Encyclopedia of Physical Science and Technology - Organic Chemistry

312 Pages·2001·7.597 MB·English

by  Robert A. Meyers (Editor)

P1:FPP 2ndRevisedPages Qu:00,00,00,00
EncyclopediaofPhysicalScienceandTechnology EN002C-64 May19,2001 20:39
Table of Contents
(Subject Area: Organic Chemistry)

Pages in the
Article Authors
Encyclopedia

Acetylene Robert J. Tedeschi Pages 55-89
Armin Guggisberg and
Alkaloids Pages 477-493
Manfred Hesse
Bioconjugate
Claude F. Meares Pages 93-98
Chemistry
Carbohydrates Hassan S. El Khadem Pages 369-416
Catalysis,
Piet W. N. M. van Leeuwen Pages 457-490
Homogeneous
Fuel Chemistry Sarma V. Pisupadti Pages 253-274
Heterocyclic
Charles M. Marson Pages 321-343
Chemistry
Organic Chemical
Josef Michl Pages 435-457
Systems, Theory
Organic Chemistry,
John Welch Pages 497-515
Synthesis
J. Ty Redd, Reed M. Izatt
Organic Macrocycles Pages 517-528
and Jerald S. Bradshaw
Organometallic
Robert H. Crabtree Pages 529-538
Chemistry
Pharmaceuticals, Giancarlo Santus and
Pages 791-803
Controlled Release of Richard W. Baker
Physical Organic
Charles L. Perrin Pages 211-243
Chemistry
Stereochemistry Ernest L. Eliel Pages 79-93
P1:GLQRevisedPages Qu:00,00,00,00
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May25,2001 16:2
Acetylene
Robert J. Tedeschi
TedeschiandAssociates,Inc.
I. Introduction VIII. ProcessesforAcetyleneProduction
II. AcetyleneandCommodityChemicals IX. ChemistryofSpecialtyProducts
III. ProductionofAcetyleneandCommodity X. VinylEthers
Chemicals XI. FlavorandFragranceCompoundsandVitamins
IV. Acetylene-Based Processes for Large-Volume AandE
Chemicals XII. AcetylenicPesticides
V. ImportantChemicalUsesforAcetylene XIII. AcetylenicReactionswithResearchand
VI. ReppeProducts CommercialPotential
VII. SpecialtyAcetylenicsandDerivatives XIV. AcetyleneResearchinRussia
GLOSSARY Carbonylation Reaction of acetylene with carbon
monoxideandalcoholstoformacrylateesters;Reppe
Acetylenic Pertainingtoorganiccompoundscontaining process.
a triple bond ( C C ) or acetylene group in the Commoditychemicals Large-volume,multitonnage
molecule. chemicals,someofwhicharederivedfromacetylene.
Adjuvant Acetylenic diol used with pesticides to en- Ethynylation Reactionofacetylenewithaldehydesand
hance activity, lower the rate of application, and in- ketonestoformacetylenicalcoholsanddiols.
creasesafety. Grignard Organomagnesium halide used in acetylenic
Alkynol Primary, secondary, or tertiary acetylenic alco- andothersyntheses.
holwiththehydroxylgroupgenerallyadjacentorαto Oil-wellacidizing Useofacetylenicalcohols(alkynols)
thetriplebond. as corrosion inhibitors to protect steel pipe during
Ammoxidation Acrylonitrilemanufacturedbyoxidation acidizingoperationsundertakentofreeoilfromlime-
ofpropyleneinthepresenceofammonia. stoneformations.
Aprotic Pertaining to highly polar solvents such as Pesticides Agricultural chemicals including herbicides,
dimethyl sulfoxide (DMSO), hexamethylphospho- insecticides, miticides, fungicides, and bacterial con-
ramide (HMPA), N-methyl-pyrrolidone (NMP), and trolagents.
acetonitrile that can hydrogen bond or complex with Reppe products and technology Pioneered by Dr.
acetyleneandacetyleniccompounds;usedtodissolve Walter Reppe of the I. G. Farben; various prod-
andactivateacetylene. ucts derived from the reaction of acetylene with
55
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
56 Acetylene
formaldehyde to yield butyne-1,4-diol and propargyl leneburnedinthepresenceofoxygenprovidedaveryhot
alcohol. flame,usefulinthejoiningofmetals.Theweldingindus-
Surfynols Acetylenichydroxylcompoundsusedashigh- trytodaystillusessignificantamountsofacetyleneinspite
speed, low-foam wetting–dispersing agents and as oftheavailabilityoflessexpensivefuelssuchaspropane.
agriculturaladjuvantsandformulationaids. Initially,acetylenewashandledinindustryastheundi-
Trofimov reaction Formation of substituted pyrroles lutedliquefiedgasbelowitscriticaltemperatureof36◦C
and N-vinylpyrroles by reaction of acetylene with at a pressure greater than 600 psig. This appeared to be
ketoximes. a safe procedure until a series of industrial explosions
Vinylation Reactionofacetylenewithalcoholsorpyrol- in the early 1900s eliminated the practice. Today acety-
lidonetoformvinylethersandvinylpyrrolidone. leneisshippedincylindersunderpressurethatcontaina
mixture of diatomaceous earth or asbestos, acetone, and
stabilizers.Anothersafemethodoftransportisviagranu-
ACETYLENE CHEMISTRY is the chemistry of the larcalciumcarbideinsealedcontainers,freeofwater.The
carbon–carbon triple bond ( C C ). This functionality large-volumeuseofacetyleneforthemanufactureofcom-
definestheuniquechemistryofthisreactivegroup,inad- moditychemicalshasledtothebuildingofplants,either
ditiontoitsdiverseandimportantapplications.Thehigh petrochemicalorcalciumcarbide,“acrossthefence”from
electrondensityofthetriplebondwithitscircular,sym- acetylene producers. Today the factors leading to acety-
metricalπ fieldmakesacetyleneanditsderivativesreac- lenehazardsarewellunderstoodandhavebeenwelldoc-
tiveandusefulintermediatesforsynthesizingawideva- umented. Acetylene now poses a minimum risk in well-
rietyoforganiccompounds.Theseorganicproductsfind operatedprocessesandplants.
wideuseinthesynthesisofflavorsandfragrances,vita-
minsA,E,andK,β-carotene,pesticides,surfactants,cor-
rosioninhibitors,andspeciallyintermediates.Thisarticle II. ACETYLENE AND COMMODITY
describes the technology and applications of acetylene, CHEMICALS
acetylenic compounds, and the chemicals derived from
them. From1965to1970morethan1billionpoundsofacetylene
In the mid-1960s more than 1 billion pounds of were used annually to manufacture a variety of chemi-
acetylene were used annually for the production of cals. Welding applications constituted ∼10% of this to-
large-volume(commodity)chemicals.Sincethen,acety- tal. After 1970, the use of acetylene for the manufac-
lene has been gradually supplanted by less expensive tureofcommoditychemicalsbegantodeclinemarkedly,
olefin feedstocks. However, acetylene is still used in and by 1979–1983 only 269 million pounds were em-
multimillion-pound levels to produce Reppe chemicals ployed.Lessexpensivepetrochemicalrawmaterialssuch
(butynediol,propargylalcohol,butanediol,butyrolactone, asethylene,propylene,butadiene,amylenes,andmethane
N-methylpyrrolidone, polyvinylpyrrolidone, and vinyl were replacing acetylene. Table I summarizes chemicals
ethercopolymers)andspecialtyacetylenicchemicalsand manufacturedmainlyfromactylenebefore1965,typesof
theirderivatives.Largevolumesofbutanediolareusedin processes, and replacement raw materials. The principal
themanufactureofengineeringplasticssuchaspolybuty- use of the monomers listed in the table was in diverse
leneterephthalate.Othersignificantusesforacetylenein polymer applications spanning plastics, latex emulsions,
specialtyareasincludeacetyleneblack,vitaminsAandE, rubbers,andresins.Chlorinatedsolventswereimportant
flavor–fragrance(F&F)compounds,corrosioninhibitors, in vapor degreasing, but their use in more recent years
acetylenicsurfactants,andpesticides.Acetylenicchemi- has been gradually limited as a result of toxicity and air
cals, polymers, and derivatives of potential value in re- pollution.
search and commerce are also discussed. Some special Theapplicationsofthepolymerproductsderivedfrom
aspectsofacetylenechemistryresearchinRussiaarealso theabovemonomersarenotwithinthescopeofthisarticle.
summarized.
III. PRODUCTION OF ACETYLENE AND
I. INTRODUCTION COMMODITY CHEMICALS
Acetylenehasalwaysbeenanimportantrawmaterialfor ThefollowingtabulationshowsthegradualdeclineinU.S.
makingchemicalproducts.Intheearlyyearsofitshistory acetylene production from its high point of 1.23 billion
(circa1890–1900)itwasusedextensivelyasanilluminant poundsin1965to∼269millionpoundsin1979.In1965
fortrainsandcitystreets.Itwassoonrealizedthatacety- bulkacetylenewasvaluedat7–12c//lb,whileethylenewas
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
Acetylene 57
TABLEI EarlyAcetylene-BasedChemicals
Product C2H2process Replacementrawmaterial Replacementprocess
Acrylatesandacrylicacid Reppecarbonylation(CO+C2H2) Propylene(C3H6) Two-stageoxidation
Acrylonitrile C2H2+HCN C3H6 Ammoxidation(C3H6–O2–NH3)
Chloroprene C2H2-Vinylacetylene-HCl Butadiene Chlorinationanddehydrochlorination
Chlorinatedhydrocarbons C2H2+Cl2 C1–C3feedstocks;C2H4 Chlorination–dehydrochlorination
Vinylacetate C2H2+aceticacid Ethylene(C2H4) Oxyacetylation
Vinylchloride C2H2+HCl Ethylene Oxychlorination
C2H2+HCl C2H2+C2H4 Balancedethylene–acetylene
3–4c//lb.By1983–1984thecostratiowasapproximately tionisamixfromcalciumcarbide,by-productacetylene
the same, with acetylene valued at about 55–75c//lb and fromcracking,andpartialoxidationprocesses.
ethyleneat23–29c//lb. ThenineU.S.acetyleneproducers,withtheircapacity
in millions of pounds, were AIRCO-BOC, Calvert City,
Year C2H2used(106lb) KY, and Louisville, KY (75); Dow, Freeport, TX (16);
Hoffmann–La Roche, Nutley, NJ (5); Monochem,
1965 1230
Geismar,LA(180);RohmandHaas,DeerPark,TX(55);
1967 1065
UnionCarbide,Ponce,P.R.(12);UnionCarbide;Seadrift,
1969 1195
TX(12);Taft,LA(10);TexasCity,TX(16).
1971 852
The 1984 demand for acetylene was 286 million
1973 571
pounds,anditwasestimatedtobe292millionpoundsin
1976 490 1988.Growthfrom1974to1983wasnegativeat−6.9%
1979 269
per year, while through 1988 it was slightly positive at
0.5%peryear.Hoffmann–LaRochegeneratesacetylene
1984 286
fromcalciumcarbideforuseinthemanufactureofvita-
minsAandEandβ-carotene.
From1967to1974,23plantsmakingsuchacetylene-
Of all the commodity chemicals listed in Table II,
basedproductsasacrylonitrile,chlorinatedhydrocarbons,
vinyl chloride showed the least decline from 1970 to
chloroprene(neoprene),vinylacetate,andvinylchloride
1984.In1984acetyleneconvertedtovinylchloriderep-
were shut down. Sixteen of these plants manufactured
resented 51% of total acetylene consumption. However,
vinyl acetate and vinyl chloride. Table II presents acety-
this production was from only one site, Monochem at
leneusageforvariousproductsin1970,1979,and1984.
Geismar, LA, and may be vulnerable in the future if
In1984totalU.S.capacityfortheproductionofacety-
Monochemdecidestoconvertcompletelytoethyleneas
lenewasestimatedtobe384millionpounds.Thisproduc-
rawmaterial.Themostpromisinggrowthareasforacety-
lene in the near term are Reppe chemicals, particularly
TABLE II U.S Acetylene Usage: Large-Volume butane-1,4-diol, used extensively in engineering plastics
Chemicals andpolyurethanes.Acetyleneblackandvinylfluorideare
alsospecialtygrowthareas,asareacetylenicsurfactants
Product 1970 1979 1984
andcorrosioninhibitors.Theseacetylene-drivedproducts
Acrylicacidandacrylates 70 16–45a 0 are discussed in greater detail in Section V.
Acrylonitrile 42 0 0
Chloroprene(neoprene) 242 0 0
Chlorinatedsolvents 91 0 0
A. AcetyleneProductiononaWorldBasis
Vinylchloride 268 100–110a 146
Vinylacetate 158 37–52a 10 Table III shows that, although U.S. acetylene production
Reppechemicalsb 41 73–80a 114 ismodest,acetyleneusageworldwideisstillsignificant,
Otheracetylenicsand 10 14 26 amountingto∼1.9billionpounds.
derivativesc Inthelongerterm,itisbelievedthatworldwideacety-
lene capacity and usage will gradually increase as oil
aMainlybutane-1,4-diolplusotherReppeproducts.
bAcetyleneblack,vinylfluoride,specialtyacetylenics. pricesescalate.Acetyleneusageforsuchproductsasvinyl
cEstimatedvalue. acetate, vinyl chloride, Reppe chemicals, and specialty
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
58 Acetylene
TABLEIII WorldAcetyleneUsagea A. AcrylatesandAcrylicAcid
Location Chemical Industrial Total 1. ReppeCarbonylation
UnitedStates 282 114 396
4C H +Ni(CO) +4C H OH+2HCl−→
WesternEurope 814 200b 1014b 2 2 4 2 5
Japan 106b 100b 206 CH CHCO C H +H +NiCl
2 2 2 5 2 2

Others 200b 150b 350b (cid:3)
Total 1402b 564b 1966b H2O
CH CHCO H+C H OH
aInmillionsofpounds. 2 2 2 5
bEstimatedvalue. t=30–40◦C;atmosphericpressure.
acetylenics is expected to increase. Worldwide acetylene
2. ReplacementProcess:Two-StagePropylene
capacityisspreadoverawidegeographicarea,asshown
Oxidation
in Table IV. The calcium carbide (CaC) process, based
2
on coal and limestone, is still extensively practiced or is A
CH CH CH + 1O −−−−−→
presentasabackupcapacity.InRussiathereisprobablya 3 2 2 2 300−450◦C
largecalciumcarbidecapacitythathasnotbeenreported.
B
The large-scale use of acetylene for the manufacture CH CHCHO−−−−−→CH CHCO H
2 2 2
of commodity chemicals will be dependent on the cost 275−365◦C (cid:9)
ROH
differencebetweencoalandoilandnaturalgas.Itiscertain
Acrylateesters
thatsometimeinthefutureoilandnaturalgasreserveswill
becomelimitedandmoreexpensivethancoal.Thetarget AandB=fixedorfluidized-bedreactors.
date is the early 21st century. Coal-based technologies
such as the calcium carbide and AVCO (coal–hydrogen
B. Acrylonitrile
plasmaarc)processesareprimecandidatesforlarge-scale
acetylene production. The AVCO process (Section VIII) 1. Acetylene–HydrogenCyanide
hasbeenstudiedsuccessfullyatthepilot-plantlevel.
C H +HCN−−−−−→H C CHCN
2 2 2
40−600◦C
IV. ACETYLENE-BASED PROCESSES Fixed-bedprocess;catalyst,Ca(CN) .
2
FOR LARGE-VOLUME CHEMICALS
2. ReplacementProcess:Ammoxidation
The processes summarized in the equations below were
ofPropylene
importantin1940–1965forproducingcommoditychem-
icals. Below each acetylene-based process is shown its
replacementprocess. H3C CH CH2+ 32O2+NH3 →H2C CHCN+3H2O
TABLEIV WorldwideAcetyleneCapacity
Capacity
Country(Company,Location) (millionsofpounds) Acetyleneprocess
WestGermany(BASF,Ludwigshaven) 176 Partialoxidationofnaturalgas
WestGermany(Chem.WerkeHuels,Marl) 264 Arcprocess–refinerygas
WestGermany(BASF,Ludwigshaven) 13 By-productC2H2fromethylene
Italy(Anic,Ravenna) 132 Naphthacracking
Italy(Montedison,PortoMarghera) 154 Partialoxidationofnaturalgas
Japan(DenkiKagakuKagyo,Ohmi) 200 Calciumcarbideprocess
Japan(IgeganaElectricCo.,Ogaki) 616 Calciumcarbideprocess
SouthAfrica(AfricanExplosives) 110 Calciumcarbideprocess
Russia(LissitChansk) 77 Partialoxidationofnaturalgas
UnitedStates(Kentucky,Texas) 384 Calciumcarbide,crackingby-product,
partialoxidation
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
Acetylene 59
Fixed-bedorfluidized-bedreactors;t=240–460◦C;typ- 2. ReplacementProcess:Oxyacetylation
ical catalysts, Bi–P–Mo (Sohio), Mo–Vo–Bi (Snam), ofEthylene
Mo–Te–Ce(Montedison–UOP),Se–CuO(BP-Dist.)
