CN102234256A - Novel diepoxide - Google Patents
Novel diepoxide Download PDFInfo
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- CN102234256A CN102234256A CN2011101071212A CN201110107121A CN102234256A CN 102234256 A CN102234256 A CN 102234256A CN 2011101071212 A CN2011101071212 A CN 2011101071212A CN 201110107121 A CN201110107121 A CN 201110107121A CN 102234256 A CN102234256 A CN 102234256A
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- 0 CCC1C(CC)C(CCC(CC2C)CC2=C*)C1 Chemical compound CCC1C(CC)C(CCC(CC2C)CC2=C*)C1 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 bicyclic oxygen compound.
Background technology
Resins, epoxy is widely used in the multiple field as tackiness agent, coating, general industry structured material and electronics/electric installation assembly or material.In recent years, along with expansion and development, to operability with comprise that there is the intensive demand in the further improvement of the various performances of thermotolerance, moistureproofness, chemical resistant properties, electrical characteristic and mechanical characteristics to the application of these Resins, epoxy.Therefore, need exploitation to be adapted to the new epoxy compound of such demand.
Till now, the diepoxides of deriving out from many multinuclear bis-phenols is known as the starting material that are used to have good stable on heating Resins, epoxy, perhaps as having low-melting diepoxides.For example, 4,4 '-[1, two (1-methyl ethylidene) two (the phenylene oxygen methylene radical 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)-1,1 '-diglycidyl ether (the diglycidyl ether of4 of biphenyl, 4 '-bis (2,3,6-trimethyl hydroxyphenyl)-1,1 '-biphenyl) (TOHKEMY 2005-314499 patent documentation), 1,1-two (4 '-propylene oxide phenoxy group)-1-(1 " biphenyl)-1-cyclohexyl-methane (1; 1-bis (4 '-epoxypropanyloxyphenyl)-and 1-(1 " biphenyl)-1-cyclohexylmethane) diglycidyl ether of (No. 2005/092826 patent documentation of international publication) or 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl) benzene (diglycidyl ether of1-(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. all is known.
Yet, these diepoxidess commonly known in the art need to improve, because when the time as cured resin, they are still unsatisfactory aspect thermotolerance, flame retardant resistance and agent of low hygroscopicity, and they are being added man-hour, and they are also unsatisfactory aspect low melting point and solvent solubility.
The present invention is exactly in order to satisfy foregoing demand.The purpose of this invention is to provide a kind of novel bicyclic oxygen compound, when as cured resin, this compound has good thermotolerance and flame retardant resistance and agent of low hygroscopicity, when being added, it has low melting point and excellent solvent solvability man-hour, this compound not only can be advantageously used in improving the performance of tackiness agent, coating and the common industrial structured material of the Resins, epoxy that adopts prior art, can also be used for wishing in recent years to have the electronics/electric installation assembly of better performance and better function or the like.
Summary of the invention
The present inventor has carried out scrutiny to the epoxy compounds that the said feature in front is provided simultaneously, has therefore finished the present invention.Particularly, the invention provides a kind of diepoxides by general formula (1) expression:
R wherein
1Expression hydrogen atom or methyl, R
2And R
3Expression independently of one another have 1 to 8 carbon atom alkyl, have the 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
3In the substituting group of expression at least one 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 by following general formula (2) or general formula (3) expression:
General formula (2):
R wherein
4Expression have 1 to 8 carbon atom alkyl, have the 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; Perhaps
General formula (3):
R wherein
5Expression have 1 to 8 carbon atom alkyl, have the 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 replaced by phenyl, so, with have identical skeleton, wherein the 4-phenoxy group at two ends is not substituted or is compared by the diepoxides that alkyl replaces, 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, when 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 man-hour, it shows good aspect solution solubleness and solidifies at a lower temperature, and it also has good flame retardant resistance and thermotolerance and agent of low hygroscopicity and base material sticking power when as cured resin.Such novel bicyclic oxygen compound according to the present invention not only can be advantageously used in adopting tackiness agent, coating and the common industrial structured material of the Resins, epoxy of prior art, 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):
R wherein
1Expression hydrogen atom or methyl, R
2And R
3Expression independently of one another have 1 to 8 carbon atom alkyl, have the 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
3In the substituting group of expression at least one 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 by following general formula (2) or general formula (3) expression:
General formula (2):
R wherein
4Expression have 1 to 8 carbon atom alkyl, have the 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; Perhaps
General formula (3):
R wherein
5Expression have 1 to 8 carbon atom alkyl, have the 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
1Be hydrogen atom or methyl, preferably hydrogen atom.In addition, for by R
2And R
3The alkyl with 1 to 8 carbon atom of expression, it can be straight chain, side chain or cyclic, 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 or the like.Among them, alkyl preferably straight chain or side chain, first-selection is methyl or ethyl.For the alkoxyl group with 1 to 8 carbon atom, it can be straight chain, side chain or the cyclic alkoxyl group, 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) or the like.Among alkyl and alkoxyl group, alkyl preferably.
