CN100516091C - Reverse ATRP initiation system and its uses in preparing high molecular compound - Google Patents
Reverse ATRP initiation system and its uses in preparing high molecular compound Download PDFInfo
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- CN100516091C CN100516091C CNB2006100489297A CN200610048929A CN100516091C CN 100516091 C CN100516091 C CN 100516091C CN B2006100489297 A CNB2006100489297 A CN B2006100489297A CN 200610048929 A CN200610048929 A CN 200610048929A CN 100516091 C CN100516091 C CN 100516091C
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- 230000000977 initiatory effect Effects 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims abstract description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims description 35
- 101710141544 Allatotropin-related peptide Proteins 0.000 title claims description 26
- 239000003999 initiator Substances 0.000 claims abstract description 43
- 239000002608 ionic liquid Substances 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- -1 methylimidazole organic acid salt Chemical class 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 3
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 27
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 27
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 20
- 229920002521 macromolecule Polymers 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 238000006392 deoxygenation reaction Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical group CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- XIMFCGSNSKXPBO-UHFFFAOYSA-N ethyl 2-bromobutanoate Chemical group CCOC(=O)C(Br)CC XIMFCGSNSKXPBO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012673 precipitation polymerization Methods 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 2
- 230000001052 transient effect Effects 0.000 abstract 2
- 239000000126 substance Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- AOOFKGIQKWSXET-UHFFFAOYSA-N C(=O)O.CC=1NC=CN1 Chemical compound C(=O)O.CC=1NC=CN1 AOOFKGIQKWSXET-UHFFFAOYSA-N 0.000 description 1
- RTNNOCFMHLBSHD-UHFFFAOYSA-N C(CCC)(=O)O.CC=1NC=CN1 Chemical class C(CCC)(=O)O.CC=1NC=CN1 RTNNOCFMHLBSHD-UHFFFAOYSA-N 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000003808 methanol extraction Methods 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- Polymerization Catalysts (AREA)
Abstract
This invention relates to a polymerization initiation system using a new ionic liquid and the application thereof in preparing high-molecular compounds, characterizing: low catalyst usage, low cost and less environmental pollution. The general formula is [mim][RCOO]/R1X/Vc/MXn, wherein: [mim][RCOO] is methylimidazole organic acid salt ionic liquid, and R is alkyl group; R1X is initiator, and R1 is alkyl group; X is halogen Br; reducer Vc is vitamin c; catalyst MXn is high valent state transient metal ionic halogenide; X is halogen Br or Cl; n indicates the valent of the transient metal ion. It can produce the polymerized high molecular compound by the reaction of the above initiation system and monomers.
Description
Technical field
The present invention relates to a kind of macromolecular compound field, specifically is a kind ofly to adopt reverse ATRP initiation system that novel ion liquid, Vc make reductive agent and in the application of preparation 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 CI, 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 (Macromolecules, 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.P olym.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; The C-Cl bonding strength of initiator is greater than the C-Br key in the catalyst system, and therefore for the Cl-ATRP system, polymerization temperature is generally at 100～130 ℃; The polymerization temperature of Br-ATRP system is at 80～110 ℃, and polymerization temperature is also higher, thereby increases production cost; As medium, environment is produced pollution with organic solvent; The toxicity of the amine part that is added; 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 the condition of living polymerization.
Summary of the invention
The technical issues that need to address of the present invention are to provide a catalyst levels few, the low and little brand-new reverse ATRP initiation system of environmental pollution of cost; And use this reverse ATRP initiation system to prepare macromolecular compound.
Reverse ATRP initiation system of the present invention is characterized in that the initiator system general formula is [mim] [RCOO]/R
1X/Vc/MXn is in the formula
[mim] [RCOO] is Methylimidazole organic acid salt ionic liquid, and wherein R is H or alkyl;
R
1X is the initiator that is selected from 2-isobutyl ethyl bromide, 2-bromo-butyric acid ethyl ester, 2-isobutyl bromide propane trimethyl or PMMA; Described PMMA is following reaction product:
Take by weighing Catalysts Cu Br
21 part, 0.5 part of reductant Vc is at 100 parts N-Methylimidazoleacetic salt ion liquid [mim] [CH
3COO] middle dissolving, letting nitrogen in and deoxidizing gas; Take by weighing 100 parts of MMA monomers, behind the letting nitrogen in and deoxidizing gas, add in the ionic liquid, continue letting nitrogen in and deoxidizing, sealing 50 ℃ of following constant temperature 20 minutes, is injected 3 parts initiator 2-isobutyl ethyl bromide, 50 ℃ of reactions of constant temperature; After one hour, handle polymer fluid, obtain Mn=6869, the PMMA of PDI=1.14 with methanol aqueous solution.
