Acid chloride polymerization

Acid anhydride-diol reaction, 65 Acid anhydride-epoxy reaction, 85 Acid binders, 155, 157 Acid catalysis, of PET, 548-549 Acid-catalyzed hydrolysis of nylon-6, 567-568 of nylon-6,6, 568 Acid chloride, poly(p-benzamide) synthesis from, 188-189 Acid chloride-alcohol reaction, 75-77 Acid chloride-alkali metal diphenol salt interfacial reactions, 77 Acid chloride polymerization, of polyamides, 155-157 Acid chloride-terminated polyesters, reaction with hydroxy-terminated polyethers, 89 Acid-etch tests, 245 Acid number, 94 Acidolysis, 74 of nylon-6,6, 568... 

Polyamide-6 (PA-6), synthesis of, 174-176. See also PA-6 entries Polyamide endgroups, 161 Poly amide-imide, synthesis of, 291 Polyamides (PAs), 135-193. See also Nylons PA entries acid chloride polymerization of, 155-157... 

In addition to its use in the synthesis of acid chlorides, polymeric phosphine dichloride also converts alcohols to the corresponding chloride. 

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

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). 

Additional phosphonic acid is derived from by-product streams. In the manufacture of acid chlorides from carboxyUc acids and PCl, phosphonic acid or pyrophosphonic acid is produced, frequentiy with copious quantities of yellow polymeric LOOP. Such mixtures slowly evolve phosphine, particularly on heating, and formerly were a disposal problem. However, purification of this cmde mixture affords commercial phosphonic acid. By-product acid is also derived from the precipitate of calcium salts in the manufacture of phosphinic acid. As a consequence of the treatments of the salt with sulfuric acid, carbonate is Hberated as CO2 and phosphonic acid goes into solution. 

Because almost any diacid can be leaddy converted to the acid chloride, this reaction is quite versatile and several variations have been developed. In the interfacial polymerization method the reaction occurs at the boundary of two phases one contains a solution of the acid chloride in a water-immiscible solvent and the other is a solution of the diamine in water with an inorganic base and a surfactant (48). In the solution method, only one phase is present, which contains a solution of the diamine and diacid chloride. An organic base is added as an acceptor for the hydrogen chloride produced in the reaction (49). Following any of these methods of preparation, the polymer is exposed to water and the acid chloride end is converted to a carboxyhc acid end. However, it is very difficult to remove all traces of chloride from the polymer, even with repeated washings with a strong base. 

Solution Polymerization. In solution polymerization, a solvent for the monomer is often used to obtain very uniform copolymers. Polymerization rates ate normally slower than those for suspension or emulsion PVC. Eor example, vinyl chloride, vinyl acetate, and sometimes maleic acid are polymerized in a solvent where the resulting polymer is insoluble in the solvent. This makes a uniform copolymer, free of suspending agents, that is used in solution coatings (99). 

UF Membranes as a Substrate for RO An important use of UF membranes is as a substrate for composite reverse-osmosis membranes. After the UF membrane (usually polysulfone) is prepared, it is coated with an aqueous solution of an amine, then dipped in an organic solution of an acid chloride to produce an interfacially polymerized membrane coating. 

Vinyl chloride (1835) formed by reacting acetylene with hydrochloric acid, was polymerized a.v polyvinyl chloride (PVC) in 1912, The theory of polymerization by Staudinger in the 1920s- led to the advances that followed. The acrylate were polymerized as polymethylmethacrylate to come into production in 1927. Polystyrene was developed. similarly and concurrently. Polyethylene came into production in 1939 for use in radar and now is ubiquitous. 

Polymerization reactions can occur in bulk (without solvent), in solution, in emulsion, in suspension, or in a gas-phase process. Interfacial polymerization is also used with reactive monomers, such as acid chlorides. 

The reaction between acid chlorides and aliphatic alcohols or phenolic compounds commonly takes place at low to moderate temperature (—10 to 100°C) in solution or by interfacial or dispersion polymerization techniques. It has been widely applied to polyester synthesis. Reviews and books are available on the polymerization techniques as well as on the chemistry of this reaction.2,207 294... 

It is also possible to prepare them from amino acids by the self-condensation reaction (3.12). The PAs (AABB) can be prepared from diamines and diacids by hydrolytic polymerization [see (3.12)]. The polyamides can also be prepared from other starting materials, such as esters, acid chlorides, isocyanates, silylated amines, and nitrils. The reactive acid chlorides are employed in the synthesis of wholly aromatic polyamides, such as poly(p-phenyleneterephthalamide) in (3.4). The molecular weight distribution (Mw/Mn) of these polymers follows the classical theory of molecular weight distribution and is nearly always in the region of 2. In some cases, such as PA-6,6, chain branching can take place and then the Mw/Mn ratio is higher. 

Acid chlorides are very reactive and have as a condensation product hydrochloric acid.4,7 9 This hydrochloric acid can form an amine salt with unreacted amine groups, which should be avoided. To prevent this happening, acid binders, which are more reactive than the amines, are added. Polyamidation can be earned out using a solution and with an interfacial method. With the interfacial method one has the choice between a stirred and an unstirred process. In an unstirred process, the polymerization is at the interface and a rope can be drawn from the interface,... 

