Maleic anhydride copolymers with olefins

Examples of stable complexes are reactions of sulfur dioxide with styrene, or vinyl ethers with maleic anhydride,also a-olefins with maleic anhydride.Also, a reaction of /ran -stilbene with maleic anhydride. In these reactions chaige-transfer complexes form. They are stable and their existence can be detected by spectroscopic means. Additional energy, such as heat or a free-radical attack, converts them to diradicals and polymerizes them into alternating copolymers.i 1 1 ... 

Tables 2 and 3 give the results of haze reduction for the polymeric red and polymeric yellow dye, respectively, based on the type of analysis described for Figure 2. Haze reductions in both the red and yellow polymeric dye were observed with the addition of both polyethylene-based Zn ionomer and polypropylene-alt-maleic anhydride copolymer. The polypropylene-graft-maleic anhydride copolymers were not effective in reducing haze in the polymeric red, but did show haze reduction in the yellow, although relatively higher loadings of this wax were necessary to give similar results to the Zn ionomer or the PP-alt-MA materials. The polyethylene-graft-maleic anhydride copolymer, the succinic anhydride- terminated isotactic PP, and the PP homopolymer wax did not reduce haze with the polymeric red. The C30 a-olefin-alt-maleic anhydride copolymer and the polyethylene-based calcium ionomer both produced increases in haze when molded with the polymeric red.

Alkenylsuccinic anhydrides made from several linear alpha olefins are used in paper sizing, detergents, and other uses. Sulfosuccinic acid esters serve as surface active agents. Alkyd resins (qv) are used as surface coatings. Chlorendric anhydride [115-27-5] is used as a flame resistant component (see Flame retardants). Tetrahydrophthalic acid [88-98-2] and hexahydrophthalic anhydride [85-42-7] have specialty resin appHcations. Gas barrier films made by grafting maleic anhydride to polypropylene [25085-53-4] film are used in food packaging (qv). Poly(maleic anhydride) [24937-72-2] is used as a scale preventer and corrosion inhibitor (see Corrosion and corrosion control). Maleic anhydride forms copolymers with ethylene glycol methyl vinyl ethers which are partially esterified for biomedical and pharmaceutical uses (189) (see Pharmaceuticals). 

In this section wc consider systems where the radical formed by propagation can eyclizc to yield a new propagating radical. Certain 1,4-dicncs undergo cyclocopolymerization with suitable olefins. For example, divinyl ether and MAH are proposed to undergo alternating copolymerization as illustrated in Scheme 4.19.167 These cyclo-copolymerizations can he quantitative only for the case of a strictly alternating copolymer. This can be achieved with certain electron donor-electron acceptor pairs, for example divinyl ether-maleic anhydride. 

In addition, borane-containing POs can be prepared by copolymerization of olefin with borane monomers or by hydroboration of polyolefins including unsaturated groups, such as olefin-divinylbenzene copolymer and olefin-diene copolymers. Many kinds of graft copolymers, such as poly-elhylene-gra/f-poly( vinyl alcohol), PE-g-PMMA, polypropylcnc-gra/f-poly-(maleicanhydride-co-styrene), polypropylene-gra/f-poly(methacrylic acid), polypropylene-gra/f-poly(vinyl alcohol), polypropylene-gra/f-polycaprolac-tone (PP-g-PCL), polypropylcnc-gra/f-poly(methyl methacrylate) (PP-g-PMMA), poly( ethylene-co-propylene)-gra/f-poly(methyl methacrylate) (EPR-g-PMMA), and poly(ethylene-co-propylene)-gra/f-poly(maleic anhydride-costyrene), have been synthesized by such a method resulting in controllable composition and molecular microstructures [63-66]. 

The interactions of a-olefins or styrene with sulfur dioxide (16) or a-olefins (24, 58, 78), frans-stilbene (64), styrene (1,63), p-dioxene (52), 2,2-dimethyl-l,3-dioxole (17), or alkyl vinyl ethers (1, 63) with maleic anhydride yield charge transfer complexes which are stable and generally readily detectable either visually or by their ultraviolet absorption spectra. However, under the influence of a sufficiently energetic attack in the form of heat or free radicals, the diradical complexes open, and alternating copolymers are formed. 

