CN113583234B - Preparation method of double-end methacrylate-based polyphenyl ether - Google Patents
Preparation method of double-end methacrylate-based polyphenyl ether Download PDFInfo
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- CN113583234B CN113583234B CN202110944537.3A CN202110944537A CN113583234B CN 113583234 B CN113583234 B CN 113583234B CN 202110944537 A CN202110944537 A CN 202110944537A CN 113583234 B CN113583234 B CN 113583234B
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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
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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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
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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Abstract
The invention discloses a preparation method of double-end methacrylate based polyphenyl ether, which comprises the following steps: the double-end hydroxyl polyphenyl ether and methacrylic acid react in a composite system of an organic solvent and water as a reaction solvent in the presence of a carbodiimide type condensing agent to generate double-end methacrylate polyphenyl ether; wherein the organic solvent is an organic solvent which does not generate any free radical, can dissolve the dihydroxy-terminated polyphenyl ether and is mutually soluble with water. According to the preparation method of the double-end methacrylate-based polyphenyl ether, the raw material does not adopt methacryloyl chloride or methacrylic anhydride, so that the problems of environmental pollution and corrosion of equipment materials caused by hydrogen chloride produced by adopting the methacryloyl chloride and the problems of inconvenience in obtaining the methacrylic anhydride raw material, high cost and low atom utilization rate can be avoided; has the advantages of simple preparation method and process, greatly reduced production cost and the like.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a preparation method of double-end methacrylate-based polyphenyl ether.
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. The conventional modification treatment method is as follows:
the method comprises the following steps of carrying out different chemical reactions by using hydroxyl-terminated polyphenyl ether resin and utilizing active-OH groups contained at two ends of a molecular chain of the hydroxyl-terminated polyphenyl ether resin to further prepare a series of modified polyphenyl ether resins meeting the application requirements in the high-frequency high-speed electronic field, wherein the phenolic hydroxyl and a compound containing a methyl propenyl group are subjected to esterification reaction to prepare methyl methacrylate-terminated polyphenyl ether, which is one example. Today, all factories and businesses in the world adopt methacryloyl chloride or methacrylic anhydride as an esterifying agent to perform esterification reaction with hydroxyl-terminated polyphenyl ether resin so as to synthesize the methyl methacrylate-terminated polyphenyl ether. However, the disadvantages of the two synthetic processes are obvious:
1. the adopted methacryloyl chloride has great toxicity and great danger, and a great amount of hydrogen chloride gas generated after the reaction causes serious environmental protection problems and great corrosivity to equipment; as is known, common stainless steel materials cannot meet the corrosion to chloride ions, so that the difficulty of selecting equipment materials for industrial devices is greatly increased.
2. Methacrylic anhydride belongs to special chemicals, the production cost is high, the market supply is less, and the market price is expensive; the double-end methacrylate group polyphenyl ether is easy to absorb water and hydrolyze in the storage process, and the atom utilization rate is very low in the chemical reaction process of synthesizing the double-end methacrylate group polyphenyl ether; in addition, the recycling can not be carried out, so that the production cost is greatly increased.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of double-end methacrylate based polyphenylene oxide. The technical problem to be solved by the invention is realized by the following technical scheme:
a method for preparing double-end methacrylate-based polyphenylene ether comprises the following steps: the method comprises the following steps of (1) taking a compound system of double-end hydroxyl polyphenyl ether and methacrylic acid in an organic solvent and water as a reaction solvent, and reacting to generate double-end methacrylate polyphenyl ether in the presence of a carbodiimide type condensing agent; the organic solvent does not generate any free radical, can dissolve the hydroxyl-terminated polyphenyl ether and is mutually soluble with water.
In one embodiment of the present invention, the organic solvent includes any one of N, N-dimethylformamide and N-methylpyrrolidone.
In one embodiment of the present invention, the carbodiimide-type condensing agent includes any one of dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
In one embodiment of the present invention, the mass ratio of the hydroxy-terminated polyphenylene ether to the organic solvent is 2-3: 10.
In one embodiment of the invention, the molar ratio of the methacrylic acid to the hydroxy-terminated polyphenylene ether is 2-2.5: 1.
In one embodiment of the present invention, the molar ratio of the carbodiimide type condensing agent to the methacrylic acid is 1: 1.
In one embodiment of the present invention, the mass ratio of the organic solvent to water is 10: 1.
In one embodiment of the invention, the reaction temperature of the reaction is room temperature to 60 ℃, and the reaction time is 4-6 h.
