CN113698591B - Preparation method of low-molecular-weight hydroxyl-terminated polyphenyl ether by one-pot method - Google Patents
Preparation method of low-molecular-weight hydroxyl-terminated polyphenyl ether by one-pot method Download PDFInfo
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- 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
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- 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
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- C08G65/485—Polyphenylene oxides
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Abstract
The invention discloses a preparation method of low molecular weight hydroxyl-terminated polyphenylene oxide by a one-pot method, which comprises the following steps: carrying out oxidative condensation polymerization reaction on 2, 6-dimethylphenol under the condition of introducing oxygen and under the catalysis of a copper-pyridine complex to obtain a polyphenylene oxide homopolymer intermediate, and controlling the reaction time to ensure that the number-average molecular weight of the generated polyphenylene oxide homopolymer intermediate is 800-1500; then the polyphenylene oxide homopolymer intermediate is subjected to condensation reaction with acetone under the catalysis of inorganic acid to generate low molecular weight double-end hydroxyl polyphenylene oxide; the number average molecular weight of the low molecular weight hydroxyl-terminated polyphenylene ether is 1600-3000. The preparation method has the advantage of simple synthesis process; more importantly, the method avoids using the tetramethyl bisphenol A raw material, does not need a matched production device of the tetramethyl bisphenol A raw material, and greatly reduces the production cost; in addition, the product also has higher yield, and the hydroxyl-terminated polyphenyl ether is low molecular weight hydroxyl-terminated polyphenyl ether, so that the application requirement in the high-frequency high-speed electronic field can be met.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a preparation method of low-molecular-weight hydroxyl-terminated polyphenyl ether by a one-pot method.
Background
The polyphenyl ether resin is formed by carrying out oxidative coupling polycondensation reaction on 2, 6-dimethylphenol, and is thermoplastic engineering plastic with excellent comprehensive performance. The molecular structure is shown as follows:
the composite material has excellent mechanical property, excellent dielectric property (dielectric constant Dk is 2.45<1MHZ > and Df is 0.0007<1MHZ >), high glass transition temperature (tg is 210 ℃), and very low water absorption (saturated water absorption at room temperature is less than 0.05%), which is very important for the application in the high-frequency field.
Although polyphenylene ether has many outstanding excellent properties, it has fatal disadvantages that heat resistance is not sufficient for soldering and solvent resistance is not sufficient for cleaning when it is used as a printed circuit substrate due to its thermoplasticity. Therefore, in order to make the thermoplastic polyphenylene ether perfectly applicable to high-frequency, high-speed electronics, it is necessary to subject the thermoplastic polyphenylene ether resin to a thermosetting modification treatment.
As is known to all, the general thermoplastic polyphenylene ether resin belongs to the category of engineering plastics, the number average molecular weight thereof is generally more than 20000, the number average molecular weight of the polyphenylene ether resin prepared by the conventional common preparation process is generally 30000-50000, and thermosetting modification treatment is difficult to perform. Therefore, the current practice in the industry is: firstly, carrying out oxidative copolymerization-condensation reaction on 2, 6-dimethylphenol and tetramethyl bisphenol A under certain conditions to prepare low-molecular-weight hydroxyl-terminated polyphenyl ether, and then carrying out different chemical reactions by utilizing active-OH groups contained at two ends of a molecular chain of the low-molecular-weight hydroxyl-terminated polyphenyl ether according to different application requirements to prepare a series of modified polyphenyl ether resins meeting the application requirements of the high-frequency high-speed electronic field.
Patent CN102604075A discloses that 2, 6-dimethylphenol and tetramethyl bisphenol A take water as reaction medium and are subjected to copolymerization reaction in the presence of oxygen and a catalyst system to obtain low-molecular-weight hydroxyl-terminated polyphenylene oxide; patent CN107353401A discloses that 2, 6-methyl phenol, toluene, acetone and catalyst (acidity) are subjected to monomer condensation reaction (to generate tetramethyl bisphenol a), the obtained monomer product is neutralized, desolventized and dehydrated, and then forms a mixed solution with solvent, metal salt and amine compound, and oxygen is introduced to perform polymerization reaction, so as to obtain dihydroxy polyphenylene ether.
