Products from the reaction of diphenyl ether with formaldehyde. Resins from formaldehyde. 86

From the reaction products of diphenyl ether with formaldehyde in the presence of acidic catalysts, six compounds were purely isolated: p-methylol and p,p′-dimethylol diphenyl ether, and four compounds of the following structures: Their structures were identified by the IR-absorptions and by the synthesis of their derivatives.     

Perfluoropolyether structures as surface modifying agents of UV-curable systems

New functionalised macromers containing perfluoropolyether (PFPE) structures and methacrylic end groups were synthesised and used as modifying additives for acrylic UV-curable systems. Their chemical structure is Rh-Rf-Rh, where and with p ≈ q. Notwithstanding their very low concentration, below 0.5 wt.-%, the fluorinated macromers cause a dramatic change of the surface properties of the films, without changing their curing conditions and their bulk properties. X-ray photoelectron spectroscopy (XPS) measurements showed that the macromers are able to concentrate selectively at the surfaces of the films, depending on their chemical structure and on the kind of substrate employed.     

Biotransformation of pinenes XVII. Transformation of α-and β-pinenes by means of Armillariella mellea (honey fungus), a parasite of woodlands

A culture of Armillariella mellea species was adapted to carry out microbial transformations of (+), (-), and (±)-α-pinene and (-)-β-pinene . The composition of products obtained indicated that allylic hydroxylation of all substrates was the most characteristic reaction for Armillariella mellea species. The hydroxylation occurred either directly in unchanged pinane skeleton yielding among other compounds verbenol ( ) and verbenone ( ) or was preceded by a cleavage of four-membered rings in substrates to form a menthane skeleton. The latter reaction leads to allylic alcohols and diols, mainly trans-sobrerol ( ) and 7-hydroxy-α-terpineol ( ).     

Synthesis of poly(phosphonylhydrazides)

Phenylphosphonic diisocyanate has been prepared and polymers from its condensation with hydrazines using the interfacial technique are reported. The polymers are believed to contain the following repeating structure:      

Synthesis and immunological properties of an artificial antigen with the repeating oligosaccharide unit of Salmonella illinois as haptenic group

The serological specificity of Salmonellae (O-specificity) is mediated by oligosaccharide subunits (repeating units) of the species-specific cell wall polysaccharides. With S. illinois (O-specificities 3, 15 and 34 of the Kauffmann-White scheme) as a representative example, it was possible to achieve the coupling of a complete repeating unit of that kind (in the case of S. illinois a tetrasaccharide) to protein, thus converting it into an artificial antigen. The repeating tetrasaccharide of the O-specific S. illinois polysaccharide has been obtained by partial acid hydrolysis of the O-specific S. illinois lipopolysaccharide and has the following structure with rhamnose as the reducing terminal sugar: In a reaction of this tetrasaccharide (TS_ill) with o-phenylenediamine and m-nitrophenylhydrazine and its subsequent reduction, TS_ill-_illl-(3-amino-phenyl)-flavazole was prepared, which was then coupled to edestin by means of the azo-method. Antisera obtained after immunization of rabbits with the TS_ill-_illl-(3-azophenyl)-flavazole-edestin conjugate contained TS_ill-specific antibodies, as shown by agglutination of S. illinois bacteria as test antigen (titers up to 1:2500). The specificity of these antibodies was tested in detail by cross-agglutination with various bacterial strains. These antibodies are predominantly directed against the non-reducing end group Glc Gal (Man) (O-factor 34), and only to a slight extent against the internal groupings' Gal Man (O-factor 15) and Man (Rha) (O-factor 3). The serum antibodies did not show cross-reactions with O-factor 12₂, which differs from O-factor 34 in the configuration of the Gal Man-linkage (12₂ :α-glycosidic, 34:β-glycosidic). Thus, by immunization of rabbits with a TS_ill-_illl-(3-azophenyl)-flavazole edestin conjugate, a largely factor-specific (anti-34) antiserum was obtained.     

