Nylon 6,6 polymerisation

Polymer Production. Three processes are used to produce nylon-6,6. Two of these start with nylon-6,6 salt, a combination of adipic acid and hexamethylenediamine in water they are the batch or autoclave process and the continuous polymerisation process. The third, the soHd-phase polymerisation process, starts with low molecular weight pellets usually made via the autoclave process, and continues to build the molecular weight of the polymer in a heated inert gas, the temperature of which never reaches the melting point of the polymer. 

The polymerisation process proceeds in a manner similar to that of other type AABB polyamides, such as nylon-6,6. The final resin had found apphcation in automotive and other high performance end uses but was withdrawn from the market in 1994. 

Fig. 4. Typical nylon-6,6 autoclave polymerisation cycle showing the changes in pressure (—) and temperature (---). To convert MPa to psi, multiply by...

Nylon-4,6. This nylon is produced from diaminobutane and adipic acid. The process is similar to that for nylon-6,6, but the amine has a high tendency to cyclize and the temperatures are therefore kept low. This results ia a low molecular weight polymer, which is subsequently iacreased ia viscosity by sohd-state polymerisation. 

D. B. Jacobs and J. Zimmerman, in C. E. Schildknecht and I. Skeist, eds.. Polymerisation Processes, High Polymers, Vol. XXIX. Wiley-Interscience, New York, 1977, pp. 424, 467. A very detailed review of nylon-6,6 polymerization. 

The thermoplastic or thermoset nature of the resin in the colorant—resin matrix is also important. For thermoplastics, the polymerisation reaction is completed, the materials are processed at or close to their melting points, and scrap may be reground and remolded, eg, polyethylene, propjiene, poly(vinyl chloride), acetal resins (qv), acryhcs, ABS, nylons, ceUulosics, and polystyrene (see Olefin polymers Vinyl polymers Acrylic ester polymers Polyamides Cellulose ESTERS Styrene polymers). In the case of thermoset resins, the chemical reaction is only partially complete when the colorants are added and is concluded when the resin is molded. The result is a nonmeltable cross-linked resin that caimot be reworked, eg, epoxy resins (qv), urea—formaldehyde, melamine—formaldehyde, phenoHcs, and thermoset polyesters (qv) (see Amino resins and plastics Phenolic resins). 

The early development of the nylons is largely due to the work of W. H. Carothers and his colleagues, who first synthesised nylon 66 in 1935 after extensive and classical researches into condensation polymerisation. Commercial production of this polymer for subsequent conversion into fibres was commenced by the Du Pont Company in December 1939. The first nylon mouldings were produced in 1941 but the polymer did not become well known in this form until about 1950. 

The polymerisation casting of nylon 6 in situ in the mould has been developed in recent years. Anionic polymerisation is normally employed a typical system uses as a catalyst 0.1-1 mol.% of acetic caprolactam and 0.15-0.50 mol.% of the... 

Reaction injection moulding techniques, developed primarily for polyurethanes (see Chapter 27), have also been adapted for nylon 6 in what must be considered as a variation of the polymerisation casting technique. 

The basic RIM process is illustrated in Fig. 4.47. A range of plastics lend themselves to the type of fast polymerisation reaction which is required in this process - polyesters, epoxies, nylons and vinyl monomers. However, by far the most commonly used material is polyurethane. The components A and B are an isocyanate and a polyol and these are kept circulating in their separate systems until an injection shot is required. At this point the two reactants are brought together in the mixing head and injected into the mould. 

Condensation polymerisation In this case reaction between two groups occurs which leads to the production of a polymer and also a simple molecule, e.g. reaction between adipic acid and hexamethylene diamine yields nylon 66 and water ... 

The name Nylon was given by the Du Pont company of America to their first synthetic condensation polymer formed by the reaction of difuncfional acids with difuncfional amines, ft had been made as part of the fundamental programme of W. H. Carothers to investigate the whole topic of polymerisation. The term has gradually been extended to other related polymers. These materials are strictly polyamides, but this term includes that otherwise distinct class of natural macromolecules, the proteins. The term nylon is retained for its usefulness in distinguishing synthetic polyamides from the broader class of such polymers. 

