CN101550204B - Atom transfer free radical polymerization initiation system with polyethyleneglycol as polymerization medium and its application in preparing macromolecular compound - Google Patents
Atom transfer free radical polymerization initiation system with polyethyleneglycol as polymerization medium and its application in preparing macromolecular compound Download PDFInfo
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- CN101550204B CN101550204B CN2009103012936A CN200910301293A CN101550204B CN 101550204 B CN101550204 B CN 101550204B CN 2009103012936 A CN2009103012936 A CN 2009103012936A CN 200910301293 A CN200910301293 A CN 200910301293A CN 101550204 B CN101550204 B CN 101550204B
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- 229920002521 macromolecule Polymers 0.000 title claims abstract description 37
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 7
- 238000010526 radical polymerization reaction Methods 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 title abstract description 17
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 12
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims abstract 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 239000003999 initiator Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 20
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 20
- -1 polyoxyethylene Polymers 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 238000006392 deoxygenation reaction Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000003808 methanol extraction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229920005553 polystyrene-acrylate Polymers 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 19
- 238000005303 weighing Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 15
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 6
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 6
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 6
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 description 4
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 4
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XIMFCGSNSKXPBO-UHFFFAOYSA-N ethyl 2-bromobutanoate Chemical compound CCOC(=O)C(Br)CC XIMFCGSNSKXPBO-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a ATRP initiation system with polyethyleneglycol as medium and its application in preparing macromolecular compound, which provides a completely new initiation system with polyethyleneglycol as polymerization medium. The invention is characterized in that the initiation system is made up of polyethyleneglycol, evocating agent and energizing agent, the general formula of initiation system is PEGn1/I/MXn/L, in which PEGn1 denotes polyethyleneglycol of different molecular mass, I denotes evocating agent, energizing agent MXn denotes transition metal ion halogenide of withhigh oxidation states, X denotes Br or Cl, n denotes the valency of transition metal ion, L denotes ligand. The molar ratio of PEGn1/I/MXn/L is 500:y:y, wherein y is equal to 5, 4, 3, 2, 1 or 0.5. Theinvention prepares macromolecular compounds of one monomer by the aforementioned initiation system with the monomer to react.
Description
Technical field
The present invention relates to the macromolecular compound field, specifically be a kind of be atom transfer radical polymerization (ATRP) initiator system of polymerisation medium and with polyoxyethylene glycol (PEG) in the application of preparation in the macromolecular compound.
Background technology
Nineteen ninety-five Wang Jinshan is first at J.Am.chem.Soc., 1995,117, in the atomic radical transferring free-radical polymerization of 5614 reports (the being called for short ATRP) initiator system, that be used as initiator is halogenated alkyl hydrocarbon R-X, and wherein X is Cl, Br, and R is the organic group that contains the conjugation inductive effect, in first-generation ATRP initiator system, be catalyzer mainly with CuX and organic ligand.Anbo and Granel (Maeromolecules, 1996,29:8576,1074) use complex compound such as the RuCl of Ru and Ni respectively
2(pph
3)/Al (OR)
3, Ni (NCN) Br, Ni[O, 0 ' (CH
2NMe
2)
2C
6H] Br, form the ATRP initiator system jointly for catalyzer and halogenated alkyl hydrocarbon initiator, successfully caused the ATRP reaction of MMA.Wei etc. are at Polym.Prep., and 1997,38 (2): reported with ferrous halide FeCl in 231,233 again
2(PPh
3), be the ATRP reaction of catalyzer.Because the inorganic metal salt of lower valency is subject to the influence of oxygenants such as oxygen, (J.Polym.sci. such as Matyjaszewski, Polym.chem..ed., 2000,38,4724) having studied a kind of is the reverse ATRP system that reductive agent and high valence state inorganic metal salt are formed catalyst system with azo type free base initiator.
