Synthesis, swelling behavior, and viscoelastic properties of functional poly(hydroxyethyl methacrylate) with ureidopyrimidinone side-groups

Lewis, Christopher L.; Anthamatten, Mitchell

doi:10.1039/c3sm27735f

Cited by 38 publications

(51 citation statements)

References 53 publications

(53 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These results are consistent with results for several other reported supramolecular polymers [63][64][65][66]. As discussed in the introduction, we predict that all our polymer samples are unentangled.…”

Section: A Linear Viscoelasticity and The Validity Of Ttssupporting

confidence: 82%

“…Generally, it is thus important to understand the rheological response for a proper control of the material behaviour. The effect of UPy addition on the linear viscoelasticity of supramolecular polymers has previously been investigated [20,[63][64][65][66]. However, few studies exist where the rheological response is characterised for a systematic variation of supramolecular side-group density [41,66,67].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

View full text Add to dashboard Cite

Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate based polymers for which the concentration of randomly distributed supramolecular side-groups are systematically varied. We perform a detailed investigation of the appplicability of Time Temperature Superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the "stickyRouse" model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the "sticky-Rouse" model, which includes more realistic assumptions with regards to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends and (iii) the chain motion upon dissociation of a sticker and re-association with a new co-ordination which involves a finite sized "hop" of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology. * k.j.l.mattsson@leeds.ac.uk 2

show abstract

Section: A Linear Viscoelasticity and The Validity Of Ttssupporting

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Cui

Boudara

Huang

et al. 2018

Journal of Rheology

View full text Add to dashboard Cite

show abstract

“…The HEMA‐HEMA(UPy) copolymers of that study initially showed a very fast swelling rate. However, at longer swelling times, for the hydrogels containing more than 6 mol% HEMA(UPy) co‐monomer contents, the rate of swelling decreased but an equilibrium swelling was not reached within even several months …”

Section: Introductioncontrasting

confidence: 77%

Impact of supramolecular interactions on swelling and release behavior of UPy functionalized HEMA‐based hydrogels

Maleki

Shokrollahi

Barzin

2018

Polymers for Advanced Techs

View full text Add to dashboard Cite

Supramolecular polymeric hydrogels based on copolymers of 2‐hydroxyethyl methacrylate (HEMA) and HEMA functionalized with ureidopyrimidinone (quadruple H‐bonding motifs and HU comonomer) were prepared at different HU comonomer ratios (PH‐Sn, n = HU mol%). For comparison, HEMA homopolymers (PH‐Cn, n = mol% of a chemical cross‐linker) were synthesized. In contrast to PH‐S0, PH‐Sn copolymers act like cross‐linked hydrogels and absorb large amounts of water while retaining shape. Viscosities of the hydrogels decreased, and elastic and loss moduli increased with increasing HU content. Compression modulus of the swollen PH‐Sn hydrogels increased with HU content and varied between 54 and 240 kPa. Study of metronidazole loading/release behaviors of PH‐S6 hydrogel against PH‐C6 revealed a negligible burst effect for the former and a sustained release that continued for about 120 hours. We conclude that modification of poly(2‐hydroxyethyl methacrylate) with HU through urethane linkages is an effective strategy to developing physical hydrogels with predictable behavior for biomedical applications.

show abstract

“…For example, hydrogen bonding copolymers of UPyMA with n-butyl acrylate, 11,19 2-ethylhexyl methacrylate, 20 and 2-hydroxyethyl methacrylate 21 have been syn-3 thesized by making use of either free or controlled radical polymerization method. With thermally tunable strength of association, these hydrogen bonding copolymers display stimuli responsive rheological behavior, and may be employed as shape memory, selfhealing, and adhesive materials.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2016

View full text Add to dashboard Cite

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.

show abstract

Synthesis, swelling behavior, and viscoelastic properties of functional poly(hydroxyethyl methacrylate) with ureidopyrimidinone side-groups

Cited by 38 publications

References 53 publications

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Impact of supramolecular interactions on swelling and release behavior of UPy functionalized HEMA‐based hydrogels

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

Contact Info

Product

Resources

About