CN101845005B - Side substitution aromatic ester diphenol, preparation method and preparation method of mesomorphic epoxy monomer - Google Patents
Side substitution aromatic ester diphenol, preparation method and preparation method of mesomorphic epoxy monomer Download PDFInfo
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- CN101845005B CN101845005B CN201010203910.1A CN201010203910A CN101845005B CN 101845005 B CN101845005 B CN 101845005B CN 201010203910 A CN201010203910 A CN 201010203910A CN 101845005 B CN101845005 B CN 101845005B
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Abstract
The invention relates to side substitution aromatic ester diphenol, a preparation method and a preparation method of a mesomorphic epoxy monomer. The side substitution aromatic ester diphenol has a general formula shown in the specification of the invention, wherein X stands for an aryl group with side substitution. In the preparation method of an aromatic ester mesomorphic epoxy monomer by using the side substitution aromatic ester diphenol, a synthetic period of the monomer is greatly shortened, the raw materials of the synthetic monomer are cheap and are easy to obtain, and the preparation method is simple and convenient.
Description
Technical field
The invention belongs to epoxy resin by using liquid crystal field, be specifically related to a kind of side substitution aromatic ester diphenol and preparation method thereof, and utilize side substitution aromatic ester diphenol to prepare the method for liquid crystalline epoxy monomer.
Background technology
Epoxy resin by using liquid crystal comes across the eighties in 20th century the earliest, is a kind of important thermosetting resin, and it has excellent optics, electricity, calorifics and mechanical property, is widely used in the fields such as communication, electronic package material, aerospace, military and national defense.
Liquid crystal polymer is a kind of polymer existing with liquid crystal state under given conditions, compares with polymer, and it has the distinctive molecular orientation of mesomorphic phase and location orientation, compares with small molecules liquid crystalline cpd, and it has again the characteristic of high molecule mass and macromolecular compound.The physicals that liquid crystal polymer can not be compared because of its excellent mechanical property or other material, obtains common concern and the attention of academia and industry member.
Thermoset liquid crystalline resin is a kind of novel liquid crystal resin growing up on the basis of liquid crystalline polymers, generally mesomorphic unit, flexible spacer chain and reactive group, consists of, and therefore has the dual nature of thermosetting resin and liquid crystal concurrently.Compare with thermoplastic liquid crystal polymer, the molecular weight of thermoset liquid crystalline resin is lower, so fusing point is lower, and melt viscosity is less, under relatively mild condition, just can reach very high orientation, and moulded manufacturability is better; Compare with traditional main chain liquid crystalline polymer, network structure can make it when keeping differently-oriented directivity high strength, high-modulus, increases substantially intensity, modulus in non-differently-oriented directivity, improves the homogeneity of liquid crystal polymer material; Compare with traditional side chain liquid crystalline polymer, network structure more can make the order of thermoset liquid crystalline resin cured product, thermostability greatly improve; Compare with ordinary hot thermosetting resin, in thermoset liquid crystalline resin and cured product thereof, the existence in the mesomorphic territory of ordered orientation makes its cure shrinkage less, and the mechanical property of cured product, thermotolerance, dimensional stability and photoelectric properties are higher.According to the difference of reactive group, thermoset liquid crystalline resin can be divided into (methyl) acrylic acid or the like, epoxies, acid imide, cyanate, acetylene class etc.
The synthetic method of epoxy resin by using liquid crystal is generally divided into two kinds of epoxy chloropropane method and partial oxidation processs.Synthesizing of epoxy resin for mesomorphic unit facile hydrolysiss such as aryl nitrones generally adopts partial oxidation process at present.Partial oxidation process is generally first reacted with excessive haloolefin by phenols, obtains end with the liquid crystalline resin of two keys, and then obtains final product by the epoxidation of two keys.The shortcoming of partial oxidation process is that synthesis step is more, difficulty is large, productive rate is lower, and the reaction time of synthon is long, and starting material are expensive, and the cost of preparation is high.
Summary of the invention
The defect that the present invention exists in order to solve above-mentioned technology, provides a kind of epoxy chloropropane legal system of using for the method for aryl nitrone liquid crystalline epoxy monomer, and the synthesis cycle of monomer shortens greatly, and the starting material of synthon are cheap and easy to get, and preparation method is easy.
