CN107151324A - Poly- fragrant imines ether sulfone of thermal response fluorescent type and preparation method thereof - Google Patents
Poly- fragrant imines ether sulfone of thermal response fluorescent type and preparation method thereof Download PDFInfo
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- CN107151324A CN107151324A CN201710364970.3A CN201710364970A CN107151324A CN 107151324 A CN107151324 A CN 107151324A CN 201710364970 A CN201710364970 A CN 201710364970A CN 107151324 A CN107151324 A CN 107151324A
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Abstract
The invention discloses the poly- fragrant imines ether sulfone of the thermal response fluorescent type shown in formula (I), the preparation method of the polymer is：Under nitrogen protection; dihydroxy diphenylamine, two fluorine monomers, salt forming agent, solvent and toluene containing sulfuryl are sequentially added in the reactor, is stirred and evenly mixed, and are heated and are warming up to 130 DEG C~140 DEG C 3~4h of reaction; steam toluene; 160 DEG C~190 DEG C are warming up to again to continue to react 4~6h, and reacting rear material is cooled to room temperature, pours into deionized water and precipitates; suction filtration; obtained solids again with methanol extracting, the solid product that suction filtration is obtained, through drying, is obtained thermal response fluorescent type polyimides ether sulfone.Thermal response fluorescent type polyimides ether sulfone of the present invention has obvious thermal response fluorescence property, good heat endurance, higher glass transition temperature, excellent solubility property, available for fields such as temperature sensor, opto-electronic device, bio-imagings.
Description
Technical field
The invention belongs to high-molecular compound and its preparation, it is related to the poly- fragrant imines ether sulfone of thermal response fluorescent type and its preparation side
Method.Transparent high-strength thin-film can be made in the poly- fragrant imines ether sulfone of high polymer material of the present invention-thermal response fluorescent type, for passing
The fields such as sensor, opto-electronic device, bio-imaging.
Background technology
With the development of science and technology, proposing higher requirement to advanced polymer-function material.Not only it is needed to have
Excellent heat endurance and good processability, also require its to environment (such as temperature, acid-base property, light, electricity) have perceive with
The specific function of response.At present, the research to the advanced function polymer with thermo-responsive has become a focus, enjoys
The favor of researcher.
Because temperature is an important environmental factor, so the material with temperature sense is quite paid close attention to by people always.
In the prior art, common temperature response type polymer has poly-N-isopropyl acrylamide (abbreviation PNIPAM), poly- ethylene methacrylic
Ether (abbreviation PMVE), polyethylene caprolactone (abbreviation PVCa) etc., these polymer (80 DEG C of ＜) can only be used at a lower temperature.
And there are some shortcomings in the high performance heat resistant high polymer material generally used itself.For example：Polyether-ketone based polymer vitrifying
Transition temperature (Tg) relatively low, it is limited in TgThe use of temperatures above scope；The insoluble insoluble property of polyimides is limited significantly
Its processing characteristics；And polysulfones material is high because of its melt viscosity, melt fluidity difference also limit its application.It is prior
It is that these common heat-proof macromolecules, almost without thermo-responsive, response type advanced function are used as which has limited them to environment
The application of material.
The content of the invention
The purpose of the present invention is intended to overcome deficiency of the prior art to gather fragrant imines ether sulfone there is provided a kind of thermal response fluorescent type
And preparation method thereof.The present invention is overcome by providing a kind of poly- fragrant imines ether sulfone containing aniline group and preparation method thereof
Existing temperature-responsive polymer exist compared with lower glass transition temperatures and the poor dissolving of heat-proof macromolecule polyether sulphone
Property the shortcomings of, the poly- fragrant imines ether sulfone containing aniline group that provides of the present invention has thermal response fluorescence property, good heat is steady
Qualitative, higher glass transition temperature, and excellent solubility property.
Present disclosure is：The poly- fragrant imines ether sulfone of thermal response fluorescent type, it is characterized in that：The poly- virtue of the thermal response fluorescent type is sub-
Amidogen ether sulfone has the chemical structural formula shown in formula (I)：
In formula (I)：
Poly- fragrant imines ether sulfone (polymer) the repeat unit ordered state of thermal response fluorescence of the present invention is common for nucleophilic aromatic substitution
Poly-, strand is arranged in " Z " font, more uniform (the weight average molecular weight M of molecular weight distributionwFor 198700~361800), have
Higher glass transition temperature (Tg>200 DEG C), while having good heat endurance and solubility property (TD5%>400 DEG C, energy
It is dissolved in conventional organic solvent dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE
In sulfolane), it can both realize that melt-processed was molded, and can also realize solution machine-shaping, the variation of molding mode is widened
The application field of such polymer；In addition, introducing the aniline group of rich electricity in polymer backbone conformation so that when temperature is raised
Cloud density on molecular backbone NH groups changes, so as to cause its fluorescence intensity to change, imparts the heat and rings
The thermal response fluorescence property for answering the poly- fragrant imines ether sulfone (polymer) of fluorescence good.
The present invention another content be：The preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, it is characterized in that including under
Row step：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, in reactor (for example：Three-necked flask) in sequentially add
10mmol is to methoxybromobenzene, 10mmol P-nethoxyaniline, palladium [the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2
(dba)3], 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine (abbreviation BINAP), 2.8mmol sodium tert-butoxides, 20~80mmol into
Salt agent, 5~30mL solvents and 2~6mL (water entrainer) toluene, stirring mixing (turn into homogeneous reaction system), heat (reactant
System) 3~4h of (band water) reaction is warming up at 100~130 DEG C, toluene is then distilled off, subsequent (quick) be warming up to 160~
180 DEG C are continued after 4~6h of stirring reaction, and (slow) is cooled to room temperature, and crude product (i.e. reacting rear material) (is used with dichloromethane
Measure preferably 15~30mL) extract, after stratification, lower floor's organic phase is collected, solids crude production is obtained after organic phase is rotated
Thing, then by solid crude product, through column chromatography, (eluant, eluent is volume ratio petroleum ether again:Ethyl acetate=8:1 mixed liquor) purification
After obtain dimethoxy diphenylamines；
B, synthesis dihydroxy diphenylamine：By the step a dimethoxy diphenylamines prepared be configured to concentration for 0.3~
The dichloromethane solution of 0.5mol/L dimethoxy diphenylamines, is reconfigured at the tribromide that 10mL concentration is 1.1~1.6mol/L
The dichloromethane solution of boron, the dichloromethane solution of this Boron tribromide is slowly dropped to the dichloromethane of dimethoxy diphenylamines
In solution, 15~20h is reacted, crude product (i.e. reacting rear material) is extracted with ethyl acetate (consumption preferably 20~40mL)
Take, after stratification, collect and solid crude product is obtained after upper organic phase, revolving, then by solid crude product through column chromatography (elution
Agent is volume ratio dichloromethane：Methanol=15:1 mixed liquor) purification, obtain dihydroxy diphenylamine (or dihydroxy diphenylamine
Monomer)；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three mouthfuls of circles
Bottom flask) in, sequentially add two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b prepare dihydroxy diphenylamine, 20~
80mmol salt forming agents, 15~30mL solvents and 2~6mL toluene, stirring mixing (turn into homogeneous reaction system), heat (reactant
System) 130 DEG C~140 DEG C (band water) 3~4h of reaction are warming up to, then distillation removes out toluene, and then (quick) is warming up to 160 DEG C again
~190 DEG C are continued to react 4~6h, and reacting rear material is made；
D, post processing：Reacting rear material (slow) made from step c is cooled to room temperature, 150~400mL deionizations are poured into
Precipitated in water or distilled water, suction filtration, obtained solids is extracted with 25~250mL methanol and (stirred and impregnated with methanol, then taken out again
Filter) 10~20h, the solid product that suction filtration is obtained prepare the poly- fragrant imines ether sulfone of thermal response fluorescent type through drying.
