Polymerization of α,α-disubstituted β-propiolactones and lactams. VII. Stereoregular polymers from optically active lactones

Optically active α-phenyl-ααethyl-β-propiolactone of high optical purity was prepared and polymerized by homogeneous anionic initiation to the isotactic polyester. The racemic and isotactic polymers had apparently different crystalline properties suggesting that the former may be syndiotactic or may crystallize with unit cells containing both R and S blocks. Similar attempts to prepare α-methyl-α-isopropyl-β-propiolactone of high optical purity were unsuccessful although a partially crystalline polymer was obtained from the racemic monomer.     

Cationic polymerization of α,β-disubstituted olefins. VI. Steric structure of poly(methyl propenyl ether) obtained by cationic catalysts

The steric structure of poly(methyl propenyl ether) obtained by cationic polymerization was studied by NMR spectra. From the analysis of β-methyl and α-methoxyal spectra, it was found that the tacticities of the α-carbon were different from those of the β-carbon in all polymers obtained. In the crystalline polymers obtained from the trans isomer by homogeneous catalysts, BF₃·O(C₂H₅)₂ or Al(C₂H₅)Cl₂, and from the cis isomer by a heterogeneous catalyst, Al₂(SO₄)₃–H₂SO₄ complex, the structure of polymers was threo-di-isotactic. Though the configurations of all α-carbons were isotactic, a small amount of syndiotactic structure was observed in the β-carbon. On the other hand, in the amorphous polymer obtained from cis isomer by the homogeneous catalyst, the configuration of the α-carbon was isotactic, but that of the β-carbon was atactic. These facts suggest that the type of opening of a monomeric double bond is complicated, or that carbon–carbon double bond in an incoming monomer rotates in the transition state. From these experimental results, a probability treatment was proposed from the diad tacticity of α,β-disubstituted polymers. It shows that the tacticity is decided by a polymerization mechanism different from that proposed by Bovey.     

Stereoregularity of polystyrene-β,β-d2

The 100-MHz methine proton spectra of polystyrene-β,β-d₂ obtained by radical and cationic initiators consisted of four peaks at 2.35, 2.25, 2.17, and 2.03 ppm, the proportion of which changed with polymerization conditions such as catalyst, solvent, and temperature. The spectrum was interpreted in terms of pentad sequences assuming Bernoullian statistics and the stereoregularity was determined. Polystyrene-β,β-d₂ prepared by radical initiators had a syndiotactic-rich configuration, independent of polymerization temperature. Polymers obtained by cationic initiators had lower racemic dyads. Cationic polymerization in toluene at 0°C gave a polymer of an almost random configuration. It was revealed that nondeuterated polystyrene of a random configuration can be distinguished from syndiotactic-rich polystyrene as well as the isotactic polymer by 100 MHz NMR spectroscopy.     

Syndiotactic and isotactic poly(tert-butylethylene oxide)

The rate of polymerization of t-BuEO by t-BuOK in DMSO is about one-tenth that of propylene oxide. The slow rate of propagation was accompanied by considerable chain transfer. In the absence of solvent, the polymer obtained was crystalline, different from the isotactic form and therefore must be syndiotactic. The NMR spectra indicate the isotactic polymer exists in solution preferentially in the skew₁ form, while syndiotactic is about 60% skew₁, 40% skew₂. Amorphous polymer accompanying isotactic exists about 50% in the trans conformer, by NMR data.     

Influence of tacticity on Tβ, Tg,and TLL in poly(methyl methacrylate)s by the method of thermally stimulated current (TSC)

The thermally stimulated-current method (TSC) has been employed to determine the temperatures and intensities of T_β, T_g, and T > T_g for pure isotactic, pure syndiotactic, and five atactic specimens with syndiotactic triad content from 49.5 to 75%; T_g was found to increase linearly with syndiotactic triad content as T_g (°C) = 48.0 + 0.856 (% syn), with R² = 0.970 standard error 5.6°C; T_g for the syndiotactic specimen is 136.6°C measured, 133.6°C calculated. Several atactic specimens exhibit a second glass temperature 15 to 35 K above the regression line ascribed to some pure syndio content, and/or some isotactic–syndiotactic stereocomplexes. All specimens exhibited the liquid–liquid or T_LL transition (relaxation) which increases linearly with 100-% isotactic triad content. Isotactic PMMA shows a T′_LL relaxation 50 K above T_LL. The T_g and T_LL values obtained correlate extremely well with values from differential scanning calorimetry (DSC) determined in a separate study, as well as with most literature data. Intensities of T_g and T_LL by TSC are greatest for isotactic, next for syndiotactic, with a broad, low minimum for atactic materials. The intensity of a β relaxation increases slowly from isotactic to syndiotactic. The T_LL found by TSC compares well with literature values for isotactic PMMA obtained by several methods, and T_LL in the atactic region compares well with literature values for atactic material. The ratio T_LL/T_g ranges from 1.09 to 1.20 with no dependence on tacticity. T_g follows simple Arrhenius behavior with enthalpies of activation about one-half of the values normally calculated from dielectric and mechanical loss. The frequency dependences of T_LL and T′_LL follow a Vogel–WLF relationship with temperature. The origin of T_LL is discussed in terms of the Frenkel hypothesis of segment–segment interaction. Evidence for T_LL and T_LL from a variety of methods indicates that these two temperatures are not artifacts of the TSC method.     

Poly(alkyl α-bromoacrylate)s. III. Tacticity analysis from 19 mHz 13C-NMR spectroscopy

Polymer tacticity was determined by 19 mHz ¹³C-NMR spectroscopy for isotactic, atactic, and syndiotactic samples of six poly(alkyl α-bromoacrylate)s. Included in this series were the methyl, ethyl, n-propyl, i-propyl, n-butyl, and n-pentyl esters. Complete assignments for the 10 pentad peaks of the carbonyl carbon resonance were achieved for all but the i-propyl ester while a complete analysis of tetrad tacticity from the backbone methylene carbon resonance was possible for all but the methyl ester. The tetrad values calculated from the experimentally determined pentad contents were found to agree with the experimental tetrad values. As a result of insufficient peak separation of the quaternary carbon resonance, complete pentad assignments were possible in only a few instances. The polymerization reaction mechanisms were discussed in terms of the propagation statistics calculated from the experimentally determined tetrads and pentads. Both the atactic and syndiotactic polymers that were synthesized by free radical techniques displayed Bernoullian or random statistics while the stereochemical statistics of the isotactic polymers synthesized by a modified Grignard complex were more consistent with nonrandom or first-order Markovian statistics.     

Structural and steric isomerism of polypropylenes

The structural and steric isomerism of propylene polymers has been estimated on the basis of solution properties as well as infrared and high-resolution nuclear magnetic resonance spectra. Three general types of polypropylenes were prepared: polymers prepared with the cationic catalytic system AlCl₃–C₂H₅Cl, stereoblock polymers obtained by successive extraction from a commercial product and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polymer followed by hydrogenation with Adam's catalyst in dioxane at 40°C. The characterization of all samples was accomplished by equilibrium ultracentrifugation, vapor-pressure osmometry, viscometry, and gel-permeation chromatography. It is found that the molecular chain of cationically prepared polymer is somewhat branched owing to structural isomerism during polymerization. Isoamyl acetate is found to be a theta solvent for stereo-block as well as for atactic and syndiotactic polymers; the theta temperature is determined as the temperature at which the light-scattering second virial coefficient A₂ vanishes. A close correlation is found between the theta temperature and stereoisomerism. The absorbances of the 1154 and 974 cm^?1 bands in the infrared spectra decrease with decreasing molecular weight; in addition to the mere existence of alternating CH₂ and CH(CH₃) groups in the polymer chain, rather long sequences of this type are required for the appearance of these bands. Changes in the absorption band at 997 cm^?1 show that chains consisting of over ten isotactically connected monomer units can assume a helical conformation. From the high-resolution NMR spectra of different polypropylenes, including isotactic polymers of low molecular weight, it is found that in estimating the microstructure, account must be taken of the effects of stereoisomerism within tetrads of monomer units on the apparent widths of the methylene proton resonances. If substantial concentrations of several of the possible types of tetrads are present (i.e., if the tactic sequence lengths are quite short), then it is difficult to determine the relative amounts of tactic dyads accurately from the 100 Mcps methylene proton resonances.     

