CN104804182B - Sulfonated polyether sulphone and its preparation method and its preparing the application in electric actuator - Google Patents
Sulfonated polyether sulphone and its preparation method and its preparing the application in electric actuator Download PDFInfo
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- CN104804182B CN104804182B CN201510164264.5A CN201510164264A CN104804182B CN 104804182 B CN104804182 B CN 104804182B CN 201510164264 A CN201510164264 A CN 201510164264A CN 104804182 B CN104804182 B CN 104804182B
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Abstract
A kind of sulfonated polyether sulphone or sulfonated polyether sulphone derivative, it is diphenyl sulphone (DPS) and 2, (4- hydroxy phenyl) propane of 2- bis- or bisphenol fluorene [BHPF, 9, bis- (4- hydroxyphenyl) fluorenes of 9-] or polyethyleneglycol modified bisphenol fluorene sulfonated block polymer: sulfonated polyether sulphone, sulfonated polyether sulphone derivative or polyethyleneglycol modified sulfonation polyarylsulfone (PAS) derivative, structural formula are as follows:Wherein: R1For H or SO3H；R2For H or SO3H.Sulfonated polyether sulphone of the invention can be used for preparing ion-exchange polymer/metallic composite electric actuator.Sulfonated polyether sulphone of the invention has higher ion-exchange equivalent, has broader mechanical performance adjustable range, and price is relatively low.
Description
Technical field
The present invention relates to sulfonated polyether sulphone (SPAES) and its derivative and ion-exchange polymer/metal composites
Material electric actuator and the application in machinery is bionical.
Technical background
Ion-exchange polymer-metallic composite (Ionic Polymer-Metal Composite, IPMC) is used as one
The emerging intellectual material of class, enjoys the good reputation of " artificial-muscle "., the actuating low with driving voltage by the electric actuator of IPMC preparation
The advantages that mode is simple, relative deformation amount is big, light-weight and safe operation, strain gauge, artificial-muscle, biomimetic material,
The fields such as flexible mechanical actuator and bio-medical material are with a wide range of applications.
IPMC is by ion-exchange polymer (perfluorinated sulfonic acid (such as Nafion), perfluor carbonic acid (such as Flemion)) and absorption
Inert metal nano-electrode in polymer two sides forms.The structure feature of Nafion is: main chain is carbon fluorine skeleton, has hydrophobic
Function；Side chain is acid group, is had the function of hydrophilic.Due to containing hydrophilic and hydrophobic group simultaneously, after crystalline film, ion is handed over
It changes in film and forms the microchannel of countless fluid molecules such as moisture movement, diameter is between 0.5~5nm.1993, day
This Asaka seminar and the Shanhinpoor seminar in the U.S. find simultaneously: under electric field, deformation occurs by IPMC, produces to the external world
Raw certain stress, therefore be expected to for IPMC to be used for electroluminescent driver.The actuation mechanism generally received for people is: electric field action
Under, hydrated cation carries certain solvent molecule (such as hydrone) by small interior conduit to movable cathode, so as to cause sun
The contraction of pole and the expansion of cathode macroscopically cause material and occur bending and deformation, and show certain power to the external world and are displaced defeated
Out.Conversely, applying mechanically deform to IPMC, leads to the uneven distribution of its surface charge, cause surface field variation, it can with this
Prepare displacement/force snesor.
Currently, IPMC there is also output powers it is relatively small, the non-aqueous working time is shorter, cost is high the disadvantages of, these
Disadvantage seriously hinders its application development.Low moisture storage capacity of the principal element from matrix membrane material, ion-exchange equivalent.But
The molecular structure (main chain is C-F structure) of existing Nafion membrane is sufficiently stable, is modified and is difficult to realize to it, and uses merely
Doping vario-property, and by the cost high in face of Nafion membrane, so that IPMC can not be promoted on a large scale.Therefore, preparation tool
There are macroion exchanging equivalent, high conductivity, high water absorbing capacity and low-cost novel ion exchange polymer, it is existing to replace
Some perfluorinated sulfonic acid polymers become the bottleneck of IPMC developmental research.In this respect, domestic and foreign scholars had accumulated it is some before
Phase is explored.Sulfonated polystyrene (SPS), sulfonated phenylethylene-ethylene copolymer (SPSE), sulfonated polyether-ether-ketone (SPEEK), benzene second
Alkene-maleimide block copolymer has been attempted for research preparation IPMC, since they have superior ion exchange energy
Power, conductivity, the IPMC thus prepared show ideal actuating performance.Compared with conventional Nafion base IPMC, gathered by these
The IPMC for closing object preparation works as in alternating voltage bottom offset output phase, but power output is remarkably reinforced；It is not deposited under direct voltage drive
In the displacement relaxation of conventional IPMC, reply phenomenon.But these amberplexes there is also water content lower, poor chemical stability etc.
