Isophthaloyl chloride reaction

MPD-1 fibers may be obtained by the polymeriza tion of isophthaloyl chloride and y -phenylenediamine in dimethyl acetamide with 5% lithium chloride. The reactants must be very carefully dried since the presence of water would upset the stoichiometry and lead to low molecular weight products. Temperatures in the range of 0 to —40° C are desirable to avoid such side reactions as transamidation by the amide solvent and acylation of y -phenylenediamine by the amide solvent. Both reactions would lead to an imbalance in the stoichiometry and result in forming low molecular weight polymer. Fibers are dry spun direcdy from solution. 

The procedure described is a modification of the general procedure of Angyal2 for the preparation of aldehydes from benzylamines by the Sommelet reaction. Isophthalaldehyde has been prepared from w-xylene by preparation of the tetrachloro derivative and hydrolysis,3 from isophthaloyl chloride by the Rosenmund reaction,4 from a,a -dibromo-m-xylene by the Sommelet reaction,5 and from isophthaloyl chloride by reduction with lithium tri-Cbutoxyaluminumhydride.6... 

Violent reaction occurred between isophthaloyl chloride and methanol when they were accidentally added in succession to the same waste solvent bottle. 

The diamine was dissolved in N,N-dimethyl-acetamide by stirring under a nitrogen stream. After the diamine was completely dissolved, equal moles of isophthaloyl chloride was added all at once. Stirring was continued for about three hours after which the reaction mixture was poured into hot water and magnetically stirred. The polymer was washed with hot water at least three times and then extracted with acetone to remove low molecular weight species. The polymer was dried in vacuum oven at about 70°C overnight. 

The first reaction, which took place at the interface and which Involved the primary and secondary amine groups of polyethyleni-mlne (PEI) with the difunctional reactant in hexane, proceeded very rapidly at room temperature to produce, in the case of isophthaloyl chloride, a polyamide surface skin (see Reaction I). 

The PA-300 membrane was commercially developed by Riley and coworkers (15), and is similar to the NS-101 membrane in structure and fabrication method. The principal difference is the substitution of a polyetheramlne, the adduct of polyepichlorohydrin with 1,2-ethanediamine, in place of polyethylenlmine. Use of the polyetheramlne was significant improvement in that considerably higher membrane fluxes were possible at salt rejections equivalent to the NS-lOO membrane system. The actual barrier layer in the PA-300 membrane is a polyamide formed by Interfaclal reaction of Isophthaloyl chloride with the polyetheramlne. 

The oxadiazolylthio portion of 5-benzoate (74c) is a good leaving group and reaction with aniline to form benzanilide and thione (73a) is rapid at room temperature. The diester formed fipom thione (73a) and isophthaloyl chloride similarly reacts with diamines, under these mild conditions, to give polyamides <85JPS(A)2727>. 

Add 6.3 g (0.0310 mol) of isophthaloyl chloride and 2.8 g (0.0311 mol) of 1,4-butanediol (1% excess) to a 50-ml ampule used for polymerization equipped with a capillary tube for a nitrogen inlet extending below the surface of the reaction mixture. 

Fig. 7. Reaction of isophthaloyl chloride with 1 to prepare the bisketone-bisbenzocyclobutene monomer 14...

A poly(arylene ether phenylquinoxaline) of structure 14 was prepared by the aluminum chloride catalyzed reaction of 6,6 -bis[2-(4-phenoxyphenyl)-3-phenylquinoxaline] and isophthaloyl chloride in 1,2-dichloroethane [51]. The polymer had an inherent viscosity of 1.29 dL/g and a Tg of 224 °C. A polymer of the same chemical structure was prepared from the reaction of 3,3, 4,4 -tetraaminobiphenyl with l,3-bis(phenylglyoxalyl-4-phenoxy-4 -benzoyl)-benzene that gave a Tg of 239 °C [16], significantly higher than that prepared by the electrophilic route. In addition, a polymer of the same chemical structure (third polymer in Table 3) prepared via nucleophilic substitution exhibited a Tg of 240 °C. 

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... 

They fabricated another two kinds of composite membranes through the interfacial reaction of triethylenetetramine 106,107). The one was the (3,(3 -dichloroethylether-triethylenetetramine-isophthaloyl chloride-trimesoyl chloride copolymer membrane, which had the water permeation rate of 2400 1/m2 day and desalination rate of 96.8 %. The other was the adipic-triethylenetetramine-isophthaloyl chloride copolymer membrane, which showed the water flux 95.8 1/m2 day and NaCl rejection 99.8 % on the reverse osmosis of a 0.5% aqueous solution at 25 °C and 42.5 kg/cm2. These characteristics for both membranes did not decrease during the continuous operation for 100 500 hr. 

Figure 2. Under high-dilution conditions, die reaction of 1 with isophthaloyl chloride 2 yields tetralactam macrocycle 3, the catenane 4, and octalactam ring 5.

In another reaction, the /wra-substitution pattern in terephthaloyl chloride that is used instead of isophthaloyl chloride induces the formation of larger octalactam macrocycles which provide two suitable binding sites for threading two semicycles and thus yield higher chain-like catenanes [18],... 

Polyethylene amine reacted with isophthaloyl chloride prodnces the PA-100 membrane as shown in the following reaction ... 

The chloride atom in isophthaloyl chloride is attached to the carboxyl group. In this reaction, the H in the amine group of polyethylene amine reacts with the chloride in the carboxyl group producing HCl, as shown by the product over the arrow, and the PA-100 membrane to the right of the reaction equation. As in the case of the NS-lOO, the reaction forms the closed loop resulting in cross-linked structure of the PA-membrane. Thus, a molecular pore is again produced. 

Again, in this reaction, the H in the amine group of the amine, epiamine, reacts with the chloride of isophthaloyl chloride forming HCl. The N, in turn, of the amine gronp, from which the H that reacts with the C chloride were taken, bonds with the C of the carboxyl group of isophthaloyl chloride producing the PA-300 membrane. As shown in its structure, this membrane is also a cross-linked membrane. 

The Schotten-Bauman condensation produces polyanhydrides with moderate molecular weights by a dehydrochlorination reaction between a diacid chloride and a dicarboxylic acid. The polymerization takes place by reacting the monomers for 1 hr at room temperature, and it can be conducted via solution or interfacial methods. Solvents that are used in solution polymerization include dichloromethane, chloroform, benzene, and ethyl ether. The degree of polymerization obtained with this method is approximately 20-30. Lower molecular weight products are obtained for less reactive monomers such as isophthaloyl chloride. 

Two types of reactions involved in the preparation of NS-100 membranes are illustrated in Figure 2. The structural representation of polyethylenimine (PEI) is simplified to show only the reactive primary and secondary amine groups. In the first step the amine groups react rapidly with isophthaloyl chloride at the interface to produce a polyamide surface skin, while amine groups below... 

Table IV lists the best performance data obtained for piperazine oligomer membranes interfacially reacted with isophthaloyl chloride. The objective of these tests was to achieve single-pass seawater desalination membranes. As such, the presence of free carboxylate groups was avoided use was made of the trimesoyl chloride or alternate triacyl halides in the oligomer formation step, and diacyl chlorides in the interfacial reaction step. A few samples of seawater desalination membranes were obtained. Best results were seen for piperazine-cyanurate pre-polymers interfacially cross-linked by isophthaloyl chloride, but fluxes were low in view of the operating test pressure of 1500 psi (10 342 kPascal). Also, individual membrane results with piperazine oligomers were equally as erratic as those experienced for piperazine directly. The only notable advantage of the piperazine oligomer approach was the ability to incorporate...

V- 6-[2-(7-methyl[l, 8]naphthyridin-2-yl)ethyl]pyridine-2-yl acetamide 356 was prepared by the reaction of 2,7-dimethyl-l,8-naphthyridines 357 with n-butyllithi-um and 2-/V-acetylamino-6-bromomethylpyridine 358. Another carrier, viz., N-(l-methyl[l,8]naphthyridin-2-yl)-7V -(6-methylpyridin-2-yl)isophtalamide 359, was synthesized from 2-amino-7-methyl-l,8-naphthyridine 360, 2-amino-6-methylpyridine 226a and isophthaloyl chloride 361 in dry dichloromethane in the presence of tri-ethylamine. N,N -bis(l-mcl y [, 8]naphthyridin-2-yl)isophthalamide 362 was prepared from naphthyridines 360 and chloride 361 under analogous conditions. Isophthalamides 359 and 362 were used for the determination of L-( + )tartaric acid as complexes (1 1) soluble in chloroform (1999JIC661, 2001T4987). 

It was found that the reaction proceeds when n = 4 or 5 but not when n = 2 or 3. Difunctional macrocyclic urea amides were made by reacting the raacrocyclic urea with diacid chlorides such as isophthaloyl chloride. The utility of these cross-linkers was proven in solvent coatings, acrylic powder coatings, and electro-deposition coatings. 

METHYL HYDRATE (67-56-1) CH O CH3OH Flammable liquid. Forms explosive mixture with air [explosion limits in air (vol %) 6.0 to 36.5 flash point 52 F/11 C autoignition temp 725°F/385°C 867°F/464°C " Fire Rating 3]. Violent reaction (possible fire and/or explosion) with strong oxidizers strong mineral acids (e.g., nitric, sulfuric, perchloric) acetyl bromide alkyl aluminum salts beryllium dihydride bromine, chromic acid l-chloro-3,3-difluoro-2-methoxycyclopropene, cyanuric chloride diethylzinc, isophthaloyl chloride potassium-ferf-butoxide phosphorus trioxide platinum-black catalyst (ignition) potassium sulfur diimide Raney-nickel catalysts 2,4,6-trichlorotriazine, triethylaluminum, 1,3,3 -trifluor o-2 -... 

This membrane is highly sensitive to chemical attack by hypochlorite ion and hypochlorous acid in chlorinated feedwaters. Wrasidlo prepared a variation of the NS-100 membrane in which the primary amine groups of polyethylenimine were cyanoethylated before reaction with isophthaloyl chloride.27 This membrane was claimed to be chlorine-resistant, but was probably not so. 

Polyepiamine, also called polyetheramine, is the reaction product of poly-epichlorohydrin with an excess of ethylenediamine. Its idealized structure and its reaction products with isophthaloyl chloride (PA-300) and 2,4-toluenediiso-cyanate (RC-100) are shown below ... 

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