Ethylene Copolymerization with Linear and End-Cyclized Olefins via a Metallocene Catalyst:Polymerization Behavior and Thermal Properties of Copolymers

Olefin solution polymerization can be used to obtain high-performance polyolefin materials that cannot be obtained via other polymerization processes.Polyolefin elastomers(POE)are a typical example.Due to cost,only a few linear a-olefins(e.g.,1-butene,1-hexene,and 1-octene)are used as comonomers in solution polymerization in industry.However,a-olefin comonomers with other structures may have different effects on polymerization in comparison with common linear ones.Moreover,the properties of the corresponding materials may differ significantly.In this work,copolymers of ethylene with linear and endcyclized a-olefins are synthesized using a metallocene catalyst.The copolymerization of ethylene with linear a-olefins results in a higher turn-over frequency(TOF)and lower incorporation than copolymerization with end-cyclized a-olefins,which may indicate that end-cyclized a-olefins have a higher coordination probability and lower insertion rate.In this reaction,the comonomer is distributed randomly in the polymer chain and efficiently destroys crystallization.End-cyclized a-olefins exhibit a much stronger crystallization destructive capacity(CDC)in the copolymer than linear a-olefins,possibly because linear a-olefins act mainly in the radial direction of the main chain of the polymer,while end-cyclized a-olefins act mainly in the axial direction of the main chain.

Syntheses and properties of associative acrylamide copolymers containing short hydrophobic chains used in a friction reducer for slick-water fracturing

Two allyldimethylalkyl quaternary ammonium salt(AQAS)monomers,N,N-dimethylallylphenylpropylammonium bromide(AQAS1)and N,N-dimethylallylnonylammonium bromide(AQAS2),were synthesized and used to prepare modified polyacrylamide materials.Two new drag reducers were synthesized from acrylamide(AM),sodium acrylate(Na AA)and a cationic modified monomer(AQAS1 or AQAS2)via aqueous solution polymerization,and the copolymers were named P(AM/Na AA/AQAS1)and P(AM/Na AA/AQAS2),respectively.The structures of the drag reduction agents were confirmed by IR and1H NMR spectroscopies.The molecular weight(Mw)of P(AM/Na AA/AQAS1)was 1.79×10^(6)g/mol.When the copolymer concentration was 1000 mg/L and the flow rate was 45 L/min,in fresh water the highest drag reduction rate was 75.8%,in 10,000 mg/L Na Cl solution the drag reduction rate decreased to 72.9%.The molecular weight of P(AM/Na AA/AQAS2)was 3.17×10^(6)g/mol.When the copolymer concentration was500 mg/L and the flow rate was 45 L/min,the drag reduction rate reached 75.2%,and in 10,000 mg/L Na Cl solution the drag reduction rate was 73.3%,decreased by approximately 1.9%.The drag reduction rate for partially hydrolyzed polyacrylamide(HPAM)was also investigated,and the results showed that the drag reduction rates for 500 and 1000 mg/L HPAM solutions were merely 43.2%and 49.0%in brine,respectively.Compared with HPAM,both of the above copolymers presented better drag reduction capacities.

Efficient and Stable Inverted Perovskite Solar Modules Enabled by Solid-Liquid Two-Step Film Formation

A considerable efficiency gap exists between large-area perovskite solar modules and small-area perovskite solar cells.The control of forming uniform and large-area film and perovskite crystallization is still the main obstacle restricting the efficiency of PSMs.In this work,we adopted a solid-liquid two-step film formation technique,which involved the evaporation of a lead iodide film and blade coating of an organic ammonium halide solution to prepare perovskite films.This method possesses the advantages of integrating vapor deposition and solution methods,which could apply to substrates with different roughness and avoid using toxic solvents to achieve a more uniform,large-area perovskite film.Furthermore,modification of the NiO_(x)/perovskite buried interface and introduction of Urea additives were utilized to reduce interface recombination and regulate perovskite crystallization.As a result,a large-area perovskite film possessing larger grains,fewer pinholes,and reduced defects could be achieved.The inverted PSM with an active area of 61.56 cm^(2)(10×10 cm^(2)substrate)achieved a champion power conversion efficiency of 20.56%and significantly improved stability.This method suggests an innovative approach to resolving the uniformity issue associated with large-area film fabrication.

A new two-step variational model for multiplicative noise removal with applications to texture images

Multiplicative noise removal problems have attracted much attention in recent years.Unlike additive noise,multiplicative noise destroys almost all information of the original image,especially for texture images.Motivated by the TV-Stokes model,we propose a new two-step variational model to denoise the texture images corrupted by multiplicative noise with a good geometry explanation in this paper.In the first step,we convert the multiplicative denoising problem into an additive one by the logarithm transform and propagate the isophote directions in the tangential field smoothing.Once the isophote directions are constructed,an image is restored to fit the constructed directions in the second step.The existence and uniqueness of the solution to the variational problems are proved.In these two steps,we use the gradient descent method and construct finite difference schemes to solve the problems.Especially,the augmented Lagrangian method and the fast Fourier transform are adopted to accelerate the calculation.Experimental results show that the proposed model can remove the multiplicative noise efficiently and protect the texture well.

Exploring the effect of cooling rate on non-isothermal crystallization of copolymer polypropylene by fast scanning calorimetry

Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.

Two-step growth of β-Ga_(2)O_(3) on c-plane sapphire using MOCVD for solar-blind photodetector

In this work,a two-step metal organic chemical vapor deposition(MOCVD)method was applied for growingβ-Ga_(2)O_(3) film on c-plane sapphire.Optimized buffer layer growth temperature(T_(B))was found at 700℃ and theβ-Ga_(2)O_(3) film with full width at half maximum(FWHM)of 0.66°was achieved.A metal−semiconductor−metal(MSM)solar-blind photodetector(PD)was fabricated based on theβ-Ga_(2)O_(3) film.Ultrahigh responsivity of 1422 A/W@254 nm and photo-to-dark current ratio(PDCR)of 10^(6) at 10 V bias were obtained.The detectivity of 2.5×10^(15) Jones proved that the photodetector has outstanding performance in detecting weak signals.Moreover,the photodetector exhibited superior wavelength selectivity with rejection ratio(R_(250 nm)/R_(400 nm))of 105.These results indicate that the two-step method is a promising approach for preparation of high-qualityβ-Ga_(2)O_(3)films for high-performance solar-blind photodetectors.

Effect of two-step solid solution on microstructure andδphase precipitation of Inconel 718 alloy

Inconel 718 is the most popular nickel-based superalloy and is extensively used in aerospace,automotive,and energy indus-tries owing to its extraordinary thermomechanical properties.The effects of different two-step solid solution treatments on microstructure andδphase precipitation of Inconel 718 alloy were studied,and the transformation mechanism fromγ″metastable phase toδphase was clarified.The precipitates were statistically analyzed by X-ray diffractometry.The results show that theδphase content firstly increased,and then decreased with the temperature of the second-step solid solution.The changes in microstructure andδphase were studied by scanning electron microscopy and transmission electron microscopy.An intragranularδphase formed in Inconel 718 alloy at the second-[100]_(δ)[011]γ step solid solution temperature of 925℃,and its orientation relationship withγmatrix was determined as//and(010)_(δ)//(111)γ.Furthermore,the Vickers hardness of different heat treatment samples was measured,and the sample treated by second-step solid solution at 1010℃ reached the maximum hardness of HV 446.84.

Advancements in Polymer Science: Synthesis, Characterization, and Biomedical Applications of Homopolymers and Copolymers

Polymer science encompasses a different range of materials critical to industries spanning from packaging to biomedicine. Understanding the synthesis, characterization, and applications of common homopolymers and copolymers is fundamental to advancing polymer research and development. In this comprehensive review, we explore various preparation methods, including free radical, anionic, and cationic polymerization, utilized for synthesizing homopolymers and copolymers. Furthermore, we investigate solvent choices commonly employed for polymer characterization, ranging from neat conditions, polar protic and polar aprotic solvents. We also explored characterization techniques, including Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (NMR), Atomic Force Microscopy (AFM), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA). In addition to industrial applications, we highlight the diverse biological applications of homopolymers, poly(2-hydroxyethyl methacrylate) (pHEMA) and polystyrene, which find its extensive use in biomedicine. By synthesizing and analyzing this wealth of information, this review aims to provide a comprehensive understanding of the synthesis, characterization, and applications of homopolymers and copolymers, with a particular focus on their biological applications. This holistic approach not only contributes to advancements in polymer science and technology but also fosters innovation in biomedicine, ultimately benefiting human health and well-being.

Preparation and properties of RE^(3+) doped luminescent co-polymer by solution copolymerization

Bonded type RE3+ doped luminescent co-polymer was synthesized by solution free radical copolymerization. The influence of charge sequence, monomers and co-polymerized method on properties and structures of the co-polymers was studied. The emission intensity of the co-polymers at different RE3+ concentrations was tested. The results showed that the co-polymers of Eu-PSt and Eu-PMMA both had wide absorption peak at 200-400 nm and the strongest peak appeared at 235 nm. The fluorescent intensity of Eu3+ doped polystyrene co-polymer was stronger than that of Eu3+ doped PMMA copolymer. The characteristic emission of europium ions was observed in the co-polymers. The copolymer doped with rare earth elements showed the 'sensitization effect' for the central ions. The bonded-type rare earth copolymer not only enhanced the energy transfer efficiency, but also improved the fluorescence intensity by increasing the rigidity of main and side chain.

Monomer reactivity ratios for fluoroacrylate and butyl methacrylate in miniemulsion copolymerizations initiated by potassium persulphate

Miniemulsion copolymerization of butyl mathacrylate （BMA） with fluoroacrylate （HFMA, TFMA） was carried out at 70 ℃ by employing potassium persulphate （KPS） as initiator. Copolymer compositions at low conversion levels were determined by ^1H NMR spectra techniques. The reactivity ratios were evaluated by employing Kellen-Tudos （K-T） methods, which yields the apparent reactivity ratios, rBMA = 0.74, rHFMA = 0.87 and rBMA = 0.73, rTFMA = 0.75, respectively, and Q- and e-values of HFMA and TFMA were calculated by the Alfrey-Price method. The results show that HFMA and TFMA are more active than BMA, and the cross-propagation rate constant is greater than the self-propagation one in these two copolymerizations.

GRAFT COPOLYMERIZATION OF VINYL MONOMERS ONTO STARCH INITIATED BY TRANSITION METAL-THIOUREA REDOX SYSTEMS

In this paper, the capabilities of grafting acrylonitrile (AN) onto starch initiated by Fe(III)-TU, V(V)-TU, Cr(VI)-TU, Mn(VII)-TU redox systems were compared in the presence of sulfuric acid of different concentrations. It was shown that the grafting capability of Mn(VII)-TU is the highest in these initiating systems. Using Mn (VII-TU as initiator, the effects of various acids (HClO4, H2SO4, HNO3, HCl) on the graft copolymerization of acrylonitrile onto starch were discussed, and the capabilities of graft copolymerization of methyl methacrylate (MMA), acrylamide (AM), acrylic acid (AA) onto starch were investigated. The experimental results show that the order of the influences of different acids is HClO4 > H2SO4 > HNO3 > HCl, and the order of grafting capabilities of different monomers grafted onto starch is MMA > AN > AM > AA. The structure and morphology of graft, copolymers were studied with infrared spectroscopy and scanning electron microscopy. The size, shape and roughness of surface of the grafted starch granules are changed after grafting.

INFLUENCE OF DIALKYLZINC IN RARE-EARTH TERNARY CATALYST ONTHE COPOLYMERIZATION OF CARBON DIOXIDE AND PROPYLENE OXIDE

Rare-earth ternary catalysts Y（CCl3COO）3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide （PO）, where dialkylzincs （ZnR2） were diethylzinc, di（n-propyl）zinc, di（n-butyl）zinc, di（i-propyl）zinc, di（i-butyl）zinc, di（s-butyl）zinc,respectively. The Y（CCl3COO）3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y（CCl3COO）3：ZnR2：glycerin = 1：20：10. In the same copolymerization condition, catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence： Y（CCl3COO）3-ZnEt2-glycerin 〉 Y（CCl3COO）3-Zn（n- Pr）2-glycerin〉Y（CCl3COO）3-Zn（n-Bu）2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.

CATALYTIC COPOLYMERIZATION OF STYRENE AND ETHYLENE BY NEUTRAL NICKEL(Ⅱ) COMPLEXES IN EMULSION

Emulsion copolymerization of styrene and ethylene catalyzed by a series of neutral nickel(Ⅱ) complexes was carried out in an aqueous system to give high-molecular-weight copolymers.The copolymers and emulsions were characterized by an array of techniques including NMR,GPC,TEM,WAXD and DSC.The results indicate that the copolymers obtained are mostly block copolymers of polyethylene with random insertion of styrene units,and their M_W is in the range of 10~5-10~6.By enhancing the electron withdrawing of the s...

Copolymerization of Styrene with N-phenylmaleimide by Rare Earth Coordination Catalysts

Copolymerization of styrene (St) with N-phenylmaleimide (NPMI) was studied with rare earth coordination catalyst Nd(naph)3-AlEt3 in toluene. Characterization of the copolymers showed that the copolymers possess an alternating structure.

Thermosensitive Particles with Unusual Morphology Prepared by Dispersion Copolymerization

The monodispersed polymeric particles with an unusual structure were prepared by the dispersion copolymerization of acrylonitrile/styrene（AN/St） in mixed solvents of ethanol/water by using the poly（N-isopropylacrylamide） （PNIPAAm） macromonomer as a reaction stabilizer. It was found that the AN monomer plays a key role in the formation of the particles with special morphology analyzed via scanning electron microscopy （SEM）. The reaction parameters have remarkable influences on the particle size and morphology. The particles possess a thermosensitive property according to the result of laser light scattering（LLS）.

i-PP/EPR REACTOR ALLOY PREPARED THROUGH ETHYLENE/PROPYLENE SLURRY COPOLYMERIZATION CATALYZED BY METALLOCENE SUPPORTED iPP PARTICLES

i-PP/m-EPR reactor alloy were prepared through ethylene/propylene slurry copolymerization catalyzed by metallocene(rac-Et(Ind)_2ZrCl_2)supported on porous iPP particles.Polar monomer(dihydromyrcene alcohol)treated with triethyaluminum was added in the preparation of porous iPP particles to introduce hydroxyl groups and thus enhance the ability for chemically supporting the metallocene catalyst.The effects of MAO/Zr ratio and monomer composition in feed on the reaction activity and property of polymer were i...

MODIFICATION OF SILK FIBER via EMULSION GRAFT COPOLYMERIZATION WITH FLUOROACRYLATE

2,2,3,3,4,4,5,5-Octafluoropentyl acrylate was grafted onto silk fiber in a two-step heterogeneous system through the vinyl bonds of acryloyloxyethyl isocyanate modified on the silk.The grafted copolylner was analyzed by FTIR and WAXD,and the results revealed that the fluoroacrylate was successfully grafted onto silk fiber and the crystalline structure of silk fibroin withβ-sheet structure was not changed after graft copolymerization.The FT-IR corrected method was used to simulate the grafting yield onto sil...

