阅读说明：本技术 一种由惰性双烯内酯单体合成高分子量聚合物的方法 (Method for synthesizing high molecular weight polymer from inert diene lactone monomer ) 是由 林柏霖 王泽凤 于 2020-12-03 设计创作，主要内容包括：本发明公开了一种由惰性双烯内酯单体合成高分子量聚合物的方法,其特征在于,将惰性双烯内酯作为聚合单体加入到溶剂中,空气氛围下搅拌,加热反应,实现该聚合单体的聚合得到高分子量、低分子量分布的含不饱和双键的聚合物。其聚合度比本体聚合高得多但分子量分布窄的聚合物,其主链或侧链仍含不饱和双键,可后续共聚、交联或侧基修饰。本发明无需催化剂即可实现惰性双烯内酯单体的聚合,而且所得聚合物产品的分子量比本体聚合高得多。(The invention discloses a method for synthesizing a high molecular weight polymer by using an inert diene lactone monomer, which is characterized in that the inert diene lactone as a polymerization monomer is added into a solvent, stirred in the air atmosphere and heated for reaction, and the polymerization of the polymerization monomer is realized to obtain a polymer containing unsaturated double bonds with high molecular weight and low molecular weight distribution. The polymer has polymerization degree higher than that of bulk polymerization and narrow molecular weight distribution, and its main chain or side chain still contains unsaturated double bond, and can be subsequently copolymerized, cross-linked or side-group modified. The invention can realize the polymerization of the inert diene lactone monomer without a catalyst, and the molecular weight of the obtained polymer product is much higher than that of bulk polymerization.)

1. A method for synthesizing high molecular weight polymer by inert diene lactone monomer is characterized in that inert diene lactone as polymerization monomer is added into solvent, stirred under air atmosphere and heated for reaction, thus realizing polymerization of the polymerization monomer to obtain polymer containing unsaturated double bond with high molecular weight and low molecular weight distribution; the inert diene lactone has a structural formula shown in a formula I:

the main chain of the obtained polymer contains four structural units of alpha, beta, gamma and delta, and the structural formula is shown as a formula II:

2. the process for synthesizing high molecular weight polymer from inert diene lactone monomers of claim 1, wherein the solvent is any one of dimethyl sulfoxide, N-dimethylacetamide, N-dimethylacetamide and N-methylpyrrolidone.

3. The method for synthesizing high molecular weight polymer from inert diene lactone monomers of claim 1, wherein the molar concentration of the inert diene lactone in the solvent is 0.95-2%.

4. The method for synthesizing high molecular weight polymer from inert diene lactone monomers of claim 1, wherein the heating reaction is carried out at 90-150 ℃ for 20-30 hours.

5. The method for synthesizing high molecular weight polymer from inert diene lactone monomers of claim 1, wherein the number average molecular weight of the polymer is 160.2-830.5 kDa, and the molecular weight distribution is 1.22-1.71.

Technical Field

The invention relates to a method for synthesizing a high molecular weight polymer based on a carbon dioxide-based inert diene lactone monomer, belonging to the technical field of polymer synthesis processes.

Background

The successful synthesis of the inert olefin monomer (L) based on the coupling of carbon dioxide with butadiene provides a new potential route to carbon dioxide for the synthesis of polymers, but Dinjus et al have attempted free radical, cationic, anionic polymerization of this monomer and have failed to obtain a homopolymer of high degree of polymerization, believed to be due to the fact that this monomer has inert alkenyl groups at both alkenyl groups: tri-substituted tiglic acid ester olefins and allyl on double bonds are difficult to homopolymerize due to large steric hindrance and stable resonance respectively. Then the Nozaki group realizes the successful polymerization of the monomer by adding V-40 as an initiator, metal salts as an additive and the like into a polymerization system to obtain a polymer containing unsaturated double bonds with the molecular weight of 2 kDa-85 kDa, but the addition of the metal salts limits the subsequent application of the polymer; the bulk polymerization of the monomer without a catalyst is also realized, and Chinese patent publication CN107383344B discloses that L is heated in the air atmosphere in the absence of a catalyst and a solvent to synthesize a polymer with the molecular weight of 50 kDa-280 kDa and the molecular weight distribution of 1.44-3.15. In view of the significance of this inert dienolide monomer for the synthesis of carbon dioxide-based polymers, it is desirable to develop new polymerization processes to obtain high molecular weight polymers with higher degrees of polymerization and narrow molecular weight distributions.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: how to more efficiently obtain a polymer with high molecular weight by polymerizing the inert diene lactone monomer of the carbon dioxide group through oxygen radical resistance.

