CN106893039B - A kind of method of photoinduction organic catalysis polymer modification - Google Patents

A kind of method of photoinduction organic catalysis polymer modification Download PDF

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CN106893039B
CN106893039B CN201710191752.4A CN201710191752A CN106893039B CN 106893039 B CN106893039 B CN 106893039B CN 201710191752 A CN201710191752 A CN 201710191752A CN 106893039 B CN106893039 B CN 106893039B
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photoinduction
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organic catalysis
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CN106893039A (en
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郭凯
掌亚军
胡欣
朱宁
李振江
崔国朋
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Nanjing Tech University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

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Abstract

The invention discloses a kind of methods of photoinduction organic catalysis polymer modification, comprising the following steps: under the conditions of anaerobic is protected from light, macromole evocating agent and organic catalyst is dissolved in solvent, obtain homogeneous phase solution;Under anaerobic illumination condition, into homogeneous phase solution obtained in step (1), monomer is added and carries out atom transition free radical polymerization reaction, after reaction, stop illumination, isolate precipitating.The method of the present invention can be simple, effectively and environmentally friendly synthesis functional polymer, and product is without metal residual, having a good application prospect in terms of electricity material.

Description

A kind of method of photoinduction organic catalysis polymer modification
Technical field
The invention belongs to synthesis of polymer material fields, and in particular to a kind of poly- (vinylidene-copolymerization-chlorotrifluoroethylene) The new method of graft copolymer.
Background technique
Poly- (vinylidene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) is due to good ferroelectric piezoelectric Energy and dielectric storage performance, have received widespread attention in high performance capacitors field.However, it also has remaining pole simultaneously The deficiencies of change value is high, dielectric loss is big limits it to a certain extent and widely applies.In order to improve P (VDF-co- CTFE performance) can carry out functional modification to it by physical method or chemical method.Compared to physical blending process, by function Change component and PVDF base fluoropolymer is introduced with more significant advantage by chemical mode.Wherein, pass through P (VDF-co- CTFE the active free radical polymerization for) directly causing functionalization monomer is considered as the optimal side of relationship between adjustment structure and performance Formula, can easily introducing PVDF base fluoropolymer that functionalization group is uniform, lasting using this method.
Atom transfer radical polymerization (ATRP) is a kind of active free radical polymerization (LRP) method being widely studied. ATRP is balanced by the redox modulating polymerization reaction of metallic catalyst [such as Cu (I), Ru (II), Fe (II)], make monomer into Row living polymerization.Zhang etc. passes through ATRP method for functionalization monomer (such as Tri- n -butyltin methacrylate and acrylonitrile monomer) P (VDF-co-CTFE) and poly- (vinylidene-trifluoro-ethylene-chlorotrifluoroethylene) P (VDF-co-TrFE-co-CTFE) are introduced, The energy storage density of polymer can be greatly improved, energy storage loss is reduced.However, need to use in the reaction process metal salt as Catalyst, so as to cause metal residual inevitable in final product, limitation functionization is polymer-modified to lead in electricity material The application in domain.
Summary of the invention
The technical problem to be solved by the present invention is to provide that a kind of poly- (vinylidene-is altogether in view of the deficiencies of the prior art Poly- chlorotrifluoroethylene) method of modifying, to solve the problems, such as metal residual existing in the prior art.
The purpose of the present invention is what is realized using following measures:
A kind of method of photoinduction organic catalysis polymer modification, comprising the following steps:
(1) under the conditions of anaerobic is protected from light, macromole evocating agent and organic catalyst is dissolved in solvent, mixed Liquid;
(2) under anaerobic illumination condition, monomer is added into homogeneous phase solution obtained in step (1) and carries out atom transfer certainly By base polymerization reaction, after reaction, stops illumination, isolate precipitating.
In step (1), the macromole evocating agent is poly- (vinylidene-copolymerization-chlorotrifluoroethylene);Every gram described big point Sub- initiator is dissolved in solvent described in 5~40mL, and preferred every gram of macromole evocating agent is dissolved in described in 10~20mL In solvent.
The organic catalyst is selected from 10- phenyl phenthazine, 10- (4- methoxyphenyl) phenthazine, 10- (1- naphthalene) pheno Thiazine, perylene, 3,7- bis- (4- (1,1'- biphenyl))-(10- (1- naphthalene)) -10- phenoxazine, 5,10- diphenyl -5,10- Dihydrophenazine, 5,10- bis- (4- methoxyphenyl) -5,10- dihydrophenazine, 5,10- bis- (4- (trifluoromethyl) phenyl) -5,10- Dihydrophenazine, 5,10- bis- (4- (itrile group) phenyl) -5,10- dihydrophenazine, (2- the naphthalene) -5,10- dihydrophenazine of 5,10- bis- or One of 5,10- bis- (1- naphthalene) -5,10- dihydrophenazine is a variety of.
