CN102887981A - Preparation method of PTFEMA (trifluoroethyl methacrylate)-b-PSt fluorine-containing block copolymer - Google Patents
Preparation method of PTFEMA (trifluoroethyl methacrylate)-b-PSt fluorine-containing block copolymer Download PDFInfo
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- CN102887981A CN102887981A CN2011102067375A CN201110206737A CN102887981A CN 102887981 A CN102887981 A CN 102887981A CN 2011102067375 A CN2011102067375 A CN 2011102067375A CN 201110206737 A CN201110206737 A CN 201110206737A CN 102887981 A CN102887981 A CN 102887981A
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 31
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 4
- 239000011737 fluorine Substances 0.000 title abstract description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 14
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 8
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 59
- 125000001246 bromo group Chemical group Br* 0.000 claims description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000002474 experimental method Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000010813 municipal solid waste Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims 6
- 238000000034 method Methods 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention provides a preparation method of a PTFEMA (trifluoroethyl methacrylate)-b-PSt fluorine-containing block copolymer. A macroinitiator takes ethyl-2-bromopropionate as an initiator, cuprous chloride/bipyridine as a catalysis system and PTFEMA as a monomer, and a PTFEMA-Br macroinitiator of which the end group contains an alpha-bromine atom is synthesized by an ATRP (atom transfer radical polymerization) method; and the macroinitiator initiates the styrene (St) polymerization to obtain a PTFEMA-b-PSt fluorine-containing block copolymer with relatively narrow molecular weight distribution.
Description
Technical field
The present invention relates to atom transfer radical polymerization (ATRP) method, be specially a kind of preparation method of PTFEMA-b-PSt fluorinated block copolymer.
Background technology
Nineteen ninety-five, the reported first such as doctor Wang Jinshan of U.S. Carnegie Mellon University, K.Maty jaszewski transition metal-catalyzed controllable free-radical polymerisation, be referred to as atom transfer radical polymerization (Atom Transfer Radical Polymerization, ATRP).
In recent years, along with the development of science and technology, the macromolecular material that preparation has specified structure and molecular weight has become the focus that people study, i.e. polymer design.By polymer design, can obtain the polymer materials of expected structure and performance, for scientific research and suitability for industrialized production provide wide development space.In the specific implementation method of various polymer designs, the ATRP technology is the comparatively ripe experimental technique of using, and is bringing into play in actual applications more and more important effect.
Compare with other polymer design means, ATRP technically with industry on sharpest edges be: practical monomer is extensive, reaction conditions is gentle, monomer, solvent, agent treated are simple, polymerization technique equipment simple (equipment of general radical polymerization gets final product), polymerization process is various, can adopt body, solution, suspension, emulsion polymerization, even also can polymerization in supercritical co.Along with the variation of the high efficiency of catalyst system, spike, polyreaction low temperature, technique simplification etc., make ATRP that very tempting industrial prospect be arranged.
Carbon-fluorine bond in the fluoropolymer
(C-F)Bond energy than hydrocarbon key
(C-H)Bond energy large; can play a protective role to high polymer main chain; so that fluoropolymer has good " three high two hate " property; be high-weatherability, high heat resistance, high stability and hydrophobic, hate oil characteristic; in modern industry, bring into play very important effect, be widely used in numerous industries and the fields such as defence and military, the top science, boats and ships, machinery, chemical industry, electronics, electrical equipment, semi-conductor, medical science (artificial organ), building.
In the preparation method of traditional fluoropolymer, a class is synthetic for the Fluorine containing olefine take PTFE, PVDF etc. as representative, mainly adopts suspension polymerization and emulsion polymerization, and the product property that obtains is excellent, but has the relatively poor problem of processed-type; Another kind of is to carry out copolymerization with various of monomer and fluorochemical monomer, the difficult control of the product structure that obtains and molecular weight, thereby be difficult to bring into play to greatest extent the premium properties of fluoropolymer, in such cases, just demonstrate its unique advantage with the synthetic fluorinated copolymer of ATRP method, this polymerization process is mainly used in the synthetic of segmented copolymer and graft copolymer.
Summary of the invention
The invention provides a kind of preparation method of PTFEMA-b-PSt fluorinated block copolymer, wherein macromole evocating agent is as initiator take ethyl-alpha-bromopropionate, take cuprous chloride/bipyridine as catalyst system, trifluoroethyl methacrylate (PTFEMA) is monomer, contains polymethyl acrylic acid trifluoro ethyl ester (PTFEMA-Br) macromole evocating agent of a α-bromine atoms by the synthetic end group of ATRP method; Cause vinylbenzene (St) polymerization with this macromole evocating agent, obtained the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution.
The present invention's realization by following technical solution:
A, a kind of end group are polymethyl acrylic acid fluorine ethyl ester (PTFEMA-Br) macromole evocating agent of α-bromine atoms, and its chemical structural formula is as shown in the formula shown in the I:
The formula I
N is the natural number of 20-100;
Described PTFEMA-Br macromole evocating agent is to be prepared from by the ATRP polymerization process, and concrete operation step is as follows:
(1) processing of trifluoroethyl methacrylate: with deionized water the trifluoroethyl methacrylate monomer is washed till neutrality, then uses successively CaCl
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is lower underpressure distillation purifying, preserves in 0-4 ℃ of sealing, for subsequent use;
(2) prepare the PTFEMA-Br macromole evocating agent by the ATRP polymerization process: trifluoroethyl methacrylate monomer, 2.0-20 mass parts ethyl-alpha-bromopropionate initiator, 0.2-20 mass parts bipyridine and 300-550 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 time to be to remove oxygen; Then under nitrogen protection, be warming up to 60-120 ℃, add 0.2-30 mass parts cuprous chloride reaction 1-10h, obtain PTFEMA-Br macromole evocating agent solution;
(3) after experiment finishes, polymer fluid poured in the beaker that a large amount of methyl alcohol are housed lentamente precipitate, the limit bevelling stirs, and then with polymer filtration, hangs, and transfers to subsequently in the vacuum drying oven and be dried to constant weight under 50 ℃ condition;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-Br macromole evocating agent to constant weight;
Described organic solvent comprises toluene, Isosorbide-5-Nitrae-dioxane and butanone etc.;
It is as follows that described cryosel is bathed freezing condition: add 20 gram CaCl in 100 gram trash ices
26H
2O stirs and obtains.
B, with PTFEMA-Br as the synthetic PTFEMA-b-PSt segmented copolymer of ATRP macromole evocating agent:
Described PTFEMA-Br ATRP macromole evocating agent is applied to the ATRP polyreaction and prepares the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution, and it may further comprise the steps:
(1) the 5%NaOH aqueous solution and deionized water wash are used respectively in cinnamic processing, and be for subsequent use behind the underpressure distillation purifying behind the anhydrous magnesium sulfate drying;
(2) 100 mass parts styrene monomers, 1-200 mass parts PTFEMA-Br ATRP macromole evocating agent and 0.01-20 mass parts bipyridine and 400-600 mass parts organic solvent are mixed, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3-5 time to be to remove oxygen; Then under nitrogen protection, be warming up to 90-120 ℃, add 0.01-30 mass parts cuprous chloride reaction 2-30h, obtain the PTFEMA-b-PSt fluorinated block copolymer;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-b-PSt fluorinated block copolymer to constant weight;
Described organic solvent comprises Isosorbide-5-Nitrae-dioxane and butanone;
It is as follows that described cryosel is bathed freezing condition: add 20 gram CaCl in 100 gram trash ices
26H
2O stirs and obtains.
The present invention has at first prepared PTFEMA-Br by the ATRP polymerization process, then causes styrene polymerization with this as the ATRP macromole evocating agent, obtains the PTFEMA-b-PSt fluorinated block copolymer.The different PTFEMA-Br macromole evocating agent of molecular weight causes vinylbenzene and carries out the ATRP polymerization, obtains different chain lengths, and the fluorinated block copolymer of different structure has realized that preparation has the macromolecular material of specified structure and molecular size.
