CN107353401B - Dihydroxy polyphenyl ether and preparation method thereof - Google Patents
Dihydroxy polyphenyl ether and preparation method thereof Download PDFInfo
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- CN107353401B CN107353401B CN201710733606.XA CN201710733606A CN107353401B CN 107353401 B CN107353401 B CN 107353401B CN 201710733606 A CN201710733606 A CN 201710733606A CN 107353401 B CN107353401 B CN 107353401B
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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
- 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
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- 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
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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
- 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
Abstract
The invention provides a dihydroxy polyphenyl ether and a preparation method thereof, and the preparation method of the dihydroxy polyphenyl ether comprises the steps of introducing oxygen-containing gas into a reaction solution consisting of a solvent, a metal salt and an amine compound to oxidize and couple a monomer product, and terminating the reaction to obtain the dihydroxy polyphenyl ether; the preparation method of the dihydroxy polyphenyl ether has the advantages of simple process operation, low production cost and high production efficiency, and can meet the requirement of industrial production of the dihydroxy polyphenyl ether with low molecular weight. The dihydroxy polyphenyl ether product has low molecular weight, stable molecular weight control, uniform molecular weight distribution, good compatibility with other matrix resins of PCB and excellent reaction performance, and is an ideal matrix resin for preparing high-frequency copper-clad plates.
Description
Technical Field
The invention relates to the technical field of preparation of polyphenyl ether, and particularly relates to dihydroxy polyphenyl ether and a preparation method thereof.
Background
With the rapid development of the information industry, higher requirements are put on the matrix resin for the copper-clad plate, and the matrix resin is required to have low dielectric constant, low dielectric loss, high glass transition temperature, high heat resistance, low water absorption rate and the like. The most widely used matrix resin in the copper clad laminate manufacturing industry is epoxy resin, which has poor dimensional stability when used at high temperature and too high dielectric constant in a high frequency range, and thus cannot meet the requirements of technical development. The polyphenyl ether resin has good comprehensive performance, particularly high glass transition temperature and excellent dielectric property, and is an ideal substitute material for a high-performance copper-clad plate base material.
Although the blending modification of the high molecular weight polyphenyl ether and the epoxy resin can improve the toughness of the epoxy resin, improve the dielectric property of the epoxy resin, and improve the defects of poor solvent resistance, poor film forming property and the like of the polyphenyl ether, the compatibility of the high molecular weight polyphenyl ether and the epoxy resin is poor due to great difference in chemical structure and performance of the polyphenyl ether and the epoxy resin, and the traditional high molecular weight polyphenyl ether serving as the copper-clad plate base resin has great difficulty in use.
Compared with the common high molecular weight polyphenyl ether, the low molecular weight dihydroxy polyphenyl ether not only maintains the original excellent performance of the polyphenyl ether, but also has the advantages of low viscosity, good fluidity, good compatibility with a plurality of resins and the like, still maintains good thermal performance at the vitrification temperature, and is suitable for matrix resin of composite materials such as high-frequency circuit boards and the like or addition components of other high molecular materials.
In the related technology, a redistribution method is adopted to prepare low-molecular-weight dihydroxy polyphenyl ether, high-molecular-weight polyphenyl ether is subjected to chain scission under the action of a peroxide initiator to form small-molecular-weight polyphenyl ether with free radicals, and then the small-molecular-weight dihydroxy polyphenyl ether is combined with a polyphenol compound to generate the low-molecular-weight dihydroxy polyphenyl ether, the method has more byproducts, and a large amount of initiator is added in the preparation process, so that a certain amount of residual is easy to exist in a final product, the treatment difficulty is high, and a high-purity product is difficult to prepare; and the method has long process cycle and large waste discharge, and is difficult to meet the requirement of industrial production. In the related technology, the low molecular weight dihydroxy polyphenyl ether is prepared by adopting an oxidative coupling method, the used raw materials of tetramethyl bisphenol F, tetrabromobisphenol A, bisphenol A and bisphenol B have low solubility in a reaction system and low reaction activity with 2, 6-dimethylphenol, and the obtained product has more bisphenol monomer residues and is difficult to separate, so that the product purity is not high, and the use requirement is difficult to meet. In addition, in the related technology, the tetramethyl bisphenol A monomer is directly used as a raw material to prepare the dihydroxy polyphenyl ether through oxidative coupling, and the tetramethyl bisphenol A monomer has low commercialization degree and high price, so that the production cost is high, and the market competitiveness of the product is reduced, and therefore, the method is not suitable for large-batch commercial production.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of dihydroxy polyphenyl ether, which can overcome the defects of the prior art, has simple process operation, low production cost and high production efficiency, and can meet the industrial production requirement of low molecular weight dihydroxy polyphenyl ether.
