CN103626900A - Manufacturing method of vinylidene fluoride system polymer - Google Patents
Manufacturing method of vinylidene fluoride system polymer Download PDFInfo
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Abstract
The object of the present invention is to provide a manufacturing method of a vinylidene fluoride system polymer, which can reduce the attachment of the the polymer in a polymerization vessel and other polymerization tanks during the occurrence of polymerization of the vinylidene fluoride polymer,and reduce the amount of suspended matter in wastewater generated from the suspension polymerization, and the vinylidene fluoride system polymer can be obtained in excellent productivity. The manufacturing method of vinylidene fluoride system polymer is through dispersing a monomer mainly composed of vinylidene fluoride in an aqueous medium containing a suspending agent to produce a vinylidene fluoride system polymer by suspension polymerization, which is characterized in that the suspension polymerization is processed in the presence of at least one kind of polycarboxylic acid-based compound selected from a polycarboxylic acid or a polycarboxylic acid.
Description
Technical field
The present invention relates to the manufacture method of vinylidene based polymer.
Background technology
Excellences such as the chemical proofing of vinylidene based polymer, weathering resistance, stain resistance and manufacture the material that various films, products formed are used as melt molding.In addition, vinylidene based polymer is also as coating, resin glue.
Vinylidene based polymer can utilize various polymerizations synthetic, during industrial production, adopts emulsion polymerization method, suspension polymerization to synthesize.In emulsion polymerization method, generate the latex (latex) of 0.2～0.5 μ m left and right small particle size, so after polymerization, implement to utilize the granulation of condensing agent to process, but in order fully to remove de-emulsifier, condensing agent etc., need complicated aftertreatment.On the other hand, in suspension polymerization, generate the bead of 50～300 μ m left and right particle diameters, by easy carrying out washing treatment, obtain the few polymkeric substance of impurity.
When manufacturing vinylidene by suspension polymerization, exist polymkeric substance to be attached to the problem of aggregation container, whipping appts etc.If in general polymkeric substance is attached to the wall of aggregation container, the heat transfer deterioration of aggregation container, if cause dirt settling to pile up by continuous production etc., becomes and is difficult to heat extraction.
In addition, at dirt settling, peel off and in being blended into product time, have the problem that causes quality product to worsen.
From the viewpoint of productivity and quality product, consider, do not wish that polymkeric substance adheres to and piles up, therefore need to remove the operation of the polymkeric substance of attachment removal, but the polymkeric substance also sometimes adhering to firmly fixes, therefore it removes the factor worsening into productivity that is operable to, and wishes to reduce adhering to of polymkeric substance.
In addition, during suspension polymerization, in polyreaction, in water, generate micro mist, thereby the suspended substance quality in draining easily increases.If suspended substance quality increases, carrying capacity of environment also becomes greatly, therefore needs for remove the drainage treatment equipment of suspended matter from draining.As the means that conventionally prevent that suspended substance quality from increasing, carried out adding the optimization of stopper, agitation condition, but effect is inadequate sometimes, polymerization reaction take place delay sometimes, product shade change, and therefore wish to reduce suspended substance quality by easy method.
In the past, proposed to have the manufacture method (for example, with reference to patent documentation 1) of the vinylidene based polymer of suspension operation and supercritical polymerization operation.In the embodiment of patent documentation 1, under trisodium phosphate exists by vinylidene polymerization, in the manufacture method of the vinylidene based polymer of recording in patent documentation 1, obtained solvability in organic solvent excellent, as the useful high-polymerization degree vinylidene based polymer of binders for electrodes for non-aqueous electrolyte battery.
Yet, in the manufacture method of the vinylidene based polymer of recording in patent documentation 1, about suspended substance quality, do not study especially.
Patent documentation 1: No. 2009/047969 brochure of International Publication
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of vinylidene based polymer, its can alleviate when polymerization vinylidene based polymer, occur, the amount of adhering to and reducing the Treating Suspended Matters in Water Drained matter that due to suspension polymerization produces of polymkeric substance on the aggregation containers such as polymerization tank, and can obtain vinylidene based polymer with excellent productivity.
