Plastics precursors

Blum, H., Pedain, J. and Hentschel, K.H., Bis-oxazolidines, oxazoUdine mixtures consisting essentially thereof and their use as hardeners for plastics precursors containing isocyanate groups. US Patent AppL, 1993, US 5,189,176. 

As we shall find in later chapters, heterocyclic compounds can be synthesized in many ways. Although some of this work is performed to study fundamental properties or establish new synthetic routes, much more is concerned with the practical aspects of heterocyclic chemistry. Thus, many synthetic (as well as natural) compounds are of extreme value as medicinals, agrochemicals, plastics precursors, dyes, photographic chemicals, and so on, and new structures are constantly being sought in research in these areas. These applications are discussed in Chapter 11. Medicinal chemistry especially is associated intimately with heterocyclic compounds, and most of all known chemicals used in medicine are based on heterocyclic frameworks. We shall observe many of the prominent biologically active heterocyclic compounds as this book proceeds to develop the field of heterocyclic chemistry. 

The feasibility of doubling the current ethylene production, which is judged one of the most efficient in the world, is being studied and initial results are promising. Also a massive project to link the islands in the southwest of the main island is underway providing the necessary space tor industry expansion. A 110 KTPA adipic acid (nylon precursor) is under construction with a completion date of 1994. Also projects have been announced for other plastic precursors and monomers such as styrene, propylene oxide, polyether polyols, acrylic acid and further aromatics capacity. 

Some of the supported Ru catalysts were evaluated for phthalate hydrogenation activity [23]. The reaction is shown in Figure 16.9. Ru selectively hydrogenates the aromatic ring of the phthalate ester and this reaction offers a route to an alternative plasticizer precursor for polyvinyl chloride polymers. 

The first plastic material to be made from non-plastic precursors was cellulose nitrate. This was obtained by Alexander Parkes (1813-1890) by treating cellulose fibres with nitric acid, and was first displayed at the Great International Exhibition in Ijondon in 1862 under the name Parkesine. Parkes moulded his new material into small decorative articles, as well as utilitarian objects such as knife handles. Parkesine was the first semi-synthetic plastic, so called because one of the starting materials was polymeric. The applications of cellulose nitrate were much extended by J. W. Hyatt (1837-1920) in the United States, who found that camphor was effective as a plasticiser, and the resulting mixture was known as celluloid. Another semi-synthetic plastic, cellulose acetate, was introduced around the end of the nineteenth century, and had the advantage over cellulose nitrate of being less flammable. 

The plasticized precursor material is injected into a heated mould. The mould temperature depends on the polymer system, but is, as a rule, considerably higher ( 100 K) than the barrel temperature. 

Porous Carbons from Various Plastic Precursors... 

Over the past few years, market forces have reduced the supply and increased the costs of the linear alcohols used to make linear sidechain phthalate plasticizers. Normal C8 alpha olefins became higher valued in copolymerized metallocene polyolefins (a very big end use) than in production of plasticizer precursors. Olefin manufacturing operations became more efficient in producing targeted olefins fewer low and high MW olefins were coproduced and available for recycling into other olefins. The North American flexible PVC producers have found themselves in the same situation which exists for producers everywhere else in the world linear plasticizers have become less plentiful and more expensive. 

The polymers of the 2-cyanoacryhc esters, more commonly known as the alkyl 2-cyaiioacrylates, are hard glassy resins that exhibit excellent adhesion to a wide variety of materials. The polymers are spontaneously formed when their Hquid precursors or monomers are placed between two closely fitting surfaces. The spontaneous polymerisation of these very reactive Hquids and the excellent adhesion properties of the cured resins combine to make these compounds a unique class of single-component, ambient-temperature-curing adhesives of great versatiUty. The materials that can be bonded mn the gamut from metals, plastics, most elastomers, fabrics, and woods to many ceramics. 

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Some propionic acid is converted iato herbicides (qv) such as Stam (Rohm and Haas) (3, 4 -dich1oropropionanilide) and iato ceUulose acetate propionate, a plastic sheeting and mol ding precursor. 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

Figure 4.16. Free-surface velocity profiles measured on 1400° C molybdenum. The free-surface velocity profile is characterized by an 0.05 km/s amplitude elastic precursor, a plastic wave front, and a spall signal (characteristic dip) upon unloading. The dashed lines represent the expected free surface velocity based on impedance-match calculation [Duffy and Ahrens, unpublished].

