CN118580484A - A kind of divinylbenzene end-capped modified fluorinated polyphenylene ether and its preparation method and application - Google Patents
A kind of divinylbenzene end-capped modified fluorinated polyphenylene ether and its preparation method and application Download PDFInfo
- Publication number
- CN118580484A CN118580484A CN202410748589.7A CN202410748589A CN118580484A CN 118580484 A CN118580484 A CN 118580484A CN 202410748589 A CN202410748589 A CN 202410748589A CN 118580484 A CN118580484 A CN 118580484A
- Authority
- CN
- China
- Prior art keywords
- divinylbenzene
- fluorine
- polyphenyl ether
- containing polyphenyl
- capped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—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 from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- 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
- C08G65/40—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 from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4081—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 from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group forming cyclic polymers or oligomers
-
- 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
- C08G65/40—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 from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—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 from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
本发明属于高分子材料技术领域，具体涉及一种双乙烯基苯封端改性含氟聚苯醚及其制备方法和应用。本发明提供的双乙烯基苯封端改性含氟聚苯醚，具有式I所示化学结构。该树脂合成制备工艺简便、易于分离提纯、产率高，具有低的分布系数，且分子量可根据反应单体官能团摩尔比进行调控；该树脂分子结构中含有活性双乙烯基苯结构，可通过自由基聚合制备得到含氟低介电高分子材料。本发明在双乙烯基苯封端改性含氟聚苯醚结构中引入含有大自由体积的六氟异丙基及氟原子，赋予了材料低的介电常数、低介电损耗和低的吸湿率，且本发明提供的产品具有高的固化活性，固化后的低介电高分子材料在覆铜板用介电常数材料中具有重要的应用价值。 The present invention belongs to the technical field of polymer materials, and specifically relates to a divinylbenzene end-capped modified fluorinated polyphenylene ether and a preparation method and application thereof. The divinylbenzene end-capped modified fluorinated polyphenylene ether provided by the present invention has a chemical structure shown in Formula I. The resin has a simple synthesis and preparation process, is easy to separate and purify, has a high yield, has a low distribution coefficient, and the molecular weight can be regulated according to the molar ratio of the functional groups of the reaction monomers; the resin molecular structure contains an active divinylbenzene structure, and a fluorinated low dielectric polymer material can be prepared by free radical polymerization. The present invention introduces hexafluoroisopropyl and fluorine atoms containing a large free volume into the divinylbenzene end-capped modified fluorinated polyphenylene ether structure, giving the material a low dielectric constant, low dielectric loss and low moisture absorption rate, and the product provided by the present invention has high curing activity, and the cured low dielectric polymer material has important application value in dielectric constant materials for copper clad laminates.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a divinylbenzene end-capped modified fluorine-containing polyphenyl ether, and a preparation method and application thereof.
Background
The 5G communication technology is one of the fastest growing technologies and industries in recent years, and has the characteristics of large bandwidth, high frequency, high speed, low latency, etc. Therefore, there is a higher demand for a matrix resin for manufacturing a copper-clad plate for 5G, which is required to have a low dielectric constant, a low dielectric loss, a low water absorption, and the like.
The most widely applied matrix resin in the traditional copper-clad plate manufacturing industry is epoxy resin, and the dielectric constant is too high in a high-frequency range due to poor dimensional stability when the epoxy resin is used at a high temperature, so that the requirement of high-speed high-frequency development of electronic industry products in the 5G field cannot be met. The thermosetting low molecular weight modified polyphenyl ether resin is a low dielectric material for a medium-high speed copper-clad plate, which is developed in recent years, and the cured resin has relatively low dielectric constant, dielectric loss and water absorption rate because the molecular structure does not contain polar groups. At present, thermosetting low molecular weight polyphenyl ether is mainly prepared by a monomer copolymerization method: firstly, 2, 6-dimethylphenol and tetramethyl bisphenol A are used as raw materials, water-methanol or chlorobenzene-methanol is used as a solvent, phase transfer catalytic oxidation copolymerization is carried out to prepare low molecular weight hydroxyl-terminated polyphenyl ether, and then the low molecular weight hydroxyl-terminated polyphenyl ether resin is prepared by reacting with a capping agent. In the first step of phase transfer catalytic oxidation copolymerization, part of 2, 6-dimethylphenol is homopolymerized to form monofunctional polyphenyl ether, the yield is only about 80%, and the molecular weight dispersion coefficient of the resin is larger (more than 1.3); and the copolymerization and the introduction of the vinyl structure need to be carried out step by step, thus increasing the difficulty of product separation and purification.
Disclosure of Invention
In order to solve the problems in the prior art, the invention prepares the modified fluorine-containing polyphenyl ether resin with low molecular weight and end capped by divinylbenzene through a one-pot method, the resin has the advantages of convenient synthesis and preparation process, easy separation and purification, high yield and high curing activity, and meanwhile, the hexafluoroisopropyl and fluorine atoms with larger free volume are further introduced into a molecular structure, so that the material has low dielectric constant, dielectric loss and low water absorption rate, and has important application value in the field of copper-clad plate low dielectric polymer materials.
In order to achieve the above object, the present invention provides the following technical solutions.
The invention provides a divinylbenzene end-capped modified fluorine-containing polyphenyl ether, which has a chemical structure shown in a formula I:
the number average molecular weight of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether is 1000-12000.
The invention also provides a preparation method of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether, which comprises the following steps:
dissolving 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl in an organic solvent, and polymerizing under the condition of an alkaline catalyst to obtain a solution containing bisphenol oligomer;
Mixing the solution containing bisphenol salt oligomer with a blocking agent, and carrying out a blocking reaction to obtain a divinylbenzene-blocked modified fluorine-containing polyphenyl ether;
the end-capping agent is p-chloromethyl styrene.
Preferably, the ratio of the amounts of the 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl is 1.2 to 1.6:1.
Preferably, the polymerization temperature is 60-80 ℃ and the heat preservation time is 4-12 h.
Preferably, the amount of material of the capping agent is 2 times the difference between the amounts of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl material.
Preferably, the temperature of the end capping reaction is 40-50 ℃, and the heat preservation time is 12-24 h.
The invention also provides application of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether or the divinylbenzene end-capped modified fluorine-containing polyphenyl ether prepared by the preparation method in a fluorine-containing polyphenyl ether polymer material, wherein the fluorine-containing polyphenyl ether polymer material has a dielectric constant of 2.6-2.7 at1 MHz.
The invention also provides a fluorine-containing polyphenyl ether polymer material which is obtained by curing and polymerizing the divinylbenzene end-capped modified fluorine-containing polyphenyl ether; the divinylbenzene end-capped modified fluorine-containing polyphenyl ether is the divinylbenzene end-capped modified fluorine-containing polyphenyl ether or the divinylbenzene end-capped modified fluorine-containing polyphenyl ether prepared by the preparation method.
The invention also provides a preparation method of the fluorine-containing polyphenyl ether polymer material, which comprises the following steps:
Dissolving the divinylbenzene end-capped modified fluorine-containing polyphenyl ether and a curing agent in a ketone solvent, adding an initiator, and performing curing polymerization to obtain the fluorine-containing polyphenyl ether polymer material.
The invention also provides an application of the fluorine-containing polyphenyl ether polymer material prepared by the technical scheme or the preparation method of the fluorine-containing polyphenyl ether polymer material in the field of dielectric polymer materials for copper-clad plates.
The invention provides a divinylbenzene end-capped modified fluorine-containing polyphenyl ether, which has a chemical structure shown in a formula I:
the number average molecular weight of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether is 1000-12000.
The divinylbenzene end-capped modified fluorine-containing polyphenyl ether provided by the invention has high curing activity, can be polymerized and cured under the action of a curing agent and an initiator, contains hexafluoroisopropyl and fluorine atoms with large free volume in the structure, endows the material with low dielectric constant and low moisture absorption rate, and has important application value in low dielectric constant materials for copper-clad plates.
