Terephthaloyl chloride , preparation

The preparation of high molecular weight PPT in HMPA/NMP shows a strong dependence of inherent viscosity on reactant concentrations. In 2 1 (by volume) HMPA/NMP, the highest inherent viscosity polymer is obtained when each reactant is present in concentrations of ca 0.25 M higher and lower concentrations result in the formation of polymer of lower inherent viscosities. A typical procedure is as foUows 1,4-phenylenediamine, HMPA, and NMP are added to an oven-dried resin ketde equipped with a stirrer and stirred for ca 15 min with cooling to — 15°C, foUowed by the addition of powdered terephthaloyl chloride to the rapidly stirred solution. The reaction mixture changes to a thick, opalescent, paste-like gel in ca 5 min. 

Polymeric diacyl peroxides (26) can be prepared from the reaction of dibasic acid chlorides, eg, succinoyl, fumaryl, sebacoyl, and terephthaloyl chlorides, with sodium or hydrogen peroxide (187). 

Derivatives. In general, the esters of terephthaHc acid derived from saturated alcohols undergo the same reactions as dimethyl terephthalate. Some physical properties of six of these esters are Hsted in Table 23. The di- -butyl and di-2-ethyIhexyl esters find use as plasticizers (qv). Terephthaloyl chloride, which is prepared by reaction of terephthaHc acid and thionyl chloride, is used to prepare derivatives of terephthaHc acid. 

Uses. A principal use of thionyl chloride is in the conversion of acids to acid chlorides, which are employed in many syntheses of herbicides (qv), surfactants (qv), dmgs, vitamins (qv), and dyestuffs. Possible larger-scale appHcations are in the preparation of engineering thermoplastics of the polyarylate type made from iso- and terephthaloyl chlorides, which can be made from the corresponding acids plus thionyl chloride (186) (see Engineering plastics). 

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). 

DSC 7g = 194°C, Tm = 260°C. A series of polyarylates can be prepared following die same procedure at various terephthaloyl chloride-isophthaloyl chloride ratios.434... 

This polymer can be prepared from p-phenylenediamine and terephthaloyl chloride. The polymer is highly crystalline and, thus, difficult to keep in solution. Sufficiently high molecular weight polymers can be obtained by solution polymerization using a special solvent system. This ridged rod polymer can form a liquid crystalline solutions.7,9 14... 

It seems reasonable that polyester cyclics could be prepared by an extension of the /wendo-high-dilution [17] chemistry used for the preparation of cyclic carbonate oligomers [18, 19] however, such proved not to be the case. Brunelle et al. showed that the reaction of terephthaloyl chloride (TPC) with diols such as 1,4-butanediol did not occur quickly enough to prevent concentration of acid chlorides from building up during condensation [14]. Even slow addition of equimolar amounts of TPC and butanediol to an amine base (triethylamine, pyridine or dimethylaminopyridine) under anhydrous conditions did not form cyclic oligomers. (The products were identified by comparison to authentic materials isolated from commercial PBT by the method of Wick and Zeitler [9].)... 

The synthesis of optically active polyamides, or nylons, is a growing area of interest. From 1980 to 1991 there have been many citations in Chemical Abstracts on this subject. For example, optically active polyamides have been prepared for the resolution of optical isomers. The polyamides are prepared from optically active amines or dicarboxylic acids. One polyamide was prepared from (-)-(ram-l,2-diaminocyclohexane and terephthaloyl chloride and was used to resolve 2,2 -dihydroxy-6,6 -dimethylbiphenyl [31]. These optically active polyamides can be used in chromatography applications to resolve other optically active compositions. 

As shown in Eq. (14), poly(arylene ether imide)s were synthesized by the Friedel-Crafts reaction of diphenoxydiimide monomers and iso or terephthaloyl chloride [51], The diphenoxydiimide monomers were readily prepared by the condensation of 4-phenoxyaniline with appropriate aromatic tetracarboxylic dianhydrides. Several poly(arylene ether imide)s of controlled molecular weight (Mn = 40,000 g/mol) prepared by this route are presented in Table 21. As... 

The polyamide-hydrazide 7 was prepared by solution polymerization in anhydrous dimethylacetamide from terephthaloyl chloride and p-amino-benzhydrazide at ca. 10 °C. The polyamide 8 resulted from the polycondensation of m-phenylenediamine with isophthaloyl chloride at —20 °C, whereas 9 was prepared by the reaction of terephthaloyl chloride with the complex diamine l,3-bis(3-aminobenzamide)benzene at —20 °C. The water flux and salt rejection through these membranes were summarized in Table 5. The polyamide-hydrazide (7) membranes were prepared from polymer solutions containing 6 7% polymer (Mv 3 34,000) by casting on glass plates. The material was placed in an oven for 30 60 min and coagulated in deionized... 