The rate of polymerization of polar monomers, for example, maleic anhydride, acrylonitrile, or methyl methacrylate, can be enhanced by coraplexing them with a metal halide (zinc or vanadium chloride) or an organoaluminum halide (ethyl aluminum sesqui-chloride). These complexed monomers participate in a one-electron transfer reaction with either an uncomplexed monomer or another electron-donor monomer, for example, olefin, diene, or styrene, and thus form alternating copolymers (11) with free-radical initiators. An alternating styrene/acrylonitrile copolymer (12) has been prepared by free-radical initiation of equimolar mixtures of the monomers in the presence of nitrile-coraplexing agents such as aluminum alkyls. 

Among such oxidations, note that liquid-phase oxidations of solid paraffins in the presence of heterogeneous and colloidal forms of manganese are accompanied by a substantial increase (compared with homogeneous catalysis) in acid yield [3]. The effectiveness of n-paraffin oxidations by Co(III) macrocomplexes is high, but the selectivity is low the ratio between fatty acids, esters, ketones and alcohols is 3 3 3 1. Liquid-phase oxidations of paraffins proceed in the presence of Cu(II) and Mn(II) complexes boimd with copolymers of vinyl ether, P-pinene and maleic anhydride (Amberlite IRS-50) [130]. Oxidations of both linear and cyclic olefins have been studied more intensively. Oxidations of linear olefins proceed by a free-radical mechanism the accumulation of epoxides, ROOH, RCHO, ketones and RCOOH in the course of the reaction testifies to the chain character of these reactions. The main requirement for these processes is selectivity non-catalytic oxidation of propylene (at 423 K) results in the formation of more than 20 products. Acrylic acid is obtained by oxidation of propylene (in water at 338 K) in the presence of catalyst by two steps at first to acrolein, then to the acid with a selectivity up to 91%. Oxidation of ethylene by oxygen at 383 K in acetic acid in... 

Photoconductive Lithographic Printing Plate Assembly. NVK has been copolymerized with olefinic monomers possessing carboxylic acid, such as acrylic acid, methacrylic acid, fumaric acid, and, maleic anhydride, or carboxylic anhydride [7]. The acid functionality yields copolymers that are soluble in aqueous alkaline media. The copolymers are intended... 

Mixtures of PPE and PS, or styrene-butadiene-styrene block copolymers have been extruded with maleic anhydride of fumaric acid to obtain compatibi-lized blends [42], In the same way, PPE with pendant glycidyl groups can be co-extruded with a poly(olefin) having anhydride groups [28], PPE can be grafted onto poly(ethylene) by melt kneading both modified polymers in the presence of a binder such as phenylenedi-amine. Both polymers are modified with maleic anhydride. The grafting takes place in situ. Amines may enhance the improvement of certain physical properties when used in combination with various compati-bilizers [29]. 

Influences due to steric hindrance are mostly swamped by those due to polarity and resonance stabilization. For example, 1,2-disubstituted ethylene monomers form random copolymers with comonomers of similar polarity, i.e., dimethyl fumarate/vinyl chloride. If the polarities differ greatly, even alternating copolymers can be formed because of the formation of CT complexes, as, for example, with maleic anhydride/styrene (see also Section 22.3). Even two 1,2-disubstituted monomers copolymerize with each other if the polarities differ very greatly, as happens with, for example, maleic anhydride and stilbene, since the polar interaction in the transition state helps to overcome the steric hindrance. Threefold substituted olefins produce an additional stabilization without steric hindrance in the transition state, and so can be easily copolymerized with comomoners of opposite polarity. 

Various types of copolymers of cyclic olefins and other monomers have been prepared by asymmetric synthesis polymerizations using monomers with optically active side groups, ° optically active additives, " cata-lysts, or solvents.Among these, the synthesis of a copolymer of maleic anhydride and (S)-(-)-a-methylbenzyl methacrylate (MBMA, 269) is the first example of preparation of an optically active polymer consisting of a C-C backbone with chiral induction to the main chain. °... 

Hydrogenated S-EB-S block-copolymers can be used with olefinic plastics such as PP and PE because of their higher temperature allowance, and even with engineering plastics that usually need melt temperatures well above 275°C. But for polar engineering plastics, such as PA 6 and 66, maleic anhydride functionalized polymers have been developed and commercialized. Systems available to improve impact resistance of high-performance plastics are given in the table below. 

