CN102504209A - Preparation method of aromatic conjugated polymer - Google Patents
Preparation method of aromatic conjugated polymer Download PDFInfo
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Abstract
The invention provides a preparation method of an aromatic conjugated polymer, comprising the following steps of subjecting a first halogenated aromatic Grignard reagent monomer to polycondensation reaction under the catalysis of a catalyst to obtain the aromatic conjugated polymer. The catalyst comprises a nickelous compound and an organic phosphine ligand which are at the molar ratio of 1: (0.5-3), wherein the nickelous compound is nickel dichloride, nckel bromide, nickel acetylacetonate, nickel acetate or nickelous perchlorate. The first halogenated aromatic Grignard reagent monomer has the following structural formula (I): X1-Q1-MgX2 (I), wherein the X1 and the X2 are independently selected from halogen, and the Q1 is the aromatic base or substituted aromatic base. The catalyst provided by the invention is easy to prepare and can be well dissolved a solvent to lead to the polymerase chain reaction at the same time to obtain the aromatic conjugated homopolymer or aromatic conjugated block copolymer with controllable molecular weight and narrow molecular weight distribution.
Description
Technical field
The present invention relates to technical field of polymer, relate in particular to a kind of preparation method of aromatic conjugated polymkeric substance.
Background technology
Electricity and optical properties that conjugated polymers not only has metal, semi-conductor and had; And have that polymkeric substance is distinctive, good processing properties and mechanical property, be widely used in luminous demonstration, solar-energy photo-voltaic cell, thin film transistor, chemistry and fields such as biosensor, polymer light-emitting diode, overall plastic diode laser, overall plastic photovoltaic cell, luminescent electrochemical cell, photomodulator and opticcoupler.
Conjugated polymers is general to adopt method preparation transition metal-catalyzed, step-reaction polymerization, and still, this method is long reaction time not only, and the conjugated polymers molecular weight that generates is difficult to control, and molecular weight distributing index is generally greater than 2.Shift the chain type polycondensation and be a kind of compound method of novel conjugated polymers, have that speed of response is fast, advantages such as molecular weight of product is controlled relatively, MWD relative narrower (Chinese science chemistry, Sci.China.Chem.2010,53,1620).
When adopt shifting the chain type polycondensation and prepare conjugated polymers, prior art generally adopts the title complex of nickelous as catalyzer, is that the USP of US6166172 discloses a kind of with Ni (dppp) Cl like the patent No.
2As the method for the synthetic Polythiophene of catalyst 2-bromo-5-magnesium chloride-3-hexyl thiophene polymerization reaction take place, the Polythiophene zone that obtains is comparatively regular, the MWD relative narrower, and wherein, dppp is 1, the two diphenylphosphino propane of 3-; It is a kind of with Ni (dppe) Cl that the patent No. is that the USP of US1010099823 discloses
2Be catalyst 1-bromine 4-magnesium chloride-2,5-two hexyloxy benzene generation polymerizations prepare the method for polyphenyl, the MWD relative narrower of the polyphenyl that obtains, and wherein, dppe is 1, the two diphenylphosphino ethane of 3-; The patent No. is that the USP of US20080146754 discloses a kind of employing Ni (dppb) Cl
2Catalysis 2-bromo-5-magnesium chloride-N-dodecyl pyrroles polymerization reaction take place prepares the method for polypyrrole, and wherein, dppb is 1, the two diphenylphosphino butane of 3-; Publication number is that the Chinese patent of CN101092475A discloses the method that a kind of preparation gathers fluorenes, at first with 2, and 7-dihalo-9; 9-dialkyl group fluorenes is a raw material; In the presence of inorganic electrolyte,, obtain polymerization single polymerization monomer 2-halogen-7 magnesium halide-9,9-dialkyl group fluorenes with the organomagnesium reagent reaction; Polymerization reaction take place under the katalysis of nickelous composition catalyst is gathered (9,9-dialkyl group fluorenes) then.
But; Because the title complex of nickelous belongs to heterogeneous catalyst; Its solvability in organic solvent is relatively poor; So cause the initiation of polymeric chain not carried out at one time, thereby influence the molecular weight and the MWD of polymerisate, make the molecular weight of the polymerisate that obtains uncontrollable, the MWD broad.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of aromatic conjugated polymkeric substance, the aromatic conjugated polymericular weight that preparation method provided by the invention obtains is controlled, MWD is narrower.
The invention provides a kind of preparation method of aromatic conjugated polymkeric substance, may further comprise the steps:
Polycondensation takes place in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain aromatic conjugated polymkeric substance; Said catalyzer is made up of nickelous compound and organophosphorus ligand, and the mol ratio of said nickelous compound and said organophosphorus ligand is 1: (0.5～3);
Said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate;
The said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen;
Q
1Be aromatic base or substituted aromatic base.
