Stimuli-Responsive Polymers in Solution Investigated by NMR and Infrared Spectroscopy

Summary: Temperature-induced and solvent composition-induced phase separation in solutions of poly(N-isopropylmethacrylamide) (PIPMAm) and other thermoresponsive polymers as studied by NMR and infrared (IR) spectroscopy is discussed. The fraction p of phase-separated units (units with significantly reduced mobility) and subsequently, e.g., thermodynamic parameters characterizing the coil-globule phase transition induced by temperature, were determined from reduced integrated intensities in high-resolution ¹H NMR spectra. This approach can be especially useful in investigations of phase separation in solutions of binary polymer systems. Information on behaviour of water during temperature-induced phase transition was obtained from measurements of ¹H NMR relaxation times of HDO molecules. NMR and IR spectroscopy were used to investigate PIPMAm solutions in water/ethanol (D₂O/EtOH) mixtures where the phase separation can be induced by solvent composition (cononsolvency). Some differences in globular-like structures induced by temperature and solvent composition were revealed by these methods.     

Polymer-Solvent Interactions in Solutions of Thermoresponsive Polymers Studied by NMR and IR Spectroscopy

Summary: NMR relaxation and diffusion coefficient measurements revealed that a portion of water molecules is bound in mesoglobules formed in poly(N-isopropylmethacrylamide) (PIPMAm) and poly(vinyl methyl ether) (PVME) aqueous solutions above the LCST, with fast exchange between bound and free states (residence time ∼1 ms). Two types of bound water molecules were assigned to water bound inside mesoglobules and on their surface. For highly concentrated PVME/D₂O solutions (c ≥ 20 wt%) a slow exchange was detected by NMR for bound water (residence time = 2.1 s). For PIPMAm aqueous solution IR spectra indicate a two-steps character of the phase transition. For PIPMAm in D₂O/ethanol (EtOH) mixtures the globular structures were observed by NMR at 298 K for certain compositions of the mixed solvent (cononsolvency effect). Virtually no EtOH is bound in these globular structures, in contrast to the temperature-induced globular structures.     

Phase Separation in Aqueous Polymer Solutions as Studied by NMR Methods

Some possibilities of ¹H NMR spectroscopy in investigations of structural-dynamic changes and polymer-solvent interactions during the temperature-induced phase transitions in aqueous polymer solutions are described. Results obtained recently on D₂O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm), negatively charged copolymers of N-isopropylmethacrylamide and sodium methacrylate, and PIPMAm/PVME mixtures are discussed. A markedly different rate of dehydration process in dilute solutions on the one hand, and in semidilute and concentrated solutions on the other hand, was revealed from ¹H spin-spin relaxation measurements.     

1H NMR relaxation study of polymer-solvent interactions during thermotropic phase transition in aqueous solutions

The dynamic-structural changes and polymer - solvent interactions during the thermotropic phase transition in poly(vinyl methyl ether) (PVME)/D₂O solutions in a broad range of polymer concentrations (c = 0.1-60 wt.-%) were studied combining the measurements of ¹H NMR spectra, spin-spin (T₂) and spin-lattice (T₁) relaxation times. Phase separation in solutions results in a marked line broadening of a major part of polymer segments, evidently due to the formation of compact globular-like structures. The minority (∼15%) mobile component, which does not participate in the phase separation, consists of low-molecular-weight fractions of PVME, as shown by GPC. Measurements of spin-spin relaxation times T₂ of PVME methylene protons have shown that globular structures are more compact in dilute solutions in comparison with semidilute solutions where globules probably contain a certain amount of water. A certain portion of water molecules bound at elevated temperatures to (in) PVME globular structures in semidilute and concentrated solutions was revealed from measurements of spin-spin and spin-lattice relaxation times of residual HDO molecules.     

Side-chain liquid crystalline copolymers with non-mesogenic comonomers – influence of comonomer content on the nature of the mesophase

Statistical copolymers with mesogenic and non-mesogenic comonomer units were synthesized by partial hydroboration of the 1,2-units of polybutadiene and subsequent conversion of the alcohol groups to mesogenic units. The nature of the LC phase proves to be dependent on the mesogen content. Below a certain content the smectic C phase vanishes, and the polymer becomes cypotactic nematic. T_g, T_s,n, T_n,i and ΔH_s,n depend on the mesogen content, whereas ΔH_n,i is independent. No difference can be detected between the phase behaviour of homopolymers and ABA-triblock copolymers with a liquid crystalline B-block and 10 wt.-% polystyrene A-blocks.     

