R
3and a is identical with b, and R
4with the R in c and general formula (2)
4identical with c.
In addition,, in the time that A is represented by general formula (3), diphenol compound is represented by following general formula (15):
Wherein R
2and R
3and R in a and b and general formula (1)
2and R
3and a is identical with b, and R
5with the R in d and general formula (3)
5identical with d.
In addition, for the epoxyhalopropane being represented by above-mentioned general formula (13), R
1with the R in general formula (1)
1identical, and X represents halogen atom.
Therefore, the diphenol compound object lesson being represented by general formula (12) comprises 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl)-1-cyclohexene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1, two (4-hydroxyl-3-phenyl) benzene (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl) benzene), 1, two (4-hydroxyl-3 of 4-, 5-diphenyl phenyl) benzene (1, 4-bis (4-hydroxy-3, 5-diphenylphenyl) benzene), 1-(4-hydroxy-5-methyl base-3-phenyl)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-5-methyl-3-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-2-phenyl)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-2-phenylphenyl)-4-(4-hydroxyphenyl) benzene),1-(4-hydroxy-5-methyl base-2-phenyl)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-5-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxy-3-methyl-2-phenyl)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-3-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-3,5-diphenyl phenyl)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-3,5-diphenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyl-3-tolyl)-2-toluene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxy-3-methylphenyl)-2-methylbenzene), 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl)-3-biphenyl (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxyphenyl)-3-phenylbenzene), 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyl-3-tolyl)-3-biphenyl (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxy-3-methylphenyl)-3-phenylbenzene), 1, two (4-hydroxyl-3-phenyl)-2-biphenyl (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl)-2-phenylbenzene), 1, two (4-hydroxyl-3-phenyl)-1-cyclohexene (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl)-1-cyclohexene), 1, two (4-hydroxyl-3 of 4-, 5-diphenyl phenyl)-1-cyclohexene (1,4-bis (4-hydroxy-3,5-diphenylphenyl)-1-cyclohexene), 1-(4-hydroxy-5-methyl base-3-phenyl)-4-(4-hydroxyphenyl)-1-cyclohexene (1-(4-hydroxy-5-methyl-3-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxyl-2-phenyl)-4-(4-hydroxyphenyl)-1-cyclohexene (1-(4-hydroxy-2-phenylPhenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxy-5-methyl base-2-phenyl)-4-(4-hydroxyphenyl)-1-cyclohexene (1-(4-hydroxy-5-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxy-3-methyl-2-phenyl)-4-(4-hydroxyphenyl)-1-cyclohexene (1-(4-hydroxy-3-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxyl-3,5-diphenyl phenyl)-4-(4-hydroxyphenyl)-1-cyclohexene (1-(4-hydroxy-3,5-diphenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyl-3-tolyl)-2-methyl isophthalic acid-cyclohexene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxy-3-methylphenyl)-2-methyl-1-cyclohexene), 1-(4-hydroxyphenyl)-4-(4-hydroxyl-3-phenyl)-2-phenyl-1-cyclohexene (1-(4-hydroxyphenyl)-4-(4-hydroxy-3-phenylphenyl)-2-phenyl-1-cyclohexene), 1-(4-hydroxyl-3-tolyl)-4-(4-hydroxyl-3-phenyl)-2-phenyl-1-cyclohexene (1-(4-hydroxy-3-methylphenyl)-4-(4-hydroxy-3-phenylphenyl)-2-phenyl-1-cyclohexene), 1, two (4-hydroxyl-3-phenyl)-2-phenyl-1-cyclohexene (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl)-2-phenyl-1-cyclohexene) etc.
In addition the epoxyhalopropane being represented by general formula (13), for example specifically comprises: epoxy chloropropane, epoxy bromopropane, β methyl epoxy chloropropane, Beta-methyl epoxy bromopropane etc.Among them, consider preferably to use epoxy chloropropane from viewpoint economically.
Next, to describe aforementioned 1 in detail) preparation method, pass through the method, the diepoxides being represented by general formula (1) according to the present invention obtains by following steps: the raw material diphenol compound being represented by above-mentioned general formula (12) is dissolved in the epoxyhalopropane being represented by above-mentioned general formula (13) and uses the quaternary ammonium salt as tetramethyl ammonium chloride or trimethyl benzyl ammonia chloride as catalyzer, they to be reacted to each other, thereby add afterwards the basic cpd as alkali metal hydroxide and/or add the basic cpd aqueous solution cyclization product as alkali metal hydroxide.
