CN110396195A - A kind of polyarylsulfone (PAS) quasi polymer and preparation method thereof containing reduction phenol piperazine structure - Google Patents
A kind of polyarylsulfone (PAS) quasi polymer and preparation method thereof containing reduction phenol piperazine structure Download PDFInfo
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- CN110396195A CN110396195A CN201910729390.9A CN201910729390A CN110396195A CN 110396195 A CN110396195 A CN 110396195A CN 201910729390 A CN201910729390 A CN 201910729390A CN 110396195 A CN110396195 A CN 110396195A
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Abstract
The present invention relates to a kind of polyarylsulfone (PAS) quasi polymers and preparation method thereof containing reduction phenol piperazine structure, which includes following formula (I) structure segments:In formula (I), n is the degree of polymerization；M is copolymerization ratios, 0 < m≤1；Ar is one of following formula (a) to formula (d):In formula (c), X is integer 1,2 or 3, i.e. benzene, biphenyl or terphenyl；In formula (d), R is the disubstituted naphthalene in Isosorbide-5-Nitrae position, 1,5 disubstituted naphthalenes, 2,6 disubstituted naphthalenes or 2,7 disubstituted naphthalenes.The polymer not only has good photoelectricity activity, also have both good thermal stability, it is anticipated that such material will have vast potential for future development and huge application potential in terms of photoelectric field especially electrochromism, information storage, carbon nanotube cladding, thermal response.
Description
Technical field
The invention belongs to polymeric material field more particularly to a kind of polyarylsulfone (PAS) quasi polymers containing reduction phenol piperazine structure
And preparation method thereof.
Background technique
Information system transmission display technology, which is widely used, to be marked the mankind and opens " information age " in the early 21st century
Revolutionary variation has occurred from this in the life style at gate, the mankind, and benefits from it.The hair at full speed of information industry technology
Exhibition needs the continuous improvement of technical matters and the development innovation of theoretical knowledge, and the exploitation of new material can both mention for theoretical research
For foundation, and the requirement of production technology can be better met, promote the improvement of production technology, so, new function material
It is developed into the key of field development, wherein the exploitation of novel organic polymer photoelectric functional material has become in weight
Weight.
Currently used polymer organic photoelectric functional material is based on conjugated polymer material, due to its synthesis cost
It is high, dissolubility is poor, middle condition color is deeper etc., and reasons limit its practical application.Therefore people begin to focus on the non-conjugated oxygen of main chain
Change reduced form opto-electrical polymers, such as polyamide, polyimides.Polyarylsulfone (PAS) is as a kind of special engineering plastics, chemical stabilization
Property and excellent heat stability, be very suitable to the backbone structure as non-conjugated photoelectric material.It is a kind of common for restoring phenol piperazine simultaneously
The excellent compound of photoelectric functional, because of its own good photoelectric activity, the macromolecule photoelectric functional material constructed with this is
Be widely used in store out in hole transport, electrochromism, electroluminescent, information, the photoelectric fields such as solar battery,
But at present with restore the macromolecule photoelectric functional material that phenol piperazine class compound is constructed be difficult to combine good photoelectricity activity,
Electrochemical stability, thermal stability and dissolubility.
Summary of the invention
The purpose of the present invention is to provide it is a kind of containing reduction phenol piperazine structure polyarylsulfone (PAS) quasi polymer and preparation method thereof,
It is active, electrochemically stable to restore the photoelectricity for the macromolecule photoelectric functional material that phenol piperazine class compound is constructed at present to improve
Property, thermal stability and dissolubility.
A kind of polyarylsulfone (PAS) quasi polymer containing reduction phenol piperazine structure of the present invention, including following formula (I) structure segments:
In formula (I), n is the degree of polymerization；M is copolymerization ratios, 0 < m≤1；Ar is one of following formula (a) to formula (d):
In formula (c), X is integer 1,2 or 3, i.e. benzene, biphenyl or terphenyl；
In formula (d), R is the disubstituted naphthalene in Isosorbide-5-Nitrae position, 1,5 disubstituted naphthalenes, 2,6 disubstituted naphthalenes or 2,7 disubstituted naphthalenes.
The present invention contains the preparation method of the polyarylsulfone (PAS) quasi polymer of reduction phenol piperazine structure, comprising the following steps:
By double fluorine monomers containing sulfuryl, bisphenol-A, reduction phenol piperazine, catalyst potassium carbonate, solvent sulfolane or N- methyl pyrrole
Pyrrolidone, water entrainer toluene investment are equipped with nitrogen port, oil water separator, in churned mechanically three-neck flask, in nitrogen atmosphere
In be heated with stirring to 140-150 DEG C and make refluxing toluene 3h, sufficiently release toluene and water with oil water separator after band water, then improve temperature
Degree obtains the phenol piperazine polyarylsulfone (PAS) polymer containing reduction, the reaction equation to 3-8h is stirred to react at 200-220 DEG C are as follows:
In formula, n is the degree of polymerization, and m is copolymerization ratios, 0 < m≤1；Ar is one of following formula (a) to formula (d):
In formula (c), X is integer 1,2 or 3, i.e. benzene, biphenyl or terphenyl；
In formula (d), R is the disubstituted naphthalene in Isosorbide-5-Nitrae position, 1,5 disubstituted naphthalenes, 2,6 disubstituted naphthalenes or 2,7 disubstituted naphthalenes.
Wherein corresponding molecular structure is obtained by changing different double fluorine monomers containing sulfuryl.That selects contains sulfuryl
Double fluorine monomer (a) formulas be 4,4 '-difluorodiphenyl sulfones；(b) formula is 4,4 '-two (4- fluorine diphenyl sulfone) ethers；(c) formula is 1,4- bis-
(4- fluorobenzene sulfuryl) benzene or 4,4 '-two (4- fluorobenzene sulfuryl) biphenyl or 4,4 '-two (4- fluorobenzene sulfuryl) terphenyls；(d) formula is 1,
Bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 4- or bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 1,5- or bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 2,6- or
Bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 2,7-.
The reaction inventory of the catalyst potassium carbonate is preferably 2 times of double fluorine monomers.
Polyarylsulfone (PAS) quasi polymer and preparation method thereof provided by the invention containing reduction phenol piperazine structure, from MOLECULE DESIGN
Angle is set out, and will have photoelectric activity group reduction phenol piperazine to be introduced into polyarylsulfone (PAS), which is not only able to show good light
It is electroactive, also there is good thermal stability and dissolubility.Simultaneously as the reduction good electron donation of phenol piperazine and strong electrophilic
Sulfuryl be connected directly by phenyl ring, may be constructed to-receptor structure (D-A), occur in charge migration phenomenon, thus further
Enhance the photoelectric properties of polymer.Moreover, because phenol piperazine is big rigid radical, relatively fixed torsion will form between sulfuryl
Bent angle causes the singlet energy level of material and triplet difference smaller, causes to generate thermal response delayed fluorescence phenomenon.This
Outside, there is good mechanical performance as a kind of special engineering plastics due to polyarylsulfone (PAS) itself, after introducing bisphenol-A copolymerization, gathers
It closes object dissolubility further to be promoted, is very easy to processing and forms a film and keep good mechanical performance, therefore have boundless
Application field and practical value.The design feature and photoelectric characteristic of the polymer provided according to the present invention, it is anticipated that such material
Material will have wide in terms of photoelectric field especially electrochromism, information storage, carbon nanotube cladding, thermal response
Wealthy development prospect and huge application potential.
The results showed that 5% thermal weight loss of the polyarylsulfone (PAS) quasi polymer provided by the invention containing reduction phenol piperazine structure
At 470 DEG C or more, tetrahydrofuran, methylene chloride, chloroform, N, N '-dimethyl formamide (DMF), N, N '-two can be dissolved in
The organic solvents such as methylformamide (DMAc), N-Methyl pyrrolidone (NMP) can express the photoelectricity of corresponding light electroactive group
Characteristic.
Polymer provided by the invention, due to improving new polymerization, makes compared with common polyarylsulfone (PAS) class material
It obtains double fluorine monomers and nucleophilic displacement of fluorine directly occurs with imino group monomer, novel optoelectronic materials can be obtained in a manner of being dirt cheap.