H C CH +CH CO H+ 1O −−−−−→
2 2 3 2 2 2 175−200◦C
C. Chloroprene(Neoprene, H C CHOCOCH +H O
2 3 2
2-Chloro-1,3-Butadiene)
Fixed-bedorfluidized-bedreactors;catalyst,palladiumor
1. Acetylene–Vinylacetylene–HydrogenChloride
mixtureofnoble-metalsaltsdepositedonsupports.
(Nieuwland–CarothersProcess)
CuCl
2C H −−−→H C CH C CH−−→ F. VinylChloride
2 2 2
NH4Cl HCI
1. Acetylene–HydrogenChloride
H C CH CCl CH +HCl
2 2 (Hydrochlorination)
Liquid-phase process; t=50–75◦C; atmospheric
pressure. C H +HCl−−−−→H C CHCl
2 2 2
90−140◦C
Fixed-bed reactor; catalyst, 10% mercuric chloride on
2. ReplacementProcess:High-Temperature
carbon.
ChlorinationofButadiene
Cl →(cid:5) 2Cl. 2. BalancedEthylene–Acetylene(Chlorination–
2 Dehydrochlorination)
H C CH CH CH +2Cl.−6−0−0→◦C
2 2
C H +Cl →ClCH CH Cl→H C CHCl+HCl
H C CH CCl CH +HCl 2 4 2 2 2 2
2 2
C H +HCl→H C CHCl
2 2 2
Overall:C H +C H +Cl →2H C CHCl
D. ChlorinatedHydrocarbons(Solvents) 2 4 2 2 2 2
1. ChlorinationofAcetyleneFollowedby
Dehydrochlorination 3. ReplacementProcess:Oxychlorination
ofEthylene
−HCl
C H +Cl →CHCl CHCl −−−→
2 2 2 2 2 C H +2HCl+ 1O →ClCH CH Cl+H O
2 4 2 2 2 2 2
CHCl CCl −→CHCl CCl
2 2 3 C H +Cl →ClCH CH Cl
Cl2 ↓(cid:5) 2 4 2 2 2
(cid:5)
Cl2C CCl2 ClCH2CH2Cl→H2C CHCl+HCl
2HCl+ 1O →Cl +H O
2 2 2 2
2. ReplacementProcess
Overall:2C H +Cl + 1O →2H C CHCl+H O
2 4 2 2 2 2 2
Thisincludesthechlorinationofhydrocarbonfeedstocks
(methane, ethane, propane, ethylene, propylene), which Fixed-bed or fluidized-bed reactors; oxychlorination,
requiresmultiproducttechnology. t=450–500◦C (atmospheric pressure); catalyst, CuCl2–
KCl on Kieselguhr; chlorination of ethylene, t=50–
140◦C (P=4–10 atm); pyrolysis of ClCH CH Cl,
2 2
E. VinylAcetate t=470–540◦C(P=24–25atm).
Theseacetylene-basedprocessesarewell-tested,high-
1. Acetylene–AceticAcid
yield,andhigh-selectivityoperations,averagingwellover
90% of theory. The extensive use of these processes is
C2H2+CH3CO2H−−−−−→H2C CHOCOCH3+H2O likelyonceoil-basedfeedstocksbecomemoreexpensive
180−210◦C
than coal, which will be the preferred raw material for
Fixed-bedreactor;catalyst,zincacetateoncarbon. acetyleneproduction.
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
60 Acetylene
V. IMPORTANT CHEMICAL follows:1981(50);1984(55);1987(60).UnionCarbide
USES FOR ACETYLENE produced ∼65% of this total, which was used internally
initsbatterydivision.
As shown in Tables II and III, there has been steady growth
intheproductionofacetylene-basedspecialtychemicals.
B. VinylFluoride
These products comprise acetylene black, vinyl fluo-
ride, vinyl ethers, Reppe chemicals, and miscellaneous Theprincipaluseforthisspecialtymonomeristheproduc-
acetylenic alcohols and diols. Reppe products consist tionofpolyvinylfluoride(PVF),apolymerconsiderably
mainly of butyne-1,4-diol, propargyl alcohol (1-propyn- more stable than polyvinyl chloride (PVC). The use of
3-ol), butane-1,4-diol, butyrolactone, tetrahydrofuran, PVFinexteriorcoatingsforaluminumsiding,steelbuild-
pyrrolidone, vinylpyrrolidone, N-methylpyrrolidone, ing panels, hardboard siding, and asbestos-impregnated
polyvinylpyrrolidone, polyvinyl ethers, and copolymers. felt roofing continues to grow. PVF was introduced by
Butane-1,4-diol has emerged as the most important Du Pont in 1963 under the registered trademark Tedlar.
user of acetylene for acetylenic chemicals and derived In 1966 acetylene consumption for PVF production was
products. Its usage in specialty polymers and chemicals estimated to be ∼1 million pounds and by 1984 it was
increased steadily during the 1977–1979 period from 6–9millionpounds,showingsteadygrowth.
82 to 92% of total acetylene consumption (74 million Vinylfluorideisproducedbytheadditionofhydrogen
poundsin1979).Theprincipalusesforbutanediolarein fluoride to acetylene in the presence of a mercuric salt
polybutyleneterphthalateandotherengineeringplastics, catalystdepositedoncarbon.Theintermediatevinylflu-
besides polyurethanes. By 1984 the total acetylene oride is not isolated due to the difficulty of separating it
usage for acetylenic chemicals had been estimated to be fromacetylene.Theresultingdifluoroethane(DFE)isin
115millionpounds. turn cracked to vinyl fluoride and the evolved hydrogen
fluorideisrecycled:
A. AcetyleneBlack C H +2HF→[H C CHF]→CH CHF
2 2 2 3 2
Vinylfluoride DFE
This unique, conductive form of carbon is made by the
(cid:5)
exothermicdecompositionofacetylene: DFE→H C CHF+HF.
2
C H −80−0→◦C 2C+H . TheprincipalU.S.producersofvinylfluorideandPVF
2 2 2
are Du Pont (Louisville, KY) and Diamond Shamrock
(Houston, TX). The intermediate DFE is also important
The reaction is highly exothermic and the evolved heat
(∼55,000cal/g)isusedtomaintainthepyrolysistemper- for the manufacture of vinylidene fluoride, as shown in
thenextsection.