The quaternary ammonium salt that is used as catalyzer in above-mentioned reaction specifically comprises: Tetrabutyl amonium bromide, etamon chloride, tetraethyl-amine bromide, benzyl trimethyl ammonium chloride etc.
The amount of the quaternary ammonium salt adding conventionally in every 1 mole of raw material xenol, 0.05 to 1 molar range, preferably 0.1 to 0.5 mole.
Basic cpd comprises: the alkali metal hydroxide as sodium hydroxide and potassium hydroxide, the alkaline earth metal hydroxides as magnesium hydroxide and hydrated barta, such as the inorganic salt of carbonate or supercarbonate (as sodium carbonate), the organic amine as pyridine, triethylamine etc.Among them, first-selected alkali metal hydroxide.
The amount of the basic cpd using conventionally in every 1 mole of raw material diphenol compound, 0.1 to 10 molar range, preferably 1 to 5 mole.These basic cpds can use with their original states, or use with the aqueous solution.
In reaction, for the mol ratio of epoxyhalopropane and diphenol compound, the amount of epoxyhalopropane is no less than the twice of the mole number of the required theoretical amount of all hydroxyl epoxidations of making in diphenol compound, and it is conventionally in the scope of 2 to 100 moles of every 1 mole of diphenol compounds, preferably 2 to 50 moles.Conventionally, in the time of charging feedstock, preferably add quaternary ammonium salt with full dose, but also can in the process of reaction, further add quaternary ammonium salt.The stage that alkali metal hydroxide disappears at the hydroxyl of raw material xenol adds.
In reaction, as long as operation, without any problem, can not use solvent.But, using solvent in the situation that, for to reacting the in addition restriction especially of inoperative condition, and solvent can use separately, or uses as the mixture of two or more solvents.Alternatively, excessive epoxyhalopropane compound can be used as reaction solvent.
Solvent for example comprises: the saturated hydrocarbon solvent as pentane, hexane, heptane, octane, nonane, decane, dodecane, pentamethylene, hexanaphthene and suberane; Aromatic hydrocarbons as benzene,toluene,xylene, sym-trimethylbenzene and unsym-trimethyl benzene; Alcoholic solvent as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol and propylene glycol; As acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone, methylcyclohexanone, 3,3,5-trimethylcyclohexanone, Methyl amyl ketone (methylpentylketone), methyln-hexyl ketone and the such ketone of methyl n-undecyl ketone; Fatty nitrile as acetonitrile and propionitrile; Aliphatic ether as dme and diethyl ether; Alicyclic ether as Isosorbide-5-Nitrae-dioxane and tetrahydrofuran (THF); The aminocompound that for example DMF and METHYLPYRROLIDONE are such; Dimethyl sulfoxide (DMSO) etc.As long as in the tolerance interval of volumetric efficiency, the amount of the solvent using without particular limitation of, but, its conventionally in the scope of raw material xenol 0.1 to 50 weight part of every 1 weight part, preferably 1 to 20 weight part.
Temperature of reaction, in the scope of 20 ° of C to 100 ° of C, is preferably in the scope of 30 ° of C to 70 ° of C.Reaction pressure can be under normal pressure or under reduced pressure.In such reaction conditions, reaction completed conventionally in 10 to 30 hours, but after supplying alkali metal hydroxide, if needed, reactive system can further keep about 1 to 5 hours in the situation that stirring, thereby makes to react completely.
In addition,, in order further these epoxidation reaction products to be converted into the epoxy compounds with small amount hydrolyzable halogen, further react and guarantee cyclisation thereby reaction product can be dissolved in toluene, methyl iso-butyl ketone (MIBK) etc.
Reaction, conventionally by charging feedstock xenol, epoxyhalopropane and quaternary ammonium salt, makes their reactions in the time heating up, and at the hydroxyl of raw material xenol because further reaction and that while disappearing adds alkali metal hydroxide and carry out.After reaction completes, reactive system is cooling, distilled water and aforesaid solvent (if needs) are added in the mixing solutions having obtained after having reacted, stir the mixture, remove afterwards the halo alkali salt and the unreacted epoxyhalopropane that in system, exist, in addition, words if necessary are further carried out neutralization reaction, and the crystallization of precipitation is filtered and removed.Alternatively, also can not filtering the crystallization of precipitation, will can not affect crystallization once their dissolve.As low-purity crystallization in the situation that, if necessary, can carry out purifying to them by one or many crystallization or precipitation.
