CN101121644A - Method for preparing 4,4'-dihydroxydiphenyl ether and intermediate 4,4'-dibromodiphenyl ether thereof - Google Patents
Method for preparing 4,4'-dihydroxydiphenyl ether and intermediate 4,4'-dibromodiphenyl ether thereof Download PDFInfo
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Abstract
The present invention discloses a preparation method for 4,4'-dibromodiphenyl ether and also discloses a preparation for 4,4'-dihydroxy diphenyl ether taking 4,4'-dibromodiphenyl ether as the raw material; the preparation steps for 4,4'-dibromodiphenyl ether is that: a) the preparation for the coarse product of 4,4'-dibromodiphenyl ether; b) the re-crystal for 4,4'-dibromodiphenyl ether. The 4,4'-dibromodiphenyl ether prepared by the above method is used as the raw material to prepare 4,4'-dihydroxy diphenyl ether; the steps is that: I) the preparation for the coarse product of 4,4'-dihydroxy diphenyl ether; II) the re-crystal for 4,4'-dihydroxy diphenyl ether. The present invention has the advantages of low resource consumption, short reaction time so as to decrease the preparation cost; both of the purity and the benefit ratio for the prepared 4,4'-dibromodiphenyl ether and the finial 4,4'-dihydroxy diphenyl ether are much better.
Description
Technical field
The invention discloses a kind of 4, the preparation method of 4 '-dibromodiphenyl ether, and disclosing by 4,4 '-dibromodiphenyl ether is a feedstock production 4, the method for 4 '-dihydroxy diphenyl ether.
Background technology
4,4 '-dihydroxy diphenyl ether abbreviates DHDE as, and DHDE requires high purity as the high molecular important intermediate of various complex functionalities, otherwise use value is little.The synthesis route of DHDE, generally report has following several route of synthesis in the world:
1, by 4, DHDE is synthesized in the hydrolysis of 4 '-diaminodiphenyl oxide diazotization, and yield probably is 50%, crude product DHDE purity general 47%.
2, by 4,4 '-dichloro-diphenyl ether pyrohydrolysis obtains DHDE, and yield probably is 40%, crude product DHDE purity general 38%.
3, obtain DHDE by the Resorcinol dehydrating condensation, yield is general 50%, crude product DHDE purity general 50%.
4, by 4, the hydrolysis of 4 '-dibromodiphenyl ether obtains the DHDE yield and has only 50%, crude product DHDE purity general 47%.
Above processing method all exists side reaction many, and yield is low, the shortcoming that cost is high, though therefore DHDE is widely used, since the production cost height, valuable product, and the popularization in market is restricted.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide that a kind of yield height, purity height, technology are simple, low production cost 4, the preparation method of 4 '-dihydroxy diphenyl ether.
Another object of the present invention provides a kind of in preparation 4, the intermediate 4 of 4 '-dihydroxy diphenyl ether, the preparation method of 4 '-dibromodiphenyl ether.
According to technical scheme provided by the invention, of the present invention 4, the preparation method of 4 '-dibromodiphenyl ether carries out as follows:
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: with phenyl ether liquid in the reaction vessel and catalyzer post-heating to 20～100 ℃ also stirring, when stirring phenyl ether liquid, in phenyl ether liquid, drip the bromine of mole number more than or equal to 2.2 times of phenyl ether mole numbers, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: use organochlorine solvent and/or ethanol and/or acetone and/or toluene mixture liquid body as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, behind stirring, cooling, crystallization, filtration solid substance, can obtain purity is 4 more than 99%, 4 '-dibromodiphenyl ether then;
The ratio of the bromine that drips in the step a) and the mole number of phenyl ether is (2.2～2.5): 1.
The weight of the catalyzer that adds in the step a) is 0.1%～10% of phenyl ether weight, and this catalyzer is a kind of or combination in titanium chloride, tin chloride and the zinc chloride.