In another content of the present invention：Meta-methoxy bromobenzene is replaced with described in step a to methoxybromobenzene, it is described to first
Epoxide aniline replaces with m-anisidine.
In another content of the present invention：Described salt forming agent can be Anhydrous potassium carbonate or Carbon Dioxide caesium.
In another content of the present invention：Two fluorine monomers containing sulfuryl described in step c can be 4,4'- difluorodiphenyls
Any of sulfone, (the fluoro- benzene sulfuryls of the 4-) benzene of 4,4'- bis- and 1,3- bis- (the fluoro- benzene sulfuryls of 4-) benzene.
In another content of the present invention：Described solvent can be dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, N- methyl
Any of pyrrolidones and sulfolane.
In another content of the present invention：Drying described in step d can be in 100 DEG C of temperature, pressure 0.1MPa condition
Under (vacuum) dry 10h or 24h dried under conditions of 100 DEG C~150 DEG C of temperature.
In another content of the present invention：Solid content described in step a and step c in reaction system is preferably controlled
20%~50% (weight percent content)；The concept of the solid content is：All solids raw material and liquid in reaction system (including
Liquid charging stock, solvent and water entrainer) percentage by weight.
Compared with prior art, the present invention has following features and beneficial effect：
(1) using the present invention, the poly- fragrant imines ether sulfone (copolymerization of thermal response fluorescence is prepared using nucleophilic aromatic substitution polycondensation reaction
High polymer material)；Due to the hydroxyl (- OH) in aniline monomer have certain acidity, in the basic conditions can and electronegativity
Aromatic nucleophilic substitution reaction occurs for stronger fragrant two fluorine monomer；Therefore, the present invention utilizes dihydroxy diphenylamine according to this principle
Monomer and nucleophilic aromatic substitution copolycondensation of two fluorine monomers in alkaline environment containing sulfuryl, are prepared a kind of new solvable
The poly- fragrant imines ether sulfone (copolymerized macromolecule material) of heat-resisting high-performance thermal response fluorescence；
(2) using the present invention, the poly- fragrant imines ether sulfone containing aniline group (- NH) has novel chemical constitution, NH institutes
Plane with neighbouring ehter bond can form electron conjugated effect, the design feature can assign such polymer good thermal response
Performance and photoelectric properties；
(3), can be by changing A using the present invention1R and A2R structure carries out structure regulating and modification to polymer；This hair
Bright polymer has unique thermal response fluorescence property and excellent solubility property, passes through casting method or spin-coating method
Transparent high-strength thin-film can be made, film thickness is uniform (up to 50 μm~150 μm), and film has preferable machinery
Performance, tensile strength is up to 105~137MPa, and elongation at break is up to 110%~130%, in battery diaphragm and inertial confinement
The fields such as fusion (ICF) film target show preferable application prospect；
(4) using the present invention, the aniline group (- NH) of rich electricity is introduced in poly- fragrant imines ether sulfone backbone structure not only can be with
The performance such as glass transition temperature, heat endurance, tensile strength of polymer is improved, being total between main polymer chain can also be increased
Yoke length, assigns the unique thermal response fluorescence property of polymer and optical property, makes polymer in terms of temperature, photoelectric sensor
Have a good application prospect；
(5) poly- fragrant imines ether sulfone polymer prepared by the present invention contains phenyl ring, imine group, ehter bond and sulfuryl, is use
Nucleophilic aromatic substitution copolycondensation is prepared from；Product preparation process is simple, and process is easy, and operation is easy, and raw material is easily obtained
, reaction condition is gentle, and preparation cost is low, and product yield is higher (more than 90%), (preparation) of the invention poly- fragrant imines ether sulfone
With thermal response fluorescence property, higher glass transition temperature (Tg>200 DEG C) and heat decomposition temperature (TD5%>400 DEG C), and
Excellent dissolubility is shown, dimethyl sulfoxide (DMSO), DMF, DMA, N- first is may be dissolved in
In base pyrrolidones and sulfolane；Prepared Polymer Processing mode is various, and both melt-processable was molded, and solution can be carried out again
Processing, it is practical, it is a kind of advanced function material of new structure.
Brief description of the drawings
Fig. 1, Fig. 2 be respectively 4,4 '-dihydroxy diphenylamine and 3,3 '-dihydroxy diphenylamine nucleus magnetic hydrogen spectrum (1HNMR) compose
Figure；Hydrogen atom under two kinds of each chemical environments of compound is corresponding with its chemical shift good, and its number matches with peak area；
Understand that experimental method can obtain target production designed according to this invention from the nuclear magnetic spectrogram analysis of two kinds of dihydroxy diphenylamines
Thing.