Reductant Vc is a vitamin c;
Catalyzer MXn is high valence state transition metal ion halogenide; X is Br or Cl; N is equivalent to the valency of transition metal ion;
[mim] [RCOO]: MXn: Vc: R
1The mol ratio of X is 500: y: 0.5y: z, y=5 wherein, 4,3,2,1 or 0.5; Y: z=5: z, z=1 wherein, 2,3,4,5,10,15,20 or 25.
As preferably, described R is H, CH
3-, CH
3CH
2-and CH
3CH
2CH
2-; Described R
1Be alkyl CH
3CH
2CHCOOC
2H
5(CH
3)
2CCOOC
2H
5Described high valence state transition metal ion is Cu
2+, Ni
2+Or Co
3+
Reverse ATRP initiation system of the present invention is in the application of preparation macromolecular compound, and its feature is as follows:
1) in proportion catalyzer MXn and reductant Vc are dissolved under the ultrasonic wave effect in the Methylimidazole organic acid salt ionic liquid [mim] [RCOO];
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 20 minutes; Described monomer is methyl methacrylate, vinylbenzene;
3) inject initiator R
1X, isothermal reaction;
4) after reaction finishes,, when the less macromolecular compound (less than 10000) of the low relative molecular weight of precipitation, more economical with methanol aqueous solution with methyl alcohol or the methanol aqueous solution precipitation polymerization liquid compound that secures satisfactory grades.Polymeric initiator when this macromolecular compound can also be used as the preparation segmented copolymer.
Use reverse ATRP initiation system of the present invention and can prepare starlike macromolecular compound, promptly described initiator R
1X is a 2-isobutyl bromide propane trimethyl for the multi-arm initiator, the reaction finish starlike macromolecular compound.
Use reverse ATRP initiation system of the present invention and can also prepare the block macromolecular compound, step is,
1) catalyzer MXn and reductant Vc are dissolved under the ultrasonic wave effect in Methylimidazole organic acid salt [mim] [RCOO] ionic liquid;
2) polymeric initiator PMMA is added in the monomer of not deoxygenation dissolving; The monomer that is dissolved with the ionic liquid of catalyzer, reductive agent and is mixed with the not deoxygenation of polymeric initiator PMMA is mixed isothermal reaction;
Perhaps polymeric initiator PMMA is added in the monomer of letting nitrogen in and deoxidizing dissolving, letting nitrogen in and deoxidizing gas; Mix sealing, isothermal reaction with being dissolved with the ionic liquid of letting nitrogen in and deoxidizing of catalyzer, reductive agent and the monomer that is mixed with the deoxygenation of polymeric initiator PMMA;
3) after reaction finishes, get the block macromolecular compound with methyl alcohol or methanol aqueous solution precipitation polymers.
Catalyzer and initiator concentration that the present invention requires are lower, as Vc: R
1X: MXn: monomeric mol ratio is 0.5: 1: 1: 500, and selected temperature is 60 ℃, has rate of polymerization faster.React after one hour, Mn=75981 is near theoretical molecular, and PDI=1.30, this polymerization system have active controlled feature.
Polymerization initiation system of the present invention, because ionic liquid has stronger solvability to catalyzer, with the methanol extraction polymkeric substance time, inorganic salt catalyst is still stayed in the ionic liquid, catalyst content is small in the polymkeric substance.At [mim] [RCOO]: R
1X: CuCl
2Be that the content of copper ion that obtains under 100: 3: 1 the polymerization system is 3.3 * 10
-3% almost can ignore.
The present invention can control the molecular weight of institute's synthetic polymkeric substance by the ratio that changes initiator and catalyzer, and the distribution of polymericular weight, [mim] [RCOO]: monomer: MXn: R
1The mol ratio of X is 500: 500: 5: z, z=1 wherein, 2,3,4,5,10,15,20,25.The molecular weight distribution of the polymkeric substance of gained can reach the polymkeric substance of narrow distributions such as 1.09.
Polymerization system of the present invention synthesizes or other the polymkeric substance of ATRP gained can serve as the macromolecular chain initiator again, need not add under the situation of any other initiator, can be respectively become reverse ATRP initiated polymerization system of the present invention with different set of monomers, carry out block polymerization, initiator and monomeric proportioning are≤800.
