CN106750436A - A kind of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane and preparation method thereof - Google Patents
A kind of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane and preparation method thereof Download PDFInfo
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Abstract
A kind of sulfonated polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane and preparation method thereof, belongs to technical field of polymer materials.The present invention is from improvement sulfonated polyether-ether-ketone film dry and wet state dimensional stability, with polyether-ether-ketone micro-and nano-particles as raw material, first use interfacial reaction, prepare sulfonated polyether-ether-ketone micro-and nano-particles, then sulfonated polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone co-blended slurries are prepared using solution blending process, sulfonated polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane is finally prepared by the way of solution is poured.Such composite membrane possesses that excellent swelling resistance is swelling and high-proton-conductivity.By sem analysis it can be seen that sulfonated polyether-ether-ketone matrix resin and sulfonated polyether-ether-ketone micro-and nano-particles are tightly combined.Composite membrane shows proton conductivity higher after the doping of sulfonated polyether-ether-ketone micro-and nano-particles, and conductivity increases with the increase of sulfonation degree.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of sulfonating surface polyether-ether-ketone micro-and nano-particles/
Sulfonated polyether-ether-ketone composite membrane and preparation method thereof.
Background technology
Polyether-ether-ketone is because of its excellent heat resistance, good chemical stability and excellent mechanical performance, it is considered to be comprehensive
Close the special engineering plastics of function admirable.Especially there is phenylate structure, easily to polyether-ether-ketone in polyether-ether-ketone resin structure
Modified.For example, sulfonated polyether-ether-ketone resin is exactly a kind of polyetheretherketonematerials materials of modification.Because sulfonic acid group introduces polyethers
In ether ketone molecular structure, material ions transmission, water transmission characteristic are imparted.Therefore sulfonated polyether-ether-ketone is in proton-conductive films, water
Process film and electrodialytic membranes field application prospect are extensive.But because the introducing of sulfonic acid group causes membrane material in dimensional stability
Aspect is deteriorated.As sulfonated polyether-ether-ketone material shows high water-swellable in highly sulfonated, the machinery of membrane material is lost
Performance.In order to solve the problems, such as that dimension stability is poor, we are using with excellent solvent resistant, the table of exceptional dimensional stability
Face sulfonated polyether-ether-ketone micro-and nano-particles strengthen sulfonated polyether-ether-ketone.
The content of the invention
The present invention from improve sulfonated polyether-ether-ketone film dry and wet state dimensional stability, with polyether-ether-ketone micro-and nano-particles
It is raw material, first using interfacial reaction, prepares sulfonating surface polyether-ether-ketone micro-and nano-particles, is then prepared using solution blending process
Sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone co-blended slurries, finally prepare by the way of solution is poured
Sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane.It is swelling that such composite membrane possesses excellent swelling resistance
And high-proton-conductivity.
The preparation method of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane of the present invention,
Its step is as follows：
1) preparation of sulfonated polyether-ether-ketone：10g polyether-ether-ketones (Te Su engineering researcies Co., Ltd of Jinlin University) are taken, 20~30
DEG C it is dissolved in the 500mL concentrated sulfuric acids (mass fraction 95%~98%), after 25~75h of stirring, reaction solution is poured into 5~10 times of bodies
In long-pending frozen water, 1~3h is persistently stirred, then stand 24~36h, sediment is through multiple water washing, filtering；Until washing is water-soluble
The pH=7 of liquid, obtains the sulfonated polyether-ether-ketone that sulfonation degree is 0.4~0.8 after drying；
2) preparation of sulfonating surface polyether-ether-ketone micro-and nano-particles：Chlorosulfonic acid is dissolved in organic solvent 1 first, is configured to dense
The solution for 0.01~1g/L is spent, it is then that particle size range 1nm~20 μm, melt index 10g/10min~30g/10min is (molten
Melt indexer) polyether-ether-ketone micro-and nano-particles be added thereto, the mass ratio of polyether-ether-ketone micro-and nano-particles and chlorosulfonic acid
It is 10：0.1~0.5；5~20min is stirred at room temperature, the solids washing that will be obtained after filtering, repetition filtering, water washing operations are more
Secondary, last filtration product obtains sulfonating surface polyether-ether-ketone micro-and nano-particles after 80~120 DEG C of vacuum dryings；
3) preparation of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane：First by step 1) system
Standby sulfonated polyether-ether-ketone is dissolved in organic solvent 2, is configured to the solution that concentration is 0.5g/10mL~3g/10mL, is subsequently adding step
The rapid sulfonating surface polyether-ether-ketone micro-and nano-particles for 2) preparing, the addition of sulfonating surface polyether-ether-ketone micro-and nano-particles is surface
The 1%~30% of sulfonated polyether-ether-ketone micro-and nano-particles and sulfonated polyether-ether-ketone quality sum, using high speed dispersor mixing or
Person's ultrasonic wave is mixed to get mix slurry, and then mix slurry is cast in horizontal glass plate, 60~80 DEG C of drying 10
~12h, then 100~130 DEG C of vacuum 8~20h of sulfonation, obtain sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether ether
Ketone composite membrane.