The structural formula of the organic catalyst see the table below:
The solvent is dimethyl sulfoxide or N,N-dimethylformamide.
In step (2), the monomer is methyl methacrylate or methyl acrylate;
The wave-length coverage of the illumination is 280~450nm;Preferably 365~450nm.
The temperature of the reaction is 20~60 DEG C, and the preferred reaction temperature is 20~25 DEG C.
The time of the reaction is 5min~for 24 hours, preferably 6~for 24 hours.
The molar ratio of monomer described in initiator described in step (1), catalyst and step (2) be 1:0.06~ 0.5:1~50.
(vinylidene-copolymerization-chlorotrifluoroethylene) poly- used in the present invention is any commercially available poly- (inclined fluorine second Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)), the P of preferably VDF:CTFE=91/9mol% and 94/6mol% (VDF-co-CTFE)。
The invention has the following advantages that
1. poly- (vinylidene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) is used as macromole evocating agent, to connect The functional polymer of branch synthesis has application prospect without metal residual on electricity material.
2. carrying out under light illumination when polymerization reaction, cutting light source post-polymerization stops immediately, illumination again, polymerization reaction Continue, polymerization process is easy to control, and method is simple and effective, economic and environment-friendly.
It is 280nm~450nm 3. the illumination wavelength range that polymerization reaction is applicable in is wide.
4. it is applied widely in the present invention, can have and be changed using a variety of organic catalysts catalysis P (VDF-co-CTFE) grafting Property.
The utility model has the advantages that the method for the present invention can be simple, effectively and environmentally friendly synthesis functional polymer, and product is without gold Belong to residual, having a good application prospect in terms of electricity material.
Detailed description of the invention
Fig. 1: being macromole evocating agent initiation with poly- (vinylidene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) Methyl methacrylate is prepared P (VDF-co-CTFE)-g-PMMA's1H NMR spectra.
Fig. 2: being macromole evocating agent initiation with poly- (vinylidene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) Methyl acrylate is prepared P (VDF-co-CTFE)-g-PMA's1H NMR spectra.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited Invention.
PC indicates organic catalyst in the present invention.[I]: [C]: [M] is indicated described in initiator, catalyst and step (2) Monomer molar ratio.Initiator, catalyst and the monomer that the present invention uses are commercially available.
VDF:CTFE=94/6mol% in P used in embodiment (VDF-co-CTFE), wherein (1g P (VDF-co- CTFE the atom 0.89mmol containing Cl in)).
The present invention is caused using poly- (vinylidene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) as macromolecular Agent causes (methyl) acrylate and carries out without metallic atom transferring free-radical polymerization.By converting monomer, synthesis has dissimilarity Poly- (vinylidene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) graft copolymer of matter, sees below formula;It is poly- by adjusting The proportion of (vinylidene-copolymerization-chlorotrifluoroethylene) and monomer synthesizes the poly- (vinylidene-copolymerization-with different grafting amounts Chlorotrifluoroethylene) (P (VDF-co-CTFE)) graft copolymer.
The preparation method of the organic catalyst refers to following documents, 10- phenyl phenthazine bibliography [1], 10- (4- Methoxyphenyl) phenthazine bibliography [2], 10- (1- naphthalene) phenthazine bibliography [3], (4- (the 1,1'- connection of 3,7- bis- Benzene))-(10- (1- naphthalene)) -10- phenoxazine bibliography [4], 5,10- diphenyl -5,10- dihydrophenazine [5], 5,10- bis- (4- methoxyphenyl) -5,10- dihydrophenazine [6], 5,10- bis- (4- (trifluoromethyl) phenyl) -5,10- dihydrophenazine, 5,10- Two (4- (itrile group) phenyl) -5,10- dihydrophenazines or 5,10- bis- (1- naphthalene) -5,10- dihydrophenazine bibliography [7], 5, 10- bis- (2- naphthalene) -5,10- dihydrophenazine bibliography [8].The compound structure and document report being prepared in the present invention It is consistent.Furthermore perylene can directly be commercially available (CAS:198-55-0, purity: 98%, manufacturer: Beijing lark prestige Science and Technology Ltd.)