Stereoregularity of poly(alkyl α-chloroacrylates) and mechanism of isotactic polymerization

The catalytic activity of the complexes prepared by the reaction of Grignard reagents with ketones, esters, and an epoxide as polymerization catalysts of methyl and ethyl α-chloroacrylates was investigated. The modifiers which gave isotactic polymers were α,β-unsaturated ketones such as benzalacetophenone, benzalacetone, dibenzalacetone, mesityl oxide, and methyl vinyl ketone, and α,β-unsaturated esters such as ethyl cinnamate, ethyl crotonate, and methyl acrylate. Catalysts with butyl ethyl ketone, propiophenone, and propylene oxide as modifiers produced atactic polymers but no isotactic polymers. It was revealed that the complex catalysts having a structure ? C?C? O? MgX (X is halogen) gave isotactic polymers. The mechanism of isotactic polymerization was discussed. In addition, for radical polymerization of ethyl α-chloroacrylate, enthalpy and entropy differences between isotactic and syndiotactic additions were calculated to give ΔH_i^* ? ΔH_s^* = 910 cal/mole and ΔS_i^* ? ΔS_s^* = 0.82 eu.     

Observation of pentads in deuterated polyacrylonitrile by NMR spectroscopy

The deuterium-decoupled methine proton spectra of polyacrylonitrile-β,β-d₂ were measured at 156°C in dimethylsulfoxide-d₆ solution. Splittings of triad peaks caused by pentad sequences were observed. The isotactic triad resonance was resolved into three peaks and the heterotactic resonance into two peaks, while the syndiotactic resonance was unresolved or resolved into three peaks. The splittings were assigned by comparing the probability of each pentad sequence with observed intensities. The pentad signal shifted to the higher magnetic field with increasing number of meso configurations as neighbors of the central triad. It was observed that the pentad of atactic polyacrylonitrile-β,β-d₂ obeyed Bernoullian statistics but that of isotactic polymer obtained by γ-ray irradiation of the canal complex seemingly obeyed first-order Markov statistics.     

Stereoregularity of poly(2-vinylpyridine) determined by 1H-NMR and 13C-NMR spectroscopy

In order to determine the stereoregularity of poly(2-vinylpyridine), 2-vinylpyridine-β,β-d₂ was synthesized. The ¹H-NMR spectra of the deuterated polymer in D₂SO₄ and o-dichlorobenzene solutions showed three peaks, which were assigned to triad tacticities. Since the absorptions of heterotactic and syndiotactic triads of methine protons overlap those of methylene protons in nondeuterated polymers, only isotactic triad intensities can be obtained from the ¹H-NMR spectra of nondeuterated poly(2-vinylpyridine). The ¹³C-NMR spectra of poly(2-vinylpyridine) were obtained in methanol and sulfuric acid solutions. In methanol solution the absorption was split into three groups, which cannot be explained by triads, and in sulfuric acid solution several peaks were observed. These splittings may be due to pentad tacticity. The results show that poly(2-vinylpyridine) obtained by radical polymerization is an atactic polymer.     

Conformational analysis of poly(2-hydroxyethyl methacrylate)

The poly(2-hydroxyethyl methacrylate) (PHEMA) is a disubstituted vinyl chain in which the substituents CO₂CH₂CH₂OH and CH₃ differ in size and shape. In order to verify the various characteristics of the PHEMA chain, the conformational energy calculations for meso and racemic diads, which are the segments consisting of the stereoregular isotactic and syndiotactic chains, respectively, were carried out using ECEPP/2 potential. From these calculations, the averaged geometry and the statistical weights were obtained in a local minima. The characteristic ratio, C∞ = (〈r²〉_o/nl²)∞, was determined from the statistical weights and geometries. The calculated C∞ for the isotactic and syndiotactic chain are 10.2 and 2.3, respectively. The characteristic ratio for isotactic chain is larger than that for syndiotactic chain. This shows that the syndiotactic chain is more folded than the isotactic chain is, and that the calculated tendency is in reasonably agreement with the experimental tendency of acrylate polymers.     

Stereoregularity of radically polymerized poly(alkyl acrylates) and poly(trimethylsilyl acrylates) and the preparation of syndiotactic poly(methyl acrylate)

Nuclear magnetic resonance (NMR) spectroscopy was used to determine the stereoregularity of radically polymerized poly(ethyl acrylates), poly(trimethylsilyl acrylates), and poly(isopropyl acrylate-α,β-d₂). The ethyl acrylate polymers consisted of a random configuration having about 50% of isotactic diads, and their stereoregularities were independent of the polymerization temperature (40 to ?78°C). Poly(trimethylsilyl acrylates) and poly(isopropyl acrylate-α,β-d₂) prepared at low temperatures had a syndiotactic configuration. Syndiotactic poly(methyl acrylate) was derived from syndiotactic poly(trimethylsilyl acrylate). For poly(methyl acrylate), an approximate estimation of the stereoregularity by infrared spectroscopy was proposed.     

