CN107540790B - Method for preparing PVDF amphiphilic polymer based on ATRP method - Google Patents
Method for preparing PVDF amphiphilic polymer based on ATRP method Download PDFInfo
- Publication number
- CN107540790B CN107540790B CN201710752121.5A CN201710752121A CN107540790B CN 107540790 B CN107540790 B CN 107540790B CN 201710752121 A CN201710752121 A CN 201710752121A CN 107540790 B CN107540790 B CN 107540790B
- Authority
- CN
- China
- Prior art keywords
- pvdf
- atrp
- amphiphilic polymer
- preparing
- solution
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A method for preparing PVDF amphiphilic polymer based on ATRP method belongs to the field of amphiphilic polymer preparation. The method comprises the following steps: preparing a PVDF solution; adding a tertiary amine substance BDMA or DMP-30; adding CuCl; adding NVP; heating for reaction; and (4) defoaming the product, cooling to room temperature, and purifying the product by adopting a non-solvent induced phase separation method. According to the invention, tertiary amine substances BDMA and DMP-30 are taken as ligands, and N is connected with electron donating groups, so that the N has strong electronegativity and good coordination effect, and is taken as a ligand to form a complex with CuCl, and the complex is applied to an ATRP method to prepare PVDF amphiphilic polymer, thereby achieving the purpose of controllable reaction activity. BDMA and DMP-30, relatively speaking, the preparation is simpler and more convenient, the price is low, the effect of serving as the ligand of ATRP is good, and the method is suitable for industrial application.
Description
Technical Field
The invention belongs to the field of preparation of amphiphilic polymers, and particularly relates to a method for preparing a PVDF amphiphilic polymer based on an ATRP method.
Background
Fluorine-containing materials such as polyvinylidene fluoride (PVDF) have high bond energy of C-F bonds in the structure, so that the fluorine-containing materials have good chemical stability, thermal stability, mechanical property and film-forming property, and are widely applied. The PVDF material has strong hydrophobicity due to higher bond energy, so that the PVDF material is easy to adsorb proteins, organic substances and the like in the application process of an aqueous medium, the pollution is caused to the material, the exertion of the good performance of the material is influenced, and the service life of the PVDF material is shortened. Hydrophilic modification of PVDF materials is therefore essential. At present, the modification of PVDF materials mainly focuses on the surface modification of finished products, and the bulk of the PVDF materials is not modified in a hydrophilic mode. The PVDF raw material is modified, so that the hydrophilicity and the pollution resistance of the PVDF can be fundamentally improved, the compatibility of the PVDF raw material and a solvent is improved, and Atom Transfer Radical Polymerization (ATRP) is widely applied to modification research of the PVDF material due to the controllability of the ATRP on a grafting reaction and the advantage that a secondary fluorine atom on the PVDF can be directly used as a macromolecular initiator.
Disclosure of Invention
The invention aims to solve the problems of poor hydrophilicity, stain resistance and solvent compatibility of PVDF in the prior art, and provides a method for preparing PVDF amphiphilic polymer based on an ATRP method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing PVDF amphiphilic polymer based on ATRP method comprises the following steps:
the method comprises the following steps: preparing a PVDF solution with the mass fraction of 1-25% by taking NMP as a solvent, N2Heating in water bath to 25-80 deg.C under protection, and mechanically stirring to mix the solution uniformly;
step two: cooling the solution prepared in the step one to room temperature, adding a tertiary amine substance according to a certain proportion to ensure that the mass fraction of the tertiary amine substance in PVDF is 3-20%, and N2Stirring for 5-20 min under protection to mix the solution uniformly;
step three: adding a certain proportion of CuCl into the solution obtained in the second step at room temperature to ensure that the added CuCl accounts for 0.5-10% of the mass fraction of PVDF and N2Stirring for 5-20 min under protection to mix the solution uniformly;
step four: adding a certain proportion of NVP into the solution obtained in the third step at room temperature to enable PVDF: the mass ratio of NVP is 1: 10-10: 1, N2Stirring for 10-40 min under protection to mix the solution uniformly;
step five: in N2Under the protection and mechanical stirring, heating the solution obtained in the fourth step to 60-100 ℃ to graft NVP onto PVDF by an ATRP method, and reacting for 2-24 hours;
step six: and (5) defoaming and cooling the product PVDF-g-PVP in the step five to room temperature, and purifying the product by using water by adopting a non-solvent induced phase separation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, tertiary amine substances BDMA and DMP-30 are respectively used as ligands, and N is connected with electron donating groups, so that the N has strong electronegativity and good coordination effect, and is used as a ligand to form a complex with CuCl, and the complex is applied to an ATRP method to prepare PVDF amphiphilic polymer, thereby achieving the purpose of controllable reaction activity.
