Characterization of diene polymers. I. Infrared and NMR studies: Nonadditive behavior of characteristic infrared bands

Extinction coefficients of the characteristic infrared bands due to isomeric structural units were measured for polybutadiene and polyisoprene in CS₂ or CCl₄ solutions and were compared with the isomer composition determined by NMR. The NMR signal assignments were made on the basis of the spectra of deutero derivatives of the polymers. In the case of polyisoprene, linear relations were obtained between the extinction coefficients and the isomer contents determined by NMR for the absorption bands at 1385 cm^?1 (characteristic of trans-1,4 units), 1376 cm^?1 (cis-1,4 units), and 889 cm^?1 (3,4 units). However, for the absorption bands at 840 cm^?1 (characteristic of cis-1,4 and trans-1,4 units), isomerized polyisoprenes did not give such a linear relationship. In polybutadiene, the extinction coefficient for the atactic 1,2 units was found to be lower than that of the syndiotactic 1,2 unit. These experimental facts lead to the conclusion that additivity of the extinction coefficients does not always hold for diene polymers. The deviation from the linear relation may be associated with regular sequences of one isomeric conformation in the chain.     

Infrared spectra of cyclic ethers and their derivatives

Data for the characteristic bands of cyclic ethers are reviewed. The infrared spectra of a number of 2-mono- and 2, 5-di-substituted derivatives of tetrahydrofuran are investigated. Absorption bands at about 900 cm⁻¹ are related to pulsation vibrations, and those at about 1200 cm⁻¹ to antisymmetric skeletal vibrations, of the tetrahydrofuran ring. It is shown that to confirm the presence of a tetrahydrofuran ring in a molecule, it is necessary to take into account not only the band of valence antisymmetric vibrations of the group C-O-C (ν _C-O-C ^as 1075 cm⁻¹), but also bands due to ring pulsation vibrations (ring symmetric valence vibrations ν _sk ^s ∼ 900 cm¹).     

Spectroelectrochemical study of poly-3,4-ethylenedioxythiophene films in the presence of different supporting electrolytes

Steady-state absorption spectra of poly-3,4-ethylenedioxythiophene (PEDOT) films at different oxidation degrees and their differential cyclic voltabsorptograms are studied in 0.1 M LiClO₄, Bu₄NBF₄, and Bu₄NPF₆ solutions in acetonitrile. Three major absorption bands are obtained in the film electronic spectra: a complex band with a pronounced maximum at λ = 600 nm that corresponds to π → π* electronic transitions in reduced fragments of a PEDOT film and two absorption bands (at λ_max = 850 nm and λ_max > 1100 nm) corresponding to two oxidized film fragments. It is shown that the position and shape of absorption bands are practically independent of the nature of dopant anions, which points to the absence of pronounced interactions with positively charged polymer fragments. An attempt is made to analyze the obtained spectroelectrochemical data qualitatively to estimate the extinction coefficients and concentrations of absorbing particles and their variation in the course of redox processes.     

IR spectra of long-chain α,ω-alkanediols: 1,22-docosanediol and 1,44-tetratetracontanediol

The IR absorption spectra of α,ω-alkanediols with different chain lengths, HO(CH₂)₂₂OH and HO(CH₂)₄₄OH, in the spectral range of 400–5000 cm^?1 are analyzed. The assignment of numerous absorption bands to vibration modes in short methylene sequences and terminal hydroxyl groups is suggested. The splitting of IR absorption bands into doublets at 720–730 cm^?1 (rocking vibrations of CH₂ groups) and 1463–1473 cm^?1 (bending vibrations of CH₂ groups) testifies that the crystal unit subcells in the lamellae of alkanediols are orthorhombic with parameters typical of normal hydrocarbons. The specific features of absorption bands due to O-H stretching and C-O-H bending vibrations have been analyzed. These bands appear during formation of lengthy associates from hydrogen bonds formed by hydroxyl groups on the surface of elementary lamellae. A sharp increase in the intensity of the absorption bands in progression of C-C stretching and CH₂ wagging vibrations due to the anharmonic Fermi resonance with the stretching vibrations of C-O groups in the terminal hydroxyl groups has been detected.     

