CN101864039B - Preparation method of temperature-sensitive graft copolymers based on polyvinylidene fluoride - Google Patents
Preparation method of temperature-sensitive graft copolymers based on polyvinylidene fluoride Download PDFInfo
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- CN101864039B CN101864039B CN200910228662A CN200910228662A CN101864039B CN 101864039 B CN101864039 B CN 101864039B CN 200910228662 A CN200910228662 A CN 200910228662A CN 200910228662 A CN200910228662 A CN 200910228662A CN 101864039 B CN101864039 B CN 101864039B
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Abstract
The invention discloses a preparation method of temperature-sensitive graft copolymers based on polyvinylidene fluoride, which belongs to the field of functional high molecular materials, in particular to a preparation method of temperature-sensitive graft copolymers. The method comprises the following steps: (1) dissolving PVDF into DMF, and cooling the materials into a room temperature; (2) adding CuCl and Me6Tren into a flask with three necks, and carrying out ultrasonic waving matching; (3) adding a PVDF solution and NIPAAm; carrying out the vacuum pumping-nitrogen gas introduction circulation for five times, sealing the flask, and fast placing the flask into oil bath for stirring reaction; and (4) cooling the materials to the room temperature, and carrying out methanol precipitation, filtration, ultrasonic cleaning, distilled water flushing and vacuum drying to obtain reaction products. The synthesis method of the invention has the advantages of simplicity, convenient operation, controllable reaction and easy realization of industrialization. The graft copolymers can be applied to the preparation of flat sheet membranes and hollow fibrous membranes.
Description
Technical field
The invention belongs to functional high polymer material field, particularly a kind of preparation method of temperature-sensitive graft copolymers.
Background technology
Pvdf (PVDF) is a kind of semi-crystalline polymer, because its C-F bond energy is extremely strong, has good chemicalstability, thermostability and physical strength, is a kind of separation membrane material of high comprehensive performance.Yet PVDF has very low surface energy, and strong-hydrophobicity makes film mass transfer motivating force when handling water-based fluid of its preparation high, and energy consumption is big; And very easily adsorb organic compound, protein etc. cause film to pollute, and cause membrane flux to descend, and membrane lifetime shortens.Therefore, for a long time,, cut down the consumption of energy through hydrophilization, the reinforcing membrane contamination resistance, to prolong film be the focus of research both at home and abroad work-ing life always.In numerous method of modifying to PVDF, chemical modification has stable and durable with respect to other method, hydrophilic component advantage such as do not come off after the film forming.The material that PVDF is carried out chemical modification is a lot, and the N-NSC 11448 is exactly wherein have application potential a kind of.
NIPAAm is a kind of typical temperature sensitive intelligent material, through chemical modification NIPAAm is grafted on the PVDF molecular chain, can synthesize the PVDF-g-PNIPAAm graft copolymer with temperature sensitive property.When its film of preparing at room temperature used, wetting ability was significantly strengthened, and changed with temperature when the temperature size also can regulate fenestra that raises simultaneously, and therefore this co-polymer membrane can also show temperature sensitive intelligent characteristic.It is at medicine control-delivery systme, and biomacromolecule separates, and all there are many potential using values in fields such as organizational project.
The chemical modification method of PVDF graft N IPAAm has ozone pre-treatment thermopolymerization, radiation grafting polymerization and ATRP etc.When adopting ozone pre-treatment thermopolymerization and radiation grafting polymeric method to prepare the PVDF graft copolymer, percentage of grafting, molecular weight and distribution thereof are difficult to control, and this research to later film forming application and separating mechanism has significant limitation.ATRP (ATRP) is a kind of activity polymerizating technology that developed and had significant application value in recent years rapidly; Because it is controlled that this Raolical polymerizable has the polymerization process activity, can synthesize the polymkeric substance of low dispersity and definite molecular weight and molecular structure.Compare with the method for preceding two kinds of chemical modifications, using ATRP is a kind of even more ideal method, can synthesize certain percentage of grafting, confirm the PVDF-g-PNIPAAm graft copolymer of molecular weight and distribution of low molecular weight.Though the C-F bond energy is very strong among the PVDF, contains halogen-F group and make its macromole evocating agent that can directly react, other molecule on its side chain graft as ATRP.
What the applicant was successful for the first time is grafted monomer with the N-NSC 11448; Pvdf is a macromole evocating agent; With the cuprous chloride is catalyzer, 4, and 4-dimethyl-2; The 2-dipyridyl is a ligand, adopts the method for ATRP to prepare temperature-sensitive polyvinylidene fluoride intelligent membrane material (one Chinese patent application number be 200510015298.4).But because 4,4-dimethyl-2, problem such as the coordination ability of 2-dipyridyl (DMDP) is not strong, and it is very long that the ATRP of this catalysis coordination system exists the reaction times, and the grafting productive rate is not high.
Summary of the invention
The object of the invention is to use ATRP reaction, and to have the polymerization process activity controlled; The synthetic polymkeric substance has the good characteristic of low dispersity and definite molecular weight and molecular structure, directly PVDF is carried out the temperature sensitive monomer NIPAAm of ATRP grafting through the method for chemical modification.To existing deficiency, stronger three (N, the N-dimethyl aminoethyl) amine (Me of coordination ability has been adopted in the ATRP reaction
6Tren) as part, with the preparation method of N (DMF) as the temperature-sensitive graft copolymers of the solvent of polyreaction.
The present invention provides a kind of chemical modification NIPAAm is grafted to the preparation method on the PVDF.This method is used the ATRP reaction, is macromole evocating agent with PVDF, at cuprous chloride (CuCl)/Me
6Under the catalysis coordination system of Tren, use DMF, synthesize the PVDF-g-PNIPAAm graft copolymer of temperature sensitive property as solvent graft polymerization NIPAAm monomer.
Preparing method of the present invention is following:
(1). get PVDF and be dissolved in the DMF solvent fully 50 ℃ of following stirrings, cool to room temperature is for use.
(2). in there-necked flask, add Catalysts Cu Cl and part Me6Tren, catalyzer and part are fully cooperated with UW.
(3). and then add the PVDF solution and the NIPAAm of cool to room temperature in the there-necked flask.Vacuumize-the Tong nitrogen circulation carries out five times, and sealed flask is put into 60-120 ℃ oil bath stirring reaction 3-12h rapidly.
(4). the reaction mixture cool to room temperature, carry out precipitating with methyl alcohol, to filter, distilled water flushing is used in ultrasonic cleaning again.50 ℃ of following vacuum-drying 12 hours obtains the reaction product PVDF-g-PNIPAAm graft copolymer of brown solid powder.
Said PVDF is 1-3: 2-10 with NIPAAm massfraction ratio, and the 5-15 that said DMF solvent load is the PVDF quality times, said Catalysts Cu Cl is 1% of a PVDF quality, and said part Me6Tren is 14: 3 with CuCl massfraction ratio.
The present invention use atom transition free radical polymerization reaction directly PVDF-the F group on graft N IPAAm.
The present invention carries out graft polymerization with DMF as reaction solvent under the catalysis coordination system of CuCl/Me6Tren.
Me6Tren is as the part of ATRP reaction among the present invention.
Beneficial effect:
Compared with prior art, the method for chemical modification can prevent polymkeric substance coming off of graft modification material in use, and the ATRP method directly on PVDF the chemical modification method technology of graft N IPAAm simple, strong operability.Simultaneously, adopted the extremely strong part Me of coordination ability
6TREN can significantly improve the grafting productive rate that ATRP reacts, and improves the ATRP reaction conversion ratio more than 20%, uses Me
6Tren can reduce temperature of reaction as new part and reach more than 20 ℃, shortens about reaction times 12h (with 4,4-dimethyl-2,2-dipyridyl must be at 80-120 ℃ of reaction 19-25h down during for ligand), so just greatly reduces cost, is convenient to suitability for industrialized production.
Compound method equipment of the present invention is simple, easy to operate, reacts controlled, easy realization of industrialization.The PVDF-g-PNIPAAm graft copolymer that synthesizes temperature sensitive property can be applied to the preparation of flat sheet membrane and hollow-fibre membrane.
Embodiment
Following embodiment can make those skilled in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1
(1). get the PVDF of 1.5g, be dissolved in the DMF of 10mL fully 50 ℃ of following stirrings, cool to room temperature, for use.
(2). in there-necked flask, add Catalysts Cu Cl 0.015g with part Me
6Tren 0.07g fully cooperates catalyzer and part with UW.
(3). and then in there-necked flask, add the PVDF solution of previous cool to room temperature and the NIPAAm of 3g.Vacuumize-Tong nitrogen-vacuumize, circulation is carried out five times, will be comparatively pure nitrogen atmosphere in the last flask, and sealed flask is put into 80 ℃ oil bath stirring reaction 6 hours rapidly.
(4). with the reaction mixture cool to room temperature, carry out precipitating with a large amount of methyl alcohol after reaction is accomplished, filter then, a large amount of distilled water flushings are used in first ultrasonic cleaning again.50 ℃ of following vacuum-drying 12 hours, finally obtaining reaction product is the brown solid powder.
Embodiment 2
(1). get the PVDF of 3g, be dissolved in the DMF of 20mL fully 50 ℃ of following stirrings, cool to room temperature, for use.
(2). in there-necked flask, add Catalysts Cu Cl 0.03g with part Me
6Tren 0.14g fully cooperates catalyzer and part with UW.
(3). and then in there-necked flask, add the PVDF solution of previous cool to room temperature and the NIPAAm of 3g.Vacuumize-Tong nitrogen-vacuumize, circulation is carried out five times, will be comparatively pure nitrogen atmosphere in the last flask, and sealed flask is put into 100 ℃ oil bath stirring reaction 10 hours rapidly.
(4). with embodiment 1
Embodiment 3
(1). get the PVDF of 3g, be dissolved in the DMF of 30mL fully 50 ℃ of following stirrings, cool to room temperature, for use.
(2). with embodiment 2
(3). and then in there-necked flask, add the PVDF solution of previous cool to room temperature and the NIPAAm of 12g.Vacuumize-Tong nitrogen-vacuumize, circulation is carried out five times, will be comparatively pure nitrogen atmosphere in the last flask, and sealed flask is put into 80 ℃ oil bath stirring reaction 8 hours rapidly.
(4). with embodiment 1
Embodiment 4
(1). get the PVDF of 1.5g, be dissolved in the DMF of 20mL fully 50 ℃ of following stirrings, cool to room temperature, for use.
(2). with embodiment 1
(3). and then in there-necked flask, add the PVDF solution of previous cool to room temperature and the NIPAAm of 10g.Vacuumize-Tong nitrogen-vacuumize, circulation is carried out five times, will be comparatively pure nitrogen atmosphere in the last flask, and sealed flask is put into 120 ℃ oil bath stirring reaction 3 hours rapidly.
(4). with embodiment 1
Embodiment 5
(1). get the PVDF of 4.5g, be dissolved in the DMF of 30m L fully 50 ℃ of following stirrings, cool to room temperature, for use.
(2). in there-necked flask, add Catalysts Cu Cl 0.045g with part Me
6Tren 0.21g fully cooperates catalyzer and part with UW.
(3). and then in there-necked flask, add the PVDF solution of previous cool to room temperature and the NIPAAm of 6g.Vacuumize-Tong nitrogen-vacuumize, circulation is carried out five times, will be comparatively pure nitrogen atmosphere in the last flask, and sealed flask is put into 60 ℃ oil bath stirring reaction 12 hours rapidly.
(4) 4. with embodiment 1
Embodiment 6
(1). get the PVDF of 4.5g, be dissolved in the DMF of 40mL fully 50 ℃ of following stirrings, cool to room temperature, for use.
(2). with embodiment 5
(3). and then in there-necked flask, add the PVDF solution of previous cool to room temperature and the NIPAAm of 15g.Vacuumize-Tong nitrogen-vacuumize, circulation is carried out five times, will be comparatively pure nitrogen atmosphere in the last flask, and sealed flask is put into 100 ℃ oil bath stirring reaction 6 hours rapidly.
(4). with embodiment 1
Claims (6)
1. the preparation method based on the graft copolymer of pvdf comprises the steps:
(1). get PVDF 50 ℃ of following stirring and dissolving in DMF solvent, cool to room temperature;
(2). in there-necked flask, add Catalysts Cu Cl and part, catalyzer and part are cooperated with UW;
(3). and then add the PVDF solution and the NIPAAm of room temperature in the there-necked flask, vacuumize-Tong nitrogen circulation five times, sealed flask reacts;
(4). the reaction mixture cool to room temperature, use the methyl alcohol precipitating, filter, ultrasonic cleaning, distilled water flushing, 50 ℃ of following vacuum-drying 12h obtain reaction product;
It is characterized in that said part is Me
6Tren, the reaction conditions of said reaction are 60-120 ℃ oil bath, stirring reaction 3-12h.
2. according to the preparation method of the said graft copolymer based on pvdf of claim 1, it is characterized in that said PVDF and NIPAAm massfraction than being 1-3: 2-10.
3. according to the preparation method of the said graft copolymer based on pvdf of claim 1, it is characterized in that 5-15 that said DMF solvent load is the PVDF quality doubly.
4. according to the preparation method of the said graft copolymer based on pvdf of claim 1, it is characterized in that said Catalysts Cu Cl is 1% of a PVDF quality.
5. according to the preparation method of the said graft copolymer based on pvdf of claim 1, it is characterized in that said part Me
6Tren is 14: 3 with CuCl massfraction ratio.
6. according to the preparation method of the said graft copolymer based on pvdf of claim 1, it is characterized in that said Me
6Tren is the part of ATRP reaction.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102091536A (en) * | 2010-12-29 | 2011-06-15 | 天津工业大学 | Method for preparing structure controlled temperature-sensitive polyvinylidene fluoride flat separation membrane and product |
| CN102008907A (en) * | 2010-12-29 | 2011-04-13 | 天津工业大学 | Preparation method of structure-controllable temperature-sensitive polyvinylidene fluoride (PVDF) hollow fiber separation membrane and product thereof |
| CN105268331B (en) * | 2014-07-09 | 2018-11-09 | 天津工业大学 | A kind of preferable PVDF seperation films of blood compatibility and preparation method thereof |
| CN107540790B (en) * | 2017-08-28 | 2020-05-15 | 哈尔滨工业大学 | Method for preparing PVDF amphiphilic polymer based on ATRP method |
| CN114159629B (en) * | 2021-12-07 | 2023-03-24 | 哈尔滨工业大学 | High-speed preparation method of blood vessel covered stent for emergency treatment of sudden coronary perforation in operation |
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|---|---|---|---|---|
| CN1594404A (en) * | 2004-07-16 | 2005-03-16 | 天津工业大学 | Method for making temperature-sensitive polyvinylidene fluoride hollow fibre intelligent film and products thereby |
| CN1743351A (en) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594404A (en) * | 2004-07-16 | 2005-03-16 | 天津工业大学 | Method for making temperature-sensitive polyvinylidene fluoride hollow fibre intelligent film and products thereby |
| CN1743351A (en) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product |
Non-Patent Citations (2)
| Title |
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| 蒋晓慧等.配体在卤化铜催化的原子转移自由基聚合反应中的作用.《西华师范大学学报(自然科学版)》.2003,(第03期), |
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