Über den einfluss der viskosität der lösung auf die racemisierung optisch aktiver atropisomerer biphenylverbindungen

Some monomers, oligomers and polymers with conjugated triple bonds

In the first part new monoaminodiacetylenes with different numbers of CH2-groups, the formation of Perowskit-type Mn complexes and their polymerizability are described. Symmetrical diaminodiacetylenes and some derivatives therefrom have also been prepared. The second part deals with different types of polymers with diacetylene units in the backbone. Under irradiation color formation and crosslinking take place. Well-defined low molecular weight model compounds of polydiacetylenes is the subject of the third part. Finally rod-like but soluble polymers with alternating p-phenylene and acetylene units are described.

Synthese und Eigenschaften von optisch aktiven Polymeren

Polymerisation von kristallinem Acrylamid durch γ-Strahlen

Untersuchungen über die Polymerisation von 2-Formyl-Δ5-dihydropyran

Nach einer kurzen Beschreibung des dimeren Acroleins (2-Formyl-Δ5-dihydropyran) wird die spontane und katalysierte Polymerisation untersucht. Fur die Spontanpolymerisate wird die Struktur eines Polyacetals vorgeschlagen. Borfluoridatherat und Eisen-III-chlorid fuhren zu Polymeren mit ganz anderen Eigenschaften. An Hand der chemischen Reaktionen und IR-Spektren werden die moglichen Strukturen der kationischen Polymerisate diskutiert. After characterization of the acrolein dimer (2-formyl-Δ5-dihydropyran) its spontaneous and catalytic polymerization has been investigated. A polyacetal structure has been suggested for the spontaneous polymer. Borofluorid-etherate and iron-trichloride lead to p…

Metalation and N-alkylation of some polyamides

Totally N-substituted polyamides were synthesized starting from poly(2,4,4-trimethylhexamethylene terephthalamide) by metalation of the amide groups and subsequent reaction with several electrophiles. Polyamides of this structure are not available from terephthalic acid and the corresponding diamines by polycondensation. This N-alkylation reaction can be used for the synthesis of comb-like graft copolymers. The solubilitity and the thermal properties of these polyamide derivatives are described.

An ionene with spirane structure (spiroionene)

The secondary diamine 1,3,5,7-tetrahydro[1,2c:4,5c'] benzodipyrrole (3) and 1,2,4,5-tetrabromomethylbenzene (1) form a polymeric ionene with spirane structure through a repetitive alkylation reaction. The structure of the product could be proven by13C-NMR spectroscopy by comparison with suitable reference compounds. Solutions in aqueous methanol exhibit a typical polyelectrolyte effect. Variation of the counterions produces sufficient solubility in organic solvents. From the crystal structure of a similar model compound one can conclude that the synthesized polymer has a rod-like shape.

Demonstrationsversuch zur lichtempfindlichkeit von N-Chlor-Nylon 66

Some examples of the modification of polymers

Reactions avec des groupes amide et amino dans la chaine principale, et avec un groupe terminal bromoacetyl. Polymerisation de la conidine en presence d'un polystyrene vivant

Optische Messungen an Amylose-Farbstoff-Komplexen

In neutralen wasrigen Losungen, die Amylose und Kongorot enthalten, treten im Bereich der Absorptionsmaxima Abweichungen von der normalen optischen Rotationsdispersion und mehrere induzierte Cotton-Effekte auf. Hieraus wird auf eine geordnete Assoziation der Farbstoffmolekule an helicale Segmente der Amylose geschlossen. Bei Methylorange, β-Naphtholorange und Chrysophenin G sind keine induzierten Cotton-Effekte zu beobachten.

Polymere Charge-transfer-Komplexe auf der Basis von Polyvinylalkoholacetalen

Poly[2-(1-naphthyl)-1,3-dioxan-4,6-diylmethylene] (3), poly[2-(2-naphthyl)-1,3-dioxan-4,6-diylmethylene] (5), 1-naphthalenecarbaldehydetrimethyleneacetal (7) and 2-naphthalenecarbaldehydetrimethyleneacetal (8) were synthesized and characterized by UV- and fluorescencespectroscopy. In addition triplet-triplet absorption maxima and triplet-lifetimes were determined by flash technique. The naphthalene derivates were found to act as donors in the charge-transfer complex formation with such electron acceptors as tetracyanoethylene, 2,5-cyclohexadien-1,4-diylidenedimalonodinitrile and 2,4,5,7-tetranitro-9-fluorenone. The equilibrium constants of the charge-transfer complexes were determined spect…

L'etude viscosimetrique, potentiometrique et conductimetrique montre que le copolymere forme un complexe de stœchiometrie 2:1 avec le chlorure de palmityltrimethylammonium. Avec le laurylsuslfate de sodium, il y a d'abord formation d'un complexe de composition 2:1 puis par addition supplementaire du surfactant, formation d'un complexe 1:1

Untersuchungen über die emulsionspolymerisation des acroleins. Polymere acroleine. 15. Mitteilung

Die Polymerisation des Acroleins mit verschiedenen Emulgatortypen wird untersucht. Es zeigt sich, das eine Losung von Polyacrolein in wasriger schwefliger Saure ein vorzuglicher Emulgator fur die Emulsionspolymerisation von Acrolein mit Redox-Systemen ist. An diesem System wird der Einflus der Emulgatorkonzentration S, der Initiatorkonzentration ci, der Monomerkonzentration und der Temperatur gepruft. Man findet folgende Beziehungen: VBr ∼ S1/5; VBr ∼ c; und VBr ∼ M. Die experimentellen Ergebnisse werden mit den nach der Theorie von SMITH und EWART zu erwartenden verglichen und diskutiert. The polymerization of acrolein with several types of emulsifiers has been investigated. There is shown…

Zur Analyse von Milchsäure-Glykolsäure-Copolyestern

Fur L-(–)-Lactid-Glykolid-Copolyester (3) wurden drei voneinander unabhangige Analysenmethoden zur Bestimmung der Copolymeren-Zusammensetzung ausgearbeitet. Die 1H-NMR-Spektroskopie wurde fur Copolyester mit Lactid-Gehalten uber 10 Gew.-% erfolgreich angewandt, nachdem mit Trifluoressigsaure ein geeignetes Losungsmittel gefunden war. Insbesondere fur die praktisch interessanten Materialien mit kleinem Lactid-Anteil, wie z. B. resorbierbares chirurgisches Nahtmaterial, eignen sich die Messung der optischen Rotation sowie eine chemische Methode, die auf der quantitativen Bestimmung der Milchsaure nach vorhergehender alkalischer Totalhydrolyse beruht. The copolymer-composition of L-(–)-lactide…

By endcapping of living polystyrene with ethylene oxide and subsequent reaction with bromoacetyl bromide a polymer with a bromoacetoxy endgroup was obtained. This was used as a macroinitiator for the living cationic polymerization of 1-azabicyclo[4.2.0]octane. The structure and composition of the so formed two-block copolymer was elucidated by different methods. The ratio of the two block and their lengths were varied within broad limits.

Copolymerisation zwischen Vinylencarbonat und Isobutylvinyläther

Bei der radikalinduzierten Copolymerisation zwischen Vinylencarbonat (M1) und Isobutylvinylather (M2) ergeben sich folgende Parameter:r1=0,160;r2=0,185. Der Einflus von Losungsmitteln und der Temperatur auf die azeotrope Copolymerisation wurde untersucht. An den verseiften Copolymeren wurden Acetalisierungsreaktionen mit Propionaldehyd und Veresterungen mit Borsaure, Ameisensaure undp-Toluolsulfochlorid durchgefuhrt.

Strukturuntersuchung von polyestern durch direkten abbau im massenspektrometer, 4. Polyester und copolyester der milchsäure und glykolsäure

Polyesters and copolyesters of 2-hydroxyacetic acid (glycolic acid) and 2-hydroxypropionic acid (lactic acid) were investigated by direct pyrolysis in the ion source of a mass spectrometer. Thermal degradation of these polyesters and copolyesters at 10−6 mbar yields cyclic oligomers which are further degraded by an electron impact induced mechanism by elimination of formaldehyde or acetaldehyde and CO2 to give characteristic series of linear ions. In the pyrolysis mass spectrum of a copolyester (mole ratio of monomeric units ≈1:1) intact sequences up to 8 monomeric units can be observed.

New monomers are described for the synthesis of rod-like poly(1,4-phenyleneethynylene)s with long flexible aliphatic side chains. By palladium catalyzed polycondensation soluble polymers with melting points around 100°C could be obtained. The molecular weight was estimated by GPC, VPO and elemental analysis: GPC showed a multimodale distribution with Pn = 9–15. NMR spectra were found to be in agreement with the assumed polymer structure, but signals of the acetylenic carbons could not be detected. A broad, structureless absorption with a maximum at λ = 410 nm is seen in the UV-VIS-spectra. The thermal decomposition of the substituted PPE's starts at about 400°C and is comparable to that of …

Polymersynthesen durch repetitive N-alkylierungen

The repetitive N-alkylation reaction, at first used by Marvel, turned out to be a very versatile method for the synthesis of polycations. Rembaum introduced the name ionenes for this type of polymers. In the first part of the lecture some examples of single-stranded ionenes are described. The second part shows how the repetitive N-alkylation can be used for the synthesis of spiro polymers. In these double-stranded polymers two spiro-conjugated rings of the main chain have a central quaternary nitrogen in common (spiro-ionenes or spiro-azonia polymers)

Darstellung, eigenschaften und umsetzungen von polyvinylsulfofluoriden

Vinylsulfofluorid wurde mit Azo-bis-isobutyronitril polymerisiert. Es wurden Polymerisationsgrade bis 390 erreicht. Die Molekulargewichte wurden durch Viskositatsmessungen an den durch Verseifung der Polyvinylsulfofluoride gewonnenen Natriumsalzen der Polyvinylsulfonsaure ermittelt. Die Polyvinylsulfofluoride wurden mit Ammoniak, aliphatischen und aromatischen Aminen umgesetzt. Dabei wurden Umsatze bis zu 80 Mol% erreicht. Vinylsulfofluoride was polymerized with azo-bis-isobutyronitrile. The degree of polymerisation was up to 390. The molecular-weights were determined by measuring the viscosity of the sodium-salts of polyvinylsulfonic acids obtained by saponification of polyvinylsulfofluori…

Polymere aus Acrolein

Als ungesattigter Aldehyd eignet sich Acrolein zur Herstellung verschiedenartiger Hochpolymere. Betrachtet man es in Analogie zum Butadien als ein 1.3-Dien, so lassen sich alle Polymerisationen einheitlich beschreiben und weitere Moglichkeiten voraussehen. Unter diesem Gesichtspunkt wird ein Uberblick uber Ergebnisse der letzten 10 Jahre gegeben. Es wird gezeigt, das Acrolein eines der wenigen Monomeren ist, die zwei polymerisationsfahige Gruppen unterschiedlicher Reaktivitat enthalten. Hieraus ergeben sich neue Moglichkeiten zur Herstellung von Homopolymerisaten, Copolymerisaten und Pfropfcopolymerisaten, die sich bei den meisten anderen Monomeren nicht bieten.

Optische Rotationsdispersion und Circulardichroismus bei Jod-Polysaccharid-Komplexen

Die wasrigen Losungen der Jodkomplexe von Starke, verschiedenen Amylosen und Amylopektinen zeigen im Bereich der betreffenden Absorptionsmaxima einen induzierten positiven Cotton-Effekt. Die Drehwerte hangen in der gleichen Weise vom Jod-Amylose-Verhaltnis ab wie die Extinktionen bei 660 und 445 mμ. Die Drehwerte einiger Jod-Polysaccharid-Komplexe nehmen mit der Zeit stark zu, obwohl die Extinktion konstant bleibt. Masnahmen, durch welche die Struktur der Jod-Einschlusverbindung verandert wird (Erwarmung, Zusatz von Salzen, Losungsmitteln, Harnstoff, Netzmitteln) haben einen starken Einflus auf den induzierten Cotton-Effekt.

