CN109422875B - Supported catalyst with surface activity effect and application thereof in preparation of polyphenyl ether in oil-water two-phase medium - Google Patents
Supported catalyst with surface activity effect and application thereof in preparation of polyphenyl ether in oil-water two-phase medium Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
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Abstract
The invention discloses a supported catalyst with surface activity, which is a complex of imidazole ligands and metal ions grafted in surface-modified nano silicon dioxide particles; the surface-modified nano-silica particles are surface-grafted nano-silica particles which are subjected to hydrophobic silane coupling agents and polyvinyl imidazole ligands with one ends provided with the silane coupling agents. The catalyst has high catalytic efficiency and good selectivity to products, catalyzes the oxidative coupling polymerization reaction of the phenol monomers in an oil-water two-phase system, can be recycled by centrifugation or filtration after the reaction is finished, is green and environment-friendly, and better meets the requirements of sustainable development.
Description
Technical Field
The invention relates to the technical field of catalyst design, in particular to a supported catalyst with a surface activity effect, a preparation method thereof and application of the supported catalyst with the surface activity effect in preparation of polyphenyl ether in an oil-water two-phase medium.
Background
Poly (2, 6-dimethylphenylene oxide) (PPO) is one of five engineering plastics, and is widely applied to the fields of electronics and electrical industry, automobile industry, mechanical manufacturing and the like because of good dimensional stability, heat resistance, acid and alkali corrosion resistance, low dielectric constant, low dissipation factor and the like. U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, 3,257,358 and the like disclose homogeneous processes for the production of polyphenylene ethers by oxidative coupling polymerization of phenolic monomers in organic solvents catalyzed by monovalent copper complexes. The crude product produced by the method contains a large amount of copper ions, so that the electrical property of the crude product is influenced, heat is intensely released in the reaction process, an explosion-proof reactor is needed, and in addition, the catalyst cannot be recycled, so that the cost is increased, and the environment is polluted.
The polymerization system of oil-water two-phase can reduce violent heat release in the initial stage of reaction to a great extent, and meanwhile, the water-soluble catalyst and the oil-soluble product can be separated by simple liquid separation operation after the reaction is finished by adopting the water-soluble catalyst, so that the residual quantity of the catalyst in the product is reduced. However, this method requires the addition of a surfactant, which makes the system more complicated, and the failure to recover the surfactant increases the cost and causes pollution.
According to the invention, aiming at the characteristic of oxidative coupling polymerization reaction of phenol monomers in an oil-water two-phase solvent, a silane coupling agent and vinyl imidazole are grafted to the surface of nano silicon dioxide, so that the nano silicon dioxide has the effect of a solid surfactant, and meanwhile, an imidazole group can be coordinated with divalent ions of copper and manganese, so that a metal-amine complex is formed and used for catalyzing the oxidative coupling polymerization reaction of the phenol monomers to prepare PPO. The method realizes higher catalytic efficiency and selectivity, after the reaction is finished, the catalyst can be separated and recycled through simple centrifugation or filtration, the residual amount of the catalyst in the product is less, and the separation of the surfactant is simple and easy.
Disclosure of Invention
The invention provides a supported catalyst with high catalytic efficiency and surface activity, which is easy to recover.
The invention also provides a preparation method of the supported catalyst with the surface activity effect, and the method is simple to operate, easy to control and suitable for industrial production.
The invention also provides an application method of the supported catalyst with surface activity in preparing polyphenyl ether in an oil-water two-phase medium, and the catalyst in the method can be recovered and reused.
A load type catalyst with surface activity is a complex of imidazole ligand and metal ions grafted in surface modified nano silicon dioxide particles:
the surface-modified nano-silica particles are surface-grafted nano-silica particles which are subjected to hydrophobic silane coupling agent and polyvinyl imidazole ligand with one end provided with silane coupling agent;
the molar ratio of imidazole groups to metal ions in the complex is 0.5-100: 1, preferably 2-40: 1;
the metal ions are divalent copper ions or divalent manganese ions;
the imidazole ligand is a homopolymer of an N-vinyl imidazole monomer;
wherein the N-vinyl imidazole monomer is a compound shown in a structural formula (I);
formula (I):
in the formula (I), R1、R2And R3Is hydrogen or C1～C4Alkyl of R1、R2And R3The same or different.
The supported catalyst with the surface activity is characterized in that the hydrophobic silane coupling agent is one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, t-butyltrimethoxysilane and t-butyltriethoxysilane.