ature. Preferred processes involve (1) continuous explo-
sion of acetylene at 1–2 atm using an electric spark and
(2)decompositionviatheelectricarc. C. VinylideneFluoride(VinylideneDifluoride)
The principal uses of acetylene black are in the man-
Vinylidenefluoride(VDF),amonomer,canbeproduced
ufacture of dry cell batteries and the fabrication of
from DFE via chlorination and cracking or from 1,1,
conductingrubberandplasticsheetingandmoldedplas-
1-trifluoroethane:
tics. Although acetylene black is too expensive to com-
petewithpetrochemicalcarbonsinlarge-volumepolymer C H +2HF→CH CHF →Cl2
2 2 3 2
compounding,ithascarvedoutforitselfagrowingspe-
(cid:5)
cialtymarketinconductiveapplications.Acetylenecon- H3C—C(Cl)F2→H2C CF2 (1)
sumption(inestimatedmillionsofpounds)foracetylene CDFE VDF
blackgrewsteadilyfrom1967to1984intheUnitedStates: (cid:5)
CH CF →H C CF +HF (2)
1967(10);1979(19);1980(20);1984(23). 3 3 2 2
ProducersofacetyleneblackareShawinigan(Canada), At present the preferred starting material for VDF
Union Carbide (Ashtabula, OH, and Ponce, P. R.), and production is 1-chloro-1,1-difluoroethane (CDFE), also
Gulf (Cedar Bayou, TX). The Gulf production facility knownasrefrigerant142b.Numerousotherintermediates
went on stream in 1979 and is rated at 15–20 million havebeendescribedforthepreparationofVDF.Theprin-
pounds/year. The markets for batteries and conducting cipaluseforthismonomeristheproductionofpolyviny-
polymer composites grew significantly from the mid- lenedifluoride(PVDF,PVF ).Thepolymerissemicrys-
2
1980s, and acetylene black participated in this growth. talline and has the following desirable properties; high
The total production of acetylene black from all sources mechanicalandimpactstrength,resistancetomostchemi-
(millions of pounds) from 1981 to 1987 is estimated as cals,veryhighdielectricconstant,andexcellentresistance
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
Acetylene 61
to ultraviolet and nuclear radiation and general weather- WalterReppeoftheI.G.Farben,whoisoneoftheleg-
ing.Itcanbecross-linkedviaelectron-beamradiationto endaryfiguresofacetylenechemistryanditsapplication
givefurtherimprovedproperties. totheproductionofvaluablechemicalsforGermanydur-
It is used extensively in the interior coating of pipes ing World War II. Reppe’s research spanned the 1930s
andasabaseforlong-lastingdecorativefinishesonalu- andreachedcommercialimportanceduringthewaryears
minum, galvanized steel, and other architectural metals. inthe1940s.Ethynylationtechnologytoproducethekey
Otherapplicationsincludewireinsulationandconnectors startingmaterials2-butyne-1,4-diolandpropargylalcohol
forcomputerboards,telecommunicationsuses,andresis- (1-propyn-3-ol) is summarized in Section IX.B.
tantcoatingsforharshenvironments.
TheU.S.suppliersofPVDFarePennwalt,Solvay,and C2H2+HCHO−C−u−C→2H
DynamitNobel.DuPontproducesPVDFforitsownin- HOCH C CCH OH+HOCH C CH
2 2 2
ternal use, primarily to produce Viton plastic. The total 2-Butyne-1,4-diol Propargylalcohol
U.S. production of this polymer is significantly greater
Productsderivedfrombutynediolare2-butene-1,4-diol,
thanthatofPVF.
1,4-butanediol, γ-butyrolactone, N-methyl-2-pyrroli-
done, 2-pyrrolidone, N-vinyl-2-pyrrolidone, polyvinyl-
VI. REPPE PRODUCTS pyrrolidone (PVP), and polypyrrolidone. The reaction
flow diagram in Fig. 1 shows the interrelationship of
Reppe products, a line of large-volume, acetylene-based these products. Other Reppe chemicals such as vinyl
specialty chemicals, bear the name of their discoverer, ethers, polyvinyl ethers, vinyl ether–maleic anhydride
FIGURE1 Reactionflowdiagram:Reppechemicals.(1)2-Butyne-1,4-diol;(1a)propargylalcohol;(2)2-butene-1,
4-diol; (3) butane-1,4-diol; (4) tetrahydrofuran; (5) γ-butyrolactone; (6) 2-pyrrolidone; (7) N-vinylpyrrolidone;
(8)polyvinylpyrrolidone;(9)N-methylpyrrolidone.
P1:GLQRevisedPages
EncyclopediaofPhysicalScienceandTechnology EN001F-4 May7,2001 16:19
62 Acetylene
TABLEV ApplicationsofReppeChemicalsa
Product Applicationsb
Propargylalcohol Metaltreatment;corrosioninhibition;oil-wellacidizing;electroplating;intermediateforvitaminAandpesticides
Butyne-1,4-diol ImportantReppestartingmaterial;metaltreatment;acidpickling;electroplatingadditive;stabilizationof
chlorinatedsolvents;intermediateforpesticides
Butene-1,4-diol Intermediateforpesticides,pharmaceuticals,fungicides,andbacteriacides;polyurethaneintermediate
Butane-1,4-diol ImportantReppeintermediateforTHF,butyrolactone,andPVPpolymers;manufactureofpolybutylene
terphthalate;polyurethanes,spandexfibers;specialtyplasticizers
γ-Butyrolactone IntermediateforpyrrolidoneandPVP;acetylenesolvent(Sacchse);specialtysolventforpolymers,lacquers,
paintremovers,andpetroleumprocessing;intermediateforherbicides,azodyes,andmethionine
Tetrahydrofuran Continuoustopcoatingofautomotivevinylupholstery,generalsolventforresins;coatingofcellophanewith
vinylidenepolymers;polymers;polyurethanepolymers;spandexfibers
Pyrrolidone IntermediateforN-vinylandPVPpolymers;powerfulsolventforresins;acetylenesolvent;polarreactionsolvent;
formulatingagent;floorwaxes;specialtyinks;reactionintermediate
N-Methylpyrrolidone Commercialacetylenesolvent;usessameaspyrrolidone;selectiveextractionsolventforbutadienepurification
(crackednaphtha);spinningsyntheticfibers;surfacecoatings;pigmentdispersant;formulatingagent
N-Vinylpyrrolidone IntermediateforPVPpolymers;functionalmonomer;lubeoilmanufacture;copolymerapplications;paints,
paper-coating adhesives, cosmetics; increased dye receptivity; pigment dispersant
aReprinted from Tedeschi, R. J. (1982). “Acetylene-Based Chemicals from Coal and Other Natural Resources,” pp. 101–102, courtesy of
Dekker,NewYork.
bTHF, tetrahydrofuran; PVP, polyvinylpyrrolidone.
copolymers, acetylenic alcohols and diols, and poly- from metal treatment and corrosion inhibition to inter-
butylene terphthalate are discussed in subsequent mediates, specialty solvents for acetylene and polymers,
sections. top coating and spinning of fibers, preparation of speci-
alty polymers and engineering plastics, vitamins A and
E, and pesticides. The most important products in terms
A. ApplicationsofReppeProducts
ofproductionandsalesarebutanediolandtetrahydrofu-
The uses of both butynediol and propargyl alcohol and ran (THF), which are key building blocks for engineer-
their derivatives are quite diverse (Table V). They vary ing plastics, polyurethanes, and spandex fibers. Table VI
TABLEVI ApplicationsofPolyvinylpyrrolidonePolymersa
Product Compositionb Applications
Polyvinylpyrrolidone — ApprovedbytheFoodandDrugAdministrationforfoodanddruguse;blood
plasmaexpander;nontoxic,biodegradable;varieduses
PolyclarAT StandardPVPgrade Beverageclarificationaid(fruitjuices,wines,beer);chillproofingofbeer;
(whitepowder) complexingagent
Plasdone Pharmaceutical-gradePVP Tabletmanufacture(granulatingagent);tabletcoating;liquiddosages;topical
preparations;stabilizer,dispersant,drainageaid(syringes);skincreams,hair
sprays,shampoos,generalcosmeticuse
Kolimaadhesive Modified,clearhigh-solids Superiorglue-linestrength;sealingofsmoothhardsurfaces;greaseand
polymers(Kolima PVPsolutions chemicalresistance;superioradhesionattemperatureextremes;superior
35,55,75) surfacewetting;residualtackandviscositycontrolapplications
GanexVpolymers ProprietaryPVPpolymers Coatings,detergents,pigmentdispersants,plasticadditives,textiles,petroleum
applications,protectivecolloidsforvinyllattices,improvedfreeze-thaw
stabilityandscrubresistance
Polectron(P)emulsion PVPcopolymerlattices:P-130 Adhesives:remoistenables,pressuresensitise,heat-sealingapplications
copolymers (ethylacrylate);P-230 Coatings:leathersizesandfinishes,metalprimers
(2-ethylhexylacrylate);P-430, Paper:boardsizing,pigmentbinding,precoating,heatsealing
450(styrene);P825L, Textiles:fabriclaminates,oilrepellentfinishes,permanentpressing,polyester
845L(vinylacetate) sizing
aReprinted from Tedeschi, R. J. (1982). “Acetylene-Based Chemicals from Coal and other Natural Resources,” pp. 134–135, courtesy of
Dekker,NewYork.
b