Copolymerization of styrene and butadiene with Ni(acac)2-methylaluminoxane catalyst

Copolymerization of styrene (St) and butadiene (Bd) with nickel(II) acetylacetonate [Ni(acac)₂]-methylaluminoxane (MAO) catalyst was investigated. Among the metal acetylacetonates [Mt(acac)_x] examined, Ni(acac)₂ showed a high activity for the copolymerization of St and Bd giving copolymers having high cis-1,4-microstructure in Bd units in the copolymer. The effect of alkylaluminum as a cocatalyst on the copolymerization of St and Bd with the Ni(acac)₂-MAO catalyst was observed, and MAO was found to be the most effective cocatalyst for the copolymerization. The monomer reactivity ratios for the copolymerization of St and Bd with the Ni(acac)₂-MAO catalyst were determined to be r_St = 0.07 and r_Bd = 3.6. Based on the obtained results, it was presumed that the random copolymers with high cis-1,4-microstructure in Bd units could be synthesized with the Ni(acac)₂-MAO catalyst without formation of each homopolymer. The polymerization mechanism with the Ni(acac)₂-MAO catalyst was also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3838–3844, 1999     

Silyl enol ethers as monomer. III. Radical polymerization and copolymerizations of 2-trimethylsilyloxy-1,3-butadiene and desilylation of the resulting polymers

2-Trimethylsilyloxy-1,3-butadiene (TMSBD), the silyl enol ether of methyl vinyl ketone, was homopolymerized with a radical initiator to afford polymers with a molecular weight of ca. 10⁴. Radical copolymerizations of TMSBD with styrene (ST) and acrylonitrile (AN) in bulk or dioxane at 60°C gave the following monomer reactivity ratios: r₁ = 0.64 and r₂ = 1.20 for the ST (M₁)–TMSBD (M₂) system and r₁ = 0.036 and r₂ = 0.065 for the AN (M₁)–TMSBD (M₂) system. The Q and e values of TMSBD determined from the reactivity ratios for the former copolymerization system were 2.34 and ?1.31, respectively. The resulting polymer and copolymers were readily desilylated with hydrochloric acid or tetrabutylammonium fluoride as catalyst to yield analogous polymers having carbonyl groups in the polymer chains.     

Vinyl monomers bearing chromophore moieties and their polymers. V. Synthesis and fluorescence behavior of a vinyloxy monomer bearing electron-accepting chromophore moiety,N-(2-(vinyloxy)ethyl)-1,8-naphthalimide,and its polymer

A vinyloxy monomer bearing electron-accepting chromophore, N-(2-(vinyloxy)ethyl)-1,8-naphthalimide (VOENI), was synthesized by reaction of potassium 1,8-naphthalimide with 2-chloroethyl vinyl ether. VOENI can be homopolymerized by cationic initiation and copolymerized with maleic anhydride (MAn) under radical initiation. The fluorescence behaviors of VOENI and its polymers were investigated. It has been found that the fluorescence intensity of the VOENI monomer is much lower than that of its polymers at the same chromophore concentration. This means that a “structural self-quenching effect” (SSQE) has been also observed in the vinyloxy monomer consisting of an electron-accepting chromophore, which has opposite electronic structure in comparison with acrylates bearing electron-donating chromophores as we have reported previously. The SSQE is attributed to the charge-transfer interaction between the electron-accepting chromophore and the electron-donating double bond in the same molecule. The fluorescence quenching of 1,8-naphthalic anhydride and P(VOENI-co-MAn) by ethyl vinyl ether (EVE), dihydrofuran, triethylamine (TEA), etc. evidences that the electron-rich vinyloxy group does act as an important role in the SSQE of VOENI. C₆₀ can also quench the fluorescence of the polymers, and an upward deviation from the linearity of the Stern–Volmer plot was observed showing that C₆₀ acted as a powerful electron donor to quench the fluorescence of the copolymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1111–1116, 1998     

Synthesis and Structures of 1-(2-Thienylmethyl)-2-(2-thienyl)bezimidazole and Its Cu(I) and Ag(I) Complexes

N,N′-1,2-phenylenebis(2-thienylideneimine) (PTI) can be obtained via the condensation of o-phenylenediamine and thiophene-2-carboxaldhyde in cyclohexane. It isomerized to its cyclic form 1-(2-thienylmethyl)-2-(2-thienyl)benzimidazole (TMTBI) readily in the presence of Fe₂(CO)₉. Coordination reactions of PTI with cuprous iodide and silver nitrate in acetonitrile resulted in the formation of [Cu(TMTBI)I]₂ and [Ag(TMTBI)₂]NO₃, respectively, in which the PTI ligand had been isomerized to TMTBI. Both PTI, TMTBI, and complexes were characterized by NMR, IR, and Mass spectroscopies as well as elemental analysis. The crystal structures of TMTBI and [Cu(TMTBI)I]₂ were determined by single-crystal X-ray diffraction. Crystallographic details for X-ray structures are as follows. TMTBI is crystallized in the monoclinic space group P2₁/n with a = 8.953(3), b = 9.150(1), c = 17.436(2) Å, β = 93.73(2)°, and Z = 4. The final R factor was 0.050 (R_w = 0.066) for 1337 observed reflections. Complex [Cu(TMTBI)I]₂ is crystallized in the triclinic space group $ {\rm P}\bar 1 $ with a = 9.961 (2), b = 10.825(2), c = 9.184(2) Å, α = 112.98(2), β = 110.78(2), γ = 88.71 (2)°, and Z = 2. The final R factor was 0.056 (R_w = 0.057) for 2363 observed reflections.     

1-( p -Fluorophenyl)-2-(2′-pyridyl)ethanol and 1-( p -fluorophenyl)-2-(2′-pyridyl)ethene obtained from the condensation reaction of 2-picoline and p -fluorophenylaldehyde under catalyst-and solvent-free conditions

The novel intermediate 1-(p-fluorophenyl)-2-(2′-pyridyl)ethanol or 2-[2′-(1-hydroxy-1-(p-fluorophenyl)ethyl]pyridine and the corresponding novel dehydration compound 1-(p-fluorophenyl)-2-(2′-pyridyl)ethene or 2-[p-fluorophenylvinyl]pyridine were obtained from the condensation reaction of p-fluorophenylaldehyde and 2-picoline under catalyst-and solvent-free conditions. The intermediate 1-(p-fluorophenyl)-2-(2′-pyridyl)ethanol was obtained at 42 h reaction time and temperature of 120°C, respectively. ¹H-NMR, IR spectroscopic data of the 1-(p-fluorophenyl)-2-(2-pyridyl)ethanol clearly showed the presence of the-CH₂-CHOH-group. The compound was obtained as a white powder with m.p. 121–122°C and a yield of 8%. For 1-(p-fluorophenyl)-2-(2-pyridyl)ethene, the reaction conditions were similar, but the reaction temperature was increased to yield the double bond in the 1-(p-fluorophenyl)-2-(2′-pyridyl)ethene. At the reaction temperature of 140°C, the compound was a slightly brown powder with a m.p. of 78°C and yield of 18%. ¹H-NMR, IR spectroscopic data for the 1-(p-fluorophenyl)-2-(2′-pyridyl)ethene showed the presence of a double bond in trans configuration (-CH=CH-), characteristic of a styrylpyridine.     

Synthesis and Characterization of New Schiff Bases 2-(2-(2-(Aryl)Methyleneamino)Phenylthio) Ethylthio)-N-((aryl)Methylene)Benzeneamine

A series of Schiff bases containing four to six coordination sites N₂S₂ X₂(X = O,N) 2-(2-(2-(aryl)methyleneamino)phenylthio)ethylthio)-N-((aryl)methylene)benzeneamine (2c–f) were prepared from the reaction of 1,2-di(2-aminophenylthio)ethane (1) with aromatic aldehydes. All compounds were characterized by means IR, mass, ¹H and ¹³C NMR spectroscopy, and elemental analysis, and in the case of 2b with a single crystal X-ray diffraction. The X-ray crystal structure of 2b showed that the resonance occurs between aromatic rings, through the C=N bonds of the molecule.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Copolymerization of ethyl α-(hydroxymethyl)acrylate with maleimide and characterization of the resulting copolymer

Copolymerization of maleimide (MI) and ethyl α-(hydroxymethyl)acrylate (EHMA) was performed at 60°C with AIBN as the initiator in THF. The monomer reactivity ratios were determined as r₁ (MI) = 0.13 and r₂ (EHMA) = 2.20. As the molar fraction of MI in the monomer feed increased, the initial rate of copolymerization decreased. TGA diagrams suggested the crosslinking reaction of the copolymer on heating. DSC and WAXD results suggested the existence of incomplete crystallinity in the copolymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1291–1299, 1998     

Cationic polymerizations of substituted 2-methylene-1,3-dioxocyclic acetals, 2-methylene-1,3-dithiolane and copolymerization of 2-methylene-1,3-dithiolane with 4-(t-butyl)-2-methylene-1,3-dioxolane1

Carbon black-supported sulfuric acid or BF₃·Et₂O-initiated polymerizations of 2-methylene-4,4,5,5-tetramethyl-1,3-dioxolane (1), 2-methylene-4-phenyl-1,3-dioxolane (2), and 2-methylene-4-isopropyl-5,5-dimethyl-1,3-dioxane (3) were performed. 1,2-Vinyl addition homopolymers of 1–3 were produced using carbon black-supported H₂SO₄ initiation at temperatures from 0°C to 60°C whereas both ring-opened and 1,2-vinyl structural units were present in the polymers using BF₃·Et₂O as an initiator. Cationic polymerizations of 2-methylene-1,3-dithiolane (4) and copolymerization of 4 with 2-methylene-4-(t-butyl)-1,3-dioxolane (5) were initiated with either carbon black-sulfuric acid or BF₃·Et₂O. Insoluble 1,2-vinyl addition homopolymers of 4 were obtained upon initiation with the supported acid or BF₃·Et₂O. A soluble copolymer of 2-methylene-1,3-dithiolane (4) and 4-(t-butyl)-2-methylene-1,3-dioxolane (5) was obtained upon BF₃·Et₂O initiation. This copolymer is composed of three structural units: a ring-opened dithioester unit, a 1,2-vinyl-polymerized 1,3-dithiolane unit, and a 1,2-vinyl polymerized 4-(t-butyl)-1,3-dioxolane unit. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2823–2840, 1999     

Synthesis of a new monomer N′‐(β‐methacryloyloxyethyl)‐2‐pyrimidyl‐(p‐benzyloxycarbonyl)aminobenzenesulfonamide and its copolymerization with N‐phenyl maleimide

The new monomer N′‐(β‐methacryloyloxyethyl)‐2‐pyrimidyl‐(p‐benzyloxy‐ carbonyl)aminobenzenesulfonamide (MPBAS) (M₁) is synthesized using sulfadiazine as parent compound. It could be homopolymerized and copolymerized with N‐phenyl maleimide (NPMI) (M₂) by radical mechanism using AIBN as initiator at 60 °C in dimethylformamide. The new monomer MPBAS and polymers were identified by IR, element analysis and ¹H NMR in detail. The monomer reactivity ratios in copolymerization were determined by YBR method, and r₁ (MPBAS) = 2.39 ± 0.05, r₂ (NPMI) = 0.33 ± 0.02. In the presence of ammonium formate, benzyloxycarbonyl groups could be broken fluently from MPBAS segments of copolymer by catalytic transfer hydrogenation, and the copolymer with sulfadiazine side groups are recovered. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2548–2554, 2000     

Syntheses,crystal structures,and catalytic activities of three new Cu(II) coordination polymers based on 2-(1H-1,2,4-triazole)-1-acetic acid

Three new coordination polymers, {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(ClO₄)} _n (1), {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(BF₄)} _n (2), and {[Cu(trza)(4,4′-bipy)]?·?(H₂O)?·?(ClO₄)} _n (3) (Htrza?=?2-(1H-1,2,4-triazole)-1-acetic acid), have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 exhibit 1-D chain structure while 3 displays 2-D layer structure. The catalytic activities of 1 and 3 in the green oxidative coupling of 2,6-dimethylphenol have been investigated.     

4-(2-(4-咪唑)苯乙烯基)吡啶和三种芳香二羧酸的Cd(Ⅱ)配位聚合物的合成、结构及荧光性质

以4-(2-(4-咪唑)苯乙烯基)吡啶(ISPE)为配体,分别与间苯二甲酸(1,3-H_2BDC)、4,4′-联苯二甲酸(4,4′-H_2BPDC)和4,4′-二苯乙烯二甲酸(4,4′-H_2STDC)及过渡金属盐Cd(NO3)2·4H_2O通过溶剂热自组装形成了3种配位聚合物晶体{[Cd_2(ISPE)_2(1,3-BDC)_2]·DMF}_n(1)、[Cd(ISPE)(4,4′-BPDC)]_n(2)和[Cd(ISPE)_2(4,4′-STDC)(H_2O)_2]_n(3)。并用单晶X射线衍射、PXRD、红外光谱、元素分析、热重等对其进行了表征。单晶解析结果表明:配位聚合物1是二维层状网格结构,配位聚合物2是一个六重穿插的类金刚烷三维网格结构,配位聚合物3是由一维网格结构通过氢键和分子间作用力堆积形成的三维网格结构。另外还研究了它们的室温固态荧光性能。     

Synthesis and polymerization of N-[4-N′- (α-methylbenzyl)aminocarbonylphenyl]maleimide

A novel type of optically active N-[4-N′-(α-methylbenzyl)aminocarbonylphenyl]maleimide [(R)-MBCP] was synthesized from maleic anhydride, p-aminobenzoic acid, and (R)-methylbenzylamine. Radical homopolymerization of (R)-MBCP was performed in tetrahydrofuran (THF) at 50 and 70°C for 24 h to give optically active polymers having [α]²⁵_D = -141° and -129°, respectively. Anionic polymerization of (R)-MBCP with n-butyllithium in THF and N,N-dimethylformamide gave an optically active polymer having ?78 to ?81° of [α]²⁵_D. Radical copolymerizations of (R)-MBCP (M₁) were performed with styrene (ST, M₂) and methyl methacrylate (MMA, M₂) in THF at 50°C. The monomer reactivity ratios (r₁, r₂) and the Alfrey-Price Q-e values were determined as follows: r₁ = 0.009, r₂ = 0.091, Q₁ = 1.30, e₁ = 1.87 in the (R)-MBCP-ST; r₁ = 0.27, r₂ = 1.21, Q₁ = 0.93, e₁ = 1.46 in the (R)-MBCP-MMA system. Chiroptical properties of the polymers were also investigated. © 1992 John Wiley & Sons, Inc.     

三[2-(2'-肟亚甲基苯氧基)乙基]胺的合成、表征及量化研究

合成了三[2-(2'-肟亚甲基苯氧基)乙基]胺, 测定了其IR, NMR和单晶结构, 晶体C₂₇H₃₀N₄O₆属三斜晶系, 空间群R-3r, 晶胞参数为: a＝1.9100(2) nm, b＝1.9100(2) nm, c＝1.9100(2) nm, ＝109.500(2), ＝109.500(2). ＝109.500(2), Z＝6. 结构解析最终一致性因子R₁＝0.0568, wR₂＝0.1766. 分子间通过氢键和范德华力形成3D网状超分子结构. 使用HyperChem6.0程序中半经验ZINDO/1方法和G98量子化学程序包, 在B3LYP/6-311G**基组水平上对化合物电荷分布进行了量子化学计算.     

Cu(II)/Cd(II) coordination polymers based on polycarboxylate and 2-(2-pyridyl)benzimidazole

Three polycarboxylate coordination polymers containing 2-(2-pyridyl)benzimidazole as co-ligand, [Cu(Bdc)(2-PyBIm)] _n (1), [Cu(HBtc)(2-PyBIm)] _n (2) and [Cd₂(HBtc)₂(2-PyBIm)₂] _n ·; nH₂O (3) (H₂Bdc?=?1,4-benzenedicarboxylic acid; H₃Btc?=?1,3,5-benzenetricarboxylic acid), have been synthesized and characterized by elemental analyses, IR spectra, TG-DSC and X-ray structural analyses. Complex 1 is a one-dimensional zigzag chain in which the Cu(II) is cis six-coordinated by two chelating carboxyl groups and a 2-PyBIm ligand. Complex 2 is a two-dimensional (4, 4) network in which H₃Btc is partially deprotonated. Complex 3 has a three-dimensional framework in which one Cd(II) is six-coordinate and the other is seven-coordinate. All 2-PyBIm groups are neutral, chelating, bidentate ligands in 1–3. These complexes are quite thermally stable. The luminescence of 3 has also been investigated.     

