Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

Poly(styrene)‐poly(lactide) (PS‐PLA), poly (tert‐butyl styrene)‐poly(lactide) (PtBuS‐PLA) diblocks, and poly(tert‐butyl styrene)‐poly(styrene)‐poly(lactide) (PtBuS‐PS‐PLA) segmented and tapered triblocks of controlled segment lengths were synthesized using nitroxide‐mediated controlled radical polymerization. Well‐defined PLA‐functionalized macromediators derived from hydroxyl terminated TEMPO (PLA_T) of various molecular weights mediated polymerizations of the styrenic monomers in bulk and in dimethylformamide (DMF) solution at 120–130°C. PS‐PLA and PtBuS‐PLA diblocks were characterized by narrow molecular weight distributions (polydispersity index (M_w/M_n) < 1.3) when using the PLA_T mediator with the lowest number average molecular weight M_n= 6.1 kg/mol while broader molecular weight distributions were exhibited (M_w/M_n = 1.47‐1.65) when using higher molecular weight mediators (M_n = 7.4 kg/mol and 11.3 kg/mol). Segmented PtBuS‐PS‐PLA triblocks were initiated cleanly from PtBuS‐PLA diblocks although polymerizations were very rapid with PS segments ～ 5–10 kg/mol added within 3–10 min of polymerization at 130°C in 50 wt % DMF solution. Tapering from the PtBuS to the PS segment in semibatch mode at a lower temperature of 120°C and in 50 wt % DMF solution was effective in incorporating a short random segment of PtBuS‐ran‐PS while maintaining a relatively narrow monomodal molecular weight distribution (M_w/M_n ≈ 1.5). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry     

Influence of an oligomer polyol and monomers on the structure and properties of core–shell polyurethane–poly(n‐butyl acrylate‐co‐styrene) hybrid emulsions

The free‐radical polymerization of alkenyl‐terminated polyurethane dispersions with styrene and n‐butyl acrylate was performed to obtain a series of stable polyurethane–poly(n‐butyl acrylate‐co‐styrene) (PUA) hybrid emulsions. The core–shell structure of the emulsions was observed by transmission electron microscopy, and the microstructure was studied by ¹H‐NMR and Fourier transform infrared spectroscopy. The effects of the poly(propylene glycol)s (number‐average molecular weights = 1000, 1500, and 2000 Da) and the mass ratios of polyurethane to poly(n‐butyl acrylate‐co‐styrene) (PBS; 50/50, 40/60, 30/70, 20/80, and 10/90) on the structure, morphology, and properties of the PUAs were investigated. The average particle size and water absorption values of the PUAs increased with increasing of PBS content. However, the surface tension decreased from 34.61 to 30.29 mN/m. PUA‐2, with a bimodal distribution, showed Newtonian liquid behaviors, and PUA‐3 showed a great thermal stability, fast drying characteristics, and excellent adhesion to packaging films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43763.     

Poly(methyl acrylate) and copolymer of acrylic acid and butyl acrylate prepared by γ‐irradiation in the presence of 1,1‐diphenylethene: Synthesis and application in emulsion polymerization

Poly(methyl acrylate) and amphiphilic copolymer of butyl acrylate and acrylic acid were prepared in the presence of 1,1‐diphenylethene (DPE) by γ‐irradiation‐induced polymerization. The influences of polymerization time, amounts of DPE in system on conversion, molecular weight (MW), and its distribution (M_w/M_n) were studied. The results indicate that the polymerization in the presence of DPE and initiated by γ‐irradiation shows the character of controlled radical reaction. The prepared copolymer was used as the polymeric emulsifier in the emulsion polymerizations of butyl acrylate (BA) and styrene (St), respectively, to assess the possibility of making monodisperse latices of relatively high solids content (～ 35–45%) in an one‐step batch process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of a foam regulator with ultra‐high molecular weight