A typical shock-compression wave-profile measurement consists of particle velocity as a function of time at some material point within or on the surface of the sample. These measurements are commonly made by means of laser interferometry as discussed in Chapter 3 of this book. A typical wave profile as a function of position in the sample is shown in Fig. 7.2. Each portion of the wave profile contains information about the microstructure in the form of the product of and v. The decaying elastic wave has been an important source of indirect information on micromechanics of shock-induced plastic deformation. Taylor [9] used measurements of the decaying elastic precursor to determine parameters for polycrystalline Armco iron. He showed that the rate of decay of the elastic precursor in Fig. 7.2 is given by (Appendix)... 

Introduction of the surface-nucleation mechanism in numerical computation of elastic-plastic wave evolution leads to enhanced precursor attenuation in thin specimens, but not in thicker ones. Inclusion of dislocation nucleation at subgrain boundaries indicates that a relatively low concentration of subgrain boundaries ( 2/mm) and nucleation density (10"-10 m ) is sufficient to obtain predicted precursor decay rates which are comparable to those obtained from the experiments. These experiments are only slightly above the threshold necessary to produce enhanced elastic-precursor decay. 

It is applicable to plastic packaging materials, where purities with respect to mobile ions, such as Cl and Na, can be checked. In addition, a-particle precursors, such as U and Th, can be determined in solid plastics with sub-ppb detection limits. 

In the book of Exodus (Chapter 2) we read that the mother of Moses when she could no longer hide him, she took for him an ark of bullrushes and daubed it with slime and with pitch, and put the child therein and she laid it in the flags by the river s brink . Biblical commentaries indicate that slime is the same as bitumen but whether or not this is so we have here the precursor of our modem fibre-reinforced plastics boat. 

Acrylic acid, the main precursor to acrylic adhesives had been synthesized in the mid 1800s and the first acrylic acid esters were made and characterized at the turn of the century [62]. The first commercial launch of acrylic polymers in the form of poly(methylmethacrylate) took place in 1927 when the German company Rohm and Haas AG introduced this new plastic to the market. Soon after, other companies such as BASF introduced acrylic dispersions. 

The thorough and persistent work on precursor decay (the dependence of Hugoniot elastic limit on propagation distance) of Duvall s Washington State University group was successful in demonstrating that precursor attenuation was due to both stress relaxation and hydrodynamic attenuation. Typical data on crystalline LiF is shown in Fig. 2.7. Observed plastic strain... 

Typical stress-time profiles for the various materials (28.5-at. % Ni, fee and bcc) and various stress regions are shown in Fig. 5.12. The leading part of the profile results from the transition from elastic to plastic deformation. The extraordinarily sharp rise in stress for the second wave in Fig. 5.12(a) and the faster arrival time compared with that in Fig. 5.12(b) is that expected if the input stress is above the transition, whereas the slower rise in Fig. 5.12(b) is that expected if the stress input to the sample is below the transition. The profile in Fig. 5.12(c) for the bcc alloy was obtained for an input particle velocity approximately equal to that in Fig. 5.12(a) for the fee alloy. The bcc alloy shows a poorly defined precursor region, but, in any event, much faster arrival times are observed for all stress amplitudes, as is indicative of lower compressibility. 

Oxidation of n-hutane to maleic anhydride is becoming a major source for this important chemical. Maleic anhydride could also be produced by the catalytic oxidation of n-butenes (Chapter 9) and benzene (Chapter 10). The principal use of maleic anhydride is in the synthesis of unsaturated polyester resins. These resins are used to fabricate glass-fiber reinforced materials. Other uses include fumaric acid, alkyd resins, and pesticides. Maleic acid esters are important plasticizers and lubricants. Maleic anhydride could also be a precursor for 1,4-butanediol (Chapter 9). 

The direct addition of chlorine to ethylene produces ethylene dichloride (1,2-dichloroethane). Ethylene dichloride is the main precursor for vinyl chloride, which is an important monomer for polyvinyl chloride plastics and resins. 

Acrylonitrile is mainly used to produce acrylic fibers, resins, and elastomers. Copolymers of acrylonitrile with butadiene and styrene are the ABS resins and those with styrene are the styrene-acrylonitrile resins SAN that are important plastics. The 1998 U.S. production of acrylonitrile was approximately 3.1 billion pounds. Most of the production was used for ABS resins and acrylic and modacrylic fibers. Acrylonitrile is also a precursor for acrylic acid (by hydrolysis) and for adiponitrile (by an electrodimerization). 

The chloride ion is the most frequent cause of contact corrosion, since chlorine is present in the many chlorinated plastics, and is also frequently retained in residual amounts from reactive intermediates used in manufacture. Thus epoxides usually contain chloride derived from the epichlor-hydin used as the precursor of the epoxide. In addition to the contaminants referred to in Table 18.18, various metal and ammonium cations, inorganic anions and long-chain fatty acids (present as stabilisers, release agents or derived from plasticisers) may corrode metals on contact. 

---