CN101735374B - Preparation method of vinylidene fluoride copolymer resin - Google Patents
Preparation method of vinylidene fluoride copolymer resin Download PDFInfo
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- CN101735374B CN101735374B CN2009102010971A CN200910201097A CN101735374B CN 101735374 B CN101735374 B CN 101735374B CN 2009102010971 A CN2009102010971 A CN 2009102010971A CN 200910201097 A CN200910201097 A CN 200910201097A CN 101735374 B CN101735374 B CN 101735374B
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Abstract
The invention provides a preparation method of vinylidene fluoride copolymer resin, including the following steps: (a) monomer mixture of vinylidene fluoride monomer and optional fluorine-containing monomers except the vinylidene fluoride is provided; (b) mixture of suspending agent in water-containing solvent is provided, and the suspending agent is water soluble cellulose derivative, polyvinyl alcohol compound or mixture thereof; (c) the monomer mixture is added into the mixture of suspending agent in water-containing solvent; (d) initiator is added to carry out polymerization. The invention has the advantages that polymerization pressure is low, no coalescent polymerized particle is existed, polymer does not adhere to kettle, particle size distribution is uniform and post processing is easy, thus being applicable to industrialized production.
Description
Technical field
The present invention relates to the preparation method of the basic copolymer resins of a kind of vinylidene (VDF), this method has reaction pressure low, sticking still, copolymer resins molecular weight and advantages such as molecular weight distribution is controlled easily, the easy processing of product, is particularly suited for suitability for industrialized production.
Background technology
Along with the development of world technology, more and more higher to material functional, device miniaturization, structure intelligent requirement because the rapid emergence of electronics, communication and the contour technology industry of control techniques, the development of intelligent material and exploitation are received much concern.
Electroactive polymer is a class can produce remarkable mechanical deformation or electrical signal under outfield (as external electric field, temperature, pressure etc.) excitation a intelligent material, for example, the vinylidene fluoride series polymer is a kind of present widely used piezopolymer owing to have characteristics such as piezoelectricity, ferroelectric, thermoelectricity and electrostriction.This electroactive polymer (EAPs) grows to even greater heights in the application demand in fields such as intelligent drives and sensing, energy storage, biologic medical, information storage.
The electroactive series polymer of vinylidene fluoride mainly comprises vinylidene fluoride homopolymer (PVDF), vinylidene/trifluoro-ethylene (TrFE) multipolymer, vinylidene/tetrafluoroethylene (TFE) multipolymer, vinylidene/R 1216 (HFP) multipolymer, vinylidene/trifluorochloroethylene (CTFE) multipolymer, vinylidene/1,1-chlorine vinyl fluoride (CFE) multipolymer, vinylidene/difluoro one vinylchlorid (CDFE) multipolymer and two or more copolymer resinses such as mixture thereof.It mainly makes with polymerization processs such as mass polymerization, solution polymerization, suspension polymerization, letex polymerizations.
GB284737 and Haisheng Xu etc. (Polymer 48 (2007) 2124-2129) have reported in the presence of borine and oxygen, utilize mass polymerization to prepare the method for vinylidene-trifluoro-ethylene-R 1216 [P (VDF-TrFE-HFP)] ter-polymers, this method product is pure.But the fluorochemical monomer that relates to is gas phase, and after poly-unit amplified, the homogeneity of reaction uniformity, product rerum natura was difficult to ensure.Safety issues such as this reaction has oxygen to participate in addition, and polymeric is explosion-proof are difficult to resolve determines, so industrial production cost is very high.
The U.S. Pat 5,087,679 of Daikin company in 1992 discloses the employing oxidation-reduction trigger system, utilizes aqueous emulsion polymerization process to synthesize P (VDF-TrFE-CTFE) terpolymer.But the shortcoming of emulsion polymerization is the residual emulsifying agent of meeting in the product, and the product purity is not enough.Be unsuitable for preparing many high-purity fluorine resins.
The European patent EP 1515799 that Daikin company applied in 1976 discloses selects for use Refrigerant R 113 to make solvent, the utilization solution polymerization process is 20 ℃ of temperature of reaction, under the 2Mpa pressure condition, synthesized the vinylidene-trifluoro-ethylene copolymer [P (VDF-TrFE)] of different compositions.But the shortcoming of solution polymerization process is the polymer particle that generates and is easy to coalescence, and product is irregular bulk, and solvent is difficult for removing and product adheres to seriously at positions such as polymeric kettle inwall and stirring rakes, is difficult for clear still.
The U.S. Pat 4 of France Atochem company application, 946,913 and Chinese patent CN 1036214A the preparation method of polymkeric substance is disclosed, in order to improve the use temperature of P (VDF-TrFE) multipolymer, add monomeric composition by control, at 50 ℃, under 90bar (9Mpa) pressure, the mole that uses the aqueous-phase suspending copolymerization to obtain VDF consists of 67～54% non-uniform copolymer.The method reaction pressure of this patent report is very high, and the poly-unit expense has high input, and is unfavorable for safety in production.
In order to reduce polymerization pressure, U.S. Pat 5,087,679 mention add 1 in water mediums, 1,2-three chloro-1,2,2-Halothane (CFC-113), with 1,1 of formation, 2-three chloro-1,2, the aqueous liquid dispersion of 2-Halothane is as polymerization reaction medium, and wherein 1,1,2-three chloro-1,2, the 2-Halothane plays the effect of solubilising fluorochemical monomer, and actual polymerization place is in the dispersant liquid drop of CFC-113, and therefore this polyreaction meets solution polymerization mechanism.In fact this U.S. Patent Publication is a kind of solution polymerization process of modification, and during 39 ℃ of its polymerization temperatures, polymerization pressure has only 7.5Kgf/cm
2The solvent of this patented method and the volume ratio of water are about 1: 1, but this method still can not solve problems such as the sticking still of polymerization process, particle are inhomogeneous, aftertreatment difficulty.
