CN104610519A - Preparation method of PVDF-PEG (polyvinylidene fluoride-polyethylene glycol) block copolymer - Google Patents
Preparation method of PVDF-PEG (polyvinylidene fluoride-polyethylene glycol) block copolymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a PVDF-PEG (polyvinylidene fluoride-polyethylene glycol) block copolymer. The method comprises steps as follows: firstly, PEG and dicarboxylic acid have an esterification reaction under the action of a catalyst to produce carboxyl-terminated PEG; then the carboxyl-terminated PEG and hydrogen peroxide have a peroxidatic reaction to produce a peroxidized PEG macroinitiator; finally, VDF polymerization is triggered by the peroxidized PEG macroinitiator, and the PVDF-PEG block copolymer is obtained. When the method is used for preparing the PVDF-PEG block copolymer, the technology is simpler, components of the block copolymer can be adjusted by selecting PEG with different molecular weight, and high-performance porous membranes for sewage treatment can be prepared through directing processing of the obtained PVDF-PEG block copolymer or mixed processing with PVDF.
Description
Technical field
The invention belongs to Chemical Engineering and Technology field, particularly relate to a kind of preparation method of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer.
Background technology
Due to fluorine atom van der Waals radius little (1.32) and carbon-fluorine bond bond energy large (485 kJ/mol), fluoropolymer has resistance to chemical attack, heat-resisting cold-resistant and have excellent weather resistance, the features such as hydrophobic oleophobic, surface energy are low.Polyvinylidene difluoride (PVDF) (PVDF) has the above characteristic of fluoropolymer, has again melt-processable characteristic and solvability simultaneously, can process multi-form goods, of many uses, is the fluoropolymer kind that consumption is only second to tetrafluoroethylene.
Using with mould material form is one of PVDF important application form, as sun power backboard membrane, lithium battery isolation membrane and the porous-film (micro-filtration, nanofiltration, ultra-filtration membrane etc.) being applied to sewage disposal.In recent years, the development of membrane bioreactor (MBR) sewage disposal technology rapidly, this technology is a kind of Novel sewage treatment technology organically combining membrane technique and biotechnology, the second pond in conventional biochemical treating processes is replaced with membrane separation plant, active sludge in biochemical reaction tank and larger molecular organics are retained, there is the advantages such as contaminant removal efficiency is high, stable effluent quality, convenient operation and management, floor space are little.At present, PVDF becomes the main flow mould material of MBR gradually, and defines non-solvent inversion of phases, thermic inversion of phases and increase the membrane preparation method of supporting tube.
Because PVDF has hydrophobic oleophobic characteristic, make it easily hole plug occur as during filter membrane, disadvantageous effect is caused to water flux and work-ing life.After hydrophilic modifying is carried out to PVDF, water flux and the work-ing life of filter membrane can be improved.
At present, hydrophilic modifying is carried out mainly through with under type to PVDF: (1) physical mixed: PVDF is carried out physical mixed with the method that hydrophilic compounds (as hydrophilic macromolecule, hydrophilic inorganic nanoparticle) is mixed by melting or solution, reaches the object to PVDF hydrophilic modifying.This modification mode is connected because hydrophilic compounds and PVDF do not have chemical bond, and hydrophilic compounds can dissolve gradually or ooze out in filter membrane use procedure, can not fundamentally improve PVDF wetting ability; (2) chemical modification, namely introduces hydrophilic radical or segment by the mode that chemical bond connects, reaches the object of hydrophilic modifying on PVDF.Means conventional at present in chemical modification are surface grafting, and by carrying out high-energy radiation, chemical etching to PVDF or utilizing PVDF chain defect structure to produce active centre, hydrophilic segment is introduced in recycling active centre.Surface grafting obviously can improve the wetting ability of PVDF, but technique relative complex, poor controllability.
Except above-mentioned two kinds of methods, it is also the important channel of carrying out hydrophilic modifying that PVDF and hydrophilic polymer form block copolymer structure, because hydrophilic polymer is connected with chemical bond with PVDF, therefore not easily run off in film use procedure, the long-acting pollution resistance of pvdf membrane and the stability of membrane flux can be kept.PVDF segmented copolymer is prepared mainly through substep active free radical polymerization, although the segmented copolymers such as PVDF and polystyrene, PVDF and poly-(methyl) esters of acrylic acid studies have reported that, but the segmented copolymer formed about PVDF and hydrophilic polymer is reported seldom, and yet there are no patent report by the segmented copolymer of general radical polymerization preparation PVDF and polyoxyethylene glycol (PEG).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer.
The step of a kind of preparation method of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer is:
1) by mol ratio be the polyoxyethylene glycol of 1:1.5 ~ 1:4 and di-carboxylic acid, relative to polyoxyethylene glycol (PEG) quality 0.5 ~ 3% catalyst dissolution in organic solvent, at 5 ~ 115 DEG C, react 8h, cooling, uses saturated NaHCO
3solution washing, to neutral, obtains end carboxyl polyoxyethylene glycol with ice ether or petroleum ether precipitation;
2) by mol ratio be 1:0.6 ~ 1:2 end carboxyl polyoxyethylene glycol and
n,N-dicyclohexylcarbodiimide catalyzer is dissolved in CH
2cl
2in, be cooled to 0 DEG C, dripping the concentration being equivalent to end carboxyl polyoxyethylene glycol quality 10 ~ 50% is the H of 30wt%
2o
2, reaction 3 ~ 9h, filters, and by filtrate with ice ether or petroleum ether precipitation ,-50 DEG C of lyophilizes, obtain peroxidation polyoxyethylene glycol macromole evocating agent;
3) in polymermaking autoclave, add the deionized water of 100 mass parts, the ammonium perfluorocaprylate of 0.2 ~ 0.6 mass parts, the peroxidation polyoxyethylene glycol macromole evocating agent of 2.0 ~ 10.0 mass parts, stirring and dissolving, after sealing, logical nitrogen deoxygenation is less than 5ppm to oxygen level, be warming up to 65 ~ 75 DEG C, passing into vinylidene fluoride monomers to pressure is 3.0MPa, start polymerization, when still internal pressure drops to 2.5MPa, supplementing vinylidene fluoride monomers to pressure is 3.0MPa, stopped reaction when repeating to reach set(ting)value 4.0 ~ 8.0MPa to accumulative pressure drop, cooling, get rid of unreacted vinylidene, separation obtains polyvinylidene difluoride (PVDF)-polyoxyethylene glycol block polymer.
Described polyoxyethylene glycol is molecular weight is the monohydroxy of 1000 ~ 10000 or two hydroxyl polyoxyethylene glycol.Described organic solvent is hexanaphthene, toluene or methylene dichloride.Described dicarboxyl is oxalic acid, propanedioic acid, succinic acid, pentanedioic acid or hexanodioic acid.Described catalyzer is the vitriol oil, methanesulfonic, tosic acid or sulfur oxychloride.
Technique effect of the present invention there is provided a kind of method being prepared PVDF segmented copolymer by general radical polymerization.Usual PVDF segmented copolymer can only be prepared by active free radical polymerization, namely first to be shifted by iodine or Reversible Addition Fragmentation Chain-Transfer Polymerization obtains active PVDF, and then obtain segmented copolymer with the active free radical polymerization that active PVDF regulates and controls another monomer, the requirement of active free radical polymerization to system is higher, and the iodine transfer polymerization of applicable VDF and Reversible Addition Fragmentation Chain-Transfer Polymerization are not suitable for hydrophilic monomer more, the difficulty therefore preparing the segmented copolymer of PVDF and hydrophilic polymer is very large.The present invention is by design and synthesis peroxidation PEG macromole evocating agent, and make it directly cause VDF general radical letex polymerization and obtain PVDF-PEG segmented copolymer, method is simple, and operating process is similar to industrial VDF letex polymerization.Adopt the block modified PVDF of PEG, the wetting ability of PVDF can be improved, therefore when directly processing or after being processed into porous-film with PVDF blending, the pollution resistance of filter membrane can being improved, keep the stable of water flux.
Embodiment
First the present invention prepares end carboxyl PEG by the esterification of PEG and di-carboxylic acid, and the PEG of employing can be both-end hydroxyl PEG and monohydroxy PEG, PEG molecular weight is 1000 ~ 10000.Di-carboxylic acid is oxalic acid, propanedioic acid, succinic acid, pentanedioic acid and hexanodioic acid.The mol ratio of PEG and di-carboxylic acid is 1:1.5 ~ 1:4.The esterification homogeneous phase of PEG and di-carboxylic acid carries out, and the solvent adopted is hexanaphthene, toluene and methylene dichloride.In order to improve speed of reaction, esterification is carried out under catalyst action, and the catalyzer of employing is the vitriol oil, methanesulfonic, tosic acid, sulfur oxychloride, and catalyst levels is 0.5 ~ 3% of PEG quality.Esterification reaction temperature is 5 ~ 115 DEG C, reaction times 8h.Esterification products is through saturated NaHCO
3after solution is washed, ether on the rocks or petroleum ether precipitation, be separated and obtain end carboxyl PEG.
Then, peroxidation PEG macromole evocating agent is prepared by the peroxidation of end carboxyl PEG.By end carboxyl PEG be used as peroxidation catalyzer
n,N-dicyclohexylcarbodiimide is dissolved in methylene dichloride, under control temperature of reaction system is 0 DEG C of condition, dripping concentration is the hydrogen peroxide of 30wt%, the consumption of hydrogen peroxide is 10 ~ 50% of end carboxyl PEG quality, reaction times 3 ~ 9h, reactant filtration, adds ice ether in filtrate or sherwood oil makes peroxidation PEG precipitate,-50 DEG C of lyophilizes after being separated, namely obtain peroxidation PEG macromole evocating agent.
Finally, with peroxidation PEG for macromole evocating agent carries out VDF polymerization, preparation PVDF-PEG segmented copolymer.Main method that industrial VDF is polymerized that to take water as medium be, different with product characters according to polymerization system composition, aqueous phase VDF is polymerized and is divided into again aqueous suspension polymerization and aqueous phase emulsion to be polymerized.Aqueous suspension polymerization generally adopts the dispersion agent such as oil-soluble initiator and modified-cellulose; And aqueous phase emulsion polymerization general employing water soluble starter and perfluorooctanoic acid salt emulsifying agent.Because peroxidation PEG macromole evocating agent is water-soluble, therefore the present invention selects aqueous phase emulsion to be polymerized the synthesis carrying out PVDF-PEG segmented copolymer.VDF aqueous phase emulsion is aggregated in polymermaking autoclave and carries out, first add deionized water, the ammonium perfluorocaprylate of 0.2 ~ 0.6 mass parts, the peroxidation PEG macromole evocating agent of 2.0 ~ 10.0 mass parts of 100 mass parts in a kettle., stirring and dissolving, after sealing, logical nitrogen deoxygenation is less than 5ppm to oxygen level, then be warming up to 65 ~ 75 DEG C, and pass into VDF monomer to pressure be 3.0MPa start polymerization.Due to the process that VDF polymerization is one gas-liquid mass transferring/chemical reaction coupling, the VDF concentration of reacting environment is relevant with solution-air mass transfer velocity with gaseous pressure, and then has influence on polymerization rate.Usual VDF gaseous pressure is larger, and polymerization rate is larger.Along with polymerization is carried out, gaseous pressure can decline gradually, in order to maintain higher rate of polymerization, after being polymerized to a constant pressure drop, needing to add VDF reaching setting pressure 3.0MPa, when repeating to reach set(ting)value 4.0 ~ 8.0MPa to accumulative pressure drop (adding VDF monomer number of times 8 ~ 16 times), continue to be polymerized to stopped reaction after certain pressure, cooling, get rid of unreacted VDF, separation can obtain PVDF-PEG segmented copolymer.
Take PVDF-PEG segmented copolymer, be dissolved in
n,Nbe made into the solution of 0.4% mass concentration in-dimethyl formamide (DMF), be that moving phase carries out gel osmoticing chromatogram analysis with the DMF containing 0.1% LiBr, molecular-weight average and the molecular weight distributing index of segmented copolymer can be obtained.
In order to evaluate the hydrophilic modifying effect to PVDF after PEG block, the water contact angle of the PVDF-PEG segmented copolymer determining commercialization PVDF and adopt the inventive method to obtain.Concrete operations are as follows: take a certain amount of PVDF or PVDF-PEG block copolymerization matter sample, be dissolved in
n,Nin-N,N-DIMETHYLACETAMIDE (DMAc), compound concentration is the solution of 7wt%, getting appropriate solution drips on glass substrate, standing, drying and forming-film at 40 DEG C, adopt the OCA-20 type video optics contact angle tester etc. of German Dataphysics company can measure the water contact angle of PVDF and PVDF-PEG block copolymer film, 3.5 μ l water droplets are dripped with microsyringe, Polymer membrane samples is upwards slowly also used camera recordings near drop from bottom, gets drips and carry out contact angle analysis to the sample surfaces image picture of the 2nd second.
embodiment 1
By 30.0g both-end hydroxyl PEG (molecular weight 1000,0.03mol), 13.2g hexanodioic acid (0.09mol), the dense H of 0.2g
2sO
4join in 250ml single port flask with 150ml hexanaphthene, logical nitrogen 30 minutes, is then slowly warming up to 90 DEG C, reacts after 8 hours and stops heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG (molecular weight 1256.3,0.016mol), 4.0g
n,N-dicyclohexylcarbodiimide (0.0192mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 10.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 0.6g ammonium perfluorocaprylate and more than 6.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 4.0MPa, cooling, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 74300, and molecular weight distributing index is 2.1, and the water contact angle after film forming is 55 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 2
By 30.0g one-ended hydroxy PEG (molecular weight 1000,0.03mol), 6.6g hexanodioic acid (0.045mol), 0.15g methanesulfonic and 150ml hexanaphthene join in 250ml single port flask, logical nitrogen 30 minutes, then 90 DEG C are slowly warming up to, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG (molecular weight 1128.1,0.018mol), 2.3g N, N-dicyclohexylcarbodiimide (0.011mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 6.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter to obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 0.6g ammonium perfluorocaprylate and more than 10.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 65 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 4.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 88310, and molecular weight distributing index is 2.1, and the water contact angle after film forming is 70 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 3
By 30.0g both-end hydroxyl PEG (molecular weight 1000,0.03mol), 13.2g hexanodioic acid (0.09mol), the dense H of 0.3g
2sO
4join in 250ml single port flask with 150ml hexanaphthene, logical nitrogen 30 minutes, is then slowly warming up to 90 DEG C, reacts after 8 hours and stops heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG(molecular weight 1256.3,0.016mol), 4.0g N, N-dicyclohexylcarbodiimide (0.0192mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 10.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 1.8g ammonium perfluorocaprylate and more than 10.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 8.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PEG-PVDF segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 49730, and molecular weight distributing index is 1.8, and the water contact angle after film forming is 40 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 4
By 30.0g one-ended hydroxy PEG (molecular weight 1000,0.03mol), 10.6g succinic acid (0.09mol), the dense p-methyl benzenesulfonic acid of 0.2g and 150ml toluene join in 250ml single port flask, logical nitrogen 30 minutes, then 115 DEG C are slowly warming up to, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG(molecular weight 1100.1,0.018mol), 4.0g N, N-dicyclohexylcarbodiimide (0.0192mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 6.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 1.2g ammonium perfluorocaprylate and more than 14.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 6.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 122300, and molecular weight distributing index is 2.3, and the water contact angle after film forming is 77 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 5
By 30.0g both-end hydroxyl PEG (molecular weight 1000,0.03mol), 9.4g propanedioic acid (0.09mol), 0.4g methanesulfonic and 150ml hexanaphthene join in 250ml single port flask, logical nitrogen 30 minutes, then 90 DEG C are slowly warming up to, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG(molecular weight 1172.1,0.017mol), 4.0g N, N-dicyclohexylcarbodiimide (0.0192mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 10.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 1.0g ammonium perfluorocaprylate and more than 10.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 5.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 79230, and molecular weight distributing index is 1.9, and the water contact angle after film forming is 60 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 6
By 30.0g both-end hydroxyl PEG (molecular weight 1000,0.03mol), 11.9g pentanedioic acid (0.09mol), 0.4g methanesulfonic and 150ml hexanaphthene join in 250ml single port flask, logical nitrogen 30 minutes, then 90 DEG C are slowly warming up to, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG (molecular weight 1228.2,0.017mol), 4.0g N, N-dicyclohexylcarbodiimide (0.0192mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 10.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 1.8g ammonium perfluorocaprylate and more than 14.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until pressure drop is 8.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 112200, and molecular weight distributing index is 2.3, and the water contact angle after film forming is 75 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 7
By 30.0g both-end hydroxyl PEG (molecular weight 1000,0.03mol), 8.1g oxalic acid (0.09mol), the 0.3g vitriol oil and 150ml hexanaphthene join in 250ml single port flask, logical nitrogen 30 minutes, then 90 DEG C are slowly warming up to, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 20.0g end carboxyl PEG(molecular weight 1144.0,0.017mol), 4.0g N, N-dicyclohexylcarbodiimide (0.0192mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 10.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 0.8g ammonium perfluorocaprylate and more than 6.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 75 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 4.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 23230, and molecular weight distributing index is 1.7, and the water contact angle after film forming is 40 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 8
30.0g both-end hydroxyl PEG (molecular weight 5000,0.006mol), 2.5g succinic acid (0.021mol), 0.5g tosic acid and 150ml toluene are joined in 250ml single port flask, passes into N
230 minutes, be then slowly warming up to 115 DEG C, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 30.0g end carboxyl PEG(molecular weight 5200.0,0.006mol), 1.2g N, N-dicyclohexylcarbodiimide (0.006mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 6.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, by filtrate petroleum ether precipitation, filter and obtain peroxidation PEG ,-50 DEG C of lyophilizes ,-20 DEG C of preservations are to be used.
In 500ml autoclave, add 300g deionized water, 0.6g ammonium perfluorocaprylate and more than 20.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 4.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PEG-PVDF segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 52870, and molecular weight distributing index is 1.7, and the water contact angle after film forming is 48 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 9
By 30.0g one-ended hydroxy PEG (molecular weight 5000,0.006mol), 1.4g succinic acid (0.012mol), 0.5g tosic acid and 150ml toluene join in 250ml single port flask, logical nitrogen 30 minutes, then 115 DEG C are slowly warming up to, react after 8 hours and stop heating, naturally cool to room temperature.Use saturated NaHCO
3solution washing, to neutral, adds ice ether sedimentation, is separated and obtains end carboxyl PEG.
By more than 30.0g end carboxyl PEG(molecular weight 5100.0,0.006mol), 1.2g N, N-dicyclohexylcarbodiimide (0.006mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 6.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, by filtrate petroleum ether precipitation, filter to obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 0.6g ammonium perfluorocaprylate and more than 25.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until pressure drop is 4.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 45330, and molecular weight distributing index is 1.8, and the water contact angle after film forming is 45 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
embodiment 10
By 30.0g both-end hydroxyl PEG (molecular weight 10000,0.003mol), 1.4g succinic acid (0.012mol), 0.9g sulfur oxychloride and 100ml methylene dichloride join in 250ml single port flask, logical nitrogen 30 minutes, 0 DEG C of reaction stopped after 8 hours.Use saturated NaHCO
3solution washing, to neutral, adds petroleum ether precipitation, is separated and obtains end carboxyl PEG.
