Depolymerization poly

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. 

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 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. 

However, Pacansky and his coworkers77 studied the degradation of poly(2-methyl-l-pentene sulfone) by electron beams and from infrared studies of the products suggest another mechanism. They claim that S02 was exclusively produced at low doses with no concomitant formation of the olefin. The residual polymer was considered to be essentially pure poly(2-methyl-l-pentene) and this polyolefin underwent depolymerization after further irradiation. However, the high yield of S02 requires the assumption of a chain reaction and it is difficult to think of a chain reaction which will form S02 and no olefin. 

This strategy is used for the synthesis of three different exact-mass telechelic oligomers. GPC, NMR, and GC/MS evidence indicates that clean depolymerization chemistry occurs for all three samples. Poly( 1,4-butadiene) (38) is broken down into oligomeric units with two, three, and four repeat units using catalyst 23. Catalyst 14 is more efficient and produces even lower molecular weight oligomers, primarily one and two repeat units. When allylchlorodimethylsilane is used instead of ethylene with 14, telechelic dimers are the only product. 

Polylactides, 18 Poly lactones, 18, 43 Poly(L-lactic acid) (PLLA), 22, 41, 42 preparation of, 99-100 Polymer age, 1 Polymer architecture, 6-9 Polymer chains, nonmesogenic units in, 52 Polymer Chemistry (Stevens), 5 Polymeric chiral catalysts, 473-474 Polymeric materials, history of, 1-2 Polymeric MDI (PMDI), 201, 210, 238 Polymerizations. See also Copolymerization Depolymerization Polyesterification Polymers Prepolymerization Repolymerization Ring-opening polymerization Solid-state polymerization Solution polymerization Solvent-free polymerization Step-grown polymerization processes Vapor-phase deposition polymerization acid chloride, 155-157 ADMET, 4, 10, 431-461 anionic, 149, 174, 177-178 batch, 167 bulk, 166, 331 chain-growth, 4 continuous, 167, 548 coupling, 467 Friedel-Crafts, 332-334 Hoechst, 548 hydrolytic, 150-153 influence of water content on, 151-152, 154... 

Industrial Engineering Chemistry Research 40, No.2, 24th Jan.2001, p.509-14 KINETICS OF DEPOLYMERIZATION OF POLY(ETHYLENE TEREPHTHALATE) IN A POTASSIUM HYDROXIDE SOLUTION Ben-Zu Wan Chih-Yu Kao Wu-Hsun Cheng... 

Journal of Applied Polymer Science 77, No. 14, 29th Sept.2000, p.3228-33 DEPOLYMERIZATION OF POLY(BUTYLENE TEREPHTHALATE) USING HIGH-TEMPERATURE AND HIGH-PRESSURE METHANOL... 

While "conventional positive photoresists" are sensitive, high-resolution materials, they are essentially opaque to radiation below 300 nm. This has led researchers to examine alternate chemistry for deep-UV applications. Examples of deep-UV sensitive dissolution inhibitors include aliphatic diazoketones (61-64) and nitrobenzyl esters (65). Certain onium salts have also recently been shown to be effective inhibitors for phenolic resins (66). A novel e-beam sensitive dissolution inhibition resist was designed by Bowden, et al a (67) based on the use of a novolac resin with a poly(olefin sulfone) dissolution inhibitor. The aqueous, base-soluble novolac is rendered less soluble via addition of -10 wt % poly(2-methyl pentene-1 sulfone)(PMPS). Irradiation causes main chain scission of PMPS followed by depolymerization to volatile monomers (68). The dissolution inhibitor is thus effectively "vaporized", restoring solubility in aqueous base to the irradiated portions of the resist. Alternate resist systems based on this chemistry have also been reported (69,70). 

Interest in solution inhibition resist systems is not limited to photoresist technology. Systems that are sensitive to electron-beam irradiation have also been of active interest. While conventional positive photoresists may be used for e-beam applications (31,32), they exhibit poor sensitivity and alternatives are desirable. Bowden, et al, at AT T Bell Laboratories, developed a novel, novolac-poly(2-methyl-l-pentene sulfone) (PMPS) composite resist, NPR (Figure 9) (33,34). PMPS, which acts as a dissolution inhibitor for the novolac resin, undergoes spontaneous depolymerization upon irradiation (35). Subsequent vaporization facilitates aqueous base removal of the exposed regions. Resist systems based on this chemistry have also been reported by other workers (36,37). 

Wang, D.-C., Chen, L.-W. and Chiu, W.-Y., Kinetic study on depolymerization by glycolysis of poly(ethylene terephthalate) with bisphenol A, Angew. Makromol. Chem., 230, 47-71 (1995). 

While depolymerizing poly(ethylene naphthalate) could be attractive on the small scale because of the high commercial price for the naphthalate moiety, even this candidate resin is in too little availability to permit economical depolymerization. Of polyesters, only poly(ethylene terephthalate) (PET) is available at sufficient quantities to make the commercial use of depolymerization potentially attractive. 

Depolymerization processes have been proposed for poly(butylene terephtha-late) by the glycolysis of PBT with 1,4-butanediol and a titanium catalyst [65]. Methanolysis of poly(ethylene naphthalate) to dimethyl naphthalate and ethylene glycol has also been proposed [66, 67], but not implemented. The lack of commercial depolymerization of PEN is probably due not to technical limitations, but to insufficient supplies of PEN polymer feedstock to meet the minimum quantities needed for economical operations. 

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