Graft Polymerization Of Acrylic Monomers Research Articles

Grafting Starch with Acrylic Acid and Fenton's Initiator: The Selectivity Challenge.

Through the graft polymerization of acrylic monomers onto starch, materials with interesting new properties can be synthesized. Fenton's chemistry, Fe2+/H2O2, is considered to be attractive for the initiation of graft polymerization with the monomer acrylic acid since it is cheap and reacts quickly at ambient conditions and should therefore be easy to scale up. However, the selectivity of the grafting versus the homopolymerization reaction poses a challenge with this monomer and this type of initiator. In the present review paper, we investigate why data from the literature on grafting systems with other monomers and initiation systems tend to show higher graft selectivity. A scheme is presented, based on reaction engineering principles, that supports an explanation for these observed differences. It is found that more selective activation of starch is a factor, but perhaps even more important is a low monomer-to-starch ratio at the starting sites of graft reactions. Since water is the most common solvent, monomers that are less water-soluble have an advantage in this respect. Based on the proposed scheme, methods to improve the graft selectivity with Fenton's initiator and acrylic acid are evaluated. Most promising appears to be a method of gradual monomer dosage. With gelatinized cassava starch in a batch reactor, both the grafting percentage (17 => 29%) and graft selectivity (18 => 31%) could be improved. This can be considered a principal breakthrough. Still, more research and development would be needed to refine the method and to implement the idea in a continuous reactor at a larger scale.

Graft Polymerization of Acrylic Monomers onto Lignin with CaCl2–H2O2 as Initiator: Preparation, Mechanism, Characterization, and Application in Poly(lactic acid)

Effective utilization of abundant industrial lignin has growingly attracted much attention besides potential environmental issues. Although chemical graft polymerization modification is one facile strategy for extending its applications, it remains an intractable challenge to select a highly efficient initiation system. We herein have attempt to understand the CaCl2–H2O2 system in initiating the graft polymerization of acrylic monomers onto acetic acid lignin (AAL) and biobutanol lignin (BBL). The initiation system is found to be highly efficient and selective, as proved by the successful graft of polyacrylates onto them, and a possible mechanism is also proposed. Thermal analysis shows that the graft modification results in a higher glass transition temperature and higher thermal stability of lignin. The graft modification make both AAL and BBL become more hydrophobic than before modification. Moreover, adding a small amount of lignin-graft-polyacrylate can considerably improve the UV blocking capability...

Plasma- and chemical-induced graft polymerization on the surface of starch-based biomaterials aimed at improving cell adhesion and proliferation.

Plasma and chemical induced graft polymerization of acrylic monomers on starch-based biomaterials has been performed with the aim to improve cell adhesion and proliferation on the surface of the polymers, in order to adequate their properties for bone tissue engineering scaffolding applications. Plasma and chemical surface activation was aimed to induce the polymerization of acrylic polar monomers being carried out by applying a radio frequency plasma and expose the samples to a mixture of Ar/O2, or by immersion in a H2O2/(NH4)2S2O8 solution with UV radiation, respectively. Both procedures were followed by the graft polymerization of the corresponding monomers. Polymer grafting was analyzed by Fourier transformed infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) and by contact angle measurements. Properties such as mechanical performance, swelling degree, and degradation behavior, as well as bioactivity, have been studied and compared for the different activation methods. Finally, preliminary cell adhesion and proliferation tests were performed, using goat bone marrow cells, showing a remarkable improvement with respect to original non-surface modified starch-based biomaterials.

Preparation and characterization of bioadhesive grafted starch copolymers as platforms for controlled drug delivery

Abstract60Co‐gamma‐radiation and ceric ammonium nitrate (CAN) redox‐induced graft polymerization of acrylic monomers (acrylonitrile, acrylic acid, and methyl acrylate) to starch was performed to produce drug‐delivery systems. The grafted starches obtained mainly by redox‐induced polymerization were characterized by chemical and physicochemical methods, and the nature and size of the polyacrylic moiety grafted to the starch were determined. Although the choice of grafting method depended in part on the particular monomer, only copolymers obtained by gamma radiation proved to be satisfactory drug delivery systems. Changes of parameters in the gamma radiation–induced polymerization, such as radiation times and changes in the amount of starch and/or acrylic monomers, were tested in terms of the release rate of model drug compounds. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1157–1162, 2002

In Vivo Activity of Salvia officinalis Oil against Botrytis cinerea

The effects of some formulations of Salvia officinalis oil and camphor on tomato plants infected with Botrytis cinerea are reported. Aqueous dispersions of the oil were prepared, absorbed in a swelling matrix of semisynthetic copolymers obtained by the graft polymerization of acrylic monomers on gelled starch. Preliminary results showed that in vivo these formulations inhibited growth of the mycelium at concentrations of between 5 and 10 g/L. Protection against experimental infection with B. cinerea was comparable to that obtained with Dichlofluanid, one of the most effective synthetic fungicides against the pathogen, at a concentration of 1.5 g/L. This encourages further research in this field to determine whether essential oils could be used in combination with synthetic fungicides as a measure to reduce environmental pollution and also to prevent the development of resistant strains.

