CN110804174A

CN110804174A - Supported catalyst and application thereof in preparation of low-molecular-weight hydroxyl-terminated polyphenyl ether

Info

Publication number: CN110804174A
Application number: CN201911244181.1A
Authority: CN
Inventors: 黄家辉; 王奂; 尚遇青; 王晓光
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: 2020-02-18
Anticipated expiration: 2039-12-06
Also published as: CN110804174B

Abstract

The invention discloses a supported catalyst and application thereof in preparing low molecular weight double-end hydroxyl polyphenylene oxide, 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 preparation process is simple and easy to implement, 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 low-molecular-weight hydroxyl-terminated polyphenyl ether

Technical Field

The invention relates to the technical field of polymer chemical industry, in particular to a supported catalyst, a preparation method thereof and application of the supported catalyst in preparation of low-molecular-weight hydroxyl-terminated polyphenyl 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 double-end hydroxyl PPO oligomer not only has all the excellent properties of the common single-end hydroxyl PPO, such as dimensional stability, low dielectric constant and the like, but also becomes a very useful modifier due to the reactivity and is easy to process.

The traditional synthesis methods of low molecular weight double-end hydroxyl PPO mainly comprise three methods. 1. Carrying out redistribution reaction on high molecular weight PPO and diphenol monomer, and degrading to obtain low molecular weight hydroxyl-terminated polyphenyl ether, wherein the molecular weight of the product is bimodal distribution; 2. two molecules of low molecular weight polyphenylene ether and trioxymethylene are condensed under the catalysis of Lewis acid to obtain low molecular weight double-end hydroxyl polyphenylene ether, however, the preparation of the low molecular weight polyphenylene ether has great difficulty; 3. DMP and 3,3 ', 5, 5' -tetramethyl bisphenol A carry out copolymerization reaction, but the copolymerization reaction carried out in an organic solvent is very quick, and the molecular weight and the structure of the product are difficult to control. Therefore, the continuous and accurate regulation and control of the molecular weight in the one-step production of the low molecular weight dihydroxy-terminated polyphenylene oxide is still an unsolved technical problem.

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.

A supported catalyst is an alumina nanoparticle modified by a silane coupling agent, and a complex is grafted on the surface of the alumina nanoparticle 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;

wherein 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);

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

The invention also provides a preparation method of the supported catalyst, which comprises the following steps:

(1) dissolving 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; the volume ratio of the toluene to the methanol is 2-9: 1; the step (1) can be summarized as follows: carrying out coupling reaction on the alumina nano particles and a silane coupling agent to obtain surface-modified nano alumina;

(2) ultrasonically dispersing imidazole monomers, a cross-linking agent and the silane coupling agent modified aluminum oxide nanoparticles in ethyl acetate, adding an 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; the step (2) can be summarized as follows: initiating a crosslinking copolymerization reaction of vinyl imidazole monomers and a crosslinking agent by free radicals in the presence of the surface-modified nano alumina particles;

(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 step (3) can be summarized as that the imidazole group and the metal ion are subjected to coordination reaction to prepare the supported catalyst.

Based on the technical scheme, preferably, when the metal ions are divalent copper ions, the metal ion precursor is at least one of copper chloride, copper bromide, copper sulfate and copper nitrate;

based on the above technical scheme, preferably, when the metal ion is a divalent manganese ion, 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.

Based on the technical scheme, preferably, the silane coupling agent is one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane and 4-mercaptobutyltriethoxysilane;

based on the technical scheme, the cross-linking agent is preferably divinylbenzene or N, N' -methylene-bis (acrylamide); the initiator, the azodiisoheptonitrile, the potassium persulfate, the sodium persulfate, the ammonium persulfate, the benzoyl peroxide, the dicumyl peroxide, the tert-butyl hydroperoxide and the cumene hydroperoxide.

The invention also provides an application of the supported catalyst, and the supported catalyst can be used for preparing low-molecular-weight hydroxyl-terminated polyphenyl ether in an oil-water two-phase medium and can be used for catalyzing oxidative polymerization reaction for preparing the low-molecular-weight hydroxyl-terminated polyphenyl ether in the oil-water two-phase medium by taking a phenol monomer, a bisphenol monomer and an oxidant as raw materials.

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 crosslinkable polyphenyl ether.

The phenol monomer and the bisphenol monomer are respectively compounds shown in the structures of a formula (II) and a formula (III):

R₄and R₅Independently hydrogen, alkyl with 1 to 4 carbon atoms, halogenated alkyl, aminoalkyl or alkoxy;

R₆is hydrogen or halogen;

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

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

Based on the above technical scheme, preferably, 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.

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 oxidative copolymerization medium oil phase is one or more of good solvents of phenol monomers such as benzene, toluene, nitrobenzene, trichloromethane or dichloromethane and the like; the volume ratio of oil to water is 50-10: 1.

The oxidant is oxygen, air or mixed gas formed by mixing 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 one or a mixture of more of carbon dioxide, nitrogen, helium, neon and argon in any proportion; the oxidizing effect of the mixed gas is oxygen, so that the amount of the oxidant is calculated by the oxygen in the invention.

Advantageous effects

(1) 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. The obtained low molecular weight double-end hydroxyl polyphenylene oxide has the characteristics of low content of residual metal catalyst, low dielectric constant and dielectric loss, good processability and the like.

(2) 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). 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, and performing vacuum drying on the separated solid for 48 hours to prepare silane coupling agent modified nano alumina particles;

(2) surface grafting of nano-alumina particlesPreparation of cross-linked polyvinyl imidazole ligand: 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 performing vacuum drying on the mixture for 48 hours and grinding to obtain the crosslinked 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) The cross-linked polyvinyl imidazole ligand grafted on the surface of the nano alumina particle coordinates with metal ions: 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

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 number	Metal compound and its use amount	Imidazole group content of ligand
			13	0.5mmol of manganese chloride	1mmol
14	0.05mmol of copper nitrate	0.4mmol
			15	0.005mmol copper sulfate	0.15mmol

Example 16

Preparation of low molecular weight double-end hydroxyl polyphenylene oxide in oil-water two-phase medium

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 a reaction product obtained 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, wherein the yield is 84.2%, the number average molecular weight is 1700 and the molecular weight distribution is 1.7.

Example 17

Low molecular weight, double-ended hydroxyl PPO was prepared in a two-phase, oil and water medium as in example 16, except that the catalyst recovered in example 16 was used in place of the original catalyst. The catalyst recovery was 93.8%. The polymerization product is prepared, the yield is 83.0 percent, the PPO number average molecular weight is 1600, and the molecular weight distribution is 2.0.

Examples 18 to 19

Low molecular weight, hydroxyl-terminated PPO was prepared in a two-phase medium, oil and water, following the procedure of example 16, with the difference that the proportions of the two monomers were varied and the polymerization results are shown in Table 6:

TABLE 6

Examples 20 to 22

Low molecular weight double-hydroxyl-terminated PPO was prepared in an oil-water two-phase medium according to the method of example 16, except that the catalysts prepared in examples 2 to 4 were respectively used, and the polymerization results are shown in Table 7.

TABLE 7

Example number	Catalyst and process for preparing same	PPO yield (%)	PPO number average molecular weight	M_w/M_n
					20	Example 2	80.2	1400	1.6
21	Example 3	75.6	2000	1.7
					22	Example 4	83.8	1700	1.8

Examples 23 to 25

Low molecular weight double-hydroxyl-terminated PPO was prepared in an oil-water two-phase medium according to the method of example 16, 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	PPO yield (%)	PPO number average molecular weight	M_w/M_n
					23	Example 5	81.8	1600	1.9
24	Example 6	77.3	1600	1.7
					25	Example 7	79.5	2000	1.8

Examples 26 to 27

Low molecular weight double-hydroxyl-terminated PPO was prepared in an oil-water two-phase medium according to the method of example 16, except that the catalysts prepared in examples 8 to 9 were used, respectively, and the polymerization results are shown in Table 9.

TABLE 9

Example number	Catalyst and process for preparing same	PPO yield (%)	PPO number average molecular weight	M_w/M_n
					26	Example 8	81.8	1900	1.9
27	Example 9	77.3	1700	1.7

Examples 28 to 30

Low molecular weight double-hydroxyl-terminated PPO was prepared in an oil-water two-phase medium according to the method of example 16, 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	PPO yield (%)	PPO number average molecular weight	M_w/M_n
					28	Example 10	83.8	1800	1.8
29	Example 11	80.3	1900	1.7
					30	Example 12	85.5	1500	1.7

Example 31

Low molecular weight, hydroxyl-terminated PPO was prepared in an oil-water two-phase medium according to the method of example 16, using tetramethylbisphenol F (g, 40mmol) instead of tetramethylbisphenol A, at a yield of 70.28%, the product number average molecular weight was 1500, and the molecular weight distribution was 1.8.

Example 32

Low molecular weight, double-hydroxyl-terminated PPO was prepared in an oil-water two-phase medium as in example 16, except that air was used instead of oxygen, the PPO yield was 77.8%, the PPO number average molecular weight was 2500, and the molecular weight distribution was 1.7.

Example 33

Low molecular weight, double-hydroxyl-terminated PPO was prepared in an oil-water two-phase medium as in example 16, except that the reaction temperature was 25 ℃ and the reaction time was 12 hours, the PPO yield was 80.9%, the PPO number average molecular weight was 1600 and the molecular weight distribution was 1.5.

Example 34

Low molecular weight, double-hydroxyl terminated PPO was prepared in an oil-water two-phase medium as in example 16, except that the reaction temperature was 60 ℃ and the reaction time was 8 hours, the yield of PPO was 86.7%, the number average molecular weight of PPO was 2700 and the molecular weight distribution was 1.9.

Claims

1. The supported catalyst is characterized by being alumina nano particles modified by a silane coupling agent, wherein a complex is grafted on the surface of the alumina nano particles modified by the silane coupling agent; the complex is a complex of an imidazole ligand and metal ions;

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.

2. A method of preparing a supported catalyst according to claim 1, comprising the steps of:

(1) dissolving 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 N-vinyl imidazole monomer, cross-linking agent and silane coupling agent modified alumina nano particles in 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;

(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.

3. The method for preparing a supported catalyst according to claim 2, wherein when the metal ion is a divalent copper ion, 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.

4. The method for preparing the supported catalyst according to claim 3, wherein the silane coupling agent is one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane and 4-mercaptobutyltriethoxysilane.

5. A process for preparing a supported catalyst according to claim 3 wherein 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.

6. Use of the supported catalyst of claim 1 in oxidative copolymerization for the preparation of low molecular weight hydroxy-terminated polyphenylene ether; the oxidative copolymerization takes a phenol monomer, a bisphenol monomer and an oxidant as raw materials to prepare the low-molecular-weight hydroxyl-terminated polyphenyl ether in an oil-water two-phase medium; 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 R₅Independently hydrogen, alkyl with 1 to 4 carbon atoms, halogenated alkyl, aminoalkyl or alkoxy; r₆Is hydrogen or halogen;

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

7. The use according to claim 6, wherein the oxidative copolymerization reaction comprises the following raw materials in a molar ratio:

8. The use of claim 6, wherein the oxidative copolymerization reaction temperature is 10 ℃ to 80 ℃, the reaction time is 4 hours to 72 hours, and the pressure is 0.1MPa to 5.0 MPa.

9. The use according to claim 6, wherein in the oxidative copolymerization, the oil phase in the oil-water two-phase medium 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.

10. The use of claim 6, wherein the oxidant 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.