阅读说明：本技术 钯源催化剂在炔烃聚合中的应用 (Application of palladium source catalyst in alkyne polymerization ) 是由 李晓芳 武晓林 闫向前 陈聚朋 于 2020-05-22 设计创作，主要内容包括：本发明涉及一种钯源催化剂在催化炔烃聚合中的应用,属于炔烃聚合领域。所述应用是作为催化剂催化炔烃聚合的聚合反应,作为催化剂催化二取代炔烃聚合。与已知的钯催化剂不同,钯源可直接购买,不需要与各种配体配位即可催化二取代炔烃的聚合,且聚合过程中无需添加助催化剂,如三氟甲烷磺酸银(AgOTf)和四(3,5-双(三氟甲基)苯基)硼酸钠(NaBAF)等,即可获得高分子量的聚合物,得到高分子量窄分子量分布的顺式选择性聚(1-氯-2-苯乙炔)(PCPAs)。本发明解决了二取代炔烃聚合催化剂合成复杂、聚合过程需要助催化剂参与、成本高等问题,更加简单经济高效,本工作为二取代炔烃的聚合提供了新的思路。(The invention relates to application of a palladium source catalyst in catalyzing alkyne polymerization, and belongs to the field of alkyne polymerization. The application is as a catalyst for catalyzing polymerization reaction of alkyne polymerization, and as a catalyst for catalyzing polymerization of disubstituted alkyne. Unlike known palladium catalysts, palladium sources can be purchased directly, and can catalyze the polymerization of disubstituted alkynes without coordination with various ligands, and a cocatalyst such as silver trifluoromethanesulfonate (AgOTf) and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (NaBAF) is not required to be added in the polymerization process, so that a high molecular weight polymer can be obtained, and cis-selective poly (1-chloro-2-phenylacetylene) (PCPAs) with high molecular weight and narrow molecular weight distribution can be obtained. The invention solves the problems of complex synthesis of the disubstituted alkyne polymerization catalyst, need of a cocatalyst in the polymerization process, high cost and the like, is simpler, more economical and efficient, and provides a new idea for the polymerization of the disubstituted alkyne.)

1. The application of a palladium source catalyst in alkyne polymerization is characterized in that: the application is as a catalyst to catalyze the polymerization reaction of alkyne monomers;

the palladium source catalyst is palladium carbon, palladium acetate, palladium dichloride, diacetonitrile palladium dichloride and diphenylnitrile palladium dichloride;

the application steps are as follows:

(1) adding a monomer and a solvent into a reactor, and uniformly stirring; adding a catalyst, and continuously stirring uniformly; reacting for 15 min-2 h under stirring, wherein the reaction temperature is 20-100 ℃;

(2) settling the reaction liquid by using petroleum ether, terminating the reaction, separating out solid substances, performing suction filtration to obtain solid substances, and drying to constant weight to obtain a polymerization product;

the molar ratio of the monomer to the catalyst is 50-500: 1;

the solvent is more than one of 1,1,2, 2-tetrachloroethane, ethanol, acetic acid, acetone and tetrahydrofuran;

the monomer is polar disubstituted alkyne, nonpolar disubstituted alkyne or disubstituted alkyne containing hetero atom.

2. The use of a palladium source catalyst according to claim 1 in the polymerization of alkynes, wherein: and (2) realizing polymerization under the condition of no promoter.

3. The use of a palladium source catalyst according to claim 1 in the polymerization of alkynes, wherein: the palladium catalyst may be purchased directly.

4. The use of a palladium source catalyst according to claim 1 in the polymerization of alkynes, wherein: the polymerization reaction is carried out in the air environment, and the polymer with high molecular weight and narrow molecular weight distribution can be obtained without nitrogen protection.

5. The use of a palladium source catalyst according to claim 1 in the polymerization of alkynes, wherein: and (2) drying at 40 ℃ in vacuum.

