CN107353401A - A kind of double hydroxyl polyphenylene oxide and preparation method thereof - Google Patents
A kind of double hydroxyl polyphenylene oxide and preparation method thereof Download PDFInfo
- Publication number
- CN107353401A CN107353401A CN201710733606.XA CN201710733606A CN107353401A CN 107353401 A CN107353401 A CN 107353401A CN 201710733606 A CN201710733606 A CN 201710733606A CN 107353401 A CN107353401 A CN 107353401A
- Authority
- CN
- China
- Prior art keywords
- alternatively
- polyphenylene oxide
- acid
- double hydroxyl
- preparation
- 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.)
- Granted
Links
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
Abstract
The invention provides a kind of double hydroxyl polyphenylene oxide and preparation method thereof, the preparation method of hydroxyl polyphenylene oxide of the invention double is included in the reaction solution being made up of solvent, metal salt, amines be passed through oxygen-containing gas oxidative coupling monomeric products after, terminating reaction, obtain double hydroxyl polyphenylene oxide；The preparation method technological operation of double hydroxyl polyphenylene oxide of the invention is simple, and production cost is low, production efficiency is high, disclosure satisfy that the industrialization production requirements of the double hydroxyl polyphenylene oxide of low molecule amount.Double hydroxyl polyphenyl ether product molecular weight of the invention are low, and molecular weight control is stable, and even molecular weight distribution, good with the other matrix resin compatibilities of PCB, reactivity worth is excellent, is the desired matrix resin for preparing high-frequency copper-clad plate.
Description
Technical field
The present invention relates to polyphenylene oxide preparing technical field, in particular to a kind of double hydroxyl polyphenylene oxide and its preparation side
Method.
Background technology
With developing rapidly for information industry, higher requirement is proposed with matrix resin to copper-clad plate, it is desirable to which it has
Low-k, low-dielectric loss, high glass-transition temperature, high-fire resistance and low water absorption etc..In copper-clad plate manufacturing industry
Most widely used matrix resin is epoxy resin, because in applied at elevated temperature, dimensional stability is bad, the dielectric in high-frequency range
Constant is too high, can not meet the needs of technology development.There is polyphenylene oxide resin good combination property, particularly high-vitrification to turn
Temperature and excellent dielectric properties are the preferable alternative materials of high performance copper clad laminate base material.
Although the blending and modifying of high-molecular-weight poly phenylate and epoxy resin can improve the toughness of epoxy resin, its Jie is improved
Electrical property, it can also improve the resistance to halogenated hydrocarbons of polyphenylene oxide and aromatic hydrocarbon equal solvent difference and the defects of film forming difference, but due to high score
Son amount polyphenylene oxide has very big difference with epoxy resin in chemical constitution and performance, causes the two poor compatibility, occurs after solidification
Phenomenon of phase separation, so conventional polymer amount polyphenylene oxide uses as copper-clad plate matrix resin has larger difficulty.
Compared with general high-molecular-weight poly phenylate, the double hydroxyl polyphenylene oxide of low molecule amount are except keeping polyphenylene oxide original excellent
It is benign can be outer, also with viscosity is low, good fluidity, have the advantages that good compatibility with many resins, in glass transition temperature
Good hot property is still kept, suitable for the addition of the matrix resin or other high polymer materials of the composites such as high-frequency circuit board
Component.
The double hydroxyl polyphenylene oxide of low molecule amount are prepared using reassignment method in correlation technique, are to utilize high-molecular-weight poly phenylate
The chain rupture in the presence of peroxide initiator, the small molecule polyphenylene oxide with free radical is formed, then combined with polyphenolic substance
The double hydroxyl polyphenylene oxide of low molecule amount are generated, this method accessory substance is more, and substantial amounts of initiator is added in preparation process, easily exists
There are a certain amount of remaining, intractability high in final products, it is difficult to prepare the product of high-purity；And this method CT Cycle Time
Length, waste discharge amount are big, it is difficult to meet industrialized production.The double hydroxyls of low molecule amount are prepared using oxidative coupling process in correlation technique
Polyphenylene oxide, used raw material tetramethyl Bisphenol F, tetrabromobisphenol A, bisphenol-A and bisphenol b be not because solubility is in reaction system
Reactivity between height, with 2,6- xylenols is low, and biphenol monomer is remaining more in products obtained therefrom and is not readily separated and causes
Product purity is not high, it is difficult to meets requirement.In addition, directly using bisphenol-A monomer as former in correlation technique
Material prepares double hydroxyl polyphenylene oxide by oxidative coupling, because bisphenol-A monomer commercialized degree is low and expensive makes
It is higher to obtain production cost, reduces the competitiveness of product in market, therefore be not suitable for large batch of commercially produce.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of double hydroxyl polyphenylene oxide, and this method can overcome existing
Technical disadvantages, technological operation is simple, and production cost is low, production efficiency is high, disclosure satisfy that the work of the double hydroxyl polyphenylene oxide of low molecule amount
Industry production requirement.
The second object of the present invention is that providing a kind of preparation method using above-mentioned double hydroxyl polyphenylene oxide is prepared
Double hydroxyl polyphenyl ether products, described double hydroxyl polyphenyl ether product molecular weight are low, and molecular weight control is stable, and molecular weight distribution is equal
Even, good with the other matrix resin compatibilities of PCB, reactivity worth is excellent, is the desired matrix resin for preparing high-frequency copper-clad plate.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of double hydroxyl polyphenylene oxide, it is anti-that single phenol, toluene, carbonyls and catalyst are subjected to monomer
Should, gained monomeric products are neutralized, after precipitation and dehydration, mixs with solvent, metal salt and amines and form mixed solution, logical
Enter oxygen-containing gas, carry out polymerisation, terminator is added after the completion of reaction, then again by separation, gained organic phase is by de-
Double hydroxyl polyphenylene oxide are obtained after molten.
