The effect of TMEDA on the kinetics of the anionic polymerization of methyl methacrylate in tetrahydrofuran using lithium as counterion

Baskaran, Durairaj; Müller, Axel H. E.; Sivaram, Swaminathan

doi:10.1002/1521-3935(20000901)201:14<1901::aid-macp1901>3.0.co;2-j

Cited by 22 publications

(13 citation statements)

References 29 publications

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“…Sylla and coworkers [28] demonstrated that addition of a crown ether (14-crown-4), up to the ratio [crown-ether]/Li + equal to 1, slightly decreased conductivity while addition of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMTAC) increased roughly conductivity by a factor of 10. Polymer chemists have known for decades about the strong lithium cation-solvating ability of TMTAC and have used it to considerably increase anionic polymerization rates [29]. Its use to improve the conductivity of liquid electrolytes was also reported by Mc Breen et al [30] However, while solvating ability is an advantage for increasing ionic conductivity, too much solvating ability may prevent the lithium cation from intercalating easily in the positive electrode.…”

Section: Influence Of Chelating Additivesmentioning

confidence: 98%

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries

Chauvin¹,

Iojoiu²,

Alloin³

et al. 2006

Electrochimica Acta

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Section: Influence Of Chelating Additivesmentioning

confidence: 98%

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries

Chauvin¹,

Iojoiu²,

Alloin³

et al. 2006

Electrochimica Acta

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“…AMS (Sigma‐Aldrich, 99%) and isoprene (Sigma‐Aldrich, 99%) were first dried over calcium hydride and then distilled over di‐ n ‐butylmagnesium under reduced pressure right before use. TMEDA (Sigma‐Aldrich, 99%) was purified using calcium hydride and sodium metal by the procedures described in the literature . sec ‐Butyllithium ( sec ‐BuLi) (1.4 m in cyclohexane) solution and di‐ n ‐butylmagnesium (1.0 m in heptane) solution were purchased from Sigma‐Aldrich and used as received.…”

Section: Methodsmentioning

confidence: 99%

“…TMEDA (Sigma-Aldrich, 99%) was purified using calcium hydride and sodium metal by the procedures described in the literature. [27,28] sec-Butyllithium (sec-BuLi) (1.4 m in cyclohexane) solution and di-n-butylmagnesium (1.0 m in heptane) solution were purchased from Sigma-Aldrich and used as received. Cyclohexane was purified by passing through columns on a commercial solvent purifier system (Inert Technology).…”

Section: Methodsmentioning

confidence: 99%

Sequential Bulk Anionic Polymerization of α‐Methylstyrene and Isoprene to Form Diblock and Triblock Copolymers

