Polybutadiene/polyhedral oligomeric silsesquioxane nanohybrid: investigation of various reactants in polyesterification reaction

Nano‐sized polyhedral oligomeric silsesquioxane (POSS) diol or ethylene glycol (EG) as diol monomer was incorporated into hydroxyl‐terminated polybutadiene (HTPBD) chain in the presence of fumaryl or thionyl chloride as extenders. Using these polyesterification reactions, two fumarate‐based polyesters and two polyester sulfites were synthesized. Each couple of polyesters and polyester sulfites includes a linear (diol:EG) and a nanohybrid macromer (diol:POSS). Full structural characterization was performed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies. Gel permeation chromatography was undertaken to study polyesterification mechanisms by deconvolution of the obtained traces. Finally, differential scanning calorimetry, thermogravimetric analysis and cell culture were performed to evaluate the structure–property relationship for the synthesized macromers in comparison with unreacted HTPBD. © 2016 Society of Chemical Industry     

Highly efficient supported AlCl3-based cationic catalysts to produce polyα-olefin oil base stocks

The main aim of this research is to decrease the amount of AlCl₃ content that is very corrosive and hazardous in the catalytic system, required for the α-olefin oligomerization without substantial change of final oil features. This was successfully achieved by supporting AlCl₃ on different carriers. More precisely, a series of supported bimetallic catalysts was synthesized by immobilization of AlCl₃ and TiCl₄ onto Al₂O₃, SiO₂, and mixed supports, that is, Al₂O₃/FeCl₃ and SiO₂/FeCl₃. It was found that silica and alumina-based catalysts had higher catalytic activities compared to support free AlCl₃; however, this enhancement for silica-based supports was more significant. According to gel permeation chromatography (GPC) results, the use of single supports, that is, Al₂O₃ and SiO₂, increased oligomer's molecular weight, while the application of mixed supports resulted in the decrease of molecular weight of the oligomers. Viscosity characteristics of the synthesized oligomers have also been studied at two different temperatures of 40 and 100°C (KV⁴⁰ and KV¹⁰⁰). The viscosity index (VI) values, derived from KV⁴⁰ and KV¹⁰⁰, of the prepared oligomers were in the range of 126–145. The molecular weight and termination mechanisms of the oligomers were studied by ¹H-NMR spectroscopy. The obtained results disclosed that the employed reaction conditions led to the production of oligomer chains with various structures including vinylidene (Vd), and di and three-substituted vinylene (2Vn, 3Vn) structures.     

Poly1‐hexene: New impact modifier in HIPS technology

Poly1‐hexene was prepared using a conventional heterogeneous Ziegler–Natta catalyst and its stereoregularity was characterized using ¹³C‐NMR analysis. New kind of high impact polystyrene (HIPS) was prepared by radical polymerization of styrene in the presence of different amounts of synthesized poly1‐hexene (PH) as impact modifier (HIPS/PH) and compared with conventional high impact polystyrene with polybutadiene (HIPS/PB) as rubber phase. Scanning electron microscopy (SEM) revealed that the dispersion of poly1‐hexene in polystyrene matrix was more uniform compared with it in HIPS/PB. The impact strength of HIPS/PH was 29–79% and 80–289% higher than that in HIPS/PB and neat polystyrene, respectively. FTIR was used to confirm more durability of HIPS/PH samples toward ozonation. To study the effect of rubber type and amount on the T_gs of polystyrene, differential scanning calorimetry was employed. Results obtained from TGA demonstrated higher thermal stability of HIPS/PH sample in comparison with conventional HIPS/PB one. Our obtained results suggest new high impact polystyrene that in all studied aspects has better performance than the conventional HIPS. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43882.     

Methacrylate-functionalized POSS as an efficient adhesion promoter in olefin-based adhesives

This study aims to investigate the effects of methacrylate-functionalized polyhedral oligomeric silsesquioxane (MA-POSS) on polyolefin-based adhesives. The so called adhesive was synthesized by the cooligomerization of 1-decene/9-decene-1-ol monomers using a Ti amine bis-phenolate catalyst, [Ti{2,2′-(OC₆H₂-4,6-^tBu₂)₂NHC₂H₄NH(OⁱPr)₂], which was subsequentlyacrylated via a simple reaction with methacryloyl chloride. Different weight fractions of MA-POSS nanoparticles were solution blended with synthesized adhesive and undergone curing reaction with blue light. Observation of a unique tan δ peak in dynamic mechanical thermal analysis (DMTA) curve was clear evidence that two employed moieties were miscible and only one hybrid polymeric phase was created. Most noticeably, significant increase in mechanical parameters was detected in the lower inclusion compositions, 0.2-1 wt% of MA-POSS, where flexural strength and flexural modulus were increased up to 99 and 110%, respectively. Furthermore, thermal stability of the synthesized nanocomposite enhanced dramatically by increasing MA-POSS weight fraction. Influence of employed nanoparticles on adhesion properties of synthesized nanocomposites was evaluated with tensile shear bond strength and pull off analysis. According to the adhesion results, the MA-POSS causes an adhesion promotion on the fabricated adhesive/POSS nanocomposites.     

The effects of solvent and initiator on anionic ring opening polymerization of ϵ‐caprolactone: synthesis and characterization

Anionic ring opening polymerization of ?‐caprolactone was studied by using different amounts of two potassium activated initiators containing ethylene glycol (EG) and polyhedral oligomeric silsesquioxane (POSS) diol, in tetrahydrofuran and toluene as solvents. The synthesized hydroxyl terminated macromers and linear poly(?‐caprolactone) (PCL) were characterized by proton and carbon nuclear magnetic resonance and gel permeation chromatography (GPC) techniques. Results showed an increase in molecular weight as the monomer/initiator molar ratio increased from 100 to 151 and 202, while the molecular weight distribution (MWD) showed a minimum by monomer concentration increase. Moreover, POSS‐diol‐initiated PCLs showed a higher MWD than the polymers initiated with the EG initiator. This was attributed to the formation of a vesicular structure of POSS diols which was confirmed by optical microscopy. By deconvolution of GPC peaks, the best conditions to synthesize PCL with the narrowest MWD were selected. Finally, the effects of some other parameters were studied in more detail.     

Microwave Absorption Properties of Polyaniline/Carbonyl Iron Composites

In this work, carbonyl iron (CI) containing polya- niline composites (PANI+CI) were prepared via in-situ polymerization of aniline in an aqueous solution containing different amounts of CI as the magnetic filler for the micro- wave absorbers. The incorporation of the magnetic powder to the PANI matrix was confirmed by X-ray diffraction (XRD), IR and SEM. Synthesized PANI+CI composite particles were subsequently added to an epoxy resin matrix to produce related R-PANI+CI composites. Study of thermal properties by thermogravimetric analysis revealed enhanced thermal stability of the composites. The electromagnetic-absorbing properties were studied by measuring the reflection loss in the frequency range of 8.0 to 12.0 GHz. The experimental results indicated that the electromagnetic wave absorbing properties of PANI+CI composites are dependent on the PANI/CI weight ratio. The good reflection loss of the composite at the optimum PANI/CI weight ratio of 1:6 suggests its potential applicability as a good radar absorber.     

Activation of Ziegler‐Natta catalysts by organohalide promoters: A combined experimental and density functional theory study

Several organohalide (HC) compounds were tested as promoters for a Ti‐based Ziegler‐Natta (Z‐N) catalyst at different polymerization conditions. Results show that the intensity of the promoting effect depends on the nature and amount of the promoters. A proper amount, especially optimum amount, of aliphatic type organohalides leads to a strong productivity, and aromatic ones leads to a weak productivity improvement; however, 3‐chloro‐1‐propene poison the catalyst even at lower HC/Ti molar ratios. Among studied compounds, chlorocyclohexane has the best activity promotion effect at HC/Ti molar ratio of 128, and with this as a promoter, the activity increases over 85%. To understand more details about this phenomenon, the rate of polymerization during time and the effect of polymerization conditions (the temperature and hydrogen partial pressure) on the performance of chlorocyclohexane as the most effective promoter were studied. Finally, to explore the mechanism of reactivation of catalyst species by organohalides, molecular modeling was employed and a new oxidation‐addition mechanism was proposed, which basically consisting of homolytic breaking of C? Cl bond in organohalides. It was found that reoxidation of the catalyst, restoring active center, by Cl rich organohalides is energetically more favored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012