阅读说明：本技术 一种杂化聚合物的制备方法 (Preparation method of hybrid polymer ) 是由 万文明 李顺顺 荆亚楠 朱能波 苏敏 赵延坤 鲍红丽 于 2019-11-15 设计创作，主要内容包括：本申请公开了一种杂化聚合物的制备方法,包括以下步骤：惰性气体氛围下,含有化合物I和化合物II的反应体系,在金属催化剂和引发剂存在的条件下,反应,得到杂化聚合物；所述化合物I选自金属卤代物、非金属卤代物中的至少一种；所述化合物II选自发生偶联反应且不发生消去反应的二卤代有机物中的至少一种。该方法为普适的聚合反应方法,用以制备包括多类非金属和金属在内的聚合物,克服了现有聚合物结构组成大都局限于碳氢氧氮等元素和聚合物结构相对简单的问题,该制备方法操作简单、制备高效,对聚合用单体的适用范围广,制备的聚合物结构新颖且难以由常规的聚合方法制备得到。(The application discloses a preparation method of a hybrid polymer, which comprises the following steps: under the inert gas atmosphere, a reaction system containing a compound I and a compound II reacts in the presence of a metal catalyst and an initiator to obtain a hybrid polymer; the compound I is at least one of metal halide and non-metal halide; the compound II is at least one selected from dihalo-organic compounds which undergo a coupling reaction and do not undergo an elimination reaction. The method is a universal polymerization reaction method, is used for preparing polymers including various non-metals and metals, overcomes the problems that the structural composition of the existing polymers is mostly limited to elements such as carbon, oxygen, nitrogen and the like and the structure of the polymers is relatively simple, has simple operation and high preparation efficiency, has wide application range on monomers for polymerization, and prepares the polymers with novel structures and difficult preparation by the conventional polymerization method.)

1. A method of preparing a hybrid polymer, comprising the steps of:

under the inert gas atmosphere, a reaction system containing a compound I and a compound II reacts in the presence of a metal catalyst and an initiator to obtain a hybrid polymer;

the compound I is at least one of metal halide and non-metal halide;

the compound II is at least one selected from dihalo-organic compounds which undergo a coupling reaction and do not undergo an elimination reaction.

2. The method for preparing hybrid polymer according to claim 1, wherein the compound I is R¹ _m-A-X¹ _n；

Wherein m is 0, 1, or 2; n is 2, 3, or 4;

R¹independently selected from at least one of aryl and alkyl; a is selected from at least one of B, P, Si, Ge, Bi and Sn; x¹Independently selected from at least one of F, Cl, Br and I;

the compound II is X²-R²-X³；

Wherein, X²、X³Independently selected from at least one of F, Cl, Br and I; r²At least one selected from the group consisting of an aromatic ring-containing group and an alkyl group;

preferably, R¹Independently selected from at least one of aryl of C4-C12 and alkyl of C1-C3;

further preferably, R¹At least one independently selected from phenyl and methyl;

preferably, R²At least one selected from aryl of C4-C20 and alkyl of C1-C20;

further preferably, R²At least one selected from phenyl, biphenyl, naphthyl, fluorenyl, alkyl substituted fluorenyl, triphenylamine, tetraphenyl vinyl, phenyl carbazolyl and alkyl of C1-C20.

3. The method for preparing a hybrid polymer according to claim 1, wherein the compound I is at least one selected from the group consisting of diphenyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, tetrachlorosilane, phenyldichlorophosphorus, phosphorus trichloride, diphenylgermanium dichloride, germanium tetrachloride, bismuth trichloride, phenylbismuth dichloride, diphenyltin dichloride, tin tetrachloride, boron trifluoride, boron trichloride, boron tribromide, and phenylboron dichloride;

the compound II is selected from o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-difluorobenzene, 4' -dibromobiphenyl, 1, 2-di (bromomethyl) benzene, 1, 3-di (bromomethyl) benzene, 1, 4-dibromonaphthalene, dichloromethane, dibromomethane, diiodomethane, 1, 4-dibromobutane, 1, 6-dibromohexane, 1, 8-dibromooctane, 1, 12-dibromododecane, 4' -dibromotetraphenylethylene, 3, 6-dibromo-9-phenylcarbazole, 4' -dibromotriphenylamine, 2, 7-dibromofluorene, 9-dihexyl-2, 7-dibromofluorene, 9-dioctyl-2, 7-dibromo fluorene.

