CN108047383B - Preparation method of polyvinylidene fluoride copolymer - Google Patents
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Abstract
The invention provides a preparation method of a polyvinylidene fluoride copolymer, which comprises the following steps: A) dissolving polyvinylidene fluoride in a solvent, mixing with an organic base, and heating to obtain an alkali-treated polyvinylidene fluoride solution; B) carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; the initiator is dibenzoyl peroxide. The invention utilizes the phase transfer catalysis of organic alkali to generate carbon-carbon double bonds in the molecular chain of the polyvinylidene fluoride, and further initiates a specific ultraviolet absorbent to carry out grafting reaction through the added free radical initiator. The method provides a novel method for preparing the ultraviolet absorption PVDF membrane, and the reaction condition is easy to control and the operation is simple and convenient. The polyvinylidene fluoride copolymer prepared by the preparation method of the polyvinylidene fluoride copolymer provided by the invention has low ultraviolet transmittance and high grafting rate. Meanwhile, the method has better environmental protection and lower cost.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of a polyvinylidene fluoride copolymer.
Background
PVDF is an important fluoropolymer, has excellent fatigue resistance, processability, weather resistance and chemical resistance, and excellent optical and electrical properties, and is widely applied to the fields of aviation, electronics, energy, automobiles, chemical industry and the like, but due to the high ultraviolet transmittance of PVDF films, the PVDF films cannot realize shielding and protection of ultraviolet sensitive materials when being used as outer protective layers of composite materials such as decorations, packages, airships and the like, so that the preparation of PVDF films with ultraviolet absorption function has important significance.
The ultraviolet absorbent can effectively prevent or delay the molecular structure damage and performance reduction of the material, and prolong the service life of the material. Besides the preparation of the macromolecular ultraviolet absorbent, grafting the reactive ultraviolet absorbent into the molecular chain of PVDF is also a very effective method for avoiding the migration and exudation of the micromolecular ultraviolet absorbent.
At present, a method of preparing a high molecular type ultraviolet absorber and grafting a small molecular ultraviolet absorber onto a polymer molecule has become a major trend. Patent CN101096391A describes a method for preparing a high molecular weight ultraviolet absorber, wherein a high molecular weight ultraviolet absorber with narrow molecular weight distribution is prepared by reflux reaction of a high molecular prepared by (reverse) Atom Transfer Radical Polymerization (ATRP) and an equimolar 2, 4-dihydroxybenzophenone (UV-0) small molecular ultraviolet absorber under the condition of a catalyst. However, the experimental operation for preparing the high molecular type ultraviolet absorbent is complex and the conditions are harsh; meanwhile, the PVDF mechanical property is greatly influenced by the high addition amount of the ultraviolet absorbent.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a polyvinylidene fluoride copolymer, and the polyvinylidene fluoride copolymer prepared by the method for preparing a polyvinylidene fluoride copolymer provided by the present invention has low ultraviolet transmittance and high grafting ratio.
The invention provides a preparation method of a polyvinylidene fluoride copolymer, which comprises the following steps:
A) dissolving polyvinylidene fluoride in a solvent, mixing with an organic base, and heating to obtain an alkali-treated polyvinylidene fluoride solution;
B) carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; the initiator is dibenzoyl peroxide.
Preferably, the organic base is selected from one or more of tetrabutylammonium hydroxide, tetraethylammonium hydroxide and tetramethylammonium hydroxide.
Preferably, the concentration of the organic base is 0.1-2.0 wt%, and the mass ratio of the organic base to the polyvinylidene fluoride is (0.0035-0.07): 1.
preferably, the heating treatment temperature in the step A) is 40-60 ℃; the treatment time is 5-40 min.
Preferably, the solvent of step a) is dimethylacetamide; the amount of the dimethylacetamide solvent required for dissolving polyvinylidene fluoride per gram is 6-14 ml, and the dissolving temperature is 45-65 ℃.
Preferably, the temperature of the grafting reaction is 60-90 ℃; the grafting reaction time is 6-12 h.
Preferably, the ultraviolet absorbent is selected from one or more of benzophenones and benzotriazoles.
Preferably, the mass ratio of the polyvinylidene fluoride subjected to the alkali treatment in the step B) to the ultraviolet absorber to the initiator is 1: (0.1-2): (0.01-0.04).
Preferably, the benzophenones include one or more of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, 2-hydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone, and 2-hydroxy-4-acryloyloxyethoxy benzophenone; the benzotriazole includes one or more of [2- (2-hydroxy-4-acryloyloxyphenyl) benzotriazole ], 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole, 2 (2-hydroxy-4-allylphenyl) 5-chloro-2H-benzotriazole, 2- (2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and 2 (2-hydroxy-4-methacryloylphenyl) 5-chloro-2H-benzotriazole.
Preferably, the alkali treatment in step a) is carried out under inert gas conditions; the grafting reaction of step B) is carried out under the condition of inert gas.
Compared with the prior art, the invention provides a preparation method of a polyvinylidene fluoride copolymer, which comprises the following steps: A) dissolving polyvinylidene fluoride in a solvent, mixing with an organic base, and heating to obtain an alkali-treated polyvinylidene fluoride solution; B) carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; the initiator is dibenzoyl peroxide. The invention utilizes the phase transfer catalysis of organic alkali to generate carbon-carbon double bonds in the molecular chain of the polyvinylidene fluoride, and further initiates a specific ultraviolet absorbent to carry out grafting reaction through the added free radical initiator. The method provides a novel method for preparing the ultraviolet absorption PVDF membrane, and the reaction condition is easy to control and the operation is simple and convenient. The polyvinylidene fluoride copolymer prepared by the preparation method of the polyvinylidene fluoride copolymer provided by the invention has low ultraviolet transmittance and high grafting rate. Meanwhile, the method has better environmental protection and lower cost.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of PVDF-g-PBPMA membrane prepared in example 1 of the present invention;
FIG. 2 is a NMR spectrum of a PVDF-g-PRUVA-93 film obtained in example 3 of the present invention;
FIG. 3 is an ATR-IR chart of modified PVDF films and PVDF films before grafting obtained in examples 1 and 3 of the present invention;
FIG. 4 is a graph of the UV-vis transmittance spectra of reacted PVDF films and PVDF films before grafting obtained in examples 1 and 3 of the present invention.
Detailed Description
The invention provides a preparation method of a polyvinylidene fluoride copolymer, which comprises the following steps:
A) dissolving polyvinylidene fluoride in a solvent, mixing with an organic base, and heating to obtain an alkali-treated polyvinylidene fluoride solution;
B) carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; the initiator is dibenzoyl peroxide.
PVDF, an important fluoropolymer, has excellent fatigue resistance, processability, weather resistance, chemical resistance, and excellent optical and electrical properties, and is widely used in the fields of aviation, electronics, energy, automobiles, chemical industry, and the like, and is generally used as an outer protective layer of a composite material such as decoration, packaging, and airship.
In the present invention, the source of the polyvinylidene fluoride is not limited and may be commercially available.
Dissolving polyvinylidene fluoride in a solvent; preferably, the polyvinylidene fluoride is dissolved in the solvent under inert gas condition. The inert gas is preferably one of nitrogen, helium, neon and argon; more preferably nitrogen.
Wherein the solvent includes, but is not limited to, dimethylacetamide.
The amount of the dimethylacetamide solvent required for dissolving each gram of polyvinylidene fluoride is preferably 6-14 ml, and more preferably 6-10 ml; most preferably 6 to 8 ml. The preferable dissolving temperature is 45-65 ℃; more preferably 45 to 55 ℃. The mixing is preferably a mechanical agitation mixing, and the mechanical agitation is not limited in the present invention.
After dissolving, mixing with organic alkali and heating to obtain alkali-treated polyvinylidene fluoride solution;
according to the invention, the organic base is preferably selected from one or more of tetrabutylammonium hydroxide, tetraethylammonium hydroxide and tetramethylammonium hydroxide.
The concentration of the organic alkali is preferably 0.1-2.0 wt%, more preferably 0.6-1.5 wt%; most preferably 0.8 to 1.2 wt%. The mass ratio of the organic base to the polyvinylidene fluoride is preferably (0.0035-0.07): 1; more preferably (0.021-0.0525): 1; most preferred are (0.028-0.042): 1.
the heat treatment is preferably a heat stirring treatment, and the stirring in the present invention is not limited thereto and may be a method known to those skilled in the art.
In the invention, the alkali treatment temperature is 40-60 ℃; more preferably 45 to 55 ℃. The alkali treatment time is 5-40 min, and more preferably 10-30 min; most preferably 15-25 min.
The PVDF solution is subjected to alkali treatment to obtain the PVDF solution containing double bonds.
In the present invention, the source of the quaternary ammonium salt-based organic alkali solution is not limited, and is preferably commercially available.
And (3) after the PVDF solution is subjected to alkali modification treatment, preferably heating to 110-120 ℃, and volatilizing excessive TEAH methanol solution and decomposition products to obtain the modified PVDF solution.
After the PVDF solution is subjected to alkali treatment, carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; preferably, in the presence of inert gas, carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; the inert gas is preferably one of nitrogen, helium, neon and argon; more preferably nitrogen.
Wherein, the initiator is preferably dibenzoyl peroxide.
The ultraviolet absorbent is preferably one or more selected from benzophenones and benzotriazoles.
The benzophenones preferably include one or more of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, 2-hydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone, and 2-hydroxy-4-acryloyloxyethoxy benzophenone; the benzotriazole preferably includes one or more of [2- (2-hydroxy-4-acryloyloxyphenyl) benzotriazole ], 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole, 2 (2-hydroxy-4-allylphenyl) 5-chloro-2H-benzotriazole, 2- (2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and 2 (2-hydroxy-4-methacryloylphenyl) 5-chloro-2H-benzotriazole.
According to the present invention, the mass ratio of the alkali-treated polyvinylidene fluoride, the ultraviolet absorber and the initiator is preferably 1: (0.1-2): (0.01 to 0.04); more preferably 1: (0.5-1.5): (0.02-0.04); most preferably 1: (0.7-1.2): (0.025-0.035).
In the invention, the temperature of the grafting reaction is preferably 60-90 ℃; more preferably 70 to 85 ℃. The time of the grafting reaction is preferably 6-12 h; more preferably 7-10 h.
In the present invention, the sources of the initiator and the ultraviolet absorber are not limited and may be those commercially available.
After the grafting reaction is finished, cooling, precipitating, extracting and drying to obtain the copolymer.
The temperature reduction is preferably carried out to room temperature, namely 20-35 ℃.
The present invention is not limited to the specific manner of precipitation and extraction, which is well known to those skilled in the art. The solvent used for the precipitation according to the invention is preferably ethanol; the solvent used for the extraction is preferably chloroform.
More preferably, it may be:
precipitating with absolute ethyl alcohol, centrifuging, dissolving in DMAc (dimethyl acetamide), repeating for 2-3 times, extracting with chloroform for 40-48 h to remove unreacted monomers and generated homopolymers, and vacuum drying the extracted product at 50-60 ℃ for 20-24 h to obtain the high-purity N-methyl pyrrolidone.
After the graft product is obtained, it is preferably prepared to obtain a PVDF membrane. In the present invention, the film forming process is not limited, and it is preferably: is prepared by a solution film forming or blow molding film forming process.
The invention adopts the specific alkali treatment concentration, temperature and time; specific parameters such as mass ratio of the ultraviolet absorbent to the polyvinylidene fluoride, reaction temperature, time and the like, and finally the modified PVDF film prepared by different molding methods has excellent ultraviolet absorption function, so that the whole absorption of ultraviolet light which has serious influence on material aging is realized; in addition, the method has the advantages of easily controlled reaction conditions, simple and convenient operation, better environmental protection and lower cost.
The modified PVDF prepared by the invention is tested in the following way:
the PVDF-g-PBPMA and PVDF-g-PRUVA-93 obtained after grafting were structurally characterized by means of a nuclear magnetic resonance spectroscopy (NMR) instrument (Bruker AV 400, Bruker, Germany) and a Fourier transform infrared spectroscopy (FT-IR) instrument (Bruker Vertex 70, Bruker, Germany).
The PVDF film obtained after grafting was subjected to UV-vis transmittance test by means of an ultraviolet-visible spectrophotometer (UV 3600 type, Shimadzu corporation, Japan).
The invention adopts the following mode to carry out performance measurement on the prepared polyvinylidene fluoride copolymer:
the fluorine content of the PVDF after grafting is tested by an Ion Chromatography (IC) instrument (ICS-1000, Dionex corporation, USA), and the reaction grafting ratio under different conditions is calculated.
The calculation formula is as follows:
DOG＝(19-32WF)/32WFin the formula WFIs the mass percentage content of fluorine element.
The invention utilizes the phase transfer catalysis of organic alkali to generate carbon-carbon double bonds in the molecular chain of the polyvinylidene fluoride, and further initiates a specific ultraviolet absorbent to carry out grafting reaction through the added free radical initiator. The method provides a novel method for preparing the ultraviolet absorption PVDF membrane, and the reaction condition is easy to control and the operation is simple and convenient.
In order to further illustrate the present invention, the polyvinylidene fluoride copolymer provided by the present invention is described in detail below with reference to examples.
Example 1
6ml of dimethylacetamide (DMAc) was added to a reaction flask containing 1g of polyvinylidene fluoride (PVDF), and the mixture was stirred at 50 ℃. After complete dissolution of PVDF, in N23.5ml of a methanol solution of tetraethylammonium hydroxide (TEAH) having a mass fraction of 0.8 wt% (mass ratio of TEAH to PVDF 0.028: 1) was added under an atmosphere, and the mixture was stirred at 45 ℃ and modified for 15 min. The temperature was raised to 120 ℃ and held for 5min to volatilize excess TEAH methanol solution and decomposition products to yield a modified PVDF solution. 0.5g of 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone and 0.025g of Benzoyl Peroxide (BPO) were added to the modified PVDF solution in this order, and N was introduced2And reacting for 6 hours at 70 ℃. After the reaction was completed, the temperature was lowered to room temperature. Precipitating with absolute ethanol, centrifuging, dissolving by DMAc, repeating for three times, extracting by chloroform for 48h to remove unreacted monomers and generated homopolymer, and drying the extracted product in vacuum at 60 ℃ for 24h to obtain the PVDF-g-PBPMA copolymer. Then, the reacted PVDF film was prepared by a solution film formation method. The PVDF-g-PBPMA copolymer prepared in example 1 of the present invention was measured, and the results are shown in FIG. 1, where FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the PVDF-g-PBPMA membrane prepared in example 1 of the present invention.
Example 2
8ml DMAc was added to a reaction flask containing 1g PVDF and stirred well at 55 ℃. After complete dissolution of PVDF, in N23.5ml of a 1.0 wt% methanol solution of tetrabutylammonium hydroxide (TBAH) (mass ratio of TBAH to PVDF: 0.035: 1) was added under an atmosphere, and the mixture was stirred at 55 ℃ for modification for 25 min. The temperature is raised to 120 ℃, and the temperature is kept for 5min to volatilize the excessive TBAH methanol solution and the decomposition products, so as to obtain the modified PVDF solution. 0.5g of 2-hydroxy-4-acryloyloxyethoxy benzophenone and 0.035g of BPO were sequentially added to the modified PVDF solution, and N was introduced2And reacting for 10 hours at 80 ℃. After the reaction is finished, precipitating with absolute ethyl alcohol, centrifuging, dissolving DMAc, repeating for three times, extracting with chloroform for 48h to remove unreacted monomers and generated homopolymers, and drying the extracted product in vacuum at 60 ℃ for 24h to obtain the modified PVDF copolymer. Then, the reacted PVDF film was prepared by a blown film method.
Example 3
7ml of dimethylacetamide (DMAc) was added to a reaction flask containing 1g of PVDF, and the mixture was stirred well at 45 ℃. After complete dissolution of PVDF, in N2Adding 3.5ml of methanol solution of tetramethylammonium hydroxide (TMAH) with the mass fraction of 0.9 wt% (the mass ratio of the TMAH to the PVDF is 0.0315: 1) under the atmosphere, stirring at 50 ℃, and modifying for 20 min. And (3) heating to 120 ℃, and keeping the temperature for 5min to volatilize the excessive TMAH methanol solution and the decomposition product, thereby obtaining the modified PVDF solution. 0.7g of 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl]Phenyl radical]Sequentially adding-2H-benzotriazole and 0.03g of BPO into the modified PVDF solution, and introducing N2And reacting for 8 hours at 75 ℃. After the reaction was completed, the temperature was lowered to room temperature. Precipitating with absolute ethyl alcohol, centrifuging, dissolving by DMAc, repeating for three times, extracting for 48 hours by using chloroform to remove unreacted monomers and generated homopolymers, and drying the extracted product to obtain the PVDF-g-PRUVA-93 copolymer. And finally, preparing the PVDF membrane after reaction by a solution film forming method.
The PVDF-g-PRUVA-93 copolymer obtained in example 3 of the present invention was measured, and the results are shown in FIG. 2, and FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of the PVDF-g-PRUVA-93 film obtained in example 3 of the present invention. The modified PVDF films obtained in examples 1 and 3 of the present invention and the PVDF film before grafting were subjected to ATR-IR and UV-vis transmittance spectrum measurement, and the results are shown in fig. 3 and 4, and fig. 3 is an ATR-IR chart of the modified PVDF films obtained in examples 1 and 3 of the present invention and the PVDF film before grafting; FIG. 4 is a graph of the UV-vis transmittance spectra of reacted PVDF films and PVDF films before grafting obtained in examples 1 and 3 of the present invention.
Example 4
6ml DMAc was added to a reaction flask containing 1g PVDF and stirred well at 55 ℃. After complete dissolution of PVDF, in N23.5ml of a 1.1 wt% solution of tetraethylammonium hydroxide (TEAH) in methanol (the mass ratio of TEAH to PVDF was 0.0385: 1) was added under an atmosphere, and the mixture was stirred at 45 ℃ and modified for 20 min. The temperature was raised to 120 ℃ and held for 5min to volatilize excess TEAH methanol solution and decomposition products to yield a modified PVDF solution. 1g2 (2-hydroxy-4-methacryloylphenyl) 5-chloro-2H-benzotriazole and 0.03g BPO were added successively to the modified PVDF solution, and N was passed through2And reacting for 6 hours at 80 ℃. After the reaction is finished, absolute ethyl alcohol is used for precipitation, centrifugation and DMAc dissolution are carried out, the three times of precipitation are carried out, chloroform extraction is carried out for 48 hours to remove unreacted monomers and generated homopolymers, and the extraction product is dried in vacuum for 24 hours at the temperature of 60 ℃ to obtain the PVDF graft copolymer. And finally, preparing the PVDF membrane after reaction by a solution film forming method.
Example 5
7ml DMAc was added to a reaction flask containing 1g PVDF and stirred well at 50 ℃. After complete dissolution of PVDF, in N2Adding 3.5ml of 1.2 wt% of tetramethylammonium hydroxide (TMAH) methanol solution (mass ratio of TMAH to PVDF is 0.042: 1) under atmosphere, stirring at 55 deg.C, and modifying for 15 min. And (3) heating to 120 ℃, and keeping the temperature for 5min to volatilize the excessive TMAH methanol solution and the decomposition product, thereby obtaining the modified PVDF solution. 1.2g of 2- (2-hydroxy-4-methacryloxyphenyl) benzotriazole and 0.035g of BPO were successively added to the modified PVDF solution, and N was introduced2And reacting for 12 hours at 70 ℃. Precipitating with anhydrous ethanol after reaction, centrifuging, dissolving in DMAc, repeating for three times, extracting with chloroform for 48h to remove unreacted monomer and generated homopolymer, and drying the extracted product to obtain PVDF graft copolymers. And finally, preparing the reacted PVDF film by a blow molding film forming method.
Example 6
8ml of dimethylacetamide (DMAc) was added to a reaction flask containing 1g of polyvinylidene fluoride (PVDF), and the mixture was stirred at 50 ℃. After complete dissolution of PVDF, in N23.5ml of a 0.7 wt% solution of tetraethylammonium hydroxide (TEAH) in methanol (the mass ratio of TEAH to PVDF was 0.0245: 1) was added under an atmosphere, and the mixture was stirred at 50 ℃ for 20 minutes for modification. The temperature was raised to 120 ℃ and held for 5min to volatilize excess TEAH methanol solution and decomposition products to yield a modified PVDF solution. 1g of 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone and 0.03g of Benzoyl Peroxide (BPO) were added in this order to the modified PVDF solution, and N was passed through2And reacting for 8 hours at 80 ℃. After the reaction was completed, the temperature was lowered to room temperature. Precipitating with absolute ethanol, centrifuging, dissolving by DMAc, repeating for three times, extracting by chloroform for 48h to remove unreacted monomers and generated homopolymer, and drying the extracted product in vacuum at 60 ℃ for 24h to obtain the PVDF-g-PBPMA copolymer. Then, the reacted PVDF film was prepared by a solution film formation method.
The grafting ratio of the modified PVDF film prepared in examples 1-6 under different conditions and the transmittance of the PVDF film at 300nm are shown in Table 1.
TABLE 1 grafting Rate and film transmittance of modified PVDF under different conditions
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for preparing a polyvinylidene fluoride copolymer, comprising:
A) dissolving polyvinylidene fluoride in a solvent, wherein the solvent is dimethylacetamide; the amount of a dimethylacetamide solvent required for dissolving polyvinylidene fluoride per gram is 6-14 mL, and the dissolving temperature is 45-65 ℃; mixing with organic alkali, and heating to obtain alkali-treated polyvinylidene fluoride solution; the organic base is selected from one or more of tetrabutylammonium hydroxide, tetraethylammonium hydroxide and tetramethylammonium hydroxide; the concentration of the organic alkali is 0.1-2.0 wt%, and the mass ratio of the organic alkali to the polyvinylidene fluoride is (0.0035-0.07): 1;
B) carrying out grafting reaction on the polyvinylidene fluoride subjected to alkali treatment under the action of an ultraviolet absorbent and an initiator to obtain a polyvinylidene fluoride copolymer; the initiator is dibenzoyl peroxide; the mass ratio of the polyvinylidene fluoride subjected to alkali treatment to the ultraviolet absorbent to the initiator is 1: (0.1-2): (0.01 to 0.04);
the temperature of the grafting reaction is 60-90 ℃; the grafting reaction time is 6-12 h.
2. The method according to claim 1, wherein the heat treatment temperature in step a) is 40 to 60 ℃; the treatment time is 5-40 min.
3. The method according to claim 1, wherein the ultraviolet absorber is one or more selected from the group consisting of benzophenones and benzotriazoles.
4. The method of claim 3, wherein the benzophenone compound comprises one or more of 2- (4-benzoyl-3-hydroxyphenoxy) ethyl 2-acrylate, 2-hydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone, and 2-hydroxy-4-acryloyloxyethoxy benzophenone; the benzotriazole includes one or more of [2- (2-hydroxy-4-acryloyloxyphenyl) benzotriazole ], 2- [ 2-hydroxy-5- [2- (methacryloyloxy) ethyl ] phenyl ] -2H-benzotriazole, 2 (2-hydroxy-4-allylphenyl) 5-chloro-2H-benzotriazole, 2- (2-hydroxy-4-methacryloyloxyphenyl) benzotriazole and 2 (2-hydroxy-4-methacryloylphenyl) 5-chloro-2H-benzotriazole.
5. The method according to claim 1, wherein the alkali treatment in step a) is performed under an inert gas condition; the grafting reaction of step B) is carried out under the condition of inert gas.
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| CN103626901A (en) * | 2013-11-29 | 2014-03-12 | 内蒙古科技大学 | Polyvinylidene fluoride powder modifying method |
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