Present ATRP system also exists defective: because rate of polymerization is relevant with the amount of catalyzer and part, and for reaching suitable polymerization velocity, catalyst levels big (1: 100) in the polymerization system; As medium, environment is produced pollution with organic solvent; The small molecules ligand catalyst of transition metal is after polymerization finishes, and catalyzer needs could separate after loaded down with trivial details processing, and processing costs is too high; Catalyzer is difficult to recycle, and the lower valency metal ion is oxidated easily, the requirement for experiment condition harshness.In reverse ATRP, the free radical itself that azo type free base initiator produces is an active group, influences living polymerization.In order to overcome organic solvent environment is produced pollution, we have studied with Methylimidazole organic acid salt ionic liquid is the ATRP system (seeing ZL 200510061318.1) of medium, and holds in order to overcome the lower valency metal ion
Easily oxidated shortcoming, utilizing Vc is the AGET ATRP system (seeing CN 101033269A) of reductive agent as the AGETATRP system (seeing CN 1880345A) of reductive agent with the Resorcinol.
Low molecular poly is a kind of common liquid oligomer, can dissolve each other with water, toluene, methylene dichloride, alcohol, acetone equal solvent.Polyoxyethylene glycol has low toxicity, advantage such as biodegradable, non-volatile, not flammable, cheap.It is to most of organic and the organometallics solubility property is good, and at acid, alkali, high temperature, O
2And H
2O
2Oxidation system and NaBH
4All very stable in the reduction system.Exactly because PEG has above-mentioned good characteristic, begun to cause people's attention as new green reaction medium and as the Yao saddle cloth Shen carrier of catalyzer with PEG.With PEG is that solvent is applied in comprising reactions such as reduction reaction, hydrogenation, oxidizing reaction, bishydroxy reaction, linked reaction and enzyme catalysis.Yet, yet there are no report with PEG as the AGET ATRP system of reaction medium, therefore, based on the above-mentioned characteristic of PEG, it is the AGET ATRP initiator system of polymerisation medium with PEG that the present invention has designed brand-new, and is used for high molecular synthetic.
Summary of the invention
The technical issues that need to address of the present invention are, provide one few with catalyst levels, it is brand-new that cost is low and environmental pollution is little is a kind of atom transfer radical polymerization (activator generated by electron transfer atom transfer radical polymerization is called for short AGET ATRP) initiator system that produces active catalyst by transfer transport of polymerisation medium with PEG; And use this AGET ATRP initiator system to prepare macromolecular compound.
Of the present invention is the atom transition free radical polymerization initiation system of polymerisation medium with the polyoxyethylene glycol, it is characterized in that the initiator system general formula is PEGn
1/ I/MXn/L is in the formula
PEGn
1The expression different molecular weight polyethylene glycol, wherein PEG is a polyoxyethylene glycol, n
1The molecular weight of representing this polyoxyethylene glycol is selected from 200,400 or 600;
I is an initiator;
Catalyzer MXn is high valence state transition metal ion halogenide, and X is Br or Cl; N is equivalent to the valency of transition metal ion;
L is a part, is selected from Methylimidazole, thanomin, hexahydroaniline or Tetramethyl Ethylene Diamine;
PEGn
1The mol ratio of/I/MXn is 500: y: y (promptly two y are with selecting a number), y=5 wherein, 4,3,2,1 or 0.5.
Described initiator is selected from CH
3CH
2CHClCOOC
2H
5(2-neoprene acid ethyl ester), (CH
3)
2CClCOOC
2H
5(2-chlorine ethyl isobutyrate), CH
3CH
2CHBrCOOC
2H
5(2-bromo-butyric acid ethyl ester), (CH
3)
2CBrCOOC
2H
5(2-isobutyl ethyl bromide) or
(CH
3)
2CBrCOOCH
2CH
2OOCBr (CH
3)
2(two 2-isobutyl bromide second diester, this is the both arms initiator).
Described initiator can also be by prepared end group band Cl of ATRP system or the macromolecular compound of Br, it can be used as polymeric initiator, be preferably the polymethylmethacrylate (PMMA) of end group band Cl or Br, polystyrene (PSt) or polymethyl acrylate (PMA); The ATRP system that wherein prepares the macromolecular compound of end group band Cl or Br can be an ATRP system of the present invention, also can be the ATRP system of other prior aries, down together.Transition metal ion in the described high valence state transition metal ion halogenide is selected from Cu
2+, Fe
3+, Ni
2+Or Co
3+
The application of initiator system of the present invention in the preparation macromolecular compound, as follows:
1) under the ultrasonic wave effect, in proportion catalyzer MXn is dissolved in polyoxyethylene glycol PEG n
1In;
2) add the monomer of not deoxygenation, constant temperature; The monomer that perhaps adds letting nitrogen in and deoxidizing, letting nitrogen in and deoxidizing gas, sealing, constant temperature; Described monomer is selected from methyl methacrylate (MMA), vinylbenzene (St) or methyl acrylate (MA);
3) inject initiator, isothermal reaction;
4) after reaction finishes, get the macromolecular compound of end group band Cl or Br with the methanol extraction polymer fluid.
Initiator system of the present invention can prepare the wire macromolecular compound, and promptly described initiator is both arms initiator (CH
3)
2CBrCOOCH
2CH
2OOCBr (CH
3)
2, the reaction finish the wire macromolecular compound.
The Another Application Zhao of ATRP initiator system of the present invention in the preparation macromolecular compound prepares the block macromolecular compound, as follows:
1) catalyzer MXn is dissolved in PEGn under the ultrasonic wave effect
1In;
2) will add in the monomer of not deoxygenation dissolving by prepared end group band Cl of ATRP system or the macromolecular compound of Br as polymeric initiator; The PEGn of catalyzer will be dissolved with
1The monomer of solution and the not deoxygenation that is mixed with polymeric initiator mixes isothermal reaction;
Perhaps dissolving, letting nitrogen in and deoxidizing gas will be added as polymeric initiator by the macromolecular compound of prepared end group band Cl of ATRP system or Br in the monomer of letting nitrogen in and deoxidizing; To be dissolved with the logical nitrogen of catalyzer
The PEGn of deoxygenation
1The monomer of solution and the deoxygenation that is mixed with polymeric initiator mixes, sealing, isothermal reaction;
3) after reaction finishes, get the block macromolecular compound with the methanol extraction polymkeric substance.
Polymerization initiation system of the present invention, because PEG has stronger solvability to catalyzer, with the methanol extraction macromolecular compound time, inorganic salt catalyst is still stayed in the PEG solution, catalyst content is small in the gained macromolecular compound.
The present invention can control the molecular weight of institute's synthetic macromolecular compound by changing initiator and monomeric ratio, and the distribution of macromolecular compound molecular weight.PEGn in polymerization system
1The mol ratio of Dan Ti MXn I is 100: 100: 1:, can get the macromolecular compound that molecular weight is distributed as narrow distributions such as 1.14 at 1 o'clock.
Polymerization system of the present invention synthesizes or other the macromolecular compound of ATRP system gained can serve as the macromolecular chain initiator again, under the situation that need not add any other initiator, can be respectively become AGET ATRP initiated polymerization system of the present invention with different set of monomers, carry out block polymerization, initiator and monomeric proportioning≤800.
AGET ATRP initiator system of the present invention can use difform multi-arm initiator and monomer reaction to make the macromolecular compound such as the wire of different shape, and is starlike etc.
Owing to AGET ATRP system of the present invention, use the inorganic metal salt of high valence state, oxygen does not almost have influence to it.PEGn
1Monomer MXn the mol ratio of I be 100: 100: 1: 1 o'clock, polymerization system obtained Mn=10600, the PMMA polymkeric substance of PDI=1.14 through nitrogen deoxygenation afterreaction; And polymerization system obtains Mn=11400 without the nitrogen deoxygenation, the PMMA polymkeric substance of PDI=1.15, and oxygen does not have influence substantially to polymerization system.
The present invention with compare with traditional ATRP system, have following characteristics: 1. PEG has good solubility to inorganic salt catalyst, and polyreaction is had good promoter action, catalyzer range of choice applicatory is wide.2. polymkeric substance just can be realized separating fully of polymkeric substance and inorganic salt through the simple methanol precipitation process, handles simply, and expense is low, helps suitability for industrialized production.3. because PEG liquid has low toxicity, advantage such as biodegradable, non-volatile, not flammable, cheap, this polymerization system is avoided the pollution to environment such as organic solvent.4. PEG and catalyzer can be recycled, and save cost.5. this polymerization system can carry out under the condition of not deoxygenation, and processing condition are simplified, and help suitability for industrialized production.6. this polymerization system adopts the transition metal salt of high valence state to make catalyzer, avoids lower valency transition metal oxidated shortcoming easily.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail, these embodiment do explanation of the present invention, are not limitations of the present invention.Material umber among the embodiment all is a molfraction.
The AGET ATRP reaction of the methyl methacrylate among the embodiment 1:PEG600 (MMA)
Take by weighing cupric bromide (CuBr
2), each 1 part of Methylimidazole, among 500 parts PEG600 (Polyethylene Glycol-600), dissolve letting nitrogen in and deoxidizing gas.Take by weighing 500 parts MMA (methyl methacrylate) monomer, behind the letting nitrogen in and deoxidizing gas, join in the PEG600 solution, continue letting nitrogen in and deoxidizing, sealing 80 ℃ of following constant temperature 10 minutes, is injected 1 part 2-chlorine ethyl isobutyrate initiator, isothermal reaction under 80 ℃ of temperature.After 4 hours, handle polymer fluid, get the PMMA (polymethylmethacrylate) of end group band Cl, Mn=65900, PDI=1.30 with methyl alcohol.
Embodiment 2:PEG600/FeBr
3The AGET ATRP reaction of the methyl methacrylate the in/thanomin catalyst system (MMA)
Take by weighing each 1 part of iron bromide, Methylimidazole, dissolving in 200 parts PEG600 (Polyethylene Glycol-600), letting nitrogen in and deoxidizing gas.Take by weighing 100 parts of MMA (methyl methacrylate) monomer, behind the letting nitrogen in and deoxidizing gas, join in the PEG600 solution, continue letting nitrogen in and deoxidizing, sealing 80 ℃ of following constant temperature 10 minutes, is injected 1 part of 2-isobutyl ethyl bromide initiator, isothermal reaction under 80 ℃ of temperature.3.5 after hour, handle polymer fluid, get the PMMA (polymethylmethacrylate) of end group band Br, Mn=29900, PDI=1.35 with methyl alcohol.
Embodiment 3:PEG600/CuBr
2The AGET ATRP reaction of the methyl methacrylate the in/hexahydroaniline catalyst system (MMA)
Take by weighing each 1 part of cupric bromide, Methylimidazole, dissolving in 200 parts PEG600 (Polyethylene Glycol-600), letting nitrogen in and deoxidizing gas.Take by weighing 100 parts of MMA (methyl methacrylate) monomer, behind the letting nitrogen in and deoxidizing gas, add in the PEG600 solution, continue letting nitrogen in and deoxidizing, sealing 80 ℃ of following constant temperature 10 minutes, is injected 3 parts 2-bromo-butyric acid ethyl ester initiator, isothermal reaction under 80 ℃ of temperature.3.5 after hour, handle polymer fluid, get the PMMA (polymethylmethacrylate) of end group band Br, Mn=11200, PDI=1.30 with methyl alcohol.
Embodiment 4:PEG200/CuBr
2The AGETATRP reaction of the methyl methacrylate the in/Tetramethyl Ethylene Diamine catalyst system (MMA)
Take by weighing each 1 part of cupric bromide, Tetramethyl Ethylene Diamine, dissolving in 100 parts PEG200 (Macrogol 200), letting nitrogen in and deoxidizing gas.Take by weighing 100 parts of MMA (methyl methacrylate) monomer, behind the letting nitrogen in and deoxidizing gas, join in the PEG200 solution, continue letting nitrogen in and deoxidizing, sealing 80 ℃ of following constant temperature 10 minutes, is injected 1 part of 2-neoprene acid ethyl ester initiator, isothermal reaction under 80 ℃ of temperature.After 3 hours, handle polymer fluid, get the PMMA (polymethylmethacrylate) of end group band Cl, Mn=14300, PDI=1.21 with methyl alcohol.
Embodiment 5: polymethylmethacrylate (PMMA) is at PEG600, cobalt chloride (CoCl
3) preparation block copolymerization macromolecular compound in the system
Take by weighing 1 part CATALYST Co Cl
3, in 200 parts PEG600, dissolve 80 ℃ of following constant temperature 20 minutes.The polymeric initiator PMMA (Mn=7300) that takes by weighing 0.12 part end group band Cl is dissolved in 100 parts of styrene monomers, and 80 ℃ of following constant temperature 20 minutes adds in the PEG600 solution sealing, 80 ℃ of reactions of constant temperature.Result: obtain the PMMA-b-St of block copolymerization macromolecular compound end group band Cl, Mn=16500, PDI=1.23.
Embodiment 6:PEG400/CuBr
2The AGETATRP reaction of the methyl methacrylate the in/Tetramethyl Ethylene Diamine catalyst system (MMA)
Take by weighing each 1 part of cupric bromide, Tetramethyl Ethylene Diamine, dissolving in 100 parts of PEG400 (poly(oxyethylene glycol) 400), letting nitrogen in and deoxidizing gas.Take by weighing 100 parts of MMA (methyl methacrylate) monomer, behind the letting nitrogen in and deoxidizing gas, add in the PEG400 solution, continue letting nitrogen in and deoxidizing, sealing 70 ℃ of following constant temperature 10 minutes, is injected 1 part of 2-isobutyl ethyl bromide initiator, isothermal reaction under 70 ℃ of temperature.After 2 hours, handle polymer fluid, get the PMMA (polymethylmethacrylate) of end group band Br, Mn=10600, PDI=1.14 with methyl alcohol
Embodiment 7:PEG600/CuBr
2The reaction of AGET ATRP under the condition of not deoxygenation of methyl methacrylate in the/Tetramethyl Ethylene Diamine catalyst system (MMA)
Take by weighing each 1 part of cupric bromide, Tetramethyl Ethylene Diamine, dissolving in 100 parts of PEG600 (Polyethylene Glycol-600).Take by weighing 100 parts of MMA (methyl methacrylate) monomer, add in the PEG600 solution, sealing 70 ℃ of following constant temperature 10 minutes, is injected 1 part 2-isobutyl ethyl bromide initiator, isothermal reaction under 70 ℃ of temperature.After 2 hours, handle polymer fluid, get the PMMA (polymethylmethacrylate) of end group band Br, Mn=11400, PDI=1.15 with methyl alcohol.
Embodiment 8:PEG400/CuBr
2The preparation of wire macromolecular compound in the/Tetramethyl Ethylene Diamine catalyst system
Take by weighing each 1 part of cupric bromide, Tetramethyl Ethylene Diamine, dissolving in 200 parts of PEG400 (poly(oxyethylene glycol) 400).(MMA (methyl methacrylate) monomer adds in the PEG400 solution, and sealing 70 ℃ of following constant temperature 10 minutes, is injected 1 part of (CH to take by weighing 200 parts
3)
2CBrCOOCH
2CH
2OOCBr (CH
3)
2The both arms initiator, isothermal reaction under 70 ℃ of temperature.After 2 hours, handle polymer fluid, get the macromolecular compound of the wire of end group band Br, Mn=9800, PDI=1.18 with methyl alcohol.
