Staudinger’s Poly(cyclopentadiene): Sintering Processing of Poly(Diels−Alder cyclopentadiene)

Veldman, Brittnee; Kaully, Tamar; Feller, Russell K.; Falcão, Eduardo H.L.; Wudl, Fred

doi:10.1021/ma901123p

Cited by 11 publications

(6 citation statements)

References 8 publications

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“…In contrast, previous Cp materials appear as glassy and brittle thermosets with high T g s, due to the uncontrolled cross-link density, which resulted from the extensive formation of trimers and oligomers. [18][19][20][21][22]24 For example, the only report of a processable Cp cross-linked homopolymer from Wudl has the lowest T g of 89 °C. 24 These results demonstrate that the viability of controlled crosslinking, via dimerization of well-defined Cp monomers, enables access to new compelling Cp-based materials.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The fast, self-reactivity of Cp led to the first single-component network formation in 1926 by Hermann Staudinger, the “father of macromolecular chemistry” (Figure a). Although pioneering, the uncontrolled nature of cross-linking resulted in a macromolecule with a high decomposition temperature and poor polymer processability. − Expanding upon this work, Stille explored the use of bis(cyclopentadienyl)alkane derivative as a telechelic monomer, however, due to the high reactivity of Cp  at room temperature, Cp is unstable, readily dimerizes, and undergoes a fast 1,5-sigmatropic hydride (1,5-H) shift  the monomer could not be purified prior to polymerization. As a result, the formed polymeric materials were contaminated with impurities and the cross-linking process was presumably attributed to random oxidative cross-linking …”

Section: Introductionmentioning

confidence: 99%

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Controlled Synthesis of a Homopolymer Network Using a Well-Defined Single-Component Diels–Alder Cyclopentadiene Monomer

Tran

Alaniz

2023

J. Am. Chem. Soc.

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Cyclopentadiene is known for its high reactivity and propensity to dimerize, making monomer synthesis and polymerization notoriously challenging. In fact, despite its long history and compelling chemistry, only two reports have appeared in the literature since the first attempt to homopolymerize cyclopentadiene by Staudinger in 1926. Herein, we present a strategy not only to synthesize, isolate, and homopolymerize a well-defined tetracyclopentadiene monomer but also to de-cross-link the network homopolymer. Mechanical properties are also investigated, including creep–recovery, shape memory, and tensile behaviors. Interestingly, the tensile test reflects a tough and elastic material, in contrast to prior Cp-based homopolymer networks. This work provides a versatile platform to access and study new cyclopentadiene-based and better-defined homopolymer networks with potential applications ranging from shape memory polymers to degradable thermosets.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Controlled Synthesis of a Homopolymer Network Using a Well-Defined Single-Component Diels–Alder Cyclopentadiene Monomer

Tran

Alaniz

2023

J. Am. Chem. Soc.

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“…All material-specific information is embedded in G(t ). For example, we note that the multimode MM is a special case of eqn (11) with G(t) given by eqn (9). The BSP illustrates how the stress response to multiple independent perturbations (say γ ¼ γ1 þ γ2 ) is the sum of the individual responses to each stimulus.…”

Section: Tutorial Review Polymer Chemistrymentioning

confidence: 99%

“…where ρ is density, R is the gas constant, T is temperature, and M 0 is the molar mass of the statistical segment. Comparison of eqn ( 25) to (9) demonstrates that the Rouse model is basically a multimode Maxwell model in which…”

Section: Gðtþmentioning

confidence: 99%

“…7 Contemporary studies even suggest that Hermann Staudinger supported his "macromolecular hypothesis" by unintentionally cross-linking cyclopentadiene monomer via a Diels-Alder mechanism. [8][9][10] The dichotomy between liquids and solids also frames the past 100 years of macromolecular science. Polymers generally divide into two broad categories: thermoplastics and thermosets.…”

Section: Introductionmentioning

confidence: 99%

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A tutorial review of linear rheology for polymer chemists: basics and best practices for covalent adaptable networks

Ricarte,

Shanbhag

2024

Polym. Chem.

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Diels–Alder Polymers

Yoshie¹

2013

Encyclopedia of Polymer Science and Technology

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The Diels–Alder (DA) cycloaddition is extensively used in polymer chemistry. Linear, network, and hyperbranched polymers have been prepared from monomers and prepolymers containing a diene and a dienophile. Because of the simple reaction conditions, high yield, and high selectivity, the DA reaction has recently been rerecognized as a member of the click‐chemistry family. Polymers with unique architectures (e.g., block and graft copolymers, star polymers, telechelic polymers, dendrimers, and dendronized polymers) have been prepared based on this concept. Many DA reactions are thermally reversible. Enthalpically favorable forward cycloaddition reaction proceeds at low temperature, whereas the opposite cycloreversion proceeds at moderate‐to‐high temperature. Among the various options for optimizing DA reactions in polymer synthesis, researchers have focused on the diene–dienophile combination. Ease of reactant preparation, reaction rate of the DA cycloaddition, equilibrium constant of the DA reaction at room temperature, and temperature above which the retro‐DA reaction proceeds are key points in choosing this option. In addition, reversibility has been exploited in developing various functional polymers such as recyclable gels and thermosets, shape‐memory polymers, and crack‐healing polymers. This article surveys DA reactions in polymer synthesis and coupling, including the click‐chemistry approach, and functionality of DA polymers mainly based on the reversibility.

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Staudinger’s Poly(cyclopentadiene): Sintering Processing of Poly(Diels−Alder cyclopentadiene)

Cited by 11 publications

References 8 publications

Controlled Synthesis of a Homopolymer Network Using a Well-Defined Single-Component Diels–Alder Cyclopentadiene Monomer

Controlled Synthesis of a Homopolymer Network Using a Well-Defined Single-Component Diels–Alder Cyclopentadiene Monomer

A tutorial review of linear rheology for polymer chemists: basics and best practices for covalent adaptable networks

Diels–Alder Polymers

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