Description of drawings
Fig. 1 is the reaction scheme figure of synthetic PTFEMA-Br macromole evocating agent;
Fig. 2 is the synthetic route chart of synthetic PTFEMA-b-PSt segmented copolymer.
Embodiment
The invention will be further described below in conjunction with Fig. 1 and Fig. 2:
Embodiment 1
Polymethyl acrylic acid trifluoro ethyl ester (PTFEMA-Br) macromole evocating agent of a, a kind of α-bromine atoms, its chemical structural formula is as shown in the formula shown in the I, and described PTFEMA-Br macromole evocating agent is to be prepared from by the ATRP polymerization process, and concrete operation step is as follows:
(1) processing of trifluoroethyl methacrylate: with deionized water the trifluoroethyl methacrylate monomer is washed till neutrality, then uses successively CaCl
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is lower underpressure distillation purifying, preserves in 0-4 ℃ of sealing, for subsequent use;
(2) prepare the PTFEMA-Br macromole evocating agent by the ATRP polymerization process: trifluoroethyl methacrylate monomer, 2g ethyl-alpha-bromopropionate initiator, 0.2g bipyridine and 300g toluene that 100g step (1) is handled well mix, and add 20 gram CaCl in 100 gram trash ices
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 3 times is with except oxygen; Then under nitrogen protection, be warming up to 120 ℃, add 30g cuprous chloride reaction 1h, obtain PTFEMA-Br macromole evocating agent solution, record number-average molecular weight Mn=4.50 * 10 by gel permeation chromatography (GPC) method
3, polydispersity coefficient PDI=1.22.Determine this macromole evocating agent structural formula I n=20 according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle;
(3) after experiment finishes, polymer fluid poured in the beaker that a large amount of methyl alcohol are housed lentamente precipitate, the limit bevelling stirs, and then with polymer filtration, hangs, and transfers to subsequently in the vacuum drying oven and be dried to constant weight under 50 ℃ condition;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-Br macromole evocating agent to constant weight;
B, with PTFEMA-Br as the synthetic PTFEMA-b-PSt segmented copolymer of ATRP macromole evocating agent:
Described PTFEMA-Br ATRP macromole evocating agent is applied to the ATRP polyreaction and prepares the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution, and it may further comprise the steps:
(1) the 5%NaOH aqueous solution and deionized water wash are used respectively in cinnamic processing, and be for subsequent use behind the underpressure distillation purifying behind the anhydrous magnesium sulfate drying;
(2) with 100g styrene monomer, 1gPTFEMA-Br ATRP macromole evocating agent and 0.01g bipyridine and 400g1, the 4-dioxane mixes, and adds 20 gram CaCl in 100 gram trash ices
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 3 times to be to remove oxygen; Then under nitrogen protection, be warming up to 90 ℃, add 0.01g cuprous chloride reaction 30h, obtain the PTFEMA-b-PSt fluorinated block copolymer; Record number-average molecular weight Mn=1.32 * 10 by gel permeation chromatography (GPC) method
4, polydispersity coefficient PDI=1.24;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-b-PSt fluorinated block copolymer to constant weight.
