Polymer Synthesis in Ionic Liquids

Haddleton, David M.; Welton, Tom; Carmichael, Adrian J.

doi:10.1002/9783527621194.ch7

Cited by 7 publications

(6 citation statements)

References 79 publications

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“…Ionic liquids (ILs) are thus the ideal solvents due to their lack of (or extremely low) vapor pressure, miscibility with polymers as well as organic compounds and metal catalysts (which makes most homogeneous catalytic reactions feasible), and high stability ranging from −30 to 300 °C. − These promising characteristics of ILs enable us to consider them as desirable solvents for synthesis of high-molecular-weight polyesters in the ADMET condensation polymerization. − Although olefin metathesis reactions in ILs have been known, − the reported examples of ADMET polymerization have been limited so far. − ,− For instance, the polymerization of 1,9-decadiene in 1- n -butyl-3-methyl imidazolium hexafluorophosphate ([Bmim]PF 6 ,) in the presence of RuCl 2 (PCy 3 ) 2 (CHPh) ( G1 ) at 50 °C afforded rather high molecular weight polymers (Scheme , M n = 1.08–1.92 × 10 4 ) . The polymerization of 1,4-bis(undec-10-en-1-yloxy)-triptycene conducted at 100 °C using G2 (initially 80 °C for 24 h, total of seven days) also gave a rather high molecular weight polymer ( M n = 1.15 × 10 4 ) .…”

Section: Introductionmentioning

confidence: 99%

“… 40 − 47 These promising characteristics of ILs enable us to consider them as desirable solvents for synthesis of high-molecular-weight polyesters in the ADMET condensation polymerization. 48 − 52 Although olefin metathesis reactions in ILs have been known, 53 − 62 the reported examples of ADMET polymerization have been limited so far. 50 − 52 , 63 − 65 For instance, the polymerization of 1,9-decadiene in 1- n -butyl-3-methyl imidazolium hexafluorophosphate ([Bmim]PF 6 ,) in the presence of RuCl 2 (PCy 3 ) 2 (CHPh) ( G1 ) at 50 °C afforded rather high molecular weight polymers ( Scheme 1 , M n = 1.08–1.92 × 10 4 ).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of High-Molecular-Weight Biobased Aliphatic Polyesters by Acyclic Diene Metathesis Polymerization in Ionic Liquids

2023

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Acyclic diene metathesis (ADMET) polymerization of an α,ω-diene monomer of bis(undec-10-enoate) with isosorbide (M1) using a RuCl2(IMesH2)(CH-2-O i Pr-C6H4) (HG2, IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) catalyst and conducted at 50 °C (in vacuo) in ionic liquids (ILs) afforded higher-molecular-weight polymers (P1, M n = 32 200–39 200) than those reported previously (M n = 5600–14700). 1-n-Butyl-3-methyl imidazolium hexafluorophosphate ([Bmim]PF6) and 1-n-hexyl-3-methyl imidazolium bis(trifluoromethanesulfonyl)imide ([Hmim]TFSI) were suitable as effective solvents among a series of imidazolium salts and the pyridinium salts. The polymerization of α,ω-diene monomers of bis(undec-10-enoate) with isomannide (M2), 1,4-cyclohexanedimethanol (M3), and 1,4-butanediol (M4) in [Bmim]PF6 and [Hmim]TFSI also afforded the higher-molecular-weight polymers. The M n values in the resultant polymers did not decrease even under the scale-up conditions (300 mg to 1.0 g scale, M1, M2, and M4) in the polymerizations in [Hmim]TFSI; the subsequent reaction of P1 with ethylene (0.8 MPa, 50 °C, and 5 h) gave oligomers (proceeded via depolymerization). Tandem hydrogenation of the resultant unsaturated polymers (P1) in a [Bmim]PF6–toluene biphasic system upon the addition of Al2O3 (1.0 MPa H2 at 50 °C) gave the corresponding saturated polymers (HP1), which waswere isolated by a phase separation in the toluene layer. The [Bmim]PF6 layer containing the ruthenium catalyst could be recycled without a decrease in the activity/selectivity of the olefin hydrogenation at least eight times.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of High-Molecular-Weight Biobased Aliphatic Polyesters by Acyclic Diene Metathesis Polymerization in Ionic Liquids

2023

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“…Moreover, ILs have been exploited in diverse applications, such as in lithium batteries [ 28 ], as electrochemical sensors and biosensors [ 29 ], for the preparation of inorganic oxide nanostructures and biopolymers [ 30 ]. Using ILs as solvents and catalysts for different types of polymerization processes has many advantages; see, e.g., [ 27 , 31 ]. Those can be exploited to produce clean polymers and to reduce costs because of the recyclability of IL-catalysts.…”