Fig. 3 and Fig. 4 are respectively polymer p-PIES-1 and m-PIES-1 nuclear magnetic spectrogram；By taking m-PIES-1 as an example, by Fig. 4
Understand, appearance one is unimodal between chemical shift 8.5-8.6ppm, this peak is the characteristic peak of imido grpup；In chemical shift 7.6-
Occur bimodal between 7.8ppm, this peak is the characteristic absorption peak of four H atoms on the phenyl ring being connected with sulfuryl；In chemical shift
Occurs bimodal, the characteristic peak of four H atoms on the phenyl ring that this peak is connected for ehter bond between 7.0-7.1ppm；Other peaks are imines
Four atoms on characteristic absorption peak between group and sour key on phenyl ring, the phenyl ring are in four kinds of different chemical environments, therefore
Occur four absworption peaks on spectrogram, each chemical shift is as shown in the figure for its；The structure of the actual polymer prepared and theory one
Cause；
Fig. 5 is that thermal response fluorescent type prepared by embodiment 1 gathers heat sound prepared by virtue imines ether sulfone p-PIES-1 and embodiment 4
Answer the poly- fragrant imines ether sulfone m-PIES-1 of fluorescent type Fourier transform infrared collection of illustrative plates；As shown in figure 5, in 3386cm-1There is benzene in place
Amine groups NH skeletal vibration characteristic peak；In 1230cm-1There is ehter bond C-O-C stretching vibration peak in place.With reference to nuclear magnetic spectrogram, then
The secondary polymeric backbone structure for proving that the present invention is synthesized is consistent with theory；
Fig. 6 is that thermal response fluorescent type prepared by embodiment 1 gathers heat sound prepared by virtue imines ether sulfone p-PIES-1 and embodiment 4
Answer the poly- fragrant imines ether sulfone m-PIES-1 of fluorescent type thermogravimetric (TG) curve and differential scanning calorimetry (DSC) curve；Sample heat point
Solution temperature is TD5%>410℃；Glass transition temperature Tg>200 DEG C, can be at higher temperature with higher glass transition temperature
Process and use under degree；
Fig. 7, Fig. 8 are that the thermal response fluorescent type prepared by embodiment 1 gathers virtue imines ether sulfone p-PIES-1 and embodiment 4 respectively
Prepared thermal response fluorescent type gathers the photo for the transparent membrane that virtue imines ether sulfone m-PIES-1 is made up of casting method；Can by figure
See that the filming performance of polymer is preferable, and film has preferably transparent and good mechanical performance, and tensile strength is reachable
82~105MPa, elongation at break is up to 110%~130%；
Fig. 9 is polymer p-PIES-1 thermal response fluorescence photo；The thermal response property of polymer is preferable as seen from the figure, plus
Color contrast is more apparent before and after hot.
Embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention
It is whole, still fall within protection scope of the present invention.
Following examples explanation：From different dihydroxy diphenylamine monomers, the thermal response fluorescence of different structure can obtain
The poly- fragrant imines ether sulfone x-PIES of type, the polymer of different structure is macroscopically showing different physical and chemical performances.
Embodiment 1：
The preparation method of the poly- fragrant imines ether sulfone of thermal response-type fluorescence, comprises the following steps：
Under nitrogen protection, 10mmol is sequentially added in three-necked flask to methoxybromobenzene, 10mmol is to methoxybenzene
Amine, palladium (the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2(dba)3), 0.3mmol 1,1 '-dinaphthalene -2, (letter of 2 ' diphenyl phosphines
Claim BINAP), 2.8mmol sodium tert-butoxides, 20mmol salt forming agents, 5mL solvents and 2mL toluene, stirring are mixed into uniform anti-
System is answered, in 100~130 DEG C of (band water) reaction 3h, then distillation removes out toluene, is then rapidly heated to 160~180 DEG C of continuation
Stirring reaction 5h, is slowly cooled to room temperature, and crude product is extracted with dichloromethane (15mL), after stratification, collects lower floor organic
Solid crude product is obtained after phase, revolving, then (eluant, eluent is petroleum ether by column chromatography：Ethyl acetate=8:1) purify, obtain 4,
4 '-dimethoxy diphenylamines；Again by the 4,4 '-dimethoxy diphenylamines purified be configured to concentration be 0.4mol/L 4,4 '-
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.3mol/L is molten
Liquid, 4, the dichloromethane of 4 '-dimethoxy diphenylamines are slowly dropped to by the dichloromethane solution (consumption 10mL) of this Boron tribromide
In alkane solution, 18h is reacted.Crude product is poured into cold water, extracted with ethyl acetate (20mL), after stratification, upper strata is collected
Solid crude product is obtained after organic phase, revolving, then through column chromatography, (eluant, eluent is dichloromethane by solid crude product：Methanol=15:
1) purify, obtain 4,4 '-dihydroxy diphenylamine；Under nitrogen protection, equipped with agitator, airway tube, condenser pipe and water knockout drum
Reactor (for example：Three neck round bottom flask) in, sequentially add 10mmol 4,4'- difluorodiphenyls sulfone, 10mmol 4,4 '-dihydroxy
Base diphenylamines, make salt forming agent by alkali of 20mmol Anhydrous potassium carbonates, with 1-METHYLPYRROLIDONE (consumption 15mL) for solvent, with first
Benzene (consumption 3mL) is water entrainer, is heated to 140 DEG C of band water and reacts 3h, then distills out toluene, then be rapidly heated to 180
DEG C continue react 4h；Then reaction system is slowly cooled to room temperature, reaction solution is poured into deionized water and precipitated, suction filtration, then is passed through
10h is extracted with methanol；Vacuum (pressure is 0.1MPa) dries 10h to extract under the conditions of 100 DEG C again, obtains target polymerization
The poly- fragrant imines ether sulfone of thing --- thermal response fluorescent type, its yield is more than 90%.The poly- fragrant imines ether sulfone of gained thermal response fluorescent type
Abbreviation p-PIES-1, particular product performance parameters are as shown in table 1 below.
Table 1：The performance parameter of the poly- fragrant imines ether sulfone p-PIES-1 products of thermal response fluorescent type：
In table 1：MwIt is weight average molecular weight, MnIt is number-average molecular weight, PDI is molecular weight distributing index, TgIt is glass transition
Temperature, TD5%It is by temperature during thermal weight loss 5%, λmaxIt is ultraviolet maximum absorption wavelength, λemIt is fluorescence maximum emission wavelength, after
Together.