However, tetramethyl bisphenol A belongs to special chemicals, no ready-made industrial product is supplied, and the tetramethyl bisphenol A is produced by a special matched production device, and the process for producing tetramethyl bisphenol A comprises two parts of condensation reaction of 2, 6-dimethyl phenol and acetone under the action of a catalyst and product purification, and the whole process is complex; in addition, the problems of complex overall production process, high production cost, large potential safety hazard, high environmental protection input cost and the like of the low-molecular-weight double-end hydroxyl polyphenylene ether resin can be caused.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a one-pot method for preparing low-molecular-weight hydroxyl-terminated polyphenylene oxide. The technical problem to be solved by the invention is realized by the following technical scheme:
a method for preparing low molecular weight hydroxyl-terminated polyphenylene oxide by a one-pot method comprises the following steps: carrying out oxidative condensation polymerization reaction on 2, 6-dimethylphenol under the condition of introducing oxygen and under the catalysis of a copper-pyridine complex to obtain a polyphenylene ether homopolymer intermediate, and controlling the reaction time to ensure that the number average molecular weight of the generated polyphenylene ether homopolymer intermediate is 800-1500; then the polyphenylene oxide homopolymer intermediate is subjected to condensation reaction with acetone under the catalysis of inorganic acid to generate the low molecular weight double-end hydroxyl polyphenylene oxide; the number average molecular weight of the low molecular weight double-end hydroxyl polyphenylene ether is 1600-3000.
In one embodiment of the present invention, the one-pot method for preparing a low molecular weight, hydroxy-terminated polyphenylene ether comprises:
step one, adding a toluene solvent into a reactor, then adding cuprous chloride and pyridine, introducing oxygen for pre-oxidation, and controlling the pre-oxidation temperature to be 25-30 ℃ to prepare the copper-pyridine complex;
step two, adding the toluene solution of the 2, 6-dimethylphenol into a reactor containing the copper-pyridine complex, controlling the reaction temperature to be 25-30 ℃ under the condition of introducing oxygen, gradually carrying out oxidative condensation polymerization reaction, and controlling the reaction time to generate the polyphenylene ether homopolymer intermediate with the molecular weight of 800-1500, and dissolving the intermediate in a toluene solvent;
and step three, stopping introducing oxygen, then adding the inorganic acid and the acetone into a reaction system in sequence, controlling the reaction temperature to be 45-50 ℃, controlling the reaction time, carrying out condensation reaction on the polyphenyl ether homopolymer intermediate and the acetone under the catalysis of the inorganic acid to generate the low-molecular-weight hydroxyl-terminated polyphenyl ether, and finishing the reaction.
In an embodiment of the present invention, after the third step, the method further includes:
and step four, using methanol as a precipitator to precipitate the low molecular weight hydroxyl-terminated polyphenylene oxide from toluene.
In an embodiment of the present invention, after the fourth step, the method further includes:
and fifthly, filtering the precipitated low-molecular-weight hydroxyl-terminated polyphenyl ether in vacuum, and drying to obtain the final product.
In one embodiment of the present invention, the toluene solution of 2, 6-dimethylphenol added in step two comprises:
the toluene solution of the 2, 6-dimethylphenol is dropwise added for 0.5 to 1.0 hour.
In one embodiment of the invention, the reaction time in the second step is controlled to be 3-3.5 h; the reaction time in the third step is controlled to be 2-3 h.
In one embodiment of the invention, the oxygen flow rate in the first step is 100ml/min, and the pre-oxidation time is 30 min.
In one embodiment of the invention, the mineral acid comprises concentrated sulfuric acid and hydrochloric acid.
In one embodiment of the invention, the mass ratio of the 2, 6-dimethylphenol to the acetone is 20: 1.
In one embodiment of the present invention, the mass ratio of methanol to the total amount of toluene is 10: 1.
The reaction mechanism of the preparation method of the low molecular weight hydroxyl-terminated polyphenyl ether by the one-pot method is as follows: 2, 6-dimethylphenol and oxygen are subjected to oxidative condensation polymerization reaction under the catalysis of a copper-pyridine complex to generate a polyphenylene oxide homopolymer intermediate with the molecular weight of 800-1500 and water, and the polyphenylene oxide homopolymer intermediate is subjected to condensation reaction with acetone under the catalysis of inorganic acid to generate the low-molecular-weight hydroxyl-terminated polyphenylene oxide with the molecular weight of 1600-3000.
The preparation method comprises the preparation process of a catalyst copper-pyridine complex, the synthesis process of generating the polyphenylene oxide homopolymer intermediate with the molecular weight of 800-1500 by oxidative condensation polymerization of 2, 6-dimethylphenol under the catalysis of the copper-pyridine complex, and the synthesis process of generating the low-molecular-weight double-end hydroxyl polyphenylene oxide with the molecular weight of 1600-3000 by condensation of the intermediate and acetone under the catalysis of inorganic acid, wherein the three processes are sequentially completed in one reactor; more importantly, the method avoids using the tetramethyl bisphenol A raw material, does not need a matched production device of the tetramethyl bisphenol A raw material, and greatly reduces the production cost; in addition, the product also has higher yield, and the hydroxyl-terminated polyphenyl ether is low molecular weight hydroxyl-terminated polyphenyl ether, so that the application requirement in the high-frequency high-speed electronic field can be met.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a GPC chart of a product prepared by a one-pot method for preparing low molecular weight hydroxy-terminated polyphenylene ether according to an embodiment of the present invention;
FIG. 2 is a graph showing the integral of molecular weight distribution of a product prepared by a one-pot method for preparing low molecular weight bishydroxyphenylene oxide according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
In order to solve the problem caused by the use of tetramethyl bisphenol A in the preparation process of low-molecular-weight hydroxyl-terminated polyphenylene oxide in the high-frequency field, the embodiment of the invention provides a method for preparing low-molecular-weight hydroxyl-terminated polyphenylene oxide without adopting tetramethyl bisphenol A. It should be noted that the "one-pot process" provided by the present invention is relative to the existing preparation method that requires a production apparatus for tetramethyl bisphenol a to synthesize tetramethyl bisphenol a first, and then a production apparatus for hydroxyl terminated polyphenylene ether to synthesize hydroxyl terminated polyphenylene ether. The preparation method of the low molecular weight hydroxyl-terminated polyphenylene oxide by the one-pot method provided by the invention can complete the whole synthesis process in one reactor at one time, and avoids using a tetramethyl bisphenol A raw material.
The embodiment of the invention provides a preparation method of low molecular weight hydroxyl-terminated polyphenylene oxide by a one-pot method, which comprises the following steps: carrying out oxidative condensation polymerization reaction on 2, 6-dimethylphenol under the condition of introducing oxygen and under the catalysis of a copper-pyridine complex to obtain a polyphenylene ether homopolymer intermediate, and controlling the reaction time to ensure that the number average molecular weight of the generated polyphenylene ether homopolymer intermediate is 800-1500; then the polyphenylene oxide homopolymer intermediate is subjected to condensation reaction with acetone under the catalytic action of inorganic acid to generate the low molecular weight double-end hydroxyl polyphenylene oxide; the number average molecular weight of the low molecular weight double-end hydroxyl polyphenylene ether is 1600-3000.
The specific preparation method of the low-molecular-weight hydroxyl-terminated polyphenylene oxide by the one-pot method provided by the embodiment of the invention can comprise the following steps of:
step one, adding a toluene solvent into a reactor, then adding cuprous chloride and pyridine, introducing oxygen for pre-oxidation, and controlling the reaction temperature to be 25-30 ℃ to prepare the copper-pyridine complex; wherein the oxygen flow is preferably 100ml/min, the pre-oxidation time is preferably 0.5h, and the mass ratio of toluene to pyridine to cuprous chloride is 58-54: 30-26: 1;
step two, adding the toluene solution of the 2, 6-dimethylphenol into a reactor containing the copper-pyridine complex, controlling the pre-oxidation temperature to be 25-30 ℃ under the condition of introducing oxygen, gradually carrying out oxidative condensation polymerization reaction, and controlling the reaction time to generate the polyphenyl ether homopolymer intermediate with the molecular weight of 800-1500, and dissolving the polyphenyl ether homopolymer intermediate in a toluene solvent; wherein, the dripping operation is preferably selected in the process of adding the toluene solution of the 2, 6-dimethylphenol, and the dripping time is 0.5 to 1.0 hour; the dropwise addition can ensure that the reaction of reactants is more uniform and more sufficient under the action of the catalyst; the time for continuing the reaction after the dropwise addition is finished is preferably controlled to be 2.5h, so that the total reaction time in the step is controlled to be 3-3.5 h; the mass ratio of toluene in the toluene solution of 2, 6-dimethylphenol in the step I to toluene in the step I is 12: 5;
stopping introducing oxygen, then adding the inorganic acid and the acetone into a reaction system in sequence, controlling the reaction temperature to be 45-50 ℃, controlling the reaction time, carrying out condensation reaction on the polyphenyl ether homopolymer intermediate and the acetone under the catalysis of the inorganic acid to generate the low-molecular-weight hydroxyl-terminated polyphenyl ether, and finishing the reaction; wherein the reaction time is preferably controlled to be 2-3h, and the mass of the added acetone is 1/20 of that of the 2, 6-dimethylphenol; the process of adding the inorganic acid and the acetone is also preferably dropwise adding; the inorganic acid used as a catalyst in this step is preferably concentrated sulfuric acid or hydrochloric acid.