Triad tacticity of polyacrylonitrile

The high-resolution NMR spectra of polyacrylonitrile-β,β-d₂ prepared by radical polymerization were determined, and the stereoregularity of the polymer was studied. The NMR spectra of methine protons of polyacrylonitrile-β,β-d₂ in dimethyl sulfoxide-d₆ and a mixture of nitromethane-d₃ and ethylene carbonate showed three partially resolved multiplets. The deuterium-decoupled spectra of the polymer were measured, and three well resolved peaks were observed in the two solvents and dimethylformamide-d₇. These three peaks were analyzed by comparison with the NMR spectra of model compounds and polyacrylonitrile-α-d, and they were assigned to isotactic, heterotactic, and syndiotactic triads with decreasing magnetic field. This order seems to be unchanged in other solvents. Triad stereoregularity of the polymer was determined according to the assignment. Polymerizations of acrylonitrile-β,β-d₂ by radical initiators between ?78°C and 60°C were explained by the Bernoulli trial propagation step. The polymers had an atactic structure, independent of polymerization temperature. This shows that in free-radical polymerization of acrylonitrile, the chain end is not represented as having any particular stereochemistry. Other stereochemical control is necessary to produce tactic polymers. The triad tacticity of isotactic polyacrylonitrile was also determined.     

Study of segmental orientation in poly (vinyl chloride)/poly (α-methyl-α-n-propyl-β-propiolactone) blends by fourier-transform infrared spectroscopy

Fourier-transform infrared (FTIR) spectroscopy has been used to investigate the segmental orientation of poly(vinyl chloride) (PVC)/poly (α-methyl-α-n-propyl-β-propiolactone) (PMPPL) blends in uniaxially stretched samples over a wide range of compositions and draw ratios. The results indicate that for pure PVC, syndiotactic segments reach a higher degree of orientation than isotactic segments and gauche conformations. Similarly, for pure PMPPL, crystalline segments orient more than amorphous segments at any given elongation. Thus, for both polymers, the higher orientation is obtained for the more rigid segments or those located in a more rigid (crystalline) phase. The addition of the macromolecular plasticizer PMPPL has no effect on the orientation of PVC syndiotactic segments, but it lowers the orientation of PVC gauche conformations, suggesting that the polyester is located in the amorphous regions of PVC. Finally, the PMPPL orientation function initially decreases with the addition of PVC and thereafter remains constant. The results are discussed in terms of interpenetrating networks and relaxation processes.     

Selective synthesis of structurally isomeric poly-β-ester and poly-δ-ester from β-(2-acetoxy-ethyl)-β-propiolactone with Al and Zn catalysts

It was found that structurally isomeric polymers were formed by the ring-opening polymerization of β-(2-acetoxy ethyl)-β-propiolactone with (EtAlO)_n and Et(ZnO)₂ZnEt catalysts; that is, the Al catalyst catalyzed normal polymerization which led to poly-β-ester and the Zn catalyst formed isomerized poly-β-ester as the main product. The polymer structure was determined by nuclear magnetic resonance (NMR), T₁-value, thermal decomposition product, and (T_g). The NMR studies for the monomer–catalyst systems indicated that the Al catalyst interacted predominately with the lactone group, whereas the Zn catalyst interacted with the side-chain ester group. These site-selective interactions could be related to the difference in the stereoregulation by the two catalysts during the poly(β-ester)-forming polymerization process.     

Stereoregularity of poly(isopropyl acrylate) and its racemization during hydrolysis

The diad tacticity of poly(isopropyl acrylate) was measured from the β-proton absorptions of poly(isopropyl acrylate-α,β-d₂) obtained with a 100 MHz NMR spectrometer, and temperature dependence of the tacticity of the polymers obtained by radical polymerization was determined. Enthalpy and entropy differences between isotactic and syndiotactic addition for poly(isopropyl acrylate) were calculated to give the following values: Δ(ΔS) = 0.7 eu; Δ(ΔH) = 0.51 kcal/mole. In the hydrolysis of poly(isopropyl acrylate-α,β-d₂), it was found that the rate of hydrolysis of poly(isopropyl acrylate) was dependent on the molecular weight rather than on the tacticity. As for the rate of racemization during hydrolysis, the rate for syndiotactic polymer was much faster than that for the isotactic polymer. The exchange reaction of deuterium at α-position with hydrogen occurred in all the polymers during hydrolysis reaction.     

