1.3.5- Trioxane properties

The Polymerization-Crystallization Stage in the (Co)polymerizations of 1,3,5-Trioxane Radiation-Initiated Solid-State Polymerization of 1,3,5-Trioxane Properties of Poly(oxymethylene)... 

It is marketed as a 35-40 per cent, solution in water (formalin). The rpactions of formaldehyde are partly typical of aldehydes and partly peculiar to itself. By evaporating an aqueous solution paraformaldehyde or paraform (CHjO), an amorphous white solid is produced it is insoluble in most solvents. When formaldehyde is distilled from a 60 per cent, solution containing 2 per cent, of sulphuric acid, it pol5unerises to a crystalline trimeride, trioxane, which can be extracted with methylene chloride this is crystalline (m.p. 62°, b.p. 115°), readily soluble in water, alcohol and ether, and devoid of aldehydic properties ... 

The many commercially attractive properties of acetal resins are due in large part to the inherent high crystallinity of the base polymers. Values reported for percentage crystallinity (x ray, density) range from 60 to 77%. The lower values are typical of copolymer. Poly oxymethylene most commonly crystallizes in a hexagonal unit cell (9) with the polymer chains in a 9/5 helix (10,11). An orthorhombic unit cell has also been reported (9). The oxyethylene units in copolymers of trioxane and ethylene oxide can be incorporated in the crystal lattice (12). The nominal value of the melting point of homopolymer is 175°C, that of the copolymer is 165°C. Other thermal properties, which depend substantially on the crystallization or melting of the polymer, are Hsted in Table 1. See also reference 13. 

The electrical insulation properties of the acetal resins may be described as good but not particularly outstanding. There are available alternative materials which are better insulators and are also less expensive. There are, however, applications where impact toughness and rigidity are required in addition to good electrical insulation characteristics, and in these instances acetal resins would be considered. Table 19.3 lists some of the more important electrical characteristics of Delrin acetal resin. Data for the trioxane-based copolymer resin (e.g. Celcon) are virtually identical. 

High modulus blends can be developed by mixing TPU with acetal copolymer (trioxane ethylene oxide copolymers) [242-244]. The highly crystalline acetal forms a second continuous phase. Kumar et al. studied behavior of such blends [245]. TPU retains none of its physical properties after immersion in water at 70°C for three weeks. The hydrolysis resistance of TPU can be improved by blending with polycarbodiimides [246]. Two parts of carbodiimide with TPU offer 87% retention of its strength, 93% of elongation, and 75% of modulus under the same... 

A cement slurry additive consisting of methylcellulose, melamine-formaldehyde resin, and trioxane has been proposed for better bonding of cement to the casing string [20]. Bisphenol-A epoxide resins, with amine-based curing agents, sand filler, and a mixture of n-butanol and dimethyl benzene as a diluent, have been proposed as additives to increase adhesion properties of cement [572]. 

Minato, K., Yasuda, R. and Yano, H. (1990a). Improvement of dimensional stability and acoustic properties of wood for musical instruments with cychc oxymethylenes. I. Formalization with trioxane. Mokuzai Gakkaishi, 36(10), 860-866. 

Properties and handling. Formaldehyde is a colorless, toxic gas at room temperature, with a pungent, irritating odor. It is flammable and explosive in presence of air. Both gaseous and liquid forms of formaldehyde polymerize at room temperature, and because of this, it can only be maintained in the pure state for a very short period. Because of these unhandy conditions, there are two ways formaldehyde gets into commerce, as a water solution called formalin and as a solid called paraformaldehyde or trioxane. 

Artemisinin, a tetracyclic 1,2,4-trioxane isolated from Artemisia annua L., is currently recommended as a first-line agent against Plasmodium falciparum malaria. Artemisinin and its synthetic derivatives have also been shown to be promising prototypes for the development of new antiproliferative agents. This chapter presents the recent advances on the analytic methods for extraction and quantification of artemisinin from A. annua plants as well as the biological properties of this natural product. 

Polyoxymethylene, also referred to as acetal resin or POM, is obtained either by anionic polymerization of formaldehyde or cationic ring-opening copolymerization of trioxane with a small amount of a cyclic ether or acetal (e.g., ethylene oxide or 1,3-dioxolane) [Cherdron et al., 1988 Dolce and Grates, 1985 Yamasaki et al., 2001]. The properties and uses of POM have been discussed in Sec. 5-6d. 

In addition to artemisinin, other synthetic trioxanes and endoperoxides (fenozan BO-7 4 and arteflene 5 " ) have enjoyed some success arteflene reached Phase II pre-clinical trials. More recently, Vennerstrom and coworkers have reported on the outstanding antimalarial properties of several 1,2,4-trioxolanes, one of which, OZ 277 (6), has entered clinical trials in man . These exciting, easily prepared drugs will be discussed in detail later in this chapter. In order to determine the parasiticidal action of this class of antimalarial, many research groups have focused their efforts on artemisinin and its semi-synthetic derivatives (artemether, arteether and artesunate Ic, Id and le), and this is the point where our discussion will begin. 

Other semi-2-IPNs [52] processed by the freeze-drying method included IPN from 4,4 -bismaleimido diphenylmethane (BMI) and linear BTDA/3,4 -ODA polyamic acid that were dissolved in 1,3,5-trioxane (Fig. 16). The resulting semi-2-IPNs exhibited higher Tgs and reduced phase separation, and contained no plasticizing solvent. A comparison of unidirectional properties of composites prepared by the freeze-dry process to those by traditional solvent evaporation process is presented in Table 13. The freeze-drying method for the preparation of IPNs appears to be superior to previous technology. 

Starting ingredients may be formaldehyde or the cyclic trimer rrioxane, CH2OCH2OCH2O. Both form polymers of similar properties. Boron trifluoride of other Lewis acids are used to promote polymerization where trioxane is the raw material. 

Attention continues to be focused on 1,2,4-trioxanes because of their antimalarial properties, with much of the work being devoted to interconversions within the artemisinins. 

The polyoxymethylenes are presently widely used in different areas. Approximatively one-third of the market is represented by homopolymers and two-thirds by copolymers. Homopolymers are produced by anionic polymerization of formaldehyde using amines, alkoxides, and other types of anionic initiators. The details of these polymerizations will not be discussed in this paper, although some of their properties will be compared to those of copolymers which are obtained by cationic copolymerization of trioxane with cyclic ethers or cyclic esters. Comprehensive reviews on general aspects of synthesis and properties of acetal resins are available [158-162],... 

Artemisinin has been converted in two steps into the stable trioxane isobutene dimer 41. Reactions at the linking unit leave the trioxane fragments intact and allow the synthesis of a variety of dimers that possess desirable pharmacological properties <03JMC1060>. 10-Bromoalkyl and 10-aminoalkyl derivatives of deoxoartemisinin have been prepared and used to form dimers and a trimer in which artemisinin residues are linked through alkylamide and alkylthio functions <03JMC987>. 

Nevertheless, an industrial process of this type62 has been instituted in the USSR. The structure and properties of the manufactured product are somewhat different from those conventionally obtained they lie between those of trioxane copolymers of the Hostaform C type and acetylated homopolymer of the Delrin type. 

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