In addition, the phenyl alkoxyl group that 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.Yet it is first-selected not having 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 and b be not 0 simultaneously, they preferably 0 or 1 to 2, first-selected a be 1 or 2 and b be 0.
In addition, in diepoxides, by R by general formula of the present invention (1) expression
2And R
3In the substituting group of expression at least one is phenyl.The compound that diepoxides is preferably such: by R
2And R
3In the substituting group of expression any one is phenyl, perhaps, a and b all be 1 or when above by R
2The substituting group neutralization of expression is by R
3Respectively there is one to be phenyl in the substituting group of expression, and first-selected such compound: by R
2And R
3In the substituting group of expression any one is phenyl.
In addition, R
2And R
3The position of substitution be preferably in the ortho position of ether on the benzene nucleus, and the first-selected ortho position that is substituted in ether on the benzene nucleus for phenyl.
In addition, in general formula, divalent group A is by the expression of general formula (2) or general formula (3), in above-mentioned general formula, and R
4Or R
5Be the alkyl with 1 to 8 carbon atom, alkoxyl group or phenyl with 1 to 8 carbon atom, and they and by R
2Or R
3The alkyl with 1 to 8 carbon atom of expression, 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 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
3In the substituting group of expression any one is phenyl, and when divalent group A is represented by general formula (2), the c in the general formula preferably 0, and perhaps when divalent group A is represented by general formula (3), the d in the general formula preferably 0.
Therefore, represent by following general formula (4) or general formula (5) by the of the present invention preferred diepoxides of general formula (1) expression:
General formula (4):
R wherein
1With the R in the general formula (1)
1Identical, R '
2And R '
3Expression has the alkyl of 1 to 8 carbon atom or has the alkoxyl group of 1 to 8 carbon atom, and a-1 is that a in the general formula (1) subtracts 1 integer that obtains, wherein a be 1 or more than, and b is identical with b in the general formula (1),
Wherein by R '
2And R '
3The alkyl with 1 to 8 carbon atom of the alkyl with 1 to 8 carbon atom of expression or the alkoxyl group with 1 to 8 carbon atom and general formula (1) or to have an alkoxyl group of 1 to 8 carbon atom identical; Perhaps
General formula (5):
R wherein
1, R '
2And R '
3And the R in a-1 and the aforementioned formula (4)
1, R '
2And R '
3And a-1 is identical, and b-1 is that b in the general formula (1) subtracts 1 integer that obtains, wherein b be 1 or more than.
In addition, if the divalent group A in the general formula (1) represents that by general formula (2) general formula (1) is represented by following general formula (6) so:
R wherein
1, R
2And R
3And the R in a and b and the general formula (1)
1, R
2And R
3And a is identical with b, and R
4With the R in c and the general formula (2)
4Identical with c.
The preferably such diepoxides of compound of general formula (6): wherein c is 0; And by R
2And R
3In the substituting group of expression any one is phenyl (general formula (7)), perhaps by R
2The substituting group neutralization of expression is by R
3Respectively there is one to be phenyl (general formula (8)) in the substituting group of expression.
General formula (7):
R wherein
1, R '
2And R '
3And the R in a-1 and b and the general formula (4)
1, R '
2And R '
3And a-1 is identical with b.
General formula (8):
R wherein
1, R '
2And R '
3And the R in a-1 and b-1 and the general formula (5)
1, R '
2And R '
3And a-1 is identical with b-1.