Thus, the production step of the low-molecular weight bishydroxypolyphenylene ether has been completed. However, the preparation method of the present invention may further comprise a fourth precipitation step and a fifth filtration and drying step in order to obtain a final purified product.
Step four, using methanol as a precipitator to precipitate the low molecular weight hydroxyl-terminated polyphenylene oxide from toluene; among them, the mass of methanol is preferably 10 times the total mass of toluene.
And fifthly, filtering the precipitated low-molecular-weight hydroxyl-terminated polyphenyl ether in vacuum, and drying to obtain the final product.
The preparation method comprises a synthesis process of a catalyst copper-pyridine complex, a synthesis process of a polyphenylene oxide homopolymer intermediate with the molecular weight of 800-1500 generated by oxidative condensation polymerization of 2, 6-dimethylphenol under the catalysis of the copper-pyridine complex, and a synthesis process of a low molecular weight double-end hydroxyl polyphenylene oxide with the molecular weight of 1600-3000 generated by condensation of the intermediate and acetone under the catalysis of inorganic acid, wherein the three synthesis processes are sequentially completed in a reactor. The preparation method has simple synthesis process, avoids using the tetramethyl bisphenol A raw material, does not need a production device matched with the tetramethyl bisphenol A raw material, and greatly reduces the production cost.
Example one
The preparation method of the low molecular weight hydroxyl-terminated polyphenylene ether by the one-pot method in this embodiment comprises the following steps:
step one, adding 50g of toluene solvent into a reactor, then adding 0.9g of cuprous chloride and 30ml of pyridine, introducing oxygen for pre-oxidation, wherein the flow of the oxygen is 100ml/min, the pre-oxidation temperature is controlled to be 25 ℃, and the pre-oxidation time is 0.5h, so as to prepare a copper-pyridine complex;
step two, dropwise adding 180g of toluene solution of 2, 6-dimethylphenol into a reactor containing the copper-pyridine complex, wherein the toluene solution contains 60g of 2, 6-dimethylphenol, the oxygen flow is 100ml/min, the reaction temperature is controlled to be 25-30 ℃, and the dropwise adding time is 0.5 h; after the dropwise addition is finished, keeping the reaction temperature unchanged, and continuing the reaction for 2.5h to generate a polyphenylene ether homopolymer intermediate with the molecular weight of 800-1500, and dissolving the polyphenylene ether homopolymer intermediate in a toluene solvent;
stopping introducing oxygen, dropwise adding concentrated sulfuric acid into the reaction system until the pH value of the system is 1-3, dropwise adding 3g of acetone, controlling the reaction temperature to be 48 ℃ and the reaction time to be 2.5h, carrying out condensation reaction on the polyphenyl ether homopolymer intermediate and the acetone under the catalysis of the concentrated sulfuric acid to generate the low-molecular-weight double-end hydroxyl polyphenyl ether, and finishing the reaction;
precipitating the low-molecular-weight hydroxyl-terminated polyphenylene oxide from toluene by using 1700g of methanol as a precipitating agent;
and step five, filtering the precipitated low-molecular-weight hydroxyl-terminated polyphenyl ether in vacuum, and drying at 70 ℃ to obtain a final product.
The product yield of the example is as follows: 85 percent.
Example two
The preparation method of the low molecular weight hydroxyl-terminated polyphenylene ether by the one-pot method in this embodiment comprises the following steps:
step one, adding 50g of toluene solvent into a reactor, then adding 0.9g of cuprous chloride and 30ml of pyridine, introducing oxygen for pre-oxidation, wherein the flow rate of the oxygen is 100ml/min, the pre-oxidation temperature is controlled to be 30 ℃, and the pre-oxidation time is 0.5h, so as to prepare a copper-pyridine complex;
step two, dropwise adding 180g of 2, 6-dimethylphenol toluene solution into a reactor containing the copper-pyridine complex, wherein the toluene solution contains 60g of 2, 6-dimethylphenol, the oxygen flow is 100ml/min, the reaction temperature is controlled to be 25-30 ℃, and the dropwise adding time is 1 h; after the dropwise addition is finished, keeping the reaction temperature unchanged, and continuing the reaction for 2.5h to generate a polyphenylene ether homopolymer intermediate with the molecular weight of 800-1500, and dissolving the polyphenylene ether homopolymer intermediate in a toluene solvent;
stopping introducing oxygen, dropwise adding hydrochloric acid into the reaction system until the pH value of the system is 1-3, dropwise adding 3g of acetone, controlling the reaction temperature to be 45 ℃ and the reaction time to be 3h, carrying out condensation reaction on the polyphenylene ether homopolymer intermediate and the acetone under the catalytic action of the hydrochloric acid to generate the low-molecular-weight double-end hydroxyl polyphenylene ether, and finishing the reaction;
precipitating the low-molecular-weight hydroxyl-terminated polyphenylene oxide from toluene by using 1700g of methanol as a precipitating agent;
and step five, filtering the precipitated low-molecular-weight hydroxyl-terminated polyphenyl ether in vacuum, and drying at 70 ℃ to obtain a final product.
The product yield of the example is as follows: 86 percent.
EXAMPLE III
The preparation method of the low molecular weight hydroxyl-terminated polyphenylene ether by the one-pot method in this embodiment comprises the following steps:
step one, adding 50g of toluene solvent into a reactor, then adding 0.9g of cuprous chloride and 30ml of pyridine, introducing oxygen for pre-oxidation, wherein the flow rate of the oxygen is 100ml/min, the pre-oxidation temperature is controlled to be 28 ℃, and the pre-oxidation time is 0.5h, so as to prepare a copper-pyridine complex;
step two, dropwise adding 180g of 2, 6-dimethylphenol toluene solution into a reactor containing the copper-pyridine complex, wherein the reactor contains 60g of 2, 6-dimethylphenol, the oxygen flow is 100ml/min, the reaction temperature is controlled to be 25-30 ℃, and the dropwise adding time is 45 min; after the dropwise addition is finished, keeping the reaction temperature unchanged, and continuing the reaction for 2.5h to generate a polyphenylene ether homopolymer intermediate with the molecular weight of 800-1500, and dissolving the polyphenylene ether homopolymer intermediate in a toluene solvent;
stopping introducing oxygen, dropwise adding concentrated sulfuric acid into the reaction system until the pH value of the system is 1-3, dropwise adding 3g of acetone, controlling the reaction temperature to be 50 ℃, reacting for 2 hours, carrying out condensation reaction on the polyphenyl ether homopolymer intermediate and the acetone under the catalysis of the concentrated sulfuric acid to generate the low-molecular-weight double-end hydroxyl polyphenyl ether, and finishing the reaction;
precipitating the low-molecular-weight hydroxyl-terminated polyphenylene oxide from toluene by using 1700g of methanol as a precipitating agent;
and step five, filtering the precipitated low-molecular-weight hydroxyl-terminated polyphenyl ether in vacuum, and drying at 70 ℃ to obtain a final product.
The product yield of the embodiment is as follows: 85 percent.
Comparative example
1. Adding 60g of methanol, 0.9g of cuprous chloride and 30ml of pyridine into a reaction bottle, controlling the oxygen flow at 100ml/min, the temperature at 25-30 ℃ and the pre-oxidation time at 30 min;
2. dropwise adding 180g of methanol solution of 2, 6-dimethylphenol and tetramethylbisphenol A into a reaction bottle, wherein the methanol solution contains 60g of 2, 6-dimethylphenol and 15g of tetramethylbisphenol A, the oxygen flow is 100ml/min, the temperature is controlled to be 25-30 ℃, and the dropwise adding time is 0.5-1.0 h; the molar ratio of 2, 6-dimethylphenol to tetramethylbisphenol A is 9.28: 1;
3. the reaction was continued for 6h and oxygen supply was stopped. In the reaction process, along with the reaction, low molecular weight hydroxyl-terminated polyphenyl ether is gradually precipitated;
4. vacuum filtering;
5. drying at 70 deg.C to obtain the final product.
Yield of the comparative example: 65 percent.
As seen from the preparation methods of the first to third examples and the comparative example, the one-pot method of the low molecular weight hydroxyl-terminated polyphenylene oxide of the embodiment of the invention does not need to use a tetramethyl bisphenol A raw material, i.e. does not need a matched production device of the tetramethyl bisphenol A raw material, and can greatly reduce the production cost. In addition, from the aspect of product yield, the yield of the low-molecular-weight hydroxyl-terminated polyphenylene oxide product prepared by the one-pot method in the embodiment of the invention is obviously higher than that of a comparative example, and the process feasibility of the preparation method provided by the embodiment of the invention is proved.
