CN104629038B - Crystalline polyethersulfone containing double biphenyl structure and preparation method thereof - Google Patents
Crystalline polyethersulfone containing double biphenyl structure and preparation method thereof Download PDFInfo
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- CN104629038B CN104629038B CN201510085001.5A CN201510085001A CN104629038B CN 104629038 B CN104629038 B CN 104629038B CN 201510085001 A CN201510085001 A CN 201510085001A CN 104629038 B CN104629038 B CN 104629038B
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Abstract
The invention relates to a crystalline polyethersulfone containing double biphenyl structure and a preparation method thereof, belonging to the technical field of high polymer materials and preparation thereof. By utilizing a synthesized double-biphenyl-structure fluorosulfone monomer, double biphenyl groups are symmetrically introduced to both sides of the sulfuryl group of the polyether sulfone main chain by a traditional nucleophilic substitution polycondensation technique, thereby completing the preparation of the all-aromatic-structure crystalline polyether sulfone containing double biphenyl structure. Compared with the known polyethersulfone, the crystalline polyethersulfone containing double biphenyl structure is crystalline high polymer under the conditions of normal temperature and pressure. After the XRD (X-ray diffraction) testing on peak-differentation and imitating, the crystallinity is 24% by calculation. The method is simple, is lower in cost, and has favorable industrialization prospects.
Description
Technical field
The invention belongs to macromolecular material and its preparing technical field, and in particular to a kind of crystallization containing double biphenyl structurals gathers
Ether sulfone and preparation method thereof.
Background technology
Polyether sulphone (PAES) resin is the special engineered modeling of a class amorphous thermoplastic succeeded in developing the sixties in last century
Material.Due to the excellent synthesis such as thermostability, hydrolytic resistance, creep resistance, dimensional stability, resistance to impact, nontoxic, fire-retardant
Performance, through application development for many years, is answered in fields such as electric, electronics, machinery, automobile, medical apparatus and instruments, food processings
With.Polyether sulphone early stage kind is the polysulfones (PSU) with bisphenol-A as polymerized monomer, but it uses temperature relatively low, it is impossible to meet one
The application requirement of a little high-temperature fields.The offshore companies such as Britain ICI pass through to adjust polymer molecular structure, with the bisphenol S of high rigidity
Replace bisphenol-A, have developed polyether sulfone (PES) kind, improve the temperature classification of material.In recent years, with '-biphenyl diphenol replacement
Bisphenol S polymerized monomer, biphenyl polyether sulfone (PPSU) kind developed, has higher temperature classification and excellent impact resistance concurrently
Can, the market space of ton scale has been defined, greatly widen the application of poly (ether ketone ketone) material.
In the strand of polyaryl ether sulphone resin, C-SO2Bond angle between-C is 105 degree；And the bond angle between C-O-C is 124
Degree, this difference hinders the regular arrangement of polyether sulphone strand, therefore the polyaryl ether sulphone resin of commercialization at present is allusion quotation
The amorphous macromolecule material of type.While applications well is obtained, the side such as chemical-resistant, wearability, thermostability is there is also
The deficiency in face.Compared with amorphous polymer, crystalline polymer, strand arranged regular, closely can preferably stop various examinations
The infiltration of agent, improves solvent resistance；Crystallization is also beneficial to improve the thermostability of product.Therefore, about the crystallization of polyether sulphone
Research is being proceeded by very early.Blackadder and Ghkvamilkta have reported PES under the conditions of some and can have been formed locally to be had
Sequence structure, and the PES samples of the dichloromethane of mass fraction 21% (DCM) contain crystal structure by X-ray diffraction confirmation, but remove
Go to be crystallized after solvent and be destroyed.Also someone introduces the rigid chain of terphenyl structure in the strand of polyether sulphone, can obtain
To crystalline polyether sulphone, but because polymer solubility is very poor, molecular weight is very low, and monomer preparation cost is too high, limit
The practical application of polymer is made.Recently, Adrien Faye in PES strands by introducing high symmetric trans vinyl
Base, is successfully realized the crystallization of PES copolymers, but because the heat resistance of PES is greatly reduced not with application conditions.
To sum up, although at present the crystallization to polyether sulphone material has carried out some research, basic research is all biased toward, institute
The material of preparation can't reach requirement useful industrially.