Raman spectral changes during the solid-state polymerization of diacetylenes

Raman spectral changes resulting from the solid-state 1,4-addition polymerization of conjugated diacetylenes are reported. The monomers show an intense C?C stretching frequency near 2260 cm^?1, where as the polymers showed two strong bands, a C?C vibration near 2100 cm^?1 and a C?C vibration near 1500 cm^?1. The presence of both double and triple bonds in the polymers suggests the backbone structure (?C? C?C? C?)_n. The alternate mesomeric structure (? C?C?C?C? )_n can be eliminated as a possibility by the presence of the strong C?C vibration in the polymer. Sequential Raman spectra obtained during radiation-induced polymerization revealed intermediate spectral states between the initial monomer and final polymer. Intermediate-state vibrations first increase and then decrease in intensity as polymerization proceeds. However, the observed vibtrational frequencies of intermediate states were not dependent upon the extent of polymerization. Whether polymerization occurred thermally or as a result of radiation did not appear to influence the spectrum of the final polymer, but the observed number of intermediate states differed. Polymerization mechanisms, required molecular motions, and resulting structural changes are discussed.     

Rate coefficients for the gas‐phase reaction of OH radicals with selected dihydroxybenzenes and benzoquinones

Rate coefficients have been determined for the gas‐phase reaction of the hydroxyl (OH) radical with the aromatic dihydroxy compounds 1,2‐dihydroxybenzene, 1,2‐dihydroxy‐3‐methylbenzene and 1,2‐dihydroxy‐4‐methylbenzene as well as the two benzoquinone derivatives 1,4‐benzoquinone and methyl‐1,4‐benzoquinone. The measurements were performed in a large‐volume photoreactor at (300 ± 5) K in 760 Torr of synthetic air using the relative kinetic technique. The rate coefficients obtained using isoprene, 1,3‐butadiene, and E‐2‐butene as reference hydrocarbons are k_OH(1,2‐dihydroxybenzene) = (1.04 ± 0.21) × 10⁻¹⁰ cm³ s⁻¹, k_OH(1,2‐dihydroxy‐3‐methylbenzene) = (2.05 ± 0.43) × 10⁻¹⁰ cm³ s⁻¹, k_OH(1,2‐dihydroxy‐4‐methylbenzene) = (1.56 ± 0.33) × 10⁻¹⁰ cm³ s⁻¹, k_OH(1,4‐benzoquinone) = (4.6 ± 0.9) × 10⁻¹² cm³ s⁻¹, k_OH(methyl‐1,4‐benzoquinone) = (2.35 ± 0.47) × 10⁻¹¹ cm³ s⁻¹. This study represents the first determination of OH radical reaction‐rate coefficients for these compounds. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 696–702, 2000     

Infrared spectrum of benzene in bromine and carbon tetrachloride solutions

The benzene—bromine complex at room temperature has been re-studied by infrared with bromine in excess of benzene. Solutions of 0.225 M benzene in bromine—carbon tetrachloride mixtures were studied. Under this condition, the spectral changes of measurable benzene absorption bands were observed more clearly than previously. The out-of-plane vibrations of benzene were observed to shift to higher frequencies. The equilibrium constant was found to be 0.11 ? mole^?1. The accord with the equilibrium constant derived from benzene rich systems supports the concept of a specific interaction. A C_6V symmetry is favoured for the geometry of the complex.     

Interaction of calf thymus DNA with N,N′-Bis(3,4-dihydroxybenzylidene)-1,2-diaminobenzene ligands