Embodiment 2
Polymethyl acrylic acid trifluoro ethyl ester (PTFEMA-Br) macromole evocating agent of a, a kind of α-bromine atoms, its chemical structural formula is as shown in the formula shown in the I, and described PTFEMA-Br macromole evocating agent is to be prepared from by the ATRP polymerization process, and concrete operation step is as follows:
(1) processing of trifluoroethyl methacrylate: with deionized water the trifluoroethyl methacrylate monomer is washed till neutrality, then uses successively CaCl
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is lower underpressure distillation purifying, preserves in 0-4 ℃ of sealing, for subsequent use;
(2) prepare the PTFEMA-Br macromole evocating agent by the ATRP polymerization process: trifluoroethyl methacrylate monomer, 8g ethyl-alpha-bromopropionate initiator, 7g bipyridine and 400g1 that 100g step (1) is handled well, the 4-dioxane mixes, and adds 20 gram CaCl in 100 gram trash ices
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 4 times is with except oxygen; Then under nitrogen protection, be warming up to 100 ℃, add 20g cuprous chloride reaction 7h, obtain PTFEMA-Br macromole evocating agent solution, record number-average molecular weight Mn=7.83 * 10 by gel permeation chromatography (GPC) method
3, polydispersity coefficient PDI=1.23.Determine this macromole evocating agent structural formula I n=45 according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle;
(3) after experiment finishes, polymer fluid poured in the beaker that a large amount of methyl alcohol are housed lentamente precipitate, the limit bevelling stirs, and then with polymer filtration, hangs, and transfers to subsequently in the vacuum drying oven and be dried to constant weight under 50 ℃ condition;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-Br macromole evocating agent to constant weight;
B, with PTFEMA-Br as the synthetic PTFEMA-b-PSt segmented copolymer of ATRP macromole evocating agent:
Described PTFEMA-Br ATRP macromole evocating agent is applied to the ATRP polyreaction and prepares the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution, and it may further comprise the steps:
(1) the 5%NaOH aqueous solution and deionized water wash are used respectively in cinnamic processing, and be for subsequent use behind the underpressure distillation purifying behind the anhydrous magnesium sulfate drying;
(2) with 100g styrene monomer, 70gPTFEMA-Br ATRP macromole evocating agent and 7g bipyridine and 470g1, the 4-dioxane mixes, and adds 20 gram CaCl in 100 gram trash ices
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 4 times to be to remove oxygen; Then under nitrogen protection, be warming up to 100 ℃, add 10g cuprous chloride reaction 21h, obtain the PTFEMA-b-PSt fluorinated block copolymer; Record number-average molecular weight Mn=2.42 * 10 by gel permeation chromatography (GPC) method
4, polydispersity coefficient PDI=1.24;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-b-PSt fluorinated block copolymer to constant weight.
Embodiment 3
Polymethyl acrylic acid trifluoro ethyl ester (PTFEMA-Br) macromole evocating agent of a, a kind of α-bromine atoms, its chemical structural formula is as shown in the formula shown in the I, and described PTFEMA-Br macromole evocating agent is to be prepared from by the ATRP polymerization process, and concrete operation step is as follows:
(1) processing of trifluoroethyl methacrylate: with deionized water the trifluoroethyl methacrylate monomer is washed till neutrality, then uses successively CaCl
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is lower underpressure distillation purifying, preserves in 0-4 ℃ of sealing, for subsequent use;
(2) prepare the PTFEMA-Br macromole evocating agent by the ATRP polymerization process: trifluoroethyl methacrylate monomer, 14g ethyl-alpha-bromopropionate initiator, 14g bipyridine and 480g1 that 100g step (1) is handled well, the 4-dioxane mixes, and adds 20 gram CaCl in 100 gram trash ices
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 5 times is with except oxygen; Then under nitrogen protection, be warming up to 80 ℃, add 20g cuprous chloride reaction 10h, obtain PTFEMA-Br macromole evocating agent solution, record number-average molecular weight Mn=1.57 * 10 by gel permeation chromatography (GPC) method
4, polydispersity coefficient PDI=1.24.Determine this macromole evocating agent structural formula I n=97 according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle;
(3) after experiment finishes, polymer fluid poured in the beaker that a large amount of methyl alcohol are housed lentamente precipitate, the limit bevelling stirs, and then with polymer filtration, hangs, and transfers to subsequently in the vacuum drying oven and be dried to constant weight under 50 ℃ condition;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-Br macromole evocating agent to constant weight;
B, with PTFEMA-Br as the synthetic PTFEMA-b-PSt segmented copolymer of ATRP macromole evocating agent:
Described PTFEMA-Br ATRP macromole evocating agent is applied to the ATRP polyreaction and prepares the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution, and it may further comprise the steps:
(1) the 5%NaOH aqueous solution and deionized water wash are used respectively in cinnamic processing, and be for subsequent use behind the underpressure distillation purifying behind the anhydrous magnesium sulfate drying;
(2) 100g styrene monomer, 140gPTFEMA-Br ATRP macromole evocating agent and 14g bipyridine and 540g butanone are mixed, in 100 gram trash ices, add 20 gram CaCl
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 4 times to be to remove oxygen; Then under nitrogen protection, be warming up to 110 ℃, add 20g cuprous chloride reaction 11h, obtain the PTFEMA-b-PSt fluorinated block copolymer; Record number-average molecular weight Mn=3.52 * 10 by gel permeation chromatography (GPC) method
4, polydispersity coefficient PDI=1.24;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-b-PSt fluorinated block copolymer to constant weight.