The second purpose of the invention is to provide a dihydroxy polyphenyl ether product prepared by the method for preparing dihydroxy polyphenyl ether, the dihydroxy polyphenyl ether product has low molecular weight, stable molecular weight control, uniform molecular weight distribution, good compatibility with other matrix resins of PCB and excellent reaction performance, and is an ideal matrix resin for preparing a high-frequency copper-clad plate.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for preparing dihydroxy polyphenyl ether includes carrying out monomer reaction on monophenol, toluene, carbonyl compound and catalyst, neutralizing, desolventizing and dehydrating the obtained monomer product, mixing the monomer product with solvent, metal salt and amine compound to form mixed solution, introducing oxygen-containing gas, carrying out polymerization reaction, adding terminator after the reaction is finished, then separating, and carrying out desolventizing on the obtained organic phase to obtain dihydroxy polyphenyl ether.
The preparation method of the dihydroxy polyphenyl ether comprises the steps of introducing oxygen-containing gas into a reaction solution consisting of a solvent, a metal salt and an amine compound to oxidize and couple a monomer product, and then terminating the reaction to obtain the dihydroxy polyphenyl ether; the preparation method of the dihydroxy polyphenyl ether has the advantages of simple process operation, low production cost and high production efficiency, and can meet the requirement of industrial production of the dihydroxy polyphenyl ether with low molecular weight.
Optionally, the monophenol is selected from one or more of phenol and alkylphenol, preferably selected from one or more of 2, 6-xylenol, 2, 3-xylenol, 2, 5-xylenol, 3, 5-xylenol, o-cresol, m-cresol, 2,3, 6-trimethylphenol, 2,3, 5-trimethylphenol and phenol, and further preferably selected from 2, 6-xylenol.
Alternatively, the carbonyl compound is selected from one or more of a ketone compound and an aldehyde compound, preferably from one or more of acetone, acetylacetone, 2-butanone, 1, 3-dichloroacetone, chloroacetone, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, and more preferably from acetone.
Optionally, the catalyst is an acid catalyst, preferably selected from one or more of concentrated sulfuric acid, hydrochloric acid, HCL gas, methanesulfonic acid, trifluoromethanesulfonic acid, polyorganosiloxane sulfonic acid resin, and sulfonated polystyrene-divinylbenzene sulfonic acid resin, further preferably selected from methanesulfonic acid and/or sulfonated polystyrene-divinylbenzene sulfonic acid resin.
Alternatively, the molar ratio of monophenol to carbonyl compound is 1:1 to 30:1, preferably 2:1 to 25:1, and more preferably 4:1 to 20: 1.
Optionally, the mass ratio of the monophenol to the acid catalyst is 1:1 to 15:1, preferably 2:1 to 10:1, and more preferably 2:1 to 6: 1.
Alternatively, the mass ratio of toluene to monophenol is from 0.01:1 to 4:1, preferably from 0.2:1 to 2:1, and more preferably from 0.5:1 to 1: 1.
Alternatively, the reaction temperature of the monomer reaction is 20 to 90 ℃, preferably 40 to 70 ℃, and more preferably 50 to 60 ℃.
Alternatively, the time for the monomer reaction is 6 to 24 hours, preferably 6 to 12 hours, and further preferably 8 to 10 hours.
Optionally, the neutralizing agent for neutralization is selected from one or more of inorganic bases, preferably from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqueous ammonia, ammonium carbonate and ammonium bicarbonate, and further preferably from sodium carbonate and/or sodium hydroxide.
Optionally, the monomer product is neutralized, washed and then desolventized.
Optionally, the washing mode is an on-line washing.
Optionally, the molar ratio of monophenol to bisphenol in the monomer product is from 1:1 to 100:1, preferably from 2:1 to 16:1, and more preferably from 2:1 to 10: 1.
Optionally, the solvent is selected from one or more of organic solvents, preferably from one or more of chloroform, toluene, benzene and xylene, preferably toluene.
Optionally, the metal salt is a mixture of copper oxide and an acid solution, preferably a mixture of cuprous oxide and a hydrogen bromide solution.
Alternatively, in the mixture of cuprous oxide and hydrogen bromide solution, the mole number of bromine atoms is 2 times or more, preferably 4 times or more, that of copper atoms.
Alternatively, the amine compound is one or more selected from the group consisting of a secondary monoamine compound, a tertiary monoamine compound and a diamine compound.
Optionally, the secondary monoamine is selected from one or more of dimethylamine, diethylamine, di-n-butylamine, di-tert-butylamine, di-n-propylamine and morpholine, preferably from di-n-butylamine and/or morpholine.
Alternatively, the mono-tertiary amine compound is selected from one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine and dimethyl-n-butylamine, preferably dimethyl-n-butylamine.
Alternatively, the diamine compound has a structure represented by the following general formula (1):
R1R2NR5NR3R4(1)
wherein R is1、R2、R3And R4Each independently selected from hydrogen or one of C1-C6 linear or branched alkyl, and R1、R2、R3And R4Not simultaneously being hydrogen, R5Is one selected from C2-C5 linear chain alkylene or branched chain alkylene.
