These radicals can induce free radical sites on the hydroxyethyl cellulose backbone by hydrogen abstraction of the acetal hydrogen see scheme 1. Synthesis and characterization of waterborne polyurethane. This is somewhat surprising as itaconic acid is a dicarboxylic acid with an. Itaconic acid, or methylidenesuccinic acid, is an organic compound. Us5223592a process for polymerization of itaconic acid. Us8410232b2 emulsion polymerization of esters of itaconic acid. Pdf copolymerization of styrene and nbutyl acrylate with itaconic. Kinetics of suspended emulsion copolymerization of acrylonitrile. Influence of temperature and butyl acrylate in the copolymerization of itaconic acid and methyl methacrylate via emulsion polymerization conference paper pdf available. In a 2004 report to the office of biomass program doeeere, itaconic acid was identified as one of the top 12 value added chemicals from biomass.
It was found that 2hydroxyparaconic and itatartaric acid are the primary oxidation products formed during free radical polymerization of itaconic acid. Emulsion polymerization of esters of itaconic acid. The polymerization and polymers of itaconic acid derivatives. Yet its polymerization was identified as a key barrier to commercial development. Itaconic acid ia has been widely used in the field of polymers and copolymers.
The effect of itaconic ia and fumaric fa acids, in the emulsion copolymerization of methyl methacrylate mma with nbutyl acrylate ba is presented in this work. Up to date, however, there are few reports related to the synthesis of itaconate. These reactive sites can initiate the emulsion polymerization of the monomers. Polymerization of itaconic acid summary poly itaconic acid pia has been prepared by various methods namely in radical polymerization in the presence of various initiators and. Historically, itaconic acid was obtained by the distillation of citric acid, but currently it is produced by fermentation.
Keywords functionalized latex, wet scrub resistance. Emulsion polymerization of esters of itaconic acid justia. Weissa,b, adepartment of chemical materials and biomolecular engineering, university of connecticut, storrs, ct 0626936, usa b polymer science program, university of connecticut, storrs, ct 0626936, usa c department of. Synthesis and characterization of itaconic acid doped. More specifically, an ester of polyitaconic acid polymer is produced via emulsion polymerization and contains greater than 50%. It forms copolymers with its esters and other monomers, which are used in the paper industry for wall paper and other paper products. Pdf influence of temperature and butyl acrylate in the.
It has a role as a fungal metabolite and a human metabolite. The effect of functional monomers on the overall conversion, on the colloidal properties of the latexes as well as on the distribution of the carboxylic groups buried, particle surface and serum was examined. As a comonomer in the polymerization of polyacrylonitrile pan to promote the thermooxidative stabilization of polymer. Emulsion polymerization is a complex process in which the radical addition polymerization proceeds in a heterogeneous system. Renewable unsaturated polyesters were prepared by direct polycondensation of dimethyl itaconate dmi with diols, whereas the ringopeningmetathesis polymerization romp of a dmi derived. Kinetics of suspended emulsion copolymerization of acrylonitrile with itaconic acid. Emulsion polymerization of esters of itaconic acid itaconix.
Previously, itaconic acid ia was known to be at best a difficult monomer to be polymerized. Acrylate latexes prepared with these two compounds have monomer conversion levels which rise as the polymerization temperature is increased, as is expected in conventional emulsion polymerizations. Renewable polymers from itaconic acid by polycondensation. Polymerization of itaconic acid and derivatives springerlink. Itaconic acid is also used in emulsion paints where it improves adhesion of the polymer. Itaconic acid, a renewable feedstock obtained by fermentation of carbohydrates, is used as a key substrate to produce aliphatic unsaturated polyesters as well as polynorbornenes. Read investigation of the persulfate itaconic acid interaction and implications for emulsion polymerization, journal of applied polymer science on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available. The polymerization and copolymerization of itaconic anhydride 1964, vol. This has generated a new toolbox for producing latexes with specific properties. Optimization and production of itaconic acid using. Here we report effective conditions for an easy polymerization of itaconic acid to high conversion and high molecular weight.
Kinetics of suspension emulsion copolymerization of an with ia were studied. Poly itaconic acid pia has been prepared by various methods namely in radical polymerization in the presence of various initiators and using water or dioxane as reaction medium, or by poly. As a polymerizable dicarboxylic acid, it shows great potential in synthesis of polymerizable surfactants. As all other diesters of itaconic acid, due to its low kp, dibutyl itaconate will. In this paper, polyaniline nanorods were successfully synthesized by chemical oxidation polymerization using itaconic acid as dopant and ammonium peroxydisulfate as oxidant under. Monomerpolymer composition curves for styreneitaconic acid. Kinetics of suspended emulsion copolymerization of. The polymers that are produced may be employed in adhesives, paints, and paper formulations. In emulsion polymerization, the replacement of standard monomers with bio.
Since pan homopolymer results in poorer quality of the carbon fibers, it is modified to improve its properties by incorporation of suitable acidic comonomer like itaconic acid ia during polymerization, which has been a subject of study in some previous works. The copolymerization of itaconic anhydride and vinyl chloride has yielded copolymers with. In this example, itaconic acid ia is used to replace acrylic acid aa in the. Amongst use in other chemistries, it can be readily applied in emulsion polymerization yielding waterbased, partially plantbased binders that can be used in wall paints. More specifically, an ester of polyitaconic acid polymer is produced via emulsion polymerization and contains greater than 50% by weight of an ester of itaconic acid along with. The polymerization may proceed via emulsion techniques i. Polymerization of polyitaconic acid on surfaces by atom. Emulsion copolymerization of styrene and butyl acrylate with itaconic acid. With itaconic acid as dopant and nh 4 2 s 2 o 8 as oxidant, itaconic acid doped polyaniline pani nanorods were prepared by onestep and templatefree polymerization method. This process involves emulsification of the relatively hydrophobic monomer in water by an oilinwater emulsifier, followed by the initiation reaction with either a watersoluble or an oilsoluble free radical initiator. Investigation of the persulfateitaconic acid interaction. Polymerization of poly itaconic acid on surfaces by atom transfer radical polymerization in aqueous solution volume 710 amit y. It is a dicarboxylic acid and an olefinic compound. The sensitivity of polymerizing esters of itaconic acid to its polymerization media has been evaluated by hirano et al, who reported on a pronounced dependence of stereospecificity in the radical polymerization of dibutyl itaconate dbi on polymerization.
The literature reports that maleic acid ma and itaconic acid ita can copolymerize on cotton fabric in the presence of potassium persulfate, and esterification of cotton by the copolymer imparts wrinkle resistance to the. To obtain suitable monomers for emulsion polymerization itaconates are synthesized by means of esterification using itaconic acid or itaconic anhydride and the appropriate fatty alcohol as starting materials. Furthermore, ia has been utilized substantially in surfactant. Poly itaconic acid pia has been prepared by various methods namely in radical polymerization in the presence of various initiators and using water or dioxane. Polyacrylonitrile pan based fibers remains one of the best materials for making carbon fibers. Renewable unsaturated polyesters were prepared by direct polycondensation of dimethyl itaconate dmi with diols, whereas the ringopeningmetathesis polymerization romp of a dmi derived norbornene led to polynorbornenes. The copolymerization of acrylonitrile an in dimethylformamide dmf was retarded by the presence of itaconic acid ia comonomer. The portal can access those files and use them to remember the users data, such as their chosen settings screen view, interface language, etc. Performance materials from itaconic acid and methacrylic.
Up to date, however, there are few reports related to the synthesis of itaconatebased surfactants. In combination with acrylamide to form polyacrylamidecoitaconicacid to synthesize biodegradable superabsorbent polymers. Insitu polymerization of maleic acid and itaconic acid. Polycarboxylic acids have been used as crosslinking agents for cellulosic materials to replace traditional formaldehydebased reagents. Emulsion polymerization of 100% biobased itaconate esters. This technical barrier was recently overcome by the university of new hampshire and licensed to itaconix. Onestep and templatefree synthesis of itaconic acid.
Furthermore new monomers based on monosaccharides and itaconic acid. At the end of the reaction, the glass tubes were carefully broken and hydrogels were cut into discs 10 mm in length. The present disclosure relates to a method for the emulsion polymerization of itaconic acid containing ester functionality, for example, the alkyl esters of itaconic acid known as alkylitaconate. The unsaturated vinyl bonds in itaconic acid and its derivatives provide the opportunity for free radical polymerization and to create polymers for various applications. Copolymerization of acrylonitrile with itaconic acid in.
The role of itaconic and fumaric acid in the emulsion. This dicarboxylic acid is a white solid that is soluble in water, ethanol, and acetone. Polymers of itaconic acid are formed at high conversion by adding completely neutralized monomer solution and initiator solution to a vessel initially containing water at a temperature sufficient for polymerization. Effects of various mass ratios of watermonomer, initiator concentrations, emulsifier concentrations and dispersant concentrations on ania copolymerization rate and changes of particle size and size distribution with the extension of polymerization time were investigated. Addition of tea helped overcome the retardation at enhanced concentrations of ia in the feed. Development of integrated production of polyitaconic acid. Esters of itaconic acid are polymerized in aqueous medium in the presence of seed particles. These structural features allow for a variety of new applications, such as an alternative for acrylated polyesters or modular building blocks for polyesters with tunable properties. Itaconic acid a versatile building block for renewable. The role of itaconic and fumaric acid in the emulsion copolymerization of methyl methacrylate and nbutyl acrylate. Itaconic acid is a renewable chemical produced at large commercial scale by fermentation of carbohydrates such as corn based dextrose or cane and beat sucrose. Us20110144265a1 emulsion polymerization of esters of. Synthesis and characterization of itaconic anhydride and stearyl methacrylate copolymers shurui shanga, samuel j.
Role of itaconic acid in latex particle nucleation wiley online library. Under emulsion polymerization conditions, free radicals are produced to initiate the polymerization. Pdf it was made the copolymerization of two different formulation. The seed particles may absorb the monomer and provide for polymerization to a desired particle size. A cation exchange resin from itaconic anhydride nagai susumu 1, yoshida keinosuke 2. The influence of the polymerization parameters such as the oxidantaniline molar ratio, the oxidant concentration, the molar ratio of itaconic acid and aniline, and the itaconic acid concentration. Polyaniline nanorods were synthesized via soapfree emulsion polymerization using itaconic acid as dopant and characterized by particle size and distribution measurement, scanning electron microscope sem, xray diffraction xrd, fourier transform infrared spectroscopy ftir and thermogravimetric analysis tga. Polymerization of itaconic acid summary poly itaconic acid pia has been prepared by various methods. Itaconic acid is a dicarboxylic acid that is methacrylic acid in which one of the methyl hydrogens is substituted by a carboxylic acid group. Synthesis and characterization of itaconic anhydride and. Itaconic acid, a carboxylated watersoluble monomer, was examined in terms of its role in. Emulsion polymers institute, center for polymer science and engineering, and departments of. Emulsion copolymerization of styrene and butyl acrylate. Furthermore, ia has been utilized substantially in surfactantfree emulsion polymerization to generate stable latexes 9, 10.