Meanwhile the introducing of tertiary amine group, it is all or part of instead of ehter bond, the main chain rigidity of material is increased, the heat of material is caused
Stabilization has great promotion, is conducive to the practical application of material.Because sulfuryl is a kind of very strong electrophilic structure, in this way with
Phenol piperazine, which is connected directly, to be formed to-receptor structure, so compared with the photoelectric material of other non-conjugated types, interior charge migration
More easily, it so that the starting voltage of material is remarkably decreased, improves the service life of material and reduces energy consumption.In short, this draw
The polyarylsulfone (PAS) material for entering phenol piperazine structure not only has good photoelectricity activity, also has both good electrochemical stability, thermostabilization
Property and dissolubility.
Detailed description of the invention
Fig. 1 is the infrared spectrum for the polymer P 1 that the embodiment of the present invention 1 provides；
Fig. 2 is thermal weight loss spectrogram under the nitrogen atmosphere that the embodiment of the present invention 1 provides；
Fig. 3 is differential scanning calorimetry spectrogram under the nitrogen atmosphere that the embodiment of the present invention 1 provides；
Fig. 4 is the cyclic voltammetry curve that the embodiment of the present invention 1 provides；
Fig. 5 is the nuclear magnetic spectrogram for the polymer P 1-50% that the embodiment of the present invention 2 provides；
Fig. 6 is the cyclic voltammetry curve that the embodiment of the present invention 2 provides；
Fig. 7 is the electrochromism spectrogram that the embodiment of the present invention 2 provides；
Fig. 8 is the nuclear magnetic spectrogram for the polymer P 2 that the embodiment of the present invention 3 provides；
Fig. 9 is the nuclear magnetic spectrogram for the polymer P 6 that the embodiment of the present invention 4 provides；
Figure 10 is the ultraviolet visible absorption spectra figure for the polymer P 6 that the embodiment of the present invention 4 provides.
Specific embodiment
Technical solution of the present invention is further clearly and completely described by following embodiment.Obviously, described
Embodiment be only a part of the embodiment of the present invention, based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
A kind of polyarylsulfone (PAS) quasi polymer containing reduction phenol piperazine structure of the present invention, including formula (I) structure segment:
In formula (I), n is the degree of polymerization, and 0 < m≤1 indicates that copolymerization ratios, Ar are one of formula (a)~(d):
In formula (c), X is selected from one of integer 1,2,3；In formula (d), R is selected from Isosorbide-5-Nitrae position, 1, and 5,2,6,2,7 double
One of substituted naphthalene.
In some embodiments provided by the invention, the main chain of the polymer is polyarylsulfone (PAS), concretely following P1
~P9 structure:
In P1~P9, n is the degree of polymerization, and 0 < m≤1 indicates copolymerization ratios.
The photoelectric activity reduction phenol piperazine group of specific structure is introduced into polyarylsulfone (PAS) polymer by polymer provided by the invention,
It is not only able to that polymer is made to show good photoelectric activity and photoelectric functional characteristic, also there is good thermal stability and dissolution
Property.Polymer provided by the invention has boundless application field and practical value, special according to its design feature and photoelectricity
Property, it is anticipated that such material will prolong in photoelectric field especially electrochromism, information storage, carbon nanotube cladding, thermal response
Slow fluorescence etc. has vast potential for future development and huge application potential.
The results showed that it is provided by the invention containing reduction phenol piperazine polyarylsulfone (PAS) polymer 5% thermal weight loss 470 DEG C with
On, the organic solvents such as tetrahydrofuran, methylene chloride, chloroform, DMF, DMAc, NMP can be dissolved in, can express corresponding photoelectricity
The photoelectric characteristic of active group.