Radiation chemical modification of rubbers on the basis of ethylene-propylene terpolymer and butadiene-styrene thermoelastoplastic

With the purpose of improving the operating characteristics of rubbers on the basis of ethylene-propylene terpolymer and butadiene-styrene thermoelastoplastic their modification by radiation graft polymerization of acrylic monomers (acrylonitrile, acrylic acid, glycidyl methacrylate, cyanoethyl methacrylate etc.) was carried out. The investigations performed made it possible to select monomers, whose grafting onto rubbers improves the adhesion properties and increases oil resistance of the latter. A continuous grafting process by the method of impregnation of rubber with monomer using a pilot plant with an electron accelerator was developed. The output of the pilot plant at a dose rate of 2.2 kGy/s is 4.2 t/year.

An approach to the knowledge of the graft polymerization of acrylic monomers onto polysaccharides using Ce(IV) as initiator

Journal of Polymer Science Part C: Polymer LettersVolume 27, Issue 5 p. 149-152 Article An approach to the knowledge of the graft polymerization of acrylic monomers onto polysaccharides using Ce(IV) as initiator M. Gurruchaga, M. Gurruchaga Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorI. Goñi, I. Goñi Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorM. B. Vázquez, M. B. Vázquez Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorM. Valero, M. Valero Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorG. M. Guzmán, G. M. Guzmán Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this author M. Gurruchaga, M. Gurruchaga Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorI. Goñi, I. Goñi Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorM. B. Vázquez, M. B. Vázquez Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorM. Valero, M. Valero Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this authorG. M. Guzmán, G. M. Guzmán Departamento de Ciencia y Tecnologia de los Polímeros, Facultad de Ciencias Químicas, P. B. Box 1072, 20030 San Sebastián, SpainSearch for more papers by this author First published: April 1989 https://doi.org/10.1002/pol.1989.140270501Citations: 18AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume27, Issue5April 1989Pages 149-152 RelatedInformation

Graft polymerization of acrylic monomers onto starch fractions. IV. Effect of reaction time on the grafting of butyl acrylate onto amylose

AbstractStudies were carried out on the grafting of butyl acrylate (BA) to amylose by the ceric ion method. After removing the homo‐PBA with THF and toluene, and the ungrafted amylose with 0.5NNaOH, the PBA content of the graft copolymers was determined by acid hydrolysis with 1N HCl. The influence of reaction time on the grafting yields was determined and the largest values were: 82% for the grafting efficiency, 246% for the percent grafting, 62% for the grafted amylose, 48% for the grafted PBA, and 64% for the total conversion.

Graft polymerization of acrylic monomers onto starch fractions. III. Effect of carbohydrate structure

AbstractGrafted PMMA was isolated by the acid hydrolysis method. Weight‐average and number‐average molecular weights were determined by gel permeation chromatography. The number‐average molecular weight of the grafted chains was about 475,000 for amylopectin and 403,000 for amylose. The number of grafted chains (mmol) ranged from 2.4 × 10−3 to 4.6 × 10−3 for amylopectin graft copolymers and from 2.9 × 10−3 to 6.8 × 10−3 for those of amylose. These results were related to others obtained from ceric ion consumption studies. The values suggest that amylopectin, because of its complex structure, favors a higher consumption of ceric ion in homopolymerization reactions and inhibits the initiation reactions of the copolymerization.

Graft polymerization of acrylic monomers onto starch fractions. II. Effect of reaction time on grafting of methyl methacrylate onto amylopectin

Journal of Polymer Science: Polymer Letters EditionVolume 22, Issue 1 p. 21-24 Article Graft polymerization of acrylic monomers onto starch fractions. II. Effect of reaction time on grafting of methyl methacrylate onto amylopectin M. Gurruchaga, M. Gurruchaga Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this authorI. Goñi, I. Goñi Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this authorM. Valero, M. Valero Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this authorG. M. Guzmán, G. M. Guzmán Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this author M. Gurruchaga, M. Gurruchaga Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this authorI. Goñi, I. Goñi Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this authorM. Valero, M. Valero Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this authorG. M. Guzmán, G. M. Guzmán Departmento de Macromoléculas, Facultad de Ciencias Químicas de San Sebastián, B° Alza s/n San Sebastián, SpainSearch for more papers by this author First published: January 1984 https://doi.org/10.1002/pol.1984.130220104Citations: 11AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume22, Issue1January 1984Pages 21-24 RelatedInformation

Graft polymerization of acrylic monomers onto starch fractions. I. Effect of reaction time on grafting methyl methacrylate onto amylose

AbstractA study was made of the ceric‐ammonium‐nitrate‐initiated graft polymerization of methyl methacrylate (MMA) onto a lineal fraction of starch (amylose). Grafting yields were determined by extraction with appropriate solvents: 1,2‐dichloroethane for homo‐PMM, and 0.5N NaOH for ungrafted amylose. Percent grafting was calculated by acid hydrolysis with 1N HCl. Molecular weights of PMMA side chains were determined by gel permeation‐chromatography. Grafting efficiencies ranged from 72 to 83%, grafting, from 190 to 271%, and frequency of attachment of side chains, from 900–1250 glucose units per chain. The results observed are discussed.

A study of the kinetics of radiational graft polymerization of acrylic monomers on a butadiene-styrene thermoelastomer

1. The kinetics of radiochemical grafting of acrylonitrile and acrylic acid to a butadiene-styrene thermoelastomer have been studied by irradiating a material impregnated with the monomer; it has been shown that kinetic chain rupture in such systems is a monomolecular process. 2. The rate constant for propagation of the graft polyacrylonitrile chain and the activation energy for grafting have been calculated, the values obtained being close to those for homogeneous acrylonitrile polymerization.