CN110002963A - A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide - Google Patents
A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide Download PDFInfo
- Publication number
- CN110002963A CN110002963A CN201910181470.5A CN201910181470A CN110002963A CN 110002963 A CN110002963 A CN 110002963A CN 201910181470 A CN201910181470 A CN 201910181470A CN 110002963 A CN110002963 A CN 110002963A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- preparation process
- reaction
- organic solvent
- xylenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/62—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the nature of monomer used
- C08G2650/64—Monomer containing functional groups not involved in polymerisation
Abstract
The present invention relates to the preparation process of a kind of bisphenol-A and both-end hydroxyl polyphenylene oxide, bisphenol-A under sour gas catalyst action, is prepared in organic solvent A system by being condensed dehydration by 2,6- xylenol and acetone；Both-end hydroxyl polyphenylene oxide by 2,6- xylenol, bisphenol-A and diallyl bisphenol compound copper ion-pyridine be catalyst, oxygen be oxidant under conditions of, in organic solvent B by oxidation coupling copolyreaction be made.The preparation process of bisphenol-A of the invention, preparation process is simple, and the bisphenol-A purity prepared is higher.The preparation process of both-end hydroxyl polyphenylene oxide of the invention, security performance is more preferable, and the both-end hydroxyl polyphenylene oxide of preparation forms higher crosslink density in further solidification, when applied to high-frequency high-speed electronic field, resin system solvent resistance well is shown, is high-frequency high-speed use for electronic products desired matrix resin.
Description
Technical field
The invention belongs to high-molecular compound synthesis technical fields, and in particular to a kind of preparation process of bisphenol-A
And a kind of preparation process of both-end hydroxyl polyphenylene oxide.
Background technique
Polyphenylene oxide resin is to be formed by 2,6- xylenol through oxidative coupling polycondensation reaction, is a kind of excellent combination property
Thermoplastic engineering plastic.Its molecular structure is as follows:
It not only has excellent mechanical property, and there are also excellent dielectric properties (dielectric constant Dk=2.45<1MHZ>, damage
Consume factor D f=0.0007<1MHz>), tg=210 DEG C of high glass transition temperature, with very low water imbibition (saturation water suction at room temperature
Rate is less than 0.05%), this is for high frequency field using particularly significant.
Polyphenylene oxide resin is known as PPO in the U.S., is known as PPE in Japan, molecular weight number-average molecular weight is generally 30000-
50000, it is used mainly as engineering plastics.
Although polyphenylene oxide has many excellent properties outstanding, due to its thermoplasticity, when being used as printed circuit substrate
When have the shortcomings that it is following fatal: (1) heat resistance is inadequate.PCB substrate action material needs high heat resistance；Because welding
When connecing, PCB substrate is necessarily exposed under high temperature, since the high glass transition temperature of polyphenylene oxide is slightly below soldering dip temperature (260 DEG C), by
The substrate that general polyphenylene oxide obtains greater than about 200 DEG C at a temperature of can deform, cause mechanical properties decrease therefrom,
And substrate surface circuit copper foil is peeled off, drilling processing is difficult.(2) the resistance to aromatic hydrocarbon of thermoplastic polyphenylene ethers and halogenated hydrocarbons equal solvent
Can be poor, and can dissolve wherein, and in PCB process, it is cleaned with aromatic hydrocarbon and halogenated hydrocarbons equal solvent, this is asked
Topic just seems critically important.
Therefore thermoplastic polyphenylene ethers are made perfectly to be applied to high-frequency high-speed electronic field, it is necessary to by thermoplastic polyphenylene ethers
Resin carries out thermosetting property modification, and industry generally tends to carry out using 2,6- xylenol and bisphenol compound single
Body copolymerization method, first synthesis both-end hydroxyl polyphenylene oxide resin, and then prepare and a series of meet high-frequency high-speed electronic field application and want
The modified polyphenylene ether resin asked.
But in the preparation process of existing both-end hydroxyl polyphenylene oxide resin, generally existing process safety performance is poor, obtains
Active group is few in polyphenylene oxide resin structure, so that the crosslink density formed when resin system further solidifies is lower, it cannot
The Thermocurable energy of resin is shown well, when being applied to high-frequency high-speed electronic field, shows the solvent resistance of resin simultaneously
The problems such as undesirable.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of preparation works of bisphenol-A
The preparation process of skill and both-end hydroxyl polyphenylene oxide.The technical problem to be solved in the present invention is achieved through the following technical solutions:
A kind of preparation process of bisphenol-A, the bisphenol-A is by 2,6- xylenol and acetone in acidity
Under gas catalyst effect, it is prepared in organic solvent A system by being condensed dehydration.