Preferably, said nickelous compound is an acetylacetonate nickel.
Preferably, said organophosphorus ligand has formula (III) or formula (IV) structure:
Wherein, R
1, R
2, R
3, R
5, R
6, R
7, R
8Be independently selected from alkyl, phenyl or substituted-phenyl;
R
4It for ferrocenyl or carbonatoms 1～4 straight chained alkyl.
Preferably, said organophosphorus ligand is a triphenylphosphine, 1,3-two (diphenylphosphino) ethane, 1, and 3-two (diphenylphosphino) propane or 1,1 '-two (diphenylphosphine) ferrocene.
Preferably, said catalyzer prepares according to following steps:
Nickelous compound and organophosphorus ligand are mixed in organic solvent, obtain catalyzer after the stirring.
Preferably, the temperature of said stirring is-20 ℃～30 ℃; Churning time is 1min～120min.
Preferably, said Q
1Be selected from formula (11)～(14) structure any one:
Wherein, R
9Be alkyl;
R
10, R
11Be independently selected from alkyl;
R
12, R
13Be independently selected from alkoxyl group;
R
14Be alkyl.
Preferably, said catalyzer and the monomeric mol ratio of the said first halogenated aromatic Grignard reagent are (0.001～0.2): 1.
Preferably, the temperature of said polycondensation is-5 ℃～30 ℃, and the time of said polycondensation is 30min～120min.
The present invention also provides a kind of preparation method of aromatic conjugated polymkeric substance, may further comprise the steps:
Polycondensation takes place in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain mixed reaction solution; Said catalyzer is made up of nickelous compound and organophosphorus ligand, and the mol ratio of said nickelous compound and organophosphorus ligand is 1: (0.5～3);
Said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate;
The said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen;
Q
1Be aromatic base or substituted aromatic base;
In said mixed reaction solution, add the second halogenated aromatic Grignard reagent monomer, polymerization reaction take place obtains the second aromatic conjugated polymkeric substance;
The said second halogenated aromatic Grignard reagent monomer has formula (II) structure:
X
3-Q
2-MgX
4(II)；
Wherein, X
3, X
4Be independently selected from halogen;
Q
2For being different from said Q
1Aromatic base or substituted aromatic base.
Preferably, the mol ratio of said second halogenated aromatic grignard reagent monomer and said catalyzer is 1: (0.005～0.2).
Preferably, the temperature of said polyreaction is 10 ℃～50 ℃, and the time of said polyreaction is 0.5h～2h.
Compared with prior art; The present invention is a raw material with the first halogenated aromatic Grignard reagent monomer with formula (I) structure; Chain type taking place under the katalysis of the catalyzer of being made up of nickelous compound and organophosphorus ligand shift polycondensation, obtains aromatic conjugated homopolymer.In the present invention; Said catalyzer is made up of nickelous compound and organophosphorus ligand; The preparation method is simple; And in solvent, have good solubility, the reaction of initiated polymerization chain simultaneously, the feed ratio through control catalyst and polymerization single polymerization monomer can obtain aromatic conjugated homopolymer or the aromatic conjugated segmented copolymer that molecular weight is controlled and MWD is narrower.Simultaneously, the present invention provides the preparation method simple, quick, and the by product of reaction is less, is suitable for suitability for industrialized production.In addition; After obtaining aromatic conjugated homopolymer; To wherein adding similar but be different from the monomeric second halogenated aromatic Grignard reagent monomer of the first halogenated aromatic Grignard reagent, continue to obtain segmented copolymer after the reaction, thereby increase the kind and the application of conjugated copolymer.
Embodiment
The invention provides a kind of preparation method of aromatic conjugated polymkeric substance, may further comprise the steps:
Polycondensation takes place in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain aromatic conjugated polymkeric substance; Said catalyzer is made up of nickelous compound and organophosphorus ligand, and the mol ratio of said nickelous compound and said organophosphorus ligand is 1: (0.5～3);
Said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate;
The said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen;
Q
1Be aromatic base or substituted aromatic base.
The present invention is a raw material with the first halogenated aromatic Grignard reagent monomer with formula (I) structure, chain type takes place under the katalysis of the catalyzer of being made up of nickelous compound and organophosphorus ligand shift polycondensation, obtains aromatic conjugated polymkeric substance.In the present invention; Said catalyzer is made up of nickelous compound and organophosphorus ligand; The preparation method is simple; And in solvent, have good solubility, the reaction of initiated polymerization chain simultaneously, the feed ratio through control catalyst and polymerization single polymerization monomer can obtain aromatic conjugated homopolymer or the aromatic conjugated segmented copolymer that molecular weight is controlled and MWD is narrower.
