CN1807472A - Method for preparing high molecular compound adopting novel ion liquid polymerization initiation system - Google Patents
Method for preparing high molecular compound adopting novel ion liquid polymerization initiation system Download PDFInfo
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Abstract
The invention relates to a method which using new ionic liquor polymerization initiation systerm prepares macromolecular compound. The technical matters of this invention needs to settle is providing a bran-new initiation systerm of atom radical transfer free radical polymerization which using ionic liquor as polymerization medium. The characteristic of this invention's method is the polymerization initiation systerm made up of ionic liquor, initiator and catalysator; the general formula of initiation systerm is [mim][RCOO]/R1X/MXn, the [mim][RCOO] is methyl imidazole organic acid salt ionic liquor, R is alkyl group; R1X is initiator, R1 is alkyl, X is halogen; catalysator MXn is transient metal inorganic salt, n is valence number equal to transition metal; initiation systerm reacts whth monomer can prepare the macromolecular compound of this monomer.
Description
Technical field
The present invention relates to adopt novel ion liquid polymerization initiation system to prepare the method for macromolecular compound.This polymerization initiation system is to be polymerisation medium by Methylimidazole organic acid salt ionic liquid ([mim] [RCOO]), and R-X is that the inorganic transition metal salt MXn of initiator and lower valency makes catalyzer and constitutes, and this polymerization initiation system does not add any transition metal organic ligand.
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 use complex compound such as the RuCl of Ru and Ni respectively in (Macromolecules, 1996,29:8576,1074)
2(pph
3)/Al (OR)
3, Ni (NCN) Br, Ni[O, O ' (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.
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.
Summary of the invention
The technical issues that need to address of the present invention are, overcome the existing deficiency of prior art, provide one brand-new be the initiator system of the atomic radical transferring free-radical polymerization of polymerisation medium with the ionic liquid.
Employing novel ion liquid polymerization initiation system of the present invention prepares the method for macromolecular compound, it is characterized in that by ionic liquid, and initiator and catalyzer constitute polymerization initiation system; The initiator system general formula is [mim] [RCOO]/R
1X/MXn, [mim] [RCOO] is Methylimidazole organic acid salt ionic liquid in the formula, and R is an alkyl, and alkyl is H (hydrogen atom) ,-CH
3(methyl) ,-CH
3CH
2(ethyl) ,-CH
3CH
2CH
2(propyl group) ,-CH
3CH
2CH
2CH
2(butyl); R
1X is an initiator, wherein R
1Be alkyl, X is a halogen: Cl, Br; Catalyzer MXn is the transition metal inorganic salt, and the metal in the transition metal inorganic salt is Cu, Ni, Fe, Ti and Co; N is the valence mumber that is equal to transition metal; Initiator system and monomer reaction are prepared into this monomeric polymerization macromolecule compound, and monomer is a vinylbenzene, or its general formula is or its general formula is CH
2=CR '-COOR, R ' and R are alkyl, R ' is H (hydrogen atom) ,-CH
3(methyl); R is-CH
3(methyl) ,-CH
3CH
2(ethyl) ,-CH
3CH
2CH
2(propyl group) ,-CH
3CH
2CH
2CH
2(butyl).Its preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas;
2) monomer of adding deoxygenation, letting nitrogen in and deoxidizing gas, sealing, constant temperature;
3) inject initiator, isothermal reaction;
4) after reaction finishes, with the methanol extraction polymkeric substance compound that secures satisfactory grades.
The present invention can also prepare segmented copolymer, and its preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas; Polymeric initiator is added in the monomer of deoxygenation dissolving, letting nitrogen in and deoxidizing gas;
2) ionic liquid and monomer are mixed sealing, isothermal reaction;
3) after reaction finishes, get segmented copolymer with the methanol extraction polymkeric substance.
Preferred monomer is a methyl methacrylate, vinylbenzene; Corresponding macromolecular compound PMMA, the PSt of obtaining of prepared in reaction.