NMR study of phase separation in D2O/ethanol solutions of poly(N-isopropylmethacrylamide) induced by solvent composition and temperature

¹H and ¹³C NMR spectroscopies were applied to investigate phase separation in solutions of poly(N-isopropylmethacrylamide) (PIPMAm) in D₂O/ethanol (EtOH) mixtures induced by solvent composition (cononsolvency) and temperature. Effects of EtOH content in D₂O/EtOH mixtures and temperature on the appearance and extent of the phase separation were characterized. Differences in mesoglobules formed during the phase separation induced by cononsolvency and temperature were found. For temperature-induced phase separation, ¹³C spin-spin relaxation times showed that besides the free EtOH expelled from the PIPMAm mesoglobules, there are also EtOH molecules bound in these mesoglobules. On the other hand, virtually no bound EtOH molecules were detected for mesoglobules formed as a consequence of the cononsolvency. For PIPMAm random copolymers containing negatively charged methacrylate units the phase separation induced by solvent composition was not observed.     

Rhodamine-conjugated acrylamide polymers exhibiting selective fluorescence enhancement at specific temperature ranges

A simple copolymer, poly(NIPAM-co-RD), consisting of N-isopropylacrylamide (NIPAM) and rhodamine (RD) units, behaves as a fluorescent temperature sensor exhibiting selective fluorescence enhancement at a specific temperature range (25–40 °C) in water. This is driven by a heat-induced phase transition of the polymer from coil to globule. At low temperature, the polymer exists as a polar coil state and shows very weak fluorescence. At >25 °C, the polymer weakly aggregates and forms a less polar domain within the polymer, leading to fluorescence enhancement. However, at >33 °C, strong polymer aggregation leads to a formation of huge polymer particles, which suppresses the incident light absorption by the RD units and shows very weak fluorescence. In the present work, effects of polymer concentration and type of acrylamide unit in the polymer have been investigated. The increase in the polymer concentration in water leads to a formation of less polar domain even at low temperature and, hence, widens the detectable temperature range to lower temperature. Addition of N-n-propylacrylamide (NNPAM) or N-isopropylmethacrylamide (NIPMAM) component to the polymer, which has lower or higher phase transition temperature than that of NIPAM, enables the aggregation temperature of the polymer to shift. This then shifts the detectable temperature region to lower or higher temperature.     

H NMR and IR study of temperature-induced phase transition of negatively charged poly(N-isopropylmethacrylamide-co-sodium methacrylate) copolymers in aqueous solutions

¹H NMR and IR spectroscopies were used to investigate the temperature-induced phase transition behaviour of poly(N-isopropylmethacrylamide-co-sodium methacrylate) [P(IPMAAm/MNa)] copolymers, containing in aqueous solutions negatively charged MNa units (i = 1-10 mol%), and the obtained results were compared with those obtained for poly(N-isopropylmethacrylamide) (PIPMAAm) homopolymer. For PIPMAAm/H₂O solution, IR spectra indicate that the transition temperatures for the hydrophilic CO groups are slightly higher (by ∼ 2 K) in comparison with hydrophobic CH₃ groups. The decreasing values of phase-separated fraction p_max and the decrescent hysteresis during gradual heating and cooling, both with increasing content of MNa units i in the copolymer, show that for copolymers with i ? 5 mol% the globular-like structures formed at temperatures above the respective LCST are rather porous and disordered with relatively low degree of polymer-polymer hydrogen bonding. While for P(IPMAAm/MNa) copolymers with i ? 5 mol% most water molecules are expelled from globular structures, for i < 5 mol% a certain portion of water (HDO) molecules is rather tightly bound in globular structures; at the same time no releasing process was detected for the bound water even for 90 h.     

Cloud point of poly(N-isopropylmethacrylamide) solutions in water: is it really a point?

Time-dependent phase separation/transition was observed in aqueous solutions of poly(N-isopropylmethacrylamide) in the temperature range 38–42°C. The time before the second phase appears is a function of temperature and may reach up to several hours.     

Structure Development in Flexible Polyurethane Foam-Layered Silicate Nanocomposites

Summary: Polyurethane foam nanocomposites were formed via in-situ copolymerisations, in which polyether polyol/water-montmorillonite mixtures were reacted with toluene diisocyanate. The unmodified Na⁺- montmorillonite (MMT) was swollen in polyol/water using an ultrasound technique resulting in intercalated layers with increased basal spacings of 2.3 ± 0.1 nm. Measurements of quasi-adiabatic temperature rise showed higher reaction rates as MMT loading increased from 0 to 10 wt.-%. Forced-adiabatic FTIR spectroscopy was used to determine the kinetics of both the copolymerisation and of the microphase separation between poly(ether-urethane) soft segments and polyurea hard segments. The apparent microphase-separation transition time decreased from 70 ± 3 to 42 ± 2 s upon addition of ≤10 wt.-% MMT, but at reaction times >100 s there was significant retardation of the development of hydrogen bonding in the urea groups of the hard-segment phase.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007     

Size-controlled synthesis of monodisperse core/shell nanogels

Small, monodisperse nanogels (∼50-nm radius) were synthesized by free-radical precipitation polymerization and were characterized using a suite of light scattering and chromatography methods. Nanogels were synthesized with either N-isopropylacrylamide or N-isopropylmethacrylamide as the main monomer, with acrylic acid or 4-acrylamidofluorescein as a comonomer and N,N′-methylenebis(acrylamide) as a cross-linker. By varying the surfactant and initiator concentrations, particle size was controlled while maintaining excellent monodispersity. An amine-containing shell was added to these core particles to facilitate subsequent bioconjugation. Successful conjugation of folic acid to the particles was demonstrated as an example of how such materials might be employed in a targeted drug delivery system.     

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid–ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T_c). Solutions of polymers containing 10% or less of AA display a constant T_c for pH above 5.5, with 15% there is a continuous increase in T_c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I ₁/I ₃ ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T_c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.     

Gel-sol transition in gellan aqueous solutions

Gel-sol transition of sodium type gellan solutions with and without salts is studied by dynamic viscoelastic measurements and differential scanning calorimetry (DSC). Mechanical spectra show that gellan aqueous solutions behave as an entangled polymer solution in the concentration range around 2 wt.-% at temperatures >15°C and as a weak gel below this temperature. Concentrated solutions (> 3 wt.-%) show a true gel behavior below 30°C. The two step transition is observed for 2∼3 wt.-% gellan aqueous solutions in thermal scanning rheological (TSR) measurements; the transition at a higher temperature is attributed to a coil-helix transition whilst the transition at a lower temperature is attributed to sol-gel transition. The transition observed in dilute solutions of gellan is attributed to the coil-helix transition whilst the sol-gel transition occurs simultaneously with coil-helix transition in more concentrated solutions (>3 wt.-%). The sol-gel transition temperature shifts to higher temperatures with increasing concentration of the added salts. Junction zones formed in the presence of divalent cations are far more heat resistant than those with monovalent cations judging from both DSC and TSR, however, the possibility of the formation of junction zones by covalent bonds or by ionic bonds is excluded.     

Effect of pressure on phase behavior in polymer blends of poly(2,6-dimethyl-1,4-phenylene oxide) and poly(styrene-co-p-fluorostyrene) copolymers

The effect of pressure on the miscibility of blends of poly(2,6-dimethyl-l,4-phenylene oxide) (PPO) with a random copolymer of styrene and para-fluorostyrene, P(S-co-p-FS), has been studied by high pressure differential thermal analysis (HPDTA). P(S-co-p-FS) copolymers less than 36 mole % p-FS are miscible with PPO in all proportions irrespective of pressure up to 200 MPa, using the customary criterion of a single calorimetric glass relaxation. P(S-co-p-FS) copolymers containing 40 to 50 mole % p-FS undergo phase separation upon annealing at elevated temperatures, indicating the existence of a lower critical solution temperature (LCST). In these blends, pressure displaces the phase boundary associated with the LCST to higher temperatures causing an apparent increase in polymer miscibility. The phase diagram for the blend of PPO and P(S-co-p-FS) containing 46 mole % p-FS, shows that the critical composition at about 50 wt % PPO does not change with pressure, but the consolute temperature T_c increases with increasing pressure. The pressure dependence of the LCST (dT_c/dP) of this system is about 0.35°C/MPa.     

