CN101792503A - Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof - Google Patents
Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as shown in the following formula as well as a preparation method and application thereof. The preparation method comprises the following steps of: uniformly mixing 100 parts by weight of fluorinated acrylate monomers, 0.1-30 parts by weight of halide initiators, 0.1-50 parts by weight of coordination agents and 0-500 parts by weight of organic solvents; freezing through ice-salt bath; vacuumizing, and blowing nitrogen by 3-5 times to remove oxygen; then heating to 30-150 DEG C under the protection of the nitrogen; adding 0.1-50 parts by weight of catalysts, and reacting for 1.5-25 hours to obtain the fluorinated acrylate ATRP macromolecule initiator. The fluorinated acrylate ATRP macromolecule initiator not only fills the blank of a fluorinated acrylate macromolecule initiator, but also has narrower molecular weight distribution, can initiate the polymerization of non-fluoride monomer matters, is used for preparing fluorinated segmented copolymers, and has low cost.
Description
Technical field
The present invention relates to a kind of ATRP reaction macromole evocating agent, particularly a kind of acrylate containing fluorine ATRP macromole evocating agent and preparation method and application.
Background technology
Nineteen ninety-five, reported first such as doctor Wang Jinshan of U.S. Carnegie Mellon University, K.Matyjaszewski transition metal-catalyzed controllable free-radical polymerisation, be referred to as atom transfer radical polymerization (Atom Transfer Radical Polymerization, ATRP).
This method is that activity/controllable free-radical polymerisation has been opened up a brand-new approach.It is an initiator with simple Organohalogen compounds, and transition metal complex is the halogen atom carrier, by redox reaction, sets up running balance between spike and dormancy kind, thereby realizes the control to polyreaction.
It is extensive that the ATRP method has monomer selectivity, the narrow advantages such as (Mw/Mn=1.1~1.5) of synthetic molecular weight distribution.Initiator one end is a halogen atom, the other end can be functional groups such as halogen atom or carboxyl, therefore the existence of functional group can not influence carrying out smoothly of controllable reaction, utilizes the ATRP method can prepare the multipolymer (as block, random, grafting, alternately, gradient, star, comb shape, high branching, crosslinked) and the homopolymer (novel end-functionalization, distant pawl, high branching etc.) of the various topological frameworks that relative molecular weight and end group determine easily.
The ATRP method is one of important means of preparation segmented copolymer.Segmented copolymer has microcosmic and divides phase behavior, and this makes it can have unique macroscopical amphiphilic nature, thereby has broad application prospects in fields such as tensio-active agent, caking agent, coating and polymer blending increase-volumes.Fluorinated block copolymer also has characteristics such as low surface energy, high unreactiveness, thereby enjoy attention in scientific research field and practical application except having macroscopical amphiphilic nature.
The ATRP method prepares segmented copolymer, and used initiator can be divided into two classes substantially, and a class is the small molecules initiator, and another kind of is macromole evocating agent.Compare with the small molecules initiator, macromole evocating agent be initiator be again the part of segmented copolymer, because of its diffusion and reactivity all lower, make the controllability of reaction stronger.At present, the report that relates to fluorine-containing macromole evocating agent in the ATRP reaction is less, the fluorine-containing macromole evocating agent of having reported is the nonactive/controllable free-radical polymerisation that causes by normal starter (as superoxide), and its shortcoming is that the polymerization degree and polymolecularity are uncontrollable.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of acrylate containing fluorine ATRP macromole evocating agent with not enough.This acrylate containing fluorine ATRP macromole evocating agent can cause other non-fluorine monomer species polymerizations, and the utilization ratio of fluorine is higher.
Another object of the present invention is to provide the preparation method of described acrylate containing fluorine ATRP macromole evocating agent.
A further object of the present invention is to provide the application of described acrylate containing fluorine ATRP macromole evocating agent.
Purpose of the present invention is achieved through the following technical solutions: a kind of acrylate containing fluorine ATRP macromole evocating agent, and its chemical structural formula is suc as formula shown in the I:
N is 2~300 natural number;
R is benzene alkyl, α-ester group, cyano group, polyhalohydrocarbon base or sulfonyl group;
R ' be H or-CH
3
R
fThe expression carbon chain lengths is C
1~C
25Polyfluoroalkyl, promptly the hydrogen atom in the alkyl partly replaced by fluorine atom or all the displacement;
X is a halogen atom;
The preparation method of described acrylate containing fluorine ATRP macromole evocating agent comprises the steps:
(1) the monomeric processing of acrylate containing fluorine: with deionized water the acrylate containing fluorine monomer is washed till neutrality, uses CaCl then successively
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is underpressure distillation purifying down, preserves in 0~4 ℃ of sealing, standby;
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: acrylate containing fluorine monomer, 0.1~30 mass parts halogenide initiator, 0.1~50 mass parts coordination agent and 0~500 mass parts organic solvent that 100 mass parts steps (1) are handled well mix, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3~5 times is with deoxygenation; Under nitrogen protection, be warming up to 30~150 ℃ then, add 0.1~50 mass parts of catalyst reaction, 1.5~25h, obtain acrylate containing fluorine ATRP macromole evocating agent.
Described acrylate containing fluorine monomer is preferably at least a in methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate or the methacrylic acid ten difluoro heptyl esters;
Described halogenide initiator comprises 1. halogenophenyl compound: as the chlorination Bian; 2. halogen ester compounds: as 2-chlorine ethyl isobutyrate, 2 bromopropionic acid methyl esters, alpha-chloro ethyl propionate etc.; 3. halo itrile group compound: as chloromethyl cyanide etc.; 4. polyhalogenide: as tetracol phenixin, trichloromethane etc.; 5. sulfuryl halide is as benzene sulfonyl chloride;
Described coordination agent comprises 1. dipyridyl and derivative thereof, as 2, and 2 '-dipyridyl; 2. the straight-chain paraffin of many nitrogen is as pentamethyl-diethylenetriamine (PMDETA); 3. triphenylphosphine;
Described organic solvent comprises toluene, 1,4-dioxane and butanone etc.;
Described catalyzer is that the lower valency metal halide (is comparatively speaking herein at a low price, bromide as copper, 2 kinds of cupric bromide and cuprous bromides are arranged, have only cuprous bromide at a low price that catalytic capability is just arranged, and cupric bromide does not have catalytic, similarly ferrous bromide and iron bromide also are that ferrous bromide has catalytic), as cuprous bromide, ferrous bromide;
Described cryosel bath refrigerated condition is as follows: add 20g CaCl in 100 gram trash ices
26H
2O stirs and obtains;
Described acrylate containing fluorine ATRP macromole evocating agent is applied to ATRP prepared in reaction fluorinated block copolymer;
Described acrylate containing fluorine ATRP macromole evocating agent is applied to ATRP prepared in reaction fluorinated block copolymer, may further comprise the steps: the non-fluorine monomer of 100 mass parts, 1~100 mass parts acrylate containing fluorine ATRP macromole evocating agent and 0.01~50 mass parts coordination agent and 0~500 mass parts organic solvent are mixed, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3~5 times is with deoxygenation; Under nitrogen protection, be warming up to 30~150 ℃ then, add 0.01~50 mass parts of catalyst reaction, 1.5~25h, obtain fluorinated block copolymer.
Described non-fluorine monomer is 1. one or more in vinylbenzene or the substituted phenylethylene class, and substituted phenylethylene is as to chloro-styrene etc.; 2. (methyl) esters of acrylic acid, comprise general (methyl) acrylate and (methyl) acrylate that has functional group, general (methyl) acrylate comprises (methyl) methyl acrylate and (methyl) isobutyl acrylate etc., and (methyl) acrylate that has a functional group comprises (methyl) Propylene glycol monoacrylate etc. or its mixture; 3. (methyl) vinyl cyanide;
Described coordination agent comprises 1. dipyridyl and derivative thereof, as 2, and 2 '-dipyridyl; 2. the straight-chain paraffin of many nitrogen is as pentamethyl-diethylenetriamine (PMDETA); 3. triphenylphosphine;
Described organic solvent comprises toluene, 1,4-dioxane and butanone etc.;
Described catalyzer is that the lower valency metal halide (is comparatively speaking herein at a low price, bromide as copper, 2 kinds of cupric bromide and cuprous bromides are arranged, have only cuprous bromide at a low price that catalytic capability is just arranged, and cupric bromide does not have catalytic, similarly ferrous bromide and iron bromide also are that ferrous bromide has catalytic), as cuprous bromide, ferrous bromide;
Described cryosel bath refrigerated condition is as follows: add 20g CaCl in 100 gram trash ices
26H
2O stirs and obtains.
The present invention has following advantage and effect with respect to prior art:
The present invention has not only filled up the blank of acrylate containing fluorine macromole evocating agent, and the fluorine-containing macromole evocating agent of preparation, and molecular weight distribution is narrower.Cause other non-fluorine monomer material polymerizations by acrylate containing fluorine macromole evocating agent of the present invention simultaneously, the utilization ratio height of fluorine, and since non-fluorine monomer material therefore than fluorochemical monomer material low price, prepare fluorinated block copolymer by acrylate containing fluorine macromole evocating agent of the present invention and will save Financial cost greatly.
Embodiment
The invention will be further described below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) the monomeric processing of acrylate containing fluorine: with deionized water methacrylic acid hexafluoro butyl ester monomer is washed till neutrality, uses CaCl then successively
2And CaH
2Soaked respectively 2 days, at last purity greater than 99% protection of nitrogen gas under and at CaH
2Have underpressure distillation purifying down, sealing is stored in 0~4 ℃ of refrigeration of refrigerator, and is standby;
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: with methacrylic acid hexafluoro butyl ester monomer, 0.1g chloromethyl cyanide and the 0.1g 2 after 100g step (1) processing, 2 '-dipyridyl joins in the there-necked flask of band high speed agitator, thermometer and prolong, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃); vacuumize; drum nitrogen repeats 3 times; under nitrogen protection, be warming up to 30 ℃; add the 0.1g cuprous bromide; continue logical nitrogen; reaction 25h; obtain polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent; (step is same: Preparation ofpoly (oligo (ethylene glycol) monomethyl ethermethacrylate) by HomogeneneousAqueous AGET ATRP by gel permeation chromatography (GPC) method; Macromolecules 2006; 39,3161-3167) record molecular weight Mn=7.51 * 10
4, polydispersity coefficient PDI=1.24.Determine shown in this macromole evocating agent structural formula II (n=300) according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle:
(3) preparation fluorinated block copolymer: the polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent and 2.70g 2, the 2 '-dipyridyl of 100g Propenoic acid, 2-methyl, isobutyl ester monomer, 100g step (2) preparation are mixed, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃); vacuumizing, rouse nitrogen repeats 3 times; under nitrogen protection, be warming up to 100 ℃; add the 3.62g cuprous bromide; continue logical nitrogen; reaction 2.5h gets polyisobutyl methacrylate-b-methacrylic acid hexafluoro butyl ester segmented copolymer, records molecular weight Mn=1.43 * 10 by gel permeation chromatography (GPC) method
5, polydispersity coefficient PDI=1.22.
Embodiment 2
(1) the monomeric processing of acrylate containing fluorine: with embodiment 1 step (1);
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: methacrylic acid hexafluoro butyl ester monomer, 30g 2-isobutyl ethyl bromide and 50g triphenylphosphine after 100g step (1) processing are joined in the there-necked flask of band high speed agitator, thermometer, prolong, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃); vacuumizing, rouse nitrogen repeats 3 times; under nitrogen protection, be warming up to 150 ℃; add the 50g ferrous bromide; continue logical nitrogen; reaction 1.5h obtains polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent, records molecular weight Mn=6.95 * 10 by gel permeation chromatography (GPC) method
2, polydispersity coefficient PDI=1.23.Determine shown in this macromole evocating agent structural formula II I (n=2) according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle:
(3) preparation fluorinated block copolymer: with polymethyl acrylic acid hexafluoro butyl ester macromole evocating agent, 31.76g pentamethyl-diethylenetriamine (PMDETA) and the 500g1 of 100g styrene monomer, 32.50g step (2) preparation, the 4-dioxane, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃); vacuumizing, rouse nitrogen repeats 3 times; under nitrogen protection, be warming up to 95 ℃; add the 31.56g cuprous bromide; continue logical nitrogen; reaction 2.5h gets polystyrene-b-methacrylic acid hexafluoro butyl ester segmented copolymer, and recording its molecular weight by gel permeation chromatography (GPC) method is Mn=2.75 * 10
3, polydispersity coefficient is PDI=1.28.
