Local chain motions of poly(β-hydroxyoctanoate) in the bulk. 13C NMR relaxation study

Variable-temperature ¹³C NMR spin-lattice relaxation times (T₁) and Nuclear Overhauser Enhancements (NOE) at two magnetic fields have been used to study the dynamics of the amorphous part of a semicrystalline sample (33% of crystallinity) of poly(β-hydroxyoctanoate) (PHO). The interpretation of the relaxation data of the backbone carbons was made by employing a number of motional models. Among these, the DLM model offered the best interpretation of the relaxation data in terms of conformational transitions and librational motions of the backbone C? H vectors, and proved to be superior to unimodal distribution functions. The interpretation of temperature- and frequency-dependent T₁ and NOE data of the carbon nuclei in the n-pentyl side chain was made by employing a newly developed composite spectral density function for multiple internal C? C bond rotations of restricted amplitude and chain segmental motion. The temperature dependence of the linewidths of the various protonated carbon resonances of PHO has been discussed in terms of the semicrystalline character of this polymer. © 1995 John Wiley & Sons, Inc.     

Anisotropy of local relaxation properties of macromolecules. Spin-lattice relaxation of 13C nuclei,the nuclear overhauser effect and the estimation of parameters of an equivalent ellipsoid for kinetic segments of polymer chains

The expressions for the functions of spectral density at different orientations of the components of the internuclear vector with respect to the chain backbone, the frequency dependences of the spin-lattice relaxation time of ¹³C nuclei (T_1C) and the values of the nuclear Overhauser effect (NOE) were obtained for the tetrahedral lattice model of a polymer chain with three-unit kinetic elements. It was shown that peculiar features of the behavior of T_1C and NOE reflect the characteristic properties of the spectra of relaxation (correlation) times for “longitudinal” and “transverse” components of the internuclear vector. It was established that in the range of relatively short times of the relaxation spectrum the dynamics of an anisotropic kinetic segment of the chain may be described with the aid of a simple model of an elongated ellipsoid of rotation with an axial ratio of about 10. It is shown that the equivalent-ellipsoid model leads to significant differences from a more specific model of chain dynamics when a broad frequency range is considered.     

Study of the side-chain relaxation of methacrylate homopolymers and copolymers by the dielectric method

Dielectric constant and dielectric loss of copolymers of methyl methacrylate (MMA) with n-butyl methacrylate (nBMA) and isobutyl methacrylate (iBMA) have been measured in the frequency range 30 cps to 1 Mcps at temperatures from 70°K to 370°K. Results lead, together with those of previously published investigations on copolymers of MMA, to the following conclusions. (1) The loss-peak temperature attributed to side-chain relaxation (β peak) of PMMA varies with the comonomer ratio when the comonomer does not have an α-methyl group, but remains almost unchanged for comonomers having an α-methyl group. (2) In both cases, the β peak height of PMMA decreases with increasing ratio of comonomer B and completely vanishes for poly-B, and the loss peak temperature plotted against the fraction of B does not extrapolate to the β peak of poly-B. It is suggested on the basis of the above facts that the moving unit in the side-chain relaxation consists of a single side chain with a segment of the backbone chain and that the change in mobility of the side chain upon copolymerization results from the distortion of the helical structure of the backbone chain due to random distribution of α-methyl groups. Dielectric studies of the low-temperature side-chain relaxation (β₂ peak) in PnBMA, poly(n-octyl methacrylate), and poly(n-dodecyl methacrylate) (130°K at 1 kcps) have been made and an interpretation is offered for the molecular nature of this relaxation.     

A successive route to amphiphilic graft copolymers with a hydrophilic poly(3‐hydroxypropyl methacrylate) backbone and hydrophobic polystyrene side chains

A successive method for preparing novel amphiphilic graft copolymers with a hydrophilic backbone and hydrophobic side chains was developed. An anionic copolymerization of two bifunctional monomers, namely, allyl methacrylate (AMA) and a small amount of glycidyl methacrylate (GMA), was carried out in tetrahydrofuran (THF) with 1,1‐diphenylhexyllithium (DPHL) as the initiator in the presence of LiCl ([LiCl]/[DPHL]₀ = 2), at −50 °C. The copolymer poly(AMA‐co‐GMA) thus obtained possessed a controlled molecular weight and a narrow molecular weight distribution (M_w /M_n = 1.08–1.17). Without termination and polymer separation, a coupling reaction between the epoxy groups of this copolymer and anionic living polystyrene [poly(St)] at −40 °C generated a graft copolymer with a poly(AMA‐co‐GMA) backbone and poly(St) side chains. This graft copolymer was free of its precursors, and its molecular weight as well as its composition could be well controlled. To the completed coupling reaction solution, a THF solution of 9‐borabicyclo[3.3.1]nonane was added, and this was followed by the addition of sodium hydroxide and hydrogen peroxide. This hydroboration changed the AMA units of the backbone to 3‐hydroxypropyl methacrylate, and an amphiphilic graft copolymer with a hydrophilic poly(3‐hydroxypropyl methacrylate) backbone and hydrophobic poly(St) side chains was obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1195–1202, 2000     

Phosphorescence studies of relaxation effects in bulk polymers. II. Emission depolarization study of relaxation mechanisms in poly(methyl methacrylate)

Phosphorescence depolarization measurements, under steady state polarized excitation, have been used to examine the relaxation behavior of bulk poly(methyl methacrylate) (PMMA). Poly(methyl methacrylate) bearing phosphorescent labels has been synthesized by copolymerization of small quantities of acenaphthylene (I), 1-vinylnaphthalene (II), 2-vinylnaphthalene (III), 1-naphthyl methacrylate (IV), and 2-naphthyl methacrylate (V), respectively, with methyl methacrylate. In no case was depolarization of emission due to probe rotation apparent below the onset of the β-relaxation of the polymer. Rotation of label V was characterized by an activation energy of 94 kJ mole^?1 in excellent agreement with that of the β relaxation measured by conventional relaxation techniques. This result clearly implicates ester motion in the β relaxation. No motion of label I, which cannot move independently of the polymer backbone, was evident in the vicinity of the β relaxation. Above 378 K the activation energy for rotational relaxation of label I of 460 kJ mole^?1 is in excellent agreement with published data for the α transition in PMMA. This result is in accord with the general assumption that backbone segmental motion is involved in the α relaxation. However, backbone motion of lesser temperature dependence (E_a = 115 kJ mole^?1) is apparent from depolarization behavior of probe I between 343 and 378 K. Label II shows three regions of relaxation behavior. In the temperature range above the β transition motion of the label independent of the polymer is evident (E_a = 44 kJ mole^?1). At temperatures in excess of 343 K this motion becomes cooperative with that of the backbone yielding activation energies comparable to those obtained in system I. Label III, while exhibiting depolarization characteristics similar to those of label II in the vicinity of the β relaxation, emitted insufficient intensity to permit estimation of an energy of activation for the motion. The phosphorescence of label IV was completely depolarized over the entire temperature range studied. While phosphorescence intensity and lifetime data may be used to detect the existence of polymeric transitions, the photophysical behavior of the naphthalene species studied is independent of the attachment to the polymer and does not primarily yield information regarding the polymer relaxations.     

Dielectric study of low-temperature relaxations in poly(isobutyl methacrylate), poly(n-butyl methacrylate), poly(isopropyl methacrylate), and poly(4-methylpentene-1)

Isochronal measurements of dielectric constant and loss are made for poly(isobutyl methacrylate) (PiBMA), poly(n-butyl methacrylate) (PnBMA), poly(isopropyl methacrylate) (PiBMA), and poly(4-methylpentene-1) (P4MP1) at temperatures ranging from 4°K to 250°K. Loss peaks are found around 120°K (10–100 Hz) for PiBMA, PnBMA, and P4MP1. By comparing the activation energy with the calculated potential barrier for the internal rotation of alkyl group in the side chain, the motion responsible for the 120°K peak is concluded to be essentially the rotation of the isopropyl group as a whole for PiBMA and P4MP1 but, for PnBMA, the rotation of n-propyl group accompanied by the rotation of the end ethyl group. Multiple paths of internal rotation are involved with the 120°K peaks of PiBMA and, in particular, PnBMA, which explain differences between PiBMA and PnBMA in the broadness and the temperature location of the 120°K peak. The 120°K peak is in general assigned to a side chain including a sequence? O? C? C? C or ? C? C? C? C. PiPMA without this sequence in the side chain does not show the 120°K peak, but it exhibits the 50°K peak (1 kHz) like poly(ethyl methacrylate). The 50°K peak is assigned to the rotation of ethyl or isopropyl group attached to COO group. Poly-L-valine in which the isopropyl group is directly attached to carbon does not have the 50°K peak. An additional loss peak at 20°K (1 kHz) for P4MP1 is also discussed on the basis of the calculated potential.     

Effect of sub-Tg relaxations on chromophore reorientation in corona-poled polymers

Activation volumes for chromophore reorientation were measured for a series of guest–host polymeric materials, indicating a significant coupling between chromophore motion and the glassy α and β relaxation dynamics of the polymer host. The specific systems studied were formed by individually dissolving N,N-dimethyl-p-nitroaniline (DpNA), 4-(dimethylamino)-4′-nitrotolane (DMANT), 4-(diethylamino)-4′-nitrotolane (DEANT), and 1-((4-(dimethylamino)phenyl)ethynyl)-4-((4-nitrophenyl)ethynyl)benzene (DMAPEANT) in poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(isobutyl methacrylate) (PiBMA). In each of these systems, the isothermal, sub-T_g decay of the second-order optical susceptibility χ⁽²⁾ was monitored as a function of pressure using second harmonic generation. In each system, the observed decay of χ⁽²⁾ was represented by a stretched exponential equation from which the decay time τ₀ and decay distribution width β_KWW were determined. For each dopant molecule, the decrease in activation volume with the increasing size of the polymer host's alkyl side group and the pressure dependence of β_KWW were indicative of partial coupling between chromophore rotation and the glassy β relaxation dynamics of the polymer host. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1013–1024, 1998     

Molecular motions of tactic poly(2-hydroxyethyl methacrylate) in solutions studied by 13C-NMR relaxation measurement

The spin-lattice relaxation time and the nuclear Overhauser enhancement were measured using Bruker AM 300 spectrometer operating at 75.5 MHz for ¹³C to investigate the molecular motional characteristics and its tacticity effect for tactic poly(2-hydroxyethyl methacrylate) (PHEMA) as a function of temperature in dimethyl sulfoxide and methanol solvents. The observed relaxation data have been analyzed for both backbone motion and methyl internal rotation according to the log-χ² distribution model and the diamond-lattice model. The correlation times thus obtained for the molecular motions show that isotactic PHEMA is more flexible than syndiotactic counterpart. The syndiotactic PHEMA seems to have intramolecular hydrogen bonding which restricts the motion of C-2 carbon at temperatures below 35°C, whereas the isotactic one indicated no hydrogen bonding at all temperatures examined in this study. The methyl group of isotactic PHEMA shows a greater degree of freedom for the internal rotation than that of syndiotactic one. From the temperature dependence of correlation times, the activation energies for both backbone segmental motion and methyl internal rotation are obtained. The activation energies, 20 kJ/mol for backbone motion and 19 kJ/mol for methyl internal rotation, for isotactic PHEMA are substantially lower than the corresponding activation energies of 30 and 32 kJ/mol obtained for syndiotactic one. An examination of these energies indicates that methyl side group and backbone motions in tactic PHEMA are linked together.     

Photon correlation spectroscopy of syndiotactic poly (n-butyl methacrylate) near the glass transition

Slow relaxing longitudinal density fluctuations in bulk syndiotactic poly (n-butyl methacrylate) [PBMA] were studied by photon correlation spectroscopy as a function of temperature from 70 to 90°C. The shape of the light-scattering relaxation function broadened as the temperature approached the glass transition (T_g = 55°C). The average relaxation time shifted with temperature, consistent with previous studies of PBMA. The relaxation functions were analyzed in terms of a distribution of relaxation rates. The calculated distribution was clearly bimodal and the shape altered with temperature. The higher frequency peak in the distribution corresponds well with previous mechanical and dielectric relaxation studies of the intramolecular relaxation of the acrylate ester side chain. The resolution of the distribution into two modes is due to a well-defined side-chain motion with relaxation strength comparable to the primary glass-rubber relaxation. © 1994 John Wiley & Sons, Inc.     

Effect of polymer architecture on self‐diffusion of LC polymers

Two LC side‐group poly(methacrylates) were synthesized, and their melt dynamics were compared with each other and a third, main‐chain side‐group combined LC polymer. A new route was developed for the synthesis of the poly(methacrylate) polymers which readily converts relatively inexpensive perdeuteromethyl methacrylate to other methacrylate monomers. Self‐diffusion data was obtained through the use of forward recoil spectrometry, while modulus and viscosity data were measured using rotational rheometers in oscillatory shear. Diffusion coefficients and complex viscosity were compared to previous experiments on liquid crystal polymers of similar architecture to determine the effect of side‐group interdigitation and chain packing on center of mass movement. The decyl terminated LC side‐group polymer possessed an interdigitated smectic phase and a sharp discontinuity in the self‐diffusion behavior at the clearing transition. In contrast, the self‐diffusion behavior of the methyl terminated LC side‐group polymer, which possessed head‐to‐head side‐group packing, was seemingly unaffected by the smectic–nematic and nematic–isotropic phase transitions. The self‐diffusion coefficients of both polymers were relatively insensitive to the apparent glass transition. The presence of moderately fast sub‐T_g chain motion was supported by rheological measurements that provided further evidence of considerable molecular motion below T_g. The complex phase behavior of the combined main‐chain side‐group polymer heavily influenced both the self‐diffusion and rheological behavior. Differences between the self‐diffusion and viscosity data of the main‐chain side‐group polymer could be interpreted in terms of the defect structure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 405–414, 1999     

Dynamic relaxation behavior of copolymers of n-butyl methacrylate with n-butyl acrylate and of 2-hydroxyethyl methacrylate with ethyl acrylate,n-butyl acrylate,and dodecyl methacrylate

The effect of the α-methyl group on the mobility of the main and side chains of methacrylateacrylate copolymers has been investigated. Poly(ethyl acrylate) shows a small secondary loss maximum (attributed to the rotation of ? COOR side chains) at 145 K, while in the case of poly(n-butyl acrylate) this relaxation process is smeared out or possibly absent. On the contrary, poly(n-butyl methacrylate) and poly(2-hydroxyethyl methacrylate) exhibit secondary relaxations at about 278 and 301 K, respectively. From the dynamic mechanical response spectra of methacrylate-acrylate copolymers one can see that the removal of the α-methyl group causes a qualitative change in the molecular mechanism of the secondary relaxation, presumably as a consequence of the different participation of the main chains. The existing data, however, are insufficient to quantify these differences. The low-temperature relaxation attributed to internal motion within the side groups is not distinctly affected by the presence of α-methyl groups. If both components of the copolymer display the low-temperature relaxation (above 77 K), the loss maxima preserve their identity to a large extent. The effect of copolymer composition on the main (glass) transition temperature has been described by means of a one-parameter equation.     