The inventor etc. are further investigation repeatedly in order to realize above-mentioned problem, found that, by carrying out suspension polymerization under the existence at specific polycarboxylic acid based compound, manufactures vinylidene based polymer, can solve above-mentioned problem, thereby complete the present invention.
; the manufacture method of vinylidene based polymer of the present invention is by being dispersed in the aqueous medium that contains suspension agent, carrying out the method that vinylidene based polymer is manufactured in suspension polymerization take the monomer that vinylidene is principal constituent; it is characterized in that, under the existence of at least a kind of polycarboxylic acid based compound of above-mentioned suspension polymerization in being selected from polycarboxylic acid and polycarboxylate, carry out.
Above-mentioned suspension polymerization is preferably carried out under the existence of polycarboxylic acid and polycarboxylate.
Preferred above-mentioned polycarboxylic acid is at least a kind of polycarboxylic acid being selected from oxalic acid, propanedioic acid, succsinic acid and citric acid, and above-mentioned polycarboxylate is at least a kind of polycarboxylate being selected from oxalate, malonate, succinate and Citrate trianion; More preferably above-mentioned polycarboxylic acid is citric acid, and above-mentioned polycarboxylate is at least a kind of Citrate trianion being selected from Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate, and particularly preferably above-mentioned polycarboxylic acid is citric acid, and above-mentioned polycarboxylate is Trisodium Citrate.
The manufacture method of vinylidene based polymer of the present invention can alleviate polymkeric substance adhering on the aggregation containers such as polymerization tank in polymerization, can reduce the amount of Treating Suspended Matters in Water Drained matter.Therefore the manufacture method of vinylidene based polymer of the present invention is compared with manufacture method in the past, can reduce the frequency that the polymkeric substance to being attached on aggregation container wall is removed, the amount of Treating Suspended Matters in Water Drained matter is few, therefore compares with manufacture method in the past, carrying capacity of environment is few, and productivity is excellent.
Embodiment
Below, the present invention is specifically described.
The manufacture method of vinylidene based polymer of the present invention is by being dispersed in the aqueous medium that contains suspension agent, carrying out the method that vinylidene based polymer is manufactured in suspension polymerization take the monomer that vinylidene is principal constituent, it is characterized in that, under the existence of at least a kind of polycarboxylic acid based compound of above-mentioned suspension polymerization in being selected from polycarboxylic acid and polycarboxylate, carry out.
(monomer that the vinylidene of take is principal constituent)
In the manufacture method of vinylidene based polymer of the present invention, will take monomer that vinylidene is principal constituent as raw material.
Should illustrate, so-called take the monomer that vinylidene is principal constituent, refer to the monomer that every 100 % by mole of monomers contain 50 % by mole of above vinylidenes, normally contain the monomer of 80 % by mole of above vinylidenes, preferably contain the monomer of 95 % by mole of above vinylidenes.
As take the monomer that vinylidene is principal constituent, can contain 50 % by mole of monomers beyond following vinylidenes and (also remember into below other monomer.), when containing other monomer, conventionally contain below 20 % by mole, preferably contain below 5 % by mole.
Should illustrate, as take the monomer that vinylidene is principal constituent, when manufacturing vinylidene fluoride homopolymer as vinylidene based polymer, only use vinylidene as monomer, at the multipolymer of manufacturing vinylidene and other monomer during as vinylidene based polymer, use vinylidene and other monomer.
As above-mentioned other monomer, such as enumerating, can be the hydrocarbon system monomers such as monomer or ethene, propylene, carboxylic monomer with the fluorine of vinylidene copolymerization, containing acid anhydride's monomer.Should illustrate, other monomer can be for a kind of separately, also can be for two or more.
As above-mentioned can be monomer with the fluorine of vinylidene copolymerization, perfluoroalkyl vinyl ether that can to enumerate vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, chlorotrifluoroethylene, R 1216, the perfluoro methyl vinyl ether of take be representative etc.
As above-mentioned carboxylic monomer, the monoesters of preferred unsaturated monoprotic acid, unsaturated dibasic acid, unsaturated dibasic acid etc.