The preparation method of polyarylsulfone (PAS) quasi polymer of the present invention containing reduction phenol piperazine structure, comprising the following steps:
By double fluorine monomers containing sulfuryl, bisphenol-A, reduction phenol piperazine, catalyst potassium carbonate, solvent sulfolane or N- methyl pyrrole
Pyrrolidone, water entrainer toluene investment are equipped with nitrogen port, oil water separator, in churned mechanically three-neck flask, in nitrogen atmosphere
In be heated with stirring to 140-150 DEG C and make refluxing toluene 3h, sufficiently release toluene and water with oil water separator after band water, then improve temperature
Degree obtains the phenol piperazine polyarylsulfone (PAS) polymer containing reduction to 3-8h is stirred to react at 200-220 DEG C, and the reaction equation is (i):
In formula, n is the degree of polymerization, and 0 < m≤1 indicates that copolymerization ratios, Ar are one of formula (a)~(d):
In formula (c), X is selected from one of integer 1,2,3；In formula (d), R is selected from Isosorbide-5-Nitrae position, 1, and 5,2,6,2,7 double
One of substituted naphthalene.
Wherein corresponding molecular structure is obtained by changing different double fluorine monomers containing sulfuryl.That selects contains sulfuryl
Double fluorine monomer (a) formulas be 4,4 '-difluorodiphenyl sulfones；(b) formula is 4,4 '-two (4- fluorine diphenyl sulfone) ethers；(c) formula is 1,4- bis-
(4- fluorobenzene sulfuryl) benzene or 4,4 '-two (4- fluorobenzene sulfuryl) biphenyl or 4,4 '-two (4- fluorobenzene sulfuryl) terphenyls；(d) formula is 1,
Bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 4- or bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 1,5- or bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 2,6- or
Bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 2,7-.
In this preparation method, catalyst and reactant are added in reaction unit first.Wherein, the reactant includes
Restore phenol piperazine monomer and double fluorine monomers.When the present invention prepares copolymer, the reactant further includes bisphenol-A.
The catalyst is preferably potassium carbonate, and its inventory is preferably 2 times of double fluorine monomer moles containing sulfuryl.
Later, solvent and water entrainer toluene, the solvent sulfolane or N-Methyl pyrrolidone are added into reaction unit.
After catalyst, reactant, solvent and water entrainer add, reacted.Wherein, the reaction is preferably removed in water entrainer toluene
It is carried out under the conditions of water；The band coolant-temperature gage of the reaction is 140~150 DEG C, releases toluene and water from oil water separator after band water, then
The temperature for improving reaction is 200-220 DEG C, and the time of reaction is 3~8h.Reaction reaches after a certain period of time, on system viscosity is quick
It rises, reactant is poured into terminate in deionized water and is reacted.The solid finally obtained to reaction is crushed, washed and is dried, and is obtained
To the phenol piperazine polyarylsulfone (PAS) polymer provided by the invention containing reduction.
It can be prepared using method provided by the invention with good photoelectricity activity, thermal stability and deliquescent
The phenol piperazine polyarylsulfone (PAS) polymer containing reduction, this method simple aggregation degree is controllable, is easy to commercially produce, and has practical value.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1: the preparation of polymer P 1
Phenol piperazine (3.685g, 20mmol), 4,4 '-difluorodiphenyl sulfones (5.334g, 20mmol), catalyst potassium carbonate will be restored
(5.521g, 40mmol), 26mLNMP (solid content 25%), 20mL water entrainer toluene investment are equipped with nitrogen port, water-oil separating
Device, churned mechanically 50mL three-neck flask in, refluxing toluene 3h is heated with stirring in nitrogen atmosphere, sufficiently band water after with oil
Separator releases toluene and water.Temperature is improved again to being stirred to react 8h at 200 DEG C.Reaction terminates, and pours into solution under stirring
In 800mL cold water.Broken into powder with tissue pulverizer, be filtered under diminished pressure, collect solid precipitating, using hot water (5 times, often
Secondary 800mL) and ethyl alcohol (3 times, each 300mL) boiling washing after be collected by filtration, be statically placed in baking oven at 80 DEG C dry 10h.
To orange-yellow polymer powder (7.433g, yield 90%).Structural analysis is carried out to the resulting polymer of the present embodiment, as a result
As shown in Figure 4, Figure 5.