Further, above-mentioned steps 2) in organic solvent 1 be dichloromethane, tetrachloroethanes, 1,2- dichloroethanes, three chloromethanes
Alkane, n-hexane or petroleum ether.
4) above-mentioned steps 3) in organic solvent 2 be N, N '-dimethyl acetamide, 1-METHYLPYRROLIDONE, N, N '-diformazan
Base formamide or dimethyl sulfoxide (DMSO).
A kind of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane, it is prepared by as above method
Obtain.
Brief description of the drawings
Fig. 1：The DSC collection of illustrative plates of sulfonating surface polyether-ether-ketone micro-and nano-particles prepared by embodiment 1；
Although as can be seen from Figure 1 polyether-ether-ketone particle has carried out sulfonating surface treatment, remain in that original
Crystalline texture, crystalline polymer melting peak and decrease temperature crystalline peak are clear that from figure.
Fig. 2：The infrared spectrogram of sulfonating surface polyether-ether-ketone micro-and nano-particles prepared by embodiment 1；
As can be seen from Figure 2 after the sulfonation of polyether-ether-ketone particle surface, in 1045cm-1Place occurs in that the feature of sulfonic acid group
Absworption peak, illustrates that sulfonic acid group is successfully introduced polyether-ether-ketone particle surface.
Fig. 3：Sulfonating surface polyether-ether-ketone micro-and nano-particles prepared by embodiment 4/sulfonated polyether-ether-ketone fine powder composite membrane is horizontal
Cross-section photographs；
As can be seen from Figure 3 stronger phase is there is between sulfonating surface polyether-ketone particle and sulfonated polyether-ether-ketone matrix
Capacitive.
Fig. 4：Sulfonating surface polyether-ether-ketone micro-and nano-particles prepared by embodiment 4,5,6/sulfonated polyether-ether-ketone composite membrane is passed
Conductance curve；
Composite membrane shows proton biography higher after the doping of sulfonating surface polyether-ether-ketone micro-and nano-particles as can be seen from Figure 4
Conductance, conductivity increases with the increase of sulfonation degree；The conductance variation of the film of ultrasonic disperse treatment and high speed decentralized processing
Less.
Specific embodiment
Embodiment 1：
The preparation of the sulfonating surface polyether-ether-ketone micro-and nano-particles of 1 micro-meter scale：It is separately added into 500mL there-necked flasks
300mL dichloromethane and 0.3g chlorosulfonic acids, are stirring evenly and then adding into the polyether-ether-ketone particle that 10g average grain diameters are 1 micron and (purchase
Te Su engineering researcies Co., Ltd of Jinlin University, melt index 10g/10min), after 5min is stirred at room temperature, the solid that will be obtained after filtering
Thing is washed, and repeats filtering, water washing operations 4 times, and stirring washing 1h, dries solids in 120 DEG C after finally filtering again every time,
Obtain sulfonating surface polyether-ether-ketone micro-and nano-particles, yield 99%.Although particle surface is sulfonated, polyether-ether-ketone particle is still
So remain the crystalline texture of script.From the DSC curve of Fig. 1 can be seen that polymer particle still have polyether-ether-ketone fusing point and
Peak crystallization.And can be analyzed from the FT-IR figures of Fig. 2 and draw, there is sulfonic acid group in particle surface.
Embodiment 2：
The preparation of 1 micrometer scale surface sulfonated polyether-ether-ketone micro-and nano-particles：It is separately added into 500mL there-necked flasks
300mL chloroforms and 0.3g chlorosulfonic acids, are stirring evenly and then adding into the polyether-ether-ketone particle that 10g average grain diameters are 1 micron and (purchase
Te Su engineering researcies Co., Ltd of Jinlin University, melt index 10g/10min), after 5min is stirred at room temperature, the solid that will be obtained after filtering
Thing is washed, and repeats filtering, water washing operations 4 times, and stirring washing 1h, dries solids in 120 DEG C after finally filtering again every time,
Obtain sulfonating surface polyether-ether-ketone micro-and nano-particles, yield 99%.
Embodiment 3：
Change the particle diameter of polyether-ether-ketone particle in embodiment 1, from 1 nanoscale level to 20 micro-meter scales, can obtain table
Face sulfonated polyether-ether-ketone micro-and nano-particles.