The invention also provides a preparation method of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether, which comprises the following steps: dissolving 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl in an organic solvent, and polymerizing under the condition of an alkaline catalyst to obtain a solution containing bisphenol oligomer; mixing the solution containing bisphenol salt oligomer with a blocking agent, and carrying out a blocking reaction to obtain a divinylbenzene-blocked modified fluorine-containing polyphenyl ether; the end-capping agent is p-chloromethyl styrene.
The preparation method of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether provided by the invention is simple and convenient in route, can be prepared by adopting a one-pot method, has a low molecular weight distribution coefficient, is high in preparation process yield, is easy to separate and purify, and is beneficial to industrial amplified production, and the molecular weight can be regulated and controlled by the mass ratio of the active fluorine-containing bisphenol monomer to the active fluorine-containing biphenyl monomer (the molar ratio of the functional groups is regulated and controlled).
Drawings
FIG. 1 is a 19 FNMR spectrum of a divinylbenzene-terminated modified fluorine-containing polyphenylene ether provided in example 1;
FIG. 2 is a 1 HNMR of the divinylbenzene-terminated modified fluorine-containing polyphenylene ether provided in example 1;
FIG. 3 is an infrared spectrum of the divinylbenzene-terminated modified fluorine-containing polyphenylene ether provided in example 1.
Detailed Description
The invention provides a divinylbenzene end-capped modified fluorine-containing polyphenyl ether, which has a chemical structure shown in a formula I:
In the present invention, the number average molecular weight of the divinylbenzene-terminated modified fluorine-containing polyphenylene ether is 1000 to 12000, preferably 2000 to 10000.
The divinylbenzene end-capped modified fluorine-containing polyphenyl ether with the chemical structure shown in the formula I provided by the invention has the advantages that hexafluoroisopropyl and fluorine atoms with large free volume are introduced into the structure, so that the material has low dielectric constant, low dielectric loss and low moisture absorption rate, and the divinylbenzene end-capped modified fluorine-containing polyphenyl ether provided by the invention has a divinylbenzene structure and high curing activity, and can be cured and polymerized under the action of a curing agent and an initiator to prepare the fluorine-containing low-dielectric high-molecular material.
The invention also provides a preparation method of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether, which comprises the following steps:
dissolving 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl in an organic solvent, and polymerizing under the condition of an alkaline catalyst to obtain a solution containing bisphenol oligomer;
and mixing the solution containing the bisphenolate oligomer with a blocking agent, and carrying out a blocking reaction to obtain the divinylbenzene-blocked modified fluorine-containing polyphenyl ether.
The invention dissolves 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl in an organic solvent, and carries out polymerization under the condition of an alkaline catalyst to obtain a solution containing bisphenol salt oligomer.
In the present invention, the organic solvent is preferably one of N-methylpyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide. In the present invention, the basic catalyst is preferably sodium carbonate and/or potassium carbonate, more preferably sodium carbonate.
In the present invention, the ratio of the amounts of the 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl is preferably 1.2 to 1.6:1, more preferably 1.3 to 1.5:1.
In the present invention, the ratio of the amounts of the basic catalyst and the substance of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane is preferably 1.0 to 1.2:1, more preferably 1.1:1. In the present invention, the mass of the organic solvent is preferably 2 to 4 times, more preferably 3 times, the sum of the mass of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl.
In the present invention, the polymerization temperature is preferably 60 to 80 ℃, more preferably 70 ℃; the holding time is preferably 4 to 12 hours, more preferably 5 to 10 hours.
In the present invention, the molecular weight of the bisphenolate oligomer is preferably 1000 to 12000, more preferably 1500 to 9000.
After the solution containing bisphenol salt oligomer is obtained, the solution containing bisphenol salt oligomer is mixed with a blocking agent for blocking reaction, and the divinylbenzene blocking modified fluorine-containing polyphenyl ether is obtained.
