228 8 Vinpl-Halogen and Vinyl-Ocrgen Compounds weir pe gos vt i commer importance of siaylowger compound ‘ny axes dominant wine ets, ined inp aca production fin 1060 tone: 199019921984 Usa usta weturope 's3h ‘S70 Sa Sapa $90 Sto 7 uni ew yan po. eileen routes LHO=CH + Aso# 2 Ch,cHo Aco BAC CH, ROH + 0. ‘oday new vinyl cea plats based sly ny asa based om acy single ep, heterogencoualy catalyse, ery 9.2. Vinyl Esters and Ethers Vinyl esters and ethers ean be reparded as derivatives of the hypothetical vinyl alcohol, i. the enol form of acctaldchyde ‘As such, they are readily saponified in weakly acidic solution to ucetaldehyde and the corresponding acid or alcohol. ‘Their industsial use as an intermediate is based solely on the readily polymerizable vinyl double bond. Vinyl acetate (VAM, vingl acetate monome) is the most impor tant of the esters of vinyl alcohol, mainly due 0 is use in the ‘manufacture of homo: and copolymer dispersions. Vinyl ethers, Which are versatile monomers with wide application, have & significantly smaller production volume than the vinyl esters 92.1. Vinyl Acetate In many countries, vinyl acetate production has stabilized following a dramatic growth period. Production figures for several countries are summarized in the adjacent table. The ‘world capacity for vinyl acetate in 1995 was about 3.8. 10" toanes per year, with about 1.5, 0.39, and 0.70 x 10* tonnes per year in the USA, Japan, and Western Europe. “The largest producer of vinyl acctatc is Hochst, mainly in the USA and Europe, with a capacity of roughly 0% 10° tones per year (1995). 4m 1970, vinyl agetae was tl being produced by three processes. Since then ihe wo elder processes ~ the addition of acetic acid toaceiylene and the two-step reaction of acetaldehyde with acetic anhydride through the intermediate cthslidene diacetate ~ have been increasingly replaced by the modern acetoxylation of ethylene process. In new plants, this processis used almost exeli- sively: In 1996, aboue ARB of the vinyl acetate capacity worldwide was based on ethylene acetoxplation, 9.2.1.1, Vinyl Acetate Based on Acetylene oF Acetaldehyde ‘The frst industrial manufacture of vinyl acctate involved addition of acetic acid to acctylene in the gas phase overio ascate manufacturing process una few years ago, the dfn! routes LHE™CH + AcOH 2 CHCHO + AGO. 3 H,C“CH, © MOH «0, ody now vay svat plants base sles ‘of ctbione Vinyl axa based on acyl: singles, nterogencously eatery selcive gasphase ation of ACOH te (CH, in fed of Midived-bed reactor AL a 60-70% acctie {n 1970, vinyl acetate was til being produced by three processes. Since then the two older processes ~ the addition of acetic acid vo acetylene and the wo-siep reaction of acetaldehyde with acetic anhydride through the intermediate cthylidene diacetate ~ have been increasingly replaced by the modern acetoxylation of hylene process. In new plants, this processis used almost exclu- ively. In 1996, about 88M of the vinyl acetate capacity worldwide was based on ethylene acetoxylation, 9.2.1.1, Vinyl Acetate Based on Acetylene oF Acetaldehyde The first industrial manufacture of vinyl acetate involved addition of acetic acid to acetylene in the gas phase over 2a(OAc),/charcoal at 170-250°C: He=cH + cH,coon, * HycmcHogeH; an oe) 92, Vinol Lsters und Liners 29 conversion, the Selectivity 10 vinyl SOmmevial we of ADH sisation with CMs i ony a few vous tay. mls acetate reaches 938 (based on C,H) and 99% (based on ACO), Fora time, He(OAc); and Zn silicate were aso used as ccaalysts. Although these processes are distinguished by high selectivities simple reaction control, and insignificant catalyst costs, the lower ethylene cost coupled with its storage and Iransport capability has plagued tf acetylene rovic. However, several vinyl acetate plans based on acetylene in Western and, Eastern Europe have been able (9 maintain thelr praxeses. In 1994, 9% of the vinvl acctate production in Western Eurone in he trmst Easier BhoACOH, Fora time, He(OAo): and Zn silicate were aso used as ‘aialyss. Although these prosewes ar distinguished by high selectivities, simple reaction control, and insignificant catalyst, costs the lower ethylene cost coupled with is storage and transport capably as plagued the acetylene route, However, several vinyl acta plants asd on aeeyene in Wesern and Eastern Europe have bavn able to maintain thir proses. fn 1994, 980 of the ving acetate production in Westen Europ, Eastern Europe, and Asia was sill based on acetylene, In the USA, al acctylene-based plants have been shut down, Vinyl propionare can be manufactured trom acetylene and ‘ropionie aid ina similar proces. One such producct is BASF jn Germany. “The second traditional process was practiced by Celanese unt 1990 in a 2S000 tonnepo-year plant inthe USA. Plants in India and China ae stil in operation. Inthe aceal dehiyde-acetic anhydride process box components react inthe fist stage at 120-140°C in the liquid phase with an FeCl, catalyst to form ethylene lactate: cicHo + (CHO ML cHeHOCCH,, t ° ° Thecthylidene diacetateisthen leavedto vinylacetateand acetic acid at 120°C using acidic catalts: cnscrocery, Ms we-cHoceH, + cH}c00H 9 1 I ° ° 9.2.12. Vingl Acetate Hased om Ethylene The catalytic modern manufacturing proces for vay! actate from ethylene and acti acid is based on an observation made by J.J Moiseev and co-workers. They found that the palladium catalvred oxidation of ethvlene 10 acealdeive becomes an a) inl aeate manusctue sd we ue ends in two aps Lteasion of CHCHO with X40 to ethene dace sermiae) 2 powonsanb ed fg, produces 25d) AcOH eminaton tidy secade oa to inl acca ‘eld wd comer ‘ui avate om: eink single ep, tt Batre acto lation of CH, wh nea ack of Ne tnseid oF OF a8 wit CHCHO.