阅读说明：本技术 一种重氮乙酸酯类单体活性可控聚合方法 (Diazoacetate monomer activity controllable polymerization method ) 是由 吴宗铨 李念念 刘娜 邹辉 侯小华 于 2019-05-13 设计创作，主要内容包括：本发明公开了一种重氮乙酸酯类单体活性可控聚合方法,该方法主要利用了以烯丙基氯化钯(II)二聚体和手性双膦配体为催化体系,实现多种重氮乙酸酯类单体的活性可控聚合,得到的聚合物具有可控的分子量和较窄的分子量分布,聚合过程不需要严格无水无氧条件,反应条件温和,而且单体合成简单,产率高。本发明的重氮乙酸脂类单体活性可控聚合的新方法在有机合成、新材料合成和材料改性中都有很大应用空间,可以通过这种方法来制备生物领域、高科技应用领域里应用广泛的材料,如生物探针、手性分离材料、光敏材料等。(The invention discloses an activity-controllable polymerization method of diazoacetate monomers, which mainly utilizes allyl palladium (II) chloride dimer and chiral diphosphine ligand as a catalytic system to realize the activity-controllable polymerization of various diazoacetate monomers, and the obtained polymer has controllable molecular weight and narrower molecular weight distribution, and the polymerization process does not need strict anhydrous and anaerobic conditions, so that the reaction conditions are mild, and the monomers are simple to synthesize and have high yield. The new method for diazoacetate monomer activity controllable polymerization has great application space in organic synthesis, new material synthesis and material modification, and can be used for preparing materials which are widely applied in the fields of biology and high-tech application, such as biological probes, chiral separation materials, photosensitive materials and the like.)

1. A diazoacetate monomer activity-controllable polymerization method is characterized by comprising the following steps:

adding a palladium chloride catalytic system into a reaction bottle, adding a polymerization solvent, stirring for 2-3h, injecting a diazoacetate monomer, stirring at room temperature for reaction for 1-14h, adding n-hexane for quenching, precipitating a polymer, washing with n-hexane for 3-5 times, and centrifuging to obtain a yellow precipitate to obtain the poly-carbene L, wherein the palladium chloride catalytic system consists of an allyl palladium chloride (II) dimer and a diphosphine ligand, the catalyst is the allyl palladium chloride (II) dimer, and the structural formula of the palladium chloride catalytic system is as follows:

The structural formula of L is:

2. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the polymerization reaction has the general formula:

wherein the polymerization degree n is 20-200, and the structure of R is as follows:

3. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the molar ratio of allyl palladium (II) chloride dimer to diazoacetate monomers is 1: (20-200).

4. the method for the activity-controlled polymerization of diazoacetate monomers as claimed in claim 1, wherein the molar ratio of allyl palladium (II) chloride dimer to diphosphine ligand is 1: 1.

5. The method for the controlled polymerization of diazoacetate monomer activity as claimed in claim 1, wherein when the amount of diazoacetate monomer is 50-100mg, the amount of tetrahydrofuran added is 0.5-2 mL.

6. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the polymerization solvent is tetrahydrofuran.

7. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the diphosphine ligand has the structural formula:

Technical Field

The invention belongs to the field of polymer reaction, and particularly relates to a diazoacetate monomer activity controllable polymerization method.

background

diazo organic compounds are a class of organic compounds which can realize unique chemical conversion and have wide application value in organic synthesis. Compared with other compounds, most of themdiazo compounds are a relatively unstable class of compounds which are susceptible to loss of N₂And a series of reactions occur following the formation of a carbene or metal carbene. Over the past century, diazo compounds have been favored by chemists. In particular diazoacetic acid esters, have attracted considerable interest because of their advantages over conventional olefin polymerizations.

researches in recent years show that the palladium complex can catalyze diazo compounds to generate novel reactions, the preparation of the polycarbocene from the diazoacetate monomers is a special polymerization, the generated main chain consists of C-C, each carbon of the main chain contains the polycarbocarbene with ester substituent, and the polymer has great application prospects in the biological field and the high-tech field, such as biological probes, chiral separation materials, photosensitive materials and the like.

Disclosure of Invention

The invention aims to provide a diazoacetate monomer activity controllable polymerization method, which takes allyl palladium (II) chloride dimer and diphosphine ligand as a catalytic system, researches the polymerization reaction kinetics of the diazoacetate monomer for the first time, designs the polymerization reaction and tracking reaction kinetics with different polymerization degrees, finds that the obtained polymer has controllable molecular weight and narrower molecular weight distribution, and finds that the reaction accords with the first-order reaction through the kinetic research. The traditional polymerization generally needs heating and anaerobic conditions, the invention does not need strict anhydrous and anaerobic conditions, and the reaction conditions are mild, so the diazoacetate monomer activity controllable polymerization method has great application space in organic synthesis, new material synthesis and material modification, and the method can be used for preparing widely applied materials in the fields of biology and high-tech application, such as biological probes, chiral separation materials, photosensitive materials and the like.

in order to achieve the purpose, the invention provides the following technical scheme:

a diazoacetate monomer activity controllable polymerization method comprises the following steps:

adding a palladium chloride catalytic system into a reaction bottle, adding a polymerization solvent, stirring for 2-3h, injecting a diazoacetate monomer, stirring at room temperature for reaction for 1-14h, adding n-hexane for quenching, precipitating a polymer, washing with n-hexane for 3-5 times, and centrifuging to obtain a yellow precipitate to obtain the poly-carbene L, wherein the palladium chloride catalytic system consists of an allyl palladium chloride (II) dimer and a diphosphine ligand, the catalyst is the allyl palladium chloride (II) dimer, and the structural formula of the palladium chloride catalytic system is as follows:

The structural formula of L is:

A diazoacetate monomer activity controllable polymerization method has a general formula as follows:

Wherein the polymerization degree n is 20-200, and the structure of R is as follows:

Preferably, the molar ratio of allyl palladium (II) chloride dimer to diazoacetate monomer is 1: (20-200).

preferably, the molar ratio of allyl palladium (II) chloride dimer to bisphosphine ligand is 1: 1.

when the dosage of diazoacetate monomer is 50-100mg, the dosage of tetrahydrofuran is 0.5-2 mL.

preferably, the polymerization solvent is tetrahydrofuran.

preferably, the bisphosphine ligand has the structural formula:

The invention has the beneficial effects that:

1. The invention takes allyl palladium (II) chloride dimer and diphosphine ligand as a catalytic system, researches the polymerization kinetics of diazoacetate monomer for the first time, designs polymerization reaction and tracking reaction kinetics with different polymerization degrees, finds that the obtained polymer has controllable molecular weight and narrower molecular weight distribution, and finds that the reaction accords with first-order reaction through kinetic research.

2. The traditional polymerization generally needs heating and anaerobic conditions, the polymerization process of the diazoacetate monomer does not need strict anhydrous and anaerobic conditions, the reaction conditions are mild, the activity controllable polymerization method of the diazoacetate monomer has great application space in organic synthesis, new material synthesis and material modification, and materials which are widely applied in the biological field and the high-tech application field, such as biological probes, chiral separation materials, photosensitive materials and the like, can be prepared by the method.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of diazoacetate monomers 1 and 5 in examples 1 and 5 of the present invention.

FIG. 2 is a nuclear magnetic hydrogen spectrum of the polycarbonylpoly-1, poly-5 in examples 1, 5 of the present invention.

FIGS. 3(a) and (b) are graphs showing the relationship between the molecular weight of the polycarbonylpoly-1 and PDI in example 1 of the present invention; (c) and (d) are respectively the conversion rate and the first-order kinetic diagram of the diazoacetate monomers 1 and 5 in the examples 1 and 5.

FIGS. 4(a) and (b) are liquid phase diagrams of diazoacetate monomers 1 and 5 in examples 1 and 5, respectively, at different reaction times.

FIGS. 5(a) and (b) are graphs showing the relationship between the molecular weight of the polycarbonylpoly-2 and PDI in example 2 of the present invention; (c) and (d) is the conversion rate and first order kinetic diagram of diazoacetate monomer 2.

FIGS. 6(a) and (b) are graphs showing the molecular weight, PDI and degree of polymerization of the polycarbonylpoly-3 in example 3 of the present invention; (c) is a graph of the molecular weight and PDI of the polycarbonylpoly-3 as a function of conversion; (d) is the conversion rate and the first-order kinetic diagram of the diazoacetate monomer 3.

FIG. 7 is a nuclear magnetic hydrogen spectrum of diazoacetate monomer 2 of example 2 of the present invention.

FIG. 8 is a nuclear magnetic hydrogen spectrum of the polymer poly-2 obtained in example 2 of the present invention.

FIG. 9 is a nuclear magnetic hydrogen spectrum of diazoacetate monomer 3 of example 3 in the present invention.

FIG. 10 is a nuclear magnetic hydrogen spectrum of poly-3, a polymer obtained in example 3 of the present invention.

FIG. 11 is the nuclear magnetic hydrogen spectrum of diazoacetate monomer 4 of example 4 in the present invention

FIG. 12 is a nuclear magnetic hydrogen spectrum of the polymer poly-4 prepared in example 4 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The process for preparing the polycarbonylpoly with the polymerization degrees of 20, 40, 60, 80, 100, 120, 160 and 200 by catalyzing a target product III by using an allyl palladium (II) chloride dimer and a diphosphine system is as follows, and the amounts of the catalyst and the ligand required when the monomer is fed by 0.56mol are as follows:

adding 35mg of palladium catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;

taking eight clean screw bottles, numbering the bottles firstly to eight, adding 0.56mol of diazoacetate monomer into the bottles respectively, taking 1.028mL, 0.514mL, 0.342mL, 0.258mL, 0.206mL, 0.171mL, 0.129mL and 0.102mL of catalyst solution by using a liquid transfer gun, sequentially adding the catalyst solution into the bottles firstly to eight screw bottles, and stirring the mixture at room temperature for reaction for 2 hours;

And (3) removing part of THF by spinning, precipitating the polymer by using n-hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the THF, precipitating the n-hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer.