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.     

Stereoregularity of poly(methyl acrylate)

The stereoregularity of poly(methyl acrylate) and poly(methyl acrylate-αd) was determined from the NMR spectra. A method of quantitative determination of stereoregularity of poly(methyl acrylate) proposed in this paper is based on the fact that in the 100 Mc./sec. NMR spectrum the absorption peaks due to methylene protons in syndiotactic configurations overlap absorptions due to only one of two methylene protons in isotactic configurations. The stereostructure of poly(methy1 acrylates) polymerized with anionic catalysts such as Grignard reagents, n-butyllithium, and LiAlH₄ is generally richer in isotactic diads than in syndiotactic diads. For example, poly(methyl acrylate) polymerized with phenylmagnesium bromide as catalyst at ?20°C. consists of 99% isotactic and 1% syndiotactic diads. In radical polymerization, the isotacticity of poly(methyl acrylate) is independent of polymerization temperature. Poly(methyl acrylates) polymerized with a Ziegler-Natta catalyst consisting of Al(C₂H₅)₂Cl and VCl₄ have configurations similar to those polymerized by radical initiators. The stereoregularity of poly(methyl acrylate-α-d) resembled that of poly(methyl acrylate) polymerized under the same conditions.     

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.     

Stereoregularity of poly(2-vinylpyridine) and poly-(4-vinylpyridine)

In order to determine the stereoregularity of poly(4-vinylpyridine), 4-vinylpyridine-β,β-d₂ was synthesized from 4-acetylpyridine. The ¹H-NMR spectra of the deuterated and nondeuterated polymers were measured and analyzed. From the ¹H-NMR spectra of poly(4-vinylpyridine-β,β-d₂), triad tacticity can be obtained, while the ¹H-NMR spectra of nondeuterated poly(4-vinylpyridine) give the fraction of isotactic triad. The ¹³C-NMR spectra of poly(4-vinylpyridine) were also observed, and the spectra of C₄ carbon of polymers were assigned by the pentad tacticities. The fraction of isotactic triad of poly(2-vinylpyridine) and poly(4-vinylpyridine) obtained under various polymerization conditions were determined. The radical polymerization and anionic polymerizations with phenylmagnesium bromide and n-butyllithium as catalysts of 4-vinylpyridine gave atactic polymers.     

NMR study of poly(vinyl chloride)-β,β-d2

The high-resolution NMR spectra at 60 and 100 Mcps of poly(vinyl chloride)-β,β-d₂ in o-dichlorobenzene, pyridine, and C₂HCl₅ solutions are reported. The use of low molecular weight samples and of {D} spin-decoupling experiments, which yield higher resolution spectra, results in the observation of a number of additional resonances for the α-proton. These can be interpreted in terms of pentad configurational sequences of monomer units. It is found that, whereas the S syndiotactic pentads cannot be resolved, two components of the H heterotactic and all of the possible I isotactic pentads are clearly discernible. From the tacticity values of polymers prepared at +40, 0, and ?40°C, enthalpy and entropy of activation for isotactic and syndiotactic monomer placement are found to be 630 cal/mole and 1.5 eu, respectively.     

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.     

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.     

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.     

Poly(alkyl α-chloroacrylates). V. Preparation and properties of methyl,ethyl, and isopropyl polymers of varied tacticity

Polymers of different tacticities, from highly isotactic to highly syndiotactic, were prepared from methyl, ethyl, and isopropyl α-chloroacrylates. These polymers were characterized for tacticity by infrared spectroscopy and 100 and 300 MHz nuclear magnetic resonance (NMR) and for thermal properties by differential scanning calorimetry (DSC). After corrections were made for molecular weight effects, the observed glass temperature-tacticity results were analyzed, and it was determined that the maximum differences in glass temperatures of the purely isotactic compared to the purely syndiotactic polymers should be 92°C for the methyl ester, 86°C for the ethyl ester, and 68°C for the isopropyl ester polymers. The highly isotactic polymers of all three esters were crystalline. Possible polymerization reaction mechanisms are discussed on the basis of the triad and tetrad tacticity values observed and the calculated propagation statistics.     

The stereoregularity of polyacrylonitrile and its dependence on polymerization temperature

The stereoregularity of polyacrylonitrile was studied by NMR spectroscopy. The methylene protons in isotactic configuration are equivalent in dimethylformamide-d₇ solution and are nonequivalent in dimethylsulfoxide-d₆ solution. In the case of the latter solution the difference in chemical shift between the isotactic methylene protons is 6.6 cps. The stereoregularity of polyacrylonitrile-α-d instead of polyacrylonitrile was determined on the dimethylformamide-d₇ solution. In the radical polymerization all the polyacrylonitrile-α-d's that polymerized at temperatures between 80 and ?78°C. have a configuration consisting of about 50% of isotactic diads and, accordingly, the stereoregularity of polyacrylonitrile does not depend upon the polymerization temperature. Analysis of the NMR spectra of isotactic polyacrylonitrile prepared from acrylonitrile–urea canal complex was also carried out. The NMR spectra of meso- and dl-2,4-dicyanopentanes, dimer models of isotactic and syndiotactic polyacrylonitriles, respectively, were analyzed by a computer program proposed by Bothner-By.     

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(methyl α-chloroacrylate)

Triad and tetrad tacticities of poly(methyl α-chloroacrylate) and poly(methyl α-chloroacrylate-β-d₁) were determined by nuclear magnetic resonance (NMR) spectroscopy. Methyl α-chloroacrylate-β-d₁ and its polymer were first synthesized. Isotactic poly(methyl α-chloroacrylate) was prepared with ethylmagnesium chloride-benzal-acetophenone in combination as catalyst. The syndiotacticity of radically polymerized polymers increased with decreasing polymerization temperature. For radical polymerization, enthalpy and entropy differences between isotactic and syndiotactic additions were calculated to give ΔH ? ΔH = 850 cal/mole and ΔS ? ΔS = 0.93 eu. The stereoregularity of the polymer prepared with phenylmagnesium bromide catalyst was analyzed in fairly good agreement with first-order Markov statistics, while polymerization with fluorenyllithium seems predominantly to proceed by a mechanism similar to free-radical mechanism. Stereoregularity-controlling power for individual substituents is briefly discussed.     

Heterotactic poly(vinyl alcohol)

Bulky substituents in vinyl trialkylsilyl ethers and vinyl trialkylcarbinyl ethers led to heterotactic polymers (H = 66%). The polymers were converted into poly(vinyl alcohol) (PVA) and further to poly(vinyl acetate), and tacticity was determined as poly(vinyl acetate). Vinyl triisopropylsilyl ether in nonpolar solvents yielded a heterotactic polymer with a higher percentage of isotactic triads than syndiotactic triads (Hetero-I). Vinyl trialkylcarbinyl ethers in polar solvents gave a heterotactic polymer with more syndiotactic triads than isotactic (Hetero-II). Heterotactic PVA was soluble in water and showed characteristics infrared absorptions. Interestingly, Hetero-I PVA showed no iodine color reaction, but Hetero-II showed a much more intense color reaction than a commercial PVA. The mechanism of heterotactic propagation was discussed in terms of the Markóv chain model.     

Stereocontrol in radical polymerization of acrylic monomers

A clear effect of Lewis acids, such. as scandium trifluoromethanesulfonate [Sc(OTf)₃], on stereocontrol during the radical polymerization of a designed monomer, benzyl α-(methoxymethyl)acrylate was found. This Lewis acid also influenced the stereochemistry in the radical polymerization of methyl methacrylate giving a less syndiotactic and more isotactic polymer, although many Lewis acids were not effective. A catalytic amount of Lewis acids, such as Y(OTf)₃ and Yb(OTf)₃, also significantly enhanced isotactic-specificity during the radical polymerization of acrylamide and its derivatives, N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide. Obvious solvent and temperature effects on tacticity were observed in these polymerizations, and poly(NIPAM) with >80% triad isotactic content has been obtained in the presence of Lewis acids.     