In the reaction system, [mim] [RCOO]: the mol ratio of monomer: MXn is 500: 500: y, y=5 wherein, 4,3,2,1,0.5; Y: z=5: z, z=1 wherein, 2,3,4,5,10,15,20,25.
Catalyzer and initiator concentration that the present invention requires are lower, and as RX: MXn: monomeric mol ratio is 1: 1: 500, and selected temperature is 50 ℃, has rate of polymerization faster.React after one hour, polymkeric substance is near theoretical molecular Mn=55514, PDI=1.34, and as can be seen, this polymerization system has 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 are still stayed in the ionic liquid, catalyst content is small in the polymkeric substance.Be that the content of copper ion that obtains under 1: 1: 100 the polymerization system is 3.8 * 10 at [mim] [RCOO]: RX: CuCl
-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, and [mim] [RCOO]: the mol ratio of monomer: MXn: RX is 500: 500: 5: z, wherein z=1,2,3,4,5,10,15,20,25.The molecular weight distribution of the polymkeric substance of gained can reach the polymkeric substance of narrow distributions such as 1.14.
This polymerization system 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 ATRP initiated polymerization system of the present invention with different set of monomers, carry out block polymerization, initiator and monomeric proportioning are≤800.
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 can be recycled, and saves cost.6. this polymerization system can be avoided the toxic influence of part without part, and saves the expense that higher part uses.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1.The atom transfer radical polymerization of the methyl methacrylate (MMA) in the Methylimidazole formate ionic liquid ([mim] [HCOO])
Take by weighing 3 parts of CuBr of 1 part of CuBr (cuprous bromide, down together)
2(cupric bromide) dissolves letting nitrogen in and deoxidizing gas in [mim] [HCOO] (Methylimidazole formate, down together) ionic liquid of 500 parts.Take by weighing 500 parts of MMA (methyl methacrylate, down with) monomer, 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 2-isobutyl ethyl bromide initiator, 50 ℃ of reactions of constant temperature.After one hour, handle polymer fluid, get PMMA (polymethylmethacrylate, down together), Mn=55514, PDI=1.34 with methyl alcohol.
Embodiment 2.N-Methylimidazoleacetic salt ([mim] [CH
3COO]) atom transfer radical polymerization of methyl methacrylate (MMA) in the ionic liquid
Take by weighing 1 part CuBr, 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 the initiator of different ratios, 50 ℃ of reactions of constant temperature.The result:
| Reaction a | The t/ branch | Transformation efficiency/%b | Mnc | Mw/Mn |
| 1d 2e 3f 4g 5h | 210 60 60 60 60 | 62.62 43.28 60.21 65.13 72.61 | 28428 13653 9723 8583 8018 | 1.32 1.17 1.17 1.22 1.14 |
(go up in the table, Mn is a number-average molecular weight, and Mw is a weight-average molecular weight)
A. respond all at MMA: [mim] [CH
3COO] be ratio under to carry out at 100: 100.
B. transformation efficiency is obtained by the hydrogen nuclear magnetic resonance spectrum analysis.
C. number-average molecular weight is obtained by the GPC that makes standard with polystyrene.
d＝100∶1∶1/3；e＝100∶1∶1；f＝100∶1∶2；g＝100∶1∶3；h＝100∶1∶4。
Embodiment 3.Polymethylmethacrylate (PMMA) is at N-Methylimidazoleacetic salt [mim] [CH
3COO] ionic liquid, repolymerization in cuprous bromide (CuBr) system
Take by weighing 1 part CuBr, in [mim] [HCOO] ionic liquid of 100 parts, dissolve, letting nitrogen in and deoxidizing gas, 50 ℃ of following constant temperature 20 minutes.The PMMA (Mn=5968) that takes by weighing 0.12 part is dissolved in 100 parts of MMA monomers, and behind the letting nitrogen in and deoxidizing gas, 50 ℃ of following constant temperature 20 minutes adds in the ionic liquid sealing, 50 ℃ of reactions of constant temperature.Result: the PMMA that obtains Mn=26533.
