CN105482013A - Polymerization method for preparing fluorine-containing alternating copolymer through gradual transfer-addition-ending step by step with free radicals under condition of visible light - Google Patents
Polymerization method for preparing fluorine-containing alternating copolymer through gradual transfer-addition-ending step by step with free radicals under condition of visible light Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 74
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 50
- 239000011737 fluorine Substances 0.000 title claims abstract description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920005603 alternating copolymer Polymers 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims description 31
- 238000005286 illumination Methods 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 8
- 229960005055 sodium ascorbate Drugs 0.000 claims description 8
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 8
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical group [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 8
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 229920002313 fluoropolymer Polymers 0.000 description 8
- 239000004811 fluoropolymer Substances 0.000 description 8
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- 238000007342 radical addition reaction Methods 0.000 description 8
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
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- 238000010526 radical polymerization reaction Methods 0.000 description 3
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- 230000005281 excited state Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001436679 Adama Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- 238000004454 trace mineral analysis Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/20—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
Abstract
The invention provides a polymerization method for preparing fluorine-containing alternating copolymer through gradual transfer-addition-ending with free radicals under the condition of visible light. The preparation method includes the following steps that 1, two types of bifunctional monomers A and B, a photocatalyst, a reducing agent and mixed organic solvent are simultaneously added into a reaction reactor and stirred till a system is in a homogeneous phase, after deoxygenization is conducted four times, the reaction container is sealed, and a homogeneous polymerization system I is obtained; 2, the temperature of the reaction container is set to be 25 DEG C, the rotation speed is set to be 1500-2000 rpm, the homogeneous polymerization system I is subjected to a polymerization reaction under visible light, and the reaction time is 0.5-24 hours; 3, after the reaction is ended, the reaction container is opened, tetrahydrofuran is added to dilute the system, the diluted substance is poured into methyl alcohol for sediment, then suction filtration and drying are conducted, and the fluorine-containing alternating copolymer is obtained. By the application of the novel polymerization method, the fluorine-containing alternating copolymer is obtained successfully, and the polymerization method is a brand-new polymerization method.
Description
Technical field
The invention belongs to sequence controllable polymerization technical field, be specifically related to a kind of free radical that utilizes under visible illumination condition and progressively shift-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation.
Background technology
Under visible illumination condition, realize organic chemical reactions is the target that scientists is pursued always.From the seventies in last century, since the proposition of " photochemistry " concept, cause the extensive concern of scientists.(see T.P.Yoon, M.A.Ischay, J.Du, NatureChemistry, 2010,2:527-532 and D.A.Nicewicz, D.W.C.MacMillan, Science, 2008,322:77-80).In recent years, the discovery of the photocatalyst of a series of economical and efficient and widespread use thereof, facilitate the development of photochemical reaction research greatly, and wherein Ru (bpy)
3cl
2be a kind ofly to be widely used, organo-metallic photocatalyst that catalytic efficiency is high.The seminars such as MacMillan, Yoon and Stephenson all utilize Ru (bpy)
3cl
2achieve many dissimilar organic chemical reactionses.(see D.A.Nagib, M.E.Scott, D.W.C.MacMillan, J.Am.Chem.Soc, 2009,131:10875-10877; M.A.Ischay, M.E.Anzovino, J.Du, T.P.Yoon, J.Am.Chem.Soc., 2008,130:12886-12887 and J.M.R.Narayanam, J.W.Tucker, C.R.J.Stephenson, J.Am.Chem.Soc., 2009,131:8756-8757).
Along with the deep development of polymer science research, scientists no longer contents just to realize active monomer (as methyl methacrylate (MMA), vinylbenzene (St)) living polymerization, obtain the polymkeric substance that molecular weight is controlled, but more and more close the microtexture of polymer injection, the behavior wishing can to generate DNA, protein as the Nature, the superpolymer that synthetic microtexture sequence is controlled, the design of implementation structure-performance integration.The radical addition polymerization method (Metal-catalyzedradicalpolyaddition) of metal catalytic is exactly a kind of method realizing sequence controllable polymerization, derive from atom transferred free radical addition reaction (Atomtransferradicaladdition, ATRA).2007, the research of the Kamigaito seminar reported first radical addition polymerization of metal catalytic (Metal-catalyzedradicalpolyaddition).A kind of novel bifunctional monomer of their design and synthesis, its one end is R-X(X=Cl, the Br that can be activated by metal catalyst) functional group, the other end is then inertia double bond (C=C), realized the progressively polymerization of bifunctional monomer by the reaction between monomer, obtain the linear polymer with certain molecular weight.Thereafter, this seminar reports again the linear polymer utilizing the different sequential structure of this polymerization process design and synthesis, but polymerization process extremely slowly (is sometimes reacted and even continued some months), and temperature of reaction is also higher, and (polymerization temperature is generally 100
oc).Thereafter Peking University of China plum minister professor is active in improve speed of reaction, to increase the molecular weight of resulting polymers by improving double bond, and the control of polymerization behavior is then by reducing temperature of reaction to 0
oc realizes (see K.Satoh, M.Mizutani, M.Kamigaito, Chem.Commun., 2007,12:1260-1262 and B.T.Dong, Y.Q.Dong, F.S.Du, Z.C.Li, Macromolecules, 2010,43:8790-8798).Although have again many scientists to utilize this polymerization process or carry out on this basis improving the synthesis realizing sequential structure polymkeric substance, but the result obtained is not fully up to expectations, the shortcoming that ubiquity polymerization reaction time is long, monomer conversion is low, polymericular weight is low.
And the above-mentioned atom transferred free radical addition (Atomtranferradicaladdition mentioned, ATRA) react, it is the Radical Addition that a class atom economy efficiency is very high, be under radical initiator (AIBN) or ultraviolet lighting (hv) condition, by halohydrocarbon (R-X), double bond (C=C) addition of alkene realized.Thereafter develop again a series of metal catalyst (as Ru, Pd, Cu etc.) and realize the ATRA reaction under heat or illumination condition.(see J.A.Tallarico, L.M.Malnick, M.L.Snapper, J.Org.Chem., 1999,64:344-345 and L.Quebatte, M.Haas, E.Solari, R.Scopelliti, Q.T.Nguyen, K.Severin, Angew.Chem.Int.Ed., 2005,44:1084-1088).Recently, due to the fast development of visible light catalytic reaction, Stephenson seminar has successfully realized the atom transferred free radical addition reaction (ATRA) at room temperature in daylight, economical in reaction efficient (generally complete in 24h, and productive rate being up to 99%)." click " chemistry of so efficient Radical Addition and classics is closely similar.As everyone knows, the predecessor of " click " chemistry is exactly the sulfydryl (S-H) of single step and the addition reaction of olefinic double bonds (C=C).Recently, due to the development of photochemical catalysis, " click " chemistry has also successfully realized the controllable polymerization under visible illumination condition.(see H.C.Kolb, M.G.Finn, K.B.Sharpless, Angew.Chem.Int.Ed., 2001,40:2004-2021; T.F.Scott, C.J.Kloxin, R.B.Draughon, C.N.Bowman, Macromolecules, 2008,41:2987-2989 and W.Xi, T.F.Scott, C.J.Kloxin, C.N.Bowman, Adv.Funct.Mater., 2014,24:2572-2590).Therefore, if we can under visible ray after this manner a kind of mild conditions, realize economical, progressively radical polymerization efficiently, obtain the polymkeric substance that sequence is controlled, this will be a tremendous expansion in radical polymerization field, it can not design effectively polymkeric substance micro-sequential structure and the radical addition polymerization (Metal-catalyzedradicalpolyaddition) that can carry out the metal catalytic of structure design to polymkeric substance that grows up thereafter by solving conventional free radical polymerization, but length consuming time, the shortcoming that catalytic efficiency is low, it is controlled that we can obtain structure sequence in shorter polymerization time, there is the high-molecular weight polymer of actual application value.In addition, due in ATRA reaction, halohydrocarbon R-X(X=Cl, Br, I) in R group can design, if we can introduce fluorine-containing fragment, so obtained polymkeric substance controls the more excellent physics of polymkeric substance, chemical property by showing with the sequence of routine, the chemical stability, thermostability etc. of such as superelevation.At present about in the research synthesis of fluoropolymer, oligopolymer or crosslinking net polymkeric substance can only be obtained, as lubricating oil or frie retardant coating aspect.The fluoropolymer obtaining the linear structure of higher molecular weight is a puzzlement scientist's difficult problem always.(see D.V.Avila, K.U.Ingold, J.Lusztyk, W.R.DolbierJr; H.Q.Pan, M.Muir, J.Am.Chem.Soc., 1994,116:99-104; L.Zhang, W.R.Dolbier, B.Sheeller, K.U.Ingold, J.Am.Chem.Soc., 2002,124:6362-6366 and C.Amato, S.Devillers, P.Calas, J.Delhalle, Z.Mekhalif, Langmuir, 2008,24:10879-10886).
Summary of the invention
The technical problem solved: the shortcoming long for existing polymerization process ubiquity polymerization reaction time, monomer conversion is low, polymericular weight is low, the invention provides a kind of utilize under visible illumination condition free radical progressively shift-addition-terminations prepares the polymerization process of fluorine-containing alternating copolymer.
Technical scheme: a kind of free radical that utilizes under visible illumination condition progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, and the preparation process of the method is as follows:
(1) two kinds of bifunctional monomer A and B, photocatalyst, reductive agent, mixed organic solvents are added in reaction vessel simultaneously, stirring makes system be homogeneous phase, carry out the rear sealed reaction vessel of four deoxygenations operation, obtain polymerization in homogeneous phase system I, wherein bifunctional monomer A is 1,8-bis-iodo PFO, bifunctional monomer B is unconjugated inertia diene Isosorbide-5-Nitrae-bis-(alkene butyl) benzene, Isosorbide-5-Nitrae-bis-(allyloxy) benzene or 1,7-octadiene, photocatalyst is Ru (bpy)
3cl
2reductive agent is sodium ascorbate, mixed organic solvents is by tetrahydrofuran (THF), 1, any one and methyl alcohol in 4-dioxane, methyl-sulphoxide, acetonitrile, trifluoroethanol, the perfluor trimethyl carbinol form, mol ratio between bifunctional monomer A, bifunctional monomer B, photocatalyst, reductive agent is 90 ~ 110:90 ~ 110:1 ~ 5:1 ~ 35, and the concentration of bifunctional monomer A and B in mixed organic solvents is 0.1 ~ 0.2mol/L.
(2) temperature arranging reaction vessel is 25 DEG C, and rotating speed is 1500 ~ 2000rpm, and polymerization in homogeneous phase system I is carried out polyreaction under visible light, and the reaction times is 0.5 ~ 24h;
(3), after reaction terminates, open reaction vessel, add tetrahydrofuran (THF) and system is diluted, be poured in methyl alcohol and precipitate, then carry out suction filtration, drying, obtain fluorine-containing alternating copolymer.
Mol ratio between bifunctional monomer A described above, bifunctional monomer B, photocatalyst, reductive agent is 100:100:1:35.
Mixed organic solvents described above is made up of Isosorbide-5-Nitrae-dioxane and methyl alcohol, and the volume ratio of Isosorbide-5-Nitrae-dioxane and methyl alcohol is 3:1.
The visible light source of step (2) described above is 23W electricity-saving lamp, LED white light or LED blue light source.
The visible light source of step (2) described above is LED blue light source.
The temperature arranging reaction vessel in step (2) described above is 25 DEG C, and rotating speed is 1800rpm, and the reaction times is 6h.
Polymerization process of the present invention is at ambient temperature, by the sealed vessel of anaerobic, carries out Light lnduced Free Radicals step-reaction polymerization by means of visible ray.After having reacted, reaction system, after dilution, is simply toppled over and can be removed unreacted monomer and metal catalyst Ru (bpy)
3cl
2, obtain purer polymkeric substance.Reaction need not be heated, and carries out at ambient temperature, and for light source used, reaction even can realize under the condition of 23W electricity-saving lamp illumination, obtains the fluoropolymer that sequence is controlled.By polymerization kinetics behavioral study and
1hNMR,
19the comprehensive analysis of FNMR, can well verify that the micro-sequential structure of (AB) n polymkeric substance and free radical progressively shift the mechanism of-addition-termination (StepTransfer-Addition & Radical-Termination, START) polyreaction.
Beneficial effect: a kind of free radical that utilizes under visible illumination condition provided by the invention progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, has following beneficial effect:
1. the present invention utilizes visible ray progressively to shift-addition-termination polymerization according to the free radical achieving two kinds of bifunctional monomers, reaction system need not heat, economical and efficient, meet the developing direction of Modern Green Chemistry, in addition, obtain fluorine-containing alternating copolymer by the application success of this novel polymeric method, this also provides a kind of new polymerization process for linear fluorine-containing alternating copolymer;
2. traditional free radical for design and synthesis sequential structure polymkeric substance progressively polymerization process carries out all in a heated condition, and polymerization temperature is usually at about 100 DEG C, this just causes very large energy dissipation, although developed again the polyreaction of carrying out at 0 DEG C afterwards, but this is to reduce polymerization rate for cost, in addition the polymerization time of traditional free radical progressively needed for polymerization process is all quite long, and to obtain polymericular weight still very low, the oligopolymer be in a liquid state under such class normal temperature does not have actual application value, the present invention then successfully overcomes above-mentioned technical problem, obtain molecular weight higher, the multipolymer that structure sequence is controlled, there is very high researching value and actual application value,
3., in traditional fluorine chemistry research, fluorine-containing oligomer or telomer can only be obtained.But at aerospace field, then need the high-performance fluorine-containing material of high molecular, to meet application request, the present invention well compensate for this breach, perfluorinated monomers is introduced in polymer chain by success, obtain the fluorine-containing alternating copolymer of higher molecular weight, have very large application prospect in hard-core technology field;
4. polyreaction operation of the present invention is all carried out under the normal condition of laboratory, there is no special operating instrument (as glove box), and the chemical reagent such as solvent for use is all direct uses, there is no further purification process, reaction still can efficiently be carried out, so more be conducive to easy, environmental protection, synthesize fluorine-containing high performance material efficiently, be conducive to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the dynamic behavior research schematic diagram of the polyreaction of embodiment 4.
Fig. 2 is the GPC elution curve figure of the polyreaction of embodiment 4.
Fig. 3 is the nucleus magnetic hydrogen spectrum spectrogram of the fluorine-containing alternating copolymer of embodiment 4.
Fig. 4 is the nuclear-magnetism fluorine spectrum spectrogram of the fluorine-containing alternating copolymer of embodiment 4.
Fig. 5 is that free radical progressively shifts-addition-termination polymerization mechanism schematic diagram.
Embodiment
1, the 8-bis-iodo PFO used in following examples is purchased from Sigma-Aldrich, and 1,7-octadiene is purchased from AlfaAesar Chemical Co., Ltd., Isosorbide-5-Nitrae-bis-(alkene butyl) benzene synthesizes according to document " Y.Takeuchi, Y.Suzuki; F.Ono, K.Manabe, J.Organomet.Chem.; 2003,678:61-67 ", and 1, two (allyloxy) benzene of 4-synthesizes according to document " Z.M.Wang, M.Shen, J.Org.Chem.; 1998,63:1414-1418 ", Ru (bpy)
3cl
2purchased from this reagent company limited of Adama, sodium ascorbate is purchased from China Medicine (Group) Shanghai Chemical Reagent Co., and tetrahydrofuran (THF) is purchased from Chinese traditional Chinese medicines (group) Solution on Chemical Reagents in Shanghai company.
Embodiment 1
Under visible illumination condition, utilize free radical progressively to shift-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, the preparation process of the method is as follows:
(1) by the Ru (bpy) of the Isosorbide-5-Nitrae of 1, the 8-bis-iodo PFO of 0.5mmol, 0.5mmol-bis-(allyloxy) benzene, 0.025mmol
3cl
2, mixed organic solvents that the sodium ascorbate of 0.175mmol adds and is made up of the acetonitrile of 3mL and the methyl alcohol of 1mL all adds in reaction vessel, add stirrer in the reactor, stirring makes system be homogeneous phase, carries out the rear sealed reaction vessel of four deoxygenations operation, obtains polymerization in homogeneous phase system I;
(2) temperature arranging reaction vessel is 25 DEG C, and rotating speed is 1800rpm, and polymerization in homogeneous phase system I is carried out polyreaction under the illumination of LED blue light, and the reaction times is 24h;
(3) after reaction terminates, open reaction vessel, add tetrahydrofuran (THF) and polymerization system is diluted, then take out to be poured in methyl alcohol and precipitate, then carry out suction filtration, drying, obtain fluorine-containing alternating copolymer.
Embodiment 2
Under visible illumination condition, utilize free radical progressively to shift-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, the preparation process of the method is as follows:
(1) by the Ru (bpy) of the Isosorbide-5-Nitrae of 1, the 8-bis-iodo PFO of 0.5mmol, 0.5mmol-bis-(alkene butyl) benzene, 0.025mmol
3cl
2, 0.175mmol sodium ascorbate and by 1 of 3mL, the mixed organic solvents of the methyl alcohol composition of 4-dioxane and 1mL all adds in reaction vessel, add stirrer in the reactor, stirring makes system be homogeneous phase, carry out the rear sealed reaction vessel of four deoxygenations operation, obtain polymerization in homogeneous phase system I;
(2) temperature arranging reaction vessel is 25 DEG C, and rotating speed is 1800rpm, and polymerization in homogeneous phase system I is carried out polyreaction under the illumination of LED blue light, and the reaction times is 24h;
(3) after reaction terminates, open reaction vessel, add tetrahydrofuran (THF) and polymer is diluted, then take out to be poured in methyl alcohol and precipitate, then carry out suction filtration, drying, obtain fluorine-containing alternating copolymer.
Embodiment 3
Under visible illumination condition, utilize free radical progressively to shift-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, the preparation process of the method is as follows:
(1) by 1, the 7-octadiene of 1, the 8-bis-iodo PFO of 0.5mmol, 0.5mmol, the Ru (bpy) of 0.025mmol
3cl
2, 0.175mmol sodium ascorbate and by 1 of 3mL, the mixed organic solvents of the methyl alcohol composition of 4-dioxane and 1mL all adds in reaction vessel, add stirrer in the reactor, stirring makes system be homogeneous phase, carry out the rear sealed reaction vessel of four deoxygenations operation, obtain polymerization in homogeneous phase system I;
(2) temperature arranging reaction vessel is 25 DEG C, and rotating speed is 1800rpm, and polymerization in homogeneous phase system I is carried out polyreaction under the illumination of LED blue light, and the reaction times is 24h;
(3), after reaction terminates, open reaction vessel, add tetrahydrofuran (THF) and polymerization system is diluted, be poured in methyl alcohol and precipitate, then carry out suction filtration, drying, obtain fluorine-containing alternating copolymer.
Embodiment 4
Under visible illumination condition, utilize free radical progressively to shift-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, the preparation process of the method is as follows:
(1) by the Ru (bpy) of the Isosorbide-5-Nitrae of 1, the 8-bis-iodo PFO of 0.5mmol, 0.5mmol-bis-(allyloxy), 0.025mmol
3cl
2, 0.175mmol sodium ascorbate and by 1 of 3mL, the mixed organic solvents of the methyl alcohol composition of 4-dioxane and 1mL all adds in reaction vessel, add stirrer in the reactor, stirring makes system be homogeneous phase, carry out the rear sealed reaction vessel of four deoxygenations operation, obtain polymerization in homogeneous phase system I;
(2) temperature arranging reaction vessel is 25 DEG C, and rotating speed is 1800rpm, and polymerization in homogeneous phase system I is carried out polyreaction under the illumination of LED blue light, and the reaction times is 24h;
(3) reaction opens reaction vessel after terminating, and adds tetrahydrofuran (THF) and dilutes polymerization system, be poured in methyl alcohol and precipitate, then carry out suction filtration, drying, obtain perfluor alternating copolymer.
Repeat the polymerization process of embodiment 4, by the fluorine-containing alternating copolymer vacuum-drying obtained at different time, its transformation efficiency is calculated with difference assay, Japanese Dong Cao company (TOSOH) HLC-8320 type GPC tests its molecular weight and molecular weight distribution index, and by carrying out In situNMR trace analysis on 600MHz nuclear magnetic resonance spectrometer, obtain 1,8-bis-iodo PFO, 1, the real-time transformation efficiency of 4-two (allyloxy), and compare analysis with the transformation efficiency that difference assay obtains.
As shown in Figures 1 and 2, the dynamics research of polyreaction shows that this polymerization system meets the behavior be progressively polymerized.No matter the monomer transformation efficiency or the residual quantity transformation efficiency analysis obtained by weighting method that obtain from the analysis of nuclear-magnetism in-situ tracking, all can find, at the polymerization initial stage, the transformation efficiency of monomer is just very high, formation dimer, the oligopolymer that the such number molecular weight of tripolymer is less, along with the further reaction of functional group, monomer conversion increases few, but the molecular weight of polymkeric substance has to be increased largely, until the completing of polyreaction, resulting polymers molecular weight distribution (PDI) is about 2, and this is also the characteristic molecular amount dispersion index be progressively polymerized.Therefore, a kind of like this polymerization process meeting progressively aggregation features, be a kind of new polymerization process, we are referred to as free radical it and progressively shift-addition-termination (StepTransfer-Addition & Radical-Termination, START) polymerization.
Due to the introducing of perfluorinated monomers, resulting polymers has the microtexture different from conventional polymer, therefore only has comprehensive analysis
1hNMR and
19fNMR collection of illustrative plates, the sequential structure of characterize polymers that just can be explicit.From Fig. 3's
1hNMR analyzes known, and the peak b at chemical shift δ 5.22 ~ 5.45 place is polymer ends double bond-CH=CH
2characteristic peak, the and-CH=CH of its correspondence
2a the characteristic peak of () just and the HCF of the other one end of polymkeric substance
2cF
2-(a ') overlap, not easily differentiate.Therefore the integral area of peak b first can be defined as 2 by us, carries out analysis verification to polymer architecture.The integral area at corresponding chemical shift peak (a+a ') is 2.13, and (a+a ') and the disproportionate such phenomenon of b, illustrate except desirable (AB)
nbeyond the polymkeric substance of sequential structure, also there is the perfluor carbochain produced by free radical coupling.By formula (1)
，
The molar percentage (%) that we can calculate two kinds of structural polymers is 11.5:88.5.The benchmark calculated using peak b as polymer core magnetism molecule gauge, can calculate the peak d (CH at δ 4.40 ~ 4.56 place
2cH (I) CH
2o) area is 7, that is has 7 new C-I keys and is formed.Whenever having one group of bifunctional monomer (A, B) to be incorporated in polymer chain by addition, a new C-I key will be produced, meet " n-1 " rule.Can extrapolate thus and have four groups of A, B bifunctional monomers and achieve step-reaction polymerization.This polymerization degree also can by c, e, f tri-place chemical shift area and corresponding ratio verify.Pass through
1the nuclear-magnetism molecular weight that HNMR atlas analysis can calculate surveyed polymkeric substance is M
n, NMR=3300g/mol, although the comparatively large (M of this value and GPC mass difference
n, GPC=9200g/mol), this is because the standard specimen of GPC calculating is PMMA, has very big-difference with the hydrodynamic volume of the fluoropolymer of our design and synthesis.In addition, the concrete structure HCF of polymer ends
2cF
2-(a ') also can pass through
1that uncouples (Fig. 3 (a), on) and do not uncouple (Fig. 3 (a), under) test result in HNMR collection of illustrative plates to fluorine atom relatively obtains checking.HCF is there is because only have
2cF
2during-so a kind of end structure, owing to being subject to the strong electrophilic impact of fluorine atom, adjacent hydrogen atom just can occur multiplely splitting swarming in the hydrogen spectrum of not uncoupling to fluorine.In addition,
19in FNMR collection of illustrative plates ,-60ppm locates chemical shift peak (ICF
2cF
2-) the strong ICF demonstrating all polymer ends and may exist of completely dissolve
2cF
2-structure is reduced into HCF completely
2cF
2-.?
1in HNMR collection of illustrative plates, owing to being subject to the strong electrophilic impact of multiple fluorine atom, peak e(-CF
2cH
2cH (I) O-) hydrogen atom that represents tests splitting of the fignal center obtained uncoupling to fluorine and point to be also very different under (Fig. 3 (b), on) and (Fig. 3 (b), under) two states of not uncoupling.
To the analysis of the fluorine-containing fragment structure of polymkeric substance then need by
19fNMR collection of illustrative plates.As described above, the ICF that the completely dissolve explanation polymer ends that-60ppm locates chemical shift peak may exist
2cF
2-group is reduced into HCF completely
2cF
2-, and the corresponding fluorine atom (HCF adjacent with hydrogen
2cF
2-), High-Field-137ppm(peak a ' has been shifted in its chemical shift) place, for convenience of the nuclear-magnetism molecular weight being calculated polymkeric substance by fluorine spectrum analysis, its integral area can be attributed to 2.By carrying out fluorine spectrum (Fig. 4 (a) that uncouples to hydrogen to polymkeric substance, on) and (Fig. 4 (a) that do not uncouple, under) two kinds of nuclear-magnetism tests, can find, the peak at a ' place at do not uncouple to hydrogen (Fig. 4 (a)), under) when, split into the double peak of symmetrical configuration, and to the uncoupling of hydrogen (Fig. 4 (a), on) when, then this splits and point to disappear.Extensive chemical dependency between a kind of like this H and F also well demonstrates polymer chain terminal HCF
2cF
2the existence of-structure.In fluorine spectrum analysis, chemical shift δ-115.0 ~-112.0ppm(a), δ-120.0 ~-122.5ppm(c+d), δ-123.0 ~-125ppm(b) integral area ratio at three places is 1:2:1, meet the characteristic peak of main polymer chain, but be greater than by the nuclear-magnetism molecular weight that its integral and calculating obtains and obtain nuclear-magnetism molecular weight by hydrogen spectrum analysis.This also describes the (per) fluoropolymer A produced due to the existence of free radical coupling side reaction from the side
m.Although (per) fluoropolymer A
min fluorine atom chemical shift and (AB)
nthe chemical shift position of the fluorine-containing fragment of sequential structure polymkeric substance is completely the same, but the existence of (per) fluoropolymer does not affect hydrogen spectrum analysis, so when we calculate the nuclear-magnetism molecular weight of polymkeric substance, with hydrogen spectrum analysis for benchmark, fluorine composes secondary proof in addition.