In addition, if the divalent group A in the general formula (1) represents that by general formula (3) general formula (1) is represented by following general formula (9) so:
R wherein
1, R
2And R
3And the R in a and b and the general formula (1)
1, R
2And R
3And a is identical with b, and R
5With the R in d and the general formula (3)
5Identical with d.The preferably such diepoxides of compound of general formula (9): wherein d is 0; And by R
2And R
3In the substituting group of expression any one is phenyl (general formula (10)), perhaps by R
2The substituting group neutralization of expression is by R
3Respectively there is one to be phenyl (general formula (11)) in the substituting group of expression.
General formula (10):
R wherein
1, R '
2And R '
3And the R in a-1 and b and the general formula (4)
1, R '
2And R '
3And a-1 is identical with b.
General formula (11):
R wherein
1, R '
2And R '
3And the R in a-1 and b-1 and the general formula (5)
1, R '
2And R '
3And a-1 is identical with b-1.
Such diepoxides by general formula (1) expression for example specifically comprises:
1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene):
1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene):
1, two (the 4-oxidation Racemic glycidol-3-phenyl benzene) benzene (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl) benzene), 1, two (the 4-oxidation Racemic glycidols-3 of 4-, the 5-diphenyl benzene) benzene (1,4-bis (4-glycidyloxy-3,5-diphenylphenyl) benzene), 1-(4-oxidation Racemic glycidol-5-methyl-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-5-methyl-3-phenylphenyl)-4-(4-glycidyloxyphenyl) benzen e), 1-(4-oxidation Racemic glycidol-2-methyl-5-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-2-methyl-5-phenylphenyl)-4-(4-glycidyloxyphenyl) benzen e), 1-(4-oxidation Racemic glycidol-2-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-2-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene), 1-(4-oxidation Racemic glycidol-5-methyl-2-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-5-methyl-2-phenylphenyl)-4-(4-glycidyloxyphenyl) benzen e), 1-(4-oxidation Racemic glycidol-3,5-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-3,5-diphenylphenyl)-4-(4-glycidyloxyphenyl) benzene), 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol-3-tolyl)-2-toluene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxy-3-methylphenyl)-2-met hylbenzene), 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-3-biphenyl (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-3-phenylbenzen e), 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol-3-tolyl)-3-biphenyl (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxy-3-methylphenyl)-3-phe nylbenzene), 1, two (4-oxidation Racemic glycidol-3-phenyl the benzene)-2-biphenyl (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl)-2-phenylbenzene), 1, two (4-oxidation Racemic glycidol-3-phenyl the benzene)-1-tetrahydrobenzene (1 of 4-, 4-bis (4-glycidyloxy-3-phenylphenyl)-1-cyclohexene), 1, two (the 4-oxidation Racemic glycidols-3 of 4-, the 5-diphenyl benzene)-1-tetrahydrobenzene (1,4-bis (4-glycidyloxy-3,5-diphenylphenyl)-1-cyclohexene), 1-(4-oxidation Racemic glycidol-5-methyl-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene (1-(4-glycidyloxy-5-methyl-3-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cycl ohexene), 1-(4-oxidation Racemic glycidol-2-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene (1-(4-glycidyloxy-2-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexene), 1-(4-oxidation Racemic glycidol-5-methyl-2-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene (1-(4-glycidyloxy-5-methyl-2-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cycl ohexene), 1-(4-oxidation Racemic glycidol-3-methyl-2-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene (1-(4-glycidyloxy-3-methyl-2-phenylphenyl)-4-(4-glycidyloxyphenyl)-1-cycl ohexene), 1-(4-oxidation Racemic glycidol-3, the 5-diphenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene (1-(4-glycidyloxy-3,5-diphenylphenyl)-4-(4-glycidyloxyphenyl)-1-cyclohexe ne), 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol-3-tolyl)-2-methyl isophthalic acid-tetrahydrobenzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxy-3-methylphenyl)-2-met hyl-1-cyclohexene), 1-(4-oxidation Racemic glycidol benzene)-4-(4-oxidation Racemic glycidol-3-phenyl benzene)-2-phenyl-1-tetrahydrobenzene (1-(4-glycidyloxyphenyl)-4-(4-glycidyloxy-3-phenylphenyl)-2-phenyl-1-cycl ohexene), 1-(4-oxidation Racemic glycidol-3-tolyl-4-(4-oxidation Racemic glycidol-3-phenyl benzene)-2-phenyl-1-tetrahydrobenzene (1-(4-glycidyloxy-3-methyl phenyl)-4-(4-glycidyloxy-3-phenylphenyl)-2-phenyl-1-cyclohexene), 1, two (4-oxidation Racemic glycidol-3-phenyl the benzene)-2-phenyl benzene-1-tetrahydrobenzene of 4-(1,4-bis (4-glycidyloxy-3-phenylphenyl)-2-phenyl-1-cyclohexene) or the like.
