Maleic anhydride/acid copolymer with vinyl acetate

Neutral and acidic polymers such as polyvinyl pyrrolidone, copolymers of polyvinyl pyrrolidone with vinyl acetate, and copolymers of methyl vinyl ether with half esters of maleic anhydride, are all used in hair styling and hair setting products. 

While most copolymers of vinyl acetate are random copolymers, alternating copolymers are formed when the reactivity ratios for the two monomers are suitable. This occurs spontaneously when vinyl acetate is polymerized with electron-poor monomers such as maleic anhydride [273]. Alternatively, it has been reported that acrylonitrile which has been precomplexed with zinc chloride gives alternating polymers with vinyl acetate [274]. Block polymers of vinyl acetate with methyl methacrylate, acrylonitrile, acrylic acid, and n-vinyl pyrrolidone have been prepared by the strategy of preparing poly(vinyl acetate) macroradicals in poor solvents in which the macroradicals are occluded. Addition of a second monomer swells the polymer coils, and polymerization continues with the addition of the new monomer [275]. 

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... 

The preparation of copolymers of butadiene and of isoprene with methacrylic acid and with acrylic acid, described by Frank, Kraus, and Haefner in 1952, for use in rubber to metal bonding, was probably the first preparation of carboxylic elastomers made specifically for use as adhesives. They indicated that their consideration of carboxyl groups as a means for enhancing adhesion was stimulated by the observations of Doolittle and Powell " in 1944. They found that low proportions of maleic anhydride (0.1-1%) when copolymerized in copolymers of vinyl chloride with vinyl acetate, improved the adhesion of such films to metal surfaces. McLaren has described an increase in adhesion with increasing carboxyl content of vinylite copolymers to unmodified cellulose. 

An interesting application of this reaction was the use of macro-molecular anhydrides, namely, styrene-maleic anhydride or vinyl acetate-maleic anhydride copolymers in the presence of perchloric acid as catalyst, these copolymers acylate mesityl oxide or d rpnone to macromolecular pyrylium salts which, with aryl substituents, are fluorescent.No crystalline products could be obtained from succinic anhydride because of the solubility and ease of decarboxylation. 

Several polymers were found to fit all or most of the above criteria and were used to prepare the carrier films. Many polymers have been used for this purpose, viz., ethyl cellulose, poly(y-benzyl glutamate), poly(vinyl acetate), cellulose acetate phthalate, and the copolymer of methyl vinyl ether with maleic anhydride. In addition to the base polymers, plasticizers were often needed to impart a suitable degree of flexibility. Plasticizers, which are found to be compatible with polymeric materials include, acetylated monoglycerides, esters of phthalic acid such as dibutyl tartarate, etc. An excipient was usually incorporated into the matrix of the carrier films. The excipients used were water-soluble materials, which are capable of creating channels in the polymer matrix and facilitate diffusion of the drug. PEGs of different molecular weights were used for this purpose. 

Alkyl phenol ethoxylates can also react with P4O10 yielding alkyl phenol etherphosphates as a mixture of mono-/diesters or with maleic anhydride to yield maleic acid monoesters, which then react with NaHS03 to yield sulphosuccinate monoesters. Alkylphenolpolyglycolether sulphates, phosphates or sulphosuccinates are mainly used as primary anionic emulsifiers for the manufacturing of acrylic, styrene/acrylic or vinyl acetate co-polymer dispersions. Another type of non-ionic emulsifier is block copolymers of ethylene oxide with propylene oxide. 

Figure 47. Dependence of API static fluid loss on bentonite-polymer suspensions on polymer type and concentration at constant bentonite content (10 g/L). PVA polyvinyl alcohol PAA polyacrylic acid NPA sodium polyacrylate PVP polyvinyl pyridinium hydrochloride VAMA vinyl acetate maleic anhydride copolymer. (Reproduced with permission from reference 141. Copyright 1983 Mineral Society.)...

Powder coatings are also formed from ethylene-vinyl acetate copolymers (see Section 3.4). Copolymers of ethylene with maleic acid (anhydride) of low molecular mass are water-soluble, form salts, and undergo cross-linking reactions. 

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... 

Most of these tie layers are based on modified polyolefins or their copolymers. lonomers such as Surlyn may also be used as a tie layer. The functionality of the adhesive layer derives from comonomers snch as acrylic acid, methacryUc acid, maleic anhydride or vinyl acetate. Styrene-isoprene-styrene thermoplastic block copolymers blended with polyolefins can be used as tie layers. The level of addition of these grafted units is... 

Graft copolymers between unsatnrated acids, especially acrylic acid and maleic anhydride (MA), and polyolefins (PE and PP) are widely used as surface modifiers and compatibilisers, sometimes in combination with bi-functional coupling agents [46], for talc, calcium carbonate and calcined clays. Such polymer coatings include polypropylene-maleic anhydride [47], polypropylene c/s-4-cyclohexene-l,2 dicarboxylic acid [48], polystearyl or polylauryl acrylate [49], polypropylene-acrylic acid, partially oxidised poly(butane diol) [50] and ethylene-vinyl acetate copolymers [51]. Acid-containing products can react with basic fillers. With most other types, they will simply adsorb on to the mineral surface, but they can form esters with some non-basic metal hydroxyls, notably silanols. 

Until 2003, Chen s [28], Qu s [29-31], and Hu s [32] groups independently reported nanocomposites with polymeric matrices for the first time the. In Hsueh and Chen s work, exfoUated polyimide/LDH was prepared by in situ polymerization of a mixture of aminobenzoate-modified Mg-Al LDH and polyamic acid (polyimide precursor) in N,N-dimethylactamide [28]. In other work, Chen and Qu successfully synthesized exfoliated polyethylene-g-maleic anhydride (PE-g-MA)/LDH nanocomposites by refluxing in a nonpolar xylene solution of PE-g-MA [29,30]. Then, Li et al. prepared polyfmethyl methacrylate) (PMMA)/MgAl LDH by exfoliation/adsorption with acetone as cosolvent [32]. Since then, polymer/LDH nanocomposites have attracted extensive interest. The wide variety of polymers used for nanocomposite preparation include polyethylene (PE) [29, 30, 33 9], polystyrene (PS) [48, 50-58], poly(propylene carbonate) [59], poly(3-hydroxybutyrate) [60-62], poly(vinyl chloride) [63], syndiotactic polystyrene [64], polyurethane [65], poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] [66], polypropylene (PP) [48, 67-70], nylon 6 [9,71,72], ethylene vinyl acetate copolymer (EVA) [73-77], poly(L-lactide) [78], poly(ethylene terephthalate) [79, 80], poly(caprolactone) [81], poly(p-dioxanone) [82], poly(vinyl alcohol) [83], PMMA [32,47, 48, 57, 84-93], poly(2-hydroxyethyl methacrylate) [94], poly(styrene-co-methyl methacrylate) [95], polyimide [28], and epoxy [96-98]. These nanocomposites often exhibit enhanced mechanical, thermal, optical, and electrical properties and flame retardancy. Among them, the thermal properties and flame retardancy are the most interesting and will be discussed in the following sections. 

Free-radical copolymerization of alkyl vinyl ethers has been carried out with the following typical monomers acrylic acid (bulk and emulsion) [39,40], acrylonitrile (emulsion) [26,27], acrylic esters (emulsion) [41], methyl methacrylate (bulk) [42], maleic anhydride (solution) [43], vinyl acetate (bulk and emulsion) [27,44,45], and vinyl chloride (emulsion) [26, 37,46]. The properties of these and other copolymers are described in a technical bulletin by General Aniline Film Corporation [38]. 

Several vinyl monomers are used to prepare thermoplastics that are useful in certain adhesive applications. The most important vinyl resins for adhesives are polyvinyl acetate, polyvinyl acetals (butyral and formal), and polyvinyl alkyl ethers. PVC and copolymers of both vinyl chloride and vinyl acetate with other monomers, such as maleic acid esters, alkyl acrylates, maleic anhydride, and ethylene, are also used to produce solvent-based adhesives. ... 

Interactions between a steel surface and an ethylene-vinyl acetate copolymer grafted with maleic anhydride were investigated by FTIR diffuse reflectance spectroscopy. The failed surfaces obtained after a mechanical separation of the polymer/steel assemblies were analysed. A two-step mechanism was proposed the opening of the anhydride cycle by a hydrolysis reaction, leading to the formation of a carboxylic diacid, followed by the reaction of the acid with some oxidised metallic elements present at the metal surface. This study underlines the contribution of FTIR reflectance techniques to the understanding of adhesion mechanisms. 7 refs. 

A typical lacquer formulation (Table 13.3) contains polymer, pigment, plasticizer (nonvolatile solvent), and volatile solvents. The vinyl resins used here are copolymers of vinyl chloride with about 10%-20% vinyl acetate. The VMCH also contains a few percent of maleic anhydride as a termonomer. This lacquer is designed for steel surfaces, and the acid functionality results in good adhesion to the iron surface. 

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