Biozide polymere, 6. Synthese und polymerisation von acryl- und methacrylsäurederivaten des 3-amino-1,2,4-triazols

Preparation and characterization (by IR and ¹H NMR spectroscopy) of isomeric methacrylic acid and acrylic acid derivatives of the herbicide 3-amino-1,2,4-traizole are described. Their radical polymerization and copolymerization with styrene or methyl methacrylate give polymers containing the herbicide moiety as pendant groups bound via acyl groups at the amino group or at the ring nitrogen. The reactivity ratios were determined for the isomeric methacrylic compounds.     

Synthese und Komplexierungseigenschaften von monomeren und polymeren 5-Methacryloylaminosalicylsäure-Derivaten

The synthesis of monomeric and polymeric 5-methacryloylaminosalicylic acid derivatives is described. The interaction of these ligands with Fe(III), Ti (IV) and Ca(II) ions was investigated by photometric, conductometric and viscosimetric measurements.     

Darstellung von neuen makromolekularen stoffen aus derivaten der 3-aminocrotonsäure und dimaleinimiden

Cross-linked polymers are formed by a new addition polymerization of dimaleinimides with bis(3-aminocrotonic acid)-esters, -amides, or -nitriles. Model reactions show that the derivatives of 3-aminocrotonic acid add to the electrophilic double bond of maleinimide. The resulting succinimid derivatives rearrange thermally to the corresponding pyrrolinones. At higher temperatures, especially in the presence of an excess of maleinimide, a second molecule of maleinimide is added to the pyrrolinone. Some properties of moulded and casted polymers are described.     

Copolymere aus methacrylsäure und dimethacryloylimid und die abhängigkeit ihrer NMR-spektren vom neutralisationsgrad

The chemical structure of syndiotactic methacrylic acid-dimethacryloylimide (MAA-MAI) copolymers is studied by the NMR-spectra of products obtained by polymeranalogous reactions and from MAA-MAI copolymers prepared according to a different route. The kinetics of formation of the imide rings is compared with kinetic equations, confirming thereby the random formation of rings along the chain. ¹³C NMR spectra of MAA-MAI copolymers depend on the degree of neutralization, α, in aqueous solution and show large changes for the carbonyl resonance region. Resolution into triads is found in organic solvents, whereas in aqueous solutions there is splitting into pentads on going from α = 0 to α = 1. The pentad assignment is made by observing the movement of the peaks with changing α and by comparison with pentad probabilities derived by a Monte-Carlo simulation. The great changes in the chemical shift are caused to a large extent by a change in the charge of the carboxyl groups. Discontinuous changes in charge, conformation, and solvation are not found.     

Synthese und Charakterisierung von Copolymeren aus Azo-Initiatoren und Styrol

Copolymers with azoinitiator functions were prepared from styrene and different arylazoalkylmalonodinitriles by copolymerization in emulsion, using redox-initiators. This type of copolymer can be used for syntheses of graft copolymers. The concentration of azo-groups per polymer chain, the polymerization rate, and the molecular weight of the isolated copolymers were determined as a function of the composition of the starting monomer mixture and the structure of the azo-compounds. It was tried to separate the crude product of the grafting reaction into the ungrafted backbone, the graft-copolymer, and the homopolymer.     

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.     

Biocide polymere, 12. Synthese und hydrolyseverhalten von copolymeren aus methacryl- und acrylsäure sowie 1-methacryloyl- und 1-acryloyl-3-methylpyrazol

The radical copolymerization of 1-acryloyl- and 1-methacryloyl-3-methylpyrazole ( 1a and 1b ) with acrylic acid or methacrylic acid in solution was studied. Copolymers containing carboxyl as well as 3-methyl-1-pyrazolylcarbonyl groups as side chains were prepared via the reaction of 3(5)-methylpyrazole with activated poly(acrylic acid)s of various molecular weights. The hydrolysis data suggest that the release rates of the biocide 3(5)-methylpyrazole from the investigated copolymers vary significantly depending on the content of carboxyl groups and their change during the hydrolysis.     

Darstellung und polymerisation von diestern aus 2,2′-methylendiphenolen und acryl-, methacryl- bzw. Crotonsäure

Several mono- and diesters of four selected 2,2′-methylenediphenols with acrylic, methacrylic, and crotonic acid were synthesized for the first time. Special emphasis was paid to the preparation of diesters with two different acyl groups which could be obtained via the corresponding monoesters. The radical polymerization of these esters with AIBN (mainly in benzene) gave insoluble (crosslinked) products from dimethacrylates and soluble (linear) polymers from mixed diesters with methacrylic and crotonic acid, while the dicrotonates are not reactive.     

Synthese von polyestern durch copolymerisation von dicarbonsäreanhydriden und ringäthern

Linear polyesters may be synthesized by copolymerization of dicarboxylic acid anhydrides and cyclic ethers according to anionic or cationic reaction mechanisms. Anionic copolymerization of dicarboxylic acid anhydrides and epoxides is catalyzed by salts of inorganic and organic acids, by alkalis, or amines. Reaction dependance from various experimental parameters was investigated. The polyesters are free from ether links and copolymerization runs strictly alternating. From experimental results a reaction mechanism for copolymerization of carboxylic acid anhydrides and epoxides was derived. Cationic copolymerization of dicarboxylic acid anhydrides with oxacyclic compounds such as five or higher membered cyclic ethers is catalyzed by complex cationic catalysts as LEWIS acid / cocatalyst or oxonium salts. The polyesters received partially contain ether links. Ether content varies with the molar ratio of monomers and especially with catalyst type and catalyst concentration. Polyesters partially containing ether or acetal links may also be prepared under the same conditions from polyethers or polyacetals and dicarboxylic acid anhydrides. Reaction mechanisms for the reactions investigated are suggested.     

Untersuchungen zur struktur der bei der reaktion von dicarbonsäureanhydriden und cyclischen carbonaten von diolen entstandenen polyster. Synthese von polyestern aus dicarbonsäureanhydriden und epoxiden oder cyclischen carbonaten von diolen. 3. Mitteilung

Polyesters from dicarboxylic acid anhydrides and cyclic carbonates of dihydric alcohols were investigated for the presence of extraneous ether linkages. In order to do this the polysters were saponified with alkali and the resulting dihydric alcohols were identified by thin layer- and gas-chromatography. The accuracy of the determination was such that there were shown to be less than 0.05% of ether linkages.     

Polymerisationen und polymerisationsinitiatoren, 16. Einfluß von Thioxo-Gruppen in barbitursäurederivaten auf die polymerisationsauslösung von methacrylsäure-methylester

In the presence of Cu²⁺ and Cl^? ions as well as atmospheric oxygen 5-alkyl-1,3-dimethylbarbituric acids initiate the radical polymerisation of methyl methacrylate. If a thioxo group is introduced in position 2 of the barbituric acid, initiating capability is slightly increased; thioxo functions in position 4 or 4,6, on the other hand, suppress initiation almost completely. In this case, the radicals formed at C-5 are stabilized by the neighbouring thioxo groups and dimerize at the sulfur atoms, yielding disulfides. Thus, these thiobarbituric acids may act as inhibitors. In the case of Cu(II)-catalyzed initiation, this inhibiting effect is enhanced by formation of almost insoluble Cu(I) thioxobarbiturates.     

Über den einbau von chlor bei der polymerisation von methacrylsäuremethylester XV. Mitteil. Polymerisationen und polymerisationsinitiatoren

It was found, that during the polymerization of methyl methacrylate in the presence of methylene active initiators, chloride, and oxygene, chlorine is incorporated into the polymer. The incorporation is measured by radiochemical methods. In the presence of α-benzoyl-propionitrile the incorporation is dependent on the concentration of chloride; this is interpreted by a destruction of the intermediate formed hydrogen peroxide effected by chloride. In the presence of N-ethyl-bis-(p-toluenesulphonylmethyl)-amine or 1.3.5-trimethyl-barbituric acid the incorporation of chlorine is independent on the concentration of chloride. In this case a preferable thermical destruction of the intermediate hydrogen peroxide is supposed.     

13C-NMR-sequenzanalyse, 5. Synthese von nylon-5 und alternierenden copolyamiden der 5-aminovaleriansäure aus 5-isothiocyanatovaleriansäure

Starting with 5-aminovaleric acid ( 2 ) the 5-isothiocyanatovaleric acid trimethylsilylester ( 1 ), 5-isothiocyanatovaleric acid ( 3 ) and its acid chloride ( 4 ) were prepared. The thermal condensation polymerization of 3 yielding nylon-5 was examined under various reaction conditions. In the same way, starting with 4 , N-(5-isothiocyanatovaleryl)-β-alanine ( 5 ) and N-(5-isothiocyanatovaleryl)-4-aminobutyric acid ( 6 ) were synthesized and condensed to alternating copolyamides of 5-aminovaleric acid. The thermal degradation of nylon-3, -4, -5, and -6 as well as of some alternating copolyamides was investigated by thermal gravimetric analysis and the degradation mechanisms are discussed. The ¹³C-NMR-spectra of alternating copolyamides from 5-aminovaleric acid, 4-aminobutyric acid, and β-alanine were compared and relationships between sequences and chemical shifts of the CO signals established.     

Stabile polysauerstoff-radikale. I. Synthese von polymerisationsfähigen monomeren mit sterisch behinderter freier oder geschützter phenolischer hydroxylgruppe

New monomers with sterically hindered free or blocked phenolic hydroxyl groups were used as starting compounds for the preparation of stable oxygen polyradicals. In this paper the synthesis of these monomers is described: 2,6-Di-(tert-butyl)-4-vinylphenol was obtained by decarboxylation of 3-[3,5-di-(tert-butyl)-4-hydroxyphenyl]acrylic acid in yields of 80–;90%. 2,6-Di-(tert-butyl)-4-isopropenylphenol was prepared from 3,5-di-(tert-butyl)-4-hydroxyphenyl methyl ketone and methyl iodide by a GRIGNARD reaction followed by the dehydration of 2-[3,5-di-(tert-butyl)-4-hydroxyphenyl]-2-propanol. 2,6-Di-(tert-butyl)-4-isopropenylphenyl methyl ether was obtained with 64% yield from 3,5-di-(tert-butyl)-4-methoxybenzonitrile by two consecutive GRIGNARD reactions with methyl iodide via the unknown compounds 3,5-di-(tert-butyl)-4-methoxyphenyl methyl ketone and 2-[3,5-di-(tert-butyl)-4-methoxyphenyl]-2-propanol, followed by dehydration of the tertiary alcohol with 89% phosphoric acid.     

Asymmetrische 1,3-induktion und solvatation bei der radikalischen polymerisation von methacrylsäure und methylmethacrylat—ein beitrag zur stereochemie der wachstumsreaktion

The influence of the polymerization medium on the configuration of polymethylmethacrylate and polymethacrylic acid, prepared with radical initiators, has been investigated. The syndiotacticity of polymethylmethacrylate does not depend on the solvent. The syndiotacticity of polymethacrylic acid, or its salts depends on the contrary highly on the extent of hydrogen bonds between the monomer and the solvent. The bigger the monomer-solvent-complex, the higher is the syndiotacticity of the polymer.     

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.     

Das 13C-NMR-spektrum von alternierenden copolymeren aus äthylen und propylen

Alternating copolymers from ethylene and propylene were prepared by hydrogenation of cis-1,4-polyisoprene and isotactic trans-1,4-poly(1,3-pentadiene). In their ¹³C-NMR spectra meso and racemic diads were identified and assigned. The chemical shift of the meso diad appears to higher field.