Physicochemical and macromolecular properties of sodium amylose xanthate in dilute solution

Sodium amylose xanthate has been studied in dilute solution. Potato starch was fractionated for this purpose into amylose and amylopectin fractions. Amylose was xanthated in solution under alkaline conditions and the Na amylose xanthate was then characterized by reaction with I₂ solution and ultraviolet spectra of the xanthate groups determined. Stability of the xanthate in alkaline condition under both oxygen and nitrogen atmospheres was also investigated. From light scattering measurements of dilute salt solutions of Na amylose xanthate, the weight-average molecular weight M _w as well as the molecular dimensions were determined. In 0.11M NaCl, which conforms to the θ solvent, Na amylose xanthate molecules appear to have a random-coil configuration. Two other configurational parameters, such as the effective bond length b, and the steric factor σ, i.e., (R₀²)^1/2/(R_f² )^1/2, where (R₀²)^1/2 is the Root-mean-square end-to-end distance in the unperturbed state and (R_f² )^1/2 is the unperturbed value calculated on the assumption of free rotation about each intermonomer C? O bond of the amylose chain were also calculated and found to be 6.24 and 1.020, respectively. It is thus concluded that the amylose chain in Na amylose xanthate behaves as a typical flexible coil in dilute salt solution.     

Polyelectrolyte behavior and macromolecular properties of sodium amylopectin xanthate in dilute solution

Sodium amylopectin xanthate was prepared by xanthation of potato amylopectin in alkaline medium. The pure product was characterized by I₂ solution and ultraviolet spectra of the xanthate groups. The polyelectrolyte behavior of Na amylopectin xanthate in aqueous and salt solutions was investigated by viscometry and light scattering. Its polyelectrolyte behavior in aqueous solution as studied viscometrically was completely different from that of Na amylose xanthate, which is characteristic of linear polyelectrolyte molecules. This difference in behavior could be partly due to the branched structure of amylopectin molecule. A dissymmetry study of Na amylopectin xanthate in aqueous and salt solutions, however, showed that Na amylopectin xanthate molecule underwent expansion in water by about 1.3 times its linear dimension in 0.5M NaCl (unperturbed value). Light-scattering measurements confirmed that the Na amylopectin xanthate molecule had a polydisperse random-coil chain configuration in 0.25M NaCl. Its molecular weight, end-to-end length, and other parameters in salt and alkali solutions were also determined, and the data were then compared with those of Na amylose xanthate in the same media. The solution behavior of Na amylopectin xanthate in 1M NaOH was further investigated and linear expansion factor α, excluded volume factor A₂M _W/[η], and Flory's hydrodynamic constant φ were evaluated.     

Biodegradation of soluble redox polymers. Part 2: (0.017ferrocene)amylose at a rotating disk electrode

The behavior of (ferrocene)amylose (FA), in the presence of amylolytic depolymerases (α-amylase from Aspergillus oryzae and human saliva), has been investigated by cyclic voltammetry at a rotating disk electrode (CVA/RDE). Growth of the limiting current with time in the presence of the enzymes is proportional to the amount of enzyme introduced. The quantitative data treatment to assay the endoamylolytic activity of enzymes at CVA/RDE involves plotting (i_dt/i_d0)^4.5 against time; the slope of the linear plot being equal to (rate) M_n0C⁻¹, where i_dt and i_d0 are the limiting currents at time t and 0, respectively, (rate) is the enzymatic activity, M_n0 is the number averaged molecular weight of FA at t = 0, and c is its concentration. The comparison of CVA/RDE with the 3,5-dinitrosalicylic acid and the Somogyi–Nelson reducing saccharides procedures shows advantages of the former, especially in assaying small quantities of enzymes. Also the CVA/RDE approach is simpler and takes place under much milder conditions. The main disadvantage of CVA/RDE is the inhibiting effect of Triton X-100 in the reaction between FA and the amylases which is not observed in the case of native, ferrocene-free amylose. In general, CVA/RDE appears to be an attractive analytical method for monitoring diverse enzymatic depolymerization reactions.     