3. The supported catalyst with surface activity as claimed in claim 1, wherein the weight average molecular weight of the polyvinyl imidazole ligand is 500-10000, preferably 1000-5000.
The supported catalyst with the surface activity function is characterized in that the divalent copper ions are one or more of cupric chloride, cupric bromide, cupric sulfate and cupric nitrate;
or the manganese ions are selected from one or more of manganese chloride, manganese bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, manganese sulfate and manganese phosphate.
The preparation method of the supported catalyst with the surface activity effect comprises the following steps:
(1) synthesizing a polyvinyl imidazole ligand with a silane coupling agent at one end by a method of homopolymerization of an N-vinyl imidazole monomer initiated by a free radical in the presence of the silane coupling agent with a mercapto group at one end;
(2) carrying out coupling reaction on the silica nanoparticles with hydroxyl groups on the surface, the hydrophobic silane coupling agent in claim 2 and the polyvinyl imidazole ligand with the silane coupling agent at one end prepared in the step (1) through the silane coupling agent to obtain nano silica particles grafted by hydrophobic groups and the polyvinyl imidazole ligand;
(3) and (3) dispersing the modified silicon dioxide nano particles prepared in the step (2) in water, mixing with a metal ion aqueous solution, and carrying out coordination reaction on an imidazole group and metal ions to prepare the supported catalyst with the surface activity.
The preparation method of the supported catalyst with the surface activity is characterized in that the silane coupling agent with a mercapto group at one end is one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.
The supported catalyst with the surface activity is applied to catalyzing the oxidative coupling polymerization reaction for preparing polyphenyl ether in an oil-water two-phase medium by taking a phenol monomer and an oxidant as raw materials.
The molar ratio of the raw materials in the oxidative coupling polymerization reaction is as follows:
a phenol monomer 1;
0.0001-0.1 of metal ions in the supported catalyst with the surface activity function;
and a proper amount of oxidant.
The phenol monomer is a compound shown in a structural formula (II):
formula (II)
In the formula (II), R4And R5Are respectively C1～C4Alkyl, alkenyl or phenyl of R4And R5The same or different.
A method for synthesizing polyphenyl ether in an oil-water two-phase medium specifically comprises the following scheme: adding a phenol monomer and a catalyst into an oil-water two-phase mixed system, and carrying out oxidative European Union polymerization of phenols in the presence of an oxygen-containing gas, wherein the oxygen-containing gas is an oxidant.
The temperature of the oxidative coupling polymerization reaction is 10-80 ℃, preferably 20-50 ℃, the reaction time is 1-20 hours, preferably 4-12 hours, and the supported catalyst is recycled through centrifugal separation after the reaction is finished.
The raw materials and reagents of the invention can adopt products sold in the market.
Compared with the prior art, the invention has the following remarkable progress:
the catalyst of the invention combines the characteristics of a solid surfactant carrier and a metal-amine complex: the silica nanoparticles are small in size and have a large surface area, so that a reaction substrate can be in full contact with a catalyst, and the hydrophilic and lipophilic properties of the silica nanoparticles can be adjusted by grafting according to needs. After the reaction is completed, the catalyst can be recovered and utilized by a relatively simple means such as centrifugation and filtration. Solves the problem that the PPO catalyst synthesized by oil and water phases is difficult to recycle at present, and meets the requirement of sustainable development.
Detailed Description
Example 1 preparation of polyvinyl imidazole ligand with silane coupling agent at one end
5.44mL (60mmol) of N-vinylimidazole and 0.6mL (3mmol) of 3-mercaptopropyltriethoxysilane were dissolved in 60mL of methanol, 0.1g of azobisisobutyronitrile was added as an initiator, and the mixture was stirred under reflux at 65 ℃ for 48 hours under nitrogen protection. Vacuum distilling, adding excessive anhydrous ether, filtering, washing, and drying to obtain polyvinyl imidazole ligand with silane coupling agent at one end
Examples 2 to 4
Polyvinyl imidazole ligands having a silane coupling agent at one end were prepared by the method of example 1, except for changing the kind of silane coupling agent having a mercapto group at one end used in the synthesis and the amount of VI used, as shown in table 1:
example 5 preparation of a Supported catalyst with surface-active action
The polyvinylimidazole having a silane coupling agent at one end, which was prepared in example 1, 30mmol of methyltrimethoxysilane and 15g of silica nanoparticles were dispersed in toluene, heated under reflux in nitrogen for 4 hours, and centrifuged to obtain particles having a surface-active effect. And dispersing the obtained particles in water, adding 15mmol of copper chloride, stirring, and centrifuging to obtain the supported catalyst with the surface activity, wherein the copper loading is 3.1%.