The polymerization of aromatic diamines with acid chlorides in solution works well.7 914 35 The basicity of the aromatic diamine is low and acid binding can be achieved with several compounds and even solvents such as TV-methylpyrrolidonc (NMP) and dimethylacetamide (DMAc). The all-para aromatic amide poly(p-phenyleneterephthalamide) can be synthesized in DM Ac.7,9,14 To prevent precipitation of the polymer, a salt such as calcium chloride or lithium chloride can be added. It is also possible to react the acid chloride with a silylated diamine ... 

This reaction is simple and qualitative36 37 the diamine can be both an aromatic and an aliphatic diamine. With this method, even star-shaped PAs have been synthesized.37 Solution polymerization from acid chlorides and aliphatic diamines is more difficult due to the strong basicity of the aliphatic amine groups. Acid binders which have been used with aliphatic diamines are the tertiary amines with high kb values these include dimethylbenzylamine and diisopropylethylamine.4 38... 

For very high melting polymers (Tm > 300°C), a solution polymerization is normally employed. If this is started from the reactive acid chloride, the reaction temperature can be low. Polymers from acid chlorides can also be prepared by the interfacial method. Semicrystalline PA can be postcondensed in the solid state to higher molecular weights. To do this, the polymer powder/particles are heated for many hours below their melting temperature in an inert atmosphere. 

Acid chlorides are very reactive and at room temperature react readily with amines. Synthesis by interfacial and solution methods is possible. However, care should be taken that the hydrochloric acid produced does not react with unreacted amine groups. With the strong basic aliphatic diamines, the acid binder must preferably be even more basic. The attainable molecular weights are strongly dependent on the concentrations this is particularly the case for easily precipitated terephthalamide polymers. Possible problems with the acid binder can be overcome by starting with silylated diamines.33,34 A typical example for interfacial polymerization of terephthalamides is PA-2,T.66... 

The molecular weights obtained by a solution polymerization starting with acid chlorides are highly dependent not only on the type of solvent but also on the acid binder used. An example of a solution polymerization is given for the high melting PA-4,T. 

Polylactides, 18 Poly lactones, 18, 43 Poly(L-lactic acid) (PLLA), 22, 41, 42 preparation of, 99-100 Polymer age, 1 Polymer architecture, 6-9 Polymer chains, nonmesogenic units in, 52 Polymer Chemistry (Stevens), 5 Polymeric chiral catalysts, 473-474 Polymeric materials, history of, 1-2 Polymeric MDI (PMDI), 201, 210, 238 Polymerizations. See also Copolymerization Depolymerization Polyesterification Polymers Prepolymerization Repolymerization Ring-opening polymerization Solid-state polymerization Solution polymerization Solvent-free polymerization Step-grown polymerization processes Vapor-phase deposition polymerization acid chloride, 155-157 ADMET, 4, 10, 431-461 anionic, 149, 174, 177-178 batch, 167 bulk, 166, 331 chain-growth, 4 continuous, 167, 548 coupling, 467 Friedel-Crafts, 332-334 Hoechst, 548 hydrolytic, 150-153 influence of water content on, 151-152, 154... 

Perhaps the most interesting finding of our synthetic studies was that the interfacial preparation of poly(iminocarbonates) is possible in spite of the pronounced hydrolytic instability of the cyanate moiety (see Illustrative Procedure 3). Hydrolysis of the chemically reactive monomer is usually a highly undesirable side reaction during interfacial polymerizations. During the preparation of nylons, for example, the hydrolysis of the acid chloride component to an inert carboxylic acid represents a wasteful loss. 

Consider the case of the production of peroxy esters (e.g. tert-buty] peroxy 2-ethyl hexanoate), based on the reaction between the corresponding acid chloride and the hydroperoxide in the presence of NaOH or KOH. These are highly temperature sensitive and violently unstable, and solvent impurities are detrimental in their applications for polymerization. Batch operations to produce even 1000 tpa will be unsafe. A continuous reactor can overcome most of the problems and claims have been made for producing purer chemicals at lower capital and operation cost the use of solvent can be avoided. Continuous reactors can produce seven to ten times more material per unit volume than batch processes. Since the amount of hazardous product present in the unit at any given time is small, protective barrier walls may be unneccessary (Kohn, 1978). 

The predominant RO membranes used in water applications include cellulose polymers, thin film oomposites (TFCs) consisting of aromatic polyamides, and crosslinked polyetherurea. Cellulosic membranes are formed by immersion casting of 30 to 40 percent polymer lacquers on a web immersed in water. These lacquers include cellulose acetate, triacetate, and acetate-butyrate. TFCs are formed by interfacial polymerization that involves coating a microporous membrane substrate with an aqueous prepolymer solution and immersing in a water-immiscible solvent containing a reactant [Petersen, J. Memhr. Sol., 83, 81 (1993)]. The Dow FilmTec FT-30 membrane developed by Cadotte uses 1-3 diaminobenzene prepolymer crosslinked with 1-3 and 1-4 benzenedicarboxylic acid chlorides. These membranes have NaCl retention and water permeability claims. 

---