Reaction catalysts polycondensation

The release of hydrogen in equimolar quantities points to simultaneous reactions of the 3.66, 3.67, 3.70, 3.71 and 3.72 type and the reaction of polycondensation at hydroxyl groups formed according to the reaction of the 3.66 type. The role of the active catalysts of the interaction of the =Si-H bond of oligoalkylhydridesiloxanes with the functional groups of the material surface and the polymerisation of oligomers can be also played by aminoalkylethoxysilanes and aminoalkylsiloxanes. A typical representative... 

The high-boiling polar organic solvents - dimethylsulfoxide, sulfolane, dimethylsulfone, dimethylformamide, dimethylacetamide - are generally used for synthesizing the polyesterketones and polyesteresterketones by means of polycondensation in this case the reaction catalysts are the anhydrous hydroxides, carbonates, fluorides and hydrides of alkali metals. 

Direct arylation polycondensation using the phosphine-free catalytic system can be adapted to the synthesis of bithiazole-based alternating copolymers (P34). In comparison with conventional polycondensation via other cross-coupling reactions, the polycondensation proceeded with a reduced amount of Pd catalyst (2 mol%) in a short reaction time (10 min to 3 h). Owing to the differenee in reactivity of the C-H bond, controlling the reaction time was effective for suppressing the side reaetion at the unexpeeted C-H bond (Scheme 1.35). ... 

Palladium-graphite (Pd-Gr) is useful heterogeneous catalyst for many organic reactions and polycondensations. The catalytic activities of Pd-Gr for die Heck reaction, oxidation, hydrogenation, and nucleophilic... 

This paper describes organic reactions and polycondensation catalyzed by Pd-Gr used as a heterogeneous catalyst. The catalytic activity of Pd-Gr for organic reactions... 

Starting with DMT, methanol is removed from the reaction starting with TA, water is removed. Catalysts ate used to transesterrfy DMT but not for direct esterification of TA. The second step is the polycondensation reaction which is driven by removing glycol. A polycondensation catalyst is used. 

Various inorganic, organic, and organometaUic compounds are known to cataly2e this polymerization (4,8,9). Among these, BCl is a very effective catalyst, although proprietary catalysts that signiftcandy lower polymerization temperature from the usual, sealed-tube reaction at 250°C are involved in the industrial manufacture of the polymer. A polycondensation process has also been developed for the synthesis of (4) (10—12). This involves elimination of phosphoryl chloride from a monomer prepared from (NH 2 04 and PCl. ... 

The second largest use at 21% is for unsaturated polyester resins, which are the products of polycondensation reactions between molar equivalents of certain dicarboxyhc acids or thek anhydrides and glycols. One component, usually the diacid or anhydride, must be unsaturated. A vinyl monomer, usually styrene, is a diluent which later serves to fully cross-link the unsaturated portion of the polycondensate when a catalyst, usually a peroxide, is added. The diacids or anhydrides are usually phthahc anhydride, isophthahc acid, and maleic anhydride. Maleic anhydride provides the unsaturated bonds. The exact composition is adjusted to obtain the requked performance. Resins based on phthahc anhydride are used in boat hulls, tubs and spas, constmction, and synthetic marble surfaces. In most cases, the resins contain mineral or glass fibers that provide the requked stmctural strength. The market for the resins tends to be cychcal because products made from them sell far better in good economic times (see Polyesters,unsaturated). 

Phosgene addition is continued until all the phenoHc groups are converted to carbonate functionahties. Some hydrolysis of phosgene to sodium carbonate occurs incidentally. When the reaction is complete, the methylene chloride solution of polymer is washed first with acid to remove residual base and amine, then with water. To complete the process, the aqueous sodium chloride stream can be reclaimed in a chlor-alkah plant, ultimately regenerating phosgene. Many variations of this polycarbonate process have been patented, including use of many different types of catalysts, continuous or semicontinuous processes, methods which rely on formation of bischloroformate oligomers followed by polycondensation, etc. 

The addition of an alkanolamine, such as diethanolamine, to TYZOR TBT, as well as the use of a less moisture-sensitive alkanolamine titanate complex such as TYZOR TE, has been reported to prolong catalyst life and minimi2e ha2e formation in the polymer (475—476). Several excellent papers are available that discuss the kinetics and mechanism of titanate-cataly2ed esterification and polycondensation reactions (477—484). 

Recently, the above mentioned model reaction has been extended to polycondensation reactions for synthesis of polyethers and polysulfides [7,81]. In recent reports crown ether catalysts have mostly been used in the reaction of a bifunctional nucleophile with a bifunctional electrophile, as well as in the monomer species carrying both types of functional groups [7]. Table 5 describes the syntheses of aromatic polyethers by the nucleophilic displacement polymerization using PTC. 

Coke formed on the catalyst surface is thought to he due to polycondensation of aromatic nuclei. The reaction can also occur through a car-honium ion intermediate of the benzene ring. The polynuclear aromatic structure has a high C/H ratio. 

Activating agents, such as trifluoroacetic anhydride 1,1 -carbonyldiimidazolc carbodiimides sulfonyl, tosyl, and picryl chlorides and a range of phosphorus derivatives can promote direct solution reactions between dicarboxylic acids and diols or diphenols in mild conditions. The activating agents are consumed during the reaction and, therefore, do not act as catalysts. These so-called direct polycondensation or activation polycondensation reactions proceed via the in situ transformation of one of the reactants, generally the carboxylic acid, into a more... 

A PEIT of 50/50 (molar ratio) composition is synthesized by a two-step reaction sequence as follows. In the first step, 97.10 g (0.5 mol) dimethyl terephthalate (DMT), 97.10 g (0.5 mol) dimethyl isophthalate (DMI), 136.55 g (2.2 mol) 1,2-ethanediol, and zinc acetate dihydrate ester interchange catalyst (2.7 x 10 4% mass of the total amount of DMI and DMT mixture) are weighed into a threenecked flask fitted with a mechanical stirrer, a nitrogen inlet, and a condenser. The medium is stirred for 2.0-2.5 h at 180-210°C under nitrogen. Ninety-two percent of the theoretical amount of methanol is removed by distillation. In the second step, antimony acetate polycondensation catalyst and trimethyl phosphate thermal stabilizer (9.9 x 10-4 and 1.5 x 10 3% mass of the total amount of DMI... 

As is die case for odier polycondensation reactions, internal interchange reactions are possible for ADMET, similar to diat of polyesters and polyamides.16 Interchange reactions involve a catalyst molecule on a polymer chain end reacting widi an internal double bond in another polymer chain. The result is two new polymer chains however, no change in the molecular weight distribution... 

Poly(unsaturated ester)-siloxane segmented copolymers have been prepared by the polycondensation of epoxy-terminated polydimethylsiloxanes and carboxy-terminated poly(ethylene adipate-co-maleate) oligomers 243). Reactions have been conducted in cellosolve solvent, at 140-150 °C, in the presence of 2% by weight potassium hydroxide catalyst. The molecular weights reported were fairly low. The same group has also prepared poly(hexamethylene adipate)-polydimethylsiloxane copolymers con-... 

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