Embodiment 3
(1) the monomeric processing of acrylate containing fluorine: with embodiment 1 step (1), difference only is that handled acrylate containing fluorine monomer is trifluoroethyl methacrylate monomer and methacrylic acid hexafluoro butyl ester, handles respectively;
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: the trifluoroethyl methacrylate monomer that 40g step (1) is handled well, methacrylic acid hexafluoro butyl ester, 5.13g alpha-chloro ethyl propionate and the 12.58g triphenylphosphine that 60g step (1) is handled well join in the there-necked flask of band high speed agitator, thermometer, prolong, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃); vacuumizing, rouse nitrogen repeats 3 times; under nitrogen protection, be warming up to 95 ℃; add the 7.58g ferrous bromide; continue logical nitrogen; reaction 3h obtains containing the fluoride mixture macromole evocating agent, records molecular weight Mn=2.65 * 10 by gel permeation chromatography (GPC) method
3, polydispersity coefficient PDI=1.23.Determine (n=12, wherein R shown in this macromole evocating agent structural formula IV according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle
fFor-CF
3Or-C
3HF
6):
(3) preparation fluorinated block copolymer: with the preparation of 100g methyl methacrylate monomer, 15.11g step (2) contain the fluoride mixture macromole evocating agent and 1.00g 2,2 '-dipyridyl mixes, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, under nitrogen protection, be warming up to 100 ℃; add the 1.80g cuprous bromide, continue logical nitrogen, reaction 2.5h; get segmented copolymer, recording molecular weight by gel permeation chromatography (GPC) method is Mn=1.96 * 10
4, polydispersity coefficient is PDI=1.25.
Embodiment 4
(1) the monomeric processing of acrylate containing fluorine: with embodiment 1 step (1), difference only is that handled acrylate containing fluorine monomer is the trifluoroethyl methacrylate monomer.
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: trifluoroethyl methacrylate monomer, 7.96g benzene sulfonyl chloride and 19.49g 2 that 100g step (1) is handled well, 2 '-dipyridyl joins in the there-necked flask of band high speed agitator, thermometer, prolong, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, be warming up to 95 ℃ under nitrogen protection, add the 11.71g cuprous bromide, continue logical nitrogen, reaction 3h obtains polymethyl acrylic acid trifluoro ethyl ester macromole evocating agent.Record molecular weight Mn=2.36 * 10 by gel permeation chromatography (GPC) method
3, polydispersity coefficient PDI=1.24.Determine shown in this macromole evocating agent structural formula V (n=13) according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle:
(3) preparation fluorinated block copolymer: with the polymethyl acrylic acid trifluoro ethyl ester macromole evocating agent and the 50g 4 of 100g acrylonitrile monemer, 100g step (2) preparation, 4 '-dinonyl-2,2 '-dipyridyl, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, be warming up to 30 ℃ under nitrogen protection, add the 50g iron protochloride, continue logical nitrogen, reaction 25h gets polyacrylonitrile-b-trifluoroethyl methacrylate segmented copolymer.Recording molecular weight by gel permeation chromatography (GPC) method is Mn=4.63 * 10
3, polydispersity coefficient is PDI=1.26.
Embodiment 5
(1) the monomeric processing of acrylate containing fluorine: with embodiment 1 step (1), difference only is that handled acrylate containing fluorine monomer is methacrylic acid ten difluoro heptyl ester monomers.
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: methacrylic acid ten difluoro heptyl ester monomers, 2.57g 2-isobutyl ethyl bromide and 2.00g pentamethyl-diethylenetriamine (PMDETA) that 100g step (1) is handled well join in the there-necked flask that has high speed agitator, thermometer, prolong, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, be warming up to 105 ℃ under nitrogen protection, add the 2.11g cuprous bromide, continue logical nitrogen, reaction 3h obtains polymethyl acrylic acid ten difluoro heptyl ester macromole evocating agents.Record molecular weight Mn=7.40 * 10 by gel permeation chromatography (GPC) method
3, polydispersity coefficient PDI=1.24.Determine shown in this macromole evocating agent structural formula VI (n=18) according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle:
(3) preparation fluorinated block copolymer: 59g Propenoic acid, 2-methyl, isobutyl ester and 41g methyl methacrylate are mixed, the polymethyl acrylic acid ten difluoro heptyl ester macromole evocating agents and the 8.25g 2 that add 13.89g step (2) preparation again, 2 '-dipyridyl, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, be warming up to 100 ℃ under nitrogen protection, add the 9.88g cuprous bromide, continue logical nitrogen, reaction 2.5h makes segmented copolymer.Recording molecular weight by gel permeation chromatography (GPC) method is Mn=5.86 * 10
4, polydispersity coefficient is PDI=1.22.
Embodiment 6
(1) the monomeric processing of acrylate containing fluorine: with embodiment 5 steps (1).
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: methacrylic acid ten difluoro heptyl ester monomers, 20.25g 2 bromopropionic acid methyl esters, 500g toluene and 5g triphenylphosphine that 100g step (1) is handled well join in the there-necked flask that has high speed agitator, thermometer, prolong, mix, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, be warming up to 95 ℃ under nitrogen protection, add the ferrous 6.03g of chlorination, continue logical nitrogen, reaction 3h obtains polymethyl acrylic acid ten difluoro heptyl ester macromole evocating agents.Record molecular weight Mn=9.67 * 10 by gel permeation chromatography (GPC) method
2And polydispersity coefficient PDI=1.23.Determine shown in this macromole evocating agent structural formula VII (n=2) according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle:
(3) preparation fluorinated block copolymer: the polymethyl acrylic acid ten difluoro heptyl ester macromole evocating agents and the 0.1g pentamethyl-diethylenetriamine (PMDETA) of 100g methyl methacrylate monomer, 1g step (2) preparation are mixed, containing 60g CaCl
26H
2Carry out cryosel in the 100 gram trash ices of O and bathe freezing (4 ℃), vacuumize, rouse nitrogen and repeat 3 times, under nitrogen protection, be warming up to 150 ℃; add the 0.1g cuprous bromide; continue logical nitrogen, reaction 1.5h gets polymethylmethacrylate-b-methacrylic acid ten difluoro heptyl ester segmented copolymers.Recording molecular weight by gel permeation chromatography (GPC) method is Mn=9.28 * 10
4, polydispersity coefficient is PDI=1.23.
Embodiment 7
The process of preparation is distinguished and is with embodiment 6 steps (1) and (2):
Preparation macromole evocating agent 1, temperature of reaction is 95 ℃, monomer and initiator quality summation 25g, catalyzer 0.8g, coordination agent 0.4g, organic solvent are toluene 20g, the reaction times is 3h.
Preparation macromole evocating agent 2, temperature of reaction is 95 ℃, monomer and initiator quality summation 30g, catalyzer 0.9g, coordination agent 0.6g, organic solvent are 1,4-dioxane 10g, the reaction times is 3h.
Preparation macromole evocating agent 3, temperature of reaction is 95 ℃, monomer and initiator quality summation 25g, catalyzer 1.1g, coordination agent 0.8g, organic solvent are butanone 15g, the reaction times is 3h.
Preparation macromole evocating agent 4, temperature of reaction is 95 ℃, monomer and initiator quality summation 25g, catalyzer 1.4g, coordination agent 0.8g, organic solvent are toluene 15g, the reaction times is 3h.
Preparation macromole evocating agent 5, temperature of reaction is 95 ℃, monomer and initiator quality summation 30g, catalyzer 0.9g, coordination agent 0.7g, organic solvent are 1,4-dioxane 15g, the reaction times is 3h.
Preparation macromole evocating agent 6, temperature of reaction is 95 ℃, monomer and initiator quality summation 25g, catalyzer 0.8g, coordination agent 0.6g, organic solvent are 1,4-dioxane 20g, the reaction times is 3h.
All record molecular weight and polydispersity coefficient by gel permeation chromatography (GPC) method, as shown in table 1.
The preparation result of the different macromole evocating agents of table 1
Sequence number | Monomer (M) | Initiator (I) | M and the I mass ratio that feeds intake | Catalyzer | Coordination agent | Molecular weight of product | Polydispersity coefficient |
Macromole evocating agent 1 | ??M 1 | The 2-isobutyl ethyl bromide | ??100∶6 | Cuprous bromide | 2,2 '-dipyridyl | ??3.1×10 3 | ??1.22 |
Macromole evocating agent 2 | ??M 1 | The chlorination Bian | ??100∶2 | Ruthenous chloride | Triphenylphosphine | ??6.2×10 3 | ??1.21 |
Macromole evocating agent 3 | ??M 2 | The alpha-chloro ethyl propionate | ??100∶3.5 | Cuprous chloride | Pentamethyl-diethylenetriamine | ??4.0×10 3 | ??1.21 |
Macromole | ??M 2 | Benzene sulfonyl | ??100∶3.0 | Ferrous bromide | Triphenylphosphine | ??6.0×10 3 | ??1.23 |
Initiator 4 | Chlorine | ||||||
Macromole evocating agent 5 | ??M 1With M 2Mixture | The chlorination Bian | ??M 1∶M 2∶I=??76∶24∶2.5 | Cuprous bromide | 2,2 '-dipyridyl | ??5.2×10 3 | ??1.22 |
Macromole evocating agent 6 | ??M 1With M 2Mixture | The alpha-chloro ethyl propionate | ??M 1∶M 2∶I=??24∶76∶1.7 | Ruthenous chloride | Triphenylphosphine | ??8.2×10 3 | ??1.24 |
Remarks: M
1Be methacrylic acid hexafluoro butyl ester, M
2Be methacrylic acid ten difluoro heptyl esters.
The data of table 1 show, the inventive method can successfully be synthesized the acrylate containing fluorine macromole evocating agent, and synthetic macromole evocating agent narrow molecular weight distribution, that is to say, can can both cause the same monomer polymerization with different initiators, different coordination agent, different catalysts, different proportioning, the preparation macromole evocating agent.
Utilizing the macromole evocating agent of preparation to cause identical non-fluorine monomer prepares fluorinated block copolymer (step is with embodiment 2 steps (3), the parameter of difference is as follows: 90 ℃ of temperature of reaction, reaction times is 2.5h, solvent is 1,4-dioxane 15g (I ' and the quality summation of M ' all be 25g, catalyst consumption is respectively 0.7g, 0.8g, 0.5g, and the consumption of coordination agent is respectively 1.23g, 1.22g, 0.54g, goes up order extremely down from table)., record molecular weight and polydispersity coefficient by gel permeation chromatography (GPC) method, as shown in table 2:
The different macromole evocating agents of table 2 cause the result that same monomer prepares fluorinated block copolymer
Utilize the identical macromole evocating agent initiation different monomers of preparation to prepare fluorinated block copolymer, 105 ℃ of temperature of reaction, reaction times is 3h, solvent be butanone 15g (I ' and the quality of M ' and be 25g, catalyst consumption is respectively 0.8g, 0.7g, 0.5g, 0.9g, and the consumption of coordination agent is respectively 1.06g, 1.23g, 0.76g, 0.98g, goes up order extremely down from table), record molecular weight and polydispersity coefficient by gel permeation chromatography (GPC) method, as shown in table 3:
The identical macromole evocating agent of table 3 causes the result that different monomers prepares fluorinated block copolymer
Can successfully cause the polymerization of non-fluorine monomer by table 2 and table 3 data acrylate containing fluorine macromole of the present invention as can be known, the preparation fluorinated block copolymer, that is to say, can cause the different monomers polymerization, the preparation fluorinated block copolymer with identical macromole evocating agent.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. acrylate containing fluorine ATRP macromole evocating agent, it is characterized in that: the chemical structural formula of described acrylate containing fluorine ATRP macromole evocating agent is suc as formula shown in the I:
N is 2~300 natural number;
R is benzene alkyl, α-ester group, cyano group, polyhalohydrocarbon base or sulfonyl group;
R ' be H or-CH
3
R
fThe expression carbon chain lengths is C
1~C
25Polyfluoroalkyl, promptly the hydrogen atom in the alkyl partly replaced by fluorine atom or all the displacement;
X is a halogen atom.
