Caprolactam initiation

The kinetics of anionic ring opening polymerization of caprolactam initiated by iso-phthaloyl-bis-caprolactam and catalyzed by caprolactam-magnesium-bromide satisfactorily fit Malkin s autocatalytic model below 50 percent conversion. The calculated value of the overall apparent activation energy for this system is 30.2kJ/mol versus about 70kJ/mol for Na/hexamethylene-l,6,-bis-carbamidocaprolactam as the initiator/catalyst system. 

Here we will consider the polymerization of caprolactam initiated by strong bases. They are usually referred to as catalysts and also as initiators by some authors (Sekiguchi, 1984). Strong bases initiate polymerization by the replacement of H in the N-H residue of caprolactam by a cation to give lactam anion e.g., for caprolactam with an alkali metal, M ... 

The rate of polymerization of an anionic polymerization of caprolactam initiated by the addition of bases and activated by acyl lactam is determined by the concentration of base. That is, the base reacts more quickly with the acyl lactam to form an anion. Every anion so formed starts a chain, so that the degree of polymerization is determined by the acyl lactam concentration. Compared to this reaction, the formation of anions by a reaction between base and monomer is very much slower, and hardly any polymer chains are formed in this way. 

The polymerization of j3-carboxymethyl caprolactam has been observed to consist of initial isomerization via a second-order kinetic process followed by condensation of the isomer to polymer ... 

Nylon-6 is the polyamide formed by the ring-opening polymerization of S-caprolactam. The polymerization of S-caprolactam can be initiated by acids, bases, or water. Hydrolytic polymerization initiated by water is often used in industry. The polymerization is carried out commercially in both batch and continuous processes by heating the monomer in the presence of 5—10% water to temperatures of 250—280°C for periods of 12 to more than 24 h. The chemistry of the polymerization is shown by the following reaction sequence. 

The first question can be answered relatively simply (although not completely exactly) from the available factual material. If the pK value of the lactam is taken as a criterion, the border of reactivity lies at about pK 12. Valerolactam and caprolactam react just noticeably with diazomethane (yields 14 and 7%). However, it should be noticed that catalysts are frequently necessary in order to initiate the reaction (methanol, water, aluminum isopropylate," fluoboric acid " ). For example, phthalimide does not react at all with diazomethane in ether, but a smooth reaction occurs if some methanol is added. 

The step-growth polymer nylon 6 is prepared from caprolactam. The reaction involves initial reaction of caprolactam with water to give an intermediate open-chain amino acid, followed by heating to form the polymer. Propose mechanisms for both steps, and show the structure of nylon 6. 

Figure 3.16 Effect of initiator on caprolactam polymerization at 260°C (o) water 0.01 mol % (x) aminocaprolic acid 0.01 mol %.28...

On an industrial scale, PA-6 is synthesized from e-caprolactam with water as the initiator. The process is very simple if the reaction is earned out at atmospheric pressure. The polymerization is earned out in a VK-reactor (Fig. 3.23), which is a continuous reactor without a stirrer, with a residence time of 12-24 h at temperatures of 260-280°C.5,28 Molten lactam, initiator (water), and chain terminator (acetic acid) are added at the top and the polymer is discharged at the bottom to an extruder. In this extruder, other ingredients such as stabilizers, whiteners, pigments, and reinforcing fillers are added. The extruded thread is cooled in a water bath and granulated. The resultant PA-6 still contains 9-12%... 

Starting with caprolactam, an initiator is required for the hydrolytic melt polymerization this can be any of the following water, >-amino acids, acids, diacids,... 

In common with all the higher AB polyamides, PA-12 can be made from either die amino acid or the lactam.12 In practice, PA-12 is made from the cheaper 12-laurolactam (12-dodecane lactam or laboratory-scale synthesis it is advisable to start with the amino acid or a combination of amino acid and lactam. 

The cyclic oligomers are only slightly soluble in water and dilute solutions of caprolactam. They tend to separate out from die extracted waste during die process of concentration and chemical purification of die caprolactam. The cyclic oligomers tend to form on the walls of the equipment used in die process equipment. 6-Aminocaproic acid or sodium 6-aminocaproate may also be found in die oligomeric waste, especially if sodium hydroxide is used to initiate die caprolactam polymerization. 

Anionic polymerization of lactams was shown to proceed according to what is called the activated monomer mechanism. With bischloroformates of hydroxy-terminated poly(tetramethyleneglycol) and poly(styrene glycol) as precursors for a polymeric initiator containing N-acyl lactam ends, block copolymers with n-pyrrol-idone and e-caprolactam were obtained by bulk polymerizations in vacuum at 30 and 80 °C, respectively361. ... 

Synthesis of PDMS-b-(e-caprolactam) ABA block copolymers was reported 343 In these reactions, anhydride-terminated PDMS oligomers were used to initiate the polymerization of -caprolactam in the presence of a catalytic amount of sodium hydride in melt at 130 °C. Under these conditions, the reaction was reported to be completed in... 

A regio- and stereoselective Beckmann rearrangement utilized diastereose-lective host guest interactions of the inclusion complexes 225 and 228 in a solid state reaction. Initially, a 1 1 mixture of the chiral host 223 and the racemic oximes 224 and 227, respectively, was treated with ultra sound in the solid state to induce the optical resolution. Then H2SO4 was added to start the Beckmann rearrangement, the corresponding c-caprolactams 226 and 229 were isolated in 68 % and 64 % yields and ee of about 80 % and 69 % (determined by HPLC analysis on chiracel OC) (Scheme 43) [46]. 

The polymerization process for nylon 6 consists primarily of the three types of reaction illustrated in Fig. 23.6. Each of the reactions is reversible, tvith the equilibrium of the products being controlled primarily by the concentration of water in the reaction vessel. The reaction is initiated by the hydrolytic ring opening of caprolactam to form 6-aminohexanoic acid, as shown in Fig. 23.6 a). Chain extension of the type shotvn in Fig. 23.6 b) dominates when water is abundant (10 to 20%) in the reaction mixture. At lower water levels (2 to 5%) chains grow primarily by the mechanism shown in Fig. 23.6 c). In order to limit the average molecular... 

Evidently, there are a number of factors that determine which of the above-mentioned pathways of polymerization occurs. One of these is the enrichment of final copolymers with the more hydrophilic comonomer (in comparison with the composition of the initial feeds), due to a higher reactivity of NVIAz. The higher (than for NVC1) reactivity of NVIAz is determined by a stronger polarization of the double bond of the vinyl group by the imidazole moiety as compared with the caprolactam cycle. Furthermore, a good solubility of hydrophilic NVIAz can also contribute to its higher reactivity in aqueous media. 

A star-branched nylon 6 may be created by using a "star initiator "--a species with three or more imide linkages as activated sites. It was initially assumed that reaction would take place only at the imide sites and that cross-linking would not occur, although the bis-caprolactam species is known as a crosslinking agent. (9-... 

Preparation of Linear and Star Nylon 6. The star-branched initiator, trimesoyl-tris-caprolactam (TTC) 6 was synthesized from the commercially available trimesoyl chloride 5 using the route shown in Figure 2. (6) Trimesoyl acid chloride in benzene was slowly added to a stirring solution of e-caprolactam, pyridene, and benzene. After addition was complete, the solution was heated to 70° C for 30 minutes to assure conversion to the initiator species. Single and difunctional analogs were synthesized using the same reaction scheme for direct comparison of the star-branched and linear aromatic initiator systems. 

Nylon-6, structurally quite similar to nylon-6,6, was initially produced in Germany by the ROP of caprolactam, partly as a way to avoid the patents established by DuPont a decade earlier. The copolymer of nylon-6 and nylon-6,6 has a smoother surface than either of the homopolymers ... 

The overall rate of conversion of e-caprolactam to polymer is higher than the polymerization rate of e-aminocaproic acid by more than an order of magnitude [Hermans et al., 1958, I960]. Step polymerization of e-aminocaproic acid with itself (Eq. 7-57) accounts for only a few percent of the total polymerization of e-caprolactam. Ring-opening polymerization (Eq. 7-58) is the overwhelming route for polymer formation. Polymerization is acid-catalyzed as indicated by the observations that amines and sodium e-aminocaproate are poor initiators in the absence of water and the polymerization rate in the presence of water is first-order in lactam and second-order in COOH end groups [Majury, 1958]. 

Strong bases such as alkali metals, metal hydrides, metal amides, metal alkoxides, and organometallic compounds initiate the polymerization of a lactam by forming the lactam anion XXXIV [Hashimoto, 2000 Sebenda, 1989 Sekiguchi, 1984], for example, for e-caprolactam with a metal... 

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