CN105294524A - Dithiocarboxylic acid pentafluorobenzyl ester, preparation method and application thereof - Google Patents
Dithiocarboxylic acid pentafluorobenzyl ester, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dithiocarboxylic acid pentafluorobenzyl ester, a preparation method and an application thereof. A structural formula of the dithiocarboxylic acid pentafluorobenzyl ester is shown in a specification, the preparation method comprises the following steps: taking pentafluoride bromo-carbons as a substrate, under iodine catalysis, reacting the substrate and magnesium powder or reacting the substrate and brominated ethyl magnesium for synthesizing a grignard reagent having a pentafiuorophenyl end group, reacting the reagent with carbon disulfide for synthesizing to obtain dithiocarboxylate, then performing an esterification reaction with alpha-bromine-2,3,4,5,6-pentafluorotoluene to prepare the dithiocarboxylic acid pentafluorobenzyl ester. According to the invention, the dithiocarboxylic acid pentafluorobenzyl ester can be taken as a high fluorine-containing RAFT reagent, can be used for a supercritical carbon dioxide system to realize RAFT polymerization of a (methyl) fluoroalkyl acrylate fluorine-containing monomer under mild condition, and the prepared fluorine-containing polymer having a highly stable pentafiuorophenyl end group. The polymer has good hydrophobicity, weatherability and soiling resistance, the high fluorine-containing end group can enhance heat stability and transmittance of the polymer, so that application requirement under special condition can be satisfied.
Description
Technical field
The invention belongs to polymer chemistry chemical technology field, be specifically related to a kind of fluorine-containing reversible addion-fragmentation chain transfer agent (RAFT reagent) dithionic acid PFBBR ester and its preparation method and application.
Background technology
Activity/controllable free-radical polymerisation is with the advantage of radical polymerization and living polymerisation process.Reversible addion-fragmentation chain transfer polymerization (RAFT polymerization) is a kind of typical activity/controllable free radical polymerization.In recent years, RAFT polymerization is because monomer whose is applied widely, polymerizing condition is gentle and effectively can control the plurality of advantages such as product structure, become a kind of important method of Polymer supported catalyst and synthesis, in the synthesis block, grafting, hyperbranched and star etc. with complex topology structure polymkeric substance, obtain investigation and application widely.
Practice shows, it is design and select the RAFT reagent being suitable for target polymerization reaction system that RAFT is polymerized the key factor that can realize smoothly, this not only requires that the selected solubility property of RAFT reagent in polymerization system is good, the diffusion of its mass transfer can not affect polymerization process, what is more important, RAFT reagent selected by requirement can match with subject monomers in reactivity worth, there is in RAFT reagent molecule excellent leavings group and suitable electron-withdrawing substituent, reversible addition-fracture chain tra nsfer process can be realized smoothly while guarantee has sound response activity.
The RAFT reagent used in controllable free-radical polymerisation is at present mainly dithiocarboxylic esters, dithiocarbamate, trithiocarbonate and xanthate etc., the common feature of these RAFT reagent is many not containing the contour fluoro-containing group of pentafluorophenyl group in its molecule, is also used for the polymerization system of some not fluorochemical monomers (as vinylbenzene, (methyl) vinylformic acid, (methyl) acrylate and part vinyl ethers monomer).
Fluorine-containing (methyl) acrylate is with the double characteristic of (methyl) acrylic ester monomer and fluorochemical monomer, there are excellent hydrophobic nature, resistance to soiling and excellent optical property etc. by the fluoropolymer of this class monomer polymerization, have broad application prospects in fields such as high performance coated material, film material with function, medical macromolecular materials, optics and photoconductive fibers.
