CN110078912A - A kind of polyphenylene oxide continuous pressure filtration washing methods - Google Patents
A kind of polyphenylene oxide continuous pressure filtration washing methods Download PDFInfo
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- CN110078912A CN110078912A CN201810079557.7A CN201810079557A CN110078912A CN 110078912 A CN110078912 A CN 110078912A CN 201810079557 A CN201810079557 A CN 201810079557A CN 110078912 A CN110078912 A CN 110078912A
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- polyphenylene oxide
- filter cake
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- 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
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- 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
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
Abstract
The present invention provides a kind of preparation method of polyphenylene oxide, using continuous filtration washing technique, pressure filtration method is used in solid-liquid separation process, polyphenylene ether slurry liquid is separated by solid-liquid separation to obtain polyphenylene oxide filter cake, then in cleaning process, polyphenylene ether filter cake carries out spray cleaning.By pressure filtration and continuous non-dispersive formula cleaning operation, the content of good solvent in filter cake can be effectively reduced, while controlling the percentage of damage of polyphenylene oxide particles in filter cake.
Description
Technical field
The invention belongs to chemical process technology fields, wash more particularly, to the continuous pressure filtration after a kind of synthesis of polyphenylene oxide
Wash method.
Background technique
Polyphenylene oxide needs filtration washing before entering drying machine after being precipitated, and technique requirement: (1) drops total fugitive constituent in filter cake
To filter cake total weight 60% hereinafter, good solvent (such as toluene) drops to the 10% of filter cake total weight hereinafter, excessively high good solvent
Content, which will cause, is adhered to drying machine inner wall in polyphenylene oxide drying process, drying efficiency is caused to decline, or even damage drying machine.
(2) the broken of particle in filtering and washing process is reduced to the greatest extent, especially less than 100 μm of particle will control within 15%,
A possibility that excessive tiny powder will increase Downstream processing dust pollution and dust explosion.
The Purification by filtration technique in polyphenylene oxide synthesis process is all made of the technique of repeatedly dispersion, centrifuge dripping, process at present
Complexity, often, Particle Breakage rate is high for intermediate agitation.
Japanese Unexamined Patent Application Publication 2004-531626 bulletin, Japanese Unexamined Patent Application Publication 2014-508208, Japanese Patent Publication 45-587 public trick,
US6407200B1, CN1531568A are only referred to the precipitation technique of optimization filtering upstream, by the way that the design of slot is precipitated, changes poly- Asia
The process conditions of aryl phenylate precipitation process, such as: the ratio of poor solvent (methanol, C1-C6 alcohols) and water, poor solvent with
The ratio of good solvent, solid phase concentration of particles control of polyphenyl ethereal solution etc., to reduce the fine particle of generation.
US6437084B1 discloses a kind of method for preparing polyphenylene oxide, the polyphenylene oxide analysis after concentration is mentioned in embodiment
Become after out in slurry, by using methanol reslurry to disperse after vacuum filter, then separated with centrifuge, finally with drying machine into
Row separation.
US6407200B1 discloses a kind of preparation method of polyphenylene oxide.In embodiment be separated by solid-liquid separation take with it is above-mentioned
The identical method of patent, polyphenylene oxide suspension first pass through vacuum separation, and then methanol disperses, then is dried after centrifuge dripping.
CN1531568A discloses a kind of method for preparing poly- (arylene ether), and by removing partial solvent, production has
Then the concentrated solution of cloud point Tcloud mixes in high shear stirred tank with methanol, form the good polyphenyl of particle size distribution
Ether suspension, to reduce fine grain content in suspension system.Processing for separation of solid and liquid refers to adopt in the patent
Include revolving filter, continuous rotation vacuum filter etc. with the filter of diversified forms, but does not refer to and how to control polyphenyl
Toluene level and Particle Breakage rate in ether filter cake.
CN1688632A refers to the process that filtering is precipitated in polyphenylene oxide, controls grain by the ratio of control toluene, methanol, water
Diameter is separated by solid-liquid separation finally by centrifuge, and rotary or vacuum rotary filter is also referred in patent.But it is specific
Form and how to reduce Particle Breakage rate and do not refer to.
CN107236124A discloses a kind of method that filtering and cleaning is precipitated in polyphenylene oxide, and same use is filtered under diminished pressure, stirs
Cleaning is mixed, the process of re-dry equally will cause the broken of particle.
In conclusion the process of prior art polyphenylene ether post-processing is usual are as follows: be separated by solid-liquid separation (filtering)-dispersion cleaning
(mode usually stirred is dispersed)-secondary separation of solid and liquid (refiltering)-drying and other steps.Majority of case at least needs: 2-3
Secondary separation of solid and liquid (filtering), 1-2 dispersion cleaning, 1-2 drying.The equipment of this process requirement is more, the long (dispersion of processing time
Time > 10min), low efficiency, Particle Breakage rate are high, it is difficult to ensure that under the premise of reducing good solvent (such as toluene) concentration as far as possible,
Particle Breakage rate is not caused to increase.
The inventors found that the main reason for causing polyphenylene oxide fine powder excessive in the prior art first is that: scavenger
In sequence, filter cake is to be easily re-dispersed in cleaning solution formation suspension slurry in the case of stirring, between particle, particle and stirring
Friction between axis and blade causes percentage of damage quickly to increase.
In addition, the prior art is to reduce the content of good solvent in filter cake, often through increasing wash number, increase methanol
Dosage extends scavenging period, increases the modes such as stirring intensity to realize.Accompanying problem is that: material handles time length, effect
Rate is low, and percentage of damage increases, and causes fine powder rate high.Therefore, prior art processes, which exist, reduces good solvent (toluene) concentration and reduction
The contradiction of fine particle content in polyphenylene oxide.
Summary of the invention
Object of the present invention is to find a kind of method of new, more efficient polyphenylene oxide post-processing, can preferably control poly-
Good solvent (such as toluene) content in phenylate filter cake, while reducing polyphenylene oxide particles percentage of damage.
Technical scheme is as follows:
A kind of preparation method of polyphenylene oxide, which is characterized in that including following processes:
Polymerization process, comprising selected from least one of the group being made of benzene,toluene,xylene and ethylbenzene aromatic series
In the polymeric solution of series solvent, phenol system compound and catalyst, make the phenol system compound oxidation polymerization, obtains polyphenylene oxide mixing
Liquid；
Process is precipitated, addition is selected from the ketone by carbon atom number for 1~10, carbon atom number in the polyphenylene oxide mixed liquor
For 1~10 at least one of the group polar solvent that forms of alcohols and water, polyphenylene oxide is precipitated, obtains comprising polyphenylene oxide grain
The slurry liquid of shape object；
Solid-liquid separation process is separated by solid-liquid separation the slurry liquid, obtains polyphenylene oxide filter cake, which, which uses, adds
Press through filtering method；
Cleaning process carries out spray to the filter cake that solid-liquid separation process obtains with cleaning solution and cleans, while will be after spray
Cleaning solution is removed；
Drying process makes the polyphenylene oxide filtration cakes torrefaction.