Embodiment 2：
The preparation method of the poly- fragrant imines ether sulfone of thermal response-type fluorescence, comprises the following steps：
Under nitrogen protection, 10mmol is sequentially added in three-necked flask to methoxybromobenzene, 10mmol is to methoxybenzene
Amine, palladium (the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2(dba)3), 0.3mmol1,1 '-dinaphthalene -2,2 ' diphenyl phosphines are (referred to as
BINAP), 2.8mmol sodium tert-butoxides, 20mmol salt forming agents, 5mL solvents and 1.5mL toluene, stirring are mixed into uniform anti-
System is answered, in 100~130 DEG C of (band water) reaction 4h, then distillation removes out toluene, is then rapidly heated to 160~180 DEG C of continuation
Stirring reaction 6h, is slowly cooled to room temperature, and crude product is extracted with dichloromethane (15mL), after stratification, collects lower floor organic
Solid crude product is obtained after phase, revolving, then (eluant, eluent is petroleum ether by column chromatography：Ethyl acetate=8:1) purify, obtain 4,
4 '-dimethoxy diphenylamines；Again by the 4,4 '-dimethoxy diphenylamines purified be configured to concentration be 0.3mol/L 4,4 '-
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.1mol/L is molten
Liquid, 4, the dichloromethane of 4 '-dimethoxy diphenylamines are slowly dropped to by this Boron tribromide dichloromethane solution (consumption 10mL)
In solution, 15h is reacted.Crude product is poured into cold water, after ethyl acetate (25mL) extraction, stratification, collecting upper strata has
Solid crude product is obtained after machine phase, revolving, then through column chromatography, (eluant, eluent is dichloromethane by solid crude product：Methanol=15:1)
Purification, obtains 4,4 '-dihydroxy diphenylamine；Under nitrogen protection, equipped with agitator, airway tube, condenser pipe and water knockout drum
Reactor is (for example：Three neck round bottom flask) in, 10mmol 4,4'- bis- (the fluoro- benzene sulfuryls of 4-) benzene, 10mmol 4 are sequentially added,
4 '-dihydroxy diphenylamine, makees salt forming agent by alkali of 20mmol Anhydrous potassium carbonates, is molten with 1-METHYLPYRROLIDONE (consumption 15mL)
Agent, with toluene (consumption 2mL) for water entrainer, is heated to 140 DEG C of band water and reacts 3h, then distill out toluene, then quick liter
Temperature continues to react 4h to 180 DEG C；Then reaction system is slowly cooled to room temperature, reaction solution is poured into deionized water and precipitated, and is taken out
Filter, then through extracting 10h with methanol；Vacuum (pressure is 0.1MPa) dries 10h to extract under the conditions of 100 DEG C again, obtains target
The poly- fragrant imines ether sulfone of polymer --- thermal response fluorescent type, its yield is more than 90%.The poly- fragrant imines of gained thermal response fluorescent type
Ether sulfone abbreviation p-PIES-2, particular product performance parameters are as shown in table 2 below.
Table 2：The performance parameter of the poly- fragrant imines ether sulfone p-PIES-2 products of thermal response fluorescent type：
Embodiment 3：
The preparation method of the poly- fragrant imines ether sulfone of thermal response-type fluorescence, comprises the following steps：
Under nitrogen protection, 10mmol is sequentially added in three-necked flask to methoxybromobenzene, 10mmol is to methoxybenzene
Amine, palladium (the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2(dba)3), 0.3mmol 1,1 '-dinaphthalene -2, (letter of 2 ' diphenyl phosphines
Claim BINAP), 2.8mmol sodium tert-butoxides, 20mmol salt forming agents, 5mL solvents and 2mL toluene, stirring are mixed into uniform anti-
System is answered, in 100~130 DEG C of (band water) reaction 4h, then distillation removes out toluene, is then rapidly heated to 160~180 DEG C of continuation
Stirring reaction 4h, is slowly cooled to room temperature, and crude product is extracted with dichloromethane (30mL), after stratification, collects lower floor organic
Solid crude product is obtained after phase, revolving, then (eluant, eluent is petroleum ether by column chromatography：Ethyl acetate=8:1) purify, obtain 4,
4 '-dimethoxy diphenylamines；Again by the 4,4 '-dimethoxy diphenylamines purified be configured to concentration be 0.5mol/L 4,4 '-
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.6mol/L is molten
Liquid, 4, the dichloromethane of 4 '-dimethoxy diphenylamines are slowly dropped to by the dichloromethane solution (consumption 10mL) of this Boron tribromide
In alkane solution, 20h is reacted.Crude product is poured into cold water, extracted with ethyl acetate (40mL), after stratification, upper strata is collected
Solid crude product is obtained after organic phase, revolving, then through column chromatography, (eluant, eluent is dichloromethane by solid crude product：Methanol=15:
1) purify, obtain 4,4 '-dihydroxy diphenylamine；Under nitrogen protection, equipped with agitator, airway tube, condenser pipe and water knockout drum
Reactor (for example：Three neck round bottom flask) in, sequentially add 10mmol 1,3- bis- (the fluoro- benzoyls of 4-) benzene, 10mmol
4,4 '-dihydroxy diphenylamine makees salt forming agent by alkali of 20mmol Anhydrous potassium carbonates, is with 1-METHYLPYRROLIDONE (consumption 15mL)
Solvent, with toluene (consumption 3mL) for water entrainer, is heated to 140 DEG C of band water and reacts 3h, then distill out toluene, then quickly
180 DEG C are warming up to continue to react 4h；Then reaction system is slowly cooled to room temperature, reaction solution is poured into deionized water and precipitated,
Suction filtration, then through extracting 10h with methanol；Vacuum (pressure is 0.1MPa) dries 10h to extract under the conditions of 100 DEG C again, obtains mesh
Mark polymer --- the poly- fragrant imines ether sulfone of thermal response fluorescent type, its yield is more than 90%.The poly- virtue of gained thermal response fluorescent type is sub-
Amidogen ether sulfone abbreviation p-PIES-3, particular product performance parameters are as shown in table 3 below.
Table 3：The performance parameter of the poly- fragrant imines ether sulfone p-PIES-3 products of thermal response fluorescent type：
Embodiment 4：
The preparation method of the poly- fragrant imines ether sulfone of thermal response-type fluorescence, comprises the following steps：
Under nitrogen protection, 10mmol meta-methoxy bromobenzenes, 10mmol meta-methoxy benzene are sequentially added in three-necked flask
Amine, palladium (the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2(dba)3), 0.3mmol 1,1 '-dinaphthalene -2, (letter of 2 ' diphenyl phosphines
Claim BINAP), 2.8mmol sodium tert-butoxides, 20mmol salt forming agents, 5mL solvents and 1.5mL toluene, stirring are mixed into uniform
Reaction system, in 100~130 DEG C of (band water) reaction 3.5h, then distillation removes out toluene, is then rapidly heated to 160~180 DEG C
Continue stirring reaction 5h, be slowly cooled to room temperature, crude product is extracted with dichloromethane (20mL), after stratification, collect lower floor
Solid crude product is obtained after organic phase, revolving, then (eluant, eluent is petroleum ether by column chromatography：Ethyl acetate=8:1) purify, obtain
To 3,3 '-dimethoxy base diphenylamines；It is 0.4mol/L's that the 3,3 '-dimethoxy diphenylamines purified is configured into concentration again
3, the dichloromethane solution of 3 '-dimethoxy diphenylamines is reconfigured at the dichloromethane for the Boron tribromide that 10mL concentration is 1.4mol/L
Alkane solution, 3, the two of 3 '-dimethoxy diphenylamines are slowly dropped to by the dichloromethane solution (consumption 10mL) of this Boron tribromide
In chloromethanes solution, 17h is reacted.Crude product is poured into cold water, after ethyl acetate (20mL) extraction, stratification, collected
Solid crude product is obtained after upper organic phase, revolving, then through column chromatography, (eluant, eluent is dichloromethane by solid crude product：Methanol
=15:1) purify, obtain 3,3 '-dihydroxy diphenylamine；Under nitrogen protection, equipped with agitator, airway tube, condenser pipe and point
The reactor of hydrophone is (for example：Three neck round bottom flask) in, sequentially add 10mmol 4,4'- difluorodiphenyls sulfone, 10mmol 3,3 '-
Dihydroxy diphenylamine, make salt forming agent by alkali of 20mmol Anhydrous potassium carbonates, with 1-METHYLPYRROLIDONE (consumption 15mL) for solvent,
With toluene (consumption 2.5mL) for water entrainer, it is heated to 140 DEG C of band water and reacts 3h, then distill out toluene, then be rapidly heated
Continue to react 4h to 180 DEG C；Then reaction system is slowly cooled to room temperature, reaction solution is poured into deionized water and precipitated, suction filtration,
Again through extracting 10h with methanol；Vacuum (pressure is 0.1MPa) dries 10h to extract under the conditions of 100 DEG C again, obtains target polymerization
The poly- fragrant imines ether sulfone of thing --- thermal response fluorescent type, its yield is more than 90%.The poly- fragrant imines ether sulfone of gained thermal response fluorescent type
Abbreviation m-PIES-1, particular product performance parameters are as shown in table 4 below.
