阅读说明：本技术 双官能化含磷聚苯醚及其制备方法与应用 (Bifunctional phosphorus-containing polyphenylene ether, and preparation method and application thereof ) 是由 周浩清 于 2019-08-28 设计创作，主要内容包括：本发明提供了一种双官能化含磷聚苯醚及其制备方法与应用,该双官能化含磷聚苯醚具有如下式Ⅰ结构：<Image he="115" wi="700" file="DDA0002182461540000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中：<Image he="235" wi="478" file="DDA0002182461540000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>m和n独立为0到50的整数,m和n至少一个不为0；R<Sub>1</Sub>、R<Sub>2</Sub>、R<Sub>3</Sub>和R<Sub>4</Sub>相同或不同,为氢、卤素、烷基、卤代烷基、烷氧基或烯烃基；R<Sub>5</Sub>、R<Sub>6</Sub>、R<Sub>7</Sub>和R<Sub>8</Sub>相同或不同,为氢、卤素、烷基、卤代烷基、烷氧基或烯烃基。本发明双官能化含磷聚苯醚与其它基体树脂相容性好,反应性能优良,是制备高频覆铜板的理想基体树脂。(The invention provides a bifunctional phosphorus-containing polyphenyl ether, a preparation method and an application thereof, wherein the bifunctional phosphorus-containing polyphenyl ether has a structure shown in the following formula I: wherein: m and n are independently integers of 0 to 50, at least one of m and n being other than 0; r 1 、R 2 、R 3 And R 4 Identical or different, is hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl; r 5 、R 6 、R 7 And R 8 Identical or different and are hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkeneAnd (4) a base. The bifunctional phosphorus-containing polyphenyl ether has good compatibility with other matrix resins and excellent reaction performance, and is an ideal matrix resin for preparing a high-frequency copper-clad plate.)

1. A bifunctional phosphorus-containing polyphenylene ether characterized by having the following structure:

wherein:

m and n are independently integers of 0 to 50, at least one of m and n being other than 0; r₁、R₂、R₃And R₄Identical or different, is hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl; r₅、R₆、R₇And R₈Identical or different, are hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl.

2. The bifunctional phosphorus-containing polyphenylene ether of claim 1, wherein R is₁、R₂、R₃And R₄Is hydrogen, methyl, halogen or methoxy, R₅、R₆、R₇And R₈Is hydrogen, methyl, halogen or methoxy.

3. The method for producing a bifunctional phosphorus-containing polyphenylene ether according to claim 1 or 2, characterized by comprising the steps of:

step 1, carrying out addition and dehydration reaction on 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dihydroxy diphenyl ketone or derivatives thereof to generate phosphorus-containing dihydric phenol;

step 2, carrying out polymerization reaction on the phosphorus-containing dihydric phenol and a phenol derivative to generate dihydroxy phosphorus-containing polyphenyl ether; and

step 3, carrying out condensation reaction on dihydroxyl phosphorus-containing polyphenyl ether and a functional compound to generate bifunctional phosphorus-containing polyphenyl ether;

wherein the functional compound comprises the following structure of formula II:

4. the method of claim 3, wherein the dihydroxydiphenyl ketone or the derivative thereof has a structure represented by the following formula III, the phosphorus-containing dihydric phenol has a structure represented by the following formula IV, the phenol derivative has a structure represented by the following formula V, and the bishydroxy phosphorus-containing polyphenylene ether has a structure represented by the following formula VI:

wherein the content of the first and second substances,

m and n are independently integers of 0 to 50, at least one of m and n being other than 0; r₁、R₂、R₃And R₄Identical or different, is hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl; r₅、R₆、R₇And R₈Identical or different, are hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl.

5. The method of preparing a bifunctional phosphorus-containing polyphenylene ether according to claim 3, wherein in step 1, the molar ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to dihydroxybenzophenone or a derivative thereof is 2-4:1, the reaction temperature is 80-260 ℃ and the reaction time is 1-10 hours.

