Synthesis and chiral recognition ability of optically active poly{N‐[(R)‐α‐methoxycarbonylbenzyl]methacrylamide} with various tacticities by radical polymerization using Lewis acids

The radical polymerization of an optically active methacrylamide, N‐[(R)‐α‐methoxycarbonylbenzyl]methacrylamide, was carried out in the absence and presence of Lewis acids such as yittribium trifluoromethanesulfonate [Yb(OTf)₃] and scandium trifluoromethanesulfonate [Sc(OTf)₃]. Catalytic amounts of the Lewis acids significantly affected the stereoregularity of the obtained polymers. The polymerization with Yb(OTf)₃ in tetrahydrofuran afforded isotactic polymers (up to mm = 87%), whereas the conventional radical method without the Lewis acid produced polymers rich in syndiotacticity (up to rr = 88%). The radical polymerization in the presence of MgBr₂ proceeded in a heterotactic‐selective manner (mr = 63%). Thus, the isotactic, syndiotactic, and heterotactic poly(methacrylamide)s were synthesized by the radical processes. The chiral recognition abilities of the obtained optically active poly(methacrylamide)s were affected by the stereoregularity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3354–3360, 2003     

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.     

Correlation between the tacticity and content of labile nondefect structures in poly(vinyl chloride)

The content of mm isotactic triads taking the GTTG^? conformation for samples of poly(vinyl chloride) (PVC) fractions of different tacticities was measured through a substitution reaction with sodium benzenethiolate. This quantity changed linearly with the ratio of rmmmrx to mmmmrx (x = m or r), as accurately determined by ¹³C NMR spectroscopy. In a comparison of this correlation and that obtained between the thermal degradation stability and overall isotactic content, as studied previously, some novel evidence for the GTTG^? conformation of a few mm triads, termini of isotactic sequences no shorter than one heptad as specific labile sites in PVC, was obtained. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3944–3949, 2002     

Selective Substitution Reactions on PVC. Lability of Some “Normal” Structures

The nucleophilic substitution reaction on PVC with sodium thiophenate in cyclohexanone solution is studied. The reaction appears to be S_N2 substitution and it involves three different steps with decreasing reaction constants. By using ¹³C-NMR spectroscopy, the fast step is proposed to be due to the high reactivity of the central chlorine in isotactic triads and, to a lesser extent, in heterotactic triads. The study of the thermal degradation of the modified samples shows that during the fast step of substitution a stabilizing effect occurs, and that as soon as the first step is over, the polymer stability decreases markedly. These effects are accompanied by changes in poly-ene distribution as proved by UV-VIS absorption spectroscopy study on degraded samples. The results, as discussed on the basis of the possible conformations of triads in PVC, suggest that some chlorine atoms in both the GTTG isotactic and the TTTG heterotactic triads should be considered as labile structures in PVC. It follows from the results obtained that on the one hand the initiation of degradation may occur by normal structures, and on the other the build-up of polyenes is favored by the presence of …TTTT… sequences. Both features contributing to a better understanding of the degradation of PVC.     

Stereoselective substitution on PVC using phase transfer catalysts

The nucleophilic substitution with sodium benzenethiolate in aqueous suspension in the presence of a phase-transfer catalyst has been studied for two samples of PVC of different tacticities. The kinetics shows two well-defined periods: one period is very fast and involves low conversions that are greater as the isotactic content of PVC increases, while another steady period is slow and its slope seems to depend on physical features, e.g., molecular weight and crystallinity, which would affect the accessibility of nucleophile. The evolution of unreacted syndio, iso, and heterotactic triad contents with degree of substitution has been followed by ¹³C-NMR spectroscopy. Since the content of syndiotactic triads does remain unreacted at the end of the reaction and that of isotactic and heterotactic triad decreases, but at a different rate, the reaction is proved to proceed by a stereospecifically controlled mechanism. The influence of degree of substitution on both the thermal degradation rate and the evolution of UV–Visible spectra of equally degraded samples has been also studied; the highest stability in terms of degradation rate and content of short polyenes is obtained when a specific fraction of isotactic triads has reacted. From the correlation between the results of this work and those previously obtained in solution, some enlightening conclusions about the reaction mechanism are drawn.     

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.     

Influence of Tacticity on Some Reactions of PVC

The influence of the tacticity on PVC reactivity is discussed on the basis of preliminary results obtained in ionic dehydrohalo, genation and chlorination reactions. From the reaction of an atactic PVC and a 70% syndiotactic PVC with LiCl in dimethyl-formamide and hexamethylphosphortriamide as solvents, it follows that both the reaction rate and the polyene sequence distribution depend markedly on the syndiotacticity content. This effect is accounted for by the fact that the isotactic parts are preferred in dimethylformamide and the syndiotactic ones in hexamethylphosphoramide. On the other hand, the chlorination of PVC appears to be easier through the heterotactic parts than through the syndiotactic sequences as shown by ¹³C-NMR.     

Stereoregular control of poly(4‐vinyl pyridine) on free radical polymerization by using the inclusion complex with randomly methylated β‐cyclodextrin

Highly heterotactic poly(4‐vinyl pyridine)s (P4VPs) with the fraction of mr content (f_mr) > 0.81 were synthesized by free radical polymerization of 4‐vinyl pyridine (4VP) with randomly methylated β‐cyclodextrin (β‐RMCD) in acidic aqueous media of HNO₃ and CF₃COOH at 40 °C. The heterotacticity of P4VP strongly depended on the neutralization of 4VP. The complete neutralization of 4VP with HNO₃ or CF₃COOH increased the heterotacticity of P4VP, whereas atactic P4VP was obtained in water. The partial decomposition of β‐RMCD by HCl reduced the heterotacticity of P4VP (f_mr ≈ 0.74). The structures of inclusion complexed monomers were determined by Job's plot, 2D NMR with nuclear Overhauser enhancement spectroscopy analyses, and simulation by MM2. The 1:2 complex with [β‐RMCD]:[4VP] with meso placement of 4VPs in β‐RMCD was formed when 4VP was completely neutralized with acid, whereas the 1:1 complex was formed in water. The mechanism of heterospecific control by using β‐RMCD was proposed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of a [60]fullerene‐functionalized poly(vinyl chloride) derivative by stereospecific chemical modification of PVC

The covalent attachment of [60]fullerene (C₆₀) to two poly(vinyl chloride) (PVC) samples with different isotactic content is achieved by direct reaction in o‐dichlorobenzene (o‐DCB) solution in the presence of AIBN. The extent of fullerenation is controlled by varying the C₆₀ feed ratio. The pendant C₆₀‐chemically modified PVC polymers are soluble in tetrahydrofuran (THF) and have been characterized by UV–vis, NMR, FTIR, DSC, TGA, cyclic voltammetry, and SEM. The quantitative microstructural analysis after covalent attachment of the bulky C₆₀ moiety to the PVC has been followed by ¹³C NMR spectroscopy. From the results it can be concluded that the modification of PVC by graft reaction through free radical reaction proceeds by a stereoselective mechanism. This conclusion has been confirmed on the basis of the increase of the glass‐transition temperature (T_g) and the thermal stability of the C₆₀‐chemical modified PVC samples. The fullerenated PVCs obtained show good electron acceptor properties, as evidenced by electrochemical investigations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5408–5419, 2007     

Heterotactic‐specific radical polymerization of N‐isopropylacrylamide and phase transition behavior of aqueous solution of heterotactic poly(N‐isopropylacrylamide)

Radical polymerization of N‐isopropylacrylamide (NIPAAm) in toluene at low temperatures, in the presence of fluorinated‐alcohols, produced heterotactic polymer comprising an alternating sequence of meso and racemo dyads. The heterotacticity reached 70% in triads when polymerization was carried out at ?40 °C using nonafluoro‐tert‐butanol as the added alcohol. NMR analysis revealed that formation of a 1:1 complex of NIPAAm and fluorinated‐alcohol through C?O···H? O hydrogen bonding induces the heterotactic specificity. A mechanism for the heterotactic‐specific polymerization is proposed. Examination of the phase transition behavior of aqueous solutions of heterotactic poly(NIPAAm) revealed that the hysteresis of the phase transition between the heating and cooling cycles depended on the average length of meso dyads in poly(NIPAAm). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2539–2550, 2009     

Synthesis of PVC‐g‐PS through stereoselective nucleophilic substitution on PVC

The substitution reaction of poly(vinyl chloride) (PVC) with sodium azide was performed in cyclohexanone. The evolution of unreacted iso‐, hetero‐ and syndiotactic triad contents with the degree of substitution has been followed by ¹³C NMR spectroscopy. By quantitatively comparing the microstructure changes with degree of substitution, taking into account that the reaction is of S_N2 type, only the mechanisms of substitution through the mm triad of mmr tetrad and the rm of rrmr pentads are shown to react. This conclusion was confirmed by FT‐IR. From this stereospecific chemical modification of PVC, the thermal decomposition of azide‐modified PVC and the consequent reaction with styrene offer a method for the preparation of stereoselective graft copolymers. After grafting, no variation of the microstructure of the chain has been demonstrated. These results have been used to study the effect of the aforementioned structures on the evolution of density as a function of free‐volume of the graft copolymers, and thus provide new approaches to a better understanding of the structure‐properties relationships at the molecular level. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2476–2486, 2006     

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.     

Chemical modification of poly(vinyl chloride): A conclusive study of the influence of tacticity

Three samples, A, B and C, of poly(vinyl chloride) (PVC) were prepared at 90, 60, and 0°C, respectively, to give them different isotactic content measured by ¹³C-NMR spectroscopy. A kinetic study of the nucleophilic substitution with sodium thiophenate, carried out for the three samples, showed that even at temperatures as high as 60°C a fraction of the units remain unreactive and that the extent of this fraction depends on the syndiotactic content of the polymer. This was also supported by a comparison of the behavior of samples B and C in substitution experiments at 5 and 60°C. In contrast the substitution experiments at ?30°C demonstrated that, as suggested, a small fraction of extremely reactive units exists in PVC, the content of which is higher as the isotactic content of the polymer increases. In this connection, and even though a slight contribution of some defect structures cannot be ruled out, a ¹³C-NMR analysis of sample B after modification at 40°C to various degrees demonstrates that the reactivity of the isotactic triads is high in relation to the heterotactic. On the basis of the results obtained and the possible conformations in PVC the substitution mechanism is related to the occurrence of isotactic TT conformations. The results, as discussed in terms of the various ways in which isotactic TT conformations appear open new prospects in the field of PVC chemical modification and stabilization mechanisms.     

Formation of crystalline inclusion compounds of poly (vinyl chloride) of different stereoregularity with γ-cyclodextrin

This work reports the formation and detailed characterization of the γ-cyclodextrin (γ-CD) inclusion compounds (ICs) formed with two poly (vinyl chloride) samples with different isotactic content. The ICs were characterized by X-ray diffraction, solid state ¹³C-NMR, solution ¹H-NMR, FT-infrared, differential scanning calorimetry, and thermogravimetric analysis. Experimental evidence of the inclusion of the guest polymer chains into the narrow channels created by the γ-CD crystalline host lattice has been obtained. Examination of coalesced poly (vinyl chlorides) (PVCs) obtained after the host γ-CD is removed reveals different characteristics specifically for the coalesced PVC sample with higher isotactic content. An increase in T_g was observed by DSC for this PVC. To the contrary, the T_g of the coalesced PVC sample with lower isotactic content is almost the same as that of the as-synthesized sample. Thermogravimetric analysis indicated that coalesced PVC with higher isotactic content acquires a degree of stabilization after modification by threading into and being extracted from its γ-CD IC. The results suggest that an irreversible conformational change takes place when PVC forms ICs with a solid host lattice like γ-CD. The PVC molecules extend and reorganize into a more stable conformation in the IC, consequently improving the properties of the coalesced sample. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2503–2513, 2007     

Polymerization of Methyl Methacrylate Initiated with Organomanganate Reagents

Organomanganate reagents [R₃Mn]^–Li⁺ (R = Bu, Me) were found to polymerize methyl methacrylate in the presence of potassium tert‐butylate. A conversion of the tacticity of the resulting poly(methyl methacrylate)s from heterotactic (mr = 54%) to isotactic (mm = 58%) was observed upon changing the R group of the initiator from Bu to Me. The addition of triisobutylaluminium was found to efficiently control M̄_w and M̄_w/M̄_n of the resulting polymers.     

