title: Aggregation of modified celluloses in aqueous solution: transition from methylcellulose to hydroxypropylmethylcellulose solution properties induced by a low-molecular-weight oxyethylene additive.
abstract: Temperature effects on the viscosity and aggregation behavior of aqueous solutions of three different cellulose ethers--methylcellulose (MC), hydroxypropylmethylcellulose (HPMC), and ethyl(hydroxyethyl)cellulose (EHEC)--were investigated using viscosity and dynamic light scattering measurements as well as cryo-TEM. In all cases, increasing temperature reduces the solvent quality of water, which induces aggregation. It was found that the aggregation rate followed the order EHEC > HPMC > MC, suggesting that cellulose ethers containing some bulky and partially hydrophilic substituents assemble into large aggregates more readly than methylcellulose. This finding is discussed in terms of the organization of the structures formed by the different cellulose ethers. The temperature-dependent association behavior of cellulose ethers was also investigated in a novel way by adding diethyleneglycolmonobutylether (BDG) to methylcellulose aqueous solutions. When the concentration of BDG was at and above 5 wt %, methylcellulose adopted HPMC-like solution behavior. In particular, a transition temperature where the viscosity was decreasing, prior to increasing at higher temperatures, appeared, and the aggregation rate increased. This observation is rationalized by the ability of amphiphilic BDG to accumulate at nonpolar interfaces and thus also to associate with hydrophobic regions of methylcellulose. In effect, BDG is suggested to act as a physisorbed hydrophilic and bulky substituent inducing constraints on aggregation similar to those of the chemically attached hydroxypropyl groups in HPMC and oligo(ethyleneoxide) chains in EHEC.
authors.affiliation: School of Chemical Science and Engineering, Department of Chemistry, Surface and Corrosion Science, KTH Royal Institute of Technology, Drottning Kristinas väg 51, SE-100 44 Stockholm, Sweden.
authors.forename: Rasmus
authors.initials: R
authors.lastname: Bodvik
authors.forename: Leif
authors.initials: L
authors.lastname: Karlson
authors.forename: Katarina
authors.initials: K
authors.lastname: Edwards
authors.forename: Jonny
authors.initials: J
authors.lastname: Eriksson
authors.forename: Esben
authors.initials: E
authors.lastname: Thormann
authors.forename: Per M
authors.initials: PM
authors.lastname: Claesson
mesh_terms: D002236:Carbohydrate Conformation; D004987:Ethers / Q000737:chemistry; D005027:Ethylene Oxide / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D008747:Methylcellulose / Q000031:analogs & derivatives / Q000737:chemistry*; D008970:Molecular Weight; D012996:Solutions; D013696:Temperature; D014783:Viscosity; D014867:Water / Q000737:chemistry
chemical_list: D004987:Ethers; D012996:Solutions; D014867:Water; D008747:Methylcellulose; D005027:Ethylene Oxide