Plastics Dutch merchant ships English banking and insurance Tar & pitch Coal tar and coal gas Malaria/artificial dyes Chemical industry Polymers.

Plastics• Dutch merchant ships

• English banking and insurance

• Tar & pitch

• Coal tar and coal gas

• Malaria/artificial dyes

• Chemical industry

• Polymers

1595- Dutch Fluyt

• Designed by merchants for trade.

• Longer, fatter with lots of block/ & tackle

17th - Britain Goes Dutch

• Sharing costs and risks to better compete with the Dutch.

• Coffeehouse banking

• Established Bill of credit in 1683.

• Nag’s head tavern in 1684 became the Bank of England.

Lloyd’s Of London

• 1688 Edward Lloyd opened his coffeehouse where insurance could be bought and sold.

• In 1700 he began publishing a list of ships, rating their seaworthiness.

Tar & Pitch for boat hulls

• Most came from Scandinavian and Baltic pine. Anaerobic heating to produce Tar and Turpentine.

• Necessary to protect boat hulls and for better insurance rating.

• Baltic war disrupted supply so went to American colony until 1776.

Tar & Pitch from Pine Trees

Anaerobic decomposition of pine yielding charcoal, tar/pitch, oils, and turpentine

Making Tar & Pitch

Coal Tar

• Archibald Cochrane, Earl of Dundonald, extracted coal tar and coal gas via anaerobic decomposition of coal.

• His coal tar was intended to replace wood tar from the colonies. Except the navy went to copper bottoms.

Coal + heat coal gas + coal tar + water + coke

Coal Decomposition Products

gases

Coal

Coke; 70% by mass

Coal gas; 17%

Lighting The Factories

• Murdock, an associate of James Watt received patent for coal gas lighting.

• He introduced gas lamps, which were brighter, safer and cheaper than candles.

Lighting The Streets

• Winsor, promoted municipal coal gas.

• Soon cities began piping coal gas throughout the town and lighting the streets.

• Night time streets became safer thus evening activities increased.

What To Do With All That Coal Tar Waste

• Macintosh sought coal tar waste as a cheap source of ammonia mordant for natural dyes.

• He subsequently extracted naphtha to clean his dyeing machines and dissolve rubber to make waterproof fabrics.

Today’s Fractional Distillation

At the RefineryIn the Laboratory

Trilaminates

• Macintosh made a waterproof trilaminate by dissolving rubber in naphtha, spreading it on a layer of fabric and gluing another fabrics to it.

Malaria A Problem In British Far Eastern

Colonies• Cinchona plant extract called quinine was treatment for malaria.

• Cinchona, native to S. America would not survive a transplant in Asia.

W.H. Perkins Discovers Artificial Aniline Dyes

• 1856 he accidentally made first synthetic dye while trying to isolate Quinine from coal tar and began production in England.

• He closed his British factory in 1870.

Britain Lost Its Lead

• Investors and banks saw investing in color chemistry to be too risky.

• Going to college to get a job in England was considered “lower class” to aristocrats. They were too embarrassed to profit from their education.

Germany’s University/Industry

Reciprocity• In 1870, Germany began the first large-scale chemical companies: BASF, Hoechst, Bayer, etc.

• The German economic boom caused a wheat crises.

• Shortage in Sodium Nitrate fertilizer led to Haber/Bosch process

N2 (g) + 3H2 (g) 2NH3 (g)

Reactants Products

Nitrogen + Hydrogen Ammonia

Making Synthetic Diamonds

• Henri Moissan accidentally discovered Calcium carbide:

• CaC2 (s)+ 2H2O C2H2 (g)+ Ca(OH)2(aq)

• Because acetylene lamps were brighter by 1899 acetylene gas jets were throughout Germany.

Gas Mantle and Cheap Electricity

• 1905 gas mantle & cheap electricity replaced acetylene.

• BASF using cheap CaC2 to fix nitrogen for fertilizer. Containing 20% nitrogen.

• War shortage of NaNO3 led back to Haber/Bosch for explosives.