As above-mentioned unsaturated monoprotic acid, can enumerate vinylformic acid, methacrylic acid, vinylformic acid 2-carboxyl ethyl ester, methacrylic acid 2-carboxyl ethyl ester etc.As above-mentioned unsaturated dibasic acid, can enumerate toxilic acid, citraconic acid etc.In addition, as the monoesters of above-mentioned unsaturated dibasic acid, the monoesters of the unsaturated dibasic acid that preferably carbonatoms is 5～8, such as enumerating monomethyl maleate, ethyl maleate, citraconic acid mono-methyl, citraconic acid mono ethyl ester etc.Wherein, as carboxylic monomer, preferred vinylformic acid, methacrylic acid, toxilic acid, citraconic acid, monomethyl maleate, citraconic acid mono-methyl.In addition, as carboxylic monomer, can use succsinic acid acryloxy ethyl ester, succsinic acid methacryloxy ethyl ester, phthalic acid acryloxy ethyl ester, phthalic acid methacryloxy ethyl ester etc.
As the above-mentioned monomer containing acid anhydride, can enumerate the acid anhydrides of above-mentioned unsaturated dibasic acid, particularly, can enumerate maleic anhydride, citraconic anhydride.
(suspension agent)
In the manufacture method of vinylidene based polymer of the present invention, use suspension agent.
As the suspension agent using, can preferably enumerate methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, partly-hydrolysed polyvinyl acetate, acrylic acid polymer etc. in suspension polymerization of the present invention.
As suspension agent, from the viewpoint of granulation, particularly preferably methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, wherein, most preferably obtain the methylcellulose gum of vinylidene based polymer with the good large particle diameter powder form of treatability.
Consumption as suspension agent, preferably with respect to whole monomers (monomer that the vinylidene of take is principal constituent) 100 mass parts of use when carrying out suspension polymerization, more than there is 0.02 mass parts～lower than 0.25 mass parts, more preferably more than there is 0.03 mass parts～lower than 0.2 mass parts, more than particularly preferably there is 0.05 mass parts～below 0.1 mass parts.In the time of in above-mentioned scope, the suspended particles of monomer are stable, produce bubble also few, thereby preferably.
(aqueous medium)
As previously mentioned, in the manufacture method of vinylidene based polymer of the present invention, make above-mentionedly to take monomer that vinylidene is principal constituent and be dispersed in and in aqueous medium, carry out suspension polymerization.
As aqueous medium, can make water or take the water of water more than principal constituent 70 quality %, with 1,1,2,2,3-five is fluoro-1,3-propylene dichloride, 1,1,1,2,2-five is fluoro-3, the blending agent of the halogenated hydrocarbon dielectrics such as 3-propylene dichloride, single hydrogen pentafluorodichloropropane etc.As aqueous medium, preferably water, as above-mentioned water, is preferably used the refined water such as ion exchanged water, pure water.
The consumption of aqueous medium when carrying out suspension polymerization is preferably 100～1000 mass parts, more preferably 200～500 mass parts with respect to whole monomers (monomer that the vinylidene of take is principal constituent) 100 mass parts of using.
(polycarboxylic acid based compound)
The manufacture method of vinylidene based polymer of the present invention is characterised in that, under the existence of at least a kind of polycarboxylic acid based compound in being selected from polycarboxylic acid and polycarboxylate, carries out suspension polymerization.
Should illustrate, so-called polycarboxylic acid, is the compound in molecule with a plurality of carboxyls, so-called polycarboxylate is at least a portion carboxyl of polycarboxylic acid with from the cationic ion bonding of alkali and compound.
Manufacture method as vinylidene based polymer of the present invention, under the existence of polycarboxylic acid based compound, carry out suspension polymerization, as polycarboxylic acid based compound, can be only polycarboxylic acid, also can be only polycarboxylate, but while using polycarboxylic acid and polycarboxylate, polycarboxylic acid based compound also plays a role as buffer reagent, thereby preferably.In addition, polycarboxylic acid, polycarboxylate can be distinguished use separately, also can use two or more.
As polycarboxylic acid, for example, can enumerate oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, citric acid, isocitric acid, equisetic acid, 1,2,3-the third three acid.As polycarboxylate, can enumerate the salt of these polycarboxylic acids.
As polycarboxylate, for example can enumerate an alkali metal salt, alkaline earth salt, be preferably lithium salts, sodium salt, sylvite, more preferably sodium salt.
As polycarboxylic acid based compound, the compound of the hydrogen abstraction reaction that preferably difficult generation is caused by free radical.The polycarboxylic acid of the hydrogen abstraction reaction being caused by free radical as difficult generation, can enumerate oxalic acid, propanedioic acid, succsinic acid and citric acid, as polycarboxylate, can enumerate their salt, i.e. oxalate, malonate, succinate and Citrate trianion.
As polycarboxylic acid, citric acid most preferably, as polycarboxylate, Citrate trianion most preferably.As Citrate trianion, optimization citric acid lithium, Trisodium Citrate, Tripotassium Citrate, most preferably Trisodium Citrate.
Manufacture method for vinylidene based polymer of the present invention, by carrying out suspension polymerization under the existence at above-mentioned polycarboxylic acid based compound, polymkeric substance the adhering on the aggregation containers such as polymerization tank occurring can be alleviated in polymerization, the amount of Treating Suspended Matters in Water Drained matter can be reduced.
Although its reason is still not clear, manufacture method of the present invention can obviously reduce in polymerization polymkeric substance polymerisation medium do not have contact gas phase portion wall, on cover adhere to, can alleviate the Quality Down that comes off, sneaks into and cause by the polymkeric substance adhering to.And manufacture method of the present invention also can reduce the suspended substance quality (SS) in draining, so carrying capacity of environment is few, draining is also effectively on processing, so productivity is also excellent.
Consumption as above-mentioned polycarboxylic acid based compound, preferably with respect to whole monomers (monomer that the vinylidene of take is principal constituent) 100 mass parts of use when carrying out suspension polymerization, there is 0.01～1 mass parts, more preferably there is 0.02～0.5 mass parts, particularly preferably have 0.05～0.4 mass parts.In the time of in above-mentioned scope, can bring into play fully above-mentioned effect, thereby preferably.
In addition, when using polycarboxylic acid and polycarboxylate as above-mentioned polycarboxylic acid based compound, as its ratio, be not particularly limited, but polycarboxylic acid: polycarboxylate in weight ratio be generally 99: 1～1: 99, be preferably 9: 1～1: 9.In the time of in above-mentioned scope, polycarboxylic acid based compound also plays a role well as buffer reagent, thereby preferably.
(suspension polymerization)
As previously mentioned, the manufacture method of vinylidene based polymer of the present invention is characterised in that, by take the monomer that vinylidene is principal constituent, be dispersed in the aqueous medium that contains suspension agent, carry out suspension polymerization, this suspension polymerization is carried out under the existence of above-mentioned multi-element metal carboxylic acid based compound.
In the manufacture method of vinylidene based polymer of the present invention, there is above-mentioned multi-element metal carboxylic acid based compound, in addition, can adopt the method same with suspension polymerization in the past to carry out.Should illustrate, as kind, the consumption of the monomer using in the manufacture method at vinylidene based polymer of the present invention, the vinylidene of take is principal constituent, suspension agent, aqueous medium, multi-element metal carboxylic acid based compound, as previously mentioned.
When suspension polymerization, conventionally adopt polymerization starter; as polymerization starter, can use di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (seven fluorine positive third) ester, di-isopropyl peroxydicarbonate, peroxidation isobutyryl, two (chlorine fluorine acyl group) superoxide, two (perfluoro acidyl) superoxide, the peroxidation trimethylacetic acid tert-butyl ester etc.For its consumption, the whole monomers that use in suspension polymerization (monomer that the vinylidene of take is principal constituent) are during as 100 mass parts, are 0.05～5 mass parts, are preferably 0.1～2 mass parts.
In addition, also can add the polymerization degree that the chain-transfer agents such as ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, n-propyl alcohol, acetaldehyde, propionic aldehyde, ethyl propionate, tetracol phenixin regulate the vinylidene based polymer obtaining.For its consumption, the whole monomers that conventionally use in suspension polymerization (monomer that the vinylidene of take is principal constituent) are during as 100 mass parts, are 0.1～5 mass parts, are preferably 0.4～3 mass parts.