By more than 30.0g end carboxyl PEG (molecular weight 10200.0,0.003mol), 1.2g
n,N-dicyclohexylcarbodiimide (0.006mol) and 30ml CH
2cl
2join in 150ml flask, stirring and dissolving.Be cooled to 0 DEG C, drip the H of 3.0g 30%wt with the speed of 1g/min
2o
2, drip and terminate rear continuation maintenance 0 DEG C reaction 3 hours.Filter, filtrate is used ice ether sedimentation, filter to obtain peroxidation PEG ,-50 DEG C of lyophilizes, preserve at-20 DEG C.
In 500ml autoclave, add 300g deionized water, 0.6g ammonium perfluorocaprylate and more than 30.0g peroxidation PEG, stirring and dissolving, passes into N
2row O
2to O
2content, lower than 5ppm, is warming up to 70 DEG C, then passes into VDF to 3.0MPa and starts reaction, when VDF Pressure Drop is mended to 3.0MPa again to during 2.5MPa, repeatedly carry out, stop until accumulative pressure drop is 4.0MPa, be down to room temperature, discharge unreacted VDF, namely centrifugation obtains PVDF-PEG segmented copolymer.
The number-average molecular weight of gained PVDF-PEG segmented copolymer is 52340, and molecular weight distributing index is 1.9, and the water contact angle after film forming is 52 o, and under being less than equal test condition, (120 o) for the water contact angle of pure pvdf membrane.
Claims (5)
1. a preparation method for polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer, is characterized in that the step of method is:
1) by mol ratio be the polyoxyethylene glycol of 1:1.5 ~ 1:4 and di-carboxylic acid, relative to polyoxyethylene glycol quality 0.5 ~ 3% catalyst dissolution in organic solvent, at 5 ~ 115 DEG C, react 8h, cooling, uses saturated NaHCO
3solution washing, to neutral, obtains end carboxyl polyoxyethylene glycol with ice ether or petroleum ether precipitation;
2) by mol ratio be 1:0.6 ~ 1:2 end carboxyl polyoxyethylene glycol and
n,N-dicyclohexylcarbodiimide catalyzer is dissolved in CH
2cl
2in, be cooled to 0 DEG C, dripping the concentration being equivalent to end carboxyl polyoxyethylene glycol quality 10 ~ 50% is the H of 30wt%
2o
2, reaction 3 ~ 9h, filters, and by filtrate with ice ether or petroleum ether precipitation ,-50 DEG C of lyophilizes, obtain peroxidation polyoxyethylene glycol macromole evocating agent;
3) in polymermaking autoclave, add the deionized water of 100 mass parts, the ammonium perfluorocaprylate of 0.2 ~ 0.6 mass parts, the peroxidation polyoxyethylene glycol macromole evocating agent of 2.0 ~ 10.0 mass parts, stirring and dissolving, after sealing, logical nitrogen deoxygenation is less than 5ppm to oxygen level, be warming up to 65 ~ 75 DEG C, passing into vinylidene fluoride monomers to pressure is 3.0MPa, start polymerization, when still internal pressure drops to 2.5MPa, supplementing vinylidene fluoride monomers to pressure is 3.0MPa, stopped reaction when repeating to reach set(ting)value 4.0 ~ 8.0MPa to accumulative pressure drop, cooling, get rid of unreacted vinylidene, separation obtains polyvinylidene difluoride (PVDF)-polyoxyethylene glycol block polymer.
2. the radical polymerization preparation method of a kind of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer according to right 1, is characterized in that described polyoxyethylene glycol be molecular weight is the monohydroxy of 1000 ~ 10000 or two hydroxyl polyoxyethylene glycol.
3. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer according to right 1, is characterized in that described organic solvent is hexanaphthene, toluene or methylene dichloride.
4. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer according to right 1, is characterized in that described dicarboxyl is oxalic acid, propanedioic acid, succinic acid, pentanedioic acid or hexanodioic acid.
5. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyethyleneglycol block copolymer according to right 1, is characterized in that described catalyzer is the vitriol oil, methanesulfonic, tosic acid or sulfur oxychloride.
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