The diamine compound is preferably N, N ' -tetramethyl-1, 3-propanediamine and/or N, N ' -di-tert-butylethylenediamine, and more preferably N, N ' -di-tert-butylethylenediamine.
Alternatively, the number of moles of nitrogen atoms in the amine compound is 20 times or more, preferably 25 times or more, the number of moles of metal atoms in the metal salt.
Alternatively, the reaction temperature of the polymerization reaction is 90 ℃ or less, preferably 70 ℃ or less, and more preferably 50 ℃ or less.
Alternatively, the reaction time of the polymerization reaction is 1 to 6 hours, preferably 2 to 5 hours, and more preferably 3 to 4 hours.
Optionally, the solvent, the metal salt and the amine compound are added in a manner that: the solvent was added while introducing nitrogen into the reactor, stirring was started, and the amine compound and the metal salt were added in this order.
Optionally, the terminating agent is an aqueous solution containing a complexing agent.
Optionally, the complexing agent is selected from one or more of citric acid, citrate, sodium ethylenediaminetetraacetate, ethylenediaminetetramethylenephosphonic acid, hydroxyethylidene diphosphonic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid and nitrilotriacetic acid salt, preferably citric acid and/or nitrilotriacetic acid trisodium salt, further preferably citric acid.
Optionally, the number of moles of the complexing agent in molecules is more than 2 times the number of moles of the metal atoms in the metal salt.
Optionally, after the reaction is terminated by adding the terminator, controlling the temperature of the obtained polyphenylene ether mixture to be over 75 ℃, and continuously stirring for 30-120 min.
Optionally, the method for separating is selected from liquid-liquid separation and/or stationary phase separation.
Optionally, the organic phase obtained after the separation is washed and then desolventized.
Optionally, the washing mode is an on-line washing.
Optionally, the equipment used for desolventizing is selected from one or more of a distillation still, a thin film evaporator and a devolatilization extruder, and is preferably selected from the combined desolventizing of the distillation still and the devolatilization extruder.
Optionally, the desolventizing pressure of the desolventizing is below-1 KPa, the desolventizing temperature is 100-300 ℃, and the extrusion temperature is 200-300 ℃.
The dihydroxy polyphenyl ether product is prepared by the method for preparing dihydroxy polyphenyl ether.
The dihydroxy polyphenyl ether product has low molecular weight, stable molecular weight control, uniform molecular weight distribution, good compatibility with other matrix resins of PCB and excellent reaction performance, and is an ideal matrix resin for preparing high-frequency copper-clad plates.
Alternatively, the bishydroxypolyphenylene ether has a number average molecular weight of 800-.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the dihydroxy polyphenyl ether comprises the steps of introducing oxygen-containing gas into a reaction solution consisting of a solvent, a metal salt and an amine compound to oxidize and couple a monomer product, and then terminating the reaction to obtain the dihydroxy polyphenyl ether; the preparation method of the dihydroxy polyphenyl ether has the advantages of simple process operation, low production cost and high production efficiency, and can meet the requirement of industrial production of the dihydroxy polyphenyl ether with low molecular weight. The dihydroxy polyphenyl ether product has low molecular weight, stable molecular weight control, uniform molecular weight distribution, good compatibility with other matrix resins of PCB and excellent reaction performance, and is an ideal matrix resin for preparing high-frequency copper-clad plates.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram of a method for preparing bishydroxypolyphenylene ether in one embodiment of the present invention.
Reference numerals:
1-monomer reaction kettle; 2-a neutralization kettle; 3-phase separation tank;
4-a dehydration column; 5-a distillation column; 6-a polymerization reaction kettle;
7-terminating the kettle; 8-liquid separator; 9-a concentration tank;
10-devolatilization extruder; 11-condensing the steel strip; 12-acetone storage tank;
13-toluene and water storage tank; 14-a phenol storage tank; 15-toluene storage tank;
16-raw material metering pump; 17-phenol metering pump.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The specific embodiment of the invention provides a preparation method of dihydroxy polyphenyl ether, wherein monophenol, toluene, carbonyl compound and catalyst are subjected to monomer reaction, the obtained monomer product is subjected to neutralization, desolventizing and dehydration, then is mixed with solvent, metal salt and amine compound to form mixed solution, oxygen-containing gas is introduced to carry out polymerization reaction, a terminator is added after the reaction is finished, then separation is carried out, and the obtained organic phase is subjected to desolventizing to obtain the dihydroxy polyphenyl ether.
The preparation method of the dihydroxy polyphenyl ether comprises the steps of introducing oxygen-containing gas into a reaction solution consisting of a solvent, a metal salt and an amine compound to oxidize and couple a monomer product, and then terminating the reaction to obtain the dihydroxy polyphenyl ether; the preparation method of the dihydroxy polyphenyl ether has the advantages of simple process operation, low production cost and high production efficiency, and can meet the requirement of industrial production of the dihydroxy polyphenyl ether with low molecular weight.
