Copolymerization of ethylene/nonconjugated dienes over a Bis(2‐methyl indenyl) zirconium dichloride/methylaluminoxane catalyst system

Ethylene was copolymerized with 1,5‐hexadiene (1,5‐HD), 1,4‐hexadiene (1,4‐HD) and 1,7‐octadiene (1,7‐OD) with bis(2‐methyl indenyl) zirconium dichloride/methylaluminoxane. 1,5‐HD units formed the trans‐structured cyclopentane rings and 1‐butenyl side chains, and cross‐linking took place during ethylene/1,5‐HD (E15HD) copolymerizations. The lower the polymerization temperature was, the larger the amount of hot xylene (XYL)‐insoluble faction was. Copolymers of ethylene/1,7‐OD (E17OD) did not have any cyclic structures and were nearly insoluble in XYL when produced below 60°C. In contrast, all the copolymers of ethylene/1,4‐HD (E14HD) were completely soluble in XYL. The broadest differential scanning calorimetry melting peak was found for E15HD and then for E17OD, and the narrowest was found for E14HD due to the presence or the absence of the cyclic structures and cross‐linking. Addition of 1,7‐OD or 1,4‐HD as a comonomer reduced the polymerization rate and the molecular weight of the respective copolymers much more than that of 1,5‐HD. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1048–1058, 2002; DOI 10.1002/app.10397     

Copolymerization of ethylene/α‐olefins using bis(2‐phenylindenyl)zirconium dichloride metallocene catalyst: structural study of comonomer distribution

Catalysts have a major role in the polymerization of olefins and exert their influence in three ways: (1) polymerization behaviour, including polymerization activity and kinetics; (2) polymer particle morphology, including bulk density, particle size, particle size distribution and particle shape; and (3) polymer microstructure, including molecular weight regulation, chemical composition distribution and short‐ and long‐chain branching. By tailoring the catalyst structure, such as the creation of a bridge or introducing a substituent on the ligand, metallocene catalysts can play a major role in the achievement of desirable properties. Kinetic profiles of the metallocene catalyst used in this study showed decay‐type behaviour for copolymerization of ethylene/α‐olefins. It was observed that increasing the comonomer ratio in the feedstock affected physical properties such as reducing the melting temperature, crystallinity, density and molecular weight of the copolymers. It was also observed that the heterogeneity of the chemical composition distribution and the physical properties were enhanced as the comonomer molecular weight was increased. In particular, 2‐phenyl substitution on the indenyl ring reduced somewhat the melting point of the copolymers. In addition, the copolymer produced using bis(2‐phenylindenyl)zirconium dichloride (bis(2‐PhInd)ZrCl₂) catalyst exhibited a narrower distribution of lamellae (0.3–0.9 nm) than the polymer produced using bisindenylzirconium dichloride catalyst (0.5–3.6 nm). The results obtained indicate that the bis(2‐PhInd)ZrCl₂ catalyst showed a good comonomer incorporation ability. The heterogeneity of the chemical composition distribution and the physical properties were influenced by the type of comonomer and type of substituent in the catalyst. Copyright © 2010 Society of Chemical Industry     

Surface modification of linear low‐density polyethylene film by amphiphilic graft copolymers based on poly(higher α‐olefin)‐graft‐poly(ethylene glycol)

In this article, a series of amphiphilic graft copolymers, namely poly(higher α‐olefin‐co‐para‐methylstyrene)‐graft‐poly(ethylene glycol), and poly(higher α‐olefin‐co‐acrylic acid)‐graft‐poly(ethylene glycol) was used as modifying agent to increase the wettability of the surface of linear low‐density polyethylene (LLDPE) film. The wettability of the surface of LLDPE film could be increased effectively by spin coating of the amphiphilic graft copolymers onto the surface of LLDPE film. The higher the content of poly(ethylene glycol) (PEG) segments, the lower the water contact angle was. The water contact angle of modified LLDPE films was reduced as low as 25°. However, the adhesion between the amphiphilic graft copolymer and LLDPE film was poor. To solve this problem, the modified LLDPE films coated by the amphiphilic graft copolymers were annealed at 110° for 12 h. During the period of annealing, heating made polymer chain move and rearrange quickly. When the film was cooled down, the alkyl group of higher α‐olefin units and LLDPE began to entangle and crystallize. Driven by crystallization, the PEG segments rearranged and enriched in the interface between the amphiphilic graft copolymer and air. By this surface modification method, the amphiphilic graft copolymer was fixed on the surface of LLDPE film. And the water contact angle was further reduced as low as 14.8°. The experimental results of this article demonstrate the potential pathway to provide an effective and durable anti‐fog LLDPE film. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of hybrid materials obtained by in situ copolymerization of ethylene and propylene in the presence of Al2O3 nanofibers (NafenTM) on catalytic system rac‐Et(2‐MeInd)2ZrMe2/isobutylalumoxane

Nanofibers of Al₂O₃ (commercial product Nafen^TM) with characteristic length of ～100 nm and diameter of ～10 nm were used to create new hybrid materials based on copolymer of ethylene and propylene. Nanocomposites were obtained by in situ catalytic copolymerization on the system rac‐Et(2‐MeInd)₂ZrMe₂/isobutylalumoxane. Formation of the nanocomposites with uniform distribution of Nafen nanoparticles in polymer matrix was confirmed by scanning and transmission electron microscopy. According to dynamic mechanical analysis data, introduction of the nanofiller in an amount of up to 3 wt % leads to an increase in glass transition temperature by 10 °C (E″) and by 21 °C (tan δ). The nanocomposites exhibit improved physico‐mechanical properties (tensile strength and elongation at break). It is shown that the nanofiller significantly improves resistance of the nanocomposite to the thermo‐oxidative and thermal degradation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44678.     

Characterization and evaluation of supported rac‐dimethylsilylenebis(indenyl)zirconium dichloride on ethylene polymerization

rac‐Dimethylsilylenebis(indenyl)zirconium dichloride was grafted onto commercial methyl aluminoxane modified silica (SMAO) at different loadings (0.1–1.5 wt % Zr/SMAO). Supported catalysts were evaluated in ethylene polymerization with isoprenylaluminum as a cocatalyst. The characterization of two supported catalysts bearing 0.3 and 0.8 wt % Zr/SiO₂ by extended X‐ray absorption fine structure indicated that the number and the intensity of the peaks beyond the coordination shell, associated with the next nearest neighbors, depended on the Zr concentration. For the catalyst with a higher Zr content, only one peak (2.8 Å) was observed. The catalyst with 0.3 wt % Zr/SMAO presented two small peaks at 2.8 and 3.8 Å. Polymers produced with the supported catalysts presented lower crystallinity and higher molar mass and polydispersity values in comparison to that produced by the homogeneous one. Gel permeation chromatogram deconvolution suggested the presence of four catalyst sites for the supported systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ethylene/1‐hexene copolymerization with supported Ziegler–Natta catalysts prepared by immobilizing TiCl3(OAr) onto MgCl2

Five titanium complexes TiCl₃(OAr) (Ar = C₆H₅? , 2,6‐Me₂C₆H₃? , 2,6‐i‐Pr₂C₆H₃? , 2,6‐t‐Bu₂C₆H₃? , 4‐Me‐2,6‐t‐Bu₂C₆H₃? ) were immobilized, respectively, on MgCl₂ in semibatch reaction to form supported catalysts for olefin polymerization. Comparing with the catalysts prepared by immobilizing TiCl₃(OAr) onto MgCl₂ in batch reaction, the catalysts prepared by semibatch reaction have lower titanium content and higher ArO/Ti ratio. The aryloxy‐containing catalysts studied in this work showed higher ethylene/1‐hexene copolymerization activity and higher 1‐hexene incorporation rate than the blank catalyst when activated by triisobutylaluminum. Similar effects of the aryloxy ligand were observed when the copolymerization is conducted in the presence of hydrogen. Introducing aryloxy ligand in the catalysts either by semibatch or batch reaction caused similar effects of enhancing copolymerization activity and α‐olefin incorporation rate. Mechanism of the effects of aryloxy ligand has been discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41329.     

Comonomer effects in copolymerization of ethylene and 1‐hexene with MgCl2‐supported Ziegler‐Natta catalysts: New evidences from active center concentration and molecular weight distribution

In this article, comonomer effects in copolymerization of ethylene and 1‐hexene with four MgCl₂‐supported Ziegler‐Natta catalysts using either ethylene or 1‐hexene as the main monomer were investigated. It was found that no matter which monomer was used as the main monomer, the polymerization activity was significantly enhanced by introducing small amount of comonomer. In copolymerization with ethylene as the main monomer, the strength of comonomer effects was much stronger in active centers producing low‐molecular‐weight polymer than those producing high‐molecular‐weight polymer. In copolymerization with 1‐hexene as the main monomer, the number of active centers ([C*]/[Ti]) was determined, and the propagation rate constants (k_p) were calculated. Deconvolution of the polymer molecular weight distribution into Flory components were made to study the active center distribution. Introduction of small amount of ethylene caused marked increase in the number of active centers and decrease in average chain propagation rate constant. Introducing internal electron donor in the catalyst enhanced not only the number of active centers but also the chain propagation rate constant. In copolymerization of 1‐hexene with small amount of ethylene, the internal donor weakened the comonomer effects to some extent and changed the distribution of comonomer effects among different types of active centers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41264.     

Kinetics of short‐duration ethylene–propylene copolymerization with MgCl2‐supported Ziegler–Natta catalyst: Differentiation of active centers on the external and internal surfaces of the catalyst particles

Ethylene–propylene copolymerization with a TiCl₄/MgCl₂ type ZN catalyst was conducted for different durations from 30 to 600 s, and changes of polymerization rate, concentration of active centers ([C^*]) and copolymer chain structure with time were traced. The copolymerization rate decayed with time, but [C^*]/[Ti] increased in the same period. This was attributed to release of more active sites through disintegration of catalyst particles by the growing polymer phase. Ethylene content of the copolymer quickly decreased in the period of 30–90 s, meaning that the active centers activated in the reaction process have stronger ability of incorporating propylene than those activated at the very beginning. The copolymer samples were fractionated into two parts, namely n‐heptane soluble fraction (random copolymer) and insoluble fraction (segmented copolymer with high ethylene content). With continuation of the copolymerization, active centers producing the random copolymer chains increased much faster than active centers producing the segmented copolymer chains, and became the dominant centers after 120 s. Consequently, proportion of the soluble fraction sharply increased with time. All these results indicate that the active centers located on the external surface of catalyst particles are highly different from those buried inside the particles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46030.     

Blending ultrahigh‐molecular‐weight polyethylene and poly(ethylene/10‐undecen‐1‐ol) in one nascent particle

Ultrahigh‐molecular‐weight polyethylene (UHMWPE)/polar polyethylene (PE) composites were blended in one nascent particle by in situ polymerization with a hybrid catalyst. Polystyrene‐coated SiO₂ particles were used to support the hybrid catalyst. Fe(acac)₃/2,6‐bis[1‐(2‐isopropylanilinoethyl)] was supported on SiO₂ for the synthesis of UHMWPE, whereas [PhN?C(CH₃)CH?C(Ph)O]VCl₂ was immobilized on a polystyrene layer to prepare a copolymer of ethylene and 10‐undecen‐1‐ol (polar PE). Importantly, the core part of the supports (the polystyrene layer) exhibited pronounced transfer resistance to 10‐undecen‐1‐ol; this provided an opportunity to keep the inside iron active sites away from the poisoning of 10‐undecen‐1‐ol. Therefore, UHMWPE was simultaneously synthesized with polar PE by in situ polymerization. Interestingly, the morphological results show that UHMWPE and the polar PE were successfully blended in one nascent polymer. This improved the miscibility of the composites, where most of the chains were difficult to crystallize because of the strong interactions between the PE chains and polar chains. The blends showed an extremely low crystallinity, that is, 9.9%. Finally, the hydrophilic properties of the polymer composites were examined. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46652.     