The described organochlorine solvent of step b) is two or more combination of chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, methylene dichloride, ethylene dichloride, trichloromethane, 1.1.1-trichloroethane, 2 cbloropropane isopropyl chloride or 1.2-propylene dichloride and they.
Make 4 according to the method described above, of the present invention 4 behind 4 '-dibromodiphenyl ether, the preparation method of 4 '-dihydroxy diphenyl ether carries out as follows:
I), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4,4 '-dibromodiphenyl ether is heated to 100～250 ℃, 4, the inorganic compound catalyst that adds copper ions in 4 '-dibromodiphenyl ether liquid, add the mixed catalyzer that closes again that big acyclic polyether compounds and quaternary ammonium salt compound are formed simultaneously, again 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction end is cooled to envrionment temperature, the precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
II), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: at water, toluene, dimethylbenzene, mono chloro benzene, sherwood oil, methyl alcohol, ethanol, butanone, two butanols, ethylene dichloride, 1.1.1-trichloroethane, two kinds of tetracol phenixin or 1.1.2-trichloroethane or they or two or more combination liquid are as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, in this recrystallization solution, add step I) make 4, the crude product of 4 '-dihydroxy diphenyl ether, be heated to the stream temperature of wandering then, the stirring stream of wandering, then through being cooled to envrionment temperature, crystallization, filtration obtains purity 4 more than 99.5%, 4 '-dihydroxy diphenyl ether finished product.
The inorganic compound catalyst of the copper ions step I) is cupric chloride, copper sulfate, cupric nitrate, cuprous chloride, cupric oxide, Red copper oxide or their two kinds or two or more combinations, and weight is 4,0.1%～10% of 4 '-dibromodiphenyl ether weight.
Step I) the big acyclic polyether compounds in be 18-hat-6 (i), dibenzo-18-hat-6 (iii), two cyclic groups amine-18-hat-6 (ii) with two or more mixture of latent alkane (2.2.2) or they, weight is 4,0.1%～10% of 4 '-dibromodiphenyl ether weight.
Step I) quaternary ammonium salt compound in is tertiary butyl chlorination amine and/or tertiary butyl bromination amine, and its weight is 4,0.1%～10% of 4 '-dibromodiphenyl ether weight.
At step I) in the reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 150～250 ℃, and the pressure of control reaction vessel is 0.8～1.5Mpa.
In Step II) in select for use 1.1.1-trichloroethane and alcohol mixed solution as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product.
Major advantage of the present invention is as follows:
1, this process using synthetic 4,4 '-dibromodiphenyl ether is the new operational path of DBDE, reduced the cost of DBDE significantly, thereby also reduced the cost of DHDE significantly, and making the DBDE of high purity and high yield, the DHDE for preparing purity and high yield for the later DHDE that passes through high purity and high yield lays a good foundation.
2, in operation, adopted composite catalyst, reduced side reaction, made yield bring up to 64% with the synthetic DHDE of DBDE hydrolysis.
3, adopt thermal zone setting-out to separate technology, shortened the reaction times greatly, reduced energy consumption.
4, adopt double solvents to carry out recrystallization and purify, DHDE purity is reached more than 99.5%.
Through the suitability for industrialized production practice, the product real cost is low than other synthesis techniques, and product purity is higher than international like product strong competitive power in the international market.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the titanium chloride post-heating to 50 ℃ of the phenyl ether of 1000kg and 1kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2260kg, bromine is amounted to 14125 moles, bromine is 2.4: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with chlorobenzene as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.3% 4,4 '-dibromodiphenyl ether 1480kg, 4, the yield of 4 '-dibromodiphenyl ether is 76.7%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 150 ℃, control reaction vessel internal pressure is 1.5Mpa, 4, add the cupric chloride of 1.480kg and the mixing of 18-hat-6 (i) composition of 148kg in 4 '-dibromodiphenyl ether liquid and close catalyzer again, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction times is 3 hours, the reaction end, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: water is as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filter 23 time, obtain purity then and be 99.74% 4,4 '-dihydroxy diphenyl ether finished product, yield are 70%.