Knauss

2017

Macro Chemistry & Physics

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to polymer. [17][18][19][20] However, this strategy usually results in a low level of control when diene monomer is copolymerized with AMS, since the polar solvents or additives result in a preference for 1,2-addition over 1,4-addition of diene, [18,19] and it is well known that only the 1,4-structured polydiene leads to an elastomeric property.Research has also been directed to synthesize triblocks through difunctional initiators (e.g., dilithio compounds) with comonomer block in the middle and PAMS blocks on both ends. [21][22][23][24][25] In this case, the PAMS block is polymerized right after the completion of comonomer. This method allows the polymerization of diene monomer in nonpolar solvent, but the crossover reaction from polydiene to AMS polymerization is usually quite slow in nonpolar solvents. It is found that the crossover reaction to AMS can be significantly enhanced through the introduction of a small amount of styrene monomers or polar additives (e.g., dimethyl ether, tetrahydrofuran (THF), and trimethylamine) before AMS addition. [21,22,26] Our objective in this research was to investigate the relative reactivity of AMS and isoprene in a bulk polymerization to develop a sequential synthetic pathway for block copolymer formation. Our approach was to develop a bulk anionic polymerization method that utilizes the AMS as solvent for isoprene polymerization in order to polymerize the isoprene in a predominately 1,4-fashion. While it is well-known that dienes are preferentially polymerized in a 1,4-fashion in nonpolar solvents, the investigation of AMS as nonpolar medium has not been widely studied as a solvent for diene polymerization. The investigation of AMS-diene triblock copolymer by sequential polymerization strategy in bulk is very rare. In the current study, we first investigated the anionic polymerization of AMS in bulk without added solvent and the relative reactivity of AMS and isoprene under the bulk AMS conditions. We have developed a simple method to use sec-butyllithium as an initiator for AMS, and block copolymers are synthesized sequentially with good control over molecular weight with relatively narrow molecular weight distributions. The synthesis of diblock copolymer (PAMS-b-PI) involves the formation of a PAMS block first followed by the introduction of isoprene in order to switch the polymerization from AMS to isoprene. N,N,N′,N′-tetramethylethylenediamine (TMEDA) was introduced as a polar additive to crossover to AMS polymerization and produce Anionic Polymerization α-Methylstyrene (AMS) is determined to polymerize anionically by initiation with sec-bultyllithium under bulk conditions with control of molecular weight depending on reaction time. Furthermore, the reactivity between AMS and isoprene in a mixture at a high AMS concentration (90% v/v) indicates a strong inclination for almost sole isoprene polymerization (>97%). The microstructure of the polyisoprene is determined to be predominately 1,4-polyisoprene in the bulk AMS polymerization. These results afford a sequential pr...

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“…[16][17][18] In addition to GTP and MFA, classical anionic polymerization can also show living characteristics with ligands capable of coordinating with enolate ion pairs. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] However, the use of ligands has several disadvantages, such as high cost, complex initiator composition, and severe reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph₂PCu) and synthesis of its block copolymer

Huang

Han

et al. 2012

J of Applied Polymer Sci

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Organolithium/cuprum diphenylphosphide (Ph2PCu) was used as a novel initiator to polymerize methyl methacrylate (MMA) and styrene in tetrahydrofuran (THF) at −50 to −10°C. The polymerizations initiated by n‐BuLi/Ph2PCu, Ph2PCu/Li (Ip)3‐6Li/Ph2PCu, and PSLi/Ph2PCu were studied in detail. The polymerization of alkyl methacrylate initiated by n‐BuLi/Ph2PCu showed a narrow molecular weight distribution (MWD) (1.08–1.25) and 100% initiation efficiency. The experimental number average molecular weight increased linearly with increasing [MMA]/[n‐BuLi/Ph2PCu]. After the second monomer addition, the molecular weight increased proportionally while the MWD remained constantly narrow. These results reveal partial living characteristics. Ph2PCu/Li (Ip)3‐6Li/Ph2PCu showed a similar behavior and was used to prepare PGMA‐b‐PBMA‐b‐PMMA‐b‐PBMA‐b‐PGMA successfully. The initiation efficiency of n‐BuLi/Ph2PCu for styrene was low. The macromolecular initiator PSLi/Ph2PCu was prepared and PS‐b‐PMMA with a narrow distribution was synthesized. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

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The effect of TMEDA on the kinetics of the anionic polymerization of methyl methacrylate in tetrahydrofuran using lithium as counterion

Cited by 22 publications

References 29 publications

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries

Sequential Bulk Anionic Polymerization of α‐Methylstyrene and Isoprene to Form Diblock and Triblock Copolymers

Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph₂PCu) and synthesis of its block copolymer

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The effect of TMEDA on the kinetics of the anionic polymerization of methyl methacrylate in tetrahydrofuran using lithium as counterion

Cited by 22 publications

References 29 publications

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries

Sequential Bulk Anionic Polymerization of α‐Methylstyrene and Isoprene to Form Diblock and Triblock Copolymers

Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph2PCu) and synthesis of its block copolymer

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Product

Resources

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Anionic polymerization of MMA initiated by organolithium/cuprum diphenylphosphide (Ph₂PCu) and synthesis of its block copolymer