High conversion copolymerization, 1. Kinetics of the copolymerization of styrene and maleic anhydride

A new monomer N-( l-acetoxy-Z,Z,Z-trichloroethyl) maleimide (MI) and its copolymer with styrene have been developed. It was found that MI can be synthesized from N-(l-hydroxy-2,2,2-trichloroethyl) maleamide in acetic anhydride with a yield of 65%. The radical copolymerization of MI with styrene in benzene solution occurs with a yield of 91%. The obtained copolymer has a melting point about 215"C, good thermal resistance, and is selfextinguishing. The monomer and copolymer compositions were determined by elementary, 'H-NMR and IR analysis. I NTRODU CTlO NIn some cases the properties of traditional mass plastics can be improved by copolymerization with maleimides. In this way, for instance, it is possible to improve hardness, water absorption, and heat resistance of the polymer materials.'-'Maleimides can be obtained from monomaleamides in dehydration reactions using the dehydrating agents such as acetic anhydride, phosphorus pentaoxide, acetyl chloride, and thionyl chloride. This study describes the reaction in the presence of acetic anhydride. The rate of maleimide formation depends, among other things, on the kind of substituent at the nitrogen atom in maleamide. Imidization occurs with a higher yield and without side reactions if the substituent is rather large, rigid, and has electron donor c h a r a~t e r .~, '~ On the other hand it is well-known that there is a possibility to improve also fire resistance of polymers by inserting halogen atoms into the polymer structure. Thus a question arises whether combining an imide group and halogen atoms in one macromolecular structure would combine their influences to obtain a polymer with good thermal stability and fire resistance. A compound that, under some conditions, can be substituted at nitrogen atoms in maleamides is chloral. It is rigid, has a big molecular mass, and, containing three chlorine atoms, is a good source of halogen.In our previous works we have found that monomaleamide reacts with chloral" and that the product of the reaction, N -( l-hydroxy-2,2,2-trichloroethyl) maleamide, copolymerizes with styrene.12The present work aims at studying the effect of l-hydroxy-2,2,2-trichloroethyl substituent at nitrogen atoms in monomaleamide on closing of imide rings and ability of N -( l-acetoxy-2,2,2-trichloroethyl) maleimide to copolymerize with styrene. Interest was focused on the thermal and fire resistance of the copolymer as well. EXPERIMENTAL Synthesis Monomaleamide ( M A )In a well-stirred and ice-cooled concentrated aqueous solution of NH40H (containing 1 mol NH3), 49 g (0.5 mol) maleic anhydride were dissolved slowly. Then 20% solution of HC1 was added dropwise until the pH of the reaction mixture was about 4. The crude product was filtered and recrystallized from ethanol and dried. The yield was 70%. 563

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High conversion copolymerization, 2. Styrene/maleic anhydride copolymer composition studies

Capek

Juraničová

Bartoň

1983

Makromol. Chem.

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The free radical initiated copolymerization of styrene with maleic anhydride at high conversions is studied. The data of the fractional conversion of the comonomers, of the fractional copolymerization rate, of the instantaneous and cumulative composition of the copolymer for the copolymerization of an equimolar mixture of styrene and maleic anhydride in ethyl methyl ketone (at 60°C) and in 1,Cdioxane (at 120'C) up to high conversions as a function of the reaction time (resp. conversion) are presented. Negligible differences at 60 "C, but significant ones at 120 "C were found between the experimentally measured fractional compositions and those calculated according to the integrated form of the copolymer composition equation (Mayo-Lewis equation), using the published values for the copolymerization reactivity ratios.

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High conversion copolymerization, 1. Kinetics of the copolymerization of styrene and maleic anhydride

Cited by 8 publications

References 17 publications

Integrated rate equation for free‐radical copolymerizations with monomer 2 in low concentration and a small r₂‐value

Integrated rate equation for free‐radical copolymerizations with monomer 2 in low concentration and a small r₂‐value

Synthesis of chloral derivative of maleimide and its copolymerization with styrene

High conversion copolymerization, 2. Styrene/maleic anhydride copolymer composition studies

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High conversion copolymerization, 1. Kinetics of the copolymerization of styrene and maleic anhydride

Cited by 8 publications

References 17 publications

Integrated rate equation for free‐radical copolymerizations with monomer 2 in low concentration and a small r2‐value

Integrated rate equation for free‐radical copolymerizations with monomer 2 in low concentration and a small r2‐value

Synthesis of chloral derivative of maleimide and its copolymerization with styrene

High conversion copolymerization, 2. Styrene/maleic anhydride copolymer composition studies

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Product

Resources

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Integrated rate equation for free‐radical copolymerizations with monomer 2 in low concentration and a small r₂‐value

Integrated rate equation for free‐radical copolymerizations with monomer 2 in low concentration and a small r₂‐value