1. A polyether amide ionic liquid catalyst is characterized in that the structural formula of the catalyst is as follows:

or the following steps:

in the formula, R¹Is phenyl or C₁-C₁₆An alkyl group; r²Is H or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; n is 3-240, m is 0, 1,2, 3 or 4; x^-Is Cl^-，Br^-Or I^-。

2. The polyether amide ionic liquid catalyst as claimed in claim 1, wherein one of the raw materials for synthesizing the catalyst is polyether monocarboxylic acid:

or is a polyether dicarboxylic acid:

in the formula, R¹Is phenyl or C₁-C₁₆Alkyl, n-3-240;

the second raw material is para-amino (or aminoalkyl) pyridine, meta-amino (or aminoalkyl) pyridine, ortho-amino (or aminoalkyl) pyridine, amino-functionalized imidazolium ionic liquid, amino-functionalized guanidinium ionic liquid, amino-functionalized quaternary ammonium salt, amino-functionalized quaternary phosphonium salt, amino-functionalized piperidine salt, amino-functionalized morpholine salt or amino-functionalized pyrrolidine salt, and the structural formulas of the salts are respectively as follows:

in the formula, R²Is H or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; m is 0, 1,2, 3 or 4; x^-Is Cl^-，Br^-Or I^-；

The third raw material is R²X, when R²When H, R²X is a halogen acid, when R²＝C₁-C₁₆When alkyl, R²X is alkyl halide, and X is Cl, Br or I;

the intermediate is amino (or aminoalkyl) pyridine polyether monoamide or amino (or aminoalkyl) pyridine polyether diamide, and the structural formula is as follows:

in the formula, R¹Is phenyl or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; n is 3-240 and m is 0, 1,2, 3 or 4.

3. The polyether amide ionic liquid catalyst as claimed in claim 1, which is prepared by the following steps: with polyether monocarboxylic acids R¹(EO)_nCOOH as raw material, and in the first step, p-amino (or aminoalkyl) pyridine Py-p- (CH) in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)₂)_mNHR³I, M-amino (or aminoalkyl) pyridine Py-m- (CH)₂)_mNH₂Or o-amino (or aminoalkyl) pyridine Py-o- (CH)₂)_mNH₂Condensing to obtain corresponding intermediate p-amino (or aminoalkyl) pyridine polyether monoamide Py-p- (CH)₂)_mR³NCO(EO)_nR¹M-amino (or aminoalkyl) pyridylpolyether monoamide Py-m- (CH)₂)_mNHCO(EO)_nR¹Or o-amino (or aminoalkyl) pyridylpolyether monoamide Py-o- (CH)₂)_mNHCO(EO)_nR¹(ii) a In the second step, the intermediate is reacted with R in toluene solvent²X

Reacting to obtain corresponding para-amino (or aminoalkyl) pyridinium salt polyether monoamide ionic liquid [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]M-amino (or aminoalkyl) pyridinium salt polyether monoamide ionic liquid [ R²Py-m-(CH₂)_mNHCO(EO)_nR¹][X]Or o-amino (or aminoalkyl) pyridinium salt polyether monoamide ionic liquid [ R²Py-o-(CH₂)_mNHCO(EO)_nR¹][X](ii) a Or with polyether monocarboxylic acids R¹(EO)_nCOOH as raw material is respectively mixed with amino functional imidazolium ionic liquid [ R ] in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)²R³IM(CH₂)_mNH₂][X]Amino-functionalized guanidine salt ionic liquid [ (R)²)₄R³AG(CH₂)_mNH₂][X]Amino-functional quaternary ammonium salt [ (R)²)₃N(CH₂)_mNH₂][X]Amino-functional quaternary phosphonium salts [ (R)²)₃P(CH₂)_mNH₂][X]Amino-functional piperidine salts [ R ]²Pi(CH₂)_mNH₂][X]Amino-functionalized morpholine salt [ R²Mor(CH₂)_mNH₂][X]Or amino-functionalized pyrrolidine salts [ R ]²Pyr(CH₂)_mNH₂][X]Condensing to obtain corresponding imidazolium salt polyether monoamide ionic liquid [ R ]²R³IM(CH₂)_mNHCO(EO)_nR¹][X]And guanidine salt polyether monoamide ionic liquid [ (R)²)₄R³AG(CH₂)_mNHCO(EO)_nR¹][X]Quaternary ammonium salt polyether monoamide ionic liquid [ (R)²)₃N(CH₂)_mNHCO(EO)_nR¹][X]Quaternary phosphonium salt polyether monoamide ionic liquid [ (R)²)₃P(CH₂)_mNHCO(EO)_nR¹][X]Piperidine salt polyether monoamide ionic liquid [ R²Pi(CH₂)_mNHCO(EO)_nR¹][X]Morpholine salt polyether monoamide ionic liquid [ R²Mor(CH₂)_mNHCO(EO)_nR¹][X]Or pyrrolidine salt polyether monoamide ionic liquid [ R ]²Pyr(CH₂)_mNHCO(EO)_nR¹][X]；

