New macromolecular silane coupling agents synthesized by living anionic polymerization; grafting of these polymers onto inorganic particles and metals

New macromolecular silane coupling agents, which are end-triethoxysilylated poly(styrene) and poly(tert-butylmethacrylate), were investigated as possible inorganic particle and metal surface treatment agents. These polymers containing poly(styrene) and poly(tert-butylmethacrylate) as the main chain, were prepared by living anionic polymerization. Grafting of the polymers onto inorganic particles and metals was performed via the hydrolysis of the triethoxysilyl group using either acidic or basic catalyst. n-Butylphosphate was used as the catalyst for grafting onto inorganic substances having an acidic surface such as silica. However, in the case of grafting onto inorganic substances having a basic surface, tetrabutylammoniumhydroxide was employed as the catalyst. Contrary to expectations, grafting onto titania was successful even in the absence of a catalyst. Particles grafted with these polymers showed excellent dispersibility in organic medium, in which the polymers are soluble. This phenomenon is in contrast to that for particles treated with polymers possessing triethoxysilyl groups at random positions of the chain or those treated with trimethylsilyl groups. Surface tension measurements of metal substrates coated with the grafted polymers, were found to be identical to the values obtained for the bulk polymers.     

Highly efficient reversible addition–fragmentation chain‐transfer polymerization in ethanol/water via flow chemistry

Utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain‐transfer (RAFT ) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high‐efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (?) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L^?1, polymerization of poly(ethylene glycol) methyl ether methacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) ? (<1.25). The strategy developed here provides a method to produce well‐defined polymers via RAFT polymerization with high efficiency in a continuous manner. © 2017 Society of Chemical Industry     

Novel conjugated patterns of PBDT‐DTNT and PBDT‐TIPS‐DTNT‐DT complicated polymers onto graphenic nanosheets

The delicacy and connectivity of conductive patterns developed via poly[benzodithiophene‐bis(decyltetradecylthien)naphthothiadiazole] (PBDT‐DTNT) and poly[bis(triisopropylsilylethynyl)benzodithiophene‐bis(decyltetradecylthien)naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT) polymers were investigated on reduced graphene oxide (rGO) nanosheets. The principal driving force for assembly of PBDT‐DTNT and PBDT‐TIPS‐DTNT‐DT chains onto the rGO nanosheets was π‐stacking. In contrast to poly(3‐hexylthiophene) (P3HT), the surface modification of rGO limited the self‐assembly of PBDT‐DTNT and PBDT‐TIPS‐DTNT‐DT complicated polymers. The structure of PBDT‐DTNT and PBDT‐TIPS‐DTNT‐DT chains having fused and infused thiophenic and benzenic rings hindered their molecular ordering compared to P3HT, and therefore the selected area electron diffraction plots demonstrated rings instead of isolated growth planes. Although 2‐thiophene acetic acid (TAA) functional groups and poly(3‐dodecylthiophene) (PDDT) grafted onto rGO nanosheets did not alter the stacking type of the complicated polymers, it made their attachment more difficult. The thickness of π‐stacked patterns ranged from 55 to 70 nm. In the modified areas of rGO, the PBDT‐DTNT and PBDT‐TIPS‐DTNT‐DT chains were not capable of being deposited with a π‐interaction. Hence, the surface modification agents prevented the complicated polymers from interconnectedly assembling and, consequently, constructing longer and larger patterns. This hindrance was more noticeable for the supramolecules based on grafted rGO (rGO‐g‐PDDT) and PBDT‐TIPS‐DTNT‐DT. The conductivity of PBDT‐DTNT/rGO superstructures was the highest (14.61–14.89 S cm^?1). The patterned nanohybrids could be considered as potential super‐materials for morphology‐templating in the active layers of organic–inorganic photovoltaics. © 2018 Society of Chemical Industry     

pH and thermo‐responsive poly(N‐isopropylacrylamide) copolymer grafted to poly(ethylene glycol)

pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by ¹H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Low protein fouling polypropylene membrane prepared by photoinduced reversible addition‐fragmentation chain transfer polymerization

In this study, 2‐hydroxyethyl methacrylate and N‐isopropyl acrylamide was block grafted onto the polypropylene macroporous membrane surface by photo‐induced reversible addition‐fragmentation chain transfer (RAFT) radical polymerization with benzyl dithiobenzoate as the RAFT agent. The degree of grafting of poly(2‐hydroxyethyl methacrylate) on the membrane surface increased with UV irradiation time and decreased with the chain transfer agent concentration increasing. The poly(2‐hydroxyethyl methacrylate)‐ grafted membranes were used as macro chain transfer agent for the further block graft copolymerization of N‐isopropyl acrylamide in the presence of free radical initiator. The degree of grafting of poly(N‐isopropyl acrylamide) increased with reaction time. Furthermore, the poly(2‐hydroxyethyl methacrylate)‐ grafted membrane with a degree of grafting of 0.48% (wt) showed the highest relative pure water flux and the best antifouling characteristics of protein dispersion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Functionalization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) films via surface‐initiated atom transfer radical polymerization: Comparison with the conventional free‐radical grafting procedure

We modified hydrophobic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBHV) films with hydrophilic chains to control their surface properties. We designed and investigated surface‐initiated atom transfer radical polymerization (SI‐ATRP) to modify the PHBHV films by grafting poly(2‐hydroxyethyl methacrylate) (PHEMA) from the surface. This method consisted of two steps. In the first step, amino functions were formed on the surface by aminolysis; this was followed by the immobilization of an atom transfer radical polymerization initiator, 2‐bromoisobutyryl bromide. In the second step, the PHEMA chains were grafted to the substrate by a polymerization process initiated by the surface‐bound initiator. The SI‐ATRP technique was expected to favor a polymerization process with a controlled manner. The experimental results demonstrate that the grafting density was controlled by the reaction conditions in the first step. The grafted films were analyzed by Fourier transform infrared spectroscopy, contact angle testing, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy. The results show that grafted chains under the SI‐ATRP method were preferentially located on the surface for surface grafting and in the bulk for conventional free‐radical polymerization initiated by benzoyl peroxide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Grafted stock synthesis of ABS at the ultimate high ratio of polybutadiene to poly(styrene‐co‐acrylonitrile)

This study describes the emulsion grafting of styrene and acrylonitrile onto 60–70% polybutadiene (PB), in the presence or absence of tert‐dodecanetiol as a chain transfer reagent with a radical initiator, and the properties of the obtained grafted stock. There was no significant difference in terms of effect of the initiation mode on the grafting efficiency resulting from the high grafting reactivity of PB. However, the grafted stock with 70% PB prepared in the presence of tert‐dodecanetiol and the adequate selection of an initiation system gave a homogeneous dispersion of the PB particles into poly(styrene‐co‐acrylonitrile) (SAN) matrix. The initiation system involves tert‐butyl peroxylaurate, tert‐butyl peroxyacetate, and tert‐butyl peroxyisopropylcarbonate coupled with ferrous sulfate. The efficient coverage of the SAN grafted layer around 70% PB particles was observed by TEM to eventually give excellent impact resistance, high surface gloss, and good thermal resistance. The absence of tert‐dodecanetiol resulted in a toughness reduction of ABS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3462–3470, 2001     

Effect of the MMA content on the emulsion polymerization process and adhesive properties of poly(BA‐co‐MMA‐co‐AA) latexes

In the past work, the shear resistance of pure poly(n‐butyl acrylate) was low, even incorporation of inorganic filler, silica in the composition. It is well‐known that the copolymerization of n‐butyl acrylate (BA) with methyl methacrylate (MMA) will increase the glass transition temperature, and enhance the shear resistance of acrylic polymers. In the current work, the preparation of a series of acrylic water‐borne pressure‐sensitive adhesives (PSAs) with the controlled composition and structure for the copolymerization of BA and acrylic acid (AA) with different MMA contents, poly(BA‐co‐MMA‐co‐AA) was reported and its effects on adhesive properties of the latices were investigated. The latices of poly(BA‐co‐MMA‐co‐AA) were prepared at a solid content of 50% by two‐stage sequential emulsion polymerization, and this process consisted of a batch seed stage giving a particle diameter of 111 nm, which was then grown by the semicontinuous addition of monomers to final diameter of 303 nm. Dynamic light scattering (DLS) was used to monitor the particle diameters and proved that no new nucleation occurred during the growth stage. Copolymerization of BA with MMA raised the glass transition temperature (T_g) of the soft acrylic polymers, and had the effect of improving shear resistance, while the loop tack and peel adhesion kept relatively high. The relationship between pressure‐sensitive properties and molecular parameters, such as gel content and molecular weight, was evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface grafting of poly(pentafluorostyrene) on the iron and iron oxide particles via reversible addition fragmentation chain transfer (RAFT) polymerization

A surface grafting technique is reported for synthesis of poly(pentafluorostyrene) via reversible addition fragmentation chain transfer onto iron (iron oxide) particles. 4‐Methoxydithiobenzoate is used for the RAFT chain transfer agent. The molecular weight, surface morphology, thickness, thermal properties, and monomer conversion of the grafted polymer are reported. The grafted poly(pentafluorostyrene)–iron particles show a higher thermal transition temperature compared to the nongrafted polymer because it is speculated that the covalent bond between the polymer backbone and the surface of the iron particles restricts the molecular mobility. The monomer conversion increases in proportion to the amount of chain transfer agent (CTA) concentration at early polymerization time. The grafted poly(pentafluorostyrene) shows a “hairy” like polymer architecture with fibril thickness in the range of 80 to 100 nm. A thin coating is expected to maintain the magnetic saturation properties of iron particles. To the best of our knowledge, this is the first time that poly(pentafluorostyrene) has been grafted onto the iron particles utilizing RAFT and 4‐methoxydithiobenzoate as a CTA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44898.     

Synthesis and characterization of high‐density polypropylene‐grafted polyethylene via a macromolecular reaction and its rheological behavior

High‐density polyethylene grafted isotactic polypropylene (PP‐g‐HDPE) was prepared by the imidization reaction between maleic anhydride grafted polyethylene and amine‐grafted polypropylene in a xylene solution. The branch density was adjusted by changes in the molar ratio between maleic anhydride and primary amine groups. Dynamic rheology tests were conducted to compare the rheological properties of linear polyolefins and long‐chain‐branched polyolefins. The effects of the density of long‐chain branches on the rheological properties were also investigated. It was found that long‐chain‐branched hybrid polyolefins had a higher storage modulus at a low frequency, a higher zero shear viscosity, a reduced phase angle, enhanced shear sensitivities, and a longer relaxation time. As the branch density was increased, the characteristics of the long‐chain‐branched structure became profounder. The flow activation energy of PP‐g‐HDPE was lower than that of neat maleic anhydride grafted polypropylene (PP‐g‐MAH) because of the lower flow activation energy of maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH). However, the flow activation energy of PP‐g‐HDPE was higher than that of PP‐g‐MAH/HDPE‐g‐MAH blends because of the presence of long‐chain branches. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of fullerene grafted poly(ε‐caprolactone)

The fullerene grafted poly(ε‐caprolactone) (PCL) was successfully synthesized with a graft efficiency of 80%. The fullerene moieties grafted onto the PCL chain aggregate into 1–2 μm particles so that a physical pseudo‐network is formed. Because of the existence of the network structure, the fullerene grafted PCL film can retain its shape at much higher temperatures than that of pure PCL film, as observed in dynamic mechanical tests. It shows a hydrophobic gelling behavior in chloroform solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mid‐chain grafting in PVB‐graft‐PVB

The polymer commonly referred to as poly(vinyl butyral) is actually the statistical terpolymer poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), the main component of the polymeric interlayer in automotive and architectural safety glass, amongst other uses. Here, the effects of ‘self‐grafting’ or ‘auto‐grafting’ in this polymer are examined using size‐exclusion chromatography (SEC) with triple detection. These and supporting experiments (eg, batch‐mode multi‐angle light scattering) allow study of the effects of induced branching in the resultant PVB‐graft‐PVB molecule, and comparison with the ungrafted (though not linear) base polymer. This was done by application and extension of the classic Zimm–Stockmayer long‐chain branching (LCB) theory, by determination of the fractal dimension (d_f) of the polymers and of the change in d_f as a function of molar mass, as well as by the multiplicity of size parameters that are measured in a multi‐detector SEC experiment. Copyright © 2004 Society of Chemical Industry     

Ibuprofen‐imprinted ultrathin poly[N‐(2‐hydroxypropyl) methacrylamide] films

Surface molecularly imprinted (MIP) poly[N‐(2‐hydroxypropyl) methacrylamide] [poly(HPMA)] films were prepared via interface‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization from 4‐cyano‐4‐(propylsulfanylthiocarbonyl) sulfanyl pentanoic acid immobilized silicon substrate using N‐(2‐hydroxypropyl) methacrylamide as the functional monomer, N,N′‐methylene(bis)acrylamide as the crosslinking agent, and ibuprofen as the template molecule. The highly crosslinked MIP layer (～12 nm) was homogeneously grafted onto the silicon surface, which favors fast mass transfer and rapid binding kinetics. Binding capacities and adsorption parameters of the MIP poly(HPMA) films were calculated from the root‐mean‐square roughness data obtained by atomic force microscopy measurements using the Luzinov and Langmuir equations adopted for this study. The target binding assays demonstrate the desirable binding capacity and imprinting efficiency of the MIP poly(HPMA) films. Meanwhile, the computational optimization and energy calculations showed the formation of the self‐assembly of monomer and template molecule via noncovalent interactions that leads to a 1:4 molecular complex between ibuprofen and N‐(2‐hydroxypropyl) methacrylamide. This study provides a versatile approach to the quantitative determination of low‐molecular‐weight biomolecules on surface‐imprinted polymers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45707.     

Synthesis of pH‐responsive polyethylene terephthalate track‐etched membranes by grafting hydroxyethyl‐methacrylate using atom‐transfer radical polymerization method

pH‐responsive polyethylene terephthalate (PET) track‐etched membranes were synthesized by grafting 2‐hydroxyethyl‐methacrylate (HEMA) on the surface of the membrane via atom transfer radical polymerization. The controllability of grafting polymerization of HEMA on membrane surface is systematically investigated. The pH‐responsive characteristics of PET‐g‐poly(2‐hydroxyethyl‐methacrylate) (PHEMA) gating membranes with different grafted PHEMA chain lengths are measured by tracking the permeation of water solution with different pH values. The results show that the grafting polymerization is controllable, and the permeation of grafted membranes is affected by the grafted PHEMA chain lengths on the surface of membrane. The results also demonstrate that the grafted PET membranes exhibit reversible pH‐response permeation to environmental pH values. Desired pH‐responsive membranes are obtained by controlling the grafted PHEMA chain lengths via atom transfer radical polymerization method. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40912.     

Emulsifier‐free reversible addition–fragmentation chain transfer emulsion polymerization of alkyl acrylates mediated by symmetrical trithiocarbonates based on poly(acrylic acid)

Emulsifier‐free batch emulsion polymerization of n‐butyl acrylate and its semi‐batch copolymerization with 2,2,3,3,4,4,5,5‐octafluoropentyl acrylate and 2,2,3,4,4,4‐hexafluorobutyl acrylate both mediated by poly(acrylic acid) containing the trithiocarbonate group in the chain was employed to produce amphiphilic triblock copolymers. The polymerization‐induced self‐assembly of these copolymers in aqueous media gave rise to spherical core–shell particles. Irrespective of the experimental conditions, the polymeric product was characterized by a bimodal molecular weight distribution. The apparent violation of the reversible addition–fragmentation chain transfer polymerization mechanism may be attributed to restricted accessibility of the trithiocarbonate group in the self‐assembled block copolymers for propagating radicals that enter into the particle. Mean‐field theoretical arguments were employed to explain the exclusively spherical morphology of the particles observed in the experiment. © 2019 Society of Chemical Industry     

Properties of PHMS‐g‐p [butylacrylate (BA)‐N‐hydroxyl‐methyl acrylamide (NMA)] graft copolymer emulsions

Emulsion graft copolymerization of poly(hydrogenmethylsiloxane) (PHMS) and butyl acrylate (BA) in the presence of functional comonomer N‐hydroxyl‐methyl acrylamide (NMA) was conducted by batch emulsion copolymerization to modify the properties of polysiloxane. Morphology of graft copolymer particles was characterized by transmission electron microscopy. The effect of polymerization method, PHMS content, initiator concentration, and NMA content on stability of emulsion, morphology, size of particle, and rheological properties were investigated. It has been found that stability of emulsion is better by semicontinuous emulsion polymerization than that of batch emulsion polymerization and it increased with increasing PHMS‐NMA concentration. Increasing PHMS concentration and NMA concentration, the particle size and the viscosities increase. The property of resistance to electrolytes of graft copolymer emulsions and swelling property of film were also discussed. Results showed PHMS‐g‐P [butylacrylate (BA)‐N‐hydroxyl‐methyl acrylamide (NMA)] graft copolymer emulsion has good resistance to electrolytes and the water absorption of its film increases with increasing BA‐NMA content grafted onto PHMS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2209–2217, 1999     

Poly (glycerol‐sebacate) bioelastomers: 2. Synthesis using Brabender Plasticoder® as a batch reactor

Poly (glycerol‐sebacate) polymers are seen as useful materials for biomedical applications. In this article, poly (glycerol‐sebacate) oligomers were synthesized by modifying a Brabender Plasticorder^® as a batch reactor. The samples collected over a reaction period of 5 h were characterized using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The number‐average molecular weight (M_n) and weight‐average molecular weight (M_w) of the oligoesters were determined using matrix‐assisted laser desorption/ionization time‐of‐flight spectroscopy (MALDI‐TOF). The polydispersity indices of these oligoesters produced were within bounds of current commercial polymers. The gel‐point of the reaction was determined from the crossover point of the storage and loss moduli, and the reaction rate constant was calculated using the torque data of the rheometer. The kinetic rate constant and the extent of the reaction in the Brabender were higher than the corresponding values obtained from the conventional laboratory reaction process. The challenges and possibilities in scaling up a batch process to a continuous process (e.g., reactive extrusion) are discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42852.     

Rubber‐toughened PLA blends with low thermal expansion

In this study, poly (lactic acid) (PLA) blended with various rubber components, i.e., poly (ethylene‐glycidyl methacrylate) (EGMA), maleic anhydride grafted poly(styrene‐ethylene/butylene‐styrene) triblock elastomer (m‐SEBS), and poly(ethylene‐co‐octene) (EOR), was investigated. It was observed that EGMA is highly compatible due to its reaction with PLA. m‐SEBS is less compatible with PLA and EOR is incompatible with PLA. Electron microscopy (SEM and TEM) revealed that a fine co‐continuous microlayer structure is formed in the injection‐molded PLA/EGMA blends. This leads to polymer blends with high toughness and very low linear thermal expansion both in the flow direction and in the transverse direction. The microlayer thickness of rubber in PLA blends was found to play key roles in reducing the linear thermal expansion and achieving high toughness of the blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of poly(ϵ‐caprolactone‐co‐p‐dioxanone)–poly(ethylene glycol)–poly(ϵ‐caprolactone‐co‐p‐dioxanone)/bioactive inorganic particle nanocomposites

With an aim to develop injectable hydrogel with improved solution stability and enhanced bone repair function, thermogelling poly(ε‐caprolactone‐co‐p‐dioxanone)‐poly(ethylene glycol)‐poly(ε‐caprolactone–co‐p‐dioxanone) (PECP)/bioactive inorganic particle nanocomposites were successfully prepared by blending the triblock copolymer (PECP) with nano‐hydroxyapatite (n‐HA) or nano‐calcium carbonate (n‐CaCO₃). The hydrogel nanocomposites underwent clear sol–gel transitions with increasing temperature from 0 to 50°C. The obtained hydrogel nanocomposites were investigated by ¹H NMR, FT‐IR, TEM, and DSC. It was found that the incorporation of inorganic nanoparticles into PECP matrix would lead to the critical gelation temperature (CGT) shifting to lower values compared with the pure PECP hydrogel. The CGT of the hydrogel nanocomposites could be effectively controlled by adjusting PECP concentration or the content of inorganic nanoparticles. The SEM results showed that the interconnected porous structures of hydrogel nanocomposites were potentially useful as injectable scaffolds. In addition, due to the relatively low crystallinity of PECP triblock copolymer, the aqueous solutions of the nanocomposites could be stored at low temperature (5°C) without crystallization for several days, which would facilitate the practical applications. The PECP/bioactive inorganic particle hydrogel nanocomposites are expected to be promising injectable tissue engineering materials for bone repair applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gas‐phase olefin polymerization over supported metallocene/MAO catalysts: influence of support on activity and polydispersity

Three catalysts obtained by supporting bis(n‐butylcyclopentadienyl)zirconium dichloride/methylaluminoxane on: (1) porous crosslinked poly(2‐hydroxyethylmethacrylate‐co‐styrene‐co‐divinylbenzene) particles (CAT1); (2) swellable crosslinked poly(styrene‐co‐divinylbenzene) particles (CAT2); and (3) by evaporating the catalyst precursors solution to dry powder, CAT3 were used in gas‐phase polymerization of ethylene, and ethylene/1‐hexene in a 2 L semi‐batch reactor at 80 °C and 1.4 MPa. The average polymerization activities of the three catalysts were 12.3–15.5, 4.2–10.1, and 14.3–62.9 ton PE (mol Zr h)^?1 respectively. CAT1 and CAT3 produced polyethylenes with a polydispersity range of 2.3–2.7, while that of CAT2 was 3.5–6.4. The supported catalysts produced polyolefin particles with bulk density of 0.36–0.43 g ml^?1, and essentially no fines. Ethylene/1‐hexene co‐polymerization (7 mol m^?3 initial 1‐hexene concentration in the reactor) increased polymerization activities and produced lower‐molar‐mass co‐polymers. At 21 mol m^?3 1‐hexene the polymerization activities decreased, but the relative amount of the low‐molar‐mass co‐polymer for CAT2 increased, leading to higher polydispersity. Copyright © 2006 Society of Chemical Industry