According to the preparation method of the double-end methacrylate-based polyphenyl ether, double-end hydroxyl polyphenyl ether and methacrylic acid are reacted in a composite system of an organic solvent and water as a reaction solvent in the presence of a carbodiimide type condensing agent to generate the double-end methacrylate-based polyphenyl ether; due to the existence of water, methacrylic acid is easy to dissociate to form carboxylate ions and hydronium ions, the carboxylate ions and the carbodiimide type special condensing agent are easy to react under very mild conditions to form an intermediate (N-acylurea derivative), the intermediate further reacts with phenolic hydroxyl in the dihydroxy-terminated polyphenylene ether to form phenolic ester and substituted urea precipitates, and the substituted urea is separated to obtain the product. The preparation method has simple process and can greatly reduce the cost of the product.
Compared with the synthesis process adopting methacryloyl chloride as an esterifying agent, the preparation method of the double-end methacrylate-based polyphenyl ether has the advantages that the production safety is greatly improved, the environmental protection problem caused by hydrogen chloride is avoided, the production equipment can adopt common stainless steel, and the production cost is reduced.
In addition, compared with the synthesis process adopting methacrylic anhydride as an esterifying agent, the atom utilization rate in the chemical reaction is basically 100 percent, the methacrylic acid raw material is easy to obtain and low in price, and the raw material cost of the product is greatly reduced.
The present invention will be described in further detail with reference to examples.
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 problems of the prior art that methacryloyl chloride or methacrylic anhydride is adopted as an esterifying agent to carry out esterification reaction with double-end hydroxyl polyphenyl ether resin to synthesize double-end methacrylate polyphenyl ether, the invention provides a preparation method of double-end methacrylate polyphenyl ether without adopting methacryloyl chloride or methacrylic anhydride.
The preparation method of the double-end methacrylate-based polyphenylene oxide provided by the embodiment of the invention comprises the following steps: the method comprises the following steps of (1) taking a compound system of double-end hydroxyl polyphenyl ether and methacrylic acid in an organic solvent and water as a reaction solvent, and reacting to generate double-end methyl acrylate polyphenyl ether in the presence of a carbodiimide type condensing agent; wherein the organic solvent is an organic solvent which does not generate any free radical, can dissolve the dihydroxy-terminated polyphenyl ether and is mutually soluble with water.
The preparation method of the double-end methacrylate-based polyphenylene oxide provided by the embodiment of the invention specifically comprises the following steps:
adding an organic solvent and dihydroxy-terminated polyphenyl ether into a reactor to dissolve the dihydroxy-terminated polyphenyl ether in the organic solvent without precipitation, and adding water;
adding methacrylic acid;
adding a carbodiimide type condensing agent for reaction to generate a product containing double-end methacrylate-based polyphenyl ether and substituted urea precipitates;
filtering the obtained product to remove the substituted urea precipitate;
and step five, precipitating the double-end methacrylate based polyphenyl ether by using alcohol or/and water as a precipitating agent, filtering and drying to obtain a target product.
It should be noted that the specific steps of the preparation method provided in the embodiment of the present invention are only used to illustrate the sequence of the operation of the preparation method, and in practical application, the specific steps are not necessarily executed according to five steps.
In the production method of the above embodiment, the organic solvent preferably includes any one of N, N-dimethylformamide and N-methylpyrrolidone.
In the production method of the above embodiment, the carbodiimide-type condensing agent preferably includes any one of dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
In the preparation method of the above example, the mass ratio of the hydroxy-terminated polyphenylene ether to the organic solvent is preferably 2-3: 10.
In the preparation method of the above example, the molar ratio of methacrylic acid to bishydroxypolyphenylene ether is preferably 2-2.5: 1.
In the production method of the above example, the molar ratio of the carbodiimide type condensing agent to methacrylic acid is preferably 1: 1.
In the preparation method of the above example, the mass ratio of the organic solvent to water is preferably 10: 1.
In the preparation method of the above embodiment, the reaction temperature is preferably room temperature to 60 ℃, and the reaction time is preferably 4 to 6 hours.
According to the preparation method of the double-end methacrylate-based polyphenyl ether, double-end hydroxyl polyphenyl ether and methacrylic acid are reacted in a composite system of an organic solvent and water as a reaction solvent in the presence of a carbodiimide type condensing agent to generate the double-end methacrylate-based polyphenyl ether; because of the existence of water, methacrylic acid is easy to dissociate to form carboxylate ions and hydronium ions, the carboxylate ions and the special condensing agent are easy to react to form an intermediate under very mild conditions, the intermediate further reacts with phenolic hydroxyl in the hydroxyl-terminated polyphenylene oxide to form phenolic ester and substituted urea precipitates, and the product is obtained after the substituted urea is separated. According to the preparation method of the double-end methacrylate-based polyphenyl ether, the raw material does not adopt methacryloyl chloride or methacrylic anhydride, so that the problems of environmental pollution and corrosion of equipment materials caused by hydrogen chloride produced by adopting methacryloyl chloride can be avoided, and the problems of inconvenience in obtaining the methacrylic anhydride raw material, high cost and low atom utilization rate can be solved; has the advantages of simple preparation method and process, greatly reduced production cost and the like.