Embodiment 4
Polymethyl acrylic acid trifluoro ethyl ester (PTFEMA-Br) macromole evocating agent of a, a kind of α-bromine atoms, its chemical structural formula is as shown in the formula shown in the I, and described PTFEMA-Br macromole evocating agent is to be prepared from by the ATRP polymerization process, and concrete operation step is as follows:
(1) processing of trifluoroethyl methacrylate: with deionized water the trifluoroethyl methacrylate monomer is washed till neutrality, then uses successively CaCl
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is lower underpressure distillation purifying, preserves in 0-4 ℃ of sealing, for subsequent use;
(2) prepare the PTFEMA-Br macromole evocating agent by the ATRP polymerization process: trifluoroethyl methacrylate monomer, 20g ethyl-alpha-bromopropionate initiator, 20g bipyridine and 550g butanone that 100g step (1) is handled well mix, and add 20 gram CaCl in 100 gram trash ices
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 4 times is with except oxygen; Then under nitrogen protection, be warming up to 60 ℃, add 0.2g cuprous chloride reaction 4h, obtain PTFEMA-Br macromole evocating agent solution, record number-average molecular weight Mn=7.15 * 10 by gel permeation chromatography (GPC) method
3, polydispersity coefficient PDI=1.22.Determine this macromole evocating agent structural formula I n=40 according to infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum, GPC data and reaction principle;
(3) after experiment finishes, polymer fluid poured in the beaker that a large amount of methyl alcohol are housed lentamente precipitate, the limit bevelling stirs, and then with polymer filtration, hangs, and transfers to subsequently in the vacuum drying oven and be dried to constant weight under 50 ℃ condition;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-Br macromole evocating agent to constant weight;
B, with PTFEMA-Br as the synthetic PTFEMA-b-PSt segmented copolymer of ATRP macromole evocating agent:
Described PTFEMA-Br ATRP macromole evocating agent is applied to the ATRP polyreaction and prepares the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution, and it may further comprise the steps:
(1) the 5%NaOH aqueous solution and deionized water wash are used respectively in cinnamic processing, and be for subsequent use behind the underpressure distillation purifying behind the anhydrous magnesium sulfate drying;
(2) 100g styrene monomer, 200gPTFEMA-Br ATRP macromole evocating agent and 20g bipyridine and 600g butanone are mixed, in 100 gram trash ices, add 20 gram CaCl
26H
2The stir cryosel that obtains of O is bathed freezingly, vacuumizes, drum nitrogen 5 times to be to remove oxygen; Then under nitrogen protection, be warming up to 120 ℃, add 30g cuprous chloride reaction 2h, obtain the PTFEMA-b-PSt fluorinated block copolymer; Record number-average molecular weight Mn=2.32 * 10 by gel permeation chromatography (GPC) method
4, polydispersity coefficient PDI=1.25;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-b-PSt fluorinated block copolymer to constant weight.