Copolymerization of 4-vinylphenyl isocyanate and styrene at 60°C in toluene in the presence of AIBN affords the expected copolymers (44). Also, 1 1 copolymers from vinyl isocyanate and maleic anhydride are known (54). The copolymeriation of n-butyl isocyanate with a variety of olefins is conducted in toluene/THF at —80°C, using sodium biphenyl as initiator (55). Anionic copolymerization of styrene and hexyl isocyanate affords rod-coil block copolymers. The st5Tene polsrmer forms the coil block, while the polyisocyanate block assumes the rod shape (56). Vinyl-, 9-decenyl-, or y3-allyloxyethyl isocyanate imdergoes copolymerization reactions with styrene or methyl methacrylate (57). 

There has been a slight increase in activity in this area compared with that in the previous two year period. For the polymeric esters of acrylic, methacrylic acids, and related polymers the simplest reaction, apart from thermal depolymerization, is hydrolysis, and one or two papers on this subject have appeared. One of these concerns a comparison of the kinetics of hydrolysis of a number of methacrylate esters and a further two deal with the formation of copolymers containing carboxylic acid functions. Methyl trifluoroacrylate forms alternating copolymers with cE-olefins (ethylene, propylene, isobutylene) and these are readily hydrolysed in boiling aqueous methanolic sodium hydroxide to yield hydrophilic fluoropolymers. Hydrolysis is reported to be nearly quantitative with no chain scission. An alternating copolymer is also formed by radical polymerization of maleic anhydride with A-vinyl succinimide. On hydrolysis this copolymer is... 

Maleic anhydride grafting (cont.) poly(styrene-co-divinylbenzene), 694 poly(styrene-co-isobutylene), 675, 689 poly(styrene-co-nfialeic anhydride), 676, 679 poly(vinyl acetate), 676, 694 poly(vinyl acetate-co-vinyl fluoride), 678 poly(vinyl alkyl ethers), 675, 679, 692, 701 poly(vinyl chloride), 683, 692, 693, 695, 702 poly(vinylidene chloride), 691 poly(vinyl toluene-co-butadiene), 689 radical—initiated, 459-462, 464-466, 471, 475, 476 radiation—initiated, 459, 461, 466, 471, 474 redox-initiated, 476 rubber, 678, 686, 687, 691, 694 to saturated polymers, 459-466, 475, 476 solvents used 460-463, 465, 466, 469, 474-476 styrene block copolymers, 679 tall oil pitch, 678, 697 terpene polymers, 679, 700 thermally-initiated, 462, 464-467, 469, 476 to unsaturated polymers, 459, 466-474 vapor-phase techniques, 464, 474, 475 to wool fibers, 476 Maleic anhydride monomer acceptor for complex formation, 207-210 acetal copolymerization, 316 acetone CTC thermodynamic constants, 211 acetone photo-adduct pyrolysis, 195, 196 acetylacetone reaction, 235 acetylenic photochemical reactions, 193-196 acrylamide eutectic mixtures, 285 acylation of aromatic acids, 97 acylation of aromatics, 91, 92 acylation of fused aromatics, 92, 95, 97, 98 acylation of olefins, 99 acylation of phenols, 94-96 acylic diene Diels-Alder reactions, 104-111, 139 addition polymer condensations, 503-505 adduct with 2-cyclohexylimino-cyclopentanedi-thiocarboxylic acid, 51 adducts for epoxy resins curing, 507-510 adduct with 2-iminocyclopentanedithiocarboxylic acid, 51... 

Partially stereoregular copolymers have been obtained by asymmetric polymer synthesis using maleic anhydride as one comonomer and optically active a-methylbenzyl methacrylate (216) or a-methylbenzyl vinyl ether (217) as the other comonomer. These copolymers were optically active even after removal of their a-methylbenzyl groups (Scheme 25). Analogous results have been obtained by Minoura s group (218, 219) on copolymerizing optically active a,3-disubstituted olefins with achiral vinyl monomers. 

EFFECT ON POLYMER AND/OR OTHER ADDITIVES All-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc. A grease release agent, which is an ethoxylated maleic anhydride/a-olefin copolymer, having a comb-like structure with both hydrophobic and hydrophilic chains, is used in the formulation. ... 

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