Search results for " polymers"

Rheological Consequences of Hydrogen Bonding: Linear Viscoelastic Response of Linear Polyglycerol and Its Permethylated Analogues as a General Model …

2014

Viscoelastic properties of linear, hydroxyl-functional polymers are only little understood with respect to the effect of functional group interactions. Melt rheology and thermal phase transitions of linear polyethers (polyglycerol, linPG-OH) and their methylated analogues (linPG-OMe) in a broad molecular weight range (Mn = 1–100 kg/mol) with low polydispersities (PDI) have been investigated as a general model for hydroxyl-functional polymers with respect to their functionality and hydrogen bond interactions. We provide detailed insight into the rheodynamics of nonentangled and well-entangled polyethers bearing one functional group per monomer unit. Booij–Palmen plots (BBP) revealed failure …

How Structure-Related Collapse Mechanisms Determine Nanoscale Inhomogeneities in Thermoresponsive Polymers

2012

Continuous wave electron paramagnetic resonance (CW EPR) spectroscopy on the amphiphilic spin probe TEMPO in solutions of selectively chosen functional, thermoresponsive poly(propylene oxide) (PPO)- and poly(ethylene oxide) (PEO)-based copolymers of both linear and branched structure is used to elucidate their host–guest interactions and inverse phase transitions. Three different fundamental types of host–guest interactions between probes and polymers could be correlated to the phase transition mechanisms (supported by MD simulations), evidencing that these proceed via nanoscale inhomogeneities of the polymers. Because of their ability to host small amphiphilic guest molecules, thermorespon…

A kinetic study of the formation of smectic phases in novel liquid crystal ionogens

2013

[EN] A multi-rate non-isothermal kinetic analysis of the isotropic-melt to liquid crystalline phase transition of novel liquid crystalline ionogenic copolymers, LCIs, the 10-(4-methoxyazobenzene-4'-oxy)decyl methacrylate]-co-2-(acrylamido-2-methyl-1-propanesulfonic acid)s, 10-MeOAzB/AMPS, copolymers, has been performed by means of calorimetric experiments. An analytical methodology which includes the study of the phase transition rate parameter, the determination of the activation energies by using Kissinger and Flynn-Wall-Ozawa models, and the study of the phase transition kinetics by the use of the Avrami theory, has been applied. The formation of the mesophases from the isotropic state o…

Third virial coefficient for 4-arm and 6-arm star polymers

2008

We discuss the computation of the third virial coefficient in polymer systems, focusing on an additional contribution absent in the case of monoatomic fluids. We determine the interpenetration ratio and several quantities that involve the third virial coefficient for star polymers with 4 and 6 arms in the good-solvent regime, in the limit of a large degree of polymerization.

Halogen bonding enhances nonlinear optical response in poled supramolecular polymers

2015

We demonstrate that halogen bonding strongly enhances the nonlinear optical response of poled supramolecular polymer systems. We compare three nonlinear optical chromophores with similar electronic structures but different bond-donating units, and show that both the type and the strength of the noncovalent interaction between the chromophores and the polymer matrix play their own distinctive roles in the optical nonlinearity of the systems. acceptedVersion Peer reviewed

Polymer stain resistance: Prediction versus experiment

2013

Switchable Supramolecular Crosslinking of Cyclodextrin-Modified Hyperbranched Polyethylenimine via Anthraquinone Dyes

2011

Two anthraquinone dyes, 5,8-di-N-adamantylamino-1,4-dihydroxyanthraquinone (AQ-OH) and 1,4-di-N-adamantylaminoanthraquinone (AQ-H), are synthesized. The combination of AQ-OH and AQ-H with hyperbranched polyethylenimine (PEI) bearing covalently attached β-cyclodextrin spontaneously formed host–guest complexes with hydrodynamic diameters of about 260 nm. Even enlarged structures of the trifunctional AQ-H were observed via DLS. Repeated measurements show that their assembly and disassembly is reversible with a critical point at 26 °C and therefore switchable via temperature. Also superstructures up to 100 μm were detected via TEM, cryo-TEM-, and SEM. Hence, a smart colored network of switchabl…

Crystallization of polymer melts under fast cooling. II. High-purity iPP

1992

SYNOPSIS Samples of a high-purity isotactic polypropylene (iPP) were quenched from the melt so as to monitor cooling history. A continuous variation of morphology and crystal structure was obtained with cooling rate. This is discussed in relation to sample thermal history evidencing that cooling history relevant to quenched samples is in the neighborhood of 90°C. In particular the samples are essentially mesomorphic when at this temperature cooling rates larger than 80°C/s were adopted, while below a few tens of °C/s only a­ monocline form is obtained. Densities of quenched samples were compared with predictions of an isokinetic extrapolation of Avrami model of polymer crystallization kinet…

Cooperative structure formation by combination of covalent and association chain polymers: 4. Designing functional groups for supramolecular structur…

1991

Abstract A small number of polar functional groups are attached to polybutadiene by a polymer analogous reaction. Depending on their molecular structure, different degrees of supramolecular ordering result from the aggregation of these polar groups. In the case of phenylurazole units, which carry a single site for hydrogen-bond complexation, binary contacts are formed; whereas linear association chain structures are formed in the case of polybutadiene carrying phenylurazole units additionally substituted with a carboxy group in meta or para positions of the phenyl ring. In the latter case, association chains aggregate cooperatively to an ordered supramolecular structure. The different struc…

A road less traveled to functional polymers: epoxide termination in living carbanionic polymer synthesis.

2010

Functional polymers possess tremendous potential both in academia and in industry. In particular, oxiranes offer manifold possibilities for the introduction of single hydroxyl or multiple orthogonal functionalities in carbanionic polymerization. Here, we present a brief overview of the fascinating possibilities arising from the employment of common as well as individually designed epoxide derivatives for the synthesis of end-functional polymers. Continuous flow techniques can be utilized for the rapid generation and screening of precisely defined hydroxyl-modified polymers. The utilization of functionalized polymers as precursors for the formation of complex macromolecular architectures (e.…