The preparation method of double hydroxyl polyphenylene oxide of the invention is included in the reaction solution being made up of solvent, metal salt, amines
In be passed through oxygen-containing gas oxidative coupling monomeric products after, terminating reaction, obtain double hydroxyl polyphenylene oxide；Double hydroxyl polyphenylene oxide of the invention
Preparation method technological operation it is simple, production cost is low, production efficiency is high, disclosure satisfy that the work of the double hydroxyl polyphenylene oxide of low molecule amount
Industry production requirement.
Alternatively, one or more of the single phenol in phenol and alkylphenol, are preferably selected from 2,6- xylenols, 2,
3- xylenols, 2,5- xylenols, 3,5- xylenols phenol, orthoresol, metacresol, 2,3,6- pseudocuminols, 2,3,5- front threes
One or more in base phenol and phenol, more preferably 2,6- xylenols.
Alternatively, one or more of the carbonyls in assimilation compound and aldehyde compound, are preferably selected from third
One or more in ketone, acetylacetone,2,4-pentanedione, 2- butanone, 1,3-DCA, chlroacetone, formaldehyde, acetaldehyde, propionic aldehyde and butyraldehyde, enter
One step is preferably acetone.
Alternatively, the catalyst is acid catalyst, is preferably selected from the concentrated sulfuric acid, hydrochloric acid, HCL gases, pyrovinic acid, trifluoro
One or more in pyrovinic acid, polysiloxane sulfonate resin and sulfonated polystyrene-divinylbenzene sulfonate resin, enter
One step is preferably selected from pyrovinic acid and/or sulfonated polystyrene-divinylbenzene sulfonate resin.
Alternatively, the mol ratio of single phenol and carbonyls is 1:1-30:1, preferably 2:1-25:1, it is further excellent
Elect 4 as:1-20:1.
Alternatively, the mass ratio of single phenol and acid catalyst is 1:1-15:1, preferably 2:1-10:1, further preferably
For 2:1-6:1.
Alternatively, the mass ratio of the toluene and single phenol is 0.01:1-4:1, preferably 0.2:1-2:1, further preferably
For 0.5:1-1:1.
Alternatively, the reaction temperature of the monomer reaction is 20-90 DEG C, preferably 40-70 DEG C, more preferably 50-
60℃。
Alternatively, the time of the monomer reaction is 6-24h, preferably 6-12h, further preferred 8-10h.
Alternatively, one or more of the nertralizer of the neutralization in inorganic base, sodium carbonate, bicarbonate are preferably selected from
One or more in sodium, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammoniacal liquor, ammonium carbonate and ammonium hydrogen carbonate, further preferably
Selected from sodium carbonate and/or sodium hydroxide.
Alternatively, the monomeric products after the neutralization, are washed and carry out precipitation again.
Alternatively, the mode of washing is online washing.
Alternatively, the mol ratio of single phenol and bis-phenol is 1 in the monomeric products:1-100:1, preferably 2:1-16:1, enter
One step is preferably 2:1-10:1.
Alternatively, one or more of the solvent in organic solvent, chloroform, toluene, benzene and diformazan are preferably selected from
One or more in benzene, preferably toluene.
Alternatively, the metal salt is the mixture of Cu oxide and acid solution, and preferably cuprous oxide and hydrogen bromide is molten
The mixture of liquid.
Alternatively, in the mixture of the cuprous oxide and hydrogen bromide solution, the molal quantity of bromine atoms is copper atom mole
Several more than 2 times, preferably more than 4 times.
Alternatively, the amines is in unitary secondary amine compound, unitary tertiary amine compound and diamine compound
One or more.
Alternatively, the unitary secondary amine is selected from dimethyl amine, diethylamide, di-n-butyl amine, di-t-butyl amine, and two positive third
One or more in base amine and morpholine, it is preferably selected from di-n-butyl amine and/or morpholine.
Alternatively, the unitary tertiary amine compound is selected from Trimethylamine, triethylamine, tripropylamine, tri-butylamine, diformazan
Base ethylamine, the preferably one or more in dimethyl propyl amine and dimethyl-n-butylamine, dimethyl n butylamine.
Alternatively, the diamine compound has the structure that general formula (1) represents：
R1R2NR5NR3R4 (1)
Wherein R1、R2、R3And R4The one kind being each independently selected from hydrogen or C1-C6 straight chained alkyls or branched alkyl, and R1、
R2、R3And R4It is asynchronously hydrogen, R5One kind in C2-C5 straight-chain alkyl-subs or branched alkylidene.
The diamine compound is preferably N, N, N', N'- tetramethyl -1,3- propane diamine and/or N, N'- di-t-butyl second two
Amine, more preferably N, N'- di-t-butyl ethylenediamines.
Alternatively, in the amines molal quantity of nitrogen-atoms be in metal salt 20 times of metallic atom molal quantity with
On, preferably more than 25 times.
Alternatively, the reaction temperature of the polymerisation is less than 90 DEG C, preferably less than 70 DEG C, more preferably 50
Below DEG C.
Alternatively, the reaction time of the polymerisation is 1-6h, preferably 2-5h, more preferably 3-4h.
Alternatively, the feed postition of the solvent, metal salt and amines is：The same of nitrogen is being passed through into reactor
When add solvent, open stirring, and sequentially add amines and metal salt.
Alternatively, the terminator is the aqueous solution containing complexing agent.
Alternatively, it is sub- to be selected from citric acid, citrate, disodium edta, ethylene diamine four for the complexing agent
Methylphosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, hydroxyethylethylene diamine tri-acetic acid, diethylene triamine pentacetic acid (DTPA), nitrilotriacetic acid and the second of ammonia three
One or more in hydrochlorate, preferably citric acid and/or nitrilotriacetic acid trisodium salt salt, more preferably citric acid.
Alternatively, the molecule molal quantity of the complexing agent is more than 2 times of metallic atom molal quantity in metal salt.
Alternatively, the addition terminator, by gained polyser mixture temperature control to more than 75 DEG C, is held after reaction terminating
Continuous stirring 30-120min.
