Effect of catalyst systems and reaction conditions on the synthesis of cellulose‐<i>g</i>‐PDMAam copolymers by controlled radical polymerization

Hiltunen, Miia; Siirilä, Joonas; Maunu, Sirkka Liisa

doi:10.1002/pola.26092

Cited by 6 publications

(3 citation statements)

References 41 publications

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“…The peak at 1.0 ppm corresponds to the -CH 3 . The broad peaks at 2.6-4.2 ppm is attributed to the -CH 2 and -CH in the AGU (Hiltunen et al 2012;Zhang et al 2007). The peak at 4.5 ppm is assigned to the -OH.…”

Section: Resultsmentioning

confidence: 96%

Thermal inverse phase transition of azobenzene hydroxypropylcellulose in aqueous solutions

Zhang

Liu

2016

Cellulose

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Water soluble 2-azobenzenoxy-ethoxyhydroxpropylcelluloses (azo-EHPC) were synthesized by etherification reaction of bromoethoxy-azobenzene (BEA) with hydroxypropylcellulose (HPC) to study their phase transition behavior in aq. solution. The degree of substitution (DS) of the water soluble azoEHPCs was less than 0.066. Their chemical structure and thermal property were characterized by proton nuclear magnetic resonance ( 1 H-NMR), fourier transform infrared spectroscopy (FT-IR), and differential scanning calorimetry. The azo-EHPC showed a reversible sol-gel transition behavior in its aq. solution, i.e. a clear azo-EHPC aq. solution became turbid when the solution temperature surpassed a lower critical solution temperature (LCST). The sol-gel transition phenomenon was investigated by optical microscopy and turbidimetric measurement. It was found that the LCST was related to the cis-/transconformation of the azobenzene side group, the type of cyclodextrin (CD), concentration of azo-EHPC, and NaCl concentration. The LCST of azo-EHPC was lower than that of HPC (36.6°C) by at most 13.6°C, and the LCST of trans-azo-EHPC was less than that of cis-azo-EHPC by ca. 3°C. Additionally, the presence of CD in solutions displayed a positive effect on the LCST, i.e. increasing the LCST by 3-5°C. And this impact was more profound on the azo-EHPC with higher DS values. The thermoreversible phase transition mechanism was discussed. We proposed that the effect of DS, conformation of azobenzene group, azo-EHPC concentration, salt concentration, and CD on the LCST of azo-EHPCs was a rearrangement of the hydrophilic/hydrophobic interaction between side azobenzene groups and water molecules.

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Section: Resultsmentioning

confidence: 96%

Thermal inverse phase transition of azobenzene hydroxypropylcellulose in aqueous solutions

Zhang

Liu

2016

Cellulose

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“…Monomers have been used to prepare cellulose graft copolymers via ATRP strategy in homogeneous conditions. N-dimethylamino-2-ethyl methacrylate (DMAEMA) [34,52], N,N-dimethylacrylamide (DMA) [40,[53][54][55], 2-(diethylamino)ethyl methacrylate (DEAEMA) [56], poly(ethylene glycol) methyl ether acrylate (PEGA) [57], isoprene [36,58,59], ethylene glycol dimethacrylate (EGDMA) [60], soybean oil-based methacrylates (SOM1 and SOM2) [61], lauryl methacrylate (LMA), and dehydroabietic ethyl methacrylate (DAEMA) [62], have been grafted from cellulose via homogeneous ATRP to develop novel cellulose graft copolymers.…”

Section: Atom Transfer Radical Polymerization (Atrp)mentioning

confidence: 99%

Cellulose-Based Thermoplastics and Elastomers via Controlled Radical Polymerization

Jiang¹,

Wang²,

Pan³

et al. 2020

Thermosoftening Plastics

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This chapter is concerned with the recent progress in cellulose-based thermoplastic plastics and elastomers via homogeneous controlled radical polymerizations (CRPs), including atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and nitroxidemediated polymerization (NMP). The first section is a brief introduction of cellulose and cellulose graft copolymers. The second section is recent developments in cellulose graft copolymers synthesized by CRPs. The third part is a perspective on design and applications of novel cellulose-based materials. The combination of cellulose and CRPs can provide new opportunities for sustainable materials ranging from thermoplastics to elastomers, and these fascinating materials can find a pyramid of applications in our daily life in the near future.

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“…Moreover, (soluble) cellulose derivatives (e.g., hydroxyisopropylcellulose, ethyl hydroxylethyl cellulose), which are commercially available, have been employed for subsequent modification with variable polymer side chains (e.g., polystyrene, poly(vinyl acetate), poly(ethyl acrylate), PNIPAM, polyacrylamide) using RAFT polymerization. − Ifuku et al synthesized 2,3-di- O -methyl cellulose and subsequently grafted PNIPAM from this cellulose derivative using atom transfer radical polymerization (ATRP) . Cellulose- graft -copolymers with poly( N , N -dimethylacrylamide) and polyacrylamide side chains have been prepared in LiCl/ N , N -dimethylacetamide (DMAc) by ATRP and single electron transfer living radical polymerization (SET-LRP). − Although a few reports on grafting-from cellulose via ATRP in ILs or via functionalization of native cellulose in ILs exist, − only one such report on grafting - from via RAFT using native cellulose as starting material is available . In the current study, we present, to the best of our knowledge, the first solution based approach toward the synthesis of thermoresponsive cellulose- graft -copolymers via RAFT polymerization using native cellulose as starting material.…”

Section: Introductionmentioning

confidence: 99%

Temperature Responsive Cellulose-graft-Copolymers via Cellulose Functionalization in an Ionic Liquid and RAFT Polymerization

Hufendiek

Trouillet²,

Meier

et al. 2014

Biomacromolecules

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Well-defined cellulose-graft-polyacrylamide copolymers were synthesized in a grafting-from approach by reversible addition-fragmentation chain transfer polymerization (RAFT). A chlorine moiety (degree of substitution DS(Cl) ≈ 1.0) was introduced into the cellulose using 1-butyl-3-methylimidazolium chloride (BMIMCl) as solvent before being substituted by a trithiocarbonate moiety resulting in cellulose macro-chain transfer agents (cellulose-CTA) with DS(RAFT) of 0.26 and 0.41. Poly(N,N-diethylacrylamide) (PDEAAm) and poly(N-isopropylacrylamide) (PNIPAM) were subsequently grafted from these cellulose-CTAs and the polymerization kinetics, the molecular weight characteristics and the product composition were studied by nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and size exclusion chromatography of the polyacrylamides after cleavage from the cellulose chains. The number-average molecular weights, Mn, of the cleaved polymers ranged from 1100 to 1600 g mol(-1) for PDEAAm (dispersity Đ = 1.4-1.8) and from 1200 to 2600 g mol (-1) for PNIPAM (Đ = 1.7-2.1). The LCST behavior of the cellulose-graft-copolymers was studied via the determination of cloud point temperatures, evidencing that the thermoresponsive properties of the hybrid materials could be finely tuned between 18 and 26 °C for PDEAAm and between 22 and 26 °C for PNIPAM side chains.

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Effect of catalyst systems and reaction conditions on the synthesis of cellulose‐g‐PDMAam copolymers by controlled radical polymerization

Cited by 6 publications

References 41 publications

Thermal inverse phase transition of azobenzene hydroxypropylcellulose in aqueous solutions

Thermal inverse phase transition of azobenzene hydroxypropylcellulose in aqueous solutions

Cellulose-Based Thermoplastics and Elastomers via Controlled Radical Polymerization

Temperature Responsive Cellulose-graft-Copolymers via Cellulose Functionalization in an Ionic Liquid and RAFT Polymerization

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