Further, the preparation process the following steps are included:
The organic solvent A, acetone are added in reaction vessel, is stirring evenly and then adding into described 2,6- diformazan for step 1
Base phenol controls in reaction vessel 0-10 DEG C of temperature, is completely dissolved described 2,6- xylenol under stirring；
Step 2 is filled with the sour gas catalyst in the reaction vessel, maintains pressure in the reaction vessel
For 0.01Mpa gauge pressure, at 0-10 DEG C, clock reaction 6-9 hours；
Step 3 makes the sour gas catalyst in the reaction vessel enter the alkali of vacuum system after reaction
Liquid absorption plant is absorbed；
Step 4, distills out unreacted acetone, and vapo(u)rizing temperature is 80 DEG C；
Step 5, temperature, which is maintained at 80-90 DEG C, in the reaction vessel carries out neutralization washing, with 80-90 DEG C of sodium carbonate
Until aqueous solution is washed till water phase PH=6-7；
Step 6 makes the product sufficient crystallising being dissolved in organic phase at room temperature and is dried to obtain the tetramethyl after filtering
Base bisphenol-A.
Further, described 2, the mass ratio of 6- xylenol and the acetone is 1:1；The matter of the organic solvent A
The mass ratio of amount and the acetone is (1.5-2.0): 1
Further, the organic solvent A is toluene；The sour gas catalyst is HCl gas.
A kind of preparation process of both-end hydroxyl polyphenylene oxide, the both-end hydroxyl polyphenylene oxide is by 2,6- xylenol, tetramethyl
Base bisphenol-A and diallyl bisphenol compound are catalyst in copper ion-pyridine, under conditions of oxygen is oxidant, organic
It is made in solvent B by oxidation coupling copolyreaction.
Further, the preparation process the following steps are included:
Step 1, be added into dissolution vessel organic solvent B, described 2,6- xylenol, the bisphenol-A and
The diallyl bisphenol compound, stirring and dissolving obtain the first mixed solution；
Organic solvent B, stannous chloride and pyridine is added in the reaction vessel simultaneously, stirs lower toward reaction container bottom
It is passed through air in fixed distribution device in gas-fluid, and is passed through nitrogen toward reaction vessel upper gaseous phase space simultaneously, makes to maintain
It is lower than the limit oxygen concentration of reaction dissolvent in the oxygen concentration of gas-phase space, keeps the reaction vessel pressure 0.4Mpa, temperature 20
DEG C, timing 30 minutes since blowing air pre-oxidize system in the reaction vessel sufficiently；After the completion of pre-oxidation, obtain
To the second mixed solution；
First mixed solution is added drop-wise in second mixed solution by step 2 with metering pump timing, control drop
It is 1-3 hours between added-time；
Step 3, after being added dropwise, keeping 20 DEG C of reaction temperature, the reaction was continued 3-4 hours；
Step 4 closes air system valve after reaction, is maintained with nitrogen to normal pressure；
System vacuum filter after reaction is obtained the both-end hydroxyl polyphenylene oxide by step 5.
Further, the diallyl bisphenol compound is diallyl bisphenol；The organic solvent B is methanol.
Further, the distribution device in gas-fluid is round stationary structure, is evenly distributed with multiple opening directions thereon
Aperture directed downwardly.
Further, the mass ratio of the bisphenol-A and diallyl bisphenol compound is 1:1；Described 2,6- bis-
The ratio between methylphenol and the bisphenol-A and the gross mass of the diallyl bisphenol compound are 5:1；It is described organic molten
The mass ratio of agent A and described 2,6- xylenol is (1.0-1.5): 1；The organic solvent B and described 2,6- dimethyl benzene
The mass ratio of phenol is 0.8:1；The mass ratio of the stannous chloride and pyridine gross mass and described 2,6- xylenol is (0.4-
0.5):1。
Further, bisphenol-A preparation process described in claim 1-3 is prepared.
