COPY No, E. I, DU PONT DE NEMOURS AND COMPANY, INC. ORGANIC CHEMICALS DEPARTMENT PLANTS TECHNICAL SECTION LOUISVILLE WORKS MONTAGUE WORKS TECHNICAL MANUAL FOR POLYCHLOROBUTADIENE MANUFACTURE Prepared by: @. J. Schaaf 0.W. Joule APPROVED BY: Louisville Plant Technical Superintendent Montague Plant Technical Superintendent AUTHORIZED BY: Plants Technical Section Managenentcai POLY I= 1 iY CHLOROJTADI SENICAL MANUAL ‘SBorTION 1 PRINCIPLES OF PROCESS PRoDuor summany Weoprene is a synthetic elastomer of, GD (2-chloro-1, butadiene) or a copolymer of CD and other compounds guch ai 2, 3-ai chloro-1, 3-butadiene), ‘The name is a generic term obtained from the Greek "Neos", new, and the prene in teoprene, 2 methyl-1,3-tutadiene, the basic unit for natural rubber, Neoprene was developed ty Dupont and first marketed in 1932. Sales and production have contimally expanded because of superior properties in resistance to weather, heat, osone, oils and many chemicals. It is available on the market ina variety of solid types and latices. Neoprene uses, in general, parallel those of natural rubber and other elastomers, tut due to higher cost, most of it is used because of ite superior properties. The largest single use is for protective Jacketing for wire and cable. Other uses for the dry products are in hose, conveyor and power belting, industrial tires, shoe soles, gaskets, seals and many industrial molded products. | @ Avout 10 per cent of neoprene is sold ae a latex, which is used as an adhesive in the leather and textile fields, paper additive, to promice @ipped goods, to produce fire resistant foams and for many specialty operations. GENURAL PROCESS | ‘The manufacture of neoprene consists of three basic steps} separate | technical manuals discuss the first two steps to produce CD monomer, vhile this manval will be concerned only with step three, polymerization. (1) Acetylene dimerization to vinylacetylene (MYA): 2HCz CH» CH, = CHC = (2) Vinylacetylene hyarochlori nation to chlorobutadiene (CD): CH =CH-CwCH+ HCl —> (Hy = CCl ~ cH» CH, (3) Chlorobutadiene polymerization to neoprene? n GH, = CCl - CH= CHy——> (-CHy ~ Ol = CH - Gy -) n In the polymerization process CD (chloroprene) containing a rosin and modifier is proportioned with an alkaline water solution into a centrifugal pump, ® where an emulsion of CD in water is formed and stabilized by the soap. 8-15-56 Liesl‘PROPERITHS OF MATERIALS. Selected Vapor Preseure (low Temperature Range) Selected Vapor Pressure (High Temperature Range) ieat Capacity of Various Chemicals Latent Heat of Vaporization of Yarious Chenicale Abietic Actd Acetaldehyde Acetic Acka Acetone Acetylene Ammonia ‘Amoniun Hydroxide Annoniun Persulfate “aquarex* WS "Aquarex"-WAQ” Calcium Chloride Brine Chlorobutadiene Chlorobutanone Cops Copper Sulfate Cunene Hydroperoxide Cuprous Chloride Oyclohexanol DC Witrosate Dichlorobutad iene Dichlorobutene Diethanolamine Disthylene Glycol Monobutyl Bther Divinylacetylene Hyamine 2389 Hydrogen Chloride Hydrogen Peroxide Todoform "Tonol" cD aca) Isochloroprene Methyl Alcohol Methylene Chloride Methyl Vinyl Ketone Mixed Phosphit Monovinylacetylene MYA Catalyst Solution MVA Reaction Tar Nancy Wood Rosin “WNeozone! A Nitrogen Mitrogen Tetroxide Phenothiazine Potassium OhIoride KCl Potassium Ferricyanide Potassiun Hydroxide Potassium Persulfate Resin 731 D Resin Staybelite-742 Rosin or Colophony "Silver Salt" Sodium Acetate Sodium Chloride Sodiun Bydroxide Sodiun Sulfite Sulfur, Amorphous, § Styrene Sulfuric Acta “Tepidone" 4/ Thiuran ¥ Toluene Versene Regular Vinyl Chloride Water Kyleneog g =~ fe > ail ate v oe es «| WETHABOL LIQUID | go) py < ze ee Gi Gh 7 S| — & op {oe eee a 2 Tans 74! couse J) Nester. = Bog |e erates fp abst = SamFep ener Oe ere au HEAT CAPACITY OF VARIOUS CHEIICALS ol LC near cabeet She wena yrs fer 7 -@ -f0 ~“ “3 -® -O© CSC 0 & S&S & TEMPERATURE - °C. kh5 Tera ig geen ts ae v goa oS 6H wu aunssad 5 16o* oe 76 iF Gi iF a PERATURE °C Mia Py °c TEMPERATURE ~e0" Reo? One: © goeren se ‘Sy ww JUNgSAad »d®G GUVGNVIS . «tVSION,, d*° a GYvGNVLS; “De ~ BSOWARIWEL ‘ai/nod ~ QOLLVZIAOdVA 3O JW3H LNA ON, d*d GYVGNVLS «XIN, d* a GUVGNVLSABIBYIC ACID (Abietinic Acide or Sylvie Acia; the principle couponent of Naney Wood rosin). Cag H3q Op Mol. We. 302.4 Melting Point: 137-166 (Var.)