CN112812230A - Catalytic load polymer and preparation method and application thereof - Google Patents

Catalytic load polymer and preparation method and application thereof Download PDF

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CN112812230A
CN112812230A CN201911120001.9A CN201911120001A CN112812230A CN 112812230 A CN112812230 A CN 112812230A CN 201911120001 A CN201911120001 A CN 201911120001A CN 112812230 A CN112812230 A CN 112812230A
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伍广朋
董同锋
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Zhejiang University ZJU
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Abstract

The invention discloses a catalytic load polymer, the structural formula is any one of formula (I) or formula (II), wherein A is a urea or thiourea group, BIs an onium salt with a positive charge, M is a comonomer, X is the corresponding negative charge counterion; m represents the number of A and is an arbitrary integer between 1 and 100000, and n represents the number of onium salt groups and is an arbitrary integer between 1 and 100000. The invention also discloses a preparation method of the catalytic load polymer and application of the catalytic load polymer in catalyzing bulk polymerization of one or more cyclic monomers to obtain a macromolecular polymer or reacting one or more cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide and carbon monoxide to obtain small molecular compounds of cyclic carbonate, cyclic lactone and cyclic thiocarbonate and the macromolecular polymer. The catalytic load polymer has higher catalytic activity and selectivity when applied to the catalytic preparation of organic micromolecules and macromolecular polymers.
Figure DDA0002275193110000011

Description

Catalytic load polymer and preparation method and application thereof
Technical Field
The invention relates to a supported cross-linked polymer containing multiple catalytic properties and a preparation method thereof.
Background
Organic catalysts have important application potentials in the preparation of organic fine chemicals. Such as: catalytic epoxidation of a substrate with carbon dioxide (CO)2) To obtain a cyclic carbonate, etc. Cyclic carbonates are important heterocyclic compounds and widely applied in polar aprotic solvents, lithium ion batteries, organic synthesis intermediates, pharmaceutical and fine chemical industries and other fields. Over the past several decades, a number of highly efficient cyclic carbonate synthesis catalysts have been developed including salen-metal complexes, quaternary ammonium/phosphonium salts, ionic liquids, metal-organic frameworks, and the like. Among these catalysts, Ionic Liquids (ILs) have proven to be an efficient, environmentally friendly CO2A cycloaddition reaction catalyst. However, ILs do not produce satisfactory catalytic activity under mild reaction conditions. Cocatalysts such as transition metal halides or Hydrogen Bond Donors (HBDs) and organic solvents are often required, as is reported in Catal.Lett.2017,147,1654 for bifunctional catalysts based on imidazole and thiourea structures; the Kass topic group investigated the effect of the number and structure of different active centers in bifunctional catalysts on catalytic activity (j. org. chem.2018,83,9991).
Homogeneous catalytic and heterogeneous catalytic systems each have their advantages over many catalytic systems. The former generally exhibits higher activity, but is often dissolved in the reaction system, and is difficult to separate and recycle, while the latter is easily separated from the system, but the catalytic effect is often not satisfactory. The immobilization of the catalyst on a suitable support effectively combines the advantages of both catalytic systems for the sake of simplifying the process and maximizing the catalytic effect. The high molecular polymer material can be used as a carrier for loading a catalyst due to the characteristics of low price, easy obtaining, excellent compatibility and the like. The tequila group introduces ionic liquids into the crosslinked polymer backbone, enabling stable catalytic cycloaddition reactions while being easy to separate (angelw. chem. int. ed.2007,46,7255). A Zhaojindo group of Nanjing university copolymerizes quaternary ammonium salt with divinylbenzene to obtain a crosslinked polymer with catalytic action (Nanoscale Res.Let.2016,11,321), and meanwhile, a catalytic loading system based on the polymer is also proposed in a number of patents (CN 201680017375; CN 201010543838; CN 201810579090). However, due to the structural limitation of the polymer systems, additional cocatalysts are often required to be introduced to improve the activity of the polymer systems, (susteable Energy Fuels,2019,3, 935; ChemSusChem 2017,10,1186), so that the development of multifunctional catalytic supported polymers with higher activity and wider application range as heterogeneous catalytic systems for preparing fine chemicals in large-scale repeated use is necessary.
Disclosure of Invention
The invention aims to provide a catalytic load polymer which is applied to the preparation of organic micromolecule and macromolecule polymers, has higher catalytic activity and selectivity, and solves the defects that the activity of an organic homogeneous catalyst is low, and a heterogeneous catalyst needs an additive and the like.
