Configurational properties of aromatic polyesters: Dipole moments of poly(diethylene terephthalate) chains

Dielectric constants have been determined for a fraction of poly(diethylene terephthalate) in benzene at several temperatures. The data indicate that the dipole moment ratio 〈μ²〉/Nm² is somewhat higher than that of poly(ethylene oxide), and its temperature coefficient is in the vicinity of zero. Both the dipole ratio and its temperature coefficient are in very good agreement with those predicted by the rotational isomeric state theory. Using this theory, the unperturbed dimensions of poly(diethylene terephthalate) were calculated and it was found that (〈r²〉/M)_∞ = 0.80 Ų (g mol wt)^?1, a value intermediate between those of poly(ethylene oxide) (0.57) and poly(ethylene terephthalate) (1.05).     

Synthesis and gas barrier characterization of poly(ethylene isophthalate)

Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by ¹H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO₂ gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004     

Random-coil dimensions of poly(methylphenylsiloxane) and their dependence on stereochemical structure

Rotational isomeric state theory was used to study the unperturbed dimensions 〈r²〉₀ of poly(methylphenylsiloxane) (PMPS) chains [Si(CH₃)(C₆H₅)? O? ]_x as a function of their stereochemical structure. The required conformational energies were obtained from semi-empirical, interatomic potential energy functions and from known results on poly(dimethylsiloxane). PMPS chains were found to differ from monosubstituted and disubstituted vinyl chains primarily in the larger distance of separation between groups in conformations giving rise to “pentanetype interactions.” In PMPS, the relatively large distance of separation, 3.8 Å, makes such in teractions attractive, particularly in the case of two phenyl groups; in contrast, such interactions are strongly repulsive at the ～2.5 Å separation characterizing vinyl chains. According to the calculated results, PMPS chains are very different from vinyl chains in that increase in isotacticity should cause a significant decrease in 〈r²〉₀ and increase in d ln 〈r²〉₀/dT. Comparison of theory with experimental results in the literature suggests that PMPS polymers which have been studied in this regard must have been significantly syndiotactic in stereochemical structure.     

Random-coil dimensions and dipole moments of propylene–vinyl chloride copolymers

Mean-square unperturbed dimensions 〈r²〉₀ and dipole moments 〈μ²〉 have been calculated for propylene–vinyl chloride copolymers by means of rotational isomeric state theory. The calculations indicate that for these chain molecules 〈mu;²〉 is much more sensitive to chemical sequence distribution than is 〈r²〉₀, a conclusion in agreement with results of previous studies of ethylene–propylene copolymers and styrene-substituted styrene copolymers. In the case of propylene–vinyl chloride chains, both 〈r²〉₀ and 〈μ²〉 are most strongly dependent on chemical sequence distribution in the case of copolymers which are significantly syndiotactic in stereochemical structure. At equimolar chemical composition, increase in average chemical sequence length generally increases 〈r²〉₀ but decreases 〈μ²〉. Under some conditions, values of these statistical properties go through a minimum with increase in the reactivity ratio product r₁r₂, thus complicating the use of experimental values of these properties in the characterization of chemical sequence distributions in these copolymers.     

Conformational Analysis,RIS Models and Single‐Chain Properties of Structurally Modified Polycarbonates, 1. Effect of Cyclohexyl and Phenyl Ring Substitutions

Conformational properties of segments and chains of structurally different polycarbonates are investigated in detail. Conformational analysis and rotational isomeric state (RIS) models for some of the polycarbonates and single‐chain properties of all the polycarbonates are reported here for the first time. Substitution of the methyl group on the bisphenol phenyl rings results in increased energy barriers to rotations as well as changes in positions of local minima, compared to the case without substitutions. Conformational structure about the isopropylidene linkage C_α atom is not altered by ortho methyl substitutions on the rings. Substitution by a cyclohexyl ring rigidly attached to the C_α atom restricts conformational mobility within the bisphenol unit. Rotational flexibility of the phenyl–oxygen bond is hindered by additional substitutions on the cyclohexyl ring. The carbonate group prefers the trans–trans conformation in all the polycarbonates. The energy difference between the cis–trans and trans–trans states of the carbonate group is lowered by the ortho methyl substituent on the phenyl rings. There is a reduction in 〈R²〉, 〈S²〉, and C_n accompanying the substitutions. The introduction of other substituents on a cyclohexyl polycarbonate results in an increase in all chain dimensions including the persistence length. Also, the cyclohexyl or trimethylcyclohexyl substituents do not significantly alter the overall average shape of the chains. Substitutions both on the phenyl rings and at the isopropylidene linkage lead to a compaction of the polymer chain, but the effect is more pronounced when due to substituents on phenyl rings.     

Temperature dependence of unperturbed dimensions for stereoirregular 1,4-polybutadiene and poly(α-methylstyrene)

The temperature coefficient of chain dimensions, d ln〈r²〉₀/dT, was determined for stereoirregular 1,4-polybutadiene and poly(α-methylstyrene) via dilute solution viscometry. The 1,4-polybutadiene was examined in oligomeric 1,4-polybutadiene (an athermal solvent), and poly(α-methylstyrene) was evaluated under near-theta conditions using 1-chloro-n-alkanes as solvents. Both approaches minimize the potential for influence by specific solvent effects. The resulting temperature coefficients, ?0.1₀ × 10^?3 deg^?1 for 1,4-polybutadiene and ?0.3₀ × 10^?3 deg^?1 for poly(α-methylstyrene) are in excellent agreement with rotational isomeric state calculations.     

Crystallization of poly(ethylene terephthalate–co–isophthalate)

Melt crystallization behaviors of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐isophthalate) (PETI) containing 2 and 12 mol % of noncrystallizable isophthalate components were investigated. Differential scanning calorimetry (DSC) isothermal results revealed that the introduction of 2 mol % isophthalate into PET caused a change of the crystal growth process from a two‐dimensional to a three‐dimensional spherulitic growth. The addition of more isophthalate up to 12 mol % into the PET structure induced a change in the crystal growth from a three‐dimensional to a two‐dimensional crystal growth. DSC heating scans after completion of isothermal crystallization at various T_c's showed three melting endotherms for PET and four melting endotherms for PETI‐2 and PETI‐12. The presence of an additional melting endotherm is attributed to the melting of copolyester crystallite composed of ethylene glycol, tere‐phthalate, and isophthalate (IPA) or the melting of molecular chains near IPA formed by melting the secondary crystallite T_m (I) and then recrystallizing during heating. Analyses of both Avrami and Lauritzen‐Hoffman equations revealed that PETI containing 2 mol % of isophthalate had the highest Avrami exponent n, growth rate constant G_o, and product of lateral and end surface free energies σσ_e. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2515–2524, 2000     

Investigation on the dynamics of aromatic polyesters by means of high resolution solid state CPMAS 13C NMR

The dynamics of amorphous aromatic polyesters consisting of poly(ethylene terephthalate) (PET), poly(ethylene isophthalate) (PEI), and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) has been investigated by means of solid state CPMAS ¹³C NMR. Proton T₂, ¹³C T_1ρ, and proton T_1ρ decays have been measured in particular, and the experimental data fitted to suitable model functions to determine best relaxation parameters. The fitting results show for proton T₂ and ¹³C T_1ρ measurements the presence of two components with different relaxation times and intensities, arising from different motional domains. The proton T_1ρ, on the contrary, shows a single component which limits the dimensions of the two regions to less than 20 Angstroms. The dependence of ¹³C T_1ρ values on two different irradiating field strengths (H₁ = 38 KHz, H₁ = 60 KHz) allowed the assignment of each component to relatively rigid and mobile regions. By comparing the three polymers we observe that PEN and PEI have a similar relaxation behavior, while a higher fraction of mobile components was found for PET. These differences are believed to arise mainly from local motions of the aromatic rings. The relaxation measurements have been evaluated to suggest a correspondence to O₂ and CO₂ gas permeabilities in PET, PEI, and PEN. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1557–1566, 1998     

Molecular orientation in poly(ethylene terephthalate) by means of laser–raman spectroscopy

The intensity of the Raman scattering from uniaxially oriented amorphous poly(ethylene terephthalate) tapes at wave number shifts of 1732, 1616, 1286, 857, and 632 cm^?1 has been observed for various combinations of incident and scattered light polarization vectors with respect to the draw direction. An attempt has been made to analyze the data to provide values of 〈P₂(ζ)〉 and 〈P₄(ζ)〉, where P_n(ζ) is the nth order Legendre polynomial in ζ,ζ is the cosine of the angle between the draw direction and a typtical chain axis in the polymer, and the angle brackets denote the average value over all repeat units. This attempt was successful for the 1616 and 632 cm^?1 lines but less successful for the other three, although the data for the 1732 and 1286 cm^?1 lines could be analyzed to provide quantities proportional, but not equal, to 〈P₂(ζ)〉. In the analysis and discussion two possible models were considered for the conformation of the terephthaloyl residues in the amorphous polymer but it was not possible to reject either model conclusively. The results suggest, in agreement with previous studies by other methods, that the drawing of PET at 80°C takes place essentially as the extension of a rubberlike network which is frozen on subsequent cooling to room temperature.     

Preparation of poly(ethylene terephthalate-co-isophthalate) by ester interchange reaction in the PET/PEI blend system

Optimum conditions for the synthesis of PEI of considerable molecular weight have been established. Poly(ethylene terephthalate-co-isophthalate) (PETI) has been prepared through the ester interchange reaction of a blend of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI). NMR analysis has indicated that the PETI changes from a block-type copolymer to a random type copolymer as the ester interchange reaction proceeds. If the reaction is limited to 20 min, the resulting PETI is crystallizable. The effects of catalysts that have been used during the synthesis of PEI on the characteristics of PETI are also discussed. © 1997 John Wiley & Sons, Inc.     

Configurational statistics of poly(ethylene terephthalate) chains

The length of the span of the terephthaloyl residue in poly(ethylene terephthalate) guarantees independence of the conformations of successive repeating units of the chain. Interactions within units of the chain are amenable to interpretation by comparisons with related polymers; cis and trans conformations of the terephthaloyl residue are given equal weighting. The mean-square dimension ratio (〈r²〉₀/M)_∞ estimated on this basis is in substantial accord with the value deduced from experiments.     

Theoretical analysis of conformational energies,unperturbed dimensions,and dipole moments of poly(dichlorophosphazene)

A theoretical analysis of the conformational energies of poly(dichlorophosphazene) (PDCP) is presented. The results indicate that the bond pair P? N? P possesses a considerable conformational freedom, whereas the bond pair N? P? N is relatively rigid. This difference explains the low glass transition temperatures T_g and large end-to-end distances measured for polyphosphazenes. A statistical model containing four rotational isomers (ie., trans, gauche, cis, and negative gauche) is developed and used to calculate unperturbed dimensions and dipole moments of PDCP. The results, obtained at 25°C with n = 400 skeletal bonds (200 repeating units), were C_n = 〈r²〉₀/nl² = 13.5; C_T = 10³d(ln〈r²〉₀)/dT = ?3.0 K^?1; D_n = 〈μ²〉/nμ = 0.35; D_T = 10³d(ln〈μ²〉)/dT = ?3.4 K^?1. All the calculated magnitudes are extremely sensitive to the energy E_σ that controls the statistical weights of the conformations tg, tc, tg^?, gt, ct, and g^?t relative to tt for the bond pair P? N? P. A qualitative explanation for this sensitivity is discussed.     

Isolation and identification of cyclic oligomers of the poly(ethylene terephthalate)–poly(ethylene isophthalate) copolymer

New cyclic oligomers of the copolymer of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI) were isolated and identified. A condensation polymerization was carried out at a high temperature, and the solid‐state polymerization that followed yielded the high molecular weight polymer. The oligomers were extracted from the high molecular weight PET–PEI copolymer and separated with preparative high performance liquid chromatography techniques. Their chemical structures and properties were analyzed and determined by ¹H NMR, differential scanning calorimetry, and mass spectroscopy. The oligomers observed at early retention times were a cyclic dimer and cyclic trimers and consisted of [GT]₃, [GI]₂, [GI]₃, [GT]₂[GI]₁, and [GT]₁[GI]₂. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 881–889, 2003     

Unperturbed dimensions of isotactic poly(tert-butylethylene oxide)

The root-mean-square end-to-end distances of isotactic poly(tert-butylethylene oxide) fractions were determined in xylene at 80°C from intrinsic viscosity measurements and in o-dichlorobenzene at 80 and 100°C by light scattering. The characteristic dimension (〈L²〉₀/M)^1/2 was 1.04 × 10^?8 cm in xylene and 0.9 and 0.7 × 10^?8 cm in o-dichlorobenzene at 80 and 100°C, respectively. The value in xylene corresponds to a C_∞ of 15.9. This observation and the large negative temperature coefficient of (〈L²〉₀/M)^1/2 suggest that poly(tert-butylethylene oxide) exists in a helical block conformation under these experimental conditions. This conclusion is in agreement with earlier reported NMR measurements.     

Random-coil configurations of the polyformals. VI. Dipole moments of the stereochemically variable polymer prepared from 4-methyl-1,3-dioxolane

Mean-square dipole moments 〈μ²〉₀ for the (atactic) poly(4-methyl-1,3-dioxolane) chain [CH₂OCH(CH₃)CH₂O? ] were determined from dielectric-constant measurements carried out on two fractions dissolved in benzene. Simple examination of the chain structure leads to the predictions that this polymer should have a significantly larger value of 〈μ²〉₀ than poly(1,3-dioxolane) itself, but that 〈μ²〉₀ should be nearly independent of stereochemical structure. The first expectation is confirmed by the experimental results obtained, and the second by calculated results based on rotational isomeric state theory.     