NH3 + 2O2 HNO3 + H2O Ammonia + Oxygen Nitric acid + Water

Fritz Klatte

• Working with the cheap acetylene, HCl and Hg made a useless milky sludge later refined to PVC.

• HCl + C2H2 C2H3Cl PVC

• Actually Henri Victor Regnault made PVC first around 1835.

acetyleneVinyl chloridepolyvinylchlorideHydro-chloric acid

1846 Christian Schoenbein

• Accidentally discovered nitrocellulose (guncotton) which found immediate use as an explosive and later the first thermoplastic.

• Later in 1906 Leo Baekeland discovered the first thermoset, phenol formaldehyde resins.

Cellulose & Nitrocellulose

Nitrocellulose

Natural or Biopolymers

• DNA• Protein

– Wool, Silk, Leather

• Cellulose– Wood, Cotton, Hemp

• Terpenoids– Rubber (polyisoprene)

DNA

Guncotton

Polymers• “Many units”• Condensation polymers are monomers A and B combined in a head and tail fashion making a continuous chain ABABABABABAB…… Such as nylon or polyethylene terephthalate (PET).

• Addition or homopolymers usually come from one monomer A reacting with itself, like AAAAAAA….. Such as PVC, Polyethylene, Polypropylene, Polystyrene, Polyisoprene.

Plastics From Coal and Petroleum

• Petroleum and coal is the raw material for most all synthetic polymers (plastics).

• Monomers are chemically modified derivatives from extracts of these sources.

Thermoplastics• These polymers are thermally moldable. That is, when warmed, they soften or flow like fresh spaghetti so they can be extruded or molded into shape.

• These types of materials are inherently recyclable.

Thermoplastics & UsesThermoplastic UsesPolyethylene (PE) Bags, milk

containers

Polystyrene (PS) Disposable eating utensil

Acrylic (PMMA) Optics, coatings

Polyvinyl chloride (PVC)

Plumbing, flooring

Polyethylene terephthalate (PET)

Beverage containers

Polypropylene (PP)

Rope, composites

Thermosets

• These materials are not thermally moldable, instead they are thermally “set” & not recyclable.

• They typically can not be unset. These are highly cross-linked polymers such as epoxies or urea-formaldyehydes, unsaturated polyester resins or highly cross-linked thermoplastics like PE.

Cross-lined Polymers

Polymer Structures

HDPE LDPE Epoxy

Crystalline“Opaque”

Noncrystalline“Clear”

Composite Materials

• There are mixtures of different materials engineered for specific functions. Such as fiber reinforced plastics (FRP)

• Filled plastics contain a filler such as calcium carbonate to make such materials as synthetic marble or onyx.

What you should know

• Differentiate Dutch Fluyt & Galleon

• Bill of credit• Coffeehouse banking

• Connection between insurance and boat hulls

• How tar and pitch was produced

• Slide #2 & B191• #4 & B193• #4-5• #5-6 & B194-195

• #6-7 & B195

What you should know

• What is “soho stink.” • How did coal gas change life in Europe

• How Macintosh made waterproof fabric.

• Why, the British let slip their lead in color chemistry to Germany

• Where natural sodium nitrate came from.

• Ammonia from coal tar #10 & B198

• #11-12 & B200• #14-15

• #16-18 & B206

• Chile

What you should know• What triggered Germany to synthesis Sodium nitrate, NaNO3

(s) and how was it made?

• Connection between wheat crises, artificial diamonds and fertilizer.

• How was acetylene made and why did it have a short life as a lamp fuel.

• #19 & #22 for fertilizer

• #20-22 & B209

• #20-21 & B209-210

What you should know

• What triggered Germany to synthesis Sodium nitrate, NaNO3 (s) and how was it made?

• Connection between wheat crises, artificial diamonds and fertilizer.

• How was acetylene made and why did it have a short life as a lamp fuel.

• #19 & #22 for fertilizer

• #20-22 & B209

• #22 & B209-210

What you should know

• What is a polymer?• Differentiate between natural and synthetic polymers

• Differentiate between thermoplastics and thermoset plastics

• A long chain of molecules

• Natural polymers come from living things, ie. Silk, wool, cotton, leather

• #31-35 thermosets are highly cross-linked