Although the preparation method according to the diepoxides by general formula (1) expression of the present invention is not particularly limited, but for example following several method or the like all is known: the 1) method of the epoxidation reaction of phenolic compound, it reacts them by the raw material phenolic compound being dissolved in the epoxyhalopropane and using the quaternary ammonium salt as tetramethyl ammonium chloride and trimethyl benzyl ammonia chloride as catalyzer, adds afterwards as the aqueous solution of basic cpd the alkali metal hydroxide and/or the basic cpd of adding 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, adding after the solid base metal hydroxides sodium hydroxide and the potassium hydroxide or adding 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 alkali metal hydroxide continuously, simultaneously therefrom continuous still battery water outlet and epoxyhalopropane under decompression or normal pressure, thereby and this mixture separation removed water and turn back to epoxyhalopropane in the reactive system continuously; 4) phenolic compound and the vinyl halide as propenyl chloride and allyl bromide 98 react in solvent existing under the situation of alkali, then after reaction is finished, the oxygenant as metachloroperbenzoic acid etc. that allows to carbon-to-carbon double bond is oxidized to epoxy group(ing) reacts to the reaction mixture that forms, perhaps for example, after reaction soln mixes with water and removes reaction product, oxygenant is reacted to reaction product, afterwards, for example, if desired, make remaining oxygenant degraded, thereby the concentration response product obtains method of epoxy compounds or the like then.Any method in these methods can be used for obtaining epoxy compounds of the present invention.
In order to obtain according to the diepoxides by general formula (1) expression of the present invention, utilize corresponding to the structure of diepoxides by the diphenol compound of following general formula (12) expression and as raw material by the epoxyhalopropane of following general formula (13) expression with regard to enough (reaction formula (1)).
Reaction formula (1):
In raw material diphenol compound by above-mentioned general formula (12) expression, R
2And R
3, the R in a, b and A and the general formula (1)
2And R
3, a, b be identical with A.Therefore, for the diphenol compound by above-mentioned general formula (12) expression, when A was represented by general formula (2), diphenol compound was represented by following general formula (14):
R wherein
2And R
3And the R in a and b and the general formula (1)
2And R
3And a is identical with b, and R
4With the R in c and the general formula (2)
4Identical with c.
In addition, when A was represented by general formula (3), diphenol compound was represented by following general formula (15):
R wherein
2And R
3And the R in a and b and the general formula (1)
2And R
3And a is identical with b, and R
5With the R in d and the general formula (3)
5Identical with d.
In addition, for the epoxyhalopropane by above-mentioned general formula (13) expression, R
1With the R in the general formula (1)
1Identical, and X represents halogen atom.
Therefore, diphenol compound object lesson by general formula (12) expression comprises 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1, two (4-hydroxyl-3-phenyl benzene) benzene (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl) benzene), 1, two (the 4-hydroxyls-3 of 4-, the 5-diphenyl benzene) benzene (1,4-bis (4-hydroxy-3,5-diphenylphenyl) benzene), 1-(4-hydroxy-5-methyl base-3-phenyl benzene)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-5-methyl-3-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-2-phenyl benzene)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-2-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxy-5-methyl base-2-phenyl benzene)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-5-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxy-3-methyl-2-phenyl benzene)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-3-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-3, the 5-diphenyl benzene)-4-(4-hydroxyphenyl) benzene (1-(4-hydroxy-3,5-diphenylphenyl)-4-(4-hydroxyphenyl) benzene), 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyl-3-tolyl)-2-toluene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxy-3-methylphenyl)-2-methylbenz ene), 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl)-3-biphenyl (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxyphenyl)-3-phenylbenzene), 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyl-3-tolyl)-3-biphenyl (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxy-3-methylphenyl)-3-phenylbenz