Polycondensates chloride

A polyester backbone with two HFIP groups (12F aromatic polyester of 12F-APE) was derived by the polycondensation of the diacid chloride of 6FDCA with bisphenol AF or bisphenol A under phase-transfer conditions (120). These polymers show complete solubkity in THF, chloroform, ben2ene, DMAC, DMF, and NMP, and form clear, colorless, tough films the inherent viscosity in chloroform at 25°C is 0.8 dL/g. A thermal stabkity of 501°C (10% weight loss in N2) was observed. 

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. ... 

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. 

As a variation on the base-catalyzed nucleopbilic displacement chemistry described, polysulfones and other polyarylethers have been prepared by cuprous chloride-catalyzed polycondensation of aromatic dihydroxy compounds with aromatic dibromo compounds. The advantage of this route is that it does not require that the aromatic dibromo compound be activated by an electron-withdrawing group such as the sulfone group. Details of this polymerization method, known as the Ullmaim synthesis, have been described (8). 

A polyether-amide with a heat distortion temperature of 198°C has been prepared by Hitachi by interfacial polycondensation of 2,2-bis-[4-(4-aminophen-oxy)phenyl]propane (VIII) with a mixture of isophthaloyl- and terephthaloyl-chloride (IX and X) (Figure 18.29). 

Interfacial polycondensation between a diacid chloride and hexamethylenediamine in the presence of small amounts of ACPC also yield polymeric azoamid, which is a macroazo initiator.[27] In this manner, azodicarbox-ylate-functional polystyrene [28], macroazonitriles from 4,4 -azobis(4-cyano-n-pentanoyl) with diisocyanate of polyalkylene oxide [29], polymeric azo initiators with pendent azo groups [3] and polybutadiene macroazoinitiator [30] are macroazoinitiators that prepare block and graft copolymers. 

To incorporate a labile azo group as the essential active site to MAI, a series of azo compounds such as 2,2 azobisisobutyronitrile (AIBN), 4,4 -azobis(4-cyanopen-tanoyl chloride) (ACPC), 2,2 azobis (2-cyanopropanol) (ACPO), 2,2 azobis [2-methyl-N-(2-hydroxyethyl)prop-ionamide] (AHPA), etc., were used as starting materials for polycondensation with various diols, diamines, diacids, or diisocyanates. 

In addition to a block copolymer, a microcapsule was made from suspension interfacial polycondensation between diacid chloride having aromatic-aliphatic azo group and aliphatic triamine [70,71]. The capsule was covered with a crosslinked structure having an azo group that was thermally stable but sensitive to light so as to be applicable to color photoprinting materials. 

Some of the typical conditions of polycondensations used for aliphatic and aromatic monomers are not suitable for furan derivatives, e.g., the melt polycondensation of 2,5-furan dicarboxylic acid chloride with 2,5-b/s(hydroxymethyl) furan at about 80 °C only yields a black insoluble product5. The hydrochloric acid liberated in the reaction is clearly responsible for the charring of the furanic diol which like its simpler homologue furfuryl alcohol, resinifies rapidly in acidic media (see below). 

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... 

Polycondensation At room temperature, 0.4% mass of Sn(II) chloride dihydrate (SnCl2-2H20) and 0.4% mass of p-toluenesulfonic acid monohydrate (p-TSA) are introduced into the mixture. The mixture is heated to 180°C under mechanical stirring. The pressure is reduced stepwise to reach 13 mbar, and file reaction is continued for 20 h. The reaction system becomes gradually viscous, and a small amount of L-lactide is formed and refluxed through the reflux condenser. At file end of the reaction, the flask is cooled down, file product is dissolved in chloroform and subsequently precipitated into diethyl ether. The resulting white fibrous solids are filtered and dried under vacuum (average yield 67%). 

The AICI3-catalyzed polycondensation of diphenyl ether with a mixture of terephthaloyl chloride and isophthaloyl chloride is a relatively inexpensive route to poly(ether ketone)s. The polymerizations were carried out in chlorinated solvents... 

Polysulfonation of self-polycondensation of 4-(phenylthio)benzenesulfonyl chloride was also used to prepare poly(arylene sulfide sulfone)s.245,246 Condensation of diphenyl sulfide with d -oxydibenzenesulfonic acid or d.d -thiodibcn/cnc-sulfonic acid247 or by poly etherification of poly condensation of DC DPS with d.d -dihydroxydiphenol sulfide occurred.5... 

Diamine 108 led to 95% ee for the alkylation of l,3-diphenyl-2-propenyl acetate with 90% yield. By polycondensation with a diacid chloride or polyaddition with a diisocyanate, this ligand led, respectively, to an insoluble poly(amide) 109 or poly(urea) 110 with excellent yields. Poly(amide) 109 gave a better ee (80%) than poly(urea) 110 (38%), albeit with a lower conversion (respectively, 38 and 72%), when they were used as palladium hgands... 

We now report a convenient method for the interfacial polycondensation of 1,1 -bis(3-aminoethyl)ferrocene (1) with a variety of diacid chlorides and diisocyanates, leading to ferrocene-containing polyamides and polyureas. In some instances, we have been able to observe film formation at the interface. Moreover, the polymerization reactions can be conveniently conducted at ambient temperatures in contrast to earlier high-temperature organometallic condensation... 

Interfacial or solution polycondensation, with or without stirring, was the general procedure utilized for the preparation of the polyamides and polyureas.l a Details are given in Table I. An important point to be noted is that, in the unstirred interfacial condensation polymerization of 1 with sebacoyl chloride or tere-phthaloyl chloride in the organic phase and triethylamine as the proton acceptor, immediate film formation took place at the interface. The polyamide films were removed after 1 h, dried, and utilized for taking electron micrographs. 

Table I. Polycondensation Reactions between 1,1 -Bis(6-amino-ethyl)ferrocene (1 and (6-hydroxyethyl)ferrocene (2) with Diacid Chlorides and Diisocyanates...

During distillation of the technical chloride, hydrogen chloride was evolved, air was bubbled through to remove it, and there was an explosion. This was attributed to a polycondensation (intermolecular Friedel-Craft) reaction, possibly catalysed by oxidation products. 

The chloride is usually (but not always) stabilised in storage by addition of aqueous alkali or anhydrous amines as acid acceptors. A 270 kg batch which was not stabilised polymerised violently when charged into a reactor. Contact of the chloride (slightly hydrolysed and acidic) with rust led to formation of ferric chloride which catalysed an intermolecular Friedel-Craft reaction to form polybenzyls with evolution of further hydrogen chloride. Contact of unstabilised benzyl chloride with aluminium, iron or rust should be avoided to obviate the risk of polycondensation. See Benzyl bromide Molecular sieve... 

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