In addition, the present invention also provides a kind of side substitution aromatic ester diphenol for the preparation of above-mentioned liquid crystalline epoxy monomer.
In addition, the present invention also provides the preparation method of above-mentioned side substitution aromatic ester diphenol.
Object of the present invention is achieved through the following technical solutions:
A side substitution aromatic ester diphenol, is characterized in that, it has following general formula:
Wherein X is the aromatic group that contains side substitution, can be in following radicals a kind of:
Wherein, R is-COOC
nh
2n+1,-PO
4c
nh
2n+1,-SO
3c
nh
2n+1or-C
nh
2n+1, n is the integer in 1-16.
Preferably, described X is a kind of in following radicals:
Preferably, described R is :-COOC
nh
2n+1or-C
nh
2n+1.
The preparation method of described side substitution aromatic ester diphenol, is characterized in that, step is as follows:
(1) to acetoxyl group Benzoyl chloride and hydroxyaromatic compounds in organic solvent, and at N, under the catalysis of N-Dimethylamino pyridine, alkaline condition, in-10～20 ℃ of reactions, after having reacted, remove impurity, obtain acetoxyl group aromatic compound; Described organic solvent energy solubilizing reaction thing, and do not react with reactant and product, can be tetrahydrofuran (THF), pyridine, triethylamine, N, N-lutidine, acetone, butanone, toluene etc.
(2) again will be to acetoxyl group aromatic compound under alkaline condition, 0～40 ℃ of hydrolysis, carries out separatory after being hydrolyzed, spin off solvent, obtains side substitution aromatic ester diphenol;
Wherein, described hydroxyaromatic compounds is
r is-COOC
nh
2n+1,-PO
4c
nh
2n+1,-SO
3c
nh
2n+1or-C
nh
2n+1, n is the integer in 1-16.
Described is 2: 1～6: 1 o'clock to acetoxyl group Benzoyl chloride and hydroxyaromatic compounds in mol ratio, reacts more abundant.
Described is with ammoniacal liquor hydrolysis to acetoxyl group aromatic compound, ammoniacal liquor and be 10: 1～5: 1 to the mol ratio of acetyl oxygen aromatic compound.
Described ammoniacal liquor and be 7.3: 1 to the mol ratio of acetyl oxygen aromatic compound.
The temperature of described ammoniacal liquor hydrolysis is 20-40 ℃.
A preparation method for liquid crystalline epoxy monomer, is characterized in that, step is as follows:
The side substitution aromatic ester diphenol of above-mentioned preparation and epoxy chloropropane are under the effect of quaternary ammonium salt consisting of phase-transferring agent, in 90～120 ℃, carry out ring-opening reaction, after having reacted, be cooled to 50～70 ℃, hydro-oxidation sodium water solution, in 50～70 ℃, carry out ring-closure reaction, after having reacted, remove impurity, obtain liquid crystalline epoxy monomer.
Described side substitution aromatic ester diphenol and epoxy chloropropane are 1: 5～1: 50 o'clock in mol ratio, react more abundant.
Described quaternary ammonium salt consisting of phase-transferring agent is benzyl trimethyl ammonium chloride, tetraethylammonium bromide, 4 bromide, Tetrabutyl amonium bromide or tetrabutylammonium chloride.
The present invention compared with prior art tool has the following advantages and beneficial effect:
(1) greatly shorten the reaction time of synthon;
(2) starting material of synthon are cheap and easy to get.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited to this, for not dated especially processing parameter, can carry out with reference to routine techniques.
Embodiment 1
(1) in being housed, the single port bottle of prolong adds 0.1mol P-hydroxybenzoic acid, 30ml acetic anhydride, and magneton stirred, 65 ℃ of reactions 3 hours.After having reacted, pour in frozen water and precipitate, suction filtration, obtains acetoxy-benzoic acid, productive rate 88%.
(2) in being housed, two mouthfuls of bottles of prolong add 0.1mol obtained above to acetoxy-benzoic acid, 30ml thionyl chloride, the pyridine of 40ml, N
2under protection, 80 ℃ of reactions 3 hours, except desolventizing and unnecessary thionyl chloride, obtain acetoxyl group Benzoyl chloride.