Nuclear magnetic relaxation of α-13C nuclei of helical poly(γ-hexyl-L-glutamate) and poly(γ-benzyl-L-glutamate)

Spin-lattice relaxation times (T₁), spin-spin relaxation times (T₂), and nuclear Overhauser enhancements (NOE), at 75.5 MHz are reported for α-¹³C nuclei of poly (γ-benzyl-L -glutamate) in deuterated dimethylformamide at 60°C and of poly(γ-hexyl-L -glutamate) in cyclohexanone at 48 and 79°C. It is shown that for molecular weights above 10⁵, the polypeptides cannot be considered as essentially rigid helices with internal librational motions; additional backbone flexing motions contribute to the relaxation behavior.     

Comparative study of the mechanical relaxation behavior of polymethacrylates containing different bulky side groups

The syntheses of poly(1,3‐dioxan‐5‐yl methacrylate), poly(cis‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate), poly(trans‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate), poly(cis‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate), and poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) are reported. The mechanical relaxation spectrum of the simplest polymer, poly(1,3‐dioxan‐5‐yl methacrylate), exhibits a prominent β relaxation centered at ?98 °C, at 1 Hz, followed in increasing order of temperature by an ostensible glass–rubber relaxation process. In addition to the β relaxation, the loss curves of poly(trans‐2‐phenyl‐1,3‐dioxan‐5‐yl methacrylate) and poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) display in the glassy state a high activation energy relaxation, named the β* process, that seems to be a precursor of the glass–rubber relaxation of these polymers. The mechanical spectra of poly(trans‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) and poly(cis‐2‐cyclohexyl‐1,3‐dioxan‐5‐yl methacrylate) exhibit a low activation energy process in the low‐temperature side of the spectra, which is absent in the other polymers. The molecular origin of the mechanical activity of these polymers in the glassy state is discussed in qualitative terms. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1154–1162, 2002     

Effect of alkyl side chain length on the properties of polyetherimides from molecular simulation combined with experimental results

Three polyetherimides (PEIs) with the same backbone of Ultem 100 but different lengths of the alkyl side chains were simulated by using molecular dynamics and molecular mechanics techniques to investigate the effect of side chain length on their properties and physical mechanism behind. Simulation results, which are consistent to the experimental data, show that PEI‐5 with four methylene units in each alkyl side chain has higher T_g (glass transition temperature) and higher tensile strength, but lower tensile elongation at break than those of PEI‐6 with five and PEI‐8 with seven methylene units in each alkyl side chain. However, unlike the traditional phenomena, conformational analysis provides that PEI‐5 with the highest T_g gives the highest flexibility to the polymer chain, whereas PEI‐8 with the lowest T_g imparts the lowest flexibility resulting from attachment of longer alkyl side chain increase the rigidity of backbone. From the calculated ratio of the accessible volume to the total volume for each system, the highest ratio of PEI‐8 indicates that long alkyl side chains generate more free volume than short side chains, acting as an internal plasticizer in bulk structure. It is the internal plasticizing effect that is predominantly responsible for the abnormal properties, instead of the rigidity from side chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 595–599, 2010     

Switching of the helical polymer conformation in a solid polymer film

A chiral photochromic polyisocyanate was incorporated into a solid polymer matrix of poly(methyl methacrylate) (PMMA), yielding an isotropic polymer film. Isomerization of the chiral photochromic azo side groups (cis‐trans) triggers a reversible conformational change of the helical polyisocyanate backbone. Thus the chirooptical properties of the film can be switched photochemically. The isomerization of the helix is much slower than the isomerization of the azo side groups. Below T_g , the photochemically modified helix conformation is thus stable, despite thermal relaxation of the azo chromophores.     