ene), 1, two (4-hydroxyl-3-phenyl the benzene)-2-biphenyl (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl)-2-phenylbenzene), 1, two (4-hydroxyl-3-phenyl the benzene)-1-tetrahydrobenzene (1 of 4-, 4-bis (4-hydroxy-3-phenylphenyl)-1-cyclohexene), 1, two (the 4-hydroxyls-3 of 4-, the 5-diphenyl benzene)-1-tetrahydrobenzene (1,4-bis (4-hydroxy-3,5-diphenylphenyl)-1-cyclohexene), 1-(4-hydroxy-5-methyl base-3-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene (1-(4-hydroxy-5-methyl-3-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexen e), 1-(4-hydroxyl-2-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene (1-(4-hydroxy-2-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxy-5-methyl base-2-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene (1-(4-hydroxy-5-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexen e), 1-(4-hydroxy-3-methyl-2-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene (1-(4-hydroxy-3-methyl-2-phenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexen e), 1-(4-hydroxyl-3, the 5-diphenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene (1-(4-hydroxy-3,5-diphenylphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene), 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyl-3-tolyl)-2-methyl isophthalic acid-tetrahydrobenzene (1-(4-hydroxy-3-phenylphenyl)-4-(4-hydroxy-3-methylphenyl)-2-methyl-1-c yclohexene), 1-(4-hydroxyphenyl)-4-(4-hydroxyl-3-phenyl benzene)-2-phenyl-1-tetrahydrobenzene (1-(4-hydroxyphenyl)-4-(4-hydroxy-3-phenylphenyl)-2-phenyl-1-cyclohexen e), 1-(4-hydroxyl-3-tolyl)-4-(4-hydroxyl-3-phenyl benzene)-2-phenyl-1-tetrahydrobenzene (1-(4-hydroxy-3-methylphenyl)-4-(4-hydroxy-3-phenylphenyl)-2-phenyl-1-c yclohexene), 1, two (4-hydroxyl-3-phenyl the benzene)-2-phenyl-1-tetrahydrobenzene of 4-(1,4-bis (4-hydroxy-3-phenylphenyl)-2-phenyl-1-cyclohexene) etc.
In addition, the epoxyhalopropane by general formula (13) expression for example specifically comprises: epoxy chloropropane, epoxy bromopropane, β-Jia Jihuanyanglvbingwan, Beta-methyl epoxy bromopropane etc.Among them, consider preferably to use epoxy chloropropane from viewpoint economically.
Next, to describe aforementioned 1 in detail) the preparation method, by this method, diepoxides according to the present invention by general formula (1) expression obtains by following steps: will be dissolved in by the raw material diphenol compound of above-mentioned general formula (12) expression by in the epoxyhalopropane of above-mentioned general formula (13) expression and use 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 as basic cpd the alkali metal hydroxide and/or the basic cpd aqueous solution cyclization product of adding 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 or the like.
The amount of the quaternary ammonium salt that is added usually in per 1 mole of raw material xenol, 0.05 to 1 molar range, preferably 0.1 to 0.5 mole.
Basic cpd comprises: as the alkali metal hydroxide sodium hydroxide and the potassium hydroxide, as the alkaline earth metal hydroxides magnesium hydroxide and the hydrated barta, such as the inorganic salt of carbonate or supercarbonate (as yellow soda ash), the organic amine as pyridine, triethylamine or the like.Among them, first-selected alkali metal hydroxide.
The amount of employed basic cpd usually in per 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, perhaps use with the aqueous solution.
In reaction, mol ratio for 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 the diphenol compound, and it is usually in the scope of 2 to 100 moles of per 1 mole of diphenol compounds, preferably 2 to 50 moles.Usually, when charging feedstock, preferably add quaternary ammonium salt, but also can in the process of reaction, further add quaternary ammonium salt with full dose.Alkali metal hydroxide added in the stage of the hydroxyl disappearance of raw material xenol.
In reaction, as long as operation without any problem, then can not use solvent.Yet, using under the situation of solvent, for to reacting the in addition restriction especially of inoperative condition, and solvent can use separately, and perhaps the mixture as two or more solvents uses.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; As 1, the alicyclic ether that 4-dioxane and tetrahydrofuran (THF) are such; N for example, dinethylformamide and the such aminocompound of N-N-methyl-2-2-pyrrolidone N-; Dimethyl sulfoxide (DMSO) or the like.As long as in the tolerance interval of volumetric efficiency, the amount of employed solvent does not limit especially, yet, its usually in the scope of raw material xenol 0.1 to 50 weight part of per 1 weight part, 1 to 20 weight part preferably.
