Influence of Random Branching on Multiple Hydrogen Bonding in Poly(alkyl methacrylate)s

McKee, Matthew G.; Elkins, Casey L.; Park, Taigyoo; Long, Timothy Edward

doi:10.1021/ma050667b

Cited by 65 publications

(65 citation statements)

References 43 publications

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“…The breakdown of TTS is most likely related to the coinciding of these two mechanisms occurring in the same frequency range. Thermorheological complexibility has been observed for other hydrogen bonding associating polymers 11,34,35 The activation energies, E a , calculated from Arrhenius relationship:…”

Section: Linear Viscoelasticitymentioning

confidence: 99%

Linear Viscoelastic and Dielectric Relaxation Response of Unentangled UPy-Based Supramolecular Networks

et al. 2016

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Supramolecular polymers possess versatile mechanical properties and a unique ability to respond to external stimuli. Understanding the rich dynamics of such associative polymers is essential for tailoring user defined properties in many products. Linear copolymers of 2-methoxyethyl acrylate (MEA) and varying amounts of 2-ureido-4[1H]-pyrimidone (UPy) quadruple hydrogen-bonding side units were synthesized via free radical polymerization. Their linear viscoelastic response was studied via small amplitude oscillatory shear (SAOS). The measured linear viscoelastic envelope (LVE) resembles that of a well entangled polymer melt with a distinct * To whom correspondence should be addressed † Technical University of Denmark ‡ University of the Basque Country ¶ Drexel University 1 plateau modulus. Dielectric relaxation spectroscopy (DRS) was employed to independently examine the lifetime of hydrogen bond units. DRS reveals a high frequency α-relaxation associated with the dynamic glass transition, followed by a slower α * -relaxation attributed to the reversible UPy hydrogen bonds. This timescale is referred to as the bare lifetime of hydrogen bonding units. Using the sticky Rouse model and a renormalized lifetime, we predict satisfactorily the LVE response for varying amounts of UPy side groups. The deviation from the sticky Rouse prediction is attributed to polydispersity in the distribution of UPy groups along the chain backbone. We conclude that the response of associating polymers in linear viscoelasticity is general and does not depend on the chemistry of association, but rather on the polymer molecular weight (MW) and MW distribution, the number of stickers per chain, n s , and the distribution of stickers along the backbone.

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Section: Linear Viscoelasticitymentioning

confidence: 99%

Linear Viscoelastic and Dielectric Relaxation Response of Unentangled UPy-Based Supramolecular Networks

et al. 2016

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“…84 Furthermore, branched structures 9c could be made by the addition of ethylene glycol dimethacrylate to the radical polymerization reaction. 85 The third class of UPy-group containing supramolecular polymers, the ''modular-domain'' UPy-polymers, were proposed by Guan et al (Fig. 21).…”

Section: 8082mentioning

confidence: 99%

Supramolecular Biomaterials. A Modular Approach towards Tissue Engineering

Dankers

Meijer²

2007

Bulletin of the Chemical Society of Japan

123

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Supramolecular chemistry is an exciting area of science that plays a central role in bringing different disciplines together, ranging from molecular medicine to nanotechnology. Materials science based on supramolecular interactions is an emerging field, which has made important steps forward in the past ten years. The self-assembly of small synthetic molecules into long-chain architectures gives rise to the careful design of supramolecular polymers or fibers based on highly directional, reversible, non-covalent interactions. Much afford is put into the development of supramolecular (polymeric) materials with true materials properties, both in solution and in the solid state. These supramolecular materials are beginning to reach the market in all kind of applications. The field of regenerative medicine in general and that of tissue engineering in particular is one of the most challenging areas in which supramolecular materials might have a high potential. In tissue engineering, the biological environment and the interactions of cells with the artificial biomaterial is of utmost importance for the functioning of the implant, i.e. the engineered tissue. Ideal biomaterials do not only have to fulfil the biomaterials trinity of tuneable mechanical properties, regulation of the degradability and the ease for bioactivity incorporation, but also have to mimic the natural environment where the materials are brought into. Therefore, a modular, self-assembly approach using several supramolecular building blocks is an exquisite way to produce such ''responsive'' biomaterials. It is proposed that the artificial materials described in this account have the same type of dynamic ability to adapt its biofunctionality as is so well known for the living cells in the host tissue. This account will highlight two systems, i.e. self-assembling oligopeptide fibers as pioneered by Stupp et al. and Zhang et al., and our hydrogen-bonded supramolecular polymers, to show the potential of a modular approach to dynamic biomaterials for tissue engineering.

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“…14,38,49,50 Although the low solubility of the UPy methacrylate monomer limited its incorporation to 10 mol % or less, a higher degree of control over the bulk properties can be achieved via this route by varying any number of parameters including the concentration of UPy's in the chain, the total molecular weight, and the type of comonomer. In particular, it has been demonstrated that the melt viscosity and adhesive properties of random copolymers of n-butyl acrylate and UPy-methacrylate 14 together with the creep compliance of random copolymers of ethylhexyl methacrylate and UPy-methacrylate 49 can be widely varied by the concentration of UPy's along the backbone.…”

Section: Introductionmentioning

confidence: 99%

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Feldman¹,

Kade²,

Meijer³

et al. 2010

Macromolecules

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Random copolymers consisting of n-butyl acrylate backbones with quadruple hydrogenbonding side chains based on 2-ureido-4[1H]-pyrimidinone (UPy) have been synthesized via controlled radical polymerization and postpolymerization functionalization. Through this synthetic strategy high UPy monomer content (15 mol %) can be reached while maintaining low polydispersity and excellent control over molecular weight, providing model reversible networks with well-defined molecular architecture. Despite low T g s and a lack of entanglements or crystallinity, these materials behave as thermoplastic elastomers through the strong but reversible association of UPy groups. Bulk properties such as the plateau modulus, tensile modulus, and relaxation time scale are primarily determined by the average distance between UPy's along the chain. Starting from a difunctional initiator, triblock copolymers can also be synthesized containing a homopolymer midblock and random copolymer end blocks, effectively concentrating the hydrogen-bonding groups near the chain ends. By controlling both the average composition and distribution of UPy's along the polymer chain, macroscopic material properties such as stiffness and resistance to creep can be independently tuned.

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Influence of Random Branching on Multiple Hydrogen Bonding in Poly(alkyl methacrylate)s

Cited by 65 publications

References 43 publications

Linear Viscoelastic and Dielectric Relaxation Response of Unentangled UPy-Based Supramolecular Networks

Linear Viscoelastic and Dielectric Relaxation Response of Unentangled UPy-Based Supramolecular Networks

Supramolecular Biomaterials. A Modular Approach towards Tissue Engineering

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

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