2. the preparation method of the described acrylate containing fluorine ATRP of claim 1 macromole evocating agent is characterized in that comprising the steps:
(1) the monomeric processing of acrylate containing fluorine: with deionized water the acrylate containing fluorine monomer is washed till neutrality, uses CaCl then successively
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is underpressure distillation purifying down, preserves in 0~4 ℃ of sealing, standby;
(2) preparation of acrylate containing fluorine ATRP macromole evocating agent: acrylate containing fluorine monomer, 0.1~30 mass parts halogenide initiator, 0.1~50 mass parts coordination agent and 0~500 mass parts organic solvent that 100 mass parts steps (1) are handled well mix, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3~5 times is with deoxygenation; Under nitrogen protection, be warming up to 30~150 ℃ then, add 0.1~50 mass parts of catalyst reaction, 1.5~25h, obtain acrylate containing fluorine ATRP macromole evocating agent;
Described catalyzer is the lower valency transition metal halide.
3. preparation method according to claim 2 is characterized in that: described acrylate containing fluorine monomer is at least a in methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate or the methacrylic acid ten difluoro heptyl esters.
4. preparation method according to claim 2 is characterized in that: described halogenide initiator is at least a in halogenophenyl compound, halogen ester compounds, halo itrile group compound, polyhalogenide or the sulfuryl halide.
5. preparation method according to claim 2 is characterized in that: described coordination agent is at least a in the straight-chain paraffin of dipyridyl and derivative thereof, many nitrogen or the triphenylphosphine.
6. preparation method according to claim 2 is characterized in that: described organic solvent is a toluene, 1, at least a in 4-dioxane or the butanone.
7. according to each described preparation method of claim 2~6, it is characterized in that: described cryosel bath refrigerated condition is as follows: add 20g CaCl in 100 gram trash ices
26H
2O stirs promptly.
8. the application of the described acrylate containing fluorine ATRP of claim 1 macromole evocating agent is characterized in that: described acrylate containing fluorine ATRP macromole evocating agent is applied to ATRP prepared in reaction fluorinated block copolymer.
9. application according to claim 8, it is characterized in that: described acrylate containing fluorine ATRP macromole evocating agent is applied to ATRP prepared in reaction fluorinated block copolymer, may further comprise the steps: the non-fluorine monomer of 100 mass parts, 1~100 mass parts acrylate containing fluorine ATRP macromole evocating agent and 0.01~50 mass parts coordination agent and 0~500 mass parts organic solvent are mixed, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3~5 times is with deoxygenation; Under nitrogen protection, be warming up to 30~150 ℃ then, add 0.01~50 mass parts of catalyst reaction, 1.5~25h, obtain fluorinated block copolymer.
10. application according to claim 9 is characterized in that:
Described non-fluorine monomer is vinylbenzene, substituted phenylethylene class material, (methyl) esters of acrylic acid material or (methyl) vinyl cyanide;
Described coordination agent is at least a in the straight-chain paraffin of dipyridyl and derivative thereof, many nitrogen or the triphenylphosphine;
Described organic solvent is a toluene, 1, at least a in 4-dioxane or the butanone;
Described catalyzer is the lower valency transition metal halide;
Described cryosel bath refrigerated condition is as follows: add 20g CaCl in 100 gram trash ices
26H
2O stirs promptly.
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