It is preferred that in the pressure filtration of the solid-liquid separation process, the pressure is 1.2-10bar, preferably 2-6bar, more excellent
It is selected as 2.5-5bar, pressurizes and can avoid low boiling point solvent boiling.
It is preferred that the thickness control of the polyphenylene oxide filter cake is 10-200mm.More preferable polyphenylene oxide filter cake with a thickness of 10-
100mm, particularly preferred 10-50mm.Certainly, can also be with lower than 10mm, but in terms of production efficiency angle, too low thickness can be led
Cause the efficiency of integral filter washing lower.In solid-liquid separation process, it can be controlled by controlling the charging rate of slurry liquid
The thickness of polyphenylene oxide filter cake.
The cleaning process can carry out once, twice or more than twice, such as 2-8 times, preferably 3-5 times.
Inventors have found that can further be obtained more preferable by control cleaning solution dosage, cleaning solution temperature and cleaning pressure
Washing effect.
It is preferred that cleaning solution dosage is 0.1-80 times of polyphenylene oxide filter cake weight, preferably 1-10 times, such as can be polyphenyl
2 times of ether filter cake weight, 3 times, 4 times, 5 times, 6 times, 7 times etc..
It is preferred that cleaning solution temperature is 30-60 DEG C, preferably 35-50 DEG C.
It is preferred that using pressurization washing, pressure 1.2-10bar, preferably 2-6bar, more preferably 2.5-5bar when cleaning.
According to the present invention, the composition of the cleaning solution can be selected and be adjusted according to washing purpose.For example, can adopt
Use poor solvent such as polar solvent as cleaning solution, the polar solvent can be selected from the ketone for being 1~10 by carbon atom number
At least one of class, the group of the alcohols that carbon atom number is 1~10 and water composition polar solvent.The cleaning solution can also be
Mixed solvent, by being selected from least one of the group being made of benzene,toluene,xylene and ethylbenzene aromatic system solvent, with choosing
At least one of the group of ketone, the alcohols that carbon atom number is 1~10 and water composition that free carbon atom number is 1~10 polarity
Solvent, the mixed solvent of composition.
It is preferred that the polar solvent is methanol.
It is preferred that the aromatic system solvent is toluene.
It is preferred that the content of the in the mixed solvent aromatic system solvent is 0.5 mass of mass %~18.0 %, polar solvent
Content be 82.0 mass of mass %~99.5 %；The content of more preferable aromatic system solvent be 3.5 mass of mass %~10 %,
The content of polar solvent is 90 mass of mass %~96.5 %；The content of further preferred aromatic system solvent is 5.5 mass %
~9.0 mass %, polar solvent content be 91 mass of mass %~94.5 %.
In an embodiment of the invention, the cleaning solution is methanol.
In yet another embodiment of the present invention, the cleaning solution is the mixed solvent of methanol and toluene.The mixing
The methanol of toluene and 82.0 mass of mass %~99.5 % containing 0.5 mass of mass %~18.0 % in solvent, more preferably contains
There are the toluene of 3.5 mass of mass %~10 % and the methanol of 90 mass of mass %~96.5 %, further preferably 5.5 matter
Measure the toluene of the mass of %~9.0 % and the methanol of 91.0 mass of mass %~94.5 %.
It is using an advantage of cleaning process of the present invention: does not disperse stirring operation, Particle Breakage rate declines to a great extent.
, according to the invention it is preferred to carry out predrying, the predry drying process can be used conventional before the drying process
Drying means, if using gas purges dry or drying mode, to remove filter cake surface solvent.It is preferred that gas purging drying
Mode is for example dry using inert gas purge, and including but not limited to nitrogen purges drying.Dry gas temperature is set as 1-200
Between DEG C.The dry inert gas of purging can recycle.
In predry drying process, and inert gas (such as: N2、CO2, Ar etc.) dosage be 0.01-50Nm3The filter of/Kg polyphenylene oxide
Cake, preferably 0.3-10Nm3/ Kg polyphenylene oxide filter cake, more preferable 0.5-5.0Nm3/ Kg polyphenylene oxide filter cake.
According to the present invention, the solid-liquid separation process, cleaning process and predry drying process are carried out with intermittent or continous way,
It is preferred that continuous and sequence carries out.
It is preferred that solid-liquid separation process, cleaning process and predry drying process carry out in a unit.The equipment can
Selected from rotary drum filter press, it is continuously finished filtering, cleaning, predry drying process in proper order and in rotary drum rotation process；Or it is selected from
Filter with rotating disk is continuously finished filtering, cleaning, predry drying process in proper order and in turntable rotary course；Or selected from level
Band filter is continuously finished filtering, cleaning, predry drying process in proper order and as transmission belt is run.
In an embodiment of the invention, using rotary drum pressure filter.
The rotary drum pressure filter is a kind of continuous filtering device known in the art.Drum surface arranges lautertuns, mistake
Filter pocket is separated into different regions with isolation board, is separated into fed filtration area, scrubbing section, predrying area according to the technological requirements and unloads
Expect area.There is a shell outside rotary drum, a distance is spaced each other on shell and offers slurry import, cleaning solution import, predry
Dry gas feed and scraper plate.The isolation board is mounted on drum surface, or is mounted on interior table of the shell towards drum surface
On face.It can sequentially complete within drum rotating one week to be filtered, washed, predrying and discharge process.
In an embodiment of the invention, slurry import be arranged in rotor cover lower part, from slurry import according to
Counterclockwise successively interval setting cleaning solution import on the shell, predrying gas feed and scraper plate.Drum surface installation every
The lautertuns of drum surface is separated into fed filtration area, scrubbing section, predrying area and discharge zone by plate.Rotary drum rotates counterclockwise.
Polyphenylene oxide slurry enters rotary drum from slurry import, is taped against filtering rooved face, and pressurized filtering forms polyphenylene oxide filter in drum surface
Cake after filter cake turns to cleaning solution entrance location with rotary drum, is added cleaning solution and carries out spray washing.Again as rotary drum turns to
It is dry with inert gas purge behind predrying gas feed position.When filter cake goes to wiper positions, through gravity from rotary drum table
Emaciated face is fallen, and what is do not fallen off scrapes through scraper plate.Slurry is continuously introduced into, and cooperates rotary drum continuous rotation, is realized filtering, is cleaned, is pre-
Dry and discharging continuous work.
Since polyphenylene oxide filter pulp is evenly distributed in filter pocket by filter progress, so that filter cake thickness reduces in single filter pocket,
It is abundant to contact detergent.Therefore, the good solvent in filter cake (such as toluene) can be rapidly decreased to index request.Meanwhile filtering,
Filter cake handles always stationary state in drum surface in washing, pre-drying process, and most of filter cake leans on gravity certainly in discharge process
It is dynamic to fall off, therefore polyphenylene oxide particles keep complete, percentage of damage is low.Rotary drum pressure filter is easy amplification, and filter cake thickness can be protected after amplification
Hold it is constant, therefore the charging and washing of single lautertuns be able to maintain it is constant.
It is preferred that providing pressure in rotor cover, complete filtering, cleaning and predrying all under elevated pressure, pressure 1.2-
10bar, preferably 2-6bar.