6. The method for preparing a bifunctional phosphorus-containing polyphenylene ether according to claim 5, wherein the dihydroxybenzophenone or the derivative thereof is selected from the group consisting of 4,4 ' -dihydroxybenzophenone, 3,3 ' -dimethyl-4, 4 ' -dihydroxybenzophenone, 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -dihydroxybenzophenone, 2 ', 3,3 ', 5,5 ' -hexamethyl-4, 4 ' -dihydroxybenzophenone, 3,3 ' -dichloro-4, 4 ' -dihydroxybenzophenone, 3,3 ' -dibromo-4, 4 ' -dihydroxybenzophenone, 3,3 ' -difluoro-4, 4 ' -dihydroxybenzophenone, 3,3 ', one or more of 5,5 ' -tetrachloro-4, 4 ' -dihydroxydiphenyl ketone and 3,3 ', 5,5 ' -tetrabromo-4, 4 ' -dihydroxydiphenyl ketone.

7. The method of preparing a bifunctional phosphorus-containing polyphenylene ether according to claim 3, wherein the step 2 is: introducing oxygen-containing gas into a mixed solution consisting of a solvent, metal salt and compound amine, then adding phosphorus-containing dihydric phenol and a phenol derivative, reacting for 1-6h at the temperature of 20-90 ℃, and adding a terminator after the reaction is finished to obtain the dihydroxy phosphorus-containing polyphenylene ether.

8. The method of preparing a bifunctional phosphorus-containing polyphenylene ether according to claim 7, wherein the molar ratio of the phenol derivative to the phosphorus-containing dihydric phenol is 1:1 to 100: 1; the solvent is selected from the group consisting of benzene, toluene, xylene, methanol, ethanol, propanol, butanol and mixtures thereof; the metal salt is a mixture of cuprous oxide and a hydrogen bromide solution, and the mole number of bromine atoms is more than 2 times that of copper atoms; the compound amine is selected from dimethylethylamine, dimethylpropylamine, dimethyl n-butylamine, di-n-butylamine, di-tert-butylethylenediamine, dimethylpropyldiamine, tetramethylbutanediamine, tetramethylpropanediamine and a composition thereof; the terminator is selected from an aqueous solution of at least one of the following substances: citric acid, citrate, ethylenediaminetetraacetic acid sodium salt, ethylenediaminetetramethylenephosphonic acid, hydroxyethylidene-diphosphonic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and nitrilotriacetate.

9. The method for producing a bifunctional phosphorus-containing polyphenylene ether according to claim 7, wherein the number of moles of nitrogen atoms in the complex amine is 20 times or more the number of moles of metal atoms in the metal salt; the phenol derivative is 2, 6-dimethylphenol.

10. The method for preparing a bifunctional phosphorus-containing polyphenylene ether as claimed in claim 3, wherein the bishydroxy phosphorus-containing polyphenylene ether has a number average molecular weight of 1000-10000 and a hydroxyl group content of 0.34-3.4% by mass.

11. The method of preparing a bifunctional phosphorus-containing polyphenylene ether according to claim 3, wherein the step 3 is: in the presence of polymerization inhibitor, acid binding agent and/or catalyst, functional compound and dihydroxy phosphorus-containing polyphenylene ether are mixed and reacted at 0-150 deg.c for 1-10 hr to obtain bifunctional phosphorus-containing polyphenylene ether.

12. The method of producing a bifunctional phosphorus-containing polyphenylene ether according to claim 11, wherein the molar ratio of the functional compound to the hydroxyl group in the bishydroxy phosphorus-containing polyphenylene ether is 1-2: 1; the polymerization inhibitor is selected from one or more of hydroquinone, tertiary butyl catechol, copper naphthenate, 2, 5-di-tertiary butyl hydroquinone, p-hydroxyanisole, methyl hydroquinone, p-benzoquinone, cuprous chloride and ferric trichloride, and the dosage of the polymerization inhibitor is 0.0-1.0% of the mass of the functional compound; the acid-binding agent is selected from one or more of triethylamine, DIEA, pyridine, sodium acetate, sodium carbonate, potassium carbonate, sodium methoxide and sodium ethoxide, and the molar ratio of the acid-binding agent to the functional compound is 1:1-3: 1; the catalyst is selected from one or more of concentrated sulfuric acid, p-toluenesulfonic acid, perchloric acid, zinc chloride, anhydrous sodium acetate, pyridine, dimethylaniline and 4-dimethylaminopyridine, and the dosage of the catalyst is 0.3-30% of the mass of the dihydroxyl phosphorus-containing polyphenylene oxide.