Compared with prior art, beneficial effects of the present invention:
1. the preparation process of both-end hydroxyl polyphenylene oxide of the invention is distributed by the way that stationary gas is arranged in reactor bottom
Device structure makes air required for reacting directly pass through connecting pipe outside reactor, is passed directly into the fixation of reactor bottom
Formula gas distributor, and then enter and participate in oxidation coupling copolyreaction in system solution, to thoroughly eliminate the generation of electrostatic；And
N is passed through in reactor gas-phase space2, so that the oxygen concentration for maintaining gas-phase space is lower than the limit oxygen concentration of reaction dissolvent, so that
Entire reaction process, which has been under the process conditions being perfectly safe, to be carried out.
2. the preparation process of both-end hydroxyl polyphenylene oxide of the invention, in obtained both-end hydroxyl polyphenyl ether structure, in phenyl ring
In addition to containing CH on side chain3Outside structure, also contain a certain number of allyl active group (CH2=CH-CH2), so that resin
System forms higher crosslink density in further solidification, when being applied to high-frequency high-speed electronic field, shows resin system
Solvent resistance well.
3. the preparation process of both-end hydroxyl polyphenylene oxide of the invention, obtained both-end hydroxyl polyphenyl ether product is further prepared
Thermosetting polyphenylene ether resin, molecular weight is low, molecular weight control stablize, even molecular weight distribution is high-frequency high-speed electronic product
With desired matrix resin.
4. the preparation process of bisphenol-A of the invention, preparation process is simple, the bisphenol-A purity prepared
It is higher.
Specific embodiment
The present invention provides a kind of preparation processes of bisphenol-A, by 2,6- xylenol and acetone in sour gas
Under body catalyst effect, it is prepared in organic solvent A system by being condensed dehydration.
Chemical equation is as follows:
Specifically, it may comprise steps of:
Organic solvent A, acetone are added in reaction vessel, is stirring evenly and then adding into 2,6- xylenol for step 1, control
0-10 DEG C of temperature in reaction vessel processed is completely dissolved 2,6- xylenol under stirring；Wherein, 2,6- xylenol and third
The mass ratio of ketone is 1:1；The quality of organic solvent A and the mass ratio of acetone are (1.5-2.0): 1；Wherein, organic solvent A is preferred
For toluene.
Step 2 is filled with sour gas catalyst in reaction vessel, and maintaining pressure in reaction vessel is 0.01Mpa table
Pressure, at 0-10 DEG C, clock reaction 6-9 hours；Wherein, sour gas catalyst is preferably HCl gas.
Step 3 makes the lye that sour gas catalyst enters vacuum system in reaction vessel absorb dress after reaction
It sets and is absorbed；
Step 4, distills out unreacted acetone, and vapo(u)rizing temperature is 80 DEG C；
Step 5, temperature, which is maintained at 80-90 DEG C, in reaction vessel carries out neutralization washing, water-soluble with 80-90 DEG C of sodium carbonate
Until liquid is washed till water phase PH=6-7；
Step 6 makes the product sufficient crystallising being dissolved in organic phase at room temperature and is dried to obtain tetramethyl pair after filtering
Phenol A.
The preparation process of bisphenol-A of the invention, the preparation process of bisphenol-A of the invention, preparation process
Simply, the bisphenol-A purity prepared is higher.
The present invention also provides a kind of preparation processes of both-end hydroxyl polyphenylene oxide, double by 2,6- xylenol, tetramethyl
Phenol A and diallyl bisphenol compound are catalyst in copper ion-pyridine, under conditions of oxygen is oxidant, in organic solvent B
In by oxidation coupling copolyreaction be made.
Chemical equation is as follows:
Specifically, it may comprise steps of:
Step 1, addition organic solvent B, 2,6- xylenol, bisphenol-A and diallyl into dissolution vessel
Bisphenol compound, stirring and dissolving obtain the first mixed solution；Wherein, diallyl bisphenol compound is preferably that diallyl is double
Phenol A；Organic solvent B is preferably methanol；The mass ratio of bisphenol-A and diallyl bisphenol compound is 1:1；2,6- diformazan
The ratio between base phenol and bisphenol-A and the gross mass of diallyl bisphenol compound are 5:1；Organic solvent A and 2,6- diformazan
The mass ratio of base phenol is (1.0-1.5): 1.
