CN102504209B - A kind of preparation method of aromatic conjugated polymer - Google Patents

Abstract

The invention provides a preparation method of an aromatic conjugated polymer, comprising the following steps: the first halogenated aromatic Grignard reagent undergoes polycondensation reaction under the action of a catalyst to obtain an aromatic conjugated polymer, and the catalyst is composed of two The molar ratio of the divalent nickel compound to the organic phosphine ligand is 1: (0.5-3); the divalent nickel compound is nickel dichloride, dibromide Nickel, nickel acetylacetonate, nickel acetate or nickel perchlorate; the first halogenated aromatic Grignard reagent monomer has the structure of formula (I): X ¹ -Q ¹ -MgX ² (I); wherein, X ¹ , X ² is independently selected from halogen; Q ¹ is aryl or substituted aryl. The preparation method of the catalyst provided by the invention is simple, has good solubility in solvents, can simultaneously initiate the reaction of the polymerization chain, and can obtain aromatic conjugated homopolymers or aromatic conjugated blocks with controllable molecular weight and narrow molecular weight distribution copolymer.

Description

A kind of preparation method of aromatic conjugated polymer

technical field

The invention relates to the technical field of polymers, in particular to a preparation method of aromatic conjugated polymers.

Background technique

Conjugated polymers not only have the electrical and optical properties of metals and semiconductors, but also have polymer-specific, good processability and mechanical properties, and are widely used in light-emitting displays, solar photovoltaic cells, thin-film transistors, chemical and biological sensors, Polymer light-emitting diodes, all-plastic diode lasers, all-plastic photovoltaic cells, light-emitting electrochemical cells, optical modulators and optocouplers, etc.

Conjugated polymers are generally prepared by transition metal-catalyzed, stepwise polymerization. However, this method not only takes a long time, but also makes it difficult to control the molecular weight of the resulting conjugated polymers, and the molecular weight distribution index is generally greater than 2. Transfer chain polycondensation reaction is a new synthetic method of conjugated polymers, which has the advantages of fast reaction speed, relatively controllable product molecular weight, and relatively narrow molecular weight distribution (Chinese Science and Chemistry, Sci.China.Chem.2010, 53 , 1620).

When adopting transfer chain type polycondensation reaction to prepare conjugated polymer, prior art generally adopts the complex compound of divalent nickel as catalyst, as the patent No. is that _US6166172 U.S. Patent discloses a kind of use Ni(dppp)Cl as catalyst catalysis 2-Bromo-5-magnesium chloride-3-hexylthiophene is a method for synthesizing polythiophene by polymerization reaction, and the obtained polythiophene region is relatively regular, and the molecular weight distribution is relatively narrow, wherein, dppp is 1,3-bis-diphenylphosphino Propane; the patent No. is US1010099823 U.S. Patent discloses a kind of with Ni(dppe)Cl ₂ as catalyst catalysis 1-bromo 4-magnesium chloride-2, the method that 5-dihexyloxybenzene generation polymerization prepares polyphenylene, the polyphenylene obtained The molecular weight distribution of benzene is relatively narrow, and wherein, dppe is 1,3-bisdiphenylphosphinoethane; The U.S. patent that the patent No. is US20080146754 discloses a kind of adopting Ni(dppb)Cl catalyzed ₂ -bromo-5- A method for preparing polypyrrole by polymerization of magnesium chloride-N-dodecylpyrrole, wherein dppb is 1,3-bisdiphenylphosphinobutane; the Chinese patent with publication number CN101092475A discloses a method for preparing polyfluorene Method, firstly use 2,7-dihalo-9,9-dialkylfluorene as raw material, react with organomagnesium reagent in the presence of inorganic electrolyte to obtain polymerized monomer 2-halogen-7 magnesium halide-9,9- Dialkyl fluorene; then, under the catalysis of a divalent nickel complex catalyst, a polymerization reaction occurs to obtain poly(9,9-dialkyl fluorene).

However, since divalent nickel complexes belong to heterogeneous catalysts, their solubility in organic solvents is poor, so the initiation of the polymerization chains is not carried out at the same time, thereby affecting the molecular weight and molecular weight distribution of the polymerization product, so that the obtained The molecular weight of the polymerized product is uncontrollable and the molecular weight distribution is wide.

Contents of the invention

The object of the present invention is to provide a method for preparing aromatic conjugated polymers. The molecular weight of the aromatic conjugated polymers obtained by the preparation method provided by the present invention is controllable and the molecular weight distribution is relatively narrow.

The present invention provides a kind of preparation method of aromatic conjugated polymer, comprises the following steps:

The first halogenated aromatic Grignard reagent monomer undergoes polycondensation reaction under the action of a catalyst to obtain an aromatic conjugated polymer. The catalyst is composed of a divalent nickel compound and an organic phosphine ligand. The divalent nickel compound and the described The molar ratio of organic phosphine ligand is 1: (0.5～3);

The divalent nickel compound is nickel dichloride, nickel dibromide, nickel acetylacetonate, nickel acetate or nickel perchlorate;

The first halogenated aromatic Grignard reagent monomer has a structure of formula (I):

X ¹ -Q ¹ -MgX ² (I);

Wherein, X ¹ and X ² are independently selected from halogen;

Q1 is ^an aromatic group or a substituted aromatic group.

