CN106893039B - Method for modifying photo-induced organic catalytic polymer - Google Patents
Method for modifying photo-induced organic catalytic polymer Download PDFInfo
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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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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000005286 illumination Methods 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- XNFHFFWRUFLEQE-UHFFFAOYSA-N 5,10-bis(4-methoxyphenyl)phenazine Chemical class COC1=CC=C(C=C1)N1C=2C=CC=CC=2N(C2=CC=CC=C12)C1=CC=C(C=C1)OC XNFHFFWRUFLEQE-UHFFFAOYSA-N 0.000 claims description 3
- KGCIHVDTVLIHTB-UHFFFAOYSA-N 5,10-bis[4-(trifluoromethyl)phenyl]phenazine Chemical compound FC(C1=CC=C(C=C1)N1C=2C=CC=CC=2N(C2=CC=CC=C12)C1=CC=C(C=C1)C(F)(F)F)(F)F KGCIHVDTVLIHTB-UHFFFAOYSA-N 0.000 claims description 3
- RCBSZGSHSLQLBI-UHFFFAOYSA-N 5,10-diphenylphenazine Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N(C=2C=CC=CC=2)C2=CC=CC=C21 RCBSZGSHSLQLBI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 36
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229920001002 functional polymer Polymers 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000013019 agitation Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 230000000873 masking effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a method for modifying a photoinduced organic catalytic polymer, which comprises the following steps: dissolving a macromolecular initiator and an organic catalyst in a solvent under the oxygen-free and light-resistant conditions to obtain a homogeneous solution; and (2) under the condition of oxygen-free illumination, adding a monomer into the homogeneous phase solution obtained in the step (1) to perform atom transfer radical polymerization, stopping illumination after the reaction is finished, and separating out a precipitate. The method can simply, effectively and environmentally synthesize the functional polymer, and the product has no metal residue and has good application prospect in the aspect of electrical materials.
Description
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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