CN103601827B - Partial fluorine ethylene polymer and preparation method thereof - Google Patents
Partial fluorine ethylene polymer and preparation method thereof Download PDFInfo
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Abstract
Disclose partial fluorine ethylene polymer and preparation method thereof, the melt flow index of described polyvinylidene difluoride (PVDF) powder is 0.20-1.50g/10min(21.6kg, 230 DEG C), heat decomposition temperature is 420-450 DEG C, volume density is 0.2-0.6g/ml and molecular weight distribution is 1.5-1.8; This polyvinylidene difluoride (PVDF) powder is obtained by following method: (i) in the reaction vessel containing initiator and reaction medium, add dispersion agent; The mixture of described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio be 0.5:1 to 1:0.5; (ii) add vinylidene fluoride monomers to be polymerized.
Description
Technical field
The present invention relates to a kind of polyvinylidene difluoride (PVDF) powder, it has high heat decomposition temperature, high volume density have 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 a small amount of fluorine-containing vinyl monomer of vinylidene fluoride homopolymer or vinylidene and other, polyvinylidene fluoride resin has the characteristic of fluoro-resin and resins for universal use concurrently, except there is 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 primarily of vinylidene fluoride monomers, dispersion agent, oil-soluble initiator, chain-transfer agent and deionized water 5 kinds of component compositions.The critical temperature of vinylidene fluoride monomers is 30.1 DEG C, vinylidene suspension polymerization is carried out usually 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 used 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, between polymer particle, coalescence occurs.
On resin particle size impact significantly, consumption is excessive, and resin particle is then too thin for dispersant dosage.The dispersant dosage of general vinylidene suspension polymerization is 0.01% ~ 1% of monomer mass, and more suitable consumption is 0.05% ~ 0.4% of monomer mass.In vinylidene suspension polymerization, must, by the dual function of dispersion agent and stirring, monomer droplet be spread out effectively, thus ensure the stable of polymerization process, and can not cause the problems such as sticky still, therefore the selection of dispersion agent be particularly important.
US Patent No. 5145921 discloses the dispersion agent HEMC(hydroxyethylmethyl-cellulose of employing) prepare the method for polyvinylidene fluoride resin, this method can reduce sticky still, thus avoids impact heat transfer, quality product and production efficiency etc.
Chinese patent CN101821298A discloses and adopts methylcellulose gum as dispersion agent, obtains 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 have low molecular weight distribution.
This area also needs the preparation method developing 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 have 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 DEG C), heat decomposition temperature (1wt% heat decomposition temperature) is 420-450 DEG C, volume density is 0.2-0.6g/ml and molecular weight distribution is 1.5-1.8; This polyvinylidene difluoride (PVDF) powder is obtained by following method:
(i) in the reaction vessel containing initiator and reaction medium, add dispersion agent; The mixture of described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio be 0.5:1 to 1:0.5;
(ii) add vinylidene fluoride monomers to be polymerized.
Another aspect of the present invention relates to the polymerization process of vinylidene, and it comprises the steps:
(i) in the reaction vessel containing initiator and reaction medium, add dispersion agent; The mixture of described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio be 0.5:1 to 1:0.5;
(ii) add vinylidene fluoride monomers to be polymerized.
Embodiment
In the present invention, temperature when term " heat decomposition temperature " refers to the polyvinylidene fluoride resin powder of decomposition 1% total mass.
The present inventor finds, 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 obtained 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 containing initiator and reaction medium, add dispersion agent
For the initiator of the inventive method and consumption 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 such as peroxy dicarbonate two C
1-6alkane ester, such as di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate diethyl ester, peroxy dicarbonate dibutylester or its two or more mixtures formed.
Reaction medium for polyreaction of the present invention is without particular limitation, can be any conventional polar reaction medium, and such as it can be water, alcohol or its mixture.From cost and toxicity angle, good reaction medium is water.
The mixture of the dispersion agent being applicable to polyreaction of the present invention to be Vltra tears and polyvinyl alcohol weight ratio be 0.5:1 to 1:0.5, better weight ratio is the mixture of 0.6:1-1:0.6, better weight ratio is the mixture of 0.7:1-1:0.7, best weight ratio is the mixture of 0.8:1-1:0.8, and preferred weight ratio is the mixture (hereafter also referred to as mixed dispersant) of 0.9:1-1:0.9.