In certain cases the organic dibasic acid is not sufficiently reactive for the purpose of polymerisation, and so it is replaced either with its anhydride or its acid chloride. For example polyamides (nylons) are often prepared by reaction of the acid chloride with the appropriate diamine. In the spectacular laboratory prepatation of nylon 6,6 this is done by interfacial polymerisation. Hexamethylenediamine is dissolved in water and adipyl chloride in a chlorinated solvent such as tetrachloromethane. The two liquids are added to the same beaker where they form two essentially immiscible layers. At the interface, however, there is limited miscibility and nylon 6,6 of good molar mass forms. It can then be continuously removed by pulling out the interface. 

Ring-opening reactions may also be used in order to make polymers by the step polymerisation mechanism. One commercially important example of this is the manufacture of nylon 6, which uses caprolactam as the starting material and proceeds via the ring-opening reaction shown in Reaction 2.15. 

Step polymerisations tend to be carried out using two different bifunctional molecules so that these give rise to molecules which are essentially copolymers. For example, nylon 6,6 is prepared from hexamethylenediamine and adipic acid it thus consists of alternating residues along the polymer chain and may be thought of as an alternating copolymer. 

A method for the depolymerisation of PETP fibres using quarternary ammonium salt phase transfer catalysts in saponification processes at atmospheric pressure and temperatures as low as room temperature is reported. Terephthalic acid was produced in yields as high as 93%. Also reported are similar processes for the depolymerisation of nylon 66 and nylon 46 fibres. Nylon 46 oligomers produced were repolymerised using solid-state polymerisation to produce high molecular weight nylon 46. Nylon 66 was depolymerised to produce oligomers and adipic acid in reasonable yields. 11 refs. USA... 

Many polymers have been processed by casting, e.g., acrylics, polystyrene, polyamide (nylon 6), phenolics, PVC/plasticiser. Many of these are used in a pre-polymer form, which polymerise on the casting belt, or the polymerisation can be completed later by application of heat. 

The first successful synthetic fibre. The term is applied to any long-chain synthetic polymeric amide and the best known commercial type is nylon 66 produced by the condensation polymerisation of adipic acid with hexamethylene diamine. 

Nitrogen is pumped in and molten polymer is extruded and cooled on a drum to form ribbons. Nylon 6, 10 is formed in similar way at a lower temperature. Nylon 6, 6 can also be prepared in a continuous process in three separate tubes wherein reaction is started, steam removed and polymerisation completed. The product is directly melt spun into fibres. 

Nylon copolymers can be prepared by either heating the blend of different nylons together or by polymerising mixed monomers. 

Ragaini [86] has reported that the ring opening polymersiation of e-caprolactam (nylon 6, Fig. 5.43), in the presence of ultrasound, takes place without the need for added water and yields larger molar masses in shorter reaction times and at lower reaction temperatures than conventional polymerisation. 

These polymers possessing amide linkages are Important examples of synthetle fibres and are termed as nylons. The general method of preparation eonslsts of the condensation polymerisation of diamines with dlearboxylle aelds and also of amino acids and their laetarns. 

The condensation polymers are formed by repeated condensation reaction between two different bi-functional or tri-functional monomeric units. In these polymerisation reactions, the eUmtnatlon of small molecules such as water, alcohol, hydrogen chloride, etc, take place. The examples are teiylene (dacron), nylon 6, 6, nylon 6, etc. For example, nylon 6, 6 is formed by the condensation of hexamethylene diamine with adipic acid. 

A development in the synthesis of macromolecular scintillators is the radical co-polymerization of alkenes with the fluorescent co-monomer 2-t-butyl-5-(4 -vinyl-4-biphenylyl)-l,3,4-oxadiazole <89MI 406-04). Basic initiators cause ring opening of 2-phenyl-l,3,4-oxadiazolin-5-one with subsequent anionic polymerisation to form A-benzamido-1-nylon [-N(NHCOPh)CO-] <90PB583>. 

In Chapter 14 (p. 226) you studied the different addition polymers produced from alkenes. Not all polymers are formed by addition reactions, though. Some are produced as a result of a different type of reaction. In 1935 Wallace Carothers discovered a different sort of plastic when he developed the thermoplastic, nylon. Nylon is made by reacting two different chemicals together, unlike poly(ethene) which is made only from monomer units of ethene. Poly(ethene), formed by addition polymerisation, can be represented by ... 

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