Poly cracking

About 35% of total U.S. LPG consumption is as chemical feedstock for petrochemicals and polymer iatermediates. The manufacture of polyethylene, polypropylene, and poly(vinyl chloride) requires huge volumes of ethylene (qv) and propylene which, ia the United States, are produced by thermal cracking/dehydrogenation of propane, butane, and ethane (see Olefin polymers Vinyl polymers). 

As may be expected of an amorphous polymer in the middle range of the solubility parameter table, poly(methyl methacrylate) is soluble in a number of solvents with similar solubility parameters. Some examples were given in the previous section. The polymer is attacked by mineral acids but is resistant to alkalis, water and most aqueous inorganic salt solutions. A number of organic materials although not solvents may cause crazing and cracking, e.g. aliphatic alcohols. 

Cracking and isomerization reactions occur readily in acidic chloroaluminate(III) ionic liquids. A remarkable example of this is the reaction of poly(ethene), which is converted into a mixture of gaseous alkanes of formula (C Ff2n+2, where n = 3-5) and cyclic alkanes with a hydrogen to carbon ratio of less than two (Figure 5.1-4, Scheme 5.1-68) [99]. 

Scheme 5.1-68 The cracking of poly(ethene) in an ionic liquid.

The distribution of the products obtained from this reaction depends upon the reaction temperature (Figure 5.1-4) and differs from those of other poly(ethene) recycling reactions in that aromatics and alkenes are not formed in significant concentrations. Another significant difference is that this ionic liquid reaction occurs at temperatures as low as 90 °C, whereas conventional catalytic reactions require much higher temperatures, typically 300-1000 °C [100]. A patent filed for the Secretary of State for Defence (UK) has reported a similar cracking reaction for lower molecular weight hydrocarbons in chloroaluminate(III) ionic liquids [101]. An... 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

Poly-2,6-dimethyl phenylene oxide (PPO) and certain related materials are similar to the nylons but have superior heat resistance. These polymers are somewhat liable to stress-cracking problems. 

The Griffith crack equation has been shown to apply, albeit with some scatter of results, to the brittle polymeric materials poly(methyl methacrylate) and poly(styrene) when cracks of controlled size have been introduced deliberately into the specimens. Such experiments give values of surface energy that are very large, typically 10 - 10 J m , which is about 100 times greater than the theoretical value calculated from the energy of the chemical bonds involved. This value of y thus seems to be made up of two terms, Le. 

Experimental values of the molar mass exponent close to 2 have been obtained. For example, for poly(methyl methacrylate), a value of 2.45 has found (see P. Prentice, Polymer, 1983, 24, 344—350). As with values of selfdiffusion coefficient, this has been regarded as close enough to 2 for reptation to be considered a good model of the molecular motion occurring at the crack tip. 

The low concentrations of ozone normally present in the atmosphere are sufficient to cause severe oxidation and cracking in polyolefins (2-13) and many other polymers such as polystyrene (6,11,12,14.15). poly(vinyl chloride) ( y, J 2,J 6) and rubbers (11,12,17-20). Where the ozone concentration is increased by air pollution, higher altitudes or the present of electrical machinery, the rate of degradation considerably increases.The prevention of such degradation represents a matter of considerable economic interest since it can greatly improve service life of polymers and plastics. An additional application of this research is to apprise the suitability of polymers for upper atmosphere application (Space Shutle flights) where a plentitude of ozone and atomic oxygen prevails. 

Crystalline polymers, e.g., nylon, poly(butylene terphthalate), are not easily impact-modified. The crystalline domains can act as crack initiation sites. Amorphous polymers with high Tgs are more amenable to modification, e.g., PS, PVC, PC, although PC is tough because of H-bonding that occurs between the polymer chains. 

The benefits related to the particular topology of ITQ-21 when used as heterogeneous catalyst have been reported for different processes, such as catalytic cracking [1], hydrocracking [2] or hidrogenation and ring opening of (poly)aromatics [3]... 

The major drawback of poly(p-xylylene) is that it reverts to a monomer when thin films are heated above ca. 400°C and it cracks when the films are annealed at 300-350°C in nitrogen. During module assembly the chip-joining (soldering)... 

The thermal stability of PNT from different polymerization methods is presented in Table 18.7. ft appears that the colored (dark brown) but transparent PNT -N film synthesized by VDP is the cleanest film among the polynaphthalenes from other polymerization processes that have been reported. These PNT-N films from VDP also have very low dielectric constants in comparison to poly(tetra-fluoro-p-xylylene) films. PNT-N and PNT-F films have higher dissociation temperatures (>570°C) and better thermal stability (>530°C), and no film cracking was observed until PNT-F was annealed at 600°C in nitrogen. Table 18.8 presents a summary of the different properties ofPNT-N and PNT-F prepared by the VDP process. 

Acidic chloroaluminate ionic liquids are excellent media for polymer cracking reactions. With the huge quantities of polymers that need to be disposed of each year the ability to break them down into useful compounds for new synthesis or to use as liquid fuels is extremely important. While certain polymers such as poly(methyl methacrylate) are easily cracked into their constituent monomers that can be reused, the majority of polymers are extremely difficult to crack into useful organic compounds. However, merely dissolving polyethylene in acidic chloroaluminate ionic liquids containing a proton source results in the formation of a mixture of alkenes and cyclic alkenes [48], The key compounds produced are shown in Figure 10.10. 

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