In addition, Gel Permeation Chromatography (GPC) detection is performed on the molecular weight double-terminal-hydroxyl-group polyphenylene ether product prepared by the preparation method provided in the first example, and the detection results are shown in FIG. 1 and FIG. 2, and specific measurement data are shown in Table 1.
TABLE 1 GPC measurement results
| Mn | Mw | Mz | Mz+1 | Mp | Polydispersity | |
| 1 | 2536 | 4525 | 8041 | 13458 | 3666 | 1.784 |
With reference to fig. 1, fig. 2 and table 1, the number average molecular weight Mn of the product of the first embodiment of the present invention is 2536, which indicates that the dihydroxy-terminated polyphenylene ether prepared by the preparation method provided by the embodiment of the present invention is low molecular weight dihydroxy-terminated polyphenylene ether, and can meet the application requirements in the high frequency and high speed electronic field.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. A preparation method of low-molecular-weight hydroxyl-terminated polyphenylene oxide by a one-pot method is characterized by comprising the following steps: carrying out oxidative condensation polymerization reaction on 2, 6-dimethylphenol under the condition of introducing oxygen and under the catalysis of a copper-pyridine complex to obtain a polyphenylene ether homopolymer intermediate, and controlling the reaction time to ensure that the number average molecular weight of the generated polyphenylene ether homopolymer intermediate is 800-1500; then the polyphenylene oxide homopolymer intermediate is subjected to condensation reaction with acetone under the catalysis of inorganic acid to generate the low molecular weight double-end hydroxyl polyphenylene oxide; the mass ratio of the 2, 6-dimethylphenol to the acetone is 20: 1; the number average molecular weight of the low molecular weight double-end hydroxyl polyphenylene ether is 1600-3000.
2. The method of claim 1, comprising:
step one, adding a toluene solvent into a reactor, then adding cuprous chloride and pyridine, introducing oxygen for pre-oxidation, and controlling the pre-oxidation temperature to be 25-30 ℃ to prepare the copper-pyridine complex;
step two, adding the toluene solution of the 2, 6-dimethylphenol into a reactor containing the copper-pyridine complex, controlling the reaction temperature to be 25-30 ℃ under the condition of introducing oxygen, gradually carrying out oxidative condensation polymerization reaction, and controlling the reaction time to generate the polyphenylene ether homopolymer intermediate with the molecular weight of 800-1500, and dissolving the intermediate in a toluene solvent;
and step three, stopping introducing oxygen, then adding the inorganic acid and the acetone into a reaction system in sequence, controlling the reaction temperature to be 45-50 ℃, controlling the reaction time, carrying out condensation reaction on the polyphenyl ether homopolymer intermediate and the acetone under the catalysis of the inorganic acid to generate the low-molecular-weight hydroxyl-terminated polyphenyl ether, and finishing the reaction.
3. The method of claim 2, further comprising, after the third step:
and step four, using methanol as a precipitator to precipitate the low molecular weight hydroxyl-terminated polyphenylene oxide from toluene.
4. The method according to claim 3, further comprising, after the fourth step:
and step five, filtering the precipitated low-molecular-weight hydroxyl-terminated polyphenyl ether in vacuum, and drying to obtain a final product.
5. The method according to claim 2, wherein the step two of adding the toluene solution of 2, 6-dimethylphenol comprises:
adding the 2, 6-dimethylphenol solution in toluene for 0.5-1.0 h.
6. The preparation method according to claim 2, wherein the reaction time in the second step is controlled to be 3-3.5 h; the reaction time in the third step is controlled to be 2-3 h.
7. The method according to claim 2, wherein the oxygen flow rate in the first step is 100ml/min, and the pre-oxidation time is 30 min.
8. The production method according to claim 1 or 2, wherein the inorganic acid is selected from concentrated sulfuric acid and hydrochloric acid.
9. The production method according to claim 1 or 2, characterized in that the mass ratio of the methanol to the total amount of toluene is 10: 1.
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| CN107353401A (en) * | 2017-08-24 | 2017-11-17 | 宋立旺 | A kind of double hydroxyl polyphenylene oxide and preparation method thereof |
| CN109161014A (en) * | 2018-07-13 | 2019-01-08 | 湘潭大学 | A kind of preparation method of low molecular weight both-end hydroxyl polyphenylene oxide resin |
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