Defect, leads to that the working time is short, mechanics output performance is unstable.
Polysulfones is a kind of special engineered modeling for possessing superior mechanical property, processing performance, thermal stability, chemical stability
Material.The structural formula of conventional bisphenol-a polysulfone (PSF) is as follows.Polysulfones after hydrophilic modifying can have certain ion exchange energy
Power, instead of conventional Nafion, in water process, the expansion application of fuel cell plasma exchanger resin field.It investigates according to us, does not have still
There are polysulfones and its derivative to be used for the report of IPMC.Before ion exchange resin, hydrophilic modifying carried out to polysulfones, make it
Hydrophilic functional groups sulfonic group, hydroxyl or carboxylic acid group etc. are taken on main chain.In addition, for phenyl ring, the electron energy of fluorenes ring
Power is stronger, therefore can be grafted more hydrophilic radicals.The sulfonation degree of polysulfones and the ion-exchange equivalent of film and water absorption rate are close
Correlation, according to our test results: the ion-exchange equivalent that the sulfonated polysulfone that sulfonation degree is 70% has is 1.65meq/g, should
Numerical value is twice or so of perfluorinated sulfonic acid polymer (Nafion) under the same terms.Meanwhile water absorption also greatly increases, and is conducive to
Water support is provided for IPMC long-term stable work.Therefore, structure design appropriate is carried out by template of polysulfones, it is expected to obtain valence
Lattice are cheap, ion-exchange performance is superior, can be used for the novel ion exchanger resin of IPMC.
United States Patent (USP) (6,475,639) and (6,109,852) describe a kind of preparation process of artificial thews material,
And some application studies of the artificial thews material as actuator and sensor, the invention including underwater fish, mechanical tong
Invention etc..Other patents are mainly also some explorative research to electroactive polymer, wherein describing in medical domain
Artificial thews material is used for the design of cardiac compression equipment, design of the human implantable for the micropump for the treatment of, as being used for
The driving device, and the reparation for human muscle etc. of " microcapsules " robot of human internal organs inspection.It answers at other
With aspect, mainly have: utilizing the actuating invention Braille display of electroactive polymer；It is deformed based on electroactive polymer material
Principle develops a kind of valve and rotation motor；By the sensor etc. of electroactive polymer design.But related artificial muscle
There is no export to have breakthrough on the problems such as small, to the dependence of wet environment in power for meat material.
A kind of porous perfluorinated ion-exchange membrane of Chinese patent and its preparation method and purposes (200710191892.8) propose system
The porous perfluorinated ion-exchange membrane of standby mechanical performance optimization, and it is used for artificial-muscle driver, power output can be improved,
It lengthens working hours；Graphene-ionomer electric actuator and the preparation method and application thereof (201110165842.9) propose
Develop the Graphene electrodes for being used for IPMC.
Different from above-mentioned patent, the present invention proposes to use polyether sulphone (SPAES) and its derivative as amberplex, system
Standby novel I PMC electric actuator.
Summary of the invention
The present invention relates to sulfonated polyether sulphone (SPAES) and its derivative and the ion-exchange polymers prepared with it
Object/metallic composite electric actuator, and the application in machinery is bionical.
Technical scheme is as follows:
A kind of sulfonated polyether sulphone or sulfonated polyether sulphone derivative, it is diphenyl sulphone (DPS) and 2, (the 4- hydroxy benzenes of 2- bis-
Base) propane or bisphenol fluorene [BHPF, 9,9- bis- (4- hydroxyphenyl) fluorenes] or polyethyleneglycol modified bisphenol fluorene sulfonated block it is poly-
Close object: sulfonated polyether sulphone, sulfonated polyether sulphone derivative or polyethyleneglycol modified sulfonation polyarylsulfone (PAS) derivative, knot
Structure formula is as follows:
Wherein: R1With R2For SO3H；
Or structural formula are as follows:
Wherein: R1With R2For SO3H, R3For H or CH2-O-(-CH2-CH2-O-)m-CH3Polyether chain, R4With R5For H or SO3H。
A method of preparing above-mentioned sulfonated polyether sulphone, it the following steps are included:
Step 1, by 1.0 moles of 4,4 '-dichloro diphenyl sulfones (DCDPS), 1.0-1.8 moles of (the 4- hydroxy benzenes of 2,2- bis-
Base) propane (bisphenol-A, BPA) and excessive 15% K2CO3Be added reaction flask in, solubilizer n,N-dimethylacetamide (DMAc) and
Then water entrainer toluene loads onto the condenser pipe with water segregator, stirring, N2It is to slowly warm up to 135 DEG C of reaction 3h under protection, and removes
The water generated is reacted, is warming up to 155 DEG C later the reaction was continued that N, N- dimethyl second are added into reaction flask after reaction by 14h
Product dilution is poured into methanol later and is settled out product polyether sulphone (PAES) by amide, filters drying, and product uses 1,2- bis- again
Chloroethanes stirring and dissolving 2h is precipitated out again thoroughly to remove the impurity such as inorganic salts, small molecule in methyl alcohol later, obtains poly- virtue
Ether sulfone；
Above-mentioned polyether sulphone is dissolved in 1,2- dichloroethanes by step 2, is added into equipped with constant pressure funnel
In reaction flask, stirring, measurement chlorosulfonic acid, which is dissolved in 1,2- dichloroethanes, to be poured into constant pressure funnel, the matter of polyether sulphone and chlorosulfonic acid
Between 1:2-2.5, coutroi velocity instills chlorosulfonic acid dropwise in polyether sulphone solution in 2h, is then further continued for the ratio between amount
2h is reacted, the solvent in reaction system is boiled off after having reacted, obtains amber solid product sulfonated polyether sulphone (SPAES),
Product is heated with stirring to 60 DEG C of 1h in 3% KOH solution, is heated with stirring in 5% HCl solution again after filtering washing
60 DEG C, after finally filtering, washing, drying, sulfonated polyether sulphone.
A method of preparing above-mentioned sulfonated polyether sulphone derivative, it the following steps are included:
Step 1, by DCDPS and bisphenol fluorene (BHPF) that molar ratio is 1:1, excessive 15% K2CO3, the diformazan dried
Sulfoxide (DMSO) and water entrainer toluene are added in reaction flask, then load onto the condenser pipe with water segregator, stir, N2It is slow under protection
It is warming up to 135 DEG C of reaction 3h, and except the water that dereaction generates, be warming up between 170-190 DEG C that the reaction was continued later 20h, reaction
After, DMSO is added into flask and dilutes product polyether sulphone derivative (BHPF-PAES), pours into methanol precipitate later
Out, drying is filtered, the product dried is used DMAc stirring and dissolving 2h again, is precipitated out in methyl alcohol again thoroughly to remove later
The impurity such as inorganic salts, small molecule, then washing filters dry to get polyether sulphone derivative；
Above-mentioned polyether sulphone derivative (BHPF-PAES) is dissolved in 1,2- dichloroethanes by step 2, by chlorosulfonic acid
(sulfonation degree that the dosage of chlorosulfonic acid determines polyether sulphone derivative) is dissolved in 1,2- dichloroethanes, polyether sulphone derivative with
Between the mass ratio 1:2-1:6.5 of chlorosulfonic acid, 1, the 2- dichloroethane solution of chlorosulfonic acid is instilled to poly- virtue dropwise at room temperature
In ether sulfone derivative solution, whole process needs 2h, is further continued for reaction 1h later and boils off 1,2- dichloroethanes after reaction,
Product sulfonated polyether sulfone derivative (SBHPF-SPAES) is washed with distilled water for several times, is filtered, dry to get sulfonated polyether
Sulfone derivative.
A method of preparing above-mentioned polyethyleneglycol modified sulfonation polyarylsulfone (PAS) derivative, it the following steps are included:
Step 1 dissolves sulfonated polyether sulfone derivative (SBHPF-SPAES) obtained above with 1,2- dichloroethanes,
After dissolution completely, the catalyst SnCl of chloromethylation reagents Isosorbide-5-Nitrae-two (chloromethane epoxide) butane (BCMB) and catalytic amount is added4,
The ratio between dosage of SBHPF-SPAES and BCMB is that every chain of SBHPF-SPAES saves BCMB 1-2.5 mole, in room temperature (25
DEG C) under react 3h, be after reaction precipitating reagent with ethyl alcohol, resulting polymer be precipitated, successively uses n,N-dimethylacetamide
(DMAc), dilute hydrochloric acid washed product polymer, then repeatedly washed with distilled water, until chloride ion-containing, vacuum drying do not obtain cleaning solution
The sulfonated polyether sulfone derivative of chloromethylation；
The sulfonated polyether sulfone derivative of chloromethylation is placed in stirring, thermometer and reflux condensing tube by step 2
Four-hole bottle in, DMAc is added and makes it completely dissolved, then is separately added into polyethylene glycol (PEGME-750) and Na2CO3, PEGME-
750 dosages are the BCMB dosage of equimolar step 1, are stirred to react at 70 DEG C, are after reaction precipitating reagent with ethyl alcohol, make
Polyethyleneglycol modified sulfonation polyarylsulfone (PAS) derivative (PEG-SBHPF-SPAES) polymer of product is precipitated, then multiple with distilled water
Washing is dried in vacuo to get polyethyleneglycol modified sulfonated polyether sulfone derivative (PEG-SBHPF-SPAES).
Above-mentioned sulfonated polyether sulphone, sulfonated polyether sulphone derivative and polyethyleneglycol modified sulfonated polyether sulphone
Derivative can be used for preparing ion-exchange polymer/metallic composite electric actuator.
Electric actuator of the invention is made of amberplex (a), electrode (b) and extraneous power supply (signal generator), such as
Shown in Fig. 1.
Amberplex described in above-mentioned electric actuator is sulfonated polyether sulphone (SPAES) or sulfonated poly- virtue
Ether sulfone derivative, with a thickness of 50 μm -300 μm；Electrode is the nano metals electrodes such as Pt, Au or Ag, with a thickness of 1 μm -10 μm；Telecommunications
Number it can be voltage 0.5-5V, sine wave, square wave or the triangular wave of frequency 0.1-20Hz.
The present invention also provides a kind of beam type electric actuators.After input electrical signal, displacement and power output are generated, it will be electric
Mechanical energy can be converted into.Its power output performance is higher than the perfluorinated sulfonic acid base beam type electric actuator of same specification；At displacement deflection
Between 5-70 °.
Substrate polymer present invention employs sulfonated polyether sulphone and polyether sulphone derivative as electric actuator
Material is embedded in conductive metal electrode in its two sides, and input electrical signal obtains new polymers electric actuator.Relative to conventional perfluor
Sulfonic acid (Nafion), perfluor carbonic acid (Flexmion), sulfonated polyether ether ketone (SPEEK), the present invention in SPAES have it is excellent
Point:
1. sulfonated polyether sulphone and polyether sulphone derivative can have higher ion-exchange equivalent.The present invention relates to
Polymer backbone in contain a large amount of phenyl ring, can replace, be grafted multiple sulfonic acid, carbonic acid group, promote the ion of basilar memebrane
Exchange capacity, and then improve the electromechanical performance of electric actuator.
2. sulfonated polyether sulphone and polyether sulphone derivative can have broader mechanical performance adjustable range.The present invention
Hydrophilic polyglycol group is grafted with above SPAES, both the mechanical performance of adjustable basilar memebrane, by the hydrophilic energy of increase film
Power, to maintain prolonged electroluminescent dynamic response.
For opposite 3. perfluorinated sulfonic acid (Nafion), perfluor carbonic acid (Flexmion), sulfonated polyether sulphone and poly- virtue
Ether sulfone derivative is cheap.
Detailed description of the invention
Infrared spectrum comparison diagram before and after the sulfonation of Fig. 1 polyether sulphone；
The scanning electron microscope (SEM) photograph of Fig. 2 sulfonated polyether sulfone derivative base IPMC.A, front；B, section；
The structural schematic diagram of Fig. 3 Inventive polymers electric actuator, wherein a is amberplex；B is electrode；
Fig. 4 IPMC power exports test device schematic diagram, wherein 1 is the drive module of IPMC；2 export measurement for the power of IPMC
Module；3 be computer；4 be IPMC；
Fig. 5 IPMC power exports test device pictorial diagram；
The electric actuation video recording screenshot of Fig. 6 sulfonated polyether sulfone derivative base IPMC.
Specific embodiment
Embodiment 1: synthesis polyether sulphone
It is added in 100mL round-bottomed flask, 4,4 '-dichloro diphenyl sulfones (DCDPS) 2.5g, 2,2- bis- (4- hydroxy phenyls) third
Alkane (bisphenol-A, BPA) 1.9861g, excessive 15% K2CO31.381g, solvent n,N-dimethylacetamide (DMAc) 13mL, band water
Agent toluene 6.5mL, then loads onto the condenser pipe with water segregator, magnetic agitation, N2135 DEG C of reaction 3h are to slowly warm up under protection,
With the water generated except dereaction, it is warming up to 155 DEG C later the reaction was continued 14h.After reaction, it is added into flask a certain amount of
Product dilution is poured into 100mL methanol later and is settled out product (polyether sulphone, PAES) by DMAc, filters drying, and product is used again
1,2- dichloroethanes stirring and dissolving 2h is precipitated out thoroughly to remove the impurity such as inorganic salts, small molecule, so in methyl alcohol again later
Washing filters drying afterwards, and weighing obtains product 3.9831g, yield 88.%.
Embodiment 2: synthesis sulfonated polyether sulphone
1g PAES is weighed to be dissolved in equipped with 15mL 1,2- dichloroethanes is connected in the round-bottomed flask of constant pressure funnel,
Magnetic agitation, then measure 100 μ L chlorosulfonic acids and be dissolved in 10ml 1, it is poured into constant pressure funnel in 2- dichloroethanes, coutroi velocity makes chlorine
Sulfonic acid instills in PAES solution dropwise in 2h, is then further continued for reaction 2h.Reaction is boiled off using Rotary Evaporators after having reacted
Solvent in system obtains amber solid product (sulfonated polyether sulphone, SPAES), by product in 3% KOH solution
60 DEG C of 1h are heated with stirring to, 60 DEG C is heated with stirring in 5% HCl solution again after filtering washing, finally filters washed several times with water
Afterwards, it dries.It repeats above step and the dosage of chlorosulfonic acid is changed to 200 μ L, 230 μ L, 250 μ L, 285 μ L, 300 μ L respectively, simultaneously
In order to keep the concentration of chlorosulfonic acid solution constant, accordingly changes the dosage of 1,2- dichloroethanes, obtain different sulfonation degrees
SPAES。
Embodiment 3: the synthesis polyether sulphone derivative (polyether sulphone that 4,4 '-dichloro diphenyl sulfones and bisphenol fluorene are condensed to yield
Derivative)
The DCDPS and bisphenol fluorene (BHPF) that molar ratio is 1:1, excessive 15% K are added in 100mL round-bottomed flask2CO3
(using it is preceding in an oven at 180 DEG C it is dry for 24 hours), then the dimethyl sulfoxide (DMSO) and water entrainer toluene dried load onto band
The condenser pipe of water segregator, magnetic agitation, N2135 DEG C of reaction 3h are to slowly warm up under protection, with the water generated except dereaction, later
The 20h that is warming up between 170-190 DEG C that the reaction was continued.After reaction, a certain amount of DMSO is added into flask by product polyarylether
Sulfone derivative (BHPF-PAES) dilution, pours into 100mL methanol later and is precipitated out, and filters drying, and the product dried is used again
DMAc stirring and dissolving 2h is precipitated out in methyl alcohol again later thoroughly to remove the impurity such as inorganic salts, small molecule, and then washing is taken out
It is filtered dry dry.
Embodiment 4: synthesis sulfonated polyether sulfone derivative
It weighs above-mentioned BHPF-PAES 1.2g and is dissolved in a certain amount of 10mL1, in 2- dichloroethanes, measure 0.22g-1.44g
Chlorosulfonic acid is dissolved in a certain amount of 5mL1, and in 2- dichloroethanes, 1, the 2- dichloroethane solution of chlorosulfonic acid is dripped dropwise at room temperature
Enter in polyether sulphone derivative solution, whole process needs 2h, is further continued for reaction 1h later, and after reaction, revolving goes 1,2-
Dichloroethanes, product (sulfonated polyether sulfone derivative, SBHPF-SPAES) is washed with distilled water for several times, filters, dry.
Embodiment 5: the sulfonation polyarylsulfone (PAS) derivative of synthesizing polyethylene glycol modification
By the 1.8gSBHPF-SPAES of embodiment 4, with 20mL1,2- dichloroethanes dissolves, after dissolution completely, addition
0.24g chloromethylation reagents 1,4- bis- (chloromethane epoxide) butane (BCMB) and a little catalyst SnCl4, anti-under room temperature (25 DEG C)
Answer 3h.Be after reaction precipitating reagent with ethyl alcohol, resulting polymer be precipitated, successively with n,N-dimethylacetamide (DMAc),
Dilute hydrochloric acid washes resulting polymer, then is repeatedly washed with distilled water, until cleaning solution not chloride ion-containing, vacuum drying.By chloromethylation
SBHPF-SPAES is placed in the four-hole bottle with stirring, thermometer and reflux condensing tube, and DMAc is added and makes it completely dissolved,
It is separately added into 1.5g PEGME-750 and 0.6gNa again2CO3, it is stirred to react at 70 DEG C, is after reaction precipitating with ethyl alcohol
Agent, make product (polyethyleneglycol modified sulfonation polyarylsulfone (PAS) derivative, PEG-SBHPF-SPAES) polymer be precipitated, then with distill
Water repeatedly washs, vacuum drying.
Embodiment 6: preparation ion exchange polymer membrane
It uses DMAc as solvent product dried in above-described embodiment 2,4,5, is made into 15% solution, pour into certainly
In the film forming grinding tool of system, a little DMSO is added, in an oven at 70 DEG C, drying film forming, then it is to slowly warm up to 140 DEG C of annealings
2h prepares the film that film thickness is between 50 μm -300 μm respectively.
Infrared spectrum analysis
The sample of embodiment 1-5 is done into infrared spectroscopy respectively, the infrared spectroscopy of embodiment 1-2 is listed in Fig. 1.PAES's is infrared
In spectrum, 1580,1500,1487cm-1There is the framework characteristic peak of phenyl ring, 3020cm in place-1Place is the flexible vibration of C-H on phenyl ring
Dynamic peak, 1241,1147cm-1For asymmetric, the symmetrical absorption peak of O=S=O, 1009cm-1There is the absorption of Ar-O-Ar in place
Peak.After sulfonation, in the infrared spectroscopy of SPAES, 3555cm-1There is the O-H vibration peak of sulfonic acid, 1400cm in place-1Place is on phenyl ring
C-H flexural vibrations peak, 1327,1280cm-1Place is asymmetric, the symmetrical absorption peak of O=S=O in sulfonic acid, 1050cm-1Place is S-
The vibration peak of OH.In the infrared spectroscopy of BHPF-PAES, the stretching vibration peak of C-H and C=C respectively appears in 3085cm in double bond-1
And 1647cm-1, 860cm-1And 991cm-1It is hydrocarbon for double bond.After sulfonation, in the infrared spectroscopy of SBHPF-SPAES, 3550cm-1Place
There are the O-H vibration peak of sulfonic acid, 1310,1260cm-1Place is asymmetric, the symmetrical absorption peak of O=S=O in sulfonic acid,
1050cm-1Place is the vibration peak of S-OH.After being grafted PEG, in the infrared spectroscopy of PEG-SBHPF-SPAES, 2962,2884cm-1Place
Newly there is C-H2Stretching vibration peak.
Mechanics Performance Testing
Tensile property survey has been carried out using sample and business Nafion blank film of the electronic universal tester to embodiment 1-5
Examination.As a result it is listed in table 1.
Water absorption rate test
At room temperature, embodiment 1-5 sample and business Nafion blank film are impregnated in deionized water for 24 hours, after taking-up,
Surface moisture carefully is dried, tests its quality with assay balance, as quality (M1) under saturation water suction state.Then, by sample
It is put into vacuum oven, drying for 24 hours, tests the quality (M2) of desciccator diaphragm at 70 DEG C.Sample is calculated by formula (M1-M2)/M2
Water absorption rate.
Ion-exchange equivalent test
The ion-exchange equivalent (IEC) of embodiment 1-5 sample and business Nafion membrane is tested into (table 1).It will be prepared
Dry membrane sample is immersed in 8h in the NaCl solution of 2mol/L, exchanges sodium ion by the hydrogen ion in sulfonic acid group, it
It is titrated afterwards using the standard NaOH solution of 0.1mol/L, the calculation formula of IEC is as follows:
V in formulaNaOHIt is the volume for the NaOH solution being consumed, MNaOHIt is the concentration of NaOH, W is the weight of dry film.
1 water absorption rate of table, IEC, mechanical property result
It prepares ion exchange polymer membrane-metallic composite (IPMC)
The film that will be prepared in embodiment 2-5 carries out surface roughening treatment using the two sides of 1200 mesh sand paper polishing film,
Then the film after being polished for several times with distilled water ultrasonic cleaning；Film is placed in the hydrochloric acid solution of 2mol/L later boil 30min with
The additive and ion in membrane removal are removed, later rinsed clean in deionized water；Then film is placed in deionized water and is boiled
30min makes film water swelling to remove the acid used.Film Jing Guo pre-treatment is placed in the platinum ammonium compound water prepared in advance
Solution ([Pt (NH3)4]Cl2, 2mg/mL, pH are about 10) to impregnate 12h at room temperature.
It is placed in being equipped in the beaker of deionized water by the film sample after ion exchange in 42 DEG C of water-baths, magnetic agitation.
Main electroless plating reaction: being added 500 μ L, 5% sodium borohydride solution every 30min, and totally 7 times, and gradually raise the temperature to 60 DEG C.
Secondary electroless plating reaction: by the film Jing Guo main electroless plating reaction again as impregnating 12h in platinum ammonium compound water solution before, it
A certain amount of 5% hydroxylamine hydrochloride solution and 20% hydrazine hydrate solution is added every 30min afterwards, and is gradually warming up to 60 DEG C.It will preparation
Good sample is spare as impregnating in 0.2mol/L LiCl solution.
Sem test
4 its surfaces of IPMC film of ion exchange polymer membrane-metallic composite of above-mentioned preparation deposit Pt nano particle
Grain, with the partial size of scanning electron microscope (SEM) observation metallic particles and the thickness of metal layer.Wherein, PEG-SBHPF-SPAES
The SEM picture of base IPMC is listed in Fig. 2.
Electromechanics performance test
Electromechanical Testing Platform includes signal generator, force snesor and multifunctional data acquisition card composition.Signal
Generator (SP864, Nanjing) can be in 0~10V voltage, 0.1~100Hz frequency downconverted sine, square wave and triangular signal, dress
It sets and sees Fig. 4；Force snesor (FEMTO-10000, Switzerland) range is 10mN, and sensitivity is 1 μ N；Multifunctional data acquisition card (NI,
Lapview (v14.0) support programs 6024E) are used, device is shown in Fig. 5.The size of embodiment 2-5 sample IPMC sample is 20 × 2
×0.33mm3, test under air atmosphere, electric actuation video recording screenshot is listed in Fig. 6.It the results are shown in Table 2.
