CN110885441B

CN110885441B - Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether

Info

Publication number: CN110885441B
Application number: CN201911245178.1A
Authority: CN
Inventors: 黄家辉; 王奂; 张好磊; 郎绪志
Original assignee: Panjin Sanli Zhongke New Material Co ltd; Dalian Institute of Chemical Physics of CAS
Current assignee: Panjin Sanli Zhongke New Material Co ltd; Dalian Institute of Chemical Physics of CAS
Priority date: 2019-12-06
Filing date: 2019-12-06
Publication date: 2021-01-05
Anticipated expiration: 2039-12-06
Also published as: CN110885441A

Abstract

The invention discloses a supported catalyst which is a complex of imidazole ligands and metal ions grafted on the surface of a nano-alumina particle subjected to surface modification; the surface-modified nano alumina particles are modified by a silane coupling agent; the catalyst has high catalytic efficiency and good selectivity, can be separated from a reaction system in a centrifugal or filtering mode, and is recycled and recycled. Solves the problem that the existing catalyst is difficult to recycle in the PPO production process. The product has the characteristics of low content of residual metal catalyst, low dielectric constant and dielectric loss, good processability and the like, the telechelic low-molecular-weight PPO can be subjected to self-crosslinking reaction and can also be subjected to chemical modification through the reaction of a terminal double bond with other substances, the preparation process is simple and easy to implement, the product has wide development space and great market application value, is suitable for industrial production and meets the requirement of sustainable development.

Description

Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether

Technical Field

The invention relates to the technical field of polymer chemical engineering, in particular to a supported catalyst, a preparation method thereof and application of the supported catalyst in preparation of a remote claw type low molecular weight polyphenylene ether in an oil-water two-phase medium.

Background

Polyphenylene Oxide (PPO) is an engineering plastic with excellent comprehensive performance, not only has good mechanical properties, but also has outstanding performances such as low dielectric constant, low dielectric loss, low hygroscopicity, high glass transition temperature, acid and alkali corrosion resistance and the like, thereby having wide application prospects in the fields of automobile parts, electronic devices, office equipment, coatings, additives and the like. However, as a thermoplastic resin, high molecular weight PPO has high melt viscosity, poor processability, and low reactivity when used in additives and composites. The low molecular weight polyphenylene ether can overcome many disadvantages, and the main method for industrially producing the low molecular weight polyphenylene ether at present is redistribution reaction, and the redistribution reaction of PPO has been intensively studied by GE plastics of original U.S. and Asahi chemical company of Japan, and many patents on redistribution reaction for synthesis of low molecular weight polyphenylene ether have been filed, such as U.S. Pat. Nos. 7858726, U.S. Pat. No. 7282554, U.S. Pat. No. 6211327, U.S. Pat. No. 3962180, U.S. Pat. No. 6455663, U.S. Pat. No. 0254257, etc., as well as methods using continuous feeding in small amounts, using. However, ordinary low molecular weight PPO can only react by means of terminal hydroxyl, and it is often difficult to meet the requirements in practical applications, and the above production method is cumbersome, and often a product cannot be obtained by one-step method or precise regulation of molecular weight cannot be achieved, and the catalyst is also difficult to recover and reuse. The remote claw type low molecular weight PPO not only has all excellent properties of common PPO, such as dimensional stability, low dielectric constant and the like, but also becomes a very useful modifier due to the reaction activity, is easy to process, and opens up a wider space for the application of PPO. The recycling of the catalyst can greatly reduce the production cost, save resources, reduce the discharge of three wastes and have high economic and environmental protection values. At present, catalysts for synthesizing polyphenylene oxide are mainly homogeneous and are not easy to separate, the catalysts are loaded on inert carriers, and the catalysts can be separated by simple filtration or centrifugation means after the reaction is finished, but the catalytic efficiency of the catalysts is greatly reduced, so that the recycling of PPO catalysts still remains to be solved.

Disclosure of Invention

The invention provides a supported catalyst which has high catalytic efficiency and good selectivity and is easy to recycle.

The invention also provides a preparation method of the supported catalyst, which is simple to operate and easy to control, and the composition of the catalyst can be adjusted according to production requirements so as to adjust the performance index of the product.

The invention also provides a method for preparing low molecular weight hydroxyl-terminated polyphenylene oxide by using the supported catalyst in an oil-water two-phase medium, wherein the catalyst can be recovered and reused as expected.