Fig. 5 is that free radical progressively shifts-mechanism the route map of addition-termination polymerization.First under visible illumination condition, photocatalyst Ru (bpy)
3cl
2be excited to obtain excited state * Ru (bpy)
3cl
2, deposit in case at reductive agent sodium ascorbate, the * Ru (bpy) of excited state
3cl
2revert to [the Ru (bpy) of lower valency
3]
+, utilize [Ru (bpy)
3]
+reductibility, open two C-I keys of 1,8-bis-iodo PFO, produce primary group of free radicals (
.c
8f
16 .), and add to an end of two bifunctional monomers (B) respectively.Each catalytic cycle is realized by the addition-termination of atomic iodine, and these atomic iodine derive from 1,8-bis-iodo PFO (A), thus cause next monomer addition process, progressively obtains dimer, tripolymer so that polymkeric substance.The enough stable existences of newly-generated C-I bond energy, this can be verified by above-mentioned nmr analysis.Certainly, as above-mentioned nuclear magnetic spectrum is analyzed, consider the feature of free radical activity, while intermolecular addition occurs for it, inevitably occur from coupled reaction, obtain (per) fluoropolymer A
m.But these side reactions only occupy the minority.In most cases, the reaction between remaining with desirable A, B monomer is carried out, and obtains the linear polymer (AB) that sequence controls
n.In addition, due to the introducing of fluorochemical monomer, obtained polymkeric substance is made to have special physics, chemical property.
Claims (6)
1. under visible illumination condition, utilize free radical progressively to shift-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, it is characterized in that the preparation process of the method is as follows:
(1) two kinds of bifunctional monomer A and B, photocatalyst, reductive agent, mixed organic solvents are added in reaction vessel simultaneously, stirring makes system be homogeneous phase, carry out the rear sealed reaction vessel of four deoxygenations operation, obtain polymerization in homogeneous phase system I, wherein bifunctional monomer A is 1,8-bis-iodo PFO, bifunctional monomer B is unconjugated inertia diene Isosorbide-5-Nitrae-bis-(alkene butyl) benzene, Isosorbide-5-Nitrae-bis-(allyloxy) benzene or 1,7-octadiene, photocatalyst is Ru (bpy)
3cl
2reductive agent is sodium ascorbate, mixed organic solvents is by tetrahydrofuran (THF), 1, any one and methyl alcohol in 4-dioxane, methyl-sulphoxide, acetonitrile, trifluoroethanol, the perfluor trimethyl carbinol form, mol ratio between bifunctional monomer A, bifunctional monomer B, photocatalyst, reductive agent is 90 ~ 110:90 ~ 110:1 ~ 5:1 ~ 35, and the concentration of bifunctional monomer A and B in mixed organic solvents is 0.1 ~ 0.2mol/L;
(2) temperature arranging reaction vessel is 25 DEG C, and rotating speed is 1500 ~ 2000rpm, and polymerization in homogeneous phase system I is carried out polyreaction under visible light, and the reaction times is 0.5 ~ 24h;
(3), after reaction terminates, open reaction vessel, add tetrahydrofuran (THF) and system is diluted, be poured in methyl alcohol and precipitate, then carry out suction filtration, drying, obtain fluorine-containing alternating copolymer.
2. a kind of free radical that utilizes under visible illumination condition according to claim 1 progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, it is characterized in that: the mol ratio between described bifunctional monomer A, bifunctional monomer B, photocatalyst, reductive agent is 100:100:1:35.
3. a kind of free radical that utilizes under visible illumination condition according to claim 1 progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, it is characterized in that: described mixed organic solvents is by 1,4-dioxane and methyl alcohol composition, the volume ratio of Isosorbide-5-Nitrae-dioxane and methyl alcohol is 3:1.
4. a kind of free radical that utilizes under visible illumination condition according to claim 1 progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, it is characterized in that: the visible light source of described step (2) is 23W electricity-saving lamp, LED white light or LED blue light source.
5. a kind of free radical that utilizes under visible illumination condition according to claim 4 progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, it is characterized in that: the visible light source of described step (2) is LED blue light source.
6. a kind of free radical that utilizes under visible illumination condition according to claim 1 progressively shifts-the polymerization process of the fluorine-containing alternating copolymer of addition-termination preparation, it is characterized in that: the temperature arranging reaction vessel in described step (2) is 25 DEG C, rotating speed is 1800rpm, and the reaction times is 6h.
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