The electric actuation performance and relevant parameter of IPMC in 2 example 11 of table
Claims (3)
1. a kind of polyether sulphone of the sulfonated fluorenes block of polyethylene glycol grafting, it is characterized in that: it is by diphenyl sulphone (DPS) and bisphenol fluorene
Copolymer through sulfonic acid, polyethylene glycol be grafted be made, it is characterized in that: main polymer chain contains fluorenes ring, phenyl ring simultaneously, be grafted on ring
There is sulfonic acid group；Polymer lateral chain is polyethylene group, is grafted in fluorenes ring, and structure is as follows:
Wherein: R1、R2For SO3H, R3For CH2-O-(-CH2-CH2-O-)m-CH3Polyether chain, R4With R5For H or SO3H。
2. a kind of method of the polyether sulphone for the sulfonated fluorenes block for preparing polyethylene glycol grafting described in claim 1, special
Sign be it the following steps are included:
Step 1, the polyarylethersulfone polymer for preparing fluorenes block
By the K of 4,4 '-dichloro diphenyl sulfones and bisphenol fluorene, excess 15% that molar ratio is 1:12CO3, the dimethyl sulfoxide dried and
Water entrainer toluene is added in reaction flask, then loads onto the condenser pipe with water segregator, stirs, N2135 DEG C are to slowly warm up under protection
React 3h, and except the water that dereaction generates, the 20h that is warming up between 170-190 DEG C that the reaction was continued later, after reaction, toward anti-
It answers and DMSO is added in bottle by the dilution of product polyether sulphone derivative, pour into methanol be precipitated out later, filter drying, dried
Product use DMAc stirring and dissolving 2h again, be precipitated out in methyl alcohol again later thoroughly to remove inorganic salts, small molecular weight impurity, so
Washing filters dry to get polyether sulphone derivative afterwards；
Step 2 prepares sulfonated fluorenes block polyarylethersulfone polymer
Polyether sulphone derivative described in step 1 is dissolved in 1,2- dichloroethanes, chlorosulfonic acid is dissolved in 1,2-, bis- chloroethene
In alkane, between the ratio between amount of polyether sulphone derivative and chlorosulfonic acid 1:2-1:6.5, by 1, the 2- dichloroethane solution of chlorosulfonic acid in
It instills in polyether sulphone derivative solution dropwise at room temperature, whole process needs 2h, is further continued for reaction 1h later, and reaction terminates
Afterwards, 1,2- dichloroethanes is boiled off, product sulfonated polyether sulfone derivative is washed with distilled water for several times, filters, dry to get sulfonic acid
The fluorenes block polyarylethersulfone polymer SBHPF-SPAES of change；
Step 3 prepares chloromethylation fluorenes block polyether sulphone sulfonated polymer
Sulfonated fluorenes block polyarylethersulfone polymer 1,2- dichloroethanes is dissolved, after dissolution completely, chloromethylation is added
The catalyst SnCl of reagent 1,4- bis- (chloromethane epoxide) butane (BCMB) and catalytic amount4, the dosage of SBHPF-SPAES and BCMB it
Than saving BCMB 1-2.5 mole for every chain of SBHPF-SPAES, 3h is reacted at room temperature, is after reaction precipitating with ethyl alcohol
Resulting polymer is precipitated in agent, successively uses n,N-dimethylacetamide, dilute hydrochloric acid washed product polymer, then more with distilled water
Secondary washing, until chloride ion-containing, vacuum drying do not obtain the fluorenes block polyether sulphone sulfonated polymer of chloromethylation to cleaning solution；
Step 4, the polyether sulphone for preparing the sulfonated fluorenes block that polyethylene glycol is grafted
The fluorenes block polyether sulphone sulfonated polymer of chloromethylation is placed in four with stirring, thermometer and reflux condensing tube
In mouth bottle, N is added, N dimethyl acetamide makes it completely dissolved, then is separately added into polyethylene glycol PEGME-750 and Na2CO3,
The ratio between dosage mole of BCMB of PEGME-750 and step 3 is 1:1, is stirred to react at 70 DEG C, is with ethyl alcohol after reaction
The polyether sulphone of precipitating reagent, the sulfonated fluorenes block for being grafted product polyethylene glycol is precipitated, then is repeatedly washed with distilled water, vacuum
The polyether sulphone of the dry sulfonated fluorenes block being grafted to get polyethylene glycol.
3. the polyether sulphone of the sulfonated fluorenes block of polyethylene glycol grafting described in claim 1 is preparing ion-exchange polymer
Application in object/metallic composite electric actuator.
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| CN111234226B (en) * | 2020-03-20 | 2022-05-27 | 宁夏清研高分子新材料有限公司 | Sulfonated polyarylethersulfone and preparation method thereof |
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