CN108530660B - A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof - Google Patents
A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof Download PDFInfo
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- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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Abstract
The present invention relates to quaternized polyfluorene ether ketone compounds of a kind of local dense and preparation method thereof.The present invention designs the novel biphenol monomer synthesized containing eight benzyls and fluorenyl first, then pass through the 9 of the monomer and different proportion, 9- bis- (4- hydroxy phenyl) fluorenes and 4, the polycondensation reaction of 4 '-difluoro benzophenones prepares the polyfluorene ether ketone compound containing benzyl, bromomethyl is converted for benzyl with N- bromo-succinimide again, and then quaternary ammonium salt group is converted for bromomethyl with trimethylamine, a series of quaternized polyfluorene ether ketone compound of local denses is made.The series compound is in N, N- dimethyl acetamide, N, dinethylformamide, N-Methyl pyrrolidone have good dissolubility in dimethyl sulfoxide isopolarity aprotic solvent, it can be formed a film with solution-cast, obtained anion-exchange membrane has the features such as thermal stability is good, oxidation stability is good, and anionic conduction rate is high, mechanical property is good.
Description
Technical field
The present invention relates to quaternized polyfluorene ether ketone compounds of a kind of local dense and preparation method thereof, belong to amberplex
Material Field.
Background technique
Anion-exchange membrane has important answer in the multiple fields such as fuel cell, flow battery, electrodialysis, water electrolysis
With, therefore receive significant attention.It is simple that ideal anion-exchange membrane should have a preparation process, low in cost, anionic conduction
The features such as rate is high, and mechanically and chemically stability is good.Currently, the application of anion-exchange membrane is primarily present, ionic conductivity is low to be asked
Topic, and ionic conductivity depends primarily on the content and micromorphology of cation group.By improving anion-exchange membrane ion
The content of group can be improved ionic conductivity, but this to will lead to film water absorption rate excessively high and influence chemical stability and mechanical performance.
If allowing ionic group dense distribution in polymer chain, ion transmission channel is advantageously formed, improves ionic conductivity
(ChemSusChem 2014,7:2621 ~ 2630).
Polyarylether containing fluorene has excellent dissolubility, good chemical stability and mechanical performance.It is modified and is drawn
Entering quaternary ammonium salt group can the good anion exchange membrane material of processability (Energy Conversion and Management
2010,51:2816 ~ 2824).Conventional synthesis quaternary anion-exchange membrane is usually first using reagents such as chloromethyl methyl ethers to poly-
It closes object and carries out chloromethylation, then reacted with trimethylamine and introduce quaternary ammonium salt cationic (CN 201510213184.4).This method without
Method accurately controls position and the quantity of quaternary ammonium salt cationic access, and chloromethylation reagents generally have severe toxicity.Yan et al. is provided
A kind of brominated method uses nontoxic N- bromo-succinimide as bromide reagent, can be accurate by quaternary ammonium salt cationic
Ground is introduced into polymer on the position of benzyl (Macromolecules 2010,43:2349 ~ 2356), this is design and closes
Thinking and operational means are provided at the anion-exchange membrane with specific cation distribution structure.Therefore, it is set by molecule
Meter introduces the quaternary ammonium salt group of integrated distribution on polyarylether containing fluorene, forms effective ion transmission channel to improve anion biography
Conductance is of great significance to the development of anion-exchange membrane.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of quaternized polyfluorene ether assimilation of local dense
Close object.The quaternized polyfluorene ether ketone compound of local dense is with preparation process is simple, ionic conductivity is high, mechanical performance
Good, good chemical stability, there is important application prospect in anion-exchange membrane field.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of quaternized polyfluorene ether ketone compound of local dense, structural formula are as follows:
In formula R be H or
, X is any anion, and m is that 1 ~ 400, n is 10 ~ 400.