Preferably, the divalent nickel compound is nickel acetylacetonate.

Preferably, the organophosphine ligand has a structure of formula (III) or formula (IV):

Wherein, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are independently selected from alkyl, phenyl or substituted phenyl;

R ⁴ is a ferrocenyl group or a linear alkyl group with 1 to 4 carbon atoms.

Preferably, the organic phosphine ligand is triphenylphosphine, 1,3-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane or 1,1'-bis (Diphenylphosphine)ferrocene.

Preferably, the catalyst is prepared according to the following steps:

The divalent nickel compound and the organic phosphine ligand are mixed in an organic solvent, and the catalyst is obtained after stirring.

Preferably, the stirring temperature is -20° C. to 30° C.; the stirring time is 1 min to 120 min.

Preferably, the Q1 is selected from any ^one of the structures of formulas (11) to (14):

Wherein, R ⁹ is an alkyl group;

R ¹⁰ and R ¹¹ are independently selected from alkyl groups;

R ¹² and R ¹³ are independently selected from alkoxy;

R ¹⁴ is an alkyl group.

Preferably, the molar ratio of the catalyst to the first halogenated aromatic Grignard reagent monomer is (0.001-0.2):1.

Preferably, the temperature of the polycondensation reaction is -5°C to 30°C, and the time of the polycondensation reaction is 30min to 120min.

The present invention also provides a method for preparing an aromatic conjugated polymer, comprising the following steps:

The first halogenated aromatic Grignard reagent monomer undergoes a polycondensation reaction under the action of a catalyst to obtain a mixed reaction solution, the catalyst is composed of a divalent nickel compound and an organic phosphine ligand, and the divalent nickel compound and the organic phosphine ligand The molar ratio is 1: (0.5～3);

The divalent nickel compound is nickel dichloride, nickel dibromide, nickel acetylacetonate, nickel acetate or nickel perchlorate;

The first halogenated aromatic Grignard reagent monomer has a structure of formula (I):

X ¹ -Q ¹ -MgX ² (I);

Wherein, X ¹ and X ² are independently selected from halogen;

Q ¹ is an aromatic group or a substituted aromatic group;

Adding a second halogenated aromatic Grignard reagent monomer into the mixed reaction liquid to undergo a polymerization reaction to obtain a second aromatic conjugated polymer;

The second halogenated aromatic Grignard reagent monomer has a structure of formula (II):

X ³ -Q ² -MgX ⁴ (II);

Wherein, X ³ and X ⁴ are independently selected from halogen;

Q ² is an aryl group or a substituted aryl group different from the above Q ¹ .

Preferably, the molar ratio of the second halogenated aromatic Grignard monomer to the catalyst is 1:(0.005-0.2).

Preferably, the temperature of the polymerization reaction is 10°C-50°C, and the time of the polymerization reaction is 0.5h-2h.

Compared with the prior art, the present invention uses the first halogenated aromatic Grignard reagent monomer having the structure of formula (I) as a raw material, and undergoes chain reaction under the catalysis of a catalyst composed of a divalent nickel compound and an organic phosphine ligand. Formula transfer polycondensation reaction to obtain aromatic conjugated homopolymer. In the present invention, the catalyst is composed of a divalent nickel compound and an organic phosphine ligand. The preparation method is simple, and it has good solubility in solvents, and can simultaneously initiate the reaction of the polymerization chain. By controlling the reaction of the catalyst and the polymerization monomer The feed ratio can obtain aromatic conjugated homopolymer or aromatic conjugated block copolymer with controllable molecular weight and narrow molecular weight distribution. At the same time, the preparation method provided by the invention is simple and fast, the by-products of the reaction are less, and it is suitable for industrial production. In addition, after the aromatic conjugated homopolymer is obtained, a second halogenated aromatic Grignard monomer that is similar in structure but different from the first halogenated aromatic Grignard reagent monomer is added to it, and the block copolymerization can be obtained after continuing the reaction. materials, thereby increasing the types and applications of conjugated copolymers.

detailed description

The present invention provides a kind of preparation method of aromatic conjugated polymer, comprises the following steps:

The first halogenated aromatic Grignard reagent monomer undergoes polycondensation reaction under the action of a catalyst to obtain an aromatic conjugated polymer. The catalyst is composed of a divalent nickel compound and an organic phosphine ligand. The divalent nickel compound and the described The molar ratio of organic phosphine ligand is 1: (0.5～3);

The divalent nickel compound is nickel dichloride, nickel dibromide, nickel acetylacetonate, nickel acetate or nickel perchlorate;

The first halogenated aromatic Grignard reagent monomer has a structure of formula (I):

X ¹ -Q ¹ -MgX ² (I);

Wherein, X ¹ and X ² are independently selected from halogen;

Q1 is ^an aromatic group or a substituted aromatic group.

In the present invention, the first halogenated aromatic Grignard reagent monomer having the structure of formula (I) is used as a raw material, and a chain transfer polycondensation reaction occurs under the catalysis of a catalyst composed of a divalent nickel compound and an organic phosphine ligand to obtain an aromatic Conjugated polymers. In the present invention, the catalyst is composed of a divalent nickel compound and an organic phosphine ligand. The preparation method is simple, and it has good solubility in solvents, and can simultaneously initiate the reaction of the polymerization chain. By controlling the reaction of the catalyst and the polymerization monomer The feed ratio can obtain aromatic conjugated homopolymer or aromatic conjugated block copolymer with controllable molecular weight and narrow molecular weight distribution.

The invention uses the first halogenated aromatic Grignard reagent monomer as a raw material, adds a catalyst composed of a divalent nickel compound and an organic phosphine ligand, undergoes polycondensation reaction, and obtains an aromatic conjugated homopolymer.

In the present invention, the first halogenated aromatic Grignard reagent monomer has the structure of formula (I):

X ¹ -Q ¹ -MgX ² (I);

Wherein, X ¹ and X ² are independently selected from halogen, preferably chlorine or bromine;

Q1 is ^an aromatic group or a substituted aromatic group, preferably selected from any structure in formulas (11) to (14):

Wherein, R ⁹ is an alkyl group, preferably an alkyl group containing 10 or less carbon atoms;

R ¹⁰ and R ¹¹ are independently selected from alkyl groups, preferably alkyl groups containing 10 or less carbon atoms;

R ¹² and R ¹³ are independently selected from alkoxy groups, preferably alkoxy groups containing 10 or less carbon atoms;

R ¹⁴ is an alkyl group, preferably an alkyl group containing 10 or less carbon atoms.

The present invention has no special limitation on the source of the first halogenated aromatic Grignard reagent monomer, and is preferably prepared according to the following method:

Add an organomagnesium reagent solution to the dihalogenated aromatic monomer solution to undergo a substitution reaction to obtain a halogenated aromatic Grignard reagent monomer, and the dihalogenated aromatic monomer has a structure of formula (V):

X ¹ -Q ¹ -X′(V);

Wherein, X ¹ and X' are independently selected from halogen, and Q ¹ is an aromatic group or a substituted aromatic group;

Described organomagnesium reagent has formula (VI) structure:

R′MgX ² (VI);

Wherein, R' is an alkyl group or an aryl group, and ^X2 is a halogen.

In the dihalogenated aromatic monomer having the structure of formula (V), said X ¹ and X' are independently selected from halogen, preferably chlorine or bromine; said Q ¹ is an aromatic group or a substituted aromatic group, preferably selected from the formula Any structure in (11) to (14), that is to say, the dihalogenated aromatic monomer is preferably 2,5-dihalogenated 3-alkylthiophene, 2,7-dihalogenated-9,9 - Dialkylfluorenes, 1,4-dihalo-2,5-dialkoxybenzenes or N,N-bis(4-halophenyl)-N-(4-alkylanilines).

In the organomagnesium reagent having the structure of formula (VI), R' is an alkyl or aryl group, preferably methyl, ethyl, propyl, isopropyl, tert ^- butyl, propenyl or phenyl; X2 is Halogen is preferably chlorine or bromine.

First, under the protection of an inert atmosphere, the dihalogenated aromatic monomer with the structure of formula (V) is dissolved in an organic solvent, and then the organic magnesium reagent solution with the structure of formula (VI) is added, and after a substitution reaction occurs, the compound with the formula ( The first halogenated aromatic Grignard reagent monomer of I) structure. The organic solvent may be tetrahydrofuran, and the concentration of the dihalogenated aromatic monomer is preferably 0.05 mol/L to 0.1 mol/L, more preferably 0.06 mol/L to 0.08 mol/L, preferably -20°C to 40 The dihalogenated aromatic monomer is dissolved in an organic solvent at ℃. The concentration of the organomagnesium reagent solution is preferably 1 mol/L˜3 mol/L, more preferably 1.5 mol/L˜2.5 mol/L. The molar ratio of the organomagnesium reagent to the halogenated aromatic monomer is preferably 1:(0.1-1.5), more preferably 1:(0.5-1).

In the present invention, the substitution reaction between the dihalogenated aromatic monomer and the organomagnesium reagent preferably occurs in the presence of an inorganic electrolyte, and the inorganic electrolyte is preferably a lithium salt, more preferably lithium tetrafluoroboride, high Lithium chlorate, lithium chloride or lithium iodide, most preferably lithium chloride. The molar ratio of the inorganic electrolyte to the dihalogenated aromatic monomer is preferably (0.5-1.5):1, more preferably (0.8-1.2):1. In the present invention, the time for the substitution reaction is 1-50 hours, preferably 1-35 hours, more preferably 1-24 hours. After the reaction is completed, the halogenated aromatic Grignard reagent monomer having the structure of formula (I) is obtained, and the conversion rate is preferably 75%-95%, more preferably 80%-90%.

After obtaining the first halogenated aromatic Grignard reagent monomer having the structure of formula (I), the first halogenated aromatic Grignard reagent monomer undergoes a transfer chain polycondensation reaction under the action of a catalyst to obtain a conjugated homopolymer . In the present invention, the catalyst is composed of a divalent nickel compound and an organic phosphine ligand. The preparation method is simple, and it has good solubility in solvents, and can initiate the reaction of the polymer chain at the same time, so that the molecular weight can be controlled and the catalyst can be obtained. Aromatic conjugated homopolymer or aromatic conjugated block copolymer with narrow molecular weight distribution.

In the catalyst provided by the present invention, the divalent nickel compound is nickel dichloride, nickel dibromide, nickel acetylacetonate, nickel acetate or nickel perchlorate, preferably nickel acetylacetonate. The divalent nickel compound may be an anhydrous compound or a hydrated compound, such as anhydrous nickel acetylacetonate, nickel dichloride hexahydrate, nickel dibromide trihydrate, etc., preferably an anhydrous compound.

In the catalyst provided by the invention, the organophosphine ligand preferably has a structure of formula (III) or formula (IV):

Wherein, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are independently selected from alkyl, phenyl or substituted phenyl;

R ⁴ is a ferrocenyl group or a linear alkyl group with 1 to 4 carbon atoms.

Among the organic phosphine ligands, those with the structure of formula (III) are monodentate phosphine ligands, including but not limited to triphenylphosphine, etc.; those with the structure of formula (IV) are bidentate phosphine ligands, including but not limited to Limited to 1,3-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp) and 1,1′-bis(diphenylphosphino)diocene Iron (dppf) and the like, preferably 1,3-bis(diphenylphosphino)propane (dppp).

In the catalyst, the molar ratio of the divalent nickel compound to the organophosphine ligand is 1:(0.5-3), preferably 1:(0.7-2), more preferably 1:(0.8-1.5 ).

The catalyst is preferably prepared as follows:

The divalent nickel compound and the organic phosphine ligand are mixed in an organic solvent, and the catalyst is obtained after stirring.

First, the divalent nickel compound and the organic phosphine ligand are mixed, an organic solvent is added to dissolve, and the catalyst is obtained after stirring. In the process of preparing the catalyst, the organic solvent includes but not limited to diethyl ether, tetrahydrofuran (THF), dioxane, benzene and toluene, etc., preferably THF.

In the solution obtained by adding an organic solvent to dissolve the divalent nickel compound and the organic phosphine ligand, the concentration of the divalent nickel compound is preferably 0.005 mol/L to 0.1 mol/L, more preferably 0.01 mol/L to 0.08 mol/L L; the concentration of the organophosphine ligand is preferably 0.005 mol/L-0.1 mol/L, more preferably 0.01 mol/L-0.08 mol/L.

In the present invention, when the divalent nickel compound and the organic phosphine ligand are mixed in an organic solvent and then stirred, the stirring temperature is preferably -20°C to 30°C, more preferably -10°C to 25°C; The stirring time is preferably 1 min to 120 min, more preferably 20 min to 100 min, and most preferably 30 min to 60 min.

The first halogenated aromatic Grignard reagent monomer with the structure of formula (I) undergoes a transfer chain polycondensation reaction under the action of a catalyst, specifically comprising:

Under the protection of an inert gas, a catalyst solution is added to the first halogenated aromatic Grignard reagent monomer, and a conjugated homopolymer is obtained after polycondensation reaction. The catalyst solution is preferably a tetrahydrofuran solution of the catalyst. The molar ratio of the catalyst to the first halogenated aromatic Grignard reagent monomer is (0.001-0.2):1, more preferably (0.005-0.15):1, more preferably (0.01-0.1):1. The temperature of the polycondensation reaction is preferably -5°C to 30°C, more preferably 0°C to 25°C; the time of the polycondensation reaction is preferably 30min to 120min, more preferably 40min to 100min.

After the reaction is complete, quench the reaction with 5mol/L hydrochloric acid, extract the reaction product obtained by chloroform, wash the organic layer obtained after the extraction with saturated brine, dry over anhydrous magnesium sulfate, settle in methanol after removing the solvent, and filter After that, a conjugated homopolymer is obtained.

After the conjugated homopolymer is obtained, GPC analysis is carried out on the conjugated homopolymer, and the results show that the number average molecular weight is 6200-30000, and the number average molecular weight can be controlled by controlling the feed ratio of the catalyst and the polymerization monomer; Its molecular weight distribution is narrow from 1.15 to 1.50.

The present invention also provides a method for preparing an aromatic conjugated polymer, comprising the following steps:

The first halogenated aromatic Grignard reagent monomer undergoes a polycondensation reaction under the action of a catalyst to obtain a mixed reaction solution, the catalyst is composed of a divalent nickel compound and an organic phosphine ligand, and the divalent nickel compound and the organic phosphine ligand The molar ratio is 1: (0.5～3);

The divalent nickel compound is nickel dichloride, nickel dibromide, nickel acetylacetonate, nickel acetate or nickel perchlorate;

The first halogenated aromatic Grignard reagent monomer has a structure of formula (I):

X ¹ -Q ¹ -MgX ² (I);

Wherein, X ¹ and X ² are independently selected from halogen;

Q ¹ is an aromatic group or a substituted aromatic group;

Adding a second halogenated aromatic Grignard reagent monomer into the mixed reaction liquid to undergo a polymerization reaction to obtain a second aromatic conjugated polymer;

The second halogenated aromatic Grignard reagent monomer has a structure of formula (II):

X ³ -Q ² -MgX ⁴ (II);

Wherein, X ³ and X ⁴ are independently selected from halogen;

Q ² is an aryl group or a substituted aryl group different from the above Q ¹ .

After the mixed reaction solution containing the conjugated homopolymer is prepared according to the method described in the above technical scheme, the second halogenated aromatic lattice having the structure of formula (II) is added to the mixed reaction solution containing the conjugated homopolymer Reagent monomer, continue to polymerize to obtain block copolymers.

In the present invention, the second halogenated aromatic Grignard reagent monomer having the structure of formula (II) has a similar structure, except that Q ² is different from Q ¹ .

The first halogenated aromatic Grignard reagent monomer undergoes a polycondensation reaction under the action of a catalyst to obtain a reaction solution containing the conjugated homopolymer. This process is the same as the technical solution described above, except that the polycondensation reaction The time is relatively short, preferably 2 min to 10 min, more preferably 3 min to 8 min.

After the polycondensation reaction is completed, the reaction is quenched with 5mol/L hydrochloric acid, and the second halogenated aromatic Grignard reagent monomer having the structure of formula (II) is added to the resulting reaction solution containing the conjugated homopolymer, After the conjugated homopolymer and the second halogenated aromatic Grignard reagent monomer having the structure of formula (II) are continuously polymerized, a block copolymer is obtained.

In the present invention, the molar ratio of the second halogenated aromatic Grignard reagent monomer to the catalyst is 1:(0.005-0.2), preferably 1:(0.01-0.18), more preferably 1:(0.1-0.15 ); the time of the polymerization reaction is 30 min to 120 min, more preferably 40 min to 100 min; the temperature of the polymerization reaction is preferably 10°C to 50°C, more preferably 20°C to 40°C.

After the polymerization reaction is completed, quench the reaction with 5mol/L hydrochloric acid aqueous solution, extract the resulting reaction mixture with chloroform, wash the organic layer obtained after extraction with saturated saline, dry over anhydrous magnesium sulfate, and remove the solvent After settling in methanol and filtering, the block copolymer was obtained.

After the block copolymer is obtained, the block copolymer is subjected to GPC analysis, and the results show that the number average molecular weight can be controlled by controlling the feed ratio of the catalyst and the polymerization monomer; the molecular weight distribution of the block copolymer is 1.15 to 1.50 , narrower.

In the present invention, the first halogenated aromatic Grignard reagent monomer having the structure of formula (I) is used as a raw material, and a chain transfer polycondensation reaction occurs under the catalysis of a catalyst composed of a divalent nickel compound and an organic phosphine ligand to obtain an aromatic Conjugated homopolymer. In the present invention, the catalyst is composed of a divalent nickel compound and an organic phosphine ligand. The preparation method is simple, and it has good solubility in solvents, and can simultaneously initiate the reaction of the polymerization chain. By controlling the reaction of the catalyst and the polymerization monomer The feed ratio can obtain aromatic conjugated homopolymer or aromatic conjugated block copolymer with controllable molecular weight and narrow molecular weight distribution. At the same time, the preparation method provided by the invention is simple and fast, the by-products of the reaction are less, and it is suitable for industrial production. In addition, after the aromatic conjugated homopolymer is obtained, a second halogenated aromatic Grignard monomer that is similar in structure but different from the first halogenated aromatic Grignard reagent monomer is added to it, and the block copolymerization can be obtained after continuing the reaction. materials, thereby increasing the types and applications of conjugated copolymers.

In order to further illustrate the present invention, the aromatic conjugated polymer provided by the present invention is described in detail below in conjunction with examples.

The preparation of embodiment 1～4 catalyst

At room temperature, under the protection of an inert gas, mix 10.3 mg of anhydrous nickel acetylacetonate with 10.5 mg of triphenylphosphine, 15.9 mg of 1,3-di(diphenylphosphino)ethane, 16.5 mg of 1,3 -bis(diphenylphosphino)propane or 22.2 milligrams of 1,1'-bis(diphenylphosphino)ferrocene were mixed to obtain a mixture, and then 2 milliliters of tetrahydrofuran were added to dissolve the mixture, so that the obtained anhydrous The concentrations of the nickel acetylacetonate and the organic phosphine ligand are both 0.02 mol/L; the obtained solutions are stirred for 30 minutes at room temperature to obtain catalysts respectively.

The preparation of embodiment 52-bromo-7-magnesium chloride-9,9-dioctylfluorene

Under the protection of inert gas at -20°C, 595 mg of 2-bromo-7-iodo-9,9-dioctylfluorene was dissolved in 20 ml of tetrahydrofuran solution to obtain 2-bromo-7-iodo with a concentration of 0.05 mol/L -9,9-dioctylfluorene solution, add 42 mg of anhydrous lithium chloride and 0.59 milliliters of 1.7 mol/L iso The tetrahydrofuran solution of propylmagnesium chloride was stirred at -20°C for 1 hour, and then 0.5 ml of the reaction solution was taken out and quenched by adding 10 ml of 5 mol/L hydrochloric acid to obtain 2-bromo-7-magnesium chloride-9,9-di Octylfluorene.

The gas chromatography-mass spectrometry analysis of the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene showed that the conversion rate was 95%.

Example 6

Under the protection of an inert gas, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 1 to make the The molar ratio of the catalyst to 2-bromo-7magnesium chloride-9,9-dioctylfluorene is 2:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and 10 milliliters of hydrochloric acid aqueous solution of 5 mol/L is added Quenching the reaction, extracting the resulting reaction mixture with chloroform, then washing the extracted organic layer with saturated brine, drying over anhydrous magnesium sulfate, removing the solvent, and dropping the obtained reaction product solution into stirring methanol for After settling, the volume ratio of the reaction product solution to methanol was 1:20. After filtration, 282 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained with a yield of 73%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 6600, and its molecular weight distribution index was 1.60.

Example 7

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 2 to make the catalyst The molar ratio of 2-bromo-7 magnesium chloride-9,9-dioctylfluorene is 2:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 254 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 65%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 22000, and its molecular weight distribution index was 1.40.

Example 8

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 3 to make the catalyst The molar ratio of 2-bromo-7 magnesium chloride-9,9-dioctylfluorene is 2:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 271 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 70%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 30000, and its molecular weight distribution index was 1.18.

Example 9

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 4 to make the catalyst The molar ratio of 2-bromo-7 magnesium chloride-9,9-dioctylfluorene is 2:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 200 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 52%.

After the poly(9,9-dioctylfluorene) is obtained, it is tested by GPC, and the result shows that its number average molecular weight is less than 1200.

Example 10

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 3 to make the catalyst The molar ratio of 2-bromo-7 magnesium chloride-9,9-dioctylfluorene is 1:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 291 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 75%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 60000, and its molecular weight distribution index was 1.20.

Example 11

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 3 to make the catalyst The molar ratio of 2-bromo-7 magnesium chloride-9,9-dioctylfluorene is 3:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 268 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 69%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 19000, and its molecular weight distribution index was 1.15.

Example 12

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 3 to make the catalyst The molar ratio of 2-bromo-7magnesium chloride-9,9-dioctylfluorene is 6:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 287 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 74%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 8900, and its molecular weight distribution index was 1.17.

Example 13

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, add 1.0 ml of the tetrahydrofuran solution of the catalyst prepared in Example 3 to make the catalyst The molar ratio of 2-bromo-7magnesium chloride-9,9-dioctylfluorene is 10:100, the reaction system is transferred to an ice-water bath, stirred for 0.5 hours, and quenched by adding 10 ml of aqueous hydrochloric acid with a concentration of 5 mol/L reaction, the obtained reaction mixture was extracted with chloroform, and then the extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into stirring methanol for precipitation after removing the solvent, The volume ratio of the reaction product solution to methanol was 1:20, and 198 mg of yellow flocculent poly(9,9-dioctylfluorene) was obtained after filtration with a yield of 51%.

After the poly(9,9-dioctylfluorene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 2800, and its molecular weight distribution index was 1.24.

Example 14

At room temperature and under the protection of an inert atmosphere, dissolve 326 mg of 2,5-dibromo-3-hexylthiophene in 10 ml of anhydrous tetrahydrofuran so that the concentration of 2,5-dibromo-3-hexylthiophene is 0.1 mol/liter, and add 42 milligrams of anhydrous lithium chloride and 0.64 milliliters of tetrahydrofuran solutions with a concentration of 1.57 mol/liter of tert-butylmagnesium chloride were stirred at room temperature for 24 hours, then 0.5 milliliters of the reaction solution was taken out and quenched by adding 10 milliliters of 5 mol/liter hydrochloric acid , to obtain 2,5-dibromo-3-hexylthiophene. The gas chromatography-mass spectrometry analysis of the 2,5-dibromo-3-hexylthiophene showed that the conversion rate was 93%.

Example 15

Under the protection of an inert atmosphere, in the reaction vessel equipped with the 2,5-dibromo-3-hexylthiophene prepared in Example 14, add 1.0 milliliters of the tetrahydrofuran solution of the catalyst prepared in Example 3 to make the catalyst and 2-bromo-7 Magnesium chloride-9, the mol ratio of 9-dioctylfluorene is 2: 100, stirs 1 hour at room temperature, adds 10 milliliters of concentrations and is the hydrochloric acid aqueous solution quenching reaction of 5mol/L, the reaction mixture obtained is extracted with chloroform, then The extracted organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After removing the solvent, the obtained reaction product solution was dropped into stirring methanol for sedimentation. The volume ratio of the reaction product solution to methanol was 1: 20. After filtration, 105 mg of purple-red floc poly(3-hexylthiophene) was obtained, with a yield of 63%.

After the poly(3-hexylthiophene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 9600, and its molecular weight distribution index was 1.24.

Example 16

At room temperature, under the protection of an inert atmosphere, 436 mg of 1,4-dibromo-2,5-dihexyloxybenzene was dissolved in 10 ml of anhydrous tetrahydrofuran to make 1,4-dibromo-2,5-dihexyl The concentration of oxybenzene is 0.1 mol/liter, adding 42 milligrams of anhydrous lithium chloride and 0.64 milliliters of concentration is the tetrahydrofuran solution of isopropylmagnesium chloride of 0.59 mol/liter, stirring at room temperature for 24 hours, then taking out 0.2 milliliters of reaction solution, Add 5 ml of 5 mol/L hydrochloric acid to quench to obtain the Grignard reagent of 1-bromo-4-magnesium chloride-2,5-dihexyloxybenzene. The Grignard reagent of 1-bromo-4-magnesium chloride-2,5-dihexyloxybenzene was analyzed by gas chromatography-mass spectrometry, and the results showed that the conversion rate was 76%.

Example 17

Under the protection of an inert atmosphere, in the reaction vessel equipped with the Grignard reagent of 1-bromo-4-magnesium chloride-2,5-dihexyloxybenzene prepared in Example 16, add 1.0 ml of the catalyst prepared in Example 3 in tetrahydrofuran Solution, make the mol ratio of the Grignard reagent of catalyst and 1-bromo-4-magnesium chloride-2,5-dihexyloxybenzene be 2: 100, stir at room temperature for 2 hours, add 10 milliliters of concentration and be the hydrochloric acid aqueous solution of 5mol/L Quenching the reaction, extracting the resulting reaction mixture with chloroform, then washing the extracted organic layer with saturated brine, drying over anhydrous magnesium sulfate, removing the solvent, and dropping the obtained reaction product solution into stirring methanol for After sedimentation, the volume ratio of the reaction product solution to methanol was 1:20, and 252 mg of white powdery solid poly(2,5-dihexyloxybenzene) was obtained after filtration, with a yield of 47%.

After the poly(2,5-dihexyloxybenzene) was obtained, it was tested by GPC, and the result showed that its number average molecular weight was 8300, and its molecular weight distribution index was 1.30.

Example 18

Dissolve 506 mg of N-(4-bromophenyl)-N-(4-iodophenyl)-N-(4-butylaniline) in 10 ml of anhydrous tetrahydrofuran at -20°C under the protection of an inert atmosphere , so that the concentration of N-(4-bromophenyl)-N-(4-iodophenyl)-N-(4-butylaniline) is 0.1 mol/L, add 42 mg of anhydrous lithium chloride and 0.59 ml The tetrahydrofuran solution of isopropylmagnesium chloride with a concentration of 1.7 mol/L was stirred at -20°C for 1 hour, then 0.2 ml of the reaction solution was taken out and quenched by adding 5 ml of 5 mol/L hydrochloric acid to obtain N-(4-bromo Phenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline). Gas chromatography-mass spectrometry analysis of the N-(4-bromophenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline) showed that the conversion rate was 97%.

Example 19

Under the protection of an inert atmosphere, add 1.0 The tetrahydrofuran solution of the catalyzer that milliliter embodiment 3 prepares makes the mol ratio of catalyst and N-(4-bromophenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline) be 4: 100 , stirred in an ice-water bath for 1 hour, adding 10 milliliters of aqueous hydrochloric acid with a concentration of 5 mol/L to quench the reaction, extracting the resulting reaction mixture with chloroform, then washing the organic layer obtained by the extraction with saturated brine, and drying over anhydrous magnesium sulfate , after removing the solvent, the reaction product solution obtained was dropped into the stirring methanol for sedimentation, the volume ratio of the reaction product solution and methanol was 1: 20, and after filtration, 252 mg of yellow powdery solid poly(N-( 4-butylphenyl) diphenylamine), the yield was 74%.

After obtaining the poly(2,5-dihexyloxybenzene), it was tested by GPC, and the result showed that its number average molecular weight was 6200, and its molecular weight distribution index was 1.50.

Example 20

Under the protection of an inert atmosphere, in the reaction vessel equipped with 10 milliliters of 0.05 mol/liter, the THF solution of 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, press the catalyst and 2- Bromo-7-magnesium chloride-9,9-dioctylfluorene molar ratio 4:100 was added to 1.0 ml of the THF solution of the catalyst prepared in Example 3 at 0.02 mol/liter, and after stirring for 5 minutes under ice-water bath conditions, 3 ml of the reaction mixture was taken out solution was added to 10 ml of hydrochloric acid with a concentration of 5 mol/liter to quench, the resulting reaction mixture was extracted with chloroform, and then the organic layer obtained by the extraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After removing the solvent, the obtained The reaction product solution was dropped into the stirring methanol for sedimentation, the volume ratio of the reaction product solution and methanol was 1:20, after filtration, a yellow solid poly(9,9-dioctylfluorene) was obtained, which was subjected to GPC test, the result shows, its number average molecular weight is 15000, and molecular weight distribution index is 1.19.

Add 8 ml of 0.1 mol/L Grignard reagent of 2,5-dibromo-3-hexylthiophene prepared in Example 14 to the remaining reaction mixture, rise to room temperature, and react under stirring for 40 minutes, then add 20 ml of mol/liter of hydrochloric acid to quench the reaction, the obtained reaction mixture was extracted with chloroform, then the organic layer obtained by the extraction was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into the stirring Settled in the methanol that was deposited, the volume ratio of the reaction product solution to methanol was 1:20, and after filtration, 169 mg of purple-red floc poly(9,9-dioctylfluorene)-b-poly(3- Hexylthiophene), yield 63%. After obtaining poly(9,9-dioctylfluorene)-b-poly(3-hexylthiophene), it was tested by GPC, and the results showed that its number average molecular weight was 21000, and its molecular weight distribution index was 1.27.

Example 21

Under the protection of an inert atmosphere, in the reaction vessel equipped with 10 milliliters of 0.05 mol/liter, the THF solution of 2-bromo-7-magnesium chloride-9,9-dioctylfluorene prepared in Example 5, press the catalyst and 2- Bromo-7-magnesium chloride-9,9-dioctylfluorene molar ratio 2:100 was added to 0.5 ml of the THF solution of the catalyst prepared in Example 3 at 0.02 mol/liter, stirred for 5 minutes under ice-water bath conditions, and 3 ml of reaction mixture was taken out solution was added to 10 ml of hydrochloric acid with a concentration of 5 mol/liter to quench, the resulting reaction mixture was extracted with chloroform, and then the organic layer obtained by the extraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After removing the solvent, the obtained The reaction product solution was dropped into the stirring methanol for sedimentation, the volume ratio of the reaction product solution and methanol was 1:20, after filtration, a yellow solid poly(9,9-dioctylfluorene) was obtained, which was subjected to GPC test, the result shows, its number average molecular weight is 30000, and molecular weight distribution index is 1.25.