[1]Eric B,Kochi K.Journal of the chemical society-perkin transactions,1995,8:1057-1064.
[2]Sunil K,Meenu S,Jwo-Huei J,et al.Journal of Materials Chemistry C: Materials for Optical and Electronic Devices,2016,4:6769-6777.
[3]Bu B P,Bong G S.Repub.Korean Kongkae Taeho Kongbo,2014,KR 2014076520 A 20140620.
[4]Pearson R M,Lim C,McCarthy B G,et al.J.Am.Chem.Soc.2016,138:11399- 11407.
[5]Pokhodenko V D,Koshechko V G,Inozemtsev AN.Oxidation Communications,1986,8:141-7.
[6]Yoshigo S,Kiyoshi S,Shunkai S,et al.Jpn.Kokai Tokkyo Koho,1990,JP 02093466 A 19900404.
[7]Theriot J C,Lim C,Yang H,et al.Science,2016,27:1082-1086.
[8]Chem-Hooi L,Matthew R,Blaine G,et al.Journal of the American Chemical Society,2017,139:348-355.
Embodiment 1:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 10- phenyl phenthazine (Ph- PTZ) (49mg, 0.178mmol) is stoppered rubber stopper and seals, and then removes the air in bottle three times using biexhaust pipe pump drainage.With Masking foil package vial is protected from light it completely.DMSO (8ml) is added under protection of argon gas, magnetic agitation 30min or more makes to draw Hair agent and organic catalyst are completely dissolved.Addition methyl methacrylate (MMA) (1.52ml, 14.24mmol) ([I]: [C]: [M]=1:0.25:20).Reaction carries out under magnetic agitation and the ultraviolet light irradiation of 380nm, is persistently exposed using compressed air band According to generated heat, reaction temperature is made to be reduced to room temperature.After reacting 6h, by product in the mixed liquor (1:1) of first alcohol and water Precipitation, and with ethyl alcohol wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, removed in product with chloroform Homopolymer.Products therefrom monomer conversion is 60.72%, grafting amount 11.21mol%.P(VDF-co-CTFE)-g-PMMA 's1H NMR spectra is shown in Fig. 1.
Embodiment 2:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 10- (1- naphthalene) phenthazine (57.9mg, 0.178mmol) is stoppered rubber stopper and seals, and then removes the air in bottle three times using biexhaust pipe pump drainage.Use tin Foil paper package vial is protected from light it completely.DMSO (8ml) is added under protection of argon gas, magnetic agitation 30min or more makes to cause Agent and organic catalyst are completely dissolved.It is added methyl methacrylate (MMA) (1.52ml, 14.24mmol) ([I]: [C]: [M] =1:0.25:20).Reaction carries out under magnetic agitation and the ultraviolet light irradiation of 365nm, persistently takes away illumination institute using compressed air The heat of generation, makes reaction temperature be reduced to room temperature.After reacting 8h, product is precipitated in the mixed liquor (1:1) of first alcohol and water It is precipitated, and with ethyl alcohol wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, removed with chloroform equal in product Polymers.Obtain subject polymer P (VDF-co-CTFE)-g-PMMA.Products therefrom monomer conversion is 60.72%, grafting amount For 9.32mol%.
Embodiment 3:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), perylene (44.9mg, 0.178mmol), it is stoppered rubber stopper and seals, then remove the air in bottle three times using biexhaust pipe pump drainage.It is wrapped up with masking foil Vial is protected from light it completely.DMSO (8ml) is added under protection of argon gas, magnetic agitation 30min or more makes initiator and organic Catalyst is completely dissolved.Addition methyl methacrylate (MMA) (1.52ml, 14.24mmol) ([I]: [C]: [M]=1:0.25: 20).Reaction carries out under magnetic agitation and radiation of visible light, persistently takes away heat caused by illumination using compressed air, makes Reaction temperature is reduced to room temperature.After reaction for 24 hours, by product in the mixed liquor (1:1) of first alcohol and water Precipitation, and use ethyl alcohol Wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, the homopolymer in product is removed with chloroform.Obtain mesh Mark polymer P (VDF-co-CTFE)-g-PMMA.Products therefrom monomer conversion is 58.67%, grafting amount 10.54mol%.