Embodiment 2
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the tin chloride post-heating to 20 ℃ of the phenyl ether of 1000kg and 100kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2070.464kg, bromine is amounted to 12940.4 moles, bromine is 2.2: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with orthodichlorobenzene as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.4% 4,4 '-dibromodiphenyl ether 1450kg, 4, the yield of 4 '-dibromodiphenyl ether is 75.2%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 100 ℃, 4, add the mixed catalyzer that closes again that 145kg copper sulfate and 1.45kg tertiary butyl chlorination amine are formed in 4 '-dibromodiphenyl ether liquid, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 24 hours, reaction finishes, cooling precipitate and separate catalyzer, and clear liquid is used in the hydrochloric acid and excessive NaOH, 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use toluene as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 1 time, obtain purity 4 more than 99.78%, 4 '-dihydroxy diphenyl ether finished product, yield 70% then.
Embodiment 3
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the zinc chloride post-heating to 50 ℃ of the phenyl ether of 1000kg and 50kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2352.8kg, bromine is amounted to 14705 moles, bromine is 2.5: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with Meta Dichlorobenzene as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.6% 4,4 '-dibromodiphenyl ether 1510kg, 4, the yield of 4 '-dibromodiphenyl ether is 78.3%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 250 ℃, control reaction vessel internal pressure is that 0.8Mpa is 4, add the mixed catalyzer that closes again that the cupric nitrate of 5.8kg and the dibenzo of 23.5kg-18-hat-6 is (iii) formed in 4 '-dibromodiphenyl ether liquid, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 2.5 hours, reaction finishes, cooling precipitate and separate catalyzer, and clear liquid is used in the hydrochloric acid and excessive NaOH, 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use dimethylbenzene as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 5 times, obtain purity then and be 99.85% 4,4 '-dihydroxy diphenyl ether finished product, yield 70%.
Embodiment 4
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the phenyl ether of 1000kg and 30kg titanium chloride post-heating to 60 ℃ and the stirring of zinc chloride and 30kg, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2164.576kg, bromine is amounted to 13528.6 moles, bromine is 2.3: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with Meta Dichlorobenzene as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.7% 4,4 '-dibromodiphenyl ether 1523kg, 4, the yield of 4 '-dibromodiphenyl ether is 78.9%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 180 ℃, 4, add the cupric nitrate of 78.4kg and the mixed catalyzer that closes again that 1.523kg two cyclic groups amine-18-hat-6 is (ii) formed in 4 '-dibromodiphenyl ether liquid, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 22 hours, reaction finishes, cooling precipitate and separate catalyzer, and clear liquid is used in the hydrochloric acid and excessive NaOH, 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use mono chloro benzene as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 2 times, obtain purity then and be 99.73% 4,4 '-dihydroxy diphenyl ether finished product, yield are 70%.
Embodiment 5
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into zinc chloride, the 20kg of the phenyl ether of 1000kg and 10kg tin chloride post-heating to 80 ℃ and the stirring of titanium chloride and 10kg, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2446.912kg, bromine is amounted to 15293.2 moles, bromine is 2.6: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with methylene dichloride as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.2% 4,4 '-dibromodiphenyl ether 1460kg, 4, the yield of 4 '-dibromodiphenyl ether is 75.7%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 210 ℃, 4, add the cuprous chloride of 145kg and the mixing of latent alkane (2.2.2) composition of 145kg in 4 '-dibromodiphenyl ether liquid and close catalyzer again, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 23 hours, reaction finishes, cooling precipitate and separate catalyzer, and clear liquid is used in the hydrochloric acid and excessive NaOH, 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use sherwood oil as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 4 times, obtain purity then and be 99.68% 4,4 '-dihydroxy diphenyl ether finished product, yield are 50%.
