Dynamics of ESIPT fluorescent methylmethacrylate-benzazole dye copolymers

The dynamics of fluorescent methylmethacrylate-benzazole dye copolymers were investigated in different concentration regimes by dynamic light scattering. In the dilute regime the polymer behaves as typical polydisperse linear chains in good solvent with a dynamics dominated by a single fast mode. In the semidilute regime, the cooperative diffusion coefficient, D_coop and the correlation length, ξ could be obtained. Above the semidilute regime the intensity autocorrelation functions show two-step decays, indicating the existence of low range correlations. The dye incorporation, even though small, affects the copolymer dynamics behavior in concentrated solutions if compared to PMMA, which is probably ascribed to a polymer-solvent interaction.     

Dynamics of polymer molecules using neutron spin—echo

The dynamics of single polymer chains have been investigated in dilute solution and in the melt using the neutron spin—echo technique. In dilute solution the intramolecular motion is described to a first approximation by that for a Rouse chain incorporating hydrodynamic interactions (Zimm). It is characterised by an inverse correlation time which may be normalised by temperature, solvent viscosity and segment size, and which for long chains varies as Q³ at small scattering angles (Q is the change in wavevector on scattering). At very low Q vectors the predicted ‘universal’ regime is observed, but over most of the accessible range chemical structure also becomes important. For short chains, deviations from this Q³ behaviour are associated with overall molecular diffusion. In the melt, chain entanglements come into play and modify the simple Rouse-type motion. The correlation functions are described by a combination of Rouse motion over short distances and times and a long-time slow-motion predicted by the reptation model of melt dynamics.     

Role of entanglements and bond scission in high strain-rate deformation of polymer gels

A key factor that limits the practical implementation of polymer gels is low gel toughness. Here, we present coarse-grained molecular dynamics simulations of the effects of solvent molecular weight on the toughness of entangled and non-entangled polymer gels in the ballistic impact regime. Our results demonstrate that higher molecular weight solvents enhance gel toughness, and that mechanical properties including strength and toughness can be influenced by bond scission. Further, we find a remarkable two-step gel fracture mechanism on the molecular level: network chains undergo scission first (and well before fracture), followed by scission of solvent chains. For strain rates greater than inverse relaxation time of the solvent, long, highly entangled solvent chains provide fracture resistance even after the network chains break by effectively increasing the number of chains that must be broken as a crack propagates.     

Diffusion of poly(ethylene oxide) in semidilute aqueous solution: Dynamic light scattering and gradient diffusion

Gradient diffusion measurements and dynamic light scattering data are presented for semidilute aqueous solutions of narrow distribution (molecular weight M: 2.5 × 10⁴ – 1.2 × 10⁶) poly(ethylene oxide) fractions. Resolution of the time correlation function using bimodal analysis gave: (a) a fast mode, identical within experimental error to the classical gradient diffusion values; (b) a slow mode, interpreted as reflecting the translational motions of clusters of entangled chains. The results are similar to those found for other aqueous polymer systems, probably reflecting the ease with which association occurs between extended, polar, chains.     

Investigation of polyacrylonitrile solution inhomogeneity by dynamic light scattering

Dynamic light scattering (DLS) has been used to quantify nanoscale heterogeneity in the industrially significant polyacrylonitrile (PAN) polymer solution. The heterogeneity in polymer solution, traced by the ratio of amplitudes of the slow to fast mode, is observed to be related to various parameters, such as molecular weight of the polymer, the type of co‐monomer, processing time, concentration of the solution, and the choice of the solvents. It has been identified that low molecular weight PAN homopolymer have the least heterogeneity issues. Amongst the chosen co‐polymers for this study, similar degree of heterogeneity was observed at concentration slightly above the critical concentration at which the polymer chains begin to overlap. Whereas, at higher concentration, PAN‐methacrylic acid (4 wt%) copolymer showed the least heterogeneity issue. The aggregate diffusion coefficient of PAN‐methacrylic acid (4 wt%) copolymer solution in dimethylformamide (DMF) and N,N‐dimethylacetamide (DMAc) are respectively determined to be ～1.6 × 10^?12 cm²/s and ～1.6 × 10^?13 cm²/s, which results in an estimated aggregate size of 9 nm and 90 nm. POLYM. ENG. SCI., 55:1403–1407, 2015. © 2015 Society of Plastics Engineers     