Stereoregular poly(methacrylic acids)

A convenient method is described for the preparation of isotactic and syndiotactic poly(trimethylsilyl methacrylates) by using the monomer trimethyl silyl methacrylate and butyllithium initiation in toluene and tetrahydrofuran, respectively. The structure of these polymers enables complete hydrolysis to the corresponding poly(methacrylic acids), which were characterized with respect to tacticity and molecular weight. The asymmetric induction in toluene produced 89% isotactic polymer, while that in tetrahydrofuran gave polymer <90% syndiotactic and heterotactic in terms of triads. A method of fractionation of the polyelectrolytes by gel-permeation chromatography on a preparative scale was shown to be applicable.     

Synthesis of polyacrylamide samples of known steric structure

The esterification of atactic, syndiotactic and isotactic samples of poly(acrylic acid) by phenol and p-nitrophenol, carried out at 95° in the presence of POCl₃, led only to atactic poly(phenyl and p-nitrophenyl acrylates) respectively, as shown by ¹H-NMR (250 MHz). These polymers and isotactic poly(phenyl acrylate), prepared by anionic polymerization of phenyl acrylate with n-butyllithium, when reacted with ammonia led to bridged polyacrylimides or to linear atactic or isotactic polyacrylamides according to the reaction conditions. Anionic homopolymerization of p-nitrophenyl acrylate did not occur.     

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.     

Optoeletronic properties of poly(N‐alkenyl‐carbazole)s driven by polymer stereoregularity

Stereoregular polymers like isotactic poly(N‐butenyl‐carbazole) (i‐PBK), isotactic and syndiotactic poly(N‐pentenyl‐carbazole) (i‐PPK and s‐PPK), and poly(N‐hexenyl‐carbazole) (i‐PHK and s‐PHK) are synthesized using the stereospecific homogeneous “single site” Ziegler‐Natta (Z‐N) catalysts: rac‐dimethylsilylbis(1‐indenyl)zirconium dichloride ( 1 )/methylaluminoxane (MAO) and diphenylmethylidene(cyclopentadienyl)‐(9‐fluorenyl)zirconium dichloride ( 2 )/MAO. Catalytic activity is rationalized by density functional theory (DFT) calculations. All synthesized polymers are fully characterized by NMR, thermal, wide‐angle X‐ray diffraction, and fourier transform infrared spectroscopy analysis. Fluorescence measurements on isotactic and syndiotactic polymer films indicate that all polymers give rise to excimers, both “sandwich‐like” and “partially overlapping.” Excimer formation is essentially driven by the polymer tacticity. Isotactic polymers generate both sandwich‐like and partially overlapping excimers, while syndiotactic polymers give rise especially to partially overlapping ones. A theoretical combined molecular dynamics–time dependent DFT approach is also used to support the experimental results. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 242–251     

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.     

Polymerization of N,N-Dialkylacrylamides with Anionic Initiators Modified by Diethylzinc

Abstract

N,N-Dimethyl-, diethyl-, and dipropylacrylamides were polymerized with 1,1-bis(4′-trimethylsilylphenyl)-3-methylpentyllithium (I) in the presence and absence of diethylzinc in THF. Although the polymers produced with I in the absence of diethylzinc have rather broad molecular weight distributions, the addition of diethylzinc to the polymerization systems causes narrow molecular weight distributions of the polymers. The addition of diethylzinc also affect the stereospecificities of the polymers obtained. The poly(N,N-diethylacrylamide) produced with I/diethylzinc (molar ratio of 1/3-15) is highly syndiotactic, while the one obtained with I is isotactic. The configuration of the poly(N,N-dimethylacrylamide) is changed from isotactic to syndio and heterotactic rich by the addition of diethylzinc to the polymerization mixture. Little effect of diethylzinc is observed on the stereospecificity of the polymerization of N,N-dipropylacrylamide. The stoichiometric additive effect of Et₂Zn toward the initiator in the polymerization of DEAA suggests that the coordination of Et₂Zn aggregates with the propagating carbanionic species narrows the molecular weight distribution and controls the tacticity of the polymer.