For rotary drum pressure filter, preferred process conditions are as follows: pressure 1.2-10bar, preferably 2-6bar；Cleaning solution is washed
The amount of washing is 0.1-80Kg/Kg filter cake, preferably 1-10Kg/Kg filter cake；It is 0.01-50Nm that predrying, which purges inert gas dosage,3/Kg
Filter cake, preferably 0.3-10Nm3/ Kg filter cake.Good solvent (such as toluene) after filtering in filter cake can control in filter cake total weight
10% hereinafter, and Particle Breakage growth rate≤2.0%.
The roller diameter of the rotary drum pressure filter can be 50-500cm, and the lautertuns of drum surface arrangement can long 5-
300cm。
In yet another embodiment of the present invention, using horizontal belt filter, along strainer horizontal length direction, successively
Fillter section, cleaning section, predrying section and unloading part are set, slurry import is set above fillter section, setting cleaning above cleaning section
Dry gas import is arranged in liquid import, predrying section top, and unloading part is arranged at horizontal end of tape revolution.Polyphenylene oxide slurry is logical
It crosses feed inlet uniformly to spread to strainer, polyphenylene oxide filter cake is formed on strainer by pressure filtration.Filter cake is moved as strainer moves ahead
To cleaning section, after cleaning solution is from cleaning solution import spray to filter cake, passes through negative pressure or pressurization removes.Filter cake continues with strainer
It moves ahead and moves to predrying section, dry gas sends out purging filter cake to drying from dry gas import.Filter cake is proceeded to strainer and is unloaded
Expect section, since strainer migrates at revolution, for filter cake because gravity falls off from strainer, the filter cake not fallen off can be further by scraper plate
It scrapes.Slurry is continuously introduced into, and the continuous winding of cooperation strainer is mobile, realizes the continuous work of filtering, cleaning, predrying and discharging.
It is preferred that a whole set of horizontal stripes filter is placed in sealing shell, pressure is provided inside the shell, makes filtering, cleaning and pre-
Drying is all completed under elevated pressure, pressure 1.2-10bar, preferably 2-6bar.
, according to the invention it is preferred to which the cleaning process uses countercurrent washing, that is, n grades are carried out altogether or n times are washed, n-th grade
Cleaning solution collection after (secondary) washing is stored in n-th grade of (secondary) cleaning solution storage container, and is sent to (n-1)th grade of (secondary) cleaning section
Spray washing is carried out, and the cleaning solution collection after (n-1)th grade of (secondary) washing simultaneously is stored in (n-1)th grade of (secondary) cleaning solution storage and holds
In device, and send to the n-th -2 grades (secondary) cleaning sections and carry out spray washing, and so on, it is washed until the 1st grade.It can not increase in this way
In the case where adding fresh cleaning solution dosage, good solvent in filter cake (such as toluene) stable content is down to 10% or less.
In an embodiment of the invention, using 2-8 times or 2-8 stage countercurrent washing, more preferably 3-5 times or 3-5
Stage countercurrent washing.
According to the present invention, catalyst removing step can also be set after above-mentioned polymerization process, that is, to polyphenylene oxide mixed liquor
Middle addition chelating agent solution extracts metallic catalyst to chelating agent solution side, and Liquid liquid Separation is at aromatic system solvent phase and chela
Mixture solution phase removes the metallic catalyst in polyphenylene oxide mixed liquor.It, can also be further in above-mentioned catalyst removing step
Water is added into the polyphenylene oxide mixed liquor after addition chelating agent solution and Liquid liquid Separation, Liquid liquid Separation is repeated, further goes
Except catalyst.
In addition, enrichment process can also be arranged after above-mentioned polymerization process or after above-mentioned catalyst removing step, that is, by
Polyphenylene oxide mixed liquor separates good solvent, and polyphenylene oxide is concentrated.
In the following, the polyphenylene oxide obtained using the manufacturing method of the present invention is described in detail.
Polyphenylene oxide (PPE)
It is to include repetitive unit knot represented by the following general formula (1) using polyphenylene oxide manufactured by the manufacturing method of the present invention
The homopolymer and/or copolymer of structure.
In formula (1), R1、R2、R3And R4It is each independently selected from by hydrogen atom, halogen atom, the alkane that carbon atom number is 1~7
Base, phenyl, halogenated alkyl, aminoalkyl, oxyl and halogen atom and oxygen atom are separated by the halogenated hydrocarbons oxygen of at least two carbon atom
Any one of the group of base composition.
In above-mentioned formula (1), as R1、R2、R3And R4It is former can to enumerate fluorine atom, chlorine atom, bromine for represented halogen atom
Son etc., preferably chlorine atom, bromine atom.
In above-mentioned formula (1), as R1、R2、R3And R4Represented alkyl, preferably carbon atom number be 1~6 straight-chain or
The alkyl of branched, the alkyl of straight-chain or branched that more preferable carbon atom number is 1~3.As abovementioned alkyl, can enumerate
Such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, hexyl etc..Wherein, preferred first
Base, ethyl, more preferable methyl.
In above-mentioned formula (1), R1、R2、R3And R4Represented alkyl can on substitutive position have 1 or 2 with
On substituent group.
As such substituent group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom) can be enumerated, carbon atom number is
1~6 alkyl (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, hexyl), virtue
Base (for example, phenyl, naphthalene), alkenyl (for example, vinyl, 1- acrylic, 2- acrylic), alkynyl are (for example, acetenyl, 1- third
Alkynyl, 2-propynyl), aralkyl (for example, benzyl, phenethyl), alkoxy (for example, methoxyl group, ethyoxyl) etc..
It as the homopolymer of above-mentioned polyphenylene oxide, is not particularly limited, can specifically enumerate poly- (2,6- dimethyl-Isosorbide-5-Nitrae-Asia
Phenyl) ether, poly- (2- methyl -6- ethyl -1,4- phenylene) ether, poly- (2,6- diethyl -1,4- phenylene) ether, poly- (2- ethyl -
6- n-propyl -1,4- phenylene) ether, poly- (2,6- diη-propyl -1,4- phenylene) ether, poly- (2- methyl -6- normal-butyl -1,4-
Phenylene) ether, poly- (2- ethyl -6- isopropyl -1,4- phenylene) ether, poly- (2- methyl -6- ethoxy -1,4- phenylene) ether,
Poly- (2- methyl -6- chloroethyl -1,4- phenylene) ether etc..Wherein, low from the price of raw material, be easy from the viewpoint of, it is excellent
Select poly- (2,6- dimethyl -1,4- phenylene) ether.
It to the copolymer of above-mentioned polyphenylene oxide, is not particularly limited, can specifically enumerate 2,6- xylenol and 2,3,6-
The copolymer of pseudocuminol, the copolymer of 2,6- xylenol and o-cresol, 2,6- xylenol and 2,3,6- front three
Base phenol and the copolymer of o-cresol etc..Wherein, low from the price of raw material, be easy from the viewpoint of, preferably 2,6- diformazan
The copolymer of base phenol and 2,3,6- pseudocuminol.
The molecular weight of polyphenylene oxide can use gel permeation chromatography measurement device and be measured.