13. The method of producing a bifunctional phosphorus-containing polyphenylene ether according to claim 11, wherein the functional compound is methacryloyl chloride or methacrylic anhydride.

14. Use of the bifunctional phosphorus-containing polyphenylene ether according to claim 1 or 2 in a resin film, a prepreg, a build-up sheet or a printed wiring board.

Technical Field

The invention relates to a low molecular weight polyphenylene ether, in particular to a bifunctional phosphorus-containing polyphenylene ether and a preparation method and application thereof.

Background

With the rapid development of the information industry, especially the arrival of the 5G era, higher requirements are put on the matrix resin for the copper-clad plate, and the matrix resin is required to have low dielectric constant, low dielectric loss, high heat resistance, low water absorption, high flame retardance and the like. The most widely used matrix resin in the copper clad laminate manufacturing industry is epoxy resin, which has poor dimensional stability when used at high temperature and too high dielectric constant in a high frequency range, and thus cannot meet the requirements of technical development.

Compared with the general high molecular weight polyphenyl ether, the low molecular weight polyphenyl ether not only maintains the original excellent performance of the polyphenyl ether, but also has the advantages of low viscosity, good fluidity, good compatibility with a plurality of resins and the like, still maintains good thermal performance at the glass transition temperature, and is suitable for matrix resin of composite materials such as high-frequency circuit boards and the like or addition components of other high molecular materials.

Since the halogen-containing flame retardant causes environmental pollution, phosphorus-containing compounds such as DOPO and derivatives thereof are generally adopted in the industry at present to realize the halogen-free flame retardant effect. In the electronic printed circuit board industry, flame retardant requirements are also achieved by adding phosphorus-containing compounds to the matrix resin, but the heat resistance and dielectric properties of the circuit board are reduced, so that the development of a matrix resin which meets the flame retardant requirements without reducing other properties is necessary.

Unsaturated groups are introduced into the tail end of low molecular weight dihydroxy polyphenyl ether, and an excellent modification system is obtained through self curing or reaction with other thermosetting resins, so that the excellent electrical property, dielectric property and heat resistance of the polyphenyl ether can be embodied to the maximum extent.

Patent CN106554498B describes a method for preparing a phosphorus-containing polyphenylene ether resin, which comprises reacting a bis (chloromethyl) compound with a dihydroxy polyphenylene ether to obtain a first intermediate product, and reacting the first intermediate product with a phosphorus-containing compound to obtain a phosphorus-containing polyphenylene ether resin, but this method does not provide a pure phosphorus-containing polyphenylene ether resin. In the first step, the reaction between the bis (chloromethyl) compound and the dihydroxy polyphenyl ether can generate two substances of formula (II) and formula (III) at the same time of generating the following formula (I), and even any two substances can continuously generate polycondensation reaction to generate high polymer, because the preparation of the high polymer by utilizing the polycondensation reaction between the dichloro compound and the dihydroxy compound is a common method in the industry.

In the second step of preparing a phosphorus-containing polyphenylene ether by adding a phosphorus-containing compound to the reaction solution, other products such as the compound (V) are formed in addition to the product (IV) described in the patent, and the compound (III) does not react with the phosphorus compound, that is, the reaction solution after the completion of the second step contains at least three polyphenylene ether resins of (IV), (V) and (III).

The phosphorus-containing polyphenylene oxide resin obtained by the method provided by the patent has complex components, and the consistency of performance indexes among batches is difficult to ensure, so that the method brings adverse effects to practical application.

Patent CN102532520A describes a method for preparing a phosphorus-containing low molecular weight polyphenylene ether resin by redistribution method, which has a lot of byproducts, and a lot of initiator is added in the preparation process, so that a certain amount of residual and difficult processing are left in the final product, and it is difficult to prepare a high-purity product, therefore, the dihydroxy phosphorus-containing polyphenylene ether prepared by the method has many impurities. Due to the above problems, the phosphorus-containing low molecular weight polyphenylene ether cannot exhibit inherent dielectric properties and heat resistance after being functionalized.

In view of the above, there is a need for a low molecular weight polyphenylene ether compound having a higher dielectric constant and better heat resistance.

Disclosure of Invention

The invention mainly aims to provide a bifunctional phosphorus-containing polyphenyl ether, and a preparation method and application thereof, so as to overcome the defects of low purity, unstable performance, poor heat resistance and the like of the polyphenyl ether in the prior art.

In order to achieve the above object, the present invention provides a bifunctional phosphorus-containing polyphenylene ether having the following structure of formula I:

wherein:

m and n are independently integers of 0 to 50, at least one of m and n being other than 0; r₁、R₂、R₃And R₄Identical or different, is hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl; r₅、R₆、R₇And R₈Identical or different, are hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl.

The bifunctional phosphorus-containing polyphenylene ether of the present invention, wherein R is₁、R₂、R₃And R₄Is hydrogen, methyl, halogen or methoxy, R₅、R₆、R₇And R₈Is hydrogen, methyl, halogen or methoxy.

In order to achieve the above object, the present invention also provides a process for preparing the above bifunctional phosphorus-containing polyphenylene ether, comprising the steps of:

step 1, carrying out addition and dehydration reaction on 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dihydroxy diphenyl ketone or derivatives thereof to generate phosphorus-containing dihydric phenol;

step 2, carrying out polymerization reaction on the phosphorus-containing dihydric phenol and a phenol derivative to generate dihydroxy phosphorus-containing polyphenyl ether; and

step 3, carrying out condensation reaction on dihydroxyl phosphorus-containing polyphenyl ether and a functional compound to generate bifunctional phosphorus-containing polyphenyl ether;

wherein the functional compound comprises the following structure of formula II:

the preparation method of the bifunctional phosphorus-containing polyphenyl ether comprises the following steps of enabling dihydroxy diphenyl ketone or derivatives thereof to have a structure shown in a formula III, enabling phosphorus-containing dihydric phenol to have a structure shown in a formula IV, enabling phenol derivatives to have a structure shown in a formula V, and enabling the dihydroxyphosphorus-containing polyphenyl ether to have a structure shown in a formula VI:

wherein the content of the first and second substances,

m and n are independently integers of 0 to 50, at least one of m and n being other than 0; r₁、R₂、R₃And R₄Identical or different, is hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl; r₅、R₆、R₇And R₈Identical or different, are hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the following step 1, wherein the molar ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to dihydroxy diphenyl ketone or derivatives thereof is 2-4:1, the reaction temperature is 80-260 ℃, and the reaction time is 1-10 hours.

The method for preparing a bifunctional phosphorus-containing polyphenylene ether according to the present invention is a method in which the dihydroxybenzophenone or derivative thereof is selected from the group consisting of 4,4 '-dihydroxybenzophenone, 3, 3' -dimethyl-4, 4 '-dihydroxybenzophenone, 3, 3', 5,5 '-tetramethyl-4, 4' -dihydroxybenzophenone, 2 ', 3, 3', 5,5 '-hexamethyl-4, 4' -dihydroxybenzophenone, 3,3 '-dichloro-4, 4' -dihydroxybenzophenone, 3,3 '-dibromo-4, 4' -dihydroxybenzophenone, 3,3 '-difluoro-4, 4' -dihydroxybenzophenone, 3,3 ', 5, 5' -tetrachloro-4, one or more of 4 '-dihydroxy diphenyl ketone and 3, 3', 5,5 '-tetrabromo-4, 4' -dihydroxy diphenyl ketone.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the following steps of 2: introducing oxygen-containing gas into a mixed solution consisting of a solvent, metal salt and compound amine, then adding phosphorus-containing dihydric phenol and a phenol derivative, reacting for 1-6h at the temperature of 20-90 ℃, and adding a terminator after the reaction is finished to obtain the dihydroxy phosphorus-containing polyphenylene ether.