Infrared spectrum analysis is carried out to the preparation-obtained polymer P of the present embodiment 1, as a result as shown in Figure 1.Fig. 1 is this
The infrared spectrogram that inventive embodiments 1 provide, P1 indicates that polymer P 1, DHPZ indicate reduction phenol piperazine in Fig. 1.In Fig. 1 we
It can be seen that in the infrared spectrum of polymer, compared to the infrared spectrum spectrogram of monomer, 3400cm-1Place belongs to N-H's
Characteristic absorption peak, 1260cm-1Place belongs to-NHAr2Characteristic absorption peak all disappeared；And in 1315cm-1, 1340cm-1Place
There is C-N and-NAr3Characteristic absorption peak, while remaining 3090cm-1The characteristic absorption peak for belonging to Ar-H at place,
1500cm-1The characteristic absorption peak for belonging to phenyl ring skeleton at place, 1150cm-1The characteristic absorption peak for belonging to S=O at place.These
The appearance of characteristic absorption peak indicates that the benzene ring structure of two kinds of reactants and sulfuryl are retained in the course of the polymerization process；And monomer
Middle N-H ,-NHAr2Disappearance of the characteristic absorption peak in polymeric infrared light spectrum spectrogram then illustrates in polymerization, with nitrogen-atoms phase
Hydrogen atom even takes part in polymerization reaction, produces new C-N key, and evidence is that C-N occur in polymeric infrared light spectrum spectrogram
With-NAr3Characteristic absorption peak.By the analysis of infrared spectroscopy, it is poly- that we can primarily determine that we have synthesized target
Close the structure of object.
Heat stability testing is carried out to the polymer P 1 that the present embodiment is prepared, as a result as shown in Figure 2 and Figure 3.Fig. 2 is
Thermogravimetric curve figure under 1 nitrogen atmosphere of polymer P that the embodiment of the present invention 1 provides.By Fig. 2 it can be seen that polymer
5% thermal weight loss is at 494 DEG C or more.Fig. 3 is the differential scanning calorimetry under 1 nitrogen atmosphere of polymer P that the embodiment of the present invention 1 provides
(DSC) characteristic curve.By Fig. 3 it can be seen that the glass transition temperature of polymer is 246 DEG C.Fig. 2, Fig. 3 the result shows that
Polymer possesses splendid thermal stability.
Carrying out cyclic voltammetry curve analysis to the polymer P 1 that the present embodiment is prepared, (electrolyte is the tetrabutyl of 0.1M
The acetonitrile solution of ammonium perchlorate, reference electrode are silver/silver nitrate reference electrode, are platinum filaments to electrode, material is dissolved in NMP
Electrode of working is spin-coated on ito glass；Test condition is 100mV/s, test scope -0.2~1.2V, as a result as shown in Figure 4.
Fig. 4 is the cyclic voltammetry curve figure that the embodiment of the present invention 1 provides.By Fig. 4 it can be seen that polymer possesses two pairs of reversible oxygen
Change reduction peak, reversible redox peaks and phenol piperazine are essentially identical.There are a pair of lesser redox peaks among two pairs of peaks, is
Incomplete oxidation, which occurs, in it causes.
Embodiment 2: the preparation of polymer P 1-50%
Phenol piperazine (1.842g, 10mmol), 4,4 '-difluorodiphenyl sulfones (5.334g, 20mmol), bisphenol-A will be restored
(2.284g, 10mmol), catalyst potassium carbonate (5.521g, 40mmol), 34mL sulfolane (solid content 20%), 20mL water entrainer
Toluene investment is equipped in the three-neck flask of nitrogen port, oil water separator, churned mechanically 100mL, is stirred in nitrogen atmosphere
It is heated to refluxing toluene 3h, sufficiently releases toluene and water with oil water separator after band water.It is anti-to stirring at 220 DEG C that temperature is improved again
Answer 4h.Reaction terminates, and pours into solution in 800mL cold water under stirring.Powder is broken into tissue pulverizer, is filtered under diminished pressure,
Solid precipitating is collected, is received using being filtered after hot water (5 times, each 800mL) and ethyl alcohol (3 times, each 300mL) boiling washing
Collection is statically placed in baking oven at 80 DEG C dry 10h.Obtain orange polymer powder (7.917g, yield 91%).It counts equal molecule
Amount is 40.9kDa, weight average molecular weight 56.5kDa, dispersion degree 1.4.Structure point is carried out to the resulting polymer of the present embodiment
Analysis, as a result as shown in Figure 1.