In the present study, at first, N,N′-bis(3,4-dihydroxyhenzylidene)-1,2-diaminobenzene (BDBDAB), has been synthesized by combination of 1,2-diaminobenzene and 3,4-dihydroxybenzaldehyde in a solvent system. These ligand containing ortho-quinone functional groups were characterized using UV-VIS and IR spectroscopies. Subsequently, the interaction between native calf thymus deoxyribonucleic acid (ct-DNA) and BDBDAB was investigated in 10 mM Tris-HCl buffer solution, pH 7.2, using UV-visible absorption and fluorescence spectroscopies, thermal denaturation technique, viscosity measurement, and cyclic voltametry. From spectrophotometric titration experiments, the binding constants of BDBDAB with double stranded DNA were found to be (0.9 ± 0.1) × 10⁴ M⁻¹. The magnitude of the interaction between the ligands and DNA can be quantified by using the Stern-Volmer equation. From the plot of I ₀/I versus [DNA]/[BDBDAB] the quenching constants (K _SV) were obtained and found to be 5.6 ± 0.2. Thermal denaturation experiments represent the increasing of melting temperature of DNA (about 3.2°C) due to binding of BDBDAB. There is no increasing of viscosity was observed in addition of BDBDAB to DNA. The electroactivity of the quinone moiety in N,N′-bis(3,4-dihydroxybenzylidene)-1,2-diaminobenzene bound to DNA could be employed as cyclic voltametry to obtain binding constant. These results suggest that interaction with the grooves could be the principal mode of binding of BDBDAB to double stranded ct-DNA.     

Cationic polymerization of 1,3-pentadiene I. infrared, 1H-NMR and 13C-NMR investigations on the microstructure of poly(1,3-pentadiene) synthesized with cationic catalysts

This study deals with cationic polymerization of the cis- and trans-isomers of 1,3-pentadiene. The microstructure of the polymer chains is studied by ¹H-NMR, ¹³C-NMR and IR spectroscopies. It is shown that the trans-diene gives strictly trans-1,4 and trans-1,2 residual linear insaturations, whereas the cis-isomer yields also cis-1,4, cis-1,2 and 3,4-units whose overall content can reach 10 mol-%. According to the cyclization degree of the macromolecules, ranging from 30 to 70 mol-%, the number of trans-(1,2+1,4) units varies between 33 to 65 mol-% and that of trans-1,2 units between 4 and 20 mol-%. An analytical method is proposed to evaluate the average number of rings present in the polycyclic sequences. It is found that the cyclic fragments of the polymer chains consist of bi- or tri-cyclohexane fused rings containing α tetrasubstituted double bond.     

Infrared spectra of cyclic ethers and their derivatives

The IR spectra of six monosubstituted and of four 2,6-disubstituted 1,4-dioxanes have been studied in the 650–1800cm^–1 region. The assignment of the bands due to the vibrations of the 1,4-dioxane ring and to the deformation vibrations of the methylene groups of the ring is given. The appearance of a whole series of new absorption bands on passing from unsubstituted 1,4-dioxane to its derivatives is explained by the change in the symmetry of the molecule and the removal of the prohibition from the vibrations previously inactive in the IR spectra connected with this reduction in symmetry. It is proposed to use, in order to confirm the presence of a 1,4-dioxane ring in a molecule from the results of IR spectroscopy, not only the 1126-cm^–1 band but the whole group of bands lying in the frequency ranges 800–950, 1000–1150, and 1200–1300 cm^–1.For part I, see [3].     

Effect of morphology and degree of crystallinity on the infrared absorption spectra of linear polyethylene

The infrared absorption spectra of selected crystalline and noncrystalline bands were studied in bulk-crystallized specimens of linear polyethylene which encompassed the extremely wide density range of 0.92–0.99 g./cm.³. The analysis of the data obtained at room temperature yield degrees of crystallinity by infrared methods which are in very good accord with the values deduced from the density measurements. Studies of the infrared spectra as a function of temperature give fusion curves which are in agreement with those obtained by thermodynamic methods. However, in order to obtain these latter results cognizance must be taken of the large negative temperature coefficient of the specific extinction coefficients of the crystalline bands from room temperature to the melting point. The necessary data to account for this phenomena were obtained from studies of the spectra of the n-paraffin, C₉₄H₁₉₀, where molecular crystals are formed. Analysis of the two gauche bands, at 1352 and 1303 cm.^?1, which are assigned to the noncrystalline regions demonstrate that for bulk-crystallized samples of lowest densities the intensity ratio at room temperature is identical to that expected from the pure melt at this temperature. The conclusion is thus reached that the noncrystalline regions in these cases and the pure melt are structurally very similar. For samples of higher density, where the crystallite size is comparable to the extended chain length, the intensity ratio of the two gauche bands is altered. This change could reflect a change in the sequential distribution of gauche bonds. This intensity ratio for crystals formed from dilute solution is very similar to that for the high-density bulk-crystallized material and indicates a similarity in structure of the noncrystalline regions in the two cases.     

Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1-Vinylcyclohexene (VCH)

We report the first anionic polymerization of 1-vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2-disubstituted 1,3-diene proceeded quantitatively in cyclohexane at 25 °C with sec-butyllithium as an initiator. The obtained polymers have well-controlled molecular weights in the range of 5 to 142 kg mol⁻¹, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ ¹H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (r_Sty=2.55, r_VCH=0.39). P(VCH) obtained in cyclohexane with sec-BuLi as an initiator showed both 1,4- and 3,4-incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4-microstructure (up to 78 %) and elevated glass-transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well-defined polymer architectures and materials.     

1,2 Enriched polymerization of isoprene by cobalt complex carrying aminophosphory fused (PN3) ligand

Metal-catalyzed selective isoprene polymerization has been a major entry toward cis-1,4, trans-1,4, and 3,4 isomers of polyisoprene, however, 1,2 selective polymerization of isoprene has not yet been achieved due to the steric problem. In this work, difluoro cobalt complexes carrying aminophosphory (-HN-P(=O) ^tBu₂-) fused pyrazol-pyridine ligand has been prepared and characterized. In combination with Mg^n-Bu₂, the formed catalyst unprecedentedly converts isoprene to polyisoprene with 1,2 enchainment up to 50 mol% in a molecular weight controlled polymerization mode. The resultant polymers are fully characterized by NMR, IR, DSC, and GPC. The 1,2 incorporation of polyisoprene is weakly dependent on feeding of Mg^n-Bu₂ and reaction temperature. The weak affinity between Mg²⁺ and allylic terminal of propagating chain is possible for the unique 1,2 irregular insertion and non-irreversible chain transfer and termination reactions throughout the chain propagation. The ability of current catalyst demonstrates a big advantage for application in the development of 1,2 selective polymerization of isoprene, and a potential for access to a new family of polyisoprene. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2286–2293     

Origin of the doublet at 1360 and 1340 cm−1 in the Raman spectra of tryptophan and related compounds

Raman spectra of indole, skatole, tryptophan and its derivatives including C₄-monodeuterated tryptophan were studied with special attention to the origin of the band around 1350 cm⁻¹. The band is observed as a doublet or triplet depending on the compound and solvent, which was ascribed to Fermi resonance between one fundamental and one or two combination bands of the out-of-plane bending vibrations. Removal of the interaction is seen for C₄D-tryptophan and some solutions of skatole. The assignments of the component vibrations were made based on the shifts in frequencies upon C₄-deuteration. In tryptophan derivatives the doublet (or triplet) peaks exhibit steep changes in relative intensity at the pK_a points of the dissociable groups, which is ascribed as arising from slight frequency shifts of a pK_a-sensitive component vibration. Relations between the relative intensity and environment of indole were obtained and their possible applicability to the analyses of Raman spectra of proteins is suggested.     

IR spectra of substituted pyrroles

The IR spectra of 52 substituted pyrroles, including 24 1-vinylpyrroles, were thoroughly analyzed. The principal analytical bands of the pyrrole ring and the vinyl group were isolated. Doublet character of the bands of the stretching vibrations of the double bond ( ^v C=C) and the C-H (CH₂=) out-of-plane deformation vibrations, which indicates the presence of rotational isomerism relative to the N-vinyl bond, was detected. The integral intensify of the principal component of the ^v C=C doublet was measured for 12 of the 1-vinylpyrroles, and it is shown that it is practically independent of the structure of the alkyl substituents in the ring. Proof for the existence of a nonplanar gauche conformation for the 1-vinylpyrroles was obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 910–914, July, 1977.     