The present invention is a raw material with the first halogenated aromatic Grignard reagent monomer, adds the catalyzer of being made up of the compound and the organophosphorus ligand of nickelous, and polycondensation takes place, and obtains aromatic conjugated homopolymer.
In the present invention, the said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen, be preferably chlorine or bromine;
Q
1Be aromatic base or substituted aromatic base, be preferably selected from any one structure in formula (11)～(14):
Wherein, R
9Be alkyl, be preferably the alkyl that contains 10 following carbon atoms;
R
10, R
11Be independently selected from alkyl, be preferably the alkyl that contains 10 following carbon atoms;
R
12, R
13Be independently selected from alkoxyl group, be preferably the alkoxyl group that contains 10 following carbon atoms;
R
14Be alkyl, be preferably the alkyl that contains 10 following carbon atoms.
The present invention does not have particular restriction to the monomeric source of the said first halogenated aromatic Grignard reagent, preferably according to following method preparation:
In dihalo fragrant monomer solution, add organomagnesium reagent solution generation substitution reaction, obtain halogenated aromatic Grignard reagent monomer, said dihalo fragrant monomer has the formula V structure:
X
1-Q
1-X′(V)；
Wherein, X
1, X ' is independently selected from halogen, Q
1Be aromatic base or substituted aromatic base;
Said organomagnesium reagent has formula (VI) structure:
R′MgX
2(VI)；
Wherein, R ' is alkyl or aromatic base, X
2Be halogen.
Have the dihalo fragrant monomer of formula V structure, said X
1, X ' is independently selected from halogen, is preferably chlorine or bromine; Said Q
1Be aromatic base or substituted aromatic base, be preferably selected from any one structure in formula (11)～(14), that is to say; The dihalo fragrant monomer is preferably 2,5-dihalo 3-alkylthrophene, 2,7-dihalo-9; 9-dialkyl group fluorenes, 1; 4-dihalo-2,5-dialkoxy benzene or N, N-two (4-halogen phenyl)-N-(4-alkyl benzene amine).
In the organomagnesium reagent with formula (VI) structure, R ' is alkyl or aromatic base, is preferably methyl, ethyl, propyl group, sec.-propyl, tertiary butyl, propenyl or phenyl; X
2Be halogen, be preferably chlorine or bromine.
At first under inert atmosphere protection; The dihalo fragrant monomer that will have the formula V structure is dissolved in the organic solvent; Add organomagnesium reagent solution then with formula (VI) structure, substitution reaction takes place after, the first halogenated aromatic Grignard reagent monomer of (I) structure that obtains having formula.Said organic solvent can be THF; The concentration of said dihalo fragrant monomer is preferably 0.05mol/L～0.1mol/L; 0.06mol/L～0.08mol/L more preferably is preferably under-20 ℃～40 ℃ said dihalo fragrant monomer is dissolved in the organic solvent.The concentration of said organomagnesium reagent solution is preferably 1mol/L～3mol/L, more preferably 1.5mol/L～2.5mol/L.The monomeric mol ratio of said organomagnesium reagent and halogenated aromatic is preferably 1: (0.1-1.5), and more preferably 1: (0.5-1).
In the present invention; Substitution reaction preferably takes place in said dihalo fragrant monomer and said organomagnesium reagent under the condition that inorganic electrolyte exists; Said inorganic electrolyte is preferably lithium salts, and more preferably tetrafluoro boronation lithium, lithium perchlorate, lithium chloride or lithium iodide most preferably are lithium chloride.The mol ratio of said inorganic electrolyte and said dihalo fragrant monomer is preferably (0.5～1.5): 1, more preferably (0.8～1.2): 1.In the present invention, the time of said substitution reaction is 1-50 hour, is preferably 1-35 hour, more preferably 1-24 hour.After reaction finishes, the halogenated aromatic Grignard reagent monomer of (I) structure that obtains having formula, transformation efficiency is preferably 75%～95%, and more preferably 80%～90%.
Behind the first halogenated aromatic Grignard reagent monomer of (I) structure that obtains having formula, the said first halogenated aromatic Grignard reagent monomer takes place to shift the chain type polycondensation under the effect of catalyzer, obtains the conjugation homopolymer.In the present invention; Said catalyzer is made up of nickelous compound and organophosphorus ligand; For the preparation method simple; And in solvent, have good solubility, the reaction of initiated polymerization chain simultaneously, thus can obtain aromatic conjugated homopolymer or the aromatic conjugated segmented copolymer that molecular weight is controlled and MWD is narrower.
In catalyzer provided by the invention, said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate, is preferably acetylacetonate nickel.Said nickelous compound can be anhydrous compound, also can be hydrated compound, like anhydrous acetylacetonate nickel, six hydration Nickel Chlorides, three hydration Nickel Bromides etc., is preferably anhydrous compound.