(3) what step (2) is obtained is directly cooled to-10 ℃ to acetoxyl group Benzoyl chloride, slowly drip 0.05mol 3-methylmesylate base-4,4 '-'-biphenyl diphenol, 0.3g N, N-Dimethylamino pyridine (DMAP) and 50ml tetrahydrofuran (THF), after dripping, this mixing solutions is reacted after 8 hours at-10 ℃, room temperature reaction 24 hours, after having reacted, remove unreacted reactant and by product, suction filtration obtains acetyl oxygen aromatic compound 3-methylmesylate base-4,4 '-bis-(4-acetyl oxygen benzoyloxy) biphenyl, its reaction equation is as follows:
(4) get 3-methylmesylate base-4 of 0.03mol, 4 '-bis-(4-acetyl oxygen benzoyloxy) biphenyl is in beaker, add 100ml trichloromethane, magneton stirs the lower ammoniacal liquor that slowly drips 21ml 28% (mass ratio) (ammoniacal liquor and be 5: 1 to the mol ratio of acetyl oxygen aromatic compound), 0 ℃ of reaction 18 hours, separatory, spun off solvent, obtain side substitution aromatic ester diphenol 3-methylmesylate base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.Reaction equation is as follows:
(5) get the above-mentioned 3-methylmesylate of 0.01mol base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl, 0.3mol epoxy chloropropane, the consisting of phase-transferring agent tetraethylammonium bromide of the Virahol of 0.28mol and 0.001mol is in round-bottomed flask.Be heated to 120 ℃ of reactions after 1 hour, be cooled to after 70 ℃, (quality is than aqueous sodium hydroxide solution, 70 ℃ of reactions 3 hours slowly to drip 6ml 50%.After having reacted, remove impurity (by product, solvent and water) and obtain liquid crystalline epoxy monomer, productive rate 95%.Reaction equation is as follows:
Embodiment 2
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO of 4 '-'-biphenyl diphenol
3cH
3) use-COOCH
3substitute, finally obtain side substitution aromatic ester diphenol 3-carboxylate methyl ester base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 94% of liquid crystalline epoxy monomer.
Embodiment 3
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-COOC
16h
33substitute, finally obtain the side substitution aromatic ester diphenol positive hexadecyl ester of 3-carboxylic acid base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 4
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-COOC
8h
17substitute, finally obtain side substitution aromatic ester diphenol 3-carboxylic acid n-octyl base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 5
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-PO
4c
2h
5substitute, finally obtain side substitution aromatic ester diphenol 3-etherophosphoric acid base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 95% of liquid crystalline epoxy monomer.
Embodiment 6
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-PO
4c
10h
21substitute, finally obtain side substitution aromatic ester diphenol 3-phosphoric acid certain herbaceous plants with big flowers ester group-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 96% of liquid crystalline epoxy monomer.
Embodiment 7
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-SO
3c
13h
27substitute, finally obtain positive 13 ester group-4 of side substitution aromatic ester diphenol 3-sulfonic acid, 4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 93% of liquid crystalline epoxy monomer.
Embodiment 8
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-SO
3c
6h
13substitute, finally obtain just own ester group-4 of side substitution aromatic ester diphenol 3-sulfonic acid, 4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 93% of liquid crystalline epoxy monomer.
Embodiment 9
The difference of the present embodiment and embodiment 1 is: 3-methylmesylate base-4 in step (3), the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-C
3h
7substitute, finally obtain side substitution aromatic ester diphenol 3-propyl group-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 10
The difference of the present embodiment and embodiment 1 is, 3-methylmesylate base-4, the methylmesylate base (SO in 4 '-'-biphenyl diphenol
3cH
3) use-C
11h
23substitute, finally obtain side substitution aromatic ester diphenol 3-n-tridecane base-4,4 '-bis-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 89% of liquid crystalline epoxy monomer.
Embodiment 11
(1) in being housed, the single port bottle of prolong adds 0.1mol P-hydroxybenzoic acid, 40ml acetic anhydride, and magneton stirred, 60 ℃ of reactions 4 hours.After having reacted, pour in frozen water and precipitate, suction filtration, obtains acetoxy-benzoic acid, productive rate 90%.