Another object of the present invention is to provide a kind of preparation method of the quaternized polyfluorene ether ketone compound of local dense,
The following steps are included:
The preparation of the quaternized polyfluorene ether ketone compound of local dense, steps are as follows:
(1) by the biphenol monomer II containing eight benzyls, 4,4 '-difluoro benzophenones and 9,9- bis- (4- hydroxy phenyl)
Fluorenes is dissolved in polar non-solute, and wherein the molar ratio of biphenol monomer and two fluorine monomers is 1:1；Then phenolic hydroxyl group is added
The potassium carbonate of 1 ~ 5 times of equivalent activates biphenol monomer, and the toluene of 10 ~ 50 times of equivalents of phenolic hydroxyl group is added as deicer, in high temperature
Lower carry out polymerization reaction；Reactant is poured slowly into water after reaction and is precipitated, then filter and collects precipitating, in 60
~ 120 DEG C are dried in vacuo 10 ~ 40 hours, and the polyfluorene ether ketone compound containing benzyl is made；
The biphenol monomer II containing eight benzyls has the following structure:
；
(II)
(2) the polyfluorene ether ketone compound containing benzyl obtained in step (1) is dissolved in 1,2- dichloroethanes
The solution of 1 ~ 10 wt.% is made, the N- bromo-succinimide and benzoyl peroxide of 0.5 ~ 1.5 times of equivalent of benzyl is added
It is reacted, obtains the polyfluorene ether ketone compound containing bromomethyl；Wherein N- bromo-succinimide and benzoyl peroxide rub
You are than being 1 ~ 2:1；
(3) the polyfluorene ether ketone compound containing bromomethyl obtained in step (2) is dissolved in polar non-solute
In the solution of 1 ~ 10 wt.% is made, the trimethylamine solution for being slowly added to 1 ~ 10 times of equivalent of bromomethyl is reacted, and it is close to obtain part
Collect quaternized polyfluorene ether ketone compound.
Polymerization temperature in step (1) is 80 ~ 200 DEG C, polymerization time 5 ~ 50 hours.
Reaction temperature in step (2) is 20 ~ 200 DEG C, the reaction time 2 ~ 20 hours.
Reaction temperature in step (3) is -20 ~ 100 DEG C, the reaction time 5 ~ 50 hours.
The biphenol monomer containing eight benzyls II's the preparation method is as follows:
(1) the bromo- 2,6- dimethylanisole of 4- and 9,9- bis- (3,5- dimethyl -4- hydroxy phenyl) fluorenes are dissolved in polarity
The solution of 1 ~ 40 wt.% is made in aprotic solvent；The potassium carbonate that 1 ~ 5 times of equivalent of phenolic hydroxyl group is added activates bis- (3,5- of 9,9-
Dimethyl -4- hydroxy phenyl) fluorenes, the cuprous bromide and pyridine for adding 0.2 ~ 1 times of equivalent of phenolic hydroxyl group as catalyst,
React 1 ~ 200 hour at 100 ~ 300 DEG C, then reactant pour into volume be 2 ~ 10 times of polar non-solute used go from
In sub- water, the compound I containing eight benzyls is obtained after purification by liquid extraction；The wherein bromo- 2,6- dimethylanisole of 4- and 9,
The molar ratio of 9- bis- (3,5- dimethyl -4- hydroxy phenyl) fluorenes is 1:2 ~ 10, and the molar ratio of cuprous bromide and pyridine is 1:2 ~ 10；
The compound I containing eight benzyls has the following structure:
(I)
(2) by the obtained compound I containing eight benzyls of step (1) and Boron tribromide, 1:2 ~ 10 add in molar ratio
Enter the solution that 5 ~ 30 wt.% are made into methylene chloride, reacts 1 ~ 100 hour, contained under the conditions of -80 DEG C ~ 30 DEG C
The biphenol monomer II of eight benzyls.
In order to preferably realize the present invention, the polar non-solute in step described above is N, N- dimethylacetamide
It is amine, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide, any one in 1,3- dimethyl-2-imidazolinone
Kind.
The obtained quaternized polyfluorene ether ketone compound of local dense of the present invention can be used for preparing anion exchange membrane material.
Preparation method of the present invention be preferred embodiment, the predictable reasonable temperature of one of skill in the art, when
Between and other reaction conditions be invention which is intended to be protected, it is not limited to above-mentioned reaction condition.