Alternatively, the separation method therefor is selected from Liquid liquid Separation machine and separates and/or stand split-phase.
Alternatively, gained organic phase is washed after the separation and carries out precipitation again.
Alternatively, the mode of washing is online washing.
Alternatively, the one kind or more of the precipitation device therefor in distillation still, thin film evaporator and devolatilization extruder
Kind, it is preferably selected from distillation still and devolatilization extruder joint precipitation.
Alternatively, the precipitation pressure of the precipitation is below -1KPa, and precipitation temperature is 100-300 DEG C, and extrusion temperature is
200-300℃。
The double hydroxyl polyphenyl ether products being prepared using a kind of preparation method of above-mentioned double hydroxyl polyphenylene oxide.
Hydroxyl polyphenyl ether product molecular weight of the invention double are low, and molecular weight control is stable, even molecular weight distribution, with PCB its
Its matrix resin compatibility is good, and reactivity worth is excellent, is the desired matrix resin for preparing high-frequency copper-clad plate.
Alternatively, the number-average molecular weight of double hydroxyl polyphenylene oxide is 800-5000.
Compared with prior art, beneficial effects of the present invention are：
The preparation method of double hydroxyl polyphenylene oxide of the invention is included in the reaction solution being made up of solvent, metal salt, amines
In be passed through oxygen-containing gas oxidative coupling monomeric products after, terminating reaction, obtain double hydroxyl polyphenylene oxide；Double hydroxyl polyphenylene oxide of the invention
Preparation method technological operation it is simple, production cost is low, production efficiency is high, disclosure satisfy that the work of the double hydroxyl polyphenylene oxide of low molecule amount
Industry production requirement.Double hydroxyl polyphenyl ether product molecular weight of the invention are low, and molecular weight control is stable, even molecular weight distribution, with
The other matrix resin compatibilities of PCB are good, and reactivity worth is excellent, are the desired matrix resins for preparing high-frequency copper-clad plate.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the process chart of the preparation method of double hydroxyl polyphenylene oxide in a kind of embodiment of the present invention.
Reference：
1- monomer reaction kettles；In 2- and kettle；3- phase separation tanks；
4- dehydrating towers；5- destilling towers；6- polymerization reaction kettles；
7- terminates kettle；8- Liquid liquid Separation machines；9- concentration tanks；
10- devolatilization extruders；11- condenses steel band；12- acetone storage tanks；
13- toluene and water storage tank；14- phenol storage tanks；15- toluene tanks；
16- raw material measuring pumps；17- phenol measuring pumps.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that following described embodiment is part of the embodiment of the present invention, it is rather than whole
Embodiment, the present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.Unreceipted actual conditions person in embodiment, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same
Or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
The specific embodiment of the invention provides a kind of preparation method of double hydroxyl polyphenylene oxide, by single phenol, toluene, carbonylation
Compound and catalyst carry out monomer reaction, and gained monomeric products are neutralized, after precipitation and dehydration, with solvent, metal salt and amination
Compound mixing forms mixed solution, is passed through oxygen-containing gas, carries out polymerisation, terminator is added after the completion of reaction, is then led to again
Separation is crossed, gained organic phase obtains double hydroxyl polyphenylene oxide after precipitation.
The preparation method of double hydroxyl polyphenylene oxide of the invention is included in the reaction solution being made up of solvent, metal salt, amines
In be passed through oxygen-containing gas oxidative coupling monomeric products after, terminating reaction, obtain double hydroxyl polyphenylene oxide；Double hydroxyl polyphenylene oxide of the invention
Preparation method technological operation it is simple, production cost is low, production efficiency is high, disclosure satisfy that the work of the double hydroxyl polyphenylene oxide of low molecule amount
Industry production requirement.
In a kind of preferred embodiment of the present invention, the one kind or more of single phenol in phenol and alkylphenol
Kind, 2,6- xylenols, 2,3- xylenols, 2,5- xylenols, 3,5- xylenols phenol, orthoresol, metacresol, 2,3 are preferably selected from,
One or more in 6- pseudocuminols, 2,3,5-TEP and phenol, more preferably 2,6- xylenols.
In a kind of preferred embodiment of the present invention, the carbonyls is in assimilation compound and aldehyde compound
One or more, be preferably selected from acetone, acetylacetone,2,4-pentanedione, 2- butanone, 1,3-DCA, chlroacetone, formaldehyde, acetaldehyde, propionic aldehyde
With the one or more in butyraldehyde, more preferably acetone.
In a kind of preferred embodiment of the present invention, the catalyst is acid catalyst, is preferably selected from the concentrated sulfuric acid, salt
Acid, HCL gases, pyrovinic acid, trifluoromethane sulfonic acid, polysiloxane sulfonate resin and sulfonated polystyrene-divinylbenzene
One or more in sulfonate resin, further preferably it is selected from pyrovinic acid and/or sulfonated polystyrene-divinylbenzene sulfonic acid tree
Fat.
Different reactants is selected, helps to obtain different types of double hydroxyl polyphenylene oxide, meets commercial Application requirement.
In a kind of preferred embodiment of the present invention, the mol ratio of single phenol and carbonyls is 1:1-30:
1, preferably 2:1-25:1, more preferably 4:1-20:1.
In a kind of preferred embodiment of the present invention, the mass ratio of single phenol and acid catalyst is 1:1-15:1,
Preferably 2:1-10:1, more preferably 2:1-6:1.
In a kind of preferred embodiment of the present invention, the mass ratio of the toluene and single phenol is 0.01:1-4:1, it is excellent
Elect 0.2 as:1-2:1, more preferably 0.5:1-1:1.
Using specific reactant usage ratio, help lend some impetus to reaction and fully carry out, reduce by-products content, improve institute
Obtain the purity of double hydroxyl polyphenylene oxide in product.