Therefore, still need to develop a kind of can reduce the sticking still of polymerization pressure, product, product size distribution evenly, aftertreatment easily, polymerization process that product purity is high.
Summary of the invention
An object of the present invention is to provide a kind of can effectively reduce the sticking still of polymerization pressure, product, product size distribution evenly, the polymerization process of aftertreatment easily, partial fluorine ethylene polymer that product purity is high.
Therefore, one aspect of the present invention relates to a kind of preparation method of partial fluorine ethylene polymer, and it comprises the steps:
(a) provide the monomer mixture of vinylidene fluoride monomers with the fluorine-containing comonomer of choosing wantonly except that described vinylidene;
(b) providing suspension agent is mixture in the water-containing solvent of 3-12 in the volume ratio of water and solvent, and described suspension agent is selected from water-soluble cellulose derivative, polyvinyl alcohol compounds or its mixture;
(c) in the mixture of described suspension agent in water-containing solvent, add described monomer mixture; With
(d) add initiator and carry out polyreaction.
Embodiment
In the present invention, term " partial fluorine ethylene polymer " is meant the multipolymer that the homopolymer of vinylidene or the fluorine-containing comonomer (being also referred to as other fluorochemical monomer herein) outside vinylidene and one or more vinylidenes form, if the multipolymer that vinylidene and one or more other fluorine-containing comonomer form, then the amount of described vinylidene accounts for 55～90mol%, better accounts for 60～85mol%.
Suitable described other fluorine-containing comonomer is without particular limitation, can be this area any known fluorochemical monomer commonly used.In an example of the present invention, described fluorine-containing comonomer can be that one or more are selected from trifluoro-ethylene (TrFE), tetrafluoroethylene (TFE), R 1216 (HFP), trifluorochloroethylene (CTFE), 1, the comonomer of 1-chlorine vinyl fluoride (CFE), difluoro one vinylchlorid (CDFE) etc.
As previously described, prior art is mentioned and can be adopted letex polymerization or solution polymerization process to prepare partial fluorine ethylene polymer.But the shortcoming of the partial fluorine ethylene polymer that emulsion polymerization makes is an emulsifying agent can be remained in the polymeric articles that makes, and is difficult to obtain highly purified product.The shortcoming of solution polymerization process is that the polymer beads that generates reunites easily, and product adheres to seriously at positions such as polymerization reaction kettle inwall and stirring rakes, is difficult for clear still.
The present inventor finds after deliberation; if the technical characterstic of solution polymerization and suspension polymerization is combined; adopt water/solvent as medium; add an amount of suspension agent simultaneously; then fluorochemical monomer can be dissolved in the small droplets of solvent; during polymerization, the suspension agent of interpolation can effectively be protected not coalescence of dispersive polymerisation of liquid droplets, sticking still under middle low temperature radical initiator causes.The present invention finishes on the basis of this discovery.
In an example of the present invention, described partial fluorine ethylene polymer is selected from the multipolymer of vinylidene fluoride homopolymer and vinylidene, the multipolymer of described vinylidene can be selected from, vinylidene/trifluoro-ethylene copolymer (P (VDF-TrFE)) for example, vinylidene/TFE copolymer (p (VDF-TFE)), vinylidene/hexafluoropropylene copolymer (P (VDF-HFP)), vinylidene/chlorotrifluoroethylene (P (VDF-CTFE)), vinylidene/1,1-chlorine fluoride copolymers (P (VDF-CFE)), vinylidene/difluoro one vinyl chloride copolymer (P (VDF-CDFE)), vinylidene/trifluoro-ethylene/chlorotrifluoroethylene (P (VDF-TrFE-CTFE)), vinylidene/trifluoro-ethylene/1,1-chlorine fluoride copolymers (P (VDF-TrFE-CFE)), vinylidene/trifluoro-ethylene/hexafluoropropylene copolymer (P (VDF-TrFE-HFP)), vinylidene/trifluoro-ethylene/difluoro one vinyl chloride copolymer (P (VDF-TrFE-CDFE)), vinylidene/tetrafluoroethylene/chlorotrifluoroethylene (P (VDF-TFE-CTFE)), vinylidene/tetrafluoroethylene/1,1-chlorine fluoride copolymers (P (VDF-TFE-CFE)), vinylidene/tetrafluoroethylene/hexafluoropropylene copolymer (P (VDF-TFE-HFP)), two or more mixture etc. of vinylidene/tetrafluoroethylene/difluoro one vinyl chloride copolymer (P (VDF-TFE-CDFE)) or its, vinylidene content is preferably between 90～55mol% in the described vinylidene fluoride copolymers.
The polymkeric substance of the inventive method preferred preparation is vinylidene/trifluoro-ethylene copolymer P (VDF-TrFE) and vinylidene/tetrafluoroethylene/chlorotrifluoroethylene P (VDF-TrFE-CTFE).
In an example of the present invention, described other comonomer is a trifluoro-ethylene, and its content accounts between 10～45mol%, and vinylidene content is between 90～55mol%.