(2) in being housed, two mouthfuls of bottles of prolong add 0.1mol obtained above to acetoxy-benzoic acid, 40ml thionyl chloride, and the DMF of 0.5ml is made catalyzer, N
2under protection, 75 ℃ of reactions 4 hours, except desolventizing and unnecessary thionyl chloride, obtain acetoxyl group Benzoyl chloride.
(3) what step (2) is obtained is cooled to 0 ℃ to acetoxyl group Benzoyl chloride with frozen water, slowly drip 0.03mol 2, the own ester of 5-resorcylic acid, 0.4g N, N-Dimethylamino pyridine, 15ml triethylamine and 50ml tetrahydrofuran (THF), after dripping, this mixing solutions is reacted after 5 hours to room temperature reaction 20 hours at ice-water bath.After having reacted, remove unreacted reactant and by product, suction filtration obtains 2,5-bis-(4-acetyl oxygen benzoyloxy) the just own ester of phenylformic acid.Reaction equation is as follows:
(4) product of getting 0.03mol is in beaker, add 100ml trichloromethane, magneton stirs the lower ammoniacal liquor that slowly drips 35ml 28% (mass ratio) (ammoniacal liquor and be 8.3: 1 to the mol ratio of acetyl oxygen aromatic compound), 20 ℃ are reacted 10 hours, separatory, spins off solvent, obtains 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) the just own ester of phenylformic acid, productive rate: 85%.Reaction equation is as follows:
(5) get 0.01mol above-mentioned 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) the just own ester of phenylformic acid, 0.05mol epoxy chloropropane, the Virahol of 0.28mol, and the consisting of phase-transferring agent benzyl trimethyl ammonium chloride of 0.001mol is in round-bottomed flask.Be heated to 110 ℃ of reactions after 2 hours, be cooled to, after 60 ℃, slowly drip the aqueous sodium hydroxide solution of 6ml 50%, 60 ℃ of reactions 4 hours.After having reacted, remove impurity (by product, solvent and water) and obtain liquid crystalline epoxy monomer, productive rate 95%.Reaction equation is as follows:
Embodiment 12
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-COOCH
3substitute, finally obtain side substitution aromatic ester diphenol 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) methyl benzoate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 13
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-COOC
15h
31substitute, finally obtain side substitution aromatic ester diphenol 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) positive ten five-esters of phenylformic acid.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 93% of liquid crystalline epoxy monomer.
Embodiment 14
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-PO
4c
3h
7substitute, finally obtain side substitution aromatic ester diphenol 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) benzenephosphonic acid propyl ester.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 15
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-PO
4c
9h
19substitute, finally obtain side substitution aromatic ester diphenol 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) benzenephosphonic acid ester in the positive ninth of the ten Heavenly Stems.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 16
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-SO
3c
4h
9substitute, finally obtain side substitution aromatic ester diphenol 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) Phenylsulfonic acid butyl ester.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 17
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-SO
3c
10h
21substitute, finally obtain side substitution aromatic ester diphenol 2,5-bis-(4-(2-hydroxybenzoyl) oxygen base) the positive certain herbaceous plants with big flowers ester of benzenephosphonic acid.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 18
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-C
5h
11substitute, finally obtain side substitution aromatic ester diphenol 2, the just own benzene of 5-bis-(4-(2-hydroxybenzoyl) oxygen base).In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 19
The difference of the present embodiment and embodiment 11 is: the just own ester group (COOC of carboxylic acid in step (3) in the own ester of DHB
6h
11) use-C
16h
33substitute, finally obtain side substitution aromatic ester diphenol 2, positive 16 benzene of 5-bis-(4-(2-hydroxybenzoyl) oxygen base).In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 20
(1) in being housed, the single port bottle of prolong adds 0.1mol P-hydroxybenzoic acid, 50ml acetic anhydride, and magneton stirred, 50 ℃ of reactions 5 hours.After having reacted, pour in frozen water and precipitate, suction filtration, obtains acetoxy-benzoic acid, productive rate 80%.
(2) in being housed, two mouthfuls of bottles of prolong add 0.12mol obtained above to acetoxy-benzoic acid, 50ml thionyl chloride, and 0.5mlN, dinethylformamide is made catalyzer, N
2under protection, 90 ℃ of reactions 3 hours, except desolventizing and unnecessary thionyl chloride, obtain acetoxyl group Benzoyl chloride.
