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Book ChapterDOI

Ionic Liquids as Solvents and/or Catalysts in Polymerization

01 Jan 2015-pp 355-387
TL;DR: In this paper, the authors discussed various ionic liquids that were employed as solvents and/or catalysts in different kinds of polymerization reactions and their advantages, influence on polymer properties, recovery, and polymerization kinetics.
Abstract: Due to their unique yet tunable properties, “ionic liquids” are widely used as solvent and/or catalysts in many organic reactions. From the past two decades, there are increasing literature reports on the usage of ionic liquids (ILs) even in the polymerization chemistry as solvent, cosolvent, initiator, catalyst, or metal-complexing ligand. IL-mediated polymerization offers faster rates, higher molecular weight polymers, good yields, easy separation of products, and recovery and reuse of catalyst over conventional organic solvent-mediated polymerization process. In this chapter, we discussed various ILs (literature reported) that were employed as solvents and/or catalysts in different kinds of polymerization reactions and their advantages, influence on polymer properties, recovery, and polymerization kinetics.
Citations
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Journal ArticleDOI
TL;DR: The application of ionic liquids and supercritical CO2 in the modification and processing of starch is summarized and the development of regioselective derivatization and controlled grafting of starch are reviewed.

119 citations

Journal ArticleDOI
TL;DR: A review of the different types of ionic liquids used for the stabilization of metal NPs can be found in this paper, where the authors provide an insight into the various types of imidazolium-based ILs, supported ILs and polyelectrolytes used so far.
Abstract: Metal nanoparticles (NPs) are a subject of global interest in research community due to their diverse applications in various fields of science. The stabilization of these metal NPs is of great concern in order to avoid their agglomerization during their applications. There is a huge pool of cations and anions available for the selection of ionic liquids (ILs) as stabilizers for the synthesis of metal NPs. ILs are known for their tunable nature allowing the fine tuning of NPs size and solubility by varying the substitutions on the heteroatom as well as the counter anions. However, there has been a debate over the stability of metal NPs stabilized by ILs over a long period of time and also upon their recycling and reuse in organocatalytic reactions. ILs covalently attached to solid supports (SILLPs) have given a new dimension for the stabilization of metal NPs as well as their separation, recovery, and reuse in organocatalytic reactions. Poly(ILs) (PILs) or polyelectrolytes have created a significant revolution in the polymer science owing to their characteristic properties of polymers as well as ILs. This dual behavior of PILs has facilitated the stabilization of PIL-stabilized metal NPs over a long period of time with negligible or no change in particle size, stability, and size distribution upon recycling in catalysis. This review provides an insight into the different types of imidazolium-based ILs, supported ILs, and PILs used so far for the stabilization of metal NPs and their applications as a function of their cations and counter anions.

101 citations


Cites background from "Ionic Liquids as Solvents and/or Ca..."

  • ...They are found to have a wide range of applications in polymer science (Lu et al. 2009; Vijayakrishna et al. 2015), chemical industry (Plechkova and Seddon 2008), organic synthesis (Hajipour and Rafiee 2015), electrochemical sensors (Wei and Ivaska 2008), and organocatalysis (Qureshi et al. 2014)…...

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  • ...They are found to have a wide range of applications in polymer science (Lu et al. 2009; Vijayakrishna et al. 2015), chemical industry (Plechkova and Seddon 2008), organic synthesis (Hajipour and Rafiee 2015), electrochemical sensors (Wei and Ivaska 2008), and organocatalysis (Qureshi et al....

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Journal ArticleDOI
TL;DR: Toxicological issues and harmful effects related to the use of ILs are discussed, including the evaluation of their biodegradability and ecological impact on diverse organisms and ecosystems.

66 citations


Cites methods from "Ionic Liquids as Solvents and/or Ca..."

  • ...Additionally, ILs have also been employed as reaction media, monomers and additives in the synthesis, in chemical modifications and physical processing of polymers (He et al., 2019; Kowsari, 2011; Vijayakrishna et al., 2015)....