Polymer‐solvent interactions during phase transition in poly(vinyl methyl eiher)/D2O solutions as studied by NMR methods

The structural‐dynamic changes and polymer‐solvent interactions during temperature‐induced phase transition in poly(vinyl methyl ether) (PVME)/D₂O solutions in a broad range of concentrations (0.1‐30 wt.‐%) were studied by ¹H NMR methods. In the whole concentration range the phase transition is manifested by line broadening (linewidth 350‐500 Hz) of a major part of PVME units, evidently due to the formation of globular‐like structures. Above the LCST transition, the fraction of phase‐separated PVME segments is equal to 0.8±0.1, independent of polymer concentration. While at low concentrations the transition is virtually discontinuous, at high concentrations the transition region is ∼ 3 K broad. Measurements of nonselective and selective ¹H spin‐lattice relaxation times T₁ of solvent (HDO) molecules evidenced that at elevated temperatures, where most PVME forms globular structures, a part of solvent molecules is bound to PVME forming a complex; the lifetime of the bound water (HDO) molecules is ≤2 s.     

Influence of crosslinker and ionic comonomer concentration on glass transition and demixing/mixing transition of copolymers poly(N-isopropylacrylamide) and poly(sodium acrylate) hydrogels

Hydrogels based on N-isopropylacrylamide and sodium acrylate as ionic comonomer were synthesized by free radical polymerization in water using N,N′-methylenebisacrylamide as crosslinker and ammonium persulfate as initiator. The glass transition of dried copolymers poly(N-isopropylacrylamide) (PNIPA) and poly(sodium acrylate) (SA) gels and demixing/mixing transition of PNIPA-SA hydrogels swollen with increasing amounts of water were studied using conventional differential scanning calorimetry. In the crosslinked polymers, the glass transition linearly increases, and the transition range becomes broader, with increasing crosslinker content. Increasing content of ionic comonomer also produces an increase of glass transition temperature, which moves to higher temperatures with higher sodium acrylate fraction. The influence of chemical structure of PNIPA-SA hydrogels on the lower critical solution temperature (LCST) of PNIPA-SA/water mixtures during heating and cooling was quantified as function of the content of the crosslinker and the ionic comonomer, as well as water content of the hydrogel in the range from 95 to 70 wt%. At parity of water content, the LCST occurs at higher temperatures for gels containing higher amounts of sodium acrylate. Similarly, the introduction of N,N′-methylenebisacrylamide causes an increase of the LCST, which grows with increasing of crosslinking degree of the hydrogel.     

Preparation of monodisperse polymer particles from 4-vinylpyridine

Dispersion polymerization of 4-vinylpyridine was performed by using polystyrene-block-polybutadiene as stabilizer in a mixture of N,N-dimethylformamide (DMF) and toluene to produce polymer particles. The weight ratio of the solvents affects the particle size and dispersity. In the range of DMF content from 5 to 20 wt.-%, uniform particles of a diameter of ca. 1 μm were obtained. The present system was expanded to the preparation of monodisperse particles of poly[(4-vinylpyridine)-co-(methacrylic acid)].     

The use of chebyshev polynomials orthogonal on a finite arbitrary system of points for interpolating changes in nematic-isotropic liquid phase transition temperatures in homologous series

Chebyshev polynomials Ψ _q (x) orthogonal on a finite arbitrary system of points x _i (i = 1−N) are used to interpolate changes in nematic-isotropic liquid phase transition temperatures t _c(x) in homologous series of liquid crystals (x = 1/n, where n is the number of the homologue). The expansion of the t _c(x) function into a series in Ψ _q (x) polynomials was found to be very effective. Already at q ≤ 3, this series describes the known types of the t _c(x) dependences with high accuracy and very small root-mean-square deviations for mesogenic molecules of various chemical structures and dimensions. The dependence of the limiting t _l = t _c(0) value on the form of X-shaped molecules and linear dimensions of N-mers with N rigid aromatic fragments linked with each other by flexible spacer chains was studied.

     

Model for the fracture energy of glassy polymer–polymer interfaces

The increase in the interfacial fracture energy (G_c) with increasing interfacial width (a_i) goes through a transition at a critical value of a_i that is unique to each polymer–polymer system. This transition point does not scale with the bulk entanglement spacing (d_t) for different systems, implying that the role of chain friction in reinforcing these interfaces is more important than previously thought. A theoretical model has been developed to calculate G_c as a function of the interfacial stress transfer due to individual polymer chains. When including the effects of chain friction only, the model reproduces the nonuniversal behavior of G_c with respect to a_i/d_t but yields poor fits for a_i/d_t > 1. The effects of entanglements are then added by calculating the fraction of entangled chains as a function of a_i/d_t. This contribution, although not material specific, matches the qualitative behavior of G_c for large values of a_i/d_t. When both contributions are included in the model, excellent fits are obtained for all data sets. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2377–2386, 2002