The technical scheme provided by the invention is as follows:
a catalytically supported polymer having the structural formula of any one of formula (I) or formula (II):
Figure BDA0002275193090000021
Figure BDA0002275193090000022
wherein A is a urea or thiourea group, B is an onium salt with a positive charge, M is a comonomer, and X is a corresponding negative charge counterion; m represents the number of A and is an arbitrary integer between 1 and 100000, and n represents the number of onium salt groups and is an arbitrary integer between 1 and 100000.
A is selected from one or more of the following structural formulas:
Figure BDA0002275193090000031
wherein D is any one of O and S; r1～R4Each independently represents H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C6-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.
B is selected from one or more of the following structural formulas:
Figure BDA0002275193090000032
Figure BDA0002275193090000041
Figure BDA0002275193090000051
Figure BDA0002275193090000061
wherein R is5～R38Each independently represents H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C3-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any one or more of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.
When the structural formula of the catalytic supported polymer is shown as the formula (I), B is selected from one or more of the structural formulas; when the structural formula of the catalytic supporting polymer is (II), B is selected from two or more of the above structural formulas.
The M is selected from one or more of the following structural formulas:
Figure BDA0002275193090000071
wherein R'1～R’6Independently represent H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C3-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any one of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.
X is selected from OH and F-、Cl-、Br-、I-、NO3 -、CH3COO-、CCl3COO-、CF3COO-、ClO4 -、BF4 -、BPh4 -、N3 -Any one or more of p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3, 5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, carbonate, bicarbonate radical, 3, 5-difluorophenol oxygen, 3, 5-bis-trifluoromethylphenol oxygen or pentafluorophenol oxygen negative ions.
Preferably, the catalytically supported polymer is selected from:
Figure BDA0002275193090000081
the invention also provides a preparation method of the catalytic load polymer, which comprises the following steps: the catalytic supported polymer provided by the invention can be prepared by a free radical polymerization method, but is not limited to the method.
Preferably, the preparation method comprises the following steps: polymerizing the solution or bulk of the raw materials A ', B ' and M ' at 20-200 ℃ for 0.1-48 hours to obtain gel, microsphere or porous block polymer material with a cross-linked structure as a catalytic load polymer; the raw material A' is selected from the following structural formulas:
Figure BDA0002275193090000091
the raw material B' is selected from the following structural formulas:
Figure BDA0002275193090000092
wherein K in the raw materials A' and B1～K10And K1’～K10' each is independently selected from the following unsubstituted or substituted groups: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C3-C30Alkenyl radical, C3-C30Alkynyl, C6-C30Aryl radical, C3-C30Heterocyclic group, C5-C30One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituent is selected from one or more of halogen atoms, branched or straight chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight chain alkoxy groups with 1 to 20 carbon atoms, branched or straight chain naphthenic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 30 carbon atoms and heteroaromatic groups with 5 to 30 carbon atoms; r'1～R”4Each independently represents H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C6-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;
Figure BDA0002275193090000102
represented as one of a double or triple bond structure;
Figure BDA0002275193090000101
represents one of a single bond, a double bond or a triple bond, and at least one double bond or triple bond for reaction exists in B';
the raw material M' is selected from the following structural formula:
Figure BDA0002275193090000111
wherein the solution is one or more selected from tetrahydrofuran, benzene, toluene, chloroform, hexane, diethyl ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1, 4-dioxane, pyridine, acetonitrile and methanol.
The content of M in the catalytic load polymer prepared by the invention is 0-99%; when the content of M is 0, the supported catalyst may be supported by crosslinking through double bonds or triple bonds in A 'and B'.
The invention also provides application of the catalytic load polymer in catalyzing bulk polymerization of one or more cyclic monomers to obtain a macromolecular polymer or reacting one or more cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide and carbon monoxide to obtain a small molecular compound of cyclic carbonate, cyclic lactone and cyclic thiocarbonate and the macromolecular polymer.
The cyclic monomer is selected from one or more of the following structural formulas:
Figure BDA0002275193090000121
Figure BDA0002275193090000131
compared with the prior art, the invention has the beneficial effects that:
(1) the catalytic supported polymer prepared by the invention has higher catalytic activity and selectivity, can obtain higher yield in the reaction for preparing the organic micromolecules in a heterogeneous catalysis mode, and does not need to introduce an additional cocatalyst.
(2) The catalytic load polymer provided by the invention has cheap and easily available sources, can be applied to the reaction of catalytic synthesis of small organic molecules in a large scale, and has simple treatment and high stability.
Drawings
FIG. 1 is a digital photograph of the catalytically supported polymers prepared in examples 1-5.