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Journal ArticleDOI
TL;DR: The main applications of ionic liquids in chemistry and material research on one of the most important natural polymers—starch—are presented in this review.
Abstract: The main applications of ionic liquids in chemistry and material research on one of the most important natural polymers-starch-are presented in this review. A brief characterization of ionic liquids and the advantages and disadvantages of using them in the modification and processing of polysaccharides is presented. The latest reports on the use of various ionic liquids as solvents or co-solvents; as media for synthesizing starch derivatives in oxidation, etherification, esterification, and transesterification, with particular emphasis on biocatalyzed reactions; and as plasticizers or compatibilizers in the processing of starch-based polymers have been investigated. The current trends, possibilities, and limitations of using this type of compound for the production of functional starch-based materials are presented.

18 citations


Cites background from "Ionic Liquids as Solvents and/or Ca..."

  • ...ILs are widely used as solvents or catalysts in various kinds of polymerization (cationic polymerization, anionic polymerization, radical polymerization, coordination polymerization, condensation polymerization, enzymatic polymerization) due to their easy miscibility with polar and non-polar organic and inorganic solvents, catalysts (inorganic and organometallic compounds), monomers, and polymers [68]....

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Journal ArticleDOI
P. Zhu1, Yi Ma1, Yangjun Wang1, Yazheng Yang1, Guangren Qian1 
TL;DR: In this article, a solvent method was used to dissociate the waste LED modules and recycle resources, and the results showed that only three organic solvents, [EMIM+]BF4− ion liquid and sodium hydroxide (NaOH) inorganic reagent were able to separate a 40 × 40 mm2 waste LED module respectively.
Abstract: Nowadays, a large quantity of Light Emitting Diodes (LEDs) have been produced and updated with the development of optoelectronic industry. At the same time, many waste LEDs are discarded. However, there are many metals and non-metals in waste LEDs, which may cause secondary pollution and waste of resources if disposed improperly. In this study, solvent method was used to dissociate the waste LED modules and recycle resources. Firstly, the components of the waste LED modules were analyzed. The main component of the transparent plastic part, usually used as packaging materials, is cured epoxy resin, and the main component of the white plastic part as the skeleton of LED modules is a mixture of polyphenylene oxide (PPO) and polystyrene (PS). Then, eight organic solvents, [EMIM+]BF4− ion liquid and sodium hydroxide (NaOH) inorganic reagent were tried to separate a 40 × 40 mm2 waste LED module respectively. The results showed that only three organic solvents—dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl-sulfoxide (DMSO) could dissociate the waste LED module very well. The used DMF solution was purified by rotary evaporation, and the regenerative DMF solution could be reused because its property has not changed. The solid residue obtained after rotary evaporating DMF was identified as polystyrene (PS). It was inferred that the waste LED module was dissociated through the DMF dissolving the PS of white plastic. In addition, the effect of DMF, DMA and DMSO dissociating the waste LED modules with the change of temperature was discussed. It was found that the choice of suitable solvent is a key for this method, and the heating temperature was also a very important factor. Finally, it was measured that the cured epoxy resin and the white plastic of the waste LED module accounted for about 31.4% (w/w) and 37.7% (w/w) respectively, which can be recycled. In short, the method not only separated completely the waste LED module and its each part was recycled easily, but the solvents can be reused. This study suggests a new route to recycle LEDs due to its environmentally friendly process, which may exert a significantly beneficial impact on our environment.

8 citations

References
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Journal ArticleDOI
TL;DR: In this paper, the authors demonstrate that cellulose can be dissolved without activation or pretreatment in, and regenerated from, 1-butyl-3-methylimidazolium chloride and other hydrophilic ionic liquids.
Abstract: We report here initial results that demonstrate that cellulose can be dissolved without activation or pretreatment in, and regenerated from, 1-butyl-3-methylimidazolium chloride and other hydrophilic ionic liquids. This may enable the application of ionic liquids as alternatives to environmentally undesirable solvents currently used for dissolution of this important bioresource.

4,276 citations

Journal ArticleDOI
TL;DR: In recent years researchers have started to explore a particular class of organic solvents called room temperature ionic liquids to identify their unique advantages for biocatalytic reactions, which include higher selectivity, faster rates and greater enzyme stability.

659 citations


"Ionic Liquids as Solvents and/or Ca..." refers background in this paper

  • ...It is observed that enzymes are more stable in ILs than in conventional organic solvents where their decomposition was noticed [119–121]....

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Journal ArticleDOI
TL;DR: The reaction of 1-n-butyl-3-methylimidazolium chloride (BMIC) with sodium tetrafluoroborate or sodium hexafluorophosphate produced the room temperature-, air-and water-stable molten salts (BMI+)(BF4−) (1) and (bMI+(PF6−)(2), respectively, in almost quantitative yield as discussed by the authors.

658 citations


"Ionic Liquids as Solvents and/or Ca..." refers background in this paper

  • ...Later several research groups successfully carried out the oligomerization (ethylene and higher olefins) [83–92] and polymerization reactions in ILs [92, 91, 93–99]....

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Journal ArticleDOI
TL;DR: Microbial polymers are synthesized from renewable low-cost feedstocks, and the polymerizations operate under mild process conditions with minimal environmental impact, providing products that, when disposed, can degrade to nontoxic products.
Abstract: In nature, living organisms are constantly producing different macromolecules for their metabolic needs. These macromolecules, such as polysaccharides, polynucleotides, proteins, or polyesters, are essential to organism survival. Their synthesis generally involves in vivo enzyme-catalyzed chaingrowth polymerization reactions of activated monomers, which are generally formed within the cells by complex metabolic processes. Because of their diversity and renewability, microbial polymers such as polysaccharides, bacterial polyhydroxyalkanoates (1) and polyanions such as poly(γ-glutamic acid) (2) have received increasing attention as candidates for industrial applications. In many cases, microorganisms carry out polymer syntheses that are impractical or impossible to accomplish with conventional chemistry. Thus, microbial catalysts enable the production of materials that might otherwise be unavailable. Microbial polymers are synthesized from renewable low-cost feedstocks, and the polymerizations operate under mild process conditions with minimal environmental impact. In addition, microbial polymers provide products that, when disposed, can degrade to nontoxic products.

640 citations


"Ionic Liquids as Solvents and/or Ca..." refers background in this paper

  • ...There are plenty of reports on the enzymatic polymerization in organic solvents [117, 118]....

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Journal ArticleDOI
TL;DR: It is shown for the first time that room-temperature ionic liquids, such as 1-butyl-3-methylimi- dazolium hexafluorophosphate, [bmim][PF(6)], can be successfully used in place of conventional solvents for the liquid-liquid extraction of erythromycin-A and for the Rhodococcus R312 catalyzed biotransformation of 1, 3-dicyanob
Abstract: Organic solvents are widely used in a range of multiphase bioprocess operations including the liquid–liquid extraction of antibiotics and two-phase biotransformation reactions. There are, however, considerable problems associated with the safe handling of these solvents which relate to their toxic and flammable nature. In this work we have shown for the first time that room-temperature ionic liquids, such as 1-butyl-3-methylimi- dazolium hexafluorophosphate, [bmim][PF6], can be successfully used in place of conventional solvents for the liquid–liquid extraction of erythromycin-A and for the Rhodococcus R312 catalyzed biotransformation of 1,3-dicyanobenzene (1,3-DCB) in a liquid–liquid, two-phase system. Extraction of erythromycin with either butyl acetate or [bmim][PF6] showed that values of the equilibrium partition coefficient, K, up to 20–25 could be obtained for both extractants. The variation of K with the extraction pH was also similar in the pH range 5–9 though differed significantly at higher pH values. Biotransformation of 1,3-DCB in both water–toluene and water–[bmim][PF6] systems showed similar profiles for the conversion of 1,3-DCB initially to 3-cyanobenzamide and then 3-cyanobenzoic acid. The initial rate of 3-cyanobenzamide production in the water-[bmim][PF6] system was somewhat lower, however, due to the reduced rate of 1,3-DCB mass transfer from the more viscous [bmim] [PF6] phase. It was also shown that the specific activity of the biocatalyst in the water-[bmim] [PF6] system was almost an order of magnitude greater than in the water–toluene system which suggests that the rate of 3-cyanobenzamide production was limited by substrate mass transfer rather than the activity of the biocatalyst. © 2000 John Wiley & Sons, Inc. Biotechnol Bioeng 69: 227–233, 2000.

544 citations


"Ionic Liquids as Solvents and/or Ca..." refers background in this paper

  • ...It is observed that enzymes are more stable in ILs than in conventional organic solvents where their decomposition was noticed [119–121]....

    [...]