In catalyzer provided by the invention, said organophosphorus ligand preferably has formula (III) or formula (IV) structure:
Wherein, R
1, R
2, R
3, R
5, R
6, R
7, R
8Be independently selected from alkyl, phenyl or substituted-phenyl;
R
4It for ferrocenyl or carbonatoms 1～4 straight chained alkyl.
In said organophosphorus ligand, have the monodentate phosphine ligand that is of formula (III) structure, include but not limited to triphenylphosphine etc.; Have the bidentate phosphine ligands that is of formula (IV) structure, include but not limited to 1,3-two (diphenylphosphino) ethane (dppe), 1; 3-two (diphenylphosphino) propane (dppp) and 1; 1 '-two (diphenylphosphine) ferrocene (dppf) etc., be preferably 1,3-two (diphenylphosphino) propane (dppp).
In said catalyzer, the mol ratio of said nickelous compound and said organophosphorus ligand is 1: (0.5～3) is preferably 1: (0.7～2), more preferably 1: (0.8～1.5).
Said catalyzer is preferably according to following method preparation:
Nickelous compound and organophosphorus ligand are mixed in organic solvent, obtain catalyzer after the stirring.
At first nickelous compound and organophosphorus ligand are mixed, add organic solvent dissolution, obtain catalyzer after the stirring.In the process of preparation catalyzer, said organic solvent includes but not limited to ether, THF (THF), dioxane, benzene and toluene etc., is preferably THF.
Add organic solvent nickelous compound and organophosphorus ligand are dissolved in the solution that obtains, said nickelous compound concentrations is preferably 0.005mol/L～0.1mol/L, more preferably 0.01mol/L～0.08mol/L; The concentration of said organophosphorus ligand is preferably 0.005mol/L～0.1mol/L, more preferably 0.01mol/L～0.08mol/L.
In the present invention, when stirring after nickelous compound and organophosphorus ligand mixed in organic solvent, the temperature of said stirring is preferably-20 ℃～30 ℃, more preferably-10 ℃～25 ℃; The time of said stirring is preferably 1min～120min, and more preferably 20min～100min most preferably is 30min～60min.
The first halogenated aromatic Grignard reagent monomer with formula (I) structure takes place to shift the chain type polycondensation under the effect of catalyzer, specifically comprises:
Under protection of inert gas, in the said first halogenated aromatic Grignard reagent monomer, add catalyst solution, take place to obtain the conjugation homopolymer after the polycondensation.Said catalyst solution is preferably the tetrahydrofuran solution of catalyzer.Said catalyzer and the monomeric mol ratio of the said first halogenated aromatic Grignard reagent are (0.001～0.2): 1, more preferably (0.005～0.15): 1, more preferably (0.01～0.1): 1.The temperature of said polycondensation is preferably-5 ℃～30 ℃, more preferably 0 ℃～25 ℃; The time of said polycondensation is preferably 30min～120min, more preferably 40min～100min.
After reaction finishes; With the hydrochloric acid cancellation of 5mol/L reaction, the reaction product that adopts chloroform extraction to obtain, with the organic layer that obtains after the extraction with saturated common salt water washing, anhydrous magnesium sulfate drying, removal solvent after sedimentation in methyl alcohol; After the filtration, obtain the conjugation homopolymer.
After obtaining the conjugation homopolymer, said conjugation homopolymer is carried out gpc analysis, the result shows that its number-average molecular weight is 6200～30000, can carry out the control of number-average molecular weight through the feed ratio of control catalyst and polymerization single polymerization monomer; Its MWD is 1.15 to 1.50, and is narrower.
The present invention also provides a kind of preparation method of aromatic conjugated polymkeric substance, may further comprise the steps:
Polycondensation takes place in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain mixed reaction solution; Said catalyzer is made up of nickelous compound and organophosphorus ligand, and the mol ratio of said nickelous compound and organophosphorus ligand is 1: (0.5～3);
Said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate;
The said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen;
Q
1Be aromatic base or substituted aromatic base;
In said mixed reaction solution, add the second halogenated aromatic Grignard reagent monomer, polymerization reaction take place obtains the second aromatic conjugated polymkeric substance;
The said second halogenated aromatic Grignard reagent monomer has formula (II) structure:
X
3-Q
2-MgX
4(II)；
Wherein, X
3, X
4Be independently selected from halogen;
Q
2For being different from said Q
1Aromatic base or substituted aromatic base.
After preparing the mixed reaction solution that contains the conjugation homopolymer according to the described method of technique scheme; In the said mixed reaction solution that contains the conjugation homopolymer, add the second halogenated aromatic Grignard reagent monomer, proceed to obtain segmented copolymer after the polyreaction with formula (II) structure.
In the present invention, the said second halogenated aromatic Grignard reagent monomer with formula (II) structure has similar structure, and difference is Q
2With Q
1Different.
