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1.
Soluble poly(4-alkylstyrene) containing 4-methyl-, 4-tert-butyl, 4-dodecyl-, and 4-octadecylstyrene were formed either with monomers containing dyes-, ligands, or catalysts or with 5–10 mol% of 4-chloromethylstyrene and studied as supports for ligands or catalysts. Studies with dye-labeled polymers showed that polymers containing longer alkyl groups alone or at ca. 10 mol% loading are highly soluble in heptane can be used to separate and recycle organo- and transition metal catalysts.  相似文献   

2.
A series of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s containing 1,1‐diphenylethylene segments in the polymer main chain, used for optical waveguide materials, were synthesized by polycondensation reaction of decafluorobiphenyl with a mixture of 4‐(4‐hydroxylphenyl)(2H)‐phthalazin‐1‐one (DHPZ), 4,4‐(hexafluoroisopropylidene)diphenol and 1,1‐bis(4‐hydroxyphenyl)ethylene (BHPE) as co‐reactant. The feed ratio of DHPZ to total bisphenols varied from 0 to 80 mol%, while that of BHPE remained at 20 mol% for all polymers. The obtained copolymers show good solubility in some common polar organic solvents. The resulting polymers were photo‐crosslinked after UV irradiation for 10 min in the presence of a photoinitiator. The cured polymers show good chemical resistance, high thermal stability (temperatures of 1% mass loss after curing of 472–496 °C under nitrogen) and high glass transition temperatures (160–249 °C) which could be further increased by about 10 °C after photochemical crosslinking. By adjusting the copolymerizing bisphenol content, the refractive indices of transverse electric and transverse magnetic modes (at 1550 nm) of films of the polymers were exactly tuned in the range 1.5029–1.5661 and 1.4950–1.5502, respectively. The propagation losses of the cured films were measured and found to be less than 0.3 dB cm?1 at 1550 nm, indicating the promise of these materials for passive optical waveguide devices. Copyright © 2011 Society of Chemical Industry  相似文献   

3.
Phthaldialdehyde and phthaldiketone were treated with substituted phenols of 2‐amino‐4‐methylphenol, 2‐amino‐5‐methylphenol and 2‐amino‐4‐t‐butylphenol, respectively, and then treated with transition metal halides of TiCl4, ZrCl4 and YCl3. A series of novel non‐metallocene catalysts (1–12) with phenoxy‐imine ligands was obtained. The structures and properties of the catalysts were characterized by 1H NMR and elemental analysis. The catalysts (1–12) were used to promote ethylene (co‐)polymerization after activation by methylaluminoxane. The effects of the structures and center atoms (Ti, Zr and Y) of these catalysts, polymerization temperature, Al/M (M = Ti, Zr and Y) molar ratio, concentration of the catalysts and solvents on the polymerization performance were investigated. The results showed that the catalysts were favorable for ethylene homopolymerization and copolymerization of ethylene with 1‐hexene. Catalyst 10 is most favorable for catalyzing ethylene homopolymerization and copolymerization of ethylene with 1‐hexene, with catalytic activity up to 2.93 × 106 gPE (mol Y)?1 h?1 for polyethylene (PE) and 2.96 × 106 gPE (mol Y)?1 h?1 for copolymerization of ethylene with 1‐hexene under the following conditions: polymerization temperature 50 °C, Al/Y molar ratio 300, concentration of catalyst 1.0 × 10?4 L?1 and toluene as solvent. The structures and properties of the polymers obtained were characterized by Fourier transform infrared spectroscopy, 13C NMR, wide‐angle X‐ray diffraction, gel permeation chromatography and DSC. The results indicated that the obtained PE catalyzed by 4 had the highest melting point of 134.8 °C and the highest weight‐average molecular weight of 7.48 × 105 g mol?1. The copolymer catalyzed by 4 had the highest incorporation of 1‐hexene, up to 5.26 mol%, into the copolymer chain. © 2012 Society of Chemical Industry  相似文献   

4.
Three alkysulfonic resins were obtained by co-polymerization of 2-acrylamido-2-methyl-propansulfonic acid with N,N-dimethylacrylamide and ethylene dimethacrylate (the cross-linker), with respectively 4, 20 and 40 mol% cross-linking degree (DAE26-4, DAE26-20, DAE26-40). These resins were employed as acidic components in physical mixtures with Ru/C (5 %, w/w) or as supports for bifunctional ruthenium and copper catalysts, to be used in the hydrogenolysis of glycerol (20 %, w/w, in water). The physical mixtures were more efficient than the bifunctional catalysts, but temperatures as high as 200 °C are required to obtain an appreciable activity. However, in view of their relatively high thermal stability in comparison with the sulfonated polystyrene-divinylbenzene ion-exchange catalysts employed so far they can withstand this temperature, while Amberlyst 70 cannot be employed above 180–190 °C. Interestingly, the catalytic systems based on physical mixtures of DAE with Ru/C resins at 200 °C are much more selective towards propylene glycol than those containing A70 are at 180 °C.  相似文献   

5.
Novel manganese complexes containing N4‐tetradentate ligands derived from chiral bipyrrolidinediamines catalyze the stereoselective epoxidation of a wide array of alkenes using low catalyst loadings (0.1 mol%) and hydrogen peroxide (1.2 equiv.) as terminal oxidant. This family of catalysts affords good to excellent yields (80–100%) and moderate to good ees (40–73%) in short reaction times (30 min) making efficient use of hydrogen peroxide.  相似文献   

6.
Hydrogen bonding among nucleobase pairs serves as an efficient noncovalent interaction for designing supramolecular polymers with desired properties for pressure sensitive adhesives. Michael addition yielded acetyl-protected cytosine/guanine containing acrylic monomers with flexible spacers between the hydrogen bonding units and the acrylic backbone. Free radical polymerization of nucleobase-containing monomers afforded acetyl-protected cytosine/guanine homopolymers and random copolymers with n-butyl acrylate. Nucleobase incorporation significantly affected thermal, thermomechanical, rheological, morphological properties, and adhesive performance of polyacrylates. Guanine/cytosine-containing copolymers each exhibited a single glass transition (Tg) that increased with increasing nucleobase content. Self-association of acetyl cytosine and acetyl guanine units converted low Tg polyacrylates to physically crosslinked networks with mechanical integrity. Solution casting acetyl guanine-containing copolymers with 8 mol% or higher guanine content yielded free-standing films with microphase-separated morphologies. Acetyl cytosine-containing copolymers with 15 mol% or more cytosine formed free-standing films with less microphase-separation compared to the guanine copolymers. 1H NMR titration experiments established a 1:1 binding stoichiometry between acetyl cytosine and acetyl guanine monomers in CDCl3, similar to guanine-cytosine association. However, the acetyl protecting group hindered the formation of triple hydrogen bonding, resulting in double hydrogen bonding between acetyl cytosine and acetyl guanine with an intermediate binding strength comparable to their self-associations. Acetyl guanine-containing copolymers with 3 mol% acetyl guanine exhibited higher peel strength on stainless steel and higher extended service frequency range compared to cytosine-containing copolymers and various pressure sensitive adhesive controls.  相似文献   

7.
This paper reviews a new family of olefin polymerization catalysts. The catalysts, named FI catalysts, are based on non‐symmetrical phenoxyimine chelate ligands combined with group 4 transition metals and were developed using “ligand‐oriented catalyst design”. FI catalysts display very high ethylene polymerization activities under mild conditions. The highest activity exhibited by a zirconium FI catalyst reached an astonishing catalyst turnover frequency (TOF) of 64,900 s –1 atm –1, which is two orders of magnitude greater than that seen with Cp2ZrCl2 under the same conditions. In addition, titanium FI catalysts with fluorinated ligands promote exceptionally high‐speed, living ethylene polymerization and can produce monodisperse high molecular weight polyethylenes (Mw/Mn<1.2, max. Mn>400,000) at 50 °C. The maximum TOF, 24,500 min –1 atm –1, is three orders of magnitude greater than those for known living ethylene polymerization catalysts. Moreover, the fluorinated FI catalysts promote stereospecific room‐temperature living polymerization of propylene to provide highly syndiotactic monodisperse polypropylene (max. [rr] 98%). The versatility of the FI catalysts allows for the creation of new polymers which are difficult or impossible to prepare using group 4 metallocene catalysts. For example, it is possible to prepare low molecular weight (Mv∼103) polyethylene or poly(ethylene‐co‐propylene) with olefinic end groups, ultra‐high molecular weight polyethylene or poly(ethylene‐co‐propylene), high molecular weight poly(1‐hexene) with atactic structures including frequent regioerrors, monodisperse poly(ethylene‐co‐propylene) with various propylene contents, and a number of polyolefin block copolymers [e.g., polyethylene‐b‐poly(ethylene‐co‐propylene), syndiotactic polypropylene‐b‐poly(ethylene‐co‐propylene), polyethylene‐b‐poly(ethylene‐co‐propylene)‐b‐syndiotactic polypropylene]. These unique polymers are anticipated to possess novel material properties and uses.  相似文献   

8.
A new monomer containing imide linkages, bis[4-(p-phenoxybenzoyl)-1,2-benzenedioyl]-N,N,N′,N′-4,4′-diaminodiphenyl ether (BPBDADPE), was prepared by the Friedel–Crafts reaction of bis(4-chloroformyl-1,2-benzenedioyl)-N,N,N′,N′-4,4′-diaminodiphenyl ether (BCBDADPE) with diphenyl ether (DPE). Novel poly(aryl ether ketone)s containing imide linkages in the main chains (PEK-I) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of terephthaloyl chloride (TPC) with a mixture of DPE and BPBDADPE. The polymers were characterized by different physico-chemical techniques. The polymers with 10–40 mol% BPBDADPE are semicrystalline and had increased T gs over commercially available poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) (70/30) due to the incorporation of imide linkages in the main chains. The polymers IV and V with 30–40 mol% BPBDADPE had not only high T gs of 182–183 °C, but also moderate T ms of 341–343 °C, having good potential for melt processing and exhibited high thermal stability and good resistance to common organic solvents.  相似文献   

9.
About 20–40 mol% Ni/ZrO2 catalysts doped with Ce and Sm were synthesized by an ultrasound-assisted method and characterized by a number of physico-chemical methods (XRD, HR TEM, BET, XPS). It was demonstrated that the synthesized catalysts had a mesoporous structure, where ca. 10 nm size Ni nanoparticles were incorporated into the rare earth metal modified tetragonal zirconium oxide. The Ni particles formed during the reduction treatment could support the porous structure in the supports, and thus the porous properties of the catalysts were related to the Ni-loading. The maximum porous volume and size were obtained for the catalyst with a 30 mol% Ni loading, which coincidentally exhibited the highest catalytic activity for the methanation of CO2. After an oxidation–reduction pretreatment, the catalytic activity could be further improved. The increase in the catalytic activity was attributed to the formation of additional active centers on the catalysts’ surface.  相似文献   

10.
Two types of catalysts containing NiW bimetallic sulfide nanostructures were prepared by a chemical method employing ammonium thiotungstate and nickel nitrate as metal-sulfide precursors followed by sulfidation in H2S/H2 at 400 °C. The nanostructures were grown with excess of Ni, at atomic ratio R = 0.75, 0.85 (R = Ni/Ni + W). High resolution electron microscopy (HRTEM) micrographs revealed the formation of two types of nanostructures, nickel sulfide nanoparticles and long nanorods of tungsten suboxide, both coated by WS2 layers. The Ni/W catalyst containing mostly nanorods presented twice the catalytic activity (pseudo-zero order constant rate k = 12 × 10−7 mol/s.g) of the Ni/W catalyst containing nanoparticles (k = 6.3 × 10−7 mol/s.g) with a low selectivity for tetrahydrodibenzothiophene (THDBT) and high selectivity to cyclohexylbenzene (CHB, 50 mol%). In turn the Ni/W catalyst containing nanoparticles presented a catalytic activity comparable to a Ni/Mo catalyst without inorganic fullerene (IF) nanostructures (k = 7.2 × 10−7 mol/s.g) but with higher selectivity for hydrogenation to THDBT, (14 mol%) than the sample with nanorods.  相似文献   

11.
Poly(fluorene-alt-carbazole) appended with meso-tetraphenylporphyrin (MTPPC) linked through oxyethylene spacer and the parent poly(N-hexyl-2,7-carbazole-alt-9,9-di-n-hexyl fluorene) (P1) were synthesized and characterized. Optical absorption properties of the polymers containing 5% of MTPPC (P2) and 10% of MTPPC (P3) in the polymer backbone show extended optical absorption toward long wavelength compared to the parent polymer P1. Optical absorption studies of the polymers showed that polymer P1 has absorption at 384 nm in solution, whereas polymers P2 and P3 have absorption at 384 nm corresponding to polymer backbone and soret band at 421 nm with Q bands at around 518 and 554 nm in solution. P1 shows photoluminescence emission around 417 nm, whereas P2 and P3 fall around 656 nm. Thermal, electrochemical, and quenching studies of the polymers have been studied and the details are reported.  相似文献   

12.
A series of novel nonmetallocene catalysts [N, O, P] with diphenyl phosphoroso ligands were synthesized by the treatment of phthaldialdehyde, substituted phenols, chlorodiphenyl phosphine with metal halides of TiCl4 and ZrCl4. The catalyst microstructure was characterized by 1H NMR and EA. After activated by methylaluminoxane (MAO), these [N, O, P] catalysts were utilized to catalyze the polymerization of ethylene and the copolymerization of ethylene with 1‐octene. The results indicated that the obtained catalysts were highly efficient for ethylene polymerization and ethylene/1‐octene copolymerization. Structures and properties of the obtained polymers were measured by WAXD, DSC, GPC, and 13C NMR. The results indicated that polyethylene catalyzed by Cat. 3 possessed the highest weight‐average molecular weight of 1.025 × 106 g/mol and the highest melting point of 136.3°C. The copolymer of ethylene/1‐octene catalyzed by Cat. 1 exhibited the highest 1‐octene incorporation content of 0.63 mol %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42225.  相似文献   

13.
A new type of π-conjugated polymers containing 2-diisopropylamino-1,3,5-triazine were prepared via Sonogashira or Suzuki coupling reaction. The structures of the polymers were performed by FT-IR, 1H-NMR, UV–vis spectroscopy, photoluminescence spectroscopy, gel permeation chromatography, thermal analysis and X-ray diffraction analysis. These derived polymers were soluble in common organic solvents such as tetrahydrofuran, chloroform, toluene, and showed good thermal stability. Polymers containing 1,4-diethynyl-2,5-bis(dialkoxy)benzene unit in polymer main chain emitted blue-green light in solution phase under UV light irradiation except with polymer containing 9,9-dioctylfluorene(blue light). Acidochromic behaviors of polymers were studied in CHCl3-CF3COOH mixtures. 9,9-Dioctylfluorene-containing polymer displayed better acidochromic property and linear relationship between absorbance and concentration with the concentration of CF3COOH from 5.384?×?10?4 to 26.92?×?10?4 mol/L. Electrochemical behaviors of polymers depicted p-doping and some hole-transporting properties. XRD results showed that polymers exhibited certain crystallinity.  相似文献   