In the present invention, the end-capping agent is preferably p-chloromethylstyrene. In the present invention, the amount of the substance of the end-capping agent is preferably 2 times the difference between the amounts of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl substance.
In the present invention, the temperature of the capping reaction is preferably 40 to 50 ℃, more preferably 45 ℃, and the holding time is preferably 12 to 24 hours, more preferably 15 to 20 hours.
In the invention, after the end capping reaction, the method preferably further comprises the steps of sequentially settling and suction-filtering the system obtained by the end capping reaction, and sequentially washing and drying a solid phase obtained by the suction-filtering.
In the present invention, the sedimentation is preferably water sedimentation, and the water mass of the water sedimentation is 10 to 20 times, more preferably 15 times, the mass of the organic solvent. In the present invention, the washing reagent is preferably ethanol or methanol; the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 40-80 ℃, more preferably 50-70 ℃; the drying time is preferably 12 to 24 hours, more preferably 15 to 20 hours.
The preparation method of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether is simple and convenient, the preparation method is prepared by adopting a one-pot method, the molecular weight can be regulated and controlled by the mass ratio of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl (the molar ratio of functional groups is regulated and controlled), the preparation method has a lower molecular weight distribution coefficient, the preparation process yield is high, and the product is easy to separate and purify and is beneficial to industrialized amplified production.
The invention also provides application of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether prepared by the technical scheme or the preparation method of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether in fluorine-containing polyphenyl ether polymer materials.
In the invention, the fluorine-containing polyphenyl ether polymer material has a dielectric constant of 2.6-2.7, preferably 2.62-2.68, at 1 MHz.
The invention also provides a fluorine-containing polyphenyl ether polymer material which is obtained by solidifying the modified fluorine-containing polyphenyl ether capped by divinylbenzene; the divinylbenzene-end-capped modified fluorine-containing polyphenyl ether is the divinylbenzene-end-capped modified fluorine-containing polyphenyl ether.
In the invention, the preparation raw materials of the fluorine-containing polyphenyl ether polymer material comprise divinylbenzene end-capped modified fluorine-containing polyphenyl ether, a curing agent, an initiator and a ketone solvent;
In the present invention, the curing agent preferably includes p, p '-divinyl-1, 2-diphenylethane or 1, 4-divinylbenzene, more preferably p, p' -divinyl-1, 2-diphenylethane. In the present invention, the initiator is preferably dibenzoyl peroxide or azobisisobutyronitrile, more preferably azobisisobutyronitrile. In the present invention, the ketone solvent preferably includes cyclohexanone and/or butanone, more preferably cyclohexanone.
In the invention, the mass ratio of the divinylbenzene-terminated modified fluorine-containing polyphenyl ether, the curing agent and the initiator is preferably 1:0.2 to 0.4:0.005 to 0.01, more preferably 1:0.3:0.006 to 0.009.
In the invention, the dosage ratio of the divinylbenzene-terminated modified fluorine-containing polyphenyl ether to the ketone solvent is preferably 1g:2 to 4mL, more preferably 1g: 2-3 mL.
The invention also provides a preparation method of the fluorine-containing polyphenyl ether polymer material, which comprises the following steps:
Dissolving the divinylbenzene end-capped modified fluorine-containing polyphenyl ether and a curing agent in a ketone solvent, adding an initiator, and performing curing polymerization to obtain the fluorine-containing polyphenyl ether polymer material.
In the present invention, the temperature of the curing polymerization is preferably 80 to 120 ℃, more preferably 90 to 110 ℃; the holding time is preferably 12 to 24 hours, more preferably 15 to 20 hours.
The invention also provides application of the fluorine-containing polyphenyl ether polymer material or the prepared fluorine-containing polyphenyl ether polymer material in the field of dielectric polymer materials for copper-clad plates.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The following raw materials and medicines used in the examples were:
P-chloromethylstyrene (purity 99%), p' -divinyl-1, 2-diphenylethane (purity 99%): shandong Star Shun New Material Co., ltd;
2, 2-bis (4-hydroxyphenyl) hexafluoropropane (purity 99%), decafluorobiphenyl (purity 99%), 1, 4-divinylbenzene (purity 99%), dibenzoyl peroxide (purity 99%), azobisisobutyronitrile (purity 99%): shanghai dari fine chemicals limited;
Potassium carbonate, sodium carbonate, N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, cyclohexanone, butanone, ethanol, methanol: shanghai national pharmaceutical Congress chemical reagent Co., ltd.