In addition, during suspension polymerization, polymerization temperature T suitably selects according to 10 of polymerization starter hours half life temperature T10, conventionally in the scope of T10-25 ℃≤T≤T10+25 ℃, selects.For example the T10 of the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate and peroxy dicarbonate di-n-propyl ester is respectively 54.6 ℃, 40.5 ℃ and 40.3 ℃.Therefore, by the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate and peroxy dicarbonate di-n-propyl ester as in the polymerization of polymerization starter, its polymerization temperature T suitably selects respectively in the scope of 29.6 ℃≤T≤79.6 ℃ and 15.5 ℃≤T≤65.5 ℃, 15.3 ℃≤T≤65.3 ℃.
Polymerization time is not particularly limited, if but consider productivity etc., be preferably below 100 hours.Pressure during polymerization carries out adding to depress conventionally, is preferably 2.0～8.0MPa-G.
In addition, can add pH adjusting agent the pH regulator in suspension polymerization is arrived to any range.As pH adjusting agent, be not particularly limited, can enumerate borate buffer, phosphoric acid buffer.
By carrying out under these conditions take the suspension polymerization of the monomer that vinylidene is principal constituent, can obtain vinylidene based polymer.
The manufacture method of vinylidene based polymer of the present invention can be implemented by carrying out suspension polymerization under the existence at above-mentioned multi-element metal carboxylic acid based compound, does not need to increase optional equipment and has aforesaid effect.
(vinylidene based polymer)
Median size as the vinylidene based polymer being obtained by manufacture method of the present invention, is not particularly limited, and is generally 80～250 μ m, is preferably 130～230 μ m.If it is large that median size becomes, washing dehydration after polymerization, add the treatability in man-hour and improve, from the viewpoint of productivity, consider preferably.
In addition, by manufacture method of the present invention vinylidene based polymer logarithmic viscosity number (inherent viscosity) (make resin 4g be dissolved in 1 liter of DMF and the logarithm viscosity of solution at 30 ℃.Same below) be preferably the value within the scope of 0.5～5.0dl/g, the more preferably value within the scope of 0.8～4.0dl/g.
As by manufacture method of the present invention vinylidene based polymer, can be for using by method for making in the past the various uses of vinylidene based polymer.That is, by manufacture method of the present invention vinylidene based polymer can manufacture the material that various films, products formed are used as melt molding, also can be used as coating, resin glue.
Embodiment
Below, embodiment is shown, and the present invention is described in more detail, but the present invention is not limited to this.The physical property of the vinylidene fluoride polymer powder obtaining in embodiment, comparative example adopts following methods to measure.
(logarithmic viscosity number)
In 1 liter of DMF, add vinylidene fluoride polymer powder 4g, the solution dissolving through preparation in 8 hours at 80 ℃.Using this solution with as the DMF of solvent, remain on 30 ℃, with dark type viscometer, determine respectively the elution time, by following formula, obtain logarithmic viscosity number.
[η]＝ln(η
rel)/C
At this, η
relthe elution time that represents the elution time/solvent of sample solution, C represents the concentration (0.4g/dl) of sample solution.
(median size)
For the size-grade distribution of vinylidene fluoride polymer powder, utilize (strain) flat work to make made Ro-tap formula II type vibratory screening apparatus D type, according to JIS K0069-3.1, by dry screen point-score, measured.The calculating of median size take size-grade distribution measurement result as basis, by lognormal distribution method, tried to achieve.Median size for demonstrating the particle diameter of 50% accumulated value (D50) in granularity cumulative distribution.
(tap density)
The tap density of vinylidene fluoride polymer powder is measured according to the assay method of JIS K6721-3.3 " bulk specific gravity ".Particularly, the about 120ml of the powdered sample fully stirring is joined bulk specific gravity determinator insertion in the funnel of orifice valve after, extract rapidly orifice valve, sample is fallen in susceptor.The sample of emerging from susceptor is wiped with glass stick, and then, the quality that weighs exactly the susceptor that has added sample is accurate to 0.1g, by following formula, tries to achieve tap density.
S＝(C-A)/B
S: tap density (g/cm
3)
A: the quality of susceptor (g)
B: the internal volume (cm of susceptor
3)
C: the quality (g) that has added the susceptor of sample
Mensuration is carried out 3 times, calculates mean value.For test-results, the 3rd of numerical value who is measured to following 3 of radix point rounded up, represent with rounding up.
(mensuration of suspended substance quality)
After polymerization completes, polymer paste centrifuge dehydration is reclaimed to draining.When centrifuge dehydration, use air permeability (JIS L1096) for 70cm
3/ cm
2the filter cloth of sec.For the draining obtaining, the measuring method of the suspended matter of recording according to JIS K0102 is measured suspended substance quality, and the suspended substance quality that this is recorded is as suspended substance quality (SS).
(dirt settling on polymerization tank (autoclave))
After polymerization completes, from polymerization tank, discharge polymer paste, after rinsing in polymerization tank with flowing water, by visual observation polymkeric substance the wall of polymerization tank and on cover adhere to.
(embodiment 1)
In being the autoclave of 14.5 liters, internal volume drops into 250 parts of ion exchanged waters, 0.05 part of methylcellulose gum, 100 parts of vinylidenes, 0.6 part of peroxy dicarbonate di-n-propyl ester, 1.0 parts of ethyl acetate, 0.03 part of citric acid, 0.16 part of trisodium citrate, at 26 ℃, carry out suspension polymerization, the time point that is 92% at yield stops polymerization.
After polymerization completes, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.To carry out polymkeric substance redispersion in water of centrifuge dehydration, at 95 ℃, thermal treatment is after 30 minutes, and centrifuge dehydration, washes, and further at 80 ℃, is dried 20 hours, obtains vinylidene fluoride polymer powder.
(embodiment 2)
Making ethyl acetate is 2.7 parts, in addition, carries out similarly to Example 1.
(comparative example 1)
In being the autoclave of 14.5 liters, internal volume drops into 250 parts of ion exchanged waters, 0.05 part of methylcellulose gum, 100 parts of vinylidenes, 0.6 part of peroxy dicarbonate di-n-propyl ester, 1.4 parts of ethyl acetate, 0.12 part of Sodium Acid Pyrophosphate, 0.07 part of tetrasodium pyrophosphate, at 26 ℃, carry out suspension polymerization, the time point that is 92% at yield stops polymerization.
After polymerization completes, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.To carry out polymkeric substance redispersion in water of centrifuge dehydration, at 95 ℃, thermal treatment is after 30 minutes, and centrifuge dehydration, washes, further at 80 ℃, is dried 20 hours, obtains vinylidene fluoride polymer powder.
(comparative example 2)
Making ethyl acetate is 2.9 parts, in addition, similarly carries out with comparative example 1.The physical property of the polymerizing condition of embodiment 1,2 and comparative example, the vinylidene based polymer that obtains is shown in to table 1.
(embodiment 3)
In being the autoclave of 14.5 liters, internal volume drops into 250 parts of ion exchanged waters, 0.05 part of methylcellulose gum, 100 parts of vinylidenes, 0.6 part of peroxy dicarbonate di-n-propyl ester, 2.5 parts of ethyl acetate, 0.06 part of citric acid, 0.32 part of trisodium citrate, at 26 ℃, carry out suspension polymerization, the time point that is 92% at yield stops polymerization.
After polymerization completes, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.To carry out polymkeric substance redispersion in water of centrifuge dehydration, at 95 ℃, thermal treatment is after 30 minutes, and centrifuge dehydration, washes, and further at 80 ℃, is dried 20 hours, obtains vinylidene fluoride polymer powder.
(embodiment 4)
In being the autoclave of 14.5 liters, internal volume drops into 250 parts of ion exchanged waters, 0.05 part of methylcellulose gum, 100 parts of vinylidenes, 0.6 part of peroxy dicarbonate di-n-propyl ester, 2.5 parts of ethyl acetate, 0.04 part of citric acid, 0.15 part of trisodium citrate, at 26 ℃, carry out suspension polymerization, the time point that is 92% at yield stops polymerization.