Trifluoracetylierung von aminosäureestern und dipeptidestern mit N-trifluoracetyl-polyamid 66.

N-Trifluoroacetyl-Polyamid 66 (1) is used for the trifluoroacetylation of amino acid- and dipeptide esters. Advantages and limitations of the polymeric reagent compared with low molecular trifluoroacetylating reagents are discussed. A mixture of amino acid methyl esters can be converted by 1 to the N-trifluoroacetyl derivatives, which are separated and identified by gas chromatography.

Cyclopolymerisation einiger glutardialdehyde. Struktur der polymeren

Die loslichen Spontanpolymerisate des Glutardialdehyds, β-Methyl- und β-Phenylglutardialdehyds bestehen auf Grund ihrer Eigenschaften und IR-Spektren vornehmlich aus Tetrahydropyranstruktureinheiten, die durch eine Cyclopolymerisation gebildet werden. Es wird ein infrarotspektroskopischer Vergleich mit verschiedenen niedermolekularen Tetrahydropyran-Modellsubstanzen durchgefuhrt. Die unkatalysierte Polymerisation last sich infrarotspektroskopisch verfolgen. Die Poly-glutardialdehyde konnen acetyliert werden. Die Polymeren erfahren durch die Acetylierung eine wesentliche thermische Stabilisierung. Die Eigenschaften und IR-Spektren der Spontanpolymerisate werden mit denen des vernetzten Poly-…

Synthesis and properties of polymers with unusual structure

This lecture summarize some recent results of our current research. The first part describes the homopolymerization and copolymerization of a monocyclic and two bicyclic unsaturated acetals. In this way polyacetals with 1,4-cis-butadiene units and cyclohexene units respectively are obtained. Secondly, the N-substitution of polyamides is described. By N-metalation and subsequent alkylation comb-like polyamides are available. Longer branches cause a side-chain crystallinity. The anionic “grafting-from” technique forms irregular branched polyamides. By termination reaction between living ends of poly(2-isopropenylnaphthalene) and suitable electrophiles new macromonomers are available. The last…

The structure of 1-azabicyclo[4.2.0]octane (1) was evaluated by NMR spectroscopy. It was found that the six-membered ring has a chair conformation with the four membered ring in the N-axial and C-6-equatorial position, and as a consequence, the monomer allows neither a ring inversion nor a nitrogen inversion. It possesses two centers of chirality, one at the nitrogen atom and one at C-6. Homopolymerization was carried out in methanol at 60°C with N-alkyl ammonium salts of 1 affording the polymer in high yield within a few hours. Its NMR spectra reveal that the polymer chain is preferably arranged in the biequatorial position of the six-membered ring. As a polybase the polymer can be titrate…

On new chemical reactions of polymers

Three major areas of work present themselves to a chemist who is concerned with polymer materials namely: synthesis and degradation of polymers; structure analysis of natural and synthetic polymers; and chemical transformations of polymers. Although these three fields are very closely related, I wish to concern myself only with the last of them.

ESR spectroscopic analyses of the deep-green solutions of living poly(2-isopropenylnaphthalene) [poly(2-IPN)] in THF at −80°C provided no evidence of the presence of radical anions as long as butyllithium (BuLi) was used as initiator. In contrast to this finding, radicals could indeed be detected if the polymerization was performed with metallic potassium in THF. These radicals were found to be only stable at low temperatures. UV/VIS spectra of solutions of 2-IPN in THF or toluene and of catalytic quantities of BuLi were recorded at temperatures between −45 and +20°C. On heating to >0°C, the colour of the deep-green solution changes irreversibly to reddish-brown, and this colour change is a…

Polyfunctional chloroformates were applied to the polymerization of 2-phenyl-2-oxazoline and 2-methyl-2-oxazoline. The use of a trifunctional initiator, viz. the chloroformate of 2,2-bis(hydroxymethyl)-1-butanol, led to three-arm star polymers of 2-oxazolines. Two macromolecular initiators, viz. poly(ethylene oxide) with two chloroformate end groups (α-chloroformyl-ω-chloroformyloxypoly(oxyethylene)) with number-average molar masses 350 g/mol ≤ Mn ≤ 6000 g/mol and α-chloroformyl-ω-methoxypoly(oxyethylene) with Mn = 350 and 750 g/mol were applied for the synthesis of poly(2-oxazoline)-block-poly(ethylene oxide)-block-poly(2-oxazoline) and poly(2-oxazoline)-block-poly(ethylene oxide) copolyme…

Dihydropyran‐Derivate durch Dien‐Synthesen von α‐β‐ungesättigten Carbonylverbindungen mit N ‐Vinyl‐Verbindungen

Durch Addition mehrerer N-Vinyl-carbamidsaureester und N-Vinyl-harnstoff-Derivate an α.β-ungesattigte Carbonylverbindungen entstehen bisher unbekannte N-[2.3-Dihydro-pyranyl-(2)]-carbamidsaureester bzw. -harnstoffe. Durch Hydrolyse erhalt man Glutardialdehyd oder 4-Acetyl-butyraldehyd. Katalytische Hydrierung liefert die entsprechenden Tetrahydropyran-Derivate. Die UV-Spektren werden beschrieben.