The preparation method of the PVDF amphiphilic polymer based on the ATRP method and taking tertiary amine substances BDMA and DMP-30 as ligands enables the modified PVDF material to have good hydrophilicity.
Tertiary amine substances BDMA and DMP-30 are relatively simple and convenient to prepare, low in price, good in effect as ligands of ATRP, and suitable for industrial application.
Drawings
FIG. 1 is an IR spectrum of PVDF-g-PVP and PVDF as raw materials obtained in example 1;
FIG. 2 is a graph showing the water contact angle of PVDF-g-PVP prepared in example 1 and PVDF as a raw material;
FIG. 3 is an IR spectrum of PVDF-g-PVP' prepared in comparative example 1, PVDF-g-PVP prepared in example 1 and PVDF as raw material;
FIG. 4 is a graph showing the water contact angle of PVDF-g-PVP' obtained in comparative example 1, PVDF-g-PVP obtained in example 1 and PVDF as a raw material.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The first embodiment is as follows: the embodiment describes a method for preparing a PVDF amphiphilic polymer based on an ATRP method, which comprises the following specific steps:
the method comprises the following steps: preparing a PVDF solution with the mass fraction of 1-25% by taking NMP as a solvent, N2Heating in water bath to 25-80 deg.C under protection, and mechanically stirring to mix the solution uniformly;
step two: cooling the solution prepared in the step one to room temperature, adding a tertiary amine substance according to a certain proportion to ensure that the mass fraction of the tertiary amine substance in PVDF is 3-20%, and N2Stirring for 5-20 min under protection to mix the solution uniformly;
step three: adding a certain proportion of CuCl into the solution obtained in the second step at room temperature to ensure that the added CuCl accounts for 0.5-10% of the mass fraction of PVDF and N2Stirring for 5-20 min under protection to mix the solution uniformly;
step four: adding a certain proportion of NVP into the solution obtained in the third step at room temperature to enable PVDF: the mass ratio of NVP is 1: 10-10: 1, N2Stirring for 10-40 min under protection to mix the solution uniformly;
step five: in N2Under the protection and mechanical stirring, heating the solution obtained in the fourth step to 60-100 ℃ to graft NVP onto PVDF by an ATRP method, and reacting for 2-24 hours;
step six: and (5) defoaming and cooling the product PVDF-g-PVP in the step five to room temperature, and purifying the product by using water by adopting a non-solvent induced phase separation method.
The second embodiment is as follows: in the first step of the method for preparing the PVDF amphiphilic polymer based on the ATRP method, the temperature is 40-60 ℃, and the mass fraction of the PVDF solution is 12-20%.
The third concrete implementation mode: in the second step of the method for preparing PVDF amphiphilic polymer based on the ATRP method, the tertiary amine is BDMA, and the mass fraction of the tertiary amine is 8-15%.
The fourth concrete implementation mode: in the second step of the method for preparing the PVDF amphiphilic polymer based on the ATRP method, the tertiary amine substance is DMP-30, and the mass fraction of the tertiary amine substance is 5-20%.
The fifth concrete implementation mode: in the third step, the mass fraction of the CuCl is 0.5-4%.
The sixth specific implementation mode: in the fourth step, the mass ratio of PVDF to NVP is 1:4-1: 1.