Table 4：The performance parameter of the poly- fragrant imines ether sulfone m-PIES-1 products of thermal response fluorescent type：
Embodiment 5：
The poly- fragrant imines ether sulfone of thermal response fluorescent type, the poly- fragrant imines ether sulfone of the thermal response fluorescent type has the change shown in formula (I)
Learn structural formula：
In formula (I)：
Poly- fragrant imines ether sulfone (polymer) the repeat unit ordered state of the thermal response fluorescence is nucleophilic aromatic substitution copolymerization, point
Subchain is arranged in " Z " font, more uniform (the weight average molecular weight M of molecular weight distributionwFor 198700~361800), with higher
Glass transition temperature (Tg>200 DEG C), while having good heat endurance and solubility property (TD5%>400 DEG C, and can be molten
Xie Yu commonly use organic solvent dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE and
In sulfolane), it can both realize that melt-processed was molded, and can also realize solution machine-shaping, the variation of molding mode is widened
The application field of such polymer；In addition, introducing the aniline group of rich electricity in polymer backbone conformation so that temperature raises the time-division
Cloud density on sub- main chain NH groups changes, so as to cause its fluorescence intensity to change, imparts polymer good
Good thermal response fluorescence property.Based on the excellent combination property of the poly- fragrant imines ether sulfone of the thermal response fluorescence, it can be considered as one
Plant the advanced function material of new structure.
Embodiment 6：
The preparation method of the poly- fragrant imines ether sulfone of thermal response-type fluorescence, comprises the following steps：
A, dispensing：By 10mmol 3,3' dihydroxy diphenylamines, 10mmol4,4'- bis- (the fluoro- benzene sulfuryls of 4-) benzene, 20mmol
Salt forming agent, 10mL solvents and 2mL (water entrainer) toluene take each component raw material, standby；The salt forming agent be Anhydrous potassium carbonate or
Carbon Dioxide caesium；
B, reaction：Under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three
Mouthful round-bottomed flask) in, sequentially add 4,4'- bis- (the fluoro- benzene sulfuryls of 4-) benzene, 3,3'- dihydroxy diphenylamines monomer, salt forming agent, molten
Agent and toluene, stirring are mixed into homogeneous reaction system, and heating response system is simultaneously warming up to 130 DEG C of (band water) reaction 4h, then
Distillation removes out toluene, and then (quick) is warming up to 160 DEG C of continuation reaction 6h again, and reacting rear material is made；
C, post processing：Reacting rear material (slow) is cooled to room temperature, pours into 150mL deionized waters or distilled water and sinks
Form sediment, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 10h with 25mL methanol again, and what suction filtration was obtained consolidates
Body product is through drying, the poly- fragrant imines ether sulfone of the thermal response fluorescent type as prepared；
The other the same as in Example 4, is omitted.
Embodiment 7：
Poly- fragrant imines ether sulfone of thermal response-type fluorescence and preparation method thereof, comprises the following steps：
A, dispensing：By 10mmol3,3' dihydroxy diphenylamines, 10mmol1,3- bis- (the fluoro- benzoyls of 4-) benzene, 20mmol
Salt forming agent, 10mL solvents and 2mL (water entrainer) toluene take each component raw material, standby；The salt forming agent be Anhydrous potassium carbonate or
Carbon Dioxide caesium；
B, reaction：Under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three
Mouthful round-bottomed flask) in, sequentially add 1,3- bis- (the fluoro- benzoyls of 4-) benzene, 3,3'- dihydroxy diphenylamines monomer, salt forming agent, molten
Agent and toluene, stirring are mixed into homogeneous reaction system, and heating response system is simultaneously warming up to 140 DEG C of (band water) reaction 3h, then
Distillation removes out toluene, and then (quick) is warming up to 190 DEG C of continuation reaction 4h again, obtains reacting rear material；
C, post processing：Reacting rear material (slow) is cooled to room temperature, pours into 400mL deionized waters or distilled water and sinks
Form sediment, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 19h with 250mL methanol again, what suction filtration was obtained
Solid product is through drying, the poly- fragrant imines ether sulfone of the thermal response fluorescent type as prepared；
The other the same as in Example 4, is omitted.
In above-described embodiment 6,7：Drying described in step c is that (vacuum) is done under conditions of 100 DEG C of temperature, pressure 0.1MPa
Dry 10h dries 24h under conditions of 100 DEG C~150 DEG C of temperature.
In above-described embodiment 6,7：Solvent described in step a can be dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, N- methyl
Any of pyrrolidones and sulfolane.
Embodiment 8：
The preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, comprises the following steps：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, in reactor (for example：Three-necked flask) in sequentially add
10mmol is to methoxybromobenzene, 10mmol P-nethoxyaniline, palladium [the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2
(dba)3], 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine (abbreviation BINAP), 2.8mmol sodium tert-butoxides, 20mmol is into salt
Agent, 5mL solvents and 2mL (water entrainer) toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to
(band water) reaction 4h, is then distilled off toluene at 100 DEG C, and subsequent (quick) is warming up to 160 DEG C and continued after stirring reaction 6h,
(slow) is cooled to room temperature, and crude product (i.e. reacting rear material) is extracted with dichloromethane (consumption preferably 15mL), stands
After layering, lower floor's organic phase is collected, solid crude product is obtained after organic phase is rotated, then again by solid crude product through column chromatography
(eluant, eluent is volume ratio petroleum ether:Ethyl acetate=8:1 mixed liquor) purification after obtain dimethoxy diphenylamines；
B, synthesis dihydroxy diphenylamine：It is 0.3mol/L's that the step a dimethoxy diphenylamines prepared is configured into concentration
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.1mol/L is molten
In liquid, the dichloromethane solution that the dichloromethane solution of this Boron tribromide is slowly dropped to dimethoxy diphenylamines, reaction
15h, crude product (i.e. reacting rear material) is extracted with ethyl acetate (consumption 20mL), after stratification, collects upper organic phase,
Solid crude product is obtained after revolving, then through column chromatography, (eluant, eluent is volume ratio dichloromethane by solid crude product：Methanol=15:1
Mixed liquor) purification, obtain dihydroxy diphenylamine (or dihydroxy diphenylamine monomer)；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three mouthfuls of circles
Bottom flask) in, sequentially add dihydroxy diphenylamine, 20mmol prepared by two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b
Salt forming agent, 15mL solvents and 2mL toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to 130 DEG C
(band water) reaction 4h, then distillation removes out toluene, and then (quick) is warming up to 160 DEG C of continuation reaction 6h again, and thing after reaction is made
Material；
D, post processing：Reacting rear material (slow) made from step c is cooled to room temperature, pour into 150mL deionized waters or
Precipitated in distilled water, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 10h with 25mL methanol again, takes out
Obtained solid product is filtered through drying, that is, prepares the poly- fragrant imines ether sulfone of thermal response fluorescent type.
Embodiment 9：
The preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, comprises the following steps：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, in reactor (for example：Three-necked flask) in sequentially add
10mmol is to methoxybromobenzene, 10mmol P-nethoxyaniline, palladium [the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2
(dba)3], 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine (abbreviation BINAP), 2.8mmol sodium tert-butoxides, 80mmol is into salt
Agent, 30mL solvents and 6mL (water entrainer) toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to
(band water) reaction 3h, is then distilled off toluene at 130 DEG C, and subsequent (quick) is warming up to 180 DEG C and continued after stirring reaction 4h,
(slow) is cooled to room temperature, and crude product (i.e. reacting rear material) is extracted with dichloromethane (consumption 30mL), after stratification, receives
Collect lower floor organic phase, solid crude product is obtained after organic phase is rotated, then (eluant, eluent is through column chromatography by solid crude product again
Volume ratio petroleum ether:Ethyl acetate=8:1 mixed liquor) purification after obtain dimethoxy diphenylamines；
B, synthesis dihydroxy diphenylamine：It is 0.5mol/L's that the step a dimethoxy diphenylamines prepared is configured into concentration
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.6mol/L is molten
In liquid, the dichloromethane solution that the dichloromethane solution of this Boron tribromide is slowly dropped to dimethoxy diphenylamines, reaction
20h, crude product (i.e. reacting rear material) is extracted with ethyl acetate (consumption preferably 40mL), after stratification, in collection
Solid crude product is obtained after layer organic phase, revolving, then through column chromatography, (eluant, eluent is volume ratio dichloromethane by solid crude product：
Methanol=15:1 mixed liquor) purification, obtain dihydroxy diphenylamine (or dihydroxy diphenylamine monomer)；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three mouthfuls of circles
Bottom flask) in, sequentially add dihydroxy diphenylamine, 80mmol prepared by two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b
Salt forming agent, 30mL solvents and 6mL toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to 140 DEG C
(band water) reaction 3h, then distillation removes out toluene, and then (quick) is warming up to 190 DEG C of continuation reaction 4h again, and thing after reaction is made
Material；
D, post processing：Reacting rear material (slow) made from step c is cooled to room temperature, pour into 400mL deionized waters or
Precipitated in distilled water, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 20h with 250mL methanol again,
The solid product that suction filtration is obtained prepares the poly- fragrant imines ether sulfone of thermal response fluorescent type through drying.
Embodiment 10：
The preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, comprises the following steps：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, in reactor (for example：Three-necked flask) in sequentially add
10mmol is to methoxybromobenzene, 10mmol P-nethoxyaniline, palladium [the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2
(dba)3], 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine (abbreviation BINAP), 2.8mmol sodium tert-butoxides, 30mmol is into salt
Agent, 10mL solvents and 3mL (water entrainer) toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to
(band water) reaction 3.5h, is then distilled off toluene at 110 DEG C, and subsequent (quick) is warming up to 170 DEG C and continued after stirring reaction 5h,
(slow) is cooled to room temperature, and crude product (i.e. reacting rear material) is extracted with dichloromethane (consumption 19mL), after stratification, receives
Collect lower floor organic phase, solid crude product is obtained after organic phase is rotated, then (eluant, eluent is through column chromatography by solid crude product again
Volume ratio petroleum ether:Ethyl acetate=8:1 mixed liquor) purification after obtain dimethoxy diphenylamines；
B, synthesis dihydroxy diphenylamine：It is 0.4mol/L's that the step a dimethoxy diphenylamines prepared is configured into concentration
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.2mol/L is molten
In liquid, the dichloromethane solution that the dichloromethane solution of this Boron tribromide is slowly dropped to dimethoxy diphenylamines, reaction
17h, crude product (i.e. reacting rear material) is extracted with ethyl acetate (consumption 26mL), after stratification, collects upper organic phase,
Solid crude product is obtained after revolving, then through column chromatography, (eluant, eluent is volume ratio dichloromethane by solid crude product：Methanol=15:1
Mixed liquor) purification, obtain dihydroxy diphenylamine (or dihydroxy diphenylamine monomer)；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three mouthfuls of circles
Bottom flask) in, sequentially add dihydroxy diphenylamine, 30mmol prepared by two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b
Salt forming agent, 20mL solvents and 3mL toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to 132 DEG C
(band water) reaction 3.5h, then distillation removes out toluene, and then (quick) is warming up to 170 DEG C of continuation reaction 4.5h again, and reaction is made
Material afterwards；
D, post processing：Reacting rear material (slow) made from step c is cooled to room temperature, pour into 200mL deionized waters or
Precipitated in distilled water, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 13h with 80mL methanol again, takes out
Obtained solid product is filtered through drying, that is, prepares the poly- fragrant imines ether sulfone of thermal response fluorescent type.
