Metallic ion-polyvinyl imidazol complex catalyst and preparation method and application thereof

Abstract

The invention discloses a metallic ion-polyvinyl imidazole complex catalyst, which is a complex of a metallic ion and a polyvinyl imidazole ligand, wherein the molar ratio of imidazole groups to the metallic ion is 0.5 to 300; the metallic ion is a copper ion or manganese ion; and the polyvinyl imidazole ligand is a homopolymer of a N-vinyl imidazole monomer or copolymer of the N-vinyl imidazole monomer and another one or various water-soluble monomers and has a weight average molecular weight of 10<3> to 10<7>. The polyvinyl imidazole ligand has a large number of imidazole groups and can significantly increase the local concentration of the catalyst in a reaction medium after the complexation with the metallic ion, so the catalyst has greatly improved catalytic efficiency, achieves high PPO yield with a very small dosage when used in the preparation of PPO in a water medium, and solves the problem of the low catalytic efficiency of the prior polyphenylether catalyst prepared in the water medium.

Description

technical field

[0001] The invention relates to the field of polymer metal complex catalysts, in particular to a metal ion-polyvinylimidazole complex catalyst and a preparation method thereof, and the preparation of the metal-polyvinylimidazole complex catalyst in an aqueous medium Application of polyphenylene ether. Background technique

[0002] Polymer metal complexes are an important content in the research field of functional polymer materials. The long-chain structure of polymer compounds provides a new arrangement for metal ions, and in many cases will produce products with new structural properties. .

[0003] In recent years, polymer metal complexes have attracted much attention due to their special functions such as high selective catalytic activity. The metal ion-polyvinylimidazole complex is one of many polymer metal complexes. Since the polyvinylimidazole molecular chain contains a large number of imidazole groups, it can be combined with Cu 2+ , Zn 2+ 、Cd 2...

Examples

Embodiment 1

[0047] Embodiment 1 prepares metal ion-polyvinylimidazole complex catalyst

[0048] Add 10 g of N-vinylimidazole, 0.1 g of azobisisobutyronitrile, and 100 mL of water into a reaction kettle connected with a thermometer, a stirring blade, a condenser tube, and a gas inlet and outlet, and stir to obtain a transparent solution. Under the protection of nitrogen atmosphere, the temperature of the reaction vessel was raised to 80° C., and the reaction was carried out for 6 hours. After the polymerization reaction was finished, the reaction solution was poured into toluene, and the polymer was precipitated out. After filtering, washing, and vacuum drying, 9.3g of polyvinylimidazole ligands were obtained, and the weight-average molecular weight was 8.0×10 4 .

[0049] 0.0086g CuCl 2 2H 2 O (the molar weight is 0.05mmol) and 0.0188g of the above-prepared polyvinylimidazole ligands (wherein, the imidazole group is 0.2mmol) were respectively dissolved in 5mL of water, mixed and stirre...

Embodiment 2～4

[0051] Except adopting the mixture of N-vinylimidazole monomer and water-soluble comonomer to replace N-vinylimidazole in Example 1, all the other operations are the same as in Example 1 to prepare metal ion-polyvinylimidazole complex Catalyst, see Table 1:

[0052] Table 1

[0053] Example

Embodiment 5～6

[0055] Except adopting potassium persulfate or tert-butyl hydroperoxide / sodium disulfide initiator system to replace the azobisisobutyronitrile in embodiment 1, all the other operations are the same as in embodiment 1 to prepare metal ion-polyvinylimidazole Complex catalyst, see table 2:

[0056] Table 2

[0057] Example serial number

technical field

[0001] The invention relates to the field of polymer metal complex catalysts, in particular to a metal ion-polyvinylimidazole complex catalyst and a preparation method thereof, and the preparation of the metal-polyvinylimidazole complex catalyst in an aqueous medium Application of polyphenylene ether. Background technique

[0002] Polymer metal complexes are an important content in the research field of functional polymer materials. The long-chain structure of polymer compounds provides a new arrangement for metal ions, and in many cases will produce products with new structural properties. .

[0003] In recent years, polymer metal complexes have attracted much attention due to their special functions such as high selective catalytic activity. The metal ion-polyvinylimidazole complex is one of many polymer metal complexes. Since the polyvinylimidazole molecular chain contains a large number of imidazole groups, it can be combined with Cu 2+ , Zn 2+ 、Cd 2...

Examples

Embodiment 1

[0047] Embodiment 1 prepares metal ion-polyvinylimidazole complex catalyst

[0048] Add 10 g of N-vinylimidazole, 0.1 g of azobisisobutyronitrile, and 100 mL of water into a reaction kettle connected with a thermometer, a stirring blade, a condenser tube, and a gas inlet and outlet, and stir to obtain a transparent solution. Under the protection of nitrogen atmosphere, the temperature of the reaction vessel was raised to 80° C., and the reaction was carried out for 6 hours. After the polymerization reaction was finished, the reaction solution was poured into toluene, and the polymer was precipitated out. After filtering, washing, and vacuum drying, 9.3g of polyvinylimidazole ligands were obtained, and the weight-average molecular weight was 8.0×10 4 .

[0049] 0.0086g CuCl 2 2H 2 O (the molar weight is 0.05mmol) and 0.0188g of the above-prepared polyvinylimidazole ligands (wherein, the imidazole group is 0.2mmol) were respectively dissolved in 5mL of water, mixed and stirre...

Embodiment 2～4

[0051] Except adopting the mixture of N-vinylimidazole monomer and water-soluble comonomer to replace N-vinylimidazole in Example 1, all the other operations are the same as in Example 1 to prepare metal ion-polyvinylimidazole complex Catalyst, see Table 1:

[0052] Table 1

[0053] Example

Embodiment 5～6

[0055] Except adopting potassium persulfate or tert-butyl hydroperoxide / sodium disulfide initiator system to replace the azobisisobutyronitrile in embodiment 1, all the other operations are the same as in embodiment 1 to prepare metal ion-polyvinylimidazole Complex catalyst, see table 2:

[0056] Table 2

[0057] Example serial number

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