Itaconic acid polymers

Recently, specific binding and controlled release of thiamine hydrochloride [THC] to and from a MIP matrix namely, THC-templated-silylated montmorillonite-itaconic acid polymer was investigated. The swelling study of MIP in distilled water showed the maximum swelling capacity is 329.0 g/g at about 8 h. In vitro release experiments showed that MIP releases drug in intestinal fluid in controlled manner [Anirudhan et al., 2013]. 

Yazdani-Redram, M. Vega, H. Quijada, R. Melt functionahzation of polypropylene with methyl esters of itaconic acid. Polymer 2001,42, 4751-4758. 

The itaconic acid polymer is, in fact, really a fully protected backbone chain polymer. If you make models, what you find is that it really has a whole lot of oxycarbonyl units protecting the backbone and you have a nonpolar alkane side chain. So, in the case of the alkane side chains, when you have a very high density of these, they don t really want to intertwine with and cross over the main backbone because they re repelled. 

Itaconic acid, anhydride, and mono- and diesters undergo vinyl polymerization. Rates of polymerization and intrinsic viscosities of the resulting homopolymers ate lower than those of the related acrylates (see Acrylic ester polymers) (8,9). 

Itaconic acid is a specialty monomer that affords performance advantages to certain polymeric coatings (qv) (see Polyesters, unsaturated). Emulsion stabihty, flow properties of the formulated coating, and adhesion to substrates are improved by the acid. Acrylonitrile fibers with low levels of the acid comonomer exhibit improved dye receptivity which allows mote efficient dyeing to deeper shades (see Acrylonitrile polymers Fibers, acrylic) (10,11). Itaconic acid has also been incorporated in PAN precursors of carbon and graphite fibers (qv) and into ethylene ionomers (qv) (12). 

Small concentrations of vinylcarboxyhc acids, eg, acryhc acid, methacrylic acid, or itaconic acid, are sometimes included to enhance adhesion of the polymer to the substrate. The abihty to crystalline and the extent of crystallization are reduced with increa sing concentration of the comonomers some commercial polymers do not crystalline. The most common lacquer resins are terpolymers of VDC—methyl methacrylate—acrylonitrile (162,163). The VDC level and the methyl methacrylate—acrylonitrile ratio are adjusted for the best balance of solubihty and permeabihty. These polymers exhibit a unique combination of high solubihty, low permeabihty, and rapid crystallization (164). 

A number of patents describe accelerators that will reduce the time required for stabilization (24,27,28). The accelerators are often inherent to the polymer or precursor but may be added to the gas phase during stabilization. For example, it is common to have an acid group present as comonomer such as itaconic acid [97-65-4] or methacrylic acid [79-41-4]. The acid groups provide initiation sites for cyclization. Alternatively, the stabilization atmosphere composition can be modified to accelerate stabilization (29). 

Because the polymer degrades before melting, polyacrylonitrile is commonly formed into fibers via a wet spinning process. The precursor is actually a copolymer of acrylonitrile and other monomer(s) which are added to control the oxidation rate and lower the glass transition temperature of the material. Common copolymers include vinyl acetate, methyl acrylate, methyl methacrylate, acrylic acid, itaconic acid, and methacrylic acid [1,2]. 

A formulation consisting of 2-acrylamido-2-methylpropane sulfonic acid, acrylamide, and itaconic acid has been proposed [676]. Such polymers are used as fluid loss control additives for aqueous drilling fluids and are advantageous when used with lime- or gypsum-based drilling muds containing soluble calcium ions. 

Copolymers of mainly acrylic acid and 2% to 20% by weight of itaconic acid are described as fluid loss additives for aqueous drilling fluids [138]. The polymers have an average molecular weight between 100,000 and 500,000 Dalton and are water dispersible. The polymers are advantageous when used with muds containing soluble calcium and muds containing chloride ions, such as seawater muds. 

A mixture of sulfonated styrene-maleic anhydride copolymer and polymers prepared from acrylic acid or acrylamide and their derivatives [759] are dispersants for drilling fluids. The rheologic characteristics of aqueous well drilling fluids are enhanced by incorporating into the fluids small amounts of sulfonated styrene-itaconic acid copolymers [761] and an acrylic acid or acrylamide polymer [755]. 

During the past decade, the properties and applications of the monoesters and diesters derived from itaconic acid have received growing interest because the monomers can be obtained biotechnologically and a great variety of related polymers can be synthesized thanks to two lateral esterifiable groups contained in the monomer [65]. The first work on poly(monomethyl itaconate) (PMMI)/ PVPo complexes was done by Bimendina et al. [66], and it was followed by Pe-... 

There is some reason to expect that conversion of the anhydride to a half-ester might reduce the sensitivity of the copolymers. Hiraoka (10) determined the relative sensitivities of PMMA, PMA (polymethacrylic acid) and PMA AN (polymethacrylic anhydride) by measuring the gaseous products (CO, C02, and H2) given off when these polymers were exposed to electron beam radiation of 2.5 keV at 297 °K. He found that the G values (number of chemical events produced per 100 eV of absorbed radiation) for the removal of side groups are 2.0, 7.4 and 16 for PMMA, PMA and PMA AN, respectively. Anderson (11) found a similar relative order of sensitivity. For copolymers of methylmethacryate with 25% dimethylitaconate, 25% monomethyl itaconate or 25% itaconic acid (or anhydride) the G(s) values were 1, 2, 3, respectively. For the copolymer of alpha-methylstyrene and monomethyl maleate, on the other hand, we find an increase in sensitivity by a factor of 2.5 over the corresponding anhydride as described below. 