Detailed Description
The purpose, technical solution and advantages of the present invention will be more clearly understood through the following detailed description of the present invention with reference to the embodiments. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Figure BDA0002275193090000141
1mmol of A was added to a 100ml round-bottom flask1，1mmol B1，1mmol M1Adding 20mL of chloroform into the solution, stirring the solution until the solution is dissolved, adding 1mmol of Azobisisobutyronitrile (AIBN), stirring the solution at 80 ℃ for 24 hours to obtain a white solid precipitate, filtering the solvent, washing the obtained precipitate with methanol for three times, and drying the precipitate in a vacuum oven at 60 ℃ for 8 hours to obtain the catalytic load Polymer 1.
Example 2
Figure BDA0002275193090000151
1mmol of A was added to a 100ml round-bottom flask1，1mmol B2，1mmol M1Adding 20mL of chloroform into the solution, stirring the solution until the solution is dissolved, adding 1mmol of Azobisisobutyronitrile (AIBN), stirring the solution at the temperature of 80 ℃ for reaction for 24 hours to obtain a white solid precipitate, filtering the solvent, washing the obtained precipitate with methanol for three times, and drying the precipitate in a vacuum oven at the temperature of 60 ℃ for 8 hours to obtain the catalytic loading Polymer 2.
Example 3
Figure BDA0002275193090000152
1mmol M was added to a 100mL round bottom flask2，1mmol B1，1mmol B2Adding 20mL of chloroform, stirring until the chloroform is dissolved, adding 1mmol of Azobisisobutyronitrile (AIBN), stirring and reacting for 24 hours at 80 ℃ to obtain white precipitates, filtering out the solvent, washing the obtained precipitates with methanol for three times, and drying the precipitates in a vacuum oven at 60 ℃ for 8 hours to obtain the catalytic loading polymer 3.
Example 4
Figure BDA0002275193090000161
1mmol of A was added to a 100ml round-bottom flask1，1mmol B2，1mmol M2Adding 20mL of chloroform into the solution, stirring the solution until the solution is dissolved, adding 1mmol of Azobisisobutyronitrile (AIBN), stirring the solution at the temperature of 80 ℃ for 24 hours to obtain yellow solid precipitate, filtering the solvent, washing the obtained precipitate with methanol for three times, and drying the precipitate in a vacuum oven at the temperature of 60 ℃ for 8 hours to obtain the catalytic supported Polymer 4.
Example 5
Figure BDA0002275193090000162
1mmol of A was added to a 100mL round-bottom flask1，1mmol B1，1mmol B2Adding 20mL of chloroform into the solution, stirring the solution until the solution is dissolved, adding 1mmol of Azobisisobutyronitrile (AIBN), stirring the solution at the temperature of 80 ℃ for reaction for 24 hours to obtain a light yellow solid precipitate, filtering the solvent, washing the obtained precipitate with methanol for three times, and drying the precipitate in a vacuum oven at the temperature of 60 ℃ for 8 hours to obtain the catalytic loading Polymer 5.
Application examples 1 to 11: method for catalyzing epoxyalkane to open ring to generate cyclic carbonate by using catalytic supported polymer 1-5
Figure BDA0002275193090000171
The catalytically supported polymer prepared in examples 1 to 5 (0.07mmol) was charged in an autoclave, and 35mmol of alkylene oxide was added and charged with 1.2MPa of CO2And reacting for 20 hours under the given temperature condition. Then releasing carbon dioxide, and taking nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer. The catalytic results and characterization are shown in table 1.
Table 1 test results of catalytic products of application examples 1 to 11
Figure BDA0002275193090000172
Application examples 12 to 16: catalyst 2 for catalytic homopolymerization of cyclic lactone
Figure BDA0002275193090000181
In a glove box, the catalytically supported polymer prepared in example 2 (0.01mmol) was added to a serum bottle and the cyclic lactone (0.01mol), 1mL of toluene, reacted at 80 ℃ for 6 h. And (3) taking reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and drying to obtain the target polyester. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 2.
Table 2 test results of the polymerization product of application example 2
Figure BDA0002275193090000182
aMnNumber average molecular weight, as determined by gel permeation chromatography
bMolecular weight distribution of PDI, as determined by gel permeation chromatography
Application examples 17 to 21: recyclability and recycle catalysis of catalytically supported polymers
The catalytically supported polymer prepared in example 2 (0.07mmol) was taken, 35mmol of alkylene oxide was added, and 1.2MPa of CO was charged2And reacted at 80 ℃ for 20 h. After the reaction is finished, filtering the insoluble catalytic supported polymer, washing the solvent, drying, carrying out catalytic reaction again under the same condition, and repeating the process. Taking reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer under different circulation times. The cycle catalysis results and characterization are shown in Table 3.