In a preferred embodiment of the present invention, the monophenol is selected from one or more of phenol and alkylphenol, preferably from one or more of 2, 6-xylenol, 2, 3-xylenol, 2, 5-xylenol, 3, 5-xylenol, o-cresol, m-cresol, 2,3, 6-trimethylphenol, 2,3, 5-trimethylphenol and phenol, and more preferably from 2, 6-xylenol.
In a preferred embodiment of the present invention, the carbonyl compound is selected from one or more of a ketone compound and an aldehyde compound, preferably from one or more of acetone, acetylacetone, 2-butanone, 1, 3-dichloroacetone, chloroacetone, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, and more preferably from acetone.
In a preferred embodiment of the present invention, the catalyst is an acid catalyst, preferably selected from one or more of concentrated sulfuric acid, hydrochloric acid, HCL gas, methanesulfonic acid, trifluoromethanesulfonic acid, polyorganosiloxane sulfonic acid resin and sulfonated polystyrene-divinylbenzene sulfonic acid resin, and further preferably selected from methanesulfonic acid and/or sulfonated polystyrene-divinylbenzene sulfonic acid resin.
Different reactants are selected, thereby being beneficial to obtaining different types of dihydroxy polyphenyl ether and meeting the requirements of industrial application.
In a preferred embodiment of the present invention, the molar ratio of the monophenol to the carbonyl compound is 1:1 to 30:1, preferably 2:1 to 25:1, and more preferably 4:1 to 20: 1.
In a preferred embodiment of the present invention, the mass ratio of the monophenol to the acid catalyst is 1:1 to 15:1, preferably 2:1 to 10:1, and more preferably 2:1 to 6: 1.
In a preferred embodiment of the present invention, the mass ratio of toluene to monophenol is 0.01:1 to 4:1, preferably 0.2:1 to 2:1, and more preferably 0.5:1 to 1: 1.
The specific reactant dosage proportion is adopted, which is helpful for promoting the reaction to be fully carried out, reducing the content of byproducts and improving the purity of dihydroxy polyphenyl ether in the obtained product.
In a preferred embodiment of the present invention, the reaction temperature of the monomer reaction is 20 to 90 ℃, preferably 40 to 70 ℃, and more preferably 50 to 60 ℃.
In a preferred embodiment of the present invention, the time for the monomer reaction is 6 to 24 hours, preferably 6 to 12 hours, and more preferably 8 to 10 hours.
The specific reaction conditions are adopted, which is helpful for promoting the full reaction, reducing the content of byproducts and improving the purity of dihydroxy polyphenyl ether in the obtained product.
In a preferred embodiment of the present invention, the neutralizing agent for neutralization is selected from one or more inorganic bases, preferably from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, ammonium carbonate and ammonium bicarbonate, and further preferably from sodium carbonate and/or sodium hydroxide.
In a preferred embodiment of the invention, the monomer product is neutralized, washed and then desolventized.
In a preferred embodiment of the present invention, the washing mode is an on-line washing.
In a preferred embodiment of the present invention, the molar ratio of monophenol to bisphenol in the monomer product is 1:1 to 100:1, preferably 2:1 to 16:1, and more preferably 2:1 to 10: 1.
The monomer product contains monophenol and bisphenol, when monomer reaction is carried out, part of monophenol can react to obtain bisphenol, the direct use of bisphenol monomers with low commercialization degree and high price is avoided, the production cost is effectively reduced under the condition that the subsequent polymerization reaction can be fully carried out, and the method is suitable for large-batch commercial production.
In a preferred embodiment of the present invention, the solvent is selected from one or more of organic solvents, preferably from one or more of chloroform, toluene, benzene and xylene, preferably toluene.
In a preferred embodiment of the present invention, the metal salt is a mixture of copper oxide and an acid solution, preferably a mixture of cuprous oxide and a hydrogen bromide solution. The metal salt used in the embodiment of the present invention was prepared by mixing cuprous oxide and 48% by mass of an aqueous solution of hydrogen bromide in an inert gas nitrogen atmosphere in a vessel.
Although the amount of cuprous oxide and hydrogen bromide is not particularly limited, in a preferred embodiment of the present invention, the molar number of bromine atoms in the mixture of cuprous oxide and hydrogen bromide solution is 2 times or more, preferably 4 times or more the molar number of copper atoms.
In a preferred embodiment of the present invention, the amine compound is one or more selected from the group consisting of a secondary monoamine compound, a tertiary monoamine compound and a diamine compound.
In a preferred embodiment of the present invention, the secondary monoamine is selected from one or more of dimethylamine, diethylamine, di-n-butylamine, di-tert-butylamine, di-n-propylamine and morpholine, preferably from di-n-butylamine and/or morpholine.
In a preferred embodiment of the present invention, the mono-tertiary amine compound is selected from one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine and dimethyl-n-butylamine, preferably dimethyl-n-butylamine.