The invention provides a preparation method of telechelic low molecular weight polyphenylene ether, which comprises the following steps:

(1) reacting low-molecular-weight double-end hydroxyl polyphenylene oxide and acyl chloride or acid anhydride serving as raw materials in a toluene solvent at the temperature of 30-90 ℃ for 2-20 hours to obtain a reaction solution;

(2) adding the reaction solution into a hydrochloric acid-methanol mixed solution, filtering, repeatedly dissolving and precipitating a product obtained by filtering for three times by using toluene-methanol, and drying to obtain the remote claw type low molecular weight polyphenylene ether; in the hydrochloric acid-methanol mixed solution, the concentration of the hydrochloric acid is 0.5-5 wt%.

Based on the technical scheme, the preferable reaction temperature is 60-80 ℃, the reaction time is 6-8 hours, the reaction rate is high under the reaction condition, and the volatilization amount of the raw materials is small.

The polyacyl chloride is methacryloyl chloride;

the acid anhydride is one or more of methacrylic anhydride and maleic anhydride;

the molar ratio of the low-molecular-weight hydroxyl-terminated polyphenyl ether to the acyl chloride or the anhydride is 1: 2-10.

Based on the technical scheme, the preferable molar ratio of the low-molecular-weight hydroxyl-terminated polyphenyl ether to the acyl chloride or the anhydride is 1: 5-8, the ratio range can ensure that the terminal hydroxyl of the polyphenyl ether can be reacted sufficiently, and meanwhile, the economic benefit is considered.

The low molecular weight hydroxyl-terminated polyphenyl ether is prepared by catalyzing a phenol monomer, a bisphenol monomer and an oxidant in an oil-water two-phase medium by using a supported catalyst to perform an oxidation copolymerization reaction; the oxidant is oxygen, air or mixed gas formed by mixing oxygen and inert gas, and the mixed gas plays an oxidizing role in being oxygen, so the oxidant is used in the amount counted by oxygen in the invention.

In practice, oxygen is not metered and is generally added in excess, so that the upper limit of the amount of the oxidant is not strictly limited.

The structure of the phenol monomer is shown as a formula (II); the structure of the bisphenol monomer is shown as a formula (III); the structure of the low molecular weight double-end hydroxyl polyphenylene oxide is shown as a formula (IV);

R₄and R₅Is hydrogen, alkyl, haloalkyl, aminoalkyl or alkoxy having 1 to 4 carbon atoms, R₆Is hydrogen or halogen;

R₇、R₈、R₉、R₁₀、R₁₁and R₁₂Independently hydrogen, alkyl with 1 to 4 carbon atoms, halogenated alkyl, aminoalkyl or alkoxy;

the number average molecular weight of the low molecular weight double-end hydroxyl polyphenylene oxide is 1000-8000;

the supported catalyst is an alumina nano particle modified by a silane coupling agent, and a complex is grafted on the surface of the alumina nano particle modified by the silane coupling agent; the complex is a complex of an imidazole ligand and metal ions;

the imidazole ligand is a cross-linked copolymer containing an N-vinyl imidazole monomer;

the metal ions are divalent copper ions or divalent manganese ions;

the N-vinyl imidazole monomer is a compound shown in a structural formula (I);

in the formula (I), R₁、R₂And R₃Independently is hydrogen or C₁～C₄Alkyl groups of (a);

in the complex, the molar ratio of the imidazole ligand to the metal ions is 0.5-200: 1, and the molar ratio of the imidazole monomer to the metal ions is preferably 2-20: 1, so that the reaction rate is higher, the selectivity is better, and the yield of the polyphenyl ether is higher. .

The mol ratio of the raw materials in the oxidation copolymerization reaction is as follows:

wherein the sum of the molar ratio composition of the phenol monomer and the bisphenol monomer is 1;

the temperature of the oxidation copolymerization reaction is 10-80 ℃, preferably 20-60 ℃, the reaction rate is high in the temperature range, and reaction byproducts are few; the reaction time is 4 to 72 hours; the pressure is 0.1MPa to 5.0MPa, preferably 0.1MPa to 2.0MPa, and the pressure range has higher safety in industrial production operation.

The oil phase in the oil-water medium in the oxidation copolymerization reaction is at least one of benzene, toluene, nitrobenzene, trichloromethane or dichloromethane; the volume ratio of the oil phase to the water phase is 50-10: 1.

The oxidant is oxygen, air or a mixed gas of oxygen and inert gas; in the mixed gas of the oxygen and the inert gas, the volume ratio of the oxygen to the inert gas is 0.05-100: 1; the inert gas is at least one of carbon dioxide, nitrogen, helium, neon and argon.

The preparation steps of the supported catalyst are as follows:

(1) dispersing a silane coupling agent and aluminum oxide nanoparticles in a mixed solvent of toluene and methanol to obtain a mixed solution, carrying out reflux reaction on the mixed solution at 110 ℃ for 24 hours, and after the reaction is finished, centrifuging, washing and drying to obtain silane coupling agent modified aluminum oxide nanoparticles; in the mixed solvent, the volume ratio of toluene to methanol is 2-9: 1;

(2) ultrasonically dispersing imidazole ligand, cross-linking agent and silane coupling agent modified aluminum oxide nanoparticles into ethyl acetate, adding initiator, and adding N₂Reacting at 110 deg.C for 24 hr, drying, and grinding to obtain alumina nanoparticlesSurface grafted cross-linked polyvinyl imidazole ligands;

(3) respectively dissolving and dispersing a metal ion precursor and the crosslinked polyvinyl imidazole ligand grafted on the surface of the alumina nano particle in water, mixing and carrying out ultrasonic treatment for 30 minutes, centrifuging and drying to obtain the supported catalyst.

The supported catalyst can be separated and recycled by a filtering or centrifuging method after the oxidative polymerization reaction is finished. The method for preparing the low-molecular-weight hydroxyl-terminated polyphenyl ether in the oil-water two-phase medium by using the supported catalyst comprises the following steps: dissolving a phenol monomer and a bisphenol monomer in an organic solvent, dispersing a supported catalyst in water, mixing oil and water, carrying out oxidative polymerization reaction in the presence of an oxidant, standing for layering after the reaction is finished, separating the supported catalyst from a reaction system by using a filtering or centrifuging method, washing and drying the recovered supported catalyst, and recycling the catalyst for the next reaction. And (3) taking methanol as a precipitator for the reaction product, and filtering and separating to obtain the dihydroxy-terminated polyphenylene oxide.

When the metal ions are bivalent copper ions, the metal ion precursor is at least one of copper chloride, copper bromide, copper sulfate and copper nitrate;

when the metal ions are divalent manganese ions, the metal ion precursor is at least one of manganese chloride, manganese bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, manganese sulfate and manganese phosphate.

The silane coupling agent is one or more of 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl methyldiethoxysilane, 4-mercaptobutyl trimethoxysilane and 4-mercaptobutyl triethoxysilane;

the cross-linking agent is divinylbenzene or N, N' -methylene-bis (acrylamide); the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, potassium persulfate, sodium persulfate, ammonium persulfate, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide and cumene hydroperoxide.

Advantageous effects

(1) The method for synthesizing the remote-claw type low-molecular-weight PPO has simple steps, and realizes the accurate regulation and control of the molecular weight according to the requirements.

(2) The catalyst combines the characteristics of the nano particles and the metal ion-crosslinked polyvinyl imidazole ligand complex; the nano particles are used as the carrier of the catalyst, have small size and large specific surface area, so that the catalyst is fully contacted with a reaction substrate, have high catalytic efficiency and are beneficial to effective loading and catalysis of the catalyst, and meanwhile, the nano particles are the core of the catalyst, and the catalyst can be recovered in a centrifugal or filtering mode.

(3) The product of the invention is characterized by low content of residual metal catalyst, low dielectric constant and dielectric loss, good processing performance and the like; the application space is wide.

(3) The preparation method disclosed by the invention is simple and easy to operate, has wide development space and great market application value, is suitable for industrial production, meets the requirement of sustainable development, is easy to control, and is suitable for industrial production.

Drawings

FIG. 1 is a schematic diagram of the structure of a supported catalyst according to the present invention; wherein: the curve of class a represents- (CH-CH)₂) -a crosslinked network formed by copolymerization with a crosslinking agent; the b-type curve represents the omitted cross-linked network.

Detailed Description

Example 1

Preparation of Supported catalysts

(1) Preparation of silane coupling agent modified nano alumina particles

Under mechanical stirring, 0.3mL (1.5mmol) of 3-mercaptopropyltrimethoxysilane and nano-alumina (1.9g) are refluxed at 110 ℃ for 24 hours in 100mL of a mixed solution of toluene/methanol 80:20 (volume ratio). And after the reaction is finished, washing the product with methanol for 3 times, washing the product with deionized water for 3 times, performing centrifugal separation, separating the obtained solid, and performing vacuum drying for 48 hours to obtain the silane coupling agent modified nano-alumina particles.

(2) Preparation of crosslinked polyvinyl imidazole ligand grafted on surface of nano alumina particle

Ultrasonically dispersing 2.72mL (30mmol) of N-vinylimidazole subjected to reduced pressure distillation, 0.42mL (3mmol) of divinylbenzene and 2g of silane coupling agent modified nano-alumina particles prepared in the step (1) in 50mL of ethyl acetate, adding azobisisobutyronitrile with the mass fraction of 5% of N-vinylimidazole monomer as an initiator, and adding N into the mixture₂Reacting for 24 hours at 110 ℃, and drying the mixture for 48 hours in vacuum and grinding to obtain the cross-linked polyvinyl imidazole ligand grafted on the surface of the nano alumina particle.

The nanometer alumina particle coated with polymer with different crosslinking degrees can be prepared by changing the charge ratio of the N-vinyl imidazole and the divinyl benzene.

(3) Nanometer alumina particle surface grafted cross-linked polyvinyl imidazole ligand and metal ion coordination

Adding CuCl₂·2H₂O (0.0086g, 0.05mmol) and the crosslinked polymer coated nano alumina particles (0.18g, wherein the content of imidazole groups is 0.2mmol) are respectively dissolved and dispersed in 5mL of water, mixed and subjected to ultrasonic treatment for 30 minutes to coordinate copper ions and imidazole groups, so that the crosslinked polymer ligand-metal ion complex catalyst loaded on the nano alumina particles is obtained.

Examples 2 to 4

With the exception of changing the charge ratio of N-vinylimidazole to divinylbenzene, the procedure of example 1 was otherwise followed to prepare a crosslinked polymer supported on nano-alumina particles, wherein the specific parameters are shown in Table 2, and finally the crosslinked polymer ligand-metal ion complex catalyst supported on nano-alumina particles was obtained.

TABLE 2

Example number	N-vinylimidazole/divinylbenzene
		2	2.72mL(30mmol)/0.84mL(6mmol)
3	2.72mL(30mmol)/1.40mL(10mmol)
		4	2.72mL(30mmol)/0.21mL(1.5mmol)

Examples 5 to 6

The preparation method is the same as the example 1 except that 3-mercaptopropyltriethoxysilane and 4-mercaptobutyltrimethoxysilane are adopted to replace the 3-mercaptopropyltrimethoxysilane in the example 1, and the silane coupling agent modified nano alumina particles are prepared to finally obtain the nano alumina particle supported cross-linked polymer ligand-metal ion complex catalyst.

Example 7

Except that N, N' -methylene-bis (acrylamide) is adopted to replace divinylbenzene in the example 1 as a crosslinking agent, the other operations are the same as the example 1, the crosslinked polymer supported by the nano alumina particles is prepared, and finally the crosslinked polymer ligand-metal ion complex catalyst supported by the nano alumina particles is obtained.

Examples 8 to 9

Except for changing the mass ratio of the vinyl imidazole monomer to the silane coupling agent modified nano-alumina, the other operations are the same as in example 1, the specific parameters are shown in table 3, and finally the nano-alumina particle supported cross-linked polymer ligand-metal ion complex catalyst is obtained.

TABLE 3

Examples 10 to 12

Except that the crosslinked polymer supported by the nano alumina particles prepared in examples 2 to 4 was used as a ligand and the kind of the metal compound was changed, the other operations were the same as in example 1, and the crosslinked polymer ligand-metal ion complex catalyst supported by the nano alumina particles was finally obtained, as shown in table 4.

TABLE 4

Example number	Metal compound and its use amount	Ligands
			10	0.04mmol of manganese acetate	Example 2
11	0.03mmol of manganese chloride	Example 3
			12	0.05mmol of copper nitrate	Example 4

Examples 13 to 15

The same operations as in example 1 were carried out except that the molar ratio of the metal ions to the imidazole groups in the polyvinyl imidazole based ligand was changed and the metal compound was changed, to finally obtain a crosslinked polymer ligand-metal ion complex catalyst supported on nano alumina particles, as shown in table 7.

