Cellulose cyanoethyl

A, purified cotton cellulose B, cellulose (75%)-polyacrylonitrile (25%) copolymer (y-radiation initiated) C, cyanoethylated cellulose (D.S. 0.7) D, cyanoethylated cellulose (D.S. 0.7) (62%)-polyacrylonitrile (38%) copolymer (y-radiation initiated) E, cellulose (75%)-polyacrylonitrile (25%) copolymer (ceric ion initiated). 

The cyanoethylation of polysaccharides has been studied extensively in starch and cellulose. The hydroxyl groups (typically the C-4) on the molecule react with acrylonitrile in the presence of alkali to form a cyanoethyl ester. O-Cyanoethylated cellulose is used in the paper industry to enhance the mechanical strength, heat resistance, and microbiological resistance of the paper. Cyanoethylated starch is used in the textile industry. 

A Monomer solution 32% acrylonitrile in 80% aqueous ZnCh B Cyanoethylated cellulose (D.S. 0.7) monomer solution same... 

Highly cyanoethylated celluloses with a DS of about 2.5 are soluble in polar organic solvents. Because of an unusually high dielectric constant and low dissipation factor they can be used as the resin matrix for the phosphorous and electroluminescent lamps. Cyanoethylated kraft wood pulp with a DS of only about 0.2 is used for making insulation paper for transformers. Cyanoethylated paper has also a good thermal and dimensional stability. 

Other substituted celluloses were found to behave similarly to ethyl cellulose. An oxidation susceptibility order was established [23aj allyl cellulose > CMC > benzyl cellulose > ethyl cellulose > cyanoethyl cellulose. The cellulose ethers were found to be less resistant to oxidation than the esters. 

Cyanocel [Cytec], TM for chemically modified (cyanoethylated) cellulose. 

ABN, aminobenzonitrile AFM, atomic force microscopy AGU, D-glucose residue, anhydroglucose unif CE, capillary electrophoresis CEC, 0-(2-cyanoethyl)cellulose CID, collision-induced dissociation CMC, 0-(carboxymethyl)cellulose CMS, 0-(carboxymethyl)starch DE, dextrose equivalents DEAEC, 0-(2-diethylaminoethyl) cellulose DMAc, A,A-dimethylacetamide DMAP, 4-dimethylaminopyridine DMF, A.A-dimetiiylformamide, DP, degree of polymerization DS, degree of substitution EC, 0-ethyleellulose ECR, effective carbon response ESI, electrospray ionization ... 

T. Morooka, M. Norimoto, and T. Yamada, Cyanoethylated cellulose prepared by homogeneous reaction in paraformaldehyde-DMSO system, J. Appl. Polym. Sci., 32 (1986) 3575-3587. 

Cyanoethylated cellulose does not appear to be used commercially in any quantity. 

Cellulose acetate Cellulose acetate butyrate Cellulose acetate propionate Cellulose triacetate Ethyl cellulose Cyanoethylated cellulose... 

He concluded that it is clear that the orientation direction between neighboring bands differs slightly and it plays an important role in grating diffraction. At the same time, although it is small, the difference of the orientation degree in the oriented film exists and plays a minor role in grating diffraction. He reports also that the grating effect is present in cyanoethyl cellulose (CEC) solutions (presumably after cessation of shear). 

Cellulose triacetate Cyanoethyl cellulose Single Tg, SEM FTIR - Guo et al. (1993b)... 

Khalil EMA, El-Wakil NA (2000) Infrared absOTption spectra of cyanoethylated cellulose fibers. Cellulose Chem Technol 34 473-479... 

Vshivkov, S.A. Rusinova, E.V. Kutsenko, L.I. Galyas, A.G. (2007). Phase transitions in liquid-crystalline cyanoethyl cellulose solutions in magnetic field. Polymer Sci. B. Vol. 49, No.7-8, pp. 200-202. 

Zhao, S. L., X. H. Wu, L. Wang, and Y. Huang (2004). Electrospinning of ethyl-cyanoethyl cellulose/tetrahydrofuran solutions. Journal of Applied Polymer Science 91(l) 242-246. 

W. Wang, R. Liu, H. Kang, W. Liu, Y. Huang, UV irradiation gradient induced banded texture in photo-polymerized ethyl-cyanoethyl cellulose / poly (acryhc acid) cholesteric hquid crystalhne films and patterns fabrication thereof Colloid Polym. Sci. 289, 371-379 (2011). 

Michael addition of acrylonitrile to cellulose represents a second class of typical derivation procedures. Lower caustic concentrations are used to activate the cellulose and the reaction occurs a lower temperatures. The effect of various caustic concentrations on the rate and extent of substitution was studied in pure acrylonitrile and in acetone. Addition of TMAC to the pretreatment step has no discernable effect upon the initial rate of cyanoethylation. Upon addition of a twenty-fold excess of acrylonitrile to activated cellulose, a small endothermic heat of mixing is observed followed by a gradual increase in temperature produced by the exothermic Michael addition. The temperature was held at 27° to prevent a comcommitant anionic polymerization of acrylonitrile. The influence of the TMAC becomes evident as the reaction proceeds. Cyanoethylated cellulose imbibes the remaining reagent when the D.S. approachs 2 and an extremely viscous mass forms. Uncatalysed reactions stop at this point catalysed systems appear to autoaccelerate to degrees of substitution... 

A major problem in cellulose cyanoethylation is control of the concommitant anionic polymerization of acrylonitrile. At base concentrations greater than 12%, exothermic polymerization occurs rapidly if the temperature is raised to 40 . In the presence of TMAC, the polymerization is suppressed, until a significant increase in the extent of substitution as evidenced by gelation occurs. However, at this point hydroxide ions must be released and a rapid polymerization ensues. Derivatives with apparent M.S. of 6.5 are isolated, but it is difficult to separate homopolyacrylonitrile from cyanoethyl cellulose to confirm if grafting has occurred. However, the initial suppression of base catalysed polymerization is a convincing demonstration of hydroxide transfer and binding in the cellulose phase. 

Cyanoethyl Cellulose. A. Neat Reaction. Wood cellulose, 5.0 g was treated with 0.15 g of tetramethylammonium chloride dissolved in 2 mL of water. The cellulose was slurried in 120 mL of acrylonitrile and 5 mL of 12% sodium hydroxide was added. The slurry was stirred at 25° for 4 hours during which time the mixture became very doughy. The reaction mixture was washed with isopropanol until a free flowing slurry formed. The product was recovered by filtration, 9.4 g, D.S. = 3.0, based upon a nitrogen content of 13.02%. 

B. Solvent Diluted Process. An activated substrate was prepared by dry-blending 5 g of cellulose, 0.3 g TMAC, and 5 ml of 10% sodium hydroxide at 25° for 15 min. A solution of acrylonitrile (100 ml) in 100 ml acetone was added and the reactor was immersed in a 40° oil bath. After 3.5 hr the mixture was a viscous yellow solution containing some unreated fibers. The product was precipitated in water, the acrylonitrile and acetone were removed by steam distillation, and the aqueous suspension of polymer neutralized with 5 % HCl. After isolating and drying in vacuo, 8.46 g of cyanoethyl cellulose, D.S.=2.14, was obtained. 

---