NMR study of poly-p-isopropyl-α-methylstyrene

220 MHz NMR spectra of sample of poly-p-isopropyl-α-methylstyrene prepared through anionic (A) and cationic (B) polymerizations are studied. Peaks at τ values of 9.07, 9.41, and 9.71 are assigned to isotactic (i), heterotactic (h), and syndiotactic (s) α-methyl triads, respectively. From the α-methyl triads and the β-proton tetrads it is found that polymer A deviates little from Bernoullian statistics and that first-order Markov configurational statistics applies to polymer B. Isopropyl methine and methyl proton resonances are also analyzed in terms of the configurational statistics of the polymer. Resonances of the phenyl protons are assigned with increasing field to s, h, i meta and ortho protons.     

Local chain configuration dependence of the mechanisms of analogous reactions of PVC. I. A conclusive study of the microstructure evolution in SN2 nucleophilic substitution

The nucleophilic substitution in poly(vinyl chloride) (PVC) with sodium benzenethiolate has been studied in two kinds of solvent differing in the molecular structure in the vicinity of the carbonyl group. From the evolution of the content of isotactic ( mm ), heterotactic ( mr ), and syndiotactic ( rr ) triads; and of mmmm, mmmr and rmmr isotactic pentads, in the unmodified parts of the polymer, as followed by ¹³C-NMR, it is unambiguously inferred that any chlorine but the central one of either the isotactic triad at mmr tetrads or the heterotactic triad at rmrr pentads is unreactive. Only a small fraction of mmr tetrads reacts occasionally by the central chlorine of its mr triad instead of the mm . Of those structures, the mmr , especially when located at the end of long isotactic sequences, proves to be highly reactive compared to the rmrr structure. By comparing quantitatively the microstructural changes with degree of substitution and taking into account that the reaction is of S_N2 type, the mechanisms of substitution through the three foregoing reactive chlorines have been stated. They are found to be independent of the type of solvent and to account for all the changes in triad and pentad content as experimentally found. Instead, the solvent dependence of the ratio between the mmr - and rmrr -based processes of substitution is such that the depletion of mmr compared to that of rmrr structure may be controlled. The conformational sensitivity of this behavior is discussed on the basis of side work in our laboratory. As a whole, the results of the present work provide some original concepts as to the role of the tacticity dependent microstructure and the related local conformations in the chemical reactions of PVC. © 1996 John Wiley & Sons, Inc.     

NMR spectrum of poly(vinyl chloride)

The 100-MHz proton NMR spectra of commercial and laboratory-prepared poly(vinyl chloride) (PVC) have been measured in various solvents at high temperature (80–150°C). Tacticity in PVC was determined by the analysis of the β-proton spectrum. The spectrum was calculated assuming that the PVC chain consists of tetrad sequences of monomer units and that their distribution in the chain is described by a simple Bernoulli-sequence statistics with a P_m (the probability of isotactic placement) of 0.45 for commercial PVC polymerized at 50°C. Tacticity calibration curves based on measurements made for the polymer in pentachloroethane and β-dichlorobenzene were established, and they provide a simple method for the measurement of tacticity in PVC directly from the observed spectra. Excluding samples prepared in butyraldehyde solution, the formation of syndiotactic structures in PVC (prepared by free-radical polymerization) was found to be favored by lowering the polymerization temperature. This preference is due to an increase in the activation enthalpy of 510 cal/mole which is required for forming an isotactic placement in the chain during the propagation step.     

Thermal and dynamic mechanical relaxation behavior of stereoregular poly(2-hydroxyethyl methacrylate)

Thermal, dynamic mechanical, and dielectric relaxation techniques were used to determine the relaxation behavior of isotactic and syndiotactic poly(2-hydroxyethyl methacrylate) (pHEMA). Activation energies E_a were determined for the dielectric γ relaxation and compared with those of poly(2-methoxyethyl methacrylate) (pMEMA) to determine the influence of hydrogen bonding on side-chain relaxation processes. No difference in E_a was observed between syndiotactic pHEMA and atactic (predominantly syndiotactic) pMEMA. Isotactic pHEMA, however, had E_a + 1 kcal/mole higher than that of syndiotactic pHEMA. This was attributed to improved side-chain packing in the isotactic polymer.