Document (JournalofPolymerScience, PartA:PolymerChemistry, 2009,47,3702-3709) disclose several trithiocarbonic acid-two (substituted-phenyl) ester compound, atom direct-connected with phenyl ring on these trithiocarbonate substituting groups is H or O or Cl etc.In view of these C-X keys on phenyl ring, (X is H, O or Cl, X is not F) bond energy less, if when this class trithiocarbonate is used as RAFT reagent, the chain tra nsfer side reaction not wishing to occur will be there is at these C-X key places in polymerization process, the controllability of polymerization process is caused significantly to decline, all the more so time particularly X is Cl atom.The document does not record any example synthesized trithiocarbonate being used for activity/controllable free-radical polymerisation.Document (painting, 2010,8,16-24) reports using trithio dibenzyl carbonic ether (DBTTC) as RAFT reagent, the polymerization that vinylbenzene and 1H, 1H, 2H, 2H-perfluoroethyl ester in the last of the ten Heavenly stems (FOA) are monomer.But in literary composition, do not prove the activity/controllable characteristics of this polymerization reaction system, thus and do not know whether DBTTC effectively can control the polymerization process of monomer (particularly fluorochemical monomer FOA).Document (University Of Ji'nan's journal, 2014,28,357-361) report using dithiobenzoic acid cumyl ester (CDB) as RAFT reagent, the polymerization that trifluoroethyl methacrylate (TFEMA) and methyl methacrylate (MMA) are monomer, and based on polymerization kinetics experimental result preliminary identification CDB for the validity of control TFEMA and MMA polymerization process.But in view of the relatively low fluorine content of polymerisate, its over-all properties is in fact being difficult to meet the application requiring under complex working condition or severe condition.Document (PolymerChemistry, 2015,6,448-458) report using trithiocarbonate DBTTC as chain-transfer agent, with vinylformic acid trifluoro ethyl ester, vinylformic acid five fluorine propyl ester and vinylformic acid seven fluorine butyl ester for the polymerization of monomer in dimethyl formamide, obtain the polymerisate of narrow molecular weight distributions, the preliminary identification controllability of DBTTC to polymerization process.Even if but trithiocarbonate like this take part in the polyreaction of fluorochemical monomer really as chain-transfer agent, gained fluoropolymer also will inevitably with the end group of instability (this end group comes from the residue of adopted RAFT reagent).The existence of unstable end-group, not only bad for the processing of fluoropolymer, also significantly can reduce the stability light transmission etc. of polymkeric substance.Obvious above-mentioned technology of preparing scheme can limit over-all properties and the range of application of fluorinated polymer material to a great extent.Chinese invention patent 201310740612.X disclose a kind of trithiocarbonic acid-two (PFBBR) ester (DPFBTTC) and as RAFT reagent supercritical carbon dioxide systems fluorine-containing (methyl) acrylate monomer polymerization in application.Disclosed DPFBTTC molecule has symmetrical structure, the PFBBR on both sides all can impel polymer chain to increase as leavings group in the course of the polymerization process, presents good control performance to the radical polymerization of height fluorine-containing (methyl) acrylate monomer (as dodecafluoroheptyl methacrylate).But, affect by factors such as steric effect and the mass transfer diffusions in polymerisation medium, the polymer chain on trithiocarbonate structural unit both sides is difficult to accomplish that symmetry (or synchronous) increases, be difficult to realize the higher levels of control of fluorochemical monomer radical polymerization process, cause polymericular weight and theoretical value to depart from more.Trithiocarbonate structural unit is in the middle of polymer chain in addition, is unfavorable for the aftertreatment of polymkeric substance or further functional modification.
Summary of the invention
A technical problem to be solved by this invention be to overcome existing RAFT reagent be difficult to effectively to control high fluorochemical monomer particularly the controllable free-radical polymerisation of high fluorine-containing (methyl) acrylic ester monomer and polymerisate there is the shortcomings such as unstable end group, provide that the solubility property of a class in supercritical co is excellent, the polymerization system be applicable in supercritical CO 2 medium, effectively can control high fluorochemical monomer radical polymerization process and the fluorine-containing RAFT reagent dithionic acid PFBBR ester of highly stable end group can be provided for gained fluoropolymer.
Another technical problem that the present invention will solve is as above-mentioned fluorine-containing RAFT reagent provides preparation method simple to operate.
The technical problem that the present invention also will solve is as above-mentioned fluorine-containing RAFT reagent provides a kind of novelty teabag.
Solving the problems of the technologies described above adopted technical scheme is: such fluorine-containing RAFT reagent is dithionic acid PFBBR ester, and its structural formula is as follows:
In formula, n is 0 or 1.
Fluorine-containing RAFT reagent dithionic acid PFBBR ester of the present invention adopts following route to synthesize:
Concrete building-up process is: under anhydrous and oxygen-free condition, five fluorine hydrobromic ethers and magnesium powder, iodine grain are reacted 3 ~ 5 hours or five fluorine hydrobromic ethers and ethyl-magnesium-bromide are reacted 2 ~ 5 hours at 40 ~ 60 DEG C at 50 ~ 70 DEG C, be prepared into Grignard reagent, five wherein said fluorine hydrobromic ethers are five bromofluorobenzenes or α-bromo-2,3,4,5,6-five toluene fluoride, solvent is ether or tetrahydrofuran (THF); In the Grignard reagent of preparation, add dithiocarbonic anhydride, 40 ~ 50 DEG C are reacted 2 ~ 4 hours, then add α-bromo-2,3,4,5,6-five toluene fluoride, 35 ~ 60 DEG C are reacted 10 ~ 20 hours, then add frozen water cancellation reaction, separation and purification product, obtains dithionic acid PFBBR ester.
The mol ratio of above-mentioned five fluorine hydrobromic ethers and magnesium powder or ethyl-magnesium-bromide, dithiocarbonic anhydride, α-bromo-2,3,4,5,6-five toluene fluorides is 1:(1 ~ 3): (1 ~ 3): (1 ~ 2).
Dithionic acid PFBBR ester of the present invention is polymerized at supercritical carbon dioxide systems fluoroalkyl base ester class fluorochemical monomer or perfluoroalkyl methacrylate class fluorochemical monomer RAFT the purposes prepared in the fluoropolymer of pentafluorophenyl group end group, and its using method is as follows:
In supercritical co, with above-mentioned dithionic acid PFBBR ester for RAFT reagent, to fluoroalkyl base ester class fluorochemical monomer or perfluoroalkyl methacrylate class fluorochemical monomer (as dodecafluoroheptyl methacrylate (DFHMA), Hexafluorobutyl mathacrylate (HFBMA) etc.), adopt document (Macromolecules2012, 45, polymerization process 4907-4919) reported is polymerized, wherein add fluoroalkyl base ester class fluorochemical monomer in autoclave or the fluorine-containing list of perfluoroalkyl methacrylate class and RAFT reagent, the mol ratio of radical initiator is (100 ~ 400): (1 ~ 2): (0.5 ~ 1), polymerization pressure is 15 ~ 30MPa, polymerization temperature is 50 ~ 90 DEG C, polymerization reaction time is 3 ~ 50 hours.
Dithionic acid PFBBR ester preparation process of the present invention is simple to operate, its fluorine-containing (methyl) acrylic ester polymer as RAFT tube-nursery is adopted to have high stability fluorine-containing end group (pentafluorophenyl group), this fluoropolymer is except having good hydrophobic nature, resistance to soiling, weathering resistance, high fluorine-containing end group can promote the stability of polymkeric substance and light transmission etc. further, thus the application requiring under being expected to meet special conditions.Dithionic acid PFBBR ester of the present invention, (methyl) fluoroalkyl base ester class fluorochemical monomer and the solubility property of polymkeric substance in supercritical co thereof are good, and the mass transfer diffusion of reaction system can not have a negative impact to polymerization process.The PFBBR that the reversible fracture of RAFT reagent dithionic acid PFBBR ester of the present invention produces afterwards is not only a kind of leavings group of good performance, for (methyl) fluoroalkyl base esters monomer that height is fluorine-containing, also have good consistency or affinity.Therefore, under fluorine-containing RAFT reagent dithionic acid PFBBR ester of the present invention participates in, fluorochemical monomer is expected to the RAFT polymerization realizing homogeneous phase in supercritical carbon dioxide systems under relatively mild pressure condition, prepares the fluoropolymer that structure-controllable performance is excellent.