Using in polyphenylene oxide manufactured by the manufacturing method of the present invention, molecular weight is containing for 500 polyphenylene oxide ingredients below
Amount is preferably 0.8 mass % or less, more preferably 0.5 mass % or less, further preferably 0.3 mass % or less.As upper
Stating molecular weight is 500 polyphenylene oxide ingredients below, it can be cited for example that the dimer of above-mentioned phenol system compound, trimer, oligomeric
Object etc..Molecular weight be 500 polyphenylene oxide ingredients below content can use the composition of polymeric solution, polymerization process condition,
Composition, condition of cleaning process of cleaning solution etc. are adjusted.
For using polyphenylene oxide manufactured by the manufacturing method of the present invention, preferably due to the metal used when polymerizeing
The kish of catalyst etc. is few.Specifically, utilizing the manufacturing method of the present invention institute from the viewpoint of heat aging raising
The concentration of kish in the polyphenylene oxide of manufacture be preferably 1.0 mass ppm or less, more preferably 0.8 mass ppm or less, into
One step is preferably 0.6 mass ppm or less.Kish for example can use the condition of catalyst removing step, the group of cleaning solution
It is adjusted at, condition of cleaning process etc..
For using polyphenylene oxide manufactured by the manufacturing method of the present invention, the remaining solvent preferably in polyphenylene oxide
It is few, preferably smaller than 1.5 mass %, more preferably 0.5 mass % or less, further preferably 0.3 mass % or less.Residual volatilization
Ingredient for example can use the composition of cleaning solution, condition of cleaning process etc. and be adjusted.
In the following, each process in the manufacturing method of polyphenylene oxide of the invention is described in detail.
<polymerization process>
Phenol system compound-
As above-mentioned phenol system compound, it can be cited for example that o-cresol, 2,6- xylenol, 2- ethyl -phenol, 2- first
Base -6- ethyl -phenol, 2,6- diethyl phenol, 2- n-propyl phenol, 2- ethyl -6- n-propyl phenol, 2- methyl -6- chlorobenzene
Phenol, 2- methyl -6- isopropyl-phenol, 2- methyl -6- n-propyl phenol, 2- ethyl -6- bromophenol, 2- methyl -6- n-butylbenzene
Phenol, 2,6- diη-propyl phenol, 2- ethyl -6- chlorophenol, 2- methyl -6- phenylphenol, 2- phenylphenol, 2,6- diphenyl benzene
Phenol, 2- methyl -6- tolyl phenol, 2,6- xylyl phenol, 2,5- xylenol, 2,3,6- pseudocuminol, 2,5-
Diethyl phenol, 2- methyl -5- ethyl -phenol, 2- ethyl -5- methylphenol, 2- allyl -5- methylphenol, bis- allyl of 2,5-
Base phenol, 2,3- diethyl -6- n-propyl phenol, 2- methyl-5-chloro phenol, Carvacrol, 2- methyl -5-
N-propyl phenol, 2- methyl -5- normal-butyl phenol, 2,5- diη-propyl phenol, 2- ethyl -5- chlorophenol, 2- methyl -5- phenyl
Phenol, 2,5- diphenyl phenol, 2- methyl -5- tolyl phenol, 2,5- xylyl phenol, 2,6- dimethyl -3- allyl
Phenol, 2,3,6- triallyl phenol, 2,3,6- tributyl phenol, 2,6- di-n-butyl -3- methylphenol, the tertiary fourth of 2,6- bis-
Base -3- methylphenol, 2,6- dimethyl -3- normal-butyl phenol etc..
For it is at low cost, be easy to get the reason of, preferably 2,6- xylenol, 2,6- diethyl phenol, 2,6- hexichol
Base phenol, 2,3,6-TMP, 2,5- xylenol, more preferable 2,6- xylenol, 2,3,6-TMP.
Above-mentioned phenol system compound can be used alone, two or more can also be applied in combination.Using phenol of more than two kinds
In the case where based compound, mixed proportion can be selected arbitrarily.2,6- xylenol and 2,6- diethyl can be used for example
The combination of base phenol, 2,6- xylenol and 2,6- diphenyl phenol combination, 2,3,6- pseudocuminol and 2,5- diformazan
Combination, 2,6- xylenol and combination of 2,3,6- pseudocuminol of base phenol etc..
Aromatic system solvent-
Above-mentioned aromatic system solvent is the good solvent of polyphenylene oxide, selected from being made of benzene,toluene,xylene and ethylbenzene
At least one of group.The angle removed, preferably toluene are easy from the residual solvents in drying process.
As above-mentioned aromatic solvent, the preferred substantial immiscible solvent with water.In addition, in above-mentioned polymeric solution preferably
Not including substantially has solvent compatible with water.
Catalyst-
As above-mentioned catalyst, the catalyst of the polymerization commonly used in polyphenylene oxide can be used, including but not limited to: metal
Catalyst, halide, amine compounds and their mixture, can specifically enumerate and be made of copper compound and amine compounds
Mixture, the mixture being made of manganese compound and amine compounds, the mixture being made of cobalt compound and amine compounds etc..
Wherein, the mixture being preferably made of copper compound and amine compounds.
-- metallic catalyst --
As above-mentioned metallic catalyst, preferably copper compound, including but not limited to cuprous compound, cupric compound or
Their mixture.It can be cited for example that stannous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, oxidation cupric, chlorination
Copper, copper bromide, copper sulphate, copper nitrate etc..Wherein, cupric, stannous chloride, copper chloride, cuprous bromide, bromination are preferably aoxidized
Copper.
These metallic catalysts may be used alone, or two or more kinds may be used in combination.
-- halide --
As above-mentioned halide, be not particularly limited, can specifically enumerate hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride,
Sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethyl ammonium chloride, 4 bromide, tetramethyl-ammonium iodide, four
Ethyl ammonium chloride, tetraethylammonium bromide, tetraethyl ammonium iodide etc..These halide with aqueous solution or can also use appropriate molten
The solution state of agent uses.Wherein, the preferred aqueous solution of the aqueous solution of hydrogen chloride, hydrogen bromide.
These halogen compounds may be used alone, or two or more kinds may be used in combination.
-- amine compounds --
As above-mentioned amine compounds, it can be cited for example that diamine compound, unitary secondary amine compound, unitary tertiary amine compound
Deng.The amine compounds may be used alone, or two or more kinds may be used in combination.
As above-mentioned diamine compound, preferably diamine compound represented by the following general formula (2).
As above-mentioned catalyst, can be used for example comprising two represented by copper compound, halide and the following general formula (2)
The catalyst of amine compounds.By using such catalyst, when can further increase polymerization speed, further shorten polymerization
Between.In addition, the molecular weight after making polymerization is easier to adjust by adjusting catalytic amount, the oxygen amount of being blown into, polymerization time etc..
In formula (2), R5、R6、R7And R8It is each independently hydrogen atom, the straight-chain or branched that carbon atom number is 1~6
Alkyl, all simultaneously be hydrogen atom.R9Indicate the alkylidene for the straight-chain or branched that carbon atom number is 2~5.