Multistage emulsion polymerization was used to prepare ultra‐high molecular weight foam regulator of low cost, with methyl methacrylate (MMA), butyl acrylate (BA), styrene (St) as main raw materials. Ubbelohde viscometer, dynamic light scattering, infrared and raman spectra, TEM, DSC, TGA, and GPC were all used to characterize constituent and structure, morphology, and molecular weight. As a result, when the ratio of soft monomer (BA) and hard monomer (St + MMA) is 1:3, MMA:St = 4:1, potassium persulfate (KPS): 0.15%, sodium hydrogen sulfite (SHS): 0.05%, azodiisobutyronitrile (AIBN): 0.15%, divinyl benzene (DVB): 0.3%, the final product terpolymer has obvious core‐shell structure and ultra‐high molecular weight (M_w = 1,400,000). This kind of foam regulator showed improvements in the melt strength, prevention of bubble coalescence and reduction on cost when compared with the traditional. Finally, the coefficients of poly (methyl methacrylate‐butyl acrylate‐styrene) terpolymer's Mark‐Houwink equation were calculated with tetrahydrofuran (THF) solvent at 25 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44479.     

Effects of the cosurfactant 1‐butanol and feed composition on nanoparticle properties produced by microemulsion copolymerization of styrene and methyl methacrylate

The concentration of the cosurfactant 1‐butanol (BuOH) determined the polymer weight and size for a series of poly(styrene‐co‐methyl methacrylate)s (P(St‐co‐MMA)) synthesized by the free‐radical (o/w) microemulsion technique. A factorial design established the levels of the experimental conditions for the polymerization i.e., concentration of the surfactant, sodium dodecyl sulfate (SDS); concentration of the cosurfactant, BuOH; temperature and ratio of the styrene (St) to methyl methacrylate (MMA). An increase in the weight‐average molecular weight (M_w) and number‐average molecular weight (M_n) was observed in the P(St‐co‐MMA) series with an increase in BuOH concentration from 1 to 5 wt %. These effects could arise from the micellar aggregation induced by interfacial BuOH. The unique micellar conditions could be exploited to synthesize copolymers of varying molecular weight and size. Additionally, the composition of the copolymers was virtually templates of the feed composition. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Control of monodisperse particle size of styrenic–acrylate copolymers in dispersion copolymerization

Syntheses of monodisperse poly[(styrene)‐co‐(n‐butyl acrylate)] and poly[(styrene)‐co‐(2‐ethylhexyl acrylate)] were carried out by dispersion polymerization. The reactions were performed in the mixed solvent of ethanol–water in the presence of azo‐bisisobutyronitrile and poly(N‐vinylpyrrolidone) as the initiator and dispersant, respectively. The effects of reaction parameters, that is the type and concentration of dispersant, ratio of the mixed solvent, reaction temperature, agitation rate, monomer composition between styrene and n‐butyl acrylate or 2‐ethylhexyl acrylate, crosslinking agent and reaction time on the particle size, size distribution and average molecular weights of the resulting copolymer were thoroughly investigated. The resulting copolymer particles were smooth on their spherical surface and the sizes were in the range 0.6–1.8 µm with a narrow size distribution. In most cases, a correlation between small particle sizes with high average molecular weights was observed. The average particle size generally increased with increasing reaction temperature, time and acrylate monomer content. In contrast, the particle size decreased as the molecular weight, concentration of dispersant, polarity of the medium or agitation rate was increased. The glass transition temperature (T_g) of the copolymers can be controlled by the mole ratio of the comonomer. The T_g values decreased when the content of acrylate monomers in the copolymer increased, and T_g values of the synthesized copolymer were in the range 66–102 °C. Instead of using n‐butyl acrylate monomer in the copolymerization, 2‐ethylhexyl acrylate copolymerization with styrene resulted in insignificant changes in the particle sizes but there were significant decreases in T_g values. In this study, the monodisperse particles can be obtained by monitoring the appropriate conditions regarding PVP K‐30 (2–8 wt%), ethanol/water (90/10 wt%), the reaction temperature (70 °C) and the agitation rate (100 rpm). © 2000 Society of Chemical Industry     

Synthesis and biological activity of medium range molecular weight polymers containing exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid

A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: M_n = 9600 g mol^?1, M_w = 9800 g mol^?1, M_w/M_n = 1.1 for poly(ETCA); M_n = 14 300 g mol^?1, M_w = 16 200 g mol^?1, M_w/M_n = 1.2 for poly(ETCA‐co‐AA); M_n = 17 900 g mol^?1, M_w = 18 300 g mol^?1, M_w/M_n = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry     

Influence of the comonomers (styrene and methyl acrylate) on the rate of photocrosslinking of 4‐{[‐3‐(4‐hydroxybenzylidene)‐2‐oxocyclohexylidene]methyl}‐ phenyl acrylate

[2,6‐Bis(4‐hydroxybenzylidene)cyclohexanone] (HBC) was prepared by reacting cyclohexanone and p‐hydroxybenzaldehyde in the presence of acid catalyst. Acrylated derivative of HBC, 4‐{[‐3‐(4‐hydroxybenzylidene)‐2‐oxocyclohexylidene]methyl}phenyl acrylate (HBA), was prepared by reacting HBC with acryloyl chloride in the presence of triethylamine. Copolymers of HBA with styrene (S) and methyl acrylate (MA) of different feed compositions were carried out by solution polymerization technique by using benzoyl peroxide (BPO) under nitrogen atmosphere. All monomers and polymers were characterized by using IR and NMR techniques. Reactivity ratios of the monomers present in the polymer chain were evolved by using Finnman–Ross (FR), Kelen–Tudos (KT), and extended Kelen–Tudos (ex‐KT) methods. Average values of reactivity were achieved by the following three methods: r₁ (S) = 2.36 ± 0.45 and r₂ (HBA) = 0.8 ± 0.31 for poly(S‐co‐HBA); r₁ = 1.62 ± 0.06 (MA); and r₂ = 0.12 ± 0.07 (HBA) for poly(MA‐co‐HBA). The photocrosslinking property of the polymers was done by using UV absorption spectroscopic technique. The rate of photocrosslinking was enhanced compared to that of the homopolymers, when the HBA was copolymerized with S and MA. Thermal stability and molecular weights (M_w and M_n) were determined for the polymer samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2494–2503, 2004     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

n‐Butyl acrylate based latex interpenetrating polymer networks used as processing modifiers and impact modifiers of poly(vinyl chloride)

A latex interpenetrating polymer network (LIPN), consisting of poly(n‐butyl acrylate), poly(n‐butyl acrylate‐co‐ethylhexyl acrylate), and poly(methyl methacrylate‐co‐ethyl acrylate) and labeled PBEM, with 1,4‐butanediol diacrylate as a crosslinking agent was synthesized by three‐stage emulsion polymerization. The initial poly(n‐butyl acrylate) latex was agglomerated by a polymer latex containing an acrylic acid residue and then was encapsulated by poly(n‐butyl acrylate‐co‐ethylhexyl acrylate) and poly(methyl methacrylate‐co‐ethyl acrylate). A polyblend of poly(vinyl chloride) (PVC) and PBEM was prepared through the blending of PVC and PBEM. The morphology and properties of the polyblend were studied. The experimental results showed that the processability and impact resistance of PVC could be enhanced considerably by the blending of 6–10 phr PBEM. This three‐stage LIPN PBEM is a promising modifier for manufacturing rigid PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1168–1173, 2004     

Synthesis of monodisperse poly(butyl acrylate) initiated by SmMe(C5Me5)2(THF) and its adhesive properties after crosslinking by electron‐beam irradiation