Embodiment 4:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 3,7- bis- (4- (1,1'- connection Benzene))-(10- (1- naphthalene)) -10- phenoxazine (109.2mg, 0.178mmol), it is stoppered rubber stopper and seals, then using double Pipe pump drainage removes the air in bottle three times.It is protected from light completely with masking foil package vial.DMSO is added under protection of argon gas (8ml), magnetic agitation 30min or more are completely dissolved initiator and organic catalyst.It is added methyl methacrylate (MMA) (1.52ml, 14.24mmol) ([I]: [C]: [M]=1:0.25:20).Reaction carries out under magnetic agitation and radiation of visible light, Heat caused by illumination persistently is taken away using compressed air, reaction temperature is made to be reduced to room temperature.After reacting 7h, by product in first Precipitation in the mixed liquor (1:1) of alcohol and water, and with ethyl alcohol wash products 3 times.Product is dried in vacuo for 24 hours at 30 DEG C Afterwards, the homopolymer in product is removed with chloroform.Obtain subject polymer P (VDF-co-CTFE)-g-PMMA.Gained produces Object monomer conversion is 71.56%, grafting amount 14.76mol%.
Embodiment 5:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 5,10- bis- (1- naphthalenes)- 5,10- dihydrophenazines (77.3mg, 0.178mmol), are stoppered rubber stopper and seal, and then remove bottle three times using biexhaust pipe pump drainage In air.It is protected from light completely with masking foil package vial.DMSO (8ml) is added under protection of argon gas, magnetic agitation 30min or more is completely dissolved initiator and organic catalyst.Addition methyl methacrylate (MMA) (1.52ml, 14.24mmol) ([I]: [C]: [M]=1:0.25:20).Reaction carries out under magnetic agitation and radiation of visible light, lasting to use Compressed air takes away heat caused by illumination, and reaction temperature is made to be reduced to room temperature.After reacting 8h, by product in first alcohol and water Precipitation in mixed liquor (1:1), and with ethyl alcohol wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, chloroform is used Extracting removes the homopolymer in product.Obtain subject polymer P (VDF-co-CTFE)-g-PMMA.The conversion of products therefrom monomer Rate is 76.42%, grafting amount 15.54mol%.
Embodiment 6:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 5,10- bis- (1- naphthalenes)- 5,10- dihydrophenazines (77.3mg, 0.178mmol), are stoppered rubber stopper and seal, and then remove bottle three times using biexhaust pipe pump drainage In air.It is protected from light completely with masking foil package vial.DMSO (8ml) is added under protection of argon gas, magnetic agitation 30min or more is completely dissolved initiator and organic catalyst.It is added methyl acrylate (MA) (1.3ml, 14.24mmol) ([I]: [C]: [M]=1:0.25:20).Reaction carries out under magnetic agitation and radiation of visible light, persistently uses compressed air band Heat caused by illumination is walked, reaction temperature is made to be reduced to room temperature.React 8h after, by product first alcohol and water mixed liquor (1: 1) Precipitation in, and with ethyl alcohol wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, is removed and produced with chloroform Homopolymer in object.Subject polymer P (VDF-co-CTFE)-g-PMA is obtained, products therefrom monomer conversion is 74.12%, grafting amount 13.16mol%.P (VDF-co-CTFE)-g-PMA's1H NMR spectra is shown in Fig. 2.
Embodiment 7:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 5,10- bis- (1- naphthalenes)- 5,10- dihydrophenazines (77.3mg, 0.178mmol), are stoppered rubber stopper and seal, and then remove bottle three times using biexhaust pipe pump drainage In air.It is protected from light completely with masking foil package vial.N,N-dimethylformamide DMF is added under protection of argon gas (8ml), magnetic agitation 30min or more are completely dissolved initiator and organic catalyst.It is added methyl acrylate (MA) (1.3ml, 14.24mmol) ([I]: [C]: [M]=1:0.25:20).Reaction carries out under magnetic agitation and radiation of visible light, holds It is continuous to take away heat caused by illumination using compressed air, so that reaction temperature is reduced to room temperature.After reacting 8h, by product in methanol With Precipitation in the mixed liquor (1:1) of water, and with ethyl alcohol wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, The homopolymer in product is removed with chloroform.Obtain subject polymer P (VDF-co-CTFE)-g-PMA.Products therefrom list Transformation rate is 72.23%, grafting amount 14.75mol%.