In another better example of the present invention, described other comonomer is trifluoro-ethylene and trifluorochloroethylene, or trifluoro-ethylene and 1,1-chlorine vinyl fluoride; Wherein, the content of trifluoro-ethylene accounts between 15～40mol%, trifluorochloroethylene or 1, and the content of 1-chlorine vinyl fluoride accounts between 5～15mol%, the content of vinylidene is between 80～55mol%.
As everyone knows, bring into play its suspension effect for making suspension agent, the inventive method is to carry out polymeric under the temperature that is lower than described suspension agent gelation point.In an example of the present invention, described polymerization is carried out under 20～70 ℃, preferred 40～60 ℃ of temperature.
In addition, polymerization process as known in the art is such, and polyreaction of the present invention is under agitation carried out.Stir one side and help the polymerized unit homodisperse, solvent is evenly distributed in the water with the form of small droplets on the other hand.
The agitator speed that is applicable to the inventive method is without particular limitation, can be any conventional rotating speed known in the art.In an example of the present invention, the rotating speed of described agitator is 400-800 rev/min, is preferably 500-700 rev/min, more preferably 550-650 rev/min.
In addition, the consideration of comprehensive for example economy and security, the polymerization rate of polymerization process of the present invention generally is controlled at 1.0～3.5gmin
-1L
-1, better be controlled at 1.2～2.5gmin
-1L
-1, the gmin of unit
-1L
-1Be meant the interior polymeric monomer mass that participates in of mixed solvent of unit volume in the unit time.Guaranteeing under the prerequisite of described speed of response, the inventor finds the amount negative correlation of solvent in the reaction pressure of polymerisation process of the present invention and the water-containing solvent, if the solvent that adds more (being that the shared ratio of solvent is higher in the water-containing solvent), then polymerization needs pressure lower.In an example of the present invention, described polyreaction is at 1.0～5.0MPa, is preferably to carry out under the pressure of 2.0～4.0MPa.
The present invention adopts the mixed phase of deionized water and solvent as polymerisation medium, and selected solvent is had following requirement:
I) be insoluble to or only be slightly soluble in water, preferably water insoluble;
Ii) can not dissolve selected suspension agent;
Iii) require solvent that fluorochemical monomers such as vinylidene are had good solubility, thereby effectively improve the monomer concentration in the unit volume, make under lower polymerization pressure and still can keep suitable speed of response; And
Iv) can not disturb the polymerization or the copolyreaction of vinylidene.
In the present invention, term " disturbs the polymerization or the copolyreaction of vinylidene " thereby is meant that can get involved polymerization process exerts an influence to polyreaction, for example has chain transfer, the free-radical generating of chain reaction is buried in oblivion effect etc. polymer chain.
In addition, under the prerequisite of low toxic and environment-friendly, the boiling point of solvent there is not particular requirement, but the consideration of converging operation for convenience, the organic solvent of removing from polymkeric substance is for first-selected easily.
Can select perhalogeno C
1-10Alkane is as solvent, and this is because the hydrogen atoms halohydrocarbon can have tangible chain transfer to the fluorochemical monomer polymerization, can not satisfy the requirement of above-mentioned " can not disturb the polymerization or the copolyreaction of vinylidene ", therefore is not suitable for being elected to be solvent of the present invention.
In an example of the present invention, select 1,1,2-three chloro-1,2,2-Halothane, 1,2-two chloro-1,1,2,2-Tetrafluoroethane, Perfluorocyclobutane, perfluor hexanaphthene, methyl perfluor hexanaphthene or two or more mixtures that form with arbitrary proportion in them etc. are as selected solvent, but are not limited to above-mentioned solvent.
For coalescence not between controlling polymers size and the particle, the add-on of organic solvent is unsuitable too many, and water and volume of organic solvent ratio should be 3～12: between 1, preferred volume ratio is 4～8: between 1.
The adding mode of solvent is that polymerization is preceding with the disposable adding of deionized water, and polyreaction is no longer added solvent midway.
In the methods of the invention, the vinylidene fluoride monomers in the water-containing solvent mixture of adding suspending agent-containing or the amount of vinylidene fluoride monomers and other monomeric mixture are without particular limitation, can be add-ons conventional in the polyreaction field.In an example of the present invention, the weight ratio of organic solvent is 1.5～5: 1 in the add-on of described vinylidene fluoride monomers or vinylidene fluoride monomers and other monomeric mixture and the described water-containing solvent, be preferably 2-4.5: 1,2.5-4.0 more preferably: 1, and the amount of the initial vinylidene fluoride monomers that adds or vinylidene fluoride monomers and other monomeric mixture accounts for 50～80wt% of monomer total amount, is preferably 60～70wt%.
In the method for the invention, organic solvent plays the effect of solubilising fluorochemical monomer, being dissolved with monomeric organic solvent drop is main polymerization place, for the controlling polymers size and make between the particle the sticking still of coalescence, polymkeric substance, needs to add suitable suspension agent.The indefiniteness example of the suspension agent that is fit to has, for example water-soluble cellulose derivative such as C
1-6Alkylcellulose or C
1-6Alkyl C
1-6Hydroxy alkyl cellulose, polyvinyl alcohol compounds or its mixture.
The C that is suitable for
1-6The indefiniteness example of alkylcellulose suspension agent has, for example methylcellulose gum, ethyl cellulose, propyl cellulose or its mixture etc.
The C that is suitable for
1-6Alkyl C
1-6The indefiniteness example of hydroxy alkyl cellulose has, for example Vltra tears, hydroxyethylmethyl-cellulose, Hydroxypropyl ethyl cellulose or its mixture etc.
The indefiniteness example of the polyvinyl alcohol compounds that is suitable for has, for example polyvinyl alcohol, poly-1-hydroxyl propylene or its mixture etc.
Perhaps also can use above-mentioned one or more described alkylcelluloses, one or more described alkyl-hydroxyalkylcelluloswith and/or one or more described polyvinyl alcohol compounds to mix the composite suspension agent that forms with arbitrary proportion.
The add-on of suspension agent is generally 0.05～5% of used monomer weight, and preferred 1.0～4.0%.
As previously described, in order to make suspension agent performance suspension effect, polymerization temperature of the present invention should be lower than the gelation point of used suspension agent, therefore selects middle low temperature initiators in an example of the present invention for use.Those of ordinary skill in the art can easily determine suitable initiator according to content disclosed by the invention.For example, can select for use:
(a) peroxy dicarbonates initiator is as peroxy dicarbonate diethyl ester, di-isopropyl peroxydicarbonate (IPP), peroxy dicarbonate di-n-propyl ester (NPP), peroxy dicarbonate two (4-tert-butylcyclohexyl) ester; Perhaps
(b) peroxidation two acyl class initiators are as perfluor propionyl superoxide, peroxidation two (dichloro one acetyl fluoride), peroxidation two (tribromo-acetyl) etc.
By the weight of the mixture of the described vinylidene fluoride monomers of 100 weight parts or vinylidene and other fluorochemical monomer, the add-on of initiator is 0.3～1.5 weight part, is preferably 0.4～0.8 weight part.
The adding method of initiator can be initial disposable adding or add in batches.In an example of the present invention, described initiator adds in batches, and the initial initiator that adds accounts for 10～60% of initiator gross weight, is preferably 30～50%.
For the molecular weight and the molecular weight distribution of controlled polymerization product, can in polymerization system, add an amount of chain-transfer agent if necessary.The example of suitable chain-transfer agent has, for example the Fatty Alcohol(C12-C14 and C12-C18) of 1～6 carbon atom, ester, ketone or hydrogeneous halogenated hydrocarbon etc.Wherein particular methanol and diethyl malonate.
Chain-transfer agent can once add or add continuously or intermittently in polymerization process when the reaction beginning.The consumption of chain-transfer agent can change in very wide scope, and this depends on the molecular weight of used monomeric species, polymerization temperature and hope.0.08～0.6wt% of the add-on of the mixture that common consumption is vinylidene or vinylidene and other fluorochemical monomer, preferred 0.1～0.4wt%.
Further specify the present invention below in conjunction with embodiment.
Embodiment
The judgement of sticking still phenomenon
For the judgement of sticking still phenomenon, the embodiment of the invention and comparative example utilization take by weighing the method for bur weight and judge.Specifically, after polyreaction finishes, open polymeric kettle bottom discharge valve, draw off most of material in the still, use washed with de-ionized water still inwall and stirring rake 3 times subsequently, open the material manual removal that kettle cover will remain on still inwall and the stirring rake then and get off, be called sticking still material.To glue the still material behind 100 ℃ of vacuum-drying 24h, and weigh, this weight is called W
b2L polymeric kettle for the embodiment of the invention and comparative example employing, adopt following standard to judge adhesion phenomenon:
Work as W
bDuring≤5g, cannot not be defined as stickingly still;
As 5g＜W
bDuring≤10g, be defined as slight sticking still;
Work as W
bDuring＞10g, be defined as the sticking still of severe;
When polymkeric substance can not draw off from polymeric kettle bottom discharge valve unobstructedly, in the time of must driving still and manually take out polymer material, then be defined as very seriously sticking still.
Embodiment 1
The preparation set of monomers becomes: vinylidene in the initial charge groove: trifluoro-ethylene=71.6: 28.4 (mol), add vinylidene in the groove: trifluoro-ethylene=69.5: 30.5 (mol).
Adopt 2L to have churned mechanically polymermaking autoclave, in still, add the mixed solvent of 500ml deionized water and 100ml Freon 113, add 1% Vltra tears aqueous solution 50ml simultaneously.Vacuumize the displacement deoxygenation then, when oxygen concentration during less than 30ppm, open and stir, stirring revolution is 600 rev/mins, when being warmed up to 50 ℃, being dosed to the still internal pressure with compressor from the initial charge groove in still is 2.5MPa, adds initial mixing monomer 140g this moment, then the anhydrous methanol of squeezing into di-isopropyl peroxydicarbonate (IPP) initiator of 1.0g and 0.25ml with volume pump is as chain-transfer agent, initiated polymerization.
Adopt compressor constantly to add monomer and keep polymerization pressure in 2.45～2.55MPa scope, when polymerization time was about 40 minutes, initial groove inlet amount reached 200g, changes into from adding the groove charging.When polyreaction reaches 1.5h, utilize volume pump in 1.0h, to squeeze into the di-isopropyl peroxydicarbonate (IPP) of 1.0g and the carbinol mixture of 0.5ml continuously, keep constant reaction pressure and stop to feed in raw material when groove adds monomer for 160g to adding, this reaction time is 4h, cooling release discharging.
With the sticking still phenomenon of aforesaid method judgement reactor, W as a result
b=3.8g less than 5g, judges not sticking still.
The polymerisate suspension liquid is filtered, and the distillation clear liquid reclaims the solvent Freon 113, with filter cake methyl alcohol repetitive scrubbing 3 times, remove the solvent that remains in polymer surfaces, use deionized water wash again 2 times, filter back 100 ℃ of vacuum-drying 24h, obtain the powdery polymer about 190g.