In order to solve the technical problems, the invention is realized by the following technical scheme:

a method for synthesizing high molecular weight polymer by inert diene lactone monomer is characterized in that inert diene lactone as polymerization monomer is added into solvent, stirred under air atmosphere and heated for reaction, thus realizing polymerization of the polymerization monomer to obtain polymer containing unsaturated double bond with high molecular weight and low molecular weight distribution; the inert diene lactone has a structural formula shown in a formula I:

the main chain of the obtained polymer contains four structural units of alpha, beta, gamma and delta, and the structural formula is shown as a formula II:

the polymer main chain and the side chain contain unsaturated C ═ C double bonds, and the post-modification potential is achieved.

Preferably, the solvent is any one of dimethyl sulfoxide, N-dimethylacetamide, N-dimethylacetamide and N-methylpyrrolidone.

Preferably, the molar concentration of the inert diene lactone in the solvent is 0.95-2%.

Preferably, the heating reaction temperature is 90-150 ℃, and the time duration is 20-30 hours.

Preferably, the number average molecular weight of the polymer is 160.2-830.5 kDa, and the molecular weight distribution is 1.22-1.71.

The solution polymerization method provided by the invention can improve the molecular weight of the polymer to 160.2-830.5 kDa, reduce the molecular weight distribution to 1.22-1.71, and still enable the main chain or the side chain of the polymer to keep unsaturated double bonds for subsequent modification, and the polymerization process does not need a catalyst or an initiator, and the polymerization method is oxygen-resistant, so that the polymerization can be carried out without oxygen removal, the operation is convenient, and the product with high polymerization degree can be efficiently obtained.

Compared with the existing synthesis method of the carbon dioxide-based polymer, the inert diene lactone monomer can be heated for a certain time in a solvent and in the air atmosphere to obtain the polymer with high molecular weight, an initiator, a catalyst and the like are not needed, the introduction of metal impurities into the polymer is avoided, the process is simple and easy to operate, the inert diene lactone monomer is efficiently polymerized into the polymer with high molecular weight, and the polymer chain still contains olefin double bonds for subsequent modification.

Drawings

FIG. 1 is a GPC chart of the product in example 1;

FIG. 2 is a drawing of the product of example 1¹H nuclear magnetic spectrum.

Detailed Description

In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.

The inert dienolide monomers used in the examples are of formula I:

the main chain of the obtained polymer contains four structural units of alpha, beta, gamma and delta, and the structural formula is shown as a formula II:

example 1

Mixing 300 microliters of inert diene lactone monomer stored in a nitrogen environment with 700 microliters of dimethyl sulfoxide in an 8mL glass bottle, adding magnetons, covering the bottle opening with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 150 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product for 3 times by using a dichloromethane-petroleum ether solvent combination, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a brownish black product, wherein the yield is 54.6%. The resulting polymer had a number average molecular weight of 830.5kDa and a molecular weight distribution of 1.28.

Example 2

Mixing 300 microliters of inert diene lactone monomer stored in a nitrogen environment with 1700 microliters of dimethyl sulfoxide in an 8mL glass bottle, adding magnetons, covering the bottle opening with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 150 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product for 3 times by using a dichloromethane-petroleum ether solvent combination, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a brownish black product, wherein the yield is 28.4%. The resulting polymer had a number average molecular weight of 704.5kDa and a molecular weight distribution of 1.46.

Example 3

Mixing 28.7 microliters of inert diene lactone monomer stored in a nitrogen environment and 71.3 microliters of dimethyl sulfoxide in a 4mL glass bottle, adding a magneton, coating the bottle mouth with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 120 ℃, magnetically stirring for 20 hours, placing the glass bottle in liquid nitrogen, adding a 0.2M dichloromethane solution of TEMPO, and quenching the reaction. The reaction solution was diluted with 1-2mL of dichloromethane, added dropwise to 30mL of petroleum ether, centrifuged, and the resulting precipitate was dried under vacuum at 60 ℃ overnight to give a brownish black product with a monomer conversion of 83%. The resulting polymer had a number average molecular weight of 644.3kDa and a molecular weight distribution of 1.46.

Example 4

Mixing 43.5 microliters of inert diene lactone monomer stored in a nitrogen environment and 156.5 microliters of dimethyl sulfoxide in an 8mL glass bottle, adding a magneton, coating the bottle mouth with aluminum foil paper, punching a hole on the bottle mouth to allow air to circulate, placing the glass bottle in a heating block heated to 120 ℃, magnetically stirring for 30 hours, placing the glass bottle in liquid nitrogen, adding a 0.2M dichloromethane solution of TEMPO, and quenching the reaction. The reaction solution was diluted with 1-2mL of dichloromethane, dropwise added to 30mL of petroleum ether, centrifuged, and the resulting precipitate was vacuum dried at 60 ℃ overnight to give a brownish black product with a monomer conversion of 82.4%. The resulting polymer had a number average molecular weight of 688.9kDa and a molecular weight distribution of 1.28.

Example 5

Mixing 57.4 microliters of inert diene lactone monomer stored in a nitrogen environment and 142.6 microliters of dimethyl sulfoxide in an 8mL glass bottle, adding magnetons, coating the bottle mouth with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 90 ℃, magnetically stirring for 24 hours, and placing the glass bottle in liquid nitrogen to freeze and stop reaction. The reaction solution was diluted with 1-2mL of dichloromethane, dropwise added to 30mL of petroleum ether, centrifuged, and the resulting precipitate was vacuum dried at 60 ℃ overnight to give a brownish black product with a monomer conversion of 66.2%. The resulting polymer had a number average molecular weight of 160.2kDa and a molecular weight distribution of 1.30.

Example 6

Mixing 300 microliters of inert diene lactone monomer stored in a nitrogen environment with 700 microliters of N-methylpyrrolidone in an 8mL glass bottle, adding magnetons, covering the bottle mouth with aluminum foil paper, poking a hole on the bottle mouth to enable air to circulate, placing the glass bottle in a heating block heated to 150 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product by using a dichloromethane-petroleum ether solvent combination for 3 times, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a light brown product, wherein the yield is 15.4%. The resulting polymer had a number average molecular weight of 797.1kDa and a molecular weight distribution of 1.22.

Example 7

Mixing 300 microliters of inert diene lactone monomer stored in a nitrogen environment with 1700 microliters of N-methylpyrrolidone in an 8mL glass bottle, adding magnetons, covering the bottle mouth with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 150 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product by using a dichloromethane-petroleum ether solvent combination for 3 times, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a light brown product, wherein the yield is 7.3%. The resulting polymer had a number average molecular weight of 717.3kDa and a molecular weight distribution of 1.32.

Example 8

Mixing inert diene lactone monomer stored in nitrogen environment with 300 microliters and 700 microliters of N, N-dimethylacetamide in an 8mL glass bottle, adding magnetons, covering the bottle mouth with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 120 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product for 3 times by using a dichloromethane-petroleum ether solvent combination, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a brownish black product, wherein the yield is 28.9%. The resulting polymer had a number average molecular weight of 367.9kDa and a molecular weight distribution of 1.71.

Example 9

Mixing 300 microliters of inert diene lactone monomer stored in a nitrogen environment with 1700 microliters of N, N-dimethylacetamide in an 8mL glass bottle, adding magnetons, covering the bottle mouth with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 120 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product by using a dichloromethane-petroleum ether solvent combination for 3 times, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a light brown product, wherein the yield is 28.2%. The resulting polymer had a number average molecular weight of 310.5kDa and a molecular weight distribution of 1.71.

Example 10

Mixing inert diene lactone monomer stored in nitrogen environment with 300 microliters and 700 microliters of N, N-dimethylformamide in a 8mL glass bottle, adding magnetons, coating the bottle mouth with aluminum foil paper, poking a hole on the bottle mouth to circulate air, placing the glass bottle in a heating block heated to 120 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product by using a dichloromethane-petroleum ether solvent combination for 3 times, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a light brown product, wherein the yield is 7%. The resulting polymer had a number average molecular weight of 692.2kDa and a molecular weight distribution of 1.25.

Example 11

Mixing 300 microliters of inert diene lactone monomer stored in a nitrogen environment with 1700 microliters of N, N-dimethylformamide in an 8mL glass bottle, adding magnetons, coating the bottle mouth with aluminum foil paper, poking a hole to circulate air, placing the glass bottle in a heating block heated to 120 ℃, and magnetically stirring for 24 hours. And after the reaction is finished, taking down the glass bottle, naturally cooling to room temperature, dissolving and diluting the reaction solution by using 1-2mL of dichloromethane, dropwise adding 30mL of petroleum ether, centrifuging to obtain a precipitate, dissolving and re-precipitating the product by using a dichloromethane-petroleum ether solvent combination for 3 times, and drying the obtained precipitate in vacuum at 60 ℃ overnight to obtain a light brown product, wherein the yield is 4.4%. The resulting polymer had a number average molecular weight of 434.8kDa and a molecular weight distribution of 1.32.