Premise : Classification of organic chemicals by:

1. Lecture Topic 3: Industrial Organic ChemistryRef: “Organic Building Blocks of the Chemical Industry”, by H.H. Szmant“Industrial Organic Chemistry”, by K. Weissermel and H.-J. Arpe Premise: Classification of organic chemicals by: • COST and PRODUCTION VOLUME • BUILDING BLOCKS derived from Goal: Ability to 1. identify bulk, fine and specialty chemicals 2. give examples of primary building blocks and of C1, C2, C3, C4 and higher acyclic and cyclic organic building blocks 3. trace the manufacture of a common chemical from primary sources to final products

2. Which ge do we live in ? (A brief history of organic chemistry) 1850- Plants, Animals 1850+ Coal Tar (side product of “coal gasification”) 1920+ Acetylene (from CaC2, Reppe Chemistry) 1950+ Ethylene (from oil) 1973+ CH4, CO/H2 (syngas) Future: CO/H2 from Coal, exothermic (~400 years) CO2 fixation via: • Plants, Animals (endothermic) • CO2 fixation (endothermic)

3. Flavours, fragrances Dyes FineChemicals Specialties Commonplastics Pseudo-commodities Resins, Elastomers Commodities Primaryorganicbuildingblocks Cost vs. Demand in the Chemical Industry >100 Medicinalsandotherspecialties 10 1 Unit cost ($/lb) Organicintermediates 0.1 Inorganicheavy chemicals 0.01 1011 107 105 106 108 109 1010 1012 Demand (lb/y)

4. Product life cycle # of products Product volumes Product prices Product differentiation Value added Capital intensity R&D focus  – – Organic Chemical Industry Characteristics INDUSTRY CHARACTERISTICS BULK CHEMICALS FINE CHEMICALS SPECIALTY CHEMICALS Long Moderate Short/moderate > 100 >1,000 >50,000 >10,000t/y <10,000t/y highly variable <5 $/kg >5 $/kg >10 $/kg none very low high low high high high moderate moderate/low process process application KEY SUCCESS FACTORS   • cost • technical service   • links with customer  

5. Example of a Specialty Chemical E.g., a heat-stabilizer additive for flexible PVC film Could be a mixture of: Zn and Ca stearates triisononyl phosphite epoxidized soybean oil Could be formulated as a liquid concentrate with a minimal amount of di(2-ethylhexyl)phthalate. The producer keeps the exact identities and proportions of the metal soaps, phosphite esters, epoxidized oils, and plasticizers secret, giving the customer only the proportions of additive to be used per 100g of resins.

6. What is meant by a “Building Block”? A building block is any (organic) chemical that can be used to synthesize other (organic) chemicals. • There are very few truly primary, large-volume organic building blocks. • These are all obtained more or less directly from: • petroleum refining • natural gas • coal • ammonia • carbon dioxide • renewable resources

7. Primary, Secondary, and Tertiary Organic Building Blocks that are in the Top 50 Chemicals in the U.S. Economy Primary Building Blocks Secondary BBs Tertiary BBs Ethylene ethylene dichloride vinyl chloride ethylene oxide ethylene glycol ethyl benzene vinyl acetate Propylene propylene oxide acrylonitrile isopropyl alcohol cumene acetone n-butyl alcohol Benzene ethyl benzene styrene cumene phenol acetone bisphenol A Methanol acetic acid vinyl acetate formaldehyde MTBE Toluene Xylenes terephthalic acid Butadiene Urea

8. A Closer Look at the Principle Sources of Primary Organic Building Blocks Boiling pt. Natural Gas: methane (85%) -161.4°C ethane (9%) -88°C propane (3%) -42°C butanes (1% -0.5°C nitrogen (1%) Liquid petroleum gasses (LPGs) Crude Petroleum : LPGs light naphtha or straight-run gasoline 50-100°C heavy naphtha ( C10) 150-200°C kerosene, jet fuel ( C16) 175-275°C gas oils, diesel fuel ( C25) 200-400°C lubricating oils 350+°C light fuel oil, heavy fuel oil, bunker oil residue: asphalt

9. Coal is used as: fuel (electric power plants, etc.) precursor of coke (crude form of elementary C) source of syngas (synthesis gas)

10. C1 Chemistry C1 building block Source Use CH4 (methane) Natural gas energy, H2, CO, CH(4-x)Clx CO (carbon monoxide) Coal (as Syngas) CH3OH, HCOOH, esters, amides, Oxo acids, etc. CH3OH (methanol) CO + 2H2 H2CO, MTBE, CH(4-x)Clx, Cracking of C3H8, C4H10 CH3COOH H2CO (formaldehyde) CH3OH, Cracking of LPG Polymers (UF, PF, POM) HCOOH (formic acid) CO + H2O Fine chemicals CO2 (carbon dioxide) Water-gas-shift rxn. Supercritical fluids (SCFs) CS2 (carbon disulfide) S8 + Coke or CH4 Cellulosics, M+SCN–, thiourea Cl2CO (phosgene) CO + Cl2 R-C=N=O for polyurethanes (H2N)2CO (urea) NH3 + CO2 Fertilizer, Resins (UF) HCN (hydrogen cyanide) HCONH2 - H2O Methacrylonitrile, ClCN byproduct (acrylonitrile)

11. C2 Chemistry C2 building block Source Use CH2=CH2 (ethylene) thermal cracking of natural Feedstock for ~30% of all gas, refinery gas, crude oil petrochemicals!! Polymers (Polyethylenes etc.) Alphaolefins (LDPE), PVC Polystyrene, Polyvinyl acetate Polyethylene oxide CH3CH2OH (ethanol) fermentation, Gasoline additive (USA), hydration of ethylene Ethylene by dehydration (Brazil, India, Peru, Pakistan), Solvent, Esters (ethyl chloride, ethyl acetate) CH3CH=O (acetaldehyde) Wacker-Hoechst (ethylene) CH3COOH, Acetic anhydride, Monsanto process (MeOH) Peracetic acid CH3C(=O)OOH, Aldol condensation products CH3COOH (acetic acid)& Monsanto process (MeOH) Vinyl acetate (PVA), Cellulose CH3COOCOCH3 (acetic Oxidation of C4-C8 hydro- acetate, Solvent, Acetate salts, anhydride) carbons or acetaldehyde Chloroacetic acids HCCH (acetylene) Coal via CaC2 or 1,4-Butanediol, vinyl acetate from hydrocarbons

12. C3 Chemistry C3 building block Source Use CH3CH2CH3 (propane) LPG Propylene, energy CH3CHCH2 (propene) Thermal cracking of LPG, Polypropylene, Acrylonitrile, natural and refinery gas Oxo products (butyraldehyde, butanol, etc.),Propylene oxide Isopropanol, Cumene, Oligomers (nonene, dodecene, heptene) CH3COCH3 Hock process (coproduct) Methyl methacrylate, Methyl (acetone) Isopropanol (dehydrogen’n) isobutyl ketone, Bisphenol A, Wacker-Hoechst (propene) Aldol condensation products, Solvent CH3CH2COOH CH2CH2 (hydroformylation) Food preservative, Amyl and (propionic acid) Vinyl propionate, Herbicides

13. C4 Chemistry C4 building block Source Use C4H10 (butanes) LPG 1-Butene, Maleic anhydride, MTBE, thiophene C4H8 (butenes, isobutene) Cracking of Cn4 Polymer/alkylategasoline, Polymers/copolymers, alcohols C4H9OH (butyl alcohols) Propene, acetaldehyde MEK, Solvent, Fuel additive CH3(CH2)2CHO Propene, acetaldehyde 2-Ethylhexanol, Trimethylol- (butyraldehydes) propane Maleic anhydride Oxidation of C4-feedstocks Unsaturated polyester resins, Benzene (V2O5 catalyst) Fumaric acid, Pesticides HO(CH2)4OH Acetylene poly(1,4-butylene terphthalate) (1,4-butanediol) 1,3-butadiene THF, H2N(C4H8)NH2 H2C=CHCH=CH2 Cracking of Cn4 Elastomers (i.e., synthetic (1,3-butadiene) rubbers), Chloroprene, THF

14. C5 and Higher Acyclic Building Blocks Primary Building Blocks Source(s) Use Petroleum: CnHn+2 (n5) Fossil fuels Solvent, Fuel, Lubricant, (pentanes, hexanes, heptanes, etc., Alkylbenzenes, Alcohols, and other n-paraffins) Chlorinated paraffins, Lower m.w. alkanes/olefins Mineral waxes: Ozocerite, Fossil fuels Coatings Montan wax (lignite) Fatty Acids: Lard, Tallow, Palm Renewable PVC stabilizer, Surfactant, oil, Corn oil, Castor oil, etc. (animal/plant) Glycerine, Methyl laurate, Fatty amines (antistatic agents) Tall-Oil Fatty Acids (TOFA) Renewable Fuel in pulping operations, (pulp byproduct) Dimer/trimer acids for coatings Terpenes Renewable Fragrance/flavour “essential” (plant) oils, Turpentine Fermentation Products: Renewable H2S removal from refinery gas, amyl alcohols, carboxylic acids, (plant) Food industry, Pharmaceuticals, Monosodium glutamate (MSG) Laundry products, etc.

15. Cyclic Building Blocks - Aromatics Building blocks Source Use Benzene Coal, Oil, Petroleum Ethylbenzene (for styrene), C6H6 (thermal/catalytic process) Cumene (for phenol/acetone), Cyclohexane, Nitroenzene Toluene Coal, Oil, Petroleum Solvent, Benzoic acid, Phenol, C6H5CH3 (thermal/catalytic process) Nitrotoluenes, aminotoluenes Xylenes Coal, Oil, Petroleum Phthalic acids and anhydrides C6H4(CH3)2 (thermal/catalytic process) (plasticizers, synthetic fibers) Cumene C6H5CH(CH3)2 Benzene Hock process (phenol/acetone) Phenol C6H5OH Cumene (Hock process) Phenol resins, Bisphenol A, Benzene, Toluene, ε-Caprolactam Cyclopentadiene C5 cracking fractions, Polymers (for resins, contact Coal tar adhesives, printing ink resin) Cyclohexane Crude gasoline, Cyclohexanone (feedstock for Benzene (hydrogenation) nylon precursors)

16. Cl2 Allyl chloride Propylene Ethylene Vinyl chloride monomer Cl2 CO2 Cl2 Phosgene • Structural adhesives • Structural sealants • Primer paints Epichlorohydrin Epoxy resin • Electrical insulation • Fiber reinforced plastic composites Bisphenol A or Brominated Bisphenol A BTX • Dashboards • Electrical insulation • Vinyl tops • Floor mats • Upholstery Vinyl • Modular window frame units • Body side moldings • Molded armrests • Exterior & interior trim • Tires • Rubber hoses • Foam for seats • Caulks & sealants • Bumpers & fenders Polyurethanes Polyisocyanates

17. Aspirin

18. Origin of the Other Reagents Cu Mined as an ore and refined Pd Mined and refined (Sudbury, Ontario: “anode slime”) H2SO4 H2O + 0.5 O2 + SO2 pyrometallurgical byproduct O2 Fractional distillation of liquid air Acetate Acetic acid Methanol + CO (Monsanto process) NaOH Electrolysis of brine (NaCl + H2O) “chloralkali cell”

19. Hydroformylation (“Oxo Process”