The Vltra tears be suitable for 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), preferably 85-98%(mol/mol), more preferably 88-98%(mol/mol) and, be preferably 90-98%(mol/mol), preferred 93-98%(mol/mol).
The amount of the mixed dispersant added 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%, preferably 0.03-0.6%, more preferably 0.04-0.4%, is preferably 0.05-0.2%, preferred 0.07-0.1%.
In an example of the present invention, the inventive method also comprises and add chain-transfer agent in described reaction medium.The chain-transfer agent be suitable for and add-on without particular limitation, can be that Conventional chain transfer agents 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 be polymerized
The inventive method also comprises the step adding vinylidene fluoride monomers and carry out being polymerized.
The temperature of polyreaction of the present invention is without particular limitation, can be any typical polymerization temperature known in the art.In an example of the present invention, described polymerization is at 31-90 DEG C, more fortunately 35-85 DEG C, better at 40-70 DEG C, carries out at the temperature of preferred 45-65 DEG C.
The pressure that the present invention has reaction is without particular limitation, 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, preferred 6-7MPa.
Polyreaction of the present invention is also included in polyreaction and terminates the step that the rear polymer paste to obtaining carries out washing and drying.Described washing and drying step without particular limitation, can be known in the art any routine washing and drying means.In an example of the present invention, described drying is at 70-100 DEG C, more fortunately 75-95 DEG C, better at 80-90 DEG C of dry 8-15 hour, and better dry 9-12 hour, best dry 9.5-10.5 hour.
In a better example of the present invention, polymerization process of the present invention comprises the steps: to add 1-2kg deionized water in autoclave, 0.1-0.5g Vltra tears, 0.1-0.5g alcoholysis degree are 90-98% polyvinyl alcohol, 0.2-0.8g di-isopropyl peroxydicarbonate, 0.8-3g diethyl malonate, 50-80 DEG C, carry out supercritical polymerization under 5-7MPa, when pressure reduces to 3MPa, terminate reaction.
After polymerization terminates, polymer paste is washed, after drying, dry 8-12 hour obtains polyvinylidene difluoride (PVDF) powder at 75-85 DEG C.
The present invention is mainly through adopting Vltra tears and high alcoholysis degree polyvinyl alcohol as polymerization dispersion agent, temperature be greater than 30.1 DEG C, pressure higher than 4.4MPa condition under carry out the polymerization of vinylidene, thus obtain tap density be 0.2 ~ 1.5g/ml and the high viscosity of good fluidity, high thermal stability and the narrower polyvinylidene difluoride (PVDF) powder of molecular weight distribution.
The polyvinylidene difluoride (PVDF) powder obtained by the inventive method has following performance:
-melt flow index (21.6kg, 230 DEG C) is 0.20-1.50g/10min, preferably 0.50-1.30g/10min, more preferably 0.70-1.10g/10min, preferred 0.80-1.00g/10min;
-heat decomposition temperature (1wt% heat decomposition temperature) is 420-450 DEG C, preferably 430-440 DEG C;
-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, preferred 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
, illustrate in greater detail the present invention by embodiment below, but the present invention is not limited to these embodiments.
In an embodiment, following method is used to test the performance of polyvinylidene fluoride resin of the present invention:
Heat decomposition temperature (heat decomposition temperature is the temperature when decomposition 1% total mass) is measured with thermogravimetric analyzer (TGA);
Molecular weight and the molecular weight distribution of polymkeric substance is measured with gel chromatograph (GPC);
The melting index (melting index test condition is: load 21.6kg, temperature 230 DEG C) of polymkeric substance is measured with fusion index instrument;
The tap density of polyvinylidene difluoride (PVDF) powder is measured with tap density instrument.
embodiment 1
To volume be add 1100g deionized water in the autoclave of 2L, 0.3g Vltra tears, 0.3g alcoholysis degree be 98% polyvinyl alcohol, 0.5g di-isopropyl peroxydicarbonate, 2g diethyl malonate, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 3MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained with aforesaid method, the results are shown in following table 1.
embodiment 2
To volume be add 1100g deionized water in the autoclave of 2L, 0.3g Vltra tears, 0.3g alcoholysis degree be 98% polyvinyl alcohol, 0.8g di-isopropyl peroxydicarbonate, 2g diethyl malonate, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 3MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained with aforesaid method, the results are shown in following table 1.