In above-mentioned diepoxides product, generally well-known as epoxidation reaction, owing to generating the oligopolymer as the dipolymer of 2-glycidyl ether compound, trimer and tetramer as the by product in epoxidation reaction on a small quantity, can comprise a small amount of such oligopolymer according to diepoxides of the present invention.In addition, can comprise a little as those compounds that contains the end group with so-called hydrolyzable chlorine, these hydrolyzable chlorines do not form epoxy group(ing) and left behind.
In addition, the raw material diphenol compound being represented by above-mentioned general formula (12) can obtain by known method, and the raw material diphenol compound that its formula of (12) represents is the raw material by the diepoxides of general formula of the present invention (1) expression.
For example, the method of describing according to TOHKEMY 2002-308809 patent documentation, A in general formula (12) is tetrahydrobenzene-1, (cyclohexene-1 when 4-bis-base, 4-diyl group) 1, two (4-the hydroxyphenyl)-1-tetrahydrobenzene of 4-can produce two (4-the hydroxyphenyl)-4-cyclohexylphenol of 1,1-by corresponding 4-(4-hydroxyphenyl) pimelinketone and phenol reactant, and in the situation that there is basic catalyst, it are carried out to thermolysis and obtain.
Alternatively, according to the 74th phase of U.S. chemical institute magazine, p.5631-5632 (1952) (Journal of American Chemical Society, Vol.74, p.5631-5632 (1952)) describe method, 1, two (4-the hydroxyphenyl)-1-tetrahydrobenzene of 4-can obtain by the following method: 4-alkoxyl phenyl pimelinketone (4-alkoxyphenylcyclohexanone) and 4-alkoxy benzene magnesium bromide (4-alkoxybenzene magnesium bromide) react and synthesize 1, two (4-the alkoxyphenyl radical)-1-tetrahydrobenzene of 4-, replace afterwards the alkoxyl group in two (the 4-alkoxyphenyl radical) obtaining with hydrogen atom by known method, for example, by utilizing the dealkylation of boron tribromide.
In addition, according to the method for describing in TOHKEMY 2002-308808 patent documentation, A in general formula (12) is benzene-1, when 4-bis-base 1, two (4-hydroxyphenyl) benzene of 4-can obtain by the tetrahydrobenzene part dehydrogenation that makes obtained Isosorbide-5-Nitrae-bis-(4-hydroxyphenyl)-1-tetrahydrobenzene.
Embodiment
By following examples, the present invention is described, although the present invention is not limited only to these embodiment.
Embodiment 1
Synthesizing of 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene)
Pack 10.0g1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl) benzene, 1.9g Tetrabutyl amonium bromide and 82.1g epoxy chloropropane into being equipped with in the 300ml four-hole boiling flask of agitator, in internal system with stirring 9 hours under 50 ° of C after nitrogen purge.In reaction soln, add 3.5g sodium hydroxide and further stir 4 hours.After having reacted, add 100g toluene and 40g distilled water, under 30 ° of C, stir 1 hour, afterwards the crystallization of precipitation is filtered.By obtained crystallization drying under reduced pressure under 50 ° of C, obtain the target substance of 11.5g, i.e. 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene: the white powder crystallization (high performance liquid chromatography) that purity is 96%.
Output based on raw material 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl) benzene is 86.5mol%.
Fusing point: 175 ° of C(are recorded by dsc (DSC)).
1h-NMR measuring result
(400MHz, solvent; CDCl
3, internal reference: tetramethylsilane)
2.69(dd,1H),2.77-2.84(m,2H),2.93(t,1H),3.29(br,1H),3.39(br,1H),3.99-4.05(m,2H),4.27(dd,2H),7.01(d,2H),7.07(d,1H),7.35(t,1H),7.44(t,2H),7.55-7.65(m,10H)
Embodiment 2
Synthesizing of 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene)
Pack 10.0g1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene, 1.9g Tetrabutyl amonium bromide and 81.0g epoxy chloropropane into being equipped with in the 300ml four-hole boiling flask of agitator, in internal system with stirring 19 hours under 50 ° of C after nitrogen purge.In reaction soln, add 3.5g sodium hydroxide and further stir 4 hours.After having reacted, thereby by distillation, reaction soln is concentrated and removes excessive epoxy chloropropane, add 100g methyl iso-butyl ketone (MIBK) and 40g distilled water, after stirring, remove water layer.