Alternatively, polyether dicarboxylic acids HOOC (EO)_nCOOH as raw material, and in the first step, p-amino (or aminoalkyl) pyridine Py-p- (CH) in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)₂)_mNHR³I, M-amino (or aminoalkyl) pyridine Py-m- (CH)₂)_mNH₂Or o-amino (or aminoalkyl) pyridine Py-o- (CH)₂)_mNH₂Condensing to obtain corresponding intermediate p-amino (or aminoalkyl) pyridine polyether diamide Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py, meta-amino (or aminoalkyl) pyridylpolyether diamide Py-m- (CH)₂)_mNHCO(EO)_nCONH(CH₂)_m-m-Py or o-amino (or aminoalkyl) pyridylpolyether diamide Py-o- (CH)₂)_mNHCO(EO)_nCONH(CH₂)_m-o-Py; in the second step, the intermediate is reacted with R in toluene solvent²X reacts to obtain corresponding para-amino (or aminoalkyl) pyridinium salt polyether diamide ionic liquid [ X][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]M-amino (or aminoalkyl) pyridinium salt polyether diamide ionic liquid [ X][R²Py-m-(CH₂)_mNHCO(EO)_nCONH(CH₂)_m-m-PyR²][X]Or o-amino (or aminoalkyl) pyridinium salt polyether diamide ionic liquid [ X][R²Py-o-(CH₂)_mNHCO(EO)_nCONH(CH₂)_m-o-PyR²][X](ii) a Alternatively, polyether dicarboxylic acids HOOC (EO)_nCOOH as raw material is respectively mixed with amino functional imidazolium ionic liquid [ R ] in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)²R³IM(CH₂)_mNH₂][X]Amino-functionalized guanidine salt ionic liquid [ (R)²)₄R³AG(CH₂)_mNH₂][X]Amino-functional quaternary ammonium salt [ (R)²)₃N(CH₂)_mNH₂][X]Amino-functional quaternary phosphonium salts [ (R)²)₃P(CH₂)_mNH₂][X]Amino-functional piperidine salts [ R ]²Pi(CH₂)_mNH₂][X]Amino-functionalized morpholine salt [ R²Mor(CH₂)_mNH₂][X]Or amino-functionalized pyrrolidine salts [ R ]²Pyr(CH₂)_mNH₂][X]Condensing to obtain corresponding imidazolium salt polyether diamide ionic liquid [ X ]][R²R³IM(CH₂)_mNHCO(EO)_nCONH(CH₂)_mIMR³R²][X]Guanidine salt polyether diamide ionic liquid [ X ]][(R²)₄R³AG(CH₂)_mNHCO(EO)_nCONH(CH₂)_mAGR³(R²)₄][X]Quaternary ammonium salt polyether diamide ionic liquid [ X ]][(R²)₃N(CH₂)_mNHCO(EO)_nCONH(CH₂)_mN(R²)₃][X]Quaternary phosphonium salt polyether diamide ionic liquid [ X][(R²)₃P(CH₂)_mNHCO(EO)_nCONH(CH₂)_mP(R²)₃][X]Piperidine salt polyether diamide ionic liquid [ X][R²Pi(CH₂)_mNHCO(EO)_nCONH(CH₂)_mPiR²][X]Morpholine salt polyether diamide ionic liquid [ X][R²Mor(CH₂)_mNHCO(EO)_nCONH(CH₂)_mMorR²][X]Or pyrrolidine salt polyether diamide ionic liquid [ X][R²Pyr(CH₂)_mNHCO(EO)_nCONH(CH₂)_mPyrR²][X]；

In the formula, R¹Is phenyl or C₁-C₁₆An alkyl group; r²Is H or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; n is 3-240, m is 0, 1,2, 3 or 4; x^-Is Cl^-，Br^-Or I^-；

Background

Carbon dioxide (CO)₂) Is a main greenhouse gas causing global warming, and is also an inexhaustible, cheap, nontoxic and recyclable green C on the earth₁And (4) resources. Realization of CO₂Resource utilization of CO₂The method has important strategic significance on reducing emission, improving environment and reducing the dependence of human on fossil fuel. In recent years, cyclic carbonates have been widely used as high value-added chemicals in the fields of fine chemical engineering, lithium battery production, synthesis of polycarbonates and polyurethanes, and the like. And is composed of CO₂Cycloaddition with epoxides to produce cyclic carbonates is a green chemical process with 100% atom economy, replacing CO as a toxic phosgene synthesis process₂One of the important ways of efficient resource utilization is always concerned by academia and industry. However, CO₂Is a thermodynamically stable molecule, realizing CO₂The key of high-efficiency conversion is the research and development of a high-efficiency catalyst. Metal-based catalysts (Dalton Trans.2018,47, 13281-13313), particularly metal complexes, generally have higher catalytic activity, however, many metal-based catalysts are less selective, sensitive to hydrolysis and/or oxidation, or toxic. Therefore, high-efficiency organic catalysts are developed to replace metal-based catalysts (Green chem.2021,23, 77-118; Catal.Sci.Technol.2017,7, 2651-₂Has been CO₂The field of resource utilization is continuously concerned. High efficiency organic catalysts generally contain multiple catalytically active sites, including: hydrogen Bond Donor (HBD) groups (activated epoxide), organic base groups (CO capture and activation)₂) And nucleophilic groups (facilitating the ring-opening reaction step), wherein the HBD group generally plays a key role, and the high-efficiency HBD group can effectively reduce CO₂Activation energy of cycloaddition reaction. The HBD groups reported in the literature include: hydroxyl (ChemSusChem 2015,8, 2655-2669; J.Catal.2016,333, 29-39.), carboxyl (ACS Sustainable Chem.Eng.2017,5, 3081-3086; Catal.Commun.2019,124, 118-122.), amino (Catal.Lett.2014,144, 1313-1321; chem.Eng.J.2012, 193-194, 267-275.), and ureido (Green Chem.2019,21, 5231-525237; Green Chem.2016,18, 2851-2863), among others. However, the above-mentioned HBD group-modified organic catalysts still have major limitations, mainly represented by: (1) the catalytic activity is not high: HBD groups have weak activation effect on epoxide, so that the activity of the catalyst is not high; (2) difficult separation of the catalyst: catalyst and product cyclic carbonateThe separation is difficult and the product phase is easy to run off, resulting in shorter cycle life. The above problems greatly limit the use of organic catalysts in CO₂Application in cycloaddition reactions.