Under the promotion of above-mentioned technical background and the market demand, the present invention is using the double biphenyl structural fluorine sulfone monomers for having synthesized
(application number：201410264880.3, the applying date：2014-02-18, denomination of invention：A kind of double fluorine sulfone lists containing double biphenyl structurals
Body and preparation method thereof), by traditional nucleophilic displacement of fluorine polycondensation technology, in polyether sulphone main chain sulfuryl both sides duplex benzene is symmetrically introduced
Group, completes the preparation of the full aromatic structure crystal type polyether sulphone containing double biphenyl structurals, and tests swarming by XRD and intend
Close, calculate degree of crystallinity for 24% (accompanying drawing 1).Method is simple, and cost is relatively low, with good industrial prospect.
The content of the invention
The present invention with 4,4 '-bis- (4- fluorophenyls) diphenyl sulphone (DPS)s and hydroquinone for reaction raw materials, using nucleophilic displacement of fluorine polycondensation
Method has prepared a kind of new crystallization polyether sulphone (DBP-PEES) containing double biphenyl structurals.With Known Species polyether sulfone phase
Than being at normal temperatures and pressures crystalline polymer.
It is an object of the invention to provide a kind of crystallization polyether sulfone polymer containing double biphenyl structurals --- polyethers ether duplex benzene
Sulfone (DBP-PEES) and preparation method thereof.
Polyethers ether duplex benzene sulfone structure is as follows：
N represents the degree of polymerization, is positive integer.
Polyethers ether duplex benzene sulfone synthetic method is as follows：
In the reactor equipped with condensation water knockout drum, nitrogen protection and mechanical agitator, organic solvent diphenyl sulphone (DPS) is added simultaneously
90~140 DEG C are heated to, mol ratio 1 is then sequentially added：0.8~1.5：The 4,4 ' of 0.9~1.1-bis- (4- fluorophenyls) hexichol
Sulfone, alkali metal salt forming agent (potassium carbonate, sodium carbonate or the two arbitrary proportion mixing), hydroquinone, the solid content of system is 20%
~35%, and the water entrainer (toluene or dimethylbenzene) of solvent volume 10~50% is subsequently added, system backflow is continuously heating to, open
Beginning salt-forming reaction, temperature control reaches table when theoretical value, epipelagic zone water preparation are changed into clarification at 140~210 DEG C whne system water yield
Show that first paragraph salt-forming reaction is completed；Then reaction temperature is risen to into 230~250 DEG C, is reacted 1~4 hour, have solid to analyse to system
Go out, then be warming up to 270~290 DEG C, react 1~4 hour, be finally warming up to 310~320 DEG C and react 2~5 hours, treat that system is glued
Constant temperature ensures that polyreaction is complete for 1~3 hour after degree rises；Stop stirring, polymerization mucus is directly injected into into the deionization of room temperature
Polymer solids into strips are cooled down in water, strip polymer solids are ground into into polymer powder in pulverizer after filtration；Again
Polymer powder acetone is boiled into 1~3 hour, while hot sucking filtration, so repeatedly 5~10 times；Again deionized water boils 2~3
Hour, sucking filtration while hot, so repeatedly 5~10 times；The powder drying that finally deionized water is cleaned, that is, obtain of the present invention
The crystallization polyether sulfone of biphenyl contenting structure --- polyethers ether duplex benzene sulfone.
The synthetic reaction formula of the above-mentioned crystallization polyether sulfone containing double biphenyl structurals is presented herein below：
Description of the drawings
Fig. 1：The XRD spectra of polyethers ether duplex benzene sulfone prepared by embodiment 2；
It is fitted by XRD spectra swarming, by formula：Degree of crystallinity=diffraction peak intensity/overall strength × 100%, calculates
Go out polymer crystallinity for 24%.
Fig. 2：The infrared spectrum of polyethers ether duplex benzene sulfone prepared by embodiment 2；
As can be seen that 1322 and 1152cm from spectrogram- 1Occur in that the characteristic absorption peak of sulfuryl；1002cm- 1Correspond to
The vibration absorption peak of biphenyl structural；1225cm- 1For phenylate characteristic absorption peak；Illustrate that we have obtained the polymer of expected structure.
Fig. 3：The TGA figures of polyethers ether duplex benzene sulfone prepared by embodiment 2；
The initial decomposition temperature for scheming visible polymer from TGA is 500 DEG C, and 5% weightless temperature is 550 DEG C.