Embodiment 6
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the zinc chloride post-heating to 90 ℃ of the phenyl ether of 1000kg and 30kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2117.52kg, bromine is amounted to 13234.5 moles, bromine is 2.25: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with ethylene dichloride as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.2% 4,4 '-dibromodiphenyl ether 1370kg, 4, the yield of 4 '-dibromodiphenyl ether is 71.0%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 230 ℃, control reaction vessel internal pressure is 1.2Mpa, 4, add the cupric oxide of 37kg and the mixing of tertiary butyl bromination amine composition of 1.37kg in 4 '-dibromodiphenyl ether liquid and close catalyzer again, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction times is 2.2 hours, the reaction end, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use ethanol as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filter 23 time, obtain purity then and be 99.55% 4,4 '-dihydroxy diphenyl ether finished product, yield are 65%.
Embodiment 7
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the titanium chloride post-heating to 75 ℃ of the phenyl ether of 1000kg and 20kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 2823.36kg, bromine is amounted to 17646 moles, bromine is 3: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with trichloromethane as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.4% 4,4 '-dibromodiphenyl ether 1350kg, 4, the yield of 4 '-dibromodiphenyl ether is 70.0%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 210 ℃, control reaction vessel internal pressure is 1.4Mpa, 4, the Red copper oxide that adds 58.6kg in 4 '-dibromodiphenyl ether liquid, 1.35kg mixing of forming of 18-hat-6 (i) and the tertiary butyl bromination amine of 1.35kg close catalyzer again, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction times is 2.6 hours, the reaction end, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use butanone as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 4 times, obtain purity then and be 99.65% 4,4 '-dihydroxy diphenyl ether finished product, yield are 72%.
Embodiment 8
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the titanium chloride post-heating to 75 ℃ of the phenyl ether of 1000kg and 20kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 3764.48kg, bromine is amounted to 23528 moles, bromine is 4: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with the 1.1.1-trichloroethane as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.5% 4,4 '-dibromodiphenyl ether 1420kg, 4, the yield of 4 '-dibromodiphenyl ether is 73.6%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 180 ℃, control reaction vessel internal pressure is 0.9Mpa, 4, the Red copper oxide that adds 142kg in 4 '-dibromodiphenyl ether liquid, the mixed catalyst that the dibenzo of 142kg-18-hat-6 is (iii) formed with the tertiary butyl chlorination amine of 142kg, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction times is 3.2 hours, the reaction end, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: with two butanols as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 5 times, obtain purity then and be 99.92% 4,4 '-dihydroxy diphenyl ether finished product, yield are 72%.
Embodiment 9
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the zinc chloride post-heating to 65 ℃ of the phenyl ether of 1000kg and 35kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 4705.6kg, bromine is amounted to 29410 moles, bromine is 5: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with 2 cbloropropane isopropyl chloride as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.6% 4,4 '-dibromodiphenyl ether 1390kg, 4, the yield of 4 '-dibromodiphenyl ether is 72.0%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 250 ℃, control reaction vessel internal pressure is 1.5Mpa, 4, the cupric chloride that adds 48.6kg in 4 '-dibromodiphenyl ether liquid, 52.4kg Red copper oxide, 38.1kg the mixed catalyst (iii) formed with the tertiary butyl chlorination amine of 78.5kg of dibenzo-18-hat-6,4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 3.5 hours, reaction finishes, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use ethylene dichloride as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 4 times, obtain purity then and be 99.82% 4,4 '-dihydroxy diphenyl ether finished product, yield are 66%.