As diamine compound represented by above-mentioned general formula (2), it is not particularly limited, can specifically enumerates N, N, N ', N '-
Tetramethylethylenediamine, N, N, N '-trimethyl ethylenediamine, N, N '-dimethyl ethylenediamine, N, N- dimethyl-ethylenediamine, N- methyl second
Diamines, N, N, N ', N '-tetraethylethylenediamine, N, N, N '-triethylethylenediamine, N, N '-diethyl ethylenediamine, N, N- diethyl
Ethylenediamine, n-ethylethylenediamine, N, N- dimethyl-N '-ethylethylenediamine, N, N '-dimethyl-n-ethylethylenediamine, N- positive third
Base ethylenediamine, N, N '-diη-propyl ethylenediamine, N- isopropyl ethylenediamine etc..Wherein, R in preferred formula (2)5Be carbon atom number be 2
Or 3 alkylidene diamine compound.
The dosage of above-mentioned diamine compound is not particularly limited, relative to 100 moles of above-mentioned phenol system compound, preferably
0.01 mole~10 moles.
As above-mentioned unitary tertiary amine compound, be not particularly limited, can specifically enumerate trimethylamine, triethylamine, tripropyl amine (TPA),
Tri-n-butylamine, triisobutylamine, dimethyl amine, dimethyl propylamine, allyl diethylamine, N- butyldimethylamine, diethylisopropylamide,
N-methylcyclohexylamine etc..The unitary tertiary amine compound may be used alone, or two or more kinds may be used in combination.
The dosage of above-mentioned unitary tertiary amine compound is not particularly limited, it is excellent relative to 100 moles of above-mentioned phenol system compound
It is selected as 15 moles or less.
Above-mentioned unitary tertiary amine compound can add whole amount before polymerization, can also add before polymerization after a part again
It is successively added in polymerization.In addition, above-mentioned unitary tertiary amine can also start after mixing with above-mentioned phenol system compound in polymerization
It is added in polymeric solution simultaneously.
It as above-mentioned unitary secondary amine compound, is not particularly limited, can specifically enumerate dimethylamine, diethylamine, two positive third
Amine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, two tert-butylamines, diamylamine, dihexylamine, dioctylamine, didecylamine, dibenzylamine, first
Base ethamine, methyl propylamine, methylbutylamine, cyclohexylamine etc..
In addition, also can be used comprising aromatic unitary secondary amine compound, not having as above-mentioned unitary secondary amine compound
It is particularly limited to, can specifically enumerate N- phenyl methanol amine, N- phenylethanol amine, N- Super Odrinex, N- (aminomethyl phenyl) second
Hydramine, N- (p-methylphenyl) ethanol amine, N- (rubigan) ethanol amine etc. N- (substituted or non-substituted phenyl) alkanolamine；N- second
The N- hydrocarbon such as base aniline, N- butylaniline, N- methyl -2-aminotoluene, N- methyl -2,6- dimethylaniline, diphenylamine replace
Aniline etc..
Above-mentioned unitary secondary amine compound may be used alone, or two or more kinds may be used in combination.
The dosage of above-mentioned unitary secondary amine compound is not particularly limited, it is excellent relative to 100 moles of above-mentioned phenol system compound
It is selected as 15 moles or less.
Alternatively, it is also possible to add the previous known surface-active to polymerization activity with improvement effect into polymeric solution
Agent.As above-mentioned surfactant, tri-n-octyl methyl ammonium chloride can be.
The dosage of above-mentioned surfactant is preferably the model for being no more than 0.1 mass % relative to the total amount of above-mentioned polymeric solution
It encloses.
In above-mentioned polymerization process, the ventilation of oxygen-containing gas can be carried out on one side, on one side polymerize above-mentioned phenol system compound.
It is not particularly limited at the beginning of to oxygen-containing gas ventilation, by phenol system compound, fragrance preferably in the preparation of polymeric solution
Any one of family solvent, catalyst import the ventilation of beginning oxygen-containing gas after reactor.
It as oxygen-containing gas, is not particularly limited, purity oxygen specifically can be used or mixes oxygen and arbitrary inert gas
Gas made of conjunction；It as inert gas, is not particularly limited, specifically, as long as the influence less for polymerization reaction
Arbitrary inert gas can be used.Representative inert gas is nitrogen, it is desirable that is reduced to reaction kettle gas-phase space oxygen content
10% or less.
<catalyst removing step>
In above-mentioned catalyst removing step, by adding chelating agent solution into the polyphenylene oxide mixed liquor after polymerization process
And stir, to the metallic catalyst used as above-mentioned catalyst be extracted to chelating agent solution side, by polyphenylene oxide mixed liquor
With chelating agent solution Liquid liquid Separation, the metallic catalyst in polyphenylene oxide mixed liquor can be removed.
As chelating agent used in above-mentioned chelating agent solution, it can be cited for example that: the acid such as hydrochloric acid, acetic acid；Ethylenediamine tetraacetic
Acetic acid (EDTA) and its salt；Nitrilotriacetic acid and its salt；Etc..For above-mentioned chelating agent, can be added with simple substance form, but
It is preferred that being added in the form of chelating agent aqueous solution etc..Using chelate aqueous solution, inactivated in conjunction with chelating agent
Metallic catalyst be extracted into water phase, it is thus possible to separate the polyphenylene oxide for including in organic phase and metallic catalyst.
About the two-phase laminated flow in catalyst removing step and aftermentioned cleaning process, can be divided by settle and separate
From Liquid liquid Separation machine also can be used.
<enrichment process>
It as the method for concentration of polyphenylene oxide, can enumerate: with the thermal medium more than boiling point of the good solvent of polyphenylene oxide to poly-
Phenylate mixed liquor is heated, and the good solvent of polyphenylene oxide is made to be discharged to the method outside system in vapour form；Polyphenylene oxide is mixed
Liquid imports relief groove, the method for flashing the polymer solvents such as aromatic system solvent；It is heated by pressurizationization polyphenylene ether mixed liquor
After depressurized, thus make the polymer solvents such as aromatic system solvent flash method；Etc..
<process is precipitated>
Polar solvent of the addition as the poor solvent of polyphenylene oxide into polyphenylene oxide mixed liquor, by the good solvent of polyphenylene oxide and
The poor solvent of polyphenylene oxide mixes, and polyphenylene oxide is precipitated, obtains the slurry liquid comprising polyphenylene oxide shot-like particle.
The polar solvent being added in polyphenylene oxide mixed liquor is almost totally insoluble polyphenylene oxide or can slightly dissolve polyphenylene oxide
Poor solvent.Above-mentioned polar solvent be selected from be 1~10 by carbon atom number ketone, carbon atom number be 1~10 alcohols and
The alcohol that at least one of the group of water composition polar solvent, preferably carbon atom number are 1~10.It, can be with as above-mentioned polar solvent
Enumerate for example methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, 2- butanol, amylalcohol, hexanol, ethylene glycol, acetone, methyl ethyl ketone,
Water etc..Wherein, preferably methanol, ethyl alcohol, isopropanol, n-butanol, 2- butanol, acetone, methyl ethyl ketone or water.