Nmr analysis is carried out to the resulting polymer of the present embodiment, as a result as shown in Figure 5.Fig. 5 is 2 institute of the embodiment of the present invention
Restore the nuclear magnetic spectrogram of phenol piperazine monomer and resulting polymer P 1-50%.
Phenol piperazine monomer is restored to the present embodiment and resulting polymer P 1-50% carries out nmr analysis, as a result such as Fig. 5 institute
Show.Fig. 5 is the nuclear magnetic spectrogram that the embodiment of the present invention 2 provides, and P1-50% indicates that polymer P 1-50%, DHPZ are indicated also in Fig. 5
Former phenol piperazine monomer.Compared to the nuclear magnetic resonance spectroscopy spectrogram of monomer, chemical shift occurs short and wide on the position 5.99ppm
Proton peak obviously disappears, while multiple peaks to overlap each other occurs in this region 7.25-8.05ppm, this is because polymer
Contain the similar different hydrogen atom of a large amount of chemical environments in duplicate fragment structure.Sulfuryl is strong electron-withdrawing group group, is caused
With its similar in the chemical shift of phenyl ring hydrogen atom it is mobile (peak 3,4) to low field；The electron-withdrawing ability of alkoxy is inferior to sulfuryl, so
With it similar in phenyl ring hydrogen atom occur chemical shift migrate (peak 1,2) too late phenyl ring hydrogen atom being connected with sulfuryl；It is miscellaneous containing N
The electron-withdrawing ability of ring is most weak, with its similar in phenyl ring hydrogen atom chemical shift (peak 5,6) it is movably minimum to low field.
Miscellaneous peak on the position 3.70ppm may be the methylene quartet of residual ethanol in sample.The sharp peak occurred on the position 1.70ppm
It is the hydrogen atom signal of methyl in bisphenol-A unit.
Carrying out cyclic voltammetry curve analysis to the polymer P 1-50% that the present embodiment is prepared, (electrolyte is 0.1M's
The acetonitrile solution of tetrabutylammonium perchlorate, reference electrode are silver/silver nitrate reference electrode, are platinum filaments to electrode, and material is dissolution
Work electrode is spin-coated on ito glass in NMP；Test condition is 100mV/s, test scope -0.2~1.1V), as a result such as
Shown in Fig. 6, Fig. 6 is the cyclic voltammetry curve figure that the embodiment of the present invention 2 provides.By Fig. 6 it can be seen that polymer possesses two pairs
The position of reversible redox peaks, oxidation peak is close with reduction phenol piperazine, but more relatively low than reduction phenol piperazine, and reason can be attributed to
Polymer, which forms charge migration in D-A structure generation, to be caused.
The polymer P 1-50% that the present embodiment is prepared carries out electrochromism analysis (electrochemical workstation and ultraviolet-
Visible spectrophotometer combination, electro-chemical test condition is identical as cyclic voltammetry curve analysis above, selects constant voltage test, surveys respectively
Measure the variation of ultraviolet absorption curve of the material within the scope of 0.00-1.20V under the influence of different voltages；Ultraviolet test condition is
The wavelength interval 1.0nm, 300~900nm of test scope), as a result as shown in fig. 6, Fig. 6 is the electroluminescent of the offer of the embodiment of the present invention 2
Change colour curve graph.By Fig. 6 it can be seen that changing when voltage increases the original UV absorption of polymer, go out at 450nm
A very strong absorption peak is showed, this peak can belong to single cation that reduction phenol piperazine is formed；Later, in higher voltage
Occurs new ultraviolet absorption peak at lower 700nm, this broad peak can belong to the dication that reduction phenol piperazine is formed.
By cyclic voltammetry curve and electrochromism analysis it can be seen that polymer P 1-50% provided in this embodiment has
Good photoelectricity activity, can express the photoelectric characteristic of corresponding light electroactive group.
Heat stability testing is carried out to the polymer P 1-50% that the present embodiment is prepared, as a result are as follows: the 5% of polymer
Thermal weight loss shows that polymer possesses splendid thermal stability at 476 DEG C or more.