Claims (4)
1. the preparation method of a PTFEMA-b-PSt fluorinated block copolymer is characterized in that, adopts following technical scheme:
A, a kind of end group are polymethyl acrylic acid fluorine ethyl ester (PTFEMA-Br) macromole evocating agent of α-bromine atoms, and its chemical structural formula is as shown in the formula shown in the I:
The formula I
N is the natural number of 20-100;
Described PTFEMA-Br macromole evocating agent is to be prepared from by the ATRP polymerization process, and concrete operation step is as follows:
(1) processing of trifluoroethyl methacrylate: with deionized water the trifluoroethyl methacrylate monomer is washed till neutrality, then uses successively CaCl
2And CaH
2Soaked respectively 2 days, at last under nitrogen protection and at CaH
2There is lower underpressure distillation purifying, preserves in 0-4 ℃ of sealing, for subsequent use;
(2) prepare the PTFEMA-Br macromole evocating agent by the ATRP polymerization process: trifluoroethyl methacrylate monomer, 2.0-20 mass parts ethyl-alpha-bromopropionate initiator, 0.2-20 mass parts bipyridine and 300-550 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 time to be to remove oxygen; Then under nitrogen protection, be warming up to 60-120 ℃, add 0.2-30 mass parts cuprous chloride reaction 1-10h, obtain PTFEMA-Br macromole evocating agent solution;
(3) after experiment finishes, polymer fluid poured in the beaker that a large amount of methyl alcohol are housed lentamente precipitate, the limit bevelling stirs, and then with polymer filtration, hangs, and transfers to subsequently in the vacuum drying oven and be dried to constant weight under 50 ℃ condition;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-Br macromole evocating agent to constant weight;
B, with PTFEMA-Br as the synthetic PTFEMA-b-PSt segmented copolymer of ATRP macromole evocating agent:
Described PTFEMA-Br ATRP macromole evocating agent is applied to the ATRP polyreaction and prepares the narrower PTFEMA-b-PSt fluorinated block copolymer of molecular weight distribution, and it may further comprise the steps:
(1) the 5%NaOH aqueous solution and deionized water wash are used respectively in cinnamic processing, and be for subsequent use behind the underpressure distillation purifying behind the anhydrous magnesium sulfate drying;
(2) 100 mass parts styrene monomers, 1-200 mass parts PTFEMA-Br ATRP macromole evocating agent and 0.01-20 mass parts bipyridine and 400-600 mass parts organic solvent are mixed, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3-5 time to be to remove oxygen; Then under nitrogen protection, be warming up to 90-120 ℃, add 0.01-30 mass parts cuprous chloride reaction 2-30h, obtain the PTFEMA-b-PSt fluorinated block copolymer;
(4) polymerisate dissolves with tetrahydrofuran (THF), and solution is through neutral Al
2O
3Copper salt catalyst is removed in post absorption, and filtrate is poured in the methyl alcohol and precipitated, filters, and 50 ℃ of vacuum-dryings of polymkeric substance are collected and obtained the PTFEMA-b-PSt fluorinated block copolymer to constant weight.
2. the preparation method of a kind of PTFEMA-b-PSt fluorinated block copolymer according to claim 1 is characterized in that, the organic solvent described in the step a comprises toluene, Isosorbide-5-Nitrae-dioxane and butanone.
3. the preparation method of a kind of PTFEMA-b-PSt fluorinated block copolymer according to claim 1 is characterized in that, the organic solvent described in the step b comprises Isosorbide-5-Nitrae-dioxane and butanone.
4. the preparation method of a kind of PTFEMA-b-PSt fluorinated block copolymer according to claim 1 is characterized in that, described cryosel is bathed the freezing 20 gram CaCl that refer to add in 100 gram trash ices
26H
2O stirs and obtains.
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| WO2003016412A1 (en) * | 2001-08-14 | 2003-02-27 | Avecia Bv | Aqueous crosslinkable coating compositions based on vinyl fluoropolymer |
| CN101792503A (en) * | 2010-02-04 | 2010-08-04 | 中科院广州化学有限公司 | Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof |
| CN101899126A (en) * | 2010-07-21 | 2010-12-01 | 常州大学 | Miniemulsion of fluorine-containing block copolymer as co-stabilizer and preparation method thereof |
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| WO2003016412A1 (en) * | 2001-08-14 | 2003-02-27 | Avecia Bv | Aqueous crosslinkable coating compositions based on vinyl fluoropolymer |
| CN101792503A (en) * | 2010-02-04 | 2010-08-04 | 中科院广州化学有限公司 | Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof |
| CN101899126A (en) * | 2010-07-21 | 2010-12-01 | 常州大学 | Miniemulsion of fluorine-containing block copolymer as co-stabilizer and preparation method thereof |
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