Above-mentioned polar solvent may be used alone, or two or more kinds may be used in combination.
In above-mentioned precipitation process, about the additive amount of above-mentioned polar solvent, it is not precipitated and gathers from the ingredient other than polyphenylene oxide
Phenylate is easy from the viewpoint of being precipitated, preferably mass ratio (pole of the polar solvent relative to the good solvent in polyphenylene oxide mixed liquor
Property solvent quality/good solvent quality) be 0.3~2.0 amount.
<solid-liquid separation process>
As the first stage of isolating polyphenylene ether, above-mentioned slurry liquid is separated into polyphenylene oxide particles using equipment for separating liquid from solid
Filter cake and filtrate (separating liquid).It as above-mentioned equipment for separating liquid from solid, is not particularly limited, Barrate type filter, band can be used
Formula filter, rotary drum filters, single chamber rotary drum filter (Young filter) etc..
<cleaning process>
It is good to be impregnated with aromatic system solvent etc. in large quantities for separated polyphenylene oxide particles filter cake in above-mentioned solid-liquid separation process
Solvent composition.By being cleaned using the cleaning solution polyphenylene ether cake of particles comprising polar solvent, polyphenylene oxide can reduce
The content for the good solvent ingredient for including in particle.
It can if reducing the content of these impurity containing low molecular weight compositions and metal impurities in polyphenylene oxide particles
Obtain the polyphenylene oxide with excellent mechanical properties, heat aging etc..If using comprising aromatic system solvent and polar solvent
It is miscellaneous can be then effectively reduced the low molecular weight compositions in wet polyphenylene oxide particles included and metal etc. as cleaning solution for cleaning solution
Matter.
Aromatic system solvent used in cleaning solution and polar solvent can be molten with aromatic system used in polymerization process
Polar solvent used in agent, precipitation process is identical, can also be different.Wherein, preferably identical from efficiency aspect
Solvent.
It is above-mentioned from the perspective of the less polyphenylene oxide of content for obtaining the impurity such as low molecular weight compositions and catalyst metals
The content of above-mentioned aromatic system solvent in cleaning solution be preferably 0.1 mass of mass %~18.0 %, more preferably 5 mass %~
15 mass %, further preferably 9.5 mass of mass %~12 %.
In addition, coming from the angle for the less polyphenylene oxide of content for obtaining the impurity such as low molecular weight compositions and catalyst metals
It sees, the content of the above-mentioned polar solvent in above-mentioned cleaning solution is preferably 82 mass of mass %~99.9 %, more preferably 85 matter
Measure the mass of %~95 %, further preferably 88 mass of mass %~90.5 %.
Wherein, above-mentioned cleaning solution be preferably include above-mentioned 0.5 mass of mass %~18.0 % of aromatic system solvent and above-mentioned
The cleaning solution of 82.0 mass of mass %~99.5 % of polar solvent more preferably includes above-mentioned 3.5 mass % of aromatic system solvent
The cleaning solution of 90 mass of mass %~96.5 % of~10 mass % and above-mentioned polar solvent further preferably includes above-mentioned fragrance
The cleaning solution of 91.0 mass of mass %~94.5 % of 5.5 mass of mass %~9.0 % of family solvent and above-mentioned polar solvent.
In the case where progress 2 times or more cleaning process, cleaning solution used in each cleaning process can be same composition,
It may be different compositions.From cost, operating efficiency angle, it is preferable to use same composition cleaning solution.
It include being separated by solid-liquid separation operation in the cleaning process, that is, cleaning in the case where progress 2 times or more cleaning process
While liquid sprays polyphenylene oxide filter cake, cleaning solution of the spray through filter cake is removed, nature is can be and discharges into cleaning solution storage appearance
Device, or online increase pressure filtration or vacuum filter operation, arrange the cleaning solution being trapped in filter cake more thoroughly from filter cake
Enter cleaning solution storage container, out to further increase detersive efficiency.
<drying process>
To polyphenylene oxide filter cake obtained in cleaning process or the polyphenylene oxide filter cake after predrying, can use drying machine etc. will
Good solvent and poor solvent therein are further separated, that is, process is dried.As above-mentioned drying machine, can be used for example
Various drying machines, the combination of heat exchanger and flash tank, devolatilization extruder etc..It is dry that steam rotary may be selected in the various drying machines
Dry machine, rotary kiln drying machine, blade drier, film drier etc..
<recovery process>
The manufacturing method of polyphenylene oxide of the invention may further include recovery process, and it is molten that recycling is obtained in the recovery process
Solution is recycled in liquid or the purification refined to above-mentioned recycling solution, and the recycling solution includes selected from by above-mentioned solid-liquid point
It will gasify from the separating liquid isolated in process, the separating liquid isolated in above-mentioned cleaning process and in above-mentioned drying process
Discharge gas liquefaction made of at least one of the group that forms of condensate liquid.Above-mentioned recycling obtained in above-mentioned recovery process is molten
Liquid or above-mentioned purification recycling solution can be used as above-mentioned cleaning solution and uses.
In above-mentioned recovery process, recycling solution can use following methods and be refined, and purification recycling solution is made.
According to water phase for the mass ratio (water/polyphenylene oxide poor solvent) for the polyphenylene oxide poor solvent for including in recycling solution
Water is added into above-mentioned recycling solution for 0.5~1.5 mode, two-phase laminated flow has at polyphenylene oxide good solvent is as main component
Machine phase and with polyphenylene oxide poor solvent and water water phase as main component.Two-phase laminated flow can be divided by settle and separate
From Liquid liquid Separation machine can be used also to be separated.
Separated organic phase is recycled, obtained organic phase is supplied from the middle section of destilling tower, is extracted out and is wrapped by tower bottom
Waste liquid containing the low molecular weight compositions such as oligomer, trimer, dimer, metallic catalyst recycles polyphenyl by tower top or tower side
Ether good solvent, amine compounds.Good solvent can be used as again in above-mentioned polymerization process etc. by the polyphenylene oxide good solvent of recovered overhead
It utilizes.
It include metallic catalyst by tower bottom recycling in addition, being supplied about separated water phase from the middle section of destilling tower
Aqueous solution, by recovered overhead polyphenylene oxide poor solvent.
For the aqueous solution comprising metallic catalyst recycled by tower bottom, the sulfide of alkali metal is added, with solid matter
It is recycled after form removal.It can be recycled in above-mentioned recovery process.In addition, by the polyphenylene oxide poor solvent of recovered overhead
It can be recycled in above-mentioned precipitation process or above-mentioned cleaning process as poor solvent.
Above-mentioned recycling solution or it can be used as above-mentioned cleaning solution using purification obtained by the above method recycling solution and make
With.
In the polyphenylene oxide poor solvent using above method purification, appropriate mixing utilizes the polyphenylene oxide of above method purification
Good solvent is used as cleaning solution, so as to oligomer, trimer, the dimer etc. for including in wet polyphenylene oxide particles
Low molecular weight compositions and kish are cleaned.