Water is joined in obtained oil reservoir, and water re-using washing and the operation of removing water layer, until the pH value of water layer reaches 7.By distillation, thereby obtained oil reservoir is concentrated and removes methyl iso-butyl ketone (MIBK).
In remaining liquid, add 15g hexanaphthene and mix for crystallization, and the crystallization of precipitation is filtered.By obtained crystallization drying under reduced pressure under 50 ° of C, obtain the target substance of 9.3g, i.e. 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene: the white powder crystallization (being recorded by high performance liquid chromatography) that purity is 97%.
Output based on raw material 1-(4-hydroxyl-3-phenyl)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene is 70mol%.
Fusing point: 113 ° of C(are recorded by dsc (DSC)).
1h-NMR measuring result
(400MHz, solvent; CDCl
3, internal reference: tetramethylsilane)
1.85-1.90(m,1H),2.07(br,1H),2.30-2.33(m,1H),2.46-2.57(m,3H),2.67(dd,1H),2.74-2.91(m,4H),3.25(br,1H),3.35(br,1H),3.94-4.00(m,2H),4.18-4.23(m,2H),6.16(s,1H)6.88(d,2H),6.95(d,1H),7.19(d,2H),7.31-7.36(m,2H),7.39-7.43(m,3H),7.55(d,2H)
Claims (17)
1. the diepoxides being represented by general formula (1):
Wherein R
1represent hydrogen atom or methyl, R
2represent to have independently of one another 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, R
3represent independently of one another to have the alkyl of 1 to 8 carbon atom or have the alkoxyl group of 1 to 8 carbon atom, a represents from 1 to 4 integer, and b represents 0 or from 1 to 4 integer, and when a, b be 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, and A is the divalent group being represented by following general formula (2) or general formula (3):
General formula (2):
Wherein R
4represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, c represents 0 or from 1 to 4 integer, and when c be 2 or when above, R
4can be identical or different; Or
General formula (3):
Wherein R
5represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, d represents 0 or from 1 to 4 integer, and when d be 2 or when above, R
5can be identical or different.
2. diepoxides according to claim 1, is characterized in that, in general formula (1), a is to be 0 or from 1 to 2 integer from 1 to 2, b.
3. diepoxides according to claim 1, is characterized in that, in general formula (2), c is 0 or from 1 to 2 integer.
4. diepoxides according to claim 1, is characterized in that, in general formula (3), d is 0 or from 1 to 2 integer.
5. diepoxides according to claim 1, is characterized in that, described compound is represented by general formula (6):
Wherein R
1represent hydrogen atom or methyl, R
2represent to have independently of one another 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, R
3represent independently of one another to have the alkyl of 1 to 8 carbon atom or have the alkoxyl group of 1 to 8 carbon atom, a represents from 1 to 4 integer, and b represents 0 or from 1 to 4 integer, and when a, b be 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, R
4represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, c represents 0 or from 1 to 4 integer, and when c be 2 or when above, R
4can be identical or different.
6. diepoxides according to claim 1, is characterized in that, described compound is represented by general formula (6):
Wherein R
1represent hydrogen atom or methyl, R
2expression independently of one another has 1 to 4 straight chain of carbon atom or the alkyl of side chain, has the cycloalkyl of 5 to 8 carbon atoms, has 1 to 8 straight chain of carbon atom or the alkoxyl group of side chain or phenyl, and alkyl and alkoxyl group can be replaced by phenyl or alkoxyl group, phenyl can be replaced by 1 to 3 alkoxyl group that has the alkyl of 1 to 4 carbon atom and/or have 1 to 4 carbon atom, or can there is no substituting group, R
3represent independently of one another to there is 1 to 4 straight chain of carbon atom or the alkyl of side chain, there is the cycloalkyl of 5 to 8 carbon atoms or there is 1 to 8 straight chain of carbon atom or the alkoxyl group of side chain, and alkyl and alkoxyl group can be replaced by phenyl or alkoxyl group, a represents from 1 to 4 integer, b represents 0 or from 1 to 4 integer, and when a, b are 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, R
4expression has 1 to 4 straight chain of carbon atom or the alkyl of side chain, has the cycloalkyl of 5 to 8 carbon atoms, has 1 to 8 straight chain of carbon atom or the alkoxyl group of side chain or phenyl, and alkyl and alkoxyl group can be replaced by phenyl or alkoxyl group, phenyl can be replaced by 1 to 3 alkoxyl group that has the alkyl of 1 to 4 carbon atom and/or have 1 to 4 carbon atom, or can there is no substituting group, c represents 0 or from 1 to 4 integer, and when c is 2 or when above, R
4can be identical or different.
7. diepoxides according to claim 1, is characterized in that, described compound is represented by general formula (6):
Wherein R
1represent hydrogen atom or methyl, R
2represent independently of one another methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, cyclohexyl, cyclopentyl, methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy, cyclopentyloxy or phenyl, and phenyl can or can not have substituting group, R by 1 to 3 methyl substituted
3represent independently of one another methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, cyclohexyl, cyclopentyl, methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy or cyclopentyloxy, a represents from 1 to 4 integer, b represents 0 or from 1 to 4 integer, and when a, b are 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, R
4represent methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, cyclohexyl, cyclopentyl, methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy, cyclopentyloxy or phenyl, and phenyl can or can not have substituting group by 1 to 3 methyl substituted, c represents 0 or from 1 to 4 integer, and when c is 2 or when above, R
4can be identical or different.
8. according to the diepoxides described in any one in claim 5～7, it is characterized in that, in general formula (6), c is 0.
9. diepoxides according to claim 5, is characterized in that, described compound is represented by general formula (7):
Wherein R
1represent hydrogen atom or methyl, R'
2and R'
3represent independently of one another the alkoxyl group that has the alkyl of 1 to 8 carbon atom or have 1 to 8 carbon atom, a-1 represents 0 or from 1 to 3 integer, and b represents 0 or from 1 to 4 integer.
10. diepoxides according to claim 1, is characterized in that, described compound is represented by general formula (9):
Wherein R
1represent hydrogen atom or methyl, R
2represent to have independently of one another 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, R
3represent independently of one another to have the alkyl of 1 to 8 carbon atom or have the alkoxyl group of 1 to 8 carbon atom, a represents from 1 to 4 integer, and b represents 0 or from 1 to 4 integer, and when a, b be 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, R
5represent to have 1 to 8 carbon atom alkyl, there is alkoxyl group or the phenyl of 1 to 8 carbon atom, d represents 0 or from 1 to 4 integer, and when d be 2 or when above, R
5can be identical or different.
11. diepoxidess according to claim 1, is characterized in that, described compound is represented by general formula (9):
Wherein R
1represent hydrogen atom or methyl, R
2expression independently of one another has 1 to 4 straight chain of carbon atom or the alkyl of side chain, has the cycloalkyl of 5 to 8 carbon atoms, has 1 to 8 straight chain of carbon atom or the alkoxyl group of side chain or phenyl, and alkyl and alkoxyl group can be replaced by phenyl or alkoxyl group, phenyl can be replaced by 1 to 3 alkoxyl group that has the alkyl of 1 to 4 carbon atom and/or have 1 to 4 carbon atom, or can there is no substituting group, R
3represent independently of one another to there is 1 to 4 straight chain of carbon atom or the alkyl of side chain, there is the cycloalkyl of 5 to 8 carbon atoms or there is 1 to 8 straight chain of carbon atom or the alkoxyl group of side chain, and alkyl and alkoxyl group can be replaced by phenyl or alkoxyl group, a represents from 1 to 4 integer, b represents 0 or from 1 to 4 integer, and when a, b are 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, R
5expression has 1 to 4 straight chain of carbon atom or the alkyl of side chain, has the cycloalkyl of 5 to 8 carbon atoms, has 1 to 8 straight chain of carbon atom or the alkoxyl group of side chain or phenyl, and alkyl and alkoxyl group can be replaced by phenyl or alkoxyl group, phenyl can be replaced by 1 to 3 alkoxyl group that has the alkyl of 1 to 4 carbon atom and/or have 1 to 4 carbon atom, or can there is no substituting group, d represents 0 or from 1 to 4 integer, when d is 1 or when above, R
5the position except 4-position of the position of substitution in 1-tetrahydrobenzene skeleton, and when d be 2 or when above, R
5can be identical or different, and on same carbon atom, do not replace.
12. diepoxidess according to claim 1, is characterized in that, described compound is represented by general formula (9):
Wherein R
1represent hydrogen atom or methyl, R
2represent independently of one another methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, cyclohexyl, cyclopentyl, methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy, cyclopentyloxy or phenyl, and phenyl can or can not have substituting group, R by 1 to 3 methyl substituted
3represent independently of one another methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, cyclohexyl, cyclopentyl, methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy or cyclopentyloxy, a represents from 1 to 4 integer, b represents 0 or from 1 to 4 integer, and when a, b are 2 or when above, R
2or R
3can be identical or different, but R
2at least one be phenyl, R
5represent methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, benzyl, cyclohexyl, cyclopentyl, methoxyl group, oxyethyl group, propoxy-, tert.-butoxy, cyclohexyloxy, cyclopentyloxy or phenyl, and phenyl can or can not have substituting group by 1 to 3 methyl substituted, d represents 0 or from 1 to 4 integer, when d is 1 or when above, R
5the position except 4-position of the position of substitution in 1-tetrahydrobenzene skeleton, and when d be 2 or when above, R
5can be identical or different, and on same carbon atom, do not replace.
13. according to the diepoxides described in any one in claim 10～12, it is characterized in that, in general formula (9), d is 0.
14. diepoxidess according to claim 10, is characterized in that, described compound is represented by general formula (10):
Wherein R
1represent hydrogen atom or methyl, R'
2and R'
3represent independently of one another the alkoxyl group that has the alkyl of 1 to 8 carbon atom or have 1 to 8 carbon atom, a-1 represents 0 or from 1 to 3 integer, and b represents 0 or from 1 to 4 integer.
15. diepoxidess according to claim 1, it is characterized in that, described diepoxides is 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene, 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene, 1-(4-oxidation Racemic glycidol-5-methyl-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene, 1-(4-oxidation Racemic glycidol-2-methyl-5-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene, 1-(4-oxidation Racemic glycidol-2-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene, 1-(4-oxidation Racemic glycidol-5-methyl-2-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene, (4-is oxidized Racemic glycidol-3 to 1-, 5-phenylbenzene phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene, 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol-3-tolyl)-2-toluene, 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-3-biphenyl, 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol-3-tolyl)-3-biphenyl, 1-(4-oxidation Racemic glycidol-5-methyl-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene, 1-(4-oxidation Racemic glycidol-2-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene, 1-(4-oxidation Racemic glycidol-5-methyl-2-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene, 1-(4-oxidation Racemic glycidol-3-methyl-2-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene, (4-is oxidized Racemic glycidol-3 to 1-, 5-phenylbenzene phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene, 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol-3-tolyl)-2-methyl isophthalic acid-tetrahydrobenzene.
16. diepoxidess according to claim 1, is characterized in that, described diepoxides is 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl) benzene.
17. diepoxidess according to claim 1, is characterized in that, described diepoxides is 1-(4-oxidation Racemic glycidol-3-phenyl)-4-(4-oxidation Racemic glycidol phenyl)-1-tetrahydrobenzene.
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| JP6017363B2 (en) * | 2013-03-29 | 2016-10-26 | 本州化学工業株式会社 | Novel diepoxy compounds |
| CN103420950B (en) * | 2013-08-23 | 2015-02-18 | 上海朗亿功能材料有限公司 | Amino acid base biodegradable 2-expoxy compound and preparation method thereof |
| WO2016006649A1 (en) * | 2014-07-10 | 2016-01-14 | Dic株式会社 | Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof |
| JP6176412B2 (en) * | 2014-12-24 | 2017-08-09 | Dic株式会社 | Epoxy resin composition for electronic material, cured product thereof and electronic member |
| CN105968071A (en) * | 2016-05-09 | 2016-09-28 | 开美化学科技(南通)有限公司 | Method for producing tetrabromobisphenol A diglycidyl ether |
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| JP特开2010-116329A 2010.05.27 * |
| JP特开2011-46623A 2011.03.10 * |
| JP特开平7-206996A 1995.08.08 * |
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| Publication number | Publication date |
|---|---|
| JP5662695B2 (en) | 2015-02-04 |
| JP2011231079A (en) | 2011-11-17 |
| CN102234256A (en) | 2011-11-09 |
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