Styrene maleic anhydride production

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. 

STYRENE-MALEIC ANHYDRIDE. A thermoplastic copolymer made by the copolymerization of styrene and maleic anhydride. Two types of polymers are available—impact-modified SMA terpolymer alloys (Cadon ) and SMA copolymers, with and without rubber impact modifiers (Dylark ). These products are distinguished by higher heat resistance than the parent styrenic and ABS families. The MA functionality also provides improved adhesion to glass fiber reinforcement systems. Recent developments include lerpolymer alloy systems with high-speed impact performance and low-temperature ductile fail characteristics required by automotive instrument panel usage. 

Typical chromatograms were observed when polystyrene was py-rolyzed in air and the pyrolytic products were analyzed by gas chromatography. A characteristic peak which was observed on the chromatograms obtained by the pyrolysis of maleic anhydride and the alternating styrene maleic anhydride copolymer but not with polystyrene was used as a reference peak. As shown in Table II, the ratio of the area under... 

The formation of block copolymers from styrene-maleic anhydride and acrylic monomers was also indicated by pyrolytic gas chromatography and infrared spectroscopy. A comparison of the pyrograms of the block copolymers in Figure 7 shows peaks comparable with those obtained when mixtures of the acrylate polymers and poly(styrene-co-maleic anhydride) were pyrolyzed. A characteristic infrared spectrum was observed for the product obtained when macroradicals were added to a solution of methyl methacrylate in benzene. The characteristic bands for methyl methacrylate (MM) are noted on this spectogram in Figure 8. 

Synthetic sizes, such as styrene maleic anhydride (SMA) copolymer or anionic polyurethane (PU) emulsion, are often added to starch-based surface size to develop water resistance, particularly in the production of label grades. This procedure may permit reducing or eliminating the use of internal size.216... 

A 1-liter reaction vessel was charged with 425 ml of styrene, maleic anhydride (100.2 g), and 2,2,6,6-tetramethyl-l-piperidinyloxy (0.0205 moles) and then treated dropwise with a mixture of 72 ml of styrene and 2,2,6,6-tetramethyl-1 -piperidinyloxy (0.0782 moles). The reaction was heated to 135°C for 45 minutes and cooled, and the mixture was dissolved in 500 ml of THE The polymer was precipitated in 3 liter of hexane, and 125.3 g solid product were isolated having a M of 3523 daltons and a polydispersity of 1.48. 

There are a few alternative approaches to imide copolymers that allow the resin producer to make imide-modified high heat ABS without incurring the cost of the synthesized imide monomer. One is by reacting styrene-maleic anhydrides with a primary amine, either during the polymerization reaction with styrene or in a separate step. Mitsubishi Monsanto has practiced imidiza-tion on a commercial scale and described a process which follows the formation of S-MA with addition of amine and AN [60]. They described the manufacture of maleimide copolymers by heating the SMA copolymers with aniline in an extruder [61]. The maleimidation of the anhydride function is not complete, as there is unreacted amine or maleic anhydride in the product. The polymer stability and physical properties depend on the mole percent of maleimidation. 

The tendency to alternation increases as the r V2 product nears zero, as long as both r and T2 are less than unity. Such copolymerizalions occur in free-radical systems when the two monomers have opposite polarities (Section 7.10.2). The styrene maleic anhydride copolymers mentioned in Chapter I are an example of a purely alternating system (ri = V2= 0), while styrene (Mi)-acrylonitrile (M2) copolymers have a pronounced tendency to alternate monomer residues (ri = 0.4, Y2 = 0). 

The first reports of successful water cleavage followed the development of RUO2 as a catalyst for O2 production from [Ru(bipy)j] . Simply mixing colloidal RUO2 and colloidal platinum protected by styrene-maleic anhydride copolymer with [Ru(bipy)j] and leads to H2... 

Some information regarding thermal stability of this type of polymer is available in literature. These polymers typically generate CO2, some maleic anhydride, and fragments related to the olefin. For example, poly(maleic anhydride-co-frans-stilbene) (alternating), when heated from ambient to 500° C, generates CO2, styrene, maleic anhydride small amounts of benzene, cyclohexadiene, dimethylbutene, ethylcyclobutanol, and 4-methoxystyrene. Major decomposition products for this polymer are chain fragments (79%), including aromatic, ketonic and unsaturated structures [5],... 

Manufacture The copolymer of styrene-maleic anhydride is slurried in mineral oil and esterified to about 70% with a Cs-is alcohol mixture, using an acid catalyst at 150-160 C. Esterification is then carried to 95% using n-butanol. N- 3-aminopropyl)-morpholine is finally added to react with the remaining acidity. The final product is sold as a 35 5% polymer concentrate. 

Table II shows typical results obtained in the carboxylation of low-density polyethylene in the Plasticorder at 150°C. Extraction of the reaction product with acetone at 25 °C for 24 hours removes unreacted monomers and ungrafted styrene-maleic anhydride copolymer.

For example, the styrene-maleic anhydride copolymer is soluble in acetone, and polyacrylonitrile is insoluble in acetone but soluble in dimethylformamide. Yet, the block copolymer obtained by addition of acrylonitrile to the styrene-maleic anhydride macroradical is soluble neither in acetone nor in dimethylformamide. Pyrolysis gas-chromatography, though, shows that this acetone and dimethylformamide-insoluble product contains styrene, maleic anhydride, and acrylonitrile. The relative area of the acrylonitrile peak was related to the amount of acrylonitrile added to the original macroradical. 

Li.gru.n-VeAd.ved Potyi ocqanaXeA Efforts to increase the incorporation of lignin into polyurethane products have concentrated on transforming polymeric lignins into polyisocyanates useful for reacting with polyols. Two alternative reaction pathways have been explored with the three lignin-like model compounds shown in Figure 3. These models were vanillic acid or a derivative thereof (Model Type A) a derivative of tetralin di-carboxylic anhydride (Model Type B) and a derivative of a styrene-maleic anhydride copolymer (Model Type C). 

Additional opportunities in the styrene plastics industry exist for the development of products having such unique properties as high heat resistance and optical transparency. Arco produces the Dylark family of heat-resistant styrene plastics, which are copolymers of styrene-maleic anhydride. These products have a good balance of mechanical properties and have a heat distortion (under ASTM D68) of 234 F (33) which is markedly higher than homo polystyrene. 

Wang and co-workers [6] used a Py-GC technique for the qualitative analysis of fumaric acid and itaconic acid as low-level monomers polymerised with other major monomers in emulsion styrene maleic anhydride co-polymers. In order for fumaric acid and itaconic acid to be detected through pyrolysis, the acids are derivatised with primary amines such as methylamine and ethylamine to form a cyclic imide. The detection of derivatised fumaric acid and itaconic acid was accomplished by atomic emission detection. The structures of the derivatisation-pyrolysis products were elucidated by MS. 

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