Example 1
To a 500mL dry three-necked flask equipped with a mechanical stirring and condensing tube, 47.072g (0.14 mol) of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane, 33.411g (0.1 mol) of decafluorobiphenyl and 170mL of N-methylpyrrolidone were added, 19.349g (0.14 mol) of potassium carbonate was added, stirring was performed for 4 hours at 80℃and then 12.208g (0.08 mol) of p-chloromethylstyrene was added, stirring was performed for 24 hours at 40℃and the reaction was completed, the reaction solution was poured into 2500mL of water and settled, the obtained solid phase was washed with ethanol and dried in vacuo (the temperature of vacuum drying was 50 ℃ for 20 hours) to obtain a divinylbenzene-end-capped modified fluorine-containing polyphenylene ether having a yield of 95%, a number average molecular weight of 3887, a weight average molecular weight of 4680 and a distribution coefficient of 1.20.
FIG. 1 is a 19 F NMR chart of a divinylbenzene-terminated modified fluorine-containing polyphenylene ether prepared in example 1, and it can be seen from FIG. 1 that three fluorine atom absorption peaks appear, wherein-64.10 ppm absorption peak is a fluorine atom on hexafluoroisopropyl group, and the absorption peaks at-137.55 ppm and-152.30 ppm are respectively two fluorine atom absorption peaks on biphenyl structural units.
FIG. 2 is a diagram of 1 HNMR of the modified fluorine-containing polyphenylene ether blocked by divinylbenzene prepared in example 1, and it can be seen from FIG. 2 that proton absorption peaks on benzene rings respectively appear at 6.91-7.07ppm and 7.27-7.44ppm, and three proton absorption peaks on styrene double bonds respectively appear at 5.24-5.28ppm, 5.74-5.80ppm and 6.66-6.76ppm due to influence of double bond shielding effect, and methine proton absorption peaks connected with benzene rings appear at 5.07 ppm.
FIG. 3 is a FT-IR chart of a divinylbenzene-terminated modified fluorine-containing polyphenylene ether prepared in example 1 from which typical vibration absorption peaks for vinyl double bonds can appear at 1622cm -1 and typical vibration absorption peaks for fluorocarbon bonds (C-F) and ether bonds (C-O-C) at 1177cm -1 and 1266cm -1, respectively.
Example 2
To a 500mL dry three-necked flask equipped with a mechanical stirring and condensing tube, 53.7968g (0.16 mol) of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane, 33.411g (0.1 mol) of decafluorobiphenyl and 320mL of N, N-dimethylformamide were added, 24.8778g (0.18 mol) of potassium carbonate was added, stirring was performed for 12 hours at 60℃and 18.312g (0.12 mol) of p-chloromethylstyrene was added, stirring was performed for 12 hours at 50℃and the reaction was ended, the reaction solution was poured into 4000mL of water and settled, suction-filtered, and the product was washed with ethanol and dried under vacuum (the temperature of vacuum drying was 50℃for 20 hours) to obtain a divinylbenzene-end-capped modified fluorine-containing polyphenylene ether having a yield of 96%, a number average molecular weight 6612, a weight average molecular weight of 66133, and a distribution coefficient of 1.26.
Example 3
To a 500mL dry three-necked flask equipped with a mechanical stirring and condensing tube, 40.3476g (0.12 mol) of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane, 33.411g (0.1 mol) of decafluorobiphenyl and 230mL of N, N-dimethylacetamide were added, 19.9022g (0.144 mol) of potassium carbonate was added, stirring was performed for 8 hours at a temperature of 70℃and then 6.104g (0.04 mol) of p-chloromethylstyrene was added, stirring was performed for 18 hours at 50℃and the reaction was ended, and the reaction solution was poured into 3000mL of water for sedimentation, suction filtration and washing the product with ethanol and vacuum drying (the temperature of vacuum drying was 50℃for 20 hours) to obtain a divinylbenzene-end-capped modified fluorine-containing polyphenylene ether having a yield of 95%, a number average molecular weight of 1837, a weight average molecular weight of 2168 and a distribution coefficient of 1.18.
Application example 1
6.0G of the divinylbenzene-terminated modified fluorine-containing polyphenyl ether prepared in the example 1 and 1.2g of p, p' -divinyl-1, 2-diphenylethane are dissolved in 12mL of cyclohexanone, 0.03g of azodiisobutyronitrile initiator is added, the resin solution is poured into a glass mold, and the resin solution is cured and polymerized in an oven at 80 ℃ for 24 hours to obtain the fluorine-containing polyphenyl ether polymer material.
Through testing, the fluorine-containing polyphenyl ether polymer material prepared in application example 1 has a dielectric constant of 2.64 and a dielectric loss of 0.0028 under 1 MHz; moisture absorption rate: 0.028%.
Application example 2
6.0G of the divinylbenzene-terminated modified fluorine-containing polyphenylene ether prepared in example 1 and 2.4g of p, p' -divinyl-1, 2-diphenylethane were dissolved in 18mL of cyclohexanone, and 0.06g of dibenzoyl peroxide initiator was added to obtain a resin solution; and pouring the resin solution into a glass mold, and curing and polymerizing for 12 hours in a baking oven at 120 ℃ to obtain the fluorine-containing polyphenyl ether polymer material.
Through testing, the fluorine-containing polyphenyl ether polymer material prepared in application example 2 has a dielectric constant of 2.62 and a dielectric loss of 0.0024 under 1 MHz; moisture absorption rate: 0.024%.
Application example 3
6.0G of the divinylbenzene-terminated modified fluorine-containing polyphenylene ether prepared in example 2 and 1.2g of 1, 4-divinylbenzene were dissolved in 12mL of cyclohexanone, and 0.045g of azobisisobutyronitrile initiator was added to obtain a resin solution; and pouring the resin solution into a glass mold, and curing and polymerizing for 18 hours in a baking oven at the temperature of 100 ℃ to obtain the fluorine-containing polyphenyl ether polymer material.
Through testing, the fluorine-containing polyphenyl ether polymer material prepared in application example 3 has a dielectric constant of 2.68 and a dielectric loss of 0.0032 under 1 MHz; moisture absorption rate: 0.031%.
Application example 4
6.0G of the divinylbenzene-terminated modified fluorine-containing polyphenylene ether prepared in example 3 and 2.4g of 1, 4-divinylbenzene were dissolved in 15mL of butanone, and 0.03g of dibenzoyl peroxide initiator was added to obtain a resin solution; and pouring the resin solution into a glass mold, and curing and polymerizing for 24 hours in an oven at 80 ℃ to obtain the fluorine-containing polyphenyl ether polymer material.
Through testing, the fluorine-containing polyphenyl ether polymer material prepared in application example 4 has a dielectric constant of 2.65 and a dielectric loss of 0.003 at 1 MHz; moisture absorption rate: 0.029%.
Test instruments and standards used in application examples 1 to 4:
The molecular weight is obtained by testing on a waters 1525 gel permeation chromatograph with reference to national standard GB/T27843-2011, and the testing solvent is N, N-dimethylformamide; the dielectric constant (Dk) and the dielectric loss (Df) are obtained by testing on an Agilent4291B impedance analyzer with reference to national standard GB/T1409-2006; the moisture absorption rate is obtained by a weighing method test with reference to national standard GB 1034-70.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. The divinylbenzene-terminated modified fluorine-containing polyphenyl ether is characterized by having a chemical structure shown in a formula I:
the number average molecular weight of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether is 1000-12000.
