Modifizierte ionenaustauscherharze — synthese und eigenschaften, 1. Sulfomethylierte styrol-divinylbenzol-harze

Sulfomethylated resins are prepared by polymer analogous reactions, starting from macroporous poly(styrene-co-divinylbenzene) matrices. Different reaction paths are discussed and used in the synthesis. Sulfomethylation can be achieved by reaction of a chloromethylated resin with dimethyl sulfide and sodium sulfonate or alternatively by oxidation of polymer-bound thiol groups. Both methods give high conversions as shown by IR spectra and titration of the sulfonic acid groups. Poly[1-(4-hydroxysulfomethylphenyl)ethylene] (3) is obtained by reaction of poly[1-(4-hydroxyphenyl)ethylene] ( 2 ) resin with formaldehyde/sodium sulfonate. The thermal stability, catalytic activity, and ion exchange equilibria of the sulfomethylated resin are investigated.     

Synthese und eigenschaften von äthylenterephthalat-pleionomeren,

In order to synthesize the higher oligomers and pleionomers of ethylenterephthalate with methylester endgroups in pure form, the monomethylesterchlorides of the mono-. di-, and trimeric dicarboxylic acids were synthesized. The synthesis of the desired dimethylesters was effected by using the monomethylesterchlorides as earboxylic components and glycol and some oligoesterdiols as bifunctional fragments. The heptameric and higher dimethylesters can be considered pleionomers because they do not differ in some solubility, melting point, IR-spectrum, and DEBYE ogramm from the polymer.     

Über die synthese polymerer indophenine und deren elektrische eigenschaften

Condensation of bis-{dioxopyrrolino[2′.3′: 1.2;2″.3″: 5.4]} benzene with thiophene and reaction of a polymer containing poly[6-vinylisatin] with isatin and thiophene gave two polymers containing indophenine units of different type. These products are polymeric vat dyes. The polymeric indophenine I with a system of conjugated double bonds and coplanarity in the molecule has a spezific dc conductivity of σ = 1.1 · 10^?4 Ω^?1 · cm^?1 at 25°C and a pressure of 1500 kp · cm^?2. The spin contents is 1.9 · 10²⁰ spins · g^?1. The electrical properties and the spin contents of some redox polymers containing indigoid dyes respectively quinoid structure were also investigated.     

Polychalkone. I. Synthese und eigenschaften thermostabiler polychalkone

The condensation polymerization (“polycrotonisation”) of aromatic dialdehydes with aromatic diacetyl compounds (CH₃CO? Ar? X? Ar? COCH₃) yielding polychalcones is discussed. The polymers obtained are thermally stable. The viscosity of only two polymers could be determined in dimethylformamide; the other polymers are insoluble in all solvents. As in the case of mono- and dichalcones, halochromy could be detected with the synthesized polychalcones. They exhibit paramagnetic properties and they are semi-conductors.     

Polymerisation von fulvenen, 1. Synthese und eigenschaften kationischer polyfulvene

The cationic polymerization of a series of pentafulvenes with two exocyclic substituents yields highly reactive unsaturated polymers, which are soluble in nonpolar organic solvents. The preparative aspects as well as some properties of the polymers are discussed. Most polymers are very sensitive to oxygen. For instance poly(5-isopropylidene-3-cyclopenten-1,2-ylene) ( 2a ), which is obtained with molecular weights up to 350 000, consumes more than one mol-equivalent of oxygen per repeating unit.     

Synthese und eigenschaften einiger höhergliedriger cyclischer ätheracetale

Optimized syntheses of 1,3,6,9-tetraoxacycloundecane ( 2 ), 1,3,6,9,12-pentaoxacylotetradecane ( 3 ), and 1,3,6,9,12,14,17,20-octaoxacyclodocosane ( 4 ) as well as some physical and chemical properties and the proof of structure are reported.     

Polymere mit phosphor-stickstoff-bindungen, 2. Synthese und eigenschaften von oligomeren mit Si?NP-struktureinheiten

Properties and syntheses of heteroorganic oligomers ( 3a–e ) from silylazides and ditertiary phosphines ( 2b–e ), or tetraphenylbiphosphine ( 2a ), respectively, are reported. One of the products ( 3a ) has a complete inorganic skeleton of the atomic sequence SiNPPN. Molecular weight measurements of oligomers synthetized in solution give values of M?_n near 1000, those of substances prepared in bulk give rise to values up to 4 300 depending on the phosphine used. The reaction can be followed by IR-spectroscopic measurements: v(P?N) of the synthesized compounds is tabulated. ³¹P-NMR measurements are of particular importance, because they permit statements about end and middle groups, i.e. about the structure of the products.     

Über polymere acide kohlenwasserstoffe. Synthese und eigenschaften von polymeren des 9-[2-vinylfluorenylidenmethyl]-fluorens

9-[2-Vinylfluorenylidenemethyl]-fluorene was prepared from 2-Vinylfluorene and 9-Bromomethylene-fluorene. The compound could be polymerized by means of radical as well as cationic initiators. A cross linked copolymer was obtained by copolymerization of the monomer with styrene and divinylbenzene. The polymers were converted to intensively red violett coloured polymer carbanions which could be discharged to polymer radicals by oxidizing agents.     

Partiell acetylierte cellulose — synthese und bestimmung der substituentenverteilung mit hilfe der 1H NMR-spektroskopie

Partially acetylated cellulose was synthesized by homogeneous acidic and basic saponification of cellulose triacetate (fully acetylated cellulose) and by homogeneous acetylation of cellulose dissolved in molten N-ethyl-pyridinium chloride. The result of ¹H NMR spectroscopic investigations was that acetylation and acid saponification lead to products with different esterification of the hydroxy groups at C², C³ and C⁶ whilst basic saponification leads to uniform acetylation. Furthermore, the solubility of the cellulose acetates depends on the method of preparation.     

Synthese,thermostabilität und elektrische eigenschaften von tiefgefärbten polymeren mit anellierten phthalocyaninartigen systemen

2.5-Diamino-3.4-dicyanothiophene reacted with terephthalic aciddichloride to a polyamide and with thiophene-2.5-dicarboxaldehyde to a polyazomethine. A phthalocyanine analogous system could be built up on both polymers by the reaction with phthalodinitrile and copper acetylacetonate. This increased the thermal stability of the polymers. A new measurement cell was used to measure the electrical conductivity of the polymers. This cell is constructed to measure in any gas atmosphere or in a vacuum at pressures up to 5000 kp · cm^?2 and at temperatures up to 150°C.     

Synthese und thermische eigenschaften von photosensiblen polyacrylsystemen mit zimtsäurehaltigen seitengruppen und deren verwendung in composite-membranen

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.     

Untersuchungen zu struktur und eigenschaften der polyamide, 2. Einkristalle aus polyamid 6,6

Polyamide 6,6 single crystals have been crystallized from dilute solutions at temperatures between 20 and 150°C and characterized by X-ray wide and small angle scattering, electron microscopy, differential calorimetry and density measurements. It turnes out that morphology, crystal thickness, density, heat of fusion and melting behaviour are strongly influenced by crystallization temperature. The degrees of crystallinity calculated either from density or heat of fusion are found in the range from 40 to 60% depending on crystallization temperature. As a result of annealing at elevated temperatures the long period increases continuously with annealing temperature and time. The obtained results are discussed in detail with regard to a model of polyamide single crystals proposed by KELLER et al. which provides a regular fold structure.     

Synthese und chemische eigenschaften einiger copolymerisate von 8-hydroxy-5-vinyl-chinolin-derivaten. 1. Teil: Darstellung der monomeren

5-Acetyl-8-quinolinol and derivatives, some substituted by me in position 2 and/or bromine in position 7 of the quinoline ring were reduced by sodium borohydride as ethyl and benzyl ethers; the vinyl compounds were formed by pyrolysis of the carbinols.     

Über Synthese und Polymerisation alicyclischer β-Isothiocyanatocarbonsäuren und 2,6-Dioxo-perhydro-1,3-thiazine

Alicyclic β-isothiocyanato carboxylic acids were synthesized from silylated alicyclic β-amino acids using thiophosgen. In contrast to the behaviour of β-isothiocyanato propionic acid alicyclic β-isothiocyanato carboxylic acids do not undergo addition polymerization. They do, however, cyclize to unstable 2-thioxo-6-oxo-perhydro-1,3-oxazines of type 3 , which in turn isomerize to give stable 2,6-dioxo-perhydro-1,3-thiazines ( 11—13 ) (β-amino acid-N-carboxylic anhydrides (NTA)). The cyclization was examined kinetically; water and tertiary amines are catalysts for this reaction. The crystalline β-amino acid-NTA ( 11—13 ) are chemically and thermally more stable than the corresponding oxazines ( 15—17 ) (β-amino acid-N-carboxylic anhydrides (NCA)). Their polymerization in the presence of protic or aprotic nucleophils leads to β-polyamides with yields and degrees of polymerization as high as in the polymerization of the β-amino acid-NCA. The degrees of polymerization were determined by ¹H-NMR-spectroscopy; they are rather low in all cases (DP<100).     

Poly-p-xylyliden. Synthesen und beziehungen zwischen struktur und elektrophysikalischen eigenschaften

Foly-p-xylylidene has been synthesized by bifunctional carbonyl olefination of terephthalaldehyde according to WITTIG'S reaction and by means of p-xylylene-bis-(diethyl phosphonate) as well as by dehydrochlorination of p-xylylene dichloride with sodium hydride in dimethyl formamide and with potassium amide in liquid ammonia. Then followed a comparative investigation of the products obtained. Methyl- and methoxy-substituted poly-p-xylylidenes II and III are obtained from 2.5-bis-(chloromethyl)-p-xylene and -hydroquinone dimethyl ether. I–III are being analyzed by IR and reflection spectra as well as by thermogravimetry. The poly-p-xylylidenes I–III possess semiconducting properties and photoconductivity, typical values for the dark conductivity and activation energy of I being σ₄₀₀°K ～ 10^?15 ohm^?1 cm^?1 and E_D = 2,4 eV. Absorption spectra and photoconductivity spectra occur in the same spectral region, photoconductivity on the long-wave edge of absorption possessing a maximum. The excitation energy for the photoconduction of I, E₀ = 2,35 eV, is of the same value as E_D and is approximately in accordance with the theoretically calculated value for the π–π* transition of the isolated macromolecule. Corresponding relations result from the substituted polyxylylidenes II and III. In order to characterize the conducting phenomena more closely measurements are being made concerning the dependence of the photocurrent and its relaxation time from voltage, temperature and radiation intensity. Also, the photoconductivity with combined optical excitation as well as the influence of oxygen on photoconduction are being examined.     

Herstellung und eigenschaften von polyacenaphthylen, 3. Photoabbau von polyacenaphthylen

Thermally prepared polyacenaphthylene when irradiated in solution undergoes random chain scission. The photodegradation is solvent- and temperature-dependent and leads to a lower limit of the degree of polymerization. Polymeranalogous reactions and crosslinking can be found to occur simultaneously. A certain fraction of „weak links”︁ was detected in the polymer.     

Darstellung und eigenschaften von 2-(N-Aryl-N-methylamino)äthylmethacrylaten

A series of new 2-(N-aryl-N-methylamino)ethyl methacrylates ( 2a–f ) was synthesized. They may serve as polymerizable components in the initiation system diacyl peroxide/tertiary amme. Their physical properties, as density, refractive index, boiling point, NMR, and IR spectra, were determined. During the reaction with benzoyl peroxide the amines were transformed into gel-polymers. To determine the reactivity of these monomers towards peroxide, the rate constants of the reactions between benzoyl peroxide and the 2-(N-aryl-N-methylamino)ethanols 1a–f and between benzoyl peroxide and 2-(N-methyl-N-phenylamino)ethyl isobutyrate ( 3 ) were measured. Bulk polymerization of the unsaturated tertiary amines prepared was also corroborated.     

Über die druckabhängigkeit der viskoelastischen und physikalisch-chemischen eigenschaften von polymeren, 2. Spezifisches volumen und thermische ausdehnung einiger polymeren beim schmelzen und kristallisieren

Measurements of specific volumes are described as function of temperature and pressure of melting or crystallizing linear polyethylene, isotactic polypropylene, and polyoxymethylene. A pressure range of 50 to 1600 bar permits determination of relative volume changes as function of temperature and pressure. Pressure influence on melting points, temperature hysteresis between melting and crystallization and their volume changes as well as the thermodynamic driving force of phase change have been investigated. Clausius-Clapeyron's equation permits calculation of heats of crystallization.     

Struktur und eigenschaften der copolymere aus 1,3,5-trioxan und 1-chlor-2,3-epoxypropan, 2. Morphologie der copolymerkristalle

The morphology of copolymers from 1,3,5-trioxane and 1-chloro-2,3-epoxypropane was studied as function of polymerization time and amount of 1-chloro-2,3-epoxypropane. Considerable changes of the morphology were observed when trespassing certain mole fractions of 1-chloro-2,3-epoxypropane monomeric units in the copolymer chain.