Polycondensation takes place in the said first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain containing the reaction solution of said conjugation homopolymer; This process is identical with technical scheme mentioned above; Difference is that the time of polycondensation is shorter, is preferably 2min～10min, more preferably 3min～8min.
After polycondensation finishes; Hydrochloric acid cancellation reaction with 5mol/L; In the reaction solution that contains said conjugation homopolymer that obtains, add the second halogenated aromatic Grignard reagent monomer simultaneously with formula (II) structure; Said conjugation homopolymer obtains segmented copolymer after proceeding polyreaction with the second halogenated aromatic Grignard reagent monomer with formula (II) structure.
In the present invention, the mol ratio of said second halogenated aromatic grignard reagent monomer and said catalyzer is 1: (0.005～0.2) is preferably 1: (0.01～0.18) more preferably 1: (0.1～0.15); The time of said polyreaction is 30min～120min, more preferably 40min～100min; The temperature of said polyreaction is preferably 10 ℃～50 ℃, more preferably 20 ℃～40 ℃.
After polyreaction finishes; Aqueous hydrochloric acid cancellation reaction with 5mol/L; With chloroform the reaction mixture that obtains is extracted, with saturated aqueous common salt to extraction after the organic layer that obtains wash, sedimentation in methyl alcohol behind the anhydrous magnesium sulfate drying, removal solvent, obtain segmented copolymer after filtering.
After obtaining segmented copolymer, said segmented copolymer is carried out gpc analysis, the result shows, can carry out the control of number-average molecular weight through the feed ratio of control catalyst and polymerization single polymerization monomer; The MWD of segmented copolymer is 1.15 to 1.50, and is narrower.
The present invention is a raw material with the first halogenated aromatic Grignard reagent monomer with formula (I) structure, chain type takes place under the katalysis of the catalyzer of being made up of nickelous compound and organophosphorus ligand shift polycondensation, obtains aromatic conjugated homopolymer.In the present invention; Said catalyzer is made up of nickelous compound and organophosphorus ligand; The preparation method is simple; And in solvent, have good solubility, the reaction of initiated polymerization chain simultaneously, the feed ratio through control catalyst and polymerization single polymerization monomer can obtain aromatic conjugated homopolymer or the aromatic conjugated segmented copolymer that molecular weight is controlled and MWD is narrower.Simultaneously, the present invention provides the preparation method simple, quick, and the by product of reaction is less, is suitable for suitability for industrialized production.In addition; After obtaining aromatic conjugated homopolymer; To wherein adding similar but be different from the monomeric second halogenated aromatic Grignard reagent monomer of the first halogenated aromatic Grignard reagent, continue to obtain segmented copolymer after the reaction, thereby increase the kind and the application of conjugated copolymer.
In order to further specify the present invention, aromatic conjugated polymkeric substance provided by the invention is described in detail below in conjunction with embodiment.
Embodiment 1～4 Preparation of catalysts
Under the room temperature condition, under protection of inert gas, with 10.3 milligrams of anhydrous acetylacetonate nickels; Respectively with 10.5 milligrams of triphenylphosphines, 15.9 milligram 1,3-two (diphenylphosphino) ethane, 16.5 milligram 1,3-two (diphenylphosphino) propane or 22.2 milligram 1; 1 '-mixing of two (diphenylphosphine) ferrocene; Obtain mixture, add 2 milliliters of THFs then respectively and make the dissolving of said mixture, make the anhydrous acetylacetonate nickel that obtains and the concentration of organophosphorus ligand be 0.02mol/L; With the solution stirring that obtains 30 minutes, obtain catalyzer respectively under the room temperature condition.
Embodiment 52-bromo-7-magnesium chloride-9, the preparation of 9-dioctyl fluorene
Under-20 ℃, protection of inert gas, with 595 milligrams of 2-bromo-, 7 iodo-9, the 9-dioctyl fluorene is dissolved in 20 milliliters of tetrahydrofuran solutions; Obtaining concentration is 2-bromo-7 iodo-9 of 0.05mol/L, and 9-dioctyl fluorene solution is to said 2-bromo-7 iodo-9; 42 milligrams of Lithium chloride (anhydrous)s of adding and 0.59 ml concn are the tetrahydrofuran solution of the isopropylmagnesium chloride of 1.7mol/L in the 9-dioctyl fluorene solution; Stirred 1 hour down at-20 ℃, take out 0.5 milliliter of reaction solution then, cancellation in the hydrochloric acid of 10 milliliter of 5 mol of adding; Obtain 2-bromo-7-magnesium chloride-9, the 9-dioctyl fluorene.
To said 2-bromo-7-magnesium chloride-9, the 9-dioctyl fluorene is carried out gas chromatography-mass spectrometry analysis, and the result shows that its transformation efficiency is 95%.
