Highly trans‐1,4‐specific polymerization of 1,3‐butadiene catalyzed by [2,6‐bis{(4S)‐ (−)‐isopropyl‐2‐oxazolin‐2‐yl}pyridine] chromium complex activated with modified methylaluminoxane

Chromium complexes with N,N,N‐tridentate ligands, LCrCl₃ (L = 2,6‐bis{(4S)‐(?)‐isopropyl‐2‐oxazolin‐2‐yl}pyridine ( 1 ), 2,2′:6′,2″‐terpyridine ( 2 ), and 4,4′,4″‐tri‐tert‐butyl‐2,2′:6′,2″‐terpyridine ( 3 )), were prepared. The structures of 1 and 2 were determined by X‐ray crystallography. Upon activation with modified methylaluminoxane (MMAO), 1 catalyzed the polymerization of 1,3‐butadiene, while 2 and 3 was inactive. The obtained poly(1,3‐butadiene) obtained with 1 ‐MMAO was found to have completely trans‐1,4 structure. The 1 ‐MMAO system also showed catalytic activity for the polymerization of isoprene to give polyisoprene with trans‐1,4 (68%) and cis‐1,4 (32%) structure. Copyright © 2011 Society of Chemical Industry     

High cis‐1,4 polyisoprene or cis‐1,4/3,4 binary polyisoprene synthesized using 2‐(benzimidazolyl)‐6‐(1‐(arylimino)ethyl)pyridine cobalt(II) dichlorides

Polyisoprene (PI) with a high content of cis‐1,4 (up to 95%) or cis‐1,4/3,4 binary structures was synthesized using a cobalt system in toluene. The cobalt system, which exhibited high activities (up to 3.50 × 10⁶ g PI (mol Co)^?1 h^?1), contained a series of 2‐(benzimidazolyl)‐6‐(1‐(arylimino)ethyl)pyridine cobalt(II) dichlorides activated with ethylaluminium sesquichloride. The nature of the ligands and the reaction conditions significantly affected both the catalytic performance of the cobalt complexes as well as the structures of the resultant PI. The stereospecific polymerization of isoprene could be tuned via changing either the co‐catalyst or solvent: for example, increased content of 3,4 PI (up to 36.6%) was achievable in heptane in the presence of diethylaluminium chloride. Sequence distribution analysis by ¹³C NMR spectroscopy indicated that most 3,4 units occurred randomly in the PI chains. © 2013 Society of Chemical Industry     

Salicylidene‐imine–zirconium(IV) complexes in combination with methylalumoxane as catalysts for the conversion of hexa‐1,5‐diene: adjusting of the catalytic activity

A variety of substituted schiff base complexes of the composition (“salen”)ZrCl₂(thf) ( 1 – 21 ) were synthesized, with methylalumoxane (“MAO”) activated and used for a systematic study of their catalytic activity towards hexa‐1,5‐diene (“salen”: substituted salicylidene–ethylene‐iminato ligands). Main product of the catalytic cycle is methylenecyclopentane. Dimers are only formed in minor amounts. The catalytic activity and selectivity of the Ziegler–Natta systems strongly depend on the nature and the position of the peripheric substituents in the Schiff base ligands. Electron‐withdrawing substituents in para‐position to the phenolato oxygen (5‐position) decrease the catalytic activity. Improved activity and selectivity were obtained with electron‐donating substituents in 5‐position. Altering the ethylene bridge causes a lowering of the activity or inactivation. According to the x‐ray analysis the metal center in the related complex (L)ZrCl₂ ( 22 ) (L: N′,N′‐bis(ethylene)‐N′‐methyl‐N,N′′‐bis(benzoylacetonato‐imine) has a pentagonal‐bipyramidal environment. The pentadentate schiff base ligand lies in the plane, and both chloro groups occupy the axial positions. In contrast to the catalytically active salene complexes 22 can not rearrange to form a species in which the both chlorides are cis to each other. Consequently 22 is catalytically inactive.     

1,3‐butadiene polymerization using Co/Nd‐based Ziegler/Natta catalyst: Microstructures and properties of butadiene rubber

Among Ziegler‐Natta catalysts used for 1,3‐butadiene (1,3‐BD) polymerization, the advantage of a neodymium (Nd)‐based catalyst is that it provides butadiene rubber (BR) with a high content of cis?1,4 configuration and a low amount of vinyl?1,2 units. Whereas, a cobalt (Co)‐based catalyst can produce BR with a low content of trans?1,4 configuration. Thus, this research was aimed to prepare BR containing a high content of cis?1,4 configuration with low amounts of both trans?1,4 and vinyl?1,2 units using a combination of Nd‐ and Co‐based Ziegler/Natta catalysts with triethyl aluminum (TEAL) and diethyl aluminum chloride (DEAC) acting as a co‐catalyst and a chlorinating agent, respectively. The effects of the molar Co/Nd ratio, TEAL concentration, DEAC loading, 1,3‐BD content, solvent type, and reaction temperature on % conversion, microstructures, molecular weight, and molecular weight distribution of the obtained BR (Co/Nd‐BR) were evaluated. The Co/Nd‐BR having >97% of cis?1,4 configuration, <2% of trans?1,4 structure, and <1% of vinyl?1,2 unit with >80% conversion was achieved when 3.01 M of 1,3‐BD concentration was treated in a toluene/cyclohexane mixture (7/3 [w/w]). The Co/Nd‐BR exhibited no gel formation with high mechanical performance, which was equivalent to commercial BR produced from a Nd‐based catalyst system. POLYM. ENG. SCI., 55:14–21, 2015. © 2014 Society of Plastics Engineers     

Synthesis of high molecular weight copolymer of styrene and butadiene bearing high 1,4‐cis butadiene unit from copolymerization with CpTiCl3/methylaluminoxane catalyst

Copolymerization of styrene (St) and butadiene (Bd) with CpTiCl₃/methylaluminoxane (MAO) catalyst in the presence or absence of chloranil (CA) was investigated. The CpTiCl₃/MAO catalyst showed a high activity for the copolymerization of St with Bd. The 1,4‐cis contents in the Bd units for the copolymerization of St and Bd with the CpTiCl₃/MAO catalyst was observed, and the 1,4‐cis content was optimum at a MAO/Ti mole ratio of around 225. The effect of the polymerization temperature on the copolymerization was noted, as was the effect of the 1,4‐cis microstructure in the Bd units for the copolymerization of St and Bd. The addition of CA to the CpTiCl₃/MAO catalyst was found to influence the molecular weight of the copolymer. The high weight‐average molecular weight copolymer (M_w = ca. 50 × 10⁴) consisting of mainly a 1,4‐cis microstructure of Bd units (1,4‐cis = 80.0%) was obtained from the copolymerization with the CpTiCl₃/MAO catalyst in the presence of CA (CA/Ti mole ratio = 1) at 0°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2942–2946, 2003     

Synthesis and characterization of poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers by combined ring‐opening polymerization and cross‐coupling processes

2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)₂) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh₃)₄ as catalyst or using the system NiCl₂/bpy/PPh₃/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by ¹H and ¹³C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry     

Enantioselective Synthesis of (−)‐CP‐55940 via Ruthenium‐ Catalyzed Asymmetric Hydrogenation of Ketones

A new and efficient catalytic asymmetric synthesis of the potent cannabinoid receptor agonist (−)‐CP‐55940 has been developed by using ruthenium‐catalyzed asymmetric hydrogenation of racemic α‐aryl ketones via dynamic kinetic resolution (DKR) as a key step. With RuCl₂‐SDPs/diamine [SDPs=7,7′‐bis(diarylphophino)‐1,1′‐spirobiindane] catalysts the asymmetric hydrogenation of racemic α‐arylcyclohexanones via DKR provided the corresponding cis‐β‐arylcyclohexanols in high yields with up to 99.3% ee and >99:1 cis‐selectivities. Both ethylene ketal group at the cyclohexane ring and ortho‐methoxy group at the phenyl ring of the substrates 6 have little effect on the selectivity and reactivity of the hydrogenations. Based on this highly efficient asymmetric ketone hydrogenation, (−)‐CP‐55940 was synthesized in 13 steps (the longest linear steps) in 14.6% overall yield starting from commercially available 3‐methoxybenzaldehyde and 1,4‐cyclohexenedione monoethylene acetal.     

But‐2‐ene‐1,4‐diamine and But‐2‐ene‐1,4‐diol as Donors for Thermodynamically Favored Transaminase‐ and Alcohol Dehydrogenase‐Catalyzed Processes

Both cis‐ and trans‐but‐2‐ene‐1,4‐diamines have been prepared and efficiently applied as sacrificial cosubstrates in enzymatic transamination reactions. The best results were obtained with the cis‐diamine. The thermodynamic equilibrium of the stereoselective transamination process is shifted to the amine formation due to tautomerization of 5H‐pyrrole into 1H‐pyrrole, achieving high conversions (78–99%) and enantiomeric excess (up to >99%) by using a small excess of the amine donor. Furthermore, when the reaction proceeded, a strong coloration was observed due to polymerization of 1H‐pyrrole. A structurally related compound, cis‐but‐2‐ene‐1,4‐diol, has been utilized as cosubstrate in different alcohol dehydrogenase (ADH)‐mediated bioreductions. In this case, high conversions (91–99%) were observed due to a lactonization process. Both strategies are convenient from both synthetic and atom economy points of view in the production of valuable optically active products.

     

Fe(PyTACN)‐Catalyzed cis‐Dihydroxylation of Olefins with Hydrogen Peroxide

A family of iron complexes with general formula [Fe(II)(^R,Y,XPyTACN)(CF₃SO₃)₂], where ^R,Y,XPyTACN=1‐[2′‐(4‐Y‐6‐X‐pyridyl)methyl]‐4,7‐dialkyl‐1,4,7‐triazacyclononane, X and Y refer to the groups at positions 4 and 6 of the pyridine, respectively, and R refers to the alkyl substitution at N‐4 and N‐7 of the triazacyclononane ring, are shown to be catalysts for efficient and selective alkene oxidation (epoxidation and cis‐dihydroxylation) employing hydrogen peroxide as oxidant. Complex [Fe(II)(^Me,Me,HPyTACN)(CF₃SO₃)₂] ( 7 ), was identified as the most efficient and selective cis‐dihydroxylation catalyst among the family. The high activity of 7 allows the oxidation of alkenes to proceed rapidly (30 min) at room temperature and under conditions where the olefin is not used in large amounts but instead is the limiting reagent. In the presence of 3 mol% of 7 , 2 equiv. of H₂O₂ as oxidant and 15 equiv. of water, in acetonitrile solution, alkenes are cis‐dihydroxylated reaching yields that might be interesting for synthetic purposes. Competition experiments show that 7 exhibits preferential selectivity towards the oxidation of cis olefins over the trans analogues, and also affords better yields and high [syn‐diol]/[epoxide] ratios when cis olefins are oxidized. For aliphatic substrates, reaction yields attained with the present system compare favourably with state of the art Fe‐catalyzed cis‐dihydroxylation systems, and it can be regarded as an attractive complement to the iron and manganese systems described recently and which show optimum activity against electron‐deficient and aromatic olefins.     

Gas phase polymerization of 1,3‐butadiene with supported neodymium‐based catalyst: Investigation of molecular weight

The gas phase polymerization of 1,3‐butadiene (Bd), with supported catalyst Nd(naph)₃/Al₂Et₃Cl₃/Al(i‐Bu)₃ or/and Al(i‐Bu)₂H, was investigated. The polymerization of Bd with neodymium‐based catalysts yielded cis‐1,4 (97.2–98.9%) polybutadiene with controllable molecular weight (MW varying from 40 to 80 × 10⁴ g mol^?1). The effects of reaction temperature, reaction time, Nd(naph)₃/Al(i‐Bu)₃ molar ratio, and cocatalyst component on the catalytic activity and molecular weight of polymers were examined. It was found that there are two kinds of active sites in the catalyst system, which mainly influenced the MW and molecular weight distribution of polybutadiene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1945–1949, 2004     

Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene

The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene ( 1 ) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ( ) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (R_p) was found to be R_p = k[AIBN]^0.5[ 1 ]^1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol^?1. The monomer reactivity ratios in copolymerization with styrene were r ₁ = 2.65 and r_st = 0.26. The glass transition temperature of the polymer of 1 was found to be ?78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry     

New fluorine‐containing bissalicylidenimine–titanium complexes for olefin polymerization

Three new titanium complexes bearing salicylidenimine ligands—bis[(salicylidene)‐2,3,5,6‐tetrafluoroanilinato]titanium(IV) dichloride ( 1 ), bis[(3,5‐di‐tert‐butylsalicylidene)‐2,3,5,6‐tetrafluoroanilinato]titanium(IV) dichloride ( 2 ), and bis[(3,5‐di‐tert‐butylsalicylidene)‐4‐trifluoromethyl‐2,3,5,6‐tetrafluoroanilinato]titanium(IV) dichloride ( 3 )—were synthesized. The catalytic activities of 1 – 3 for ethylene polymerization were studied with poly(methylaluminoxane) (MAO) as a cocatalyst. Complex 1 was inactive in ethylene polymerization. Complex 2 at a molar ratio of cocatalyst to pre catalyst of Al_MAO/Ti = 400–1600 showed very high activity in ethylene polymerization comparable to that of the most efficient metallocene complexes and titanium compounds with phenoxy imine and indolide imine chelating ligands. It gave linear high‐molecular‐weight polyethylene [weight‐average molecular weight (M_w) ≥ 1,700,000. weight‐average molecular weight/number‐average molecular weight (M_w/M_n) = 4–5] with a melting point of 142°C. The ability of the 2 /MAO system to copolymerize ethylene with hexene‐1 in toluene was analyzed. No measurable incorporation of the comonomer was observed at 1:1 and 2:1 hexene‐1/ethylene molar ratios. However, the addition of hexene‐1 had a considerable stabilizing effect on the ethylene consumption rate and lowered the melting point of the resultant polymer to 132°C. The 2 /MAO system exhibited low activity for propylene polymerization in a medium of the liquid monomer. The polymer that formed was high‐molecular‐weight atactic polypropylene (M_w ～ 870,000, M_w/M_n = 9–10) showing elastomeric behavior. The activity of 3 /MAO in ethylene polymerization was approximately 70 times lower than that of the 2 /MAO system. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1040–1049, 2005     

Light‐induced cooperative electron–proton transfer in hydrogen‐bonded networks of N,N‐diaryl substituted 1,4‐bisimines and meso‐1,2‐diaryl‐1,2‐ethanediols

The 1:1 cocrystallization of 1,4‐diaryl‐1,4‐bisimines (Ar–CHN–CH₂‐)₂ 4 – 11 and substituted meso‐1,2‐diaryl‐1,2‐ethanediols 1 – 3 leads to supramolecular structures in which the diol is hydrogen bonded by one of its hydroxy groups to an imine nitrogen atom of a 1,4‐bisimine. The second functionality in each molecule leads to the generation of ladderlike polymeric structures where each molecule of the diol is linked to two molecules of the 1,4‐bisimine and vice versa. If the diol carries electron donor groups in the aromatic residue and the 1,4‐bisimine correspondingly acceptor groups, then charge transfer interactions are observed. The excited CT complex which corresponds to a radical ion pair is stabilized by migration of a proton of a hydroxy group to the nitrogen atom of an imino group. This is supported by the appearance of a N–H vibration in the IR spectra. The reorganization is also accompanied by changes in the UV/Vis spectra and by the generation of paramagnetism in the crystalline material. The results represent a type of photochromism which has its origin in a light‐induced cooperative electron–proton transfer. The photochromism is thermally reversible.     

Poly(1,4‐cyclohexylenedimethylene‐1, 4‐cyclohexanedicarboxylate): analysis of parameters affecting polymerization and cis–trans isomerization

Weatherable semicrystalline polyesters based on 1,4‐cyclohexanedimethanol, 1,4‐cyclohexanedicarboxylic acid (CHDA) or dimethyl 1,4‐cyclohexane dicarboxylate (DMCD) can be prepared under normal melt‐phase conditions, using titanium tetrabutoxide as catalyst. The effect of monomer ratio, reaction temperature and catalyst loading on the final polymer properties was studied. Under the proper polymerization conditions, poly(1,4‐cyclohexylenedimethylene‐1,4‐cyclohexanedicarboxylate) polymers with high molecular weight can be obtained. During polymerization, isomerization can occur towards the thermodynamically stable cis‐trans ratio of 34–66 mol%. Carboxylic acid end groups can catalyze the isomerization and therefore the polymerization is more critical starting from CHDA rather than DMCD. Moreover, temperature control becomes a key factor to avoid or to limit isomerization. The study of the isomerization of the different monomers permitted a better understanding of the isomerization and therefore of the polymerization process. Copyright © 2011 Society of Chemical Industry     

Efficient Catalytic Asymmetric Synthesis of trans‐5‐Aryl‐2‐substituted Cyclohexanones by Rhodium‐Catalyzed Conjugate Arylation of Racemic 6‐Substituted Cyclohexenones

Catalytic asymmetric conjugate arylation of racemic 6‐substituted cyclohexenones with arylboronic acids was catalyzed by 3 mol % of chiral amidophosphane‐[RhCl(C₂H₄)]₂ in a 10:1 mixture of 1,4‐dioxane and water at 70 °C to afford a nearly 1:1 mixture of trans‐ and cis‐5‐aryl‐2‐substituted cyclohexanones in high enantioselectivity, which was subsequently epimerized with sodium ethoxide in ethanol to give thermodynamically stable trans‐5‐aryl‐2‐substituted cyclohexanones with 99–97 % ee in high two‐step yields.     

Semiconductive poly[N1,N4‐bis(thiophen‐2‐ylmethylene)benzene‐1,4‐diamine]‐nickel oxide nanocomposite based ethanol sensor

This study aims to use the conductivity of a synthetic polymer as the sensing probe for ethanol. In order to enhance the sensitivity of the sensor, a composite of the polymer and nickel oxide (NiO) nanoparticles was formed as it improved the conductivity. This composite exhibited 100 times more conductivity than the neat polymer. The semiconductive nanocomposite of poly [N¹,N⁴‐bis(thiophen‐2‐ylmethylene)benzene‐1,4‐diamine]‐nickel oxide (PBTMBDA‐NiO) was prepared by in situ chemical oxidative polymerization. The monomer was N¹,N⁴‐bis(thiophen‐2‐ylmethylene)benzene‐1,4‐diamine (BTMBDA). The monomer (BTMBDA), polymer (PBTMBDA), and NiO nanoparticles used in this study were synthesized. The monomer was prepared by refluxing together 2‐thiophene carboxaldehyde, benzene‐1,4‐diamine, and few drops of glacial acetic acid in ethanol medium for 3 h. The polymer, PBTMBDA, was formed by the chemical oxidative polymerization of BTMBDA in chloroform by FeCl₃. NiO nanoparticles were prepared by slow addition of aqueous ammonia to anhydrous nickel chloride at room temperature (28 ± 2 °C), and at a pH of 8 under constant stirring condition. The composite was formed by in situ chemical oxidative polymerization of BTMBDA in chloroform by FeCl₃ in the presence of the dispersed NiO nanoparticles. The molecular structure of BTMBDA and PBTMBDA were confirmed by nuclear magnetic resonance (NMR) (¹H, ¹³C, and Dept‐90°), Fourier transform infrared spectroscopy, and ultraviolet (UV)–visible spectroscopy. The PBTMBDA and PBTMBDA‐NiO nanocomposite were characterized by X‐ray diffraction, thermogravimetric analysis, field emission scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy analysis. The results of characterization studies indicate the strong interaction between PBTMBDA and NiO in the nanocomposite. The broadness of ¹H NMR peaks in PBTMBDA was due to the increased number of monomer units. The disappearance of the peak of α‐hydrogens on thiophene confirms the polymerization involving the fifth position of thiophene part of BTMBDA. The Fourier transform infrared spectroscopy spectra revealed that position of the characteristic peaks of the functional groups in the monomer shifted toward lower wave numbers in PBTMBDA and PBTMBDA‐NiO nanocomposite. This shifting confirms the presence of extended conjugation along the polymer backbone. Electronic spectra of these compounds showed three absorption bands corresponding to π→π*, n→π* and n→π* transitions of π electron of carbon, lone pair electrons of S, and lone pair electrons of N (imine) groups, respectively. From the Tafel plot, the exchange current density evaluated for the BTMBDA and PBTMBDA are 0.2815 × 10⁻⁸ and 1.1508 × 10⁻⁸ A cm⁻², respectively. PBTMBDA is evaluated to be a better electrode material than the BTMBDA. The X‐ray diffraction plots showed that the characteristic peak of NiO in PBTMBDA‐NiO nanocomposite suggested successful incorporation of NiO in PBTMBDA‐NiO nanocomposite. The thermogravimetric analysis revealed the improved thermal stability of the composite. Field emission scanning electron microscopy and energy‐dispersive X‐ray spectroscopy analysis confirmed the presence of the NiO in the composite. Incorporation of nickel oxide nanoparticles improved the electrical conductivity and stability of PBTMBDA. The conductivity of the polymer was found to be of the order of 10⁻⁵ S cm⁻¹ while that of the composite was of the order of 10⁻³ S cm⁻¹. The nanocomposite was found to be thermally more stable than PBTMBDA and exhibited better direct‐current electrical conductivity and isothermal stability than the PBTMBDA as revealed by the four‐probe study. The electrical conductivity as inferred from the four‐probe method was used as the parameter to study the isothermal stability of the composite. The PBTMBDA‐NiO nanocomposite based vapor sensor was constructed for the sensing of ethanol vapor in commercial ethanol and real samples (alcoholic drinks: Beer, Wine, Brandy, Vodka, Whisky, and Rum) It was observed that on exposure to ethanol vapor at ambient temperature, the electrical resistivity of the nanocomposite increased indicating suppression of charge carriers. The interaction of ethanol vapor with PBTMBDA in PBTMBDA‐NiO nanocomposite was confirmed by IR spectral technique. The change in the structure of the PBTMBDA on interaction with ethanol was highlighted by the changes in the infrared spectrum. The conductivity of the polymer was explained using the structure‐activity relationship of the monomer evaluated using Gaussian 09 software. This study also analyzed the total electron density with electrostatic potential of the monomer and its correlation with chemical reactivity in order to explain the ethanol vapor sensing‐property of the nanocomposite. A new method of ethanol vapor sensing by a conducting polymer composite is hereby reported. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45918.     

Investigation of kinetics of 4‐methylpentene‐1 polymerization using Ziegler–Natta‐type catalysts

The kinetics of 4‐methylpentene‐1 (4MP1) polymerization by use of Ziegler–Natta‐type catalyst systems, M(acac)₃‐AlEt₃ (M = Cr, Mn, Fe, and Co), are investigated in benzene medium at 40°C. The effect of various parameters such as Al/M ratio, reaction time, aging time, temperature, catalyst, and monomer concentrations on the rate of polymerization and yield are examined. The rate of polymerization increased linearly with increasing monomer concentration with first‐order dependence, whereas the rate of polymerization with respect to catalyst concentration is found to be 0.5. For all cases, the polymer yield is maximum at an Al/M ratio of 2. The activation energies obtained from linear Arrhenius plots are in the range of 25.27–33.51 kJ mol^?1. It is found that the aging time to give maximum percentage yield of the polymer varies with the catalyst systems. Based on the experimental results, a plausible mechanism is proposed that envisages a free‐radical mechanism. Characterization of the resulting polymer product, for all the cases, through FTIR, ¹H‐NMR, and ¹³C‐NMR studies, showed isomerized polymeric structures with 1,4‐structure as dominant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2468–2477, 2003     

In Situ Preparation of a Compatibilized Poly(cis‐1,4‐butadiene)/Poly(ε‐caprolactone) Blend

The ternary Ziegler‐Natta‐type catalyst system based on neodymium versatate (NdV), diisobutylaluminium hydride (DIBAH) and ethylaluminium sesquichloride (EASC) was used for the in situ preparation of a compatibilized blend consisting of poly(cis‐1,4‐butadiene) (BR = butadiene rubber) and poly(ε‐caprolactone) (PCL). Poly(cis‐1,4‐butadiene)‐block‐poly(ε‐caprolactone) which acts as compatibilizer for the two immiscible polymers BR and PCL was obtained by a two step sequential polymerization with the preparation of a living cis‐1,4‐BR building block in the first stage and the subsequent polymerization of CL during the second stage. This preparation method resulted in a polymer blend comprising the homopolymers BR and PCL as well as the block copolymer BR‐block‐PCL. For detailed characterization the block copolymer was separated from the respective homopolymers BR and PCL by means of fractionation with the binary solvent mixture dimethylformamide/methylcyclohexane (DMF/MCH) which mixes well at elevated temperature and exhibits phase separation at ambient temperature. ¹H NMR, IR, SEC and TEM were used for characterization of the block copolymer.

TEM of BR‐block‐PCL.     

Synthesis and characterization of poly (styrene‐b‐[(butadiene)1−x‐(ethylene‐co‐butylene)x] ‐b‐styrene) star‐like molecular polymers produced by partial hydrogenation of SBS

This article reports the synthesis and characterization of four arm star‐shaped poly(styrene‐b‐[(butadiene)_1?x‐(ethylene‐co‐butylene)_x]‐b‐styrene) (SBEBS) copolymers. A series of SBEBS copolymers with different compositions of the elastomeric block were produced by hydrogenating a given poly(styrene‐b‐butadiene‐b‐styrene) (SBS) copolymer using a catalyst prepared from bis(η⁵‐cyclopentadienyl)titanium(IV) dichloride and n‐butyllithium. The characterization was accomplished by proton nuclear magnetic resonance spectroscopy (¹H NMR), infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The results indicate that there is a selective saturation of the polybutadiene block over the polystyrene block; this selectivity was determined by the Ti/Li molar ratio and the concentration of Ti. It was observed that the saturation rate of the 1,2‐vinyl was higher than that of the 1,4‐trans and 1,4‐cis poly(butadiene)‐b isomers. The DSC and DMA results indicate that the degree of hydrogenation had a profound effect on the polymer's relaxation behavior. All samples exhibited a biphasic system behavior with two distinct transitions corresponding to the elastomeric and polystyrene blocks. SBEBS copolymers with higher saturation levels (>33%) exhibited a crystalline character. The TGA results indicated a characteristic weight loss temperature in all samples, with slightly higher thermal degradation stabilities in the materials with higher degrees of saturation. POLYM. ENG. SCI., 54:2332–2344, 2014. © 2013 Society of Plastics Engineers     

Synthesis and Characterization of 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) and silver 5‐nitrotetrazolate. Both new compounds ( 1, 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁴N, ¹⁵N), elemental analysis and single crystal X‐ray diffraction. 1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) represents the first example of an energetic material which contains both a tetrazole based cation and anion. Compound 2 is hydrolytically stable with a high melting point of 190 °C (decomposition). The impact sensitivity of compound 2 is very low (30 J), it is not sensitive towards friction (>360 N). The molecular structure of 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) in the crystalline state was determined by X‐ray crystallography: orthorhombic, F_ddd, a=1.3718(1) nm, b=1.4486(1) nm, c=1.6281(1) nm, V=3.2354(5) nm³, Z=16, ρ=1.979 g cm⁻¹, R₁=0.0169 (F>4σ(F)), wR₂ (all data)=0.0352.