6. The use of a palladium source catalyst according to claim 1 in the polymerization of alkynes, wherein: the monomer is 1-chloroethynyl-4-toluene, 1-chloroethynyl-3-toluene, (chloroethynyl) benzene, 1-chloroethynyl-4-methoxybenzene, 1-chloroethynyl-4-fluorobenzene, 1-chloroethynyl-4-chlorobenzene, 61-chloroethynyl-4-ethyl benzoate, 1-chloroethynyl-4-acetophenone and 1-chloroethynyl-4-methyl benzoate.

7. The use of a palladium source catalyst according to claim 1 in the polymerization of alkynes, wherein: the palladium catalyst does not need to be coordinated with a ligand.

8. The use of a palladium source catalyst according to claim 2 in the polymerization of alkynes, wherein: the cocatalyst is silver trifluoromethanesulfonate and sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate.

Technical Field

The invention relates to application of a palladium source catalyst in disubstituted alkyne and functional alkyne polymerization, belonging to the technical field of alkyne polymerization.

Background

Poly (di-substituted acetylenes), PDSAs for short, is receiving increasing attention due to its higher stability, selective gas permeability and efficient light emitting properties than Poly (mono-substituted ethynyl). Poly (1-chloro-2-phenylacetylene) (PCPAs) has an electron withdrawing group chlorine atom on one side of a double bond of a polymer chain and a substituted phenyl group on the other side, and has been widely noticed by academia and industry because of its excellent liquid and gas permeability, high stability in air even at high temperature, and excellent light emitting properties, and has potential applications in many fields. For the polymerization of disubstituted alkyne, the polymerization process is different from that of monosubstituted acetylene, the polymerization process of disubstituted phenylacetylene has strict requirements on factors such as monomers, polymerization environment and the like, the catalyst of disubstituted phenylacetylene is usually very sensitive to water, oxygen and the like, and a catalytic system is easy to lose activity due to poisoning. Therefore, the development and design of novel and efficient catalysts capable of polymerizing 1-chloro-2-phenylacetylene and derivatives thereof has become a research hotspot of broad researchers.

In recent years, catalyst systems for the polymerization of disubstituted alkynes have been reported in succession. Catalyst systems for the polymerization of disubstituted alkynes are broadly divided into two classes, early transition metal catalyst systems and late transition metal catalyst systems, wherein the early transition metal catalyst systems are predominantly group five and group six transition metals, e.g., M (CO)₆(M ═ Mo, W) and MCl₅The base catalyst (M ═ Nb, Ta, Mo or W) catalyzes the polymerization of disubstituted alkyne by a double decomposition mechanism, because the group V and VI metal catalysts have higher oxygen affinity, the polymerization of disubstituted alkyne containing polar group can not be realized, the late transition metal catalyst mainly comprises Rh and Pd catalyst systems, the Rh catalyst system is mainly used for the polymerization of monosubstituted alkyne, at present, the palladium metal catalyst system used for the polymerization of disubstituted alkyne is mainly a palladium metal catalyst system, palladium metal coordinates with various ligands, and the polymerization of different types of disubstituted alkyne can be realized under the action of specific ligandsCatalysts in which the agent participates in the polymerization process appear to be necessary. Palladium sources are widely used in organic synthesis, but no examples of direct use in polymerization have been reported. The invention can realize the polymerization of disubstituted alkyne without an additional cocatalyst, improves the economy of the catalyst, saves the cost, and has important scientific significance and wide application prospect.

Disclosure of Invention

In view of the above, the present invention aims to provide an application of a palladium source catalyst in alkyne polymerization.

In order to achieve the purpose of the invention, the following technical scheme is provided.

The application of the palladium source catalyst in alkyne polymerization is that the palladium source is used as the catalyst to catalyze the polymerization reaction of alkyne monomers, and the palladium source can be directly purchased to obtain the alkyne polymer with high molecular weight and narrow molecular weight distribution.

Preferably, the palladium source catalyst is palladium carbon, palladium chloride, palladium acetate, diacetonitrile palladium dichloride and dibenzonitrile palladium dichloride.

The method comprises the following specific application steps:

(1) dissolving a palladium source in a solvent, and uniformly stirring; adding a disubstituted alkyne monomer, and continuously stirring uniformly; heated in an oil bath for 2 hours at 60 ℃.

(2) Adding a chain terminator into the reaction solution to terminate the reaction; adding a chain terminator, separating out a solid substance, carrying out suction filtration to obtain a solid substance, washing with petroleum ether for 3 times, drying to constant weight to obtain a polymerization product, and weighing to calculate the yield.

Wherein the molar ratio of the monomer to the catalyst is 50-500: 1.

Preferably at 40 ℃ under vacuum.

The solvent is one of 1,1,2, 2-tetrachloroethane, ethanol, acetic acid, tetrahydrofuran, pyridine, water, acetonitrile, diethyl ether and acetone.

The monomer is 1-acetylene chloride-4-toluene, 1-acetylene chloride-3-toluene, (chloroethynyl) benzene, 1-chloroethynyl-4-methoxybenzene, 1-chloroethynyl-4-fluorobenzene, 1-chloroethynyl-4-chlorobenzene, 1-chloroethynyl-4-ethyl benzoate, 1-chloroethynyl-4-acetophenone and 1-chloroethynyl-4-methyl benzoate.

The chain terminator is petroleum ether solution.

Advantageous effects

1. The invention provides an application of a palladium source catalyst in disubstituted alkyne polymerization, wherein the application is used as a catalyst for catalyzing polymerization reaction of alkyne monomers, the catalyst is used for catalyzing the disubstituted alkyne polymerization, the catalyst can be directly purchased without complex synthesis steps, the catalyst is not easy to be poisoned, the catalyst is simpler, more economical and efficient, and the application range of a late transition metal catalyst in the disubstituted alkyne polymerization is expanded;

2. the invention provides an application of a palladium source catalyst in disubstituted alkyne polymerization, wherein the application is used as a catalyst for catalyzing polymerization reaction of alkyne monomers, the catalyst is used for catalyzing disubstituted alkyne polymerization, and alkyne polymerization can be catalyzed without adding a cocatalyst, so that the polymerization cost is reduced;

3. the invention provides an application of a palladium source catalyst in disubstituted alkyne polymerization, the application is used as a catalyst to catalyze the polymerization reaction of alkyne monomers, the polymerization reaction is insensitive to water and oxygen, the polymer yield is high, the polymerization activity is high, the molecular weight distribution is relatively narrow, and the alkyne polymerization method is expanded.

Drawings

FIG. 1 is a Gel Permeation Chromatography (GPC) spectrum of palladium on carbon catalyzed polymerization of 1-chloroethynyl-4-toluene in example 1 to obtain a polymer.

FIG. 2 is a Gel Permeation Chromatography (GPC) spectrum of the polymer obtained by the palladium acetate catalyzed polymerization of 1-chloroethynyl-4-toluene in example 2.

FIG. 3 is a Gel Permeation Chromatography (GPC) spectrum of palladium dichloride catalyzed polymerization of 1-chloroethynyl-4-toluene in example 3 to give a polymer.

FIG. 4 is a Gel Permeation Chromatography (GPC) spectrum of 1-chloroethynyl-4-toluene polymerization catalyzed by diacetonitrile dichloride in example 4, which gives a polymer.

FIG. 5 is a Gel Permeation Chromatography (GPC) spectrum of a polymer obtained by palladium dichloride-catalyzed polymerization of 1-chloroethynyl-4-toluene using dibenzonitrile in example 5.

FIG. 6 is the NMR spectrum of the polymer obtained by the palladium dichloride-catalyzed polymerization of 1-chloroethynyl-4-toluene in example 6.

