CN115651111B - Environment-friendly polyvinylidene fluoride resin and preparation method thereof - Google Patents
Environment-friendly polyvinylidene fluoride resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of environment-friendly polyvinylidene fluoride resin, which comprises the following steps: (1) Adding a dispersing agent, a chain transfer agent, an initiator and deionized water into a high-pressure reaction kettle; (2) Continuously adding vinylidene fluoride monomers after the temperature of the reaction kettle is raised to the polymerization temperature, suspending the addition of the vinylidene fluoride monomers after adding a certain proportion of the vinylidene fluoride monomers each time, and simultaneously adding cyclic ketene acetal monomers and tetrafluoroethylene with the same proportion as the vinylidene fluoride monomers; (3) Removing unreacted monomers after polymerization, washing, centrifuging and drying to obtain polyvinylidene fluoride resin; the degradability is improved by introducing hetero atoms into the main chain of the polyvinylidene fluoride resin, the performance attenuation of the polyvinylidene fluoride resin caused by introducing the hetero atoms is compensated by adding tetrafluoroethylene through a specific process, and the prepared polyvinylidene fluoride resin is environment-friendly and degradable and has excellent basic performance.
Description
Technical Field
The invention relates to the field of polymers, in particular to a method for preparing polyvinylidene fluoride resin
Background
Polyvinylidene fluoride (PVDF) resin refers to vinylidene fluoride (VDF) homopolymer or a copolymer of VDF and other small amount of fluorine-containing vinyl monomers, and the repeating units of the polyvinylidene fluoride (VDF) homopolymer or the copolymer are alternately arranged of-CH 2-CF2-, CH 2-and CF 2-groups, so that the PVDF resin has the characteristics of both fluorine resin and general resin. Besides good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance, ultraviolet resistance and radiation resistance, the PVDF resin has special properties such as piezoelectricity and thermoelectric property, and meanwhile, compared with polytetrafluoroethylene, the PVDF resin has better processing property and can be molded by various methods such as injection, extrusion, mould pressing, blow molding and pouring, and the main products are plates, pipes, bars, films, pumps, valves, fillers and the like. The polyvinylidene fluoride resin has wide application in the fields of chemical industry, electronic and electric industry, construction, military industry and the like, and has wide development and utilization prospects.
Along with the rapid increase of the usage amount of the polyvinylidene fluoride resin, how to treat the waste after the use is related to environmental protection and sustainable development of human beings, a large amount of polyvinylidene fluoride resin remains in the soil layer of the ocean or cultivated land, so that the ecological environment of human beings is seriously polluted, if the polymer garbage is treated by burying, burning and other methods, the defects are present, and the problem of the polymer garbage can be better solved by adopting the degradable resin.
The invention does not fundamentally realize the degradation of the polyvinylidene fluoride resin because the degradation is limited to the added cellulose and the polyvinylidene fluoride which is the main component is still not degradable.
In conclusion, how to improve the degradability of the polyvinylidene fluoride resin on the basis of maintaining the performance of the polyvinylidene fluoride resin is of great importance to realize environmental protection and no pollution. The invention adopts the technology of introducing degradable groups into the polymer chain of the polyvinylidene fluoride resin to realize degradability, and simultaneously, tetrafluoroethylene is added through a specific technology to compensate the performance attenuation caused by the introduction of the degradable groups, so that the polyvinylidene fluoride resin with excellent performance and degradability is finally obtained.
Disclosure of Invention
The invention aims to provide a preparation method of environment-friendly polyvinylidene fluoride resin, which adopts a process of introducing degradable groups into a polymer chain of the polyvinylidene fluoride resin to realize degradability, and simultaneously, tetrafluoroethylene is added through a specific process to compensate for performance attenuation caused by the introduction of the degradable groups, so that the polyvinylidene fluoride resin with excellent performance and degradability is finally obtained.
In order to solve the problems in the prior art, the invention provides a preparation method of environment-friendly polyvinylidene fluoride resin, which comprises the following steps:
(1) Adding a dispersing agent, a chain transfer agent, an initiator and deionized water into a high-pressure reaction kettle;
(2) Continuously adding vinylidene fluoride monomers after the temperature of the reaction kettle is raised to the polymerization temperature, suspending the addition of the vinylidene fluoride monomers after adding a certain proportion (X%) of the vinylidene fluoride monomers, and simultaneously adding cyclic ketene acetal monomers and tetrafluoroethylene with the same proportion (X%) of the vinylidene fluoride monomers;
(3) And removing unreacted monomers after polymerization, and washing, centrifuging and drying to obtain the polyvinylidene fluoride resin.
In the invention, the dispersing agent in the step (1) is one or more of methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose and polyethylene glycol 600, and the adding amount of the dispersing agent is 0.18-0.45wt% of vinylidene fluoride monomer.
In the invention, the chain transfer agent in the step (1) is one or more of dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, octanyl mercaptan, acetone, ethyl propionate, butyl propionate, diethyl malonate, ethyl acetate and butyl acetate, and the dosage of the chain transfer agent is 0.25-0.52 wt% of vinylidene fluoride monomer.
In the invention, the initiator in the step (1) is one or more of dibenzoyl peroxide, diethyl peroxide, diisopropyl peroxide, di-n-propyl peroxide, di-tert-butyl peroxide and tert-butyl peroxide pivalate, and the use amount of the initiator is 0.16-0.46 wt% of vinylidene fluoride monomer.
In the invention, the dosage of the deionized water in the step (1) is 1.2-2.5 times of that of the vinylidene fluoride monomer.
In the present invention, the suspension polymerization temperature in step (2) is 32 to 55℃and preferably 38 to 52 ℃.
In the invention, after the vinylidene fluoride monomer is added in a certain proportion in the step (2), the vinylidene fluoride is stopped being added to be X percent of the total amount of the vinylidene fluoride, and the X percent range is as follows: 4-8%.
In the invention, the cyclic enone acetal monomer in the step (2) is one of 5, 6-benzo-2-methylene-1, 3-dioxepane (BMDO), 2-methylene-4 phenyl-1, 3-dioxolane (MPDL) and 2-methylene-1, 3-dioxepane (MDO), and the cyclic enone acetal monomer is 2.0-3.7% of vinylidene fluoride monomer; the adding amount of the tetrafluoroethylene is 2-3.2 times of that of the cyclic ketene acetal monomer, the cyclic ketene acetal monomer and the tetrafluoroethylene are added after being premixed, and the adding amount of each time of the cyclic ketene acetal monomer and the tetrafluoroethylene is X% of the total amount, and the value is consistent with the X% of the adding proportion value of the vinylidene fluoride each time.
The invention also provides the polyvinylidene fluoride resin prepared by the preparation method.
The invention has the beneficial effects that: the invention provides an environment-friendly polyvinylidene fluoride resin preparation method, which can degrade polyvinylidene fluoride resin and has better product performance. The polyvinylidene fluoride resin has compact arrangement among molecular chains, and the main chain is a carbon chain, and the molecular weight is tens or even millions, so that the resin has excellent performance and is not easy to degrade. CF 2-and CH2 are alternately arranged in a polyvinylidene fluoride molecular chain, CF 2-groups are spirally distributed on the periphery of a molecular main chain, and an effective shielding effect is formed on a resin structure, so that degradation caused by outdoor environment, such as photocatalysis, oxidization, pulverization, cracking, air pollution, contamination and the like, can be resisted, and the product performance can be additionally enhanced by adjusting the density of the CF 2-groups.
The inventor can introduce degradable group ester bond into resin after copolymerizing cyclic ketene acetal and vinylidene fluoride monomer, greatly improve the degradability, solve the problem how to treat the waste vinylidene fluoride resin, and add a certain proportion of tetrafluoroethylene to improve the density of CF 2-groups around the degradable group when adding cyclic ketene acetal, thereby improving the problem of poor local performance caused by the introduction of the degradable group. Finally, the polyvinylidene fluoride resin which is degradable and has better product performance is prepared.
Detailed Description
The process according to the invention is further illustrated by the following specific examples, but the invention is not limited to the examples listed but encompasses any other known modifications within the scope of the claims.
The main test method is as follows:
1. degradability of
The test method refers to ISO 17556, a certain amount of polyvinylidene fluoride resin samples are taken and placed in soil for test for 3 months, and the degradation proportion is calculated.
2. Bond strength
The adhesive strength of the polymers after preparation into electrodes was determined according to IS04624 standard (adhesion pull-off test). The preparation process of the electrode is as follows: 1g of the resin produced in example 1 was dissolved in 50g of NMP at room temperature under mechanical stirring. 2g of conductive carbon black and 30g of lithium cobalt oxide (LiCo 02) were added with stirring, and thoroughly mixed to ensure uniformity. Then the mixture was degassed under vacuum and spread on an aluminum foil with a doctor blade, finally the aluminum foil on which the electrode material mixture was spread was placed in a vacuum oven and dried for 12 hours at 60 ℃ to prepare an electrode sheet. And measuring the bonding strength of the electrode material on the electrode plate by using an INSTRON tensile machine measuring instrument.
The main raw material information is as follows:
vinylidene fluoride: vanhua chemical group Co., ltd., industrial products;
tetrafluoroethylene: beijing enokie, industrial product;
dodecyl mercaptan: sigma, analytically pure;
butyl propionate: sigma, analytically pure;
hydroxypropyl methylcellulose: aladine, analytically pure;
methylcellulose: aladine, analytically pure;
5, 6-benzo-2-methylene-1, 3-dioxepane: beijing enokie, analytically pure;
2-methylene-1, 3-dioxepane: beijing enokie, analytically pure;
2-methylene-4 phenyl-1, 3-dioxolane: beijing enokie, analytically pure;
tert-butyl peroxypivalate: beijing enokie, analytically pure;
diisopropyl peroxydicarbonate: zibo Red chemical Co., ltd.
Example 1
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate, and then heating to the reaction temperature of 46 ℃, continuously adding 1100g of vinylidene fluoride monomer into the reaction kettle at a flow rate of 3.67g/min, suspending the addition after each 4.5% of vinylidene fluoride is added, and simultaneously adding 1.04g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 2.08g of tetrafluoroethylene during suspension, and adding 23.1g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 46.2g of tetrafluoroethylene. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Example 2
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water is added into a reaction kettle, 4.73g of dispersant hydroxypropyl methylcellulose, 5.5g of chain transfer agent butyl propionate, 3.41g of initiator diisopropyl peroxydicarbonate are added, the temperature is raised to 52 ℃ after that, then 1100g of vinylidene fluoride monomer is continuously added into the kettle at a flow rate of 3.67g/min, the addition is suspended after 5.6% of vinylidene fluoride is added, 2.16g of 2-methylene-1, 3-dioxepane and 6.68g of tetrafluoroethylene are simultaneously added during suspension, and 38.5g of 2-methylene-1, 3-dioxepane and 119.4g of tetrafluoroethylene are added. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Example 3
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate, and then heating to the reaction temperature of 46 ℃, continuously adding 1100g of vinylidene fluoride monomer into the reaction kettle at a flow rate of 3.67g/min, suspending the addition after each 7.8% of vinylidene fluoride is added, and simultaneously adding 2.23g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 6.02g of tetrafluoroethylene during suspension, and adding 28.6g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 77.22g of tetrafluoroethylene. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Example 4
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. Adding 2090g of deionized water into a reaction kettle, adding 2.86g of dispersing agent methyl cellulose, 4.62g of chain transfer agent butyl propionate, adding 2.75g of initiator tert-butyl peroxypivalate, heating to the reaction temperature of 50 ℃, continuously adding 1100g of vinylidene fluoride monomer into the kettle at a flow rate of 3.67g/min, suspending the addition after adding 4% of vinylidene fluoride, simultaneously adding 1.06g of 2-methylene-4 phenyl-1, 3-dioxolane and 2.53g of tetrafluoroethylene during suspension, and adding 26.4g of 2-methylene-4 phenyl-1, 3-dioxolane and 63.36g of tetrafluoroethylene. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Comparative example 1
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate, and then heating to the reaction temperature of 46 ℃ are added into a reaction kettle, and then the vinylidene fluoride monomer is continuously added into the kettle at the flow rate of 3.67g/min, and the total amount of the vinylidene fluoride monomer is 1100 g. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Comparative example 2
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate, and 23.1g of 5, 6-benzo-2-methylene-1, 3-dioxepane are simultaneously added during suspension, wherein the reaction temperature is raised to 46 ℃, then 1100g of vinylidene fluoride monomer is continuously added into the reaction kettle at a flow rate of 3.67g/min, and the addition is suspended after each 4.5% of vinylidene fluoride is added. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Comparative example 3
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate and then heating to the reaction temperature of 46 ℃, 1100g of vinylidene fluoride monomer, 23.1g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 46.2g of tetrafluoroethylene are added into a reaction kettle at one time, the temperature is reduced after the reaction is carried out for 5 hours, and the product is filtered, washed and dried to obtain the polyvinylidene fluoride resin.
Comparative example 4
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate, and 58.3g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 4.62g of tetrafluoroethylene are simultaneously added during suspension, and 256.5g of tetrafluoroethylene are added after adding 1100g of vinylidene fluoride monomer and suspending after adding 1.8% of vinylidene fluoride. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
Comparative example 5
The experiment was performed in a 5L reactor equipped with a stirrer, the reactor was evacuated and then filled with nitrogen to positive pressure, and the experiment was started after several cycles of testing the oxygen content in the reactor below 20 ppm. 1800g of deionized water, 2.09g of dispersing agent methyl cellulose, 3.19g of chain transfer agent dodecyl mercaptan, 4.84g of initiator tert-butyl peroxypivalate, and then heating to the reaction temperature of 46 ℃, continuously adding 1100g of vinylidene fluoride monomer into the reaction kettle at a flow rate of 3.67g/min, suspending the addition after each 14% of vinylidene fluoride is added, simultaneously adding 1.39g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 1.11g of tetrafluoroethylene during suspension, and adding 9.9g of 5, 6-benzo-2-methylene-1, 3-dioxepane and 7.9g of tetrafluoroethylene. And (3) cooling after reacting for 5 hours, and filtering, washing and drying the product to obtain the polyvinylidene fluoride resin.
The properties of the super absorbent resins obtained in the above examples and comparative examples are shown in Table 1 below:
table 1 example and comparative example performance parameters
| Degradation ratio | Bond Strength (N/m) | |
| Example 1 | 5.4％ | 35 |
| Example 2 | 5.0％ | 36 |
| Example 3 | 6.1％ | 39 |
| Example 4 | 5.5％ | 39 |
| Comparative example 1 | 0.6％ | 31 |
| Comparative example 2 | 5.20％ | 22 |
| Comparative example 3 | 1.8％ | 27 |
| Comparative example 4 | 7.3％ | 13 |
| Comparative example 5 | 0.9％ | 29 |
As can be seen from the table, the polyvinylidene fluoride resin prepared by adopting the method of introducing the degradable group and the tetrafluoroethylene by adopting the specific process has better degradability and better product performance.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (8)
1. The preparation method of the environment-friendly polyvinylidene fluoride resin comprises the following steps:
(1) Adding a dispersing agent, a chain transfer agent, an initiator and deionized water into a high-pressure reaction kettle;
(2) Continuously adding vinylidene fluoride monomers after the temperature of the reaction kettle is raised to the polymerization temperature, suspending the addition of the vinylidene fluoride monomers after adding a certain proportion of the vinylidene fluoride monomers each time, and simultaneously adding a cyclic enone acetal monomer and tetrafluoroethylene;
(3) Removing unreacted monomers after polymerization, washing, centrifuging and drying to obtain polyvinylidene fluoride resin;
and (2) after adding a certain proportion of vinylidene fluoride monomers, suspending the addition of the vinylidene fluoride, wherein the amount of the vinylidene fluoride monomers added each time is X% of the total amount of the vinylidene fluoride, and the range of X% is as follows: 4-8%;
the dosage of the cyclic enone-containing acetal monomer is 2.0-3.7% of that of the vinylidene fluoride monomer; the adding amount of the tetrafluoroethylene is 2-3.2 times of that of the monomer containing the cyclic ketene acetal; the addition amount of each time of the cycloolefin-containing ketone acetal monomer and the tetrafluoroethylene is X% of the total amount of each time, and the addition amount is consistent with the addition ratio value X% of the vinylidene fluoride.
2. The preparation method according to claim 1, wherein the dispersing agent in the step (1) is one or more of methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose and polyethylene glycol 600, and the adding amount of the dispersing agent is 0.18-0.45wt% of vinylidene fluoride monomer.
3. The process according to claim 1, wherein the chain transfer agent in the step (1) is one or more of dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, octanethiol, acetone, ethyl propionate, butyl propionate, diethyl malonate, ethyl acetate, and butyl acetate, and the amount of the chain transfer agent is 0.25% by weight and 0.52% by weight of vinylidene fluoride monomer.
4. A process according to any one of claims 1 to 3, wherein the initiator in step (1) is one or more of dibenzoyl peroxide, diethyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-t-butyl peroxide, t-butyl peroxypivalate, and the initiator is used in an amount of 0.16-0.46 wt% of vinylidene fluoride monomer.
5. A process according to any one of claims 1 to 3, wherein the polymerization temperature in step (2) is from 32 to 55 ℃.
6. The process according to claim 5, wherein the polymerization temperature in step (2) is 38 to 52 ℃.
7. The method of any one of claims 1-3, wherein the cyclic enone acetal-containing monomer in step (2) is one of 5, 6-benzo-2-methylene-1, 3-dioxepan (BMDO), 2-methylene-4 phenyl-1, 3-dioxepan (MPDL), 2-methylene-1, 3-dioxepan (MDO).
8. A polyvinylidene fluoride resin produced by the production method according to any one of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136219A (en) * | 1992-10-23 | 1994-05-17 | Shin Etsu Chem Co Ltd | Vinylidene fluoride-based resin film and composition for forming thereof |
| CN110061175A (en) * | 2019-04-26 | 2019-07-26 | 东莞东阳光科研发有限公司 | Lithium battery, lithium battery diaphragm and preparation method thereof |
| CN111303326A (en) * | 2020-04-09 | 2020-06-19 | 中国科学技术大学 | Polyolefin material with controllable degradation units and high monomer utilization rate and preparation method thereof |
| CN114989344A (en) * | 2022-06-14 | 2022-09-02 | 万华化学集团股份有限公司 | Vinylidene fluoride copolymer, preparation method thereof and application thereof in lithium ion battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136219A (en) * | 1992-10-23 | 1994-05-17 | Shin Etsu Chem Co Ltd | Vinylidene fluoride-based resin film and composition for forming thereof |
| CN110061175A (en) * | 2019-04-26 | 2019-07-26 | 东莞东阳光科研发有限公司 | Lithium battery, lithium battery diaphragm and preparation method thereof |
| CN111303326A (en) * | 2020-04-09 | 2020-06-19 | 中国科学技术大学 | Polyolefin material with controllable degradation units and high monomer utilization rate and preparation method thereof |
| CN114989344A (en) * | 2022-06-14 | 2022-09-02 | 万华化学集团股份有限公司 | Vinylidene fluoride copolymer, preparation method thereof and application thereof in lithium ion battery |
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