Polar, functionalized diene‐based material. III. Free‐radical polymerization of 2‐[(N,N‐dialkylamino)methyl]‐1,3‐butadienes

Sheares, Valerie V.; Wu, Lifen; Li, Yunxiao; Emmick, Tatania K.

doi:10.1002/1099-0518(20001115)38:22<4070::aid-pola70>3.3.co;2-g

Cited by 11 publications

(15 citation statements)

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“…The integration ratio of the peaks at 64 (cis‐1,4) and 56 ppm (trans‐1,4) was 70:30. Although the accuracy of this technique does not allow it to be a stand alone measurement, the result was quite consistent with results from the studies of other amino‐functionalized diene‐based polymers with more cis‐microstructure than trans‐microstructure 20. Other crosspeaks in the HETCOR spectrum could be used to further verify the assignments of peaks that appeared in the 1 H NMR and 13 C NMR spectra.…”

Section: Resultssupporting

confidence: 73%

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Polar, functionalized diene‐based materials. V. Free‐radical polymerization of 2‐[(N‐benzyl‐n‐methylamino)methyl]‐1,3‐butadiene and copolymerization with styrene

Sheares

2001

J. Polym. Sci. A Polym. Chem.

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2-[(N-Benzyl-N-methylamino)methyl]-1,3-butadiene (BMAMBD), the first asymmetric tertiary amino-containing diene-based monomer, was synthesized by sulfone chemistry and a nickel-catalyzed Grignard coupling reaction in high purity and good yield. The bulk and solution free-radical polymerizations of this monomer were studied. Traditional bulk free-radical polymerization kinetics were observed, giving polymers with ͗M n ͘ values of 21 ϫ 10 3 to 48 ϫ 10 3 g/mol (where M n is the numberaverage molecular weight) and polydispersity indices near 1.5. In solution polymerization, polymers with higher molecular weights were obtained in cyclohexane than in tetrahydrofuran (THF) because of the higher chain transfer to the solvent. The chaintransfer constants calculated for cyclohexane and THF were 1.97 ϫ 10 Ϫ3 and 5.77 ϫ 10 Ϫ3 , respectively. To further tailor polymer properties, we also completed copolymerization studies with styrene. Kinetic studies showed that BMAMBD incorporated into the polymer chain at a faster rate than styrene. With the Mayo-Lewis equation, the monomer reactivity ratios of BMAMBD and styrene at 75°C were determined to be 2.6 Ϯ 0.3 and 0.28 Ϯ 0.02, respectively. Altering the composition of BMAMBD in the copolymer from 17 to 93% caused the glass-transition temperature of the resulting copolymer to decrease from 64 to Ϫ7°C.

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Section: Resultssupporting

confidence: 73%

“…Additionally, the ratio of cis‐1,4/trans‐1,4 is dependent on the size of the pendent group 16, 22. The cis/trans ratio of polyaminoisoprenes was previously determined with the ratios of the C‐5 methylene peaks around 3 ppm in the 1 H NMR spectrum of the corresponding polymer 20, 22…”

Section: Resultsmentioning

confidence: 99%

Polar, functionalized diene‐based materials. V. Free‐radical polymerization of 2‐[(N‐benzyl‐n‐methylamino)methyl]‐1,3‐butadiene and copolymerization with styrene

Sheares

2001

J. Polym. Sci. A Polym. Chem.

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“…2-(N,N-Bistrimethylsilylaminomethyl)-1,3-butadiene (SA1Bd) and 2-[4(N,N-bistrimethylsilylamino)-butyl]-1,3butadiene (SA4Bd) were prepared as shown in Scheme 2. 2-Bromomethyl-1,3-butadiene was prepared from isoprene via reaction with SO 2 , bromination of allylic methyl group, and thermal decomposition 11) .…”

Section: Methodsmentioning

confidence: 99%

Anionic polymerization of 2-(N,N-bistrimethylsilylaminomethyl)-1,3-butadiene and 2-(4-(N,N-bistrimethylsilylamino)butyl)-1,3-butadiene

et al. 2013

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Anionic polymerization of two 1,3-butadiene derivatives containing trimethylsilyl-protected primary amino groups, 2-(N,N-bistrimethylsilylaminomethyl)-1,3-butadiene (SA1Bd) and 2-(4-(N,N-bistrimethylsilylamino)butyl)-1,3butadiene (SA4Bd) were carried out under various conditions. When anionic polymerization of SA1Bd was attempted in cyclohexane at room temperature with using sec-BuLi as an initiator, no polymerization took place at all. Polystyrene having dienyl end group was obtained if anionic living polystyrene was used as an initiator, presumably due to the isomerization of carbanion accompanied with elimination of bistrimethylsilylamide anion. Such a side reaction was not observed in the anionic polymerization of SA4Bd. Polymer of predictable molecular weight with narrow molecular weight distributions was obtained in the polymerization in toluene. Microstructure of the resulting polymer was 86% 1,4-structure though its geometry was not clear. Block copolymer with styrene was also obtained.

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“…Although the reaction of allenes with amines is effective, bis(dienyl)amines were observed as by‐products. Other methods include the reaction of 2‐halomethyl‐1,3‐dienes with secondary amines, but this requires the tedious preparation of 2‐halomethyl‐1,3‐dienes 15f,15g. The Grignard cross‐coupling reaction of 2‐bromo‐3‐aminopropene and vinyl bromides is reported to proceed with poor chemoselectivity 15h,15i.…”

Section: Introductionmentioning

confidence: 99%

Iron‐Catalyzed Allylic C–H Amination of Substituted 1,3‐Dienes

Murru

Srivastava

2014

Eur J Org Chem

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A catalytic method for the selective allylic C–H amination of dienes and trienes using arylhydroxylamines has been developed. This iron‐catalyzed approach involves the in situ generation of activated nitrosoarenes, which in turn react with dienes or trienes to give the corresponding aminomethyl dienes or trienes as the major products, and hetero‐Diels–Alder adducts as minor products. The selectivity depends on the structures of both the catalyst and the substrate. We have also studied substituent effects using p‐substituted phenylhydroxylamines.

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Polar, functionalized diene‐based material. III. Free‐radical polymerization of 2‐[(N,N‐dialkylamino)methyl]‐1,3‐butadienes

Cited by 11 publications

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Polar, functionalized diene‐based materials. V. Free‐radical polymerization of 2‐[(N‐benzyl‐n‐methylamino)methyl]‐1,3‐butadiene and copolymerization with styrene

Polar, functionalized diene‐based materials. V. Free‐radical polymerization of 2‐[(N‐benzyl‐n‐methylamino)methyl]‐1,3‐butadiene and copolymerization with styrene

Anionic polymerization of 2-(N,N-bistrimethylsilylaminomethyl)-1,3-butadiene and 2-(4-(N,N-bistrimethylsilylamino)butyl)-1,3-butadiene

Iron‐Catalyzed Allylic C–H Amination of Substituted 1,3‐Dienes

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