The seventh embodiment: in the fifth step of the method for preparing a PVDF amphiphilic polymer based on the ATRP method, the reaction temperature is 80-100 ℃ and the reaction time is 4-8 hours.
Example 1:
this example illustrates BDMA as a ligand
A method for preparing PVDF amphiphilic polymer based on ATRP method comprises the following steps:
the method comprises the following steps: preparing a PVDF solution with the mass fraction of 20% by taking NMP as a solvent, N2Under protection, heating in water bath to 60 ℃ and mechanically stirring to uniformly mix the solution;
step two: cooling the solution prepared in the step one to room temperature, adding BDMA into the solution prepared in the step one to ensure that the mass fraction of BDMA in PVDF is 12 percent, and N2Stirring for 5-10 min under protection to mix the solution uniformly;
step three: adding CuCl into the solution obtained in the second step at room temperature to enable the mass fraction of CuCl in the PVDF to be 2%, and enabling N to be2Stirring for 5-10 min under protection to mix the solution uniformly;
step four: adding NVP into the solution in the third step at room temperature, so that the mass ratio of PVDF to NVP = 1: 2, N2Stirring for 20-30 min under protection to mix the solution uniformly;
step five: in N2Under the protection and mechanical stirring, heating the solution obtained in the fourth step to 90 ℃, and reacting for 6 hours to graft NVP onto PVDF by an ATRP method;
step six: and (5) defoaming and cooling the product PVDF-g-PVP in the step five to room temperature, and purifying the product by using water by adopting a non-solvent induced phase separation method.
Step seven: and C, carrying out infrared and water contact angle tests on the product obtained in the sixth step. The infrared test is shown in figure 1, and the comparison of the infrared spectra of the modified product PVDF-g-PVP and PVDF shows that the infrared spectrum is 1666cm-1The new absorption peak appears as a characteristic peak of C = O in the grafted NVP; 1277cm-1Absorption peak ofIntensification as contribution of C-N in grafted NVP; and 976cm-1The absorption peak at C-F is reduced because the position of F in PVDF is replaced by PVP, and the above analysis demonstrates successful grafting of the monomeric NVP onto PVDF. Water contact angle test as shown in figure 2, the initial contact angle of the modified PVDF compared to the unmodified one decreased from 90 ° to 60 °, and the contact angle reached around 22 ° after 1 minute, further demonstrating the successful preparation of PVDF amphiphilic polymers. Water contact angle tests prove that PVDF has certain hydrophilicity, so that PVDF materials can be applied to more fields.
Comparative example 1:
in the comparative example, 4 ' -dimethyl-2, 2 ' -bipyridine (DMDP) which is good in common coordination effect but expensive is used as a ligand, an ATRP method is used for preparing a PVDF amphiphilic polymer (PVDF-g-PVP '), the infrared spectrogram of which is shown in figure 3, the position of the characteristic peak of the prepared PVDF amphiphilic polymer is the same as that of the PVDF-g-PVP, and a new absorption peak appearing at 1666cm-1 is the characteristic peak of C = O in grafted NVP; the absorption peak at 1277cm-1 became stronger as a contribution of C-N in the grafted NVP; while the C-F absorption peak at 976cm-1 is diminished because the F position in the PVDF is replaced by PVP, and the above analysis demonstrates successful grafting of the monomeric NVP onto the PVDF. The water contact angle test is shown in fig. 4, the initial contact angle of PVDF-g-PVP 'is reduced from 90 degrees to about 65 degrees compared with PVDF, the contact angle after one minute is about 58 degrees, and the contact angle after one minute of PVDF-g-PVP is about 22 degrees, which shows that the hydrophilicity of PVDF-g-PVP prepared by the ATRP method with BDMA as a ligand and PVDF-g-PVP' prepared by the ATRP method with DMDP as a ligand are improved, but the improvement effect of the former is more obvious, which shows that BDMA can be used as an excellent ligand to be applied to the preparation of PVDF amphiphilic polymer by the ATRP method.
Claims (6)
1. A method for preparing PVDF amphiphilic polymer based on ATRP method is characterized in that: the method comprises the following specific steps:
the method comprises the following steps: preparing a PVDF solution with the mass fraction of 1-25% by taking NMP as a solvent, N2Heating in water bath to 25-80 deg.C under protection, and mechanically stirring to mix the solution uniformly;
step two: cooling the solution prepared in the step one to room temperature, adding BDMA according to a certain proportion to ensure that the mass fraction of the BDMA in the PVDF is 3-20 percent, and N2Stirring for 5-20 min under protection to mix the solution uniformly;
step three: adding a certain proportion of CuCl into the solution obtained in the second step at room temperature to ensure that the added CuCl accounts for 0.5-10% of the mass fraction of PVDF and N2Stirring for 5-20 min under protection to mix the solution uniformly;
step four: adding a certain proportion of NVP into the solution obtained in the third step at room temperature to enable PVDF: the mass ratio of NVP is 1: 10-10: 1, N2Stirring for 10-40 min under protection to mix the solution uniformly;
step five: in N2Under the protection and mechanical stirring, heating the solution obtained in the fourth step to 60-100 ℃ to graft NVP onto PVDF by an ATRP method, and reacting for 2-24 hours;
step six: defoaming and cooling the PVDF-g-PVP product obtained in the step five to room temperature, and purifying the product by using water by adopting a non-solvent induced phase separation method;
the ATRP refers to atom transfer radical polymerization, the PVDF is polyvinylidene fluoride, the NMP is N-methyl pyrrolidone, the NVP is N-vinyl pyrrolidone, and the BDMA is N, N-dimethylbenzylamine.
2. The method for preparing PVDF amphiphilic polymer based on ATRP method according to claim 1, characterized by that: in the first step, the water bath is heated to 40-60 ℃, and the mass fraction of the PVDF solution is 12-20%.
3. The method for preparing PVDF amphiphilic polymer based on ATRP method according to claim 1, characterized by that: in the second step, the mass fraction of the BDMA in the PVDF is 8-15%.
4. The method for preparing PVDF amphiphilic polymer based on ATRP method according to claim 1, characterized by that: in the third step, the CuCl accounts for 0.5-4% of the PVDF by mass percent.
5. The method for preparing PVDF amphiphilic polymer based on ATRP method according to claim 1, characterized by that: in the fourth step, the mass ratio of PVDF to NVP is 1:4-1: 1.
6. The method for preparing PVDF amphiphilic polymer based on ATRP method according to claim 1, characterized by that: in the fifth step, the reaction temperature is 80-100 ℃, and the reaction time is 4-8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710752121.5A CN107540790B (en) | 2017-08-28 | 2017-08-28 | Method for preparing PVDF amphiphilic polymer based on ATRP method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710752121.5A CN107540790B (en) | 2017-08-28 | 2017-08-28 | Method for preparing PVDF amphiphilic polymer based on ATRP method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107540790A CN107540790A (en) | 2018-01-05 |
| CN107540790B true CN107540790B (en) | 2020-05-15 |
Family
ID=60959031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710752121.5A Expired - Fee Related CN107540790B (en) | 2017-08-28 | 2017-08-28 | Method for preparing PVDF amphiphilic polymer based on ATRP method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107540790B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452964A (en) * | 2010-10-20 | 2012-05-16 | 中国石油化工股份有限公司 | Amphipathic polymerizable monomer and amphipathic tackifying copolymer and preparation method and application thereof |
| CN104801234A (en) * | 2015-03-09 | 2015-07-29 | 江苏摩力顿石油化工有限公司 | Amphipathic hyperdispersant and preparation method thereof |
| CN106432607A (en) * | 2016-09-30 | 2017-02-22 | 郑州大学 | Preparation method and application of amphiphilic polymer |
| CN108794709A (en) * | 2017-04-27 | 2018-11-13 | 西南大学 | A kind of amphiphilic star-like block polymer preparation method of superelevation pH stimuli responsives |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864039B (en) * | 2009-11-23 | 2012-10-17 | 天津工业大学 | Preparation method of temperature-sensitive graft copolymers based on polyvinylidene fluoride |
| CN102675546B (en) * | 2012-05-15 | 2013-12-04 | 中国科学院上海应用物理研究所 | Polyvinylidene fluoride-g-polyvinyl pyrrolidone (PVDF-g-PVP) graft copolymer and preparation method thereof |
| CN104945635A (en) * | 2015-06-30 | 2015-09-30 | 哈尔滨工业大学 | Amphiphilic polymer PVP-g-PVDF-g-DMF and preparation method and application thereof |
-
2017
- 2017-08-28 CN CN201710752121.5A patent/CN107540790B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452964A (en) * | 2010-10-20 | 2012-05-16 | 中国石油化工股份有限公司 | Amphipathic polymerizable monomer and amphipathic tackifying copolymer and preparation method and application thereof |
| CN104801234A (en) * | 2015-03-09 | 2015-07-29 | 江苏摩力顿石油化工有限公司 | Amphipathic hyperdispersant and preparation method thereof |
| CN106432607A (en) * | 2016-09-30 | 2017-02-22 | 郑州大学 | Preparation method and application of amphiphilic polymer |
| CN108794709A (en) * | 2017-04-27 | 2018-11-13 | 西南大学 | A kind of amphiphilic star-like block polymer preparation method of superelevation pH stimuli responsives |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107540790A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105363359B (en) | A kind of cross-linking type lotus positive electricity chlorine-containing polymer filter membrane and preparation method thereof | |
| CN102558595B (en) | Surface modification method for polyvinylidene fluoride (PVDF) film or polyvinyl chloride (PVC) film | |
| CN109400771B (en) | Preparation method and application of super-crosslinked porous polyion liquid material | |
| CN109400922B (en) | Preparation method and application of super-crosslinked porous polyion liquid material | |
| CN105985495A (en) | Cationic functional fluorine-containing polymer and preparation method thereof | |
| CN103865275A (en) | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol | |
| CN105542205A (en) | Preparation method of electrically-driven shape memory polyimide | |
| CN109400781B (en) | Preparation method and application of super-crosslinked porous polyion liquid material | |
| CN113549008A (en) | Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, Teleger base polymer, preparation and application thereof | |
| CN104725596A (en) | Nano-silver/carbon nano tube/polyurethane hybrid membrane and preparation method thereof | |
| CN108530626A (en) | A method of improving polyimides slurry production efficiency | |
| CN107540790B (en) | Method for preparing PVDF amphiphilic polymer based on ATRP method | |
| CN110713600B (en) | Preparation method of self-healing silicon elastomer based on metal coordination bond-hydrogen bond double crosslinking and elastomer | |
| CN104959047A (en) | Preparation method for monoamine-grafted-and-modified crosslinked polyimide solvent-resistant nanofiltration membrane | |
| CN103804914A (en) | Method for improving hydrophilicity of polypeptide membrane by using polypropylene glycol and polyvinyl alcohol | |
| CN101864039B (en) | Preparation method of temperature-sensitive graft copolymers based on polyvinylidene fluoride | |
| CN110467703A (en) | A method of solid polymer electrolyte membrane is prepared based on in-situ polymerization matrix | |
| CN110801739B (en) | Blending modification method of polyvinylidene fluoride membrane | |
| CN106492659A (en) | A kind of temperature and pH double-bang firecrackers answer PVDF semi-interpenetrating network polymer films and preparation method thereof | |
| CN103937270A (en) | Method for improving water resistance of polyvinyl alcohol film through polypropylene glycol and poly(caprolactone-lactide) | |
| CN105418922B (en) | A kind of shape memory random copolymerization polyimides that can be recycled and preparation method thereof | |
| CN106431793B (en) | The method that the amino surface of HMX is modified | |
| CN111533865B (en) | Anti-protein-adsorption self-cleaning block copolymer, preparation method and application thereof | |
| CN113717384B (en) | Modified polyamide imide material and preparation method thereof | |
| CN109400923B (en) | Preparation method and application of super-crosslinked porous polyion liquid material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200515 Termination date: 20210828 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |