Styrene polymerizations with tert‐butyl hydroperoxide and metal acetylacetonates

Indictor, N.; Linder, Christophe

doi:10.1002/pol.1965.100031032

Cited by 7 publications

(4 citation statements)

References 14 publications

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“…The nmr spectrum of 2 showed only one singlet (4.37 ppm) for the benzylic protons in deuteriochloroform solution, even down to -60°, whereas two signals would have been expected for a mixture of syn and anti forms12-14 in the absence of rapid interconversion. Since syn-anti isomerization of similarly constituted N-halimines has been shown to be slow at room temperature,12,13 the predominance of a single isomer is suggested.15 Treatment of 2 with silver tetrafluoroborate in dioxane-water gave, in addition to partial hydrolysis to deoxybenzoin, rearrangement only to N-phenylphenylacetamide (4) free from N-benzylbenzamide (5). Since this Beckmannlike rearrangement has been shown in similar cases to occur with concerted stereospecific migration If the rate of interconversion is similar to that for diaryl cases,12 this may still have not been drastic enough treatment to effect isomerization.…”

Section: Resultsmentioning

confidence: 99%

“…CtifiCHr + CH2=CHCeH13 -> CeH6CH2CH2CHC6H13 (4) C«H6CH2CH2CHC6Hi3 + 2 -> 12 + 13 (5) chain. The addition of benzyl radicals to terminal olefins has been observed previously.25 No products derived from addition of ketimino radical 13 to 1octene were observed.…”

Section: Discussionmentioning

confidence: 99%

“…The reduction of 1 with BuaSnH at 50-60°could be inhibited by oxygen and accelerated by di-l-butyl peroxyoxalate as anticipated for a radical chain process. Silver ion catalyzed Beckmann rearrangement of 2 gave N-phenylphenylacetamide (4) free from N-benzylbenzamide (5), so that chlorine appears to be syn to the benzyl group. Similar treatment of 3 gave no amides but only benzonitrile and 1,1-diphenylethylene.…”

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Thermal cleavage reactions of N-chloroketimines. Behavior of imino radicals

Poutsma¹,

Ibarbia²

1969

J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Thermal cleavage reactions of N-chloroketimines. Behavior of imino radicals

Poutsma¹,

Ibarbia²

1969

J. Org. Chem.

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“…The mechanism of thermal initiation of styrene , methyl methacrylate (MMA), and acrylonitrile (AN) by Mn Щ (acac) 3 and Mn Щ (facac) 3 complexes, were studied in detail by Bamford and Lind (7) . On the other hand, Indicator and Linder (8) reported that Cu Ц , Co Ц and Fe Щ (acac) 3 enhanced the polymerization of MMA in the presence of tbutyl hydroperoxide. Also the polymerization of MMA by cyclic ether hydro peroxidetransition metal acetylacetonates at 50˚C was studied (9) .…”

Section: Introductionmentioning

confidence: 99%

Thermal Initiation of Methylmethacrylate by Methoxy–oxobis [N-(4-bromophenyl) Salicylideneiminato] Vanadium (V)

Saleh

2007

ETJ

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Methoxyoxo -bis [N -(4-bromophenyl ) Salicylideneiminato ] Vanadium (V) : [VO (Br C 6 H 4 N : C H O C 6 H 4 ) 2 OCH 3 can initiate methylmethacrylate thermally at 80°C . Under the experimental conditions employed, no retardation or inhibition is observed.The order with respect to the initiator concentration is (0.5), while the order with respect to monomer concentration is (1.8) which gives an indication that the rate of initiation is dependent on monomer concentration. Spectroscopic studies suggest that during the thermal polymerization a reduction in the oxidation state of vanadium occurs with heterolytic scission of the V-OCH 3 bond and this might be induced by MMA molecule which forms intermediate complex between VOL 2 OCH 3 and methyl methacrylate monomer before the formation of the primary radical responsible for the initiation process. Activation energies of polymerization as well as initiation processes in the present system were also determined . The tacticity of polymer produced is examined. According to the experimental results obtained a mechanism of thermal initiation reaction is proposed.

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Metallacetylacetonate bei der Synthese von Makromolekülen. Teil I

Schellenberg

Opitz

1982

Acta Polymerica

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Metallacetylacetonate sind eine der am vielseitigsten einsetzbaren Substanzklassen bei der Synthese von Hochpolymeren. Im ersten Teil der Arbeit wird eine Zusammenfassung uber die Verwendung dieser Chelate als Initiatoren bei Kettenwachstumsreaktionen gegeben. Dabei wird besonders auf die Mechanismen der radikalischen Homo-und Copolymerisation und deren Beeinflussung durch verschiedene Aktivatoren eingegangen. Weiterhin werden die Verwendung von Metallacetylacetonaten zusammen rnit normalen radikalischen Polymerisationsinitiatoren besprochen und die Einsatzmoglichkeiten dieser Metallchelate bei der ionischen, der koordinativen und der Ringoffnungspolymerisation erlautert. Memannayemunayemonama npu cunmeae mar;po.Mo&eqn. uacmb I KonoamepoB. B rrepBot qacm p a 6 o~n c o o 6 q a m~c~ EamHe o npmeHeHm aTnx xenaToB B KarIecTBe MHHquaTopoB ~e p u a a q m EI m n m n e p a a~~~r~b n r aKTmaTopoB H a HUX. &im.rue 0 6 c y~m~c s 1 acnoabaoswwe MeTaanaqeTMaaqeaTax MeTamoxenaToB npn E I O H H O~ u KoopJ(maqHomiot n o n~~e p u a a q u~x M n o n~~e p~s a q~~ c pacKpbITneM qMHtna. Metal aeetylacetonates in the synthesis of maeromolecules. Part IMetal acetylacetonates are one of the multilateral applicable substances in the synthesis of high polymers. A summary on the application of these chelates as initiators of chain polymerization is provided in the first part of the work. Especially the mechanisms of free radical homo-and copolymerization and the influence of different activators are explained. Further, the use of metal acetylacetonates together with free radical initiators in the free radical polymerization is discussed and possibilities of application of these metal chelates in the ionic, coordination and ring opening polymerization are illustrated. MeTaJIJIaqeTMJIaeTOHaTbI RBJIRIOTCR OnHMMEI 113 CaMbIX MHOrOCTOpOHHe MCnOJIb3yeMhIX BeUeCTb EPEI CUHTe3e BbICOIlpEI PeaKqMRX pOCTa qelIEI. npEI BTOM, B gaCTHOCTM, paCCMaTpHBaIoTGR MeXaHU3MbI P~S i K a J I b H O f i TOMO-H COIlOJIEITOHaTOB COBMeCTAO G 06bIqHbIM%i paJ(MKaJlbHbIMEI HHHqHaTOPaMH nOJIUMepH3~HE EI BOaMOHtHOCTEI IIpHMeHeHUR

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Styrene polymerizations with tert‐butyl hydroperoxide and metal acetylacetonates

Cited by 7 publications

References 14 publications

Thermal cleavage reactions of N-chloroketimines. Behavior of imino radicals

Thermal cleavage reactions of N-chloroketimines. Behavior of imino radicals

Thermal Initiation of Methylmethacrylate by Methoxy–oxobis [N-(4-bromophenyl) Salicylideneiminato] Vanadium (V)

Metallacetylacetonate bei der Synthese von Makromolekülen. Teil I

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