Dreikomponentenreaktionen. XVII. Endständig reaktive Oligooxyethylenstrukturen aus Alkenen,Chlor und O-Nucleophilen und deren Umsetzung zu Oxathiaalkanen

Three Component Reactions. XVII. Terminal Reactive Oligooxyethylene Structures from Alkenes, Chlorine and O-Nucleophiles and Their Transformation into Oxathiaalkanes The reaction of alkenes, chlorine and oxirane, dioxane, ethyleneglycole, oligoethylenglycoles, the monoethers of oligoethyleneglycoles, ethylene chlorohydrine or α-hydro-ω-chloro-oligooxyethylenes leads to compounds 6--9 , which contain mono or oligoether functions and one or two reactive terminal chlorine atoms. Oxathiaalkanes ( 10 and 12 ) were obtained in the reaction of such compounds with sodium mercaptides.     

Die elektrische leitfähigkeit von α,ω-bis-polyenen

The preparation and isolation of the coloured reaction products of maleic anhydride-methylvinylether-copolymer (Gantrez AN) and aprotic liquids yields α,ω-bis-polyenes of the copolymer each containing double bond sequences of equal length, irrespective of the order of reaction. Prior to the formation of the polyenes in hexamethylphosphoramide (HMPA), a chemical reaction involving this aprotic substance occurs at the anhydride ring of the Gantrez AN. The electrical conductivity is improved by addition of iodine, dichloro-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and tetracyanoquinonedimethane (TCNQ) to the resultant α,ω-bis-polyenes. If the unsubstituted α,ω-bis-polyenes are treated with boiling xylene or pressure sintered, specific resistances as high as that of polyacetylene (PA) are obtained. On the whole, the specific resistance is reduced by ten orders of magnitude, Gantrez AN: 2.8·10¹³ Ω. cm, pressure-sintered α,ω-bis-polyene: 1.1·10⁴ Ω·cm, α,ω-bis-polyene containing iodine: 2·10³ Ω·cm. IR spectroscopy can be used to detect the polyene and complex formation and to demonstrate that the actively conducting reaction product is a 3- or 4-substituted α,ω-(bis-polyene)-1,2-polybutene.     

Mixing of ethylene oxide and propylene oxide oligomers: 1. Enthalpy and volume changes

Calorimetry and dilatometry have been used to determine the enthalpy and volume changes on mixing oligomers of ethylene oxide ($\text{M}\text{?}{}_{\mathrm{n}}\text{< 600}$) and propylene oxide ($\text{M}\text{?}{}_{\mathrm{n}}\text{< 2025}$). The mixing of α,ω-hydroxy-oligomers is markedly affected by end-group interactions. The enthalpies of mixing of α,ω-methoxy-oligomers are determined predominantly by differences in chain-segment interaction energies and surface areas. The volumes of mixing of α,ω-methoxy-oligomers can be explained only by accounting additionally for slight differences in their liquid properties.     

New multiblock terpoly(ester-ether-amide) thermoplastic elastomers

A new block terpolymer of poly(tetramethylene terephthalate)-block-poly(oxytetramethylene)-block-polydodecanelactam with potential application as elastomers have been obtained by melt polycondensation of α,ω-dihydroxypoly(butylene terephthalate), α,ω-dihydroxypoly(oxytetramethylene) (M_n ≈ 1000) and α,ω-dicarboxyoligo(dodecanelactam) (M_n ≈ 2000). The synthesis and some physical and chemical properties of this block poly(ester-ether-amide) thermoplastic elastomer is presented. A variety of different methods was used to study the phase structure, thermal and relaxational properties.     

Polymerization of lactams, 87. Block copolymers of poly(ϵ-caprolactam) and polybutadiene prepared by anionic polymerization. Part I: Preparation and properties

The effect of the polymerization conditions on the properties of poly(?-caprolactam)-polybutadiene block copolymers prepared by polymerization casting through anionic polymerization of ?-caprolactam initiated with potassium salt of ?-caprolactam in the presence of α,ω-dihydroxy-polybutadiene and isocyanates or their blocked derivatives as functionalizing agents was investigated. The influence of the content of telechelic polybutadiene, its molecular weight, type of diisocyanate, and polymerization temperature on the fundamental mechanical properties of the prepared materials and on the polymerization rate was evaluated.     

Surface segregation of chain ends in α,ω-fluoroalkyl-terminated polystyrenes films

α,ω-Fluoroalkyl-terminated polystyrenes (α,ω-PS(R_f)₂) with various molecular weights were synthesized by an anionic polymerization. Then, chain end distribution in the surface region of the α,ω-PS(R_f)₂ films was studied by angular-dependent X-ray photoelectron spectroscopy in conjunction with neutron reflectivity. The α,ω-PS(R_f)₂ films annealed under vacuum exhibited surface localization of chain ends. Since the fluoroalkyl chain ends possess a lower surface free energy compared with the main chain part, they energetically prefer to partition to the surface. The extent to which the chain ends were segregated at the surface was examined as a function of molecular weight. Also, it was presented how surface orientation of the fluoroalkyl end groups was dependent on molecular weight. On the other hand, no segregation of the chain ends was observed at the surface of the α,ω-PS(R_f)₂ film annealed in boiled water. This is because the chain ends with a lower surface free energy tend to stay away from the higher energy medium of the boiled water. This result reveals that the surface concentration of chain ends can be regulated by selecting an appropriate annealing condition based on surface thermodynamics.     

Die Emulgierung oxidierter Polyäthylen-Wachse mit ionisch-nichtionischen Emulgator-Systemen

Emulsification of Oxidized Polyethylene Waxes with Ionic-Nonionic Emulsifier Systems The author reports on the emulsification of oxidized polyethylene waxes with varying acid values and molecular weight distributions. The emulsifier system comprised of predominantly a nonionic ethoxylated surfactant based on alkyl phenol in combination with a small amount of alkali hydroxide to which the water for emulsification was added. Emulsion properties, such as viscosity, pH-value, particle size (light transmission), and glaze of the dry films on plane surface, were used to formulate the optimum emulsifier systems. Thus, the optimum ratio of the components and the degree of ethoxylation of the nonionic surfactant were determined. Similarly, the method of emulsifying was optimized and the differences among the various existing polyethylene waxes were determined.     

Polyimide–polysiloxane block copolymers synthesized from α, ω-(3-aminophenoxy) terminated poly[oxy(dimethylsilyl)-1,4-phenylene(dimethylsilylene)]s

A method has been worked out for the synthesis of α,ω-(3-aminophenoxy) terminated poly[oxy(dimethylsilyl)-1,4-phenylene(dimethylsilylene)]oligomers with controlled molecular weight. From these oligomers were synthesized polyimide-polysiloxane block copolymers via a transimidization route, with polyimide moieties based on 2-aminopyridine terminated 5,5′-oxybis-1,3-isobenzofuranedione-4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline oligomers. The copolymers obtained show higher thermooxidative stability in comparison with copolymers having siloxane moiety based on α,ω-aminopropyl or α,ω-arylamine terminated poly(dimethylsiloxane) oligomers.     

Polymer networks based on α,ω-methacrylate-terminated poly(1,3-dioxolane)

α,ω-Methacrylate-terminated poly(1,3-dioxolane)s (polyDXL) were synthesized by cationic ring-opening polymerization of DXL in the presence of methylene-bis(oxyethylmethacrylate) as transfer agent. If the initiator concentration is small compared with the transfer agent concentration, the molecular weights of the polymers are governed by the ratio of the reacted monomer to the reacted transfer agent. The α,ω-methacrylate-terminated polyDXLs obtained undergo free radical polymerization with formation of polyacetal networks. The properties of the networks as function of the molecular weight of the corresponding prepolymers are reported.     

Neuartige emulgierbare Polyäthylenwachse

Novel Emulsifiable Polyethylene Waxes In comparison to naturally occuring waxes and their derivatives, the group of synthetically prepared emulsifiable polyethylene waxes known so far exhibit a relatively small proportion of polar centers in their molecular structure. Using a new process of preparation, products having a high content of hydrophilic groups are obtained. The properties and emulsifying techniques are described. This report also includes the development of a new group of purely non-ionic emulsifiable very hard polymer waxes.     

Zur Molekülverknüpfung mit Schwefelchloriden. IV. Die Addition von Dichlorsulfan an Allyl-phenyl-äther. Anti-Markovnikov-Struktur der 1:2-Addukte

Molecule Linkage by Sulfur Chlorides. IV. The Addition Reaction of Dichlorosulfane with Allyl-phenyl-ethers. Anti-Markovnikov-Structure of the 1:2 - Adducts Allyl-phenyl-ethers react with dichlorosulfane (sulfur dichloride) to anti-Markovnikov-adducts. This was demonstrated by the ¹H-n.m.r. spectra and dehydrohalogenation of the isolated bis-(β-chloroalkyl)-thio ethers.     

Mixing of ethylene oxide and propylene oxide oligomers: 2. Phase separation

Equilibrium phase compositions and cloud point curves have been determined for mixtures of ethylene oxide and propylene oxide oligomers. Large differences in miscibility are noted between α,ω-hydroxy- and α,ω-methoxy-oligomers. The data for the α,ω-methoxy-oligomers are simply interpreted in terms of the Flory—Huggins equation with concentration dependent X, i.e. X = X₀ + X₁ø₁ where ø₁ is the volume fraction of component 1. The approximate value of X for the α,ω-methoxy-oligomer mixtures is found to be 0.1.     

Neue elastomerfasersysteme

Elastomeric fibres available by the wet-spinning process were produced by solution polycondensation of α,ω-bis-(4-amino-benzoates) of aliphatic α,ω-dioxy-polybutyleneethers with terephthaloyl chloride. The discussion of the thermodynamic and structural conditions for the formation of the elastic properties of these polymers shows, that the formation is dependent on the tendency of disintegration of the macromolecule centres having high respectively low cohesion energy density. These findings could also be confirmed with polyetheresterureas and polyetheresterimides, made from amines mentioned above by reaction with 1,4-phenylene diisocyanate respectively with pyromellitic dianhydride.     

Derivate des Phosphorsäure-o-phenylenesters. XII[1]. Reaktion von Orthosäurechloriden mit Äthylenoxid

Derivatives of o-Phenylene Phosphate. XII. Reaction of Ortho-acid Chlorides with Ethylene Oxide Ortho-acid chlorides react with ethylene oxide in dependence of their structure either to ortho-acid β-chloroethylester or by splitting off 1,2-dichloroethane to the corresponding carbonyl- and phosphoryl derivatives, respectively. Using this method i. a. pentacovalent P-derivatives (pentaoxyphosphoranes 14, 16 ) are available.     

固体光气法合成2-氧-5-甲基-3-氢-1,3,4一噁二唑

研究了以乙酸乙酯为原料,用固体光气代替光气合成2-氧-5-甲基-3-氢-1,3,4-(口恶)二唑,为该中间体的合成提供了一条环境友好的新途径。考察了反应温度、反应物配比、反应溶剂等因素对收率的影响,在最佳条件下,合成总收率为81.8%。目标化合物经红外光谱、核磁共振谱、质谱验证。     

Kristallinflüssige trans-4-(ω-Cyanalkyl)cyclohexylester und 4-(ω-Cyanalkyl)phenylester

Liquid Crystalline trans-4-(ω-Cyanalkyl)cyclohexylester and 4-(ω-Cyanalkyl)phenylesters The synthesis of the title esters 1 and 2a–e (n = 0 – 3) and their mesomorphic properties are described. When the alkyl-spacer n between the polar CN-group and the cyclohexane ring of cyanalkyl-cyclohexylesters 1 is increased the difference of the clearing points between the phenylesters 2 and the cyclohexylesters 1 decreases to nearly zero. The reason of higher clearing temperatures of 2 is a dynamic conformational effect of ring inversion of cyclohexane in the ester 1 with two polar substituents at the ring.     

Beiträge zum maschinellen Geschirrspülen 1. Mitteilung: Entfetten von Glasoberflächen unter den Bedingungen des maschinellen Geschirrspülens

Contributions on Mechanical Dish Washing 1: Defatting of Glass Surfaces Under the Conditions of Mechanical Dish Washing Tracer technique was used to study the dissolution of a film of butter fat or lard from glass surface during the conditions used in mechanical dish washing. Washing temperature was found to be the determining factor in the removal of fat residue. The major amount of the fat can be dissolved only at temperatures above its melting point, and, sufficient amounts of the cleansing agent ensure its stable emulsification, thus preventing the redeposition on the glass. Hot prewashing reduces the requirement of cleansing agent, since the quantity of cleansing increases linearly with the fat level of the goods to be washed. Polyethylene, because of its higher affinity to fat, is more difficult to defat than glass.     

Surface modification of γ-Fe2O3 nanoparticles with aminopropylsilyl groups and interparticle linkage with α,ω-dicarboxylic acids

An investigation was carried out on the surface modification of γ-Fe₂O₃ nanoparticles with aminopropylsilyl (APS) groups in 3-aminopropyltriethoxysilane and the interparticle linkage with α,ω-dicarboxylic acids (succinic acid and suberic acid) through the terminal amino groups of APS moiety at the surface of γ-Fe₂O₃ nanoparticles. It was demonstrated that the change in interparticle distance caused by these surface modifications influences the magnetic property of the composites. When γ-Fe₂O₃ nanoparticles were modified with APS groups, coercivity increased and when they were further modified with α,ω-dicarboxylic acids, the larger decrease in coercivity was observed with the longer dicarboxylic acid.     

Synthesis of α,ω-hydroxyalkyl telechelic polydimethylsiloxane soft segments and preparation of waterborne polyurethane–polydimethylsiloxane block copolymers

In this paper, by optimizing synthesis process of α,ω-hydroxyalkyl telechelic polydimethylsiloxane, α,ω-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)polydimethyl siloxane (PMTS), the yield of hydrosilylation product, 1,3-bis(glycidoxypropyl) tetramethyldisiloxane exceed 86.5%. By tracing the change of methanol (gravimetry) and measuring the change of molecular weights of polydimethylsiloxanes at different reaction time (titration), the optimum reaction time of methoxylation reaction and ring-opening polymerization was determined as 8 and 12 h. Using α,ω-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)polydimethyl siloxane with different molecular weights, waterborne polyurethane–polydimethylsiloxane block copolymer were prepared. The influences of molecular weights and content of α,ω-hydroxyalkyl telechelic polydimethylsiloxane on the waterborne polyurethane–polydimethylsiloxane block copolymers were investigated in detail. The addition of α,ω-hydroxyalkyl telechelic polydimethylsiloxane could improve the water-resistance property obviously and increase the elongation at break. However, the mechanical property was reduced with increase of content and molecular weight of α,ω-hydroxyalkyl telechelic polydimethylsiloxane.     

Synthesis and characterization of a new block copolymer: Poly(butylene terephthalate-co-olefin) application on PP/PBT blend and PBT homopolymer

The synthesis of a new block copolymer was investigated by the condensation of terephthaloyl chloride, hydrogenated α,ω-dihydroxy polybutadiene and butanediol. The resulting (PBT) product is termed as the hard segment, and the hydrogenated α,ω-dihydroxy poly-butadiene is termed as the corresponding soft segment. This block copolymer was characterized by FTIR, ¹H and ¹³C-NMR, DSC, and SEC. Quantitative estimations of the contents of block segments have been carried out by NMR. The product was used either to increase the properties of PBT/PP blends or the impact strength of PBT. In both cases the mechanical properties are described. © 1995 John Wiley & Sons, Inc.