Facile synthesis of blocky styrene(1,3)‐butadiene copolymers having stereoregular monomeric sequences

Half titanocenes (CpCH₂CH₂O)TiCl₂ 1 and (CpCH₂CH₂ OCH₃)TiCl₃ 2 , activated by methylaluminoxane are tested in styrene–1,3‐butadiene copolymerization. The titanocene 1 is able to copolymerize styrene and 1,3‐butadiene, with a facile procedure, to give products with high molecular weight. The analysis of microstructure by ¹³C‐NMR reveals that the styrene homosequences in copolymers are in syndiotactic arrangement, while the butadiene homosequences are, prevailingly, in 1,4‐cis configuration, according with behavior of 1 in the homopolymerizations of styrene and 1,3‐butadiene, respectively. The reactivity ratios of copolymerization are estimated by diad composition analysis. All obtained copolymers have r₁ × r₂ values much larger than 1, indicating blocky nature of homosequences. The structural characterization by wide‐angle X‐ray powder diffraction and differential scanning calorimetry indicates that all copolymers are crystalline, with T_m varying from 171 to 239 °C, depending on the styrene content. The titanocene 2 did not succeed in styrene–1,3‐butadiene copolymerization, giving rise to a blend of homopolymers. Compounds 1 and 2 were also tested in the polymerization of several conjugated dienes, and the obtained results were very useful to rationalize the behavior of both catalysts in the copolymerization of styrene and butadiene. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 815–822, 2010     

Superhydrophobic surfaces of microspheres obtained by self-assembly of poly[2-(perfluorooctyl)ethyl acrylate-<Emphasis Type="Italic">ran</Emphasis>-2-(dimethylamino)ethyl acrylate] in supercritical carbon dioxide

Superhydrophobic surfaces were obtained by coating with microspheres formed by the self-assembly of poly[2-(perfluorooctyl)ethyl acrylate-ran-2-(dimethylamino)ethyl acrylate] (P[POA-r-DAA]) in the presence of dicarboxylic acids in supercritical carbon dioxide. The P[POA-r-DAA] random copolymer aggregated into micellar microspheres through the hydrogen bond cross-linking of the amino groups via the carboxylic acids. The size of the microspheres and the amount of the acids needed to produce them were dependent on the kinds of acids. Glutaric acid (Glu) and perfluorosuccinic acid (Psuc) provided microspheres at a 0.5 molar ratio of the acid/DAA. Psuc produced smaller microspheres than Glu. Maleic acid (Ma), succinic acid (Suc), and azelaic acid (Az) required a higher molar ratio to produce the microspheres. These acids provided spherical particles at the ratio of 1.0. The microspheres produced by Suc and Az contained particles with a several hundred nanometer size. The surface coated with the microspheres showed high water contact angles of 164°–172°.

Synthesis,Antimicrobial Activity and Semi-conducting Properties of Novel 2-(4-Chloro-1-Naphtyloxy)-2-Oxoethyl Methacrylate with 2-(Diethylamino)Ethyl Methacrylate Copolymers

The free-radical initiated copolymerization of 2-(4-chloro-1-naphtyloxy)-2-oxoethyl methacrylate (ClNOEMA) with 2-(diethylamino) ethyl methacrylate (DEAEMA) was carried out in 1,4-dioxane solution at 70 ± 1°C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios (ranging from 0.15 to 0.85) in the feed. The copolymer composition obtained by elemental analysis led to the determination of reactivity ratios employing Fineman-Ross (F-R) and Kelen-Tüdös (KT) linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The prepared homo and copolymers were tested for their antimicrobial activity against bacteria and yeast. These copolymers have been converted into novel salts by reaction with the iodemethane (CH₃I). The copolymers and the corresponding salts have been characterized fully by a range of spectroscopic analysis techniques. The electrical conductivity dependence of temperature of the polymers were measured and the polymers exhibit the semi-conducting behavior, confirming that the electrical conductivity increases with increasing temperature. The poly(CINOEMA-co-DEAEMA) polymer doped by CH₃I for 15 min shows the highest conductivity. The optical band gap, activation energy and room temperature conductivity values of these polymers were obtained. These electronic parameters suggest that the poly(CINOEMA-co-DEAEMA)s doped by CH₃I for 15 min is an organic semiconductor with the thermally activated conduction mechanism.     

Solvent extraction of rare earth metal ions with 1-(2-pyridylazo)-2-naphthol (PAN)

The formation of the Tm(III) complex with 1-(2-pyridylazo)-2-naphthol (PAN or HL) in aqueous-methanol mixtures (50 and 75%v/v) was studied by a spectrophotometric method. The equilibrium constant for the complexing reaction and the stability constant of the complex TmL ²⁺ were calculated. The solvent extraction of Tm(III) byPAN in carbon tetrachloride from aqueous and aqueous-methanol phase was investigated. The extraction equilibrium constants and two-phase stability constants for the TmL ₃ and the TmL ₃(MeOH)₃ complexes were evaluated. It was confirmed that the addition of methanol to the aqueous phase (above 25%v/v) causes a synergistic effect.

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Extraktion von Ionen der Seltenerdmetalle mit 1-(2-Pyridylazo)-2-naphthol (PAN), 5. Mitt.: Komplexbildung und Gleichgewichtsverteilung von Thulium (III) mitPAN

Zusammenfassung Die Bildung des Komplexes von Tm(III) mit 1-(2-Pyridylazo)-2-naphthol (PAN oder HL) in Wasser-Methanol Mischungen (50 und 75%v/v) wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstante für die Reaktion der Komplexbildung und die Stabilitätskonstante des Komplexes TmL ²⁺ wurden berechnet. Die Extraktion von Tm(III) mittelsPAN in Kohlenstofftetrachlorid aus Wasser oder Wasser-Methanol wurde untersucht. Die Werte der Extraktionsgleichgewichtskonstante sowie der zweiphasigen Beständigkeitskonstante für die Komplexe TmL ₃ und TmL ₃(MeOH)₃ wurden berechnet. Es wurde festgestellt, daß die Zugabe von Methanol zur wäßrigen Phase (25%v/v) einen synergistischen Effekt hat.

     

Synthesis and characterization of new poly(amide–imide)s from 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene with various diamines

New poly(amide–imide)s were prepared from a diimide–dicarboxylic acid, 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene ( BTTB ), with various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. The new diimide–dicarboxylic acid BTTB containing an ether linkage and tert-butyl substituent was synthesized by the condensation reaction of 1,4-bis(4-aminophenoxy)-2-tert-butylbenzene with trimellitic anhydride. All the polymers were obtained in quantitative yields with inherent viscosities of 0.62–1.06 dL g⁻¹. The polymers were amorphous, and most of them were readily soluble in aprotic polar solvents such as NMP, N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF), as well as in less polar solvents such as dimethyl sulfoxide (DMSO), m-cresol, pyridine, and γ-butyrolactone, and also even in tetrahydrofuran. The glass transition temperatures of the polymers were determined by DSC method, and they were in the range of 238–279°C. These polymers were stable up to 408–449°C in air and 451–483°C in nitrogen and lose 10% weight in the range of 479–525°C in air and 480–528°C in nitrogen atmosphere. The polymer films had a tensile strength range of 71–115 MPa, an elongation at break range of 4–14%, and a tensile modulus range of 2.3–3.1 GPa. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2301–2307, 1998     

COPOLYMERIZATION OF BUTADIENE AND ISOPRENE CATALYZED BY V(acac)_3-Al(i-Bu)_2Cl-Al_2Et_3Cl_3 CATALYST AND CHARACTERIZATION OF THE PRODUCTS

Copolymerization of butadiene and isoprene catalyzed by the catalyst system V(acac)_3-Al(i-Bu)_2Cl-Al_2Et_3Cl_3 has been studied. Composition, microstructure, crystallinity and melting point of the copolymer obtained were determined by PGC, IR, X-ray diffraction and DSC methods respectively. The results revealed that the product was a copolymer and not a blend. The butadiene units presented in the copolymer were of trans-1,4-configuration, while the isoprene units were of both trans-1,4-and 3,4-forms. The melting point and crystallinity of the copolymer decrcascd with increase of molar ratio of isoprene to hutadiene.