CN103601827A - Vinylidene fluoride polymer and preparation method thereof - Google Patents
Vinylidene fluoride polymer and preparation method thereof Download PDFInfo
- Publication number
- CN103601827A CN103601827A CN201310631285.4A CN201310631285A CN103601827A CN 103601827 A CN103601827 A CN 103601827A CN 201310631285 A CN201310631285 A CN 201310631285A CN 103601827 A CN103601827 A CN 103601827A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- powder
- polyvinylidene difluoride
- mixture
- weight ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a vinylidene fluoride polymer and a preparation method thereof. The vinylidene fluoride polymer has a melt flow index of 0.20-1.50 g/10 min (21.6 Kg, 230 DEG C), a thermal decomposition temperature of 420-450 DEG C, the volume density of 0.2-0.6 g/mL and the molecular weight distribution of 1.5-1.8. The polyvinylidene fluoride powder is prepared according to the following method: (i) adding a dispersant into a reaction container containing an initiator and a reaction medium, wherein the dispersant is a mixture of hydroxypropyl methyl cellulose and polyvinyl alcohol with a weight ratio of 0.5:1-1:0.5; and (ii) adding vinylidene fluoride monomer for polymerization.
Description
Technical field
The present invention relates to a kind of polyvinylidene difluoride (PVDF) powder, it has high heat decomposition temperature, high volume density and has low molecular weight distribution.The invention still further relates to the preparation method of described polyvinylidene difluoride (PVDF) powder.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) resin mainly refers to the multipolymer of vinylidene fluoride homopolymer or vinylidene and other a small amount of fluorine-containing vinyl monomers, polyvinylidene fluoride resin has the characteristic of fluoro-resin and resins for universal use concurrently, except having good chemical resistance, high thermal resistance, scale resistance, weathering resistance, resistance to x radiation x performance, also having the properties such as piezoelectricity, dielectricity, pyroelectricity, is the large product that in current fluoro-containing plastic, output is at the second place.
Vinylidene suspension polymerization system is mainly comprised of vinylidene fluoride monomers, dispersion agent, oil-soluble initiator, chain-transfer agent and 5 kinds of components of deionized water.The critical temperature of vinylidene fluoride monomers is 30.1 ℃, vinylidene suspension polymerization is carried out conventionally at a lower temperature, this just needs highly active initiator, and the highly active peroxycarbonates compounds such as di-isopropyl peroxydicarbonate (IPP), peroxy dicarbonate di-n-propyl ester are that the topmost initiator of polyvinylidene difluoride (PVDF) is prepared in industrial suspension polymerization.
The water soluble dispersing agent using in vinylidene suspension polymerization formula, is generally cellulose ethers and polyvinyl alcohol, as methylcellulose gum and Vltra tears etc.The Main Function of dispersion agent is:
1) be adsorbed on VDF monomer droplet surface, keep the stable of polymerization system;
2) prevent from occurring between polymer particle coalescence.
On resin particle size impact significantly, consumption is excessive for dispersant dosage, and resin particle is too thin.The dispersant dosage of general vinylidene suspension polymerization is monomer mass 0.01%～1%, and more suitable consumption is monomer mass 0.05%～0.4%.In vinylidene suspension polymerization process, must monomer droplet be spread out effectively by the dual function of dispersion agent and stirring, thereby guarantee the stable of polymerization process, and can not cause the problems such as sticky still, so the selection of dispersion agent be particularly important.
US Patent No. 5145921 discloses the dispersion agent HEMC(hydroxyethylmethyl-cellulose adopting) prepare the method for polyvinylidene fluoride resin, this method can reduce sticky still, thereby avoids impact to conduct heat, quality product and production efficiency etc.
Chinese patent CN101821298A discloses employing methylcellulose gum as dispersion agent, has obtained the polyvinylidene fluoride resin that tap density is less, be applicable to lithium cell binding agent.
This area still needs to develop a kind of polyvinylidene difluoride (PVDF) powder, and it has high heat decomposition temperature, high volume density and has low molecular weight distribution.
This area also needs to develop the preparation method of described polyvinylidene difluoride (PVDF) powder.
Summary of the invention
A goal of the invention of the present invention is to provide a kind of polyvinylidene difluoride (PVDF) powder, and it has high heat decomposition temperature, high volume density and has low molecular weight distribution.
Another goal of the invention of the present invention is to provide a kind of preparation method of described polyvinylidene difluoride (PVDF) powder.
Therefore, one aspect of the present invention relates to a kind of polyvinylidene difluoride (PVDF) powder, its melt flow index is 0.20-1.50g/10min(21.6kg, 230 ℃), heat decomposition temperature (1wt% heat decomposition temperature) for 420-450 ℃, volume density be that 0.2-0.6g/ml and molecular weight distribution are 1.5-1.8; This polyvinylidene difluoride (PVDF) powder is made by following method:
(i) in the reaction vessel that contains initiator and reaction medium, add dispersion agent; Described dispersion agent is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.5:1 to 1:0.5;
(ii) add vinylidene fluoride monomers to carry out polymerization.
Another aspect of the present invention relates to the polymerization process of vinylidene, and it comprises the steps:
(i) in the reaction vessel that contains initiator and reaction medium, add dispersion agent; Described dispersion agent is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.5:1 to 1:0.5;
(ii) add vinylidene fluoride monomers to carry out polymerization.
Embodiment
Temperature when in the present invention, term " heat decomposition temperature " refers to the polyvinylidene fluoride resin powder that decomposes 1% total mass.
Inventor's discovery, when using Vltra tears and high alcoholysis degree polyvinyl alcohol to carry out vinylidene suspension polymerization as composite dispersing agent, the thermostability of the polyvinylidene fluoride resin obtaining is very high, and molecular weight distribution is narrower.
Therefore, one aspect of the present invention relates to a kind of preparation method of vinylidene, and the method comprises the steps:
(i) in the reaction vessel that contains initiator and reaction medium, add dispersion agent
Initiator and consumption thereof for the inventive method are without particular limitation, can be any normal starter known in the art and consumption.In an example of the present invention, described initiator is selected from for example peroxy dicarbonate two C
1-6alkane ester, for example mixture of di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate diethyl ester, peroxy dicarbonate dibutylester or its two or more formation.
Reaction medium for polyreaction of the present invention is without particular limitation, can be any conventional polar reaction medium, and for example it can be water, alcohol or its mixture.From cost and toxicity angle, reaction medium is water preferably.
The dispersion agent that is applicable to polyreaction of the present invention is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.5:1 to 1:0.5, the mixture that better weight ratio is 0.6:1-1:0.6, the mixture that better weight ratio is 0.7:1-1:0.7, the mixture that preferably weight ratio is 0.8:1-1:0.8, the mixture that preferred weight ratio is 0.9:1-1:0.9 (below also referred to as mixed dispersant).
Applicable Vltra tears and polyvinyl alcohol are commercially available.In an example of the present invention, the alcoholysis degree of described polyvinyl alcohol is 80wt%-99%(mol/mol), 85-98%(mol/mol preferably), 88-98%(mol/mol more preferably) and, be preferably 90-98%(mol/mol), preferred 93-98%(mol/mol).
The amount of the mixed dispersant adding in reaction medium is without particular limitation, can be any convention amount known in the art.In an example of the present invention, by vinylidene fluoride monomers weighing scale, the add-on of described dispersion agent is 0.01-1%, is preferably 0.02-0.8%, 0.03-0.6% preferably, and more preferably 0.04-0.4%, is preferably 0.05-0.2%, preferably 0.07-0.1%.
In an example of the present invention, the inventive method also comprises in described reaction medium and adds chain-transfer agent.Applicable chain-transfer agent and add-on thereof are without particular limitation, can be that conventional chain-transfer agent known in the art and consumption are to meet required product requirement.In an example of the present invention, described chain-transfer agent is selected from C
2-6paraffinic acid two C
1-6alkane ester, such as diethyl malonate, dipropyl malonate, diethyl succinate, dipropyl succinate etc.
(ii) add vinylidene fluoride monomers to carry out polymerization
The inventive method also comprises the step that adds vinylidene fluoride monomers to carry out polymerization.
The temperature of polyreaction of the present invention is without particular limitation, can be any conventional polymerization temperature known in the art.In an example of the present invention, described polymerization is at 31-90 ℃, and 35-85 ℃, better at 40-70 ℃, preferably carries out at the temperature of 45-65 ℃ more fortunately.
It is without particular limitation that the present invention has the pressure of reaction, can be the polymerization pressure of any routine known in the art.In an example of the present invention, described polymerization pressure is 4.5-10MPa, preferably 5-9MPa, more preferably 5.5-8.5MPa, preferably 6-7MPa.
Polyreaction of the present invention is also included in polyreaction and finishes rear the polymer paste obtaining to be washed and dry step.Described washing and drying step are without particular limitation, can be any conventional washing known in the art and drying means.In an example of the present invention, described being dried is at 70-100 ℃, and 75-95 ℃, better at 80-90 ℃ of dry 8-15 hour, is better dried 9-12 hour, preferably dry 9.5-10.5 hour more fortunately.
In a better example of the present invention, polymerization process of the present invention comprises the steps: to add in autoclave polyvinyl alcohol, 0.2-0.8g di-isopropyl peroxydicarbonate, the 0.8-3g diethyl malonate that 1-2kg deionized water, 0.1-0.5g Vltra tears, 0.1-0.5g alcoholysis degree are 90-98%, under 50-80 ℃, 5-7MPa, carry out supercritical polymerization, when pressure reduces to 3MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 8-12 hour at 75-85 ℃.
The present invention is mainly by adopting Vltra tears and high alcoholysis degree polyvinyl alcohol as polymerization dispersion agent, in temperature, be greater than 30.1 ℃, pressure and carry out the polymerization of vinylidene under higher than 4.4MPa condition, thereby obtain the narrower polyvinylidene difluoride (PVDF) powder of high viscosity, high thermal stability and molecular weight distribution that tap density is 0.2～1.5g/ml and good fluidity.
The polyvinylidene difluoride (PVDF) powder making by the inventive method has following performance:
-melt flow index (21.6kg, 230 ℃) is 0.20-1.50g/10min, preferably 0.50-1.30g/10min, more preferably 0.70-1.10g/10min, preferably 0.80-1.00g/10min;
-heat decomposition temperature (1wt% heat decomposition temperature) is 420-450 ℃, preferably 430-440 ℃;
-volume density is 0.2-0.6g/ml, is preferably 0.25-0.55g/ml, preferably 0.3-0.5g/ml, more preferably 0.35-0.45g/ml, preferably 0.38-0.42g/ml; And
-molecular weight distribution is 1.5-1.8, preferably 1.55-1.75, more preferably 1.60-1.70.
embodiment
Below, by embodiment, illustrate in greater detail the present invention, but the present invention is not limited to these embodiment.
In an embodiment, use the performance of following method test polyvinylidene fluoride resin of the present invention:
With thermogravimetric analyzer (TGA), measure heat decomposition temperature (heat decomposition temperature is the temperature when decomposing 1% total mass);
With gel chromatograph (GPC), measure molecular weight and the molecular weight distribution of polymkeric substance;
With fusion index instrument, measure the melting index (melting index test condition is: load 21.6kg, 230 ℃ of temperature) of polymkeric substance;
With tap density instrument, measure the tap density of polyvinylidene difluoride (PVDF) powder.
embodiment 1
In the autoclave that is 2L to volume, add polyvinyl alcohol, 0.5g di-isopropyl peroxydicarbonate, 2g diethyl malonate that 1100g deionized water, 0.3g Vltra tears, 0.3g alcoholysis degree are 98%, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 3MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
embodiment 2
In the autoclave that is 2L to volume, add polyvinyl alcohol, 0.8g di-isopropyl peroxydicarbonate, 2g diethyl malonate that 1100g deionized water, 0.3g Vltra tears, 0.3g alcoholysis degree are 98%, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 3MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
embodiment 3
In the autoclave that is 2L to volume, add polyvinyl alcohol, 0.8g di-isopropyl peroxydicarbonate, 3g diethyl malonate that 1100g deionized water, 0.3g Vltra tears, 0.3g alcoholysis degree are 98%, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 2.5MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
embodiment 4
In the autoclave that is 2L to volume, add polyvinyl alcohol, 1.0g di-isopropyl peroxydicarbonate, 2g diethyl malonate that 1100g deionized water, 0.3g Vltra tears, 0.3g alcoholysis degree are 98%, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 2.5MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
comparative example 1
In the autoclave that is 2L to volume, add 1100g deionized water, 0.6g Vltra tears, 0.5g di-isopropyl peroxydicarbonate, 2g diethyl malonate, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 3MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
comparative example 2
In the autoclave that is 2L to volume, add 1100g deionized water, 0.6g Vltra tears, 0.8g di-isopropyl peroxydicarbonate, 3g diethyl malonate, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 2.5MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
comparative example 3
In the autoclave that is 2L to volume, add 1100g deionized water, 0.6g Vltra tears, 1.0g di-isopropyl peroxydicarbonate, 2g diethyl malonate, under 60 ℃, 6MPa, carry out supercritical polymerization, when pressure reduces to 2.5MPa, finish reaction.
After polymerization finishes, after polymer paste is washed, is dried, the dry polyvinylidene difluoride (PVDF) powder that obtains for 10 hours at 85 ℃.
The performance of measuring the polyvinylidene difluoride (PVDF) powder obtaining with aforesaid method, the results are shown in following table 1.
Table 1: partial fluorine ethylene polymer performance
Claims (10)
1. a polyvinylidene difluoride (PVDF) powder, its melt flow index is 0.20-1.50g/10min(21.6kg, 230 ℃), heat decomposition temperature is that 420-450 ℃, volume density are that 0.2-0.6g/ml and molecular weight distribution are 1.5-1.8; This polyvinylidene difluoride (PVDF) powder is made by following method:
(i) in the reaction vessel that contains initiator and reaction medium, add dispersion agent; Described dispersion agent is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.5:1 to 1:0.5;
(ii) add vinylidene fluoride monomers to carry out polymerization.
2. polyvinylidene difluoride (PVDF) powder as claimed in claim 1, its melt flow index is 0.50-1.30g/10min; Heat decomposition temperature is 430-440 ℃; Volume density is 0.25-0.55g/ml; And molecular weight distribution is 1.55-1.75.
3. polyvinylidene difluoride (PVDF) powder as claimed in claim 2, its melt flow index is 0.70-1.10g/10min, preferably 0.80-1.00g/10min;
Volume density is 0.3-0.5g/ml, more preferably 0.35-0.45g/ml, preferably 0.38-0.42g/ml; And
Molecular weight distribution is 1.60-1.70.
4. the polyvinylidene difluoride (PVDF) powder as described in any one in claim 1-3, it is characterized in that described dispersion agent is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.6:1-1:0.6, the mixture that better weight ratio is 0.7:1-1:0.7, the mixture that preferably weight ratio is 0.8:1-1:0.8, the mixture that preferred weight ratio is 0.9:1-1:0.9.
5. the polyvinylidene difluoride (PVDF) powder as described in any one in claim 1-3, the alcoholysis degree that it is characterized in that described polyvinyl alcohol is 80%-99mo l%, 85-98mol% preferably, more preferably 88-98mol%, is preferably 90-98mol%, preferably 93-98mol%.
6. the polyvinylidene difluoride (PVDF) powder as described in any one in claim 1-3, it is characterized in that by vinylidene fluoride monomers weighing scale, the add-on of described dispersion agent is 0.01-1%, be preferably 0.02-0.8%, 0.03-0.6% preferably, more preferably 0.04-0.4%, is preferably 0.05-0.2%, preferably 0.07-0.1%.
7. a preparation method for polyvinylidene difluoride (PVDF) powder, it comprises the steps:
(i) in the reaction vessel that contains initiator and reaction medium, add dispersion agent; Described dispersion agent is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.5:1 to 1:0.5;
(ii) add vinylidene fluoride monomers to carry out polymerization.
8. the preparation method of polyvinylidene difluoride (PVDF) powder as claimed in claim 7, it is characterized in that described dispersion agent is the mixture that Vltra tears and polyvinyl alcohol weight ratio are 0.6:1-1:0.6, the mixture that better weight ratio is 0.7:1-1:0.7, the mixture that preferably weight ratio is 0.8:1-1:0.8, the mixture that preferred weight ratio is 0.9:1-1:0.9.
9. the preparation method of the polyvinylidene difluoride (PVDF) powder as described in any one in claim 7-8, the alcoholysis degree that it is characterized in that described polyvinyl alcohol is 80%-99mol%, preferably 85-98mol%, more preferably 88-98mol%, be preferably 90-98mol%, preferably 93-98mol%.
10. the preparation method of the polyvinylidene difluoride (PVDF) powder as described in any one in claim 7-8, it is characterized in that by vinylidene fluoride monomers weighing scale, the add-on of described dispersion agent is 0.01-1%, be preferably 0.02-0.8%, 0.03-0.6% preferably, more preferably 0.04-0.4%, is preferably 0.05-0.2%, preferably 0.07-0.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310631285.4A CN103601827B (en) | 2013-12-02 | 2013-12-02 | Partial fluorine ethylene polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310631285.4A CN103601827B (en) | 2013-12-02 | 2013-12-02 | Partial fluorine ethylene polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103601827A true CN103601827A (en) | 2014-02-26 |
| CN103601827B CN103601827B (en) | 2016-04-27 |
Family
ID=50120100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310631285.4A Active CN103601827B (en) | 2013-12-02 | 2013-12-02 | Partial fluorine ethylene polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103601827B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448076A (en) * | 2014-12-06 | 2015-03-25 | 常熟丽源膜科技有限公司 | Production method of polyvinylidene fluoride |
| CN105924554A (en) * | 2016-06-12 | 2016-09-07 | 巨化集团技术中心 | Preparation method of polyvinylidene fluoride resin |
| CN109456434A (en) * | 2018-12-26 | 2019-03-12 | 内蒙古三爱富万豪氟化工有限公司 | Polyvinylidene fluoride resin preparation method and consersion unit |
| CN111040059A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | High alkali-resistant 1, 1-difluoroethylene polymer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283302A (en) * | 1991-08-01 | 1994-02-01 | Kureha Chemical Industry Co., Ltd. | Vinylidene fluoride polymer and method of making same |
| CN1583809A (en) * | 2004-06-09 | 2005-02-23 | 上海三爱富新材料股份有限公司 | Vinylidene polyme and preparing method thereof |
| CN101735374A (en) * | 2009-12-15 | 2010-06-16 | 上海三爱富新材料股份有限公司 | Preparation method of vinylidene fluoride copolymer resin |
-
2013
- 2013-12-02 CN CN201310631285.4A patent/CN103601827B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283302A (en) * | 1991-08-01 | 1994-02-01 | Kureha Chemical Industry Co., Ltd. | Vinylidene fluoride polymer and method of making same |
| CN1583809A (en) * | 2004-06-09 | 2005-02-23 | 上海三爱富新材料股份有限公司 | Vinylidene polyme and preparing method thereof |
| CN101735374A (en) * | 2009-12-15 | 2010-06-16 | 上海三爱富新材料股份有限公司 | Preparation method of vinylidene fluoride copolymer resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448076A (en) * | 2014-12-06 | 2015-03-25 | 常熟丽源膜科技有限公司 | Production method of polyvinylidene fluoride |
| CN105924554A (en) * | 2016-06-12 | 2016-09-07 | 巨化集团技术中心 | Preparation method of polyvinylidene fluoride resin |
| CN105924554B (en) * | 2016-06-12 | 2018-12-25 | 巨化集团技术中心 | A kind of preparation method of polyvinylidene fluoride resin |
| CN109456434A (en) * | 2018-12-26 | 2019-03-12 | 内蒙古三爱富万豪氟化工有限公司 | Polyvinylidene fluoride resin preparation method and consersion unit |
| CN109456434B (en) * | 2018-12-26 | 2023-08-08 | 内蒙古三爱富万豪氟化工有限公司 | Polyvinylidene fluoride resin preparation method and reaction equipment |