Reverse ATRP system of the present invention can use difform multi-arm initiator and monomer reaction to make the polymkeric substance such as the wire of different shape, and is starlike etc.
Owing to reverse ATRP system of the present invention, use the inorganic metal salt of high valence state, oxygen does not almost have influence to it.[mim] [RCOO]: monomer: MXn: R
1The mol ratio of X: Vc is 100: 100: 3: 1: 0.5 o'clock, polymerization system obtained Mn=6869, the PMMA polymkeric substance of PDI=1.14 through nitrogen deoxygenation afterreaction; And polymerization system obtains Mn=6370 without the nitrogen deoxygenation, the PMMA polymkeric substance of PDI=1.11, and oxygen does not have influence to polymerization system.
The present invention with compare with traditional ATRP system, have following characteristics: 1. [mim] [RCOO] ionic liquid is to the good solubility of inorganic salt catalyst with to the good promoter action of polyreaction, and 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. polymerization system polymerization temperature of the present invention just can realize at normal temperatures, and has rate of polymerization faster, overcomes the defective of high temperature polymerization.4. because ionic liquid has almost approaching zero vapour pressure, this polymerization system is avoided the pollution of organic solvent to environment.5. ionic liquid and catalyzer can be recycled, and save cost.6. this polymerization system can be avoided the toxic influence of part without part, and saves the expense that higher part uses.7. this polymerization system can carry out under the condition of not deoxygenation, and experiment condition is simple, help suitability for industrialized production 8. this polymerization system adopt the transition metal salt of high valence state to make catalyzer, avoid easily oxidated shortcoming of lower valency transition metal.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: N-Methylimidazoleacetic salt ion liquid ([mim] [CH
3COO]) in the reverse atom transfer radical polymerization of methyl methacrylate (MMA)
Take by weighing Catalysts Cu Br
2(cupric bromide) 1 part, 0.5 part of reductant Vc is at [mim] [CH of 500 parts
3COO] dissolve letting nitrogen in and deoxidizing gas in (Methylimidazole formate) ionic liquid.Take by weighing 500 parts MMA (methyl methacrylate) monomer, behind the letting nitrogen in and deoxidizing gas, add in the ionic liquid, continue letting nitrogen in and deoxidizing, sealing 60 ℃ of following constant temperature 20 minutes, is injected 1 part 2-isobutyl ethyl bromide initiator, isothermal reaction under 50 ℃ of temperature.After one hour, handle polymer fluid, get PMMA (polymethylmethacrylate), Mn=75981, PDI=1.30 with methyl alcohol.
Embodiment 2: N-Methylimidazoleacetic salt ([mim] [CH
3COO]) reverse atom transfer radical polymerization of methyl methacrylate (MMA) in the ionic liquid
Take by weighing Catalysts Cu Br
21 part, 0.5 part of reductant Vc is at [mim] [CH of 100 parts
3COO] dissolve letting nitrogen in and deoxidizing gas in the ionic liquid.Take by weighing 100 parts of MMA monomers, behind the letting nitrogen in and deoxidizing gas, add in the ionic liquid, continue letting nitrogen in and deoxidizing, sealing 50 ℃ of following constant temperature 20 minutes, is injected 3 parts initiator 2-isobutyl ethyl bromide ((CH
3)
2CBrCOOC
2H
5), 50 ℃ of reactions of constant temperature.After one hour, handle polymer fluid, obtain Mn=6869, the PMMA of PDI=1.14 with methanol aqueous solution.
Embodiment 3: N-Methylimidazoleacetic salt ([mim] [CH
3COO]) reverse atom transfer radical polymerization under the condition of not deoxygenation of methyl methacrylate (MMA) in the ionic liquid
Take by weighing 1 part Catalysts Cu Br
2, 0.5 part of reductant Vc is at [mim] [CH of 100 parts
3COO] dissolve in the ionic liquid, take by weighing 100 parts of MMA monomers, add in the ionic liquid, 50 ℃ of following constant temperature 20 minutes, inject 3 parts initiator 2-isobutyl ethyl bromide ((CH
3)
2CBrCOOC
2H
5), 50 ℃ of following isothermal reactions.After one hour, handle polymer fluid with methanol aqueous solution, the result obtains Mn=6370, the PMMA of PDI=1.11.
