Polymerization procedures

25 g (0.22 mol) of e-caprolactam and 0.6 g (0.025 mol) of sodium hydride are placed in a flask, which is then evacuated and filled with nitrogen several times.The sample is melted to allow the sodium hydride to react. When the evolution of hydrogen has ceased, 0.33 g (0.002 mol) of A/-acetylcaprolactam are added, the flask is well shaken, and then heated in an oil bath to 140 °C.The contents rapidly solidify and after 30 min can be cooled and ground up. 

The limiting viscosity number is determined in m-cresol or concentrated sulfuric acid. 

The polyamide-6 (Nylon-6) so obtained has a crystallite melting point around 216 °C. It still contains monomer and low-molecular-weight cyclic oligomers which can be removed by extraction with water or lower alcohols.These oligomers can be separated and identified chromatographically (see Example 4-9). 

The reaction of a nucleophilic monomer with an electrophilic monomer can, under suitable circumstances, lead to the formation of macromolecules that carry at least one charge at a chain end. Although the reaction has been known for a long time, it has gained importance for technical applications only recently. On the basis of the following scheme, the reaction mechanism can be explained by 

First of all a 2-substituted oxazoline (1) is formed by cyclocondensation of a carboxylic acid ester with 2-aminoethanol and a small amount of (1) is converted with an alkylating agent (e.g., methyl tosylate) to the activated, ionic form (2). 

---

Aromatic hydrocarbon resins. The polymerization procedure and variables in the reactions of the aromatic hydrocarbon resins are similar to those for the coumarone-indene resins. However, the Cg feedstreams used in the polymerization of the aromatic hydrocarbon resins do not contain significant amounts of phenols or pyridine bases, so they are submitted directly to fractional distillation. Distillation produced more byproducts than light coal-tar oils. The aromatic hydrocarbon resins obtained have softening points between liquid and 125°C and Gardner colour of 6 to 11. By changing distillation conditions, aromatic hydrocarbon resins with softening points between 65 and 170°C and Gardner colour of 5 to 10 can also be obtained. 

Another metathesis polymerization procedure uses terminal dienes such as hexa-1,5-diene (16) (acyclic diene metathesis (ADMET)). Here again, the escape of the gaseous reaction product, i.e. ethylene, ensures the irreversible progress of the reaction ... 

The free radical initiators are more suitable for the monomers having electron-withdrawing substituents directed to the ethylene nucleus. The monomers having electron-supplying groups can be polymerized better with the ionic initiators. The water solubility of the monomer is another important consideration. Highly water-soluble (relatively polar) monomers are not suitable for the emulsion polymerization process since most of the monomer polymerizes within the continuous medium, The detailed emulsion polymerization procedures for various monomers, including styrene [59-64], butadiene [61,63,64], vinyl acetate [62,64], vinyl chloride [62,64,65], alkyl acrylates [61-63,65], alkyl methacrylates [62,64], chloroprene [63], and isoprene [61,63] are available in the literature. 

In summary, our synthetic studies led to the development of interfacial and solution polymerization procedures for the preparation of poly(iminocarbonates) of high molecular weight. These procedures have so far been employed for the synthesis of a small number of structurally diverse poly(iminocarbonates). 

Poly(l,4-naphthylenevinylene) (106) is accessible via the Wessling polymerization procedure. Lenz, Karasz, Wegner et al. have published the synthesis of PNV 106, starting from l,4-bis(chloromethyl)naphthalene [127, 128]. The poly(l,4-naphthylenevinylene) (106) displays an optical absorption energy of 2.05 eV, slightly red-shifted by about 0,3 eV relative to the parent PPV 60-system, due to the electronic effect of the annelated benzene ring. 

As mentioned above, poly(9,10-anthrylenevinylene) is not accessible by means of the Wessling polymerization procedure. Well defined oligo(9,10-anthrylene-vinylene)s (111) were synthesized via Horner-type coupling [132]. Extrapolation of the optical absorption energies in the 111 series against the corres-... 

The corresponding polyiminocarbonates (Figure 5) were prepared first, using recently developed polymerization procedures (5). Poly(Dat-Tym iminocarbonate), the polymer carrying no pendent chains at all, was an insoluble material. Thermal processing techniques could not be used due to the low thermal stability of the polymer in the molten state. Thus poly(Dat-Tyr iminocarbonate) was a virtually non-processible material without practical applications. 

However the formation of thin polymer film on the electrode, i.e. passivation of the electrode, resulted in cessation of the polymerization, which restricted the electro-oxidation as a polymerization procedure. The electro-oxidative polymerization as a method of producing poly(phenyleneoxide)s had not been reported except in one old patent, in which a copper-amine complex was added as an electron-mediator during the electrolysis (4). The authors recently found that phenols are electro-oxidatively polymerized to yield poly-(2,6-disubstituted phenyleneoxide)s, by selecting the electrolysis conditions This electro-oxidative polymerization is described in the present paper. 

The first attempts at ROP have been mainly based on anionic and cationic processes [4,5]. In most cases, polyesters of low molecular weight were recovered and no control on the polymerization course was reported due to the occurrence of side intra- and intermolecular transesterification reactions responsible for a mixture of linear and cyclic molecules. In addition, aliphatic polyesters have been prepared by free radical, active hydrogen, zwitterionic, and coordination polymerization as summarized in Table 2. The mechanistic considerations of the above-mentioned processes are outside the scope of this work and have been extensively discussed in a recent review by some of us [2 ]. In addition, the enzyme-catalyzed ROP of (di)lactones in organic media has recently been reported however, even though this new polymerization procedure appears very promising, no real control of the polyesters chains, or rather oligomers, has been observed so far [6]. 

---