CN109679088A - A kind of polyarylether and preparation method thereof and polyarylether cured film and its preparation method and application - Google Patents
A kind of polyarylether and preparation method thereof and polyarylether cured film and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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Abstract
The invention belongs to polymeric material fields, more particularly to a kind of polyarylether and its preparation and polyarylether cured film and its preparation method and application, polyarylether provided by the invention has structure shown in Formulas I, the present invention also provides the polyarylether cured films being prepared by the polyarylether, polyarylether cured film provided by the invention contains aromatic ring structure, be conducive to improve the thermal stability of polyarylether cured film, mechanical performance and solvent resistance, polyarylether cured film provided by the invention contains a large amount of fluorine elements simultaneously, increase the free volume of polyarylether cured film, be conducive to improve the gas flux of polyarylether cured film.In addition, polyarylether cured film provided by the invention contains the cross-linking products of polyarylether high polymer and biphenol monomer, the presence of cross-linking products further improves the stability of polyarylether cured film.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of polyarylether and its preparation and polyarylether cured film
And its preparation method and application.
Background technique
Since scientist in 1829 has found transport phenomena of the gas in film, membrane separation technique is obtained in gas separation field
Rapid development is arrived.Membrane material is the core of membrane separation technique, is mainly had using more extensive gas separation membrane material at present
Polyimides, polyphenylene oxide, polysulfones and dimethyl silicone polymer etc..With going deep into for research, for gas separation membrane material
Research direction is concentrated mainly on two aspects, first is that the gas separating property of membrane material is improved, second is that improving the stabilization of membrane material
Performance.But the gas separating property and stability of gas separation membrane material in the prior art can not meet simultaneously people's
Demand.
Summary of the invention
For the gas separating property and stability for improving gas separation membrane material, the present invention provides a kind of polyarylether and
Preparation method and a kind of polyarylether cured film and its preparation method and application.Polyarylether provided by the present invention is prepared into
To polyarylether cured film there is preferable gas separating property and stability simultaneously.
The present invention provides a kind of polyarylethers, have structure shown in Formulas I:
The number-average molecular weight of the polyarylether is 6w~18w Daltons；
Wherein, Ar has structure shown in Formula II~any one of formula IV in-O-Ar-O-:
The present invention provides the preparation methods of polyarylether described in above-mentioned technical proposal, comprising the following steps:
(1) biphenol monomer, catalyst, dehydrating agent and organic solvent are mixed, obtains mixture；The catalyst includes carbon
One of sour sodium, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide are a variety of；
(2) mixture for obtaining the step (1) carries out azeotropic dehydration, then removes dehydrating agent, obtains reaction material liquid；
(3) after the reaction material liquid for obtaining the step (2) is cooling, polycondensation reaction is carried out after mixing with decafluorobiphenyl, is obtained
To the polyarylether of structure shown in Formulas I.
Preferably, the molar ratio of biphenol monomer and catalyst is 0.9~1.2:0.9~1.2 in the step (1)；It is described
The volume ratio of dehydrating agent and organic solvent is 0.2~0.5:1；The solid content of the mixture is 5%~25%.
Preferably, the temperature of azeotropic dehydration is 85~140 DEG C in the step (2), and the time is 3~5h；The step (2)
Dehydrating agent is removed by the way of reflux, the temperature of the reflux is 150~180 DEG C.
Preferably, the molar ratio of step (3) decafluorobiphenyl and biphenol monomer in reaction material liquid is 0.9~1.2:0.9
~1.2.
Preferably, the temperature of polycondensation reaction is 70~90 DEG C in the step (3), and the time is 20~35h.
The present invention also provides a kind of preparation methods of polyarylether cured film, comprising the following steps:
(a) after mixing biphenol monomer, catalyst, dehydrating agent and organic solvent, azeotropic dehydration is carried out, then removes dehydration
It is cooling after agent, it obtains building film liquid；The catalyst includes in sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide
It is one or more；
(b) by polyarylether and the step (a) obtain build film liquid mix after, successively carry out pouring at film forming and heating
Reason, obtains polyarylether cured film；The polyarylether is side described in polyarylether described in above-mentioned technical proposal or above-mentioned technical proposal
The polyarylether that method is prepared.
Preferably, the temperature heated in the step (b) is 200 DEG C~400 DEG C, and the time is 0.5~3h.
The present invention also provides the polyarylether cured films that above-mentioned technical proposal the method is prepared.
The present invention also provides polyarylether cured films described in above-mentioned technical proposal in the application of gas separation field.
The present invention provides a kind of polyarylether, the polyarylether has structure shown in Formulas I, and the present invention also provides gathered by this
The polyarylether cured film and preparation method thereof that aryl oxide is prepared, the preparation method of polyarylether cured film provided by the invention
For a kind of new cross-linking method, method is simple, and effectively increases the thermostabilization for the polyarylether cured film being finally prepared
Performance, mechanical performance and gas separating property.Polyarylether cured film provided by the invention contains aromatic ring structure, is conducive to improve
The thermal stability and mechanical performance of polyarylether cured film, while polyarylether cured film provided by the invention contains a large amount of fluorine members
Element increases the free volume of polyarylether cured film, is conducive to the gas flux for improving polyarylether cured film.In addition, this
The polyarylether cured film that invention provides contains the cross-linking products of polyarylether high polymer and biphenol monomer, the presence of cross-linking products,
Further improve the stability of polyarylether cured film.Embodiment the result shows that, polyarylether cured film provided by the invention
Thermal stability with higher, glass transition temperature up to 211 DEG C, meanwhile, polyarylether cured film provided by the invention also has
Preferable dimensional stability and gas separating property, the CO of the polyarylether cured film2Permeability is 71.92barrer, N2It seeps
Permeability is 4.89barrer, O2Permeability is 19.69barrer, CH4Permeability is 3.22barrer, CO2/N2Selectively it is
14.71 CO2/CH4Selectivity is 22.34, O2/N2Selectivity is 4.03.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic spectrogram for the polyarylether that the embodiment of the present invention 1 is prepared；
Fig. 2 is the fluorine nuclear magnetic spectrogram for the polyarylether that the embodiment of the present invention 1 is prepared；
Fig. 3 is the DSC song of the polyarylether that embodiment 1 is prepared and the polyarylether cured film that embodiment 1 is prepared
Line；
Fig. 4 is the polyarylether that the embodiment of the present invention 1 is prepared and the polyarylether cured film that embodiment 1 is prepared
TMA curve；
Fig. 5 is the TGA curve for the polyarylether cured film that the embodiment of the present invention 4 is prepared.
Specific embodiment
The present invention provides a kind of polyarylethers, have structure shown in Formulas I:
The number-average molecular weight of the polyarylether be 6w~18w Daltons, preferably 10~16w Daltons, more preferably
For 12~14w Daltons；
Ar has structure shown in Formula II~any one of formula IV:
The present invention provides the preparation methods of polyarylether described in above-mentioned technical proposal, comprising the following steps:
(1) biphenol monomer, catalyst, dehydrating agent and organic solvent are mixed, obtains mixture；The catalyst includes carbon
One of sour sodium, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide are a variety of；
(2) mixture for obtaining the step (1) carries out azeotropic dehydration, then removes dehydrating agent, obtains reaction material liquid；
(3) it after the reaction material liquid for obtaining the step (2) is cooling, is mixed with decafluorobiphenyl, then carries out polycondensation reaction,
Obtain the polyarylether of structure shown in Formulas I.
The present invention mixes biphenol monomer, catalyst, dehydrating agent and organic solvent, obtains mixture.In the present invention, institute
It states biphenol monomer and preferably includes one of hydroquinone, resorcinol, fluorenes diphenol, '-biphenyl diphenol, bisphenol-A, bisphenol AF or more
Kind；The molar ratio of the biphenol monomer and catalyst is preferably 0.9~1.2:0.9~1.2, further preferably 0.95~
1.15:0.95~1.15, more preferably 1:1.In the present invention, the dehydrating agent preferably includes benzene,toluene,xylene and hexamethylene
One or more of alkane；The organic solvent preferably includes dioxane, dimethylformamide, dimethyl acetamide, diformazan
One or more of base sulfoxide, sulfolane and N-Methyl pyrrolidone；The volume ratio of the dehydrating agent and organic solvent is preferred
For 0.2~0.5:1, further preferably 0.3~0.4:1.In the present invention, the quality of the biphenol monomer and organic solvent
Volume ratio is preferably 5~10g:100mL, further preferably 6~8g:100mL.
After obtaining mixture, the mixture is carried out azeotropic dehydration by the present invention, is then removed dehydrating agent, is obtained reaction material
Liquid.In the present invention, the temperature of the azeotropic dehydration is preferably 85~140 DEG C, and further preferably 90~130 DEG C, more preferably
It is 100~120 DEG C, the time is preferably 3~5h, further preferably 3.5~4.5h.The present invention can be taken off by azeotropic dehydration
The water that the water of raw material and nucleophilic substitution by-product generate in dereaction system.Present invention preferably employs the modes of reflux to remove
Dehydrating agent is removed, the temperature of the reflux is preferably 150~180 DEG C, and further preferably 160~170 DEG C, the time of the reflux
Preferably 1.5~2.5h.
After obtaining reaction material liquid, the present invention mixes with decafluorobiphenyl by after reaction material liquid cooling, then carries out polycondensation
Reaction, obtains the polyarylether of structure shown in Formulas I.
In the present invention, reaction material liquid temperature after cooling is preferably room temperature, and the present invention is to the specific type of cooling
Do not specially require.In the present invention, in the decafluorobiphenyl and reaction material liquid the molar ratio of biphenol monomer be preferably 0.9~
1.2:0.9~1.2, further preferably 0.95~1.15:0.95~1.15, more preferably 1:1.In the present invention, the contracting
The temperature of poly- reaction is preferably 70~90 DEG C, and further preferably 75~85 DEG C, the time is preferably 20~35h, further preferably
For 25~30h.In polycondensation reaction, biphenol monomer reacts the present invention with decafluorobiphenyl, generates polyarylether, reaction equation such as formula
Shown in VIII:
The present invention also provides a kind of preparation methods of polyarylether cured film, comprising the following steps:
(a) after mixing biphenol monomer, catalyst, dehydrating agent and organic solvent, azeotropic dehydration is carried out, then removes dehydration
It is successively cooled down after agent, obtains building film liquid；The catalyst includes sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and hydrogen-oxygen
Change one of sodium or a variety of；
(b) by polyarylether and the step (a) obtain build film liquid mix after, successively carry out pouring at film forming and heating
Reason, obtains polyarylether cured film；The polyarylether is side described in polyarylether described in above-mentioned technical proposal or above-mentioned technical proposal
The polyarylether that method is prepared.
After the present invention mixes biphenol monomer, catalyst, dehydrating agent and organic solvent, azeotropic dehydration is carried out, is then removed
It is successively cooled down and is filtered after dehydrating agent, obtain building film liquid.
The present invention mixes biphenol monomer, catalyst, dehydrating agent and organic solvent, obtains mixture.In the present invention, institute
It states biphenol monomer and preferably includes one of hydroquinone, resorcinol, fluorenes diphenol, '-biphenyl diphenol, bisphenol-A, bisphenol AF or more
Kind；The molar ratio of the biphenol monomer and catalyst is preferably 0.9~1.2:0.9~1.2, further preferably 0.95~
1.15:0.95~1.15, more preferably 1:1.In the present invention, the dehydrating agent preferably includes benzene,toluene,xylene and hexamethylene
One or more of alkane；The organic solvent preferably includes dioxane, dimethylformamide, dimethyl acetamide, diformazan
One or more of base sulfoxide, sulfolane and N-Methyl pyrrolidone；The volume ratio of the dehydrating agent and organic solvent is preferred
For 0.2~0.5:1, further preferably 0.3~0.4:1.In the present invention, the biphenol monomer, catalyst, dehydrating agent and have
The solid content for the mixture that solvent is formed is preferably 5%~25%, further preferably 10%~20%, more preferably 15~
18%.
After obtaining mixture, the mixture is carried out azeotropic dehydration by the present invention, is then removed cooling after dehydrating agent, is obtained
Build film liquid.In the present invention, the temperature of the azeotropic dehydration is preferably 85~140 DEG C, and further preferably 90~130 DEG C, more
Preferably 100~120 DEG C, the time is preferably 3~5h, further preferably 3.5~4.5h.The present invention passes through azeotropic dehydration, energy
Enough slough the water that the water of raw material and nucleophilic substitution by-product generate in reaction system.Present invention preferably employs the sides of reflux
Formula removes dehydrating agent, and the temperature of the reflux is preferably 150~180 DEG C, and further preferably 160~170 DEG C, the reflux
Time is preferably 1.5~2.5h.
After removing dehydrating agent, the present invention cools down the mixture for removing dehydrating agent, obtains building film liquid.In the present invention
In, the temperature after cooling is preferably room temperature.The present invention does not specially require cooling specific embodiment, using ability
Mode known to field technique personnel.
The present invention preferably after the cooling period, is filtered processing, to remove excessive catalyst, obtains even-grained building film
Liquid.The specific embodiment of filtering is not particularly limited in the present invention, using filter type well-known to those skilled in the art
?.
It obtains after building film liquid, the present invention successively carries out pouring film forming and heating by the polyarylether and after building film liquid mixing
Processing, obtains polyarylether cured film.
In the present invention, the polyarylether is polyarylether or above-mentioned technical proposal the method described in above-mentioned technical proposal
The polyarylether being prepared.In the present invention, the polyarylether and to build the amount ratio of film liquid be preferably 0.06~0.1g:1mL, into
One step is preferably 0.07~0.08g:1mL.The present invention does not specially require the specific embodiment for pouring film forming, using ability
Well known method described in field technique personnel.
After pouring film forming, the present invention heats obtained membranoid substance, obtains polyarylether cured film.In this hair
In bright, the heat treatment preferably carries out in a vacuum or inert atmosphere, and the temperature of the heat treatment is preferably 200 DEG C~
400 DEG C, further preferably 250~350 DEG C, the time is preferably 0.5~3h, further preferably 1.0~2.5h, more preferably
1.5~2.0h.In particular during a heating process, the polyarylether and the biphenol monomer built in film liquid crosslink reaction to the present invention,
The product structure of the cross-linking reaction is preferably as shown in Formula IX:
It is provided by the invention polyarylether cured the present invention also provides the polyarylether cured film that the above method is prepared
Film contains aromatic ring structure, is conducive to the thermal stability, the mechanical performance that improve polyarylether cured film, while provided by the invention
Polyarylether cured film contains a large amount of fluorine elements, increases the free volume of polyarylether cured film, is conducive to improve polyarylether
The gas flux of cured film.In addition, polyarylether cured film provided by the invention contains cross-linking products shown in Formula IX, crosslinking
The presence of product further improves the stability of polyarylether cured film.
