Auto-catalytic chemistry for the solvent-free synthesis of isobutylene-rich ionomers
Ionomer derivatives of brominated poly(isobutylene-co-isoprene) rubber (BIIR) are prepared by alkylation of PPh3,imidazole and 2-[2-(dimethylamino)ethoxy]ethanol under solvent-free conditions. Halide displacement is shown to be accompanied by allylic bromide rearrangement to kinetically more reactiv...
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| Veröffentlicht in: | Green chemistry : an international journal and green chemistry resource : GC 2011-01, Vol.13 (10), p.2818-2824 |
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| container_title | Green chemistry : an international journal and green chemistry resource : GC |
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| creator | PARENT, J. Scott MALMBERG, Sean M WHITNEY, Ralph A |
| description | Ionomer derivatives of brominated poly(isobutylene-co-isoprene) rubber (BIIR) are prepared by alkylation of PPh3,imidazole and 2-[2-(dimethylamino)ethoxy]ethanol under solvent-free conditions. Halide displacement is shown to be accompanied by allylic bromide rearrangement to kinetically more reactive endo-allylic bromide isomers. Alkylation to give quaternary onium-halide salts produces an isomerisation catalyst in situ, owing to a rapid SN2[prime or minute] isomerisation by free bromide. As a result, a continuous process for PPh3 alkylation can be catalyzed by the recycling of a small amount of IIR-PPh3Br product to the feed, thereby supporting an irreversible ionomer synthesis that proceeds to full conversion without the generation of reaction byproducts. |
| doi_str_mv | 10.1039/c1gc15638a |
| format | Article |
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Scott ; MALMBERG, Sean M ; WHITNEY, Ralph A</creator><creatorcontrib>PARENT, J. Scott ; MALMBERG, Sean M ; WHITNEY, Ralph A</creatorcontrib><description>Ionomer derivatives of brominated poly(isobutylene-co-isoprene) rubber (BIIR) are prepared by alkylation of PPh3,imidazole and 2-[2-(dimethylamino)ethoxy]ethanol under solvent-free conditions. Halide displacement is shown to be accompanied by allylic bromide rearrangement to kinetically more reactive endo-allylic bromide isomers. Alkylation to give quaternary onium-halide salts produces an isomerisation catalyst in situ, owing to a rapid SN2[prime or minute] isomerisation by free bromide. As a result, a continuous process for PPh3 alkylation can be catalyzed by the recycling of a small amount of IIR-PPh3Br product to the feed, thereby supporting an irreversible ionomer synthesis that proceeds to full conversion without the generation of reaction byproducts.</description><identifier>ISSN: 1463-9262</identifier><identifier>EISSN: 1463-9270</identifier><identifier>DOI: 10.1039/c1gc15638a</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Catalysis ; Catalysts: preparations and properties ; Chemistry ; Exact sciences and technology ; General and physical chemistry ; Heterocyclic compounds ; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings ; Kinetics and mechanisms ; Organic chemistry ; Preparations and properties ; Reactivity and mechanisms ; Theory of reactions, general kinetics. Catalysis. 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As a result, a continuous process for PPh3 alkylation can be catalyzed by the recycling of a small amount of IIR-PPh3Br product to the feed, thereby supporting an irreversible ionomer synthesis that proceeds to full conversion without the generation of reaction byproducts.</description><subject>Catalysis</subject><subject>Catalysts: preparations and properties</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Heterocyclic compounds</subject><subject>Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Reactivity and mechanisms</subject><subject>Theory of reactions, general kinetics. Catalysis. 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Alkylation to give quaternary onium-halide salts produces an isomerisation catalyst in situ, owing to a rapid SN2[prime or minute] isomerisation by free bromide. As a result, a continuous process for PPh3 alkylation can be catalyzed by the recycling of a small amount of IIR-PPh3Br product to the feed, thereby supporting an irreversible ionomer synthesis that proceeds to full conversion without the generation of reaction byproducts.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/c1gc15638a</doi><tpages>7</tpages></addata></record> |
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| identifier | ISSN: 1463-9262 |
| ispartof | Green chemistry : an international journal and green chemistry resource : GC, 2011-01, Vol.13 (10), p.2818-2824 |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Catalysis Catalysts: preparations and properties Chemistry Exact sciences and technology General and physical chemistry Heterocyclic compounds Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings Kinetics and mechanisms Organic chemistry Preparations and properties Reactivity and mechanisms Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry |
| title | Auto-catalytic chemistry for the solvent-free synthesis of isobutylene-rich ionomers |
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