Section: Introductionmentioning

confidence: 99%

A Comprehensive Study of Photorefractive Properties in Poly(ethylene glycol) Dimethacrylate— Ionic Liquid Composites

et al. 2016

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A detailed investigation of the recording, as well as the readout of transmission gratings in composites of poly(ethylene glycol) dimethacrylate (PEGDMA) and ionic liquids is presented. Gratings with a period of about 5.8 micrometers were recorded using a two-wave mixing technique with a coherent laser beam of a 355-nm wavelength. A series of samples with grating thicknesses d0=10…150 micrometers, each for two different exposure times, was prepared. The recording kinetics, as well as the post-exposure properties of the gratings were monitored by diffracting a low intensity probe beam at a wavelength of 633 nm for Bragg incidence. To obtain a complete characterization, two-beam coupling experiments were conducted to clarify the type and the strength of the recorded gratings. Finally, the diffraction efficiency was measured as a function of the readout angle at different post-exposure times. We found that, depending on the parameters, different grating types (pure phase and/or mixed) are generated, and at elevated thicknesses, strong light-induced scattering develops. The measured angular dependence of the diffraction efficiency can be fitted using a five-wave coupling theory assuming an attenuation of the gratings along the thickness. For grating thicknesses larger than 85 microns, light-induced scattering becomes increasingly important. The latter is an obstacle for recording thicker holograms, as it destroys the recording interference pattern with increasing sample depth. The obtained results are valuable in particular when considering PEGDMA-ionic liquid composites in the synthesis of advanced polymer composites for applications, such as biomaterials, conductive polymers and holographic storage materials.

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“…Ionic liquids (ILs), low-melting molten salts composed entirely of ions, are a relatively recent class of liquids attracting increasing interest as greener alternatives to conventional organic solvents with the aim of facilitating sustainable chemistry . Because of their unusual physical and chemical properties, such as high thermal stability, lack of inflammability, low volatility, chemical stability, and excellent solubility of many organic compounds, many potential applications, such as synthesis, (bio)catalysis, separation processes, material science, and development of new electrical and electrochemical devices, continue to expand significantly.…”

Section: Introductionmentioning

confidence: 99%

Studies on the Reaction of Iron(II) with NO in a Noncoordinating Ionic Liquid

et al. 2015

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In an earlier study we investigated the reaction of iron(II) chloride with NO in a strongly coordinating ionic liquid 1-ethyl-3-methylimidazolium dicyanamide [emim][dca] and showed that the actual reactive species in solution was [Fe(II)(dca)5Cl](4-). For the present report we investigated in detail how this reaction could proceed in a noncoordinating ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate [emim][OTf]. The donor ability of OTf(-) is much lower than that of dca(-), such that the solubility of FeCl2 in [emim][OTf] strongly depended on other donors like water or chloride ions present or added to the ionic liquid. On increasing the chloride concentration in [emim][OTf], the tetrachloridoferrate complex [emim]2[FeCl4] was formed, as verified by X-ray crystallography. This complex undergoes reversible binding of NO, for which the UV-vis spectral characteristics of the green-brown nitrosyl product resembled that found for the corresponding nitrosyl complexes formed in water and [emim][dca] as solvents. A detailed analysis of the spectra revealed that the {Fe-NO}(7) species has Fe(II)-NO(•) character in contrast to Fe(III)-NO(-) as found for the other solvents. The formation constant, however, is much higher than in [emim][dca], lying closer to the value found for water as solvent. Surprisingly, the Mössbauer spectrum found in [emim][OTf] is very unusual and unsimilar to that found in water and [emim][dca] as solvents, pointing at a different electron density distribution between Fe and NO in {Fe-NO}.7 First, the high isomer shift points to the presence of iron(II) species in solution, thus indicating that upon NO binding no oxidation to iron(III) occurs. Second, the negligible quadrupole splitting suggests a high local symmetry around the iron center. The nitrosyl product is suggested to be [Fe(II)Cl3NO](-), which is supported by electron paramagnetic resonance (EPR) and IR measurements. The nature of the Fe(II) complexes formed in [emim][OTf] depends on the additives required to dissolve FeCl2 in this ionic liquid.

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Polymer Synthesis in Ionic Liquids

Cited by 7 publications

References 79 publications

Synthesis of High-Molecular-Weight Biobased Aliphatic Polyesters by Acyclic Diene Metathesis Polymerization in Ionic Liquids

Synthesis of High-Molecular-Weight Biobased Aliphatic Polyesters by Acyclic Diene Metathesis Polymerization in Ionic Liquids

A Comprehensive Study of Photorefractive Properties in Poly(ethylene glycol) Dimethacrylate— Ionic Liquid Composites

Studies on the Reaction of Iron(II) with NO in a Noncoordinating Ionic Liquid

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