Stereoselective nucleophilic substitution of poly(vinyl chloride) with sodium thiophenate in cyclohexanone solution: Influence of the reaction temperature on the mechanism

Nucleophilic substitution of PVC with sodium thiophenate was carried out in cyclohexanone solution at 5, 25, 40, 60, and 70°C. The initial rate obeys an Arrhenius law from 25 to 60°C, with an activation energy of 70 kJ/mol. Conversion limits are observed which strongly depend on the temperature. The stereoselectivity of the reaction with respect to the configurational triads does not depend on the temperature: the distribution of configurations is only dependent on the conversion. Assuming an S_N2 substitution mechanism governed by steric factors, the Monte Carlo simulation procedure described in a prior study is shown to give a good account for all temperatures above 40°C assuming for the mm, mr or rm, and rr triads a reactivity such as R_mm = 2 R_mr and R_rr nil at low temperature and very low at temperatures ≥ 40°C. The low conversion limits observed at 5 and 25°C cannot be explained by a limited accessibility of a part of the polymer. Finally, it is shown that the elimination reaction, which remains limited, does not interfere with the substitution process.     

Studies on the tacticity of polyacrylonitrile. III. NMR spectra of stereoisomers of 2,4,6-tricyanoheptane as model compounds of polyacrylonitrile

The three stereoisomers of 2,4,6-tricyanoheptane were separated and their NMR spectra were studied as the three-unit model compounds of polyacrylonitrile. The chemical shifts and coupling constants obtained from the NMR spectra were compared to those of the two-units model compounds. The geminal protons for the isotactic methylene are not equivalent, but the difference of the chemical shifts is smaller than that in the meso two-unit model. The racemic methylene signals appear at higher field than the meso methylene in the heterotactic three-unit model as in the case of the racemic and the meso two-unit models. The signals of the methinic protons in triads appear in the order: isotactic CH, heterotactic CH, and syndiotactic CH from the high field. From the observed values of the vicinal coupling constants, the chain conformations of the model compounds are also discussed.     

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.     

The grafting of luminescent side groups onto poly(vinyl chloride) and the identification of local structural features

The phosphorescence and fluorescence emitted by both the chromophores existing in raw PVC (allylic and ketoallylic structures and polyenes) and luminescent probes introduced by substitution of chlorine atoms have been used to study local features of the chain microstructure, namely the formation of blocky sequences during the nucleophilic substitution of chlorine atoms and the length and nature of the chain segments relaxing below T_g, i.e., the β relaxation. The comparison with results obtained by dynamic mechanical analysis of some of the copolymers has been carried out. Blocky sequences are found to exist and all isotactic sequences over a diad together with their heterotactic associated triads are found to participate in the β motions.     

End‐functionalization of isotactic polypropylene via consecutive chain transfer reaction to norbornadiene and hydrogen

Structurally well‐defined end functionalized isotactic polypropylene (iPP) is prepared by conducting a selective chain transfer reaction during the isospecific polymerization of propylene in the presence of norbornadiene (NBD) and hydrogen using rac‐Me₂Si(2‐Me‐4‐Ph‐Ind)₂ ZrCl₂/MAO as the catalyst. The production of NBD‐capped iPP involves a unique consecutive chain transfer reaction, first to NBD and then to hydrogen, for situating the incorporated NBD at the iPP chain end. The NBD end group of NBD‐capped iPP can be converted into other reactive functional group through functional group transformation reactions. The resulting functional group end‐capped iPP can be used for the construction of stereoregular block copolymers (e.g., iPP‐b‐PMMA and iPP‐b‐PS) through postpolymeriztion reactions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011