4. The method for preparing hybrid polymer according to claim 1, wherein the molar ratio of halogen in compound I to halogen in compound II is 1: 0.2 to 2.

5. The method for preparing the hybrid polymer according to claim 1, wherein the metal catalyst is at least one of a simple metal and an organometallic reagent;

the metal elementary substance is selected from at least one of magnesium, lithium, sodium, potassium or aluminum;

the organic metal reagent is selected from at least one of a Grignard reagent, an organic lithium reagent and an organic sodium reagent;

preferably, the organolithium reagent is an alkyl lithium or phenyl lithium; the organic sodium reagent is selected from at least one of alkyl sodium, sodium borohydride and sodium ethoxide;

preferably, the molar amount of the metal catalyst is 1.1-5 times of the total molar amount of the dihalogenated organic substances.

6. The method for preparing a hybrid polymer according to claim 1, wherein the initiator is at least one selected from the group consisting of elemental iodine, methyl iodide, methyl chloride, red aluminum, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-diiodoethane, and methyl bromide;

preferably, the molar amount of the initiator is 0 to 0.2 times of the molar amount of the compound II.

7. The method for preparing the hybrid polymer according to claim 1, wherein the reaction system further comprises a solvent;

the solvent is at least one of tetrahydrofuran, diethyl ether, methyl tetrahydrofuran, methyl tert-butyl ether and benzene;

preferably, the solvent is a mixed solution of benzene and tetrahydrofuran, and the volume ratio is 1: 1-5;

preferably, the solvent is a mixed solution of toluene and tetrahydrofuran, and the volume ratio is 1: 1-5;

preferably, the concentration of the compound I in the solvent is 0.1 mol/L-5 mol/L;

the concentration of the compound II in the solvent is 0.1 mol/L-5 mol/L.

8. The method for preparing the hybrid polymer according to claim 1, wherein the reaction temperature is-40 to 100 ℃ and the reaction time is 1 to 48 hours.

9. The method for preparing the hybrid polymer according to claim 1, wherein the method comprises:

adding a compound II, a metal catalyst and an initiator into a reactor, reacting for 1-2h, then adding a compound I, and reacting to obtain a hybrid polymer; (ii) a

Or adding the compound I, the compound II, the metal catalyst and the initiator into the reactor at one time for reaction to obtain a hybrid polymer;

preferably, the method further comprises a purification step:

after the reaction is finished, adding a quenching agent, and obtaining the hybrid polymer through extraction, drying, concentration and precipitation;

preferably, the quenching agent is selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;

preferably, the extracting agent for extraction is selected from one of dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran and methyl tetrahydrofuran;

preferably, the drying agent is selected from one of anhydrous sodium sulfate and anhydrous magnesium sulfate;

preferably, the precipitating agent used for precipitation is selected from one of petroleum ether, diethyl ether, acetone, n-hexane, methanol and ethanol.

10. The hybrid polymer prepared by the method for preparing a hybrid polymer according to any one of claims 1 to 9, wherein the hybrid polymer has a structure represented by formula III;

wherein p is 10-1000.

Technical Field

The invention relates to the field of polymerization methodology and polymer material preparation, in particular to a universal polymerization method for preparing a hybrid polymer by taking metal or nonmetal halides and dihalogenated hydrocarbon as raw materials and a hybrid polymer material prepared by the same.

Background

Many polymer materials such as rubber, plastic, fiber, paint and adhesive provide great convenience for national life, and occupy a significant position in important fields such as biological medicine, even national defense and aerospace industry, so that the method for synthesizing and polymerizing the polymer materials is concerned all the time. The development of polymer disciplines is not driven by organic synthesis chemistry, and the existing polymerization methods are evolved from organic synthesis, so that the introduction of organic reactions into the preparation of polymers has become more and more an interesting synthesis mode of polymer materials.