In a kind of preferred embodiment of the present invention, the reaction temperature of the monomer reaction is 20-90 DEG C, is preferably
40-70 DEG C, more preferably 50-60 DEG C.
In a kind of preferred embodiment of the present invention, time of the monomer reaction is 6-24h, preferably 6-12h,
Further preferred 8-10h.
Using special reaction condition, help lend some impetus to reaction and fully carry out, reduce by-products content, improve in products obtained therefrom
The purity of double hydroxyl polyphenylene oxide.
In a kind of preferred embodiment of the present invention, the one kind or more of the nertralizer of the neutralization in inorganic base
Kind, it is preferably selected from sodium carbonate, sodium acid carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammoniacal liquor, ammonium carbonate and ammonium hydrogen carbonate
One or more, be further preferably selected from sodium carbonate and/or sodium hydroxide.
In a kind of preferred embodiment of the present invention, the monomeric products after the neutralization, are washed and taken off again
It is molten.
In a kind of preferred embodiment of the present invention, the mode of washing is online washing.
In a kind of preferred embodiment of the present invention, the mol ratio of single phenol and bis-phenol is 1 in the monomeric products:1-
100:1, preferably 2:1-16:1, more preferably 2:1-10:1.
Single phenol and bis-phenol are included in monomeric products of the present invention, when carrying out monomer reaction, the part in single phenol can react
Bis-phenol is obtained, avoids direct commodity in use degree low and expensive biphenol monomer, subsequent polymerisation reaction can ensured
In the case of fully carrying out, production cost is effectively reduced, is adapted to large batch of commercially produce.
In a kind of preferred embodiment of the present invention, one or more of the solvent in organic solvent are excellent
Select the one or more in chloroform, toluene, benzene and dimethylbenzene, preferably toluene.
In a kind of preferred embodiment of the present invention, the metal salt is the mixture of Cu oxide and acid solution,
The preferably mixture of cuprous oxide and hydrogen bromide solution.For metal salt in the specific embodiment of the invention in the preparation, it is
Mixed in a vessel in inert nitrogen gas atmosphere for 48% aqueous solution by cuprous oxide and with hydrogen bromide mass fraction
Close.
Although being had no particular limits to the amount of cuprous oxide and hydrogen bromide, a kind of preferred embodiment of the present invention
In, in the mixture of the cuprous oxide and hydrogen bromide solution, the molal quantity of bromine atoms is more than 2 times of copper atom molal quantity,
Preferably more than 4 times.
In a kind of preferred embodiment of the present invention, the amines is selected from unitary secondary amine compound, unitary
One or more in tertiary amine compound and diamine compound.
In a kind of preferred embodiment of the present invention, the unitary secondary amine is selected from dimethyl amine, and diethylamide, two just
Butylamine, di-t-butyl amine, the one or more in di-n-propyl amine and morpholine, it is preferably selected from di-n-butyl amine and/or morpholine.
In a kind of preferred embodiment of the present invention, the unitary tertiary amine compound is selected from Trimethylamine, triethyl group
Amine, tripropylamine, tri-butylamine, dimethylethyl amine, the one or more in dimethyl propyl amine and dimethyl-n-butylamine,
Preferably dimethyl n butylamine.
In a kind of preferred embodiment of the present invention, the diamine compound has the knot that general formula (1) represents
Structure：
R1R2NR5NR3R4 (1)
Wherein R1、R2、R3And R4The one kind being each independently selected from hydrogen or C1-C6 straight chained alkyls or branched alkyl, and R1、
R2、R3And R4It is asynchronously hydrogen, R5One kind in C2-C5 straight-chain alkyl-subs or branched alkylidene.
The diamine compound is preferably N, N, N', N'- tetramethyl -1,3- propane diamine and/or N, N'- di-t-butyl second two
Amine, more preferably N, N'- di-t-butyl ethylenediamines.
It is described in a kind of preferred embodiment of the present invention although being had no particular limits to the amount of amines
The molal quantity of nitrogen-atoms is more than 20 times, preferably more than 25 times of metallic atom molal quantity in metal salt in amines.
Using special component and the metal salt and amines of dosage composition catalyst, filling for polymerisation is helped lend some impetus to
Divide and carry out, reduce by-products content, improve the purity of double hydroxyl polyphenylene oxide in products obtained therefrom.
In a kind of preferred embodiment of the present invention, the reaction temperature of the polymerisation is less than 90 DEG C, preferably
For less than 70 DEG C, more preferably less than 50 DEG C.
In a kind of preferred embodiment of the present invention, the reaction time of the polymerisation is 1-6h, preferably 2-
5h, more preferably 3-4h.
Using special reaction condition, help lend some impetus to reaction and fully carry out, reduce by-products content, improve in products obtained therefrom
The purity of double hydroxyl polyphenylene oxide.
Preparation method for catalyst in the present invention is extremely important, in a kind of preferred embodiment of the present invention,
The feed postition of the solvent, metal salt and amines is：Solvent is added while nitrogen is passed through into reactor, is opened
Stirring, and sequentially add amines and metal salt.Under conditions of having nitrogen and stirring, a small amount of oxygen is passed through from reactor bottom
Gas, the preparation process of catalyst is completed after leading to the oxygen time not less than ten minutes.
In a kind of preferred embodiment of the present invention, the terminator is the aqueous solution containing complexing agent.
In a kind of preferred embodiment of the present invention, the complexing agent is selected from citric acid, citrate, ethylenediamine tetraacetic
Acetic acid sodium salt, ethylenediaminetetramethylene phosphonic acids, 1-hydroxy ethylidene-1,1-diphosphonic acid, hydroxyethylethylene diamine tri-acetic acid, diethylenetriamine
One or more in pentaacetic acid, nitrilotriacetic acid and nitrilotriacetic acid salt, preferably citric acid and/or nitrilotriacetic acid trisodium salt salt, enter
One step is preferably citric acid.
Although being had no particular limits to the amount of complexing agent, in a kind of preferred embodiment of the present invention, the network
The molecule molal quantity of mixture is more than 2 times of metallic atom molal quantity in metal salt.
In a kind of preferred embodiment of the present invention, the addition terminator is by after reaction terminating, by gained polyphenyl
Ether mixture temperature control persistently stirs 30-120min to more than 75 DEG C.Purpose is to ensure the accessory substance biphenyl in stage of reaction generation
Diquinone can sufficiently be reacted with polyphenylene oxide, is improved product yield and is reduced the content of biphenyl diquinone in product.
In a kind of preferred embodiment of the present invention, the separation method therefor be selected from the separation of Liquid liquid Separation machine and/
Or stand split-phase.
In a kind of preferred embodiment of the present invention, gained organic phase is washed after the separation and taken off again
It is molten.
In a kind of preferred embodiment of the present invention, the mode of washing is online washing.
In a kind of preferred embodiment of the present invention, the precipitation device therefor is selected from distillation still, thin film evaporator
With the one or more in devolatilization extruder, distillation still and devolatilization extruder joint precipitation are preferably selected from.
In a kind of preferred embodiment of the present invention, the precipitation pressure of the precipitation is below -1KPa, precipitation temperature
For 100-300 DEG C, extrusion temperature is 200-300 DEG C.
The double hydroxyl polyphenyl ether products being prepared using a kind of preparation method of above-mentioned double hydroxyl polyphenylene oxide.
Hydroxyl polyphenyl ether product molecular weight of the invention double are low, and molecular weight control is stable, even molecular weight distribution, with PCB its
Its matrix resin compatibility is good, and reactivity worth is excellent, is the desired matrix resin for preparing high-frequency copper-clad plate.
In a kind of preferred embodiment of the present invention, the number-average molecular weight of double hydroxyl polyphenylene oxide is 800-
5000。
Embodiment 1
A kind of preparation method of double hydroxyl polyphenylene oxide, comprises the following steps：
1. prepared by monomer：In 1200g 2,6- xylenols, 1200g toluene and 300g sulfonated polystyrenes-divinylbenzene sulphur
Acid resin is fitted into 5000mL monomer reactions kettle 1, opens and stirs and after being warming up to 70 DEG C, with raw material measuring pump 16 by 142.6g third
Ketone is added to reactor 1, adds time 80min, after acetone adds timing start, reaction solution moves after filtering after 480min
To neutralizing in kettle 2, split-phase is moved into neutralizing to add in kettle 2 after the sodium carbonate liquor that 100g mass fractions are 20% stirs 10min
Tank 3, light phase is distilled into destilling tower 5 after split-phase, and tower top material enters acetone storage tank 12 after cooling, and materials at bottom of tower enters
Toluene is further processed with water storage tank 13；The heavy phase of phase separation tank 3, which enters after dehydrating tower 4 is dehydrated, enters phenol storage tank 14 for polymerizeing instead
Should.
2. prepared by pair hydroxyl polyphenylene oxide：2750g toluene is added in the polymerization reaction kettle 6 of the 5000mL with EGR
And nitrogen is passed through, stirring is opened, adds the compound amine aqueous solutions of 45g and 13g cuprous bromide solutions after 2 minutes into reactor respectively,
Mixing speed is lifted, oxygen is passed through from reactor bottom.After 10 minutes, with phenol measuring pump 17 by 1000g 2,6- xylenols
Polymerization reaction kettle 6, oxygen flow and 2,6- dimethyl are added to out of phenol storage tank 1460min with the mixed liquor of bisphenol-A
The mol ratio of phenol flow is not less than 1:1, reaction temperature is 35 DEG C.Phenol mixed liquor continues logical oxygen 180min after all adding
Afterwards by material move into terminate kettle 7 in, add the citric acid containing 10g aqueous solution terminating reaction and temperature control to 75 DEG C, continue to stir
1.0h.Polymerization liquid is separated by Liquid liquid Separation machine 8, and oil phase enters concentration tank 9 and sloughs part toluene, and the cooling of toluene gas phase is laggard
Enter toluene tank 15, it is 80% that material, which is concentrated into solid content, and concentrate is extruded into the devolatilization of devolatilization extruder 10, precipitation pressure
For below -1KPa, precipitation temperature is 200 DEG C, and extrusion temperature is 250 DEG C, and toluene gas enters toluene tank 15 after cooling, extrusion
The condensed steel band 11 of material is cooled down, and the double hydroxyl polyphenyl ether products of low molecule are obtained after crushing.Experimental result is listed in Table 1.
Embodiment 2
Method according to embodiment 1 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that toluene is used in prepared by monomer
Measure as 4800g, acid catalyst levels 1200g, acetone dosage is 570.4g, and monomer reaction temperature is 20 DEG C, during monomer reaction
Between be 24h, the reaction temperature of polymerisation is 90 DEG C, and reaction time of polymerisation is 1h, after terminating reaction temperature control to 90 DEG C,
30min is persistently stirred, precipitation temperature is 100 DEG C, and extrusion temperature is 200 DEG C.Experimental result is listed in Table 1.
Embodiment 3
Method according to embodiment 1 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that toluene is used in prepared by monomer
Measure as 12g, acid catalyst levels 80g, acetone dosage is 285.2g, and monomer reaction temperature is 90 DEG C, and the monomer reaction time is
6h, the reaction temperature of polymerisation are 70 DEG C, and reaction time of polymerisation is 3h, after terminating reaction temperature control to more than 80 DEG C,
90min is persistently stirred, precipitation temperature is 300 DEG C, and extrusion temperature is 300 DEG C.Experimental result is listed in Table 1.
Embodiment 4
Method according to embodiment 2 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that toluene is used in prepared by monomer
Measure as 240g, acid catalyst levels 600g, acetone dosage is 71.3g, and monomer reaction temperature is 40 DEG C, and the monomer reaction time is
12h, the reaction temperature of polymerisation are 80 DEG C, and reaction time of polymerisation be 2h, and temperature control is to 75 DEG C after terminating reaction, persistently
Stir 120min.Experimental result is listed in Table 1.