Embodiment 4.Methylimidazole formate ionic liquid ([mim] [HCOO]) is made polymerisation medium, cobaltous acetate [Co (CH3COO)
2] make the atom transfer radical polymerization of the methyl methacrylate (MMA) of catalyzer
Take by weighing 1 part Co (CH
3COO)
2, in [mim] [HCOO] ionic liquid of 500 parts, dissolve letting nitrogen in and deoxidizing gas, 60 ℃ of following constant temperature 20 minutes.Take by weighing 500 parts of MMA monomers, 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, 60 ℃ of reactions of constant temperature.After 4 hours, handle polymer fluid, get PMMA, Mn=146867, PDI=1.38 with methyl alcohol.
Embodiment 5.Take by weighing 1 part Ni (CH
3COO)
2, in [mim] [HCOO] ionic liquid of 500 parts, dissolve letting nitrogen in and deoxidizing gas, 60 ℃ of following constant temperature 20 minutes.Take by weighing 500 parts of MMA monomers, 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-bromo-butyric acid ethyl ester initiator, 60 ℃ of reactions of constant temperature.After 5 hours, handle polymer fluid, get PMMA, Mn=302191, PDI=1.28 with methyl alcohol.
Embodiment 6.The atom transfer radical polymerization of the Jia Jibingxisuanyizhi in the Methylimidazole formate ionic liquid ([mim] [HCOO])
Take by weighing 1 part of CuBr at [mim] [CH of 100 parts
3CH
2COO] dissolve letting nitrogen in and deoxidizing gas in (Methylimidazole formate, down with) ionic liquid.Take by weighing 100 parts of Jia Jibingxisuanyizhi 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 0.2 part 2-isobutyl ethyl bromide initiator, 50 ℃ of reactions of constant temperature.After 2 hours, handle polymer fluid, get (polyethyl methacrylate, Mn=23826, PDI=1.29 with methyl alcohol.
Embodiment 7.The atom transfer radical polymerization of the propyl methacrylate (MMA) in the Methylimidazole formate ionic liquid ([mim] [HCOO])
Take by weighing 1 part of CuBr at [mim] [CH of 100 parts
3HCOO] dissolve letting nitrogen in and deoxidizing gas in the ionic liquid.Take by weighing 100 parts of propyl methacrylate 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 6 parts 2-isobutyl ethyl bromide initiator, 50 ℃ of reactions of constant temperature.After 1 hour, handle polymer fluid, get polypropylmethacryla,es, Mn=4917, PDI=1.27 with methyl alcohol.
Claims (10)
1, a kind of method that adopts novel ion liquid polymerization initiation system to prepare macromolecular compound is characterized in that by ionic liquid, and initiator and catalyzer constitute polymerization initiation system; The initiator system general formula is [mim] [RCOO]/R
1X/MXn, [mim] [RCOO] is Methylimidazole organic acid salt ionic liquid in the formula, R is an alkyl; R
1X is an initiator, wherein R
1Be alkyl, X is a halogen; Catalyzer MXn is the transition metal inorganic salt, and n is the valence mumber that is equal to transition metal; Initiator system and monomer reaction are prepared into this monomeric polymerization macromolecule compound, and monomer is a vinylbenzene, or its general formula is CH
2=CR '-COOR, R ' and R are alkyl.
2, the method for preparing macromolecular compound according to claim 1 is characterized in that described monomer is a methyl methacrylate, vinylbenzene; Corresponding macromolecular compound PMMA, the PSt of obtaining of prepared in reaction.
3, the method for preparing macromolecular compound according to claim 1 and 2 is characterized in that alkyl R is H ,-CH
3,-CH
3CH
2,-CH
3CH
2CH
2,-CH
3CH
2CH
2CH
2Halogen X is Cl, Br; Metal in the transition metal inorganic salt is Cu, Ni, Fe, Ti and Co.