In a preferred embodiment of the present invention, the diamine compound has a structure represented by the following general formula (1):
R1R2NR5NR3R4(1)
wherein R is1、R2、R3And R4Each independently selected from hydrogen or one of C1-C6 linear or branched alkyl, and R1、R2、R3And R4Not simultaneously being hydrogen, R5Is one selected from C2-C5 linear chain alkylene or branched chain alkylene.
The diamine compound is preferably N, N ' -tetramethyl-1, 3-propanediamine and/or N, N ' -di-tert-butylethylenediamine, and more preferably N, N ' -di-tert-butylethylenediamine.
Although the amount of the amine compound is not particularly limited, in a preferred embodiment of the present invention, the number of moles of nitrogen atoms in the amine compound is 20 times or more, preferably 25 times or more the number of moles of metal atoms in the metal salt.
The catalyst consisting of the metal salt and the amine compound with specific components and dosage is helpful for promoting the full progress of polymerization reaction, reducing the content of byproducts and improving the purity of the dihydroxy polyphenyl ether in the obtained product.
In a preferred embodiment of the present invention, the reaction temperature of the polymerization reaction is 90 ℃ or lower, preferably 70 ℃ or lower, and more preferably 50 ℃ or lower.
In a preferred embodiment of the present invention, the reaction time of the polymerization reaction is 1 to 6 hours, preferably 2 to 5 hours, and more preferably 3 to 4 hours.
The specific reaction conditions are adopted, which is helpful for promoting the full reaction, reducing the content of byproducts and improving the purity of dihydroxy polyphenyl ether in the obtained product.
The manner of preparation of the catalyst used in the present invention is very important, and in a preferred embodiment of the present invention, the solvent, the metal salt and the amine compound are added in the following manner: the solvent was added while introducing nitrogen into the reactor, stirring was started, and the amine compound and the metal salt were added in this order. Under the condition of nitrogen and stirring, introducing a small amount of oxygen from the bottom of the reactor, wherein the oxygen introducing time is not less than ten minutes, and then completing the preparation process of the catalyst.
In a preferred embodiment of the present invention, the terminating agent is an aqueous solution containing a complexing agent.
In a preferred embodiment of the present invention, the complexing agent is selected from one or more of citric acid, citrate, sodium ethylenediaminetetraacetate, ethylenediaminetetramethylenephosphonic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid and nitrilotriacetic acid salt, preferably citric acid and/or nitrilotriacetic acid trisodium salt, more preferably citric acid.
Although there is no particular limitation on the amount of the complexing agent, in a preferred embodiment of the present invention, the number of moles of the complexing agent is 2 times or more the number of moles of the metal atoms in the metal salt.
In a preferred embodiment of the invention, after the reaction is terminated by adding the terminator, the obtained polyphenylene ether mixture is controlled to be over 75 ℃, and the stirring is continued for 30-120 min. Aims to ensure that the by-product biphenyl diquinone generated in the reaction stage can fully react with the polyphenyl ether, improve the product yield and reduce the content of the biphenyl diquinone in the product.
In a preferred embodiment of the invention, the separation is carried out by a method selected from the group consisting of liquid-liquid separation and/or stationary phase separation.
In a preferred embodiment of the invention, the organic phase obtained after the separation is washed and then desolventized.
In a preferred embodiment of the present invention, the washing mode is an on-line washing.
In a preferred embodiment of the present invention, the equipment used for desolventizing is selected from one or more of a distillation still, a thin film evaporator and a devolatilization extruder, and is preferably selected from the combined desolventizing of the distillation still and the devolatilization extruder.
In a preferred embodiment of the invention, the desolventizing pressure of the desolventizing is below-1 KPa, the desolventizing temperature is 100-300 ℃, and the extrusion temperature is 200-300 ℃.
The dihydroxy polyphenyl ether product is prepared by the method for preparing dihydroxy polyphenyl ether.
The dihydroxy polyphenyl ether product has low molecular weight, stable molecular weight control, uniform molecular weight distribution, good compatibility with other matrix resins of PCB and excellent reaction performance, and is an ideal matrix resin for preparing high-frequency copper-clad plates.
In a preferred embodiment of the present invention, the bishydroxypolyphenylene ether has a number average molecular weight of 800-.
Example 1
A method for preparing dihydroxy polyphenyl ether comprises the following steps:
1. monomer preparation: putting 1200g of 2, 6-xylenol, 1200g of toluene and 300g of sulfonated polystyrene-divinylbenzene sulfonic acid resin into a 5000mL monomer reaction kettle 1, starting stirring, heating to 70 ℃, adding 142.6g of acetone into the reaction kettle 1 by using a raw material metering pump 16, wherein the adding time is 80min, timing is started after the acetone is added, after 480min, the reaction liquid is filtered and then moved into a neutralization kettle 2, adding 100g of sodium carbonate solution with the mass fraction of 20% into the neutralization kettle 2, stirring for 10min, and then moving into a phase separation tank 3, after phase separation, feeding a light phase into a distillation tower 5 for distillation, cooling a material at the top of the tower, feeding the material into an acetone storage tank 12, and feeding a material at the bottom of the tower into a toluene and water storage tank 13 for further treatment; the heavy phase in the phase separation tank 3 enters a dehydration tower 4 for dehydration and then enters a phenol storage tank 14 for polymerization reaction.
