摘要:

AbstractThe polymerization of 1‐vinylindole (1a) induced by free radical and cationic initiators is studied and the structure of the resulting polymers is elucidated by13C NMR spectroscopy. Also 2‐methyl‐1‐vinylindole (1b), 3‐methyl‐1‐vinylindole (1c), and 2,3‐dimethyl‐1‐vinylindole (1d) are polymerized in order to understand the polymerization mechanism of this class of monomers. Radical polymerization affords a linear polyvinylic structure in the case of1band1d, and cyclic indoline type structures in the case of1aand1c. Cationic polymerization gives linear structures for poly(1c) and poly(1d), but cyclic structures for1a. Evidence is given that cyclization involves position 2 of the indole ring in the radical polymerization, and position 3 in the cationic polymerization. Five and six membered rings are formed, respectively. The indole ring was found to be unreactive, under the adopted conditions, in the linear radical p

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800101

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe formation of a charge‐transfer complex between 1‐vinylindole (1a) and maleic anhydride (MA) was detected by1H NMR analysis, and the correspondingKeqwas measured (Keq=0,251 mol in CDCl3at 25°C). It could be shown that this complex can be involved both in the initiation and propagation steps of the1a‐MA copolymerization by carrying out spontaneous copolymerization experiments and studying the influence of the feed composition on the conversion and [η] of the copolymer. The structure of the1a‐MA copolymer, investigated by13C NMR spectroscopy, was found to be complicated due to the formation of indoline rings along the chains by an attack of the propagating MA radical at position 2 in the indole ring. As a consequence an excess of MA, with respect to a 1:1 mole ratio of monomer feed, was usually found in the copolymer. The mechanism of the cyclization reaction was clarified by copolymerizing MA with 2‐methyl‐1‐vinylindole (1b), 3‐methyl‐1‐vinylindole (1c), or 2,3‐dimethyl‐1‐vinylindole (1d). An alternating copolymer with MA (mole ratio 1:1 of monomeric units), without irregularities, was obtained only b

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800102

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe aminolysis ofN‐benzoylethanesultam (1) was conducted as a model compound study and was found to give almost exclusively ring‐opened adduct. The ring‐opening polyaddition ofN,N′‐sebacoylbis(ethanesultam) (5), synthesized from a sebacoyl chloride and ethanesultam (3), with aliphatic diamines in HMPT afforded a new class of polyamide‐sulfonamides having inherent viscosities of 0,1–0,8dl.g−1in excellent yields. All of the polymers were soluble in polar aprotic solvents and some acidic solvents. These polymers began to decompose at around 300°C in air, as

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800103

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe thermal polymerization of dihydro‐exo‐dicyclopentadienyl acrylate (DDA) (tricyclo[5.2.1.02.6]dec‐3‐en‐9‐yl acrylate) was carried out under nitrogen in the absence of any initiator to investigate the kinetics and mechanism for it. The polymerization rate was found to follow the equation:Rp=k[DDA]1.6. The rate was nearly the same as those obtained for the polymerization of other alkyl acrylates. The overall activation energy for the polymerization was determined to be 57,3 kJ/mol (13,7 kcal/mol). The kinetic data and the data obtained by spin trapping technique during the polymerization showed that the double bond of the acryl group was polymerized much faster than that of the cyclopentene ring to form the straight chain polymer and that the double bond of the cyclopentene ring began to polymerize to a small extent, at a stage where most of acryl groups were polymerized, to give some crosslinking

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800104

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractPolymerisation of butadiene using different Rh‐compounds, specially Rh(NO3)3, in allyl alcohol results in oligobutadienes with carbonyl functionality of 1 and hydroxyl functionality between 0—1. Under proper conditions telechelics are formed. Catalysis by Rh(NO3)3can be accelerated by the addition of alcoholate or phosphine. The oligomers have exclusively 1,4‐trans‐structure. The combined use of alcoholate and triphenylphosphine results in oligobutadienes with 40% 1,4‐cis‐, 35% 1,4‐trans‐ and 25% 1,2 structure. Determination of the structure of isolated oligomers shows that both functional groups are incorporated by insertion of a complete allyl alcohol unit. According to the frequently found endgroup CH2C(CH2OH) … the incorporation of the hydroxyl group in the termination reaction by β‐hydride transfer is most likely. The carbonyl functionality is formed in the initiation step by hydride transfer from allyl alcohol to Rh. Analogous use of allyl chloride or allyl bromide results in telechelic oligobutadienes containing two halogens per molecule. but the structure of isolated oligomers shows that only one allyl halogenide unit is incorporated. The second terminal halogen is fixed to a butadiene unit. Again the characteristic group CH2C(CH2Cl)—… is found, suggesting a ter

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800105

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractVanadium tetrachloride combined with alkylaluminium could be shown to produce two types of polypropylenes, the syndiotactic and the isotactic ones, depending on both the kind of alkylaluminium component and polymerization temperature. It was found that the syndiotactic polypropylenes always have narrow molecular weight distributions (1,5≤M̄w/M̄n≤2,5), whereas the isotactic polypropylenes always have wide distributions (16≤M̄w/M̄n≤19), suggesting that the isotactic polymerizations are not induced by homogeneous but by heterogeneous catalysis. With the aid of ESR analysis for catalyst systems it was concluded that the syndiotactic polymerizations take place in a soluble complex of trivalent vanadium, whereas the isotactic polymerizations proceed on the insoluble vanadium dichlorides formed from the catal

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800106

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

Abstract1,4‐Bis(2‐diethylaminoethyl)benzene (4), synthesized from 1,4‐divinylbenzene (1) and diethylamine (2) with lithium diethylamide as catalyst, was successively quaternized with 1,4‐dibromobutane (5) to prepare a cationic polyelectrolyte6of the ionene type. Apparent molecular weights of the ionene samples were estimated by the sedimentation equilibrium method, and the result is discussed in connection with the true molecular weight. The rate constants for quaternization of first and second nitrogen atom of4(k1andk2) were determined by the use of13C NMR. It was found that the ratio of the rate constants, (k2/(k1/2)), markedly decreased in the4/5system, though it remained unity in the4ethyl bromide

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800107

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe polymerization of 1‐(1‐cyclopentenyl)vinyl acetate (1) and (3‐methyl‐1,3‐butadien‐2‐yl) acetate (7) under radical conditions, leading to 1,4‐polymers, and the copolymerization with vinyl monomers were studied. The reactivity ratios are compared with those previously described for some acetoxydienes. Polyketones and copolyketones were obtained by alkaline hydrolysis of the polymers of1and7and copolymers of1a

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800108

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe activated anionic polymerization of 2‐pyrrolidone in the initial stage was studied at 30–70°C in the range of 1–60 min. Potassiumtert‐butoxide andN‐benzoyl‐2‐pyrrolidone were used as initiator and activator, respectively. It can be seen from the polymerization process that side reactions occur parallel to the fast propag

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800109

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY

摘要:

AbstractThe polymerization of styrene initiated by titanium(III) chloride/alkyl halide redox systems was studied. Among the alkyl halides examined, the highest rate of polymerization was found in the system titanium(III) chloride/carbon tetrachloride. The polymerization rate can be described by the equationRp=k·[Ti(III)]0,5·[CCl4]0,5·[St]1,0. The polymerization proceeded via a radical mechanism. The overall activation energy was estimated as 57,3 kJ/mol. It was found that titanium(III) chloride/chloroacetic acid systems, too, could initiate the polymerization of styre

ISSN:0025-116X    

DOI:10.1002/macp.1979.021800110

出版商:Hüthig&Wepf Verlag    

年代:1979

数据来源: WILEY