Embodiment 4：
According to prior art, the sulfonated polyether-ether-ketone that sulfonation degree is 0.65 is prepared：By 10g polyether-ether-ketones (the special modeling work of Jinlin University
Journey research Co., Ltd) at 25 DEG C the 500mL concentrated sulfuric acids (mass fraction 98%) are dissolved in, it is stirred vigorously, after continuing 48h, then
Reaction solution is poured into 10 times of frozen water of volume, 1h is persistently stirred, 24h is stood, sediment through multiple water washing, filtering, directly
To washings pH=7, drying obtains sulfonated polyether-ether-ketone, yield 95%.
The sulfonation degree for weighing above-mentioned preparation is 0.65 sulfonated polyether-ether-ketone 0.9g, is dissolved in 10mL N, N '-dimethyl acetyl
In amine aqueous solution, sulfonated polyether-ether-ketone solution is obtained；1 micrometer scale surface for adding embodiment 1 to prepare in the dispersion bottle of 50mL
Sulfonated polyether-ether-ketone micro-and nano-particles 0.1g, is subsequently adding sulfonated polyether-ether-ketone solution, is disperseed using high speed dispersor,
22000rad/min dispersions 30min obtains blend slurries, is cast in horizontal glass plate, and 80 DEG C dry 12h, 120 DEG C
Vacuum sulfonation 12h, obtains sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone fine powder composite membrane.By sem analysis
Sulfonated polyether-ether-ketone matrix and the polyether-ether-ketone particle direct binding ability of doping, as can be seen from Figure 3 sulfonated polyether ether
Ketone matrix resin and sulfonating surface polyether-ether-ketone micro-and nano-particles are tightly combined.
Embodiment 5：
The sulfonated polyether-ether-ketone 0.9g that sulfonation degree is 0.65 is taken, 10mL N are dissolved in, in N '-dimethyl acetamide solution, obtained
To sulfonated polyether-ether-ketone solution；The 1 micrometer scale surface sulfonated polyether-ether-ketone for adding embodiment 1 to prepare in the dispersion bottle of 50mL
Micro-and nano-particles 0.1g, is subsequently adding sulfonated polyether-ether-ketone solution, is disperseed using ultrasonic dispersing machine, 100Hz dispersions
30min obtains blend slurries, is cast in horizontal glass plate, 80 DEG C of drying 12h, 120 DEG C of vacuum drying 12h, obtains
Sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone fine powder composite membrane.
Embodiment 6：
Prepare the sulfonated polyether-ether-ketone that sulfonation degree is 0.4：By 10g polyether-ether-ketones (Te Su engineering researcies Co., Ltd of Jinlin University)
In being dissolved in the 500mL concentrated sulfuric acids (mass fraction 98%) at 25 DEG C, it is stirred vigorously, after continuing 25h, reaction solution is then poured into 10
In the frozen water of times volume, persistently stir 1h, stand 24h, sediment through multiple water washing, filtering, until washings pH=7, baking
It is dry, obtain the sulfonated polyether-ether-ketone that sulfonation degree is 0.4, yield 95%.
Prepare the sulfonated polyether-ether-ketone that sulfonation degree is 0.8：By 10g polyether-ether-ketones (Te Su engineering researcies Co., Ltd of Jinlin University)
In being dissolved in the 500mL concentrated sulfuric acids (mass fraction 98%) at 25 DEG C, it is stirred vigorously, after continuing 75h, reaction solution is then poured into 10
In the frozen water of times volume, persistently stir 1h, stand 24h, sediment through multiple water washing, filtering, until washings pH=7, baking
It is dry, obtain the sulfonated polyether-ether-ketone that sulfonation degree is 0.8, yield 95%.
With sulfonated polyether-ether-ketone that sulfonation degree is 0.4 or 0.8 as raw material, other are identical with embodiment 4 or 5, can prepare
Go out sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane.
Embodiment 7：
Change the addition of sulfonating surface polyether-ether-ketone micro-and nano-particles in embodiment 4,5 for sulfonating surface polyether-ether-ketone is micro-
The 1%~30% of nano-particle and sulfonated polyether-ether-ketone quality sum, can prepare sulfonating surface polyether-ether-ketone micro-and nano-particles/sulphur
Change polyether-ether-ketone composite membrane.
Embodiment 8：
The particle diameter of sulfonating surface polyether-ether-ketone micro-and nano-particles is in 1 nanometer to 20 micrometer ranges in change embodiment 4,5
Sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane can be prepared.
Claims (3)
1. a kind of preparation method of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane, its step is as follows：
1) preparation of sulfonated polyether-ether-ketone：10g polyether-ether-ketones are taken, 500mL, mass fraction 95%~98% are dissolved at 20~30 DEG C
In the concentrated sulfuric acid, after 25~75h of stirring, reaction solution is poured into 5~10 times of frozen water of volume, persistently stir 1~3h, Ran Houjing
24~36h is put, sediment is through multiple water washing, filtering；Until the pH=7 of wash water solution, it is 0.4 that sulfonation degree is obtained after drying
~0.8 sulfonated polyether-ether-ketone；
2) preparation of sulfonating surface polyether-ether-ketone micro-and nano-particles：Chlorosulfonic acid is dissolved in organic solvent 1 first, being configured to concentration is
The solution of 0.01~1g/L, then by particle size range 1nm~20 μm, the polyethers ether of melt index 10g/10min~30g/10min
Ketone micro-and nano-particles are added thereto, and surface polyether-ether-ketone micro-and nano-particles are 10 with the mass ratio of chlorosulfonic acid：0.1~0.5；Room temperature
5~20min of lower stirring, the solids washing that will be obtained after filtering, repeats filtering, water washing operations repeatedly, and last filtration product exists
Sulfonating surface polyether-ether-ketone micro-and nano-particles are obtained after 80~120 DEG C of vacuum dryings；
3) preparation of sulfonated polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane：First by step 1) prepare sulfonation
Polyether-ether-ketone is dissolved in organic solvent 2, is configured to the solution that concentration is 0.5g/10mL~3g/10mL, is subsequently adding step 2) prepare
Sulfonating surface polyether-ether-ketone micro-and nano-particles after obtain mix slurry, the addition of sulfonated polyether-ether-ketone micro-and nano-particles is
The 1%~30% of sulfonating surface polyether-ether-ketone micro-and nano-particles and sulfonated polyether-ether-ketone quality sum, then pours mix slurry
Build in horizontal glass plate, 60~80 DEG C of 10~12h of drying, then 100~130 DEG C of vacuum 8~20h of sulfonation, obtain surface sulphur
Change polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane；
Step 2) in organic solvent 1 be dichloromethane, tetrachloroethanes, 1,2- dichloroethanes, chloroform, n-hexane or oil
Ether；Step 3) in organic solvent 2 be N, N '-dimethyl acetamide, 1-METHYLPYRROLIDONE, N, N '-dimethyl formamide or
Dimethyl sulfoxide (DMSO).
2. a kind of system of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane as claimed in claim 1
Preparation Method, it is characterised in that：Step 3) in be using high speed dispersor mixing or ultrasonic wave be mixed to get mix slurry.
3. a kind of sulfonating surface polyether-ether-ketone micro-and nano-particles/sulfonated polyether-ether-ketone composite membrane, it is characterised in that：Being will by right
1 or 2 methods describeds are asked to prepare.
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| CN107198698A (en) * | 2017-06-12 | 2017-09-26 | 深圳大学 | Sulfonated polyether-ether-ketone is being prepared for treating purposes and people's bone alternate material in the medicine of osteoma |
| CN108192120A (en) * | 2017-12-29 | 2018-06-22 | 武汉理工大学 | A kind of proton exchange membrane of high-quality electron conductivity suitable under middle low temperature environment and preparation method thereof |
| CN108424605A (en) * | 2018-03-23 | 2018-08-21 | 杭州科技职业技术学院 | A kind of polyether-ether-ketone 3D printing material and its 3D printing forming method |
| CN109971121A (en) * | 2019-04-03 | 2019-07-05 | 山东星火科学技术研究院 | A kind of preparation method of sulfonated polyether-ether-ketone composite membrane |
| CN109988278A (en) * | 2019-04-03 | 2019-07-09 | 山东星火科学技术研究院 | A method of improving polyether-ether-ketone sulfonation degree |
| CN111184913A (en) * | 2020-01-13 | 2020-05-22 | 吉林大学 | Artificial bone composite material based on polyether-ether-ketone and preparation method thereof |
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| CN107198698A (en) * | 2017-06-12 | 2017-09-26 | 深圳大学 | Sulfonated polyether-ether-ketone is being prepared for treating purposes and people's bone alternate material in the medicine of osteoma |
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| CN108424605A (en) * | 2018-03-23 | 2018-08-21 | 杭州科技职业技术学院 | A kind of polyether-ether-ketone 3D printing material and its 3D printing forming method |
| CN108424605B (en) * | 2018-03-23 | 2020-03-20 | 杭州科技职业技术学院 | Polyether-ether-ketone 3D printing material and 3D printing forming method thereof |
| CN109971121A (en) * | 2019-04-03 | 2019-07-05 | 山东星火科学技术研究院 | A kind of preparation method of sulfonated polyether-ether-ketone composite membrane |
| CN109988278A (en) * | 2019-04-03 | 2019-07-09 | 山东星火科学技术研究院 | A method of improving polyether-ether-ketone sulfonation degree |
| CN111184913A (en) * | 2020-01-13 | 2020-05-22 | 吉林大学 | Artificial bone composite material based on polyether-ether-ketone and preparation method thereof |
| CN111184913B (en) * | 2020-01-13 | 2021-06-04 | 吉林大学 | Artificial bone composite material based on polyether-ether-ketone and preparation method thereof |
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