Fig. 4：The DSC figures of polyethers ether duplex benzene sulfone (viscosity 0.35) of embodiment 2；
The glass transition temperature for scheming visible this polymer from DSC is 225 DEG C, and cold crystallization temperature is 292 DEG C, and fusing point is
375℃。
Fig. 5：The DSC figures of polyethers ether duplex benzene sulfone (viscosity 0.22) of embodiment 1；
The glass transition temperature for scheming visible this polymer from DSC is 198 DEG C, and cold crystallization temperature is 258 DEG C, and fusing point is
366℃。
Specific embodiment
Embodiment 1：The process of synthesizing polyether ether duplex benzene sulfone
In the 1000mL there-necked flasks equipped with thermometer, nitrogen port, condensation water knockout drum and mechanical agitator, addition has
400 grams of machine solvent diphenyl sulphone (DPS) is simultaneously heated with stirring to 100 DEG C, sequentially adds 4,4 '-bis- 103 grams of (4- fluorophenyls) diphenyl sulphone (DPS)s, carbonic acid
30 grams of sodium, 27 grams of hydroquinone is subsequently added 150 milliliters of dimethylbenzene.Continue to be warmed up to 170 DEG C under stirring, reaction starts, system
In water and xylenes, coolant is begun with condensing tube and is dripped, in water knockout drum be layered.Temperature maintains 170 DEG C, treats
Upper strata dimethylbenzene is changed into clear from muddiness, is further continued for backflow and completely, steams water entrainer to ensure salt-forming reaction in 30 minutes.Again
Be warming up to 240 DEG C, react 2 hours, have solid to be continuously heating to 270 DEG C after separating out after system, react 2 hours, when system again
When there is precipitation or caking phenomenon, 320 DEG C are continuously heating to, response speed is accelerated, and system viscosity rises, while it is fast to accelerate stirring
Degree, reaction stops heating after 2 hours, and polymer mucus is directly poured in deionized water, makes cooling obtain solid.By solid mistake
Crush after filter.Pressed powder is boiled with acetone, while hot sucking filtration, is cleaned 8 times repeatedly, remove diphenyl sulphone (DPS), then with going of boiling from
Sub- water washing 8 times, by clean powder, in an oven 120 DEG C of dryings obtain the knot of benzene containing duplex of the present invention after 10 hours
The crystallization polyether sulfone of structure.Its reduced viscosity is surveyed during with 40 DEG C of Ubbelohde viscometer m-Chlorophenol for 0.22.
Embodiment 2：The process of synthesizing polyether ether duplex benzene sulfone
In the 250mL there-necked flasks equipped with thermometer, nitrogen port, condensation water knockout drum and mechanical agitator, addition has
90 grams of machine solvent diphenyl sulphone (DPS) is simultaneously heated with stirring to 100 DEG C, sequentially adds 4,4 '-bis- 37 grams of (4- fluorophenyls) diphenyl sulphone (DPS)s, potassium carbonate
0.7 gram, 10 grams of sodium carbonate, 10 grams of hydroquinone is subsequently added 25 milliliters of toluene.Continue to be warming up to 140 DEG C under stirring, reaction is opened
Beginning, the water in system and toluene azeotropic, begin with coolant and drip in condensing tube, be layered in water knockout drum.Temperature maintains 160
Between DEG C.Treat that upper toluene is changed into clear from muddiness, be further continued for backflow and completely, steam band to ensure salt-forming reaction in 30 minutes
Water preparation.250 DEG C are warming up to again, are reacted 2 hours, have solid to be continuously heating to 290 DEG C after separating out after system, reacted 2 hours, work as body
When system precipitation or caking phenomenon occurs again, 320 DEG C are continuously heating to, response speed is accelerated, and system viscosity rises, while accelerating
Mixing speed, reaction stops heating after 4 hours, and polymer mucus is directly poured in deionized water, makes cooling obtain solid.Will
Solid is crushed after filtering.Pressed powder is boiled with acetone, while hot sucking filtration, cleaned 8 times repeatedly, remove diphenyl sulphone (DPS), then with boiling
Deionized water wash 8 times, by clean powder, in an oven 120 DEG C of dryings obtain of the present invention containing double after 10 hours
The crystallization polyether sulfone of biphenyl structural.Its reduced viscosity is surveyed during with 40 DEG C of Ubbelohde viscometer m-Chlorophenol for 0.35.