2. Preparation of dihydroxy polyphenylene ether: 2750g of toluene is added into a 5000mL polymerization reaction kettle 6 with a circulating device, nitrogen is introduced, stirring is started, after 2 minutes, 45g of compound amine solution and 13g of cuprous bromide solution are respectively added into the reactor, the stirring speed is increased, and oxygen is introduced from the bottom of the reactor. After 10 minutes, 1000g of the mixed solution of 2, 6-dimethylphenol and tetramethylbisphenol A was fed from the phenol tank 1460min to the polymerization reactor 6 by the phenol metering pump 17 at a reaction temperature of 35 ℃ at a molar ratio of oxygen flow to 2, 6-dimethylphenol flow of not less than 1: 1. After the phenol mixed solution is completely added, oxygen is continuously introduced for 180min, the materials are transferred into a termination kettle 7, an aqueous solution containing 10g of citric acid is added to terminate the reaction, the temperature is controlled to be 75 ℃, and the stirring is continued for 1.0 h. The polymerization reaction liquid is separated by a liquid-liquid separator 8, the oil phase enters a concentration tank 9 to remove partial toluene, the toluene gas phase is cooled and then enters a toluene storage tank 15, the material is concentrated until the solid content is 80%, the concentrated solution enters a devolatilization extruder 10 to be devolatilized and extruded, the desolventizing pressure is below-1 KPa, the desolventizing temperature is 200 ℃, the extruding temperature is 250 ℃, the toluene gas is cooled and then enters the toluene storage tank 15, the extruded material is cooled by a condensation steel belt 11, and the low-molecular dihydroxy polyphenyl ether product is obtained after crushing. The results of the experiment are shown in table 1.
Example 2
A low molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 1, except that the amount of toluene used in the preparation of the monomers was 4800g, the amount of the acid catalyst was 1200g, the amount of acetone was 570.4g, the monomer reaction temperature was 20 ℃, the monomer reaction time was 24 hours, the polymerization reaction temperature was 90 ℃, the polymerization reaction time was 1 hour, the temperature was controlled to 90 ℃ after the termination of the reaction, the stirring was continued for 30min, the desolventizing temperature was 100 ℃ and the extrusion temperature was 200 ℃. The results of the experiment are shown in table 1.
Example 3
A low molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 1, except that the amount of toluene used in the monomer preparation was 12g, the amount of acid catalyst was 80g, the amount of acetone was 285.2g, the monomer reaction temperature was 90 ℃, the monomer reaction time was 6 hours, the polymerization reaction temperature was 70 ℃, the polymerization reaction time was 3 hours, the temperature was controlled to 80 ℃ or higher after the termination of the reaction, stirring was continued for 90min, the desolventizing temperature was 300 ℃, and the extrusion temperature was 300 ℃. The results of the experiment are shown in table 1.
Example 4
A low molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 2, except that the amount of toluene used in the monomer preparation was 240g, the amount of acid catalyst was 600g, the amount of acetone was 71.3g, the monomer reaction temperature was 40 ℃, the monomer reaction time was 12 hours, the polymerization reaction temperature was 80 ℃, the polymerization reaction time was 2 hours, the temperature was controlled to 75 ℃ after the termination of the reaction, and the stirring was continued for 120 min. The results of the experiment are shown in table 1.
Example 5
A low-molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 4, except that the amount of toluene used in the preparation of the monomers was 2400g, the amount of the acid catalyst was 200g, the amount of acetone was 28.5g, the reaction temperature of the monomers was 70 ℃ and the reaction time of the monomers was 6 hours, the reaction temperature of the polymerization was 60 ℃ and the reaction time of the polymerization was 4 hours. The results of the experiment are shown in table 1.
Example 6
A low molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 2, except that the amount of acetone used in the preparation of the monomers was 19g, the reaction temperature of the monomers was 50 ℃ and the reaction time of the monomers was 10 hours, and that the reaction temperature of the polymerization was 50 ℃ and the reaction time of the polymerization was 5 hours. The results of the experiment are shown in table 1.
Example 7
A low-molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 4, except that the amount of acetone used in the preparation of the monomers was 22.8g, the reaction temperature of the monomers was 60 ℃ and the reaction time of the monomers was 8 hours, the reaction temperature of the polymerization was 40 ℃ and the reaction time of the polymerization was 6 hours. The results of the experiment are shown in table 1.