embodiment 3
To volume be add 1100g deionized water in the autoclave of 2L, 0.3g Vltra tears, 0.3g alcoholysis degree be 98% polyvinyl alcohol, 0.8g di-isopropyl peroxydicarbonate, 3g diethyl malonate, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 2.5MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained with aforesaid method, the results are shown in following table 1.
embodiment 4
To volume be add 1100g deionized water in the autoclave of 2L, 0.3g Vltra tears, 0.3g alcoholysis degree be 98% polyvinyl alcohol, 1.0g di-isopropyl peroxydicarbonate, 2g diethyl malonate, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 2.5MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained with aforesaid method, the results are shown in following table 1.
comparative example 1
Be add 1100g deionized water, 0.6g Vltra tears, 0.5g di-isopropyl peroxydicarbonate, 2g diethyl malonate in the autoclave of 2L to volume, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 3MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained with aforesaid method, the results are shown in following table 1.
comparative example 2
Be add 1100g deionized water, 0.6g Vltra tears, 0.8g di-isopropyl peroxydicarbonate, 3g diethyl malonate in the autoclave of 2L to volume, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 2.5MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained with aforesaid method, the results are shown in following table 1.
comparative example 3
Be add 1100g deionized water, 0.6g Vltra tears, 1.0g di-isopropyl peroxydicarbonate, 2g diethyl malonate in the autoclave of 2L to volume, 60 DEG C, carry out supercritical polymerization under 6MPa, when pressure reduces to 2.5MPa, terminate reaction.
After polymerization terminates, polymer paste washed, after drying, dryly at 85 DEG C within 10 hours, obtain polyvinylidene difluoride (PVDF) powder.
Measure the performance of the polyvinylidene difluoride (PVDF) powder obtained 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 DEG C), heat decomposition temperature is 420-450 DEG C, volume density is 0.2-0.6g/ml and molecular weight distribution is 1.5-1.8; This polyvinylidene difluoride (PVDF) powder is obtained by following method:
I () adds dispersion agent in the reaction vessel containing initiator and reaction medium; The mixture of described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio be 0.5:1 to 1:0.5, the alcoholysis degree of described polyvinyl alcohol is 88%-99mol%;
(ii) add vinylidene fluoride monomers to be polymerized.
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 DEG C; 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; Volume density is 0.3-0.5g/ml; And
Molecular weight distribution is 1.60-1.70.
4. the polyvinylidene difluoride (PVDF) powder according to any one of claim 1-3, is characterized in that described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio is the mixture of 0.6:1-1:0.6.
5. the polyvinylidene difluoride (PVDF) powder according to any one of claim 1-3, is characterized in that the alcoholysis degree of described polyvinyl alcohol is 90-98mol%.
6. the polyvinylidene difluoride (PVDF) powder according to any one of claim 1-3, is characterized in that by vinylidene fluoride monomers weighing scale, and the add-on of described dispersion agent is 0.01-1%.
7. a preparation method for polyvinylidene difluoride (PVDF) powder, it comprises the steps:
I () adds dispersion agent in the reaction vessel containing initiator and reaction medium; The mixture of described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio be 0.5:1 to 1:0.5, the alcoholysis degree of described polyvinyl alcohol is 88%-99mol%;
(ii) add vinylidene fluoride monomers to be polymerized.
8. the preparation method of polyvinylidene difluoride (PVDF) powder as claimed in claim 7, is characterized in that described dispersion agent to be Vltra tears and polyvinyl alcohol weight ratio is the mixture of 0.6:1-1:0.6.
9. the preparation method of the polyvinylidene difluoride (PVDF) powder according to any one of claim 7-8, is characterized in that the alcoholysis degree of described polyvinyl alcohol is 90-98mol%.
10. the preparation method of the polyvinylidene difluoride (PVDF) powder according to any one of claim 7-8, is characterized in that by vinylidene fluoride monomers weighing scale, and the add-on of described dispersion agent is 0.01-1%.
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| CN104448076A (en) * | 2014-12-06 | 2015-03-25 | 常熟丽源膜科技有限公司 | Production method of polyvinylidene fluoride |
| 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 |
| 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 |
| CN111040059B (en) * | 2019-12-31 | 2022-04-26 | 山东华夏神舟新材料有限公司 | High alkali-resistant 1, 1-difluoroethylene polymer and preparation method thereof |
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|---|---|---|---|---|
| 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 |
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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 |
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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. |