Organic solvent B, stannous chloride and pyridine is added in reaction vessel simultaneously, is fixed under stirring toward reaction container bottom
Distribution device in gas-fluid in be passed through air, and be passed through nitrogen toward reaction vessel upper gaseous phase space simultaneously, make to maintain gas phase sky
Between oxygen concentration be lower than the limit oxygen concentration of reaction dissolvent, reaction vessel pressure 0.4Mpa (gauge pressure), 20 DEG C of temperature are kept, from logical
Air starts timing 30 minutes, pre-oxidizes system in reaction vessel sufficiently；After the completion of pre-oxidation, it is molten to obtain the second mixing
Liquid；Wherein, the mass ratio of organic solvent B and 2,6- xylenol is 0.8:1；Stannous chloride and pyridine gross mass and 2,6- bis-
The mass ratio of methylphenol is (0.4-0.5): 1.
As an implementation, distribution device in gas-fluid is round stationary structure, is evenly distributed with multiple apertures thereon
The aperture being directed downward；Specifically, the shape for the distribution device in gas-fluid that the present invention uses can be circular ring shape, and annulus has multiple
With the radius pipe of connection circle ring center's point, central point and the reactor bottom of round tube are fixed, and annulus is connected to air inlet pipe；Annulus and
The lower part of radius pipe is evenly arranged with multiple apertures, and aperture, which is directed downward the purpose opened up, is, with the progress of reaction, product meeting
It is gradually precipitated in reactor bottom, air is passed through by system to the lower part, the reaction for keeping the solution of bottom full and uniform makes
The reaction of entire reaction system is more uniform.
The cylinder air stream of big stock is divided into the air stream of many thin stocks by distribution device in gas-fluid of the invention when working, stirred
It mixes and is ground into more minute bubbles under the cooperation of device, be passed through in liquid and reacted by multiple uniform small pores on distribution device in gas-fluid, it should
Device can be uniformly distributed in wherein when air can be made to be passed through liquid, more uniform abundant using reacting；In addition make to react institute
The air needed directly passes through connecting pipe outside reactor, is passed directly into the stationary gas distributor of reactor bottom, into
And enter in system solution and participate in oxidation coupling copolyreaction, to thoroughly eliminate the generation of electrostatic.
First mixed solution is added drop-wise in the second mixed solution by step 2 with metering pump timing, and control time for adding is
1-3 hours.
Step 3, after being added dropwise, keeping 20 DEG C of reaction temperature, the reaction was continued 3-4 hours.
Step 4 closes air system valve after reaction, is maintained with nitrogen to normal pressure.
System vacuum filter after reaction is obtained both-end hydroxyl polyphenylene oxide by step 5.
It should be noted that in the preparation process of both-end hydroxyl polyphenylene oxide of the invention, used raw material tetramethyl
Bisphenol-A can be the common bisphenol-A bought in the market, but the preparation work of the preferably above-mentioned bisphenol-A of the present invention
Bisphenol-A prepared by skill.
The preparation process of both-end hydroxyl polyphenylene oxide of the invention, by the way that stationary gas distributor is arranged in reactor bottom
Structure makes air required for reacting directly pass through connecting pipe outside reactor, is passed directly into the fixed of reactor bottom
Gas distributor, and then enter and participate in oxidation coupling copolyreaction in system solution, to thoroughly eliminate the generation of electrostatic；And
Reactor gas-phase space is passed through N2, so that the oxygen concentration for maintaining gas-phase space is lower than the limit oxygen concentration of reaction dissolvent, so that whole
A reaction process has been under the process conditions being perfectly safe and carries out.
In the preparation process of both-end hydroxyl polyphenylene oxide of the invention, the limit oxygen concentration of methanol system is 10% (VOL/VOL),
Specifically it can be lower than 10% in the oxygen concentration of gas-phase space using DCS control system combination on-line analysis instrument control system.In reality
In production technology, other than in-line analyzer real-time monitoring is passed through the concentration of oxygen and nitrogen, set of safety phase relation is gone back
It unites (such as safety instrumented systems SIS), substantial risk technique real-time perfoming is monitored, and before there is major safety risks generation,
Realize Feed Shut-Off and system protection, it is ensured that all safety measures meet country safety supervision general pipeline tri- [2009] No. 116 numbers and
The safety requirements of the dangerous chemical process of [2013] No. 3 emphasis being related to supervision.
The preparation process of both-end hydroxyl polyphenylene oxide of the invention, in obtained both-end hydroxyl polyphenyl ether structure, in phenyl ring side
In addition to containing CH on chain3Outside structure, also contain a certain number of allyl active group (CH2=CH-CH2), so that resinite
Higher crosslink density is formed when tying up to further solidification, when being applied to high-frequency high-speed electronic field, shows resin system very
Solvent resistance well.In addition, the thermosetting polyphenylene ether resin that obtained both-end hydroxyl polyphenyl ether product is further prepared, molecule
Measure it is low, molecular weight control stablize, even molecular weight distribution is high-frequency high-speed use for electronic products desired matrix resin.
In order to further illustrate the present invention, below in conjunction with specific embodiment to the system of bisphenol-A provided by the invention
Standby technique and the preparation process of both-end hydroxyl polyphenylene oxide are described in detail, and embodiments of the present invention are not limited thereto.
Embodiment one
A kind of preparation process of bisphenol-A, comprising the following steps:
A, into reaction kettle plus toluene 50kg, acetone 30kg, after mixing evenly plus 2,6- xylenol (DMP) 30kg,
0-10 DEG C of reactor temperature of control, is completely dissolved DMP under stirring.
B, HCl gas is filled in reaction kettle, maintaining pressure in kettle is micro-positive pressure (0.01Mpa gauge pressure), at 0-10 DEG C, meter
Shi Fanying 8 hours.
C, HCl gas in kettle after reaction, is made to enter the lye absorption plant of vacuum system.
D, unreacted acetone is distilled out, vapo(u)rizing temperature is 80 DEG C.
E, it during temperature in the kettle carries out at 80-90 DEG C and washs, is washed till water phase PH=6- with 80-90 DEG C of aqueous sodium carbonate
Until 7.
F, dry bisphenol-A finished product after making sufficient crystallising at room temperature and filtering.
The purity of obtained bisphenol-A is 99%.
Embodiment two
A kind of preparation process of both-end hydroxyl polyphenylene oxide, comprising the following steps:
A, methanol 120kg, DMP100kg and bisphenol-A 10kg, diallyl bisphenol are added into dissolution kettle
10kg makes to be completely dissolved under stirring.
Add methanol 80kg, stannous chloride 0.5kg, pyridine 40kg into reaction kettle simultaneously, stirs lower solid toward reactor bottom
It is passed through air in fixed pattern distribution device in gas-fluid and is passed through N toward reactor upper gaseous phase space simultaneously2, make to maintain gas-phase space
Oxygen concentration is lower than the limit oxygen concentration of reaction dissolvent, keeps reactor pressure 0.4Mpa (gauge pressure), 20 DEG C of temperature；It is opened from blowing air
Beginning timing 30 minutes, pre-oxidize system in kettle sufficiently.
B, after the completion of pre-oxidation, DMP/ bisphenol-A/diallyl bisphenol methanol solution in dissolution kettle is used tricks
Amount pump timing is added in reaction kettle, and the control time is 2 hours.
C, after being added dropwise, being kept for 20 DEG C, the reaction was continued 3.5 hours, and as reaction carries out, the product of generation is constantly from first
It precipitates, and disperses in methyl alcohol in alcohol.
D, air system valve after reaction, is closed, N is used2Maintain normal pressure.
E, vacuum filter obtains both-end hydroxyl polyphenyl ether product.
Embodiment three
A kind of preparation process of both-end hydroxyl polyphenylene oxide, comprising the following steps:
A, into reaction kettle plus toluene 75kg, acetone 45kg, after mixing evenly plus 2,6- xylenol (DMP) 45kg,
0-10 DEG C of reactor temperature of control, is completely dissolved DMP under stirring.
B, HCl gas is filled in reaction kettle, maintaining pressure in kettle is micro-positive pressure (0.01Mpa gauge pressure), at 0-10 DEG C, meter
Shi Fanying 7 hours.
C, HCl gas in kettle after reaction, is made to enter the lye absorption plant of vacuum system.
D, unreacted acetone is distilled out, vapo(u)rizing temperature is 80 DEG C.
E, it during temperature in the kettle carries out at 80-90 DEG C and washs, is washed till water phase PH=with heat (80 DEG C) aqueous sodium carbonate
Until 6-7.
F, dry bisphenol-A finished product after making sufficient crystallising at room temperature and filtering.
G, methanol 180kg, DMP150kg and bisphenol-A 15kg, diallyl bisphenol are added into dissolution kettle
15kg makes to be completely dissolved under stirring.
Add methanol 120kg, stannous chloride 0.75kg, pyridine 60kg into reaction kettle simultaneously, stirs lower toward reactor bottom
It is passed through air in stationary gas distribution apparatus and is passed through N toward reactor upper gaseous phase space simultaneously2, make to maintain gas-phase space
Oxygen concentration be lower than reaction dissolvent limit oxygen concentration, keep reactor pressure 0.4Mpa (gauge pressure), 20 DEG C of temperature；From blowing air
Start timing 30 minutes, pre-oxidizes system in kettle sufficiently.
H, after the completion of pre-oxidation, DMP/ bisphenol-A/diallyl bisphenol methanol solution in dissolution kettle is used tricks
Amount pump timing is added in reaction kettle, and the control time is 3 hours.
I, after being added dropwise, being kept for 20 DEG C, the reaction was continued 3.5 hours, and as reaction carries out, the product of generation is constantly from first
It precipitates, and disperses in methyl alcohol in alcohol.
J, air system valve after reaction, is closed, N is used2Maintain normal pressure.
K, vacuum filter obtains both-end hydroxyl polyphenyl ether product.
The preparation process of both-end hydroxyl polyphenylene oxide of the invention, in addition to entire reaction process has been at the work being perfectly safe
Except carrying out under the conditions of skill, obtained both-end hydroxyl polyphenylene oxide resin has following better characteristics:
(1), both-end hydroxyl polyphenylene oxide resin number-average molecular weight (Mn) adjustable extent: 1500-5000；
(2), both-end hydroxyl polyphenylene oxide resin molecular weight distribution (Mn/Mw) range: 1.4-1.6
(3), allyl active group (CH in both-end hydroxyl polyphenylene oxide resin2=CH-CH2) content: 2-4%.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of preparation process of bisphenol-A, which is characterized in that the bisphenol-A by 2,6- xylenol with
Acetone is prepared in organic solvent A system by being condensed dehydration under sour gas catalyst action.
2. preparation process according to claim 1, which comprises the following steps:
The organic solvent A, acetone are added in reaction vessel, is stirring evenly and then adding into described 2,6- dimethyl benzene for step 1
Phenol controls in reaction vessel 0-10 DEG C of temperature, is completely dissolved described 2,6- xylenol under stirring；
Step 2 is filled with the sour gas catalyst in the reaction vessel, maintains the pressure in the reaction vessel to be
0.01Mpa gauge pressure, at 0-10 DEG C, clock reaction 6-9 hours；
Step 3 inhales the lye that the sour gas catalyst enters vacuum system in the reaction vessel after reaction
Receiving apparatus is absorbed；
Step 4, distills out unreacted acetone, and vapo(u)rizing temperature is 80 DEG C；
Step 5, temperature, which is maintained at 80-90 DEG C, in the reaction vessel carries out neutralization washing, water-soluble with 80-90 DEG C of sodium carbonate
Until liquid is washed till water phase PH=6-7；
Step 6 makes the product sufficient crystallising being dissolved in organic phase at room temperature and is dried to obtain the tetramethyl pair after filtering
Phenol A.
3. preparation process according to claim 2, which is characterized in that described 2, the matter of 6- xylenol and the acetone
Amount is than being 1:1；The mass ratio of the quality of the organic solvent A and the acetone is (1.5-2.0): 1.
4. preparation process according to claim 2, which is characterized in that the organic solvent A is toluene；The sour gas
Catalyst is HCl gas.
5. a kind of preparation process of both-end hydroxyl polyphenylene oxide, which is characterized in that the both-end hydroxyl polyphenylene oxide is by 2,6- dimethyl
Phenol, bisphenol-A and diallyl bisphenol compound are catalyst in copper ion-pyridine, and oxygen is the condition of oxidant
Under, it is made in organic solvent B by oxidation coupling copolyreaction.
6. preparation process according to claim 5, which comprises the following steps:
Organic solvent B, described 2,6- xylenol, the bisphenol-A and described are added into dissolution vessel for step 1
Diallyl bisphenol compound, stirring and dissolving obtain the first mixed solution；
Organic solvent B, stannous chloride and pyridine is added in the reaction vessel simultaneously, is fixed under stirring toward reaction container bottom
Distribution device in gas-fluid in be passed through air, and be passed through nitrogen toward reaction vessel upper gaseous phase space simultaneously, make to maintain gas
The oxygen concentration of phase space is lower than the limit oxygen concentration of reaction dissolvent, keeps 20 DEG C of the reaction vessel pressure 0.4Mpa, temperature, from
Blowing air starts timing 30 minutes, pre-oxidizes system in the reaction vessel sufficiently；After the completion of pre-oxidation, second is obtained
Mixed solution；
First mixed solution is added drop-wise in second mixed solution by step 2 with metering pump timing, when control is added dropwise
Between be 1-3 hours；
Step 3, after being added dropwise, keeping 20 DEG C of reaction temperature, the reaction was continued 3-4 hours；
Step 4 closes air system valve after reaction, is maintained with nitrogen to normal pressure；
System vacuum filter after reaction is obtained the both-end hydroxyl polyphenylene oxide by step 5.
7. preparation process according to claim 6, which is characterized in that the diallyl bisphenol compound is diallyl
Bisphenol-A；The organic solvent B is methanol.
8. preparation process according to claim 6, which is characterized in that the distribution device in gas-fluid is round fixed knot
Structure is evenly distributed with multiple opening directions aperture directed downwardly thereon.
9. preparation process according to claim 6, which is characterized in that the bisphenol-A and diallyl are bisphenol
The mass ratio for closing object is 1:1；Described 2,6- xylenol and the bisphenol-A and the diallyl bisphenol compound
The ratio between gross mass be 5:1；The mass ratio of the organic solvent A and described 2,6- xylenol is (1.0-1.5): 1；It is described
The mass ratio of organic solvent B and described 2,6- xylenol is 0.8:1；The stannous chloride and pyridine gross mass with described 2,
The mass ratio of 6- xylenol is (0.4-0.5): 1.
10. preparation process according to claim 5, which is characterized in that the bisphenol-A is by claim 1-3 institute
The preparation process stated is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910181470.5A CN110002963A (en) | 2019-03-11 | 2019-03-11 | A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910181470.5A CN110002963A (en) | 2019-03-11 | 2019-03-11 | A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110002963A true CN110002963A (en) | 2019-07-12 |
Family
ID=67166826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910181470.5A Pending CN110002963A (en) | 2019-03-11 | 2019-03-11 | A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110002963A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627622A (en) * | 2019-09-12 | 2019-12-31 | 广东省石油与精细化工研究院 | Preparation method of high-purity tetramethyl bisphenol A |
| CN111909371A (en) * | 2020-07-22 | 2020-11-10 | 广东省石油与精细化工研究院 | Tetrallyl polyphenylene oxide and preparation method thereof |
| CN113698592A (en) * | 2021-09-06 | 2021-11-26 | 洛阳理工学院 | Curable polyphenyl ether resin and preparation method thereof |
| CN113773632A (en) * | 2021-09-06 | 2021-12-10 | 洛阳理工学院 | Composition containing curable polyphenylene ether resin and application thereof |
| CN115490847A (en) * | 2022-09-30 | 2022-12-20 | 四川轻化工大学 | Sulfone-containing dihydroxy polyphenyl ether, crosslinkable polyphenyl ether and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194520A (en) * | 1991-08-22 | 1993-03-16 | Eastman Kodak Company | Blend of a polyester and a polycarbonate |
| CN203790949U (en) * | 2014-05-04 | 2014-08-27 | 杭州百事特实业有限公司 | Methyl capped polyether production device |
| WO2017100164A1 (en) * | 2015-12-11 | 2017-06-15 | Sabic Global Technologies B.V. | Method of bisphenol manufacture |
| KR20190004131A (en) * | 2017-07-03 | 2019-01-11 | 국도화학 주식회사 | Multifunctional radical curable poly phenylene ether resin and preparation method of the same |
-
2019
- 2019-03-11 CN CN201910181470.5A patent/CN110002963A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194520A (en) * | 1991-08-22 | 1993-03-16 | Eastman Kodak Company | Blend of a polyester and a polycarbonate |
| CN203790949U (en) * | 2014-05-04 | 2014-08-27 | 杭州百事特实业有限公司 | Methyl capped polyether production device |
| WO2017100164A1 (en) * | 2015-12-11 | 2017-06-15 | Sabic Global Technologies B.V. | Method of bisphenol manufacture |
| KR20190004131A (en) * | 2017-07-03 | 2019-01-11 | 국도화학 주식회사 | Multifunctional radical curable poly phenylene ether resin and preparation method of the same |
Non-Patent Citations (2)
| Title |
|---|
| CURTIS, R. F. VON BRAUN: "diphenylcyclobutane derivative ": 6,6 ′-dihydroxy-3,3,3 ′ ,3 ′-teramethyl-1,1 ′ -spirobi-Indane and a related com-pound", 《J. CHEM. SOC.》 * |
| YIJIAN WU等: "Synthesis and Characterization of α , ω -bis(2,6-dimethylphenol)-poly(2,6-dimethyl-1,4-phenylene oxide) Oligomers in Water and the End-Group Modifi cation", 《IND. ENG. CHEM. RES.》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627622A (en) * | 2019-09-12 | 2019-12-31 | 广东省石油与精细化工研究院 | Preparation method of high-purity tetramethyl bisphenol A |
| CN111909371A (en) * | 2020-07-22 | 2020-11-10 | 广东省石油与精细化工研究院 | Tetrallyl polyphenylene oxide and preparation method thereof |
| CN111909371B (en) * | 2020-07-22 | 2022-12-27 | 广东省石油与精细化工研究院 | Tetraalkenyl polyphenyl ether and preparation method thereof |
| CN113698592A (en) * | 2021-09-06 | 2021-11-26 | 洛阳理工学院 | Curable polyphenyl ether resin and preparation method thereof |
| CN113773632A (en) * | 2021-09-06 | 2021-12-10 | 洛阳理工学院 | Composition containing curable polyphenylene ether resin and application thereof |
| CN113698592B (en) * | 2021-09-06 | 2023-11-14 | 洛阳理工学院 | Curable polyphenyl ether resin and preparation method thereof |
| CN113773632B (en) * | 2021-09-06 | 2023-11-14 | 洛阳理工学院 | Composition containing curable polyphenyl ether resin and application thereof |
| CN115490847A (en) * | 2022-09-30 | 2022-12-20 | 四川轻化工大学 | Sulfone-containing dihydroxy polyphenyl ether, crosslinkable polyphenyl ether and preparation method thereof |
| CN115490847B (en) * | 2022-09-30 | 2024-01-30 | 湖南长炼新材料科技股份公司 | Sulfonyl-containing dihydroxy polyphenyl ether, crosslinkable polyphenyl ether and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110002963A (en) | A kind of preparation process of bisphenol-A and both-end hydroxyl polyphenylene oxide | |
| CN109836575A (en) | A kind of preparation process of the methacrylate functionalized polyphenylene oxide of thermosetting property | |
| CN111253574B (en) | Preparation method of polysulfone resin material with low cyclic dimer content | |
| CN113388112B (en) | Preparation method of double-end-capped polysulfone | |
| CN109929104A (en) | A kind of preparation process of thermosetting property allyl (ether) functionalized polyphenylene ether | |
| CN104961652B (en) | Bisphenol A type cyanate resin monomer preparation method | |
| CN106279672B (en) | From tool micro-porous copolymers, its preparation method and application | |
| CN113292719B (en) | Polyamide resin containing imide structure and preparation method thereof | |
| CN109796590A (en) | A kind of polyimide resin and transparent polyimide film | |
| CN105175722A (en) | Preparation method of aromatic polyamic acid with characteristics of high relative molecular mass and narrow molecular weight distribution | |
| CN103709398A (en) | Preparation method of polyphenyl ether | |
| CN101463128B (en) | Polyarylether polymer containing amino-benzene lateral group and method for synthesizing the same | |
| CN111072462A (en) | Bio-based bisphenol monomer, bio-based epoxy resin, composite material of bio-based bisphenol monomer and bio-based epoxy resin and preparation method of composite material | |
| CN109012528A (en) | A kind of tubular reactor and the method for preparing monodisperse polyamic acid solution with it | |
| CN109535413A (en) | The synthesis of side chain poly (arylene ether nitrile) containing amino-functional group | |
| CN103059290B (en) | Continuous polymerization method of high-viscosity poly-p-phenylene terephthamide | |
| CA1233600A (en) | Continuous process for preparing polyphenylene oxides | |
| CN106750302B (en) | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone | |
| CN114605629B (en) | Preparation system and preparation method of dihydroxyl polyphenyl ether | |
| CN109912437B (en) | Polyamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film | |
| CN115304764B (en) | Epoxidized fluorine-containing polyarylether compound and preparation method thereof | |
| CN110918021A (en) | Micro-reaction device and method for preparing xylene formaldehyde resin by using same | |
| CN116199875B (en) | Method for preparing small-molecular-weight double-end hydroxyl polyphenyl ether by using micro-channel reactor | |
| CN108559080A (en) | A kind of continuous polymerization preparation method of thermoplastic polyimide | |
| CN101024680B (en) | Binaphthyl-radicle-contained di-phenol A-type resin and its preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190712 |
|
| RJ01 | Rejection of invention patent application after publication |