Therefore, the organic catalyst which is designed and synthesized efficiently, is easy to separate and has ultra-long service life is designed and synthesized for efficiently catalytically converting CO₂The synthesis of cyclic carbonates is of great significance.

Disclosure of Invention

Aiming at the limitations existing in the prior art, the invention aims to provide a high-efficiency polyether amide ionic liquid catalyst and a preparation method thereof. In order to realize the aim, the invention utilizes the characteristic that the structure of the ionic liquid can be designed and is easy to functionalize, takes polyether monocarboxylic acid or polyether dicarboxylic acid as a parent structure, and assembles one or two amino (or aminoalkyl) functionalized ionic liquid building blocks at one end or two ends of the parent structure through amido bonds to create a novel multifunctional integrated organic catalyst-polyether amide ionic liquid catalyst based on a polyether amide hydrogen bond donor.

Compared with the prior art, the polyether amide ionic liquid catalyst has the following outstanding advantages:

(1) high catalytic activity and selectivity: HBD group, organic base, nucleophilic reagent and polyether chain are assembled in a single molecular structure, so that high-efficiency integration of multiple catalytic active sites is realized, and the method has the advantages that the coupling synergistic effect among the multiple active sites improves the activity and selectivity of the reaction; for example, amide bonds are effective as highly efficient HBD groups to activate epoxides, and also as organic bases to capture and activate CO by formation of carbamic acid₂A molecule; halide ion (Cl)^-，Br^-Or I^-) As nucleophilic group to promote ring-opening reaction; the polyether chain having a CO affinity₂Can solubilize CO₂Etc.;

(2) homogeneous catalysis-two-phase separation: the introduction of the polyether chain enables catalyst molecules to be easily dissolved in epoxide, and homogeneous catalysis is realized; meanwhile, the catalyst is insoluble in a weak polar solvent, and the two-phase separation of the catalyst and the product cyclic carbonate can be realized through liquid-liquid extraction, so that the efficient cyclic utilization of the catalyst is realized;

(3) long life and low run-off: the amido bond has higher chemical and thermal stability, the catalyst can keep long-term stability in the circulating process, and meanwhile, the polyether side chain greatly increases the molecular weight of the catalyst, thereby reducing the relative loss proportion of the catalyst and being beneficial to prolonging the service life of the catalyst.

In order to realize the purpose of the invention, the adopted technical scheme is as follows:

a polyether amide ionic liquid catalyst is characterized in that the structural formula of the catalyst is as follows:

or the following steps:

in the formula, R¹Is phenyl or C₁-C₁₆An alkyl group; r²Is H or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; n is 3-240, m is 0, 1,2, 3 or 4; x^-Is Cl^-，Br^-Or I^-。

A polyether amide ionic liquid catalyst is characterized in that one of raw materials for synthesizing the catalyst is polyether monocarboxylic acid:

or is a polyether dicarboxylic acid:

in the formula, R¹Is phenyl or C₁-C₁₆Alkyl, n-3-240;

the second raw material is para-amino (or aminoalkyl) pyridine, meta-amino (or aminoalkyl) pyridine, ortho-amino (or aminoalkyl) pyridine, amino-functionalized imidazolium ionic liquid, amino-functionalized guanidinium ionic liquid, amino-functionalized quaternary ammonium salt, amino-functionalized quaternary phosphonium salt, amino-functionalized piperidine salt, amino-functionalized morpholine salt or amino-functionalized pyrrolidine salt, and the structural formulas of the salts are respectively as follows:

in the formula, R²Is H or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; m is 0, 1,2, 3 or 4; x^-Is Cl^-，Br^-Or I^-；

The third raw material is R²X, when R²When H, R²X is a halogen acid, when R²＝C₁-C₁₆When alkyl, R²X is alkyl halide, and X is Cl, Br or I;

the intermediate is amino (or aminoalkyl) pyridine polyether monoamide or amino (or aminoalkyl) pyridine polyether diamide, and the structural formula is as follows:

in the formula, R¹Is phenyl or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; n is 3-240 and m is 0, 1,2, 3 or 4.

