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  • 1985-1989  (18,910)
  • Polymer and Materials Science  (16,437)
  • Engineering General  (2,473)
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  • 201
    Electronic Resource
    Electronic Resource
    Small-angle X-ray diffraction study of the monoclinic modification of poly(3,3-dimethyloxetane) (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 613-621 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The long spacings of several samples of poly(3,3-dimethyloxetane) (PDMO) were determined by small-angle X-ray diffraction as a function of molecular weight and crystallization temperature, in the interval where only the monoclinic modification is produced. The equilibrium melting temperature and the basal interfacial free energy of the mature crystals were determined from the correlation between long spacings and melting temperatures. Finally, an estimation of the critical sizes of the nuclei was made from nucleation theory, and the results were compared with the actual sizes of the crystallites, assuming a two-phase model. Our results show that both the nuclei and the mature crystals have rather small sizes, which is attributed to the high under-coolings involved in the crystallization of PDMO.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900317
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  • 202
    Electronic Resource
    Electronic Resource
    Polymerisation durch [3+2]-cycloaddition, 2.Teil 1: cf.1. Reaktionen von hexafluoracetonazin mit substituierten diolefinen (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 623-629 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hexafluoroacetone azine reacts with esters of 1,6-heptadien-4-ol to form polymers 1 containing 4,4,8,8-tetrakis(trifluoromethyl)-1,5-diazabicyclo[3.3.0]octan-2,6-diyl groups linked with trimethylene chains with acyloxy side groups. Due to these ester functions the polymers are completely soluble in common solvents. DSC measurements proved these polymers to be partly crystalline.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900318
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  • 203
    Electronic Resource
    Electronic Resource
    Synthesis and structure of a “living” copolymer of propylene and 1,5-hexadiene (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 643-651 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A soluble V(acac)3/Al(C2H5)2Cl system was found to polymerize 1,5-hexadiene to give a living polymer in toluene at -78°C. Hydrogenation of poly(1,5-hexadiene) was conducted to determine the chain microstructure. The 13C NMR analysis of hydrogenated poly(1,5-hexadiene) indicated that the poly(1,5-hexadiene) is composed of alternating units of 1,3-cyclopentylenemethylene and 1-vinyltetramethylene. In addition, living copolymers of propylene and 1,5-hexadiene were prepared and characterized by analysis of the 1H and 13C NMR spectra. A chain propagation mechanism of living poly(1,5-hexadiene) is proposed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900320
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  • 204
    Electronic Resource
    Electronic Resource
    Polymers from multifunctional isocyanates, 3.Part 2: cf.1. Synthesis and polyaddition reactions of (liquid-crystalline) fully aromatic diisocyanatoesters (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 631-642 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The regioselective reaction of aliphatic ω-isocyanatoacyl chlorides with silyl-protected hydroxy-nucleophiles was extended to aromatic isocyanatoacyl chlorides. Starting with 3- or 4-isocyanatobenzoyl chloride and 3- or 4-trimethylsiloxyphenyl isocyanate, the four isomeric isocyanatobenzoic acid isocyanatophenyl esters were synthesized in high yields. From terephthaloyl chloride and two moles of a siloxyphenyl isocyanate or from 1,4-bis(trimethylsiloxybenzene) and two moles of an isocyanatobenzoyl chloride, diesterdiisocyanates were obtained containing 3 benzene rings. The para-substituted diisocyanates show liquid-crystalline behaviour. Polyaddition reaction with various diols led to poly(esterurethane)s with a regular sequence of urethane and ester groups. The poly(urethane)s from the para-substituted diisocyanates have very high melting points (225-350°C). Liquid crystallinity could not be proven unambiguously due to the instability of the urethane linkage at these temperatures.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900319
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  • 205
    Electronic Resource
    Electronic Resource
    Anionic polymerization of one-ended “living” strontium-polystyrene in tetrahydropyran in the presence of tetraglyme and in benzeneDedicated to Prof. Dr. P. Rempp on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 653-659 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The anionic polymerization of the strontium salt of one-ended living polystyrene (SrS2) was investigated at 20°C in tetrahydropyran (THP) in the presence of two different concentrations of added tetraglyme. Similarly to BaS2 in tetrahydrofuran (THF) and to SrS2 in THF and in pure THP, the observed pseudo-first-order rate constant of propagation, kobs, was nearly independent of the total concentration of salt, their values being 7,5.10-3 s-1 and 9 · 10-3 s-1, respectively, i. e. about 100 to 120 times higher than in pure THP. This indicates that the propagation occurs mainly via an increased but constant amount of free S- anions resulting from the two already known equilibria SrS2 ⇌ (SrS)+ + S-(K1) and 2 SrS2 ⇌ (SrS)+ + (SrS3)- (K2) and the equilibrium of glymation (SrS+) + G ⇌ G, (SrS)+ (Ki). A small not exactly determinable contribution of glymated ion-pairs and/or triple ions, whose rate constants would then probably be of the order of 18 l · mol-1 · s-1 and 80 l · mol-1 · s-1, respectively, could not be excluded. The glymation constant Ki was found to be about 3 · 106 1 · mol-1, i.e., approximately 17 times greater than for the Na+ cation. Finally, a kinetic experiment with SrS2 at 20°C in pure benzene (contaminated, however, with some remaining THP from the preparation of SrS2) indicated that propagation by ion-pairs is possible with a bimolecular apparent rate constant Kapp = 1,1 · 10-1 l · mol-1 · s-1.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900321
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  • 206
    Electronic Resource
    Electronic Resource
    Strictly alternating polyamides with stiff and flexible chain segments: Effects on thermotropic liquid crystallinity of the introduction of an ethylene unit into the mesogenic group (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1303-1308 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bipolyamides containing mesogenic groups were prepared by solution polycondensation from aromatic dicarbonyl dichlorides and novel diamines. Ortho-substitution and the aliphatic chain length of α,ω-bis(4-aminophenyl)alkylenes affected the thermal transitions of the resulting polyamides profoundly. Introduction of an ethylene unit into the stiff biphenylene segment not only reduced the isotropization temperatures, but also depressed the tendency to form liquid crystals.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900610
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  • 207
    Electronic Resource
    Electronic Resource
    A calorimetric investigation of interactions in aqueous solutions of poly(oxyethylene), 2.Part 1: cf.4. Determination of excess heat capacities and application of association theoryTo Prof. O. Wichterle on the occassion of his 75th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1345-1359 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Excess heat capacities are given as functions of composition and temperature for non-dilute aqueous solutions of poly(oxyethylene) and its oligomeric models, i. e. from the glycol monomer to tetramer and dimethyl ethers of these compounds. A theoretical model based on the concept of association equilibria was used to predict the excess heat capacities of aqueous mixtures of dimethyl ethers at 298K and 350K. Numerical values of parameters of the model were obtained by treatment of the heats of mixing reported in the first part of this study. It was sufficient to adjust two parameters of self-association of water, and for each system also the parameter characterizing hydration of ether groups in oligomers. The agreement between theory and experiment was very good for both enthalpy and heat-capacity data, with the exception of the concentration range rich in water, where the interaction scheme is probably more complicated.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900615
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  • 208
    Electronic Resource
    Electronic Resource
    Purification of thermotropic liquid-crystalline siloxane oligomer with supercritical carbon dioxide (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1407-1412 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of the purification of thermotropic liquid-crystalline siloxane oligomer with supercritical carbon dioxide were investigated. It was found that low-molar-mass contaminants, presumably the two alkene precursors, can be effectively removed at 80°C and carbon dioxide pressures up to 31,0 MPa. In support of this observation is the fact that glass transition temperature goes up as a result of purification. In addition, the selective reflection wavelength was found to increase at increasing purity level, as achieved by extraction at increasing carbon dioxide pressure.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900620
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  • 209
    Electronic Resource
    Electronic Resource
    Kinetics of polymer degradation in transient elongational flowDedicated to Prof. P. Rempp on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1389-1406 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An expression of the kinetics describing the rate of bond scission under stress is proposed and applied to the case of degradation of polymers in transient elongational flow. The new equation permits to take into account the existence of critical values, either for molecular weight or strainrate, below which no chain scission occurs. Compared with the other types of mechano-chemical degradation, depolymerization in transient elongational flow is characterized by a short residence time and an inhomogeneous flow field in which the scission rate constants change drastically with the spatial coordinates. The evolution of molecular size distribution during the degradation process has been investigated using a general polymer fragmentation scheme. The set of differential equations was solved exactly with a matrix technique. Excellent concordance between calculations and experimental results from dilute polystyrene solutions was obtained, providing the spatial distribution of the strain-rate was properly incorporated into the degradation kinetics.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900619
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  • 210
    Electronic Resource
    Electronic Resource
    Remark on the polymolecularity correction of the Burchard-Stockmayer-Fixman relationship (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1453-1455 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900625
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  • 211
    Electronic Resource
    Electronic Resource
    Water-soluble and photosensitive copolymers from methyl methacrylate and sodium 3-vinylphenylazosulfonate (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1325-1332 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of sodium 3-vinylphenylazosulfonate (4) and its copolymerization with acrylamide and methyl methacrylate (MMA) is described. Copolymers of 4/MMA containing more than 15 mol-% of 4 are water-soluble. The trans-azosulfonate is perfectly stable up to 200°C. However, it decomposes at room temperature after transformation into the cis-isomer by UV light. This irradiation reaction was used to convert completely water-soluble copolymers from 4/MMA into water-insoluble products.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900613
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  • 212
    Electronic Resource
    Electronic Resource
    Transient effects in diffusion-controlled polymer cyclizationCyclization Dynamics of Polymers 24 and paper No. 7 on Transient Effects in Diffusion Controlled Reactions.Dedicated to Paul Rempp on the occasion of his 60th birthday with best wishes and thanks for many years of scientific interaction (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1333-1343 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fluorescence decay measurements were carried out to study the kinetics of intramolecular exciplex formation in two low-molecular-weight samples of polystyrene (1) with narrow molecular weight distribution capped on one end with a pyrene moiety and on the other with an N,N-di-methylaminophenyl group. Monomer and excimer decay profiles, IM(t) and IE(t), resp., were inconsistent with the predictions of the simple two-state (Birks) model, but could be well-fitted by assuming that the diffusion-controlled rate coefficient for exciplex formation, k1(t), is time dependent. Using a Smoluchowski formulation for this rate coefficient k1(t) = a(1 + bt-1/2), we could use the a and b parameters to calculate values for the chain-end diffusion coefficient characterizing the reaction for samples of the polymers in cyclopentane and cyclohexane solutions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900614
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  • 213
    Electronic Resource
    Electronic Resource
    Electrosynthesis of poly(N-ethyl-3,6-carbazolediyl) catalyzed by a Ni(0)-based complex (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1361-1368 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-ethyl-3,6-carbazolediyl) was synthesized by electroreduction of the NiBr2/2,2′-bipyridine/3,6-dibromo-N-ethylcarbazole system in N,N-dimethylacetamide. Both gel permeation chromatography analyses of the polymer formed and electrochemical studies of the system during the course of polymerization in homogeneous phase point at a constant efficiency of the catalytic complex. The latter generates potentially active species which contain the transition metal inserted into a C—Br bond. Mechanisms of formation of the growing chains are proposed on the basis of the electrochemical behaviour of the catalytic system. Chemical doping of the polymer leads to a material the conductivity of which is in the range 10-4 〈 σ/(Ω-1 · cm-1) 〈 10-3.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900616
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  • 214
    Electronic Resource
    Electronic Resource
    Synthese und thermische eigenschaften von photosensiblen polyacrylsystemen mit zimtsäurehaltigen seitengruppen und deren verwendung in composite-membranen (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1369-1377 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of comb-like polymers containing cinnamic acid derivatives in the side chains is described. The disappearance of thermal transitions after UV-irradiation of the polymer samples was demonstrated by DSC measurements in the case of the liquid-crystalline homopolymer poly[4-propoxyphenyl 4-(6-acryloyloxyhexyloxy)cinnamate] and the side-chain crystallizable copolymers poly[(4-(6-acryloyloxyhexyloxy)cinnamic acid-co-hexadecyl acrylate)]. A significant influence of UV-irradiation on the permeation activation energy of 1-butanol through polyamide composite membrance containing a film of the photosensible comb-like polymers was observed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900617
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  • 215
    Electronic Resource
    Electronic Resource
    Crystallization behavior of block copolyarylates synthesized via two-step interfacial polycondensation (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1413-1423 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: DSC, X-ray diffraction and solid-state 13C NMR were used to investigate the crystallization properties of block copolyarylates prepared via two-step interfacial polycondensation. The block copolyarylates obtained from 1,1,2,2-tetrachloroethane solution were found to have low crystallinity. This could be explained as the influence of amorphous blocks on the crystalline blocks. When the block copolyarylates were redissolved in dichloromethane, the annealed, cast films exhibited considerably higher crystallinity. It was concluded that the crystallization behavior of block copolyarylates is very much dependent on their sample history.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900621
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  • 216
    Electronic Resource
    Electronic Resource
    Preparation and crystalline structure of random copolymers of glycine and β-alanine (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1379-1387 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of glycine and β-alanine within a range of amount-of-substance compositions from 3:1 to 1:9 were prepared by polycondensation of mixtures of the respective pentachlorophenyl ester hydrobromides. Number-average molecular weights between 2 500 and 9 000 were obtained, the lower values corresponding to those copolymers with a higher content in glycine. Sequence distributions were evaluated by means of 50,3 MHz 13C NMR spectroscopy and the crystalline structure was examined by wide-angle X-ray diffraction. Random copolymers having similar contents in glycine and β-alanine were found to crystallize in a bidimensional hexagonal lattice (a = 4,79 Å) with chains packed in a similar manner as they do in the crystalline structure of polyglycine II. On the contrary, a heterogeneous product consisting of homopolymer and random copolymer fractions results from mixtures which are enriched in one of the two amino acids. The random copolymer poly(glycine-ran-β-alanine) adopts a packing scheme similar to that found for the helical form of the alternating copolymer nylon 2/3. Chains are hexagonally arranged and interlinked by a three-dimensional network of hydrogen bonds as described for the well known model of polyglycine II, although in the present case no order along the chain axis should be expected.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900618
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  • 217
    Electronic Resource
    Electronic Resource
    Structural models for crystallographic disorder in poly(tetrafluoroethylene) (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1425-1431 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some structurally disordered models for poly(tetrafluoroethylene) were elaborated and the corresponding calculated X-ray diffraction patterns compared with experimental patterns. This and differential scanning calorimetry results suggest some differences between the virgin powder and a sintered polycrystalline plate of poly(tetrafluoroethylene). These differences may be related to the crystal phase transitions that occur in a range of temperatures close to room temperature.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900622
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  • 218
    Electronic Resource
    Electronic Resource
    Ternary and partial ternary azeotropes (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1445-1452 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A paper in 1983 of Ham postulating the non-existence of ternary azeotropes resulting from ternary copolymerization is contradicted on the basis of mathematical solutions and further experimental results from other authors. A broader view of the problem of ternary azeotropy must include the partial azeotropes, which are almost absent from recent literature, although they contain the potential for hundreds of polymers with still largely unknown physical properties. Ham has hitherto been supported by the apparent necessity of using comparatively complex mathematical equations. However, it will be shown that many of these can be reduced to simple relationships.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900624
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  • 219
    Electronic Resource
    Electronic Resource
    Acid- and base-functionalization of ethylene-propene rubbers, 3.Parts 1 and 2: cf. refs. 12 and 17, resp. Mechanical and dynamic-mechanical characterization of the elastomer networks (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1457-1470 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Influences of type and content of functional groups on the mechanical response of various functionalized (grafted) ethylene-propene rubbers (EPRs) are reported. Grafted molecules include succinic anhydride (SA), monomethyl succinate (MMS) and 2-(dimethylamino)ethylsuccinimide (DAESI). A semiquantitative correlation between the decrease of the mechanical properties at high grafting degree and degradation of the polyolefinic backbone is given. Also a study of the dynamic-mechanical properties of the functionalized rubbers is reported. A rubbery plateau is found, the strength and temperature dependence of which is a function of the type and content of the grafted molecules.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900626
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  • 220
    Electronic Resource
    Electronic Resource
    Liquid membranes with organic polyphosphates as ionic carriers (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1501-1506 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(hexylene phosphate) (1) and poly[poly(ethylene glycol)phosphate] (2) were examined as ionic carriers for concentration/separation processes, applying the liquid membrane technique. Experiments were performed with nickel and cobalt ions pertracted both from a single solution and bicomponent mixtures. 2, dissolved in 1,2-dichloroethane, was found to be an effective carrier of nickel ions. The system seems to offer efficient separation of Ni(II)/Co(II) ions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900630
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  • 221
    Electronic Resource
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    Studies of formation of bivalent metal ion complexes with poly-U (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1595-1602 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential UV spectroscopy is employed to investigate the interaction of poly-U with Mg2+, Ca2+, Mn2+ and Cu2+ ions in aqueous solution. Mg2+ and Mn2+ ions are observed to bind only to the polynucleotide phosphates, while Cu2+ and Ca2+ also interact with the poly-U bases. The most probable coordination sites are O(4) and also N(3) for Cu2+ ions. N(3) is a coordination site of Cu2+ ions in UMP and uridine. The rest of the ions do not interact with the bases of the free monomers. Unlike the non-cooperative Cu2+-UMP binding, the ion interaction (including Ca2+) with the poly-U bases is characterized by a positive cooperativity. The association constant of Ca2+ (45 1.mol-1) is 45 times lower than that of Cu2+.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900711
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  • 222
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    Synthesis of amphiphilic star-shaped and graft copolymers based on polystyrene and poly(ethylene oxide) (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1515-1522 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amphiphilic block macromonomers possessing a central unsaturation were synthesized by condensation of polystyrene half-ester of maleic acid {α-[2-(3-carboxyacryloyloxy)ethyl]-ω-sec-butylpoly[1-phenylethylene]} with poly(ethylene glycol) monoether or polystyrene-block-poly(ethylene oxide). In the radical monomer cis-trans-isomerization homopolymerization of the diblock macromonomers, four-to eight-armed amphiphilic star-shaped copolymers were obtained. Radical copolymerization of the diblock macromonomers with styrene led to graft copolymers with low degree of grafting. The triblock macromonomers proved to be unable to polymerize.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900702
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    Reactivity of a polyamine macromonomer in radical copolymerization with 2-hydroxyethyl methacrylateDedicated to Professor Dr. Paul F. Rempp on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1635-1647 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of copolymerization reactions of polyamine macromonomer 1 having controlled molecular weight with 2-hydroxyethyl methacrylate (HEMA) were examined, in order to obtain a reliable estimation of the reactivity of the macromonomer in radical copolymerization. The monomer reactivity ratio r2 (HEMA as M2) was estimated to be 0,49 by a newly developed method which is expressed by Eqs. (4) and (5). This method, however, could basically be applied only to the estimation of the r2 value. On the other hand, a novel method for the evaluation of the copolymer composition from the conversion of each monomer using gas chromatography and ultraviolet fourth-order derivative spectra enabled us to estimate r1 as well as r2. Numerical values obtained for the system macromonomer 1 (M1)/HEMA (M2) amounted to r1 = 0,16 and r2 = 0,48; r1 is much smaller than the reactivity ratio of a low-molecular-weight analogue of 1, a fact which indicates that the reactivity of the growing radical with a 1 terminal toward 1 should be remarkably smaller than in case of a low-molecular-weight analogue of 1. This may be explained by the presence of the kinetic excluded volume effect.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900715
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  • 224
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    Mesomorphism  -  structure relationships in polyesters based on twin p-oxybenzoate mesogens (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1655-1662 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three homologous series of semiflexible polyesters constituted by twin spaced p-oxybenzoyl diads were studied with respect to their mesomorphic behaviour as a function of the relative length of the two different spacers [oligo(oxyethylene) and polymethylene] connected in an alternating fashion in the repeating unit. Within each series the oligo(oxyethylene) segment was maintained constant (n = 2, 3, 4), whereas the polymethylene segment varied in steps of one methylene unit from pentamethylene to decamethylene (m = 5 to 10). Indications are gained of how the parity of both ether and hydrocarbon spacers may affect the phase diagrams of the samples. The parity of the oligo(oxyethylene) segments appears in particular very effective in maximizing the orientational correlation between the mesogenic p-oxybenzoyl diads.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900717
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  • 225
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    Enzyme-analogue built polymers, 25Part 24: cf.1.. Synthesis of macroporous copolymers from α-amino acid based vinyl compoundsDedicated to Prof. Dr. Hansjörg Sinn on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1717-1726 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The suitability of a variety of newly prepared polymerizable a-amino acid derivatives for the preparation of template-imprinted polymers was investigated. The polymerizable binding sites were attached to the α-amino acid template via azomethine, carboxylic ester or boronic ester linkages. Macroporous polymers containing these monomers were prepared. The extent to which the templates could be split off from the polymer, the degree of racemization of the a-amino acids during polymerization and cleavage as well as the degree of rebinding to the polymers were studied.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900723
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  • 226
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    Enzyme-analogue built polymers, 26Part 25: cf.1.. Enantioselective synthesis of amino acids using polymers possessing chiral cavities obtained by an imprinting procedure with template molecules (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1727-1735 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The asymmetric synthesis of a-amino acids within chiral cavities of special crosslinked polymers was investigated. Chiral cavities prossessing definite shapes and specific arrangements of the functional groups were obtained by preparation of crosslinked polymers in the presence of suitable templates. Best results with an enantiomeric excess of 36% were obtained by using a polymer which was imprinted by L-DOPA. The cavities contained a salicylaldehyde and a phenylboronic acid moiety each. L-Threonine was prepared by reaction of the polymer bound anion of a salicylideneglycine nickel complex with acetaldehyde.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900724
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  • 227
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    Cationic polymerization of bis(1-alkylvinyl)benzenes and related monomers, 1. Structure elucidation of 1,1,3-trimethyl substituted polyindaneDedicated to Prof. J. P. Kennedy on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1755-1770 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,4-Bis(1-chloro-1-methylethyl)benzene (BINIFER)/borontrichloride is known to be a very efficient initiating system for cationic polymerization of e.g. isobutene at low temperature (〈 -60°C). However, at higher temperature this system polymerizes by its own. The obtained polymers show a remarkable, high thermal stability and are soluble in common solvents. The analytical results indicate a very uniform structure consisting exclusively of 1,1,3-trimethyl indane-3,5-diyl units. Other possible structures could be excluded. A mechanism explaining the surprisingly selective polyindane formation is discussed.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900802
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  • 228
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    Cationic polymerization of bis(1-alkylvinyl)benzenes and related monomers, 2Part 1: cf.13.. Controlled syntheses of 1,1,3-trimethyl substituted polyindanesDedicated to Prof. P. Rempp on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1771-1790 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,1,3-Trimethyl substituted polyindanes were synthesized in the presence of Brønsted acids (H2SO4, CF3COOH) or Lewis acids (BCl3, AlCl3) using 1,4-diisopropenylbenzene (1), 1,4-bis(1-hydroxy-1-methylethyl)benzene (2) or 1,4-bis(1-chloro-1-methylethyl)benzene (3) as monomers. The effects of experimental conditions on yields, molar masses and polymer structure were studied in detail with respect to monomer and initiator used, their concentrations, reaction time and experimental procedure. It was shown, that polymerization temperatures above the ceiling temperature and low monomer concentrations favour the formation of indane units. However, in particular the uniformity of the polymer structure is sensitive to the experimental conditions, mainly to the initiator and to the procedure used. DSC measurements on the polymers proved the remarkable heat-resistance of polyindanes (Tdec. ≥ 450°C; Tg ≈ 210°C). The thermal properties were related to the polymer structure and were compared with those of some commercial polymers.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900803
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  • 229
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    An example of polymer reactivity affected by the presence of another polymer (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1809-1815 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The acid hydrolysis of the cellulose portion of cellulose-g-poly(vinyl acetate-co-methyl acrylate) was carried out. The effect of the synthetic polymer in the reaction medium on the reactivity of cellulose in its acid depolymerization was studied. It could be shown that this effect is the same whether the synthetic polymer is covalently linked to cellulose or not and it was found that the hydrolysis time needed to degrade the cellulosic part of the graft copolymer is strongly dependent on the composition of the reaction mixture. This work showed that only a restricted range of graft copolymer compositions can be hydrolyzed in the shortest reaction time here established (14h). In order to hydrolyze graft copolymer samples with different compositions to those of the cited range, in the same hydrolysis time of 14h, two methods are suggested: (a) elimination of an adequate portion of cellulose from the graft copolymer and (b) addition of an appropriate amount of synthetic polymer to the graft copolymer sample. The second method is not useful from the point of view of polymer characterization. A molecular description of the reaction medium on the basis of the system components is attempted.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900806
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  • 230
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    Synthesis and structure of nitro-substituted poly(phthalidylidenebiphenyl-4,4′-ylene)s (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1837-1842 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nitro-substituted derivatives of poly(phthalidylidenebiphenyl-4,4′-ylene) (l), containing a controlled amount of nitro groups within 0,3 and 3,0 per mol of repeating unit, were prepared by nitrations under various conditions. The nitration was carried out either in nitric acid or by potassium nitrate and nitric acid in sulfuric acid solution. 13C NMR spectroscopy was used to study the structure of the resulting nitroderivatives. The trinitroderivative was found to contain the nitro groups in position 6 of the phthalide moiety and in positions 2 and 2′ of the biphenylylene unit. At lower degrees of nitration, some di-, tri- as well as unsubstituted units are present in the polymer.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900809
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  • 231
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    Synthesis, polymerization and copolymerization of a new organotin monomer. Application of a copolymer as catalyst for reductive dehalogenation of alkyl halides (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1827-1836 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new organotin monomer, N-[3-(tributylstannyl)propyl]methacrylamide (5) was synthesized in 49% yield by hydrostannylation of acrylonitrile with tributyltin hydride and subsequent reduction of the resulting 3-tributylstannylpropionitrile (3) with lithium aluminium hydride into 3-tributylstannylpropylamine (4) which reacted with methacryloyl chloride to afford 5. Polymerization of 5 and copolymerization of 5 with styrene gave homopolymer 6 and copolymer 7, respectively. In a model study on the stability toward solvolysis, N-(3-tributylstannylpropyl)propionamide (8) showed no reactivity, whereas the corresponding ester derivative, 3-tributylstannylpropyl propionate (9), easily reacted with ethanol to release the tin moiety. Monobromostannyl derivative 10, formed by the reaction of 7 with bromine, showed the catalytic activity in the reductive debromonation of dodecyl bromide with sodium borohydride under photoirradiation conditions at room temperature.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900808
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  • 232
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    Synthesis, characterization and polymerization of new epoxy compounds containing azomethine linkages (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1867-1879 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New epoxy compounds bearing azomethine linkages were synthesized and characterized. A series of epoxy derivatives of bis(azomethine)s (2a - d) was synthesized by reacting an aromatic diamine with 4-hydroxybenzaldehyde in a 1:2 mole ratio to afford the corresponding bis(azomethine)s (1a - d), and subsequent reaction with excess 1-chloro-2,3-epoxypropane in presence of a quarternary ammonium bromide as catalyst. In addition, epoxy compounds 4a, b and 5b were synthesized by reacting 1,4-benzenedicarbaldehyde with 4-aminophenol, 4-aminobenzoic acid or 5-aminoisophthalic acid in a 1:2 mole ratio and then with 1-chloro-2,3-epoxypropane. The epoxy compounds were characterized by elemental analyses as well as by IR and 1H NMR spectroscopy. All epoxy compounds were thermally polymerized in the presence of 4,4′-sulfonyl dianiline (6). The polymerization was investigated by DTA. The thermal stabilities of the resulting polymers were evaluated by dynamic TG and isothermal gravimetric analysis (IGA). The polymers derived from diepoxy compounds are stable in nitrogen up to 293-340°C and afford an anaerobic char yield of 43-62% at 800°C.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900812
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  • 233
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    Polymers from multifunctional isocyanates, 4Part 3: cf.8.. Synthesis of alkylene(or arylene)bis(ω-isocyanatocarboxamide)s and polyaddition to sequential poly(diamidodiurethane)s and poly(diamidodiurea)sDedicated to Professor Ernst Grigat, Leverkusen, on the occasion of his 60th birthday with best wishes (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1919-1930 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkylene- and arylenebis(ω-isocyanatodicarboxamide)s were obtained in high yields by regioselective reaction of isocyanatoacyl chlorides with silyl protected diamines (1,2-ethanediamine, 1,6-hexanediamine, piperazine, p- and m-phenylenediamine). 3-Isocyanatopropanamides undergo cyclization through intramolecular attack of the amide nitrogen by the isocyanate group to form six-membered acylureas (5,6-dihydro-(1 H, 3 H)-2,4-pyrimidinediones), which do not react further with amines or alcohols. Poly(diamidodiurethane)s and poly(diamidodiurea)s were made from bis(isocyanatobutanamide)s and bis(isocyanatohexanamide)s by polyaddition with 1,4-butanediol or diamines. The polymers have a regular sequence of two amido and two urethane (urea) groups; they are crystalline materials. Starting from a given diisocyanatodicarboxamide the urea melts about 40 to 60°C higher than the urethane. The poly(urethane)s from piperazine-based diisocyanatodicarboxamides have rather low melting points due to the missing possibility of the amide group to act as hydrogen bond donor. Thermogravimetric results show higher thermostability for the poly(diamidodiurea)s than for the corresponding poly(diamidodiurethane)s and increasing thermostability with increasing length of the isocyanatoalkanamide applied.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900816
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    13C Nuclear magnetic resonance characterization of poly(propylene) prepared with homogeneous catalysts (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1931-1943 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The minor resonances in the 13C NMR spectrum of poly(propylene) prepared with soluble Group 4 metallocene/methylalumoxane catalysts are fully characterized. The 13C shifts for regioirregular sequences, chain-end structures, and 1,3-propylene adduct are obtained for both isotactic and atactic components. In both components the dominating mechanism is 1,2-insertion, with much lower amounts of 2,1-insertion and 1,3-insertion depending on the catalysts used. The isotactic component is stereoregular in all insertion modes. In the atactic components random stereosequences are observed. The regiostructures suggest that the propagation step is catalyticsite controlled even for the atactic component.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900817
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  • 235
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    Kinetic effect of radiation intensity and thermal after-treatment in the photopolymerization of diallyl oxydiethylene dicarbonate (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1945-1952 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of radiation intensity (from 1,08 · 10-7 to 2,48 · 10-4 einstein.s-1 · 1-1) on the photopolymerization of diallyl oxydiethylene dicarbonate was investigated systematically not only in the initial stages of reaction, but also at high monomer conversion (x), in order to detect possible variations in the polymerization mechanism. In some of the runs irradiation was stopped at x = 0,55-0,65 and thermal after-treatments were carried out both in the presence and absence of air by following kinetically x-values during the self-decelerating cross-linking. To rationalize experimental data a model is proposed which assumes two basically different mechanisms occurring simultaneously (bimolecular termination and radical trapping), but with different “weights” as a function of time. Long living radicals produced by irradiation continue to react in the dark. The rate of this reaction, which is enhanced in the presence of oxygen, is fitted by a relaxation model that considers double bonds, particularly of pendant groups, as traps, with increasing lifetimes, able to transfer to radical sites. The role of oxygen is also discussed.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900818
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    Synthesis and characterization of copolymers from acrylamide and methacrylamide carrying peptide side chainsThe present work is a part of Doctorate Thesis of J. Boulahia presented at the Université Pierre et Marie Curie, Paris 1988. (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1975-1986 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Benzylacrylamide (1) and N-(3-aminopropyl)methacrylamide hydrochloride (2) were copolymerized to give poly[N-benzylacrylamide-co-N-(3-aminopropyl)methacrylamide hydrochloride] (3). The reactivity ratios r1 and r2 were found to be r1 = 0,87 and r2 = 0,66 in which r1r2 〈 1 indicate a statistical copolymer composition. Dehydrochlorination of the copolymer liberated primary amino groups to which peptide chains were grafted by reaction with L-alanine-NCA. The solubility of the resulting graft copolymers (6) in trifluoroacetic acid allowed the characterization of the products both by NMR and polarimetry. These methods and IR spectroscopy showed that the primary amino groups have only partially participated in initiating the NCA polymerization. The length of grafted peptide chains was found to be always higher than the one calculated from the ratio [NCA]/[NH2].
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900821
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    Poly(alkylene phosphate)s by polycondensation of phosphonic diamides with diols (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1903-1917 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycondensation of diols with phosphonic bis(dialkylamide)s leads to high-molecular-weight polyphosphites (M̄n up to 4 · 104). Model reactions of 1-butanol, 2-butanol and phenol with phosphonic bis(diethylamide) (1) were studied and it was established, that these reactions exhibit characteristic induction periods. Linearization of the kinetic curves after addition of amines prior to reaction enabled us to postulate the mechanism of esterification, involving activation of 1 by hydrogen-bonding to amines. However, the major side reaction lowering the degree of polymerization was found to be dealkylation of the formed ester units by added and/or evolved amine. Therefore, in order to increase the rate of polycondensation and to prevent the formed polymer chain from breaking down by dealkylation, the process was conducted at increased temperature (90°C) in a nonsolvent for the polymer of higher molecular weight. Thus, the polymer separates from the major solution and becomes less prone to dealkylation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900815
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    Polymerization by [3 + 2] cycloaddition, 3Part 2: cf.4.. Polyimides (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1953-1965 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between hexafluoroacetone azine and bis(bicyclo[2.2.1]hept-5-en-2,3-dicarboximide)s (5 and 6) (dinadimides) (mole ratio 1:1) yields polymers with number-average molar masses between M̄n = 1700 and M̄n = 5700 depending on the reactants. The possible isomeric structures of the polymers are discussed in detail. From steric considerations which are supported by 13C and 19F NMR spectral data the number of realized isomers is reduced from sixteen to only three (12, 13 and 14). In contrast to these results, hexafluoroacetone azine and dimaleimides do not react to form polymers. This is explained on the basis of a spontaneous rearrangement of the primarily formed 1:1 adduct to 1 H-pyrazolines.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900819
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    Polymeric prodrugs, 6Part 5: cf. M. Azori, J. Pató, E. Csákvári, F. Tüdős, Makromol. Chem. 187, 2073 (1986).. Synthesis and examination of 6-purinethiol bound to poly(1-vinyl-2-pyrrolidone-co-maleic acid)Part of the results was included in a poster, presented at the 31st IUPAC Macromolecular Symposium, Merseburg (1987). (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1967-1974 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A low-molecular-weight disulfide derivative of the antileukemic agent 6-purinethiol (2) was used for coupling with a macromolecular carrier, poly(1-vinyl-2-pyrrolidone-co-maleic acid) via spacer groups. The in vitro hydrolytic stabilities of the polymeric prodrugs were examined at pH 7,2 and 8,8. An enhanced cleavage of the disulfide bridge yielding 6-purinethiol was observed. Enzymatic hydrolysis of the prodrug containing an enzyme-sensitive spacer was also done in the presence of elastase.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900820
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    Preparation of ABCBA-type block copolymers by use of macro-initiators containing peroxy and azo groups (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1987-1996 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some new macroinitiators (5) containing azo and peroxy groups were synthesized by transformation of esters of poly(ethylene glycol) (1) (PEG) of different molecular weight with hydroxyl end groups and an azo group in the middle into the corresponding polymers with tert-butylperoxycarbonyl end groups by reaction with terephthaloyl chloride and subsequently with tert-butyl hydroporoxide. Decomposition in the presence of styrene at 60°C or with 3,6,9-triazaun-decane-1,11-diamine in presence of methyl methacrylate gave the corresponding ABA block copolymer 6 and the ABBA block copolymer 7, respectively. Both block copolymers were used as polymeric initiators. The ABCBA block copolymer 8 was synthesized from 6 and methyl methacrylate or from 7 and styrene by thermally induced polymerization at 80°C. The resulting block copolymers were separated from the homopolymers by selective solvent extraction and characterized by spectroscopic and fractional precipitation methods.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900822
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  • 241
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    Preparation and characterization of a series of poly[oxy-1-(ω-bromoalkyl)ethylene]sThis paper is dedicated to Professor Paul Rempp on the occasion of his sixtieth birthday, with best personal regards (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2019-2030 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Bromoethyloxirane (2b), 3-bromopropyloxirane (2c), and 4-bromobutyloxirane (2d), were prepared by epoxidation of the corresponding bromoalkenes. Treatment of the oxiranes with a triethylaluminium/acetylacetone/water mixture afforded the polyethers 3b-d in good yield as tacky, white elastomers. Substitution of bromide by benzoate ion established essentially equal reactivities for the three polymers; each was substantially more reactive than any of the halogenated polyether elastomers available heretofore.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900902
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    Autoxidation von dienen mit polyfulven-strukturelementenKurzmitteilung: vgl.1. (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2983-2994 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactivity of dienes 1-8, trienes 9, 10 and polymer 11 towards autoxidation in benzene solution was studied systematically. Incorporation of oxygen into 1-8 and 10 was found to be characterized by an induction period, a nearly linear oxygen uptake during several days and a limit of 1 mol oxygen per diene or triene unit. 9 takes up two mole of oxygen, and solutions of 11 show no linear oxygen uptake. The rates of oxygen uptake of olefins 1-11 were measured using standardized reaction conditions. The resulting autoxidation rates are strongly influenced by the number of methyl groups at the diene unit as well as by the ring size. 13C NMR and GPC measurements of the isolated oxydation products from 1,4,5,6,7 and 10 show that linear chains of oligomeric polyperoxides are formed, which can be considered to be alternating copolymers of oxygen and the olefin. O2-incorporation predominantly takes place in 1,4-position of dienes 1,4,5,6,7 and in 1,6-position of triene 10. The formation of low-molecular-weight endoperoxides was not observed. A plausible reaction mechanism involves diradical intermediates of type 20 and 21-23.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901129
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    Copolymerizations of styrene with magnesium, calcium, strontium and barium acrylates in dimethyl sulfoxide (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2063-2069 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Radical copolymerizations of styrene with acrylates of magnesium, calcium, strontium and barium were carried out in dimethyl sulfoxide. The monomer reactivity ratios were determined by the Yezrielev-Brokhina-Roskin and the Kelen-Tüdős methods. In all cases the monomer reactivity ratio for styrene exceeded one and those for the salts were less than one. The Q-values of the Alfrey-Price scheme for the metal acrylates were within the range 0,1 - 0,2. For the values of the polarity parameter e the following sequence was found: eMgA2 〈 eCaA2 〈 eSrA2 〈 eBaA2 and the tendency for alternation in copolymerizations increased in the same order. The results indicate that the course of copolymerizations under study is predominantly affected by polarization of the vinyl groups in the salts.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900906
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    Reductive transformations, 12Part 11: G. Krummel, K. Müllen, Tetrahedron Lett. 29, 2809 (1988).. Poly(9,10-anthrylenetrimethylene) as an efficient electron acceptor (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2071-2078 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(9,10-dihydroanthrylenetrimethylene) (2) comprises a novel chain-type structure in which 9,10-dihydroanthracene units are linked by flexible spacer groups. Upon dehydrogenation with sulfur at elevated temperature, polymer 2 is converted into the corresponding polyanthrylene system 3. NMR- and UV-spectroscopic data provide firm evidence for the dehydrogenation process. The polymer 3 was subjected to reduction with active lithium, and the resulting polyanions were characterized by NMR spectroscopy and by quenching experiments. It appears that each anthracene unit of the chain can be charged with two electrons.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900907
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  • 245
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    Liquid-crystalline polyurethanes, 6.Part 5: cf.10. Amphiphilic polyurethanes containing long alkyl chains in the side chains and amino or quaternary ammonium groups in the main chains (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3067-3072 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amphiphilic polyurethanes 5a-c, 6a-c, 10a-c and 11a-c containing hydrophilic amino or quaternary ammonium groups in the main chain, and hydrophobic ocatadecyl or docosyl groups in the side chain, were synthesized by polycondensation of 2,2′-octadecyliminodiethanol (3a), 2,2′-docosyliminodiethanol (3b), bis(2-hydroxyethyl)methyloctadecylammonium bromide (8) and bis(2-hydroxyethyl)docosylmethylammonium bromide (9) with a diisocyanate such a hexamethylene diisocyanate (4a), 2,4-toluylene diisocyanate (4b) and 4,4′-methylenediphenyl isocyanate (4c). Some of them show a thermotropic liquid-crystalline state, as determined by DSC and polarizing microscopy.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901204
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  • 246
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    Anionic polymerization of butyl cyanoacrylate by tetrabutylammonium salts, 2.Part 1: cf.6 Propagation rate constants (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3095-3103 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anionic polymerizations of butyl cyanoacrylate were initiated in tetrahydrofuran (plus a few experiments in 1,2-dimethoxyethane) by the salts tetrabutylammonium hydroxide, bromide, acetate and three substituted acetates. The hydroxide gives near-ideal ‘living polymerization’ kinetics, with kp close to 106l·mol-1. s-1 at 20°C. The kinetics of the reactions initiated by the acetates and bromide are analysed by the slow-initiation-no-termination theory, using values of the initiation rate constants evaluated in Part 1. The kp values derived are in the same range as those from the OH-initiated reactions and those of the zwitterionic polymerizations initiated with covalent bases, i.e., tertiary phosphines and amines. A ca. 4-fold variation of kp with concentration of active species is given a speculative analysis in terms of dissociation from paired to free ions, yielding tentative estimates for kp± ≈ 105 and kp- ≈ 107l·mol-1·s-1 in THF at 20°C. Molecular weights were all high Mn ≈ 106, with Mw/Mn ≈ 2.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901207
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    Graft polymerization onto a polystyrene resin containing thermolabile azo groups and the effect of the grafted resin on asymmetric reduction of oxime ethers (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3127-3136 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Graft polymerization of various vinyl monomers onto a polystyrene resin (6) containing azo groups having the ability to initiate the radical polymerization was performed. The graft efficiency of vinyl monomers onto 6 increases with time of polymerization and achieves more than 85%. The swelling of 6 affects remarkably the graft efficiency. Scanning electron microscopy (SEM) shows that considerable amounts of graft copolymers are located at the surface of 6. The graft copolymer of chloromethylstyrene onto 6 was treated with (S)-(-)-2-amino-3-(p-hydroxyphenyl)-1,1-diphenyl-1-propanol to yield a resin (9) carrying chiral amino alcohol functions. Resin 9/borane was used for asymmetric reductions of acetophenone oxime O-methyl and O-benzyl ethers, leading to 1-phenylethylamine with 43% and 46% enantiomeric excess (e.e.), respectively. These values are higher than those obtained with the generally used polystyrene resin, suggesting that the enantioselectivity can be improved by modification of the support resin.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901210
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    Stabilization of polystyrene/poly(methyl methacrylate) blends by in situ compatibilization with graft copolymers (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3153-3166 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of styrene and ortho-vinylbenzaldehyde (o-VBA) are useful precursors to multicomponent polymer systems. Graft copolymers of poly(styrene-stat-o-VBA) can be produced by free-radical chain transfer to methyl methacrylate monomer to yield materials that display some potential as interfacial agents with binary blends of polystyrene and poly(methyl methacrylate). Significant improvements in ultimate tensile strengths and energy to rupture values have been witnessed for polystyrene/poly(methyl methacrylate) mixtures that contain various levels of the graft component. Scanning electron microscopy of representative fracture surfaces demonstrate a decrease in the particle size of the dispersed phase; it is suggested that this morphological factor contributes to the superior mechanical properties of these composites. In this regard, both the isolated and the crude graft copolymers are able to compatibilize, and thereby enhance, the material properties of polystyrene/poly(methyl methacrylate) blends.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901213
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    Orientational behaviour of polymer blends containing a liquid-crystalline component (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3185-3194 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper describes the orientational behaviour of polymer blends containing a side-group liquid-crystalline polymer (LCP). The macroscopic orientation of the LC phase in these blends, and the possibility to freeze in this state are of technical interest. The orientation of LCP-containing blends through mechanical forces depends on a variety of structural, thermal, energetical and also morphological properties, which are strongly dependent on the kinetical and thermal history. This report describes the optical- and scanning electron microscopy (SEM), X-ray diffraction and interfacial tension studies of the liquid-crystalline polyacrylate 1a and the poly(methacrylate) 1b in poly(methyl methacrylate) (PMMA) and polycarbonate matrices. 1a droplets in thermoplastic matrices can be oriented macroscopically during fibre-drawing, but, as a result of higher interfacial tension between the components, 1b-containing blends can not.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901216
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    On the relationship between room-temperature conductivity and morphology of polyacetylene (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3217-3229 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several sets of samples of elongated Naarmann-type polyacetylene were investigated by conductivity measurements and scanning electron microscopy. For the latter investigations, a special kind of sample preparation was developed to ensure authentic information about the internal morphology of polyacetylene. We found two different types of fibrillar morphologies, one exhibiting thick bundels or strings along the elongation direction and an intermediate tissue of nonaligned fibrils, the other showing only individual, well aligned fibrils. The first type of structure has low conductivities after oxidation with iodine, whereas the second one tends to have significantly higher values. A comparison of the geometrical and electrical anisotropy shows that charge transport takes place mainly in highly aligned regions, the conductivity being a weighted average over all possible conducting paths.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901219
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    Synthèse de polysiloxanes acyloxyméthylés par réaction des acides acétique, benzoïque et méthacrylique, en présence de triéthylamine, sur des polysiloxanes chlorométhylés, 2.Partie 1: cf.1. Etude de la réaction sur trisiloxane et tétrasiloxane modèles (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3241-3250 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of acetic, benzoic and methacrylic acids with 3-chloromethylheptamethyltrisiloxane and 3,5-bis(chloromethyl)octamethyltetrasiloxane in toluene in the presence of triethylamine was studied. Beside the expected transformation of oxy(chloromethyl)methylsilanediyle (A) units into oxy(acyloxymethyl)methylsilanediyle (C) units, redistributions of A, C and trimethylsilyl/oxytrimethylsilyl (M) were observed. The conversion versus time curves of distribution of the former oligomers (mole fractions of trisiloxanes: F1 = mM-X-M = mM-A-M + mM-C-M and tetrasiloxanes: F2 = mM-X-X-M = mM-A-A-M + mM-A-C-M + mM-C-C-M) were followed. The reaction rates were not only controlled by the acid used but also by the starting oligosiloxane (trisiloxane or tetrasiloxane). The distributions of the homogeneous and heterogeneous oligomers seem to result from controlled combinations of A, C and M according to orientations of cleavages and to relative affinities of RCOOH/NEt3 towards various siloxanes. For the total conversions the mole fractions F1 and F2 fit with those calculated by a law based on a hazard combination of C and M. This result may be explained by the compensation of electronic and steric factors.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901221
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  • 252
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    Rigid rods with flexible side chains  -  A route to molecular reinforcement? (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3295-3316 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Liquid-crystalline main-chain polyesters with polystyrene side chains of different length and number per main chain were synthesized using aromatic hydroxyfunctional polystyrene (PS) macromonomers, terephthalic acid derivatives and tert-butylhydroquinone as co-diol. The molecular weight of the polystyrene side chain was varied in the range from 1000 to 20000. The influence of this novel type of substituent on the solubility, thermal behaviour and miscibility with PS as a flexible matrix polymer is discussed. The properties of the new compounds are compared to those of the respective homopolyester. The graft copolyesters are, depending on the characteristics of the polymeric substituent, soluble in common organic solvents and their thermal transition points are lowered compared to the homopolyester. Compared to blends of the homopolyester, the improvement of miscibility of the polymer-substituted rigid rods with PS as an example for a flexible matrix polymer can be valued as a step to molecular reinforcement.
    Additional Material: 21 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901226
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    Photo-oxydation de résines phénoliques (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2311-2324 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analytical and kinetic aspects of photo-oxidation in the solid state of phenolic resins (phenolformaldehyde polycondensates) are described. On the basis of Fourier-transform infrared analysis it should be noted that resins contain, in addition to methylene-bridged structures, ether linkages (—CH2—O—CH2) between aromatic structures. Photochemistry of the phenolic resins involves two primary processes. Photolysis of the phenolic groups leads to the formation of quinone methide structures and photo-oxidation of the dimethylene ether linkages to hydroperoxy groups which are photo- and thermo-unstable. These hydroperoxy groups are converted into ester and formate groups.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900932
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    Investigations on the decomposition of lateral perester groups in maleic anhydride copolymers (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2325-2328 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of maleic anhydride (MAn) copolymers with tert-butyl hydroperoxide results in copolymers with lateral perester and carboxyl groups. As these copolymers are of interest as initiators of free-radical polymerization, their decomposition mechanism and their decomposition constants were investigated. Surprisingly, a dependence of the decomposition constants on the comonomer of MAn was found. The interaction of the carboxyl group with the perester group is discussed as an essential reason of the comonomer influence.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900933
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    Fixation of pharmacologically active amines on polyphosphonates, 2Part 1: cf. 6. Application to benzocaïne and phenethylamine (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2339-2345 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Atherton-Todd reaction was used for the preparation of a new class of hydrophilic drug carriers with an organic polyphosphate main chain. Chemical modification of poly(propy1ene phosphonate) (3) and poly(3,6,9-trioxaundecamethylene phosphonate) (4) with benzocaine (ethyl 4-aminobenzoate) (1) and phenethylamine (2) led in one step to polyphosphoramidates 7a, b and 8a, b bearing pharmacologically active amines in the side chain with modification yields of 60 to 75%.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900935
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    Behaviour of homogenous catalysts for propene polymerization in methylene chloride (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2357-2361 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Propene polymerizations in the presence of the homogeneous catalytic system Cp2Ti(C6H5)2-Al(CH3)3-Al(CH3)2F were performed at different monomer concentrations in CH2Cl2. A relevant increase of the polymerization rate is observed, resulting in polymer productivities higher than those obtained with methylaluminoxane cocatalyst in toluene. The dependence of the monomer conversion on the propene concentration seems to support the hypothesis of a cationic catalytic site. Similar results were obtained with a homogeneous catalyst based on a chiral zirconocene and Al(CH3)3-Al(CH3)2F.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901001
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    Synthèse de composé photoréticulables, 9.Partie 8: cf. B. Boutevin, Y. Piétrasanta, J. P. Parisi, Makromol. Chem. 188, 1621 (1987). Modification du polybutadiène carboxytéléchélique par des monomères acryliques (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2363-2372 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The addition of mercaptoacetic acid upon radical initiation onto carboxytelechelic polybutadienes (1) which have an average mass M̄n = 4400 gives polyacids having about twelve carboxylic groups. The reaction is followed by 13C NMR, 1H NMR and by GPC. The thiol disappears according to a first order law. Besides, the value of the modification rate obtained from acido-basic titration confirms that obtained from NMR. In a second step, 2,3-epoxypropyl methacrylate is added to the acid groups to obtain an insaturated and carboxylated polydienic oligomer 5. An application of these oligomers processed with a reactive diluter shows their high cross-linking ability under UV irradiation and confirms the improvement of the flexibility properties compared to those of traditional insaturated oligomers.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901002
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    Synthesis and properties of macromonomers carrying phosphatidylcholine analogous and azobenzene moieties (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2381-2390 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Macromonomers 6a, b, carrying phosphatidylcholine analogous and azobenzene moieties as a photoresponsive pigment, were prepared from the reaction of 2-oxo-1,3,2λ5-dioxaphospholane derivatives 2 and poly[2-dimethylaminoethyl methacrylate] macromonomer 5. 6b shows a nematic phase. The mesogenic group is connected with the chromophore via a flexible spacer group. Phase transition temperatures were determined by measurement of the rapid change in conductivity of the solutions of the amphiphiles with the temperature. From the result of photoreversible cis-trans isomerization it can be concluded that 6b can possibly be used as a photoresponsive material of a membrane.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901004
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    Synthesis of biodegradable poly(L-lactic acid-co-D,L-mandelic acid) with relatively low molecular weight (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2407-2415 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A homopolymer of L-lactic acid (LA), which was synthesized by direct polycondensation in the absence of a catalyst at 200°C, is crystalline, in contrast to the homopolymer of D,L-mandelic acid (MA) which is amorphous. Poly(LA-co-MA), obtained under the above conditions, is amorphous over a wide range of composition from 15 to 100 mol-% of monomeric units of MA. The in vitro degradation mechanism of these homopolymers shows a parabola-type degradation pattern for poly(LA) and no degradation throughout an experimental period of 15 weeks for poly(MA). In poly(LA-co-MA) the degradation mechanism leads to a typical S-type degradation pattern, which may be divided into two processes, initial swelling at the surface of the matrix without degradation (induction period), followed by the erosion of oligomers produced by degradation of the main chain in the swollen state.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901007
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    TiCl4/MgH2-supported Ziegler-type catalyst system, 1. Determination of active centresDedicated to Prof. Dr. Hansjörg Sinn on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2427-2436 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Determination of active centres using TiCl4/MgH2-supported catalyst system in ethylene polymerization is reported. A radio-tagging technique, whereby 14CO is used to label the polymerization active centres, is employed. Optimization of the 14CO/Ti ratio showed that the polymer radioactivity remained constant after a 14CO/Ti ratio of about 8 was attained. At the optimal 14CO/Ti ratio, it is found that up to 14% of the titanium on the catalyst surface are active in polymerizations at 40°C, 10 min reaction time, and 30 min contact time period of 14CO with the polymerization medium. Moreover, the value of the corresponding propagation rate constant, Kp, was found to be about 230 dm3/(mol·s).
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901009
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    Conformational study of sodium pectate from circular dichroism induced in dyes (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2501-2509 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sodium pectate (1c) induces strong circular dichroism (CD) in 3,7-bis(dimethylamino)-1,9-dimethylphenothiazinium chloride (2b) and weak CD in 1-ethyl-2-[3-(1-ethyl-2-(1H)-quinolylidene)propen-2-yl]quinolinium chloride (pinacyanol chloride) (4) and 2,8-bis(dimethylamino)-acridinium chloride (Acridine Orange) (3), and no CD in 3,7-bis(dimethylamino)phenothiazinium chloride (Methylene Blue) (2a), besides inducing strong metachromasia in all these dyes. The signs of the CD spectra induced in the dyes 2b, 3 and 4 by pectate are opposite to those induced by hyaluronate (HYAT). Pectate is, thus, inferred to have a 31 helical conformation (like HYAT) with the sense of helicity opposite to that of HYAT. Such an inference is also in harmony with the reported 3-fold screw axis of pectate fibre from X-ray crystallography. Since left-handed extended helical polyglutamate induces negative biphasic CD, 1c, depicting positive biphasic CD with the same dye, may be assigned by analogy to have a right-handed helicity.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901016
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  • 262
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    Rheo-optical fourier-transform infrared spectroscopy of polymers, 15.Part 14: H. W. Siesler, Ber. Bunsenges. Phys. Chem. 92, 641 (1988). Orientational and modificational changes during uniaxial elongation of high-, low- and linear low-density polyethylenes (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2653-2663 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transient structural changes of high-, low- and linear low-density polyethylenes were studied by simultaneous mechanical and Fourier-transform infrared (FTIR) spectroscopic measurements. The rheo-optical FTIR data provide a detailed picture of the progress and extent of crystal-axis orientation and orthorhombic-to-monoclinic phase transition during elongation up to 400% strain. Apart from a higher degree of orientation as a consequence of the mechanical treatment, high-density polyethylene may be differentiated from the low-density types by running through a maximum in the content of monoclinic phase upon neck formation. With reference to the investigated structural changes, the linear low-density polyethylenes generally exhibit a behaviour intermediate to the high-density and low-density types.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901029
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    Unvernetzte epoxid-amin-additionspolymere, 2726. Mitteilung: cf.1.. Hybridnetzwerke  -  Möglichkeiten der carbonsäureanhydridmodifizierung und nachvernetzung von epoxid-amin-prepolymeren (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2673-2681 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of cyclic dicarboxylic anhydrides (3) with prepolymers 2 (from aniline and 2,2-bis[4-(2,3-epoxypropoxy)phenyl]propane (1)) results in new modified prepolymers 4-6 containing carboxylic groups and reactive glycidyl end groups. The structure of 4-6 was determined by IR, 1H NMR, 13C NMR spectroscopy, elemental analyses and M̄n (by v. p.o.) values. By simple heating to 100-140°C prepolymers 4-6 were crosslinked to hybrid networks (7). Their structure was studied by IR and solid-state 13C NMR spectroscopy.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901101
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  • 264
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    New initiators for group transfer polymerization. Triphenylphosphonium-containing ketene silyl acetals (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3061-3066 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New initiators for group transfer polymerization (GTP), triphenylphosphonium-containing ketene silyl acetals, were synthesized by addition of triphenylphosphine and chlorotrimethylsilane to methyl acrylate or methyl methacrylate, respectively, giving 3-methyoxy-3-trimethylsiloxy-2-propenyltriphenylphosphonium chloride (4a) and its 2-methyl substituted derivative (4b), together with their corresponding oligomers (8). These phosphonium salts initiate GTP of ethyl acrylate using zinc halides as catalysts. The resulting polymers, containing a terminal triphenylphosphonium group, show a small polydispersity. In the presence of zinc halides, triphenylphosphine and chlorotrimethylsilane can be used directly to initiate GTP of acrylates and methacrylates. In this case triphenylphosphonium terminated polymers with a larger polydispersity are obtained.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901203
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  • 265
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    Synthèse de polystyrènes chlorométhylés renfermant des radicaux tétrathiafulvalénylphénoxyméthyles (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2759-2771 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to study the influence of the nature of the moiety bearing a tetrathiafulvalenyl group in the polymers upon the microlithographic properties of resists, poly(p-chloromethylstyrene)s and poly(styrene-co-p-chloromethylstyrene)s containing the 4-tetrathiafulvalenylphenoxymethyl group with a variety of controlled molecular weights and molecular weight distributions were studied. The copolymers were all prepared by reaction of poly(4-vinylbenzyl chloride) with potassium 4-tetrathiafulvalenylphenolate (3). Without exception, the resulting poly[p-chloromethylstyrene-co-p-(tetrathiafulvalenylphenoxymethyl)styrene]s are highly insoluble. However, by reaction of potassium 4-tetrathiafulvalenylphenolate with poly(styrene-co-p-chloromethylstyrene) soluble copolymers could be prepared.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901109
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    Synthesis of polysulfone-block-polysiloxane copolymers, 5Part 4: cf. ref. 1.. A model study on the hydrosilylation side-reactions (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2789-2803 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: All the side-reactions of a hydrosilylating model system (1-allyloxy-3-phenoxy-2-propanol/. . .-Si(CH3)2H in the presence of hexachloroplatinic acid (CPA); R = [CPA]/[SiH] 〉 10-4) are identified by 13C and 1H NMR. In such conditions the vinyl ether isomers and the residual silanes, formed when R 〈 10-4, are changed into several new species. The most important side-reaction consists in a silane-alcohol condensation (secondary alcohol of the model and, to a much lower extent, tertiary alcohol(tert-butyl alcohol) used as solvent of CPA), which leads to silyloxygrafted moieities. Hydrogen formed in this condensation can partially saturate the vinyl ether isomers the remaining fraction of which is cyclized into a 2-ethyl-1,3-dioxolane derivative. All the side-reactions observed in the case of the model system take place when α,β-diallyloligosulfones are polycondensated with α-dimethylsilyl-ω-hydrooligosiloxanes.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901111
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    Analysis of fluorinated polymers: Several approaches by wide-line nuclear magnetic resonance (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 2815-2819 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two different ways of analyzing the composition of insoluble, partly hydrogenated, partly fluorinated copolymers by NMR are described. The first relies on a quantitative comparison of 1H and 19F free induction decays, as observed in the solid state, with those of reference samples. The second relies on medium resolution spectra which can be achieved, thanks to the large scale of 19F chemical shifts, on softening of the samples at high temperature. A special probe working up to 400°C was built for this purpose. The two methods are in good agreement in the case of vinylidene fluoride (VF2)/tetrafluoroethylene (VF4) copolymers, leading to a determination of the rectivity ratios; the special usefulness of the second method is illustrated by the identification of a third comonomer in VF2/VF4 terpolymers.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901113
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    In-situ photopolymerization of oriented liquid-crystalline acrylates, 4.Part 3, cf.4. Influence of a lateral methyl substituent on monomer and oriented polymer network properties of a mesogenic diacrylate (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3201-3215 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mesomorphism and the molecular orientation of 1,4-phenylene bis{4-(6-(acryloyloxy)hexyloxy)benzoate} (1) and its derivative with a methyl-substituent in the central phenylene group (2) are studied. The methyl group affects the transition temperatures and the thermodynamic parameters, but not the order parameter of the monomers. The photoinitiated polymerization of the diacrylate monomers in their uniaxially oriented state leads to highly oriented and densely crosslinked polymer networks. The order parameter of these networks depends on the polymerization temperature, but becomes nearly temperature-independent after polymerization. The presence of the methyl group leads to a significant lower degree of order in the polymeric state. In addition, data are presented on the monomeric viscosity of 2 and on the tensile moduli, glass transitions and refractive indices of the oriented polymer networks. In order to extend the mesomorphous temperature range, mixtures of 1 and 2 are also investigated.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901218
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    On the distribution of the degree of polymerization occurring in the third kinetic stage of dilute-acid-catalyzed degradation of cellulose (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3251-3256 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The distributions of the degree of polymerization (DP) of cellulose degraded in the third kinetic stage, i.e. in the second stage of decreasing reaction rate, obey throughout the most probable (Schulz-Flory) type, and consequently cellulose specimens degraded at different conditions but with coinciding average DP coincide also with their DP distributions.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901222
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    Nematic elastomers: The influence of external mechanical stress on the liquid-crystalline phase behaviorWith best wishes dedicated to Prof. H. Ringsdorf on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3269-3284 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of external mechanical stress on the nematic-isotropic phase transformation of nematic elastomers was investigated. The experimental results of IR-dichroism measurements in the nematic phase and stress-optical measurements in the isotropic phase are in good agreement with the theoretical predicitions of the phenomenological Landau-de Gennes theory. This is for the first time that a significant influence of an external field on the nematic-isotropic phase transformation temperature and on the nematic order parameter S has been proved.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901224
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    Announcements of conferences on macromolecular chemistry and physics in 1990 (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3319-3325 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021901227
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    Effect of hydrogen on propene polymerization with solvay-type TiCl3/Cp2 TiMe2 catalyst (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3137-3142 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerization of propene with a highly isospecific Solvay-type TiCl3/Cp2TiMe2 catalyst in the presence and absence of hydrogen was investigated. It was found that hydrogen exerts almost no effect on the molecular weight and the stereoregularity of the resulting polypropylene. Furthermore, the H2/D2 exchange reaction hardly proceeds over the catalyst. To discuss this unusual behavior, plausible mechanistic explanations on the basis of the structure of active species are proposed.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901211
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    Transition temperatures of thermotropic liquid-crystalline copolyesters (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3167-3172 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of thermotropic copolyesters with glass transition temperatures (Tg) ranging from 70°C up to 180°C based on terephthaloyl chloride (1), chlorohydroquinone (2a) or hydroquinone (2b), 4,4′-isopropylidenediphenol (bisphenol-A) (3) and ethylene glycol (4) was synthesized. The mesomorphic properties of the copolyesters were examined by visual observation of stiropalescence and birefringence under a polarizing microscope. The Tg values of the copolyesters depend mainly on the composition of non-mesogenic or spacer segments and are practically independent of the content of mesogenic units. The structure of mesogenic units also shows a relatively small influence on the Tg behaviour.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901214
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    Molecular structure of 1,7-dichlorotetradecaphenylheptasilane as a model of poly(diphenylsilane) (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3195-3200 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular and crystal of 1,7-dichlorotetradecaphenylheptasilane Cl(SiPh2)7ClDedicated to Prof. Dr. H. Sinn on the occasion of his 60th birthday (I) was determined. The molecule has a helical conformation with the torsion angles SiSiSiSi in the range of 154°-162°. Crystal I is built of infinite polysilane chains extended along the [111] direction and separated by solvating benzene and toluene molecules.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021901217
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    Synthèse de polysiloxanes acyloxyméthylés par réaction des acides acétique, benzoïque et méthacrylique, en présence de triéthylamine, sur des polysiloxanes chlorométhylés, 1. Synthèse et identification de trisiloxanes et tétrasiloxanes modèles (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3231-3239 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 3-(Acyloxymethyl)-1,1,1,3,5,5,5-heptamethyltrisiloxanes 7b1, 7c1, 7d1 and 3,5-bis(acyloxymethyl)-1,1,1,3,5,7,7,7-octamethyltetrasiloxanes 7b2, 7c2, 7d2 (7b: acetoxymethyl, 7c: benzoyloxymethyl and 7d: methacryloyloxyméthyl derivatives) were synthesized from 3-(chloromethyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane (7a1) or from 3,5-bis(chloromethyl)-1,1,1,3,5,7,7,7-octamethyltetrasiloxane (7a2), respectively. Spectroscopic (1H NMR) and chromatographic (GPC and CG) characteristics of the isolated products were defined in order to standardize the analytical tools used for the study of the carboxylic acid reaction with chloromethylated polysiloxanes in the presence of triethylamine.
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    The effect of donor-acceptor complexes on the stereochemistry of alternating copolymers of alkyl vinyl ethers with maleonitrile and fumaronitrile (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 93-112 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper presents the results of a study of the alternating copolymerization of alkyl vinyl ethers, as electron-donors (D), with maleonitrile and fumaronitrile, respectively, as electronacceptors (A), and a 13C NMR evaluation of the stereochemistry of the copolymers. The results show that the two copolymers are stereochemically different. By use of model compounds as well as UV studies and quantum chemical (PVCILO) calculations, attempts to correlate the relationship of the complex (C) to copolymer structure have been made. We have previously reported studies on copolymerization of alkyl vinyl ethers and N-substituted maleimides. Stereochemical consequences resulting from variation of five parameters, each of which according to Mulliken theory should vary the concentration of C relative to that of the free monomers, in every case, were that the cis-trans ratio of the succinimide unit of the copolymer chain varied in accord with theory, being higher at higher [C].
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989111
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    Cyclization dynamics of polymers, 26Part 25: S. Boileau, F. Méchin, J. M. G. Martinho, M. A. Winnik, Makromolecules 22, 215 (1989).. End-to-end cyclization of polystyrene in mixed solvents. Effect of chain length (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 113-125 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclization rate measurements were carried out on polystyrene chains of different molecular weights and labelled at both ends with 1-pyrenyl groups, using as solvents cyclopentane (a thetasolvent), acetone (a poor solvent), and their mixtures. These mixtures exhibit a cosolvency effect for polystyrene. The results show that the rate constants for cyclization and ring-opening are solvent- and chain-length-dependent. This was interpreted in terms of the influence of excluded volume effects on these processes. The results indicate that the solvent giving the largest excluded volume effect is an equimolar mixture of cyclopentane and acetone, which agrees with the light scattering and viscometry results for polystyrene in cyclohexane/acetone mixtures.
    Additional Material: 9 Ill.
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    Poly(2,6-dimethyl-1,4-phenylene oxide)/poly(dimethylsiloxane) system - Architecture and selected properties (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 137-145 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We compare the ultimate mechanical properties and glass transition temperatures of various polyblends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(dimethylsiloxane) (PDMS) including full and pseudo interpenetrating polymer networks (IPN), in which the PPO is crosslinked to different extent with both ethylenediamine and 1,6-hexanediamine. Most of the polyblends of this system exhibit at least microphase separation with domain size varying with both composition and architecture. The full IPN's have at certain compositions a higher tensile stress to break than the crosslinked pure polymer networks. Most polyblends also exhibit multiple glass transition temperatures.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989114
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    Living cationic polymerization of 4-tert-butoxystyrene and synthesis of poly(4-vinylphenol) with narrow molecular weight distribution (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 127-136 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cationic polymerization of 4-tert-butoxystyrene (1) initiated by hydrogen iodide/zinc iodide (HI/ZnI2) led to well-defined living polymers at temperatures up to +25°C in either toluene or methylene chloride, the latter containing a small amount of tetrabutylammonium iodide (mole ratio nBu4NI/HI = 1/100). The number-average molecular weight of the polymers increased in direct proportion to the monomer conversion, and the linear increase further continued upon addition of a second feed of 1 to the completely polymerized reaction mixture. Both before and after the monomer addition, the molecular weight distributions of the products were invariably very narrow (M̄w/M̄n ≤ 1,1). In the polymerization in salt-free methylene chloride, in contrast, the polymers showed broader molecular weight distributions, particularly at low conversions, and thus the presence of the ammonium salt proved mandatory for attaining living polymerization in this polar solvent. By treatment with hydrobromic acid the HI/ZnI2-initiated poly(1) could readily be converted into poly(4-vinylphenol) (3) that inherited the narrow molecular weight distribution and controlled molecular weight of the precursor.
    Additional Material: 9 Ill.
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    The role of hafnium in supported titanium/hafnium catalysts for olefin polymerization (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 147-165 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several MgCl2-supported catalysts containing different amounts of titanium and hafnium were prepared. These systems are active for the polymerization of ethylene and α-olefins as well as for their copolymerization, giving much broader molecular weight distributions as compared with similar systems containing titanium only. Polymer properties, such as melt flow index and shear sensitivity can be varied by catalyst composition and addition of a Lewis base (ethyl benzoate). Gel permeation chromatography curves obtained in a single reactor (one-stage process) are comparable to those obtained in two reactors (two-stage process). An analysis of comparative kinetics for various conditions and the corresponding polymer properties suggests that Hf-containing sites produce much longer chains than do Ti-containing sites; at the same time Hf-containing sites display lower activity and higher tendency to interact with ethyl benzoate. Similar investigations with model catalysts are described to support these hypotheses.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989115
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    Synthesis and degradation of aromatic polyamides containing nitro groups (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 187-218 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various aromatic polyamides (aramids) which contain a nitro group at the amino substituted ring were synthesized and their thermal properties and degradation mechanisms were studied. Our present work showed that the nitro group in ortho position to the amide bond acts as an excellent leaving group for intramolecular nucleophilic displacement via the enol form to yield poly-(benzoxazole)s. Thermal decomposition of ortho-substituted aramids proceeds via a two-stage mechanism, whereas unsubstituted aramids decompose in one step. The first step represents the loss of HNO2 and the second step is due to degradation of the resulting benzoxazole polymer. Model compound and high-temperature FT-IR studies of these materials also give supportive evidences for the cyclization reaction.
    Additional Material: 25 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989117
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  • 282
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    Heterogene polymeranaloge Reaktionen zwischen Polybutadienepoxiden und anorganischen FeststoffoberflächenHerrn Professor Dr. Paul Rempp zum 60. Geburtstag gewidmet (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 9-18 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Heterogeneous, polymeranalogous reactions between polybutadieneepoxides (PBDE) and inorganic surfaces (SiO2, Al2O3, hydroxyapatite) were investigated. The composition of the resulting composites was determined by gravimetric methods and expressed as “degree of reaction” (RG). Interface reactions could be followed by spectroscopic methods and by differential scanning calorimetry. The results of the reaction mechanisms are discussed. Infrared and 13C solid state NMR studies suggest that the PBDE macromolecules are linked by bonds to the SiO2 surface and by and bonds to the Al2O3 surface.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900102
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  • 283
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    In situ photopolymerization of an oriented liquid-crystalline acrylate, 2Part 1: cf.1. (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 19-30 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: During the photo-initiated free-radical bulk polymerization of 4-biphenylyl 4-(6-acryloyloxy-hexyloxy)benzoate (1) in the liquid-crystalline state, the ordering is maintained, leading to an oriented liquid-crystalline side-chain polymer. The course of the photopolymerization depends on the phase of monomer 1. In the monotropic smetic-A and in the monotropic nematic phase the polymerization rate and conversion are affected by crystallization during polymerization. In the stable nematic phase the bulk polymerization is fast and complete. In this temperature region the transition from nematic 1 to smectic poly(1) is passed during which temporary segregation may occur, affecting the molecular ordering. Starting with isotropic 1, the polymerization proceeds considerably more slowly.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900103
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  • 284
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    Propene polymerization with MgCl2-supported transition metal catalysts activated by Cp2MtMe2(Mt = Ti, V, Zr, Hf) (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 31-35 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several kinds of MgCl2-supported catalysts were prepared by grinding the mixtures of MgCl2 and MtCln(MtCln = TiCl4, ZrCl4, HfCl4, VCl3). Polymerization of propene was conducted at 40°C and 1 atm with these solid catalysts by using Cp2MtMe2 (Mt = Ti, Zr, Hf, V) as cocatalyst. Polymerization took place only with the use of the TiCl4/MgCl2 catalyst. Both the activity and isospecificity were found to strongly depend upon the cocatalyst used. The polymers produced were fractionated with boiling heptane and analyzed by means of 13C NMR, the results of which suggested the existence of two types of catalytic centers, isospecific and aspecific. Plausible models of these catalytic centers are proposed.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900104
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  • 285
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    Evaluation of olefin reactivity ratios over highly isospecific Ziegler-Natta catalyst (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 37-44 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The recently found catalyst system, composed of Solvay-type TiCl3 and (RCp)2TiMe2, producing extremely high isospecific polyolefins, was used for copolymerizations of ethylene with various α-olefins (propene, 1-butene,1-hexene and 4-methyl-1-pentene) to obtain monomer reactivity ratios for isospecific centers. It was found that no homopolymer was formed actually. Using the copolymer composition obtained by 13C NMR, the monomer reactivity ratios were calculated according to the Fineman-Ross and Kelen-Tüdős method. For the ethylene/propene pair the same values of reactivity ratio were also obtained from the diad distribution of comonomers. The relative reactivity of these olefins was found to decrease in the following order; ethylene 〉 propene 〉 1-butene 〉 1-hexene 〉 4-methyl-1-pentene.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900105
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  • 286
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    Studies on functional diene oligomers with an amino end group, 3Part 2: cf.6.. Synthesis of oligoisoprenes containing a secondary amino end group (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 53-60 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lithium monoalkylamide, in the presence of monoalkylamine, was found to initiate the polymerization of isoprene to form oligoisoprenes. The molecular weight distribution of products formed in the lithium isobutylamide initiated isoprene oligomerization strongly depends on the initial mole ratio [Isoprene]0/[Amine]0/[Amide]0; with an initial mole ratio of 60/1/8, oligomers with a number-average molecular weight of about 800 were obtained. The presence of N,N,N′,N′-tetramethylethylenediamine in the reaction system was found to be effective for the selective formation of secondary amino-ended oligoisoprenes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900107
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  • 287
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    Polymerization of macromonomers, 3Part 2: cf.1. Monomer reactivity ratios in radical copolymerization of poly(tetrahydrofuran) macromonomers with 2-vinylnaphthaleneDedicated to Prof. P. Rempp on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 45-51 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methacrylate-terminated poly(tetrahydrofuran) (MA-PTHF) and acrylate-terminated poly-(tetrahydrofuran) (A-PTHF) macromonomers (M2) were radically copolymerized with 2-vinylnaphthalene (2-VN, M1). The composition of copolymers was determined by UV spectroscopy taking advantage of the very high absorption coefficient (UV) of the monomeric units of 2-VN in copolymer. The monomer reactivity ratios r1 and r2 evaluated are as follows. MA-PTHF: r1 =1,3 ± 0,21, ± 0,05; A-PTHF: r1 = 2,5 ± 0,35, r2 = 0,10 ± 0,05. These reactivity ratios were compared with those in the copolymerizations of 2-VN with the corresponding small monomers and were discussed in terms of polymer (hindering) effect and the concept of equal reactivity of growing chain.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900106
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  • 288
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    Anionic block polymerization initiated by potassium solutions, 2Part 1, cf. Z. Jedliński, M. Kowalczuk, P. Kurcok, L. Brzoskowska, J. Franek, Makromol. Chem. 188, 1575 (1987). Synthesis of poly(2-oxetanone)-block-polystyrene-block-poly(2-oxetanone)To Prof. Paul Rempp on the occasion of his 60th birthday with deep feelings of admiration for his outstanding scientific achievements (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 61-67 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The block polymerization of styrene with 2-oxetanone (β-propiolactone) proceeds fast with a yield of more than 90%, in the presence of potassium solutions in THF containing 18-crown-6. Poly(2-oxetanone)-block-polystyrene-block-poly(2-oxetanone) ABA triblock polymers having the expected molecular mass and composition are formed. Their glass transition and melting temperatures as well as their melting enthalpies determined by DSC show a strict correlation with block polymer composition. The mechanism of this block polymerization involving acyloxygen and alkyl-oxygen bond scission in 2-oxetanone is in good agreement with previous results of the homopolymerization of β-lactones by alkali metal solutions abounding in potassium anions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900108
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  • 289
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    Compatibility of poly(ethylene oxide) and poly(methyl methacrylate) chains in solutions of their blends, diblock and triblock copolymers (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 145-154 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent activity data were obtained from vapour pressure measurements at 50°C, 70°C, 100°C and reduced to χ-functions in systems consisting of benzene or toluene on the one hand and blends or block copolymers of poly(ethylene oxide) and poly(methyl methacrylate) on the other. The χBC-values are negative for all polymer subsystems, but miscibility on a segmental scale is somewhat different for block copolymers and blends. χBC depends on the concentration of solvent and is mainly influenced by the Δχ-effect in solution and correlated with the syndiotacticity of the PMMA chains. There is only a small influence of temperature and blend composition or block ratio.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900116
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  • 290
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    Effect of the degree of saponification on the rheological and thermal properties of poly(vinyl alcohol) gels (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 155-163 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological and thermal properties of poly(vinyl alcohol) (PVA) gels prepared through freezing-thawing cycles were studied, in order to clarify the relation between structure and functional properties. The breaking strength of PVA gels increases with increasing the degree of saponification (DS), i.e. the degree of deacetylation, while the breaking deformation decreases. The endothermic differential scanning calorimetry (DSC) peak accompanying the transition from gel to sol shifts to higher temperatures with increasing concentration and DS. The endothermic enthalpy as a function of concentration increases gradually up to 25 wt.-%, then it increases rapidly for PVA with DS = 96,0,97,5 and 98,5 mol-%. A sharp diffraction peak is observed in the X-ray pattern for PVA gels with DS = 99,9 mol-% but not for PVA gels with DS = 96,0 mol-%. All results from rheology, DSC and X-ray analysis show that only a slight increase in DS from 96,0 mol-% to 97,5 mol-% promotes the formation of ordered regions in PVA remarkably.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900117
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  • 291
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    Thermodynamic stability of mixtures containing statistical copolymers, 1. Phantom-lattice treatment of chemically modified polymersDedicated to professor Paul Rempp on the occasion of his 60th birthday (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 419-426 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For two statistical copolymers containing the same repeating units to be miscible their chemical compositions should not differ by more than a maximum tolerable composition difference. Measurements of the miscibility behaviour of mixtures of brominated polystyrenes by Kambour et al. can be interpreted if the small changes in molecular volume caused by bromination are taken into account with a simple extension of Scott's model. The feature is in accordance with the well-known sensitivity of polymer blend miscibility to small changes in chain length. The relatively small extension of the model already changes the value of the pairinteraction parameter (χ) drastically, which exemplifies the necessity to let χ values in literature be accompanied by precise information about the model used in the evaluation.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900220
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  • 292
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    Chromatographic cross-fractionation of statistical copolymers of styrene and 2-methoxyethyl methacrylate (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 427-435 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chromatographic cross-fractionation (CCF) by preparative size-exclusion chromatography (SEC) and gradient high-performance liquid chromatography was applied to stat-copoly-(styrene/2-methoxyethyl methacrylate). Two specimens were analyzed, which had been polymerized from the same batch of monomer mixture in benzene solution to either low or high conversion (10,1 or 86,4 mass-%, respectively). The initial monomer mixture contained more styrene (76,7 mass-%) than the azeotropic one (39,4%). The integral chemical composition distribution (CCD) of the low-conversion sample agreed with the theoretical curve, whereas the calculated CCD of the high-conversion specimen was broader than the one determined experimentally. The contour map of the low-conversion sample exhibited the tapering effect of molar mass predicted by theory. The corresponding map of the high-conversion sample showed that the composition shift towards the initial monomer ratio induced production of macromolecules of higher molar mass.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900221
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  • 293
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    Investigations of poly(vinyl alcohol)/poly(N-vinyl-2-pyrrolidone) blends, 1. Compatibility (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 437-448 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVP) made from aqueous solutions appear to be miscible in the whole composition range according to DSC results. A large negative value of the interaction parameter between the two polymers was found from melting point depressions. IR spectroscopy evidenced compatibility of the two polymers on a molecular level. DSC, density and IR results all show a proportion of pure PVA crystallites in blends, which decreases with increasing PVP content and becomes nil at about 50 wt.-% of PVP. However, close examination of the hydroxyl stretching region of the blends indicates the presence of organized regions of PVA beyond this limit. According to IR results, the sequence of decreasing hydrogen-bonding power should be the following: multiple hydroxyl-hydroxyl bonding in organized PVA regions, hydroxyl-carbonyl bonding between the two polymers, and simple hydrogen-hydrogen bonding in amorphous PVA regions. It appears that the PVA component can be held in the amorphous state by hydrogen bonding with the PVP component when there is a sufficient amount of the latter in the blend. The amorphous part of PVA is compatible with PVP, but the crystallizable part is not in its most stable form.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900222
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  • 294
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    Active species in the anionic ring-opening polymerization of cyclic carbonates (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 9-13 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anionic ring opening polymerization of 5,5-dimethyl-1,3-dioxan-2-one (2,2-dimethyltrimethylene carbonate) (1) initiated by sec-butyllithium, sodium methoxide or potassium dihydronaphthylide was found to proceed via alcoholate anions. This finding is based on 31P NMR spectroscopic studies of the polymer end groups, which result from the reaction of the living polymer with diphenyl chlorophosphate.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989102
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    Sulfur-containing azoinitiators and their properties (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1015-1024 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermolysis and photolysis of arylazosulfonates (1-3) and of arylazo phenyl sulfones (4-6) was studied. Compounds 1 to 3 are soluble in water. They are thermally stable up to 200°C; however, if they are irradiated with the light of a mercury-xenon high-pressure lamp, they decompose at room temperature. Their photolysis was studied either in water or in ethanol as solvent. For the photolysis in water an ionic mechanism of decomposition is suggested, while the results of the photolysis in ethanol can be explained on the basis of a competition of a radical with an ionic mechanism. Compounds 4 to 6 are thermally and photochemically instable. The thermal decomposition of 5 was studied in detail and found to be comparable to that of AIBN. Its decomposition follows first-order kinetics. The photolysis of 4-6 was carried out in ethanol or chloroform. The mechanism of photolysis depends on the solvent polarity. 5 was successfully used as initiator for the polymerization of methyl methacrylate.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900510
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  • 296
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    Photoconductive polymers and copolymers of N-(2-propynyl) carbazole and N-(2-propynyl)phenothiazine (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1025-1035 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Homopolymers of N-(2-propynyl)carbazole, its copolymers with acetylene, and the homopolymer of N-(2-propynyl)phenothiazine were prepared using Ti(OBu)4/AIEt3 as the catalyst. The homopolymer of the carbazole derivative was also prepared by its metathetic polymerization catalyzed with the system WOCl4/Ph4Sn. Homopolymers of both monomers and the copolymer of N-(2-propynyl)carbazole with a small quantity of acetylene are photoconductive.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.021900511
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  • 297
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    Phase transitions and structure changes in poly[bis(phenoxy)-λ5-phosphazene] (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1047-1055 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase transition behavior in poly[bis(phenoxy)-λ5-phosphazene] (PBPP) was studied by electron microscopy, X-ray diffraction techniques and differential scanning calorimetry. Several polymorphic forms were detected. Relative changes in enthalpy associated with the thermotropic transition, T(1), are examined as a function of heat treatment. Correspondingly, structural and morphological changes have been established in line with enthalpy results.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900513
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  • 298
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    Alkyllithium-initiated polymerization of butadiene in presence of a bi-1,3-dioxane derivative (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 31-37 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some results are reported on the alkyllithium-initiated polymerization of butadiene in cyclopentane in presence of 2,′2-bis(4,4,6-trimethyl-1,3-dioxane). The effect of this lithium chelating agent on one-unit model active centres is also reported. Comparisons are made with another highly efficient polymer structure modifier, 1,2-dipiperidinoethane. Conclusions are reached on the reasons why both are particularly effective in inducing the formation of polydienes having extremely high vinyl content.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989104
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  • 299
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    Specificity of initiating systems based on allyl derivatives of group VI-metals in the formation of graft and block copolymers (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 39-47 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyvinylpyridines activated by tris(π-allyl)chromium and by tetrakis (σ-allyl)molybdenum or tetrakis(σ-allyl)tungsten, complexed with tetrahydrofuran, were used for grafting with acrylonitrile. The products obtained, differing in the degree of branching, were characterized by various physical methods. Block copolymers of the types butadiene-acrylonitrile and styrene-oligobutadiene-acrylonitrile were synthesized by the use of tris(π-butadienyl)chromium as the initial active agent. Some molecular parameters of these block copolymers were established.
    Additional Material: 4 Tab.
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  • 300
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    Polymerization of propylene oxide by activated monomer mechanism - kinetics (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 15 (1989), S. 49-60 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of propagation in the polymerization of propylene oxide proceeding by the activated monomer (AM) mechanism is studied. Propagation in this system involves addition of a protonated monomer molecule to the terminal hydroxyl group of the growing oligomer. A kinetic analysis of the reaction allowed the determination of the equilibrium constant K, governing the distribution of protons between monomer and HO- groups, which in turn enables to calculate the propagation rate constant kp. This composite value has been further separated into the rate constants of four reactions, involving two different modes of ring opening in reactions with two different types of hydroxyl groups, viz. primary and secondary ones. The corresponding values are (all rate constants in mol-1 · L · s-1 and for CH2Cl2 at 25°C):K = 5,3; k1,1 = 0,170, k1,2 = 0,190, k2,1 = 0,105, k2,2 = 0,135
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1989.020151989106
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