Examples 6 and 7
A supported catalyst having surface-active action was prepared by the method of example 5, except that the kind of the silane coupling agent was changed, as shown in Table 2:
examples 8 to 10
A supported catalyst having surface-active action was prepared by the method of example 5, except that the kind and amount of the divalent copper compound were changed, as shown in Table 3:
EXAMPLE 11 oxidative coupling polymerization of phenol monomers in oil-Water two-phase System
2, 6-Dimethylphenol (DMP) (2.4432g, 0.02mol) and 25mL of toluene and 50mL of water were charged into a jacketed reaction vessel equipped with a stirring paddle, a thermometer and a gas inlet and outlet, after stirring uniformly, 0.4129g of the catalyst prepared in example 3 (Cu/DMP 1/100) was added, oxygen was introduced, and the reaction was carried out for 6 hours at a stirring speed of 1000 rotor/min. The catalyst was recovered by centrifugation, and the catalyst recovery rate was 96.6%. The toluene part is dripped into excessive methanol and centrifuged to obtain a product, the yield of the crude product is 90.8 percent, the content of a byproduct DPQ is 0.3 percent, and the number average molecular weight Mn58000, molecular weight distribution DP 2.0.
Examples 12 to 16
PPO was prepared according to the method of example 11, except that the catalysts prepared in examples 6-10 were used, and the reaction results are shown in Table 4:
examples 17 to 19
PPO was prepared according to the method of example 11, except that the molar ratio of copper to monomer in the catalyst was varied and the results are shown in table 5:
example 20
PPO was prepared as in example 11, except that DMP was replaced with 2, 6-diethylphenol. The yield of the crude product is 90.8 percent, wherein the content of a byproduct DPQ is 0.3 percent, and the number average molecular weight MnWhen the molecular weight distribution DP was 53000, 2.3, the catalyst recovery was 97.2%.
Example 21
PPO was prepared according to the method of example 11, except thatThe oxygen is replaced by air, the yield of the crude product is 91.0 percent, wherein the content of a by-product DPQ is 0.4 percent, and the number average molecular weight M isn45000, molecular weight distribution DP 2.5, catalyst recovery 95.8%.
Example 22
PPO was prepared according to the method of example 11, except that 25mL of toluene and 10mL of water were used. The yield of the crude product is 94.3 percent, wherein the content of the by-product DPQ is 0.6 percent, and the number average molecular weight Mn60000, molecular weight distribution DP 2.0, catalyst recovery 93.8%.
Example 23
PPO was prepared as in example 11 except that the catalyst obtained in example 1 was recovered. The yield of the crude product is 83.9 percent, wherein the content of the by-product DPQ is 0.7 percent, and the number average molecular weight Mn50000, molecular weight distribution DP 2.1.
TABLE 1
| Example number | Silane coupling agent | VI dose (mmol) |
| 2 | 3-mercaptopropyl-trimethoxysilane | 40 |
| 3 | 3-mercaptopropyl-methyldimethoxysilane | 20 |
| 4 | 3-mercaptopropyl-methyldiethoxysilane | 50 |
TABLE 2
| Example number | Silane coupling agent | Copper loading (%) |
| 6 | Methyltriethoxysilane | 2.71 |
| 7 | Ethyl triethoxysilane | 1.78 |
TABLE 3
| Example number | Copper compound | Copper compound dosage (mmol) | Copper loading (%) |
| 8 | Copper nitrate | 10 | 1.71 |
| 9 | Copper sulfate | 8 | 1.23 |
| 10 | Copper bromide | 15 | 3.3 |
TABLE 4
TABLE 5
The catalyst has high catalytic efficiency and good selectivity to products, catalyzes the oxidative coupling polymerization reaction of the phenol monomers in an oil-water two-phase system, can be recycled by centrifugation or filtration after the reaction is finished, is green and environment-friendly, and better meets the requirements of sustainable development.