Temperature of reaction is preferably in 30 ℃ to 70 ℃ the scope in 20 ℃ to 100 ℃ scope.Reaction pressure can be under normal pressure or under reduced pressure.In such reaction conditions, reaction was finished in 10 to 30 hours usually, but supplied after the alkali metal hydroxide, and if desired, reactive system can further keep about 1 to 5 hours under condition of stirring, reacted completely thereby make.
In addition, in order further these epoxidation reaction products to be converted into epoxy compounds, guarantee cyclisation thereby reaction product can be dissolved in further to react in toluene, methyl iso-butyl ketone (MIBK) or the like with a small amount of hydrolyzable halogen.
Reaction makes their reactions when heating up usually by charging feedstock xenol, epoxyhalopropane and quaternary ammonium salt, and at the hydroxyl of raw material xenol because further reaction and when disappearing that adds alkali metal hydroxide and carry out.After reaction is finished, reactive system is cooled off, with distilled water and aforesaid solvent (if desired) be added to reaction finish after in the resulting mixing solutions, stir the mixture, remove the halo alkali salt and the unreacted epoxyhalopropane that exist in the system afterwards, in addition, words are if necessary further carried out neutralization reaction, and sedimentary crystallization is filtered and removed.Alternatively, also can the sedimentary crystallization of not filtering, their will not be in case dissolving will can influence crystallization.Under as low-purity crystalline situation, if necessary, can carry out purifying to them by one or many crystallization or precipitation.
In above-mentioned diepoxides product, as epoxidation reaction is generally well-known, owing to generate on a small quantity as the oligopolymer the dipolymer as the 2-glycidyl ether compound, trimer and the tetramer of the by product in the epoxidation reaction, can comprise a small amount of such oligopolymer according to diepoxides of the present invention.In addition, can comprise a little and contain the compound of the end group with so-called hydrolyzable chlorine as those, these hydrolyzable chlorines do not form epoxy group(ing) and left behind.
In addition, the raw material diphenol compound of being represented by above-mentioned general formula (12) can obtain by known method, and the raw material diphenol compound of its formula of (12) expression is the raw material by the diepoxides of general formula of the present invention (1) expression.
For example, method according to the description of TOHKEMY 2002-308809 patent documentation, A in the general formula (12) is a tetrahydrobenzene-1, (cyclohexene-1 during 4-two bases, 4-diyl group) 1, two (4-the hydroxyphenyl)-1-tetrahydrobenzene of 4-can produce 1 by corresponding 4-(4-hydroxyphenyl) pimelinketone and phenol reactant, 1-pair of (4-hydroxyphenyl)-4-cyclohexylphenol, and under the situation of basic catalyst it is carried out thermolysis and obtain existing.
Alternatively, according to the 74th phase of U.S. chemical institute magazine, p.5631-5632 (1952) (Journal ofAmerican Chemical Society, Vol.74, p.5631-5632 (1952)) method described, 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 alkoxyl group in resulting two (4-alkoxyphenyl radical) by known method with hydrogen atom afterwards, for example, by utilizing the dealkylation of boron tribromide.
In addition, according to the method for describing in the TOHKEMY 2002-308808 patent documentation, the A in the general formula (12) is a benzene-1,1 during 4-two bases, two (4-hydroxyphenyl) benzene of 4-can be resulting 1 by making, the tetrahydrobenzene part dehydrogenation of two (4-the hydroxyphenyl)-1-tetrahydrobenzene of 4-and obtaining.
Embodiment
By following examples explanation the present invention, although the present invention is not limited only to these embodiment.
Embodiment 1
Synthesizing of 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene (1-(4-glycidyloxy-3-phenylphenyl)-4-(4-glycidyloxyphenyl) benzene)
Pack in the 300ml four-hole boiling flask that agitator is housed 10.0g 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl) benzene, 1.9g Tetrabutyl amonium bromide and 82.1g epoxy chloropropane stirred 9 hours down at 50 ℃ after internal system is with nitrogen purge.In reaction soln, add 3.5g sodium hydroxide and further stirred 4 hours.After reaction is finished, add 100g toluene and 40g distilled water, stirred 1 hour down, afterwards sedimentary crystallization is filtered at 30 ℃.Resulting crystallization at 50 ℃ of following drying under reduced pressure, is obtained the target substance of 11.5g, i.e. 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene) benzene: purity is 96% white powder crystallization (high performance liquid chromatography).
