Synthesis and Catalyst Issues Associated with ADMET Polymerization

Schwendeman, John E.; Church, Allen C.; Wagener, Kenneth B.

doi:10.1002/1615-4169(200208)344:6/7<597::aid-adsc597>3.0.co;2-p

Cited by 101 publications

(51 citation statements)

References 23 publications

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“…Typically C1 and C2 are soluble in dichloromethane, toluene, or THF, and metathesis reactions are carried out in these solvents at temperatures ranging from room temperature to about 80 8C. [28] However, the synthesized a,v-diene monomers 4a-4d were insoluble in all of these solvents and their ADMET polycondensations had to be carried out with minimal amounts of DMF to assure a homogeneous reaction mixture. These ADMET reactions were tested with up to 10% of C1 and C2 and all polymerizations were monitored by GPC.…”

Section: Resultsmentioning

confidence: 99%

Unsaturated PA X,20 from Renewable Resources via Metathesis and Catalytic Amidation

Mutlu

Meier

2009

Macro Chemistry & Physics

112

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The synthesis of unsaturated polyamides that can be obtained from plant oil derivatives via two different approaches is described. First, long chain aliphatic α,ω‐dienes with two symmetrically spaced amide segments were polymerized via ADMET polymerization. Secondly, dimethyl(E)‐icos‐10‐enedioate, a bio‐based unsaturated monomer that was obtained via metathesis, was polymerized with different aliphatic diamines using strong organic bases, such as TBD, as catalysts. Both reaction pathways led to unsaturated PA X,20 and the two different routes were investigated, optimized and compared. Moreover, the polymers were characterized by 1H NMR analysis and SEC, and the properties of the resulting polyamides were investigated by DSC and TGA.magnified image

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Section: Resultsmentioning

confidence: 99%

Unsaturated PA X,20 from Renewable Resources via Metathesis and Catalytic Amidation

Mutlu

Meier

2009

Macro Chemistry & Physics

112

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“…Undecenyl chains are commonly used in ADMET monomers as the competing formation of cyclic monomers is disfavored when chain lengths exceed ten atoms. 43 Under identical bulk polymerization conditions, GII proved to produce polymers of higher molecular weight (M n = 2.07  10 4 g/mol) than HGII (M n = 1.75  10 4 g/mol). Both catalysts afforded polymers with a dispersity (Ð) of 2.2, which is consistent with the theoretical Ð value of 2 for step-growth addition polymerizations.…”

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confidence: 99%

Synthesis of poly(sulfonate ester)s by ADMET polymerization

et al. 2014

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Many hydrocarbon polymers containing heteroatom defects in the main chain have been investigated as degradable polyethylene-like materials, including aliphatic polyesters. Here, acyclic diene metathesis (ADMET) polymerization was used for the synthesis of aliphatic poly(sulfonate ester)s. The requisite sulfonate ester containing α,ω-diene monomers with varying numbers of methylene groups were synthesized, and their polymerization in the presence of ruthenium-N-heterocyclic (Ru-NHC) alkylidene catalysts was studied. A clear negative neighboring group effect (NNGE) was observed for shorter dienes , either inhibiting polymerization or resulting in low-molecular-weight oligomers. The effect was absent when undec-10-en-1-yl undec-10-ene-1-sulfonate was employed as the monomer, and its ADMET polymerization afforded polymers with appreciable number-average molecular weights of up to 37,000 g/mol and a dispersity Đ of 1.8. These polymers were hydrogenated to afford the desired polyethylene-like systems. The thermal and morphological properties of both saturated and unsaturated polymers were investigated. The incorporation of sulfonate ester groups in the polymer backbone offers an interesting alternative to other heteroatoms and helps further the understanding of the effects of these defects on the overall polymer properties.

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“…As it can be seen, all these monomers are difunctional, thus fulfilling the requirements to obtain lineal polymers via acyclic diene metathesis (ADMET) polymerization. Metathesis of a,u-dienes has been shown to be an efficient and powerful tool for the synthesis of a wide variety of linear polymers and polymer architectures that are not available using other polymerization methods [14]. The development of new, highly active and robust metathesis catalysts allows polymerizing dienic monomers in the presence of several functional groups.…”

Section: Methodsmentioning

confidence: 99%