The double bond polymerization is a common preparation mode of high molecular materials, the method has strong operability, relatively simple preparation process and relatively high preparation efficiency, but the types of monomers are often greatly limited, for example, the synthesis of monomers containing double bonds is relatively difficult, the monomers are not easy to store, and the like. Therefore, the coupling reaction is widely developed and applied as another effective method for synthesizing high molecular materials, and the prepared polymers are now applied to various fields such as polyurethane, polyamide and the like. The coupling reaction reported at present is mainly coupling by C-C, C-N, C-O bonds, and the polymerization reactions involving other heteroatoms and even metal elements are less, and different coupling modes are corresponding to different polymerization methods and conditions. Based on the method, the invention provides a novel, simple and efficient universal method for preparing the hybrid polymer material, and the preparation of the polymer material containing various nonmetal or metal elements such as B, P, Si, Ge, Bi and the like is realized.

Disclosure of Invention

According to one aspect of the application, a universal hybrid polymerization reaction method is provided, which is used for preparing polymers including various types of non-metals and metals, and overcomes the problems that the structural composition of the existing polymers is mostly limited to elements such as hydrocarbon, oxygen and nitrogen, and the like, and the structure of the polymers is relatively simple.

The preparation method of the hybrid polymer is characterized by comprising the following steps:

under the inert gas atmosphere, a reaction system containing a compound I and a compound II reacts in the presence of a metal catalyst and an initiator to obtain a hybrid polymer;

the compound I is at least one of metal halide and non-metal halide;

the compound II is at least one selected from dihalo-organic compounds which undergo a coupling reaction and do not undergo an elimination reaction.

Optionally, the inert gas atmosphere is selected from at least one of nitrogen, argon, helium, neon.

Alternatively, the compound I is R¹ _m-A-X¹ _n；

Wherein m is 0, 1, or 2; n is 2, 3, or 4;

R¹independently selected from at least one of aryl and alkyl; a is selected from at least one of B, P, Si, Ge and Bi; x¹Independently selected from at least one of F, Cl, Br and I;

the compound II is X²-R²-X³；

Wherein, X²、X³Independently selected from at least one of F, Cl, Br and I; r²At least one selected from the group consisting of aromatic ring-containing groups and alkyl groups.

Alternatively, R¹Independently selected from aryl of C4-C12 and alkyl of C1-C3One of them is less.

Alternatively, R¹Independently selected from at least one of phenyl and methyl.

Alternatively, R²At least one selected from aryl of C4-C20 and alkyl of C1-C20.

Alternatively, R²At least one selected from phenyl, biphenyl, naphthyl, fluorenyl, alkyl substituted fluorenyl, triphenylamine, tetraphenyl vinyl, phenyl carbazolyl and alkyl of C1-C20.

In the present application, the nonmetal or metal halide is one or more of fluoride, chloride, bromide and iodide, and the dihalohydrocarbon is one or more of dihalohydrocarbons which can undergo a coupling reaction and does not undergo an elimination reaction. Further, the nonmetal or metal halide is selected from one or more of bromide, chloride or fluoride of related elements; further, the non-metal or metal halide may be one or more of a dihalide, a trihalide or a tetrahalide. As an exemplary embodiment of the present invention, the compound I is selected from at least one of diphenyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, tetrachlorosilane, phenyldichlorophosphorus, phosphorus trichloride, diphenylgermanium dichloride, germanium tetrachloride, bismuth trichloride, phenylbismuth dichloride, diphenyltin dichloride, tin tetrachloride, boron trifluoride, boron trichloride, boron tribromide, and phenylboron dichloride;

according to an embodiment of the present invention, the dihalo-hydrocarbon may be a dihalo-aromatic compound or a dihalo-alkyl compound that does not undergo an elimination reaction in the presence of the metal or the metal-organic compound. As an exemplary embodiment of the present invention, the compound II is selected from the group consisting of o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-difluorobenzene, 4' -dibromobiphenyl, 1, 2-di (bromomethyl) benzene, 1, 3-di (bromomethyl) benzene, 1, 4-dibromonaphthalene, methylene chloride, dibromomethane, diiodomethane, 1, 4-dibromobutane, 1, 6-dibromohexane, 1, 8-dibromooctane, 1, 12-dibromododecane, 4' -dibromotetraphenylethylene, 3, 6-dibromo-9-phenylcarbazole, 4' -dibromotriphenylamine, 2, 7-dibromofluorene, 9-dihexyl-2, 7-dibromofluorene, 9, 9-dioctyl-2, 7-dibromo fluorene.