The effect of additives,solvent type,and polymer concentration on macromolecule dimensions

An equation is derived to estimate the hydrodynamic volume occupied by a typical linear polymer molecule, knowing only the polymer molecular weight and concentration of polymer in the solution. This equation may be applied to solutions above a minimum polymer concentration. Accuracy of the equation is determined by comparing it to an established method of calculating macromolecule dimensions. Above dilute solution conditions, the volume pervaded by a macromolecule is affected mainly by the polymer molecular weight and concentration of polymer in the solution. Chain dimensions are generally unaffected by the type of polymer, solvent, or additive in the solution.     

Molecular dynamics simulation of a flexible polymer network in a liquid crystalline solvent; dynamical properties

Molecular dynamics simulation was performed for the systems consisting of a flexible regular tetrafunctional polymer network and a low molecular liquid crystal (LC) solvent. The LC solvent comprises of anisotropic rod-like semiflexible linear molecules composed of beads bonded by a FENE potential. Rigidity was induced by a bending potential, proportional to the cosine of the angle between neighbouring valence bonds. All interactions between non-bonded beads are described by the repulsive part of the Lennard–Jones potential. For comparison the simulations of the system of flexible polymer chains in a low molecular LC solvent and a system of pure low molecular LC solvent were also carried out. The influence of the network and linear chain polymer on the translational and rotational mobility of low molecular LC solvent was studied. The influence of the LC solvent ordering on the local translational mobility of the polymer chains was also observed.     

Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles

The synthesis of magnetite nanoparticles coated with a well-defined graft polymer is reported. The magnetite nanoparticles with an initiator group for copper-mediated atom transfer radical polymerization (ATRP), 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride. Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer consumption and a proportional relationship between molecular weight of the graft polymer and monomer conversion, thus providing well-defined, low-polydispersity graft polymers with an approximate graft density of 0.7 chains/nm². The molecular weight and polydispersity of the graft polymer were nearly equal to those of the free polymer produced in the solution, meaning that the free polymer is a good measure of the characteristics of the graft polymer. The graft polymer possessed exceptionally high stability and remarkably improved dispersibility of the magnetite nanoparticles in organic solvent.     

Viscoelasticity of magnesium neutralized telechelic poly(ethylene butylene) ionomer

The associative and mechanical properties of magnesium neutralized telechelic poly(ethylene butylene) ionomer, CTPEB-Mg, in a nonpolar solvent of decalin were studied from very dilute solution up to the bulk in the range of temperature from 15 to 55 °C with rheological methods and dynamic light scattering (DLS) technique. Dilute solution viscometry and DLS revealed that CTPEB-Mg molecules are associated as ring polymer in very dilute solution, followed by linear association of rings above polymer concentration C=1 wt%. The linearly associated rings formed huge polymeric clusters at around C=10 wt%, where the viscosity η of CTPEB-Mg solution increased thirty times over that of an esterified sample of CTPEB. A viscoelastic network was formed around C=15 wt%, above which disengagement of the magnesium dicarboxylate (MDC) ionic bond played a deterministic role for relaxation of the network up to the bulk. In referring to viscosity behaviors of the prepolymer CTPEB as well as esterified samples, changes in dynamic viscoelasticity of the network with increasing C were found to be closely related to corresponding changes in the average size of ionic clusters as well as fractions of elastically effective chains and dangling loops emanating from ionic clusters.     

A facile preparation of highly interconnected macroporous poly(d,l-lactic acid-co-glycolic acid) (PLGA) scaffolds by liquid-liquid phase separation of a PLGA-dioxane-water ternary system

Regular and highly interconnected macroporous scaffolds ranging in size from 50 to 150 μm were fabricated from poly(d,l-lactic acid-co-glycolic acid) (PLGA)-dioxane-water ternary systems via thermally induced phase separation (TIPS) without any surfactant or other additives. The effect on scaffold morphology of processing parameters including quenching temperature, polymer concentration, solvent composition and molecular weight, was investigated as a function of quenching time. The cloud-point temperature of the polymer solution was found to depend on polymer concentration, solvent composition, and polymer molecular weight. The water content in the solvent mixture had the greatest effect on the cloud-point temperature. The optimal quenching temperature for preparing macroporous inter-connected scaffolds from a 9 wt% PLGA solution (dioxane-water=87/13, by wt) was less than −7 °C. In low viscosity PLGA solutions, sedimentation of the polymer rich phase occurred due to the segregation of the separated phases under gravity. This led to the formation of scaffolds with irregular and closed pores.     