2. The method for preparing the divinylbenzene-terminated modified fluorine-containing polyphenylene ether according to claim 1, comprising the steps of:
dissolving 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl in an organic solvent, and polymerizing under the condition of an alkaline catalyst to obtain a solution containing bisphenol oligomer;
Mixing the solution containing bisphenol salt oligomer with a blocking agent, and carrying out a blocking reaction to obtain a divinylbenzene-blocked modified fluorine-containing polyphenyl ether;
the end-capping agent is p-chloromethyl styrene.
3. The method according to claim 2, wherein the ratio of the amounts of the 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl is 1.2 to 1.6:1.
4. A process according to claim 2 or 3, wherein the polymerization temperature is 60 to 80 ℃ and the incubation time is 4 to 12 hours.
5. The method of claim 2, wherein the amount of the end-capping agent is 2 times the difference between the amounts of 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and decafluorobiphenyl materials.
6. The method according to claim 2 or 5, wherein the temperature of the capping reaction is 40 to 50 ℃ and the incubation time is 12 to 24 hours.
7. The application of the divinylbenzene end-capped modified fluorine-containing polyphenyl ether as claimed in claim 1 or the divinylbenzene end-capped modified fluorine-containing polyphenyl ether prepared by the preparation method of any one of claims 2 to 6 in fluorine-containing polyphenyl ether polymer materials is characterized in that the fluorine-containing polyphenyl ether polymer materials have dielectric constants of 2.6 to 2.7 at 1 MHz.
8. The fluorine-containing polyphenyl ether polymer material is characterized in that the fluorine-containing polyphenyl ether modified by end capping of divinylbenzene is obtained by curing; the divinylbenzene-end-capped modified fluorine-containing polyphenyl ether is the divinylbenzene-end-capped modified fluorine-containing polyphenyl ether disclosed in claim 1 or the divinylbenzene-end-capped modified fluorine-containing polyphenyl ether prepared by the preparation method disclosed in any one of claims 2 to 6.
9. The method for preparing the fluorine-containing polyphenyl ether polymer material as set forth in claim 8, which is characterized by comprising the following steps:
Dissolving the divinylbenzene end-capped modified fluorine-containing polyphenyl ether and a curing agent in a ketone solvent, adding an initiator, and performing curing polymerization to obtain the fluorine-containing polyphenyl ether polymer material.
10. The application of the fluorine-containing polyphenyl ether polymer material disclosed in claim 8 or the fluorine-containing polyphenyl ether polymer material prepared by the preparation method disclosed in claim 9 in the field of dielectric polymer materials for copper-clad plates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410748589.7A CN118580484A (en) | 2024-06-11 | 2024-06-11 | A kind of divinylbenzene end-capped modified fluorinated polyphenylene ether and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410748589.7A CN118580484A (en) | 2024-06-11 | 2024-06-11 | A kind of divinylbenzene end-capped modified fluorinated polyphenylene ether and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118580484A true CN118580484A (en) | 2024-09-03 |
Family
ID=92524100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410748589.7A Pending CN118580484A (en) | 2024-06-11 | 2024-06-11 | A kind of divinylbenzene end-capped modified fluorinated polyphenylene ether and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118580484A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160130395A1 (en) * | 2013-08-16 | 2016-05-12 | Exxonmobil Chemical Patents Inc. | Stabilized Poly(Arylene Ether) Compositions and Methods of Making Them |
| CN110746594A (en) * | 2019-11-14 | 2020-02-04 | 杭州聚丰新材料有限公司 | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof |
| CN111363140A (en) * | 2020-03-09 | 2020-07-03 | 吉林大学 | Crosslinkable fluorine-containing polyarylether and preparation method and application thereof |
| CN113603883A (en) * | 2021-08-03 | 2021-11-05 | 珠海宏昌电子材料有限公司 | Modified polyphenyl ether, preparation method and application in high-frequency circuit board |
| CN113698590A (en) * | 2021-09-17 | 2021-11-26 | 吉林大学 | Melt-processable end-capped fluorine-containing polyarylether resin and preparation method and application thereof |
| CN115746290A (en) * | 2022-10-14 | 2023-03-07 | 大连理工大学 | Fluorine-containing polyarylether, electrolyte solution thereof, and preparation method and application of proton exchange membrane |
-
2024
- 2024-06-11 CN CN202410748589.7A patent/CN118580484A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160130395A1 (en) * | 2013-08-16 | 2016-05-12 | Exxonmobil Chemical Patents Inc. | Stabilized Poly(Arylene Ether) Compositions and Methods of Making Them |
| CN110746594A (en) * | 2019-11-14 | 2020-02-04 | 杭州聚丰新材料有限公司 | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof |
| CN111363140A (en) * | 2020-03-09 | 2020-07-03 | 吉林大学 | Crosslinkable fluorine-containing polyarylether and preparation method and application thereof |
| CN113603883A (en) * | 2021-08-03 | 2021-11-05 | 珠海宏昌电子材料有限公司 | Modified polyphenyl ether, preparation method and application in high-frequency circuit board |
| CN113698590A (en) * | 2021-09-17 | 2021-11-26 | 吉林大学 | Melt-processable end-capped fluorine-containing polyarylether resin and preparation method and application thereof |
| CN115746290A (en) * | 2022-10-14 | 2023-03-07 | 大连理工大学 | Fluorine-containing polyarylether, electrolyte solution thereof, and preparation method and application of proton exchange membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6976981B2 (en) | A functionalized poly (2,6-dimethylphenylene oxide) oligomer having dicyclopentadiene, a method for producing the same, and its use. | |
| CN110746594B (en) | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof | |
| US6756441B2 (en) | Low dielectric loss tangent resin composition, curable film and cured product, electrical part using the same and method for production thereof | |
| US9642249B2 (en) | Resin composition, prepreg, and substrate employing the same | |
| CN115677940B (en) | Resin for high-frequency high-speed copper-clad plate and polymerization method thereof | |
| CN107163244B (en) | Copper-clad plate polyphenylene oxide resin | |
| CN111793203B (en) | Polyphenyl ether and synthesis method thereof | |
| CN110305312B (en) | Method for synthesizing high molecular weight poly (arylene ether nitrile) | |
| CN113603883B (en) | Modified polyphenyl ether, preparation method and application in high-frequency circuit board | |
| CN114409900A (en) | Preparation method of polysulfone with low cyclic dimer content | |
| CN112679734B (en) | A class of soluble polyimides containing bistrifluoromethylbenzene substituted asymmetric meta structure and preparation method thereof | |
| CN111518241B (en) | Olefin-benzoxazine co-oligomer, crosslinked resin and preparation method thereof | |
| CN109305896B (en) | A kind of low polarity resin and its preparation method and application | |
| CN118580484A (en) | A kind of divinylbenzene end-capped modified fluorinated polyphenylene ether and its preparation method and application | |
| CN109912618B (en) | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film | |
| CN113698590B (en) | Melt-processable end-capped fluorine-containing polyarylether resin as well as preparation method and application thereof | |
| US20250075033A1 (en) | Low-molecular asymmetric thermosetting polyphenylene oxide resin polymer, and preparation method, purification method and use thereof | |
| CN116199559B (en) | Low-dielectric and high-heat-resistance calixarene resin and preparation method and application thereof | |
| CN116199872A (en) | Adamantyl group-containing low-dielectric polyarylester material, and preparation method and application thereof | |
| CN115160516B (en) | Thermosetting polyphenyl ether material containing trifluoromethyl and preparation method and application thereof | |
| CN109251320B (en) | A kind of polyionic liquid with ionic bond as skeleton and its preparation | |
| CN119176942B (en) | A bio-based polyimide and preparation method thereof | |
| CN115611821B (en) | Low-dielectric and high-heat-resistance aza calixarene resin, and preparation method and application thereof | |
| CN120647919A (en) | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method thereof | |
| CN117106173A (en) | Thermosetting low dielectric polyphenylene ether resin polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20240903 |