Well‐defined amphiphilic polymethylene‐b‐poly(acrylic acid) diblock copolymers: New synthetic strategy and their self‐assembly

Well‐defined amphiphilic polymethylene‐b‐poly (acrylicacid) diblock copolymers have been synthesized via a new strategy combining polyhomologation and atom transfer radical polymerization (ATRP). Hydroxyl‐terminated polymethylenes (PM‐OH) with different molecular weights and narrow molecular weight distribution are obtained through the polyhomologation of dimethylsulfoxonium methylides following quantitative oxidation via trimethylamine‐N‐oxide dihydrate. Subsequently, polymethylene‐based macroinitiators (PM‐MIs M_n = 1,300 g mol^?1 [M_w/M_n = 1.11] and M_n = 3,300 g mol^?1 [M_w/M_n = 1.04]) are synthesized by transformation of terminal hydroxyl group of PM‐OH to α‐haloester in ～100% conversion. ATRPs of tert‐butyl acrylate (t‐BuA) are then carried out using PM‐MIs as initiator to construct PM‐b‐P(t‐BuA) diblock copolymers with controllable molecular weight (M_n = 8,800–15,800 g mol^?1 M_w/M_n = 1.04–1.09) and different weight ratio of PM/P(t‐BuA) segment (1:1.7–1:11.2). The amphiphilic PM‐b‐PAA diblock copolymers are finally prepared by hydrolysis of PM‐b‐P(t‐BuA) copolymers and their self‐assembly behavior in water is preliminarily investigated via the determination of critical micelle concentrations, dynamic light scattering, and transmission electron microscope (TEM). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Iron‐catalyzed living radical polymerization of acrylates: Iodide‐based initiating systems and block and random copolymerizations

A half‐metallocene iron iodide complex [Fe(Cp)I(CO)₂] induced living radical polymerization of methyl acrylate (MA) in conjunction with an iodide initiator [(CH₃)₂C(CO₂Et)I, 1 ] and Al(Oi‐Pr)₃ to give polymers of controlled molecular weights and narrow molecular weight distributions (MWDs) (M_w/M_n < 1.2). With the use of chloride and bromide initiators, the MWDs were broader, whereas the molecular weights were similarly controlled. Other acrylates such as n‐butyl acrylate (nBA) and tert‐butyl acrylate (tBA) can be polymerized with 1 /Fe(Cp)I(CO)₂ in the presence of Ti(Oi‐Pr)₄ and Al(Oi‐Pr)₃, respectively, to give living polymers. The 1 /Fe(Cp)I(CO)₂ initiating system is applicable for the synthesis of block and random copolymers of acrylates (MA, nBA, and tBA) and styrene of controlled molecular weights and narrow MWDs (M_w/M_n = 1.2–1.3). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2033–2043, 2002     

Entanglement properties of cellulose and amylose in an ionic liquid

Concentrated solutions of cellulose and amylose were prepared with an ionic liquid 1‐butyl‐3‐methylimidazolium chloride (BmimCl), which was chosen as a good solvent for these polysaccharides. Dynamic viscoelasticity of the concentrated solutions was examined to obtain the molecular weight between entanglements, M_e. The value of M_e in the molten state (M_e,melt), a material constant that reflecting the entanglement properties, was determined for cellulose and amylose by extrapolating M_e to the “melt.” A marked difference in M_e,melt was found: 3.2 × 10³ for cellulose and 2.5 × 10⁴ for amylose. The value of M_e,melt for cellulose, which is composed of β‐(1,4) bonding of D ‐glucose units, is very close to those for polysaccharides with a random‐coil conformation such as agarose and gellan in BmimCl. The much larger M_e,melt for amylose can be attributed to the helical nature of the amylose chain, α‐(1,4)‐linked D ‐glucose units. The effect of concentration on the zero‐shear viscosity for the solutions of cellulose and amylose was also examined. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Emulsion polymerization of vinyl acetate using iodine‐transfer and RAFT radical polymerizations