The present invention also provides the polyarylether cured film gas separation field application.The present invention is to the poly- virtue
The concrete application mode of ether cured film does not specially require, using mode well-known to those skilled in the art.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
By 500mLN, N'- dimethyl acetamide, 250mL hexamethylene, 0.15mol bisphenol AF and 0.18mol Carbon Dioxide
Potassium is fitted into three-necked flask, under an argon atmosphere, after mechanical stirring 1h, is warming up to 85 DEG C, azeotropic dehydration reflux 4h is warming up to
130 DEG C, azeotropy dehydrant is excluded, temperature of reaction system is cooled to room temperature, 0.1mol decafluorobiphenyl is added in reaction system,
120mL DMAc, mechanical stirring 1h are added, 80 DEG C of reaction 25h are warming up to, by obtained polymer solution in deionized water
Middle precipitation obtains high fluorine content polyarylether polymer through crushing, washing, drying.
50mLN- methyl pyrrolidone, 25mL toluene, 0.001mol bisphenol AF and 0.0012mol Anhydrous potassium carbonate are filled
Enter in three-necked flask, under an argon atmosphere, after mechanical stirring 1h, is warming up to 140 DEG C, azeotropic dehydration reflux 4h is warming up to 160
DEG C, azeotropy dehydrant is excluded, temperature of reaction system is cooled to room temperature, acquired solution is filtered, obtains building film liquid.Room temperature condition
Under, the high fluorine content polyarylether polymer that above-mentioned steps are obtained, which is dissolved in, to be built in film liquid, and high fluorine content polyarylether polymer is being built
Concentration in film liquid is 0.06g/mL, and after pouring film forming, under an inert atmosphere, 350 DEG C of chemical crosslinkings, the reaction time is
0.5h obtains polyarylether cured film.
Embodiment 2
By 500mL N, N'- dimethyl acetamide, 250mL hexamethylene, 0.1mol bisphenol-A and 0.12mol Carbon Dioxide
Potassium is fitted into three-necked flask, under an argon atmosphere, after mechanical stirring 1h, is warming up to 90 DEG C, azeotropic dehydration reflux 4h is warming up to
125 DEG C, azeotropy dehydrant is excluded, temperature of reaction system is cooled to room temperature, 0.1mol decafluorobiphenyl is added in reaction system,
Add 150mLN, N'- dimethyl acetamide, mechanical stirring 1h is warming up to 70 DEG C of reaction 35h, and obtained polymer is molten
Liquid is precipitated in deionized water, through crushing, washing, drying, obtains high fluorine content polyarylether polymer.
50mLN- methyl pyrrolidone, 25mL toluene, 0.001mol bisphenol-A and 0.0012mol Anhydrous potassium carbonate are filled
Enter in three-necked flask, under an argon atmosphere, after mechanical stirring 1h, is warming up to 140 DEG C, azeotropic dehydration reflux 4h is warming up to 160
DEG C, azeotropy dehydrant is excluded, temperature of reaction system is cooled to room temperature, acquired solution is filtered, obtains building film liquid.Room temperature condition
Under, the high fluorine content polyarylether polymer that above-mentioned steps are obtained, which is dissolved in, to be built in film liquid, and high fluorine content polyarylether polymer is being built
Concentration in film liquid is 0.08g/mL, and after pouring film forming, under vacuum, 300 DEG C of chemical crosslinkings, reaction time 1.0h is obtained
To polyarylether cured film.
Embodiment 3
500mL dimethyl sulfoxide, 250mL toluene, 0.13mol '-biphenyl diphenol and 0.156mol Anhydrous potassium carbonate are packed into
In three-necked flask, under an argon atmosphere, after mechanical stirring 1h, 145 DEG C being warming up to, azeotropic dehydration reflux 4h is warming up to 165 DEG C,
Azeotropy dehydrant is excluded, temperature of reaction system is cooled to room temperature, 0.1mol decafluorobiphenyl is added in reaction system, argon atmospher
Lower mechanical stirring 1h is enclosed, 85 DEG C of reaction 20h is warming up to, obtained polymer solution is precipitated in deionized water, crushed,
Washing, drying, obtain high fluorine content polyarylether polymer.
By 50mL N-Methyl pyrrolidone, 25mL toluene, 0.001mol '-biphenyl diphenol and 0.0012mol Carbon Dioxide
Potassium is fitted into three-necked flask, under an argon atmosphere, after mechanical stirring 1h, is warming up to 140 DEG C, azeotropic dehydration reflux 4h is warming up to
160 DEG C, azeotropy dehydrant is excluded, temperature of reaction system is cooled to room temperature, acquired solution is filtered, obtains building film liquid.Room temperature item
Under part, the high fluorine content polyarylether polymer that above-mentioned steps are obtained, which is dissolved in, to be built in film liquid, and high fluorine content polyarylether polymer exists
The concentration built in film liquid is 0.1g/mL, and after pouring film forming, under vacuum, 250 DEG C of chemical crosslinkings, reaction time 1.5h is obtained
To polyarylether cured film.
Structural characterization and performance test
Nuclear-magnetism characterization is carried out to the high fluorine content polyarylether that embodiment 1 is prepared, Fig. 1 is the hydrogen of 1 polyarylether of embodiment
Nuclear magnetic spectrogram, Fig. 2 are the fluorine nuclear magnetic spectrogram of 1 polyarylether of embodiment.By Fig. 1 and Fig. 2 it is known that the polyarylether that the present invention obtains
With structure shown in Formulas I.
The polyarylether cured film that the polyarylether and embodiment 1 be prepared to embodiment 1 is prepared carries out DSC survey
Examination, test results are shown in figure 3, and dotted line represents polyarylether cured film in Fig. 3, and solid line represents polyarylether.As seen from Figure 3
The glass transition temperature of the polyarylether cured film obtained by heat treatment is significantly improved, and up to 211 DEG C, is higher than poly- virtue
180 DEG C of ether, it was demonstrated that cross-linking reaction has occurred during heating.
Fig. 4 is the polyarylether that the embodiment of the present invention 1 is prepared and the polyarylether cured film that embodiment 1 is prepared
TMA curve.Dotted line represents polyarylether in Fig. 4, and solid line represents polyarylether cured film.As seen from Figure 4, the present invention is prepared into
The polyarylether cured film arrived has preferable dimensional stability.
TGA test is carried out to the polyarylether cured film that embodiment 4 is prepared, test results are shown in figure 5, by Fig. 5
It is found that the polyarylether cured film heat stability that embodiment 4 is prepared is preferable, under air atmosphere, 5% thermal weight loss temperature is
487℃。
The polyarylether use that embodiment 1 is prepared is poured into membrane formation process and obtains polyarylether film, it is thin to above-mentioned polyarylether
The tensile property for the polyarylether cured film that film and embodiment 1 are prepared is tested, and test equipment is Shimadzu AG-I 20KN
Electronic universal material testing machine.Test result is as shown in table 1:
The tensile property of polyarylether film and polyarylether cured film that 1 embodiment 1 of table is prepared
As shown in Table 1, polyarylether cured film provided by the invention has preferable mechanical performance.
The polyarylether use that embodiment 1 is prepared is poured into membrane formation process and obtains polyarylether film, it is thin to the polyarylether
The gas permeability for the polyarylether cured film that film and embodiment 1 are prepared can be carried out test, test method are as follows: using permanent body
The gas permeability matter of product-transformation strong method test polyarylether film and polyarylether cured film, during the test,
Polyarylether film or polyarylether cured film are sealed in test pond with epoxy resin, upstream pressure is set as 2atm, and will
Downstream is evacuated to vacuum, after a period of stabilisation to downstream pressure, is tested at 35 DEG C, with gas permeability coefficient (P) and choosing
Coefficient (α) is selected to characterize polyarylether film or polyarylether cured film to the separating effect of gas component.Test result such as 2 institute of table
Show:
The gas separating property of polyarylether film and polyarylether cured film that 2 embodiment 1 of table is prepared
As shown in Table 2, polyarylether cured film provided by the invention is to CO2、N2、O2And CH4Permeability it is higher, this hair
The polyarylether cured film of bright offer is to CO2/N2、CO2/CH4And O2/N2Selectivity it is preferable.
To sum up, polyarylether cured film thermal stability with higher provided by the invention, glass transition temperature is up to 211
DEG C, meanwhile, polyarylether cured film provided by the invention also has preferable dimensional stability and gas separating property, described poly-
The CO of aryl oxide cured film2Permeability is 71.92barrer, N2Permeability is 4.89barrer, O2Permeability is
19.69barrer CH4Permeability is 3.22barrer, CO2/N2Selectivity is 14.71, CO2/CH4Selectivity is 22.34, O2/
N2Selectivity is 4.03.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of polyarylether has structure shown in Formulas I:
The number-average molecular weight of the polyarylether is 6w~18w Daltons；
Wherein, Ar has structure shown in Formula II~any one of formula IV in-O-Ar-O-:
2. the preparation method of polyarylether described in claim 1, comprising the following steps:
(1) biphenol monomer, catalyst, dehydrating agent and organic solvent are mixed, obtains mixture；The catalyst includes carbonic acid
One of sodium, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide are a variety of；
(2) mixture for obtaining the step (1) carries out azeotropic dehydration, then removes dehydrating agent, obtains reaction material liquid；
(3) after the reaction material liquid for obtaining the step (2) is cooling, polycondensation reaction is carried out after mixing with decafluorobiphenyl, obtains Formulas I
The polyarylether of shown structure.
3. preparation method according to claim 2, which is characterized in that biphenol monomer and catalyst in the step (1)
Molar ratio is 0.9~1.2:0.9~1.2；The volume ratio of the dehydrating agent and organic solvent is 0.2~0.5:1；The mixture
Solid content be 5%~25%.
4. preparation method according to claim 2, which is characterized in that the temperature of azeotropic dehydration is 85 in the step (2)
~140 DEG C, the time is 3~5h；The step (2) removes dehydrating agent by the way of reflux, and the temperature of the reflux is 150~
180℃。
5. preparation method according to claim 2, which is characterized in that in step (3) decafluorobiphenyl and reaction material liquid
The molar ratio of biphenol monomer is 0.9~1.2:0.9~1.2.
6. preparation method according to claim 2 or 5, which is characterized in that the temperature of polycondensation reaction is in the step (3)
70~90 DEG C, the time is 20~35h.
7. a kind of preparation method of polyarylether cured film, comprising the following steps:
(a) after mixing biphenol monomer, catalyst, dehydrating agent and organic solvent, azeotropic dehydration is carried out, after then removing dehydrating agent
It is cooling, it obtains building film liquid；The catalyst includes one of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide
Or it is a variety of；
(b) by polyarylether and the step (a) obtain build film liquid mix after, successively carry out pouring film forming and heat treatment, obtain
To polyarylether cured film；The polyarylether is any one of polyarylether described in claim 1 or claim 2~6 the method
The polyarylether being prepared.
8. preparation method according to claim 7, which is characterized in that the temperature heated in the step (b) is 200
DEG C~400 DEG C, the time is 0.5~3h.
9. the polyarylether cured film that claim 7 or 8 the methods are prepared.
10. application of the polyarylether cured film in gas separation field described in claim 9.
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| CN111363140A (en) * | 2020-03-09 | 2020-07-03 | 吉林大学 | Crosslinkable fluorine-containing polyarylether and preparation method and application thereof |
| CN113234221A (en) * | 2021-05-10 | 2021-08-10 | 吉林大学 | Fluorine-containing polyarylether containing fluorene as well as preparation method and application thereof |
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| CN111363140A (en) * | 2020-03-09 | 2020-07-03 | 吉林大学 | Crosslinkable fluorine-containing polyarylether and preparation method and application thereof |
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| CN113234221B (en) * | 2021-05-10 | 2022-06-21 | 吉林大学 | Fluorine-containing polyarylether containing fluorene as well as preparation method and application thereof |
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| CN109679088B (en) | 2020-09-01 |
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