Lyotropic liquid crystal formation of polystyrene polymacromonomers in dichloromethane

Liquid crystallinity of dichloromethane (DCM) solutions of five samples of polymacromonomer F65 consisting of 65 styrene residues in each side chain was studied by birefringence observation and phase separation experiments at different temperatures in a molecular weight range from 9.4 × 10⁵ to 4.1 × 10⁶. Dilute-solution characterization was also made by light scattering and viscometry in DCM at 20 °C. The polymer concentration c_I on the phase boundary between the isotropic and biphasic regions was lower than the previously determined c_I for a polymacromonomer with a shorter side-chain length of 33 styrene residues at the same molecular weight, reflecting the higher chain stiffness and larger diameter of the F65 polymer. The molecular weight dependence of c_I for the two polymacromonomers (at 20 °C) was explained almost quantitatively by the scaled-particle theory for worm-like cylinders with the model parameters (the Kuhn length, the linear mass density, and the chain diameter) describing gyration radius and intrinsic viscosity data in DCM but without chain-end effect. It was concluded that this theory is capable of predicting the phase boundary concentration of brush-like polymers with essentially the same degree of accuracy as that known for linear, stiff chains.     

Diffusion of linear macromolecules and spherical particles in semidilute polymer solutions and polymer networks

The dynamics of fluorescently labeled linear macromolecules and spherical particles that are enclosed in semidilute polymer matrixes was studied by fluorescence recovery after photobleaching. The experiments were designed such that the transition from a semidilute solution to a permanent network could be covered. This was achieved by employing a matrix polymer, polyacrylamide, carrying pendant dimethylmaleimide groups. Stepwise irradiation of such samples in the presence of a triplet sensitizer causes successive dimerization of the maleimides leading to progressive crosslinking.Studies were performed with varying concentrations of matrix polymer (20-80 g L⁻¹) as well as different molar masses (200,000-1,300,000 g mol⁻¹) and particle radii (17 and 36 nm) of enclosed labeled probes. Results show notable differences between the behavior of linear and spherical tracers: while the mobility of flexible linear chains remains nearly unaffected by the transition from a semidilute polymer solution into a chemically crosslinked network, spherical tracers get completely immobilized when the degree of crosslinking exceeds a certain threshold.     

A tunable mixture solvent for poly(?-caprolactone): Acetone + CO2

We report on a tunable, versatile solvent system for poly(?-caprolactone) (PCL). It is shown that acetone + carbon dioxide mixtures are efficient solvents for this biodegradable polymer. Phase behavior and volumetric properties of PCL + acetone + CO₂ mixtures were determined in a variable-volume view cell. Effect of temperature (323-398 K), pressure (0.1-50 MPa), polymer concentration (1-20 wt%), polymer molecular weight (14k and 65k) and carbon dioxide concentration (0-60 wt%) on the liquid-liquid (L-L) phase boundaries and the densities was explored. Complete miscibility of mixtures with polymer concentrations up to 20 wt% could be achieved in the fluid mixtures containing up to 50 wt% carbon dioxide at modest pressures (5-40 MPa). The solutions all showed LCST-type phase behavior. Comparisons with literature data on the miscibility pressures in other solvent mixtures such as dimethyl ether + carbon dioxide or chlorodifluoromethane + carbon dioxide show that complete miscibilities of PCL in acetone + carbon dioxide mixtures are achievable at much lower pressures.The mixture densities were in the range 0.58-1.20 g/cm³. Mixtures with carbon dioxide content more than 20 wt% showed higher sensitivity and larger change in density with pressure. Densities of the polymer solutions were found to increase significantly with PCL concentration. The densities of solutions with different polymer molecular weights were close to each other, with the lower molecular weight polymer samples showing slightly higher densities.A unique contribution of the present paper is the comparison of compressibility and expansivity of the solutions with the corresponding properties of the solvents. Analysis of the data shows that the compressibilities of PCL solutions are lower than that of the acetone + carbon dioxide solvent mixture at temperatures lower than 373 K. At around 373 K, compressibilities become equal to each other and a switchover is observed at higher temperatures. The difference in the isothermal compressibility of the polymer solution and the solvent decreases with pressure, but reaches a plateau value for pressures greater than 25 MPa. Compared to their solvent mixture, the polymer solutions display a higher isobaric expansivity at the same pressure.     