Example one
The method for preparing a double-terminal methacrylate-based polyphenylene ether according to the embodiment includes:
step one, adding 100kg of N, N-Dimethylformamide (DMF) and 30kg of hydroxyl-terminated polyphenylene oxide (Mn 1600, 0.0188kmol) into a reaction kettle, completely dissolving the hydroxyl-terminated polyphenylene oxide in an organic solvent under stirring, and adding 10kg of water;
adding 2.632kg (0.0376kmol) of methacrylic acid, wherein the molar ratio of the methacrylic acid to the hydroxyl-terminated polyphenyl ether is controlled to be 2: 1;
step three, adding 7.43kg (0.0376kmol) of Dicyclohexylcarbodiimide (DCC) for reaction at 40 ℃ for 5h to generate a product containing a bis (terminal methacrylate) polyphenylene oxide and substituted urea precipitate, wherein the molar ratio of dicyclohexylcarbodiimide to methacrylic acid is controlled to be 1: 1;
step four, filtering the obtained product to remove the substituted urea precipitate (dicyclohexylurea DCU);
and step five, precipitating the double-end methacrylate based polyphenyl ether by taking water with the weight being 10 times that of DMF as a precipitating agent, filtering in vacuum, and drying at 80 ℃ to obtain a target product.
The product yield of the example is as follows: 91 percent.
Example two
The method for preparing a double-terminal methacrylate-based polyphenylene ether according to the embodiment includes:
step one, adding 100kg of N-methyl pyrrolidone (NMP) and 30kg of hydroxyl-terminated polyphenylene oxide (Mn 1600, 0.0188Kmol) into a reaction kettle, completely dissolving the hydroxyl-terminated polyphenylene oxide in an organic solvent under stirring, and adding 10kg of water;
adding 2.632kg (0.0376kmol) of methacrylic acid, wherein the molar ratio of the methacrylic acid to the hydroxyl-terminated polyphenyl ether is controlled to be 2: 1;
adding 5.42kg (0.0376kmol) of Diisopropylcarbodiimide (DIC) for reaction at 40 ℃ for 5h to generate a product containing bis (terminal methacrylate) polyphenyl ether and substituted urea precipitate (diisopropylurea DIU), wherein the molar ratio of diisopropylcarbodiimide to methacrylic acid is controlled to be 1: 1;
filtering the obtained product to remove the substituted urea precipitate;
and step five, precipitating the double-end methacrylate based polyphenyl ether by using water with the weight being 10 times that of NMP as a precipitating agent, filtering in vacuum, and drying at 80 ℃ to obtain a target product.
The product yield of the example is as follows: 90 percent.
EXAMPLE III
The method for preparing a double-terminal methacrylate-based polyphenylene ether according to the embodiment includes:
step one, adding 100kg of N-methyl pyrrolidone (NMP) and 20kg of hydroxyl-terminated polyphenylene oxide (Mn is 3000 and 0.0067kmol) into a reaction kettle, completely dissolving the hydroxyl-terminated polyphenylene oxide in an organic solvent under stirring, and adding 10kg of water;
step two, adding 1.167kg (0.0167kmol) of methacrylic acid, and controlling the molar ratio of the methacrylic acid to the hydroxyl-terminated polyphenyl ether to be 2.5: 1;
step three, adding 2.407kg (0.00167kmol) of Diisopropylcarbodiimide (DIC) for reaction at the temperature of 60 ℃ for 4 hours to generate a product containing bis (terminal methacrylate) polyphenyl ether and substituted urea precipitate (diisopropylurea DIU), wherein the molar ratio of diisopropylcarbodiimide to methacrylic acid is controlled to be 1: 1;
step four, filtering the obtained product to remove the substituted urea precipitate;
and step five, precipitating the double-end methacrylate-based polyphenyl ether by using water with the weight 10 times that of NMP as a precipitating agent, filtering in vacuum, and drying at 80 ℃ to obtain the target product.
The product yield of the example is as follows: 91 percent.