A polyether amide ionic liquid catalyst is characterized in that the synthesis process of the catalyst is as follows: with polyether monocarboxylic acids R¹(EO)_nCOOH as raw material, and in the first step, p-amino (or aminoalkyl) pyridine Py-p- (CH) in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)₂)_mNHR³I, M-amino (or aminoalkyl) pyridine Py-m- (CH)₂)_mNH₂Or o-amino (or aminoalkyl) pyridine Py-o- (CH)₂)_mNH₂Condensing to obtain corresponding intermediate p-amino (or aminoalkyl) pyridine polyether monoamide Py-p- (CH)₂)_mR³NCO(EO)_nR¹M-amino (or aminoalkyl) pyridylpolyether monoamide Py-m- (CH)₂)_mNHCO(EO)_nR¹Or o-amino (or aminoalkyl) pyridylpolyether monoamide Py-o- (CH)₂)_mNHCO(EO)_nR¹(ii) a In the second step, the intermediate is reacted with R in toluene solvent²X reacts to obtain corresponding para-amino (or aminoalkyl) pyridinium salt polyether monoamide ionic liquid [ R ]²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]M-amino (or aminoalkyl) pyridinium salt polyether monoamide ionic liquid [ R²Py-m-(CH₂)_mNHCO(EO)_nR¹][X]Or o-amino (or aminoalkyl) pyridinium salt polyether monoamide ionic liquid [ R²Py-o-(CH₂)_mNHCO(EO)_nR¹][X](ii) a Or with polyether monocarboxylic acids R¹(EO)_nCOOH as raw material is respectively mixed with amino functional imidazolium ionic liquid [ R ] in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)²R³IM(CH₂)_mNH₂][X]Amino-functionalized guanidine salt ionic liquid [ (R)²)₄R³AG(CH₂)_mNH₂][X]Amino-functional quaternary ammonium salt [ (R)²)₃N(CH₂)_mNH₂][X]Amino-functional quaternary phosphonium salts [ (R)²)₃P(CH₂)_mNH₂][X]Amino-functional piperidine salts [ R ]²Pi(CH₂)_mNH₂][X]Amino-functionalized morpholine salt [ R²Mor(CH₂)_mNH₂][X]Or amino-functionalized pyrrolidine salts [ R ]²Pyr(CH₂)_mNH₂][X]Condensing to obtain corresponding imidazolium salt polyether monoamide ionic liquid [ R ]²R³IM(CH₂)_mNHCO(EO)_nR¹][X]And guanidine salt polyether monoamide ionic liquid [ (R)²)₄R³AG(CH₂)_mNHCO(EO)_nR¹][X]Quaternary ammonium salt polyether monoamide ionic liquid [ (R)²)₃N(CH₂)_mNHCO(EO)_nR¹][X]Quaternary phosphonium salt polyether monoamide ionic liquid [ (R)²)₃P(CH₂)_mNHCO(EO)_nR¹][X]Piperidine salt polyether monoamide ionic liquid [ R²Pi(CH₂)_mNHCO(EO)_nR¹][X]Morpholine salt polyether monoamide ionic liquid [ R²Mor(CH₂)_mNHCO(EO)_nR¹][X]Or pyrrolidine salt polyether monoamide ionic liquid [ R ]²Pyr(CH₂)_mNHCO(EO)_nR¹][X]；

Alternatively, polyether dicarboxylic acids HOOC (EO)_nCOOH as raw material, and in the first step, p-amino (or aminoalkyl) pyridine Py-p- (CH) in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)₂)_mNHR³I, M-amino (or aminoalkyl) pyridine Py-m- (CH)₂)_mNH₂Or o-amino (or aminoalkyl) pyridine Py-o- (CH)₂)_mNH₂Condensing to obtain corresponding intermediate p-amino (or aminoalkyl) pyridine polyether diamide Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py, meta-amino (or aminoalkyl) pyridylpolyether diamide Py-m- (CH)₂)_mNHCO(EO)_nCONH(CH₂)_m-m-Py or o-amino (or aminoalkyl) pyridylpolyether diamide Py-o- (CH)₂)_mNHCO(EO)_nCONH(CH₂)_m-o-Py; in the second step, the intermediate is reacted with R in toluene solvent²X reacts to obtain corresponding para-amino (or aminoalkyl) pyridinium salt polyether diamide ionic liquid [ X][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]And m-amino (or aminoalkyl) pyridinium salt polyether diamide ionic liquid

Body [ X ]][R²Py-m-(CH₂)_mNHCO(EO)_nCONH(CH₂)_m-m-PyR²][X]Or o-amino (or aminoalkyl) pyridinium salt polyether diamide ionic liquid [ X][R²Py-o-(CH₂)_mNHCO(EO)_nCONH(CH₂)_m-o-PyR²][X](ii) a Alternatively, polyether dicarboxylic acids HOOC (EO)_nCOOH as raw material is respectively mixed with amino functional imidazolium ionic liquid [ R ] in dichloromethane in the presence of N, N' -Dicyclohexylcarbodiimide (DCC)²R³IM(CH₂)_mNH₂][X]Amino-functionalized guanidine salt ionic liquid [ (R)²)₄R³AG(CH₂)_mNH₂][X]Amino-functional quaternary ammonium salt [ (R)²)₃N(CH₂)_mNH₂][X]Amino-functional quaternary phosphonium salts [ (R)²)₃P(CH₂)_mNH₂][X]Amino-functional piperidine salts [ R ]²Pi(CH₂)_mNH₂][X]Amino-functionalized morpholine salt [ R²Mor(CH₂)_mNH₂][X]Or amino-functionalized pyrrolidine salts [ R ]²Pyr(CH₂)_mNH₂][X]Condensing to obtain corresponding imidazolium salt polyether diamide ionic liquid [ X ]][R²R³IM(CH₂)_mNHCO(EO)_nCONH(CH₂)_mIMR³R²][X]Guanidine salt polyether diamide ionic liquid [ X ]][(R²)₄R³AG(CH₂)_mNHCO(EO)_nCONH(CH₂)_mAGR³(R²)₄][X]Quaternary ammonium salt polyether diamide ionic liquid [ X ]][(R²)₃N(CH₂)_mNHCO(EO)_nCONH(CH₂)_mN(R²)₃][X]Quaternary phosphonium salt polyether diamide ionic liquid [ X][(R²)₃P(CH₂)_mNHCO(EO)_nCONH(CH₂)_mP(R²)₃][X]Piperidine salt polyether diamide ionic liquid [ X][R²Pi(CH₂)_mNHCO(EO)_nCONH(CH₂)_mPiR²][X]Morpholine salt polyether diamide ionic liquid [ X][R²Mor(CH₂)_mNHCO(EO)_nCONH(CH₂)_mMorR²][X]Or pyrrolidine salt polyether diamide ionic liquid [ X][R²Pyr(CH₂)_mNHCO(EO)_nCONH(CH₂)_mPyrR²][X]；