Embodiment 6
Under protection of inert gas, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 1 preparation, make said catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 2: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 282 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 73%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 6600, and molecular weight distributing index is 1.60.
Embodiment 7
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 2 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 2: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 254 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 65%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 22000, and molecular weight distributing index is 1.40.
Embodiment 8
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 3 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 2: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 271 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 70%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 30000, and molecular weight distributing index is 1.18.
Embodiment 9
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 4 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 2: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 200 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 52%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is less than 1200.
Embodiment 10
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 3 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 1: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 291 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 75%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 60000, and molecular weight distributing index is 1.20.
Embodiment 11
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 3 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 3: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 268 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 69%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 19000, and molecular weight distributing index is 1.15.
Embodiment 12
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 3 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 6: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 287 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 74%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 8900, and molecular weight distributing index is 1.17.
Embodiment 13
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that embodiment 5 preparations are housed, in the reaction vessel of 9-dioctyl fluorene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 3 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 10: 100; Reaction system is transferred in the ice-water bath, stirred 0.5 hour, adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 198 milligrams of cotton-shaped gathering of yellow (9, the 9-dioctyl fluorene) after the filtration, productive rate is 51%.
After being gathered (9, the 9-dioctyl fluorene), it is carried out the GPC test, the result shows that its number-average molecular weight is 2800, and molecular weight distributing index is 1.24.
Embodiment 14
Under room temperature, inert atmosphere protection, with 326 milligram 2,5-dibromo 3-hexyl thiophene is dissolved in 10 milliliters of anhydrous tetrahydro furans; Make 2, the concentration of 5-dibromo 3-hexyl thiophene is 0.1 mol, adds the tetrahydrofuran solution that 42 milligrams of Lithium chloride (anhydrous)s and 0.64 ml concn are the tertiary butyl chlorination magnesium of 1.57 mol; Stirred 24 hours under the room temperature, take out 0.5 milliliter of reaction solution then, cancellation in the hydrochloric acid of 10 milliliter of 5 mol of adding; Obtain 2,5-dibromo 3-hexyl thiophene.To said 2,5-dibromo 3-hexyl thiophene carries out gas chromatography-mass spectrometry analysis, and the result shows that its transformation efficiency is 93%.
Embodiment 15
Under inert atmosphere protection, to 2 of embodiment 14 preparation is housed, in the reaction vessel of 5-dibromo 3-hexyl thiophene; Add the tetrahydrofuran solution of the catalyzer of 1.0 milliliters of embodiment, 3 preparations, make catalyzer and 2-bromo-7 magnesium chlorides-9, the mol ratio of 9-dioctyl fluorene is 2: 100; Stirred 1 hour under the room temperature; Add 10 ml concns and be the aqueous hydrochloric acid cancellation reaction of 5mol/L, the reaction mixture that obtains is used chloroform extraction, the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying; Remove behind the solvent reaction product solution that obtains splashed into and carry out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20, obtains 105 milligrams of red-purple flosss after the filtration and gathers (3-hexyl thiophene), and productive rate is 63%.
After being gathered (3-hexyl thiophene), it is carried out the GPC test, the result shows that its number-average molecular weight is 9600, and molecular weight distributing index is 1.24.
Embodiment 16
Under room temperature, inert atmosphere protection, with 436 milligram 1,4-two bromo-2; 5-two hexyloxy benzene are dissolved in 10 milliliters of anhydrous tetrahydro furans, make 1,4-two bromo-2; The concentration of 5-two hexyloxy benzene is 0.1 mol, and adding 42 milligrams of Lithium chloride (anhydrous)s and 0.64 ml concn is the tetrahydrofuran solution of the isopropylmagnesium chloride of 0.59 mol, stirs 24 hours under the room temperature; Take out 0.2 milliliter of reaction solution then; Cancellation in the hydrochloric acid of 5 milliliter of 5 mol of adding obtains 1-bromo-4-magnesium chloride-2, the grignard reagent of 5-two hexyloxy benzene.To said 1-bromo-4-magnesium chloride-2, the grignard reagent of 5-two hexyloxy benzene carries out gas chromatography-mass spectrometry analysis, and the result shows that its transformation efficiency is 76%.
Embodiment 17
Under inert atmosphere protection, to the 1-bromo-4-magnesium chloride-2 that embodiment 16 preparations are housed, in the reaction vessel of the grignard reagent of 5-two hexyloxy benzene; The tetrahydrofuran solution that adds the catalyzer of 1.0 milliliters of embodiment, 3 preparations; Make catalyzer and 1-bromo-4-magnesium chloride-2, the mol ratio of the grignard reagent of 5-two hexyloxy benzene is 2: 100, stirs 2 hours under the room temperature; Adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 252 milligrams of white powder solids after the filtration and gather (2,5-two hexyloxy benzene), productive rate is 47%.