FIG. 7 is a Gel Permeation Chromatography (GPC) spectrum of 1-chloroethynyl-4-toluene polymerization catalyzed by palladium dichloride diacetonitrile in example 6 to obtain a polymer.

FIG. 8 is the NMR spectrum of the polymer obtained by the palladium dichloride-catalyzed polymerization of 1-chloroethynyl-3-toluene in example 7.

FIG. 9 is a Gel Permeation Chromatography (GPC) spectrum of 1-chloroethynyl-3-toluene polymerization catalyzed by palladium dichloride diacetonitrile in example 7 to obtain a polymer.

FIG. 10 is the nuclear magnetic hydrogen spectrum of the polymer obtained by the polymerization of chloroethynylbenzene catalyzed by diacetonitrile palladium dichloride in example 8.

FIG. 11 is a Gel Permeation Chromatography (GPC) spectrum of example 8, wherein diacetonitrile palladium dichloride catalyzes the polymerization of ethynyl benzene to obtain a polymer.

FIG. 12 is the NMR spectrum of a polymer obtained by polymerizing 1-chloroethynyl-4-methoxybenzene under the catalysis of diacetonitrile palladium dichloride in example 9.

FIG. 13 is a Gel Permeation Chromatography (GPC) spectrum of palladium dichloride-catalyzed polymerization of 1-chloroethynyl-4-methoxybenzene in example 9 to obtain a polymer.

FIG. 14 is the NMR spectrum of polymer obtained by the palladium dichloride-catalyzed polymerization of 1-chloroethynyl-4-fluorobenzene in example 10.

FIG. 15 is a Gel Permeation Chromatography (GPC) spectrum of palladium dichloride-catalyzed polymerization of 1-chloroethynyl-4-fluorobenzene in example 10 to obtain a polymer.

FIG. 16 is a nuclear magnetic hydrogen spectrum of a polymer obtained by polymerizing 1-chloroethynyl-4-chlorobenzene under the catalysis of diacetonitrile palladium dichloride in example 11.

FIG. 17 is a Gel Permeation Chromatography (GPC) spectrum of 1-chloroethynyl-4-chlorobenzene polymerized by palladium dichloride diacetonitrile catalysis in example 11 to obtain a polymer.

FIG. 18 is the NMR spectrum of a polymer obtained by polymerizing 1-chloroethynyl-4-ethyl benzoate with palladium dichloride diacetonitrile as a catalyst in example 12.

FIG. 19 is a Gel Permeation Chromatography (GPC) spectrum of palladium dichloride-catalyzed polymerization of 1-chloroethynyl-4-ethyl benzoate in example 12 to obtain a polymer.

FIG. 20 is the NMR spectrum of a polymer obtained by polymerizing 1-chloroethynyl-4-acetylbenzene with palladium dichloride diacetonitrile as a catalyst in example 15.

FIG. 21 is a Gel Permeation Chromatography (GPC) spectrum of 1-chloroethynyl-4-acetylbenzene polymerization catalyzed by palladium dichloride diacetonitrile in example 15 to obtain a polymer.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the following embodiments.

The main reagent information mentioned in the following examples is shown in Table 1, and the main instruments and equipment are shown in Table 2.

TABLE 1

TABLE 2

The polymerization Activity of the polymerization product prepared in the following examples is represented by the formula Activity ═ m yeiled)/(n_catTime) is calculated. Wherein Activity is polymerization Activity, and the unit is kg & mol_Pd ^-1·h^-1M is 1-ethynylchloro-4-toluene, 1-ethynylchloro-3-toluene, (chloroethynyl) benzene, 1-chloroethynyl-4-methoxybenzene, 1-chloroethynyl-4-fluorobenzene, 1-chloroethynyl-4-chlorobenzene, ethyl 1-chloroethynyl-4-benzoate, 1-chloroethynyl-4-acetylbenzene, methyl 1-chloroethynyl-4-benzoate, yield n_catTime is the time taken for the polymerization, as the amount of catalyst material.