| CN111040059A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | High alkali-resistant 1, 1-difluoroethylene polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103601827B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103601827B (en) | Partial fluorine ethylene polymer and preparation method thereof | |
| EP3285316B1 (en) | Electrode structure and method for manufacturing same | |
| CN102336854B (en) | Preparation method for high heat resistance polyvinylidene fluoride | |
| CN106103508A (en) | Vinylidene fluoride analog copolymer, its manufacture method, gel electrolyte and non-aqueous class battery | |
| US11133506B2 (en) | Binder composition, electrode mixture, electrode, and non-aqueous electrolyte secondary battery | |
| CN101735374B (en) | Preparation method of vinylidene fluoride copolymer resin | |
| KR102362769B1 (en) | Binder composition, electrode mixture, electrode, non-aqueous electrolyte secondary battery, and binder composition production method | |
| CN101072801A (en) | Vinylidene fluoride polymer and process for producing the same | |
| CN103588922A (en) | Vinylidene fluoride copolymer, and preparation method and application thereof | |
| US11643486B1 (en) | Non-linear vinylidene fluoride copolymers | |
| CN104725545A (en) | Novel high-cohesiveness vinylidene fluoride copolymer | |
| JP2017059527A (en) | Binder composition for secondary battery electrode, secondary battery electrode, and secondary battery | |
| CN104725544B (en) | A kind of high-adhesion vinylidene fluoride copolymers | |
| CN106674412B (en) | A kind of 1,1- fluoride polymer and preparation method thereof | |
| US11329288B2 (en) | Secondary battery negative electrode binder composition, secondary battery negative electrode, and secondary battery | |
| CN114940721A (en) | Modified polyvinylidene fluoride dispersion liquid and preparation method and application thereof | |
| CN102585078B (en) | Vinylidene fluoride copolymer used as solar back panel film and preparation method of vinylidene fluoride copolymer | |
| CN102718915B (en) | Method for making 1,1-difluoroethylene polymer | |
| CN106380533B (en) | A kind of polyvinylidene fluoride polymer and preparation method thereof | |
| CN110343211A (en) | A kind of polyvinylidene fluoride copolymer resin and preparation method thereof | |
| CN104710550A (en) | High molecular weight polyvinylidene fluoride resin and preparation method thereof | |
| CN114989344B (en) | Vinylidene fluoride copolymer, preparation method thereof and application thereof in lithium ion battery | |
| JPH07179507A (en) | Production of vinyl chloride polymer | |
| CN103524647A (en) | Method for preparing polyvinylidene fluoride resin | |
| CN114920867B (en) | Vinylidene fluoride copolymer with controllable particle size distribution and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180801 Address after: 012100 Fengzhen City Industrial Park, Wulanchabu, the Inner Mongolia Autonomous Region Co-patentee after: Shanghai 3F new Mstar Technology Ltd Patentee after: Inner Mongolia 3F Wanhao Fluoro-chemical Co., Ltd. Address before: 012100 Fengzhen City Industrial Park, Wulanchabu, the Inner Mongolia Autonomous Region Co-patentee before: Sanaifu New Material Co., Ltd., Shanghai Patentee before: Inner Mongolia 3F Wanhao Fluoro-chemical Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 012100 Fengzhen Industrial Park, the Inner Mongolia Autonomous Region, Wulanchabu Patentee after: INNER MONGOLIA 3F WANHAO FLUORO CHEMICAL Co.,Ltd. Patentee after: Shanghai Huayi sanaifu New Material Co., Ltd Address before: 012100 Fengzhen Industrial Park, the Inner Mongolia Autonomous Region, Wulanchabu Patentee before: INNER MONGOLIA 3F WANHAO FLUORO CHEMICAL Co.,Ltd. Patentee before: SHANGHAI 3F NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |