Crystallization-induced reactions of copolymers. II. Cis-trans isomerization of 1,4-poly-1,3-butadiene

The cis-trans photoisomerization reaction of 1,4-polybutadiene was carried out below the melting points on films of polymers containing high trans-1,4 contents. Under the proper conditions of temperature and polymer composition, the reaction was observed to undergo an anti-equilibrium behavior, which was attributed to an irreversible crystallization of repeating units after isomerization from cis to trans structure. As a result, the trans composition passed through a minimum with reaction time while crystallinity increased throughout the reaction, and unexpectedly the β crystalline form was observed well below the α–β transition temperature. The composition–time behavior observed was rationalized on the basis of incorporation of trans units into crystalline regions on the lamellar fold surfaces and discussed within the framework of the proposed requirements for crystallization-induced reactions of copolymers.     

Syndiotactic 1,2-polybutadiene with Co-CS2 catalyst system. I. Preparation,properties, and application of highly crystalline syndiotactic 1,2-polybutadiene

Highly crystalline syndiotactic 1,2-polybutadiene (s-PB) having melting point (mp) up to 216°C was obtained by using a Co(acac)₃-AIEt₃-CS₂ catalyst. The polymer with mp 208°C was found to have 99.7% 1,2 content and 99.6% syndiotacticity by ¹H and ¹³C-NMR measurements. The s-PB can be molded by addition of a stabilizer such as 2,6-di-t-butyl-4-hydroxymethylphenol into fiber, film, and various shaped articles. The physical properties presented in the present article include stress-strain and dynamic mechanical behavior. The highly crystalline syndiotactic 1,2-polybutadiene was applied to a carbon fiber and UBEPOL VCR (cis-1,4-polybutadiene reinforced by fibrous syndiotactic 1,2-polybutadiene).     

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.     

Synthesis and characterization of polymers of 1,4-hexadienes

The homopolymerization of trans-1,4-hexadiene, cis-1,4-hexadiene, and 5-methyl-1,4-hexadiene was investigated with a variety of catalysts. During polymerization, 1,4-hexadienes undergo concurrent isomerization reactions. The nature and extent of isomerization products are influenced by the monomer structure and polymerization conditions. Nuclear magnetic resonance (NMR) and infrared (IR) data show that poly(trans-1,4-hexadiene) and poly(cis-1,4-hexadiene) prepared with a Et₃Al/α-TiCl₃/hexamethylphosphoric triamide catalyst system consist mainly of 1,2-polymerization units arranged in a regular head-to-tail sequence. A 300-MHz proton NMR spectrum shows that the trans-hexadiene polymer is isotactic; it also may be the case for the cis-hexadiene polymer. These polymers are the first examples of uncrosslinked ozone-resistant rubbers containing pendant unsaturation on alternating carbon atoms of the saturated carbon-carbon backbone. Polymerization of the 1,4-hexadienes was also studied with VOCl₃- and β-TiCl₃-based catalysts. Microstructures of the resulting polymers are quite complicated due to significant loss of unsaturation, in contrast to those obtained with the α-TiCl₃-based catalyst. In agreement with the literature, there was no discernible monomer isomerization with the VOCl₃ catalyst system.     

Synthesis of difunctional 1,4-dimethyl-1,4-disilacyclohexanes

Transformations of HVinSiCl₂, HVinSi(Me)Cl, HVinSi(Me)Ph, and HVinSi(Me)NEt₂ in the presence of Pt catalyst were studied. In dilute solutions, the reaction gave a mixture of structural and stereoisomers of five- and six-membered disilacyclanes, resulting from intramolecular cyclization of the initially formed linear dimer. In the case of methyl(phenyl)disilacyclane, the structural isomers were separated andtrans-1,4-dimethyl-1,4-diphenyl-1,4-disilacyclohexane was isolated. The reaction of this product with HCl in the presence of AlCl₃ followed by hydrolysis resulted in the synthesis oftrans-1,4-dichloro- andtrans-1,4-dihydroxy-1,4-dimethyl-1,4-disilacyclohexanes. The structures of the structural and stereoisomers synthesized were confirmed by¹H,¹³C, and²⁹Si NMR and IR spectroscopies and mass spectrometry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1734–1738, September, 1999.     

Configurational characteristics of trans-1,4-polychloroprene: Experimental results on the unperturbed dimensions and their temperature coefficient

Polychloroprene [CCl?CH? CH₂? CH₂? ]_x of approximately 95% trans-1,4 stereochemical structure was prepared by low-temperature emulsion polymerization. Fractions, obtained by liquid–liquid precipitations were studied in toluene solutions at 30°C by viscometry and osmometry. In addition, force–temperature measurements were carried out on networks of the polymer in the amorphous state. The results obtained on the polymer solutions indicate that the unperturbed dimensions of trans-1,4-polychloroprene are essentially the same as those of trans-1,4-polybutadiene of the same molecular weight. This observation, that substitution of a relatively large Cl atom for one of the methine H atoms in the trans-1,4-polybutadiene repeat unit has little effect on the chain dimensions, suggests that this increase in substituent size is offset by the fact that the length of a C? Cl bond is very much greater than that of a C? H bond. The results obtained on the polymer networks indicate that the unperturbed dimensions of trans-1,4-polychloroprene decrease significantly with increasing temperature, as has also been reported for both trans-1,4-polybutadiene and trans-1,4-polyisoprene.     

PREPARATION AND CHARACTERIZATION OF cis-,4-POLYBUTADIENE CONTAINING A FRACTION OF trans-1,4-POLYBUTADIENE

Polymerization of butadiene catalysed first with V(acac)_3-Al(i-Bu)_2Cl, then with Co(acac)_3-H_2O-Al(i-Bu)_2Cl has been studied. The polymer obtained was identified to be a new variety of cis-1,4-polybutadiene which contained a fraction of trans-1,4-polybutadiene chemically bonded to the cis-1,4-polybutadiene chains. Its molecular weight and trans-1,4 content can be regulated by varying the catalyst composition and concentration as well as other polymerization conditions. The trans-1,4 fraction, although it presents only in 9—16%, forms a crystalline phase in the matrix at room temperature and facilitates the crystallization of the polymer.     

Microstructure of polyisoprene produced by cationic polymerization: NMR spectroscopic study

High-resolution ¹H and ¹³C NMR spectroscopy, including two-dimensional heteronuclear experiments, has been used to study the microstructure of polyisoprene produced by cationic polymerization. It is shown that macromolecules resulting from both regular and inverse additions are predominantly composed of trans-1,4-units, while 1,2- and 3,4-units are present in small amounts. NMR spectra demonstrate the absence of cis-1,4-units in the polymer, whereas broad signals (pedestals) are related to the presence of saturated structures. It is proposed to determine the content of trans-1,4-, 1,2-, and 3,4-units in cationic polyisoprene via the combined measurements of intensities of signals in the olefinic regions of ¹H and ¹³C NMR spectra.     

Structure of polypiperylene chain segments according to high-resolution 13C NMR spectra

The microstructure of stereoregular 1,4-trans-and 1,4-cis-polypiperylenes, as well as polymers prepared from the trans-and cis-piperylene isomers via cationic polymerization in the presence of TiCl₄, was studied by high-resolution ¹³C NMR spectroscopy. Polypiperylene synthesized through the cationic polymerization of the cis isomer had a more diversified morphology of the macromolecular chain, i.e., had higher relative amounts of 1,2-cis-units and combinations of irregular-addition 1,4-trans-units. It was shown that ¹³C NMR spectra give the most comprehensive and independent information on the details of structure of the piperylene macromolecular chain.     

Kinetics of the reactions of cyclopropane derivatives. V. The gas-phase unimolecular reactions of 1 α-chloro-2α,3α-dimethylcyclopropane and 1α-chloro-2α,3β-dimethylcyclopropane

Thermolysis of the “all-cis” compound 1α-chloro-2α,3α-dimethylcyclopropane (A) at 550–607 K and 6–115 torr is a first-order homogeneous non-radical-chain process giving penta-1,3-diene (PD) and HCl as products. The Arrhenius parameters are log₁₀A(sec^?1) = 13.92 ± 0.08 and E = 199.6 ± 0.9 kJ/mol. The isomer with trans-methyl groups, 1α-chloro-2α,3β-dimethylcyclopropane (B) reacts by two parallel first-order processes giving as observed products trans-4-chloropent-2-ene (4CP) and PD + HCl, with log₁₀A(sec^?1) = 14.6 and 13.8, respectively, and E = 199.5 and 190.2 kJ/mol, respectively. The 4CP undergoes secondary decomposition to PD + HCl (as investigated previously). Comparison of the results for compounds (A) and (B) with those for other gas-phase and solution reactions leads to the conclusion that the gas-phase thermolyses proceed by rate-determining ring opening to form olefins which may decompose further by thermal or chemically activated reactions, and that the ring opening is a semiionic electrocyclic reaction in which alkyl groups in the 2,3-positions trans to the migrating chlorine semianion move apart, with appropriate consequences for the rate of reaction and the stereochemistry of the products.     

Crystallization of trans-1,4-polyisoprene and of hydrochlorinated segmented block copolymer derivatives from solution

Crystallization of trans-1,4-polyisoprene from the mixed solvent pair hexane/2-pentanone was carried out and the effects on the morphology of seeding and the solvent composition were studied. α-TPI lamellae obtained by crystallization from a single solvent, hexane, at 20°C and by mixed-solvent crystallization at 40°C were characterized by DSC, FTIR, and suspension epoxidation/C-13 NMR. Crystalline stem lengths of 14.5 and 18 and a fold length of 10 monomer units were found. Segmented block copolymers were prepared by reaction of TPI lamellae in acetone suspension with HCl at ?7°C. These products were dissolved in 2-pentanone and precipitated at 0°C. A lamellar morphology, the details of which depend on the TPI block length, was observed by SEM; both preparations showed sharp endotherms; and the FTIR was characteristic of a combination of amorphous TPI, amorphous hydrochlorinated TPI, and of either the β crystalline form or both the α and β forms for TPI depending on the sample.     

Carbon-13 NMR of polybutadiene

By using the carbon-13 NMR technique, it is shown that there are no cis-1,4–trans-1,4 linkages in a n-BuLi-catalyzed polybutadiene. The polymer consists of “blocks” of cis-1,4 units and trans-1,4 units separated by isolated vinyl units. Preliminary evidence suggests this might also be true for other types of 1,3-diene polymerization. Some of the implications of this finding on the mechanism of polymerization are discussed. Tacticity triad distributions are readily determined in polybutadienes with high 1,2 addition contents.     

Stimuli-responsive polymers. III. Poly(aryl ether ketone amide)s with reversible trans- ↔ cis-4,4′-azobenzene and fixed 2,2′-binaphthyl kinking elements in the main chain

The low-temperature polycondensation of trans-azobenzene-4,4′-dicarbonyl chloride with (S)-(−)-1,1′-binaphthyl-2,2′-diamine and/or 1,4-bis(3-aminophenoxy-4′-benzoyl)benzene afforded a new series of poly(aryl ether ketone amide)s with both fixed and photoinducible kinking elements positioned randomly along the main chain. In their lower energy, trans-azobenzene configurations, the orange, film-forming materials were amorphous, highly tractable, and thermally stable under air or nitrogen up to about 420°C. Variants endowed with higher loadings of the bent binaphthyl monomer were soluble in a variety of organic solvent media including THF and acetone. The introduction of cis-azobenzene backbone kinks into these materials was carried out by irradiating the polymer solutions with near-UV light. Up to 70% of the azobenzene moieties in these polymers were capable of assuming the higher energy cis-configuration, thus greatly increasing the number of bent or kinked sites positioned along each polymer backbone. In solution, reverse cis → trans isomerization reactions were triggered thermally and were quantitatively tracked by both optical absorbance and ¹H NMR spectroscopies. Activation parameters calculated for cis → trans reorganization of the polymer backbone were not dependent upon the chemical composition or molecular weight of the polymers but did exhibit a small dependence upon the nature of the solvent medium used to conduct the isomerization experiment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2827–2837, 1998     

Kinetic study of chemically activated chlorocyclopropane

Chlorocyclopropane has been produced by addition of CH₂(¹A₁) and CH₂(³B₁) to chloroethene. CH₂ was generated by the photolysis of ketene at 313 and 366 nm. Chlorocyclopropane was formed in a chemically activated state, had an energy content between 378 and 427 kJ/mol, and reacted in three parallel channels to 3-chloropropene, cis- and trans-1-chloropropene. As secondary reactions elimination of HCl from the chemically activated primary products occurred to form allene and propyne. The apparent rate constants for the isomerization and elimination reactions are reported. The results of RRKM calculations including distribution functions for the activated chlorocyclopropane and a stepladder model for the deactivation support the proposed reaction scheme.     

STUDIES ON THE ~(13)C-NMR SPECTRA OF ALTERNATING COPOLYMERS OF CONJUGATED DIENES WITH METHYL ACRYLATE

The ~(13)C-NMR spectra of alternating copolymers of conjugated dienes, butadiene (BD), isoprene(IP) and chloroprene (CP), with methyl acrylate (MA) were studied. It is proved that they are allalternating copolymers. The BD units in Poly (BD-alt-MA) are joined to MA mainly in the formof trans 1,4-structure. The contents of trans 1,4-, cis 1,4-and 1,2-structure are 88, 7 and 5%, res-pectively. The IP and CP units in Poly(IP-alt-MA) and Poly(CP-alt-MA) exist essentially as trans1,4-configuration and connect with MA units in "head to head" arrangement predominantly, whileCP-CP units present in Poly(CP-alt-MA) in a small quantity.     