Example four
The method for preparing double terminal methacrylate based polyphenylene ether of the embodiment comprises the following steps:
step one, adding 100kg of N, N-Dimethylformamide (DMF) and 25kg of hydroxyl-terminated polyphenylene oxide (Mn 2500, 0.01kmol) into a reaction kettle, completely dissolving the hydroxyl-terminated polyphenylene oxide in an organic solvent under stirring, and adding 10kg of water;
step two, adding 1.540kg (0.022kmol) of methacrylic acid, and controlling the molar ratio of the methacrylic acid to the hydroxyl-terminated polyphenyl ether to be 2.2: 1;
step three, adding 4.347kg (0.022kmol) of Dicyclohexylcarbodiimide (DCC) to react, wherein the reaction temperature is room temperature, the reaction time is 6 hours, a product containing double-end methacrylate-based polyphenyl ether and substituted urea precipitates is generated, and the molar ratio of dicyclohexylcarbodiimide to methacrylic acid is controlled to be 1: 1;
step four, filtering the obtained product to remove the substituted urea precipitate (dicyclohexylurea DCU);
and step five, precipitating the double-end methacrylate-based polyphenyl ether by using water with the weight being 10 times that of DMF as a precipitating agent, filtering in vacuum, and drying at 80 ℃ to obtain the target product.
The product yield of the example is as follows: 90 percent.
The number average molecular weight of the bishydroxyphenylene ether used in the embodiment of the present invention is not limited to the number average molecular weight given in the above examples, and the number average molecular weight of the bishydroxyphenylene ether is not limited.
Comparative example 1
1. Adding 100kg of toluene and 20kg of bis (hydroxy-terminated polyphenylene ether) (Mn 1600, 0.0125kmol) into a reaction kettle, and completely dissolving the mixture under stirring;
2. after the temperature is raised to 70 ℃, 3.9Kg (0.0375kmol) of methacryloyl chloride is dripped for 0.5 hour;
3. 0.5kg of triethylamine is added dropwise, and after the reaction is continued for 10 hours, the reaction is finished;
4. methanol with 10 times of toluene amount is used as a precipitator to precipitate products;
5. vacuum filtering;
6. drying at 80 ℃ to obtain the product.
The product yield is as follows: 84 percent
In the reaction process, a large amount of HCl gas is generated and needs to be further treated, and production equipment needs special materials, so that the production cost of the product is greatly increased.
Comparative example II
1. 100kg of toluene and 32kg of bishydroxyphenylene oxide (Mn 1600, 0.02kmol) were charged into a reaction vessel and completely dissolved with stirring;
2. after the temperature is raised to 80 ℃, 10Kg (0.06kmol) of methacrylic anhydride is dripped for 0.5 hour;
3. dropwise adding 5kg of triethylamine, and after continuously reacting for 5 hours, finishing the reaction;
4. methanol with 10 times of toluene amount is used as a precipitator to precipitate products;
5. vacuum filtering;
6. drying at 80 ℃ to obtain the product.
The product yield is as follows: 85 percent of
In the reaction process, the atom utilization rate of methacrylic anhydride is only about 33%, and the production cost of the product can be greatly increased.
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 (8)
1. A method for preparing double-end methacrylate group polyphenyl ether is characterized by comprising the following steps: the method comprises the following steps of (1) taking a compound system of double-end hydroxyl polyphenyl ether and methacrylic acid in an organic solvent and water as a reaction solvent, and reacting to generate double-end methacrylate polyphenyl ether in the presence of a carbodiimide type condensing agent; the organic solvent does not generate any free radical, can dissolve the dihydroxy-terminated polyphenyl ether, and is mutually soluble with water.
2. The production method according to claim 1, wherein the organic solvent includes any one of N, N-dimethylformamide and N-methylpyrrolidone.
3. The production method according to claim 1, characterized in that the carbodiimide-type condensing agent includes any one of dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
4. The production method according to claim 1, wherein the mass ratio of the hydroxy-terminated polyphenylene ether to the organic solvent is 2-3: 10.
5. The production method according to claim 1, wherein the molar ratio of the methacrylic acid to the hydroxy-terminated polyphenylene ether is 2-2.5: 1.
6. The production method according to claim 1, characterized in that the molar ratio of the carbodiimide-type condensing agent to the methacrylic acid is 1: 1.
7. The production method according to claim 1, wherein the mass ratio of the organic solvent to water is 10: 1.
8. The method of claim 1, wherein the reaction is carried out at a temperature of room temperature to 60 ℃ for 4 to 6 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109836575A (en) * | 2019-03-11 | 2019-06-04 | 陕西硕博电子材料有限公司 | A kind of preparation process of the methacrylate functionalized polyphenylene oxide of thermosetting property |
| CN110437439A (en) * | 2019-08-27 | 2019-11-12 | 广东省石油与精细化工研究院 | A kind of synthetic method of alkenyl blocking polyphenyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109836575A (en) * | 2019-03-11 | 2019-06-04 | 陕西硕博电子材料有限公司 | A kind of preparation process of the methacrylate functionalized polyphenylene oxide of thermosetting property |
| CN110437439A (en) * | 2019-08-27 | 2019-11-12 | 广东省石油与精细化工研究院 | A kind of synthetic method of alkenyl blocking polyphenyl ether |
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