This study deals with control of the molecular weight and molecular weight distribution of poly(vinyl acetate) by iodine‐transfer radical polymerization and reversible addition‐fragmentation transfer (RAFT) emulsion polymerizations as the first example. Emulsion polymerization using ethyl iodoacetate as the chain transfer agent more closely approximated the theoretical molecular weights than did the free radical polymerization. Although ¹H NMR spectra indicated that the peaks of α‐ and ω‐terminal groups were observed, the molecular weight distributions show a relatively broad range (M_w/M_n = 2.2–4.0). On the other hand, RAFT polymerizations revealed that the dithiocarbamate 7 is an excellent candidate to control the polymer molecular weight (M_n = 9.1 × 10³, M_w/M_n = 1.48), more so than xanthate 1 (M_n = 10.0 × 10³, M_w/M_n = 1.89) under same condition, with accompanied stable emulsions produced. In the M_n versus conversion plot, M_n increased linearly as a function of conversion. We also performed seed‐emulsion polymerization using poly(nonamethylene L ‐tartrate) as the chiral polyester seed to fabricate emulsions with core‐shell structures. The control of polymer molecular weight and emulsion stability, as well as stereoregularity, is also discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Enzymatic synthesis and characterization of amphiphilic block copolymers of poly(ethylene oxide) and amylose

Amphiphilic A‐B block copolymers, ω‐methoxypoly(ethylene oxide)‐amylose copolymers (MPEO‐amylose), were synthesized by an enzymatic reaction using potato phosphorylase from an MPEO (M_w = 5.0×10³)‐maltopentaosylamine derivative as a primer and α‐D ‐glucose‐1‐phosphate as a substrate. MPEO‐amyloses with various molecular weights of amylose (DP = 26, 36, 73 and 112) were obtained. None of the MPEO‐amyloses (5 mg/ml) precipitate in water containing 10 vol.‐% DMSO even after 24 h. The MPEO‐amyloses effectively form complexes with iodine in water.     

Effect of prepolymer molecular weight on solid state polymerization of poly(bisphenol a carbonate) with nitrogen as a sweep fluid

The effect of prepolymer molecular weight on the solid‐state polymerization (SSP) of poly(bisphenol A carbonate) was investigated using nitrogen (N₂) as a sweep fluid. Prepolymers with different number–average molecular weights, 3800 and 2400 g/mol, were synthesized using melt transesterification. SSP of the two prepolymers then was carried out at reaction temperatures in the range 120–190 °C, with a prepolymer particle size in the range 20–45 μm and a N₂ flow rate of 1600 mL/min. The glass transition temperature (T_g), number–average molecular weight (M_n), and percent crystallinity were measured at various times during each SSP. The phenyl‐to‐phenolic end‐group ratio of the prepolymers and the solid‐state synthesized polymers was determined using 125.76 MHz ¹³C and 500.13 MHz ¹H nuclear magnetic resonance (NMR) spectroscopy. At each reaction temperature, SSP of the higher‐molecular‐weight prepolymer (M_n = 3800 g/mol) always resulted in higher‐molecular‐weight polymers, compared with the polymers synthesized using the lower molecular weight prepolymer (M_n = 2400 g/mol). Both the crystallinity and the lamellar thickness of the polymers synthesized from the lower‐molecular‐weight prepolymer were significantly higher than for those synthesized from the higher‐molecular‐weight prepolymer. Higher crystallinity and lamellar thickness may lower the reaction rate by reducing chain‐end mobility, effectively reducing the rate constant for the reaction of end groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4959–4969, 2008     

Well‐defined amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chains

A series of well‐defined amphiphilic graft copolymers containing hydrophilic poly(acrylic acid) (PAA) backbone and hydrophobic poly(vinyl acetate) (PVAc) side chains were synthesized via sequential reversible addition‐fragmentation chain transfer (RAFT) polymerization followed by selective hydrolysis of poly(tert‐butyl acrylate) backbone. A new Br‐containing acrylate monomer, tert‐butyl 2‐((2‐bromopropanoyloxy)methyl) acrylate, was first prepared, which can be polymerized via RAFT in a controlled way to obtain a well‐defined homopolymer with narrow molecular weight distribution (M_w/M_n = 1.08). This homopolymer was transformed into xanthate‐functionalized macromolecular chain transfer agent by reacting with o‐ethyl xanthic acid potassium salt. Grafting‐from strategy was employed to synthesize PtBA‐g‐PVAc well‐defined graft copolymers with narrow molecular weight distributions (M_w/M_n < 1.40) via RAFT of vinyl acetate using macromolecular chain transfer agent. The final PAA‐g‐PVAc amphiphilic graft copolymers were obtained by selective acidic hydrolysis of PtBA backbone in acidic environment without affecting the side chains. The critical micelle concentrations in aqueous media were determined by fluorescence probe technique. The micelle morphologies were found to be spheres. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6032–6043, 2009     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Study of the ceric ion behavior on the initiation of butyl acrylate polymerization onto amylose

A study of the Ce(IV) ion consumption during graft polymerization of butyl acrylate with amylose was carried out. The Ce(IV) consumed was ca. 80% and the ratio of Ce(IV) to anhydroglucose units was 1/15. Poly(butyl acrylate) (PBA) chains were isolated from the grafted copolymer by the perchloric acid hydrolysis method. The molecular distribution was obtained by gel permeation chromatography (GPC). The number-average molecular weight (M_n) of the grafted chains was 276,000 and the weight-average molecular weight (M_w) was 1,320,000. The total number of grafted chains (mmol) ranged from 0.4410^?3 to 8.710^?3 (amylose from 0.08 g to 1.23 g). Frequency of grafting ranged from 1042 to 704.     

Degradation on freezing dilute polystyrene solutions in p-xylene

Chain scission was observed during the crystallization of p-xylene in dilute polystyrene solutions. Degradation yields were determined by gel permeation chromatography, as a function of the number of freeze-and-thaw cycles, polymer concentration, and initial polymer molecular weight (M). The rate constant for chain scission K_c increases with the polymer chain length, from 0.021%/cycle at M = 110·10³ to 4.7%/cycle at M = 8.5·10⁶. Over the two decades range of investigated molecular weights, K_c follows an empirical scaling law of the form K_c ～ (M ? M_lim)^1.17578, where M_lim is a limiting molecular weight ? 29,000 g. mol^?1 below which no degradation could be induced. Some propensity for midchain scission was detected, although this tendency was much weaker in comparison to flow-induced degradation. A chain scission model based on crack propagation failed to reproduce the experimental results. To explain the observed dependence of K_c with the square of the radius of gyration, an interfacial stress transmission mechanism between the crystallization fronts and the polymer coil has been proposed. © 1994 John Wiley & Sons, Inc.     

Diffuse interface between polymers: Structure and kinetics

The interfacial structure and diffusion kinetics of two compatible polymers, poly(methyl methacrylate) and poly(vinylidene fluoride) are studied in the melt. The interdiffusion rates of the two components are found to be unequal, giving unequal diffusion coefficients, a net mass flow across the interface, and an asymmetric interfacial composition profile. The structure and kinetics confirm the predictions of the reptation theory. The interfacial thickness d grows with t^1/2, and the interdiffusion coefficient is proportional to M^?2, where t is the time and M is the molecular weight. The scaling law for the interfacial thickness is therefore d ∝ M^?1t^1/2. The number of chains per unit area crossing the original interface reaches a constant value independent of diffusion time after a short induction time on the order of the tube disengagement time (about 0.1–10 s in the present cases depending on the molecular weights). The adhesive bond strength σ is scaled by σ ∝ t^1/4M^?1/2 and σ/σ∞ ∝ t^1/4M^?1/2 [1- (M_c/M)]^?1, where σ _∞is the σ at infinite molecular weight and M_c is the entanglement molecular weight.     

Controlled Release of Model Drug from Biodegradable Segmented Polyurethane Ureas: Morphological and Structural Features

Segmented polyurethane ureas (SPUUs), which are being used in implant devices, were evaluated as drug delivery matrices using theophylline as a model drug without much sacrificing the mechanical properties of films after drug doping. SPUUs were synthesized from aliphatic diisocyanate (lysine methyl ester diisocyante (LDI)), poly(caprolactone) diol with molecular weights 530, 1250 and 2000 and 1,4-butanediamine. Three series of segmented SPUUs were prepared with various soft segment lengths and were characterized by Fourier transform infrared spectroscopy, dynamic viscoelastic measurements and tensile testing. A single tanδ peak was observed in dynamic viscoelastic measurements, which revealed phase mixing of hard and soft segments. Low elongation at break was observed in case of PCL 2000 based SPUUs, may be due to partial cystallization of PCL segment. The degradation of SPUUs in alkaline solution and in vitro drug release of theophylline in pH 7.4 buffer were also investigated. The drug release behavior from these films were analyzed by the exponent relation M_t/M_∞ = ktⁿ, where k and n are constants and M_t/M_∞ is the fraction of drug released until time, t. The constant n was found to be close to 0.5 in all samples, which suggests the release of drug from these polymers can be explained by the Fickian diffusion model.     

Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

In this work, high molecular weight polyvinyl acetate (PVAc) (M_n,GPC = 123,000 g/mol, M_w/M_n = 1.28) was synthesized by reversible addition‐fragmentation chain transfer polymerization (RAFT) under high pressure (5 kbar), using benzoyl peroxide and N,N‐dimethylaniline as initiator mediated by (S)‐2‐(ethyl propionate)‐(O‐ethyl xanthate) (X1) at 35 °C. Polymerization kinetic study with RAFT agent showed pseudo‐first order kinetics. Additionally, the polymerization rate of VAc under high pressure increased greatly than that under atmospheric pressure. The “living” feature of the resultant PVAc was confirmed by ¹H NMR spectroscopy and chain extension experiments. Well‐defined PVAc with high molecular weight and narrow molecular weight distribution can be obtained relatively fast by using RAFT polymerization at 5 kbar. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1430–1436     

Maximum tensile properties of oriented polyethylene,achieved by uniaxial drawing of solution‐grown crystal mats: Effects of molecular weight and molecular weight distribution

The effects of molecular weight (MW) and MW distribution on the maximum tensile properties of polyethylene (PE), achieved by the uniaxial drawing of solution‐grown crystal (SGC) mats, were studied. The linear‐PE samples used had wide ranges of weight‐average (M_w = 1.5–65 × 10⁵) and number‐average MWs (M_n = 2.0–100 × 10⁴), and MW distribution (M_w/M_n = 2.3–14). The SGC mats of these samples were drawn by a two‐stage draw technique, which consists of a first‐stage solid‐state coextrusion followed by a second‐stage tensile drawing, under controlled conditions. The optimum temperature for the second‐stage draw and the resulting maximum‐achieved total draw ratio (DR_t) increased with the MW. For a given PE, both the tensile modulus and strength increased steadily with the DR_t and reached constant values that are characteristic for the sample MW. The tensile modulus at a given DR_t was not significantly affected by the MW in the lower DR_t range (DR_t < 50). However, both the maximum achieved tensile modulus (80–225 GPa) and strength (1.0–5.6 GPa), as well as those at higher DR_ts > 50, were significantly higher for a higher MW. Although the maximum modulus reached 225 ± 5 for M_n ≥ 4 × 10⁵, the maximum strength continued to increase with M_n even for M_n > 4 × 10⁵, showing that strength is more strongly dependent on the M_n, even at higher M_n. Furthermore, it was found that each of the maximum tensile modulus and strength achieved could be expressed by a unique function of the M_n, independently of the wide variations of the sample MW and MW distribution. These results provide an experimental evidence that the M_n has a crucial effect on the tensile properties of extremely drawn and chain‐extended PE fibers, because the structural continuity along the fiber axis increases with the chain length, and hence with the M_n. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 153–161, 2006     

Photoinitiated Cationic Polymerization of 3-Ethyl-3-(phenoxymethyl)-oxetane in Nitrogen Atmosphere

Abstract

The photoinitiated cationic polymerizations of 3-ethyl-3-(phenoxymethyl)-oxetane (PhO) and phenyl glycidyl ether (PhE) with diphenyl-4-thiophenoxyphenyl sulfonium hexafluoroantimonate as the cationic photoinitiator were carried out in air and nitrogen atmospheres. A real time FT-IR method was used to estimate the polymerization rates. The number-average molecular weight (M _n) of the resulting polymers were measured by gel permeation chromatography. In nitrogen, the photopolymerization rate of PhO was more than four times greater than in air, while there was no essential difference for PhE. The M _n of the PhO polymer increased from 13,900 (in air) to 61,200 (in nitrogen) at the peak top. The fast polymerization mechanism in nitrogen was postulated to be the radical-assisted decomposition of the sulfonium salt.     

Studies on poly(iminomethylenes)

A variety of simple alkyl and aryl isocyanides have been polymerized using 0.5% NiCl₂ in ethanol as a catalyst. The resulting poly(iminomethylenes) have been characterized by carbon-13 NMR spectroscopy and their polystyrene-equivalent molecular weights have been determined by gel permeation chromatography. Straight chain aliphatic isocyanides having from three to ten carbon atoms in the chain form readily solyble polymers having molecular weights (M_w) in the general range 10,000 to 30,000. Neopentyl isocyanide unlike tert-butyl isocyanide forms an insoluble polymer. A number of new soluble aryl isocyanide polymers have been obtained. However, aryl isocyanides having a single alkyl substituent (CH₃, C₂H₅, CF₃) in the ortho position give only insoluble polymers, whereas aryl isocyanides having alkyl substituents in both ortho positions (e.g., 2,6-(CH₃)₂C₆H₃NC and 2,4,6-(CH₃)₃C₆H₂NC) fail to polymerize under these conditions. The highest molecular weight soluble aryl isocyanide homopolymer is obtained from 3-CH₃OC₆H₄NC(M_w = 26,000). The trimethylsilyl substituted isocyanide (CH₃)₃SiCH₂CH₂NC has been obtained from LiCH₂NC and (CH₃)SiCH₂Cl and gives a brown soluble homopolymer with a molecular weight (M_w) of 19,000.     

Synthesis of branched polyethylenes by the tandem catalysis of silica‐supported linked cyclopentadienyl‐amido titanium catalysts and a homogeneous dibromo nickel catalyst having a pyridylimine ligand

The synthesis of branched polyethylenes by ethylene polymerization with new tandem catalyst systems consisting of methylaluminoxane‐preactivated linked cyclopentadienyl‐amido titanium catalysts [Ti(η⁵:η¹‐C₅Me₄SiMe₂NR)Cl₂ (R = Me or ^tBu)] supported on pyridylethylsilane‐modified silica (PySTiNMe and PySTiN^tBu) and homogeneous dibromo nickel catalyst having a pyridyl‐2,6‐diisopropylphenylimine ligand (PyminNiBr₂) in the presence of modified methylaluminoxane was investigated. Ethylene polymerization with only PyminNiBr₂ yielded a mixture of 1‐ and 2‐olefin oligomers with methyl branches [weight‐average molecular weight (M_w) ～ 460)] with a ratio of about 1:7. By the combination of this nickel catalyst with PySTiN^tBu, polyethylenes with long‐chain branches (M_w = 15,000–50,000) were produced. No incorporation of 2‐olefin oligomers was observed in the ¹³C NMR spectra. Unexpectedly, the combination of the nickel catalyst with PySTiNMe produced lower molecular weight polyethylenes with only methyl branches. The molecular weight distributions of branched polyethylenes obtained with both PySTiNMe and PySTiN^tBu combined with the nickel catalyst were broad (weight‐average molecular weight/number‐average molecular weight < 9). Bimodal gel permeation chromatography (GPC) curves were clearly observed in the PySTiNMe system, whereas GPC curves with small shoulders in low molecular weight areas were observed for PySTiN^tBu. The synthesis of branched polyethylenes with tandem catalyst systems of corresponding homogeneous titanium catalysts and the nickel catalyst was also investigated for comparison. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 528–544, 2003