Embodiment 8:
At room temperature, polytetrafluoroethylene (PTFE) magnetic stir bar, poly- (inclined fluorine second are sequentially added into 20ml transparent glass sample bottle Alkene-copolymerization-chlorotrifluoroethylene) (P (VDF-co-CTFE)) (0.8g, the atom 0.712mmol containing Cl), 5,10- bis- (1- naphthalenes)- 5,10- dihydrophenazines (77.3mg, 0.178mmol), are stoppered rubber stopper and seal, and then remove bottle three times using biexhaust pipe pump drainage In air.It is protected from light completely with masking foil package vial.N,N-dimethylformamide DMF is added under protection of argon gas (16ml), magnetic agitation 30min or more are completely dissolved initiator and organic catalyst.It is added methyl acrylate (MA) (1.3ml, 14.24mmol) ([I]: [C]: [M]=1:0.25:20).Reaction carries out under magnetic agitation and radiation of visible light, holds It is continuous to take away heat caused by illumination using compressed air, so that reaction temperature is reduced to room temperature.After reacting 8h, by product in methanol With Precipitation in the mixed liquor (1:1) of water, and with ethyl alcohol wash products 3 times.After product is dried in vacuo for 24 hours at 30 DEG C, The homopolymer in product is removed with chloroform.Obtain subject polymer P (VDF-co-CTFE)-g-PMA.Products therefrom list Transformation rate is 72.23%, grafting amount 14.75mol%.
Comparative example 1:
Poly- (vinylidene-copolymerization-chlorotrifluoroethylene) P (VDF-co- of 2.0g is sequentially added into tri- mouthfuls of vials of 250ml CTFE) (VDF:CTFE=94:6) (atom of Cl containing 1.8mmol), Cu (0) (28.8mg, 0.45mmol) empty in there-necked flask Air is re-filled with nitrogen, is added dimethyl sulfoxide (DMSO), and magnetic agitation is completely dissolved P (VDF-co-CTFE).It is protected in nitrogen Shield is lower to be added ligand Me6- TREN (104 μ L, 0.45mmol), monomers methyl methacrylate MMA (5.7ml, 54mmol) make [Cl]:[Cu(0)]:[Me6- TREN]: [MMA]=1:0.25:0.25:30.2h is reacted at 30 DEG C.After reaction with methanol and The mixed liquor (1:1) of water precipitates.With ethyl alcohol wash products 3 times, to remove residual monomer and solvent in product.By product at 30 DEG C Lower vacuum drying is for 24 hours.Products therefrom grafting amount is 7.62mol%.

Claims (8)

1. a kind of method of photoinduction organic catalysis polymer modification, which comprises the following steps:
(1) under the conditions of anaerobic is protected from light, macromole evocating agent and organic catalyst is dissolved in solvent, obtain homogeneous phase solution;
(2) under anaerobic illumination condition, monomer is added into homogeneous phase solution obtained in step (1) and carries out atom transferred free radical Polymerization reaction stops illumination, isolates precipitating after reaction;
In step (1), the macromole evocating agent is poly- (vinylidene-copolymerization-chlorotrifluoroethylene), and every gram of macromolecular is drawn Hair agent is dissolved in solvent described in 5~40mL.
2. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that in step (1), institute It states organic catalyst and is selected from 10- phenyl phenthazine, 10- (4- methoxyphenyl) phenthazine, 10- (1- naphthalene) phenthazine, dinaphthyl Embedding benzene, 3,7- bis- (4- (1,1 '-biphenyl))-(10- (1- naphthalene)) -10- phenoxazine, 5,10- diphenyl -5,10- dihydrophenazine, 5,10- bis- (4- methoxyphenyl) -5,10- dihydrophenazines, 5,10- bis- (4- (trifluoromethyl) phenyl) -5,10- dihydrophenazine, 5,10- bis- (4- (itrile group) phenyl) -5,10- dihydrophenazines, 5,10- bis- (2- naphthalene) -5,10- dihydrophenazine or 5, bis- (1- of 10- Naphthalene) one of -5,10- dihydrophenazine or a variety of.
3. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that in step (1), institute Stating solvent is dimethyl sulfoxide or n,N-Dimethylformamide.
4. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that in step (2), institute Stating monomer is methyl methacrylate or methyl acrylate.
5. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that in step (2), institute The wave-length coverage for stating illumination is 280~450nm.
6. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that in step (2), institute The temperature for stating reaction is 20~60 DEG C.
7. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that in step (2), institute The time for stating reaction is 5min~for 24 hours.
8. the method for photoinduction organic catalysis polymer modification according to claim 1, which is characterized in that institute in step (1) The molar ratio of monomer described in initiator, catalyst and the step (2) stated is 1: 0.06~0.5: 1~50.
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CN103387642B (en) * 2013-07-12 2016-05-04 西安交通大学 The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer
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