Output based on raw material 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl) benzene is 86.5mol%.
Fusing point: 175 ℃ ((DSC) records by dsc).
1The H-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
(1-(4-glycidyloxy-3-phenylphenyl)-4-'s (4-glycidyloxyphenyl)-1-cyclohexene) is synthetic for 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene
Pack in the 300ml four-hole boiling flask that agitator is housed 10.0g 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene, 1.9g Tetrabutyl amonium bromide and 81.0g epoxy chloropropane stirred 19 hours down at 50 ℃ after internal system is with nitrogen purge.In reaction soln, add 3.5g sodium hydroxide and further stirred 4 hours.After reaction is finished, remove excessive epoxy chloropropane thereby by distillation reaction soln concentrated, adding 100g methyl iso-butyl ketone (MIBK) and 40g distilled water are removed water layer after the stirring.
Water is joined in the resulting oil reservoir, repeat to wash with water and remove the operation of water layer, reach 7 up to the pH of water layer value.Thereby by distillation resulting oil reservoir concentrated and to remove methyl iso-butyl ketone (MIBK).
Adding 15g hexanaphthene and mixing are used for crystallization in remaining liquid, and sedimentary crystallization is filtered.With resulting crystallization at 50 ℃ of following drying under reduced pressure, obtain the target substance of 9.3g, i.e. 1-(4-oxidation Racemic glycidol-3-phenyl benzene)-4-(4-oxidation Racemic glycidol benzene)-1-tetrahydrobenzene: purity is 97% white powder crystallization (being recorded by high performance liquid chromatography).
Output based on raw material 1-(4-hydroxyl-3-phenyl benzene)-4-(4-hydroxyphenyl)-1-tetrahydrobenzene is 70mol%.
Fusing point: 113 ℃ ((DSC) records by dsc).
1The H-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 (5)
1. diepoxides by general formula (1) expression:
R wherein
1Expression hydrogen atom or methyl, R
2And R
3Expression independently of one another have 1 to 8 carbon atom alkyl, have the 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
3In the substituting group of expression at least one 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 by following general formula (2) or general formula (3) expression:
General formula (2):
R wherein
4Expression have 1 to 8 carbon atom alkyl, have the 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; Perhaps
General formula (3):
R wherein
5Expression have 1 to 8 carbon atom alkyl, have the 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, described compound is represented by general formula (6):
R wherein
1, R
2And R
3And the R in a and b and the general formula (1)
1, R
2And R
3And a is identical with b, and R
4With the R in c and the general formula (2)
4Identical with c.
3. diepoxides according to claim 2 is characterized in that, c is 0, and by R
2And R
3In the substituting group of expression any one is phenyl, perhaps by R
2The substituting group neutralization of expression is by R
3Respectively there is one to be phenyl in the substituting group of expression.
4. diepoxides according to claim 1 is characterized in that, described compound is represented by general formula (9):
R wherein
1, R
2And R
3And the R in a and b and the general formula (1)
1, R
2And R
3And a is identical with b, and R
5With the R in d and the general formula (3)
5Identical with d.
5. diepoxides according to claim 4 is characterized in that, d is 0, and by R
2And R
3In the substituting group of expression any one is phenyl, perhaps by R
2The substituting group neutralization of expression is by R
3Respectively there is one to be phenyl in the substituting group of expression.
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| CN103420950A (en) * | 2013-08-23 | 2013-12-04 | 上海朗亿功能材料有限公司 | Amino acid base biodegradable 2-expoxy compound and preparation method thereof |
| 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 |
| TWI679219B (en) * | 2014-12-24 | 2019-12-11 | 日商迪愛生股份有限公司 | Epoxy composition for electronic materials, hardened product thereof, and electronic component |
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| JP6250453B2 (en) * | 2013-03-28 | 2017-12-20 | 本州化学工業株式会社 | Trisphenol compound |
| JP6017363B2 (en) * | 2013-03-29 | 2016-10-26 | 本州化学工業株式会社 | Novel diepoxy compounds |
| 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 |
| JP6819961B2 (en) * | 2017-03-31 | 2021-01-27 | 本州化学工業株式会社 | New diepoxy compound |
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| TWI679219B (en) * | 2014-12-24 | 2019-12-11 | 日商迪愛生股份有限公司 | Epoxy composition for electronic materials, hardened product thereof, and electronic component |
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