Methyl methacrylate grafting cellulose

H. Yamagishi, K. Saito, S. Furusaki, T. Sugo and J. Okamoto, Permeability of Methyl Methacrylate Grafted Cellulose Triacetate Membrane, Chem. Mater., 2 (1990) 705. 

Gel permeation chromatography (GPC) of poly(methyl methacrylate) and cellulose nitrate showed elution volume peaks at 62.5 ml for PMMA and at 87.5 for cellulose nitrate (Figure 5), due to their difference in molecular weight. A mixture of poly(methyl methacrylate) and cellulose nitrate of the same ratio as that of the graft copolymer was recorded and two peaks in elution volume at almost identical positions were observed. This shows that the constituent homopolymers retain their identity in a physical mixture. The isolated graft copolymer showed a single peak in elution volume at 80.0 ml. The second peak in elution volume is absent in spite of poly(methyl methacrylate) attached to cellulose nitrate as revealed by infrared spectrum. Hence, these results indicate that GPC can be used as a technique to differentiate between homopolymer, physical mixture, and graft copolymer. 

Figure 6. Effect of grafting time on the graft copolymerization of methyl methacrylate onto cellulose nitrate with ceric ammonium nitrate as initiator. (Reprinted, with permission, from Ref. 19. Copyright 1979, Wiley.)...

Figure 10. Effect of initiator concentration on the graft copolymerization of methyl methacrylate onto cellulose nitrate initiated by a, benzoyl peroxide and b, azobisisobutyronitrile. Key O, grafting efficiency 9, percent grafting.

Figure 13. Probable mechanism of grafting of methyl methacrylate onto cellulose nitrate. Key Enol, enolization In, initiator M, monomer.

Sodium bisulfite-china clay proved to be an efficient initiator for homopolymerization and graft polymerization of methyl methacrylate onto cellulose. Grafting reactions using ceric ammonium sulfate, sodium bisulfite-soda lime glass or -china clay are inhibited or retarded on adding soda lignin to the grafting medium. 

Preparation of Cellulose-Methyl Methacrylate Graft Copolymer. 

Thakur, V. K., Singha, A. S., Misra, B. N. (2011). Graft copolymerization of methyl methacrylate onto cellulosic biofibers. 

It is believed that the above dye monoradicals disproportionate to hydroquinones and quinones. Transfer reactions to solvent lead to formations of homopolymers. This gives high yields of graft copolymers of methyl methacrylate with cellulose. The same is true of acrylonitrile. On the other hand, only small quantities of graft copolymers form with styrene or vinyl acetate monomers. ... 

Thakur VK, Singha AS, Misra BN (2011) Graft copolymerization of methyl methacrylate onto cellulosic biofibers. J Appl Polym Sci 122(l) 532-544. doi 10.1002/app.34094 Thakur VK, Singha AS, Thakur MK (2012a) Green composites from natural fibers mechanical and chemical aging properties. Int J Polym Anal Charact 17(6) 401-407. doi 10.1080/... 

Kubota, H., and Ogiwara, Y. (1969) Effect of Lignin in Graft Copolymerization of Methyl Methacrylate on Cellulose by Ceric Ion, J. Appl Polym. ScL, 13, 1569-1575. 

Fe -induced redox reactions were used in grafting methyl methacrylate onto cellulose [234] and acrylonitrile and acrylamide onto polyamides such as Nylon 6,6 and 6,10 [235]. 

A review covers the preparation and properties of both MABS and MBS polymers (75). Literature is available on the grafting of methacrylates onto a wide variety of other substrates (76,77). Typical examples include the grafting of methyl methacrylate onto mbbers by a variety of methods chemical (78,79), photochemical (80), radiation (80,81), and mastication (82). Methyl methacrylate has been grafted onto such substrates as cellulose (83), poly(vinyl alcohol) (84), polyester fibers (85), polyethylene (86), poly(styrene) (87), poly(vinyl chloride) (88), and other alkyl methacrylates (89). 

ACPA azobis(4-cyanopentanoic acid) AIBN azobis isobutyronitrile) BPO benzoyl peroxide DVB divinyl benzene, EGA 2-ethylcyano-acrylate HPC hydroxypropyl cellulose MMA methyl methacrylate PAAc polyacrylic acid PEI polyethyleneimine, PEO/PPO polyethylene oxide/polypyropylene oxide copolymer PVME polyvinylmethylether PVP polyvinylpyrrolidone K-30 DMSO dimethylsulfoxide PGA polyglutaraldehyde CMS chloromethylstyrene PMMA-g-OSA polymethylmethacrylate grafted oligostearic acid. 

The presence of sulphonic and carboxylic groups enables the iron ions to be in the vicinity of the cellulose backbone chain. In this case, the radicals formed can easily attack the cellulose chain leading to the formation of a cellulose macroradical. Grafting of methyl methacrylate on tertiary aminized cotton using the bi-sulphite-hydrogen peroxide redox system was also investigated [58]. 

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