烃基硅铜酸盐与2-芳基-2-环烯酮1,4-加成反应的立体选择性及2-取代- 3-硅基环烷酮的合成

研究了烷基苯基硅铜酸盐与2-环烯酮的1,4-加成反应的立体选择性, 并合成了一系列新的2-取代-3-硅基环烷酮. 结果表明, 在0 ℃下用饱和NH₄Cl溶液处理, 烷基苯基硅铜酸盐与2-芳基-2-环烯酮的1,4-加成反应的立体选择性不同程度地受芳基和环的大小影响, 得到顺、反两种产物; 并首次发现室温下用甲醇处理反应时, 其立体选择性不受或者很少受环大小、芳基的性质以及与硅原子相连的取代基的影响, 只得到反式产物. 芳基溴甲烷与由烷基苯基硅铜酸盐与2-环烯酮1,4-加成所得的烯醇盐反应时, 只得到反式产物. 合成产物的结构用IR, ¹H NMR, ¹³C NMR, MS和HRMS等进行了表征.     

Syndiotactic 1,2-polybutadiene with Co-CS2 catalyst system. III. 1H- and 13C-NMR study of highly syndiotactic 1,2-polybutadiene

The ¹H and ¹³C-NMR spectra of highly crystalline syndiotactic 1,2-polybutadiene (s-PB) are discussed in order to clarify the mechanism of butadiene polymerization with cobalt compound–organoaluminum–CS₂ catalysts. Cis opening of the double bonds in the syndiotactic polymerization is affirmed by the study of the copolymer from perdeuteriobutadiene and cis,cis-1,4-dideuteriobutadiene. S-PB (mp 210°C) has 99.7% 1,2 units, 0.3% isolated cis-1,4 units, and 99.6% syndiotacticity. Polymer ends (2-methyl-3-butenyl group and conjugated diene structure) are also determined. The differences in free energy of activation between 1,2 and cis-1,4 propagation and between syndiotactic and isotactic propagation are 14.0 and 9.6 kcal/mol, respectively, for Co(acac)₃-AlEt₃-AlEt₂Cl-CS₂, and 6.7 and 5.7 kcal/mol, respectively, for the aluminum-free Co(C₄H₆)(C₈H₁₃)CS₂ system. The conformation of s-PB in o-dichlorobenzene at 150°C is described by the sequence (tt)_1.6(gg)(tt).     

Thermotropic copolyesters. II. Synthesis and characterization of liquid-crystal copolyesters containing the bicyclo[2.2.2]octane ring system

The syntheses and characterizations of poly(oxy-trans-1,4-cyclohexyleneoxycarbonyl-1,4-bicyclo[2.2.2]octylenecarbonyl) (I) and poly(oxy-trans-1,4-cyclohexyleneoxycarbonyl-1,4-bicyclo[2.2.2]octylenecarbonyl-co-oxy-trans-1,4-cyclohexyleneoxysebacoyl) (II) are described. The polymer systems were characterized by infrared spectroscopy, proton magnetic resonance spectroscopy, solution viscosity, and differential scanning calorimetry. The random copolyester prepared from 1:0.65:0.35 mol of trans-1,4-cyclohexanediol, bicyclo[2.2.2]octane-1,4-dicarbonyl chloride, and sebacoyl chloride, respectively, formed a birefringent fluid state in the melt.     

A Novel Transparent Polyacetylene Bearing a Triphenylamine Moiety Prepared with a [Rh(norbornadiene)Cl]2 Catalyst

Novel soluble polyacetylenes having a triphenylamine moiety were synthesized by a [Rh(norbornadiene)Cl]₂ catalyst under quite mild conditions in fairly high yields. The obtained polymer showed to have trans-transoid sequence as the major main-chain structure which was generated through the so-called cis-to-trans isomerization was already induced even during the polymerization. The HCl doping of the polymer was resulted in the formation of the oxidized polymer where the so-called polaron or bipolaron was produced. In addition, we found that in the case of the pristine polymer unpaired electrons mainly localized on the triphenylamine moiety as the side chain. On the other hand, after the doping the unpaired electron delocalized on the main chain of the polymer.     

Quantitative estimation of trans-1,4 and cis-1,4 isomers in polychloroprene by high-resolution NMR

In the ¹H-NMR spectrum of polychloroprene dissolved in C₆D₆, the ?CH proton signal was separated into two triplet peaks. These triplet signals were assigned to the ?CH proton in the trans-1,4 and cis-1,4 isomers by measurement of ¹H-NMR spectra of 3-chloro-1-butene and a mixture of trans- and cis-2-chloro-2-butene as model compounds for the 1,2, trans-1,4 and cis-1,4 isomers. In ¹H-NMR spectra (220 Mcps) of polychloroprene dissolved in C₆D₆, two triplet signals were separated completely from which the relative concentrations of trans-1,4 and cis-1,4 isomers could be obtained quantitatively.