°C Solubinity: Steter_ Ethyl Alcohol Ethyl Ether, Insoluble Very soluble Very soluble in ethyl ether, soluble in glsc. acetic acid, acetone, benzene, (8p and methyl alcohol. 8/1/56CRLORGBUTADINWE (2-Shloro-1,3-Butadiene) HyC = CCL-CH = CHp Mol. Wt. 88.537 Boiling Poiat: 59:70, @1b-7 pple Gritical Constants: t, = 255.6°C- (aprrox.) Dens: (Liguia) c. bs. /ou.ft, -20 62.6 9 61.5 20 58-7 40 58.2 60 56.5 (Gas) 02466 Ibs./ou.ft. @ O°C. and 14.7 psia Vapor Pressure: mn. Bg. mm. Bg. 20 40 400.0 -10 50 555.0 - 594 760.0 10 60.0 175.0 20 70 1030.0 30 80 1370-0 For vapor pressure data in chart form see front of secvicn. Coefficient of Cubical Expansion: (Liquid) 0,001235/°C. (range 20° te 61°C.) Ips. /far.)(tt.) (Liquid) (@as) Thermal Conductivity: (Laquia) (Ges) 8/a/s6GHLOROBUTADTENE, Heat Capacity: (Geesitis Hast) Gas) Latent Heat of Vaporizetion: Heat_of Reaction Heat_of Polymerization: ve Range: Flash Foint: 20 0 20 ho 60 Tor latent heat of vaporization in graph form see froat of ‘this section MYA + HOL to CD = 372-7 POU/Ib. 170 Pou/Ie Lower Limit Upper Limit $ by volums in air are Sa A.8.T.M. open cup -20°C. 50% CD in Xylene 19°C. Solubility of Water in CD.MVA Mixtures: In comection with the study to substitute brine coolers for calcium chloride dryers at the CD aren wet colums, the foregoing date, was obtained on the solubility of water in GD ond CD-MVA mixtures: % MVA in mixture $ OP in mixture $ Vater et -50°C. ~ho -30” -20 -10 0 +20 8/i/s6 ae Oo 20 30 100 80 70 0.007 0.008 0.008 0.014 0.017 0.019 0.021 0.028 0.032 0.030 0.080 0.0lk 0.038 0.050 0.055, 0.086 0.060 0.068 0.055, 0.070 0,080 0.064 0.081 0.092 0.072 0.093® CHLORCBUTADTENE: Hazardous Properties: Meximm allovable concentration in air 25 ppm. cD may enter the body either by inhalation or by absorption through the skin. Eighty-three ppm may cause toxic symptoms upon inhalation. CD is anesthetic. It causes depression of the central nervous system and damage to vital organs. Exposure to only suall doses may be severe enough to cause death. CD is flammable. STANDARD BaP “NSIEAR” ©CHLOROBUTANONE Mol. Wt. 106.5 Bolling Point: 125? atm., pressure Forms rapidly from MVK and HCl. Most of so-called MVK in CD is usually chlorobutenone because HC1 is present. Without HCl, or in alkaline medium, chlorobutanone will not form and any previously formed, will be hydrolyzed to WK. MWK + HCL G—=—— > CHLOROBUTANONE. ° ° co. Cig + C = CH = Cy + HCL =———— CH - C - Cy - CH, Mol. We. 86 36.5 122.5 8/1/56e DICHLOROBUTADIENE (DED) (cHy = ccl-cc1-cH,) Mol. Wt. 123:0 Specific Gravity: 1,190 20°C. /20°C. Viscosity: 0.62 @ 20°C. Ob) Fitwpeae: to%e. (closed ew) t Vapor Pressure: ce IS} Vapor Pressure ‘Temp Yapor Pressure c am of Hg. 70 mm of Hg. Re 10 62.0 200 o 20 72.5 300 a 2 82.0 hoo fo 0 88.5 500 50 93.0 600 o 60 99.0 700 & To 202. 800 < ho.0 80 107.5 900 DQ hes 90 no.5 1000 Z is.0 100 < eo For vapor pressure in chart form, see front: of this section. Latent Heat POU/tb. ‘Rem. Latent ‘Temp Latent sae Heat fo. Heat 50 The5 0 66.5 60 73.0 120 65.0 70 72.0 130 63.5 80 a0 ako 62:5 90 69.0 150 61.0 100 68.0 Specific Heat: No data available. Heat of Poljmerization: No mumerical data is available. However, DCD polymerizes readily in a highly exothermic reaction. 8/1/56STANDARD B «P “N&SIBAR” © DICHLOROBUTENE (DC) (1,3-Dicaloro-2-Butene) CHsC1-Ciz © G1-CHy Mol Wt, 123.994 Boiling Point: Melting Point: Gritical Constants: Density: (Liquid) (Gas) Vapor Pressure: Viscosity: (Liquid (Gas ) 128°C te = 36480. (approx.) sae Ibs./eu.ft. -20 hg ° 73.6 20 72.2 ho 70.7 £0 67.8 13 63.9 ° 0.348 100 0.25% 200 0.201 Sc. 10 50 100 128 For vapor pressure data in chart form see front of this section and DG 15.010A. ls./(hr.) (ft.)DICHLOROBUTENE Thermal Conductivity: (higquidy Pou/(hr.) (Sq.ft.) (*c/rt. -20 0.0710 ° 0.0805 ho 0.0970 80 0.108 128 0.122 (cas) ° 0,042 100 0.00805, 200 0.01185, Heat Capacity: “(Specific Heat) _ ° PCU/Ib. (Liquia) 20 0.267 ° 0.277 ko 0.298 80 0.318 128 0.3 e (cas) 0 0.203 100 ov2ha 200 0.276 Latent Heat of Vaporization: Flash Point: - Hazardous Propertie: De is described as @ flammable liquid and a dangerous fire hazard, but bas no toxic properties. From plant experience, it has been learned that DC is a powerful lachrymator anda skin irritant. It has physiological effects somewhat like CD. 8/1/56