In the formula, R¹Is phenyl or C₁-C₁₆An alkyl group; r²Is H or C₁-C₁₆An alkyl group; r³Is H or C₁-C₄An alkyl group; n is 3-240, m is 0, 1,2, 3 or 4; x^-Is Cl^-，Br^-Or I^-。

Detailed Description

The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the scope of the examples.

Example 1

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Me，R³＝H，m＝0，n＝15)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Me, n 15), p-aminopyridine Py-p- (CH)₂)_mNHR³(R³H, m-0) are sequentially added into a three-neck flask, dichloromethane is added under the protection of argon, the system is placed into an ice water bath after being uniformly stirred, and a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) is slowly dripped into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/p-aminopyridine/DCC 1/1/1 mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal under reduced pressureDichloromethane gave a pale yellow viscous liquid with a yield of 94.5%.

Example 2

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Ph，R³＝H，m＝0，n＝15)

Replacement of polyether monocarboxylic acid by R¹(EO)_nCOOH(R¹Ph, n ═ 15), the other operations were performed as in example 1, and the yield was 96%.

Example 3

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝n-C₁₆H₃₃，R³＝H，m＝0，n＝15)

Replacement of polyether monocarboxylic acid by R¹(EO)_nCOOH(R¹＝n-C₁₆H₃₃And n is 15), the same procedure as in example 1 was repeated, and the yield was 93%.

Example 4

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Ph，R³＝H，m＝0，n＝3)

Replacement of polyether monocarboxylic acid by R¹(EO)_nCOOH(R¹Ph, n is 3), the same procedure as in example 1 was repeated, and the yield was 95%.

Example 5

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Ph，R³＝H，m＝0，n＝44)

Replacement of polyether monocarboxylic acid by R¹(EO)_nCOOH(R¹Ph, n-44), the same procedure as in example 1 was repeated, and the yield was 91%.

Example 6

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Me，R³＝H，m＝0，n＝112)

Replacement of polyether monocarboxylic acid by R¹(EO)_nCOOH(R¹Me, n 112), the other operations were performed as in example 1, and the yield was 92%.

Example 7

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Me，R³＝H，m＝1，n＝15)

Replacement of the organic base with p-aminomethylpyridine Py-p- (CH)₂)_mNHR³(R³Other than H and m is 1), the same procedure as in example 1 was repeated, yielding 94%.

Example 8

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Me，R³＝Me，m＝0，n＝15)

Replacement of organic base with p-methylaminopyridine Py-p- (CH)₂)_mNHR³(R³Me, m ═ 0), the other operations were performed as in example 1, and the yield was 92%.

Example 9

Intermediate Py-m- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Me，R³＝H，m＝0，n＝15)

Replacement of organic base with meta-aminopyridine Py-m- (CH)₂)_mNHR³(R³Other than H, m is 0), the same procedure as in example 1 was repeated, and the yield was 96%.

Example 10

Intermediate Py-o- (CH)₂)_mR³NCO(EO)_nR¹Synthesis of (R)¹＝Me，R³＝H，m＝0，n＝15)

Replacement of organic base with o-aminopyridine Py-o- (CH)₂)_mNHR³(R³Other than H, m is 0), the same procedure as in example 1 was repeated, and the yield was 93%.

Example 11

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) p-Py³＝H，m＝0，n＝12)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12) and p-aminopyridine (Py-p- (CH)₂)_mNHR³，R³H, m-0) in sequence, adding dichloromethane under the protection of argon, stirring the system uniformly, placing the system in an ice-water bath, cooling to about 0 ℃, and slowly dropwise adding a dichloromethane solution (hooc (eo) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system_nCOOH/p-aminopyridine/DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 94%.

Example 12

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) p-Py³＝H，m＝0，n＝4)

Replacement of polyether dicarboxylic acids by HOOC (EO)_nCOOH (n is 4), the same procedure as in example 11 was repeated, yielding 92%.

Example 13

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) p-Py³＝H，m＝0，n＝43)

Replacement of polyether dicarboxylic acids by HOOC (EO)_nCOOH (n: 43) was carried out in the same manner as in example 11, whereby the yield was 95%.

Example 14

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) p-Py³＝H，m＝0，n＝112)

Replacement of polyether dicarboxylic acids by HOOC (EO)_nCOOH (n 112), the same procedure as in example 11 was repeated, yielding 93%.