The molar ratio of the nonmetal or metal halide and the dihalo-organic compound is not particularly limited, and polymers having a specific molecular structure can be obtained by varying the molar ratio. As an exemplary embodiment of the present invention, the molar ratio of the halogen in compound I to the halogen in compound II is 1: 0.2 to 2.

Alternatively, the molar ratio of halogen in compound I to halogen in compound II is 1: 1.

according to an embodiment of the invention, the metal catalyst is a metal scrap or an organometallic reagent. Optionally, the metal catalyst is at least one of a metal simple substance and an organic metal reagent;

the metal elementary substance is selected from at least one of magnesium, lithium, sodium, potassium or aluminum;

the organic metal reagent is selected from at least one of a Grignard reagent, an organic lithium reagent and an organic sodium reagent.

Optionally, the organolithium reagent is an alkyl lithium or phenyl lithium; the organic sodium reagent is selected from at least one of alkyl sodium, sodium borohydride and sodium ethoxide.

Optionally, the molar amount of the metal catalyst is 1.1 to 5 times of the total molar amount of the dihalo-organic matter. For example, 1.2 times, 1.5 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, or 5 times.

Optionally, the initiator is selected from at least one of elementary iodine, methyl iodide, methyl chloride, red aluminum, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-diiodoethane and methyl bromide.

Optionally, the molar amount of the initiator is xx to xx times the molar amount of xx.

Optionally, the reaction system further comprises a solvent;

the solvent is at least one of tetrahydrofuran, diethyl ether, methyl tetrahydrofuran, methyl tert-butyl ether and benzene.

Optionally, the solvent is a mixed solution of benzene and tetrahydrofuran, and the volume ratio is 1: 1-5. For example 1:5, 1:4, 1:3, 1:2, 1: 1.

Optionally, the solvent is a mixed solution of toluene and tetrahydrofuran, and the volume ratio is 1: 1-5. For example 1:5, 1:4, 1:3, 1:2, 1: 1.

According to the present invention, the polymerization may be solution polymerization or bulk polymerization; the concentration of the compound I and the compound II in the solvent is 0.1-5 mol/L in the range of a solution system; when both compounds I and II are liquids or one of them is miscible in the other, solventless bulk polymerization can be achieved, and therefore this concentration range is not intended to limit the present invention. Optionally, the concentration of the compound I in the solvent is 0.1 mol/L-5 mol/L;

the concentration of the compound II in the solvent is 0.1 mol/L-5 mol/L.

Optionally, the reaction temperature is-40 to 100 ℃, and the reaction time is 1 to 48 hours.

In the application, the polymerization reaction method can be carried out in a step method or a one-pot method, and further, the step method comprises the steps of firstly reacting dihalogenated hydrocarbon with a metal catalyst and an initiator for 1-2h, and then adding nonmetal or metal halide; the one-pot method is to directly add dihalogenated hydrocarbon, nonmetal or metal halide, metal catalyst and initiator into one-step reaction at the same time.

Optionally, the method comprises:

adding a compound II, a metal catalyst and an initiator into a reactor, reacting for 1-2h, then adding a compound I, and reacting to obtain a hybrid polymer; (ii) a

Or adding the compound I, the compound II, the metal catalyst and the initiator into the reactor at one time for reaction to obtain the hybrid polymer.

In one embodiment, the method comprises adding a quenching agent to terminate the reaction after the reaction is complete; further, the reaction quenching agent may be one of deionized water, a saturated ammonium chloride solution, a saturated sodium chloride solution, dilute hydrochloric acid, dilute sulfuric acid, and the like.

Wherein the method further comprises a purification step of the polymer: after adding a reaction quenching agent into the polymer, extracting the polymer by using a solvent, drying by using a drying agent, concentrating, and precipitating in a precipitating agent to obtain pure polymer powder. Further, the quenching agent hydrolyzes, extracts and concentrates the polymer, and a precipitator is added for precipitation to obtain purified polymer powder. Further, the reaction quenching agent can be one of deionized water, saturated ammonium chloride solution, saturated sodium chloride solution, dilute hydrochloric acid, dilute sulfuric acid and the like; the organic solvent for extraction can be one of dichloromethane, trichloromethane, toluene, ethyl acetate, tetrahydrofuran or methyltetrahydrofuran; the drying agent is one of anhydrous sodium sulfate and anhydrous magnesium sulfate; the precipitant is one of petroleum ether, diethyl ether, acetone, n-hexane, methanol or ethanol.

Optionally, the method further comprises a purification step:

and after the reaction is finished, adding a quenching agent, and performing extraction, drying, concentration and precipitation to obtain the hybrid polymer.

Optionally, the quenching agent is selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid, sulfuric acid.

Optionally, the extracting agent for extraction is selected from one of dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran and methyl tetrahydrofuran.

Optionally, the drying agent is one selected from anhydrous sodium sulfate and anhydrous magnesium sulfate.

Optionally, the precipitating agent used for precipitation is selected from one of petroleum ether, diethyl ether, acetone, n-hexane, methanol and ethanol.

According to another aspect of the present application, there is provided a hybrid polymer prepared according to the method for preparing a hybrid polymer, the hybrid polymer having a structure represented by formula III;

wherein p is 10-1000.

The polymerization process of the present invention is carried out with R_a-X_bAnd X-R' -X, possible polymerization principles are:

definition and description of terms

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs. All patents, patent applications, and publications cited herein are incorporated by reference in their entirety unless otherwise indicated. If there are multiple definitions of terms herein, the definition in this section controls.

It is to be understood that a definition of standard chemical terms may be found in the literature. Unless a specific definition is set forth, the terms used herein in the pertinent description of analytical chemistry, organic chemistry, and polymer chemistry are known in the art.

The term non-metallic halide is understood to mean a compound containing a non-metal in the molecule, typically a compound obtained by reacting an elemental non-metal with a halogen.

The term metal halide is understood to mean a compound containing a metal element in the molecule, generally a compound obtained by reacting an elemental metal with a halogen.

The term "dihalo-organic" as used herein refers to an organic compound having two halogen atom substitutions.

The term "polymeric material" or "high molecular polymer" as used herein refers to compounds having a molecular weight greater than 1000 daltons.

In the present application, the term "alkyl" refers to a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound.

In the present application, the term "aryl" refers to a group formed by the loss of one hydrogen atom on an aromatic ring on an aromatic compound molecule; for example, toluene loses the hydrogen atom para to the methyl group on the phenyl ring to form a p-tolyl group.

In the present application, the term "halogen" refers to at least one of fluorine, chlorine, bromine, iodine.

The beneficial effects that this application can produce include:

1) the polymer prepared by the polymerization method provided by the application has universality, and the prepared polymer has the characteristics of novel structure and excellent property. Therefore, the polymerization method is a great complement to the traditional polymerization method and is used for preparing the high polymer material with special structural properties which is difficult to prepare by the traditional polymerization method.

2) The polymer is prepared by using nonmetal or metal halide and dihalogenated hydrocarbon as monomers to react with metal or organic metal reagents, the preparation process is simple, and the polymer has the following advantages:

3) the preparation method successfully introduces nonmetal or metal halide into the preparation of the high polymer, greatly enriches the monomer types of the high polymer, expands the types of the polymers, has diversified product structures, and has universality on various elements.

4) The preparation method provided by the application has various reaction conditions, and various kinds of metal and organic metal reagents can realize the preparation of the compound related to the invention from a monomer to a polymer.

5) The preparation method provided by the application is simple to operate, mild in reaction conditions and low in cost, can be used for preparing the polymer material with various structures and excellent properties, and is a brand-new polymer synthesis method.

6) The method for preparing the polymer containing the nonmetal or metal elements is provided, and the prepared polymer is difficult to obtain by other traditional polymerization methods.

Drawings

FIG. 1 is a gel permeation chromatogram of the product of example 1 of the present invention;

FIG. 2 is a NMR spectrum of the product of example 1 of the present invention;

FIG. 3 is a gel permeation chromatogram of the product of example 2 of the present invention;

FIG. 4 is a NMR spectrum of the product of example 2 of the invention;

FIG. 5 is a gel permeation chromatogram of the product of example 3 of the present invention;

FIG. 6 is a NMR spectrum of the product of example 3 of the present invention;

FIG. 7 is a gel permeation chromatogram of the product of example 4 of the present invention;

FIG. 8 is a NMR spectrum of the product of example 4 of the present invention;

FIG. 9 is a NMR spectrum of the product of example 5 of the present invention;

FIG. 10 is a NMR spectrum of the product of example 6 of the invention;

FIG. 11 is a NMR spectrum of the product of example 7 of the present invention.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the starting materials and catalysts in the examples of the present application were commercially available, wherein phenyldichlorophos, diphenyldichlorosilane, 1, 4-dibromobenzene and 4, 4-dibromobiphenyl were obtained from Shanghai Allantin Biotechnology Co., Ltd, and other chemicals were obtained from the national drug group Chemicals Ltd.

The tetrahydrofuran refining process includes the following steps: cutting a proper amount of metal sodium into filaments, adding the filaments into tetrahydrofuran dried by potassium hydroxide in advance, adding benzophenone serving as a color developing agent, refluxing the filaments by using a solvent drying device at normal pressure until the tetrahydrofuran is changed into bright bluish purple, collecting the dried tetrahydrofuran, and sealing for preparation.

The analysis method in the examples of the present application is as follows:

NMR analysis is carried out by using a Bruk Ascend TM 400 nuclear magnetic resonance spectrometer, and the test concentration is 10 mg/mL-50 mg/mL.

The gel permeation chromatography analysis is carried out by a Viscotek TDA 302 type gel permeation chromatograph, the mobile phase is tetrahydrofuran, and the testing concentration is 1 mg/mL.

Example 1:

this example provides a method for preparing a polymer by reacting phenyl phosphorus dichloride and 1, 4-dibromobenzene in the presence of magnesium metal, comprising the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.244g, 0.01mol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeatedly and circularly vacuumizing, heating, cooling and introducing nitrogen for three times, and connecting a branch port of the reaction tube with a nitrogen balloon after introducing nitrogen for the last time so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

Phenylphosphonium dichloride (1.07g, 0.004mol) and 1, 4-dibromobenzene (1g, 0.004mol) were weighed out accurately, dissolved in 25mL of dry tetrahydrofuran, magnetically stirred while turned on, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe. Then 0.1mL of 1, 2-dibromoethane is injected into the reaction tube and reacts for 24h at the temperature of 45 ℃ to obtain a crude product of the polymer.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 50mL of a saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 100mL of dichloromethane, washing with 50mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product.

Example 2:

this example provides a method for preparing a polymer by reacting phenyl phosphorus dichloride and 1, 4-dibromobenzene in the presence of magnesium metal, comprising the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.244g, 0.01mol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeatedly and circularly vacuumizing, heating, cooling and introducing nitrogen for three times, and connecting a branch port of the reaction tube with a nitrogen balloon after introducing nitrogen for the last time so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

Phenyl phosphorus dichloride (0.76g, 0.004mol) and 1, 4-dibromobenzene (1g, 0.004mol) were accurately weighed, dissolved in 25mL of dry tetrahydrofuran, magnetically stirred, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe. Then 0.1mL of 1, 2-dibromoethane is injected into the reaction tube and reacts for 24h at the temperature of 45 ℃ to obtain a crude product of the polymer.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 50mL of a saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 100mL of dichloromethane, washing with 50mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product.