(3) what step (2) is obtained is cooled to 10 ℃ to acetoxyl group Benzoyl chloride, slowly drip 0.02mol3-n-hexadecyl-4,4 '-dihydroxyl phenylate, 0.4g N, N-Dimethylamino pyridine, 15ml triethylamine and 50ml tetrahydrofuran (THF), after dripping, this mixing solutions is reacted after 5 hours to room temperature reaction 20 hours at ice-water bath.After having reacted, remove unreacted reactant and by product, obtain 3-hexadecyl-4,4 '-(4-acetoxyl group benzoyloxy) phenylate.Reaction equation is as follows:
(4) get 3-hexadecyl-4 of 0.03mol, 4 '-(4-acetoxyl group benzoyloxy) phenylate product is in beaker, add 100ml trichloromethane, magneton stirs the lower ammoniacal liquor that slowly drips 30ml 28% (mass ratio) (ammoniacal liquor and be 7.3: 1 to the mol ratio of acetyl oxygen aromatic compound), 30 ℃ of reactions 6 hours, separatory, spin off solvent, obtain 3-hexadecyl-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate, productive rate: 86%.Reaction equation is as follows:
(5) get the above-mentioned 3-of 0.01mol hexadecyl-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate, 0.5mol epoxy chloropropane, the Virahol of 0.3mol, and the consisting of phase-transferring agent Tetrabutyl amonium bromide of 0.001mol is in round-bottomed flask.Be heated to 100 ℃ of reactions after 3 hours, be cooled to, after 55 ℃, slowly drip the aqueous sodium hydroxide solution of 6ml 50%, 55 ℃ of reactions 5 hours.After having reacted, remove impurity (by product, solvent and water) and obtain liquid crystalline epoxy monomer, productive rate 88%.Reaction equation is as follows:
Embodiment 21
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-COOC
4h
9substitute, finally obtain side substitution aromatic ester diphenol 3-synthesis base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 22
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-COOC
8h
17substitute, finally obtain side substitution aromatic ester diphenol 3-carboxylic acid n-octyl base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 95% of liquid crystalline epoxy monomer.
Embodiment 23
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-PO
4c
2h
5substitute, finally obtain side substitution aromatic ester diphenol 3-etherophosphoric acid base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 95% of liquid crystalline epoxy monomer.
Embodiment 24
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-PO
4c
14h
29substitute, finally obtain positive 14 ester group-4 of side substitution aromatic ester diphenol 3-phosphoric acid, 4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 25
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-SO
3c
6h
13substitute, finally obtain just own ester group-4 of side substitution aromatic ester diphenol 3-sulfonic acid, 4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 26
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-SO
3c
12h
25substitute, finally obtain positive 12 ester group-4 of side substitution aromatic ester diphenol 3-sulfonic acid, 4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 27
The difference of the present embodiment and embodiment 20 is: 3-n-hexadecyl-4 in step (3), the n-hexadecyl (C in 4 '-dihydroxyl phenylate
16h
31) use-C
2h
5substitute, finally obtain side substitution aromatic ester diphenol 3-ethyl-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 28
(1) in being housed, prolong single port bottle adds 0.1mol P-hydroxybenzoic acid, 30ml acetic anhydride, and magneton stirred, 65 ℃ of reactions 3 hours.After having reacted, pour in frozen water and precipitate, suction filtration, obtains acetoxy-benzoic acid, productive rate 87%.
(2) in being housed, two mouthfuls of bottles of prolong add 0.1mol obtained above to acetoxy-benzoic acid, 30ml thionyl chloride, the pyridine of 40ml, N
2under protection, 80 ℃ of reactions 3 hours, except desolventizing and unnecessary thionyl chloride, obtain acetoxyl group Benzoyl chloride.
(3) what step (2) is obtained is cooled to 20 ℃ to acetoxyl group Benzoyl chloride, slowly drip 0.04mol3-carboxylic acid monooctyl ester base-4,4 '-dihydroxy-benzene methane, 0.3g N, N-Dimethylamino pyridine, 50ml tetrahydrofuran (THF), after dripping, mixing solutions, room temperature reaction 6 hours, is removed to unreacted reactant and by product after having reacted, suction filtration obtains 3-carboxylic acid monooctyl ester base-4,4 '-(4-acetoxyl group benzoyloxy) phenylmethane.Reaction equation is as follows:
(4) product of getting 0.03mol is in beaker, add 100ml trichloromethane, magneton stirs the lower ammoniacal liquor that slowly drips 42ml 28% (mass ratio) (ammoniacal liquor and be 10: 1 to the mol ratio of acetyl oxygen aromatic compound), 40 ℃ are reacted 4 hours, separatory, spins off solvent, obtains 3-carboxylic acid monooctyl ester base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylmethane, productive rate: 90%.Reaction equation is as follows:
(5) get the above-mentioned 3-carboxylic acid monooctyl ester of 0.01mol base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) phenylmethane, 0.45mol epoxy chloropropane, the Virahol of 0.28mol, and the consisting of phase-transferring agent tetrabutylammonium chloride of 0.001mol is in round-bottomed flask.Be heated to 90 ℃ of reactions after 4 hours, be cooled to, after 50 ℃, slowly drip the aqueous sodium hydroxide solution of 6ml 50%, 50 ℃ of reactions 6 hours.After having reacted, remove impurity (by product, solvent and water) and obtain liquid crystalline epoxy monomer, productive rate 85%.Reaction equation is as follows:
Embodiment 29
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-PO
4c
5h
11, finally obtain side substitution aromatic ester diphenol 3,3 '-dimethyl-5-phosphoric acid pentyl ester base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 30
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-SO
3c
6h
13, finally obtain side substitution aromatic ester diphenol 3, just own ester group-4 of 3 '-dimethyl-5-sulfonic acid, 4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 31
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-COOC
7h
13, finally obtain side substitution aromatic ester diphenol 3, the positive heptyl ester of 3 '-dimethyl-5-carboxylic acid base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 32
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-CH
3, finally obtain side substitution aromatic ester diphenol 3,3 '-bis-trifluoromethyls-3-methyl-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 33
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-SO
3c
10h
21, finally obtain the chloro-5-sulfonic acid certain herbaceous plants with big flowers of side substitution aromatic ester diphenol 3,3 '-bis-ester group-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Embodiment 34
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-COOC
2h
5, finally obtain the chloro-5-carboxylic acid, ethyl ester of side substitution aromatic ester diphenol 3,3 '-bis-base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 90% of liquid crystalline epoxy monomer.
Embodiment 35
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-PO
4c
9h
19, finally obtain the chloro-5-phosphoric acid of side substitution aromatic ester diphenol 3,3 '-bis-ester group-4 in the ninth of the ten Heavenly Stems, 4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 89% of liquid crystalline epoxy monomer.
Embodiment 36
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-C
15h
31, finally obtain the chloro-5-Pentadecane of side substitution aromatic ester diphenol 3,3 '-bis-base-4,4 '-(4-(2-hydroxybenzoyl) oxygen base) biphenyl.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 93% of liquid crystalline epoxy monomer.
Embodiment 37
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-C
13h
27, finally obtain side substitution aromatic ester diphenol 2-(4-(2-hydroxybenzoyl) oxygen base phenyl)-5-(4-(2-hydroxybenzoyl) oxygen base propyloxy phenyl fork base) n-tridecane base benzene.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 93% of liquid crystalline epoxy monomer.
Embodiment 38
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-COOC
3h
7, finally obtain side substitution aromatic ester diphenol 2-(4-(2-hydroxybenzoyl) oxygen base phenyl)-5-(4-(2-hydroxybenzoyl) oxygen base propyloxy phenyl fork base) propyl benzoate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 89% of liquid crystalline epoxy monomer.
Embodiment 39
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-PO
4c
7h
15, finally obtain side substitution aromatic ester diphenol 2-(4-(2-hydroxybenzoyl) oxygen base phenyl)-5-(4-(2-hydroxybenzoyl) oxygen base propyloxy phenyl fork base) benzenephosphonic acid heptyl ester.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 92% of liquid crystalline epoxy monomer.