The multipolymer that obtains characterizes: consist of VDF through 400MHz nucleus magnetic hydrogen spectrum and this binary polymer mole of fluorine spectrum test: TrFE=70/30.Nitrogen protection is tested through DSC, and fusing point is 148.6 ℃, and melting enthalpy is 25.7J/g, and the Curie temperature that ferroelectric material generation ferroelectric phase changes paraelectric phase into is 87.9 ℃.Melting index be 2.5g/10min (230 ℃, 5kg), GPC test number-average molecular weight is 18.3 ten thousand, molecular weight distribution is 1.904, the relative permittivity under the room temperature is 22.
Embodiment 2
The preparation set of monomers becomes: vinylidene in the initial charge groove: trifluoro-ethylene=82.1: 17.9 (mol), the monomer composition in the polymerization process remains unchanged.
Adopt 2L to have churned mechanically polymermaking autoclave, in still, add the mixed solvent of 500ml deionized water and 150ml Freon 113, add 1% methylated cellulose aqueous solution 50ml simultaneously.Vacuumize the displacement deoxygenation then, when oxygen concentration during less than 30ppm, open and stir, stirring revolution is 600 rev/mins, when being warmed up to 50 ℃, being dosed to the still internal pressure with compressor from the initial charge groove in still is 2.0MPa, adds initial mixing monomer 150g this moment, then the anhydrous methanol of squeezing into di-isopropyl peroxydicarbonate (IPP) initiator of 1.0g and 0.25ml with volume pump is as chain-transfer agent, initiated polymerization.
Adopt compressor constantly to add monomer and keep polymerization pressure in 1.95～2.05MPa scope, when polymerization time was about 40 minutes, initial groove inlet amount reached 235g, changes into from adding the groove charging.When polyreaction reaches 1.5h, utilize volume pump in 1.0h, to squeeze into the di-isopropyl peroxydicarbonate (IPP) of 1.0g and the carbinol mixture of 0.5ml continuously, keeping constant reaction pressure stops to feed in raw material when groove adds monomer for 180g to adding, this the reaction time is 4h, cooling release discharging obtains copolymer resins and is about 225g after the aftertreatment.
With the sticking still phenomenon of aforesaid method judgement reactor, W as a result
b=3.3g less than 5g, judges not sticking still.
The copolymer resins characterizing method that obtains is identical with embodiment 1, and this binary polymer mole consists of VDF: TrFE=84.2/15.8, fusing point are 153.2 ℃, and melting enthalpy is 29.3J/g, and Curie temperature is 95.1 ℃.Melting index be 3.7g/10min (230 ℃, 5kg), GPC test number-average molecular weight is 16.2 ten thousand, molecular weight distribution is 1.99, the relative permittivity under the room temperature is 18.
Embodiment 3
The preparation set of monomers becomes: vinylidene in the initial charge groove: trifluoro-ethylene=65.2: 34.8 (mol), add vinylidene in the groove: trifluoro-ethylene=67.0: 33.0 (mol).
Adopt 2L to have churned mechanically polymermaking autoclave, in still, add the mixed solvent of 600ml deionized water and 50ml Freon 113, add 1% Vltra tears aqueous solution 150ml simultaneously.Vacuumize the displacement deoxygenation then, when oxygen concentration during less than 30ppm, open and stir, stirring revolution is 600 rev/mins, when being warmed up to 50 ℃, being dosed to the still internal pressure with compressor from the initial charge groove in still is 3.0MPa, adds initial mixing monomer 130g this moment, then the anhydrous methanol of squeezing into di-isopropyl peroxydicarbonate (IPP) initiator of 1.2g and 0.3ml with volume pump is as chain-transfer agent, initiated polymerization.
Adopt compressor constantly to add monomer and keep polymerization pressure in 2.95～3.05MPa scope, when polymerization time was about 50 minutes, initial groove inlet amount reached 205g, changes into from adding the groove charging.When polyreaction reaches 1.5h, utilize volume pump in 1.0h, to squeeze into the di-isopropyl peroxydicarbonate (IPP) of 1.5g and the carbinol mixture of 0.6ml continuously, keeping constant reaction pressure stops to feed in raw material when groove adds monomer for 170g to adding, this the reaction time is 3.5h, cooling release discharging obtains copolymer resins and is about 206g after the aftertreatment.
With the sticking still phenomenon of aforesaid method judgement reactor, W as a result
b=4.0g less than 5g, judges not sticking still.
The copolymer resins characterizing method that obtains is identical with embodiment 1, and this binary polymer mole consists of VDF: TrFE=66.6/33.4, fusing point are 141.6 ℃, and melting enthalpy is 22.7J/g, and Curie temperature is 82.1 ℃.Melting index be 6.7g/10min (230 ℃, 5kg), GPC test number-average molecular weight is 15.0 ten thousand, molecular weight distribution is 2.18, the relative permittivity under the room temperature is 15.4.
Embodiment 4
The preparation set of monomers becomes: vinylidene in the initial charge groove: trifluoro-ethylene=59.7: 40.3 (mol), add vinylidene in the groove: trifluoro-ethylene=62.3: 37.7 (mol).