Table 3 test results of the catalytic products of application example 3
Figure BDA0002275193090000183
Figure BDA0002275193090000191
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (9)

1. A catalytically supported polymer, wherein the catalytically supported polymer has the structural formula of either formula (I) or formula (II):
Figure FDA0002275193080000011
Figure FDA0002275193080000012
wherein A is a urea or thiourea group, B is an onium salt with a positive charge, M is a comonomer, and X is a corresponding negative charge counterion; m represents the number of A and is an arbitrary integer between 1 and 100000, and n represents the number of onium salt groups and is an arbitrary integer between 1 and 100000.
2. The catalytically supported polymer of claim 1 wherein a is selected from one or more of the following structural formulas:
Figure FDA0002275193080000013
wherein D is any one of O and S; r1～R4Each independently is represented by H, having the formulaSubstituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C6-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.
3. The catalytically supported polymer of claim 1 wherein B is selected from one or more of the following structural formulas:
Figure FDA0002275193080000021
Figure FDA0002275193080000031
Figure FDA0002275193080000041
wherein R is5～R38Each independently represents H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C3-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any one or more of heterocyclic groups; the substituent is one or at least two selected from halogen atom, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atomsA combination of species;
when the structural formula of the catalytic supported polymer is shown as the formula (I), B is selected from one or more of the structural formulas; when the structural formula of the catalytic supporting polymer is (II), B is selected from two or more of the above structural formulas.
4. The catalytically supported polymer of claim 1 wherein said M is selected from one or more of the following structural formulas:
Figure FDA0002275193080000051
wherein R'1～R’6Independently represent H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C3-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any one of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.
5. The catalytically supported polymer of claim 1, wherein X is selected from the group consisting of OH and F-、Cl-、Br-、I-、NO3 -、CH3COO-、CCl3COO-、CF3COO-、ClO4 -、BF4 -、BPh4 -、N3 -P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3, 5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, carbonate, bicarbonate radicalAny one or more of 3, 5-difluorophenoxyl, 3, 5-bis-trifluoromethylphenoxyl or pentafluorophenoxyanion.
6. The catalytically supported polymer of claim 1, wherein said catalytically supported polymer is selected from the group consisting of:
Figure FDA0002275193080000061
Figure FDA0002275193080000071
7. a process for preparing a catalytically supported polymer according to any of claims 1 to 6, wherein the process comprises: reacting the raw materials A ', B ' and M ' at 20-200 ℃ for 0.1-48 hours through solution or bulk polymerization to obtain gel, microsphere or porous blocky polymer material with a cross-linked structure as a catalytic load polymer;
the raw material A' is selected from the following structural formulas:
Figure FDA0002275193080000072
the raw material B' is selected from the following structural formulas:
Figure FDA0002275193080000081
wherein K in the raw materials A' and B1～K10And K1’～K10' each is independently selected from the following unsubstituted or substituted groups: c1-C30Alkyl radical, C3-C30Cycloalkyl radical, C3-C30Alkenyl radical, C3-C30Alkynyl, C6-C30Aryl radical, C3-C30Heterocyclic group, C5-C30One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituent is selected from one or more of halogen atoms, branched or straight chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight chain alkoxy groups with 1 to 20 carbon atoms, branched or straight chain naphthenic groups with 3 to 20 carbon atoms, aromatic groups with 6 to 30 carbon atoms and heteroaromatic groups with 5 to 30 carbon atoms; r'1～R”4Each independently represents H, substituted or unsubstituted C1-14Aliphatic carbon chain, substituted or unsubstituted C6-14Alicyclic radical, substituted or unsubstituted C6-14Aromatic group, substituted or unsubstituted C3-14Any of heterocyclic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;
Figure FDA0002275193080000091
represented as one of a double or triple bond structure;
Figure FDA0002275193080000092
represents one of a single bond, a double bond or a triple bond, and at least one double bond or triple bond for reaction exists in B';
the raw material M' is selected from one or more of the following structural formulas:
Figure FDA0002275193080000093
8. use of a catalytically supported polymer according to any of claims 1 to 6 for catalysing the bulk polymerisation of one or more cyclic monomers to give a macromolecular polymer or the reaction of one or more cyclic monomers with carbon dioxide, carbon disulphide, carbon oxysulphide, carbon monoxide to give a cyclic carbonate, cyclic lactone, cyclic thiocarbonate and a macromolecular polymer.
9. Use of the catalytically supported polymer according to claim 8, wherein the cyclic monomer is selected from one or more of the following formulae:
Figure FDA0002275193080000101
Figure FDA0002275193080000111
Figure FDA0002275193080000121
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