IN SITU MONITORING OF COORDINATION COPOLYMERIZATION OF BUTADIENE AND ISOPRENE VIA ATR-FTIR SPECTROSCOPY

FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance （ATR） immersion probe was utilized to study in situ the copolymerization of butadiene （Bd） and isoprene （Ip） with neodymium-based catalyst in hexane. The relationship between the signal intensity of monomer and its concentration was investigated. The kinetic study of copolymerization of Bd and Ip was further conducted, and the monomer reactivity ratios were determined via in situ ATR FTIR. The signal band at 1010 cm^-1 was assigned to wagging vibration of Bd and its intensity was proportional to Bd concentration （[Bd]） in the range of 0.46-3.88 mol.L^-1. The signal bands at 890 and 989 cm^-1 were assigned to wagging vibration of Ip and the signal intensity was also proportional to Ip concentration （[Ip]） in the range of 0.08-4.73 mol·L^-1 at 890 cm^-1 and 0.08-7.49 mol·L^-1 at 989 cm^-1, respectively. Thus the signal band at 1010 cm^-1 was chosen to monitor Bd concentration and bands at 989 and 890 cm^-1 to monitor Ip concentration during the copolymerization, respectively. It was demonstrated that the conversions of Bd and Ip calculated from FTIR data agreed very well with those obtained gravimetrically. The poiymerization rates were first order with respect to both [Bd] and [Ip], respectively at different polymerization temperatures. The apparent propagation activation energy for Bd and Ip could be determined to be 54.4 kJ·mol^-1 and 57.7 kJ·mol^-1, respectively. The monomer reactivity ratios were calculated to be 1.08 for Bd （rBd） and 0.48 for IP （rIp） based on FTIR data. The Bd-Ip copolymer products with random sequence could be obtained with only one glass transition temperature.

Research on the Graft Copolymerization of EH-lignin with acrylamide

Lignin isolated from enzymatic hydrolyzed corn-stalks (EH-lignin) is a renewable natural polymer noted for its versatility and applicability in a vari-ety of uses. Graft copolymerization of EH-lignin with acrylamide (AM) and the application of this copolymer as a flocculant in dye wastewater treatment were studied in this article. The influ-ences of some factors on yield of copolymer and the grafting ratio were investigated and the structure of EH-lignin/AM graft copolymer was characterized by FT-IR. According to the yield and the grafting ratio, the optimum conditions for graft copolymerization were as follows: initiator K2S2O8-Na2S2O3 with a quantity 3 wt% of EH-lignin, mass ratio of AM to EH-lignin was 2~3, reaction time 4h and temperature at 50℃. It was found that the absorption capacity of graft copolymer to two azo-dyes was enhanced with the increase of grafting ratio. Furthermore, the residue concen-tration of EH-lignin/AM graft copolymer remained in the supernatant after flocculation was much lower than that of pure EH-lignin.

Research on poly(styrene-acrylic acid)-supported neodymium complex in catalytic copolymerization of styrene and 4-vinylpyridine

The catalytic activity of poly（styrene-acrylic acid） （PSAA） supported neodymium chloride （NdCl3） complex for the copolymerization of styrene and 4-Vinylpyridine was studied. The influence of various factors, such as Al/Nd molar ratio, reaction time, macromolecular carder （PSAA）, and ratio of styrene to 4-vinypyridine （g/g）, on the copolymerization yield of styrene and 4-Vinylpyridine was investigated. The results showed that the copolymerization of polar monomers with olefins occurred efficiently and the catalytic activity of polymer-supported catalyst was higher than that of the similar small molecular catalysts. The activity of PSAA.Nd complex increased with in- creasing Al/Nd molar ratios and decreased with increasing polymerization time. The highest activity of PSAA＇Nd was observed at 120 min, and the highest yield was found at the ratio of styrene to 4-vinylpyridine of 4：2. DSC analysis presented that the resulted polymer had only one glass transition temperature, and showed very good thermal stability.