Production of organometallic polymers by the interfacial technique. XXI. A study of some associated reaction variables in the synthesis of poly[imino-1.4-phenyleneimino(dibutylstannylene)]

Polymers of the below form are synthesized via the interfacial polycondensation route. A study has been made of the influence of the nature of the solvents employed and base and reactant concentration. New interfacial solvent systems are presented.     

Production of organometallic polymers by the interfacial technique. XXII. Synthesis of poly[alkylene(arylene)oxystannanes] using a new modified system

Poly[alkylene(arylene)oxystannanes] of the form below have been synthesized from dichlorostannanes and diols using a modified nonaqueous interfacial system consisting of acetonitrile and hydrocarbons. The products are preferentially capped with alcohol end-groups.     

The synthesis of dicarboxylie acids containing oxadiazole rings and polyamides derived from them

Novel dicarboxylic acids containing one or two 1,3,4-oxadiazole rings in a molecule were synthesized by the reaction between orthoesters and acid hydrazides These dicarboxylic acids have the following structures: and where R represents a phenylene or an alkylene group and n = 1-4. The polyamides from p-xylylenediamine with these dicarboxylic acids were also prepared. The polymers are generally insoluble in m-cresol but soluble in conc. sulfuric acid. The melting points were estimated at above 350°C. Copolyamides of high molecular weights with aliphatic polyamides were obtained.     

Macromol. Chem. Phys. 13/2011

Reactive blending of functionalized polyethylenes (PE) and polyamides (PA) is performed by carefully choosing extrusion conditions and polymeric materials in order to obtain two types of stable morphologies. The first blend type yields a co‐continuous morphology and the second type a dispersion of sub‐micron droplets of the PA phase in a PE matrix. The crystallization kinetics of the PA change from a sigmoidal classical type (for the co‐continuous blend) to first‐order kinetics in the case of the sub‐micron PA droplets. The results demonstrate an intimate relationship between blend morphology and nucleation and crystallization kinetics of the blend components.

     

The synthesis of polymers from phenylphosphonic diisocyanate and diamines

Phenylphosphonic diisocyanate has been prepared and polymers from its condensation with diamines using the interfacial technique are reported. The polymers are believed to contain the following repeating structure:      

Reduction of nitrile end groups in styrene polymers and their subsequent determination by dye partition technique

Nitrile groups were incorporated in polystyrene through (i) initiation with azoisobutyronitrile (AIBN) and (ii) copolymerization with a trace of acrylonitrile. Their detection and estimation by dye partition technique were experimentally realized. The method consists in first converting nitrile end groups to primary amino end groups by reducing with lithium aluminium hydride in tetrahydrofuran medium followed by testing and quantitatively estimating the amino end groups in the resultant polymer by the usual dye partition technique. AIBN initiated polystyrene was found to contain on the average 2 nitrile end groups per polymer molecule supporting the fact that combination is the predominant mode of termination in styrene polymerization. The copolymer reactivity ratio (r₁) for styrene (M₁) – acrylonitrile (M₂) copolymers as determined by this technique agrees fairly well with the existing literature values. This verifies the quantitative applicability of the dye partition method for the study of macromolecular reactions.     

Radikalbildung und Kettenbruch bei der Radiolyse von Polypropylensulfid

Radiolysis of polypropylene sulfide with thiol and thioether endgroups was investigated. The results of change in average molecular weight with radiation dose show that statistical main chain scission takes place (G_sc = 0.4–0.7). The following radicals could be identified by ESR-spectroscopy: A mechanism is proposed, which correlates the radical formation with chain scission. It can be shown that predominantly C? C bond scission and not C? S bond scission takes place.     

Synthesis of some new poly(phosphonylhydrazides)

Polymers have been prepared from the condensation of phenylphosphonic diisocyanate with hydrazides using the interfacial technique. The polymers are believed to contain the following repeating structure: The reactivity of nitrogen compounds with phenylphosphonic diisocyanate is of the order amines > hydrazines ≈ hydrazides > ureas.     

Infrared spectroscopic study of the structural change of polymethacrylonitrile following heat-treatment and subsequent treatment with water

The infrared spectrum of polymethacrylonitrile (PMAN) exhibits noticeable change on heat-treatment up to 240°C, the color of the sample changed from yellowish at 120°C, through yellow and red, to deep red at 210°C or above. A new structure was proposed as a plausible structure for the chromophore of the heat-treated PMAN film, on the basis of comprehensive consideration of details of the spectral change in reference to the corresponding spectral change of polyacrylonitrile (PAN) and the spectra of compounds having similar structures. Subsequent treatment of the deep-red PMAN with hot water further drastically changed the infrared spectrum, and in turn the color changed from deep red to yellowish. The spectrum of the hydrolyzed product was in complete agreement with that of the copolymer of methacrylonitrile and methacrylic acid. Thus the structure was found to be from infrared spectral comparison.     

Oligomerization of styrene by trichloroacetyl chloride

The thermal oligomerization of styrene at 60°C with trichloroacetyl chloride (TAC) was investigated. The initial rate of oligomerization can be described by the equation The analysis of the oligomers showed that the main component of the oligomers was a styrene trimer of the structure      

Production of organometallic polymers by the interfacial technique. XVII. Synthesis and spectral study of germanium polyesters

Polyesters of the form below are prepared by the interfacial method. Infrared frequency band assignments are given.      

The synthesis of α-tert-butyl-ω-[p-vinylphenyl]-terminated poly(2-methylpropene) macromonomers

In this communication a novel synthetic route to α-tert-butyl-ω-[p-vinylphenyl]xy1terminated poly(2-methylpropene) (PIB) macromonomers ( P3 (VB); P5 ) is described: and Attempts to synthesize such macromonomers in both one- and two-step syntheses are described. The one-step method using 4-chloromethylstyrene/AlR3 as initiating system for the polymerization of 2-methylpropene did not yield linear macromonomers but rather highly branched products. The alternative two-step synthesis using 1-(2-bromoethyl)-4-chloromethylbenzene (BCB) or BCB/AgSbF, as initiator also failed to yield the desired products. Successful syntheticroutes, optimised on the basis of model experiments with low molar mass compounds, are also described for preparing the above macromonomers. Both of these routes involve isopropenylterminated PIB, which is easily assessible by Inifer technique followed by dehydrohalogenation. Friedel-Crafts alkylation of phenol by the terminal olefin group of PIB, followed by subsequentesterification of the phenolic end-groups with 4-vinylbenzoyl chloride, affords the macromonomer P3(VB). Conversion of the terminal olefin group of PIB into a primary alcohol using 9-bora[3,3, I]-bicyclononane/H202, followed by esterification, yields the macromonomer P5 .     

Hapten-carrier relationships in immunological unresponsiveness

Cyclophosphamide-treated mice received 10 mg of a hapten-protein conjugate 4-Hydroxy-5-iodo-3-nitro-phenacetyl bovine serum albumin (NIP_1.1BSA) over 10 weeks. Three and seven weeks later they were challenged. The responses of the paralyzed mice relative to control mice are given below in a simplified form. We concluded that the paralysis-treatment had caused unresponsiveness to some antigenic determinants (at least NIP) but priming to others.     

Polymerisationsauslösung mit substituierten Ethanen, 1. Polymerisation von Methylmethacrylat mit 1,1,2,2-Tetraphenyl-1,2-diphenoxyethan

1,1,2,2-Tetraphenyl-1,2-diphenoxyethane (TPPA) initiates at 70°C the polymerization of methyl methacrylate. In the first period oligomers of the type 1 with two phenoxydiphenylmethyl end groups (P_n ≈ 1 – 20) are formed by primary radical termination. These telechelics are effective initiators of the further free radical polymerization of vinyl monomers.     

Production of organometallic polymers by the interfacial technique. XI. Synthesis of poly(organotin esters) and a study of some associated reaction variables

Polyesters of the form below are prepared by the interfacial method. Isolation procedures are presented and discussed. Polymer yield is constant as stirring rate, stirring time and nature of the organic solvent are varied. Molecular weight is constant as stirring rate and organic solvent nature are varied. Molecular weight increases as reaction time increases. No correlation is found between polymer molecular weight and polymer softening range.