Claims (10)
1. The supported catalyst with the surface activity is characterized by being a complex of imidazole ligands and metal ions grafted in surface-modified nano silica particles:
the surface-modified nano-silica particles are surface-grafted nano-silica particles which are subjected to hydrophobic silane coupling agent and polyvinyl imidazole ligand with one end provided with silane coupling agent;
the molar ratio of imidazole groups to metal ions in the complex is 0.5-100: 1;
the metal ions are divalent copper ions or divalent manganese ions;
the imidazole ligand is a homopolymer of an N-vinyl imidazole monomer;
wherein the N-vinyl imidazole monomer is a compound shown in a structural formula (I);
formula (I):
in the formula (I), R1、R2And R3Is hydrogen or C1~C4Alkyl of R1、R2And R3The same or different.
2. The supported surface-active catalyst according to claim 1, wherein the hydrophobic silane coupling agent is one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, t-butyltrimethoxysilane, and t-butyltriethoxysilane.
3. The supported catalyst with surface activity as claimed in claim 1, wherein the weight average molecular weight of the polyvinyl imidazole ligand is 500-10000.
4. The supported surface-active catalyst of claim 1, wherein the cupric ions are selected from the group consisting of cupric chloride, cupric bromide, cupric sulfate, cupric nitrate;
or the manganese ions are selected from one or more of manganese chloride, manganese bromide, manganese iodide, manganese carbonate, manganese acetate, manganese nitrate, manganese sulfate and manganese phosphate.
5. A process for preparing a supported catalyst having surface-active action according to any one of claims 1 to 4, comprising the steps of:
(1) synthesizing a polyvinyl imidazole ligand with a silane coupling agent at one end by a method of homopolymerization of an N-vinyl imidazole monomer initiated by a free radical in the presence of the silane coupling agent with a mercapto group at one end;
(2) carrying out coupling reaction on the silica nanoparticles with hydroxyl groups on the surface, the hydrophobic silane coupling agent in claim 2 and the polyvinyl imidazole ligand with the silane coupling agent at one end prepared in the step (1) through the silane coupling agent to obtain nano silica particles grafted by hydrophobic groups and the polyvinyl imidazole ligand;
(3) and (3) dispersing the modified silicon dioxide nano particles prepared in the step (2) in water, mixing with a metal ion aqueous solution, and carrying out coordination reaction on an imidazole group and metal ions to prepare the supported catalyst with the surface activity.
6. The method for preparing the supported catalyst with surface activity according to claim 5, wherein the silane coupling agent having a mercapto group at one end is one or more of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.
7. The use of the supported catalyst with surface activity as claimed in any one of claims 1 to 4 in catalyzing an oxidative coupling polymerization reaction for preparing polyphenylene ether in an oil-water two-phase medium by using a phenol monomer and an oxidant as raw materials.
8. The use according to claim 7, wherein the oxidative coupling polymerization reaction comprises the following raw materials in a molar ratio:
a phenol monomer 1;
0.0001-0.1 of metal ions in the supported catalyst with the surface activity function;
and a proper amount of oxidant.
9. The use of claim 7, wherein the phenolic monomer is a compound of formula (II):
formula (II)
In the formula (II), R4And R5Are respectively C1~C4Alkyl, alkenyl or phenyl of R4And R5The same or different.
10. The application of claim 7, wherein the temperature of the oxidative coupling polymerization reaction is 10-80 ℃, the reaction time is 1-20 hours, and the supported catalyst is recycled by centrifugal separation after the reaction is finished.
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| CN110280314B (en) * | 2019-07-16 | 2021-07-23 | 中国科学院兰州化学物理研究所 | Method for improving water resistance and dust resistance of manganese-based low-temperature SCR catalyst |
| CN110804174B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight hydroxyl-terminated polyphenyl ether |
| CN110885441B (en) * | 2019-12-06 | 2021-01-05 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether |
| CN111286023B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of crosslinkable polyphenyl ether |
| CN111286022B (en) * | 2019-12-06 | 2022-07-08 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of low-molecular-weight polyphenylene ether |
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| CN102060990A (en) * | 2010-11-26 | 2011-05-18 | 浙江大学 | Magnetic supported catalyst and application thereof in preparing polyphenyleneoxide in aqueous medium |
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| CN102060990A (en) * | 2010-11-26 | 2011-05-18 | 浙江大学 | Magnetic supported catalyst and application thereof in preparing polyphenyleneoxide in aqueous medium |
| CN102513158A (en) * | 2011-12-05 | 2012-06-27 | 上海师范大学 | Method for preparing ethylene carbonate through continuous heterogeneous catalysis and catalyst |
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