Depolymerization

Depolymerization of coal is a technique which, it is claimed, solubilizes coal by cleaving methylene bridges in the coal. The methylene chains joining aromatic groups can be cleaved at the ring and the free alkyl group and then alkylate another aromatic substrate (Larsen et al., 1981 Mastral-Lamarca, 1987 Sharma, 1988)  

This technique has been used to estimate the molecular weight distribution in coal but the (number average) molecular weights (Mn) of the material soluble in pyridine after depolymerization can be affected by the presence of colloidal material. Whilst the reported value may be in the region of 400, removal of the colloidal material (by, say, centrifugation) may increase this value to ca. 1000. 

However, there is evidence to indicate that this particular reaction does not produce the anticipated low-molecular-weight materials as the major products and, thus, the presence of coUoidal material and the higher-molecular-weight products certainly casts some doubt on the validity of any conclusions drawn from the data acquired by this method. 

Depolymerization also decreases molecular weight. Some common examples are merely the polymerization reactions previously considered taken in reverse. With 

The finished product is a cross-linked polymer very useful as high-temperature electrical insulation. Cross-linking can also be induced by gamma radiation or high-energy electron beams  

Now in a separate test we can measure the relaxation of stress in a sample held at constant elongation. Any chain scission that occurs also decreases this relaxation modulus E. However, cross-linking of the strained sample does not increase the modulus, because only the cross-links that were put in the relaxed sample and were 

FIGURE 12.5 Continuous stress relaxation and intermittent stress measurements at 130°C. (Data from Tobolsky, A. V., Properties and Structure of Polymers, Wiley, New York, 1960, chap. V.) 

The major disadvantage of chemical depolymerization is that it is almost completely restricted to the recycling of condensation polymers, and is of no use for the decomposition of most addition polymers, which are the main components of the plastic waste stream. Condensation polymers are obtained by the random reaction of two molecules, which may be monomers, oligomers or higher molecular weight intermediates, which proceeds with the liberation of a small molecule as the chain bonds are formed. Chemical depolymerization takes place by promoting the reverse reaction of the polymer formation, usually through the reaction of those small molecules with the polymeric chains. Several resins widely used on a commercial scale are based on condensation polymers, such as polyesters, polyamides, polyacetals, polycarbonates, etc. However, these polymers account for less than 15% of the total plastic wastes (see Chapter 1). 

Depending on the chemical agent used to break down the polymer, different depolymerization routes can be envisaged glycolysis, methanolysis, hydrolysis, ammonolysis, etc. In the following sections of this chapter, these alternatives are reviewed for those condensation polymers having the most significant commercial applications. It must be pointed out that a majority of the studies on chemical depolymerization of plastic wastes is reported in patents works published in the scientific literature are relatively scarce. 

Although the acid-catalyzed deprotection discussed in the earlier chapter is the paradigm for essentially all the advanced positive resists, polymers that undergo depolymerization might provide lower LER and/or higher resolution and are currently being revisited. 

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Zigmond, 1988). The ATP-hydrolysis that accompanies actin polymerization, ATP —> ADP + Pj, and the subsequent release of the cleaved phosphate (Pj) are believed to act as a clock (Pollard et ah, 1992 Allen et ah, 1996), altering in a time-dependent manner the mechanical properties of the filament and its propensity to depolymerize. Molecular dynamics simulations suggested a so-called back door mechanism for the hydrolysis reaction ATP ADP - - Pj in which ATP enters the actin from one side, ADP leaves from the same side, but Pj leaves from the opposite side, the back door (Wriggers and Schulten, 1997b). This hypothesis can explain the effect of the toxin phalloidin which blocks the exit of the putative back door pathway and, thereby, delays Pi release as observed experimentally (Dancker and Hess, 1990). 

Different types of other coal liquefaction processes have been also developed to convert coals to liqnid hydrocarbon fnels. These include high-temperature solvent extraction processes in which no catalyst is added. The solvent is usually a hydroaromatic hydrogen donor, whereas molecnlar hydrogen is added as a secondary source of hydrogen. Similar but catalytic liquefaction processes use zinc chloride and other catalysts, usually under forceful conditions (375-425°C, 100-200 atm). In our own research, superacidic HF-BFo-induced hydroliquefaction of coals, which involves depolymerization-ionic hydrogenation, was found to be highly effective at relatively modest temperatnres (150-170°C). 

This is the least desirable of all three processes [What do you mean by that This is really easy to do And the yield are fine ]. The yields are lower than the two rearrangements, and it requires substantial labor to get a decently pure product. Not "labor" as In difficult but "labor" as in a lot of it. I would suggest this only for those who have a large supply of Formaldehyde available to them (note - N. Coffey found formaldehyde at Home Depot - look for "Mildewcide" and dissolve it in enough water to make a 37% solution to depolymerize the paraformaldehyde). 

Place 3 3oz packets of Mildewcide into a 1L flask with an electric heating mantle and cork in the neck connected to a gas bubbler immersed in at least 550mL of distilled water. Heat the paraformaldehyde (what is in the Mildewcide) to between 180-200C (a temp, regulator is absolutely necessary for this step or use a silicone oil bath). The paraformaldehyde will depolymerize making formaldehyde gas in about 91% yield. Alternatively, the gas can be bubbled through the Ammonia solution directly (only for the brave ). If the Formaldehyde solution will not be used immedi-... 

Glycolysis is claimed to be somewhat less cosdy than methan olysis (33). Depolymerization is not taken completely to monomers (34). Rather, recovered PET is depolymerized to low molecular weight oligomers. Contaminants are removed using proprietary technology. The oligomers are then fed to a melt polymerization vessel in which PET is produced. 

Results obtained for two mixed plastics are summarized in Table 4. A balance exists between process temperature, plastics feed rate, and product yields (67). For example, lower temperatures increase wax formation due to incomplete depolymerization. Slower feed rates and increased residence times reduce wax formation and increase the yield of Hquids. The data summarized in Table 4 illustrate that the addition of PET to a HDPE PP PS mixture changes the performance of the Conrad process. Compared to the reference HDPE PP PS mixture, increased amounts of soHds ate formed. These are 95% terephthahc acid and 5% mono- and bis-hydroxyethyl esters. At higher temperatures, apparentiy enough water remains to promote decarboxylation. 

Polymerization. Paraldehyde, 2,4,6-trimethyl-1,3-5-trioxane [123-63-7] a cycHc trimer of acetaldehyde, is formed when a mineral acid, such as sulfuric, phosphoric, or hydrochloric acid, is added to acetaldehyde (45). Paraldehyde can also be formed continuously by feeding Hquid acetaldehyde at 15—20°C over an acid ion-exchange resin (46). Depolymerization of paraldehyde occurs in the presence of acid catalysts (47) after neutralization with sodium acetate, acetaldehyde and paraldehyde are recovered by distillation. Paraldehyde is a colorless Hquid, boiling at 125.35°C at 101 kPa (1 atm). 

Metaldehyde [9002-91-9] a cycHc tetramer of acetaldehyde, is formed at temperatures below 0°C in the presence of dry hydrogen chloride or pyridine—hydrogen bromide. The metaldehyde crystallizes from solution and is separated from the paraldehyde by filtration (48). Metaldehyde melts in a sealed tube at 246.2°C and sublimes at 115°C with partial depolymerization. 

Polyacetaldehyde, a mbbery polymer with an acetal stmcture, was first discovered in 1936 (49,50). More recentiy, it has been shown that a white, nontacky, and highly elastic polymer can be formed by cationic polymerization using BF in Hquid ethylene (51). At temperatures below —75° C using anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained (52). This polymer also has an acetal [poly(oxymethylene)] stmcture. Molecular weights in the range of 800,000—3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with poly acetaldehyde and the polymer has no practical significance (see Acetalresins). 

Historically, the development of the acrylates proceeded slowly they first received serious attention from Otto Rohm. AcryUc acid (propenoic acid) was first prepared by the air oxidation of acrolein in 1843 (1,2). Methyl and ethyl acrylate were prepared in 1873, but were not observed to polymerize at that time (3). In 1880 poly(methyl acrylate) was reported by G. W. A. Kahlbaum, who noted that on dry distillation up to 320°C the polymer did not depolymerize (4). Rohm observed the remarkable properties of acryUc polymers while preparing for his doctoral dissertation in 1901 however, a quarter of a century elapsed before he was able to translate his observations into commercial reaUty. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Rohm s laboratory, the first limited production of acrylates began in 1927 by the Rohm and Haas Company in Darmstadt, Germany (6). Use of this class of compounds has grown from that time to a total U.S. consumption in 1989 of approximately 400,000 metric tons. Total worldwide consumption is probably twice that. 

At room temperature, PET is resistant to organic and moderate strength mineral acids. At elevated temperatures, PET strength loss in moderate strength acids can be appreciable. Strong acids such as concentrated sulfuric acid dissolve and depolymerize PET. 

Polyester composition can be determined by hydrolytic depolymerization followed by gas chromatography (28) to analyze for monomers, comonomers, oligomers, and other components including side-reaction products (ie, DEG, vinyl groups, aldehydes), plasticizers, and finishes. Mass spectroscopy and infrared spectroscopy can provide valuable composition information, including end group analysis (47,101,102). X-ray fluorescence is commonly used to determine metals content of polymers, from sources including catalysts, delusterants, or tracer materials added for fiber identification purposes (28,102,103). 

The process operated by ACl is outlined in Figure 7. Bales of cotton linter are opened, cooked in dilute caustic soda, and bleached with sodium hypochlorite. The resulting highly purified ceUulose is mixed with pre-precipitated basic copper sulfate in the dissolver, and 24—28% ammonium hydroxide cooled to below 20°C is added. The mixture is agitated until dissolution is complete. If necessary, air is introduced to aUow oxidative depolymerization and hence a lowering of the dope viscosity. 

