1. A method for preparing a functionalized sulfimide polymer by an alkyne-based four-component polymerization method is characterized by comprising the following steps:

accurately weighing 1 molar equivalent of a diacetylene monomer, 0.9-1.1 molar equivalent of a nucleophilic reagent, 2.2-10 molar equivalents of phenylsulfonyl azide and 0.5-5 molar equivalents of an electrophilic reagent, and dissolving the four monomers in tetrahydrofuran or N, N' -dimethylformamide, wherein the concentration of the monomers is in the range of 0.05M-0.4M; continuously stirring the reaction bottle at room temperature for 2-96h, and stopping reaction; settling and washing with methanol for three times, using 10-100mL of solvent each time, centrifuging, collecting precipitate, and drying the product in a vacuum drying oven to constant weight;

the four-component polymerization reaction has the following general reaction formula:

(I)

(II)

(III)

R₁is an aryl or aryl derivative, R₃Is aliphatic chain or aromatic group with 6-10 carbon inequality; r₂、R₄、R₅And R₆The polymerization degree n is more than 20 for different types of substituents; the weight average molecular weight of the four-component polymer is in the range of 20000-90000 g/mol.

2. The method of claim 1,

the diyne monomer comprises:

3. the method according to claim 1 or 2,

the phenylsulfonyl azide monomer comprises:

4. the method according to claim 1 or 2,

the nucleophilic reagent comprises:

5. the method of claim 3,

the nucleophilic reagent comprises:

6. the method of claim 1, 2 or 5,

the electrophile comprises:

7. the method of claim 3,

the electrophile comprises:

8. the method of claim 4,

the electrophile comprises:

Background

In recent years, due to the advantages of high atom economy, simple synthesis steps, easiness in post-modification, mild reaction conditions and the like, domestic and foreign scientists have developed a series of novel multi-component polymerization reactions, and introduce different functional molecules on the polymer skeleton through the multi-component polymerization reactions, so as to efficiently synthesize photoelectric functional materials, biomedical materials and adsorption separation materials, thereby effectively expanding the application field of multi-component polymerization, wherein common multi-component polymerization mainly comprises Passerini polymerization, Biginelli polymerization, copper-catalyzed multi-component polymerization and the like.

Most of the multi-component polymerizations reported so far are three-component polymerizations (3-CP), since more monomers add complexity to the system and even lead to polymerization failure. Therefore, it is desired to efficiently construct a multifunctional polymer by developing a new four-component polymerization (4-CP) method, and Ugi 4-CP or some special tandem polymerizations have been developed at present, but problems of low polymerization efficiency, great difficulty in monomer synthesis, severe reaction conditions, and the like still exist. Thus, improving the existing 3-CP process by adding a suitable component 4 remains a long standing challenge for multicomponent polymerization.

Disclosure of Invention

In order to solve the existing defects and shortcomings of the prior art, the invention aims to provide an alkyne-based four-component polymerization method for efficiently preparing an alpha-modified sulfimide polymer.

The invention provides a four-component polymerization method based on alkyne, sulfonyl azide, nucleophilic reagent and electrophilic reagent. The four-component polymerization method has the advantages of mild reaction conditions, high atom economy, high molecular weight and the like.

The technical scheme of the invention is as follows:

a method for preparing a functionalized sulfimide polymer by an alkyne-based four-component polymerization method comprises the following steps:

accurately weighing 1 molar equivalent of a diacetylene monomer, 0.9-1.1 molar equivalent of a nucleophilic reagent, 2.2-10 molar equivalents of phenylsulfonyl azide and 0.5-5 molar equivalents of an electrophilic reagent, and dissolving the four monomers in tetrahydrofuran or N, N' -dimethylformamide, wherein the concentration of the monomers is in the range of 0.05M-0.4M; the reaction flask was kept stirring at room temperature for 2-96h (the target polymer could be formed quickly within 2 h) and the reaction was stopped. Settling and washing with methanol three times, each time using 10-100mL of solvent, centrifuging to collect precipitate, and drying the product in a vacuum drying oven to constant weight.