TABLE 5

Example 16

Preparation of remote-claw type low molecular weight polyphenylene ether

In a reaction kettle connected with a thermometer, a stirring paddle, a condenser tube and a gas inlet and outlet, 2, 6-dimethylphenol (4.93g, 40mmol) and tetramethylbisphenol A (1.5mL, 10mmol) are dissolved in 15mL of toluene, the supported catalyst prepared in example 1 is ultrasonically dispersed in 2mL of water, the two media are mixed and stirred uniformly, the reaction kettle is heated to 40 ℃, oxygen is introduced, and the reaction is carried out for 6 hours at the stirring speed of 600 revolutions per minute.

After the polymerization reaction, the reaction mixture was allowed to stand, and the catalyst was recovered by filtration, washed with distilled water 5 times, and vacuum-dried at room temperature for 24 hours, with the recovery rate of the catalyst being 97.2%. Adding excessive methanol into the reaction product after the catalyst is recovered for precipitation, filtering, washing and drying to obtain a polymerization product, namely the low-molecular-weight double-end hydroxyl PPO.

Dissolving the obtained low-molecular-weight double-end hydroxyl PPO (2g) and 0.35g of methacryloyl chloride in 50mL of toluene, reacting for 10 hours, adding methanol containing 1% hydrochloric acid, filtering, repeatedly dissolving and precipitating the product for 3 times by using toluene-methanol, and drying in vacuum at 100 ℃ to obtain white powder, namely the remote-claw type low-molecular-weight polyphenylene ether, wherein the yield is 84.2%, the number average molecular weight is 1800, and the molecular weight distribution is 1.7.

Example 17

The preparation of the remote claw type low molecular weight PPO was carried out according to the method of example 16 except that the catalyst recovered in example 16 was used instead of the original catalyst. The catalyst recovery was 93.8%. The product was obtained in 83.0% yield, number average molecular weight 1700, molecular weight distribution 2.0.

Examples 18 to 19

The preparation of the low molecular weight PPO of the remote claw type in a two-phase medium, oil and water, was carried out according to the method of example 16, with the difference that the proportions of the two monomers were varied during the copolymerization, the results being shown in Table 6:

TABLE 6

Examples 20 to 22

The method of example 16 was followed to prepare the remote claw type low molecular weight PPO except that the catalysts prepared in examples 2-4 were used, respectively, and the polymerization results are shown in Table 7.

TABLE 7

Examples 23 to 25

The method of example 16 was followed to prepare the remote claw type low molecular weight PPO except that the catalysts prepared in examples 5 to 7 were used, respectively, and the polymerization results are shown in Table 8.

TABLE 8

Example number	Catalyst and process for preparing same	Yield (%)	Number average molecular weight	M_w/M_n
					23	Example 5	81.8	1800	1.9
24	Example 6	77.3	1700	1.7
					25	Example 7	79.5	2200	1.8

Examples 26 to 27

Low telechelic low molecular weight PPO was prepared according to the method of example 16, except that the catalysts prepared in examples 8-9 were used, respectively, and the polymerization results are shown in Table 9.

TABLE 9

Example number	Catalyst and process for preparing same	Yield (%)	Number average molecular weight	M_w/M_n
					26	Example 8	81.8	2100	1.9
27	Example 9	77.3	1900	1.7

Examples 28 to 30

The method of example 16 was followed to prepare the remote claw type low molecular weight PPO except that the catalysts prepared in examples 8 to 10 were used, respectively, and the polymerization results are shown in Table 10.

Watch 10

Example number	Catalyst and process for preparing same	Yield (%)	Number average molecular weight	M_w/M_n
					28	Example 10	83.8	1900	1.8
29	Example 11	80.3	2000	1.7
					30	Example 12	85.5	1700	1.7

Example 31

The remote claw type low molecular weight PPO was prepared according to the method of example 16, replacing tetramethylbisphenol A with tetramethylbisphenol F (g, 40mmol), the yield was 70.28%, the number average molecular weight of the product was 1600, and the molecular weight distribution was 1.8.

Example 32

The remote claw type low molecular weight PPO was prepared according to the method of example 16, except that air was used instead of oxygen, the yield was 77.8%, the number average molecular weight was 2600, and the molecular weight distribution was 1.7.

Example 33

The remote claw type low molecular weight PPO was prepared according to the method of example 16 except that the copolymerization temperature was 25 ℃ and the copolymerization time was 12 hours, the yield was 80.9%, the number average molecular weight was 1700 and the molecular weight distribution was 1.5.

Example 34

The remote claw type low molecular weight PPO was prepared according to the method of example 16 except that the copolymerization temperature was 60 ℃ and the copolymerization time was 8 hours, the yield was 86.7%, the number average molecular weight was 3000 and the molecular weight distribution was 1.9.

Example 35

The remote claw type low molecular weight PPO was prepared according to the method of example 16, except that methacrylic anhydride was used instead of methacryloyl chloride, the yield was 85.1%, the number average molecular weight was 1700, and the molecular weight distribution was 1.8.

Example 36

The remote-claw type low molecular weight PPO was prepared according to the method of example 16, except that the reaction temperature of the low molecular weight double-terminal hydroxyl PPO with methacryloyl chloride was 50 ℃, the yield was 80.8%, the number average molecular weight was 1800, and the molecular weight distribution was 1.9.

Example 37

The telechelic low molecular weight PPO was prepared according to the method of example 16 except that methacryloyl chloride was used in an amount of 0.7g, the yield was 90.8%, the number average molecular weight was 1800, and the molecular weight distribution was 1.7.

Claims

1. A method for producing a telechelic low-molecular-weight polyphenylene ether, characterized by comprising the steps of:

(2) adding the reaction solution into a hydrochloric acid-methanol mixed solution, filtering, repeatedly dissolving and precipitating a product obtained by filtering for three times by using toluene-methanol, and drying to obtain the remote claw type low molecular weight polyphenylene ether; in the hydrochloric acid-methanol mixed solution, the concentration of the hydrochloric acid is 0.5-5 wt%;

the low molecular weight hydroxyl-terminated polyphenyl ether is prepared by catalyzing a phenol monomer, a bisphenol monomer and an oxidant in an oil-water two-phase medium by using a supported catalyst to perform an oxidation copolymerization reaction; the number average molecular weight of the low molecular weight double-end hydroxyl polyphenylene oxide is 1000-8000;

the preparation steps of the supported catalyst are as follows:

(2) ultrasonically dispersing imidazole ligand, cross-linking agent and silane coupling agent modified aluminum oxide nanoparticles into ethyl acetate, adding initiator, and adding N₂Reacting for 24 hours at 110 ℃, drying and grinding to obtain the crosslinked polyvinyl imidazole ligand grafted on the surface of the alumina nano particles;

2. The production method according to claim 1,

the acyl chloride is methacrylic acid chloride;

3. The production method according to claim 1,

the metal ions are divalent copper ions or divalent manganese ions;

the N-vinyl imidazole monomer is a compound shown in a structural formula (I);

in the complex, the molar ratio of the imidazole ligand to the metal ions is 0.5-200: 1;

R₇、R₈、R₉、R₁₀、R₁₁and R₁₂Independently hydrogen, alkyl with 1 to 4 carbon atoms, halogenated alkyl, amino alkyl or alkoxy.

4. The preparation method according to claim 1, wherein the molar ratio of the raw materials in the oxidative copolymerization reaction is as follows:

wherein the sum of the molar ratio composition of the phenol monomer and the bisphenol monomer is 1.

5. The preparation method according to claim 1, wherein the temperature of the oxidative copolymerization reaction is 10 ℃ to 80 ℃, the reaction time is 4 hours to 72 hours, and the pressure is 0.1MPa to 5.0 MPa.

6. The process according to claim 1, wherein the oil phase in the oil-water two-phase medium in the oxidative copolymerization reaction is at least one of benzene, toluene, nitrobenzene, chloroform or dichloromethane; the volume ratio of the oil phase to the water phase is 50-10: 1.

7. The method according to claim 1, wherein the oxidizing agent is oxygen, air or a mixture of oxygen and an inert gas; in the mixed gas of the oxygen and the inert gas, the volume ratio of the oxygen to the inert gas is 0.05-100: 1; the inert gas is at least one of carbon dioxide, nitrogen, helium, neon and argon.

8. The method according to claim 1, wherein when the metal ion is a cupric ion, the metal ion precursor is at least one of cupric chloride, cupric bromide, cupric sulfate and cupric nitrate;

9. The preparation method according to claim 1, wherein the silane coupling agent is one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane and 4-mercaptobutyltriethoxysilane;