The preparation of optically active addition polymers has raised some interest among chemists since the end of last century, when Walden (140) investigated polymers of optically active 2-methylbutyl-esters of itaconic acid in order to find out possible differences in the optical activity of monomer and polymers. 

Analogous poly(itaconate)s polymers like poly(ditetrahydrofurfuryl methacrylate) have been also studied because there are at least two advantages in using ita-conate acid based polymers over methacrylate acid derivatives itaconic acid can be obtained through fermentation from renewable, non petrochemical sources and the toxicity of its derivatives is lower than for methacrylate derivatives [64,140],... 

Polymers derived from itaconic acid show several relaxations below room temperature [245], When these polymers contain cyclohexyl groups in the side chain like... 

For unplasticized chlorinated PVC, unplasticized chlorinated polymer blends of vinyl chloride and mixtures of these copolymers with other polymer blends, the following starting materials can be used PVC (homopolymer) polymer blends of vinyl chloride, vinylidene chloride, trans-dichloroethylene, ethylene, propylene, butylene, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid as well as chlorine. 

Itaconic acid was isolated in 1836 from the pyrolysis products of citric acid (7) and the pol3mierization of the ethyl ester was observed by SwAETS in 1873 (2). While many patents relating to the acid and its esters as monomers have issued since that time, only recently have reports begun to appear in the scientific journals. The voluminous patent literature describes the use of polymeric itaconic acid derivatives in such applications as protective and decorative coatings, synthetic fibers, oil additives and rigid plastics as well as many others. Several summaries of the patent art and present commercial applications are available (3). Such information has been omitted from this review, which is directed primarily toward chemical behavior of the itaconic monomers and polymers. 

Polyitaconic add is converted completdy to the methyl ester with diazomethane (7), while Fisher esterification results in partial esterification of both itaconic acid homo- and copolymers (6). DMI homopolymers and its copolymer with butadiene can be reduced with lithium aluminum hydride to the polymeric alcohols, which on the basis of solubility, may under some conditions be partially cross-linked by intermolecular ester formation (6). Hydrazine converts polydimethyl itaccmate to the polymeric dihydrazide which is water-soluble and exhibits reducing properties. The hydrazide can be treated with aldehyde or ketones to form polymeric hydrazones (45). A cross-linked polymer of bi chloroethyl ita-conate) on treatment with trietlylamine, has been converted by partial quatemization to an anion exchange resin (46). 

Itaconic acid is a useful feedstock for the synthesis of polymers. This is due to the ability of the methylene group of this acid to engage in polymerization reactions. The resulting polymers are used in carpet backing and paper coating. Another significant reaction product of itaconic acid is the formation of N-sub-stituted pyrrolidinones with amines. The products are used in detergents, shampoos, and other products in which their surface activity is useful [106]. 

Essentially, the same basic protocol can be adapted for the preparation of non-covalently imprinted polymers. In this case, the cholesterol template monomer is replaced by the template to be imprinted and additional functional monomer (or monomers) is included in the polymerization mixture, at a predetermined molar ratio with respect to the template. Typical functional monomers might be chosen from amongst methacrylic acid, itaconic acid, vinylpyridine, dimethylaminoethyl methacrylate, acrylamide, hydroxyethyl methacylate, and many more. Typical solvents for non-covalent imprinting Include chloroform, THF, and acetonitrile. Templates are removed from non-covalently imprinted polymers by exhaustive washing with a suitable solvent. 

The methyl methacrylate-itaconic acid copolymer, P(MMA-co-ItaA), was prepared by slow free-radical solution polymerization in methanol under nitrogen using 2,2 -azobis-(2,4-dimethyl valeronitrile)(du Pont Vazo 52) as initiator. The molar ratio of monomer to initiator was in the range of 5xl03 to 10xl03. Reaction at 50°C for 30 to 40 hrs gave conversions of 10 to 30%. The reaction mixture was added to cold, deionized water and the precipitated polymer obtained was rinsed with 2-propanol. 

In order to have a uniform exposure to electrons over the entire wafer, a standard transmission microscope (RCA EMV-3) was used. The apertures were opened and the 40 kv beam spread out over a circle larger than the wafer itself. The coated wafer was introduced into the microscope via the film cassette drawer (below the fluorescent screen). Charge density was measured with a Faraday Cup. Each polymer was irradiated at doses of 2, 5, 10, and 20 yC/cm. The radiation chemical yield was measured from plots of 1/Mjj versus the incident dose. A sample plot is shown in Figure 1, in this case for itaconic acid-MMA copolymers. The slope of such a plot is given by ... 

In the absence of anhydride, one might expect Itaconic acid to fall In the same category as methacryllc acid. That Is, an Increase of 2x that of PDMel might be reasonable. However, the results show a dramatic Increase In G(s) with Itaconic acid content (Figure 1 and 3). Looking at polymers In the 30-40% comonomer range, the acid stands quite apart from the esters. The apparent sensitivity Is probably not due to the pendant methylene group which Is present In all three copolymers, but likely to be associated with the free carboxyls. 

Polymer blends from the structurally-related monoesters of itaconic acid have also been investigated [Radice and GargaUo, 1991]. 

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