Example 8
A low molecular weight bishydroxypolyphenylene ether was prepared according to the method of example 5, except that the acid catalyst used in the monomer preparation was methanesulfonic acid in an amount of 120g and that 350g of a 20% aqueous solution of sodium carbonate was used for neutralization. The results of the experiment are shown in table 1.
Example 9
A low molecular weight bishydroxypolyphenylene ether was prepared according to the procedure in example 1, except that the carbonyl compound used in the monomer preparation was chloroacetone in an amount of 227.4 g. The results of the experiment are shown in table 1.
Table 1 shows the data of the results of the experiments conducted in the examples of the present invention, wherein the molecular weight and molecular weight distribution of the bishydroxypolyphenylene ether were measured by gel chromatography, the hydroxyl value of the bishydroxypolyphenylene ether was measured by NMR internal standard method in g/100g, and the copper content of the bishydroxypolyphenylene ether was measured by atomic absorption spectrophotometer in ppm.
TABLE 1 data of experimental results of various examples of the invention
(note: acid catalyst: A represents sulfonated polystyrene-divinylbenzene sulfonic acid resin; B represents methanesulfonic acid. Monobisphenol A mass ratio means the mass ratio of 2, 6-dimethylphenol to tetramethylbisphenol A)
As can be seen from Table 1, according to the method provided by the invention, the low molecular weight dihydroxy polyphenyl ether with the number average molecular weight of 800-. In addition, the dihydroxy polyphenyl ether has high purity, the raw materials can be fully polymerized to obtain a product, and the contained impurities are only a small amount of catalyst (the copper content is below 2.5 ppm).
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (36)
1. A method for preparing dihydroxy polyphenyl ether is characterized in that monophenol, toluene, carbonyl compound and catalyst are subjected to monomer reaction, the obtained monomer product is neutralized, desolventized and dehydrated, and then is mixed with solvent, metal salt and amine compound to form mixed solution, oxygen-containing gas is introduced to carry out polymerization reaction, a terminator is added after the reaction is finished, then separation is carried out, and the obtained organic phase is desolventized to obtain dihydroxy polyphenyl ether;
the monophenol is 2, 6-xylenol; the carbonyl compound is any one of acetone, chloropropone and formaldehyde;
the molar ratio of the monophenol to the carbonyl compound is 1:1-8: 1;
the catalyst is an acid catalyst, and the acid catalyst is selected from methanesulfonic acid and/or sulfonated polystyrene-divinylbenzene sulfonic acid resin;
the molar ratio of monophenol to bisphenol in the monomer product is 2:1-10: 1;
the mass ratio of the monophenol to the acid catalyst is 1:1-15: 1;
the mass ratio of the toluene to the monophenol is 0.01:1-4: 1;
the reaction temperature of the monomer reaction is 20-90 ℃;
the time for the monomer reaction is 6-24 h;
the solvent, the metal salt and the amine compound are added in the following modes: adding a solvent while introducing nitrogen into the reactor, starting stirring, and sequentially adding an amine compound and a metal salt;
and after the reaction is ended by adding the terminator, controlling the temperature of the obtained polyphenylene ether mixture to be over 75 ℃, and continuously stirring for 30-120 min.
2. The method for producing a bishydroxyphenyl ether according to claim 1, wherein the mass ratio of the monophenol to the acid catalyst is 2:1 to 10: 1.
3. The method for producing a bishydroxyphenyl ether according to claim 2, wherein the mass ratio of the monophenol to the acid catalyst is 2:1 to 6: 1.
4. The method for producing a bishydroxyphenyl ether according to claim 1, wherein the mass ratio of toluene to monophenol is 0.2:1 to 2: 1.
5. The method of producing a bishydroxyphenyl ether according to claim 4, wherein the mass ratio of toluene to monophenol is 0.5:1 to 1: 1.
6. The method for producing a bishydroxypolyphenylene ether according to claim 5, wherein the reaction temperature of the monomer reaction is 40 to 70 ℃.
7. The method for producing a bishydroxypolyphenylene ether according to claim 6, wherein the reaction temperature of the monomer reaction is 50 to 60 ℃.
8. The method for preparing a bishydroxypolyphenylene ether according to claim 7, wherein the reaction time of the monomers is 6 to 12 hours.
9. The method for preparing a bishydroxypolyphenylene ether according to claim 8, wherein the reaction time of the monomers is 8 to 10 hours.
10. The method for producing a bishydroxyphenyl ether according to claim 1, wherein the neutralizing agent is one or more selected from inorganic bases.
11. The method for producing a bishydroxypolyphenylene ether according to claim 10, wherein the neutralizing agent for neutralization is one or more selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, ammonium carbonate and ammonium bicarbonate.
12. The method for producing a bishydroxyphenyl ether according to claim 11, wherein the neutralizing agent is selected from sodium carbonate and/or sodium hydroxide.
13. The method for producing a bishydroxypolyphenylene ether according to claim 10, wherein the monomer product is neutralized, washed and then desolventized;
the washing mode is online washing.
14. The method for producing a bishydroxyphenyl ether according to claim 1, wherein the solvent is one or more selected from the group consisting of chloroform, toluene, benzene and xylene.
15. The method for producing a bishydroxypolyphenylene ether according to claim 14, wherein the solvent is toluene.
16. The method for producing a bishydroxypolyphenylene ether according to claim 1, wherein the metal salt is a mixture of copper oxide and an acid solution.
17. The method for producing a bishydroxypolyphenylene ether according to claim 16, wherein the metal salt is a mixture of cuprous oxide and hydrogen bromide solution.
18. The process for producing a bishydroxypolyphenylene ether according to claim 17, wherein the molar number of bromine atoms in the mixture of cuprous oxide and hydrogen bromide solution is 2 times or more the molar number of copper atoms.
19. The method for producing a bishydroxypolyphenylene ether according to claim 1, wherein the amine compound is one or more selected from the group consisting of a secondary monoamine compound, a tertiary monoamine compound and a diamine compound;
the secondary monoamine is selected from one or more of dimethylamine, diethylamine, di-n-butylamine, di-tert-butylamine, di-n-propylamine and morpholine;
the monobasic tertiary amine compound is selected from one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine and dimethyl-n-butylamine;
the diamine compound has a structure represented by the following general formula (1):
R1R2NR5NR3R4(1)
wherein R is1、R2、R3And R4Each independently selected from hydrogen or one of C1-C6 linear or branched alkyl, and R1、R2、R3And R4Not simultaneously being hydrogen, R5Is one selected from C2-C5 linear chain alkylene or branched chain alkylene.
20. The method for producing a bishydroxyphenyl ether according to claim 19, wherein the secondary monoamine is di-n-butylamine and/or morpholine; the monobasic tertiary amine compound is dimethyl n-butylamine;
the diamine compound is N, N, N ', N ' -tetramethyl-1, 3-propane diamine and/or N, N ' -di-tert-butyl ethylene diamine.
21. The method for producing a bishydroxypolyphenylene ether according to claim 19, wherein the mole number of nitrogen atoms in the amine compound is 20 times or more the mole number of metal atoms in the metal salt.
22. The method for producing a bishydroxypolyphenylene ether according to claim 1, wherein the reaction temperature of the polymerization is 90 ℃ or lower.
23. The method for producing a bishydroxypolyphenylene ether according to claim 22, wherein the reaction temperature of the polymerization is 70 ℃ or lower.
24. The method for producing a bishydroxypolyphenylene ether according to claim 23, wherein the reaction temperature of the polymerization is 50 ℃ or lower.
25. The method for producing a bishydroxypolyphenylene ether according to claim 22, wherein the polymerization reaction time is 1 to 6 hours.
26. The method for producing a bishydroxypolyphenylene ether according to claim 25, wherein the polymerization reaction time is 2 to 5 hours.
27. The method for producing a bishydroxypolyphenylene ether according to claim 2, wherein the polymerization reaction time is 3 to 4 hours.
28. The method for producing a bishydroxyphenyl ether according to claim 1, wherein the terminator is an aqueous solution containing a complexing agent;
the complexing agent is selected from one or more of citric acid, citrate, ethylene diamine tetraacetic acid sodium salt, ethylene diamine tetramethylene phosphonic acid, hydroxy ethylidene diphosphonic acid, hydroxyethyl ethylene diamine triacetic acid, diethylene triamine pentaacetic acid, nitrilotriacetic acid and nitrilotriacetic acid salt.
29. The method for preparing a bishydroxyphenyl ether according to claim 28, wherein the complexing agent is citric acid and/or trisodium nitrilotriacetate.
30. The method for preparing a bishydroxyphenyl ether according to claim 29, wherein the complexing agent is citric acid.
31. The method for producing a bishydroxyphenyl ether according to claim 28, wherein the number of moles of the complexing agent is 2 times or more the number of moles of the metal atom in the metal salt.
32. The process for producing a bishydroxypolyphenylene ether according to claim 1, wherein the separation is carried out by a method selected from the group consisting of liquid-liquid separation and/or stationary phase separation.
33. The process for producing a bishydroxypolyphenylene ether according to claim 32, wherein the organic phase obtained after the separation is washed and then desolventized;
the washing mode is online washing.
34. The method for producing a bishydroxypolyphenylene ether according to claim 1, wherein the desolventizing step is carried out by one or more apparatuses selected from the group consisting of a still, a thin film evaporator and a devolatilizing extruder.
35. The method for producing a bishydroxyphenyl ether according to claim 34, wherein the desolventizing is a combination of a still pot and a devolatilizing extruder.
36. The method for preparing a bishydroxypolyphenylene ether as claimed in claim 34, wherein the desolvation pressure is-1 KPa or less, the desolvation temperature is 100-300 ℃ and the extrusion temperature is 200-300 ℃.
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