In order to compare chiral recognition of the substrate p-chlorostyrene in the presence of chiral picket fences and basket handles carrying the same amino acids the porphyrins 167-169 were prepared in a straightforward manner from the known a,j8,a,j -tetra(o-aminophenyl)porphyrin 170, Fig. 28 [113]. Reaction with t-butoxycarbonyl-L-phenylalanine, removal of the protecting group and subsequent condensation with terephthaloyl chloride e.g. furnished the free base of 169. Iron was always introduced using Fe(CO)5/I2 and the... 

Polyesters synthesized from terephthaloyl chloride and isohexides were prepared, and characterized by differential scanning calorimetry, n.m.r. spectroscopy, and viscosity measurement.25,128 Another polyester, prepared by copolymerization of (2-hydroxyethyl)methacrylate with isoman-nide dimethacrylate (172), forms a hydrogel when allowed to swell in isotonic sodium chloride solution. This gel has useful properties for manufacturing contact-lens material.265... 

Multiblock polymers were prepared from PPO prepolymers with molecular weights 400, 1000, 2000, 3000, and weight fractions of PPO 25, 50, and 75%. PPO homopolymers were prepared by reacting PPO prepolymer with terephthaloyl chloride alone. A sample also was prepared containing 50% PDEGA of mol wt 2550. 

Diaryl phthalides, particularly phenolphthalein 281 and several phthalides derived from it, are widely used for the preparation of cardo polymers. The term is derived from the latin word for hinge or pivot, which is an apt name given that the aryl substituents are hinged on the C-3 carbon of the phthalide. In one application, compound 281 was used to prepare phthalamide 282 and both bisphenols were copolymerized with terephthaloyl chloride 283 to form polyesters. These formed strong flexible fdms with improved thermal stability and solubility <1997PSA3227>. 

Macrocyclic esters were prepared according to the method of Brunelle [1], which cyclo-oligomerizes terephthaloyl chloride and 1,4-butanediol with triethylamine dissolved in CH2CI2. 

Diphenyl terephthalate (DPT) was prepared by interfacial reaction of sodium phenoxide in water and terephthaloyl chloride (TPC) in methylene chloride, using benzyl triethylammonium chloride as catalyst, followed by washing with hot water and recrystallization from toluene. The yield was usually 90% or higher. 

Water-soluble polymers prepared from a hydrophilic polyester have been shown to be highly effective water-soluble polymer-supported catalysts for aqueous biphasic hydrogenations [169]. The necessary amphiphilic polyester 134 with a BINAP ligand in the main polymer chain was prepared according to Eq. 74 using terephthaloyl chloride, dihydroxy-PEG4000) a diaminated BI-... 

Thermoplastic polymers were also earlier reported to have been prepared by heating tricyclodecane dithiol with terephthaloyl chloride in a chlorinated solvent [16b]. Additional examples are cited for polythioesters based on bis-phenol A and random other polythioesters derived from bicyclic thiols. The starting diolefins for the dithols are prepared by the Diels-Alder synthesis using cyclopentadiene, acetylene, butadiene, etc. 

Poly(ether-ester)s have been prepared by condensation of adipoyl or terephthaloyl chloride with an isosorbide-based ether-diol (Scheme 3.10). The parent isosorbide is obtained from renewable resources, hydrogenation, and subsequent dehydration of D-glucose. The polymerizations were accelerated about five times under microwave heating using a scientific microwave unit as compared to conventional methods, and a 95% yield of the desired polymers was obtained within 5 min at 180 °C. 

Already in 1965, the formation of lyotropic liquid crystalline solutions of poly-(p-aminobenzoic acid) in concentrated sulfuric acid was observed. This work was the basis for the commercialization of high strength, high modulus, and heat-resistant poly-(p-phenylene terephthalate) (PPDT) fibers under the trade name Kevlar (Dupont) and Twaron (Akzo) (Fig. 15) [31]. PPDT is typically prepared by the polycondensation of terephthaloyl chloride and 1,4-pheny-lenediamine in tertiary amidic solvents such as A-methylpyrrolidinone or dimethylacet-... 

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