The present invention is by first synthesizing the biphenol monomer II containing eight benzyls, then with 4,4 '-difluoro benzophenones and
9,9- bis- (4- hydroxy phenyl) fluorenes carry out polycondensation reaction and obtain the polyfluorene ether ketone compound containing benzyl, then pass through bromination and season
The quaternized polyfluorene ether ketone compound of local dense is finally made in ammonium.
Compared with prior art, the present invention has the effect that
(1) raw material used is cheap for common industrial chemicals, is easy to get；
(2) it using N- bromo-succinimide as bromide reagent, and then is oriented with trimethylamine and introduces quaternary ammonium salt group, instead
Mild condition is answered, and the ion exchange capacity of change inventory simple adjustment product can be passed through；
(3) the gained quaternized polyfluorene ether ketone compound of local dense can be formed effectively due to quaternary ammonium salt group dense distribution
Ion transmission channel, therefore anionic conduction rate is higher；
(4) the gained quaternized polyfluorene ether ketone compound of local dense has excellent dissolubility, chemical stability and machinery
Performance.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of the compound I containing eight benzyls prepared in the embodiment of the present invention 1.
Fig. 2 is the nuclear magnetic resonance spectroscopy of the biphenol monomer II containing eight benzyls prepared in the embodiment of the present invention 2.
Fig. 3 is a kind of nuclear magnetic resonance spectroscopy of the polyfluorene ether ketone compound A containing benzyl in the embodiment of the present invention 3.
Fig. 4 is a kind of infrared spectroscopy of the polyfluorene ether ketone compound A containing benzyl in the embodiment of the present invention 3.
Fig. 5 is a kind of nuclear magnetic resonance spectroscopy of the polyfluorene ether ketone compound C containing bromomethyl in the embodiment of the present invention 5.
Fig. 6 is a kind of infrared spectroscopy of the polyfluorene ether ketone compound C containing bromomethyl in the embodiment of the present invention 5.
Fig. 7 is a kind of nuclear magnetic resonance spectroscopy of the quaternized polyfluorene ether ketone compound E of local dense in the embodiment of the present invention 7.
Fig. 8 is a kind of infrared spectroscopy of the quaternized polyfluorene ether ketone compound E of local dense in the embodiment of the present invention 7.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The preparation of compound I of the embodiment 1 containing eight benzyls
By 25.00 g (61.5 mmol) 9,9- bis- (3,5- dimethyl -4- hydroxy phenyl) fluorenes, 33.84 g (157.3
Mmol) the bromo- 2,6- dimethylanisole of 4-, 34.04 g (246.5 mmol) Anhydrous potassium carbonate, 5.83 g (40.6
Mmol) cuprous bromide, 21 mL (270.4 mmol) pyridine, and 300 mL N,N-dimethylformamides are added to 500 mL
In three-necked flask, under the protection of argon gas, 165 DEG C magnetic agitation 170 hours, then by product be acidified to pH be 2, filtering, then
It is extracted using water and methylene chloride, is finally purified with chromatography, obtain the compound I of eight benzyls.Yield: 29.1%.
The data of the nuclear magnetic resonance spectroscopy of the compound are as follows:1H NMR (400 MHz, CDCl3, ppm)δ 2.05 (s, 12H),
2.22 (s, 12H), 3.69 (s, 6H), 6.40 (s, 4H), 6.94 (s, 4H), 7.36 (t, 2H), 7.43
(t, 2H), 7.55 (d, 2H), 7.83 (d, 2H)。
The preparation of biphenol monomer II of the embodiment 2 containing eight benzyls
By the 5.17 g(7.66 mmol of compound I in embodiment 1 containing eight benzyls), 130 mL methylene chloride add
Enter into 250 mL three neck round bottom flask, system temperature is down to -78 DEG C using liquid nitrogen and acetone under the protection of argon gas, delays
It is slow that 4.66 g(18.5 mmol are added) Boron tribromide, then the reaction was continued at room temperature 10 hours.After reaction, by product
It pours into 200 mL deionized waters, reuses water and methylene chloride extraction, then purify to obtain containing eight by chromatography
The biphenol monomer II of benzyl.Yield: 99%.The data of the nuclear magnetic resonance spectroscopy of the compound are as follows:1H NMR (400 MHz,
CDCl3, ppm) δ 2.05 (s, 12H), 2.19 (s, 12H), 4.32 (s, 2H), 6.39 (s, 4H), 6.93
(s, 4H), 7.36 (t, 2H), 7.43 (t, 2H), 7.56 (d, 2H), 7.83 (d, 2H)。
The preparation of polyfluorene ether ketone compound A of the embodiment 3 containing benzyl
By the 0.3881 g(0.6 mmol of biphenol monomer II in embodiment 2 containing eight benzyls), 0.8410 g
(2.4 mmol) 9,9- bis- (4- hydroxy phenyl) fluorenes, 0.6546 g (3 mmol), 4,4 '-difluoro benzophenone, 0.6219 g
(4.5 mmol) Anhydrous potassium carbonate, 6 mL toluene and 10 mL n,N-dimethylacetamide are added in 25 mL three-necked flasks,
It is warming up to 145 DEG C under the protection of argon gas to react 2 hours, then temperature is risen to 165 DEG C the reaction was continued 15 hours, reaction terminates
Afterwards, product is poured into be precipitated in deionized water and is precipitated, be re-dissolved in methylene chloride after precipitating is collected by filtration, be subsequently poured into first
Precipitating is precipitated in alcohol, precipitating is collected by filtration, dries 24 hours at 80 DEG C of vacuum drying oven to get the polyfluorene ether containing benzyl is arrived
Ketone compound A.Yield: 96%.The data of the nuclear magnetic resonance spectroscopy of the compound are as follows:1H NMR (400 MHz, CDCl3, ppm)
δ 2.08 (d, 4.8H), 6.51 (s, 0.8H), 6.84 (d, 1.2H), 6.97 (m, 7.2H), 7.27 (d,
1.2H), 7.33 (t, 2H), 7.43 (m, 1.5H), 7.54(d, 0.6H),7.80 (m,6H).Infrared data are as follows: FT-
IR (cm-1) υ 3062,3036,2952,2918,2857,1656,1593,1498,1305,1277,1242,
1157, 1014, 928, 856, 745, 607。
The preparation of polyfluorene ether ketone compound B of the embodiment 4 containing benzyl
Experimental procedure is same as Example 3, the difference is that biphenol monomer II and 9,9- bis- (4- hydroxy phenyl) fluorenes feed intake
Amount.In the present embodiment, the inventory of biphenol monomer II is 0.5822 g(0.9 mmol)；The throwing of 9,9- bis- (4- hydroxy phenyl) fluorenes
Doses is 0.7359 g(2.1 mmol).Reaction obtains the polyfluorene ether ketone compound B containing benzyl.Yield: 98%.
The preparation of polyfluorene ether ketone compound C of the embodiment 5 containing bromomethyl
By the 1.00 g(1.7 mmol of polyfluorene ether ketone compound A containing benzyl in embodiment 3), 0.50 g (2.7
Mmol) N- bromo-succinimide, 0.03 g (0.14 mmol) dibenzoyl peroxide and 20 mL 1,2- dichloroethanes
It is added in three-necked flask, is reacted 5 hours for 85 DEG C under the protection of argon gas, then product, which pours into, is precipitated precipitating, mistake in deionized water
Filter is re-dissolved in methylene chloride after collecting precipitating, is subsequently poured into methanol and precipitating is precipitated, precipitating is collected by filtration, and is dried in vacuum
80 DEG C of case dry 24 hours to get the polyfluorene ether ketone compound C containing bromomethyl is arrived.Yield: 97%.The nuclear-magnetism of the compound is total
The data for hydrogen spectrum of shaking are as follows:1H NMR (400 MHz, CDCl3, ppm) δ 2.08 (d, 0.6H), 4.32 (d, 2H),
6.93 (m, 12.5H), 7.23 (d, 4H), 7.32 (d, 2H), 7.42 (m, 4.4H), 7.74 (m, 6H).It is red
Outer data are as follows: FT-IR (cm-1) υ 3064,3034,1723,1656,1594,1493,1305,1277,1240,
1157, 1014, 930, 856, 745, 607。
The preparation of polyfluorene ether ketone compound D of the embodiment 6 containing bromomethyl
Experimental procedure is same as Example 5, the difference is that reaction raw materials are the polyfluorene ether containing benzyl in embodiment 4
Ketone compound B, inventory are 0.70 g(1.1 mmol).Reaction obtains the polyfluorene ether ketone compound D containing bromomethyl.It produces
Rate: 98%.
The preparation of the quaternized polyfluorene ether ketone compound E of 7 local dense of embodiment
By the 0.55 g(0.75 mmol of polyfluorene ether ketone compound C containing bromomethyl in embodiment 5) and 10 mL N,
N- dimethyl acetamide is added in vial, and system temperature is down to 0 DEG C, it is water-soluble to be slowly added to 0.6 mL 30wt.% trimethylamine
Then liquid seals vial, be stirred at room temperature 24 hours.Then product is poured into surface plate, is placed at 80 DEG C and dries
It does to get the quaternized polyfluorene ether ketone compound E of local dense is arrived.Yield 95%.The data of the nuclear magnetic resonance spectroscopy of the compound
Are as follows:1H NMR (400 MHz, CDCl3, ppm) δ 2.16 (s, 0.6H), 3.15 (s, 10.3H), 4.56 (m,
1.7H),6.91 (s, 9.3H), 7.19 (s, 4H), 7.40 (s, 6.9H), 7.71 (s, 5.3H), 7.93 (s,
2.1H), 8.07 (s, 0.6H).Infrared data are as follows: FT-IR (cm-1) υ 3417,3064,3033,3010,2952,
1710,1652,1594,1496,1309,1275,1240,1162,1015,930,871,749,607.
The preparation of the quaternized polyfluorene ether ketone compound F of 8 local dense of embodiment
Experimental procedure is same as Example 7, the difference is that reaction raw materials are the polyfluorene ether containing bromomethyl in embodiment 6
Ketone compound D, inventory are 0.41 g(0.50 mmol).Reaction obtains the quaternized polyfluorene ether ketone compound F of local dense.
Yield: 98%.
Embodiment 9 is based on the quaternized polyfluorene ether ketone compound of above-mentioned local dense and prepares anion-exchange membrane
The above-mentioned local dense of 0.5 g quaternized polyfluorene ether ketone compound E and F are taken, 10 mL N, N- diformazans are dissolved separately in
It in yl acetamide, then pours and casts from horizontal positioned plate glass, 80 DEG C drying 12 hours, then exist in constant temperature oven
80 DEG C drying 12 hours, i.e., form membranaceous product in glass plate in vacuum drying oven.Film is peeled from glass plate, is then soaked
In deionized water, desired anion exchange membrane E and F is made in bubble.Through characterizing, the ion exchange capacity of anion-exchange membrane E is
1.76 mmol/g, tensile strength are 30.2 MPa, and elongation at break 19.1%, bromide ion conductivity is 15.9 mS/cm；Yin
The ion exchange capacity of amberplex F be 2.23 mmol/g, tensile strength be 24.6 MPa, elongation at break 14.3%,
Bromide ion conductivity is 24.4 mS/cm.
Claims (7)
1. a kind of preparation method of the quaternized polyfluorene ether ketone compound of local dense, which is characterized in that its structure of the compound
Formula are as follows:
In formula R be H or
, X is any anion, and m is that 1 ~ 400, n is 10 ~ 400；Its specific preparation method,
The following steps are included:
(1) by the biphenol monomer II containing eight benzyls, 4,4 '-difluoro benzophenones and 9,9- bis- (4- hydroxy phenyl) fluorenes is molten
Solution is in polar non-solute, and wherein the molar ratio of biphenol monomer and two fluorine monomers is 1:1；Then it is added the 1 ~ 5 of phenolic hydroxyl group
The potassium carbonate of times equivalent activates biphenol monomer, the toluene of 10 ~ 50 times of equivalents of phenolic hydroxyl group is added as deicer, at high temperature into
Row polymerization reaction；Reactant is poured slowly into water after reaction and is precipitated, then filter and collects precipitating, in 60 ~ 120
DEG C vacuum drying 10 ~ 40 hours, be made the polyfluorene ether ketone compound containing benzyl；
The biphenol monomer II containing eight benzyls has the following structure:
(2) the polyfluorene ether ketone compound containing benzyl obtained in step (1) is dissolved in 1,2- dichloroethanes and is made 1
The solution of ~ 10 wt.%, the N- bromo-succinimide and benzoyl peroxide that 0.5 ~ 1.5 times of equivalent of benzyl is added carry out
Reaction, obtains the polyfluorene ether ketone compound containing bromomethyl；Wherein N- bromo-succinimide and benzoyl peroxide molar ratio
For 1 ~ 2:1；
(3) the polyfluorene ether ketone compound containing bromomethyl obtained in step (2) is dissolved in polar non-solute and is made
At the solution of 1 ~ 10 wt.%, the trimethylamine solution for being slowly added to 1 ~ 10 times of equivalent of bromomethyl is reacted, and obtains local dense season
Ammonium polyfluorene ether ketone compound.
2. a kind of preparation method of the quaternized polyfluorene ether ketone compound of local dense according to claim 1, feature exist
In the polymerization temperature in step (1) is 80 ~ 200 DEG C, polymerization time 5 ~ 50 hours.
3. a kind of preparation method of the quaternized polyfluorene ether ketone compound of local dense according to claim 1, feature exist
In the reaction temperature in step (2) is 20 ~ 200 DEG C, the reaction time 2 ~ 20 hours.
4. a kind of preparation method of the quaternized polyfluorene ether ketone compound of local dense according to claim 1, feature exist
In the reaction temperature in step (3) is -20 ~ 100 DEG C, the reaction time 5 ~ 50 hours.
5. a kind of preparation method of the quaternized polyfluorene ether ketone compound of local dense, feature exist according to claim 1
In, the biphenol monomer containing eight benzyls II's the preparation method is as follows:
(1) the bromo- 2,6- dimethylanisole of 4- and 9,9- bis- (3,5- dimethyl -4- hydroxy phenyl) fluorenes are dissolved in the non-matter of polarity
The solution of 1 ~ 40 wt.% is made in sub- solvent；The potassium carbonate that 1 ~ 5 times of equivalent of phenolic hydroxyl group is added activates (the 3,5- diformazan of 9,9- bis-
Base -4- hydroxy phenyl) fluorenes, the cuprous bromide and pyridine for adding 0.2 ~ 1 times of equivalent of phenolic hydroxyl group as catalyst, 100 ~
It is reacted at 300 DEG C 1 ~ 200 hour, it is 2 ~ 10 times of polar non-solute of deionized water used that reactant, which is then poured into volume,
In, the compound I containing eight benzyls is obtained after purification by liquid extraction；The wherein bromo- 2,6- dimethylanisole of 4- and 9,9- bis-
The molar ratio of (3,5- dimethyl -4- hydroxy phenyl) fluorenes is 1:2 ~ 10, and the molar ratio of cuprous bromide and pyridine is 1:2 ~ 10；
The compound I containing eight benzyls has the following structure:
(2) by the obtained compound I containing eight benzyls of step (1), 1:2 ~ 10 are added in molar ratio with Boron tribromide
The solution of 5 ~ 30 wt.% is made in methylene chloride, reacts 1 ~ 100 hour, is obtained containing eight benzene under the conditions of -80 DEG C ~ 30 DEG C
The biphenol monomer II of methyl.
6. the preparation method of the quaternized polyfluorene ether ketone compound of a kind of local dense according to claim 1 or 5, feature
Be, the polar non-solute be n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone,
Any one in dimethyl sulfoxide, 1,3- dimethyl-2-imidazolinone.
7. a kind of quaternized polyfluorene ether ketone compound of local dense of method preparation as described in claim 1 is preparing anion friendship
Change the application on membrane material.
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