Steady-state behavior of star polymers in dilute flowing solutions via Brownian dynamics

A bead and spring model is considered for the Brownian dynamics simulation of the behavior of regular star polymer chains in a dilute solution under both shear flow and extensional (or elongational) flow. Finite extensibility, excluded volume, and hydrodynamic interaction are taken into account to make the polymer model as realistic as possible. The behavior of star-like chains in flow is similar to that of linear and ring polymers. Thus, dependence of a given property with the arm molecular weight is analogous to that found for linear polymers when using the total molecular weight. In shear flow, the deformation of the chain and the shear rate viscosity dependence (the flow curve), are studied. We find a slope for the shear-thinning region of the flow curve close to −2/3. In elongational flow the coil-stretch transition is characterized by giving the relationship between the critical elongational rate and the arm molecular weight, which turns out to be similar to the power law found in linear chains.     

Synthesis, characterization and evaluation of amphiphilic diblock copolymer emulsifiers based on methoxy hexa(ethylene glycol) methacrylate and benzyl methacrylate

Linear, amphiphilic diblock copolymers based on the nonionic, hydrophilic monomer methoxy hexa(ethylene glycol) methacrylate (HEGMA) and the hydrophobic monomer benzyl methacrylate (BzMA) of different molecular weights and compositions were synthesized by group transfer polymerization. The molecular weights and comonomer compositions of these copolymers were characterized by gel permeation chromatography and proton nuclear magnetic resonance (¹H NMR) spectroscopy, respectively. Dynamic light scattering on aqueous solutions of the diblock copolymers indicated that all the copolymers formed aggregates whose size increased with the % w/w BzMA composition and with the overall molecular weight of the linear chains. Turbidimetry on 1% w/w aqueous copolymer solutions was used to determine the cloud points, which were found to increase with the composition in hydrophilic units and the linear chain molecular weight. After polymer characterization, xylene/water and diazinon (pesticide)/water emulsions were prepared using the above polymers as stabilizers at 1% w/w polymer concentration and at different overall organic phase/water ratios. At an organic phase/water mass ratio of 4/1, the lower molecular weight (2500 and 5000 g mol⁻¹) diblock copolymers provided stable single-phase o/w emulsions, matching the behavior of commercially available hydrophilic Pluronics.     

Thermal response of low molecular weight poly-(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) polymers in aqueous solution

Temperature-induced phase transition of three low-molecular-weight samples (M _w  < 1.2 × 10⁴) of poly(N-isopropylacrylamide) was studied with the aid of turbidimetry, dynamic light scattering, and rheology. We have demonstrated that the lower critical solution temperature depends on the length of the chain and the concentration of the polymer in the low molecular weight range. The turbidity results show a transition peak in the turbidity curve at intermediate temperatures. This peak, as well as the cloud point, is shifted toward lower temperatures when the molecular weight and the concentration of the polymer increase. The DLS measurements disclose a fast and a slow relaxation mode, which in both cases are found to be diffusive. The fast mode is linked to the diffusion of small species in the solution, and the slow mode is associated with the formation of large aggregates. The formation of these aggregates is less pronounced in solutions of polymers with low molecular weight and the incipient aggregation is shifted to higher temperatures. The shear viscosity measurements show the formation of weak aggregates, which are easily broken in solutions of short polymers. This effect is less pronounced when the molecular weight of the sample is increased. At certain shear rates, temperature-induced transition peaks of the viscosity are observed.     

Effects of solvent and concentration on scission of polymers with high-speed stirring

The effects of solvent and concentration on scission of polymers such as poly(methyl methacrylate) (PMMA) and polystyrene (PSt) in solution by high-speed stirring were investigated. Solvents were chloroform (good), benzene (intermediate), and ethyl acetate (poor) for PMMA and methyl ethyl ketone (good), toluene (intermediate) and dioxane (poor) for PSt, respectively. Concentration was varied from 0.04 to 2% w/v. The rate of scission of polymer chains was higher and the final molecular weight was lower in a good solvent than in a poor solvent at a low concentration for both polymers, but vice versa at a high concentration except for PSt in methyl ethyl ketone. Concentration dependence of the scission was large in a good solvent but small in a poor one. Polymer chains were ruptured to lower molecular weights with decreasing concentration, regardless of kind of polymer and solvent, showing that they were more easily broken in the isolated state.     

