Terephthaloyl chloride

CIHOROCARBONSANDCIHOROHYDROCARBONS - BENZYL CIHORIDE, BENZAL CIHORIDE AND BENZOTRICIHORIDE] (Vol 6) Terephthaloyl chloride [10020-9]... 

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. 

Technora. In 1985, Teijin Ltd. introduced Technora fiber, previously known as HM-50, into the high performance fiber market. Technora is based on the 1 1 copolyterephthalamide of 3,4 -diaminodiphenyl ether and/ -phenylenediamine (8). Technora is a whoUy aromatic copolyamide of PPT, modified with a crankshaft-shaped comonomer, which results in the formation of isotropic solutions that then become anisotropic during the shear alignment during spinning. The polymer is synthesized by the low temperature polymerization of/ -phenylenediamine, 3,4 -diaminophenyl ether, and terephthaloyl chloride in an amide solvent containing a small amount of an alkaU salt. Calcium chloride or lithium chloride is used as the alkaU salt. The solvents used are hexamethylphosphoramide (HMPA), A/-methyl-2-pyrrohdinone (NMP), and dimethyl acetamide (DMAc). The stmcture of Technora is as follows ... 

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. 

Table 23. Properties of terephthalic acid ester and Terephthaloyl Chloride...

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). 

The fully side-chaia chloriaated products, 1,3-his(trichioromethy1)henzene [881-99-1] and 1,4-his(trichioromethy1)henzene [68-36-0] are manufactured by exhaustive chlorination of meta and para xylenes. For the meta compounds, ring chlorination cannot be completely eliminated ia the early stages of the reactioa. The xyleae hexachlorides are iatermediates ia the manufacture of the xylene hexafluorides and of iso- and terephthaloyl chloride [100-20-9] (see Phthalic acids). 

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). 

Rather similar materials have been made available by Monsanto, made by reacting p-aminobenzhydrazide with terephthaloyl chloride (Figure 18.33). The fibre is marked as PABH-T X-500. 

In a later work, Tunca and Yagci [40,41] used two other acid chlorides (adipoyl and terephthaloyl chloride) along with ACPC. By changing the ratio of the different acid chlorides the number of thermally labile azo bonds in the polymer backbone could be regulated. 

Terephthaloyl Chloride/Isophthaloyl Chloride/Bisphenol-A Solution Polyesterification... 

Terephthaloyl Chloride-Isophthaloy l Chloride-Bisphenol-A Interfacial Polyesterification... 

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... 

To an 8-L beaker a solution of 3.78 g (0.630 mol) of ethylene diamine and 0.126 mol of potassium hydroxide in 4.5 L of distilled water are added and stirred with a high-speed mixer. To this, 12.79 g (0.634 mol) of terephthaloyl chloride dissolved in 1 L of methylene chloride (a safer solvent is THF) is added and stirred for 10 min. The suspension is filtered and washed twice with methanol. After drying, the polymer has an of 1.0 as measured in 96% sulfuric acid (0.5% solution at 30°C). The melting temperature of the polymer is 455° C. 

To terephthaloyl chloride (0.015 mol) in 100 mL ofTHF cooled to —15°C, tetram-ethylenediamine (0.015 mol) anddiisopropylethylamine (0.030 mol) in 20 mL THF are added while stirring vigorously. A suspension is formed directly. Stirring is continued for 15 min, after which the precipitated polymer is filtered and washed with boiling water. The resultant polymer has an i]i h of 0.39 in 96% sulfuric acid (1% solution at 25° C). 

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... 

Example 18. Polyfp-phenylene terephthalamide) from terephthaloyl chloride.69... 

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... 

Amine-terminated siloxane oligomers have also been utilized in the synthesis of various siloxane-amide and siloxane-imide copolymers, High molecular weight siloxane-amide copolymers have been synthesized by the solution or interfacial co-polymerization of siloxane oligomers with sebacoyl chloride or terephthaloyl chloride respectively 1S5,165). In some reactions diamine chain extenders have also been utilized. Thermal and dynamic mechanical characterization of these copolymers have shown the formation of multiphase systems160). Compression molded films displayed very good elastomeric properties. 

Cross-linked xylan-based microparticles are produced by the emulsification of an alkaline solution of xylan with a lipophilic phase formed by a mixture of chloroform and cyclohexane by using 5% (w/v) sorbitan triesterate as the surfactant. Subsequently, the cross-linking reaction is carried out for 30 minutes with 5% (w/v) terephthaloyl chloride in order to yield a hard and rigid polymeric shell (Nagashima et al., 2008). 

Nevertheless, SDM showed a maximum decrease in the cell survival rate of approximately 12% and 27% at the lowest and highest concentrations of microparticles, respectively (Figure 14). The massive cytotoxicity induced by CLM may be explained by the presence of remaining molecules of terephthaloyl chloride, which plays the role of cross-linking agent during the formation of CLM and is well known as a toxic substance. 

Edwards-Levy, F., Andry, M. C. Levy, M. C. (1994). Determination of free amino group content of serum-albumin microcapsules. II. Effect of variations in reaction-time and terephthaloyl chloride concentration. International Journal of Pharmaceutics, Vol. 103, 3, (March 1994), pp. (253-257), ISSN 0378-5173 Friend, D. R. (2005). New oral delivery systems for treatment of inflammatory bowel disease. Advanced Drug Delivery Reviews, Vol. 57, 2, (January 2005), pp. (247-265), ISSN 0169-409X... 

A suspension of 8-aminoethylferrocene (3) in deoxygenated water, containing an excess of sodium hydroxide, was found to form a yellow precipitate immediately on being shaken vigorously with one equivalent of pure terephthaloyl chloride in dry benzene. Elemental analysis and an IR spectrum indicated the yellow precipitate to have the structure 4 (yield 100%). 

General Considerations. The following chemicals were commercially available and used as received 3,3,3-Triphenylpropionic acid (Acros), 1.0 M LiAlH4 in tetrahydrofuran (THF) (Aldrich), pyridinium dichromate (Acros), 2,6 di-tert-butylpyridine (Acros), dichlorodimethylsilane (Acros), tetraethyl orthosilicate (Aldrich), 3-aminopropyltrimethoxy silane (Aldrich), hexamethyldisilazane (Aldrich), tetrakis (diethylamino) titanium (Aldrich), trimethyl silyl chloride (Aldrich), terephthaloyl chloride (Acros), anhydrous toluene (Acros), and n-butyllithium in hexanes (Aldrich). Anhydrous ether, anhydrous THF, anhydrous dichloromethane, and anhydrous hexanes were obtained from a packed bed solvent purification system utilizing columns of copper oxide catalyst and alumina (ether, hexanes) or dual alumina columns (tetrahydrofuran, dichloromethane) (9). Tetramethylcyclopentadiene (Aldrich) was distilled over sodium metal prior to use. p-Aminophenyltrimethoxysilane (Gelest) was purified by recrystallization from methanol. Anhydrous methanol (Acros) was... 

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