The preparation method of the bifunctional phosphorus-containing polyphenyl ether comprises the following steps of (1) preparing a phosphorus-containing dihydric phenol by using a phenol derivative and a phosphorus-containing dihydric phenol in a molar ratio of 1:1-100: 1; the solvent is selected from the group consisting of benzene, toluene, xylene, methanol, ethanol, propanol, butanol and mixtures thereof; the metal salt is a mixture of cuprous oxide and a hydrogen bromide solution, and the mole number of bromine atoms is more than 2 times that of copper atoms; the compound amine is selected from dimethylethylamine, dimethylpropylamine, dimethyl n-butylamine, di-n-butylamine, di-tert-butylethylenediamine, dimethylpropyldiamine, tetramethylbutanediamine, tetramethylpropanediamine and a composition thereof; the terminator is selected from an aqueous solution of at least one of the following substances: citric acid, citrate, ethylenediaminetetraacetic acid sodium salt, ethylenediaminetetramethylenephosphonic acid, hydroxyethylidene-diphosphonic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and nitrilotriacetate.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the following steps of (1) enabling the mole number of nitrogen atoms in the compound amine to be more than 20 times of that of metal atoms in the metal salt; the phenol derivative is 2, 6-dimethylphenol.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the following steps of obtaining the dihydroxyl phosphorus-containing polyphenylene ether with the number average molecular weight of 1000-10000 and the mass percentage of hydroxyl groups of 0.34-3.4%.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the following steps of 3: in the presence of polymerization inhibitor, acid binding agent and/or catalyst, functional compound and dihydroxy phosphorus-containing polyphenylene ether are mixed and reacted at 0-150 deg.c for 1-10 hr to obtain bifunctional phosphorus-containing polyphenylene ether.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the following steps of (1) enabling the molar ratio of a functional compound to hydroxyl in the dihydroxyphosphorus-containing polyphenylene ether to be 1-2: 1; the polymerization inhibitor is selected from one or more of hydroquinone, tertiary butyl catechol, copper naphthenate, 2, 5-di-tertiary butyl hydroquinone, p-hydroxyanisole, methyl hydroquinone, p-benzoquinone, cuprous chloride and ferric trichloride, and the dosage of the polymerization inhibitor is 0.0-1.0% of the mass of the functional compound; the acid-binding agent is selected from one or more of triethylamine, DIEA, pyridine, sodium acetate, sodium carbonate, potassium carbonate, sodium methoxide and sodium ethoxide, and the molar ratio of the acid-binding agent to the functional compound is 1:1-3: 1; the catalyst is selected from one or more of concentrated sulfuric acid, p-toluenesulfonic acid, perchloric acid, zinc chloride, anhydrous sodium acetate, pyridine, dimethylaniline and 4-dimethylaminopyridine, and the dosage of the catalyst is 0.3-30% of the mass of the dihydroxyl phosphorus-containing polyphenylene oxide.

The preparation method of the bifunctional phosphorus-containing polyphenylene ether comprises the step of preparing a functional compound, wherein the functional compound is methacryloyl chloride or methacrylic anhydride.

In order to achieve the above object, the present invention further provides the use of the above bifunctional phosphorus-containing polyphenylene ether in a resin film, a prepreg, a laminate or a printed wiring board.

The invention has the beneficial effects that:

according to the method provided by the invention, relatively pure phosphorus-containing dihydroxy polyphenyl ether and functionalized resin thereof can be obtained, wherein the dihydroxy phosphorus-containing polyphenyl ether has excellent dielectric property and heat resistance, and the cured product obtained by curing the functionalized phosphorus-containing polyphenyl ether resin through heat or light or radiation has excellent dielectric property and relatively high Tg, so that the commercial requirement can be met.

The bifunctional phosphorus-containing polyphenyl ether has good compatibility with other matrix resins and excellent reaction performance, and is an ideal matrix resin for preparing a high-frequency copper-clad plate.

Detailed Description

The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.

The invention provides a preparation method of bifunctional phosphorus-containing polyphenylene ether, which comprises the following steps:

step 1, reacting 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with dihydroxy diphenyl ketone or derivatives thereof to generate phosphorus-containing dihydric phenol;

step 2, carrying out polymerization reaction on the phosphorus-containing dihydric phenol and a phenol derivative to generate dihydroxy phosphorus-containing polyphenyl ether; and

step 3, carrying out condensation reaction on dihydroxyl phosphorus-containing polyphenyl ether and a functional compound to generate bifunctional phosphorus-containing polyphenyl ether;

wherein the functional compound comprises the following structure of formula II:

in detail, step 1 is: mixing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with 2-4:1 molar ratio and dihydroxydiphenyl ketone or derivative thereof in a reaction kettle with stirring, preferably at 2.5:1-3:1 molar ratio, carrying out reaction at the reaction temperature of 80-260 ℃, preferably at 120-200 ℃, more preferably at 160-180 ℃, for 1-10h, preferably at 2-8h, more preferably at 3-5h, and then carrying out precipitation, filtration, washing and drying to obtain the phosphorus-containing dihydric phenol.

The post-treatment of the phosphorus-containing dihydric phenol in the present invention is not particularly limited, and may be, for example: and conveying the generated mixture into a settling kettle with stirring and tetrahydrofuran, maintaining the temperature of the settling kettle at 5-10 ℃, continuing stirring for 20min after the material is conveyed, stopping stirring and standing for 8h, filtering and washing the material, conveying the material into a vacuum drier, drying at 60 ℃ for 10h, and obtaining the white phosphorus-containing dihydric phenol solid.

Among them, the dihydroxybiphenylketone or the derivative thereof preferably has the following structure of formula iii:

R₁、R₂、R₃and R₄Identical or different, is hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl; r₁、R₂、R₃、R₄Preferably each independently hydrogen, methyl, halogen or methoxy, more preferably hydrogen, methyl or halogen. Further, the dihydroxybiphenylmethanone is 4,4 ' -dihydroxybiphenylmethanone, 3 ' -dimethyl-4, 4 ' -dihydroxybiphenylmethanone, 3 ', 5,5 'Tetramethyl-4, 4 ' -dihydroxydiphenyl ketone, 2 ', 3,3 ', 5,5 ' -hexamethyl-4, 4 ' -dihydroxydiphenyl ketone, 3,3 ' -dichloro-4, 4 ' -dihydroxydiphenyl ketone, 3,3 ' -dibromo-4, 4 ' -dihydroxydiphenyl ketone, 3,3 ' -difluoro-4, 4 ' -dihydroxydiphenyl ketone, 3,3 ', 5,5 ' -tetrachloro-4, 4 ' -dihydroxydiphenyl ketone, 3,3 ', 5,5 ' -tetrabromo-4, 4 ' -dihydroxydiphenyl ketone, and combinations thereof, particularly preferred is 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -dihydroxybiphenylketone.

In step 1, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide undergoes addition and dehydration with the ketocarbonyl group of dihydroxybenzophenone or its derivatives to produce a compound having the structure of formula iv below:

the step 2 is as follows: introducing oxygen-containing gas into a mixed solution consisting of a solvent, a metal salt and a compound amine, adding the mixed solution of a phenol derivative and the prepared phosphorus-containing dihydric phenol into a reaction kettle, wherein the molar ratio of the phenol derivative to the phosphorus-containing dihydric phenol is 1:1-100:1, preferably 3:1-75:1, more preferably 6.7:1-35.5:1, carrying out polymerization reaction at the temperature of 20-90 ℃, preferably at the temperature of 25-70 ℃, more preferably at the temperature of 25-60 ℃, the reaction time is 1-6 hours, preferably 3.5-4.5 hours, more preferably 2.5-3.5 hours, adding a terminator after the reaction is finished, removing the catalyst through centrifugal separation, and then carrying out desolventizing to obtain the dihydroxy phosphorus-containing polyphenylene ether.

In the present invention, the solvent used is not particularly limited, and preferred solvents include benzene, toluene, xylene, methanol, ethanol, propanol, butanol and a mixture thereof, and a mixture of toluene and methanol is more preferred. The metal salt is a mixture of cuprous oxide and a hydrogen bromide solution, and the number of moles of bromine atoms is preferably 2 times or more the number of moles of copper atoms.

The composite amine used in the present invention is not particularly limited, and preferred composite amines include dimethylethylamine, dimethylpropylamine, dimethyln-butylamine, di-n-butylamine, di-t-butylethylenediamine, dimethylpropyldiamine, tetramethylbutanediamine, tetramethylpropanediamine, and combinations thereof, more preferably combinations of dimethyln-butylamine, di-n-butylamine, and di-t-butylethylenediamine, and the preferred molar ratio of the combinations is 1:5.5: 6.4. The number of moles of nitrogen atoms in the complex amine is preferably 20 times or more the number of moles of metal atoms in the metal salt.

The kind of the terminator to be used is not particularly limited in the present invention, and preferred terminators include citric acid, citrate, ethylenediaminetetraacetic acid sodium salt, ethylenediaminetetramethylenephosphonic acid, hydroxyethylethylenediaminediphosphonic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid salt and a combination thereof, further preferably citric acid and/or nitrilotriacetic acid trisodium salt, and more preferably citric acid.

Among them, the phenol derivative of the present invention preferably has the following structure of formula v:

wherein R is₅、R₆、R₇And R₈Identical or different, are hydrogen, halogen, alkyl, haloalkyl, alkoxy or alkenyl. Preferably, R is₅And R₆Is methyl, R₇And R₈As hydrogen, the phenol derivative is preferably 2, 6-dimethylphenol.

In step 2, the phenol derivative and the phosphorus-containing dihydric phenol are subjected to a polymerization reaction to generate a compound having a structure shown in the following formula VI:

wherein m and n are integers of 0 to 50, at least one is not 0, and the sum of both is not more than 100. The dihydroxy phosphorus-containing polyphenylene ether with the structure of the formula VI has the number average molecular weight of 1000-10000, more preferably 1500-5000, and the hydroxyl content by mass percent of 3.40-0.34 percent, more preferably 2.20-0.68 percent.

The step 3 is: in the presence of a polymerization inhibitor, an acid binding agent and/or a catalyst, a functional compound and a solvent are mixed, slowly added into a solution of the dihydroxyl phosphorus-containing polyphenylene ether, functionalized reaction is carried out at 0-150 ℃, preferably at 0-130 ℃, more preferably at 0-110 ℃, the reaction time is 1-10h, preferably 2.5-8h, more preferably 4-6h, and after the reaction is finished, the bifunctional phosphorus-containing polyphenylene ether is obtained by settling, washing and drying. Wherein the solvent is preferably dichloromethane, dimethylformamide, pyridine or toluene.

The post-treatment of the bifunctional phosphorus-containing polyphenylene ether of the present invention is not particularly limited, and the following are more preferable: after the reaction, the reaction solution is washed by water and separated by a liquid-liquid centrifuge to remove salt, then the reaction solution is concentrated to about 60 percent of solid content, methanol solution with 5 percent of water content is added to precipitate low molecular weight phosphorus-containing bifunctional polyphenyl ether powder particles, and the low molecular weight phosphorus-containing bifunctional polyphenyl ether powder particles are filtered, washed by methanol and dried in a vacuum drying oven at 70 ℃ for 24 hours to obtain the finished product. The low molecular weight functionalized polyphenylene ether is melted, degassed and molded and cured, and the dielectric properties of the low molecular weight functionalized polyphenylene ether cured sheet are determined according to ASTM D test method.

The polymerization inhibitor of the present invention is not particularly limited, and preferred polymerization inhibitors include hydroquinone, t-butylcatechol, copper naphthenate, 2, 5-di-t-butylhydroquinone, p-hydroxyanisole, methylhydroquinone, p-benzoquinone, cuprous chloride, iron trichloride and mixtures thereof, and these polymerization inhibitors may be used alone or in combination. The amount of the polymerization inhibitor used in the present invention is 0.0 to 1.0g, more preferably 0.2 to 0.5g, for 100g of methacryloyl chloride.

The acid-binding agent is not particularly limited in the present invention, and preferred acid-binding agents include triethylamine, DIEA, pyridine, sodium acetate, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, and mixtures thereof, and these acid-binding agents may be used alone or in combination. The amount of the acid-binding agent used in the reaction of 1mol of methacryloyl chloride in the present invention is 1.0 to 3.0mol, more preferably 1.5 to 2.0 mol.

The catalyst of the present invention is not particularly limited, and preferred catalysts include concentrated sulfuric acid, p-toluenesulfonic acid, perchloric acid, zinc chloride, anhydrous sodium acetate, pyridine, dimethylaniline or 4-dimethylaminopyridine, and mixtures thereof, and these catalysts may be used alone or in combination. The amount of the catalyst used in the reaction of the present invention with 100g of bishydroxyphosphorous polyphenylene ether is 0.3 to 30g, more preferably 1.0 to 15.0 g.

Wherein the molar ratio of the functional compound to the hydroxyl groups in the dihydroxyphosphorus-containing polyphenylene ether is 1:1 to 2:1, preferably 1.1:1 to 1.8:1, and more preferably 1.2:1 to 1.5: 1.

In the present invention, the functional compound includes the following formula II, and further, the functional compound is preferably methacryloyl chloride or methacrylic anhydride.

In step 3, the functionalized compound and dihydroxy phosphorus-containing polyphenylene ether are subjected to functionalization reaction to generate a compound with a structure shown as the following formula I:

as a preferred embodiment, the bifunctional phosphorus-containing polyphenylene ether has the following structure:

m and n are integers of 0 to 50, at least one is not 0, and the sum of both is not more than 100.

In summary, as a preferred technical scheme, the invention firstly reacts DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) with dihydroxy diphenyl ketone to prepare the phosphorus-containing dihydric phenol; secondly, carrying out oxidative polymerization on the 2, 6-dimethylphenol and the mixed solution of the phosphorus-containing dihydric phenol prepared by the method under the action of a catalyst to prepare dihydroxyl phosphorus-containing polyphenylene oxide; finally, carrying out end-capping reaction on methacryloyl chloride or methacrylic anhydride and the dihydroxy phosphorus-containing polyphenylene ether prepared by the method to obtain the final bifunctional phosphorus-containing polyphenylene ether.

Hydroxyl Value (OHV) of the bishydroxyphosphorous polyphenylene ether was measured by phthalic anhydride method in GB/T12008.3-2009, and the hydroxyl value was expressed as milligrams of sodium hydroxide consumed per gram of sample, calculated according to formula (1):

in the formula: v₃-the volume of sodium hydroxide standard solution consumed by the titration of the sample, in ml;

V₄titration of the volume of the blank depleted standard solution of sodium hydroxide in ml;

c, concentration of the sodium hydroxide standard solution, wherein the unit is mol/l;

m is the mass of the sample in g.

The hydroxyl group percentage content of the bishydroxy phosphorus-containing polyphenylene ether can be calculated by the following formula (2):

the purity of the bishydroxyphosphorus polyphenylene ether in the present invention is defined as the molar percentage of bishydroxyphenylene ether in the polyphenylene ether, and the purity can be calculated according to the formula (3):

in the formula M_nThe number average molecular weight of the bishydroxy phosphorus-containing polyphenylene ether.

According to the preparation method of the present invention, the obtained bifunctional phosphorus-containing polyphenylene ether can be cured by heat or light or radiation to give a cured product having excellent dielectric properties, flame retardancy and heat resistance with a low impurity content, and the method can satisfy the industrial production requirements of a low molecular weight functionalized polyphenylene ether.

The technical solution of the present invention is further illustrated by the following specific examples.