Upper critical solution temperature—type cononsolvency of poly(N,N-dimethylacrylamide) in water—organic solvent mixtures

The behaviour of linear poly(N,N-dimethylacrylamide) (PDMAM) chains was studied by turbidimetry and viscometry in mixtures of water with the polar organic solvents methanol, dioxane and acetone. The swelling-deswelling behaviour of PDMAM gels in the same solvent mixtures was also investigated. Contrary to the behaviour in water-methanol mixtures, in water-dioxane and water-acetone mixtures a significant shrinkage of polymer chains and deswelling of polymer gels, followed by phase separation, was observed for high organic solvent fractions. Cononsolvency phenomena were found to be temperature-dependent, as demixing occurred upon decreasing temperature. This upper critical solution temperature (UCST) phase separation behaviour in mixed solvents was studied by turbidimetry and compared to the well-known lower critical solution temperature (LCST) behaviour of poly(N-isopropylacrylamide) (PNIPAM) in similar solvents mixtures.     

Polymerization of vinyl ethers using titanium catalysts containing tridentate triamine ligand of the type N[CH2CH(Ph)(Ts)N]2

Titanium complexes having tridentate triamine of the type N[CH₂CH(Ph)(Ts)N]₂²⁻ in combination with methylaluminoxane (MAO) was able to polymerize ethyl vinyl ether in good yields. The polymers obtained in general were having molecular weight in the order of 10⁵ with narrow molecular weight distributions. Polymerization conditions had an impact on the molecular weight and the polydispersity index (PDI). Using chlorobenzene as the solvent the polymer had an M_n of 350?000 and PDI of 1.21, where as under neat conditions the M_n was 255?000 with PDI of 1.21. The type of solvent and the temperature dictated the polymerization rate and the polymer stereo regularity. The molecular weight of the polymer is distinctly governed by the polymerization temperature. Temperature ranging between −50 and ambient (30 °C) resulted in high molecular weight polymers and vice versa at a temperature of 60-70 °C resulted in low molecular weight polymers in moderate yields. The polymers obtained below 30 °C are highly stereo-regular compared to that of the ones produced at and above ambient temperature. The polymerization of iso-butyl vinyl ether (IBVE) was faster than that of linearly substituted n-butyl vinyl ether (BVE) and less bulky ethyl vinyl ether (EVE). The order of isotacticities of the polymers obtained are polyIBVE > polyBVE > polyEVE. The use of borate cocatalyst for activation generated narrow molecular weight polymers with a linear increase in the yield and molecular weight over time suggesting the living nature of the catalyst system.     

Aggregation behavior of new cyclic saturated copolymers synthesized via ring-opening metathesis polymerization

Cyclic saturated copolymers were prepared from 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodec-3-ene (MMT) with polar ester group and dicyclopentadiene (DCP) without polar group. This procedure consisted of ring-opening metathesis polymerization (ROMP) followed by hydrogenation. Monomer reactivity of DCP was higher than that of MMT; the monomer reactivity ratio r_DCP/r_MMT varied from 2.135 to 1.159 in a temperature range from 80 to 130 °C. These kinetic results indicated that the copolymer had distribution of DCP composition in a macromolecule chain, which could provide the interesting aggregation behavior. The aggregation behaviors of the hydrogenated copolymer and the homopolymer in various solvents were also examined using dynamic light scattering (DLS) and static light scattering (SLS). DLS analysis indicated that the fast mode in each polymer is attributed to the diffusive motion of each single polymer chain, while the slow mode in the copolymer is caused by aggregated polymer. The aggregation degree of the copolymer decreased with increasing hydrophobicity of solvent, decreasing polymer concentration, decreasing molecular size of solvent and increasing temperature. Based on these findings, the mechanism of aggregation behavior was clarified that the DCP-rich unit in a macromolecule might be acting as core to give the aggregation in poor solvent.