Embodiment 3: the preparation of polymer P 2
It will reduction phenol piperazine (3.685g, 20mmol), 4,4 '-two (4- fluorine diphenyl sulfone) ethers (9.721g, 20mmol), catalysis
Agent potassium carbonate (5.521g, 40mmol), 53mL NMP (solid content 20%), 20mL water entrainer toluene investment equipped with nitrogen port,
Oil water separator, churned mechanically 100mL three-neck flask in, refluxing toluene 3h is heated with stirring in nitrogen atmosphere, sufficiently
Toluene and water are released with oil water separator after band water.Temperature is improved again to being stirred to react 6h at 200 DEG C.Reaction terminates, under stirring
Solution is poured into 800mL cold water.Powder is broken into tissue pulverizer, is filtered under diminished pressure, solid precipitating is collected, using heat
It is collected by filtration after water (5 times, each 800mL) and ethyl alcohol (3 times, each 300mL) boiling washing, is statically placed in baking oven at 80 DEG C and does
Dry 10h.Obtain orange polymer powder (10.875g, yield 86%).Structure point is carried out to the resulting polymer of the present embodiment
Analysis, as a result as shown in Figure 8.
Nmr analysis is carried out to the resulting polymer of the present embodiment, as a result as shown in Figure 8.Fig. 8 is 3 institute of the embodiment of the present invention
The nuclear magnetic spectrogram of the polymer P 2 obtained.Nuclear magnetic resonance spectroscopy spectrogram compared to P1-50%, the bisphenol-A list on the position 1.70ppm
The hydrogen atom signal peak of methyl disappears in member, and other peaks are almost the same.
Embodiment 4: the preparation of polymer P 6
Phenol piperazine (3.685g, 20mmol) will be restored, bis- ((4- fluorophenyl) sulfuryl) naphthalenes of Isosorbide-5-Nitrae-(8.889g, 20mmol), urged
Agent potassium carbonate (5.521g, 40mmol), 49mL NMP (solid content 20%), 20mL water entrainer toluene investment are logical equipped with nitrogen
Mouth, oil water separator, churned mechanically 100mL three-neck flask in, refluxing toluene 3h is heated with stirring in nitrogen atmosphere, is filled
Divide after band water and releases toluene and water with oil water separator.Temperature is improved again to being stirred to react 6h at 200 DEG C.Reaction terminates, stirring
It is lower to pour into solution in 800mL cold water.Powder is broken into tissue pulverizer, is filtered under diminished pressure, solid precipitating is collected, using
It is collected by filtration, is statically placed in baking oven at 80 DEG C after hot water (5 times, each 800mL) and ethyl alcohol (3 times, each 300mL) boiling washing
Dry 10h.Obtain orange polymer powder (10.875g, yield 92%).Structure is carried out to the resulting polymer of the present embodiment
Analysis, as a result as shown in Figure 8.
Nmr analysis is carried out to the resulting polymer of the present embodiment, as a result as shown in Figure 9.Fig. 9 is 4 institute of the embodiment of the present invention
The nuclear magnetic spectrogram of the polymer P 6 obtained.Nuclear magnetic resonance spectroscopy spectrogram compared to P2, peak position is almost the same, but obvious in High-Field
The hydrogen atom signal peak on some phenyl ring is had more.
Ultraviolet-visible spectrum absorption analysis is carried out to benzene embodiment resulting polymers, the results are shown in Figure 10.Due to material
Rigidity obviously increase and form to-receptor structure, it is very wide that the pi-electron degree increase of material results in its ultraviolet absorption peak,
It demonstrates material and interior charge migration has occurred.
Dissolubility test
A series of dissolubility of polymer prepared by the present invention is tested, the results are shown in Table 2:
2 dissolubility of table tests table
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 (3)
1. a kind of polyarylsulfone (PAS) quasi polymer containing reduction phenol piperazine structure, which is characterized in that including following formula (I) structure segments:
In formula (I),
N is the degree of polymerization；M is copolymerization ratios, 0 < m≤1；Ar is one of following formula (a) to formula (d):
In formula (c), X is integer 1,2 or 3, i.e. benzene, biphenyl or terphenyl；
In formula (d), R is the disubstituted naphthalene in Isosorbide-5-Nitrae position, 1,5 disubstituted naphthalenes, 2,6 disubstituted naphthalenes or 2,7 disubstituted naphthalenes.