Example 3:

the embodiment provides a method for preparing a polymer by reacting diphenyldichlorosilane and 4,4' -dibromobiphenyl in the presence of magnesium metal, which comprises the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.244g, 0.01mol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeatedly and circularly vacuumizing, heating, cooling and introducing nitrogen for three times, and connecting a branch port of the reaction tube with a nitrogen balloon after introducing nitrogen for the last time so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

Diphenyldichlorosilane (1.07g, 0.004mol) and 4,4' -dibromobiphenyl (1.32g, 0.004mol) were accurately weighed, dissolved in 25mL of dry tetrahydrofuran, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe with magnetic stirring. Then 0.1mL of 1, 2-dibromoethane is injected into the reaction tube and reacts for 24h at the temperature of 45 ℃ to obtain a crude product of the polymer.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 50mL of a saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 100mL of dichloromethane, washing with 50mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product.

Example 4:

the embodiment provides a method for preparing a polymer by reacting diphenyldichlorosilane and 4,4' -dibromobiphenyl in the presence of magnesium metal, which comprises the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.244g, 0.01mol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeatedly and circularly vacuumizing, heating, cooling and introducing nitrogen for three times, and connecting a branch port of the reaction tube with a nitrogen balloon after introducing nitrogen for the last time so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

Diphenyldichlorosilane (0.76g, 0.004mol) and 4,4' -dibromobiphenyl (1.32g, 0.004mol) were accurately weighed, dissolved in 25mL of dry tetrahydrofuran, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe with magnetic stirring. Then 0.1mL of 1, 2-dibromoethane is injected into the reaction tube and reacts for 24h at the temperature of 45 ℃ to obtain a crude product of the polymer.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 50mL of a saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 100mL of dichloromethane, washing with 50mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product.

The molecular structure and molecular weight of all target macromolecules were determined by Nuclear Magnetic Resonance (NMR) spectrometer and gel permeation chromatography.

Table 1 reaction conditions and reaction results in examples

The nmr hydrogen spectra and the gel permeation chromatograms of the products of examples 1-4 are shown in fig. 1-8, respectively, and the successful preparation of the polymer can be clearly demonstrated from the gel permeation liquid chromatography curve for testing the molecular weight of the polymer, and the data in table 1 indicates that the products of specific examples 1-4 are all polymers, which demonstrates the feasibility of the polymerization method for preparing the polymer by the reaction of nonmetal or metal halide and dihalogenated hydrocarbon in the presence of metal or organic metal reagent. FIG. 1 and FIG. 2 are a GPC chart and an NMR chart of the high molecular polymer prepared in example 1, respectively, and the elution volume in FIG. 1 is compared with a standard elution volume to give a molecular weight of 4800Da of the high molecular polymer prepared in example 1; in fig. 2, δ is 7.74 to 7.10ppm, corresponding to a benzene ring group. FIGS. 3 and 4 are a GPC chart and an NMR chart, respectively, of the high molecular polymer prepared in example 2, and the elution volume in FIG. 3 is compared with a standard elution volume to give a molecular weight of 3900Da for the high molecular polymer prepared in example 2; in fig. 4, δ is 7.85 to 7.06ppm, corresponding to a benzene ring group. FIGS. 5 and 6 are a GPC chart and an NMR chart, respectively, of the high molecular polymer prepared in example 3, and the elution volume in FIG. 5 is compared with a standard elution volume to give a molecular weight of 4300Da of the high molecular polymer prepared in example 3; in fig. 6, δ is 7.93 to 7.12ppm, corresponding to a benzene ring group. Fig. 7 and 8 are a GPC diagram and an NMR diagram of the high molecular polymer prepared in example 4, respectively, and the elution volume in fig. 7 is compared with a standard elution volume to obtain a molecular weight of 4600 for the high molecular polymer prepared in example 4; in fig. 8, δ is 7.83 to 7.16ppm, corresponding to a benzene ring group. Fig. 9 is an NMR chart of the high molecular weight polymer prepared in example 5, and in fig. 9, δ is 7.85 to 7.27ppm, corresponding to a benzene ring group.

Example 5:

the embodiment provides a method for preparing a polymer by reacting bismuth trichloride with 1, 4-dibromobenzene in the presence of magnesium metal, which comprises the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.244g, 0.01mol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeating the operation of circularly vacuumizing, heating, cooling and introducing nitrogen for three times, accurately weighing bismuth trichloride (0.84g, 2.67mmol) after the last nitrogen introduction, and placing the bismuth trichloride in the reaction tube, wherein a branch port of the reaction tube is connected with a nitrogen balloon so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

1, 4-dibromobenzene (1.0g, 0.004mol) was accurately weighed, dissolved in 25mL of dry tetrahydrofuran, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe with magnetic stirring. Then 0.1mL of 1, 2-dibromoethane is injected into the reaction tube and reacts for 24h at the temperature of 45 ℃ to obtain a crude product of the polymer.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 50mL of a saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 100mL of dichloromethane, washing with 50mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product.

Example 6:

the embodiment provides a method for preparing a polymer by reacting dichlorodiphenyl germanium and 4,4' -dibromobiphenyl in the presence of magnesium metal, which comprises the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.035g, 1.2mmol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeatedly and circularly vacuumizing, heating, cooling and introducing nitrogen for three times, accurately weighing 0.15g (0.5 mmol) of diphenyl-germanium dichloride after the last nitrogen introduction, placing the diphenyl-germanium dichloride into the reaction tube, and connecting a nitrogen balloon to a branch port of the reaction tube so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

4,4' -dibromobiphenyl (0.16g, 0.5mmol) was accurately weighed, dissolved in 5mL of dry tetrahydrofuran, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe with opening of magnetic stirring. Then, 0.05mL of 1, 2-dibromoethane was injected into the reaction tube, and after reaction at 45 ℃ for 24 hours, a crude polymer product was obtained.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 20mL of saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 50mL of dichloromethane, washing with 20mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product. FIG. 10 is an NMR spectrum of the polymer prepared in example 6, showing the successful preparation of the polymer in Table 1.

Example 7:

this example provides a method for preparing a polymer by reacting tetrachlorosilane and 1, 2-dibromobenzene in the presence of magnesium metal, comprising the following steps:

(1) preparation of crude Polymer

A100 mL Schlenk reaction tube was charged with magnesium chips (0.244g, 0.01mol) and magnetons, and the mouth of the reaction tube was sealed with a rubber stopper. Vacuumizing the reaction tube, heating by using a hot air gun, naturally cooling, introducing nitrogen, repeating the operations of vacuumizing, heating, cooling and introducing nitrogen for three times, accurately weighing tetrachlorosilane (0.34g and 0.002mol) after the last nitrogen introduction, and placing the tetrachlorosilane into the reaction tube, wherein a branch port of the reaction tube is connected with a nitrogen balloon so as to ensure that the whole system is in an anhydrous nitrogen atmosphere.

1, 2-dibromobenzene (1.0g, 0.004mol) was accurately weighed, dissolved in 25mL of dry tetrahydrofuran, and the solution was injected into the reaction tube through the rubber stopper by means of a syringe with magnetic stirring. Then 0.1mL of 1, 2-dibromoethane is injected into the reaction tube and reacts for 24h at the temperature of 45 ℃ to obtain a crude product of the polymer.

(2) Purification of crude polymer

The crude polymer obtained in step (1) was filtered to remove insoluble matter, and then 50mL of a saturated aqueous ammonium chloride solution was added and the mixture was magnetically stirred for 1 hour to quench the reaction. Extracting with 100mL of dichloromethane, washing with 50mL of saturated ammonium chloride aqueous solution for 3 times, drying the organic phase obtained by extraction with a proper amount of anhydrous magnesium sulfate for 1h, performing suction filtration to obtain a clear solution, concentrating the solution, precipitating in petroleum ether twice, and finally drying in a vacuum drying oven to obtain a pure polymer product. FIG. 11 is an NMR spectrum of the polymer prepared in example 7, showing successful preparation of the polymer in Table 1.

The invention takes nonmetal or metal halide and dihalogenated hydrocarbon as reactants to prepare high molecular polymer by reaction in the presence of metal or organic metal reagent, and the one-pot method and the fractional method can successfully realize the preparation of corresponding polymer by the polymerization method, and have simple operation steps and high preparation efficiency, thus providing great advantages for the polymerization method. The invention successfully introduces nonmetal or metal halide into the preparation field of macromolecules to prepare the nonmetal heteroatom and metal element polymer, which greatly enriches the monomer library of polymerization reaction and widens the scope of the chemical structure and the characteristics of the existing macromolecules.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.