Accompanying drawing explanation
Fig. 1 is that the monomer conversion of dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester prepared of embodiment 1 as dodecafluoroheptyl methacrylate polyreaction in supercritical co under RAFT reagent is with the relation curve in reaction times.
Fig. 2 is the ln ([M] of dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester as dodecafluoroheptyl methacrylate polyreaction under RAFT reagent of embodiment 1 preparation
0/ [M]) with the relation curve in reaction times.
Fig. 3 is that dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester prepared of embodiment 1 is as the monomer conversion of Hexafluorobutyl mathacrylate polyreaction under RAFT reagent and ln ([M]
0/ [M]) with the relation curve in reaction times.
Fig. 4 is that the monomer conversion of dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester prepared of embodiment 2 as dodecafluoroheptyl methacrylate polyreaction under RAFT reagent is with the relation curve in reaction times.
Fig. 5 is the ln ([M] of dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester as dodecafluoroheptyl methacrylate polyreaction under RAFT reagent of embodiment 2 preparation
0/ [M]) with the relation curve in reaction times.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but protection scope of the present invention is not limited only to these embodiments.
Embodiment 1
Dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester that composite structure formula is following
1.75mL (14mmol) five bromofluorobenzene is dissolved in 30mL tetrahydrofuran (THF), then under anhydrous and oxygen-free condition, the tetrahydrofuran solution of five bromofluorobenzenes is dropwise dripped in the three-necked flask that 0.36g (15mmol) magnesium powder and iodine grain (2 ~ 3) be housed, after purple in reaction mixture (color of iodine) disappears, raised temperature to 70 DEG C also under agitation dropwise drips the tetrahydrofuran solution of remaining five bromofluorobenzenes in three-necked flask, controlling rate of addition makes system keep slight boiling condition, dropwise latter 70 DEG C and continue reaction 2 hours, magnesium powder is made to react completely or substantially disappear, be prepared into Grignard reagent.The Grignard reagent of preparation is cooled to 40 DEG C, 1.14g (15mmol) dithiocarbonic anhydride is dripped wherein under whipped state, 40 DEG C of insulation reaction 3 hours, add 2.61g (10mmol) α-bromo-2 again, 3,4,5,6-five toluene fluoride, 45 DEG C of insulation reaction 12 hours, after reaction terminates, add 15mL frozen water cancellation reaction, extract three times with tetrahydrofuran (THF), the drying and except after desolventizing successively of the organic phase after merging, obtains crude product (Red oil thick liquid).Crude product is separated through column chromatography chromatogram again, and obtain red needle-like solid dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester, its chemical name is S, S '-dithio (2,3,4,5,6-pentafluorobenzoic acid)-(2,3,4,5,6-PFBBR) ester, yield is 83% (after pillar layer separation data), fusing point: 104 ~ 106 DEG C, structural characterization data are:
1hNMR (CDCl
3): 4.524ppm (2H, s);
13cNMR (CDCl
3): 28.314,109.121,127.988,128.523,132.871,138.494,144.688,146.373,223.164ppm; FT-IR (KBr): 3000 ~ 2815,1650 ~ 1450,1171,1127,1038cm
-1.
Embodiment 2
In embodiment 1, the consumption of dithiocarbonic anhydride is increased to 1.52g (20mmol), and other steps are identical with embodiment 1, obtains dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester, and its yield is 76% (after pillar layer separation data).The outward appearance of product, fusing point and spectroscopic data are identical with embodiment 1.
Embodiment 3
In embodiment 1,1.75mL (14mmol) five bromofluorobenzene is dissolved in 15mL tetrahydrofuran (THF), then under anhydrous and oxygen-free, the condition of 40 DEG C, the tetrahydrofuran solution of five bromofluorobenzenes is dropwise dripped in the three-necked flask that 3.73g (28mmol) ethyl-magnesium-bromide and 30mL tetrahydrofuran (THF) be housed, 50 DEG C of reactions 2 hours are warming up to after dripping, constantly steaming the monobromethane except generating in reaction process, being prepared into Grignard reagent.Other steps are identical with embodiment 1, obtain dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester, and its yield is 71% (after pillar layer separation data).The outward appearance of product, fusing point and spectroscopic data are identical with embodiment 1.
Embodiment 4
Dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester that composite structure formula is following
By 1.31g (5mmol) α-bromo-2, 3, 4, 5, 6-five toluene fluoride is dissolved in 30mL anhydrous diethyl ether, then under anhydrous and oxygen-free condition, the tetrahydrofuran solution of five bromofluorobenzenes is dropwise dripped in the three-necked flask that 0.24g (10mmol) magnesium powder and iodine grain (2 ~ 3) be housed, after purple in reaction mixture (color of iodine) disappears, raised temperature to 70 DEG C also under agitation dropwise drips the tetrahydrofuran solution of remaining five bromofluorobenzenes in three-necked flask, controlling rate of addition makes system keep slight boiling condition, reaction 3 hours is continued at 70 DEG C after dropwising, magnesium powder is made to react completely or substantially disappear, be prepared into Grignard reagent.The Grignard reagent of preparation is cooled to 40 DEG C, 0.76g (10mmol) dithiocarbonic anhydride is dripped wherein under whipped state, 40 DEG C of insulation reaction 2 hours, add 1.31g (5mmol) α-bromo-2 again, 3,4,5,6-five toluene fluoride, 50 DEG C of insulation reaction 10 hours, after reaction terminates, add 15mL frozen water cancellation reaction, by extracted with diethyl ether three times, the drying and except after desolventizing successively of the organic phase after merging, obtains crude product (brown oil thick liquid).Crude product is again after column chromatography chromatogram is separated, and obtain orange-yellow needle-like solid dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester, its chemical name is S, S '-dithio (2,3,4,5,6-penta fluoro benzene acetic acid)-(2,3,4,5,6-PFBBR) ester, yield is 78% (after pillar layer separation data), fusing point: 95 ~ 96 DEG C, structural characterization data are:
1hNMR (CDCl
3): 4.528 (2H, s), 4.294ppm (2H, s);
13cNMR (CDCl
3): 28.314,42.608,110.511 ~ 145.112,229.564ppm; FT-IR (KBr): 3000 ~ 2800,1650 ~ 1443,1171,1127,1038cm
-1.
Embodiment 5
In example 4, the consumption of dithiocarbonic anhydride is reduced to 0.38g (5mmol), and other steps are identical with embodiment 1, and obtain yellow dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester, its yield is 57% (after pillar layer separation data).The outward appearance of product, fusing point and spectroscopic data are identical with embodiment 4.
Embodiment 6
In example 4, by 1.31g (5mmol) α-bromo-2,3,4,5,6-five toluene fluoride is dissolved in 15mL tetrahydrofuran (THF), then, under anhydrous and oxygen-free, the condition of 45 DEG C, in the three-necked flask that 2.00g (15mmol) ethyl-magnesium-bromide and 30mL tetrahydrofuran (THF) be housed, dropwise drip the tetrahydrofuran solution of five bromofluorobenzenes, after dripping, be warming up to 60 DEG C of reactions 3 hours, constantly steaming the monobromethane except generating in reaction process, being prepared into Grignard reagent.Other steps are identical with embodiment 4, obtain dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester, and its yield is 69% (after pillar layer separation data).The outward appearance of product, fusing point and spectroscopic data are identical with embodiment 4.
Embodiment 7
Dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester prepared by embodiment 1 is polymerized the purposes prepared in the dodecafluoroheptyl methacrylate polymkeric substance of pentafluorophenyl group end group at supercritical carbon dioxide systems dodecafluoroheptyl methacrylate (DFHMA), its using method is as follows:
Take supercritical co as solvent, at 70 DEG C, 10.0g (25mmol) DFHMA, 0.0205g (0.125mmol) Diisopropyl azodicarboxylate, 0.0531g (0.125mmol) dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester are added in autoclave, being filled with carbonic acid gas regulates pressure to 25.0MPa, isothermal reaction 42 hours.Adopt situ high pressure near infrared light spectra system according to document (JournalofPolymerScience, PartA:PolymerChemistry, 2015,53, DOI:10.1002/pola.27919) the method on-line monitoring polymerization process reported, obtains polymerization kinetics curve (as shown in Figure 1).Result display polymerization process is homogeneous phase, and DFHMA transformation efficiency grows steadily with the growth in reaction times, simultaneously ln ([M]
0/ [M]) be close to relation with increase (as shown in Figure 2) linearly with the growth in reaction times, this fluorine-containing RAFT reagent dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester of result verification has good controllability to fluorochemical monomer DFHMA radical polymerization process.After reaction terminates, autoclave is cooled to room temperature, slow venting is decompressed to normal pressure, open autoclave and collect polymerisate (white or colourless unformed powder), namely obtain the dodecafluoroheptyl methacrylate polymkeric substance of the following pentafluorophenyl group end group of structural formula
Its yield is 52%, number-average molecular weight (M
n) be 41100 (theoretical value is 42025), structural characterization data are:
1hNMR (CDCl
3): 0.96 ~ 1.13 (3H, CH
3), 1.90 ~ 2.1 (2H, CH
2), 4.0 ~ 4.6 (2H, COCH
2), 5.43 ~ 5.61ppm (1H, CHF); FT-IR (KBr): 3000 ~ 2815,1756,1310 ~ 1040,1057cm
-1.
Embodiment 8
Dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester prepared by embodiment 1 is polymerized the purposes prepared in the Hexafluorobutyl mathacrylate ester polymer of pentafluorophenyl group end group at supercritical carbon dioxide systems Hexafluorobutyl mathacrylate (HFBMA), its using method is as follows:
Take supercritical co as solvent, at 70 DEG C, 6.25g (25mmol) HFBMA, 0.0205g (0.125mmol) Diisopropyl azodicarboxylate, 0.0797g (0.188mmol) dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester are added in autoclave, being filled with carbonic acid gas regulates pressure to 25MPa, isothermal reaction 12 hours.Adopt situ high pressure near infrared light spectra system on-line tracing monitoring polymerization process, obtain polymerization kinetics curve (as shown in Figure 3).Result display fluorochemical monomer HFBMA transformation efficiency grows steadily with the growth in reaction times, ln ([M] simultaneously
0/ [M]) be close to relation with increase (as shown in Figure 3) linearly with the growth in reaction times, this fluorine-containing RAFT reagent dithio pentafluorobenzoic acid five fluoro-methylbenzyl ester of result verification has good controllability to fluorochemical monomer HFBMA radical polymerization process.By autoclave cooling decompression after reaction terminates, open autoclave and collect polymerisate (white or colourless unformed powder), namely obtain the Hexafluorobutyl mathacrylate ester polymer of the following pentafluorophenyl group end group of structural formula,
Its yield is 35%, number-average molecular weight (M
n) be 11910 (theoretical value is 12300), structural characterization data are:
1hNMR (CDCl
3): 0.96 ~ 1.20 (3H, CH
3), 1.85 ~ 2.10 (2H, CH
2), 4.0 ~ 4.4 (2H, OCH
2), 4.65 ~ 5.03ppm (1H, CHF); FT-IR (KBr): 3000 ~ 2850,1755,1460,1400,1295,1185,1107cm
-1.
