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An attempt was made to synthesize steroregular polyacrylonitrile (PAN) with a high triad isotacticity (i.e. the content of mm (m, meso)) exceeding 0.70 by the anionic polymerization method. In the stereospecific polymerization of acrylonitrile (AN) initiated by diethylberyllium (Et2Be) in xylene at 130°C, the (mm) content as well as the viscosity-average molecular weight (MÞv) of PAN increased by addition of diisobutylaluminum hydride (i-C4H9)2AlH) as an additive to the polymerization system. Maximum (mm) content, attained in the molar ratio region of (i-C4H9)2AlH/Et2Be > 1.0, was about 0.73. The stereospecific polymerization of AN was also initiated using a mixture of Et2Be and di-n-hexylamagnesium ((Et2Be/(n-C6H13)2 Mg system), where both Et2Be and (n-C6H13)2 Mg can induce the stereospecific polymerization of AN at 130°C. The (mm) content of the PAN sample prepared using the Et2Be/(n-C6H13)2 Mg system ((mm) = 0.64) was higher than that of PAN samples synthesized using Et2Be alone ((mm) = 0.56) and (n-C6H13)2Mg alone ((mm) = 0.51) under the same conditions except initiator. A significant difference in 13C chemical shifts of α-carbons between Et2Be (1.35 ppm) and (n-C6H13)2Mg (10.72 ppm) dissolved in hydrocarbon solvent at 110°C leads us to the conclusion that when Et2Be induces the stereospecific polymerization in the Et2Be/(n-C6H13)2Mg system as initiator, the main role of (n-C6H13)2Mg is considered to be the suppression of the association of Et2Be (active site) itself. 相似文献
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The aim of this work is to combine the microstructure of a radical-polymerized diene (butadiene and isoprene) with the functionality of an anionically prepared one, which could be used for polyurethane preparation after functionalization. A two-step anionic procedure was used in order to obtain a hydrocarbon-soluble lithium-based initiator. When compared with the related anionic polymers obtained under classical conditions, the vinyl content of the polydienes was three times greater. These findings are discussed on a mechanistic basis. © 1998 Society of Chemical Industry 相似文献
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Anionic polymerization of butadiene was conducted in cyclohexane using 1,1,4,4‐tetraphenyl‐1,4‐dilithium butane (TPB–DiLi) as initiator and dipiperidinoethane (DPE) as modifier. The polymer design effects of DPE/TPB–DiLi (simplified as DPE/Li) and polymerization temperature on the 1,2 content of polybutadiene (PB) were examined and 1,2‐polybutadiene (1,2‐PB) with a nearly 100% 1,2 content was obtained. 1,2–1,4–1,2‐Stereotriblock polybutadiene (STPB) can be synthesized easily by means of one feed reaction. DSC and DMA analyses showed that STPB with the designed molecular structure (molecular weight, block ratio, and 1,2 content in 1,2 blocks) has two Tg's and two loss moduli and exhibits microphase separation. Studies on reaction kinetics established the polymerization kinetics equation of 1,4‐PB as ?d[M]/dt = 0.356[C]0.5[M], indicating the first‐order relationship between polymerization rate and monomer concentration. At 50°C, the addition of the strong polar modifier DPE into the system increased the reaction rate. The apparent propagating activating energies before and after DPE addition were also determined in this study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1049–1054, 2003 相似文献
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Zhaohui Tang Yongkun Yang Xuan Pang Junli Hu Xuesi Chen Ninghai Hu Xiabin Jing 《应用聚合物科学杂志》2005,98(1):102-108
A single‐site ethyl aluminum complex, [2,2‐ diethyl‐1,3‐propylenebis(3,5‐di‐tert‐butyl‐salicylideneiminato)] ethyl aluminum (2), with a geminal diethyl substitutent on the diamino bridge was synthesized by the reaction of AlEt3 with 1 equiv of N,N′‐(2,2‐diethyl‐1,3‐propylene)bis(3,5‐di‐tert‐butylsalicylideneimine). X‐ray diffraction showed that complex 2 contained a five‐coordinate aluminum atom with a distorted trigonal bipyramidal geometry in the solid state. 1H‐NMR and 13C‐NMR spectra indicated that the two conformational enantiomers of 2 tautomerized quickly on the NMR timescale in solution. In the presence of isopropyl alcohol, the ring‐opening polymerization (ROP) of rac‐lactide with complex 2 produced a crystalline stereoblock polylactide (PLA). The stereoblocks contained an average of 12 units (L? = 12) of enantiomerically pure lactic acid. There was a linear relationship between the monomer conversion and number‐average molecular weights of the polymer. An induction period was observed for the polymerization. The induction period increased with decreasing concentration of catalyst 2 and isopropyl alcohol. In the presence of poly(ethylene glycol) (PEG), a PLA/PEG/PLA stereocomplex was prepared directly by the ROP of rac‐lactide with complex 2, which was confirmed by NMR, gel permeation chromatography, wide‐angle X‐ray diffraction, and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 102–108, 2005 相似文献
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We have developed a facile method to prepare polyacrylonitrile/montmorillonite (PAN/MMT) nanocomposites using the surface‐initiated redox polymerization of acrylonitrile (AN) in the aqueous phase. The MMT silicate surfaces were first treated with diethanolamine, and the modified MMT (DEA‐MMT) was subsequently used together with the Ce(IV) salt to serve as a redox system. The PAN chains growing on a surface‐tethered DEA expand the interlayer space, and thus lead to intercalated/exfoliated nanocomposites. The nano‐morphology of the prepared nanocomposites depends on the AN/OH molar ratio in feed. An exfoliated PAN/MMT nanocomposite was obtained when the feeding AN/OH molar ratio = 300 was used. The molecular weight of PAN in the nanocomposites prepared by the present method is also dependent on the AN/OH molar ratio in feed and can be up to ca. 160,000 g/mol. The differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) analyses show that the increasing fraction of exfoliated silicate structures should enhance the contact interface between the silicate and polymer, resulting in the higher glass transition temperature and thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
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Polymerization of isoprene (IP) with alkyllithium (RLi) catalysts in the presence of amines such as triethylamine (TEA), 1,2-dipiperidinoethane (DPPE) and N,N,N′,N′-tetramethyldiaminoalkanes [(CH3)2N(CH2)nN(CH3)2 where n=1, 2, 3, 4 and 6 (TMDAA)] has been studied. By adding the amines, the polymerization rate of IP was accelerated, and the contents of 3,4- and 1,2-units in the resulting polymers increased. The effects of methylene chain length of the TMDAA on the polymerization were examined. It was found that both the polymerization rates and the microstructure of the polymers depend on the methylene length of the TMDAA. The amines having 2 and 3 methylenes in (CH3)2N(CH2)nN(CH3)2 favoured production of the polymer consisting of predominantly 1,2- and 3,4-units. It was proposed that two types of active sites for the polymerization of IP were produced depending on the number n of the TMDAA. Two types of active species were confirmed to be produced with sec-BuLi in the presence of N,N,N′,N′-tetramethylethylenediamine (TMEDA) depending on the TMEDA/sec-BuLi mole ratios. © 1998 SCI. 相似文献
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The mechanism of stereospecific polymerization of propylene (catalysed by a modified Ziegler-Natta system, TiCl4/MgCl2/C6H5COOC2H5/Al(C2H5)3), has been analysed using the values of triad and pentad tacticity determined using 125 MHz 13C n.m.r. spectroscopy. The well-known single active-site models, such as the Bernoullian, first- and second-Markovian, and enantiomorphic models, were found to be inadequate to describe the observed tacticity. A two-sites model, in which at one site the stereospecific polymerization proceeds in obedience to the Bernoullian model and at the other proceeds under the control of enantiomorphic-site model, is proposed. It was found that the pentad tacticities of both soluble and insoluble (in boiling heptane) fractions of polypropylene agreed well with the two-sites model. 相似文献
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Electroinduced dispersion polymerization of acrylonitrile initiated by Ce(IV) was performed in an electrolytic cell in the presence of poly(acrylic acid) (PAA). Micron‐size polyacrylonitrile (PAN) particles were stabilized with PAA by electrostatic interaction or by a PAA–Ce(III)–PAN ternary complex formation. A PAA–PAN stable polymer was formed in the cathodic compartment, and the reduced initiator was reoxidized in the anode, thus allowing for the continuation of the process. A possible mechanism of polymerization is suggested. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 723–728, 2002; DOI 10.1002/app.10076 相似文献
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Fernanda M. B. Coutinho Tereza C. J. Rocha Ivana L. Mello Denise S. S. Nunes Bluma G. Soares Marcos A. S. Costa 《应用聚合物科学杂志》2005,98(6):2539-2543
High‐cis polybutadiene produced by catalyst systems based on a rare earth is an elastomer used to produce green tires. This type of tire presents lower rolling resistance, which allows higher fuel economy, and thus fewer chemical compounds are discharged into the atmosphere. In this work, the influence of electron donors [tetrahydrofuran (THF) and tetramethylethylenediamine (TMEDA)] present in the polymerization solvent on the microstructure and molecular weight characteristics of the polybutadiene produced by neodymium catalysts was studied. The catalyst synthesis was carried out in glass bottles for 1 h at a temperature between 5 and 10°C. The catalyst components were diisobutylaluminum hydride, neodymium versatate, and tert‐butyl chloride. The polymerization reaction was carried out for 2 h. The reaction temperature was kept at 70± 3°C. The addition of TMEDA or THF above a determined concentration reduced the catalytic activity, molecular weight, and concentration of cis‐1,4 units (<96%), whereas the polydispersity increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2539–2543, 2005 相似文献
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异戊二烯/THF负离子聚合产物的微观结构 总被引:1,自引:1,他引:1
研究了20~50℃下,以n-BuLi为引发剂,环己烷为溶剂,THF为极性调节剂的异戊二烯负离子聚合产物的微观结构。结果表明:随聚合温度升高,聚异戊二烯的3,4-结构含量降低;在同一温度下,随THF用量的增加,3,4-结构含量增加。[THF]/[n-BuLi](R,摩尔比)大于12时,才会出现1,2-结构,且聚合温度越高,出现1,2-结构时的R值越高,并随R值的继续升高,1,2-结构含量也不断增加。此外,还建立了4个微观结构含量与THF用量的定量关系式。 相似文献
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The chemical redox system of ceric ammonium nitrate(Ce4+) and poly(dimethylsiloxane)s (PDMS) with monohydroxy (MH), dihydroxy (DH), and diamine(DA) chain ends was used to polymerize acrylonitrile (AN) to produce monohydroxy poly(dimethylsiloxane)s‐b‐polyacrylonitrile (MH.PDMS‐b‐PAN), dihydroxy poly(dimethylsiloxane)s‐b‐polyacrylonitrile (DH.PDMS‐b‐PAN), and α, ω‐diamine poly(dimethylsiloxane)s‐b‐polyacrylonitrile (DA.PDMS‐b‐PAN) block copolymers. The concentration, reaction time, and the type of poly(dimethylsiloxane) affect the yield and the molecular weight of the copolymers. The ratio of AN/ceric salt/PDMS has remarkably affects the properties of formed copolymers. DH.PDMS‐b‐PAN copolymers were also prepared by electroinduced polymerization in the presence of catalytic amount of Ce4+ in a divided electrochemical cell where Ce3+ is readily oxidized into Ce4+ at the anode. The products were characterized by Fourier transform infrared spectroscopy, 1H‐NMR spectroscopy, DSC, and their surface properties were investigated through contact‐angle measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
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Heterophase polymerization of different methacrylates: Effect of alkyl ester group on kinetics and colloidal behavior 下载免费PDF全文
Víctor M. Ovando‐Medina Miguel A. Corona‐Rivera Alfredo Márquez‐Herrera Tania E. Lara‐Ceniceros Ricardo Manríquez‐González René D. Peralta 《应用聚合物科学杂志》2014,131(8)
In this article, methyl‐ (MMA), ethyl‐ (EMA), n‐butyl‐ (BMA), n‐hexyl (HMA), and 2‐ethyl hexyl (2‐EHMA) methacrylates were homopolymerized in heterophase at 60°C using sodium dodecyl sulfate as surfactant and potassium persulfate as initiator. The effects of monomer content in the reaction mixture (2.5 and 3.5 wt %) and the alkyl ester groups of the methacrylates on the kinetics, average particle diameter (Dp), molar masses, tacticity, and glass transition temperature (Tg) were studied. The final weight average molecular weights were in the range of 4.53 × 105 to 2.78 × 106 g/mol with polydispersities between 1.7 and 3.1 for different methacrylates. For 2.5 wt % of monomer concentration, the order of increase in polymerization rate was RpHMA > RpBMA > Rp2‐EHMA > RpEMA > RpMMA, whereas for 3.5 wt % of monomer concentration was RpBMA > RpHMA > Rp2‐EHMA > RpEMA > RpMMA. This behavior was ascribed to the differences in the water solubility, monomer partitioning between the different phases, and monomers reactivity. The Dp values varied between 42 and 65 nm, increasing according to the hydrophobicity of each monomer. 13C‐NMR (nuclear magnetic resonance) and differential scanning calorimetry analysis demonstrated that 79–87% of syndiotactic configuration was obtained for the different polymers. The steric effect of the alkyl ester length in the methacrylates contributed directly to promote the syndiotactic configuration. Nevertheless, Tg values (between ?7 and 120°C) for these polymers decreased when the alkyl ester length increased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40191. 相似文献
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The butadiene polymerization in toluene at 25°C on VOCl3? (n‐C4H9)Mg(iso‐C8H17) catalytic system was investigated. The kinetic parameters of polymerization and molecular characteristics of polybutadiene were determined. It was shown that substitution of traditional organoaluminum cocatalysts in trans‐regulating vanadium systems does not have an effect on its stereospecificity, but significantly influences on the active centers reaction ability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 596–600, 2003 相似文献
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To study the effect of the substituents in the N-position of the carbazole on anionic polymerization, 2-vinylcarbazole derivatives of 9-butyl-2-vinylcarbazole (NBu2VCz), 9-phenyl-2-vinylcarbazole (NPh2VCz), and 9-(pyridin-2-yl)-2-vinylcarbazole (NPy2VCz) were synthesized. The anionic polymerization of NBu2VCz and NPh2VCz using s-BuLi was performed at −78 °C with a 100% yield, but the polymerization of NBu2VCz showed a broader molecular weight distribution (Mw/Mn = 1.23) than NPh2VCz (Mw/Mn = 1.11). The anionic polymerization of NPy2VCz using s-BuLi and DPM-K had a yield below 5%. In particular, the living anionic polymerization of NPh2VCz with s-BuLi/styrene ([s-BuLi/St]0 = 0.33) shows a narrower Mw/Mn. The block copolymerization of NPh2VCz with styrene, α-methylstyrene (α-MeSt), and 2-vinylpyridine (2VP) was achieved successfully. The resulting block copolymers of PNPh2VCz-b-P2VP with fPNPh2VCz = 17.7, 34.6, 48.1, 62.4, and 82.9 were synthesized for investigation of living characteristics. 相似文献
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A new asymmetric H-shaped block copolymer (PS)2-PEO-(PMMA)2 has been designed and successfully synthesized by the combination of atom transfer radical polymerization and living anionic polymerization. The synthesized 2,2-dichloro acetate-ethylene glycol (DCAG) was used to initiate the polymerization of styrene by ATRP to yield a symmetric homopolymer (Cl-PS)2-CHCOOCH2CH2OH with an active hydroxyl group. The chlorine was removed to yield the (PS)2-CHCOOCH2CH2OH ((PS)2-OH). The hydroxyl group of the (PS)2-OH, which is an active species of the living anionic polymerization, was used to initiate ethylene oxide by living anionic polymerization via DPMK to yield (PS)2-PEO-OH. The (PS)2-PEO-OH was reacted with the 2,2-dichloro acetyl chloride to yield (PS)2-PEO-OCCHCl2 ((PS)2-PEO-DCA). The asymmetric H-shaped block polymer (PS)2-PEO-(PMMA)2 was prepared via ATRP of MMA at 130 °C using (PS)2-PEO-DCA as initiator and CuCl/bPy as the catalyst system. The architectures of the asymmetric H-shaped block copolymers, (PS)2-PEO-(PMMA)2, were confirmed by 1H NMR, GPC and FT-IR. 相似文献