Acrylic acid maleic anhydride example

PMA homopolymer is also available as a neutralized salt and in several grades, often with precise molecular weight distributions, for special applications such as antiscalent duty in seawater distillation and sugar evaporator processes. Maleic anhydride chemistry has also been successfully developed to provide functional components in copolymers [examples are acrylic acid, maleic anhydride (AA/MA) and sulfonated styrene, maleic anhydride (SS/MA)] and terpolymers [example is maleic anhydride, ethyl acrylate, vinyl acrylate (MA/EA/VA)]. 

Nitrile, azo, and nitroso groups, and even the oxygen molecule, take part in such reactions, and acetylenic triple bonds in particular confer reactivity as philodiene. As for dienes, so for philodienes the reactivity depends on the constitution. Activating groups particularly favor addition. The most reactive components include <%,/ -unsaturated carbonyl compounds such as acrolein, acrylic acid, maleic acid and its anhydride, acetylenedicarboxylic acid, p-benzo-quinone and cinnamaldehyde, as well as saturated nitriles and <%,/ -unsaturated nitro compounds. Tetracyanoethylene also reacts with dienes.41,42 Conjugation of the double bond to an active group is not absolutely essential for a philodiene, for dienes add under certain conditions also to philodienes with isolated double bonds examples of the latter type are vinyl esters and vinyl-acetic acid. Ketenes do not undergo the Diels-Alder reaction with dienes, but instead yield cyclobutanone derivatives 43,44... 

Among the carboxylic acid and anhydride functional monomers that have been employed in the synthesis of these thickener polymers are acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride, and citraconic anhydride. The copolymers containing maleic and citraconic anhydride monomers are either hydrolyzed or partially esterified to obtain the required carboxyl functionality. Among these carboxylic monomers, maleic anhydride and particularly methacrylic acid are most frequently favored. Carboxylic homopolymers, where they can be formed, might be considered the simplest examples of ASTs were it not for the fact that they are not copolymers as defined, and some are water soluble in their un-ionized states. Examples of carboxylic homopolymers are the un-ionized free-radical-polymerized atactic forms of polyacrylic acid (i) and polymethacrylic acid (2), which are both readily soluble in water. 

In order to improve the physical properties of HDPE and LDPE, copolymers of ethylene and small amounts of other monomers such as higher olefins, ethyl acrylate, maleic anhydride, vinyl acetate, or acryUc acid are added to the polyethylene. Eor example, linear low density polyethylene (LLDPE), although linear, has a significant number of branches introduced by using comonomers such as 1-butene or 1-octene. The linearity provides strength, whereas branching provides toughness. 

Polymers having ionisable groups along the chain are known as polyelectrolytes. They generally exhibit properties in solution which are quite different from those with non-ionisable structures. Examples of polyelectrolytes include polyacids like poly (acrylic acid) and hydrolysed copolymers of maleic anhydride, polybases like poly (vinyl amine) and poly (4-vinyl pyridine), polyphosphates, nucleic acids, and proteins. 

Alder s endo rule applies not only to cyclic dienes like cyclopentadiene and to disubstituted dienophiles like maleic anhydride, but also to open chain dienes and to mo no-substituted dienophiles diphenylbutadiene and acrylic acid, for example, react by way of an endo transition structure 2.113 to give largely (9 1) the adduct 2,114 with all the substituents on the cyclohexene ring cis, and equilibration again leads to the minor isomer 2.115 with the carboxyl group trans to the two phenyl groups. 

Further examples of attempts to replace olefins by alkanes as a starting materials, as in the maleic anhydride process, are the development of processes for selective oxidation and ammoxidation. Examples are processes for acrolein, acrylic acid (Table 2, entry 19) and acrylonitrile (Table 2, entry 20) using propane as a feedstock... 

Drawn from these examples it is apparent that controlling the chemose-lectivity in inter-intermolecular Heck-Diels-Alder reactions of two different alkenes can be tedious if the alkenes show comparable reactivities. Nevertheless, the stepwise approach was realized in several other cases. In a synthesis of a derivative of cephalostatin 1 containing a central benzene instead of the pyrazine ring, Winterfeldt et al. linked two steroidal systems by a Heck coupling and subsequently performed high pressure Diels-Alder reactions of the conjugated diene with electron-deficient alkynes [34], Another example, reported by Hayashi et al., involves a selective Heck reaction of a bromoglu-cal with ethylene or acrylic acid derivatives followed by cycloadditions with maleic anhydride or N-phenylmaleimide [35]. 

Examples of acid modified polyolefins are the copolymers of ethylene with acrylic acid or methacrylic acid. Variations include the partially neutralised acid copolymers with metal ions (ionomers) or terpolymers of ethylene, an acid and an acrylate such as methyl acrylate or isobutyl acrylate. Acid-containing extrudable adhesives are widely used to bond to aluminium foil. Examples of anhydride-modified polyolefins include terpolymers of ethylene, maleic anhydride and acrylates such as ethyl acrylate or butyl acrylate and the anhydride-grafted polyolefins. Some typical applications and stmctures of a variety of multilayer materials with extruded polymer tie-layer adhesives, as described in Du-Pont trade literature, are detailed in Table 16.2. 

Alder diene for example it reacts with maleic anhydride in an autoclave at 180° to give the adduct (4). With the less reactive dienophiles acrylic acid and cyclohexene, a small amount of hydroquinone or of trichloroacetic acid is added as catalyst. 

Multitubular reactors are mainly used in gas-phase partial oxidation processes, such as the air oxidation of light olefins, paraffins, and aromatics. Examples of chemistries where these reactors are used include the partial oxidation of methanol to formaldehyde, ethylene to ethylene oxide, ethylene and acetic acid to vinyl acetate, propylene to acrolein and acrylic acid, butane to maleic anhydride, isobutylene to methacrolein and methacrylic acid, and o-xylene to phthalic anhydride. An overview of the multitubular reactor process for the partial oxidation of n-butane to maleic anhydride is given here. 

Neutral or negatively charged polymeric resins are commonly employed to provide styling benefits in products such as mousses, gels, hairsprays, and setting lotions. Typical examples in use today are the copolymer of vinyl acetate and cro-tonic acid, the copolymer of polyvinyl pyrrolidone and vinyl acetate (PVP/VA), the ethyl ester of the copolymer of polyvinyl methyl ether and maleic anhydride (PVM/MA), and the copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate (Amphomer). 

Previous investigators have drawn attention to the beneficial effect of lime when added in small quantities to asphaltic bitumen. The lime helps retard oxidative hardening (13) and reduces the tendency towards water-stripping (4,11,12). Most asphalts are slightly acidic because of the presence of phenolic or carboxylic substituents and would therefore react with basic oxides to form insoluble salts. For example, Fromm (10) has described the use of iron salts of naphthenic acids as adhesion promoters to improve the water resistance of asphalt concretes. This promising approach is now undergoing commercial trials. The literature also describes methods of chemically modifying asphalt with maleic anhydride or acrylic acid (14), sulfur trioxide (15), sulfur dioxide (16), acetyl sulfate (17-21), and sulfuric acid (20). (For a recent review of the interfacial phenomena in asphaltic compositions see Ref. 4.)... 

In the late 1970 s, the reactive blending of PC/ABS has begun to dominate the technology. Initially, the PC blends with ABS modified by incorporation of the maleic anhydride moieties (ABS-MA), later ABS with acrylic acid groups (ABS-AA) were developed. The third generation blends comprise ABS modified by copolymerization with glycidylmethacrylate (ABS-GMA). Examples are listed in Table 1.18. 

Examples of various coupling agents in order of appearance are maleic anhydride (59), alkyl vinyl ether (65), acrylic or methacrylic acid (67), vinyl... 

Special post-functionalizable copolymers have also been used to derive acid ionomers by hydrolysis, thus avoiding the difficulties of copolymerizing ionic and nonionic monomers. To this end there are many examples where carboxylic acid polymers are formed by hydrolyzing copolymers containing acrylate esters, acrylonitrile, or maleic anhydride. As described later, a sulfonic acid ionomer, Nafion, is formed by hydrolysis of tetrafluoroethylene copolymerized with a sulfonyl fluoride. 

The components of the copolymers are cycloaliphatic monomers (norbor-nene), and vinyl ether, maleic anhydride, acrylate, and methacrylate. In addition, vinyl sulfonamides have been used as co-monomers in the synthesis of random copolymers capable of functioning as acid-amplified resists. An example is presented in Chart 9.5. A high sensitivity, S = 2mJ cm, was measured for a copolymer (Chart 9.5) with n=0.4 and m=0.6 (resist thickness d=220nm, developer aqueous tetramethylammonium hydroxide solution). Triphenylsulfonium perfluoro-1-butane sulfonate served as acid generator [33]. 

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