4, the method for preparing macromolecular compound according to claim 1 and 2 is characterized in that, [mim] [RCOO]: the mol ratio of monomer: MXn is 500: 500: y, y=5 wherein, 4,3,2,1,0.5; Y: z=5: z, z=1 wherein, 2,3,4,5,10,15,20,25.
5, the method for preparing macromolecular compound according to claim 3 is characterized in that, [mim] [RCOO]: the mol ratio of monomer: MXn is 500: 500: y, y=5 wherein, 4,3,2,1,0.5; Y: z=5: z, z=1 wherein, 2,3,4,5,10,15,20,25.
6, the method for preparing macromolecular compound according to claim 1 and 2 is characterized in that preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas;
2) monomer of adding deoxygenation, letting nitrogen in and deoxidizing gas, sealing, constant temperature;
3) inject initiator, isothermal reaction;
4) after reaction finishes, with the methanol extraction polymer fluid compound that secures satisfactory grades.
7, the method for preparing macromolecular compound according to claim 3 is characterized in that preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas;
2) monomer of adding deoxygenation, letting nitrogen in and deoxidizing gas, sealing, constant temperature;
3) inject initiator, isothermal reaction;
4) after reaction finishes, with the methanol extraction polymer fluid compound that secures satisfactory grades.
8, the method for preparing macromolecular compound according to claim 4 is characterized in that preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas;
2) monomer of adding deoxygenation, letting nitrogen in and deoxidizing gas, sealing, constant temperature;
3) inject initiator, isothermal reaction;
4) after reaction finishes, with the methanol extraction polymer fluid compound that secures satisfactory grades.
9, the method for preparing macromolecular compound according to claim 6 is characterized in that preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas; Polymeric initiator is added in the monomer of deoxygenation dissolving, letting nitrogen in and deoxidizing gas;
2) ionic liquid and monomer are mixed sealing, isothermal reaction;
3) after reaction finishes, get segmented copolymer with the methanol extraction polymkeric substance.
10, the method for preparing macromolecular compound according to claim 7 is characterized in that preparation process is:
1) with catalyst dissolution in ionic liquid, letting nitrogen in and deoxidizing gas; Polymeric initiator is added in the monomer of deoxygenation dissolving, letting nitrogen in and deoxidizing gas;
2) ionic liquid and monomer are mixed sealing, isothermal reaction;
3) after reaction finishes, get segmented copolymer with the methanol extraction polymkeric substance.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550204B (en) * | 2009-04-02 | 2011-01-12 | 杭州师范大学 | Atom transfer free radical polymerization initiation system with polyethyleneglycol as polymerization medium and its application in preparing macromolecular compound |
| CN102492155A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method for preparing nylon powder with waste nylon dissolving by using ionic liquid |
| CN106928387A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of method for preparing ring-alkylated styrenes polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345059A (en) * | 1981-05-18 | 1982-08-17 | Fmc Corporation | Fire retardant epoxy resins containing 3-hydroxyalkylphosphine oxides |
| EP1399487A4 (en) * | 2001-03-30 | 2005-08-17 | Uab Research Foundation | Polymer formation in room temperature ionic liquids |
| CN1209391C (en) * | 2002-09-23 | 2005-07-06 | 北京师范大学 | Method for manufacturing polyesters with ion liquid and such products |
| CN100490898C (en) * | 2004-12-06 | 2009-05-27 | 河北师范大学 | Non-toxic ionic liquid, preparation method and its application |
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2005
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550204B (en) * | 2009-04-02 | 2011-01-12 | 杭州师范大学 | Atom transfer free radical polymerization initiation system with polyethyleneglycol as polymerization medium and its application in preparing macromolecular compound |
| CN102492155A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method for preparing nylon powder with waste nylon dissolving by using ionic liquid |
| CN106928387A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of method for preparing ring-alkylated styrenes polymer |
| CN106928387B (en) * | 2015-12-30 | 2019-06-11 | 中国石油天然气股份有限公司 | A method of preparing ring-alkylated styrenes polymer |
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