Example 15

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) p-Py³＝H，m＝1，n＝12)

Replacement of the organic base with p-aminomethylpyridine (Py-p- (CH)₂)_mNHR³，R³The same procedures as in example 11 were repeated except for changing m to 1), and the yield was 93.6%.

Example 16

Intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) p-Py³＝Me，m＝0，n＝12)

Replacement of the organic base with p-methylaminopyridine (Py-p- (CH)₂)_mNHR³，R³Me, m ═ 0), the other operations were performed as in example 11, and the yield was 90%.

Example 17

Intermediate Py-m- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of (R) m-Py³＝H，m＝0，n＝12)

Replacement of the organic base with m-aminopyridine (Py-m- (CH)₂)_mNHR³，R³Other than H and m is 0), the same procedure as in example 11 was repeated, and the yield was 96%.

Example 18

Intermediate Py-o- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_mSynthesis of-o-Py (R)³＝H，m＝0，n＝12)

Replacement of the organic base with o-aminopyridine (Py-o- (CH)₂)_mNHR³，R³Other than H and m is 0), the same procedure as in example 11 was repeated, yielding 95%.

Example 19

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝0，n＝15，X＝Cl)

Reacting the intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m-0, n-15) to highPressing a reaction kettle, adding a solvent toluene under the protection of argon, stirring uniformly, adding 1-n-butyl chloride R²X(R²＝n-C₄H₉，X＝Cl)，Py-p-(CH₂)_mR³NCO(EO)_nR¹/R²And reacting for 48h at 95 ℃ under the condition of X being 1/3. The solvent toluene was removed under reduced pressure to give a tan viscous liquid with a yield of 90%.

Example 20

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝0，n＝15，X＝Br)

Reacting the intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m-0, n-15) into a three-neck flask, argon protecting, adding toluene solvent, stirring uniformly, adding 1-n-butyl bromide R²X(R²＝n-C₄H₉，X＝Br)，Py-p-(CH₂)_mR³NCO(EO)_nR¹/R²And reacting for 48h at 95 ℃ under the condition of X being 1/3. The solvent toluene was removed under reduced pressure to give a tan viscous liquid with a yield of 99%.

Example 21

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝0，n＝15，X＝I)

Replacement of haloalkanes with 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 99%.

Example 22

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝H，R³＝H，m＝0，n＝15，X＝Br)

Reacting the intermediate Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m-0, n-15) is added into a three-neck flask, argon is used for protection, solvent toluene is added, stirring is carried out evenly, and hydrobromic acid R is added²X(R²H, X ═ Br) in water, Py-p- (CH)₂)_mR³NCO(EO)_nR¹/R²And reacting for 12h at 50 ℃ under the condition of X being 1/1. The solvent was removed under reduced pressure to give a tan viscous liquid with a yield of 99%.

Example 23

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝n-C₁₂H₂₅，R³＝H，m＝0，n＝15，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Ph，R³H, m-0, n-15), haloalkane is replaced with 1-n-dodecyliodoalkane R²X(R²＝n-C₁₂H₂₅And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 96%.

Example 24

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝n-C₁₆H₃₃，R²＝n-C₄H₉，R³＝H，m＝0，n＝15，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝n-C₁₆H₃₃，R³H, m-0, n-15), haloalkane is replaced with 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 94%.

Example 25

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝n-C₄H₉，R³＝H，m＝0，n＝3，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Ph，R³H, m-0, n-3) haloalkane is replaced by 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed as in example 20, and the yield was 95%.

Example 26

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝n-C₄H₉，R³＝H，m＝0，n＝44，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Ph，R³H, m-0, n-44), haloalkane is replaced with 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed as in example 20, and the yield was 95%.

Example 27

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝0，n＝112，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m 0, n 112), haloalkane to 1-iodo-n-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 96%.

Example 28

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝1，n＝15，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m 1, n 15) haloalkane is replaced by 1-n-iodo-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 94%.

Example 29

Catalyst [ R²Py-p-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝Me，m＝0，n＝15，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³Me, m-0, n-15), haloalkane to 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 93%.

Example 30

Catalyst [ R²Py-m-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝0，n＝15，X＝I)

Replacement of the intermediate with Py-m- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m-0, n-15), haloalkane is replaced with 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed in the same manner as in example 20, giving a yield of 96%.

Example 31

Catalyst [ R²Py-o-(CH₂)_mR³NCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝0，n＝15，X＝I)

Replacement of the intermediate by Py-o- (CH)₂)_mR³NCO(EO)_nR¹(R¹＝Me，R³H, m-0, n-15), haloalkane is replaced with 1-iodon-butane R²X(R²＝n-C₄H₉And X ═ I), the other operations were performed as in example 20, and the yield was 90%.

Example 32

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝12，X＝Cl)

Reacting the intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³H, m is 0, n is 12) is added into a high-pressure reaction kettle, the solvent toluene is added into the high-pressure reaction kettle under the protection of argon, the mixture is evenly stirred, and 1-chloro n-butane R is added²X(R²＝n-C₄H₉，X＝Cl)，Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py/R²And reacting for 96h at 95 ℃ under the condition that X is 1/6. The solvent toluene was removed under reduced pressure to give a tan viscous liquid with a yield of 93%.