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     

Ethylene/α‐olefin copolymerization using diphenylcyclopentadienyl‐phenoxytitanium dichloride/Al(iBu)3/[Ph3C][B(C6F5)4] catalyst systems

Copolymerization of ethylene with 1‐octene and 1‐octadecene using constrained geometry catalysts 2‐(3,4‐diphenylcyclopentadienyl)‐4,6‐di‐tert‐butylphenoxytitanium dichloride (1), 2‐(3,4‐diphenylcyclopentadienyl)‐6‐tert‐butylphenoxytitanium dichloride (2), 2‐(3,4‐diphenylcyclopentadienyl)‐6‐methylphenoxytitanium dichloride (3), and 2‐(3,4‐diphenylcyclopentadienyl)‐6‐phenylphenoxytitanium dichloride (4) was studied in the presence of Al(ⁱBu)₃ and [Ph₃C][B(C₆F₅)₄](TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was also examined. The 1 /TIBA/B catalyst system exhibits high catalytic activity and produces high molecular weight copolymers. The melting temperature and the degree of crystallinity of the copolymers show a decrease with the increase in the comonomer incorporation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics of short‐duration ethylene polymerization with MgCl2‐supported Ziegler–Natta catalyst: Two‐stage initiation evidenced by changes in active center concentration

The kinetics of ethylene polymerization with a TiCl₄/MgCl₂‐type Ziegler–Natta catalyst was studied. Changes in polymerization activity and concentration of active centers ([C*]) in the first 5 min were determined. Initiation of the active centers was found to proceed in two stages. In the first stage, [C*]/[Ti] quickly rose to about 1% in less than 30 s and then remained stable in the subsequent 60 s. Then the [C*]/[Ti] value started to increase again, forming the second buildup stage. The polymerization activity was found to change roughly in parallel with the change in [C*]/[Ti]. Changes in the polymer/catalyst particle morphology and polymer molecular weight distribution with polymerization time were studied. A mechanistic model was proposed to explain the two‐stage kinetics: initiation of active sites on the outer surface of catalyst particles takes place in the first stage, and initiation of active sites buried inside the particles takes place in the second stage. These buried sites are released when the catalyst particles are fragmented by the expanding polymer phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45187.     

Synthesis and application of sodium 2‐acrylamido‐2‐methylpropane sulphonate/N‐vinylcaprolactam/divinyl benzene as a high‐performance viscosifier in water‐based drilling fluid

Aiming at good thickening ability and temperature resistance in water‐based drilling fluid, a novel copolymer viscosifier (SDKP) of sodium 2‐acrylamido‐2‐methylpropane sulfonate (NaAMPS) with N‐vinylcaprolactam (NVCL) and cross‐linking divinylbenzene (DVB) was prepared by micellar radical polymerization. The composition and molecular structure of optimal SDKP under the optimum reaction conditions was characterized by FT‐IR, ¹H‐NMR, and elemental analysis, and the molecular weight was determined by GPC. Thermal gravimetric analysis showed that the SDKP was even stable when the temperature was not higher than 330 °C. The performance of SDKP as viscosifier for aqueous, brines, and saturated brine bentonite drilling fluid was evaluated before and after aging tests at 230 °C for 16 h. The evaluation results indicated that the SDKP had excellent thickening ability, thermal resistant, and salt tolerance. HTHP rheology test showed that the SDKP containing drilling fluids displayed a thermo‐thickening effect in temperature range of 150 to 180 °C, which was beneficial to increase the viscosity and strength of fluids at high temperatures. Shear test showed that the SDKP illustrated a similar shear thinning to xanthan gum. ESEM observations demonstrated that the continuous three‐dimensional network was formed in the SDKP aqueous and brines solution, which was probably the main reason for its excellent thickening properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44140.     

Preparation of organo‐soluble co‐polyimides using N‐methyl‐2‐pyrrolidone as the solvent via one‐pot high‐temperature polymerization

A series of organo‐soluble co‐polyimides (co‐PIs) were successfully synthesized from 3,3′,4,4′‐benzophenonetetracarboxylic‐dianhydride (BTDA), 1,4‐bis‐(4‐amino‐2‐trifluoromethyl‐phemoxy)‐benzene (p‐6FAPB) and 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (BIA) via the one‐pot high‐temperature polymerization using N‐methyl‐2‐pyrrolidone (NMP) as the solvent. The imidization reaction of poly(amic acid)s in solution state was discussed in detail by attenuated total reflectance‐Fourier transform infrared spectra (ATR‐FTIR), and the results illustrate that the introduced benzimidazole moiety has a catalytic activity on the imidization process. The number‐average molecular weights and polydispersity index of these PIs measured by gel permeation chromatography range from 1.11 × 10⁵ to 2.20 × 10⁵ and 1.82 to 3.84, respectively. The prepared co‐PIs exhibit sufficient solubility in some polar solvents and high optical transparency. Meanwhile, these co‐PI films show good mechanical performances, and the strength and modulus of the sample with the molar ratio of p‐6FAPB/BIA = 5/5 reach 183 MPa and 4.71 GPa, respectively. Moreover, the obtained co‐PIs possess high glass transition temperatures (T_g) (above 260 °C) and good thermal stability with 5% weight loss temperature in the range of 502–531 °C in the nitrogen atmosphere. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45497.     

Immobilization of Trametes versicolor laccase on different PGMA‐based polymeric microspheres using response surface methodology: Optimization of conditions

Enzymatic immobilization is a versatile alternative to improve enzyme stability and enable its reuse. In this study, the change in the immobilized enzyme properties due to the type of functional group on the carrier was evaluated. For that, monodisperse polymeric microspheres with two functional groups widely used in laccase immobilization—oxirane [poly(glycidyl methacrylate) (PGMA)] and hydrazide—were synthesized by dispersion polymerization to covalently immobilize the laccase Trametes versicolor. Using a response surface methodology, laccase immobilization was optimized for each microsphere type. As a result, laccase immobilization on PGMA carriers appears to broaden the pH and temperature ranges, storage stability, and reusability compared to free and hydrazide enzymes. These aforementioned characteristics indicate that PGMA microspheres could act as an ideal support for enzyme immobilization in biotechnological applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45249.     

Phototransparency and water vapor sorption properties of ABA‐type triblock copolymers derived from 6FDA‐TeMPD and poly(2‐methyl‐2‐adamantylmethacrylate)

The phototransparency and water vapor sorption properties of ABA‐type triblock copolymer membranes derived from 4,4‐(hexafluoroisopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (PI) and poly(2‐methyl‐2‐adamantylmethacrylate) (PMAdMA) were investigated, with focus on the effect of the adamantane component. The phototransparency of PMAdMA‐block‐PI‐block‐PMAdMA [Block(PI/PMAdMA)] was about 10–20% higher than that of poly(methyl methacrylate)‐block‐PI‐block‐Poly(methylmethacrylate) [Block(PI/PMMA)] because the high symmetric structure of adamantane inhibited photoabsorbance. The water vapor solubility of Block(PI/PMAdMA) decreased with increased PMAdMA because the PMAdMA had a hydrophobic property. Interestingly, in all relative‐pressure regions, Block(PI/PMAdMA) with the least PMAdMA content showed a higher solubility coefficient than PI because the high mobility of PMAdMA in Block(PI/PMAdMA) resulted in additional sorption sites in the PI segment. A comparison of Block(PI/PMAdMA) with Block(PI/PMMA) in terms of relative pressure at the beginning of clustering further revealed that cluster formation in Block(PI/PMAdMA) was inhibited compared with Block(PI/PMMA) because bulky structure of adamantane restricted the mobility of the polymer main chain. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43795.     

A novel approach for synthesis of poly(norbornene)‐co‐poly(styrene) block copolymers via metathesis polymerization and free‐radical polymerization

It is successfully realized that block copolymers are synthesized via metathesis polymerization followed by free‐radical polymerization. This method is performed using styrene (St) and norbornene, one block is synthesized using the Grubbs second generation catalyst in the presence of chain transfer agents, and the subsequent polymerization of St is initiated by azo compounds to complete the additional blocks in the copolymers. The use of free‐radical polymerization instead of controlled radical polymerization or ionic polymerization can be potentially superior for industrialization. As a result, the molecular weights of the block copolymers ranging from 10.4 to 54.3 kDa and polydispersity indices ranging from 1.30 to 1.91 are obtained. In principle, this new method can be potentially useful to prepare a broad range of block copolymers with cyclic olefin groups in the main chains, which may be used in some particular applications.     

Copolymerization and characterization of ethene–1‐hexene copolymers prepared by using the (Me5Cp)2ZrCl2–MAO catalyst system

It is demonstrated that the catalyst system bis(pentamethylcyclopentadienyl)‐zirconium dichloride (Me₅Cp)₂ZrCl₂–methylaluminoxane (MAO) is able to produce random copolymers of ethene and 1‐hexene. The 1‐hexene incorporation in the copolymers is extremely small. Even in the case of a molar ratio of [ethene] to [1‐hexene] of 1/20 in the monomer feed, only 1.4 mol % 1‐hexene are incorporated according to ¹³C nuclear magnetic resonance (NMR) spectra. Nevertheless, the physical properties of the random copolymers change significantly in this small range of 1‐hexene incorporation, from a high‐density polyethene to a linear low‐density polyethene. Thus, the melting temperature, the degree of crystallinity, the density and lamella thickness, and the long period of the alternating crystalline and amorphous regions decrease with increasing 1‐hexene content in the random copolymers. Blends of high‐density polyethene prepared with the system (Me₅Cp)₂ZrCl₂–MAO and an elastomeric random copolymer of ethene and 1‐hexene are phase‐separated and show good compatibility, as demonstrated by transmission electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 439–447, 1999     

Simultaneous measurement of the molecular weight distribution and 5‐ethylidene‐2‐norbornene content across the molecular weight distribution of ethylene–propylene–diene terpolymer via a new size exclusion chromatography–ultraviolet–refractive index method

A size exclusion chromatography (SEC)–UV–refractive index (RI) method was developed to measure the 5‐ethylidene‐2‐norbornene (ENB) content across the molecular weight distribution (MWD) in ethylene–propylene–diene terpolymer (EPDM) at room temperature. The ratio of the UV and RI signals at the same effective elution volume was converted to ENB content. The feasibility of using this method to measure the ENB content across the MWD in EPDM at high temperature was also demonstrated. Prior understanding was that ENB had insufficient UV absorbance relative to high‐temperature SEC solvents to allow for useful measurements. We demonstrated this by using high‐boiling‐point solvents, such as decalin, with a low UV absorbance in the UV wavelength range of interest for ENB. These solvents also gave rise to a high enough specific RI increment (dn/dc) for EPDM that a suitable RI detector response was obtained. Additionally, this methodology could be readily applied to other polymers soluble at high temperature as long as the polymers contained a UV chromophore. These include polymers containing vinyl, conjugated vinyl, aromatic ring, carbonyl, or halocarbon groups. This UV‐absorption‐based detection concept might also be extended to high‐temperature thermal‐gradient interactive chromatography‐UV, high‐temperature solvent‐gradient interactive chromatography‐UV (high‐temperature liquid chromatography‐UV), temperature‐rising elution fractionation‐UV, crystallization analysis fractionation‐UV, and crystallization elution fractionation‐UV. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43911.     

5,6‐bis(tetradecyloxy)‐2,1,3‐benzoselenadiazole‐based polymers for photovoltaic applications

A series of new 5,6‐bis(tetradecyloxy)‐2,1,3‐benzoselenadiazole‐based copolymers ( PBDT‐DTBSe, PC‐DTBSe , and PF‐DTBSe) have been first synthesized by Stille or Suzuki coupling polymerization reaction. The synthesized copolymers show good solubility in common organic solvents, such as chloroform, tetrahydrofuran, and chlorobenzene with excellent film‐forming properties. The molecular weight was determined by gel permeation chromatography and the thermal properties were investigated by thermogravimetric analysis. All the copolymers exhibited broad absorption from 350 to 700 nm. The preliminary results showed the device based on the structure of indium tin oxide/PEDOT : PSS/ PC‐DTBSe : PC₆₁BM (1 : 2, w/w)/Ca/Al displayed the best photovoltaic performance with a power conversion efficiency of 1.35%, a V_oc of 0.87 V, a J_sc of 3.84 mA/cm² and a fill factor of 40.4%, under illumination of AM 1.5 G (100 mW/cm²). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013