Embodiment 10
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the zinc chloride post-heating to 65 ℃ of the phenyl ether of 1000kg and 35kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 4705.6kg, bromine is amounted to 29410 moles, bromine is 5: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with the 1.2-propylene dichloride as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.7% 4,4 '-dibromodiphenyl ether 1450kg, 4, the yield of 4 '-dibromodiphenyl ether is 75.2%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 150 ℃, control reaction vessel internal pressure is 0.8Mpa, 4, the cuprous chloride that adds 145kg in 4 '-dibromodiphenyl ether liquid, 1.45kg cupric nitrate and the mixed catalysts (ii) formed of 45kg two cyclic groups amine-18-hat-6,4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction times is 3.6 hours, the reaction end, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use the 1.1.1 trichloroethane as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 4 times, obtain purity then and be 99.71% 4,4 '-dihydroxy diphenyl ether finished product, yield are 68%.
Embodiment 11
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the zinc chloride post-heating to 65 ℃ of the phenyl ether of 1000kg and 35kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 4705.6kg, bromine is amounted to 29410 moles, bromine is 5: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with chlorobenzene and ethanol as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.5% 4,4 '-dibromodiphenyl ether 1490kg, 4, the yield of 4 '-dibromodiphenyl ether is 77.2%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 250 ℃, control reaction vessel internal pressure is 1.3Mpa, 4, the cuprous chloride that adds 25.6kg in 4 '-dibromodiphenyl ether liquid, 54.3kg cupric nitrate, 22.4kg cupric oxide and the 18-of 41.6kg hat-6 (i), 58.6kg the mixed catalysts (iii) formed of dibenzo-18-hat-6,4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 2.9 hours, reaction finishes, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use tetracol phenixin as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 4 times, obtain purity then and be 99.68% 4,4 '-dihydroxy diphenyl ether finished product, yield are 64%.
Embodiment 12
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: at 1.5M
3Enamel still in drop into the zinc chloride post-heating to 65 ℃ of the phenyl ether of 1000kg and 35kg and stir, phenyl ether is amounted to 5882 moles, when stirring phenyl ether liquid in the phenyl ether liquid bromine of dropping 4705.6kg, bromine is amounted to 29410 moles, bromine is 5: 1 with the ratio of the mole number of phenyl ether, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: with toluene and ethanol as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, stir then, be cooled to envrionment temperature again, and after crystallization, filtering solid substance, can obtain purity and be 99.6% 4,4 '-dibromodiphenyl ether 1420kg, 4, the yield of 4 '-dibromodiphenyl ether is 73.6%.
C), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 195 ℃, control reaction vessel internal pressure is 0.9Mpa, 4, the cuprous chloride that adds 29.6kg in 4 '-dibromodiphenyl ether liquid, 37.1kg Red copper oxide, 42.8kg the mixed catalyst formed of the tertiary butyl chlorination amine of latent alkane (2.2.2) and 33.6kg, 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, reaction times is 3.3 hours, reaction finishes, cooling precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
D), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: use the 1.1.2 trichloroethane as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, add in this recrystallization solution that step c) makes 4, the crude product of 4 '-dihydroxy diphenyl ether being heated to the stream temperature (about 80 ℃) of wandering then, the stirring stream of wandering, after cooling, crystallization, filtration 4 times, obtain purity then and be 99.58% 4,4 '-dihydroxy diphenyl ether finished product, yield are 65.3%.
Embodiment 13
With the solvent replacing in the step b) recrystallization is chlorobenzene, orthodichlorobenzene and alcoholic acid mixed solution, solvent replacing in the step d) recrystallization is toluene and dimethylbenzene, other conditions are identical with embodiment 10,4,4 '-dihydroxy diphenyl ether finished product, make 4, the purity of 4 '-dihydroxy diphenyl ether is 99.86%, yield is 68.2%.
Embodiment 14
With the solvent replacing in the step b) recrystallization is the mixed solution of 1.1.1-trichloroethane, 2 cbloropropane isopropyl chloride and toluene, solvent replacing in the step d) recrystallization is mono chloro benzene, sherwood oil, methyl alcohol, ethanol, butanone and two butanols, other conditions are identical with embodiment 11,4,4 '-dihydroxy diphenyl ether finished product, 4, the purity of 4 '-dihydroxy diphenyl ether is 99.75%, and yield is 64.5%.