After polymerization completes, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.To carry out polymkeric substance redispersion in water of centrifuge dehydration, at 95 ℃, thermal treatment is after 30 minutes, and centrifuge dehydration, washes, and further at 80 ℃, is dried 20 hours, obtains vinylidene fluoride polymer powder.
The physical property of the polymerizing condition of embodiment 3,4, the vinylidene based polymer that obtains is shown in to table 1.
Table 2
Can be clear and definite by above-mentioned table 1 and 2, the manufacture method suspended substance quality of vinylidene based polymer of the present invention is few, can reduce polymkeric substance adhering on polymerization tank skin, so productivity is excellent.
Claims (5)
1. a manufacture method for vinylidene based polymer, is by being dispersed in the aqueous medium that contains suspension agent, carrying out the method that vinylidene based polymer is manufactured in suspension polymerization take the monomer that vinylidene is principal constituent,
It is characterized in that, under the existence of at least a kind of polycarboxylic acid based compound of described suspension polymerization in being selected from polycarboxylic acid and polycarboxylate, carry out.
2. the manufacture method of vinylidene based polymer according to claim 1, wherein, described suspension polymerization is carried out under the existence of polycarboxylic acid and polycarboxylate.
3. the manufacture method of vinylidene based polymer according to claim 1 and 2, wherein, described polycarboxylic acid is at least a kind of polycarboxylic acid being selected from oxalic acid, propanedioic acid, succsinic acid and citric acid,
Described polycarboxylate is at least a kind of polycarboxylate being selected from oxalate, malonate, succinate and Citrate trianion.
4. the manufacture method of vinylidene based polymer according to claim 1 and 2, wherein, described polycarboxylic acid is citric acid,
Described polycarboxylate is at least a kind of Citrate trianion being selected from Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate.
5. the manufacture method of vinylidene based polymer according to claim 1 and 2, wherein, described polycarboxylic acid is citric acid,
Described polycarboxylate is Trisodium Citrate.
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| JP2012183282A JP5916562B2 (en) | 2012-08-22 | 2012-08-22 | Method for producing vinylidene fluoride polymer |
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| CN105470461A (en) * | 2014-10-15 | 2016-04-06 | 万向A一二三系统有限公司 | High-nickel base cathode paste for lithium-ion battery and preparation method of high-nickel base cathode paste |
| CN109843946A (en) * | 2016-10-05 | 2019-06-04 | 索尔维特殊聚合物意大利有限公司 | Vinylidene fluoride polymer |
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| CN105016415B (en) * | 2014-04-30 | 2019-08-27 | 中国石油化工股份有限公司 | A kind of round-robin method of organic acid lithium Sewage treatment organic acid |
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| CN101821298A (en) * | 2007-10-11 | 2010-09-01 | 株式会社吴羽 | Vinylidene fluoride polymer powder and use thereof |
| CN101855752A (en) * | 2007-11-14 | 2010-10-06 | 株式会社吴羽 | Nonaqueous battery anode mixture and anodal structure |
| CN102336854A (en) * | 2011-07-07 | 2012-02-01 | 浙江孚诺林化工新材料有限公司 | Preparation method for high heat resistance polyvinylidene fluoride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105470461A (en) * | 2014-10-15 | 2016-04-06 | 万向A一二三系统有限公司 | High-nickel base cathode paste for lithium-ion battery and preparation method of high-nickel base cathode paste |
| CN105470461B (en) * | 2014-10-15 | 2018-03-23 | 万向一二三股份公司 | High Ni-based anode sizing agent of a kind of lithium ion battery and preparation method thereof |
| CN109843946A (en) * | 2016-10-05 | 2019-06-04 | 索尔维特殊聚合物意大利有限公司 | Vinylidene fluoride polymer |
Also Published As
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| JP2014040519A (en) | 2014-03-06 |
| JP5916562B2 (en) | 2016-05-11 |
| CN103626900B (en) | 2016-01-06 |
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