The Preparation of 1,3-Divinylparabanic Acid (1,3-Divinylimidazoletrione) and its 4-Imino Derivative

Beiträge zur polymerisation von 2-isopropenylnaphthalin, 4. Über die copolymerisation mit maleinsäureanhydrid und mit maleinimid

Synthetische makromolekulare Stoffe mit reaktiven Gruppen

Es wird uber Synthese, Eigenschaften und Reaktionen einiger makromolekularer Stoffe mit reaktiven Gruppen berichtet, und zwar uber Derivate der Polyacrylsaure (Polyacrylsaure-hydrazid, Polyacrylhydroxamsaure, Polyacrylsaureamid), des Polyvinylalkohols, uber Polyacrolein und Polymethacrolein, Polyvinylsulfonsaure und ihre Derivate sowie uber Copolymere aus Styrol und Maleinsaureanhydrid. An den reaktiven Gruppen dieser polymeren Stoffe werden chemische Reaktionen ausgefuhrt. Dabei zeigt sich, das unter Bedingungen, die dem makromolekularen Bau des Reaktionspartners angepast sind, eine Reihe von Reaktionen, die aus der niedermolekularen Chemie gut bekannt sind, auf solche Polymere ubertragen …

Synthese a partir de l'hexahydro-1,5,5a,6,9,9a benzodioxepinne-2,4. Polymerisation en masse en un produit incolore, cireux (Tg=−11°C)

Umsetzungen zwischen zwei Polymeren mit reaktionsfähigen Gruppen

Beim Mischen von Polymeren-Losungen kann als Folge physikalisch-chemischer Wechselwirkungen eine Phasentrennung eintreten. Beispiele fur die Salzbildung zwischen Polyanionen und Polykationen werden besprochen. Zwischen Polymeren mit reaktiven Gruppen konnen auch chemische Umsetzungen ablaufen, die zur Vernetzung uber Hauptvalenzbindungen fuhren. Die Reaktionen von Polyacroleinen mit synthetischen oder naturlichen Polymeren werden geschildert. Sie ergeben unlosliche Fallungen oder Oberflachen-Pfropfungen. Uberschussige Aldehyd-Gruppen in den vernetzten Produkten konnen durch Farbreaktionen nachgewiesen werden. Die physikalischen Eigenschaften (Quellung und Schrumpfung) der erhaltenen „Verbun…

Some new examples of polymer modification

This lecture summarizes some of our recent results about reactions with synthetic polymers. By cationic ring-opening polymerization of 4H, 7H-1,3-dioxepin a linear polyacetal containing one C-C-double bond per repeating unit is obtained. Copolymerization of this monomer with trioxane or dioxolane is possible. Various addition reactions can be carried out with these unsaturated polyacetals, polymeric epoxides being of special interest. Some other unsaturated cycloacetals are briefly mentioned. Amide moieties in linear polyamides can be modified by different reactions. Preparation and properties of poly-N-chloroamides and poly-N-trifluoroacetyl-amides are described. By reaction of metalated p…

Darstellung und eigenschaften von N-3,5-dinitrobenzoyl- und N-2,4,6-trinitrophenyl-nylon 66

Blockcopolymere aus 2-Isopropenylnaphthalin und Hexamethylcyclotrisiloxan, 7

Anionic polymerization of 2-isopropenylnaphthalene (2-IPN), with butyllithium in THF at −78°C was terminated with ethylene oxide and the resulting terminal alkoxide was used to initiate the polymerization of hexamethylcyclotrisiloxane (D3) at +40°C. This led to the formation of AB-block copolymers which were coupled to ABBA-block copolymers by addition of dichlorodimethylsilane. ABBA-blockcopolymers were obtained with contents of polymethylsiloxane (poly(DMS)) between 77 and 84% of weight and block molecular weights between 1 700 and 27 000 (poly(2-IPN)) and 13 000 and 240 000 (poly(DMS)). Phase separation in polymer films casted from different solvents was studied by electron microscopy an…

Enantioselektive Trifluoracetylierung mit Hilfe chiraler Polyamide

(S)-Poly(2-aminobutyric acid) (1) [(S)-poly(imino-1-methyl-3-oxotrimethylene)] was transformed into its N-trifluoroacetyl derivative 4. The IR spectra and the circular dichroism of both substances were compared. In addition, (S)-poly[N-(1-phenylethyl)acrylamide] (2) ((S)-poly-[1-(1-phenylethylaminocarbonyl)ethylene]) was trifluoroacetylated leading to polymer 5. 4 was found to react as trifluoroacetylating agent with L-1-phenylethylamine (L-3) twice as fast as it reacts with D-3. Accordingly, the reaction of 4 with D,L-3 leads preferentially to the L-form of N-(1-phenylethyl)trifluoroacetamide with optical yields up to 6%. The reaction of 5 with D,L-3 affords the D-form of N-(1-phenylethyl)…

Reaktionen bei der Bestrahlung von poly(N-chloramid)en

On irradiating poly(N-chloroamide)s in films or in solution in the range of 325–375 nm carboxamide groups are formed. The irradiated polymer contains chlorine which is linked to C-atoms. This reaction can certainly not be explained with an intramolecular photorearrangement but with a sequence of photoreactions and dark reactions satisfactorily accounting for all observations.

Über Segmentlängenverteilung und Lichtabsorption bei Copolymeren aus Methacrylnitril und Acrolein oder Methacrolein. Polymere Acroleine. 31. Mitt.

Copolymere aus Methacrylnitril und Acrolein oder Methacrolein werden hinsichtlich der Absorption der Carbonylgruppe im Ultravioletten und Infraroten untersucht. Zur Beschreibung des Absorptionsverhaltens wird die statistische Theorie von ALFREY und GOLDFINGER uber die Segmentlangenverteilung in copolymeren benutzt. Es ergibt sich, das im wesentlichen die isoliert stehenden Aldehydgrundbausteine einen Beitrag zur Carbonyl-absorption liefern. Bei Sequenzen aus zwei und drei Aldehydgrundbausteinen reagieren die Carbonylgruppen zu cyclischen Aldehydhydratathern, wahrend bei langeren Sequenzen ungefahr 20% der Carbonylgruppen nicht cyclisieren. Copolymers from methacrylnitrile and acrolein or me…

Polymerization of methyl and phenyl oxazoline initiated with alkyl chloroformates

It has been shown that alkyl chloroformates are capable of initiating the polymerization of oxazolines. Esters itself initiate rather slowly and the polymerization proceeds via covalent growing species. Exchange of counter ions with triflate or iodide anions leads to faster initiation and higher reaction rates. The polymerization is of living character.

Untersuchungen zur radikalischen copolymerisation von 2-isopropenylnaphthalin mit maleinsäreanhydrid

Branched polymers starting from ethylene-vinyl acetate copolymers

Abstract Polyethylene-graft-poly-2-phenyl-2-oxazoline, polyethylene-graft-poly-2-methyl-2-oxazoline and polyethylenegraft-poly(ethylene oxide) were prepared using poly(ethylene-co-vinyl chloroformate) as macroinitiator or polyfunctional precursor. The vinyl acetate groups of ethylene-vinyl acetate copolymer were hydrolyzed, the corresponding alcohol functions were converted into chloroformate, which in turn was used for grafting of oxazolines. Comb-like polymers with hydrophilic poly(ethylene oxide) grafts with definite length were synthesized as well. The resulting graft copolymers were characterized by GPC, IR, and 1 H-NMR spectroscopy and differential scanning calorimetry.

Aktivierung der anionischen lactam-polymerisation durch N-trifluoracetyl-polyamide

Synthesis and properties of aromatic ionenes

Cationic polyelectrolytes with aromatic segments can be synthesized by a repetitive alkylation reaction. The structure of the products, their synthesis and their solubility are described. All ionenes are not, or only in small amounts, water soluble. The best solubility can be achieved by mixtures of polar protic and aprotic solvents. Variations of the counterion produces sufficient solubility in THF. All ionenes show a typical polyelectrolyte effect. The thermal stability of aromatic ionenes and the glass transition temperature is dominated by the nature of the counterion. The molecular weight of oligomers can be described by using a combination of a conductive titration method and an ion s…

Über die massenspektrometrische Bestimmung des Einbauverhältnisses in Copolymeren, 2. Copolyester der Milchsäure und Glykolsäure

Polymides 3a and 3b with stiff-chains bearing trioxaoctyl or tetraoxaundecyl side chains were synthesized and characterized. The polycondensation was done with pyromellitic anhydride and N,N′-bis(1-imidazolylcarbonyl)-2,5-(1,4,7-trioxaoctyl)- or 2,5-(1,4,7,10-tetraoxaundecyl)-1,4-phenylenediamine (2a or 2b). 3b, being sufficiently soluble, was characterized by 13C NMR spectroscopy. The results of IR and 13C NMR spectroscopy prove the presence of the correct imide structure. In solid state 3a and 3b form layered structures with the side chains being in a disordered state.

Analyse von Copolymeren aus Vinylestern und Acrylestern

Die Copolymeren aus Vinyl- und Acrylestern werden in abgeschmolzenen Ampullen durch 2 M NaOH verseift. Die aus den Vinylester-Grundbausteinen gebildeten Sauren werden durch potentiometrische Titration bestimmt; liegen verschiedene Vinylester nebeneinander vor, so wird das Mengenverhaltnis der Sauren gaschromatographisch ermittelt. Die bei der Verseifung aus den Acrylester-Grundbausteinen entstehenden Alkohole werden gaschromatographisch identifiziert und gegen tert-Butanol als internen Standard quantitativ bestimmt. Ein besonderer Vorteil der Methode besteht darin, das auch wasrige Dispersionen ohne vorherige Abtrennung des Copolymeren eingesetzt werden konnen. The copolymers from vinyl est…

Pfropfung von vinylverbindungen auf polyamide

Die polymerisation und pfropf-mischpolymerisation des acroleins unter dem einfluß von Co - 60 - gamma - strahlen. Polymere acroleine. 14. Mitteilung

Die Polymerisation des Acroleins im reinen Zustand und in Losung unter dem Einflus von γ-Strahlen wird beschrieden und mit anderen Polymerisations-Methoden verglichen. Bei der Block-Polymerisation entsteht ein stark vernetztes, glasartiges Polymerisat, das in wasriger schwefliger Saure unloslich ist. In Losung polymerisiert das Acrolein viel rascher; die relative Geschwindigkeit der Polymerisation ist am grosten in wasriger Losung. Das hier erhaltene Polymere enthalt reaktionsfahige Aldehyd-Gruppen und ist loslich in schwefliger Saure. Acrolein last sich auf Polymethacrylester aufpfropfen. Sowohl oberflachliche als auch durchgehende Pfropfung vorgeformter Proben des Polymethacrylesters ist …

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.

Optisch aktive N,N-disubstituierte polyacrylsäureamide

Introduction des groupes alkyl dans le polyamide commercial Trogamid T. Formation d'anions polyamides par l'hydrure de sodium puis alkylation par les bromures d'alkyle

Modification of Chiral Properties Due to Interaction of Polymers and Small Molecules or Ions

The first part of this report deals with changes in the optical rotatory dispersion and circular dichroism resulting from the chemical modification of optically active polymers. Amylose derivatives have very different chiroptical properties compared with cellulose derivatives. Variations in glucosidic bonds and differing secondary structures are described and suggested as causes for this. The N-chlorination of synthetic optically active polyamides is also described, which in all probability proceeds without changing the configuration at the asymmetric C atoms. Reactions of inactive polymers with low molecular weight chiral reagents usually give optical rotation values proportional to the de…

Oxidation of tertiary amines with N-chloronylon 66 (NCN) was investigated in several organic solvents. NCN was found to oxidize N,N-dimethylaniline (DMA) at room temperature to give N-methylaniline with 15–50% yield, depending on the solvents used. Oxidation of N,N-dimethylbenzylamine (DMBA) gave benzaldehyde with 15–30% yield and a small amount of N-methylbenzylamine. A mechanism was discussed. For comparison, N-chlorosuccinimide, a low molecular N-chloro-compound, was also used for oxidation of DMA and DMBA.

Some new examples of cationic polymerization

Preparation, proprietes et polymerisation cationique de cis et trans-methoxyvinylchlorure. Le polymere trans est surtout threodiisotactique. Copolymerisation du cis avec le trans ou le styrene ou le dioxolanene-1,3. Polymerisation de la phenyl-2 oxazoline et de la conidine

Optisch aktive synthetische Polymere

Es wurde ein kurzgefaster Uberblick gegeben uber die derzeit bekannten Verfahren zur Herstellung von optisch aktiven Polymeren. Bei der grosen Zahl von Veroffentlichungen zu diesem Thema war es im Rahmen eines Vortrages nur moglich, eine kleine Zahl ausgewahlter Beispiele zu behandeln. Es sollten daran die verschiedenartigen Ziele und Fragestellungen erlautert werden. Unter anderem wurde auch uber eigene, zum Teil unveroffentlichte Versuchsergebnisse berichtet.

Darstellung einiger phosphorhaltiger Carbamoyl-Verbindungen

Durch Umsetzung von Vinylisocyanat mit Triathylammoniumsalzen von Monoarylphosphorsaureestern entstehen N-Vinylcarbamoylphosphate; diese reagieren mit prim. und sek. Aminen wie das freie Isocyanat. Aus Vinylisocyanat und Dialkylphosphorigsaureestern entstehen N-Vinylcarbamoylphosphonsaureester. Isocyanate addieren sich an Diphenylphosphinoxyd in Gegenwart katalytischer Mengen Triathylamin unter Bildung von Carbamoyl-diphenyl-phosphinoxyden.

Polyradikale mit verdazyl-gruppen

Um Polyradikale mit Verdazylgruppen zu gewinnen, wurden verschiedene Wege erprobt. Die Methylierung von Polyacrolein-formazan fuhrte nicht zum Ziel. Herstellung und Eigenschaften von 1.5-Diphenyl-3-(p-vinylphenyl)-verdazyl werden beschrieben; eine radikalische Polymerisation dieser Verbindung war nicht moglich. Ausgehend von Poly-p-vinylbenzaldehyd gelang es aber, durch polymeranaloge Umsetzungen Polymere mit Verdazylgruppen darzustellen. Diese Polyradikale enthalten in jedem zweiten Grundbaustein ein ungepaartes Elektron. For the synthesis of polymeric verdazyles different routes were investigated. Methylation of poly(acroleinformazanes) was not successful. Synthesis and properties of 1.5-…

Block and graft copolymers of 2-oxazolines

The cationic ring-opening polymerization of 2-oxazolines is known to be initiated by alkyl halides, Lewis acids and esters of strong acids. The polymerization proceeds by a living mechanism. Numerous block and graft copolymers have already been described. Recently it was found that chloroformates (R-O-CO-CI) are also useful initiators. The mechanism of the initiation and propagation is discussed. This type of initiators allows the synthesis of different novel two-block and three-block copolymers, star-shape polymers, and a graft copolymer with a polyvinylacetate backbone.

Darstellung und eigenschaften von N-trichloracetyl-nylon 66

Copolymers with ordered chemical structure

Copolymers with well defined sequences can be obtained for instance by ring-opening polymerization of selected acetals. In this way regular copolymers of formaldehyde and ethylenoxide of the following structure are available2. In the same way some other copolymers with formaldehyde units were obtained. Of special interest are unsaturated polyacetales; for instance3 They can be modified by chemical reactions, for instance by hydrogenation, addition of bromine, iodine isocyanate or epoxidation. Recently a bicyclic unsaturated cycloacetal was prepared and polymerized4 Branched copolymers with a definite number of uniform sidechains are prepared by N-alkylation of polyamides5 The dependence of …

Optically active polyamides with regular structural sequences have been prepared from L-lysine and adipic acid. A novel optically active symmetrical diamine, N.N'-bis(L-5-amino-5-carboxyl-amyl)adipamide, was obtained by treating L-lysine with adipyl chloride in the presence of copper(II) ions. The interfacial polycondensation of this diamine with adipyl chloride afforded a regular polymer, while the polycondensation of L-lysine with adipyl chloride gave an irregular polymer of the same analytical composition. The melting points, optical rotations and the optical rotatory dispersions of these polymers were investigated. Optisch aktive Polyamide mit regelmasiger Struktur wurden aus L-Lysin un…

Beiträge zur polymerisation von 2-isopropenylnaphthalin, 3. Anionische homopolymerisation von 2-isopropenylnaphthalin

The anionic homopolymerization of 2-isoprenylnaphthalene with butyllithium in tetrahydrofuran at –78°C is described. The refractive index increment amounts to dn/dc = 0,2084 ml/g for these polymers in toluene at 25°C and wavelength λ = 436 nm. Determination of the molecular weights by light scattering yielded values between 13 000 and 270 000. The second virial coefficients also determined by light scattering measurements are comparable with the corresponding data of poly(α-methylstyrene). A calibration curve is given for gel permeation chromatography of the poly(2-isoprenylnaphthalene)s, whose polymolecularity indexes Mw/Mn lie between 1,06 and 1,2. Their intrinsic viscosity/molecular weig…

Synthetic approaches to new polymers

A plenary lecture should be an introduction into the main topic of the symposium and a review about the state of art. Therefore, in the first part of this presentation different possibilities for the preparation of new polymers are briefly discussed from a chemical point of view. Some selected examples from the literature show how methods of organic chemistry can be utilized for polymer science: new catalytic systems, new monomers, modification of polymers, new poly-reactions. In the second part, several polyelectrolytes are described: polymers with sec., tert. and quart. N-atoms in the main chain, block copolymers and block polyampholytes. The third part deals with the problems of rod-like…

Some New Copolymers by Ionic Polymerization

In the first part the cationic polymerization of a homologous series of cyclic ether–acetals with ring sizes of 11, 14, and 17 atoms is described. During the polymerization of triethylene glycol formal (TGF) an equilibrium is reached and besides high polymers cyclic oligomers are formed. The oligomers and the polymers are built up of a regular sequence of one oxymethylene unit and three oxyethylene units –[–(OCH2) (OC2H4)3–]–x. They are therefore be labelled a “sequenced copolymer.” The equilibrium concentrations of the cyclic oligomers with a polymerization degree from 2 to 15 follow the Jacobson–Stockmayer equation. The 14- and 17-membered monomers POC and HOC forms cyclic oligomers and h…

Darstellung von 1.3-Divinylparabansäure-4-imid und 1.3-Divinylparabansäure

Optical rotatory dispersion and circular dichroism of poly-L-lactide. A reply to a letter by M. Goodman and M. D'alagni (1)

Synthesis and characterization of optically active 2,4-disubstituted-2-oxazolines and their polymerization

Four different optically active 2,4-disubstituted-2-oxazolines were synthesized and characterized. Cationic polymerization of these oxazolines were studied. Three of the oxazolines could be polymerized using methyl trifluoromethanesulfonate as initiator. S-(–)-2-Phenyl-4-isopropyl-2-oxazoline could not be polymerized under the conditions used.

Solid state polymerization of new polyesters containing diacetylenic groups

Synthesis and properties of some new polyesters of 10, 12-docosadiyn-1, 22-diol are described. The diyn-polyesters as films became coloured polydiacetylenic films on exposure to UV radiation and their properties were studied.

Macromonomers on the basis of 2-phenyl-2-oxazoline

By initiation of the ring-opening polymerization of 2-phenyl-2-oxazoline (1) with p-iodomethylstyrene a macromonomer with a styrene end-group (2) is obtained. The degree of polymerization was varied between 10 and 16. The radical copolymerization of 2 with styrene is described. 1 forms with methyl triflate a very stable oxazolinium salt which is a good initiator for the bulk polymerization of 1 at temperatures of 50–70°C. It was conclusively proved that under these conditions the polymerization proceeds by a living mechanism. By termination with N, N-dimethylaminopropylmeth-acrylamide a macromonomer (5) was obtained. 5 can be radically homopolymerized. This comb-like polymer 6 has the typic…

Synthesis of polyvinyl acetate-graft-poly-2-oxazolines

Poly(vinyl acetate-co-vinyl chloroformate) (1) was synthesized via phosgenation of poly(vinyl acetate-co-vinyl alcohol). It was shown that (1) is capable of initiating the polymerization of 2-phenyl-2-oxazoline and 2-methyl-2-oxazoline, when the counter ion is exchanged using potassium iodide. Polyvinyl acetate-graft-poly-2-phenyl-2-oxazoline and polyvinyl acetate-graft-poly-2-methyl-2-oxazoline are obtained in the grafting reaction.

Some new polyelectrolytes

Revue de methodes de preparation de polyelectrolytes: alkylation du poly(iminohexamethylene), homo- et copolymeres sequences de l'aza-1 bicyclo [4.2.0] octane, polymeres-peignes prepares a partir de macromeres obtenus par polymerisation de la phenyl-2 oxazoline. Preparation de polyampholytes ayant une distribution statistique ou sequencee des motifs ioniques

Cyclopolymerisation bei zweifach-ungesättigten Monomeren

Das Prinzip der Cyclopolymerisation wird erlautert; an Beispielen wird gezeigt, welche Verbindungen zu intra-intermolekularen Wachstumsschritten befahigt sind. Der Gehalt an cyclischen Grundbausteinen in den gebildeten Polymerisaten hangt auser von der Struktur der Monomeren auch von den Polymerisationsbedingungen ab. Es werden stereochemische Fragen behandelt, die im Zusammenhang mit Ringschlusreaktionen an 6- und hohergliedrigen Ringen auftreten. Chemische Umsetzungen an Cyclopolymeren konnen zu Copolymeren mit bestimmter Zusammensetzung und regelmasigem Aufbau fuhren.

It is shown that the block-like structure of the polyampholyte poly(methacrylic acid)-block-poly(1-methyl-4-vinylpyridinium chloride) considerably influences its conformational behaviour. This specific behaviour is explained by the formation of intra-macromolecular polyelectrolyte complexes stabilized by cooperative ionic contacts between acidic and basic units near the isoelectric point (i. e. p.). The structure of the block-polyampholyte at the i. e. p. is suggested to be close to the structure of non-stoichiometric polyelectrolyte complexes. The complex formation ability of the block-polyampholyte with respect to anionic, cationic, and nonionic polymers is also studied. By means of poten…

N-trifluoracetyl-nylon 66 als polymeres reagenz

N-Trifluoroacetyl-Nylon 66 (2) obtained by the reaction of Nylon 66 (1) with trifluoroacetic anhydride is very suitable as a polymeric reagent for the trifluoroacetylation of amines and alcohols. The advantages of 2 compared with low molecular trifluoroacetylating reagents are discussed. The selectivity against different substituted anilines and against structurally isomeric secondary amines was studied intensively by kinetic measurements.

Die Redox-Polymerisation des Acroleins in wäßrigem Medium. Polymere acroleine. 6. Mitteilung

Die Polymerisation wasriger Acrolein-Losungen mit Hilfe von Redox-Systemen wird untersucht. Es wird der Einflus der Temperatur, der Monomeren-und der Initiator-Konzentration beschrieben. Die Charakterisierung der Polymerisate erfolgt durch Bestimmung des Aldehydgruppengehaltes und der spezifischen Viskositat in wasriger Schwefeldioxyd- Losung. Die hier beschriebene Polymerisation des Acroleins hat die Merkmale der radikalischen Vinylpolymerisation. The polymerisation of aqueous solution of acrolein by the action of redox-systems has been investigated. The influence of the temperature and the concentration of the initiator and of the monomer is described. The polymers are characterized by th…

Untersuchungen zur kationischen polymerisation von 2-isopropenylnaphthalin

Optische rotationsdispersion bei wässrigen lösungen von jod-amylose und jod-amylopektin

Polarographische Untersuchungen an monomeren und polymeren N-Chlorcarbonamiden

The polarographic reduction of low molecular and high molecular N-chlorocarboxamides at the dropping mercury electrode proceeds in two one-electron-transfer steps, which are highly irreversible. In the case of the low molecular models 1 and 2 the reaction is diffusion-controlled, whereas in the case of the poly(N-chloroamide) 3 the reaction is adsorption-controlled. Reduction of several poly(N-chloroamide)s shows always two reduction waves with a distance of 0,5 V. There is, however, no relation between the polyamide-type and the position of the half-wave potentials. The polarographic reduction can be used as an analytical method for quantitative determination of N-chlorocarboxamide groups …

Über die polymerisation von 2,3-dihydropyran

Dihydropyran kann mit verschiedenen FRIEDEL-CRAFTS-Katalysatoren polymerisiert werden; am besten eignet sich Bortrifluorid-Atherat. Die Polymeren lassen sich in einen in Petrolather unloslichen und einen loslichen Anteil auftrennen. An Hand von IR-Spektren und chemischen Umsetzungen wird gezeigt, das neben Tetrahydropyran-Grundbausteinen auch solche mit freien Aldehydgruppen auftreten. Ein Ringoffnungsmechanismus wird diskutiert. Dihydropyran can be polymerized by means of various FRIEDEL-CRAFTS catalysts, the most effective being BF3 -etherate. The polymers can be separated into a petroleum ether-soluble and a petroleum ether-insoluble fraction. Infrared-spectra and chemical reactions show…

Die Anwendung von Dicyclopentadienyl-Eisen bei der Eisen-Redox-Polymerisation von Styrol

Es wird gezeigt, das Dicyclopentadienyl-Eisen die Redoxreaktion zwischen Benzoylperoxyd und Benzoin katalysiert und daher zur Eisen-Redox-Polymerisation von Styrol in benzolischer Losung gut geeignet ist.

Some linear and branched macromolecules by ring-opening polymerization

In the first part the ring-opening polymerization of some macrocyclic ether-acetals is briefly described. Of special interest are acetal polymers with functional groups, for instance C=C-double bonds. Appropriate unsaturated monomers and their polymerizability are discussed. The second part deals with the polymerization of oxazolines, substituted in 2- and/or 4-position. Branched polymers are obtained by copolymerization of 2-ethyl-2-oxazoline with 2-hexyl-2-oxazoline or 2-undecyl-2-oxazoline. The properties of the random copolymers and corresponding block copolymers are compared. By a “mixed mechanism technique” a block copolymer composed of a poly(tert -butyl methacrylate) block and a pol…

A novel synthesis of polymers with anthracene and dihydroanthracene subunits in the main chain

A new polycondensation method to connect redox-active and chromophoric subunits by forming a C-C bond and leading to a polyhydrocarbon is described. 1,ω-bis(9,10-Dihydro-9-anthry)alkanes with various alkylene spacers can be deprotonated by butyllithium to afford a monoanion in each dihydroanthracene moiety. Alkylation with dielectrophiles such as dibromoalkanes yields soluble polymers with dihydroanthracene units in the main chain. The reaction proceeds regioselectively in the 9,10-position. Aromatization generates a polymer with anthracene units. The molecular weights are determined by GPC up to Mn = 10 000. To prove the structure and to calibrate the GPC, suitable model compounds were syn…

Gleichgewichtskonzentrationen der cyclischen Oligomeren bei der Polymerisation von 1,3,6,9-Tetraoxacycloundecan

Versuche zur elektrochemischen Polymerisation von Acrolein

Es wird eine temperierbare Elektrolysezelle mit Diaphragma und das Bauprinzip eines Galvanostaten beschrieben. Die Elektrolyse einer Losung von Acrolein und Natriumtetraphenylborat inTHF liefert im Kathodenraum ein losliches Polyacrolein. Die Abnahme der Konzentration des Monomeren verlauft nach 1. Ordnung. Die elektrochemische Ausbeute hangt von den Versuchsbedingungen ab und betragt z. B. bei 0°C, 1,3 mA und einer Monomer-Konzentration von 2 Mol/l etwa 103 Mol pro Faraday. Aus Inhibierungsversuchen und aus der Struktur der polymeren folgt, das es sich um eine anionische Polymerisation handelt. Bei Verwendung von Tetramethylammoniumperchlorat in Nitrobenzol tritt ebenfalls eine anionische …

Some Soluble Polydiacetylenes Derived from 10, 12-Docosadiyn-1, 22-Diol

Abstract Synthesis and physical properties of some new soluble polydiacetylenes obtained by solid state polymerization of derivatives of 10,12-Docosadiyn-1,22-diol(1) are described.

Synthesis and some reactions of linear poly(iminohexamethylene)

By complete reduction of polyamide-6, poly(iminohexamethylene) (PIH) was obtained. This new linear polyamine was characterized by i.r. and by n.m.r. spectroscopy as well as by titration. Differential scanning calorimetry measurements and X-ray diffraction found a high degree of crystallinity whose extent strongly depends upon the pre-treatment. The polyammonium salts that form with inorganic and organic acids show the typical polyelectrolyte effect in viscometry. PIH was alkylated with methyl iodide or acrylic acid and was acylated with N-BOC-l-α-amino acids or N-BOC-ω-amino-alkylenecarboxylic acids. The properties of these derivatives are described.

Alternating, all-trans polyenynes: Model compounds for poly(diacetylene)s with defined conjugation length

The syntheses of polyenynes as model compounds for poly(diacetylene)s (PDAs) are described. Variation of properties (UV–VIS, Raman, NMR and bond geometries) as a function of the chain length was investigated. After extrapolation to infinite chain length these data were compared to those for PDAs. From UV–VIS spectra a value of λ = 551 nm (2.25 eV) was calculated corresponding to the electronic transition of a single polyenyne chain. This energy is located at the low energy end of a yellow PDA solution spectrum. From Raman scattering v(CC) = 2108–2128 cm−1 and v(CC) = 1505–1532 cm−1 were calculated after extrapolation. Similarly sp-C13C NMR data yielded a shift of δ = 100 ppm. These data are…

Über die Synthese einiger N-Vinyl-verbindungen

Die Umsetzungen zwischen Vinylisocyanat und verschiedenen Alkoholen, Aminen und Triathylammoniumsalzen von Monoaryl-phosphorsaureestern werden beschrieben. Die erhaltenen N-Vinylderivate werden durch Angabe der Schmelz- oder Siedepunkte sowie der UV-Spektren charakterisiert. Die meisten der genannten Verbindungen sind polymerisierbar. Die Umsetzungen konnen zu analytischen Zwecken bei der Identifizierung von Alkoholen und Aminen verwendet werden.