The anionic polymerization of dialkylaminoisoprenes‐5‐copolymerization with 1,3‐butadiene

Mannebach, Gerd; Bieringer, R.; Morschhäuser, Roman; Stadler, Reimund

doi:10.1002/masy.19981320123

Cited by 8 publications

(14 citation statements)

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“…[1][2][3][4] as well as on block terpolymers with styrene and methacrylic acid. [5] All these experiments were carried out in hexane or benzene, i.e.…”

Section: Introductionmentioning

confidence: 99%

“…With increasing bulkiness of the amino groups the difference in reactivity decreases. Because of this, copolymerization of 5-(N,N-dimethylamino)isoprene (DMAI) with 1,3-butadiene results in a perfect block copolymer, [4] whereas with the other aminoisoprenes a tapered structure becomes more and more favorable.…”

Section: Introductionmentioning

confidence: 99%

“…[3,4] The monomer with the highest basicity, DMAI, has thestrongestinfluenceonthemicrostructureofpolybutadiene (PB). With 10 mol-% of DMAI in the monomer feed the 1,2-units in PB increases up to 50 mol-%.…”

Section: Introductionmentioning

confidence: 99%

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Anionic Copolymerization of 5‐(N,N‐Dialkylamino)isoprenes

Mannebach

Müller

2004

Macro Chemistry & Physics

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Summary: The anionic copolymerization of various 5‐(N,N‐dialkylamino)isoprenes initiated by sec‐butyllithium in hexane is investigated. The bulkiness of the alkyl side chains has a strong influence on the copolymerization behavior, monomer reactivity decreasing in the order of alkyl groups methyl > ethyl ≈ propyl > isopropyl. Polymer structures vary from nearly block over tapered and gradient to random, depending on the relative reactivities of comonomers. Since the basicity of the tertiary amino groups depends on the nature of the alkyl groups, it is possible to vary the basicity along the polymer backbone by a suitable choice of the comonomers. Copolymerization kinetics do not seem to follow first‐ or second‐order with respect to monomer conversion and they cannot be described using the terminal model.General structure of obtained polymers.magnified imageGeneral structure of obtained polymers.

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“…[1][2][3][4] as well as on block terpolymers with styrene and methacrylic acid. [5] All these experiments were carried out in hexane or benzene, i.e.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Anionic Copolymerization of 5‐(N,N‐Dialkylamino)isoprenes

Mannebach

Müller

2004

Macro Chemistry & Physics

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“…This was the first type of non‐silicon amino‐ functionalized diene‐based monomer with which Stadler et al13 began anionic polymerization studies in 1993. Their work showed the potential of amino‐functionalized diene‐based monomers as a polar modifier to manipulate the microstructures of polybutadiene and to obtain novel, polar, functionalized materials 14…”

Section: Introductionmentioning

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-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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“…Poly(4' -fluoro-2,5-diphenylsulfonc) was made using Ni(0)-catalyzed coupling. 26 The resulting polymer has a pendant aryl fluoride that can be used post-polymerization for nucleophilic aromatic substitution with a…”

Section: Introductionmentioning

confidence: 99%

Functionalized materials from elastomers to high performance thermoplastics

Salazar

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High molecular weight polymer was successfully synthesized from 2-(Npiperidylme thy I)-1,3-butadiene using free radical polymerization techniques. Previously, only low molecular weight polymers (5.2 x 10 3 g/mol) accompanied by low conversions (13%) were synthesized from this monomer using anionic polymerization techniques. The key to higher molecular weight material is the purity of the monomer. Sulfur dioxide chemistry that we previously used to synthesize pure 2-(MJV-dialkylaminomethy 1)-1,3butadienes was adapted here to make 2-(JV-piperidylmethyl)-1,3-butadiene from isoprene in > 99% purity. The bulk free radical and emulsion polymerizations were studied. Under bulk free radical conditions, traditional kinetics were observed yielding a polymer with a (number average molecular weight) of 17.1 x 10 3 g/mol and a polydispersity (PDI) near 1.4. Significantly higher molecular weights were achieved using emulsion polymerization yielding a polymer with a of 41.0 x 10 3 g/mol and a PDI of 2.0. Copolymers with styrene were also investigated using bulk free radical polymerization techniques to 17 synthesize materials that could be tailored by altering the feed ratio of the two monomers. This led to a series of polymers that had glass transition temperatures ranging from 24 to 77 °C. The reactivity ratios calculated from kinetic studies were found to be 2.35 ± 0.02 for 2-(yV-piperidylmethyl)-1,3-butadiene and 0.49 ± 0.01 for styrene. These two monomers gave nonideal, nonazeotropic copolymerizations where the final materials always contained more 2-(7V-piperidy Imethyl)-1,3-butadiene than the feed.

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The anionic polymerization of dialkylaminoisoprenes‐5‐copolymerization with 1,3‐butadiene

Cited by 8 publications

References 2 publications

Anionic Copolymerization of 5‐(N,N‐Dialkylamino)isoprenes

Anionic Copolymerization of 5‐(N,N‐Dialkylamino)isoprenes

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

Functionalized materials from elastomers to high performance thermoplastics

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