Embodiment 9
Dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester prepared by embodiment 2 is polymerized the purposes prepared in the dodecafluoroheptyl methacrylate polymkeric substance of pentafluorophenyl group end group at supercritical carbon dioxide systems dodecafluoroheptyl methacrylate (DFHMA), its using method is as follows:
Take supercritical co as solvent, at 70 DEG C, 10.0g (25mmol) DFHMA, 0.0205g (0.125mmol) Diisopropyl azodicarboxylate, 0.109g (0.25mmol) dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester are added in autoclave, being filled with carbonic acid gas regulates pressure to 25.0MPa, isothermal reaction 24 hours.Adopt situ high pressure near infrared light spectra system on-line monitoring polymerization process, obtain polymerization kinetics curve (as shown in Figure 4).Result display polymerization process is homogeneous phase, and DFHMA transformation efficiency grows steadily with the growth in reaction times, simultaneously ln ([M]
0/ [M]) be close to relation with increase (as shown in Figure 5) linearly with the growth in reaction times, this fluorine-containing RAFT reagent dithio penta fluoro benzene acetic acid five fluoro-methylbenzyl ester of result verification has good controllability to fluorochemical monomer DFHMA radical polymerization process.After reaction terminates, by autoclave cooling decompression, open autoclave and collect polymerisate (white or colourless unformed powder), namely obtain the dodecafluoroheptyl methacrylate polymkeric substance of the following pentafluorophenyl group end group of structural formula,
Its yield is 56%, number-average molecular weight (M
n) be 22020 (theoretical value is 23238).
Integrated embodiment 7 ~ 9 is known, shows good controllability, ln ([M] in polymerization process using dithionic acid PFBBR ester of the present invention as RAFT reagent to the radical polymerization process of (methyl) fluoroalkyl base ester class fluorochemical monomer
0/ [M]) with the growth in the reaction times relation with increase linear in (being close to), polymericular weight experimental value and theoretical value are very close.Result demonstrates dithionic acid PFBBR ester of the present invention and is suitable for the fluorochemical monomer activity in supercritical CO 2 medium/controllable free-radical polymerisation system, is the novel fluorine RAFT reagent that a class performance and application has good prospects.
Claims (4)
1. a dithionic acid PFBBR ester, is characterized in that its structural formula is as follows:
In formula, n is 0 or 1.
2. the preparation method of a dithionic acid PFBBR ester according to claim 1, it is characterized in that: under anhydrous and oxygen-free condition, five fluorine hydrobromic ethers and magnesium powder, iodine grain are reacted 3 ~ 5 hours or five fluorine hydrobromic ethers and ethyl-magnesium-bromide are reacted 2 ~ 5 hours at 40 ~ 60 DEG C at 50 ~ 70 DEG C, be prepared into Grignard reagent, five wherein said fluorine hydrobromic ethers are five bromofluorobenzenes or α-bromo-2,3,4,5,6-five toluene fluoride, solvent is ether or tetrahydrofuran (THF); In the Grignard reagent of preparation, add dithiocarbonic anhydride, 40 ~ 50 DEG C are reacted 2 ~ 4 hours, then add α-bromo-2,3,4,5,6-five toluene fluoride, 35 ~ 60 DEG C are reacted 10 ~ 20 hours, then add frozen water cancellation reaction, separation and purification product, obtains dithionic acid PFBBR ester.
3. the preparation method of dithionic acid PFBBR ester according to claim 2, it is characterized in that: described five fluorine hydrobromic ethers and magnesium powder or ethyl-magnesium-bromide, dithiocarbonic anhydride, α-bromo-2,3,4, the mol ratio of 5,6-five toluene fluoride is 1:(1 ~ 3): (1 ~ 3): (1 ~ 2).
4. dithionic acid PFBBR ester according to claim 1 is polymerized at supercritical carbon dioxide systems fluoroalkyl base ester class fluorochemical monomer or perfluoroalkyl methacrylate class fluorochemical monomer RAFT the purposes prepared in the fluoropolymer of pentafluorophenyl group end group.
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| CN108102010A (en) * | 2017-11-22 | 2018-06-01 | 杭州吉华高分子材料股份有限公司 | A kind of new RAFT reagents based on pyridine and preparation method and application |
| CN108102010B (en) * | 2017-11-22 | 2020-04-10 | 杭州吉华高分子材料股份有限公司 | RAFT reagent based on pyridine and preparation method and application thereof |
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| CN105294524B (en) | 2017-10-20 |
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