Bio-ethylene

Solvay Indupa announced the expansion of their manufacturing plant of polyvinyl chloride (PVC) in Santo Andre (Brazil) to a total amount of 360,000 mto per year. Thereby for this capacity extension the required monomer feedstock vinyl chloride should also be based on bio-ethylene (based on bioethanol sourced from Copersucar) and thus finally on sucrose and salt. " ... 

Bio-Ethylene/Ethylene Oxide/Ethylene Glycol, www.chemtex.com/templates/ethylene.html (accessed 15 May 2009). 

During this early period, a very ingenious free-radical route to polyesters was used to introduce weak linkages into the backbones of hydrocarbon polymers and render them susceptible to bio degradabihty (128—131). Copolymerization of ketene acetals with vinyl monomers incorporates an ester linkage into the polymer backbone by rearrangement of the ketene acetal radical as illustrated in equation 13. The ester is a potential site for biological attack. The chemistry has been demonstrated with ethylene (128—131), acryhc acid (132), and styrene (133). 

Bionolle PBSU poly(butylene succinate) Bionolle PESU poly(ethylene succinate), ref. 110. eEastar Bio poly(tetramethylene adipate-co-terephthalate), ref. 457. 

Kataoka M, Sasaki M, Hidalgo AR, Nakano M, Shimizu S (2001) Glycolic acid production using ethylene glycol-oxidizing microorganism. Biosci Bio-technol Biochem 65(10) 2265-2270... 

Dichlorodibenzo- -dioxin. 2-Bromo-4-chlorophenol (31 grams, 0.15 mole) and solid potassium hydroxide (8.4 grams, 0.13 mole) were dissolved in methanol and evaporated to dryness under reduced pressure. The residue was mixed with 50 ml of bEEE, 0.5 ml of ethylene diacetate, and 200 mg of copper catalyst. The turbid mixture was stirred and heated at 200°C for 15 hours. Cooling produced a thick slurry which was transferred into the 500-ml reservoir of a liquid chromatographic column (1.5 X 25 cm) packed with acetate ion exchange resin (Bio-Rad, AG1-X2, 200-400 mesh). The product was eluted from the column with 3 liters of chloroform. After evaporation, the residue was heated at 170°C/2 mm for 14 hours in a 300-cc Nestor-Faust sublimer. The identity of the sublimed product (14 grams, 74% yield) was confirmed by mass spectrometry and x-ray diffraction. Product purity was estimated at 99- -% by GLC (electron capture detector). 

Laboratory tests of ethylene glycol containing formulations have shown a complete bio-oxidation within 20 days. The rate of bio-oxidation is stationary over the full period. On the other hand, propylene glycol initially degrades more rapidly during the first 5 days of the test to an extent of 62%, slowing to 79% conversion after 20 days. 

As discussed in this book (Chapter 2, for example) a main difference between fossil fuels and biomass as feedstocks is that in the former case the functionalization of base chemicals obtained from the oil (ethylene, propylene, aromatics, etc.) occurs essentially by introduction of heteroatoms, while in the case of biomass-derived based chemicals (glycerol, for example) it is necessary to eliminate heteroatoms (oxygen, in particular). Consequently, the catalysts required to develop a petrochemistry based on bio-derived raw materials need to be discovered and cannot simply be translated from existing ones, even if the knowledge accumulated over many years will make this discovery process much faster than that involved in developing the petrochemical catalytic routes. 

Different routes for converting biomass into chemicals are possible. Fermentation of starches or sugars yields ethanol, which can be converted into ethylene. Other chemicals that can be produced from ethanol are acetaldehyde and butadiene. Other fermentation routes yield acetone/butanol (e.g., in South Africa). Submerged aerobic fermentation leads to citric acid, gluconic acid and special polysaccharides, giving access to new biopolymers such as polyester from poly-lactic acid, or polyester with a bio-based polyol and fossil acid, e.g., biopolymers . 

Photolysis of the unsubstituted poly(ethylene sebacamide) (A), methylated poly(l,2-propylene sebacamide) (B), and poly(l,l-dimethylethylene sebacamide) (C) resulted in mostly chain fragmentation as indicated by the decreases in intrinsic viscosities of the polymer samples, Table 1. The same decrease in intrinsic viscosity was also observed for polyurea D. Polymer A and D remained bio-inert under the testing condition whereas the abilities for polymers B and C to support the growth of Apergillus niger were improved by photolysis. 

Working PK, Smith-Oliver T, Butterworth BE. 1985. Glutathione dependent induction of unscheduled DMA synthesis by ethylene dibromide in rat spermatocytes and hepatocytes. J Cell Bio. Vol. 101,462A. 

Linear ethoxylates are the preferred raw materials for production of ether sulfates used in deteigent formulations because of uniformity, high purity, and bio degradability. The alkyl chain is usually in the C12 to C13 range having a molar ethylene oxide alcohol ratio of anywhere from 1 1 to 7 1. 

I. Romieu et al., Breast Cancer, Lactation History, and Serum Organochlorines, Am. J. Epidemiol. 152 (2000) 565-70 R. Millikan et al., Dichlorodiphenyldichloroethene, Polychlorinated Biphenyls, and Breast Cancer Among African-American and White Women in North Carolina, Cancer Epidemiol. Biomarkers. Prev. 9 (2000) 1255-40 S. D. Stellman et al., Breast Cancer Risk in Relation to Adipose Concentrations of Organochlorine Pesticides and Polychlorinated Biphenyls in Long Island, New York, Cancer Epidemiol. Biomarkers. Prev. 9 (2000) 1241-49 T. Zheng et al., Risk of Female Breast Cancer Associated with Serum Polychlorinated Biphenyls and l,l-dichloro-2,2 -bis(p-chlorophenyl)ethylene, Cancer Epidemiol. Bio-... 

Other blends such as polyhydroxyalkanoates (PHA) with cellulose acetate (208), PHA with polycaprolactone (209), poly(lactic acid) with poly(ethylene glycol) (210), chitosan and cellulose (211), poly(lactic acid) with inorganic fillers (212), and PHA and aliphatic polyesters with inoiganics (213) are receiving attention. The different blending compositions seem to be limited only by the number of polymers available and the compatibility of the components. The latter blends, with all natural or biodegradable components, appear to afford the best approach for future research as property balance and bio degradability is attempted. Starch and additives have been evaluated in detail from the perspective of structure and compatibility with starch (214). 

Poly(ethylene oxide) (PEO) macromonomers constitute a new class of surface active monomers which give, by emulsifier-free emulsion polymerization or copolymerization, stable polymer dispersions and comb-like materials with very interesting properties due to the exceptional properties of ethylene oxide (EO) side chains. They are a basis for a number of various applications which take advantage of the binding properties of PEO [39], its hydrophilic and amphipathic behavior [40], as well as its bio compatibility and non-absorbing character towards proteins [41]. Various types of PEO macromonomers have been proposed and among them the most popular are the acrylates and methacrylates [42]. 

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