Embodiment 15
With the solvent replacing in the step b) recrystallization is the mixed solution of Meta Dichlorobenzene, methylene dichloride, ethylene dichloride, acetone, solvent replacing in the step d) recrystallization is mono chloro benzene, sherwood oil, methyl alcohol and ethanol, and control recrystallization solution and 4, the weight ratio of the crude product of 4 '-dihydroxy diphenyl ether is 3: 1, and other conditions are identical with embodiment 12,4,4 '-dihydroxy diphenyl ether finished product, make 4, the purity of 4 '-dihydroxy diphenyl ether is 99.67%, yield is 66.8%.
Claims (10)
1. one kind 4, the preparation method of 4 '-dibromodiphenyl ether is characterized in that this method carries out as follows:
A), 4, the preparation of 4 '-dibromodiphenyl ether crude product: with phenyl ether liquid in the reaction vessel and catalyzer post-heating to 20～100 ℃ also stirring, when stirring phenyl ether liquid, in phenyl ether liquid, drip the bromine of mole number more than or equal to 2.2 times of phenyl ether mole numbers, after reaction finishes, steam excess bromine and HBr gas, washing then, the residual HBr of flush away, bromine and catalyzer, obtain 4, the crude product of 4 '-dibromodiphenyl ether;
B), 4, the recrystallization of 4 '-dibromodiphenyl ether crude product: use organochlorine solvent and/or ethanol and/or acetone and/or toluene mixture liquid body as 4, the recrystallization solvent of 4 '-dibromodiphenyl ether crude product, this recrystallization solvent step a) make 4, the crude product of 4 '-dibromodiphenyl ether is heated to boiling and insulation, behind stirring, cooling, crystallization, filtration solid substance, can obtain purity is 4 more than 99%, 4 '-dibromodiphenyl ether then.
2. as claimed in claim 14, the preparation method of 4 '-dibromodiphenyl ether is characterized in that: the ratio of the bromine that drips in the step a) and the mole number of phenyl ether is (2.2～2.5): 1.
3. as claimed in claim 14, the preparation method of 4 '-dibromodiphenyl ether is characterized in that: the weight of the catalyzer that adds in the step a) is 0.1%～10% of phenyl ether weight, and this catalyzer is a kind of or combination in titanium chloride, tin chloride and the zinc chloride.
4. as claimed in claim 14, the preparation method of 4 '-dibromodiphenyl ether is characterized in that: the described organochlorine solvent of step b) is two or more combination of chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, methylene dichloride, ethylene dichloride, trichloromethane, 1.1.1-trichloroethane, 2 cbloropropane isopropyl chloride or 1.2-propylene dichloride and they.
One kind by the described method of claim 1 make 4,4 '-dibromodiphenyl ether preparation 4, the method for 4 '-dihydroxy diphenyl ether is characterized in that this method carries out as follows:
I), 4, the preparation of 4 '-dihydroxy diphenyl ether crude product: in reaction vessel with 4,4 '-dibromodiphenyl ether is heated to 100～250 ℃, 4, the inorganic compound catalyst that adds copper ions in 4 '-dibromodiphenyl ether liquid, add the mixed catalyzer that closes again that big acyclic polyether compounds and quaternary ammonium salt compound are formed simultaneously, again 4, add the reaction that is hydrolyzed of liquid caustic soda solution in 4 '-dibromodiphenyl ether liquid, the reaction end is cooled to envrionment temperature, the precipitate and separate catalyzer, clear liquid is used in the hydrochloric acid and excessive NaOH, and 4, the thick product formation solid of 4 '-dihydroxy diphenyl ether is standby after separating out and drying after filtration;
II), 4, the recrystallization of 4 '-dihydroxy diphenyl ether crude product: at water, toluene, dimethylbenzene, mono chloro benzene, sherwood oil, methyl alcohol, ethanol, butanone, two butanols, ethylene dichloride, 1.1.1-trichloroethane, two kinds of tetracol phenixin or 1.1.2-trichloroethane or they or two or more combination liquid are as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, in this recrystallization solution, add step I) make 4, the crude product of 4 '-dihydroxy diphenyl ether, be heated to the stream temperature of wandering then, the stirring stream of wandering, then through being cooled to envrionment temperature, crystallization, filtration obtains purity 4 more than 99.5%, 4 '-dihydroxy diphenyl ether finished product.