Polymer Structures and Glass Transition: A Molecular Dynamics Simulation Study

Full atomistic molecular dynamics (MD) simulations on five polymers with different chain backbone (C—C, Si—O, and C—O) and different side groups (—H, one —CH₃, and two —CH₃) are performed to study the effects of chain flexibility and side groups on the glass transition of polymers. Molecular dynamics simulations of NPT (constant pressure and constant temperature) dynamics are carried out to obtain specific volume as a function of temperature for polyethylene (PE), poly(propylene) (PP), polyisobutylene (PIB), poly(oxymethylene) (POM), and poly(dimethylsiloxane) (PDMS). The volumetric glass transition temperature has been determined as the temperature marking the discontinuity in slope of the plots of V–T simulation data. Various energy components at different temperatures of the polymers are investigated and their roles played in the glass transition process are analyzed. In order to understand the polymer chain conformations above and below the glass transition temperature, dihedral angle distributions of polymer chains at various temperatures are also studied.     

Chain microstructure and conformation of partially quaternized poly(dimethylaminoethyl methacrylate)

¹H-NMR spectroscopy was used to establish the chain microstructure and conformation produced by the quaternization reaction of syndiotactic poly[2-(dimethylamino)ethyl methacrylate], a polymer with tertiary amino groups in the side chains. A chain microstructure with mini blocks of modified units was found by analyzing the N⁺CH₃ signal that was proved to be split in accordance with the composition triads. The macromolecular backbone changes its form by quaternization, from a close to an expanded coil, was confirmed by light scattering measurements and NOE spectra modifications. The two linked processes, the block formation and chain expansion can be the key in developing a reaction mechanism explaining both positive and negative deviations from a second-order kinetic model.     

A novel fluorine‐containing graft copolymer bearing perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains

A series of novel graft copolymers consisting of perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of thermal [2π + 2π] step‐growth cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of methyl methacrylate. A new aryl bistrifluorovinyl ether monomer, 2‐methyl‐1,4‐bistrifluorovinyloxybenzene, was first synthesized in two steps from commercially available reagents, and this monomer was homopolymerized in diphenyl ether to provide the corresponding perfluorocyclobutyl aryl ether‐based homopolymer with methoxyl end groups. The fluoropolymer was then converted to ATRP macroinitiator by the monobromination of the pendant methyls with N‐bromosuccinimide and benzoyl peroxide. The grafting‐from strategy was finally used to obtain the novel poly(2‐methyl‐1,4‐bistrifluorovinyloxybenzene)‐g‐poly(methyl methacrylate) graft copolymers with relatively narrow molecular weight distributions (M_w/M_n ≤ 1.46) via ATRP of methyl methacrylate at 50 °C in anisole initiated by the Br‐containing macroinitiator using CuBr/dHbpy as catalytic system. These fluorine‐containing graft copolymers can dissolve in most organic solvents. This is the first example of the graft copolymer possessing perfluorocyclobutyl aryl ether‐based backbone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

The effect of polymer side chains on vapor sorption in polyacrylate and polymethacrylate solutions

The segment fraction Ψ₁ activity coefficients, a₁/Ψ₁, of solvents have been determined by the piezoelectric sorption method for 0.1 ≤ Ψ₁ ≤ 0.5 in binary solutions of chlorinated methanes [carbon tetrachloride (CCl₄), chloroform (CHCl₃), and dichloromethane (CH₂Cl₂)] with aromatic hydrocarbons (benzene and toluene) in poly(methyl methacrylate), poly(methyl acrylate), poly(ethyl methacrylate), and poly(n-butyl acrylate) at 23.5°C. The present results for toluene in PMMA agree with previously published values obtained by gas-liquid chromatography. For CCl₄ and the aromatic hydrocarbons, the polymer–solvent interaction parameter χ is positive and constant, while for the polar solvents (CHCl₃ and CH₂Cl₂), χ is negative and increases with increasing Ψ₁. The effect of the polymer side chains on vapor sorption in nonpolar and polar solvent systems is discussed in terms of the χ parameter.