The effect of additives of strong inorganic acids on IR-spectroscopic determination of water in organic solutions

The possibility of the quantitative determination of water in organic solvents containing strong acids by IR spectrophotometry at 3500–3700 cm^?1 was studied. The molar absorption coefficients at the maximum of the most intense absorption bands of water in acetonitrile, chloroform, and 1,2-dichloroethane were 115, 43, and 88 M^?1 cm^?1, respectively. The study of the effect of acid additions to acetonitrile showed that hydrochloric and nitric acids had little on the shape and intensity of the IR spectra of water. The presence of perchloric acid reduces the intensity (for 0.027 M HClO₄, by 40% at 3618 cm^?1), which was due to the state of acids in the solvents. Conductometric measurements showed that, under these conditions, HCl and HNO₃ were unionized, while HClO₄ dissociated almost completely.     

Fourier-transform infrared spectroscopic studies of dithia tetraphenylporphine

We present here infrared absorption spectra of dithia tetraphenylporphine and its cation in the 450–1600 and 2900–3400 cm⁻¹ regions. Most of the allowed IR bands are observed in pairs due to overallD _2h point group symmetry of the molecule. The observed bands have been assigned to the porphyrin skeleton and phenyl ring modes. Some weak bands, which are forbidden underD _2h , also appear in the spectra due to the distortion of the molecule from planarity-caused by the out-of-plane positioned N and S atoms. Increased intensity of some phenyl ring bands compared to free-base tetraphenylporphine is explained on the basis of rotation of phenyl rings towards the mean molecular plane. Contrary to the point group symmetry of cation of dithia tetraphenylporphine, certain bands are observed to be degenerate due to identical bonding arrangements in pyrrole rings of the cation     

UV spectroscopy of monosubstituted derivatives of 1,2-dihydro-C60-fullerenes

UV spectroscopy is used to determine the molar absorption coefficients of C₆₀ fullerene and monosubstituted 1,2-dihydro-C₆₀-fullerenes in different solvents. It is found that the extinction coefficient of C₆₀ at 330 nm (the main absorption band most frequently used for qualitative and quantitative determination of the C₆₀ content) is independent of the nature of the solvent and is ～54400 M^?1·cm^?1. The molar absorption coefficients of a series of monosubstituted 1,2-dihydro-C₆₀-fullerenes are practically independent of the chemical structure and the length of the substituent and are 35700 M^?1·cm^?1 (λ ～ 328 nm) and 115250 M^?1·cm^?1 (λ ～ 257 nm). It is shown that the substitution in fullerene proceeds via the double 6,6 bond, as evidenced by the absorption band at 424 nm in the spectra of these compounds, which is characteristic of monosubstituted methanofullerenes.     

Two types of protons in ferrocene

Two absorption bands of ferrocene, the in-plane bending C-H vibrations (β_CH) at 1002 cm^?1 and out-of-plane C-H vibration (γ_CH) at 816 cm^?1, are accompanied with high-frequency satellites β_CH (1055) and γ_CH (837 cm^?1). In the spectrum of 1,1′-dideuteroferrocene, only the high-frequency bands suffer an isotopic shift, from 1055 to 859 cm^?1, and from 837 to 668 cm^?1. Only additional incorporation of deuterium into 1,1′-dideuteroferrocene results also in an isotopic shift of the basic bands: 1002 to 771 and 816 to 632 cm^?1. Therefore, one of the five carbon atoms of cyclopentadienyl ring of ferrocene differs from the other in the static state. It is assumed that just this carbon atom is bonded with the iron atom by the σ-bond.     

Tetraazacoronenes and Their Dimers,Trimers and Tetramers

Tetraazacoronenes were synthesized from bay-functionalized tetraazaperylenes by Zr-mediated cyclization and four-fold Suzuki–Miyaura cross coupling. In the Zr-mediated approach, an η⁴-cyclobutadiene-zirconium(IV) complex was isolated as an intermediate to cyclobutene-annulated derivatives. Using bis(pinacolatoboryl)vinyltrimethylsilane as a C₂ building block gave the tetraazacoronene target compound along with the condensed azacoronene dimer as well as higher oligomers. The series of extended azacoronenes show highly resolved UV/Vis absorption bands with increased extinction coefficients for the extended aromatic cores and fluorescence quantum yields of up to 80 % at 659 nm.