Claims (4)
1. one kind is the atom transition free radical polymerization initiation system of polymerisation medium with the polyoxyethylene glycol, it is characterized in that the initiator system general formula is PEGn
1/ I/MXn/L is in the formula
PEGn
1The expression different molecular weight polyethylene glycol, wherein PEG is a polyoxyethylene glycol, n
1The molecular weight of representing this polyoxyethylene glycol is selected from 200,400 or 600;
I is an initiator;
Catalyzer MXn is high valence state transition metal ion halogenide, and X is Br or Cl; N is equivalent to the valency of transition metal ion;
L is a part, is selected from Methylimidazole, thanomin, hexahydroaniline or Tetramethyl Ethylene Diamine;
PEGn
1The mol ratio of/I/MXn is 500:y:y, y=5,4 wherein, 3,2,1 or 0.5;
Described initiator is selected from CH
3CH
2CHClCOOC
2H
5, (CH
3)
2CClCOOC
2H
5, CH
3CH
2CHBrCOOC
2H
5, (CH
3)
2CBrCOOC
2H
5Or (CH
3)
2CBrCOOCH
2CH
2OOCBr (CH
3)
2Transition metal ion in the described high valence state transition metal ion halogenide is selected from Cu
2+, Fe
3+, Ni
2+Or Co
3+
Described initiator is by prepared end group band Cl of ATRP system or the polymkeric substance of Br; Transition metal ion in the described high valence state transition metal ion halogenide is selected from Cu
2+, Fe
3+, Ni
2+Or Co
3+Describedly be selected from polymethylmethacrylate, polystyrene or polymethyl acrylate by prepared end group band Cl of ATRP system or the polymkeric substance of Br.
2. the application of initiator system as claimed in claim 1 in the preparation macromolecular compound, its feature is as follows:
1) under the ultrasonic wave effect, in proportion catalyzer MXn is dissolved in polyoxyethylene glycol PEG n
1In;
2) add the monomer of not deoxygenation, constant temperature; The monomer that perhaps adds letting nitrogen in and deoxidizing, letting nitrogen in and deoxidizing gas, sealing, constant temperature; Described monomer is selected from methyl methacrylate, vinylbenzene or methyl acrylate;
3) inject initiator, isothermal reaction;
4) after reaction finishes, get the macromolecular compound of end group band Cl or Br with the methanol extraction polymer fluid.
3. the application of initiator system according to claim 2 in the preparation macromolecular compound is characterized in that described initiator is (CH
3)
2CBrCOOCH
2CH
2OOCBr (CH
3)
2, the reaction finish the wire macromolecular compound.
4. the application of initiator system according to claim 2 in preparation block macromolecular compound is characterized in that
1) catalyzer MXn is dissolved in PEGn under the ultrasonic wave effect
1In;
2) will add in the monomer of not deoxygenation dissolving by prepared end group band Cl of ATRP system or the macromolecular compound of Br as polymeric initiator; The PEGn of catalyzer will be dissolved with
1The monomer of solution and the not deoxygenation that is mixed with polymeric initiator mixes isothermal reaction;
Perhaps dissolving, letting nitrogen in and deoxidizing gas will be added as polymeric initiator by the macromolecular compound of prepared end group band Cl of ATRP system or Br in the monomer of letting nitrogen in and deoxidizing; The PEGn of catalyzer letting nitrogen in and deoxidizing will be dissolved with
1The monomer of solution and the deoxygenation that is mixed with polymeric initiator mixes, sealing, isothermal reaction;
3) after reaction finishes, get the block macromolecular compound with the methanol extraction polymkeric substance.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807472A (en) * | 2005-10-31 | 2006-07-26 | 杭州师范学院 | Method for preparing high molecular compound adopting novel ion liquid polymerization initiation system |
| CN1880345A (en) * | 2006-01-06 | 2006-12-20 | 杭州师范学院 | Reverse ATRP initiation system and its uses in preparing high molecular compound |
| CN101033269A (en) * | 2007-02-12 | 2007-09-12 | 杭州师范学院 | Atom transition free radical polymerization initiation system and application of the same for preparing macromolecular compound |
| CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807472A (en) * | 2005-10-31 | 2006-07-26 | 杭州师范学院 | Method for preparing high molecular compound adopting novel ion liquid polymerization initiation system |
| CN1880345A (en) * | 2006-01-06 | 2006-12-20 | 杭州师范学院 | Reverse ATRP initiation system and its uses in preparing high molecular compound |
| CN101033269A (en) * | 2007-02-12 | 2007-09-12 | 杭州师范学院 | Atom transition free radical polymerization initiation system and application of the same for preparing macromolecular compound |
| CN101260219A (en) * | 2008-04-25 | 2008-09-10 | 华南理工大学 | Method for preparing triblock copolymer micelle system used for realizing reversible fluorescence regulation and control |
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