Embodiment 4: polymethylmethacrylate (PMMA) is at N-Methylimidazoleacetic salt [mim] [CH
3COO] ionic liquid, cobalt chloride (CoCl
3) preparation block copolymerization macromolecular compound in the system
Take by weighing 1 part CATALYST Co Cl
3, reductant Vc dissolves in [mim] [HCOO] ionic liquid of 100 parts for 0.5 part, 50 ℃ of following constant temperature 20 minutes.The PMMA initiator (Mn=6869) that takes by weighing 0.12 part is dissolved in 100 parts of St monomers, and 50 ℃ of following constant temperature 20 minutes adds in the ionic liquid sealing, 50 ℃ of reactions of constant temperature.Handle polymer fluid with methyl alcohol, the result obtains block copolymerization macromolecular compound PMMA-St, Mn=38912, PDI=1.15.
Embodiment 5: N-Methylimidazoleacetic salt ([mim] [CH
3COO]) ionic liquid, Ni (CH
3COO)
2The reverse atom transfer radical polymerization of the methyl methacrylate in the catalyzer (MMA)
Take by weighing 1 part catalyst n i (CH
3COO)
2, 0.5 part of reductant Vc is at [mim] [CH of 100 parts
3COO] dissolve letting nitrogen in and deoxidizing gas in the ionic liquid.Take by weighing 100 parts of MMA monomers, behind the letting nitrogen in and deoxidizing gas, add in the ionic liquid, continue letting nitrogen in and deoxidizing, sealing 50 ℃ of following constant temperature 20 minutes, is injected 1 part CH
3CH
2CH (Br) COOC
2H
5Initiator, 50 ℃ of reactions of constant temperature.After one hour, handle polymer fluid, obtain Mn=87073, the PMMA of PDI=1.32 with methyl alcohol.
Embodiment 6: N-Methylimidazoleacetic salt ([mim] [CH
3COO]) reverse atom transfer radical polymerization of methyl methacrylate (MMA) in the ionic liquid prepares star-shape polymer.
Take by weighing 1 part Catalysts Cu Br
2, 0.5 part of reductant Vc is at [mim] [CH of 100 parts
3COO] dissolve letting nitrogen in and deoxidizing gas in the ionic liquid.Take by weighing 100 parts of MMA monomers, behind the letting nitrogen in and deoxidizing gas, add in the ionic liquid, continue letting nitrogen in and deoxidizing, sealing 50 ℃ of following constant temperature 20 minutes, is injected 3 parts initiator 2-isobutyl bromide propane trimethyl, 50 ℃ of reactions of constant temperature.After one hour, handle polymer fluid, obtain Mn=124593, the starlike PMMA polymkeric substance of PDI=1.25 with methyl alcohol.
Embodiment 7: Methylimidazole propionic salt ([mim] [CH
3CH
2COO]) reverse atom transfer radical polymerization under the condition of not deoxygenation of methyl methacrylate (MMA) in the ionic liquid
Take by weighing 1 part Catalysts Cu Br
2, 0.5 part of reductant Vc is at [mim] [CH of 100 parts
3CH
2COO] dissolve in the ionic liquid, take by weighing 100 parts of MMA monomers, add in the ionic liquid, 60 ℃ of following constant temperature 20 minutes, inject 3 parts initiator 2-isobutyl ethyl bromide ((CH
3)
2CBrCOOC
2H
5), 60 ℃ of following isothermal reactions.After one hour, handle polymer fluid with methanol aqueous solution, the result obtains Mn=7358, the PMMA of PDI=1.20.
Embodiment 8: Methylimidazole butyrates ([mim] [CH
3CH
2CH
2COO]) reverse atom transfer radical polymerization under the condition of not deoxygenation of methyl methacrylate (MMA) in the ionic liquid
Take by weighing 1 part Catalysts Cu Br
2, 0.5 part of reductant Vc is at [mim] [CH of 100 parts
3CH
2CH
2COO] dissolve in the ionic liquid, take by weighing 100 parts of MMA monomers, add in the ionic liquid, stir, 60 ℃ of following constant temperature 20 minutes, inject 3 parts initiator 2-isobutyl ethyl bromide ((CH
3)
2CBrCOOC
2H
5), 60 ℃ of following isothermal reactions.After one hour, handle polymer fluid with methanol aqueous solution, the result obtains Mn=8307, the PMMA of PDI=1.16.
