CN111286023A - Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether - Google Patents

Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether Download PDF

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CN111286023A
CN111286023A CN201911245177.7A CN201911245177A CN111286023A CN 111286023 A CN111286023 A CN 111286023A CN 201911245177 A CN201911245177 A CN 201911245177A CN 111286023 A CN111286023 A CN 111286023A
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manganese
supported catalyst
catalyst
silane coupling
coupling agent
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CN111286023B (en
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黄家辉
王奂
陈锴
王晓光
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Panjin Sanli Zhongke New Material Co ltd
Dalian Institute of Chemical Physics of CAS
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Panjin Sanli Zhongke New Material Co ltd
Dalian Institute of Chemical Physics of CAS
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56Polyhydroxyethers, e.g. phenoxy resins
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Abstract

The invention discloses a supported catalyst and application thereof in preparing crosslinkable polyphenyl ether, which is a complex of imidazole ligands and metal ions grafted on the surface of surface-modified nano alumina particles; 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, organic solvent resistance after crosslinking and curing, high temperature resistance, good processing performance 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 crosslinkable 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 cross-linkable 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, but as a thermoplastic resin, PPO can not bear the welding requirement at high temperature, is easy to dissolve in aromatic hydrocarbon or chlorinated aliphatic hydrocarbon, and has poor solvent resistance. The introduction of unsaturated carbon-carbon double bonds into PPO is a good solution to the above problem, with the advantages: (1) because the proportion of unsaturated carbon-carbon double bonds in the whole PPO is small, the excellent characteristics of the original thermoplastic PPO resin, such as low dielectric constant, high glass transition temperature, low hygroscopicity and the like, can be basically maintained. (2) The solvent resistance of the crosslinked and cured PPO resin is greatly improved. (3) The unsaturated carbon-carbon double bond is a nonpolar group, and has the advantages of good dielectric property, proper curing temperature, no volatile matter during curing and the like. The cross-linkable PPO is applied to the manufacture of the copper-clad plate, so that the good electrical property of the copper-clad plate can be maintained, the solvent resistance and the welding property at high temperature of the copper-clad plate can be obviously improved after the copper-clad plate is solidified, the process is simple and feasible, and the requirements of a high-frequency printed circuit board can be met.
The traditional PPO synthesis method is carried out in an organic solvent, the PPO synthesized in a homogeneous medium has large molecular weight, the variable regulation and control of the molecular weight are difficult to realize, the glass transition temperature is high, the processing is difficult, the content of residual catalyst metal ions in a product is high, and the electrical property of the product is reduced to a certain extent. The continuous regulation and control of molecular weight 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 process for preparing a crosslinkable polyphenylene ether in a two-phase medium of oil and water with a supported catalyst, in which process the catalyst can be recovered and reused as desired. The technical scheme is as follows:
the invention provides a supported catalyst, wherein 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;
wherein the N-vinyl imidazole monomer is a compound shown in a structural formula (I);
Figure BDA0002307321280000021
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; in the mixed solvent, the volume ratio of toluene to 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;
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.
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;
the cross-linking agent is 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 the cross-linked polyphenyl ether in an oil-water two-phase medium and catalyzing the oxidative polymerization reaction for preparing the cross-linked polyphenyl ether in an oil-water two-phase medium by taking the phenol monomer, the phenol monomer containing unsaturated carbon-carbon double bonds 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 cross-linkable polyphenylene oxide in the oil-water two-phase medium by using the supported catalyst comprises the following steps: dissolving a phenol 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 phenol monomer containing unsaturated carbon-carbon double bonds are compounds respectively shown in the structures of a formula (II) and a formula (III): the oxidative copolymerization reaction product of the crosslinkable polyphenyl ether is a compound with a structure shown in a formula (IV):
Figure BDA0002307321280000031
Figure BDA0002307321280000041
R4and R5Independently hydrogen, alkyl with 1 to 4 carbon atoms, halogenated alkyl, aminoalkyl or alkoxy;
R6is hydrogen or halogen;
R7and R8Independently hydrogen, a group containing an unsaturated carbon-carbon double bond having 2 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group, an aminoalkyl group or an alkoxy group, and R7And R8At least one of the two groups is a group containing unsaturated carbon-carbon double bond with carbon atom number of 2-4;
m is 10 to 120, n is 1 to 30;
the weight average molecular weight of the crosslinkable polyphenyl ether is 2500-50000.
Based on the above technical scheme, preferably, the molar ratio of the raw materials in the oxidative copolymerization reaction is as follows:
Figure BDA0002307321280000042
wherein the sum of the molar ratio of the phenol monomer and the phenol monomer containing unsaturated carbon-carbon double bonds 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 between normal pressure and 5.0MPa, preferably between 0.1MPa and 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.
The product synthesized by the method is subjected to temperature programming or ultraviolet irradiation under the action of a peroxide initiator or a photoinitiator, unsaturated carbon-carbon double bonds on a side chain can be subjected to crosslinking reaction to obtain the cured modified polyphenyl ether, and the product has good solvent resistance and temperature resistance after being cured.
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.
(2) The product prepared by the invention has the characteristics of low content of residual metal catalyst, low dielectric constant and dielectric loss, organic solvent resistance after crosslinking and curing, high temperature resistance, good processability and the like.
(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 (volume ratio) 8: 2. 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
Figure BDA0002307321280000071
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 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 crosslinkable polyphenyl ether in oil-water two-phase medium
4.93g of 2, 6-dimethylphenol (DMP, 40mmol) and 2-allyl-6-methylphenol (AMP, 1.5mL, 10mmol) are dissolved in 15mL of toluene in a reaction kettle connected with a thermometer, a stirring paddle, a condensing tube and a gas inlet and outlet, the supported catalyst prepared in example 1 is dispersed in 2mL of water by ultrasound, the two media are mixed and stirred uniformly, then the reaction kettle is heated to 40 ℃, oxygen is introduced, and the reaction is carried out for 6 hours at a 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 cross-linked PPO, wherein the yield is 94.2%, the weight average molecular weight is 4000 and the molecular weight distribution is 2.0.
Example 17
The preparation of cross-linkable PPO was carried out in a two-phase oil-water medium according to the procedure 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 polymerization product was obtained in a yield of 93.0%, PPO weight-average molecular weight of 4200, molecular weight distribution of 2.0.
Examples 18 to 19
The preparation of cross-linkable PPO in a two-phase oil-water medium was carried out as described in example 16, with the difference that the ratio of the two phenolic monomers was varied and the polymerization results are shown in Table 6:
TABLE 6
Figure BDA0002307321280000081
Examples 20 to 22
Cross-linkable PPO was prepared in a two-phase medium of oil and water by the method of example 16, except that the catalysts prepared in examples 2-4 were used, respectively, and the polymerization results are shown in Table 7.
TABLE 7
Example number Catalyst and process for preparing same PPO yield (%) PPO weight average molecular weight Mw/Mn
20 Example 2 80.2 5400 1.9
21 Example 3 75.6 4400 1.7
22 Example 4 93.8 5600 1.8
Examples 23 to 25
Cross-linkable PPO was prepared in a two-phase medium of oil and water by the method of example 16, except that the catalysts prepared in examples 5-7 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 weight average molecular weight Mw/Mn
23 Example 5 91.8 3600 1.9
24 Example 6 87.3 4600 1.7
25 Example 7 89.5 6000 1.8
Examples 26 to 27
Cross-linkable PPO was prepared in a two-phase medium of oil and water by 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 PPO yield (%) PPO weight average molecular weight Mw/Mn
26 Example 8 91.8 3900 1.9
27 Example 9 87.3 5700 1.7
Examples 28 to 30
Cross-linkable PPO was prepared in a two-phase medium of oil and water by the method of example 16, except that the catalysts prepared in examples 8-10 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 weight average molecular weight Mw/Mn
28 Example 10 93.8 3800 1.8
29 Example 11 90.3 4900 1.9
30 Example 12 95.5 6500 1.9
Example 31
Cross-linkable PPO was prepared in a two-phase oil-water medium as described in example 16, replacing 2, 6-dimethylphenol by 2, 6-diethylphenol (5.053g, 40mmol), giving a yield of 80.28%, a product having a weight-average molecular weight of 6200 and a molecular weight distribution of 2.3.
Example 32
Cross-linkable PPO was prepared in the oil-water two-phase medium as in example 16, except that air was used instead of oxygen, the PPO yield was 87.8%, the PPO weight-average molecular weight was 3500 and the molecular weight distribution was 1.7.
Example 33
Cross-linkable PPO was prepared in the 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 83.9%, the PPO weight average molecular weight was 2900 and the molecular weight distribution was 1.9.
Example 34
Cross-linkable 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 PPO yield was 96.7%, the PPO weight average molecular weight was 8700 and the molecular weight distribution was 2.2.

Claims (10)

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 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);
Figure FDA0002307321270000011
in the formula (I), R1、R2And R3Independently is hydrogen or C1~C4Alkyl groups of (a);
in the complex, the molar ratio of the imidazole group to the metal ion is 0.5-200: 1.
2. A method of preparing a supported catalyst according to claim 1, comprising the steps of:
(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 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. The application of the supported catalyst as claimed in claim 1, wherein the catalyst is applied to an oxidative copolymerization reaction for preparing the crosslinkable polyphenylene ether, and the oxidative copolymerization reaction takes a phenol monomer, a phenol monomer containing an unsaturated carbon-carbon double bond and an oxidant as raw materials to prepare the crosslinkable polyphenylene ether in an oil-water two-phase medium; the structure of the phenol monomer is shown as a formula (II); the structure of the unsaturated carbon-carbon double bond phenol monomer is shown as a formula (III); the structure of the crosslinkable polyphenyl ether is shown as a formula (IV);
Figure FDA0002307321270000021
R4and R5Independently hydrogen, alkyl with 1 to 4 carbon atoms, halogenated alkyl, amino alkyl or alkoxy,
R6is hydrogen or halogen;
R7and R8Independently is a group containing an unsaturated carbon-carbon double bond having 2 to 4 carbon atoms, hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group, an aminoalkyl group or an alkoxy group, and R7And R8At least one of the two groups is a group containing an unsaturated carbon-carbon double bond having 2 to 4 carbon atoms,
R9is hydrogen or halogen;
m is 10 to 120, n is 1 to 30; the weight average molecular weight of the crosslinkable polyphenyl ether is 2500-50000.
7. The use according to claim 6, wherein the oxidative copolymerization reaction comprises the following raw materials in a molar ratio:
Figure FDA0002307321270000031
wherein the sum of the molar ratio of the phenol monomer and the phenol monomer containing unsaturated carbon-carbon double bonds is 1.
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 said oxidative polymerization, in said oil-water two-phase medium, the oil phase is at least one of benzene, toluene, nitrobenzene, chloroform or dichloromethane; the volume ratio of oil to water 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.
CN201911245177.7A 2019-12-06 2019-12-06 Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether Active CN111286023B (en)

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US4207406A (en) * 1978-05-09 1980-06-10 General Electric Company Process for preparing polyphenylene oxide copolymers
CN101544755A (en) * 2009-04-28 2009-09-30 浙江大学 Metallic ion-polyvinyl imidazol complex catalyst and preparation method and application thereof
CN109422875A (en) * 2017-08-30 2019-03-05 中国科学院大连化学物理研究所 A kind of loaded catalyst with surface-active action and its application that polyphenylene oxide is prepared in water-oil phase medium
CN109422874A (en) * 2017-08-28 2019-03-05 中国科学院大连化学物理研究所 A kind of imidazole radicals cross-linked polymer supported copper nano-particle catalyst and preparation and application
CN109776790A (en) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 A kind of method of oxidative coupling polymerization synthesis polyphenylene oxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207406A (en) * 1978-05-09 1980-06-10 General Electric Company Process for preparing polyphenylene oxide copolymers
CN101544755A (en) * 2009-04-28 2009-09-30 浙江大学 Metallic ion-polyvinyl imidazol complex catalyst and preparation method and application thereof
CN109422874A (en) * 2017-08-28 2019-03-05 中国科学院大连化学物理研究所 A kind of imidazole radicals cross-linked polymer supported copper nano-particle catalyst and preparation and application
CN109422875A (en) * 2017-08-30 2019-03-05 中国科学院大连化学物理研究所 A kind of loaded catalyst with surface-active action and its application that polyphenylene oxide is prepared in water-oil phase medium
CN109776790A (en) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 A kind of method of oxidative coupling polymerization synthesis polyphenylene oxide

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