Embodiment 11：
The preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, comprises the following steps：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, in reactor (for example：Three-necked flask) in sequentially add
10mmol is to methoxybromobenzene, 10mmol P-nethoxyaniline, palladium [the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2
(dba)3], 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine (abbreviation BINAP), 2.8mmol sodium tert-butoxides, 50mmol is into salt
Agent, 18mL solvents and 4mL (water entrainer) toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to
(band water) reaction 3.5h, is then distilled off toluene at 115 DEG C, and subsequent (quick) is warming up to 170 DEG C and continued after stirring reaction 5h,
(slow) is cooled to room temperature, and crude product (i.e. reacting rear material) is extracted with dichloromethane (consumption 23mL), after stratification, receives
Collect lower floor organic phase, solid crude product is obtained after organic phase is rotated, then (eluant, eluent is through column chromatography by solid crude product again
Volume ratio petroleum ether:Ethyl acetate=8:1 mixed liquor) purification after obtain dimethoxy diphenylamines；
B, synthesis dihydroxy diphenylamine：It is 0.4mol/L's that the step a dimethoxy diphenylamines prepared is configured into concentration
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.4mol/L is molten
In liquid, the dichloromethane solution that the dichloromethane solution of this Boron tribromide is slowly dropped to dimethoxy diphenylamines, reaction
18h, crude product (i.e. reacting rear material) is extracted with ethyl acetate (consumption preferably 30mL), after stratification, in collection
Solid crude product is obtained after layer organic phase, revolving, then through column chromatography, (eluant, eluent is volume ratio dichloromethane by solid crude product：
Methanol=15:1 mixed liquor) purification, obtain dihydroxy diphenylamine (or dihydroxy diphenylamine monomer)；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three mouthfuls of circles
Bottom flask) in, sequentially add dihydroxy diphenylamine, 50mmol prepared by two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b
Salt forming agent, 22mL solvents and 4mL toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to 135 DEG C
(band water) reaction 3.5h, then distillation removes out toluene, and then (quick) is warming up to 180 DEG C of continuation reaction 5h again, is made after reaction
Material；
D, post processing：Reacting rear material (slow) made from step c is cooled to room temperature, pour into 280mL deionized waters or
Precipitated in distilled water, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 15h with 130mL methanol again,
The solid product that suction filtration is obtained prepares the poly- fragrant imines ether sulfone of thermal response fluorescent type through drying.
Embodiment 12：
The preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, comprises the following steps：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, in reactor (for example：Three-necked flask) in sequentially add
10mmol is to methoxybromobenzene, 10mmol P-nethoxyaniline, palladium [the abbreviation Pd of 0.1mmol tri- (dibenzalacetone) two2
(dba)3], 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine (abbreviation BINAP), 2.8mmol sodium tert-butoxides, 60mmol is into salt
Agent, 20mL solvents and 5mL (water entrainer) toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to
(band water) reaction 3h, is then distilled off toluene at 130 DEG C, and subsequent (quick) is warming up to 170 DEG C and continued after stirring reaction 4h,
(slow) is cooled to room temperature, and crude product (i.e. reacting rear material) is extracted with dichloromethane (consumption 25mL), after stratification, receives
Collect lower floor organic phase, solid crude product is obtained after organic phase is rotated, then (eluant, eluent is through column chromatography by solid crude product again
Volume ratio petroleum ether:Ethyl acetate=8:1 mixed liquor) purification after obtain dimethoxy diphenylamines；
B, synthesis dihydroxy diphenylamine：It is 0.4mol/L's that the step a dimethoxy diphenylamines prepared is configured into concentration
The dichloromethane solution of dimethoxy diphenylamines, the dichloromethane for being reconfigured at the Boron tribromide that 10mL concentration is 1.5mol/L is molten
In liquid, the dichloromethane solution that the dichloromethane solution of this Boron tribromide is slowly dropped to dimethoxy diphenylamines, reaction
18h, crude product (i.e. reacting rear material) is extracted with ethyl acetate (consumption 33mL), after stratification, collects upper organic phase,
Solid crude product is obtained after revolving, then through column chromatography, (eluant, eluent is volume ratio dichloromethane by solid crude product：Methanol=15:1
Mixed liquor) purification, obtain dihydroxy diphenylamine (or dihydroxy diphenylamine monomer)；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum (for example：Three mouthfuls of circles
Bottom flask) in, sequentially add dihydroxy diphenylamine, 60mmol prepared by two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b
Salt forming agent, 22mL solvents and 5mL toluene, stirring mixing (turn into homogeneous reaction system), and heating (reaction system) is warming up to 140 DEG C
(band water) reaction 3h, then distillation removes out toluene, and then (quick) is warming up to 180 DEG C of continuation reaction 6h again, and thing after reaction is made
Material；
D, post processing：Reacting rear material (slow) made from step c is cooled to room temperature, pour into 320mL deionized waters or
Precipitated in distilled water, suction filtration, obtained solids extracts and (stirred and impregnated with methanol, then suction filtration) 16h with 220mL methanol again,
The solid product that suction filtration is obtained prepares the poly- fragrant imines ether sulfone of thermal response fluorescent type through drying.
Embodiment 13：
A kind of preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, will be replaced described in step a to methoxybromobenzene
M-anisidine is replaced with for meta-methoxy bromobenzene, the P-nethoxyaniline；
It is any in other be the same as Example 8-12, omit.
In above-described embodiment：The salt forming agent is Anhydrous potassium carbonate or Carbon Dioxide caesium.
In above-described embodiment 8-13：Two fluorine monomers containing sulfuryl described in step c are 4,4'- difluorodiphenyls sulfone, 4,4'- bis-
Any of (the fluoro- benzene sulfuryls of 4-) benzene and 1,3- bis- (the fluoro- benzene sulfuryls of 4-) benzene.
In above-described embodiment 8-13：The solvent is dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, N- crassitudes
Any of ketone and sulfolane.
In above-described embodiment 8-13：Drying described in step d can be under conditions of 100 DEG C of temperature, pressure 0.1MPa
(vacuum) dries 10h or 24h is dried under conditions of 100 DEG C~150 DEG C of temperature.
The poly- fragrant imines ether sulfone (polymer) of thermal response fluorescence prepared by above-described embodiment has obvious thermal response fluorescence
Can, higher glass transition temperature (Tg>200 DEG C), while having the excellent solubility property of excellent dissolution performance and uniqueness
Photoelectric properties, transparent high-strength thin-film can be made up of casting method, concretely comprise the following steps：It will be obtained prepared by above example
Polymer be dissolved in concentration (quality (g) of polymer/NMP volume (mL)) be configured in 1-METHYLPYRROLIDONE (NMP)
For 5% polymer solution, impurity is filtered to remove, levelling on clean smooth glass plate is cast to.Dried in 70 DEG C of baking ovens
12h, then after the dry 24h of 85 DEG C of vacuum (0.1MPa), obtains the poly- fragrant imines ether sulfone film of thermal response fluorescent type.
