CN103626900B - The manufacture method of vinylidene based polymer - Google Patents
The manufacture method of vinylidene based polymer Download PDFInfo
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- CN103626900B CN103626900B CN201310376791.3A CN201310376791A CN103626900B CN 103626900 B CN103626900 B CN 103626900B CN 201310376791 A CN201310376791 A CN 201310376791A CN 103626900 B CN103626900 B CN 103626900B
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Abstract
Problem of the present invention is the manufacture method providing a kind of vinylidene based polymer, its amount that can alleviate that occur when being polymerized vinylidene based polymer, that polymkeric substance is on the aggregation containers such as polymerization tank attachment and reduce the Treating Suspended Matters in Water Drained matter produced due to suspension polymerization, and vinylidene based polymer can be obtained with the productivity of excellence.The manufacture method of vinylidene based polymer of the present invention be by by with vinylidene be principal constituent monomer dispersion containing in the aqueous medium of suspension agent, carry out the method that suspension polymerization manufactures vinylidene based polymer, it is characterized in that, above-mentioned suspension polymerization is carried out under the existence being selected from least a kind of polycarboxylic acid based compound in polycarboxylic acid and polycarboxylate.
Description
Technical field
The present invention relates to the manufacture method of vinylidene based polymer.
Background technology
The chemical proofing, weathering resistance, stain resistance etc. of vinylidene based polymer are excellent and be used as the material that melt molding manufactures various film, products formed.In addition, vinylidene based polymer is also used as coating, resin glue.
Vinylidene based polymer can utilize various polymerization to synthesize, and during industrial production, adopts the synthesis of emulsion polymerization method, suspension polymerization.In emulsion polymerization method, generate the latex (latex) of about 0.2 ~ 0.5 μm small particle size, therefore implement the granulation process utilizing condensing agent after polymerization, but in order to fully except de-emulsifier, condensing agent etc., need complicated aftertreatment.On the other hand, in suspension polymerization, generate the bead of about 50 ~ 300 μm particle diameters, obtain the few polymkeric substance of impurity by easy carrying out washing treatment.
When manufacturing vinylidene by suspension polymerization, there is the problem that polymkeric substance is attached to aggregation container, whipping appts etc.If in general polymkeric substance is attached to the wall of aggregation container, then the heat transfer deterioration of aggregation container, if cause dirt settling to pile up by continuous seepage etc., then becomes and is difficult to heat extraction.
In addition, when dirt settling is peeled off and is mixed in product, there is the problem causing quality product to worsen.
From the viewpoint of productivity and quality product, do not wish polymkeric substance attachment and pile up, therefore need the operation of the polymkeric substance except attachment removal, but the polymkeric substance also sometimes adhered to firmly fixing, therefore its removing operation becomes the factor that productivity worsens, and wishes the attachment reducing polymkeric substance.
In addition, during suspension polymerization, in aqueous phase, generate micro mist in the polymerization, thus the suspended substance quality in draining easily increases.If suspended substance quality increases, then carrying capacity of environment also becomes large, therefore needs the drainage treatment equipment for removing suspended matter from draining.As the means usually preventing suspended substance quality from increasing, carried out the optimization of adding stopper, agitation condition, but effect is inadequate sometimes, polymerization reaction take place delay sometimes, product shade change, therefore wish to reduce suspended substance quality by easy method.
In the past, the manufacture method (such as with reference to patent documentation 1) of the vinylidene based polymer with suspension operation and supercritical polymerization operation is proposed.In the embodiment of patent documentation 1, by vinylidene fluoride polymerization under trisodium phosphate exists, in the manufacture method of the vinylidene based polymer recorded in patent documentation 1, obtain solvability excellence in organic solvent, as the useful high-polymerization degree vinylidene based polymer of non-aqueous electrolyte battery binders for electrodes.
But, in the manufacture method of the vinylidene based polymer recorded in patent documentation 1, do not study especially about suspended substance quality.
Patent documentation 1: International Publication No. 2009/047969 brochure
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of vinylidene based polymer, its amount that can alleviate that occur when being polymerized vinylidene based polymer, that polymkeric substance is on the aggregation containers such as polymerization tank attachment and reduce the Treating Suspended Matters in Water Drained matter produced due to suspension polymerization, and vinylidene based polymer can be obtained with the productivity of excellence.
The present inventor etc. further investigate repeatedly in order to realize above-mentioned problem, found that, manufacturing vinylidene based polymer by carrying out suspension polymerization under the existence of specific polycarboxylic acid based compound, then can solve above-mentioned problem, thus complete the present invention.
Namely, the manufacture method of vinylidene based polymer of the present invention be by by with vinylidene be principal constituent monomer dispersion containing in the aqueous medium of suspension agent, carry out the method that suspension polymerization manufactures vinylidene based polymer, it is characterized in that, above-mentioned suspension polymerization is carried out under the existence being selected from least a kind of polycarboxylic acid based compound in polycarboxylic acid and polycarboxylate.
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 be selected from oxalic acid, propanedioic acid, succsinic acid and citric acid, and above-mentioned polycarboxylate is at least a kind of polycarboxylate be 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 be 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 the attachment of polymkeric substance 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 removed the polymkeric substance be attached on aggregation container wall, the amount of Treating Suspended Matters in Water Drained matter is few, therefore compared 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 be by by with vinylidene be principal constituent monomer dispersion containing in the aqueous medium of suspension agent, carry out the method that suspension polymerization manufactures vinylidene based polymer, it is characterized in that, above-mentioned suspension polymerization is carried out under the existence being selected from least a kind of polycarboxylic acid based compound in polycarboxylic acid and polycarboxylate.
(taking vinylidene as the monomer of principal constituent)
In the manufacture method of vinylidene based polymer of the present invention, the monomer taking vinylidene as principal constituent is used as raw material.
Should illustrate, what is called take vinylidene as the monomer of principal constituent, refer to that every 100 % by mole of monomers contain the monomer of more than 50 % by mole vinylidenes, the monomer normally containing more than 80 % by mole vinylidenes, the monomer preferably containing more than 95 % by mole vinylidenes.
As the monomer taking vinylidene as principal constituent, (can also remember into other monomer below containing the monomer beyond less than 50 % by mole vinylidenes.), when containing other monomer, usually containing less than 20 % by mole, preferably containing less than 5 % by mole.
Should illustrate, as the monomer taking vinylidene as principal constituent, when manufacturing vinylidene fluoride homopolymer as vinylidene based polymer, only use vinylidene as monomer, when the multipolymer manufacturing vinylidene and other monomer is as vinylidene based polymer, use vinylidene and other monomer.
As other monomer above-mentioned, such as can enumerate can with the fluorine system monomer of vinylidene copolymerization or the hydrocarbon system such as ethene, propylene monomer, carboxylic monomer, monomer containing acid anhydride.Should illustrate, other monomer can be a kind of separately, also can be two or more.
As above-mentioned can with the fluorine system monomer of vinylidene copolymerization, vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, chlorotrifluoroethylene, R 1216 can be enumerated, take perfluoro methyl vinyl ether as the perfluoroalkyl vinyl ether etc. of representative.
As above-mentioned carboxylic monomer, the monoesters etc. of preferred unsaturated monoprotic acid, unsaturated dibasic acid, unsaturated dibasic acid.
As above-mentioned unsaturated monoprotic acid, vinylformic acid, methacrylic acid, vinylformic acid 2-carboxyethyl, methacrylic acid 2-carboxyethyl etc. can be enumerated.As above-mentioned unsaturated dibasic acid, toxilic acid, citraconic acid etc. can be enumerated.In addition, as the monoesters of above-mentioned unsaturated dibasic acid, preferred carbonatoms is the monoesters of the unsaturated dibasic acid of 5 ~ 8, such as, can enumerate 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, succsinic acid acryloyloxyethyl ester, succsinic acid methacryloyloxyethyl, phthalic acid acryloyloxyethyl ester, methyl acryloyloxyethyl ester etc. can be used.
As the above-mentioned monomer containing acid anhydride, the acid anhydrides of above-mentioned unsaturated dibasic acid can be enumerated, specifically, maleic anhydride, citraconic anhydride can be enumerated.
(suspension agent)
Suspension agent is used in the manufacture method of vinylidene based polymer of the present invention.
As the suspension agent used in suspension polymerization of the present invention, methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, partly-hydrolysed polyvinyl acetate, acrylic acid polymer etc. preferably can be enumerated.
As suspension agent, from the viewpoint of granulation, particularly preferably methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, wherein, most preferably obtains the methylcellulose gum of vinylidene based polymer with the Large stone powder that treatability is good.
As the consumption of suspension agent, preferably relative to whole monomers (taking vinylidene as the monomer of principal constituent) 100 mass parts of the use when carrying out suspension polymerization, there is more than 0.02 mass parts ~ lower than 0.25 mass parts, more preferably there is more than 0.03 mass parts ~ lower than 0.2 mass parts, particularly preferably there is below more than 0.05 mass parts ~ 0.1 mass parts.Time in above-mentioned scope, the suspended particles of monomer are stablized, and produce bubble also few, thus preferably.
(aqueous medium)
As previously mentioned, in the manufacture method of vinylidene based polymer of the present invention, making above-mentioned is that the monomer dispersion of principal constituent carries out suspension polymerization in an aqueous medium with vinylidene.
As aqueous medium, water can be used or take water as the water of more than principal constituent 70 quality %, the blending agent etc. with the halogenated hydrocarbon dielectric such as 1,1,2,2,3-five fluoro-1,3-propylene dichloride, 1,1,1,2,2-five fluoro-3,3-propylene dichlorides, single hydrogen pentafluorodichloropropane.As aqueous medium, preferably water, as above-mentioned water, preferably uses the refined water such as ion exchanged water, pure water.
As the consumption of aqueous medium when carrying out suspension polymerization, be preferably 100 ~ 1000 mass parts relative to whole monomers (taking vinylidene as the monomer of principal constituent) 100 mass parts used, be more preferably 200 ~ 500 mass parts.
(polycarboxylic acid based compound)
The feature of the manufacture method of vinylidene based polymer of the present invention is, under the existence being selected from least a kind of polycarboxylic acid based compound in polycarboxylic acid and polycarboxylate, carry out suspension polymerization.
Should illustrate, so-called polycarboxylic acid, be the compound in molecule with multiple carboxyl, so-called polycarboxylate, is carboxyl at least partially and the cationic ion bonding from alkali of polycarboxylic acid and the compound that obtains.
As the manufacture method of vinylidene based polymer of the present invention, suspension polymerization is carried out under the existence of polycarboxylic acid based compound, as polycarboxylic acid based compound, polycarboxylic acid can be only, may also be only polycarboxylate, but when using polycarboxylic acid and polycarboxylate, polycarboxylic acid based compound also plays a role as buffer reagent, thus preferably.In addition, polycarboxylic acid, polycarboxylate can individually use, and also can use two or more.
As polycarboxylic acid, such as, 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, the salt of these polycarboxylic acids can be enumerated.
As polycarboxylate, such as, can enumerate an alkali metal salt, alkaline earth salt, be preferably lithium salts, sodium salt, sylvite, be more preferably sodium salt.
As polycarboxylic acid based compound, preferably not easily there is the compound of the hydrogen abstraction reaction caused by free radical.As the polycarboxylic acid that the hydrogen abstraction reaction caused by free radical not easily occurs, oxalic acid, propanedioic acid, succsinic acid and citric acid can be enumerated, as polycarboxylate, their salt can be enumerated, i.e. oxalate, malonate, succinate and Citrate trianion.
As polycarboxylic acid, most preferably citric acid, as polycarboxylate, most preferably Citrate trianion.As Citrate trianion, optimization citric acid lithium, Trisodium Citrate, Tripotassium Citrate, most preferably Trisodium Citrate.
For the manufacture method of vinylidene based polymer of the present invention, by carrying out suspension polymerization under the existence of above-mentioned polycarboxylic acid based compound, the attachment of polymkeric substance on the aggregation containers such as polymerization tank occurred in polymerization can be alleviated, 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 the gas phase portion wall that polymerisation medium does not contact, on the attachment that covers, can alleviate and be come off by the polymkeric substance adhered to, be mixed into and the Quality Down caused.And manufacture method of the present invention also can reduce the suspended substance quality (SS) in draining, and therefore carrying capacity of environment is few, and drainage sunk well is also effective, therefore productivity is also excellent.
As the consumption of above-mentioned polycarboxylic acid based compound, preferably relative to whole monomers (taking vinylidene as the monomer of principal constituent) 100 mass parts of the 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 there is 0.05 ~ 0.4 mass parts.Time in above-mentioned scope, above-mentioned effect can be played fully, thus 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 is generally 99: 1 ~ 1: 99 with mass ratio range, is preferably 9: 1 ~ 1: 9.Time in above-mentioned scope, polycarboxylic acid based compound also plays a role well as buffer reagent, thus preferably.
(suspension polymerization)
As previously mentioned, the feature of the manufacture method of vinylidene based polymer of the present invention is, by with vinylidene be the monomer dispersion of principal constituent containing in the aqueous medium of suspension agent, carry out suspension polymerization, this suspension polymerization is carried out under the existence of above-mentioned multi-element metal carboxylic serials compound.
In the manufacture method of vinylidene based polymer of the present invention, there is above-mentioned multi-element metal carboxylic serials compound, in addition, the method same with suspension polymerization in the past can be adopted to carry out.Should illustrate, as use in the manufacture method of vinylidene based polymer of the present invention, kind, the consumption of the monomer that take vinylidene as principal constituent, suspension agent, aqueous medium, multi-element metal carboxylic serials compound, as previously mentioned.
Usually polymerization starter is adopted when suspension polymerization; as polymerization starter, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (seven fluorine positive third) ester, di-isopropyl peroxydicarbonate, isobutyryl peroxide, two (chlorine fluorine acyl group) superoxide, two (perfluoro acidyl) superoxide, the peroxidation trimethylacetic acid tert-butyl ester etc. can be used.For its consumption, when the whole monomers (taking vinylidene as the monomer of principal constituent) used in suspension polymerization are 100 mass parts, are 0.05 ~ 5 mass parts, are preferably 0.1 ~ 2 mass parts.
In addition, 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 obtained can also be added.For its consumption, when the whole monomers (taking vinylidene as the monomer of principal constituent) usually used in suspension polymerization are 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 hr half-life temperature T10 of polymerization starter, usually selects in the scope of T10-25 DEG C≤T≤T10+25 DEG C.Such as the T10 of the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate and peroxy dicarbonate di-n-propyl ester is respectively 54.6 DEG C, 40.5 DEG C and 40.3 DEG C.Therefore, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate and peroxy dicarbonate di-n-propyl ester are being used as in the polymerization of polymerization starter, its polymerization temperature T suitably selects respectively in the scope of 29.6 DEG C≤T≤79.6 DEG C and 15.5 DEG C≤T≤65.5 DEG C, 15.3 DEG C≤T≤65.3 DEG C.
Polymerization time is not particularly limited, if but consider productivity etc., be then preferably less than 100 hours.Pressure during polymerization carries out usually under elevated pressure, is preferably 2.0 ~ 8.0MPa-G.
In addition, pH adjusting agent can be added by the pH regulator in suspension polymerization to any range.As pH adjusting agent, be not particularly limited, borate buffer, phosphoric acid buffer can be enumerated.
By carrying out the suspension polymerization of the monomer taking vinylidene as principal constituent under these conditions, vinylidene based polymer can be obtained.
The manufacture method of vinylidene based polymer of the present invention can, by carrying out suspension polymerization to implement under the existence of above-mentioned multi-element metal carboxylic serials compound, not need increase optional equipment and have aforesaid effect.
(vinylidene based polymer)
As the median size of the vinylidene based polymer obtained by manufacture method of the present invention, be not particularly limited, be generally 80 ~ 250 μm, be preferably 130 ~ 230 μm.If median size becomes large, then washing dehydration after polymerization, add the treatability in man-hour and improve, from the viewpoint of productivity preferably.
In addition, the logarithmic viscosity number (inherentviscosity) of the vinylidene based polymer obtained by manufacture method of the present invention (makes resin 4g be dissolved in 1 liter of DMF and the log viscosities of solution at 30 DEG C obtained.Same below) be preferably value within the scope of 0.5 ~ 5.0dl/g, be more preferably the value within the scope of 0.8 ~ 4.0dl/g.
As the vinylidene based polymer obtained by manufacture method of the present invention, may be used for the various uses using the vinylidene based polymer obtained by method for making in the past.That is, the vinylidene based polymer obtained by manufacture method of the present invention can be used as melt molding to manufacture the material of various film, products formed, 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 obtained in embodiment, comparative example adopts following methods to measure.
(logarithmic viscosity number)
Vinylidene fluoride polymer powder 4g is added, through the solution of preparation dissolving in 8 hours at 80 DEG C in 1 liter of DMF.Remain on 30 DEG C using this solution with as the DMF of solvent, determine the elution time respectively with dark type viscometer, obtain logarithmic viscosity number by following formula.
[η]＝ln(η
rel)/C
At this, η
relrepresent sample solution elution time/elution time of solvent, 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, measured by dry screen point-score according to JISK0069-3.1.The calculating of median size, based on the measurement result of size-grade distribution, is tried to achieve by lognormal distribution method.Median size for demonstrating the particle diameter of 50% accumulated value (D50) in granularity cumulative distribution.
(tap density)
The assay method of tap density foundation JISK6721-3.3 " bulk specific gravity " of vinylidene fluoride polymer powder measures.Specifically, fully stirred powdered sample is about 120ml and joins inserting after in the funnel of orifice valve of bulk specific gravity determinator, extract orifice valve rapidly, sample is fallen in susceptor.The sample glass stick of emerging from susceptor is wiped, then, weighs the quality adding the susceptor of sample exactly and be accurate to 0.1g, try to achieve tap density by following formula.
S＝(C-A)/B
S: tap density (g/cm
3)
A: the quality (g) of susceptor
B: the internal volume (cm of susceptor
3)
C: the quality (g) adding the susceptor of sample
Mensuration carries out 3 times, calculates mean value.For test-results, the 3rd that is measured to the numerical value of below radix point 3 is rounded up, comes to represent with rounding up.
(mensuration of suspended substance quality)
After being polymerized, draining is reclaimed in polymer paste centrifuge dehydration.Air permeability (JISL1096) is used to be 70cm when centrifuge dehydration
3/ cm
2the filter cloth of sec.For the draining obtained, the measuring method of the suspended matter recorded according to JISK0102 measures suspended substance quality, and the suspended substance quality this recorded is as suspended substance quality (SS).
(dirt settling on polymerization tank (autoclave))
After being polymerized, from polymerization tank, discharge polymer paste, after in running water polymerization tank, by visual observation polymkeric substance the wall of polymerization tank and on the attachment that covers.
(embodiment 1)
Be in the autoclave of 14.5 liters, drop into ion exchanged water 250 parts, methylcellulose gum 0.05 part, vinylidene 100 parts, peroxy dicarbonate di-n-propyl ester 0.6 part, ethyl acetate 1.0 parts, citric acid 0.03 part, trisodium citrate 0.16 part at internal volume, at 26 DEG C, carry out suspension polymerization, the time point being 92% at yield stops polymerization.
After being polymerized, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.By the polymkeric substance redispersion in water carrying out centrifuge dehydration, at 95 DEG C, thermal treatment is after 30 minutes, centrifuge dehydration, washing, at 80 DEG C dry 20 hours further, obtains vinylidene fluoride polymer powder.
(embodiment 2)
Make ethyl acetate be 2.7 parts, in addition, carry out similarly to Example 1.
(comparative example 1)
Be in the autoclave of 14.5 liters, drop into ion exchanged water 250 parts, methylcellulose gum 0.05 part, vinylidene 100 parts, peroxy dicarbonate di-n-propyl ester 0.6 part, ethyl acetate 1.4 parts, Sodium Acid Pyrophosphate 0.12 part, tetrasodium pyrophosphate 0.07 part at internal volume, at 26 DEG C, carry out suspension polymerization, the time point being 92% at yield stops polymerization.
After being polymerized, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.By the polymkeric substance redispersion in water carrying out centrifuge dehydration, at 95 DEG C, thermal treatment is after 30 minutes, centrifuge dehydration, washing, at 80 DEG C dry 20 hours further, obtains vinylidene fluoride polymer powder.
(comparative example 2)
Make ethyl acetate be 2.9 parts, in addition, carry out in the same manner as comparative example 1.The polymerizing condition of embodiment 1,2 and comparative example, the physical property of vinylidene based polymer that obtains are shown in table 1.
(embodiment 3)
Be in the autoclave of 14.5 liters, drop into ion exchanged water 250 parts, methylcellulose gum 0.05 part, vinylidene 100 parts, peroxy dicarbonate di-n-propyl ester 0.6 part, ethyl acetate 2.5 parts, citric acid 0.06 part, trisodium citrate 0.32 part at internal volume, at 26 DEG C, carry out suspension polymerization, the time point being 92% at yield stops polymerization.
After being polymerized, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.By the polymkeric substance redispersion in water carrying out centrifuge dehydration, at 95 DEG C, thermal treatment is after 30 minutes, centrifuge dehydration, washing, at 80 DEG C dry 20 hours further, obtains vinylidene fluoride polymer powder.
(embodiment 4)
Be in the autoclave of 14.5 liters, drop into ion exchanged water 250 parts, methylcellulose gum 0.05 part, vinylidene 100 parts, peroxy dicarbonate di-n-propyl ester 0.6 part, ethyl acetate 2.5 parts, citric acid 0.04 part, trisodium citrate 0.15 part at internal volume, at 26 DEG C, carry out suspension polymerization, the time point being 92% at yield stops polymerization.
After being polymerized, by polymer paste centrifuge dehydration, draining is for the mensuration of suspended substance quality.By the polymkeric substance redispersion in water carrying out centrifuge dehydration, at 95 DEG C, thermal treatment is after 30 minutes, centrifuge dehydration, washing, at 80 DEG C dry 20 hours further, obtains vinylidene fluoride polymer powder.
The polymerizing condition of embodiment 3,4, the physical property of vinylidene based polymer that obtains are shown in 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, and can reduce the attachment of polymkeric substance on polymerization tank skin, therefore productivity is excellent.
Claims (3)
1. the manufacture method of a vinylidene based polymer, monomer dispersion by every 100 % by mole of monomers being contained more than 50 % by mole vinylidenes containing in the aqueous medium of suspension agent, carry out the method that suspension polymerization manufactures vinylidene based polymer, it is characterized in that, described suspension polymerization is carried out under the existence of polycarboxylic acid and polycarboxylate
Wherein, described polycarboxylic acid is at least a kind of polycarboxylic acid be selected from oxalic acid, propanedioic acid, succsinic acid and citric acid, and described polycarboxylate is at least a kind of polycarboxylate be selected from oxalate, malonate, succinate and Citrate trianion,
Wherein, polycarboxylic acid: polycarboxylate take mass ratio range as 99:1 ~ 1:99.
2. the manufacture method of vinylidene based polymer according to claim 1, wherein, described polycarboxylic acid is citric acid, and described polycarboxylate is at least a kind of Citrate trianion be selected from Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate.
3. the manufacture method of vinylidene based polymer according to claim 1, wherein, described polycarboxylic acid is citric acid, and described polycarboxylate is Trisodium Citrate.
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| 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 |
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| JP2014040519A (en) | 2014-03-06 |
| JP5916562B2 (en) | 2016-05-11 |
| CN103626900A (en) | 2014-03-12 |
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