Embodiment 3：Impact of the viscosity to polyethers ether duplex benzene sulfone hot property
We can show that, with the increase of viscosity, glass transition temperature is changed into 225 by 198 DEG C to contrast Fig. 4 and Fig. 5
DEG C, cold crystallization temperature is also significantly improved, and fusing point is not significantly increased.Illustrate that, with the growth of molecular weight, polymer is resistance to
Processing temperature does not substantially change while hot property increases, compensate for the heat-resistant polymers such as similar polyether-ether-ketone with
Temperature classification is improved, and processing temperature is also improved constantly, not the shortcoming of easy processing.
Claims (3)
1. a kind of preparation method of the crystallization polyether sulfone polymer containing double biphenyl structurals, its step is as follows：
(1) in the reactor equipped with condensation water knockout drum, nitrogen protection and mechanical agitator, add organic solvent diphenyl sulphone (DPS) and add
Then heat sequentially add mol ratio 1 to 90~140 DEG C：0.8~1.5：The 4,4 ' of 0.9~1.1-bis- (4- fluorophenyls) diphenyl sulphone (DPS),
Alkali metal salt forming agent, hydroquinone, the solid content of system is 20%~35%；
(2) water entrainer of solvent volume 10~50% is subsequently added, system backflow is continuously heating to, starts salt-forming reaction, temperature
Control reaches when theoretical value, epipelagic zone water preparation are changed into clarification whne system water yield and represents that first paragraph is anti-into salt at 140~210 DEG C
Should complete；
(3) 230~250 DEG C are risen to and then by reaction temperature, is reacted 1~4 hour, have solid to separate out to system, then be warming up to 270
~290 DEG C, react 1~4 hour, be finally warming up to 310~320 DEG C react 2~5 hours, after system viscosity rise after constant temperature 1~
Ensure within 3 hours that polyreaction is complete；
(4) stop stirring, polymerization mucus is directly injected in the deionized water of room temperature and cools down polymer solids into strips, after filtration
Strip polymer solids are ground into into polymer powder in pulverizer；Polymer powder acetone is boiled 1~3 hour again,
Sucking filtration while hot, so repeatedly 5~10 times；Again deionized water boils 2~3 hours, while hot sucking filtration, so repeatedly 5~10 times；Most
Deionized water is cleaned powder drying afterwards, that is, obtain the crystallization polyether sulfone polymer of biphenyl contenting structure --- polyethers ether duplex benzene
Sulfone；Its structural formula is as follows,
N represents the degree of polymerization, is positive integer.
2. the preparation method of a kind of crystallization polyether sulfone polymer containing double biphenyl structurals described in claim 1, it is characterised in that：
Alkali metal salt forming agent is potassium carbonate, sodium carbonate or the two arbitrary proportion mixing.
3. the preparation method of a kind of crystallization polyether sulfone polymer containing double biphenyl structurals described in claim 1, it is characterised in that：
Water entrainer is toluene or dimethylbenzene.
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|---|---|---|---|---|
| CN1066450A (en) * | 1992-04-10 | 1992-11-25 | 吉林大学 | Aromatic polyether-ether ketone-the contain preparation of biphenyl polyether sulfone tactic block copolymer |
| JPH0656996A (en) * | 1992-08-07 | 1994-03-01 | Ube Ind Ltd | Aromatic polysulfone resin molding |
| CN101120035A (en) * | 2005-02-16 | 2008-02-06 | 索维高级聚合物股份有限公司 | Poly (aryl ether sulfone) material and use thereof |
| CN102391447A (en) * | 2011-09-07 | 2012-03-28 | 金发科技股份有限公司 | Preparation method of polyether ketone/sulfone high-temperature resistant material |
| CN104016892A (en) * | 2014-06-13 | 2014-09-03 | 吉林大学 | Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066450A (en) * | 1992-04-10 | 1992-11-25 | 吉林大学 | Aromatic polyether-ether ketone-the contain preparation of biphenyl polyether sulfone tactic block copolymer |
| JPH0656996A (en) * | 1992-08-07 | 1994-03-01 | Ube Ind Ltd | Aromatic polysulfone resin molding |
| CN101120035A (en) * | 2005-02-16 | 2008-02-06 | 索维高级聚合物股份有限公司 | Poly (aryl ether sulfone) material and use thereof |
| CN102391447A (en) * | 2011-09-07 | 2012-03-28 | 金发科技股份有限公司 | Preparation method of polyether ketone/sulfone high-temperature resistant material |
| CN104016892A (en) * | 2014-06-13 | 2014-09-03 | 吉林大学 | Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof |
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