14.
This work aims to produce triacylglycerols (TAG) containing a medium-chain fatty acid (M) at positions sn-1,3 and a long-chain fatty acid (L) at sn-2 position, i.e. TAG of MLM type, by acidolysis of virgin olive oil with caprylic (C8:0) or capric (C10:0) acids, catalyzed by 1,3-selective Rhizopus oryzae heterologous lipase (rROL) immobilized in Eupergit® C and modified sepiolite. This lipase was produced by the methylotrophic yeast Pichia pastoris. Reactions were performed at 25 and 40 °C, for 24 h, either in solvent-free or in n-hexane media, at a molar ratio 1:2 (olive oil:free fatty acid). Higher incorporations of C8:0 (21.6 mol%) and C10:0 (34.8 mol%) into the TAG were attained in solvent-free media, at 40 °C, when rROL immobilized in Eupergit® C was used. In organic media, at 40 °C, only 15.9 and 14.1 mol%, incorporation of C8:0 or C10:0 were, respectively observed. Lower incorporations were attained for both acids (3.4–7.0 mol%) when native ROL (nROL) in both supports and rROL in modified sepiolite were used. rROL in Eupergit® C maintained its activity during the first four or three 23-h batches, respectively when C8:0 (half-life time, t 1/2 = 159 h) or C10:0 (t 1/2 = 136 h) were used, decreasing thereafter following a time delay model.  相似文献   

15.
In this work the sol-gel process was used to prepare Ce-doped yttrium aluminium garnet (Y 3 A l 5 O 12, YAG) samples. The synthesis products were characterized by infrared spectroscopy (IR), X-ray powder diffraction analysis (XRD), and transmission electron microscopy (TEM). The particle size and luminescence properties of synthesized samples were also determined. The XRD patterns of Y 3 A l 5 O 12:Ce samples showed that phase purity of garnets depends on the synthesis temperature and concentration of dopant. The YAG:Ce samples calcined at 1000°C showed the formation of single-phase YAG in the whole doping range (from 0 up to 10 mol% of Ce). However, during calcination at 1300°C the formation of CeO2 as an impurity phase at >4 mol% of Ce was observed. The mean particle size of Y 3 A l 5 O 12:Ce sample (4 mol% of Ce) synthesized at 1300°C was determined to be approximately 180–280 nm. The luminescence properties of Ce-doped YAG also depend on cerium concentration in the samples. The highest emission (λ ex  = 450nm) intensity was determined for Y 3 A l 5 O 12:Ce samples doped by 5–6 mol% of Ce.  相似文献   

16.

In this paper Ru-containing catalysts based on hypercrosslinked polystyrene (MN-270) and its functional analogues (MN-100 and MN-500) were studied for the first time in cellulose hydrolytic hydrogenation. The catalysts were characterized using transmission electron microscopy (TEM), high resolution TEM, and porosity measurements. Catalytic studies demonstrated that the catalyst containing 1.0 % Ru and based on MN-270 is the most active. The total yield of sorbitol and mannitol was 50 % on the average at 85 % cellulose conversion.

  相似文献   

17.
The impact of incorporating additional steric restrictions into highly sterically encumbered sulfonated polyaromatic polymers was investigated. Copolymers possessing between 0 and 10% nonlinear ortho or meta biphenyl units in an otherwise linear para biphenyl‐containing sulfo‐phenylated poly(phenylene) were synthesized in yields >80% and evaluated on the basis of their physical and electrochemical properties. When incorporated into sulfonated copolymers in ≤5 mol%, ortho and meta linked biphenyl moieties reduced membrane swelling in water by up to 23 and 19 vol%, respectively, compared to strictly para biphenyl‐linked copolymers. Despite this, copolymers possessing nonlinear, biphenyl‐linked monomers displayed a decrease in proton conductivity and mechanical strength. This study reinforces the importance of considering restricted rotation, backbone flexibility, and chain entanglement in the design of polymers aimed at improving their physical and electrochemical properties. © 2020 Society of Industrial Chemistry  相似文献   

18.
New polymer-bound hydrogenation catalysts were made by complexing PdCl2, RhCl3·3H2O, or NiCl2 with anthranilic acid anchored to chloromethylated polystyrene. The Pd(II) and Ni(II) polymers were reduced to the corresponding Pd(O) and Ni(O) catalysts with NaBH4. In the hydrogenation of methyl sorbate, these polymer catalysts were highly selective for the formation of methyl 2-hexenoate. The diene to monoene selectivity decreased in the order: Pd(II), Pd(O), Rh(I), Ni(II), Ni(O). Kinetic studies support 1,2-reduction of the Δ4 double bond of sorbate as the main path of hydrogenation. In the hydrogenation of soybean esters, the Pd(II) polymer catalysts proved superior because they were more active than the Ni(II) polymers and produced lesstrans unsaturation than the Rh(I) polymers. Hydrogenation with Pd(II) polymers at 50~100 C and 50 to 100 psi H2 decreased the linolenate content below 3% and increasedtrans unsaturation to 10~26%. The linolenate to linoleate selectivity ranged from 1.6 to 3.2. Reaction parameters were analyzed statistically to optimize hydrogenation. Recycling through 2 or 3 hydrogenations of soybean esters was demonstrated with the Pd(II) polymers. In comparison with commercial Pd-on-alumina, the Pd(II) polymers were less active and as selective in the hydrogenation of soybean esters but more selective in the hydrogenation of methyl sorbate. Presented at ISF-AOCS Meeting, New York, April 1980.  相似文献   

19.
A series of new poly(1,2,4-triazole)s (PTAs) containing pyridine heterocyclic ring, bearing bulky aromatic pendent groups, were synthesized from the reaction of the corresponding polyhydrazides with aniline or 4-aminobenzenesulfonic acid in polyphosphoric acid (PPA) at 175 °C. The non-sulfonated PTAs showed glass transition temperatures (T gs) of 220–250 °C and inherent viscosities (η inh) equal to 0.48–0.78 dL/g, and the sulfonated poly(1,2,4-triazole)s (S-PTAs) exhibited T gs of 235–265 °C and inherent viscosities equal to 0.50–0.83 dL/g. The former polymers were soluble in conc. H2SO4 and partially soluble in hot N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), and 1-methyl-2-pyrrolidone (NMP), and the latter were soluble in DMF, NMP, DMSO and DMAc at room temperature. All polymers had useful levels of thermal stability and were stable up to 450 °C in nitrogen. The proton conductivities of undoped sulfonated polytriazole membranes and the acid-doped sulfonated polytriazole membranes lie in the range of 5 × 10?4–8.1 × 10?3 and 5 × 10?3–2.3 × 10?2 S/cm, respectively, at 90 °C and 100 % relative humidity.  相似文献   

20.
A conducting composite of polyaniline, poly(o-anisidine), and poly(aniline-co-o-anisidine) using incorporation of TiO2 and SiO2 was prepared by electrochemical polymerization. The films were electropolymerized in a solution containing 0.1 M monomer(s), 1 M sulfuric acid as supporting electrolyte, and 10?5 M TiO2 and SiO2 by applying a sequential linear potential scan rate of 50 mV/s between ? 0.2 and 1.0 V versus an Ag/AgCl electrode. The composites were characterized by cyclic voltametry, UV-visible spectroscopy, electrical conductivity, and thermogravimetric analysis. It was observed that the UV-visible peaks appeared in the region of the conducting emerladine salt phase. In an overall study, the polymers prepared using TiO2 had a higher conductivity than those prepared with SiO2; however, higher conductivity was observed for the polyaniline-TiO2 conducting composite than for the other polymers. The composites did not lose their color at higher temperature and hence can be utilized as the conductive pigments required for antielectrostatic applications.  相似文献   

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