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  • 1
    ISSN: 1520-4804
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Polymer bulletin 3 (1980), S. 285-290 
    ISSN: 1436-2449
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Summary Asymmetric induction copolymerization and Diels-Alder reaction were investigated between acrylic monomer and olefin or diolefin with use of an optically active aluminum compound as the complexing agent. In the copolymerization, only benzofuran gave an optically active alternating copolymer, while butadiene and indene gave alternating copolymers but with no optical activity. EtAlCl2-l-menthol was the most effective complexing agent. However, EtAlCl2-d-neomenthol was ineffective. On the other hand, Diels-Alder reaction was in general more easily stereocontrolled. For instance, both complexing agents were effective for the synthesis of optically active Diels-Alder adducts with butadiene or cyclopentadiene, perhaps due to the rigid cyclic structure in a transition state of the reaction.
    Materialart: Digitale Medien
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  • 3
    ISSN: 0887-624X
    Schlagwort(e): living cationic polymerization ; alkoxyethyl vinyl ether ; pendant oxyethylene unit ; water-soluble polymer ; phase separation ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Living cationic polymerization of alkoxyethyl vinyl ether [CH2=CHOCH2CH2OR; R: CH3 (MOVE), C2H5 (EOVE)] and related vinyl ethers with oxyethylene units in the pendant was achieved by 1-(isobutoxy)ethyl acetate (1)/Et1.5AlCl1.5 initiating system in the presence of an added base (ethyl acetate or THF) in toluene at 0°C. The polymers had a very narrow molecular weight distribution (M̄w/M̄n = 1.1-1.2) and the M̄n proportionally increased with the progress of the polymerization reaction. On the other hand, the polymerization by 1/EtAlCl2 initiating system in the presence of ethyl acetate, which produces living polymer of isobutyl vinyl ether, yielded the nonliving polymer. When an aqueous solution of the polymers thus obtained was heated, the phase separation phenomenon was clearly observed in each polymer at a definite critical temperature (Tps). For example, Tps was 70°C for poly(MOVE), and 20°C for poly(EOVE) (1 wt % aqueous solution, M̄n ∼ 2 × 104). The phase separation for each case was quite sensitive (ΔTps = 0.3-0.5°C) and reversible on heating and cooling. The Tps or ΔTps was clearly dependent not only on the structure of polymer side chains (oxyethylene chain length and ω-alkyl group), but also on the molecular weight (M̄n = 5 × 103-7 × 104) and its distribution. © 1992 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 879-887 
    ISSN: 0887-624X
    Schlagwort(e): living cationic polymerization ; isobutyl vinyl ether ; added Lewis base ; EtAlCl2 ; Et1.5AlCl1.5 ; polymerization mechanism ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the living cationic polymerization of isobutyl vinyl ether (IBVE) by the CH3CH (OiBu) OCOCH3 (1)/EtAlCl2 initiating system in the presence of the added base in hexane at +40°C, the stability of the initiating system 1/EtAlCl2, which form initiating species CH3CH⊕ (OiBu) derived from 1, was investigated. In the presence of the Lewis base such as ethyl acetate or 1,4-dioxane, the active species was stable for 300 min even at +40°C in the absence of IBVE, and the living polymers were quantitatively obtained by adding IBVE. However, the active species was partly consumed by side reactions during the standing time for 60 min in the presence of a less basic additive such as ethyl benzoate, and about 50% of the active species was deactivated in the presence of methyl chloroacetate. Consequently, in the case of a less basic additive such as methyl chloroacetate (which was effective for the fast living polymerization), it can be seen that the careful selection of polymerization conditions was required. The living polymerization rate was dependent on the second order of EtAlCl2 concentration. EtAlCl2 induced the cleavage of 1 into CH3CH⊕ (OiBu) and EtAl⊖Cl2(OCOCH3), and the reactivity of CH3CH⊕ (OiBu) and propagating carbocation may be controlled by EtAl⊖Cl2(OCOCH3) with the aid of other EtAlCl2. Et1.5AlCl1.5 exists as a bimetallic complex of EtAlCl2 and Et2AlCl, and it is expected that the polymers having a bimodal molecular weight distribution will be obtained due to two kinds of counteranions coming from EtAlCl2 and Et2AlCl. However, in the cationic polymerization of IBVE by 1/Et1.5AlCl1.5 in the presence of ethyl acetate, the living polymer exhibiting a unimodal and very narrow molecular weight distribution was obtained. Thereby, it was suggested that the counteranions, EtAl⊖Cl2(OCOCH3) and Et2Al⊖Cl(OCOCH3), exchange rapidly with each other. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 5
    ISSN: 0887-624X
    Schlagwort(e): polyaddition ; phosphorus-containing polymer ; saturated polymer ; phenylphosphine ; 1,4-divinylbenzene ; 1,4-diisopropenylbenzene ; flame resistance ; thermal stability ; DSC ; TG ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A polyaddition of phenylphosphine (PH) to 1,4-divinylbenzene (DVB) or 1,4-diisopropenylbenzene (DIPB) was carried out by radical initiations or UV irradiation at 60-80°C in toluene under a nitrogen atmosphere. The soluble polymer with higher molecular weight ($\[ \bar M_w = 2 \times 10^4 \]$) was obtained in a high yield with AIBN initiator for 95 h in the presence of 5% excess of PH to DVB (monomer feed ratio [DVB]0/[PH]0 = 1/1.05). On the other hand, a polyaddition of PH to DIPB proceeded much slower than the case of DVB, but the high polymer was obtained in a high yield by choosing polyaddition conditions such as polyaddition temperature and initiator concentration. From 1H-NMR, IR analyses, and phosphorus content of the polymers, it was characterized that both polymers have the alternating structure consisting of PH and DVB or DIPB units in 1 : 1 ratio. The glass transition and decomposition temperatures of both polymers under a nitrogen atmosphere were almost similar: 15-30°C and 380-385°C, respectively; but, the polymers were oxidized by heating under an atmosphere of air. The polymers had a self-extinguishing property and the polymer blend of the flammable polymers such as polystyrene and polyethylene with the phosphorus-containing polymers exhibited an excellent flame resistance. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1609-1617 
    ISSN: 0887-624X
    Schlagwort(e): selenium-containing polymer ; radical addition polymerization ; 1,4-benzene-diselenol ; 1,4-divinylbenzene ; 2,2′-azobisisobutyronitrile ; dimethyl 2,2′-azobisisobutyrate ; 1,1′-azobis(1-acetoxy-1-phenylethane) ; model addition reaction ; side reaction ; properties of polymer ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A novel addition polymerization of 1,4-benzenediselenol (BDSe) to 1,4-divinylbenzene (DVB) was carried out with various azo radical initiators [dimethyl 2,2′-azobisisobutyrate (DAIB), 1,1′-azobis(1-acetoxy-1-phenylethane) (AAPE), and AIBN] in toluene at 65 and 75°C under a nitrogen atmosphere. The polymerization proceded without an induction period, and pale-yellowish powder polymers were obtained in 89% yields for 75 h (DAIB), 89% yields for 24 h (AAPE), and 60% yields for 8 h (AIBN). The molecular weight (Mw) of the insoluble polymers in toluene was about 4000 (IBN) to 14,000 (DAIB or AAPE) by GPC. The polymer had an alternating structure of BDSe to DVB units by 1H-NMR, IR analyses, and selenium contents, but the polymer contained the diselenide linkage by Raman spectroscopy. By AIBN initiator, the yield of the polymers did not increase over 60% and higher molecular weight polymer was hardly obtained. According to the model addition reaction of benzeneselenol to styrene by AIBN, it was found that AIBN was consumed by the side reaction between dimethyl-N-(2-cyano-2-propyl)ketenimine derivedAppl 11 from AIBN and benzeneselenol to give the adduct C, MH+ 295 by DCI MS. On the other hand, DAIB and AAPE initiators, which do not form a ketenimine intermediate, gave the polymers of higher molecular weight in a higher yield. The polymer film exhibited high refractive index (n25D = 1.81) and a reversible phase transition between a transparency and an opaque by thermal mode. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2175-2182 
    ISSN: 0887-624X
    Schlagwort(e): gadolinium tricarboxylate ; copolymerization of butadiene and styrene ; effect of pKa of ligand ; diad analysis ; cis polymerization mechanism ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)3: R = CH3, CH2Cl, CHCl2, CCl3, and CF3], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)3 - (i - Bu)3Al - Et2AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97-99%) in 22-85% yields for 2-24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)3: CF3 〉 CCl3 〉 CHCl2 〉 CH2Cl ∼ CH3. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI3)3- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ∼ 14.5 mol %) by 13C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)2 and Co(acac)3-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2591-2597 
    ISSN: 0887-624X
    Schlagwort(e): Gd(OCOCCl3)3 catalyst ; copolymerization of styrene and methyl methacrylate ; monomer reactivity ratio ; HOMO and LUMO levels ; e value of monomers ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization of polar monomers such as methyl methacrylate (MMA), methyl acrylate (MA), methacrylonitrile (MAN), and acrylonitrile (AN) was carried out with gadolinium-based Ziegler-Natta catalysts [Gd(OCOCCl3)3-(i-Bu)3Al-Et2AlCl] in hexane at 50°C under N2 to elucidate the effect of the monomer's HOMO(highest occupied moleculor orbital) and LUMO (lowest unoccupied molecular orbital) levels on the polymerizability. In the case of homopolymerization, all monomers were found to polymerize and the order of relative polymerizability was as follows: MM 〉 MA 〉 MAN 〉 AN. On the other hand, the result of copolymerization of St with MMA shows that the values of the monomer reactivity ratios are r1 = 0.06 and r2 = 1.98 for St(M1)/MMA(M2). The monomer reactivity ratios of styrene (St), p-methoxystyrene (PMOS), p-methylstyrene (PMS), and p-chlorostyrene (PCS) evaluated as r1 = 0.55 and r2 = 1.07 for St(M1)/PMOS(M2), r1 = 0.38 and r2 = 0.51 for St(M1)/PMS(M2), and r1 = 0.72 and r2 = 1.25 for St(M1)/PCS(M2) were compared with those for St(M1)/MMA(M2). The copolymerization behavior is apparently different from the titanium-based Ziegler - Natta catalyst, regarding a larger monomer reactivity ratio of PCS. The lower LUMO level of PCS and MMA may enhance a back-donation process from the metal catalyst, therefore resulting in high polymerizability. These results are discussed on the basis of the energy level of the gadolinium catalyst and the HOMO and LUMO levels of the monomers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2591-2597, 1997
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 241-247 
    ISSN: 0887-624X
    Schlagwort(e): neodymium tricarboxylate ; polymerization of butadiene or styrene ; copolymerization of butadiene and styrene ; cis-1,4 polymerization mechanism ; back-biting coordination model ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Homo- and copolymerizations of butadiene (BD) and styrene (St) with rare-earth metal catalysts, including the most active neodymium (Nd)-based catalysts, have been examined, and the cis-1,4 polymerization mechanism was investigated by the diad analysis of copolymers. Polymerization activity of BD was markedly affected not only by the ligands of the catalysts but also by the central rare-earth metals, whereas that of St was mainly affected by the ligands. In the series of Nd-based catalysts [Nd(OCOR)3:R = CF3, CCl3, CHCl2, CH2Cl, CH3], Nd(OCOCCl3)3 gave a maximum polymerization activity of BD, which decreased with increasing or decreasing the pKa value of the ligands. This tendency was different from that for Gd(OCOR)3 catalysts, where the CF3 derivative led to the highest polymerization activity of BD. For the polymerization of St and its copolymerization with BD, the maximum activities were attained at R = CCl3 for both Nd- and Gd-based catalysts. The copolymerization of BD and St with Nd(OCOCCl3)3 catalyst was also carried out at various monomer feed ratios, to evaluate the monomer reactivity ratios as rBD = 5.66 and rSt = 0.86. The cis-1,4 content in BD unit decreased with increasing St content in copolymers. From the diad analysis of copolymers, it was indicated that Nd(OCOCCl3)3 catalyst controls the cis-1,4 structure of the BD unit by a back-biting coordination of the penultimate BD unit. Furthermore, the long range coordination of polymer chain by the neodymium catalyst was suggested to assist the cis-1,4 polymerization. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 241-247, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1719-1728 
    ISSN: 0887-624X
    Schlagwort(e): living cationic polymerization ; isobutyl vinyl ether ; cyclic ether additives ; cyclic formal additives ; acyclic ether additives with oxyethylene units ; EtAlCl2 ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The living cationic polymerization of isobutyl vinyl ether (IBVE) was investigated in the presence of various cyclic and acyclic ethers with 1-(isobutoxy)ethyl acetate [CH3CH(OiBu)OCOCH3, 1]/EtAlCl2 initiating system in hexane at 0°C. In particular, the effect of the basicity and steric hindrance of the ethers on the living nature and the polymerization rate was studied. The polymerization in the presence of a wide variety of cyclic ethers [tetrahydrofuran (THF), tetrahydropyran (THP), oxepane, 1,4-dioxane] and cyclic formals (1,3-dioxolane, 1,3-dioxane) gave living polymers with a very narrow molecular weight distribution (MWD) (M̄ω/M̄n ≤ 1.1). On the other hand, propylene oxide and oxetane additives resulted in no polymerization, whereas 1,3,5-trioxane gave the nonliving polymer with a broader MWD. The polymerization rates were dependent on the number of oxygen and ring sizes, which were related to the basicity and the steric hindrance. The order of the apparent polymerization rates in the presence of cyclic ether and formal additives was as follows: nonadditive ∼ 1,3,5-trioxane ≫ 1,3-dioxane 〉 1,3-dioxolane ≫ 1,4-dioxane ≫ THP 〉 oxepane ≫ THF ≫ oxetane, propylene oxide ≫ 0. The polymerization in the presence of the cyclic formals was much faster than that of the cyclic ethers: for example, the apparent propagation rate constant k in the presence of 1,3-dioxolane was 103 times larger than that in the presence of THF. Another series of experiments showed that acyclic ethers with oxyethylene units were effective as additives for the living polymerization with 1/EtAlCl2 initiating system in hexane at 0°C. The polymers obtained in the presence of ethylene glycol diethyl ether and diethylene glycol diethyle ether had very narrow molecular weight distribution (M̄ω/M̄n ≤ 1.1), and the M̄n was directly proportional to the monomer conversion. The polymerization behavior was quite different in the polymerization rates and the MWD of the obtained polymers from that in the presence of diethyl ether. These results suggested the polydentate-type interaction or the alternate interaction of two or three ether oxygens in oxyethylene units with the propagating carbocation, to permit the living polymerization of IBVE. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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