The diyne monomers are mainly aromatic diynes, and the main preferred structures include, but are not limited to, the following structures (1a-1 d):

the phenylsulfonyl azide monomer is mainly selected from phenylsulfonyl azides with different electronic types, and the main preferred structure comprises but is not limited to the following structures (2a-2 d):

the nucleophiles are various types of diols (aliphatic and aromatic diols such as 1, 6-hexanediol, degradable diols, hydroquinone), with major preferred structures including, but not limited to, the following structures (3a-3 d):

the electrophilic reagent monomer is three types of electrophilic reagents, mainly comprising trans-nitrostyrene, Baylis-Hillman addition derivatives and glyoxylic acid ethyl esters. The electrophile is preferably of any one of the following formulae 4a to 4 i:

the four-component polymerization reaction has the following general reaction formula:

R₁is an aryl or aryl derivative, R₃Is aliphatic chain or aromatic group with 6-10 carbon inequality; r₂、R₄、R₅And R₆For different types of substituents (electron donating substituents or electron withdrawing substituents), the degree of polymerization n is greater than 20. The weight average molecular weight (absolute molecular weight) of the four-component polymer was in the range of 20000-90000 g/mol.

The invention has the beneficial effects that:

(1) the invention provides a method for preparing alpha-modified sulfimide polymer based on a multi-component polymerization one-step method, which does not need to prepare polymer in advance and modify after polymerization, can put four components into one step at the initial stage of polymerization, and can prepare target polymer efficiently.

(2) The sulfonyl imide polymer prepared by the invention has the advantages of easily available raw materials, mild reaction conditions, simple operation steps, high atom economy, simple post-treatment and few byproducts.

(3) The four-component polymerization method provided by the invention can realize side chain modification in the polymerization process, multi-step purification and reaction based on a high molecular weight polymer are avoided, and the prepared polymer has high molecular weight and economic steps.

Drawings

FIG. 1 is a nuclear magnetic diagram of a four-component sulfonamide polymer prepared in example 1 of the present invention.

FIG. 2 is a nuclear magnetic diagram of degradable four-component polymers prepared in examples 2 and 3 of the present invention.

Detailed Description

The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.

Example 1

1, 4-Diethynylbenzene 1a (0.2mmol, 25.2mg), p-methylbenzenesulfonylazide 2a (0.6mmol, 170. mu.L), 1, 6-hexanediol 3a (0.2mmol, 23.6mg), CuBr (0.04mmol, 5.6mg), and nitrostyrene 4a (0.2mmol, 29.8mg) were dissolved in 1-2mL of anhydrous tetrahydrofuran. Then triethylamine (1mmol, 140. mu.L) was slowly added to the reaction system, and the reaction was magnetically stirred at room temperature for 6-48 h. After the reaction was complete, the product was purified by settling with methanol and dried under vacuum at room temperature to give polymer P1a/2a/3a/4 a.

Example 2

1, 4-Diethynylbenzene 1a (0.2mmol, 25.2mg), p-methylbenzenesulfonylazide 2a (0.6mmol, 170. mu.L), degradable diol 3b (0.2mmol, 23.6mg), CuBr (0.04mmol, 5.6mg), and nitrostyrene 4a (0.2mmol, 29.8mg) were dissolved in 1-2mL of anhydrous tetrahydrofuran. Triethylamine (1mmol, 140. mu.L) was then slowly added to the reaction system and reacted for 12h with magnetic stirring at room temperature. After the reaction was complete, the product was purified by settling with methanol and dried under vacuum at room temperature to give polymer P1a/2a/3b/4 a.

Example 3

Dissolving P1a/2a/3b/4a (20mg) in d₆Preparing 40mg/mL solution of-DMSO, preparing solution and H₂O₂(21. mu.L) were mixed and added to a nuclear magnetic tube, and reacted at a constant temperature of 37 ℃ for 6 hours. By passing¹HNMR monitored P1a/2a/3b/4a for degradation products.