Embodiment 40
The difference of the present embodiment and embodiment 28 is: 3-carboxylic acid monooctyl ester base-4 in step (3), 4 '-dihydroxy-benzene methane
with
substitute, R is-SO
3cH
3, finally obtain side substitution aromatic ester diphenol 2-(4-(2-hydroxybenzoyl) oxygen base phenyl)-5-(4-(2-hydroxybenzoyl) oxygen base propyloxy phenyl fork base) methyl benzenesulfonate.In step (5), with this side substitution aromatic ester diphenol, make the productive rate 91% of liquid crystalline epoxy monomer.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (2)
1. a preparation method for liquid crystalline epoxy monomer, is characterized in that, step is as follows:
First, the preparation method of side substitution aromatic ester diphenol, step is as follows:
(1) to acetoxyl group Benzoyl chloride and hydroxyaromatic compounds in organic solvent, and at N, under the catalysis of N-Dimethylamino pyridine, alkaline condition, in-10～20 ℃ of reactions, after having reacted, remove impurity, obtain acetoxyl group aromatic compound;
(2) again will be to acetoxyl group aromatic compound under alkaline condition, 0～40 ℃ of hydrolysis, carries out separatory after being hydrolyzed, spin off solvent, obtains side substitution aromatic ester diphenol, and described side substitution aromatic ester diphenol has following structure:
Wherein X is
Wherein, described hydroxyaromatic compounds is
or
wherein, R is-COOC
nh
2n+1,-PO
4c
nh
2n+1,-SO
3c
nh
2n+1or-C
nh
2n+1, n is the integer in 1-16;
Described is 2:1～6:1 to the mol ratio of acetoxyl group Benzoyl chloride and hydroxyaromatic compounds; Described is with ammoniacal liquor hydrolysis to acetoxyl group aromatic compound, ammoniacal liquor and be 10:1～5:1 to the mol ratio of acetyl oxygen aromatic compound;
Secondly, the side substitution aromatic ester diphenol of preparation and epoxy chloropropane are under the effect of quaternary ammonium salt consisting of phase-transferring agent, in 90～120 ℃, carry out ring-opening reaction, after having reacted, be cooled to 50～70 ℃, hydro-oxidation sodium water solution, carry out ring-closure reaction in 50～70 ℃, after having reacted, remove impurity, obtain liquid crystalline epoxy monomer;
Described quaternary ammonium salt consisting of phase-transferring agent is benzyl trimethyl ammonium chloride, tetraethylammonium bromide, 4 bromide, Tetrabutyl amonium bromide or tetrabutylammonium chloride; The mol ratio of described side substitution aromatic ester diphenol and epoxy chloropropane is 1:5～1:50.
2. preparation method according to claim 1, is characterized in that: described ammoniacal liquor and be 7.3:1 to the mol ratio of acetyl oxygen aromatic compound.
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| CN102336635B (en) * | 2011-07-12 | 2014-03-12 | 中国科学院化学研究所 | Epoxy resin and preparation method and application thereof |
| CN102952013B (en) * | 2011-08-17 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method of high-purity p-acetoxybenzoic acid |
| KR101620168B1 (en) * | 2013-07-01 | 2016-05-12 | 주식회사 엘지화학 | Hydroxyl capping monomer, its polycarbonate and article containing the same |
| FR3012069B1 (en) * | 2013-10-22 | 2015-10-23 | Saint Gobain | GLAZING FOR VISUALIZATION SYSTEM |
| CN103588684A (en) * | 2013-10-29 | 2014-02-19 | 中科院广州化学有限公司 | Glycol sulfonate used as hydrophilic chain-extender and its preparation method and application thereof |
| CN104497270B (en) * | 2014-12-18 | 2016-08-31 | 中科院广州化学有限公司 | Side base substituted biphenyl type shape memory epoxy resin by using liquid crystal and preparation method thereof and application |
| CN105254534A (en) * | 2015-10-16 | 2016-01-20 | 中科院广州化学有限公司南雄材料生产基地 | Bisphthalonitrile monomer containing side chain substituted aromatic ester type mesogenic unit as well as preparation and application of bisphthalonitrile monomer |
| CN113788931A (en) * | 2021-09-28 | 2021-12-14 | 泉州师范学院 | Acrylic liquid crystal photosensitive resin and preparation method thereof |
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