Claims (5)
1, a kind of reverse ATRP initiation system is characterized in that the initiator system general formula is [mim] [RCOO]/R
1X/Vc/MXn is in the formula
[mim] [RCOO] is Methylimidazole organic acid salt ionic liquid, and wherein R is H or alkyl;
R
1X is 2-isobutyl ethyl bromide, 2-bromo-butyric acid ethyl ester, 2-isobutyl bromide propane trimethyl or PMMA;
Reductant Vc is a vitamin c;
Catalyzer MXn is high valence state transition metal ion halogenide; X is Br or Cl; N is equivalent to the valency of transition metal ion; Described high valence state transition metal ion is Cu
2+, Ni
2+Or Co
3+
[mim] [RCOO]: MXn: Vc: R
1The mol ratio of X is 500: y: 0.5y: z, wherein y=5,4,3,2,1 or 0.5; Z=1,2,3,4,5,10,15,20 or 25;
Above-mentioned PMMA is following reaction product:
Take by weighing Catalysts Cu Br
21 part, 0.5 part of reductant Vc is at 100 parts N-Methylimidazoleacetic salt ion liquid [mim] [CH
3COO] middle dissolving, letting nitrogen in and deoxidizing gas; Take by weighing 100 parts of MMA monomers, behind the letting nitrogen in and deoxidizing gas, add in the ionic liquid, continue letting nitrogen in and deoxidizing, sealing 50 ℃ of following constant temperature 20 minutes, is injected 3 parts initiator 2-isobutyl ethyl bromide, 50 ℃ of reactions of constant temperature; After one hour, handle polymer fluid, obtain Mn=6869, the PMMA of PDI=1.14 with methanol aqueous solution.
2, initiator system according to claim 1 is characterized in that described R is H, CH
3-, CH
3CH
2-or CH
3CH
2CH
2-.
3, a kind of reverse ATRP initiation system as claimed in claim 1 or 2 is characterized in that as follows in the application of preparation macromolecular compound:
1) in proportion catalyzer MXn and reductant Vc are dissolved under the ultrasonic wave effect in the Methylimidazole organic acid salt ionic liquid [mim] [RCOO];
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 20 minutes; Described monomer is methyl methacrylate or vinylbenzene;
3) inject initiator R
1X, isothermal reaction;
4) after reaction finishes, with methyl alcohol or the methanol aqueous solution precipitation polymerization liquid compound that secures satisfactory grades.
4, reverse ATRP initiation system according to claim 3 is characterized in that described initiator R in the application of preparation macromolecular compound
1X is a 2-isobutyl bromide propane trimethyl, the reaction finish starlike macromolecular compound.
5, a kind of reverse ATRP initiation system as claimed in claim 1 or 2 is characterized in that in the application of preparation macromolecular compound
1) catalyzer MXn and reductant Vc are dissolved under the ultrasonic wave effect in Methylimidazole organic acid salt [mim] [RCOO] ionic liquid;
2) polymeric initiator PMMA is added in the monomer of not deoxygenation dissolving; The monomer that is dissolved with the ionic liquid of catalyzer, reductive agent and is mixed with the not deoxygenation of polymeric initiator PMMA is mixed isothermal reaction;
Perhaps polymeric initiator PMMA is added in the monomer of letting nitrogen in and deoxidizing dissolving, letting nitrogen in and deoxidizing gas; Mix sealing, isothermal reaction with being dissolved with the ionic liquid of letting nitrogen in and deoxidizing of catalyzer, reductive agent and the monomer that is mixed with the deoxygenation of polymeric initiator PMMA;
3) after reaction finishes, get the block macromolecular compound with methyl alcohol or methanol aqueous solution precipitation polymers.
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| CN110746529A (en) * | 2019-11-08 | 2020-02-04 | 铜仁学院 | Synthesis method of zwitterionic polymer |
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Non-Patent Citations (4)
| Title |
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| Atom transfer radical polymerization of acrylates in an ionicliquid: synthesis of block copolymers. Biedron, etc.Journal of Polymer Science, Part A: Polymer Chemistry,Vol.40 No.16. 2002 |
| Atom transfer radical polymerization of acrylates in an ionicliquid: synthesis of block copolymers. Biedron, etc.Journal of Polymer Science, Part A: Polymer Chemistry,Vol.40 No.16. 2002 * |
| 甲基丙烯酸甲酯的反向原子转移自由基聚合反应研究. 刘兵等.化学学报，第59卷第1期. 2001 |
| 甲基丙烯酸甲酯的反向原子转移自由基聚合反应研究. 刘兵等.化学学报，第59卷第1期. 2001 * |
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