After being gathered (2,5-two hexyloxy benzene), it is carried out the GPC test, the result shows that its number-average molecular weight is 8300, and molecular weight distributing index is 1.30.
Embodiment 18
Under-20 ℃, inert atmosphere protection; 506 milligrams of N-(4-bromophenyl)-N-(4-iodophenyl)-N-(4-butylaniline) is dissolved in 10 milliliters of anhydrous tetrahydro furans; Making the concentration of N-(4-bromophenyl)-N-(4-iodophenyl)-N-(4-butylaniline) is 0.1 mol; Adding 42 milligrams of Lithium chloride (anhydrous)s and 0.59 ml concn is the tetrahydrofuran solution of the isopropylmagnesium chloride of 1.7 mol, and-20 ℃ were stirred 1 hour down, take out 0.2 milliliter of reaction solution then; Cancellation in the hydrochloric acid of 5 milliliter of 5 mol of adding obtains N-(4-bromophenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline).Said N-(4-bromophenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline) is carried out gas chromatography-mass spectrometry analysis, and the result shows that its transformation efficiency is 97%.
Embodiment 19
Under inert atmosphere protection; In the reaction vessel of N-(4-bromophenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline) that embodiment 18 preparations are housed; The tetrahydrofuran solution that adds the catalyzer of 1.0 milliliters of embodiment, 3 preparations; Making the mol ratio of catalyzer and N-(4-bromophenyl)-N-(4-magnesium chloride phenyl)-N-(4-butylaniline) is 4: 100, and ice-water bath stirred 1 hour down, and adding 10 ml concns is the aqueous hydrochloric acid cancellation reaction of 5mol/L; The reaction mixture that obtains is used chloroform extraction; The organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring, and the volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtain 252 milligrams of yellow powder shape solids after the filtration and gather (N-(4-butyl phenyl) pentanoic), productive rate is 74%.
After being gathered (2,5-two hexyloxy benzene), it is carried out the GPC test, the result shows that its number-average molecular weight is 6200, and molecular weight distributing index is 1.50.
Embodiment 20
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that 10 milliliter of 0.05 mol, embodiment 5 preparations are housed, in the reaction vessel of the THF solution of 9-dioctyl fluorene; Press catalyzer and 2-bromo-7-magnesium chloride-9,9-dioctyl fluorene molar ratio adds the THF solution of the catalyzer of 1.0 milliliter of 0.02 mol embodiment 3 preparation at 4: 100, stirs under the ice-water bath condition after 5 minutes; Take out 3 milliliters of reaction mixtures and join cancellation in the hydrochloric acid that 10 ml concns are 5 mol, the reaction mixture that obtains is used chloroform extraction, the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying; Remove behind the solvent reaction product solution that obtains splashed into and carry out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20, obtains yellow solid after the filtration and gathers (9, the 9-dioctyl fluorene); It is carried out the GPC test; The result shows that its number-average molecular weight is 15000, and molecular weight distributing index is 1.19.
With 2 of 8 milliliter of 0.1 mol embodiment 14 preparation; The grignard reagent of 5-dibromo 3-hexyl thiophene joins in the residue reaction mixture, rises to room temperature, stirs reaction down after 40 minutes; Adding 20 ml concns is the hydrochloric acid cancellation reaction of 5 mol; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtaining 169 milligrams of red-purple flosss after the filtration gathers (9, the 9-dioctyl fluorene)-b-and gathers (3-hexyl thiophene), productive rate 63%.After being gathered (9, the 9-dioctyl fluorene)-b-and gathering (3-hexyl thiophene), it is carried out the GPC test, the result shows that its number-average molecular weight is 21000, and molecular weight distributing index is 1.27.
Embodiment 21
Under inert atmosphere protection, to the 2-bromo-7-magnesium chloride-9 that 10 milliliter of 0.05 mol, embodiment 5 preparations are housed, in the reaction vessel of the THF solution of 9-dioctyl fluorene; Press catalyzer and 2-bromo-7-magnesium chloride-9,9-dioctyl fluorene molar ratio adds the THF solution of the catalyzer of 0.5 milliliter of 0.02 mol embodiment 3 preparation at 2: 100, stirs under the ice-water bath condition after 5 minutes; Take out 3 milliliters of reaction mixtures and join cancellation in the hydrochloric acid that 10 ml concns are 5 mol, the reaction mixture that obtains is used chloroform extraction, the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying; Remove behind the solvent reaction product solution that obtains splashed into and carry out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20, obtains yellow solid after the filtration and gathers (9, the 9-dioctyl fluorene); It is carried out the GPC test; The result shows that its number-average molecular weight is 30000, and molecular weight distributing index is 1.25.