Detailed description of the invention
Rotary drum pressure filter structural schematic diagram used in Fig. 1 present invention
Specific embodiment
The present invention is described further with reference to embodiments.It should be noted that embodiment cannot function as to this hair
The limitation of bright protection scope, it will be understood by those skilled in the art that, any improvements introduced on the basis of the present invention and variation all exist
Within protection scope of the present invention.
Chemical reagent used in following embodiment is all conventional reagent, commercially available.
Test method description:
1, the preparation of polyphenylene oxide suspension
15 kilograms of toluene are added into the reaction kettle of 30L, then by 5.6 grams of Cu2O and 54 gram of 47%HBr lysate and 12
Gram N, N- di-t-butyl ethylenediamine, 164 grams of N, N- dimethyl butylamine, 56 grams of N, N- di-n-butylamine and 6 grams of tricaprylmethyl chlorinations
Reaction kettle is added in ammonium, and with fixed speed, in 39 DEG C of 2,6- of addition xylenols, (4 kilograms of 2,6- xylenols are dissolved in 2.5
Kilogram toluene in), while being passed through oxygen-enriched air (oxygen content >=50%), carry out polymerization reaction.Adding 2,6- dimethyl benzene
After phenol solution, the reaction was continued 80 minutes.
After reaction, 2000 grams of aqueous solutions containing 48 grams of disodium ethylene diamine tetraacetates are added into reaction solution, 70
Degree lower stirring 2.0 hours.3 hours are stood, is layered, the aqueous solution of reactor bottom after discharge layering.To reacting kettle jacketing
100 degree of hot water are passed through, reaction kettle top connects vacuum pump by condenser, is evaporated concentration.By measuring good solvent toluene
The amount of steaming, after control concentration in solution the content of polyphenylene oxide in 30-40%.Stop heating, be passed through cold water in reacting kettle jacketing,
The solution in reaction kettle after concentration is set to cool to 50 degree or so.Under agitation, twice of concentration of reaction solution quality of first is added
Alcohol solution forms polyphenylene oxide suspension.
2, two kinds of filter method comparisons: the polyphenylene oxide suspension of multiple batches is obtained by the 1 repetition experiment, is respectively adopted
Two ways is filtered washing.Wherein the primary sample refers to: suspension direct sample, and vacuum filter forms filter cake, point
Analyse toluene level in filter cake；It is sieved after drying, analyzes micro mist ratio therein.Comparative example 1: filtering -1 time disperses-after
Filter-drying means
Experimental facilities: 2L suction funnel, vacuum pump, 4L glass jacket stirred tank
Operating method:
A. the polyphenylene oxide suspension 2L that will be obtained by step 1 forms 0.516 kilogram of filter cake using vacuum filtration；
B. obtained filter cake is put into the 4L stirred tank equipped with 1.56Kg methanol, is kept stirring operation, carry out filter cake
Redisperse；
C. it is controlled in stirred tank by the hot water temperature in control collet and stirs end line speed for 40-50 DEG C, control paddle
Filter cake dispersion is carried out under the conditions of 1-2m/s, every 10min samples 100 grams at timed intervals, is filtered by vacuum and is filtered with Buchner funnel
Cake sample detects toluene level in filter cake；
D. filter cake samples are dried under the conditions of 100 degree in vacuum drying oven, the sample of drying screens out≤100 microns of grain
Son calculates ratio after weighing.Count the variation of micro mist ratio in slurry.
Comparative example 2: it filters -1 time and disperses-refilter-drying means
Polyphenylene oxide suspension from different batches repeats all operationss of comparative example 1, detects toluene in filter cake and contains
Amount and micro mist ratio.
Comparative example 3: it filters -1 time and disperses-refilter-drying means
Polyphenylene oxide suspension from different batches repeats all operationss of comparative example 1, detects toluene in filter cake and contains
Amount and micro mist ratio.
Table 1: the result of comparative test 1-3
From experimental result comparison in as can be seen that filtering-disperse-refilter-drying means in, jitter time is more than
20min, the probably toluene in 30min or so, polyphenylene oxide filter cake can just drop to satisfactory 10% or so.
Comparative example 4: it filters -1 time and disperses-refilter -3 filtering-drying means of -2 dispersions
Experimental facilities: 2L suction funnel, vacuum pump, 4L glass jacket stirred tank
Operating method:
A. the polyphenylene oxide suspension 2L that will be obtained by step 1 forms about 0.5 kilogram of filter cake using vacuum filtration；
B. obtained filter cake is put into the 4L stirred tank equipped with 1.56Kg methanol, is kept stirring operation, carry out filter cake
Redisperse；
C. it is controlled in stirred tank by the hot water temperature in control collet and stirs end line speed for 40-50 DEG C, control paddle
Filter cake dispersion is carried out under the conditions of 2m/s, jitter time 30 minutes, Buchner funnel was filtered by vacuum to obtain filter cake samples.
D. obtained filter cake is put into the 4L stirred tank equipped with 1.56Kg methanol, is kept stirring operation, carry out filter cake 2
Secondary redisperse；Dispersing method is with step C, difference: every 5min samples 100 grams at timed intervals, is taken out with Buchner funnel vacuum
Filter obtains filter cake samples, detects toluene level in filter cake；
E. filter cake samples are dried under the conditions of 100 degree in vacuum drying oven, the sample of drying screens out≤100 microns of grain
Son calculates ratio after weighing.Count the variation of micro mist ratio in slurry.
Table 2: Comparability test 4 (filters -1 time and disperses-refilter -3 filtering-drying means of -2 dispersions) result
* primary sample 4 is by once dispersing and filtered sample herein.
As can be seen that 2 dispersion steps will lead to powder content substantial increase in filter cake from experimental result comparison, from
20.2% ratio increases to 26.1% ratio.
Embodiment 5-7: continuous pressure filtration washing methods
Using rotary drum pressure filter as shown in Figure 1, roller diameter 60cm.Drum surface arranges lautertuns, filters flute length
15cm, wide 10cm, high 2cm.Filter pocket on rotary drum is separated into fed filtration area, scrubbing section, predrying area and discharging with isolation board
Area.It can complete within drum rotating one week filtering, repeatedly washing, drying and discharge process.Control inlet amount 60L/h.It is continuous reverse
Washing 5 times, dosage of scour is mutually all 53.1L/h each time, and filtering and washing pressure are 4bar, dry purging N2Flow
15Nm3/h.Filter cake samples are taken to carry out toluene level analysis detection from discharge port after stable；Then by sample in vacuum drying oven
In dry under the conditions of 100 degree, the sample of drying screens out≤100 microns of particle, calculates ratio after weighing.
Embodiment 5-7 implements the polyphenylene oxide suspension of 1-3 same batch using comparison respectively, and every 10min detection is primary, inspection
Rope the results are shown in Table 3 data.
Table 3: continuous pressure filtration washing methods result
Although table 3 the result is that every 10 minutes primary from discharge port detection, the place that practical filter cake is dried up by filtering cleaning
Setting the time is usually less than 10 minutes, and generally at 0.5-5 minutes, this and rotary drum revolving speed, rotary drum radius size are related.
