Search results for "Depolymerization"
showing 10 items of 26 documents
1967
Durch Viskositatsmessungen und spektroskopische Bestimmung des gebildeten Monomeren wird der saurekatalysierte Abbau von Poly-3,4-acrolein verfolgt. Er erfolgt fast ausschlieslich durch Kettenspaltung; eine Depolymerisation tritt nur in untergeordnetem Mase auf. Diese im Vergleich zu anderen polymeren Aldehyden unerwarteten Ergebnisse werden mit dem Auftreten eines durch Resonanz stabilisierten Kettenendes bei der Spaltung erklart. The acid-catalyzed degradation of poly-3,4-acrolein was investigated by viscosity and spectroscopic determination of the monomer formed. The degradation occurs predominantly by chain scission; depolymerization is of minor importance. The results are unexpected in…
Electro-conversion as sustainable method for the fine chemical production from the biopolymer lignin
2018
Lignin, one of the most abundant polymers in nature, qualifies itself by the polyphenolic structure as potential renewable feedstock for the production of bio-based aromatic fine chemicals. However, the natural complexity and degradation stability of lignin make the depolymerization a highly challenging task. Several efforts have been pursued for the selective degradation of the biopolymer into suitable compounds. However, there are only a few technical approaches for the degradation of lignin to aromatic fine chemicals. Organic electrosynthesis is the synthetic method that enables the direct use of electricity for the production of valuable compounds. Moreover, electro-organic synthesis re…
Blockcopolymere aus 2-Isopropenylnaphthalin und Hexamethylcyclotrisiloxan, 7
1985
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…
Amino acid-based cholinium ionic liquids as sustainable catalysts for pet depolymerization
2021
Chemical recycling to monomers is one of the key strategies in tackling the issues deriving from persistent plastic pollution in the environment, and poly(ethylene terephthalate) (PET) is among the most used polymers in modern society. In this context, we herein describe the glycolysis of PET to bis-hydroxyethyl terephthalate (BHET), promoted by basic cholinium salts differing for the anions, also comprising amino acid anions. We investigated the optimal reaction conditions, finding that the best-performing catalyst is [Ch][Gly], in the presence of which a conversion of 85% and a yield of 51% are achieved at 150 °C after 6 h, from PET deriving from a clear water bottle. We used our protocol…
1991
The thermal degradation mechanisms of amphiphilic acrylic copolymers containing mesogenic pyrimidine side chains and hydrophilic 2-hydroxyethyl acrylate (HEA) main-chain spacer units were investigated by thermogravimetry (TG) and pyrolysis-field ionization mass spectrometry (Py-FIMS). The degradation behaviour of these polymers depends on the amount of HEA incorporated. Thermogravimetry revealed that the main decomposition occurs in a single step for the pyrimidine homopolymer, whereas with increasing HEA content a two-step process evolves. The major products identified by Py-FIMS are two alcohols and one olefin split from the aromatic side chains. Depolymerization is only a minor degradati…
1979
The thermal degradation behavior of head-to-head (H-H) and head-to-tail (H-T) polystyrenes and poly(vinylcyclohexane)s has been investigated by direct pyrolysis in a mass spectrometer. Both H-H and H-T isomers show only small differences in their initial temperatures of decomposition but remarkably different degradation processes. Whereas H-T polystyrene decomposes in accordance with earlier investigations mainly by a radicalic depolymerization into the monomer and yields only a small amount of dimer and trimer, the H-H polystyrene shows no unzipping and only a statistic degradation into oligomeric styrenes. The formation of stilbene is a diagnostic reaction of H-H polystyrene. The pyrolysi…
1984
The decomposition reactions of the lithiated dimer, trimer, and tetramer of methyl methacrylate (MMA) in THF at 25°C were investigated. The decomposition of the lithiated dimer proceeds via depolymerization to lithiated monomer and MMA, addition of MMA to residual lithiated dimer, resulting the trimer (“disproportionation” of the dimer), and subsequent autocondensation of the products. The lithiated trimer almost exclusively undergoes cyclo-autocondensation, whereas for the lithiated tetramer both reactions proceed simultaneously to a remarkable degree. It is shown that the relative rate of autocondensation, which is highly dependent on the degree of polymerization of the oligomer, controls…
Über die depolymerisation von polyoxymethylendiolen, katalysiert durch carbonsäuren. 38. Mitt. Über polyoxymethylene1
1969
Nach einem Uberblick uber bisherige Arbeiten uber den Mechanismus des sauer katalysierten Abbaus von Polyoxymethylendiolen wird der Abbau in 1-proz. Losung in Nitrobenzol bei 135°C unter dem Einflus verschiedener Carbonsauren untersucht. Phenylessigsare verursacht keine nennenswerte Kettenspaltung, sondern katalysiert lediglich die Depolymerisation an den halbacetalischen Kettenenden. Die Depolymerisationsgeschwindigkeit ist etwa proportional der Saurekonzentration und umgekehrt proportional dem Polymerisationsgrad. Wahrend des Abbaus andert sich der durchschnittliche Polymerisationsgrad nicht wesentlich. Diese Befunde lassen sich mit keinem der diskutierten Reaktionsmechanismen widerspruch…
Die acidolytische depolymerisation von trioxan in stationärer phase. 21. Mitt. über polyoxymethylene1
1964
Die Depolymerisation von Trioxan mit verschiedenen Phosphorsauren wurde im Temperaturbereich von 100–160°C untersucht. Sie fuhrt zu einem temperaturabhangigen Gleichgewicht zwischen Trioxan und Formaldehyd, das oberhalb 180°C weitgehend auf der Seite des Formaldehyds liegt. Zu einer schnellen Einstellung des Gleichgewichtes eignen sich Ortho- und Pyrophosphorsaure. Die bevorzugte Nebenreaktion ist die Bildung von Methylformiat; die Ausbeute an Methylformiat wird durch Erhohung der Reaktionszeit und der Katalysatoroberflache vergrosert. Das geschilderte Verfahren eignet sich zur Darstellung von monomerem Formaldehyd (Reinheitsgrad etwa 99,8%) im Laboratorium. Depolymerization of trioxane by …
Anomalien bei der kationischen copolymerisation von trioxan. 32. Mitt. über polyoxymethylene
1967
Die kationische Copolymerisation von Trioxan mit Styrol, 1,3-Dioxolan und anderen Comonomeren last sich wegen folgender Nebenreaktionen nicht durch die ubliche MAYO-sche Copolymerisationskinetik erfassen: 1. Depolymerisation der Trioxymethylenbausteine zu Formaldehyd wahrend der Induktionszeit und daher Bildung sehr styrolreicher bzw. dioxolanreicher Prapolymerer. 2. Bildung und Polymerisation von Formaldehyd, welcher wahrend der gesamten Polymerisation in seiner ceiling-Gleichgewichtskonzentration zugegen ist. 3. Abspaltung oxacyclischer Verbindungen von den aktiven Kettenenden; Bildung von Tetroxan und 4-Phenyl-1,3-dioxan bei der Copolymerisation von Trioxan mit Styrol. 4. Ubertragung am …