Terephthaloyl chloride polymerization

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). 

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... 

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). 

Figure 2-7 shows similar behavior for the polymerization between terephthaloyl chloride and /ra/i.v-2.5-di methyl piperazine in mixtures of chloroform with carbon tetrachloride or... 

Fig. 2-7 Polymerization of terephthaloyl chloride and mmv-2,5-dimethyl piperazine in mixed solvents. After Morgan [1963, 1965] (by permission of Wiley-Interscience, New York).

Another potential lignin modification method concerns the reaction with difunctional acid chlorides, especially terephthaloyl chloride, to form cross-linked polymeric materials (1,10,14,20). Several studies have dealt with... 

The modification of lignin sulfonates with terephthaloyl chloride produces new polymeric materials containing ester groups. This modification can be used to utilize lignins also for improvement of chemical fiber properties. This is presently under investigation. 

An alternate approach was the synthesis [85,86] of PBZT copolymers (XIX) containing pendent 2,6-dimethylphenoxy graft sites. Such copolymers do not lead to any breaks within the rigid-rod backbone thereby, they have no adverse effects upon rod reinforcement efficiency. Using the conventional PBZT polymerization procedure, 2-(2,6-dimethylphenoxy)terephthaloyl chloride was substituted for terephthaloyl chloride up to 30 mol %. The pendent dimethylphenoxy copolymers were then reacted with m-phenoxybenzoic acid in PPMA. 

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... 

The molar ratio of soft block to propane 1,2-diol and terephthaloyl chloride was A B (A + B) X 1.01. Four moles of pyridine per mole of acid chloride was added to react with the HCL produced in the polymerization. Pyridine hydrochloride was removed at the end of the reaction by washing with dilute HCL... 

Poly(p-phenylene terephthalamide) PPD-T, also called para-aramid, can be polymerized to a fiber-forming molecular weight by polycondensation of terephthaloyl chloride and 1,4-phenylene diamine. 

Ferrocene-containing liquid crystalline polymers 30 have been reported from the solution polymerization of l,T-bis(chlorocarbonyl)ferrocene, terephthaloyl chloride, and methylhydroquinone in refluxing dichloromethane [38], as indicated in Scheme 10-11. With one exception, these ferrocene containing copolyesters were reported to have birefringent melts. The presence of liquid crystallinity was verified by differential scanning calorimetry (DSC), polarized light microscopy, and X-ray diffraction studies. 

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. 

The electrophilic route for the production of aromatic polyether ketones involves the use of Friedel-Crafts catalysts. AICI3 is used as a catalyst for the polymerization of p-phenoxybenzoyl chloride as such, or p-phenoxy-benzoyl chloride or terephthaloyl chloride and 1,4-diphenoxybenzene to give a PEK. A PEEK is obtained by the use of p-phenoxyphenoxybenzoyl chloride, respectively. The process is carried out at low temperamres, such as 0-30°C. Due to the heterogeneous nature of this reaction, generally undesirable lower molecular weight polymers are produced. 

The positive ions MALDI-TOF spectrum of poly(butylene adipate diol)s, made by bulk polymerization of terephthaloyl chloride with a molar excess of 1,4 butanediol, shows only one series of peaks, extending over mass range 1000-6000 Da. These may be assigned to dihydroxyl-terminated oligomers. ° ... 

Later, Braun et al. reported the synthesis of a broad range of polyesters from isosor-bide/isomannide and acid dichlorides via melt condensation [12], The acid chlorides used include linear C4-C16 alkanoyl, ortho/iso/terephthaloyl, and 1,8- and 2,6-naphthalenoyl. Relatively high aliphatic polyesters were obtained, with up to 60 000 (GPC) for poly(isosorbide sebacate). Contrary to the aliphatic polyesters, the semi aromatic polyesters are highly viscous at high temperatures, hampering polycondensation. The TgS recorded for polyesters obtained by melt polymerization of isosorbide or isomannide with terephthaloyl chloride were 147 and 156 °C, respectively. 

In this section we discuss not only wholly aromatic polyamides, but also some mixed polyamides, prepared from aromatic diacids and aliphatic diamines, or vice versa. One such material was already described in Section 6.3.2. Another one, called Nylon 6T, is formed by interfacial polymerization of terephthaloyl chloride and hexamethylenediamine ... 

Definition Produced by the polymerization of terephthaloyl chloride with p-phenylenediamine Uses Food pkg. fibers yarn... 

Aromatic copolyamides, including the 50/50 (molar) copolymer of 3,4 -diamino-diphenyl ether with terephthaloyl chloride, are synthesized in a similar manner using amide solvent-salt combinations, in practice NMP-CaCl2- This 50/50 copolymer is in fact not processed via lyotropic solution, but rather directly as the (relatively dilute) polymerization reaction mixture the impressive yarn properties are realized only after hot drawing. Concentrated LC solutions in sulfuric acid are inaccessible due to degradation of the polymer in that medium. 

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