2. a kind of preparation method of the polyarylsulfone (PAS) quasi polymer containing reduction phenol piperazine structure described in claim 1, it is characterised in that
The following steps are included:
By double fluorine monomers containing sulfuryl, bisphenol-A, reduction phenol piperazine, catalyst potassium carbonate, solvent sulfolane or N- crassitude
Ketone, water entrainer toluene investment are stirred in nitrogen atmosphere equipped in nitrogen port, oil water separator, churned mechanically three-neck flask
It mixes and is heated to 140-150 DEG C and makes refluxing toluene 3h, sufficiently release toluene and water with oil water separator after band water, then improve temperature extremely
It is stirred to react 3-8h at 200-220 DEG C, obtains the phenol piperazine polyarylsulfone (PAS) polymer containing reduction, the reaction equation are as follows:
In formula, n is the degree of polymerization, and m is copolymerization ratios, 0 < m≤1；Ar is one of following formula (a) to formula (d):
In formula (c), X is integer 1,2 or 3, i.e. benzene, biphenyl or terphenyl；
In formula (d), R is the disubstituted naphthalene in Isosorbide-5-Nitrae position, 1,5 disubstituted naphthalenes, 2,6 disubstituted naphthalenes or 2,7 disubstituted naphthalenes.
Wherein corresponding molecular structure is obtained by changing different double fluorine monomers containing sulfuryl.That selects is double containing sulfuryl
Fluorine monomer (a) formula is 4,4 '-difluorodiphenyl sulfones；(b) formula is 4,4 '-two (4- fluorine diphenyl sulfone) ethers；(c) formula is bis- (4- of 1,4-
Fluorobenzene sulfuryl) benzene or 4,4 '-two (4- fluorobenzene sulfuryl) biphenyl or 4,4 '-two (4- fluorobenzene sulfuryl) terphenyls；(d) formula is that 1,4- is bis-
((4- fluorophenyl) sulfuryl) naphthalene or bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 1,5- or bis- ((4- fluorophenyl) sulfuryl) naphthalenes of 2,6- or 2,7-
Bis- ((4- fluorophenyl) sulfuryl) naphthalenes.
3. preparation method according to claim 2, which is characterized in that the reaction inventory of the catalyst potassium carbonate be containing
There are 2 times of double fluorine monomer moles of sulfuryl.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104641504A (en) * | 2012-07-18 | 2015-05-20 | 株式会社村田制作所 | Secondary battery |
| CN106467516A (en) * | 2016-07-25 | 2017-03-01 | 江苏三月光电科技有限公司 | A kind of compound with triazine as core and its application on organic electroluminescence device |
| CN107118334A (en) * | 2017-06-05 | 2017-09-01 | 盐城工学院 | Single white light polymer and electroluminescent organic material and organic electroluminescence device and preparation method thereof |
| FR3065962A1 (en) * | 2017-05-05 | 2018-11-09 | Cdp Innovation | NEW OPTICAL MATERIALS AND APPLICATIONS THEREOF |
| CN109467681A (en) * | 2018-10-11 | 2019-03-15 | 武汉华星光电半导体显示技术有限公司 | A kind of macromolecule thermal activation delayed fluorescence material and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104641504A (en) * | 2012-07-18 | 2015-05-20 | 株式会社村田制作所 | Secondary battery |
| CN106467516A (en) * | 2016-07-25 | 2017-03-01 | 江苏三月光电科技有限公司 | A kind of compound with triazine as core and its application on organic electroluminescence device |
| FR3065962A1 (en) * | 2017-05-05 | 2018-11-09 | Cdp Innovation | NEW OPTICAL MATERIALS AND APPLICATIONS THEREOF |
| CN107118334A (en) * | 2017-06-05 | 2017-09-01 | 盐城工学院 | Single white light polymer and electroluminescent organic material and organic electroluminescence device and preparation method thereof |
| CN109467681A (en) * | 2018-10-11 | 2019-03-15 | 武汉华星光电半导体显示技术有限公司 | A kind of macromolecule thermal activation delayed fluorescence material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FRANC°OIS TRAN VAN: "Polyethyleneoxide±dihydrophenazine block", 《ELECTROCHIMICA ACTA》 * |
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