Study of molecular motion of block copolymers in solution by high-resolution proton magnetic resonance

Molecular motions of hydrophobic–hydrophilic water-soluble block copolymers in solution were investigated by high-resolution proton magnetic resonance (NMR). Samples studied include block copolymers of polystyrene–poly(ethylene oxide), polybutadiene–poly(ethylene oxide), and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide). NMR measurements were carried out varying molecular weight, temperature, and solvent composition. For AB copolymers of polystyrene and poly(ethylene oxide), two peaks caused by the phenyl protons of low-molecular-weight (M?_n = 3,300) copolymer were clearly resolved in D₂O at 100°C, but the phenyl proton peaks of high-molecular-weight (M?_n = 13,500 and 36,000) copolymers were too broad to observe in the same solvent, even at 100°C. It is concluded that polystyrene blocks are more mobile in low-molecular-weight copolymer in water than in high-molecular-weight copolymer in the same solvent because the molecular weight of the polystyrene block of the low-molecular-weight copolymer is itself small. In the mixed solvent D₂O and deuterated tetrahydrofuran (THF-d₈), two peaks caused by the phenyl protons of the high-molecular-weight (M?_n = 36,000) copolymer were clearly resolved at 67°C. It is thought that the molecular motions of the polystyrene blocks are activated by the interaction between these blocks and THF in the mixed solvent.     

Photoresponsive biodegradable poly(carbonate)s with pendent o‐nitrobenzyl ester

Photoresponsive amphiphilic diblock poly(carbonate)s mPEG₁₁₃‐b‐PMNC_n with pendent o‐nitrobenzyl ester group were synthesized through ring‐opening polymerization (ROP) using 1,8‐diazabi‐cyclo[5.4.0]undec‐7‐ene (DBU) as catalyst and monomethoxy poly(ethylene glycol) (mPEG) as macroinitiator. In aqueous solution, the copolymers can self‐assemble to spherical micelles with a PC core and a PEG shell. The critical micelle concentration (CMC), size, and morphology of the micelles were demonstrated by means of fluorescence spectroscopy, transmission electron microscopes (TEM), and dynamic light scattering (DLS). Under UV light irradiation, the amphiphilic copolymer micelles disassembled because of the photocleavage of o‐NB ester, and the light‐controlled release behaviors of payload Nile red were further proved. This study provides a convenient way to construct smart poly(carbonate)s nanocarriers for controlled drug release. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2770–2780     

Mean-square Radius of Gyration of Poly[oxy(1-alkylethylenes)]

Taking account of the influences of both side groups and hetero-atoms in backbone, the mean-square radius of gyration of poly[oxy(1-alkylethylenes)] has been derived by the method of the rotational isomeric state approximation and matrix algebra. Numerical calculation with the parameters available in literature indicated that the dependence of 〈S²〉 on the molecular weight can be expressed as the general formula, 〈S²〉 = aM^b with b = 1 ± 0.02, for poly(oxypropylene), poly[oxy(1-ethylethylene)] and poly[oxy(1-tert-butylethylene)]. © 1997 John Wiley & Sons, Ltd.     

Influence of tertiary aromatic diamines on the n-buLi-initiated polymerization of isoprene in hexane solution

The influence of three aromatic tertiary diamines, bis(4-dimethylamino phenyl) methane (DMAPM), N,N,N′,N′-tetramethyl-p-phenylenediamine (p-TMPDA), and N,N,N′,N′-tetramethyl-o-phenylenediamine (o-TMPDA), on the kinetics of polymerization of isoprene in hexane solution, with n-BuLi as initiator, was studied for different values of ratio r = [amine]/[n-BuLi]. It is shown that added amine increases initiation rate according to its complexing ability (DMAPM < p-TMPDA « o-TMPDA); this result is explained by the formation of complexes between amine A and n-BuLi, (n-BuLi, A)_x, where x = 6, 4, and 1 for the three amines, respectively. The propagation rate and the structure of polyisoprene are modified with o-TMPDA only; the decrease in propagation rate and the increase in 3,4 units in the polymer obtained when r increases are assigned to the formation of solvated ion pairs PI^?Li⁺, o-TMPDA.     

Some INDO perturbation calculations of nJ(NC) values

Standard INDO parameters are used in ‘sum-over-states’ perturbation calculations of ⁿJ(NC) in a variety of molecular environments. Good agreement with the experimental data is, in general, obtained when the integral products S_N²(o)S_C²(o) and 〈r^?3〉_N〈r^?3〉_C assume the values of 35.167 a.u.^?3 and 4.980 a.u.^?3, respectively. For ‘pyridine-type’ nitrogen atoms the major contribution to ⁿJ(NC) usually arises from the orbital term whereas the contact term dominates the values of ⁿJ(NC) for ‘pyrrole-type’ and amino nitrogen atoms.