With 2 of 4 milliliter of 0.1 mol embodiment 14 preparation; The grignard reagent of 5-dibromo 3-hexyl thiophene joins in the residue reaction mixture, rises to room temperature, stirs reaction down after 40 minutes; Adding 20 ml concns is the hydrochloric acid cancellation reaction of 5 mol; The reaction mixture that obtains is used chloroform extraction, and the organic layer that then extraction is obtained is with saturated common salt water washing, anhydrous magnesium sulfate drying, removes behind the solvent reaction product solution that obtains splashed into and carries out sedimentation in the methyl alcohol that is stirring; The volume ratio of said reaction product solution and methyl alcohol is 1: 20; Obtaining 144 milligrams of red-purple flosss after the filtration gathers (9, the 9-dioctyl fluorene)-b-and gathers (3-hexyl thiophene), productive rate 71%.After being gathered (9, the 9-dioctyl fluorene)-b-and gathering (3-hexyl thiophene), it is carried out the GPC test, the result shows that its number-average molecular weight is 37000, and molecular weight distributing index is 1.32.
Can be known that by above embodiment preparation method provided by the invention can obtain conjugation homopolymer and segmented copolymer, its molecular weight is controlled, and MWD is narrower.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (12)
1. the preparation method of an aromatic conjugated polymkeric substance may further comprise the steps:
Polycondensation takes place in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain aromatic conjugated polymkeric substance; Said catalyzer is made up of nickelous compound and organophosphorus ligand, and the mol ratio of said nickelous compound and said organophosphorus ligand is 1: (0.5～3);
Said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate;
The said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen;
Q
1Be aromatic base or substituted aromatic base.
2. method according to claim 1 is characterized in that, said nickelous compound is an acetylacetonate nickel.
3. method according to claim 1 is characterized in that, said organophosphorus ligand has formula (III) or formula (IV) structure:
Wherein, R
1, R
2, R
3, R
5, R
6, R
7, R
8Be independently selected from alkyl, phenyl or substituted-phenyl;
R
4It for ferrocenyl or carbonatoms 1～4 straight chained alkyl.
4. method according to claim 3 is characterized in that, said organophosphorus ligand is a triphenylphosphine, 1,3-two (diphenylphosphino) ethane, 1, and 3-two (diphenylphosphino) propane or 1,1 '-two (diphenylphosphine) ferrocene.
5. method according to claim 1 is characterized in that, said catalyzer prepares according to following steps:
Nickelous compound and organophosphorus ligand are mixed in organic solvent, obtain catalyzer after the stirring.
6. method according to claim 5 is characterized in that, the temperature of said stirring is-20 ℃～30 ℃; Churning time is 1min～120min.
7. method according to claim 1 is characterized in that, said Q
1Be selected from formula (11)～(14) structure any one:
Wherein, R
9Be alkyl;
R
10, R
11Be independently selected from alkyl;
R
12, R
13Be independently selected from alkoxyl group;
R
14Be alkyl.
8. method according to claim 1 is characterized in that, said catalyzer and the monomeric mol ratio of the said first halogenated aromatic Grignard reagent are (0.001～0.2): 1.
9. method according to claim 1 is characterized in that, the temperature of said polycondensation is-5 ℃～30 ℃, and the time of said polycondensation is 30min～120min.
10. the preparation method of an aromatic conjugated polymkeric substance may further comprise the steps:
Polycondensation takes place in the first halogenated aromatic Grignard reagent monomer under the effect of catalyzer; Obtain mixed reaction solution; Said catalyzer is made up of nickelous compound and organophosphorus ligand, and the mol ratio of said nickelous compound and organophosphorus ligand is 1: (0.5～3);
Said nickelous compound is Nickel Chloride, Nickel Bromide, acetylacetonate nickel, nickelous acetate or nickelous perchlorate;
The said first halogenated aromatic Grignard reagent monomer has formula (I) structure:
X
1-Q
1-MgX
2(I)；
Wherein, X
1, X
2Be independently selected from halogen;
Q
1Be aromatic base or substituted aromatic base;
In said mixed reaction solution, add the second halogenated aromatic Grignard reagent monomer, polymerization reaction take place obtains the second aromatic conjugated polymkeric substance;
The said second halogenated aromatic Grignard reagent monomer has formula (II) structure:
X
3-Q
2-MgX
4(II)；
Wherein, X
3, X
4Be independently selected from halogen;
Q
2For being different from said Q
1Aromatic base or substituted aromatic base.
11. method according to claim 10 is characterized in that, the mol ratio of said second halogenated aromatic grignard reagent monomer and said catalyzer is 1: (0.005～0.2).
12. method according to claim 10 is characterized in that, the temperature of said polyreaction is 10 ℃～50 ℃, and the time of said polyreaction is 0.5h～2h.
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