The poly- fragrant imines ether sulfone (polymer) of thermal response fluorescence prepared by above-described embodiment is respectively provided with following good comprehensive
Energy：(1) obvious thermal response fluorescence property (between 20~220 DEG C of scopes), has larger answer in terms of temperature sensor
With the higher heat endurance of prospect (2)：With higher glass transition temperature (Tg>200 DEG C) and heat decomposition temperature (TD5%>
400℃)；(3) excellent solubility property：The poly- fragrant imines ether sulfone of thermal response fluorescence can be dissolved in dimethyl sulfoxide (DMSO), N, N- diformazans
In base formamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE and sulfolane；Good dissolubility can cause the Type of Collective
Thing can both realize that melt-processed was molded, and solution machine-shaping can be realized again, polymer has been widened in the variation of molding mode
Application field；(4) due to introducing rich electric aniline-NH groups in polymer backbone conformation, make it have preferably optical
Can, sending green, (p-PIES-x, x represent 1, and 2,3 is any.) and blueness (m-PIES-x, x represent 1, and 2,3 is any.) fluorescence,
There is larger application prospect in terms of photoelectron luminescent device；(5) property modification space is big：Can be by changing A1R and A2R group
To regulate and control and polymer-modified structure and performance.
In above-described embodiment：Each raw material used is commercially available prod.
In above-described embodiment：It is especially not dated in the percentage used, be quality (weight) percentage or
Well known to a person skilled in the art percentage；Described quality (weight) part can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, pressure, concentration etc.) and each component consumption number in each step
Value etc. is scope, and any point is applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology.
It can implement the invention is not restricted to above-described embodiment, described in present invention and with the good result.
Claims (7)
1. the poly- fragrant imines ether sulfone of thermal response fluorescent type, it is characterized in that：The poly- fragrant imines ether sulfone of the thermal response fluorescent type has formula (I) institute
The chemical structural formula shown：
In formula (I)：
2. the preparation method of the poly- fragrant imines ether sulfone of thermal response fluorescent type, it is characterized in that comprising the following steps：
A, synthesis dimethoxy diphenylamines：Under nitrogen protection, sequentially add in the reactor 10mmol to methoxybromobenzene,
10mmol P-nethoxyaniline, the palladiums of 0.1mmol tri- (dibenzalacetone) two, 0.3mmol 1,1 '-dinaphthalene -2,2 '-diphenyl phosphine,
2.8mmol sodium tert-butoxides, 20~80mmol salt forming agents, 5~30mL solvents and 2~6mL toluene, stirring mixing, are heated to
3~4h is reacted at 100~130 DEG C, toluene is then distilled off, 160~180 DEG C is then raised temperature to and continues 4~6h of stirring reaction
Afterwards, room temperature is cooled to, crude product is extracted with dichloromethane, after stratification, lower floor's organic phase is collected, after organic phase is rotated
Solid crude product is obtained, dimethoxy diphenylamines is obtained after then solid crude product is purified through column chromatography again；
B, synthesis dihydroxy diphenylamine：It is 0.3~0.5mol/L's that the step a dimethoxy diphenylamines prepared is configured into concentration
The dichloromethane solution of dimethoxy diphenylamines, is reconfigured at the dichloromethane for the Boron tribromide that 10mL concentration is 1.1~1.6mol/L
In alkane solution, the dichloromethane solution that the dichloromethane solution of this Boron tribromide is slowly dropped to dimethoxy diphenylamines, instead
15~20h is answered, crude product is extracted with ethyl acetate, after stratification, collects and solids crude production is obtained after upper organic phase, revolving
Thing, then solid crude product is purified through column chromatography, obtain dihydroxy diphenylamine；
C, under nitrogen protection, in the reactor equipped with agitator, airway tube, condenser pipe and water knockout drum, is sequentially added
Two fluorine monomers of the 10mmol containing sulfuryl, 10mmol steps b prepare dihydroxy diphenylamine, 20~80mmol salt forming agents, 15~
30mL solvents and 2~6mL toluene, stirring mixing are heated to 130 DEG C~140 DEG C 3~4h of reaction, and then distillation removes out first
Benzene, is then warming up to 160 DEG C~190 DEG C and continues to react 4~6h, reacting rear material is made again；
D, post processing：Reacting rear material made from step c is cooled to room temperature, 150~400mL deionized waters or distilled water is poured into
Middle precipitation, suction filtration, obtained solids extracts 10~20h with 25~250mL methanol again, and the solid product that suction filtration is obtained is through dry
It is dry, that is, prepare the poly- fragrant imines ether sulfone of thermal response fluorescent type.
3. the preparation method of the poly- fragrant imines ether sulfone of the thermal response fluorescent type as described in claim 2, it is characterized in that：Described in step a
Meta-methoxy bromobenzene is replaced with to methoxybromobenzene, the P-nethoxyaniline replaces with m-anisidine.
4. the preparation method of the poly- fragrant imines ether sulfone of the thermal response fluorescent type as described in Claims 2 or 3, it is characterized in that：It is described into salt
Agent is Anhydrous potassium carbonate or Carbon Dioxide caesium.
5. the preparation method of the poly- fragrant imines ether sulfone of the thermal response fluorescent type as described in Claims 2 or 3, it is characterized in that：Institute in step c
It is 4,4'- difluorodiphenyls sulfone, (the fluoro- benzene sulfuryls of the 4-) benzene of 4,4'- bis- and (the fluoro- benzene of 4- of 1,3- bis- to state two fluorine monomers containing sulfuryl
Any of sulfuryl) benzene.
6. the preparation method of the poly- fragrant imines ether sulfone of the thermal response fluorescent type as described in Claims 2 or 3, it is characterized in that：The solvent
It is any of dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE and sulfolane.
7. the preparation method of the poly- fragrant imines ether sulfone of the thermal response fluorescent type as described in Claims 2 or 3, it is characterized in that：Institute in step d
It is that 10h is dried under conditions of 100 DEG C of temperature, pressure 0.1MPa or is dried under conditions of 100 DEG C~150 DEG C of temperature to state drying
24h。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109053955A (en) * | 2018-08-20 | 2018-12-21 | 安徽理工大学 | A kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone |
| CN115612093A (en) * | 2022-11-04 | 2023-01-17 | 西南科技大学 | Hydrogen-bond-crosslinked high-performance polyaryl imino ether nitrile and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109053955A (en) * | 2018-08-20 | 2018-12-21 | 安徽理工大学 | A kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone |
| CN115612093A (en) * | 2022-11-04 | 2023-01-17 | 西南科技大学 | Hydrogen-bond-crosslinked high-performance polyaryl imino ether nitrile and preparation method thereof |
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