Example 33

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝12，X＝I)

Reacting the intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³H, m is 0, n is 12) is added into a three-neck flask, the mixture is protected by argon, solvent toluene is added, the mixture is stirred evenly, and 1-iodo-n-butane R is added²X(R²＝n-C₄H₉，X＝I)，Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py/R²And reacting for 96h at 95 ℃ under the condition that X is 1/6. The solvent toluene was removed under reduced pressure to give a tan viscous liquid with a yield of 99%.

Example 34

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝12，X＝Br)

Replacement of haloalkanes with 1-bromobutane R²X(R²＝n-C₄H₉X ═ Br), the other operations were performed in the same manner as in example 33, giving a yield of 99%.

Example 35

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝H，R³＝H，m＝0，n＝12，X＝Br)

Reacting the intermediate Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³H, m-0, n-12) is added into a three-neck flask, argon is used for protection, solvent toluene is added, stirring is carried out evenly, and hydrobromic acid R is added²X(R²H, X ═ Br) in water, Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py/R²And reacting for 12h at 50 ℃ under the condition of X being 1/2. The solvent was removed under reduced pressure to give a tan viscous liquid with a yield of 99%.

Example 36

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₁₂H₂₅，R³＝H，m＝0，n＝12，X＝I)

Replacement of haloalkanes with 1-iodo-n-dodecane R²X(R²＝n-C₁₂H₂₅And X ═ I), the other operations were performed in the same manner as in example 33, giving a yield of 96%.

Example 37

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝4，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³Other than H, m is 0 and n is 4), the same procedures as in example 33 were carried out, and the yield was 94%.

Example 38

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝43，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³Other than H, m is 0 and n is 43), the same procedures as in example 33 were carried out, and the yield was 93%.

Example 39

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝112，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³H, m is 0 and n is 112), the same procedure as in example 33 was repeated, and the yield was 95%.

Example 40

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝1，n＝12，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³Other than H, m is 1 and n is 12), the same procedures as in example 33 were carried out, and the yield was 92%.

EXAMPLE 41

Catalyst [ X ]][R²Py-p-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝Me，m＝0，n＝12，X＝I)

Replacement of the intermediate with Py-p- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-p-Py(R³Me, m ═ 0, and n ═ 12), the other operations were performed in the same manner as in example 33, and the yield was 99%.

Example 42

Catalyst [ X ]][R²Py-m-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-m-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝12，X＝I)

Replacement of the intermediate with Py-m- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-m-Py(R³Other than H, m is 0 and n is 12), the same procedures as in example 33 were carried out, and the yield was 97%.

Example 43

Catalyst [ X ]][R²Py-o-(CH₂)_mR³NCO(EO)_nCONR³(CH₂)_m-o-PyR²][X]Synthesis of (R)²＝n-C₄H₉，R³＝H，m＝0，n＝12，X＝I)

Replacement of the intermediate by Py-o- (CH)₂)_mR³NCO(EO)_nCONR³(CH₂)_m-o-Py(R³Other than H, m is 0 and n is 12), the same procedures as in example 33 were carried out, and the yield was 92%.

Example 44

Catalyst [ R²R³IM(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Me，R²＝n-C₄H₉，R³＝H，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Me, n-15), amino-functionalized imidazolium ionic liquids [ R²R³IM(CH₂)_mNH₂][X](R²＝n-C₄H₉，R³Sequentially adding H, m-2 and X-I) into a three-neck flask, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[R²R³IM(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 94%.

Example 45

Catalyst [ X ]][R²R³IM(CH₂)_mNHCO(EO)_nCONH(CH₂)_mIMR³R²][X]Synthesis of (R)²＝n-C₄H₉，R³＝Me，m＝2，n＝43，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-43), amino-functionalized imidazolium ionic liquid [ R ═ R²R³IM(CH₂)_mNH₂][X](R²＝n-C₄H₉，R³Me, m-2 and X-I) are sequentially added into a three-neck flask, dichloromethane is added under the protection of argon, the system is placed into an ice-water bath after being uniformly stirred, and N, N are slowly dripped into the system when the temperature is reduced to about 0 DEG C' -Dichloromethane solution of Dicyclohexylcarbodiimide (DCC) (HOOC (EO))_nCOOH/[R²R³IM(CH₂)_mNH₂][X]DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 93%.

Example 46

Catalyst [ (R)²)₄R³AG(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝Me，R³＝H，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Ph, n 15) and amino-functionalized guanidine salt ionic liquid [ (R)²)₄R³AG(CH₂)_mNH₂][X](R²＝Me，R³Sequentially adding H, m-2 and X-I) into a three-neck flask, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[(R²)₄R³AG(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 95%.

Example 47

Catalyst [ X ]][(R²)₄R³AG(CH₂)_mNHCO(EO)_nCONH(CH₂)_mAGR³(R²)₄][X]Synthesis of (R)²＝Me，R³＝H，m＝2，n＝12，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12) and amino-functionalized guanidine salt ionic liquid [ (R)²)₄R³AG(CH₂)_mNH₂][X](R²＝Me，R³Me, m-2 and X-I) are added into a three-neck flask in sequence, and dichloromethane is added under the protection of argonAfter the system is stirred uniformly, the mixture is placed in an ice-water bath, and after the temperature is reduced to about 0 ℃, methylene dichloride solution (HOOC (EO)) of N, N' -Dicyclohexylcarbodiimide (DCC) is slowly dripped into the system_nCOOH/[(R²)₄R³AG(CH₂)_mNH₂][X]DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 95%.