In embodiment 5-7, filter cake is completely filtered, washed and dries up the time of circulation in 1min or so by one.It can
See relative to comparative example 1-3, for embodiment 5-7 within the processing time of 1min or so, the toluene in filter cake can stablize control
System is below 9%.Meanwhile the Particle Breakage rate of the processing is low, fine particle (≤100 microns) increment rate controls below 2%.
Compared with comparative example 4, the toluene level of comparative example 4 by dispersion cleaning twice, control 10% with
It is interior, but micro mist rate is up to 20%-26%, and the micro mist rate of embodiment 5-7 is controlled 14% hereinafter, effect is obvious.
Claims (10)
1. a kind of preparation method of polyphenylene oxide, which is characterized in that including following processes:
Polymerization process, comprising molten selected from least one of the group being made of benzene,toluene,xylene and ethylbenzene aromatic system
In the polymeric solution of agent, phenol system compound and catalyst, makes the phenol system compound oxidation polymerization, obtain polyphenylene oxide mixed liquor；
Be precipitated process, in the polyphenylene oxide mixed liquor addition selected from by carbon atom number be 1~10 ketone, carbon atom number 1
At least one of~10 group of alcohols and water composition polar solvent, is precipitated polyphenylene oxide, obtains granular comprising polyphenylene oxide
The slurry liquid of object；
Solid-liquid separation process is separated by solid-liquid separation the slurry liquid, obtains polyphenylene oxide filter cake, which uses and pressurizeed
Filtering method；
Cleaning process carries out spray to the filter cake that solid-liquid separation process obtains with cleaning solution and cleans, while by the cleaning after spray
Liquid is removed；
Drying process makes the polyphenylene oxide filtration cakes torrefaction.
2. preparation method as described in claim 1, which is characterized in that described in the pressure filtration of the solid-liquid separation process
Pressure is 1.2-10bar, preferably 2-6bar, more preferably 2.5-5bar.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the polyphenylene oxide filter cake with a thickness of 10-200mm,
More preferably 10-100mm, particularly preferred 10-50mm.
4. preparation method as described in any one of claims 1-3, which is characterized in that cleaning solution dosage is polyphenylene oxide filter cake weight
0.1-80 times, preferably 1-10 times；
It is preferred that cleaning solution temperature is 30-60 DEG C, preferably 35-50 DEG C；
It is preferred that using pressurization washing, pressure 1.2-10bar, preferably 2-6bar, more preferably 2.5-5bar when cleaning.
5. preparation method according to any one of claims 1-4, which is characterized in that the cleaning solution is polar solvent, described
Polar solvent be selected from be 1~10 by carbon atom number ketone, carbon atom number be 1~10 alcohols and the group that forms of water in
At least one polar solvent；Alternatively, the cleaning solution is mixed solvent, it is made of by being selected from benzene,toluene,xylene and ethylbenzene
At least one of group aromatic system solvent, with selected from be 1~10 by carbon atom number ketone, carbon atom number be 1~10
At least one of the group of alcohols and water composition polar solvent, the mixed solvent of composition；
It is preferred that the content of the in the mixed solvent aromatic system solvent is 0.5 mass of mass %~18.0 %, polar solvent contains
Amount is 82.0 mass of mass %~99.5 %；The content of more preferable aromatic system solvent is 3.5 mass of mass %~10 %, polarity
The content of solvent is 90 mass of mass %~96.5 %；The content of further preferred aromatic system solvent is 5.5 mass %~9.0
Quality %, polar solvent content be 91 mass of mass %~94.5 %；
It is preferred that the polar solvent is methanol；
It is preferred that the aromatic system solvent is toluene.
6. preparation method as described in any one in claim 1-5, which is characterized in that the cleaning process uses 2-8 times or 2-8
Stage countercurrent washing, more preferably 3-5 times or the washing of 3-5 stage countercurrent.
7. preparation method as claimed in any one of claims 1 to 6, which is characterized in that before the drying process, using pre-
Drying steps remove filter cake surface solvent；
It is preferable to use inert gas purge mode predryings；
It is preferred that predrying gas temperature is 1-200 DEG C；
It is preferred that the dosage of inert gas is 0.01-50Nm3/ Kg polyphenylene oxide filter cake, preferably 0.3-10Nm3/ Kg polyphenylene oxide filter cake, more
It is preferred that 0.5-5.0Nm3/ Kg polyphenylene oxide filter cake.
8. preparation method as claimed in claim 7, which is characterized in that the solid-liquid separation process, cleaning process and predrying
Process is continuous and sequence carries out；
It is preferred that solid-liquid separation process, cleaning process and predry drying process carry out in a unit；
It is preferred that the equipment is selected from rotary drum filter press, filter with rotating disk, horizontal belt filter.
9. preparation method as claimed in claim 8, which is characterized in that the rotary drum pressure filter surface layout lautertuns, filtering
Slot is separated into fed filtration area, scrubbing section, predrying area and discharge zone with isolation board, has a shell outside rotary drum, on shell
It is spaced each other a distance and opens up slurry import, cleaning solution import, predrying gas feed and scraper plate；The isolation board peace
Mounted in drum surface, or shell is mounted on towards on the inner surface of drum surface；
It is preferred that providing pressure in rotor cover, keep solid-liquid separation process, cleaning process and predry drying process all complete under elevated pressure
At pressure 1.2-10bar, preferably 2-6bar.
10. preparation method as claimed in claim 9, which is characterized in that the washing amount of cleaning solution is 0.1-80Kg/Kg filter cake,
It is preferred that 1-10Kg/Kg filter cake；
It is preferred that predrying purging inert gas dosage is 0.01-50Nm3/ Kg filter cake, preferably 0.3-10Nm3/ Kg filter cake.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281780A (en) * | 1999-03-31 | 2000-10-10 | Mitsubishi Gas Chem Co Inc | Production of polyphenylene ether excellent in melt flowability |
| CN102432864A (en) * | 2011-08-31 | 2012-05-02 | 蓝星化工新材料股份有限公司 | Method for reducing content of quinine in polyphenyl ether product and recovering biphenyl diquinone |
| CN104744686A (en) * | 2015-04-16 | 2015-07-01 | 腾辉电子（苏州）有限公司 | Method for separating out polyphenyl ether from polyphenyl ether solution |
| CN107236124A (en) * | 2016-03-28 | 2017-10-10 | 旭化成株式会社 | The manufacture method of polyphenylene oxide |
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2018
- 2018-01-26 CN CN201810079557.7A patent/CN110078912B/en active Active
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|---|---|---|---|---|
| JP2000281780A (en) * | 1999-03-31 | 2000-10-10 | Mitsubishi Gas Chem Co Inc | Production of polyphenylene ether excellent in melt flowability |
| CN102432864A (en) * | 2011-08-31 | 2012-05-02 | 蓝星化工新材料股份有限公司 | Method for reducing content of quinine in polyphenyl ether product and recovering biphenyl diquinone |
| CN104744686A (en) * | 2015-04-16 | 2015-07-01 | 腾辉电子（苏州）有限公司 | Method for separating out polyphenyl ether from polyphenyl ether solution |
| CN107236124A (en) * | 2016-03-28 | 2017-10-10 | 旭化成株式会社 | The manufacture method of polyphenylene oxide |
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