6. as claimed in claim 54, the synthetic method of 4 '-dihydroxy diphenyl ether, it is characterized in that: the inorganic compound catalyst of the copper ions step I) is cupric chloride, copper sulfate, cupric nitrate, cuprous chloride, cupric oxide, Red copper oxide or their two kinds or two or more combinations, and weight is 4,0.1%～10% of 4 '-dibromodiphenyl ether weight.
7. as claimed in claim 54, the synthetic method of 4 '-dihydroxy diphenyl ether, it is characterized in that: the big acyclic polyether compounds step I) be 18-hat-6 (i), dibenzo-18-hat-6 (iii), two cyclic groups amine-18-hat-6 (ii) with two or more mixture of latent alkane (2.2.2) or they, weight is 4,0.1%～10% of 4 '-dibromodiphenyl ether weight.
8. as claimed in claim 54, the synthetic method of 4 '-dihydroxy diphenyl ether is characterized in that: the quaternary ammonium salt compound step I) is tertiary butyl chlorination amine and/or tertiary butyl bromination amine, and its weight is 4,0.1%～10% of 4 '-dibromodiphenyl ether weight.
9. as claimed in claim 54, the synthetic method of 4 '-dihydroxy diphenyl ether is characterized in that: at step I) in the reaction vessel with 4 behind the recrystallization, 4 '-dibromodiphenyl ether is heated to 150～250 ℃, and the pressure of control reaction vessel is 0.8～1.5Mpa.
10. as claimed in claim 14, the synthetic method of 4 '-dihydroxy diphenyl ether, it is characterized in that: in Step II) in select for use 1.1.1-trichloroethane and alcohol mixed solution as 4, the recrystallization solution of 4 '-dihydroxy diphenyl ether crude product, and the 1.1.1-trichloroethane of selecting for use and alcoholic acid mixed volume ratio are 10: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110590515A (en) * | 2019-09-23 | 2019-12-20 | 遵义医科大学 | Synthesis method of brominated hydroxydiphenyl ether compound |
| CN111233639A (en) * | 2019-11-22 | 2020-06-05 | 甘肃金盾化工有限责任公司 | Preparation method of 4,4' -dihydroxy diphenyl ether |
| CN111533646A (en) * | 2020-05-25 | 2020-08-14 | 徐新海 | Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether |
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| CN86103093A (en) * | 1986-05-07 | 1987-11-18 | 北京市化工研究院 | Preparation process of polybromodiphenyl ether |
| IL92465A (en) * | 1989-11-27 | 1994-02-27 | Bromine Compounds Ltd Beersheb | Process for the preparation of 4,4'- dibromodiphenylether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110590515A (en) * | 2019-09-23 | 2019-12-20 | 遵义医科大学 | Synthesis method of brominated hydroxydiphenyl ether compound |
| CN110590515B (en) * | 2019-09-23 | 2022-08-12 | 遵义医科大学 | Synthesis method of brominated hydroxydiphenyl ether compound |
| CN111233639A (en) * | 2019-11-22 | 2020-06-05 | 甘肃金盾化工有限责任公司 | Preparation method of 4,4' -dihydroxy diphenyl ether |
| CN111533646A (en) * | 2020-05-25 | 2020-08-14 | 徐新海 | Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether |
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