Example 48

Catalyst [ (R)²)₃N(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝Et，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Ph, n 15), amino-functionalized quaternary ammonium salts [ (R)²)₃N(CH₂)_mNH₂][X](R²Sequentially adding Et, m-2 and X-I) into a three-neck flask, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[(R²)₃N(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 93%.

Example 49

Catalyst [ X ]][(R²)₃N(CH₂)_mNHCO(EO)_nCONH(CH₂)_mN(R²)₃][X]Synthesis of (R)²＝Et，m＝2，n＝12，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12), amino-functional quaternary ammonium salt [ (R)²)₃N(CH₂)_mNH₂][X](R²Sequentially adding Et, m-2 and X-I) into a three-neck flask, adding dichloromethane under the protection of argon, uniformly stirring the system, putting the system into an ice-water bath, and cooling to 0 DEG COn the other hand, a methylene chloride solution (HOOC (EO)) of N, N' -Dicyclohexylcarbodiimide (DCC) was slowly added dropwise to the system_nCOOH/[(R²)₃N(CH₂)_mNH₂][X]DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 96%.

Example 50

Catalyst [ (R)²)₃P(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝Et，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Ph, n 15), amino-functional quaternary phosphonium salt [ (R)²)₃P(CH₂)_mNH₂][X](R²Sequentially adding Et, m-2 and X-I) into a three-neck flask, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[(R²)₃P(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 94%.

Example 51

Catalyst [ X ]][(R²)₃P(CH₂)_mNHCO(EO)_nCONH(CH₂)_mP(R²)₃][X]Synthesis of (R)²＝Et，m＝2，n＝12，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12), amino-functional quaternary phosphonium salt [ (R)²)₃P(CH₂)_mNH₂][X](R²Sequentially adding Et, m-2 and X-I) into a three-neck flask, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding dichloromethane of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG CSolution (HOOC (EO)_nCOOH/[(R²)₃P(CH₂)_mNH₂][X]DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 95%.

Example 52

Catalyst [ R²Pi(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝Me，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Ph, n 15), amino-functionalized piperidinium salt [ R²Pi(CH₂)_mNH₂][X](R²Adding Me, m-2 and X-I) into a three-neck flask in sequence, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[R²Pi(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 92%.

Example 53

Catalyst [ X ]][R²Pi(CH₂)_mNHCO(EO)_nCONH(CH₂)_mPiR²][X]Synthesis of (R)²＝Me，m＝2，n＝12，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12), amino-functionalized piperidine salt [ R ═ R²Pi(CH₂)_mNH₂][X](R²Adding Me, m-2 and X-I) into a three-neck flask in sequence, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (HOOC (EO) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C_nCOOH/[R²Pi(CH₂)_mNH₂][X]1/2/2 mol/mol/mol/DCC), reacting at room temperature for 24 hr, filtering, and reducingThe dichloromethane was removed under pressure to give a pale yellow viscous liquid with a yield of 96%.

Example 54

Catalyst [ R²Mor(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝Me，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Ph, n 15), amino-functionalized morpholine salt [ R²Mor(CH₂)_mNH₂][X](R²Adding Me, m-2 and X-I) into a three-neck flask in sequence, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[R²Mor(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 94%.

Example 55

Catalyst [ X ]][R²Mor(CH₂)_mNHCO(EO)_nCONH(CH₂)_mMorR²][X]Synthesis of (R)²＝Me，m＝2，n＝12，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12), amino-functionalized morpholine salt [ R²Mor(CH₂)_mNH₂][X](R²Adding Me, m-2 and X-I) into a three-neck flask in sequence, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (HOOC (EO) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C_nCOOH/[R²Mor(CH₂)_mNH₂][X]DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 96%.

Example 56

Catalyst and process for preparing same[R²Pyr(CH₂)_mNHCO(EO)_nR¹][X]Synthesis of (R)¹＝Ph，R²＝Me，m＝2，n＝15，X＝I)

Polyether monocarboxylic acid R¹(EO)_nCOOH(R¹Ph, n 15), amino functionalized pyrrolidine salt [ R²Pyr(CH₂)_mNH₂][X](R²Adding Me, m-2 and X-I) into a three-neck flask in sequence, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (R) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C¹(EO)_nCOOH/[R²Pyr(CH₂)_mNH₂][X]DCC 1/1/1, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 96%.

Example 57

Catalyst [ X ]][R²Pyr(CH₂)_mNHCO(EO)_nCONH(CH₂)_mPyrR²][X]Synthesis of (R)²＝Me，m＝2，n＝12，X＝I)

Polyether dicarboxylic acid HOOC (EO)_nCOOH (n-12), amino-functionalized pyrrolidine salt [ R ═ R²Pyr(CH₂)_mNH₂][X](R²Adding Me, m-2 and X-I) into a three-neck flask in sequence, adding dichloromethane under the protection of argon, uniformly stirring the system, placing the system in an ice-water bath, slowly dropwise adding a dichloromethane solution (HOOC (EO) of N, N' -Dicyclohexylcarbodiimide (DCC) into the system when the temperature is reduced to about 0 DEG C_nCOOH/[R²Pyr(CH₂)_mNH₂][X]DCC 1/2/2, mol/mol/mol), followed by reaction at room temperature for 24h, filtration and removal of dichloromethane under reduced pressure to give a pale yellow viscous liquid with a yield of 95%.