Chemical degradation (141), whether thermally or photo-iaduced, primarily results from depolymerization, oxidations, and hydrolysis. These reactions are especially harmful ia objects made from materials that coataia ceUulose, such as wood, cottoa, and paper. The chemistry of these degradation processes is quite complex, and an important role can be played by the reaction products, such as the acidic oxidation products which can catalyze hydrolysis. 

A second degradation process is oxidation, often photo-induced especially by exposure to light not filtered for uv. The radicals resulting from this reaction promote depolymerization of the cellulose, as well as yellowing and fa ding of paper and media. Aging causes paper to become more crystalline and fragile, and this can be exacerbated particularly if the paper is subjected to poor conditions. 

Deterioration. The causes of degradation phenomena in textiles (155—158, 164) are many and include pollution, bleaches, acids, alkaUes, and, of course, wear. The single most important effect, however, is that of photodegradation. Both ceUulosic and proteinaceous fibers are highly photosensitive. The natural sensitivity of the fibers are enhanced by impurities, remainders of finishing processes, and mordants for dyes. Depolymerization and oxidation lead to decreased fiber strength and to embrittlement. 

Tetrafluoroethylene was first synthesized in 1933 from tetrafluoromethane, CF, in an electric arc furnace (11). Since then, a number of routes have been developed (12—18). Depolymerization of PTFE by heating at ca 600°C is probably the preferred method for obtaining small amounts of 97% pure monomer on a laboratory scale (19,20). Depolymerization products contain highly toxic perfluoroisobutylene and should be handled with care. 

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

For a ceUulosic material containing hydroxyl groups, the reactions might consist of dehydroxylation and depolymerization by hydrogenolysis, during which there is a transition from soHd to Hquid to gas. 

Most glass-ceramics have low dielectric constants, typically 6—7 at 1 MHz and 20°C. Glass-ceramics comprised primarily of network formers can have dielectric constants as low as 4, with even lower values (K < 3) possible in microporous glass-ceramics (13). On the other hand, very high dielectric constants (over 1000) can be obtained from relatively depolymerized glasses with crystals of high dielectric constant, such as lead or alkaline earth titanate (11,14). 

Cychc carbonates are prepared in satisfactory quaUty for anionic polymerization by catalyzed transesterification of neopentyl glycol with diaryl carbonates, followed by tempering and depolymerization. Neopentyl carbonate (5,5-dimethyl-1,3-dioxan-2-one) (6) prepared in this manner has high purity (99.5%) and can be anionically polymerized to polycarbonates with mol wt of 35,000 (39). 

Manufacture. The manufacture of 1,4-cyclohexanedimethanol can be accompHshed by the catalytic reduction under pressure of dimethyl terephthalate ia a methanol solution (47,65). This glycol also may be prepared by the depolymerization and catalytic reduction of linear polyesters that have alkylene terephthalates as primary constituents. Poly(ethylene terephthalate) may be hydrogenated ia the presence of methanol under pressure and heat to give good yields of the glycol (see Polyesters) (66,67). 

The influences of herbicides on cell division fall into two classes, ie, dismption of the mitotic sequence and inhibition of mitotic entry from interphase (G, S, G2). If ceU-cycle analyses indicate increases in abnormal mitotic figures, combined with decreases in one or more of the normal mitotic stages, the effect is upon mitosis. Mitotic effects usually involve the microtubules of the spindle apparatus in the form of spindle depolymerization, blocked tubulin synthesis, or inhibited microtubule polymerization (163). Alkaloids such as colchicine [64-86-8J,viahla.stiae [865-21-4] and vincristine [57-22-7] dismpt microtubule function (164). Colchicine prevents microtubule formation and promotes disassembly of those already present. Vinblastine and vincristine also bind to free tubulin molecules, precipitating crystalline tubulin in the cytoplasm. The capacities of these dmgs to interfere with mitotic spindles, blocking cell division, makes them useful in cancer treatment. 

Cyclic ether and acetal polymerizations are also important commercially. Polymerization of tetrahydrofuran is used to produce polyether diol, and polyoxymethylene, an excellent engineering plastic, is obtained by the ring-opening polymerization of trioxane with a small amount of cycHc ether or acetal comonomer to prevent depolymerization (see Acetal resins Polyethers, tetrahydrofuran). 

The thermal stability of polymers of types (1) and (2) is also dependent on the nature of the substituents on phosphoms. Polymers with methoxy and ethoxy substituents undergo skeletal changes and degradation above about 100°C, but aryloxy and fluoroalkoxy substituents provide higher thermal stability (4). Most of the P—N- and P—O-substituted polymers either depolymerize via ring-chain equilibration or undergo cross-linking reactions at temperatures much above 150—175°C. 

The chemical resistance and excellent light stabiUty of poly(methyl methacrylate) compared to two other transparent plastics is illustrated in Table 5 (25). Methacrylates readily depolymerize with high conversion, ie, 95%, at >300° C (1,26). Methyl methacrylate monomer can be obtained in high yield from mixed polymer materials, ie, scrap. 

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