Embodiment 5
Method according to embodiment 4 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that toluene is used in prepared by monomer
It is 28.5g to measure as 2400g, acid catalyst levels 200g, acetone dosage, and monomer reaction temperature is 70 DEG C, the monomer reaction time
For 6h, the reaction temperature of polymerisation is 60 DEG C, and the reaction time of polymerisation is 4h.Experimental result is listed in Table 1.
Embodiment 6
Method according to embodiment 2 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that acetone is used in prepared by monomer
It is 50 DEG C to measure as 19g, monomer reaction temperature, and the monomer reaction time is 10h, and the reaction temperature of polymerisation is 50 DEG C, and polymerization is anti-
The reaction time answered is 5h.Experimental result is listed in Table 1.
Embodiment 7
Method according to embodiment 4 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that acetone is used in prepared by monomer
It is 60 DEG C to measure as 22.8g, monomer reaction temperature, and the monomer reaction time is 8h, and the reaction temperature of polymerisation is 40 DEG C, and polymerization is anti-
The reaction time answered is 6h.Experimental result is listed in Table 1.
Embodiment 8
Method according to embodiment 5 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that acid catalysis in monomer preparation
Agent is pyrovinic acid, dosage 120g, neutralizes the aqueous solution 350g with 20% sodium carbonate.Experimental result is listed in Table 1.
Embodiment 9
Method according to embodiment 1 prepares the double hydroxyl polyphenylene oxide of low molecule amount, except that carbonyl used in monomer preparation
Based compound is chlroacetone, dosage 227.4g.Experimental result is listed in Table 1.
Table 1 is various embodiments of the present invention experimental result data, wherein the molecular weight and molecular weight distribution of double hydroxyl polyphenylene oxide
Determined using gel permeation chrommatograph, double hydroxyl polyphenylene oxide hydroxyl values are gathered using nuclear magnetic resonance phosphorus spectrum internal standard method, unit g/100g, double hydroxyls
The copper content of phenylate is determined using atomic absorption spectrophotometer, unit ppm.
The various embodiments of the present invention experimental result data of table 1
(note：Acid catalyst：A represents sulfonated polystyrene-divinylbenzene sulfonate resin；B represents pyrovinic acid.Single bis-phenol
Mass ratio refers to 2,6- xylenols and the mass ratio of bisphenol-A)
It can be seen from Table 1 that according to method provided by the invention, can be existed with relatively simple number-average molecular weight of preparing
The 800-5000 double hydroxyl polyphenylene oxide of low molecule amount, and technique is simple, workable, waste discharge amount is few, product yield is high
It is low with production cost, it can fully meet the commercialization requirement of industrial circle.In addition, the double hydroxyl polyphenylene oxide purity of the present invention are higher,
Raw material can fully polymerize to obtain product, and contained impurity is only a small amount of catalyst (copper content is in below 2.5ppm).
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than its limitations；It will be understood by those within the art that：Without departing substantially from this hair
In the case of bright spirit and scope, the technical scheme described in foregoing embodiments can be modified, or to wherein
Some or all of technical characteristic carries out equivalent substitution；And these are changed or are replaced, the essence of appropriate technical solution is not made
Depart from the scope of various embodiments of the present invention technical scheme；It is, therefore, intended that include belonging to the present invention in the following claims
In the range of all these substitutions and modifications.
Claims (10)
1. a kind of preparation method of double hydroxyl polyphenylene oxide, it is characterised in that enter single phenol, toluene, carbonyls and catalyst
Row monomer reaction, gained monomeric products are neutralized, after precipitation and dehydration, and it is mixed that composition is mixed with solvent, metal salt and amines
Solution is closed, is passed through oxygen-containing gas, polymerisation is carried out, terminator is added after the completion of reaction, it is then organic by separation, gained again
Double hydroxyl polyphenylene oxide are mutually obtained after precipitation.
2. the preparation method of a kind of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that single phenol is selected from benzene
One or more in phenol and alkylphenol, it is preferably selected from 2,6- xylenols, 2,3- xylenols, 2,5- xylenols, 3,5- diformazans
One or more in phenol phenol, orthoresol, metacresol, 2,3,6-TMP, 2,3,5-TEP and phenol, enter
One step is preferably 2,6- xylenols；
Alternatively, one or more of the carbonyls in assimilation compound and aldehyde compound, acetone, second are preferably selected from
One or more in acyl acetone, 2- butanone, 1,3-DCA, chlroacetone, formaldehyde, acetaldehyde, propionic aldehyde and butyraldehyde, it is further excellent
Elect acetone as；
Alternatively, the catalyst is acid catalyst, is preferably selected from the concentrated sulfuric acid, hydrochloric acid, HCL gases, pyrovinic acid, trifluoromethyl
One or more in sulfonic acid, polysiloxane sulfonate resin and sulfonated polystyrene-divinylbenzene sulfonate resin, further
It is preferably selected from pyrovinic acid and/or sulfonated polystyrene-divinylbenzene sulfonate resin.
3. the preparation method of a kind of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that single phenol and carbonyl
The mol ratio of compound is 1:1-30:1, preferably 2:1-25:1, more preferably 4:1-20:1；
Alternatively, the mass ratio of single phenol and acid catalyst is 1:1-15:1, preferably 2:1-10:1, more preferably 2:
1-6:1；
Alternatively, the mass ratio of the toluene and single phenol is 0.01:1-4:1, preferably 0.2:1-2:1, more preferably
0.5:1-1:1。
4. the preparation method of a kind of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that the monomer reaction
Reaction temperature is 20-90 DEG C, preferably 40-70 DEG C, more preferably 50-60 DEG C；
Alternatively, the time of the monomer reaction is 6-24h, preferably 6-12h, further preferred 8-10h.
A kind of 5. preparation method of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that the neutralization of the neutralization
One or more of the agent in inorganic base, are preferably selected from sodium carbonate, sodium acid carbonate, sodium hydroxide, potassium hydroxide, hydroxide
One or more in calcium, ammoniacal liquor, ammonium carbonate and ammonium hydrogen carbonate, further preferably it is selected from sodium carbonate and/or sodium hydroxide；
Alternatively, the monomeric products after the neutralization, are washed and carry out precipitation again；
Alternatively, the mode of washing is online washing.
6. the preparation method of a kind of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that in the monomeric products
The mol ratio of single phenol and bis-phenol is 1:1-100:1, preferably 2:1-16:1, more preferably 2:1-10:1；
Alternatively, one or more of the solvent in organic solvent, it is preferably selected from chloroform, toluene, benzene and dimethylbenzene
One or more, preferably toluene；
Alternatively, the metal salt is the mixture of Cu oxide and acid solution, preferably cuprous oxide and hydrogen bromide solution
Mixture；
Alternatively, in the mixture of the cuprous oxide and hydrogen bromide solution, the molal quantity of bromine atoms is the 2 of copper atom molal quantity
More than times, preferably more than 4 times；
Alternatively, the amines is one in unitary secondary amine compound, unitary tertiary amine compound and diamine compound
Kind is a variety of；
Alternatively, the unitary secondary amine is selected from dimethyl amine, diethylamide, di-n-butyl amine, di-t-butyl amine, di-n-propyl amine
With the one or more in morpholine, di-n-butyl amine and/or morpholine are preferably selected from；
Alternatively, the unitary tertiary amine compound is selected from Trimethylamine, triethylamine, tripropylamine, tri-butylamine, dimethyl second
Base amine, the preferably one or more in dimethyl propyl amine and dimethyl-n-butylamine, dimethyl n butylamine；
Alternatively, the diamine compound has the structure that general formula (1) represents：
R1R2NR5NR3R4 (1)
Wherein R1、R2、R3And R4The one kind being each independently selected from hydrogen or C1-C6 straight chained alkyls or branched alkyl, and R1、R2、R3
And R4It is asynchronously hydrogen, R5One kind in C2-C5 straight-chain alkyl-subs or branched alkylidene；
The diamine compound is preferably N, N, N', N'- tetramethyl-1,3-propane diamines and/or N, N'- di-t-butyl ethylenediamine,
More preferably N, N'- di-t-butyl ethylenediamine；
Alternatively, the molal quantity of nitrogen-atoms is more than 20 times of metallic atom molal quantity in metal salt in the amines, excellent
Elect more than 25 times as.
7. the preparation method of a kind of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that the polymerisation
Reaction temperature is less than 90 DEG C, preferably less than 70 DEG C, more preferably less than 50 DEG C；
Alternatively, the reaction time of the polymerisation is 1-6h, preferably 2-5h, more preferably 3-4h；
Alternatively, the feed postition of the solvent, metal salt and amines is：Add while nitrogen is passed through into reactor
Enter solvent, open stirring, and sequentially add amines and metal salt.
A kind of 8. preparation method of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that the terminator be containing
The aqueous solution of complexing agent；
Alternatively, the complexing agent is selected from citric acid, citrate, disodium edta, ethylenediaminetetramethylene
Phosphonic acids, 1-hydroxy ethylidene-1,1-diphosphonic acid, hydroxyethylethylene diamine tri-acetic acid, diethylene triamine pentacetic acid (DTPA), nitrilotriacetic acid and nitrilotriacetic acid salt
In one or more, preferably citric acid and/or nitrilotriacetic acid trisodium salt salt, more preferably citric acid；
Alternatively, the molecule molal quantity of the complexing agent is more than 2 times of metallic atom molal quantity in metal salt；
Alternatively, the addition terminator, by gained polyser mixture temperature control to more than 75 DEG C, persistently stirs after reaction terminating
Mix 30-120min；
Alternatively, the separation method therefor is selected from Liquid liquid Separation machine and separates and/or stand split-phase；
Alternatively, gained organic phase is washed after the separation and carries out precipitation again；
Alternatively, the mode of washing is online washing.
9. the preparation method of a kind of double hydroxyl polyphenylene oxide according to claim 1, it is characterised in that set used in the precipitation
Alternatively from the one or more in distillation still, thin film evaporator and devolatilization extruder, distillation still and devolatilization extruder are preferably selected from
Joint precipitation；
Alternatively, the precipitation pressure of the precipitation is below -1KPa, and precipitation temperature is 100-300 DEG C, extrusion temperature 200-
300℃。
10. the double hydroxyls being prepared using a kind of preparation method of any described double hydroxyl polyphenylene oxide of claim 1-9 are gathered
Phenylate product；
Alternatively, the number-average molecular weight of double hydroxyl polyphenylene oxide is 800-5000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710733606.XA CN107353401B (en) | 2017-08-24 | 2017-08-24 | Dihydroxy polyphenyl ether and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710733606.XA CN107353401B (en) | 2017-08-24 | 2017-08-24 | Dihydroxy polyphenyl ether and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107353401A true CN107353401A (en) | 2017-11-17 |
| CN107353401B CN107353401B (en) | 2020-06-30 |
Family
ID=60288394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710733606.XA Active CN107353401B (en) | 2017-08-24 | 2017-08-24 | Dihydroxy polyphenyl ether and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107353401B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371932A (en) * | 2017-12-29 | 2018-08-07 | 安丽华 | A kind of reaction system and method preparing small-molecular-weight polyphenylene oxide |
| CN110387037A (en) * | 2018-04-19 | 2019-10-29 | 旭化成株式会社 | Polyphenylene oxide and its manufacturing method |
| CN110628013A (en) * | 2019-08-28 | 2019-12-31 | 河北健馨生物科技有限公司 | Bifunctional phosphorus-containing polyphenylene ether, and preparation method and application thereof |
| CN111440311A (en) * | 2020-05-06 | 2020-07-24 | 李同军 | Technological method for producing polyphenyl ether |
| CN113698591A (en) * | 2021-08-17 | 2021-11-26 | 陕西硕博电子材料有限公司 | Preparation method of low-molecular-weight hydroxyl-terminated polyphenyl ether by one-pot method |
| CN114349955A (en) * | 2021-06-18 | 2022-04-15 | 山东圣泉新材料股份有限公司 | Polyfunctional poly (arylene ether) resin and preparation method thereof |
| CN115894197A (en) * | 2022-12-06 | 2023-04-04 | 湖南久日新材料有限公司 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816583A (en) * | 2003-07-02 | 2006-08-09 | 三菱瓦斯化学株式会社 | Process for production of bifunctional phenylene ether oligomers |
| CN101305030A (en) * | 2005-11-10 | 2008-11-12 | 通用电气公司 | Polyfunctional poly(arylene ether) method |
| CN102516532A (en) * | 2011-12-27 | 2012-06-27 | 四川东材科技集团股份有限公司 | Preparation method for amination polyphenyl ether |
-
2017
- 2017-08-24 CN CN201710733606.XA patent/CN107353401B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816583A (en) * | 2003-07-02 | 2006-08-09 | 三菱瓦斯化学株式会社 | Process for production of bifunctional phenylene ether oligomers |
| CN101305030A (en) * | 2005-11-10 | 2008-11-12 | 通用电气公司 | Polyfunctional poly(arylene ether) method |
| CN102516532A (en) * | 2011-12-27 | 2012-06-27 | 四川东材科技集团股份有限公司 | Preparation method for amination polyphenyl ether |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108371932A (en) * | 2017-12-29 | 2018-08-07 | 安丽华 | A kind of reaction system and method preparing small-molecular-weight polyphenylene oxide |
| CN110387037A (en) * | 2018-04-19 | 2019-10-29 | 旭化成株式会社 | Polyphenylene oxide and its manufacturing method |
| CN110387037B (en) * | 2018-04-19 | 2022-05-13 | 旭化成株式会社 | Polyphenylene ether and process for producing the same |
| CN110628013A (en) * | 2019-08-28 | 2019-12-31 | 河北健馨生物科技有限公司 | Bifunctional phosphorus-containing polyphenylene ether, and preparation method and application thereof |
| CN111440311A (en) * | 2020-05-06 | 2020-07-24 | 李同军 | Technological method for producing polyphenyl ether |
| CN111440311B (en) * | 2020-05-06 | 2023-03-14 | 李同军 | Process method for producing polyphenyl ether |
| CN114349955A (en) * | 2021-06-18 | 2022-04-15 | 山东圣泉新材料股份有限公司 | Polyfunctional poly (arylene ether) resin and preparation method thereof |
| CN114349955B (en) * | 2021-06-18 | 2024-01-19 | 山东圣泉新材料股份有限公司 | Multifunctional poly (arylene ether) resin and preparation method thereof |
| CN113698591A (en) * | 2021-08-17 | 2021-11-26 | 陕西硕博电子材料有限公司 | Preparation method of low-molecular-weight hydroxyl-terminated polyphenyl ether by one-pot method |
| CN113698591B (en) * | 2021-08-17 | 2022-07-19 | 陕西硕博电子材料有限公司 | Preparation method of low-molecular-weight hydroxyl-terminated polyphenyl ether by one-pot method |
| CN115894197A (en) * | 2022-12-06 | 2023-04-04 | 湖南久日新材料有限公司 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107353401B (en) | 2020-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107353401A (en) | A kind of double hydroxyl polyphenylene oxide and preparation method thereof | |
| US7671167B2 (en) | Poly(arylene ether) copolymer | |
| US6300461B1 (en) | Process for the manufacture of low molecular weight polyphenylene ether resins | |
| JP2011512453A5 (en) | ||
| CN113980265B (en) | Preparation method of high-purity low-molecular-weight dihydroxy polyphenyl ether | |
| US20220002485A1 (en) | Method for synthesizing dihydroxyl-terminated polyphenylene oxide oligomer | |
| KR20240046545A (en) | Polyetheretherketone and method for producing the same | |
| CN113683772B (en) | Low-molecular-weight functionalized star-shaped polyphenyl ether and preparation method thereof | |
| CN103145975B (en) | Method for preparing polyphenyl ether with side chain containing unsaturated carbon-carbon double bond in water medium | |
| JP2004504429A (en) | Poly (arylene ether) and method for producing the same | |
| CN112079978B (en) | DCPD-bisphenol type benzoxazine resin and copper-clad plate composition and preparation method thereof | |
| CN110628013B (en) | Bifunctional phosphorus-containing polyphenylene ether, and preparation method and application thereof | |
| US10259762B2 (en) | Method of forming phenylene ether oligomer | |
| CN114409900B (en) | Preparation method of polysulfone with low cyclic dimer content | |
| CN112409596A (en) | Polysulfone and preparation method thereof | |
| JPS5974124A (en) | Continuous manufacture of polyphenylene ether resin using high concentration bromide ion | |
| CN107892746A (en) | A kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin | |
| TWI548693B (en) | Polyphenylene ether modified phenol-benzaldehyde multifunctional epoxy resin and use | |
| CN116120540B (en) | Method for preparing polyether-ether-ketone at low temperature | |
| CN115322365B (en) | Low molecular weight poly (arylene ether) and method of making the same | |
| KR101799365B1 (en) | Epoxy resin, method for manufacturing the same, intermediate, epoxy resin composition and cured product | |
| Wang et al. | Oxidative coupling copolymerization for synthesis of poly (phenylene oxide) containing allyl groups in water | |
| JPH0340734B2 (en) | ||
| CN118240200A (en) | Low-dielectric fluorine-containing polyarylether resin and preparation method and application thereof | |
| CN118076662A (en) | Resin curing agent, curable resin composition, cured product, electronic device, laminate material, electronic component sealing material, ester compound, method for producing ester compound, and method for producing novolac resin |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |