RUBBER INDUSTRY February 13 and 15,2013
RUBBER INDUSTRY A. Definition of rubber A tough elastic polymeric substance made from the latex of a tropical plant or made synthetically. Scientists and engineers often use the term "elastomer" to refer to any elastic material such as rubber.
B. Properties of Rubber Rubbers are elastic Rubbers are waterproof. Rubbers are good electrical insulators. Rubbers are resilient and resistant to tearing.
C. History of Rubber RUBBER TIMELINE 1499- Discovery of rubber by Christopher Columbus. 1525- Padre d'Anghieria reported that he had seen Mexican tribespeople playing with elastic balls. 1736-The first scientific study of rubber was undertaken by Charles de la Condamine, when he encountered it during his trip to Peru. 1815- a humble sawyer Thomas Hancock - became one of the leading manufacturers in the UK. He had invented a rubber mattress and through an association with MacIntosh he produced the famous waterproof coat known as the "macintosh". 1820- British industrialist Nadier produced rubber threads and attempted to use them in clothing accessories. This was the time when America was seized by rubber fever, and the waterproof footwear used by the indigenous peoples became a success. Waterproof fabrics and snow-boots were produced in New England. 1832- the Rosburg factory was set up. Unfortunately, cold weather affected goods made from non-vulcanized natural rubber, leaving them brittle and with a tendency to gum together if left in the sun, all discouraging consumers. After a long period attempting to develop a process to upgrade rubber qualities (such as including nitric acid) . 1840- Goodyear discovered vulcanization, quite by accident. 1845- R.W. Thomson invented the pneumatic tire, the inner tube and even the textured tread. 1850- rubber toys were being made, as well as solid and hollow balls for golf and tennis. 1869- The invention of the velocpede by Michaux which led to the invention of solid rubber, followed by hollow rubber and finally the re-invention of the tire, because Thomson's invention had been forgotten Between 1879 and 1882- Bouchardt discovered how to polymerize isoprene obtaining products with properties similar to rubber. 1830- first bicycle tire. 1895- Michelin had the daring idea of adapting the tire to the automobile. Since then, rubber has held an outstanding position on the global market. CHEMICAL PROCESS INDUSTRIES Page 1
RUBBER INDUSTRY February 13 and 15,2013
1928- Walter Diemer invented conventional bubblegum. 1933- Waldo Semon accidentally invented vinyl at BF Goodrich trying to bond rubber to steel. Semon also invented synthetic rubber bubblegum. D. Classification of Rubber a. Natural Rubber b. Synthetic Rubber b.1 vulcanizable b.2 nonvulcanizable c. Reclaimed Rubber D.a. Natural Rubber Natural rubber (NR) is cis-1,4-polyisoprene and, when stretched, the molecules crystallize producing a superior form of reinforcement. Natural rubber contains 6 to 8% nonrubber materials and has an outstanding heat-build up balance. Natural rubbers are also called INDIA RUBBER or CAOUTCHOUC.
MANUFACTURING PROCESS: RAW MATERIAL: Rubber trees 01. Cultivation Rubber trees are not grown directly from seed, for trees thus grown vary greatly in production of latex, and the average yield is low. To obtain trees of high production, buds from high-producing trees are grafted on year-old seedlings. After the bud has sprouted, the top of the seedling is removed, and the shoot from the bud is allowed to replace it. The resulting tree has the properties of that from which the bud was taken. The best budded trees produce up to 2,000 pounds of dry rubber per acre (2,240 kg per hectare). Budded seedlings are transplanted at the rate of about 100 to 150 per acre (250 to 370 per hectare). They grow rapidly, and at about six years of age, when their trunks are about six inches (15 cm) in diameter, they can be tapped. 02. Tapping A shallow, diagonal cut extending about halfway around the trunk is made in the bark. A spout leads from the bottom of the incision to a cup into which the latex drips. Trees are usually tapped every other day. The first cut is begun about five feet (1.5 m) above the ground. In making the next cut, the worker first strip off a layer of coagulated (thickened or solidified) latex and then makes a single cut below the previous incision. By the time the channel nears the ground, bark has grown over most of the upper incisions. Work then begins on the other side of the tree. Thus managed, trees produce for 25 years or longer. CHEMICAL PROCESS INDUSTRIES Page 2
RUBBER INDUSTRY February 13 and 15,2013
The latex is then carried to collection stations where it is strained and a preservative (NH3) is added. 03. Coagulation The rubber is separated by a process known as coagulation, which occurs when various acids or salts are added and the rubber separates from the liquid as a white, doughlike mass, which is then milled and sheeted to remove contaminants and to allow drying. A newer method is to form the coagulated latex into granules by cutting with rotating knives or by shear between two rollers running at different speeds. The granules are dried in mechanical dryers in hours, instead of the days that air or woodsmoke dryers required. Either the dried sheet or granules are compressed into bales weighing 33 kg. Some natural rubber is marketed as latex, concentrated after stabilization with ammonia and centrifugation to about 60% rubber. 04. Softening Rubber must be softened before it can be compounded with various necessary additives. This may be dine with a two-roll mill whose rolls revolve at different speeds, or a mixer in which an eccentrically shaped rotor works the rubber against the walls of the mixer. 05. Mixing After softening, the compounding materials, such as carbon black (for filler), sulfur or sulfur compounds (for vulcanization), vulcanizing accelerator, protective antioxidant, and oil, are mixed either in the same mixer or rolls. Only the smallest factories use roll mixers. The mixers are very large and can only handle a small amount of rubber at one time. A typical mixer may be two stories high, and only handles a batch of about 250 kg. 06. Extruding and molding After mixing, the rubber is shaped into the desired product. 07. Vulcanization Vulcanization leads to a cross-linked thermoset polymer that cannot be softened or melted by reheating to the original melting point. It is important to carefully control the heat vulcanization (140 C or more) to obtain optimum properties in the finished rubber. D.b. Synthetic Rubber D.b.1 Classification of synthetic rubbers Class 1 Elastomers A. Vulcanizable CHEMICAL PROCESS INDUSTRIES Page 3
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01. Diene rubbers 02. Nondiene rubbers B. Nonvulcanizable and other elastomers Class 2 Hard Plastics Class 3 Reinforcing resins Class 4 Paint vehicles Rubbers are further classified and coded from the chemical composition of the polymer chain:
M N O R Q T U Z
Saturated chain of the polymethylene group Nitrogen in the polymer chain, but not oxygen or phosphorus Oxygen in the polymer chain Unsaturated carbon chain Silicon and oxygen in the polymer chain Sulfur in the polymer chain Carbon, oxygen and nitrogen in the polymer chain Phosphorus and nitrogen in the polymer chain
Note: The R class shall be defined by inserting the name of the monomer or monomers from which it was prepared before the word rubber (except for natural rubber). The letter immediately preceding the letter R shall signify the diolefin from which the rubber was prepared. ABR BIIR BR CIIR CR IIR IR NBR Acrylate-butadiene Bromoisobuteneisoprene Butadiene Chloroisobuteneisoprene Chloroprene Isobutene-isoprene Isoprene, synthetic Nitrile-butadiene NCR NIR NR PBR PSBR SBR SCR SIR Nitrile-chloroprene Nitrile-isoprene Natural rubber Vinyl pyridinebutadiene Vinyl pyridinestyrene-butadiene Styrene-butadiene Styrene-chloroprene Styrene-isoprene
D.b.2 MANUFACTURING PROCESS: RAW MATERIALS: oil, coal and other hydrocarbons 01. Monomer production
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a. Butadiene most of it is obtained as a coproduct of the steam cracking of petroleum for ethylene manufacture. TWO PROCESSES: A.One step process or Houdry process n-butane is the feedstock, the catalyst is aluminum and chromium oxides, and the yield of 1,4-butadiene is 57 to 63 percent. The butadiene is not pure enough for polymerization, so it is purified by absorption from the reaction product with cuprous ammonium acetate. B.Two stage process n-butane is converted first to n-butenes, and then using an oxidation-dehydrogenation catalyst plus compressed air or steam, the n-butenes are converted to 1,4-butadiene. b. Styrene- is a monomer for rubber but is mainly used in the production of polystyrene plastics. c. Acrylonitrile is principally made by the Sohio process that treats propylene with air and ammonia in a fluid bed catalytic converter. The effluent is scrubbed in a countercurrent absorber, and the acrylonitrile is purified by fractionation. The yield is about 0.9 kg. per kilogram of propylene fed. d. Chloroprene- the monomer from which neoprene is produced, is manufactured from acetylene and hydrogen chloride. Acetylene is dimerized to monovinylacetylene, which is then reacted with hydrogen chloride to form chloroprene. e. Isobutylene- is recovered from refinery light-end operations by distillation. It is the monomer for butyl rubber. f. Isoprene- may be produced by the dehydrogenation of isopentane. g. Ethylene and proplylene are readily available from refinery light-end cuts or may be produced by the steam cracking of propane or heavier fractions. 02. Polymerization Chains of polymers are created that result in latex or rubber substance. 03. Monomer Recovery The rubber quality and rate of reaction both fall off as polymerization proceeds and it is customary to stop the reaction short of complete conversion to rubber. Recovery of the unreacted monomers and purification is an essential step in economical syntheticrubber production. 04. Coagulation and Drying Ordinary lattices may be easily coagulated by the addition of sodium chloride and dilute sulfuric acid, alum or virtually any combination of electrolyte and dilute acid. The rubbers which result from solution polymerization can be precipitated into crumb form by adding the solution to a tank of hot water under violent agitation, with or without the addition of wetting agents, to control crumb size and prevent reagglomeration. The coagulated crumb is separated from the serum and washed on vibrating screens or rotating filters and dried at appropriate temperatures. Rubber is a difficult material to dry, and care must be taken not to overheat it or otherwise cause its deterioration. Drying times is conventional hot-air apron dryers may be as long as several hours.
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05. Packaging Most rubber is now wrapped in polyethylene film as a 34-kg bale of reasonably standard dimensions. In most cases, it is possible to throw the bale and polyethylene wrapping into the rubber mill or internal mixer, since polyethylene melts at a temperature lower than the usual rubber-processing temperatures. D.b.3 COPOLYMER PRODUCED DURING POLYMERIZATION: BUTADIENE-STYRENE COPOLYMERS- The copolymers of styrene and butadiene that contain over 50% butadiene are known as SBR. The usual monomer ratio is 70 to 75 parts of butadiene to 30 to 25 parts of styrene. USE/S: Latex paint NITRILE RUBBERS- Copolymers of butadiene and acrylonitrile. PROPERTIES: Resistant to oils, solvents, water, salts, aliphatic compounds, soaps and most foods. NEOPRENE-Polychloroprene was developed by Dupont and sold commercially in 1932, first under the name DuPrene, but later as Neoprene. PROPERTIES: Resistant to oxidation, oil and heat. USES: used in automotive parts, adhesives, sealants, and coatings. THIOKOL- A polysulfide type of rubber developed in the early 1920s and was first commercial synthetic rubber produced in the United States. USES: Used particularly in building and caulking ptties, cements, and sealants, and lately for rocket- fuel binders, ablative coatings, and other items requiring ease of application and good weathering resistance. SILICON RUBBERS- Mixed inorganic-organic polymers produced by the polymerization of various silanes and siloxanes PROPERTIES: Outstanding resistance to heat, solubility in organic solvents, insolubility in water and alcohols, heat stability, chemical inertness, high dielectric properties, relatively low flammability, low viscosity at high resin content, low viscosity change with temperature, and nontoxicity. USES: Used for high-temperature applications, in fluids for hydraulics and heat transfer, lubricants and greases, sealing compounds for applications, resins for lamination and for high-temperature resistant varnishes and enamels, silicone rubber, water repellents, and waxes and polishes. BUTYL RUBBER- Copolymer of isobutylene with about 2% isoprene is known as butyl rubber. PROPERTIES: low permeability to gases, inert to oxidation, has better resistance to ageing. USES: use in inner tubes and in linings for tubeless tires, weatherstripping.
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URETHANE RUBBER- The reaction products of certain organic diisocyanates and polyglycols are rubbery products known as polyurethanes. PROPERTIES: high abrasion resistance USES: Useful at high temperatures and with high concentrations of solvents and oxygen or ozone, use in the production of flexible foam and elastic fibers, use in upholstery, mattresses, insulation, vibration damping. HYPALON- results from the free-radical catalyzed reaction of chlorine and SO2 with polyethylene, transforming the thermoplastic polyethylene into a vulcanizable elastomer. PROPERTIES: Extreme resistant to ozone attack, weathering, chemicals and heat. STEREOSPECIFIC RUBBER- POLYISOPRENE AND POLYBUTADIENE- Identical with natural rubber and has the advantages of being of better color, more uniform in quality, faster processing breakdown and mixing, better extrusion and calendaring, excellent mold flow, and controlled molecular weight. ETHYLENE PROPYLENE POLYMERS AND TERPOLYMERS- Copolymers of ethylene and propylene (EPM), made by solution polymerization using a Ziegler-type catalyst, are elastomers but do not contain any double bonds. Thus they cannot be vulcanized but neither are they attacked by oxygen and ozone. D.b.3 RUBBER COMPOUNDING Plasticity, elasticity, toughness, hardness or softness, abrasion resistance, impermeability, and the myriad combinations possible are achieved by the art of the rubber compounder. RUBBER COMPOUNDING AGENT TYPE OF AGENT CHEMICAL COMPOUNDS VULCANIZING OR CURING Sulfur, sulfur monochloride, selenium, tellurium, thiuram disulfide, polysulfide polymers, polymers, p-quinone dioxime ACCELERATORS 2- Mercaptobenzothiazole, benzothiozolyl disulfide, zinc diethyldithiocarbamate, tetramethyl mono- and disulfides, 1,3diphenylguanidine. ACCELERATOR ACTIVATORS Zinc and magnesium oxides, stearic acid litharge, amines, amine soaps. RETARDERS Salicylic and benzoic acids, phtalic anhydride ANTIOXIDANTS N-Phenyl-2-napthylamine, alkylated diphenylamine, acetone-diphenylamine condensate ANTIOZONATES Derivatives of p-phenylene diamine FILLERS Carbon black, clays, silica, zinc oxide, calcium carbonate SOFTENERS AND EXTENDERS Petroleum oils, pine tars and resins, coal-tar fractions. CHEMICAL PROCESS INDUSTRIES Page 7
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BLOWING Sodium or ammonium bicarbonate, diazoaminobenzene, dinitrosopentamethylenetetramine, fluorocarbons, azodicarbonamide nitrosoterephthalimide 2-Napthalenethiol, bis(o- benzaminophenyl) disulfide, mixed xlene thiols Aromatic mercaptans(thiophenols)
CHEMICAL PLASTICIZERS PEPTIZERS
D.b.4 RUBBER FABRICATION 01. CALENDERING OR COATING 02. MOLDING 03. EXTRUDING D.c Reclaimed Rubber Rubber salvaged from tires and other rubber products is used to make hard rubber goods, garden hose, floor mats, and a variety of other rubber goods. The used rubber is shredded and passed under a magnet that removes pieces of metal. The rubber is then processed by either of two methods: The Mark Process The rubber is cooked in a caustic-soda solution in a pressure cooker, or digester, at 375 F. (191 C.) for 12 to 20 hours. This step destroys any fabric that might be in the rubber and softens the rubber itself. Next, the rubber is washed, dried, and screened to remove foreign substances. It is then passed through a series of rollers that reduce it to a paperthin sheet. Finally, the rubber is formed into a roll and sliced preparatory to milling. The Open Steam Process is used to salvage rubber that does not contain fabric. The rubber is ground, mixed with oils and caustic soda, and then placed in pans that are heated with steam. Further processing, beginning with washing and drying.
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MANUFACTURING PROCESS OF MAKING RUBBER
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