Add 4 ml of 0.1 mol/L Grignard reagent of 2,5-dibromo-3-hexylthiophene prepared in Example 14 to the remaining reaction mixture, rise to room temperature, and react under stirring for 40 minutes, then add 20 ml of 5 mol/liter of hydrochloric acid to quench the reaction, the obtained reaction mixture was extracted with chloroform, then the organic layer obtained by the extraction was washed with saturated brine, dried over anhydrous magnesium sulfate, and the obtained reaction product solution was dropped into the stirring Settled in methanol, the volume ratio of the reaction product solution to methanol was 1:20, and filtered to obtain 144 mg of purple-red floc poly(9,9-dioctylfluorene)-b-poly(3- Hexylthiophene), yield 71%. After obtaining poly(9,9-dioctylfluorene)-b-poly(3-hexylthiophene), it was tested by GPC, and the results showed that its number average molecular weight was 37000, and its molecular weight distribution index was 1.32.

It can be seen from the above examples that the preparation method provided by the present invention can obtain conjugated homopolymers and block copolymers, the molecular weight of which is controllable and the molecular weight distribution is relatively narrow.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (9)

1. a preparation method for aromatic conjugated polymer, comprises the following steps:

Polycondensation is there is in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer, obtain aromatic conjugated polymer, described catalyzer is made up of acetylacetonate nickel and organophosphorus ligand, and the mol ratio of described acetylacetonate nickel and described organophosphorus ligand is 1:(0.5 ~ 3);

Described first halogenated aromatic Grignard reagent monomer has formula (I) structure:

X ¹-Q ¹-MgX ²(I)；

Wherein, X ¹, X ²independent selected from halo;

Q ¹for aromatic base or substituted aromatic base;

Described catalyzer is prepared according to following steps:

Acetylacetonate nickel and organophosphorus ligand are mixed in tetrahydrofuran (THF), after stirring, obtains catalyzer;

The temperature of described stirring is-20 DEG C ~ 30 DEG C; Churning time is 1min ~ 120min.

2. method according to claim 1, is characterized in that, described organophosphorus ligand has formula (III) or formula (IV) structure:

Wherein, R ¹, R ², R ³, R ⁵, R ⁶, R ⁷, R ⁸independently selected from alkyl, phenyl or substituted-phenyl;

R ⁴for ferrocenyl or carbonatoms are the straight chained alkyl of 1 ~ 4.

3. method according to claim 2, it is characterized in that, described organophosphorus ligand is triphenylphosphine, 1,2-bis-(diphenylphosphino) ethane, 1,3-bis-(diphenylphosphino) propane or two (diphenylphosphine) ferrocene of 1,1'-.

4. method according to claim 1, is characterized in that, described Q ¹be selected from formula (11) ~ (14) structure any one:

Wherein, R ⁹for alkyl;

R ¹⁰, R ¹¹independently selected from alkyl;

R ¹², R ¹³independently selected from alkoxyl group;

R ¹⁴for alkyl.

5. method according to claim 1, is characterized in that, the mol ratio of described catalyzer and described first halogenated aromatic Grignard reagent monomer is (0.001 ~ 0.2): 1.

6. method according to claim 1, is characterized in that, the temperature of described polycondensation is-5 DEG C ~ 30 DEG C, and the time of described polycondensation is 30min ~ 120min.

7. a preparation method for aromatic conjugated polymer, comprises the following steps:

Polycondensation is there is in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer, obtain mixed reaction solution, described catalyzer is made up of acetylacetonate nickel and organophosphorus ligand, and the mol ratio of described acetylacetonate nickel and organophosphorus ligand is 1:(0.5 ~ 3);

Described first halogenated aromatic Grignard reagent monomer has formula (I) structure:

X ¹-Q ¹-MgX ²(I)；

Wherein, X ¹, X ²independent selected from halo;

Q ¹for aromatic base or substituted aromatic base;

In described mixed reaction solution, add the second halogenated aromatic Grignard reagent monomer, polymerization reaction take place, obtains the second aromatic conjugated polymer;

Described second halogenated aromatic Grignard reagent monomer has formula (II) structure:

X ³-Q ²-MgX ⁴(II)；

Wherein, X ³, X ⁴independent selected from halo;

Q ²for being different from described Q ¹aromatic base or substituted aromatic base;

Described catalyzer is prepared according to following steps:

Acetylacetonate nickel and organophosphorus ligand are mixed in tetrahydrofuran (THF), after stirring, obtains catalyzer;

The temperature of described stirring is-20 DEG C ~ 30 DEG C; Churning time is 1min ~ 120min.

8. method according to claim 7, is characterized in that, the mol ratio of described second halogenated aromatic grignard reagent monomer and described catalyzer is 1:(0.005 ~ 0.2).

9. method according to claim 7, is characterized in that, the temperature of described polyreaction is 10 DEG C ~ 50 DEG C, and the time of described polyreaction is 0.5h ~ 2h.