Polymerization reactions of butyl acrylate (BuA) were carried out using an organosamarium complex, SmMe(C₅Me₅)₂(THF), as an initiator. Polymerization proceeds quantitatively to give high number‐average molecular mass polymers (M_n > 200,000) and narrow molecular weight distributions (M_w/M_n < 1.07). Irradiation of the resulting poly(BuA) with an electron beam (EB) gave crosslinked poly(BuA). Improved viscoelastic and adhesive properties of these polymers were useful for high‐temperature applications. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 432–437, 2001     

Molecular weight development in emulsion copolymerization of n‐butyl acrylate and styrene

The seeded emulsion copolymerization of n‐butyl acrylate and styrene in a weight ratio of 50/50 was investigated. The effect of the type of process (batch vs. semicontinuous) and the amounts of initiator and emulsifier charged into the reactor on the time evolution of the fractional conversion, number of polymer particles, and weight‐average molecular weight (M_w) was analyzed. It was found that the M_w depends to a slight extent on the type of process and the emulsifier concentration and to a larger extent on the initiator concentration. The molecular weight distributions (MWDs) and the gel content of the final latexes were also analyzed. In the absence of chain transfer agents (CTAs), the fraction of gel was higher in the semicontinuous processes. It was also found that the gel content increased with increasing initiator concentration in the recipe. The addition of 1 wt % CTA avoided gel formation and led to an important reduction of the M_w. Nevertheless, the MWDs presented a shoulder or even a second peak at high molecular weights that was due to reactions of chain transfer to the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1918–1926, 2003     

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     

Preparation of poly(styrene‐b‐2‐hydroxyethyl acrylate) block copolymer using reverse iodine transfer polymerization

Reverse iodine transfer polymerizations (RITP) of 2‐h‐ydroxyethyl acrylate (HEA) were performed in N,N‐dimethylformamide at 75°C using AIBN as initiator. Poly(2‐hydroxyethyl acrylate) (PHEA) with M_n = 3300 g mol^?1 and M_w/M_n <1.5 were obtained. Homopolymerization of styrene in RITP was also carried out under similar conditions using toluene as solvent. The resulting iodo‐polystyrene (PS‐I) with (M_{n, SEC} = 607 g mol^?1, polydispersity index (PDI) = 1.31) was used as a macroinitiator for the synthesis of amphiphilic block copolymers based on HEA with controlled well‐defined structure. Poly(styrene‐b‐2‐hydroxyethyl acrylate) (PS‐b‐PHEA) with M_n = 13,000 g mol^?1 and polydispersity index (M_w/M_n) = 1.4 was obtained, copolymer composition was characterized using ¹H‐NMR and FTIR, whereas SEC and gradient HPLC were used to confirm the formation of block copolymer and the living character of polymer chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Synthesis and characterization of copolymer grafted magnetic nanoparticles via surface‐initiated nitroxide‐mediated radical polymerization

“Grafting from” surface‐initiated nitroxide‐mediated radical polymerization (SI‐NMRP) techniques were used to synthesize poly[styrene‐co‐(maleic anhydride)] copolymer brushes from the Fe₃O₄ surfaces. Well‐defined polymer chains were grown from the Fe₃O₄ surfaces to yield particles with a Fe₃O₄ core and a polymer outer layer. The observed narrow molecular weight distributions (M_w/M_n), linear kinetic plots and linear plots of molecular weight (M_n) versus conversion for the free polymer indicated that the chain growth from the Fe₃O₄ surface was a controlled process by adding an excess of 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO). The modified nanoparticles were subjected to detailed characterization using XRD, TEM, FT‐IR, and TGA. The analyses of vibration sample magnetometer (VSM) verified that the nanoparticles owned good magnetic property. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Cationic polymerization of 1,3‐pentadiene coinitiated by zinc halides

Technology of industrial production of liquid rubber under trademark “SKOP” is based on the cationic polymerization of 1,3‐penadiene (piperylene) in the presence of TiCl₄ or AlCl₃‐based catalytic systems. The disadvantage of these catalytic systems is the high probability of formation of branched and insoluble fractions due to the chain transfer to polymer. This deteriorates the useful qualities of SKOP. Here we propose the new initiating systems for the cationic polymerization of 1,3‐pentadiene based on the homogeneous (dissolved in a minimal amount of diethyl ether) zinc halides (ZnCl₂ and ZnBr₂) as coinitiators and hydrochloric acid, tert‐butyl chloride or trichloroacetic acid as initiators. These initiating systems allow to synthesize fully soluble low molecular weight (M_n = 1000–3000 g mol^?1) poly(1,3‐pentadiene)s with relatively narrow molecular weight distribution (M_w/M_n < 2.0), which do not contain any high molecular weight and insoluble fractions in the whole range of monomer conversion. The polymers synthesized in the presence of zinc halides possess the same microstructure that those prepared with TiCl₄ as coinitiator. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and application of sulfonated poly(1‐octene‐co‐styrene)

In this article, 1‐octene and styrene was copolymerized by the supported catalyst (TiCl₄/ID/MgCl₂). Subsequently, by sulfonation reaction, sulfonated poly(1‐octene‐co‐styrene)s which were amphiphilic copolymers were prepared. The copolymerization behavior between 1‐octene and styrene is moderate ideal behavior. Copolymers prepared by this catalyst contain appreciable amounts of both 1‐octene and styrene. Increase in the feed ratio of styrene/1‐octene leads to increase in styrene content in copolymer and decrease in molecular weight. As the polymerization temperature increases, the styrene content in the copolymers increases, however, the molecular weight decreases. Hydrogen is an efficient regulator to lower the molecular weights of poly(1‐octene‐co‐styrene)s. The sulfonation degree of the sulfonated poly(1‐octene‐co‐styrene)s increased as the styrene content in copolymer increased or the molecular weight decreased. Thirty‐six hour is long enough for sulfonation reaction. The sulfonated poly(1‐octene‐co‐styrene)s can be used as effective and durable modifying agent to improve the wettability of polyethylene film and have potential application in emulsified fuels and for the stabilization of dispersions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of graft copolymers of syndiotactic polystyrene with polybutadiene and 4‐methylstyrene

The basic method for synthesizing syndiotactic polystyrene‐g‐polybutadiene graft copolymers was investigated. First, the syndiotactic polystyrene copolymer, poly(styrene‐co‐4‐methylstyrene), was prepared by the copolymerization of styrene and 4‐methylstyrene monomer with a trichloro(pentamethyl cyclopentadienyl) titanium(IV)/modified methylaluminoxane system as a metallocene catalyst at 50°C. Then, the polymerization proceeded in an argon atmosphere at the ambient pressure, and after purification by extraction, the copolymer structure was confirmed with ¹H‐NMR. Lastly, the copolymer was grafted with polybutadiene (a ready‐made commercialized unsaturated elastomer) by anionic grafting reactions with a metallation reagent. In this step, poly(styrene‐co‐4‐methylstyrene) was deprotonated at the methyl group of 4‐methylstyrene by butyl lithium and further reacted with polybutadiene to graft polybutadiene onto the deprotonated methyl of the poly(styrene‐co‐4‐methylstyrene) backbone. After purification of the graft copolymer by Soxhlet extraction, the grafting reaction copolymer structure was confirmed with ¹H‐NMR. These graft copolymers showed high melting temperatures (240–250°C) and were different from normal anionic styrene–butadiene copolymers because of the presence of crystalline syndiotactic polystyrene segments. Usually, highly syndiotactic polystyrene has a glass‐transition temperature of 100°C and behaves like a glassy polymer (possessing brittle mechanical properties) at room temperature. Thus, the graft copolymer can be used as a compatibilizer in syndiotactic polystyrene blends to modify the mechanical properties to compensate for the glassy properties of pure syndiotactic polystyrene at room temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009