Adopt 2L to have churned mechanically polymermaking autoclave, in still, add the mixed solvent of 600ml deionized water and 100ml Perfluorocyclobutane, add 1% Vltra tears aqueous solution 80ml simultaneously.Vacuumize the displacement deoxygenation then, when oxygen concentration during less than 30ppm, open and stir, stirring revolution is 600 rev/mins, when being warmed up to 50 ℃, being dosed to the still internal pressure with compressor from the initial charge groove in still is 2.5MPa, adds initial mixing monomer 140g this moment, then the anhydrous methanol of squeezing into di-isopropyl peroxydicarbonate (IPP) initiator of 1.0g and 0.25ml with volume pump is as chain-transfer agent, initiated polymerization.
Adopt compressor constantly to add monomer and keep polymerization pressure in 2.45～2.55MPa scope, when polymerization time was about 50 minutes, initial groove inlet amount reached 250g, changes into from adding the groove charging.When polyreaction reaches 1.5h, utilize volume pump in 1.0h, to squeeze into the di-isopropyl peroxydicarbonate (IPP) of 1.0g and the carbinol mixture of 0.5ml continuously, keeping constant reaction pressure stops to feed in raw material when groove adds monomer for 175g to adding, this the reaction time is 4h, cooling release discharging obtains copolymer resins and is about 256g after the aftertreatment.
With the sticking still phenomenon of aforesaid method judgement reactor, Wb=3.0g less than 5g, is judged to be slight sticking still as a result.
The copolymer resins characterizing method that obtains is identical with embodiment 1, and this binary polymer mole consists of VDF: TrFE=60.1/39.9, fusing point are 139.6 ℃, and melting enthalpy is 24.9J/g, and Curie temperature is 80.9 ℃.Melting index be 6.0g/10min (230 ℃, 5kg), GPC test number-average molecular weight is 16.6 ten thousand, molecular weight distribution is 2.20, the relative permittivity under the room temperature is 18.3.
Embodiment 5
Present embodiment is VDF monomeric homopolymerization, adopts 2L to have churned mechanically polymermaking autoclave, adds the mixed solvent of 600ml deionized water and 100ml Perfluorocyclobutane in still, adds 1% polyvinyl alcohol water solution 80ml simultaneously.Vacuumize the displacement deoxygenation then, when oxygen concentration during less than 30ppm, open and stir, stirring revolution is 600 rev/mins, when being warmed up to 55 ℃, being dosed to the still internal pressure with compressor from the initial charge groove in still is 3.0MPa, adds initial mixing monomer 150g this moment, then the anhydrous methanol of squeezing into peroxy dicarbonate di-n-propyl ester (NPP) initiator of 1.5g and 0.25ml with volume pump is as chain-transfer agent, initiated polymerization.
Adopt compressor constantly to add monomer and keep polymerization pressure in 2.95～3.05MPa scope, when polyreaction reaches 1.5h, utilize volume pump to squeeze into the NPP of 1.0g and the carbinol mixture of 0.5ml fast, when amounting to adding monomer 380g, stop to feed in raw material, this the reaction time is 4.2h, cooling release discharging obtains the PVDF resin and is about 210g after the aftertreatment.
With the sticking still phenomenon of aforesaid method judgement reactor, W as a result
b=3.0g less than 5g, is judged to be slight sticking still.
The homopolymerization PVDF resin characterizing method that obtains is identical with embodiment 1, and fusing point is 171.6 ℃, and melting enthalpy is 50.9J/g.Melting index be 2.3g/10min (230 ℃, 5kg), GPC test number-average molecular weight is 12.6 ten thousand, molecular weight distribution is 1.98, the relative permittivity under the room temperature is 10.3.
Comparative example 1
Method therefor is identical with embodiment 2 with equipment, monomer composition and polymerization process condition are identical with embodiment 2, difference is not add the methylated cellulose aqueous solution as suspension agent, promptly do not have suspension agent in the presence of polymerization 4h, add monomer 380g altogether, product can't be emitted from the polymeric kettle discharge port, is forced to out the still discharging.
With the sticking still phenomenon of aforesaid method judgement reactor, be judged to be very seriously sticking still.Aftertreatment obtains irregular particulate state and block copolymer 208g.
The copolymer resins characterizing method that obtains is identical with embodiment 1, and this binary polymer mole consists of VDF: TrFE=82.8/17.2, fusing point are 150.6 ℃, and melting enthalpy is 25.0J/g, and Curie temperature is 92.8 ℃.Melting index be 21.8g/10min (230 ℃, 5kg), GPC test number-average molecular weight is 10.9 ten thousand, molecular weight distribution is 3.360, the relative permittivity under the room temperature is 12.Compare with embodiment 2, the molecular weight distribution of resulting polymers is very wide in range, and this is that the easy coalescence of polymer particles forms particle or bulk, causes inhomogeneous reaction, and is unfavorable for aftertreatment owing to there is not suspension agent to exist.
Comparative example 2
Method therefor is identical with embodiment 2 with equipment, and monomer composition and polymerization process condition are identical with embodiment 2, and difference is not add Freon 113, but adds methylated cellulose aqueous solution, i.e. polymerization in the single medium of pure water.Polymerization 4h adds the monomer about 210g altogether, and polymerization velocity is very slow, does not observe the still pressure drop substantially.Can only observe the floating matter of small amount of polymer in the product that puts down after the end.This is owing to there is not the solubilising monomer effect of Freon 113 solvent, under lower polymerization pressure 2.0MPa, participates in the polymeric monomer seldom in the unit volume, causes polymerization velocity very slow, and the resulting polymers molecular weight is very little.Only done the GPC test, number-average molecular weight is 5.7 ten thousand, and molecular weight distribution is 2.15.
Embodiment 6
Present embodiment is used to prepare the ter-polymers (P (VDF-TrFE-CTFE)) of vinylidene, trifluoro-ethylene and trifluorochloroethylene.Adopt 2L to have churned mechanically polymermaking autoclave, in still, add the mixed solvent of 600ml deionized water and 100ml Freon 113, add 1% Vltra tears aqueous solution 80ml simultaneously.Vacuumize the displacement deoxygenation then, when oxygen concentration during less than 30ppm, open and stir, stirring revolution is 700 rev/mins, when being warmed up to 55 ℃, being dosed to the still internal pressure with compressor from the initial charge groove in still is 2.0MPa, and this moment, the initial mixing monomer added 130g altogether, and initial charge groove mix monomer mol ratio is VDF: TrFE: CTFE=64.6/28.1/7.3.Then squeeze into di-isopropyl peroxydicarbonate (IPP) initiator of 1.0g simultaneously, initiated polymerization with volume pump.Adopt compressor constantly to add monomeric mode and keep polymerization pressure at 2.0MPa, when initial groove inlet amount reaches 200g, this moment, polymerization time was about 1h, stop from initial groove reinforced, change into from adding the groove charging, the mol ratio of adding mix monomer in the groove is VDF: TrFE: CTFE=66.4/28.6/5.0.When polyreaction reaches 1.5h, utilize volume pump to squeeze into the carbinol mixture of the di-isopropyl peroxydicarbonate of 1.0g (IPP) and 0.5ml fast, keep constant reaction pressure and stop to feed in raw material when groove adds monomer for 140g to adding, this reaction time is 4.5h, cooling release discharging.
With the sticking still phenomenon of aforesaid method judgement reactor, W as a result
b=5.2g, this embodiment 5g＜W
b≤ 10g is judged to be slight sticking still.
The polymerisate suspension liquid is filtered, and the distillation clear liquid reclaims the solvent Freon 113, with filter cake methyl alcohol repetitive scrubbing 3 times, remove the solvent that remains in polymer surfaces, use deionized water wash again 2 times, filter back 100 ℃ of vacuum-drying 24h, obtain the powdery polymer about 150g.
The multipolymer that obtains characterizes: consist of VDF through 400MHz nucleus magnetic hydrogen spectrum and this ter-polymers mole of fluorine spectrum test: TrFE: CTFE=63.0/28.7/8.3.Nitrogen protection is tested through DSC, and fusing point is 133.2 ℃, and melting enthalpy is 15.6J/g.GPC test number-average molecular weight is 18.0 ten thousand, and molecular weight distribution is 2.223, and the relative permittivity under the room temperature is 35.
Embodiment 7
Equipment used, used mixed solvent proportioning and experimental technique are all identical with embodiment 6, and the charging monomer is formed identical with embodiment 6.Difference is that initiator is a perfluor propionyl superoxide, polymerization temperature is 40 ℃, and it is 2.0MPa that initial charge groove mix monomer is fed to the still internal pressure, and this moment, the initial mixing monomer added 130g altogether, then squeeze into the perfluor propionyl peroxide initiator of 1.1g simultaneously, initiated polymerization with volume pump.Adopt compressor constantly to add monomeric mode and keep polymerization pressure at 2.0MPa, when initial groove inlet amount reaches 200g, this moment, polymerization time was about 40min, change into from adding the groove charging, when polyreaction reaches 1.2h, utilize volume pump to squeeze into the perfluor propionyl superoxide of 1.1g and the carbinol mixture of 0.5ml fast, keep constant reaction pressure and stop to feed in raw material when groove adds monomer for 220g to adding, this the reaction time is 4.5h, cooling release discharging.
With the sticking still phenomenon of aforesaid method judgement reactor, W as a result
b=5.6g, this embodiment 5g＜W
b≤ 10g is judged to be slight sticking still.
The polymerisate suspension liquid is filtered, and the distillation clear liquid reclaims the solvent Freon 113, with filter cake methyl alcohol repetitive scrubbing 3 times, remove the solvent that remains in polymer surfaces, use deionized water wash again 2 times, filter back 100 ℃ of vacuum-drying 24h, obtain the powdery polymer about 260g.
The terpolymer characterizing method is identical with embodiment 6, and the ter-polymers mole consists of VDF: TrFE: CTFE=63.4/28.9/7.7.Nitrogen protection is tested through DSC, and fusing point is 135.5 ℃, and melting enthalpy is 16.4J/g.GPC test number-average molecular weight is 21.1 ten thousand, and molecular weight distribution is 2.03, and the relative permittivity under the room temperature is 38.
Claims (11)
1. the preparation method of a partial fluorine ethylene polymer, it comprises the steps:
(a) provide the monomer mixture of vinylidene fluoride monomers with the fluorine-containing comonomer of choosing wantonly except that described vinylidene;
(b) provide the mixture of suspension agent in water-containing solvent, described suspension agent is selected from water-soluble cellulose derivative, polyvinyl alcohol compounds or its mixture, and described water-soluble cellulose derivative is selected from C
1-6Alkylcellulose, C
1-6Alkyl C
1-6Hydroxy alkyl cellulose or its mixture, described water-containing solvent comprise that volume ratio is 3～12: 1 water and perhalogeno C
1-10The mixture of alkane;
(c) in the mixture of described suspension agent in water-containing solvent, add described monomer mixture; With
(d) add initiator and carry out polyreaction, described initiator is selected from peroxy dicarbonates initiator or peroxidation two acyl class initiators.
2. the method for claim 1, it is characterized in that described partial fluorine ethylene polymer is selected from vinylidene fluoride homopolymer, vinylidene/trifluoro-ethylene copolymer, vinylidene/TFE copolymer, vinylidene/hexafluoropropylene copolymer, vinylidene/chlorotrifluoroethylene, vinylidene/1,1-chlorine fluoride copolymers, vinylidene/difluoro one vinyl chloride copolymer, vinylidene/trifluoro-ethylene/chlorotrifluoroethylene, vinylidene/trifluoro-ethylene/1,1-chlorine fluoride copolymers, vinylidene/trifluoro-ethylene/hexafluoropropylene copolymer, vinylidene/trifluoro-ethylene/difluoro one vinyl chloride copolymer, vinylidene/tetrafluoroethylene/chlorotrifluoroethylene, vinylidene/tetrafluoroethylene/1,1-chlorine fluoride copolymers, vinylidene/tetrafluoroethylene/hexafluoropropylene copolymer, two or more mixture of vinylidene/tetrafluoroethylene/difluoro one vinyl chloride copolymer or its.
3. method as claimed in claim 1 or 2 is characterized in that described partial fluorine ethylene polymer is the multipolymer of vinylidene and the fluorochemical monomer except that described vinylidene, and vinylidene content is 90～55mol%.
4. method as claimed in claim 2 is characterized in that described partial fluorine ethylene polymer is the multipolymer of vinylidene and trifluoro-ethylene, and vinylidene content is 90～55mol%, and trifluoro-ethylene content is 10～45mol%; Or the multipolymer of vinylidene, trifluoro-ethylene, trifluorochloroethylene, vinylidene content is 80～55mol%, trifluoro-ethylene content is that 15～40mol%, trifluorochloroethylene content are 5～15mol%.
5. method as claimed in claim 1 or 2 is characterized in that described perhalogeno C
1-10Alkane is selected from 1,1,2-three chloro-1,2,2-Halothane, 1,2-two chloro-1,1,2, two or more mixture of 2-Tetrafluoroethane, Perfluorocyclobutane, perfluor hexanaphthene, methyl perfluor hexanaphthene or its.
6. method as claimed in claim 1 or 2 is characterized in that, by the weight of vinylidene fluoride monomers with the monomer mixture of the fluorine-containing comonomer of choosing wantonly except that described vinylidene, the add-on of described suspension agent is 0.05～5 ‰.
7. method as claimed in claim 6 is characterized in that, the add-on of described suspension agent is 1.0～4.0 ‰.
8. method as claimed in claim 1 or 2 is characterized in that polymerization temperature is 20～70 ℃; Polymerization pressure is 1.0～5.0MPa.
9. method as claimed in claim 8 is characterized in that polymerization temperature is 40～60 ℃; Polymerization pressure is 2.0～4.0MPa.
10. the method for claim 1 is characterized in that described C
1-6Alkylcellulose is selected from methylcellulose gum, ethyl cellulose, propyl cellulose or its mixture; Described C
1-6Alkyl C
1-6Hydroxy alkyl cellulose is selected from Vltra tears, hydroxyethylmethyl-cellulose, Hydroxypropyl ethyl cellulose or its mixture.
11. the method for claim 1 is characterized in that described polyvinyl alcohol compounds is selected from polyvinyl alcohol, poly-1-hydroxyl propylene or its mixture; Described vinylidene fluoride monomers is 1.5-5 with the monomer mixture of the fluorine-containing comonomer of choosing wantonly except that described vinylidene and the weight ratio of described solvent: 1.
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| CN102585077B (en) * | 2011-12-16 | 2013-11-06 | 中昊晨光化工研究院 | Preparation method of modified polyvinylidene fluoride through chlorotrifluoroethylene |
| CN102807645B (en) * | 2012-08-27 | 2014-07-02 | 中昊晨光化工研究院有限公司 | Method for preparing low molecular weight polyvinylidene fluoride |
| CN103601827B (en) * | 2013-12-02 | 2016-04-27 | 内蒙古三爱富万豪氟化工有限公司 | Partial fluorine ethylene polymer and preparation method thereof |
| CN104710550A (en) * | 2013-12-11 | 2015-06-17 | 浙江蓝天环保高科技股份有限公司 | High molecular weight polyvinylidene fluoride resin and preparation method thereof |
| CN104448094A (en) * | 2014-12-06 | 2015-03-25 | 常熟丽源膜科技有限公司 | Production process of polyvinylidene fluoride with thermal stability |
| KR102446216B1 (en) * | 2016-10-05 | 2022-09-22 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | Polymer latex containing vinylidene fluoride and trifluoroethylene |
| CN110684142A (en) * | 2019-10-29 | 2020-01-14 | 追信数字科技有限公司 | Manufacturing method of honeycomb solid-liquid composite heat dissipation material for CPU heat dissipation |
| CN110776706A (en) * | 2019-10-29 | 2020-02-11 | 追信数字科技有限公司 | Method for manufacturing CPU heat dissipation material by heat absorption, heat transfer and radiation combined mechanism |
| KR20230014947A (en) * | 2021-07-22 | 2023-01-31 | 한국화학연구원 | Preparation method of polyvinylidene fluoride and polyvinylidene fluoride prepared by the method |
| CN114773660B (en) * | 2022-04-26 | 2023-08-29 | 浙江工业大学 | Porous ultrahigh molecular weight fluorine-containing olefin hollow microsphere and preparation method thereof |
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