e-SBREmulsion

Styrene-Butadiene Rubber

Proprietary process technology

Polimeri EuropaPolimeri Europa – the petrochemicalcompany of Eni – manages the productionand marketing of Basic Chemicals,Polyethylene, Elastomers and Styrenics.

With its 17 production sites throughoutEurope and a widespread sales network,Polimeri Europa can present itself to the intermediates, thermoplastic resinsand elastomers market as a sound andcomprehensive supplier whose key strengthis its integration. From raw materials toproduction plants, from research laboratoriesto technology, through to the interface withthe market which can turn to a single sourcewith the certainty of finding solutions to itsrequirements not only in terms of products,but also in terms of assistance and service. Thanks to the definition of the e-commerceand the logistic portal express, Polimeri Europacan offer to its customers the opportunity to use their tailored made e-shopping and logistics. Saving time and money.

On the basis of its first hand experience,Polimeri Europa can also license its proprietaryproduction technologies aiming to satisfy the even more specific customers needs.

Polimeri Europa’s commitment to quality,improvement and innovation continues, as does its pledge to promote sustainablegrowth with regard to the community and the environment.

POLIMERI EUROPA PRODUCTION TECHNOLOGIESFOR LICENSING

LicensingProprietary process technologiesPhenol and derivativesPBE-1 Zeolite catalyst based Cumene *Phenol, Acetone, Alphamethylstyrene *Isopropyl Alcohol Acetone hydrogenation *Isopropyl Alcohol to Cumene *PBE-1 Zeolite catalystTS-1 Titanium silicalite catalyst based AmmoximationDMC and derivativesDimethylcarbonatevia Carbon Monoxide and Methanol *Dimethylcarbonate / Diphenylcarbonate *PolyethyleneLDPEHDPEEVAStyrenicsPBE-1 and PBE-2 Zeolite catalyst based EthylbenzeneStyrene monomerGPPSHIPSEPSABS continuous mass polymerizationSANElastomerse-SBRs-SBRSBS / SB / LCBRPolybutadiene

Proprietary catalyst technologiesTitanium silicalitePBE-1 ZeolitePBE-2 Zeolite

* Co-licensing in cooperation with Lummus Technology

Introduction to Polimeri EuropaEmulsion SBR technologyEmulsion polymerized styrene-butadienerubber is one of the most worlwide usedpolymers, employed in a large variety ofapplications which significantly contribute to our standards of living as well as inenhancing our quality of life. The unusually wide range of productsachievable by the Polimeri Europaproprietary technology covers all e-SBR field of application like tires, footwears, light coloured mechanical goods, flooring,adhesives, pharmaceutical and food contactarticles, microcellular articles, hoses,conveyor belts, high hardness soles and sheeting, technical goods with highhardness. High Solids SBR Latices, whose mainapplications are in moulded foam, gel andnon-gel carpet foam and stiffness enhancerLatices, are also leading product based onPolimeri Europa proprietary technology.

Basics of Emulsion SBRpolymerizationStyrene and Butadiene monomerspolymerize in the presence of an emulsifier(fatty or rosin acid soaps), an initiatorsystem, a modifier (mercaptan) and water.Initiator agent in case of cold polymerizationis the redox reaction between chelatediron/organic peroxide and sodiumformaldehyde sulfoxilate as reducing agent.The molecular weight distribution isprimarily controlled by addition of mercaptanwhich terminates the growing chains beside initiating the new ones.Polymerization takes then place at the mild conditions typical of emulsionpolymerization, controlling at the same timethe reactants flowrate up to the addition of the shortstop agent – when desiredconversion is reached – which rapidly reactswith free radicals blocking reaction. Residual butadiene and styrene are thenremoved from the shortstopped latice whichis first stabilized by addition of appropriateantioxidant agents and then coagulated by using an inorganic acid and chemical aids to regulate the crumb dimensions. The coagulated crumb is then washed,dewatered, dried, baled and packaged.

NOW AVAILABLE

TECHNICALDATA

Material balance and process economics

Per MT of Oil Extended Europrene® SBR 1712Butadiene (1) + Styrene + Aromatic oilElectricity (2)

Low pressure steam (2)

Cooling chilled water (delta T + 8 °C)Per MT of Dry Europrene® SBR 1502Butadiene (1) + StyreneElectricityLow pressure steamCooling chilled water (delta T + 8 °C)(1) Reject butadiene recovery included. (2) Expected consumption

Expected properties

Oil Extended TypesBound

styrene %Grades ASTM D5775

Europrene® / Intol® 1712 23.5

Europrene® / Intol® 1778 23.5

Dry TypesBound

styrene %Grades ASTM D5775

Europrene® / Intol® 1500 23.5

Europrene® / Intol® 1502 23.5

Europrene® / Intol® 1509 23.5

TREAD (NR/BR/SBR)Ease of extrusion, Abrasion resistance, Low rolling resistance, Skid resistance

The Europrene® e-SBR randomcopolymers properties and portfolioEmulsion SBR is available in a range of Mooney viscosities, with 1500 seriesdisplaying some properties like easierincorporation of fillers and oil, less heatgeneration during mixing, higher extrusionrates and extrudate superior appearancewhile 1700 series have better green strength and higher acceptance of filler and oil loadings.

Increase in molecular weight strengths the vulcanizate resilience and mechanicalproperties while SBR processabilityimproves when molecular weight distribution broadens. Processability is also affected bypolymerization temperature leading to less chain branching at low temperaturecompared to the high temperature. The emulsifier system also affects rubberproperties as polymer emulsified with 100% Rosin acid gives better extrusionrates, slower cure rates and higher tack of the green compound while the use of 100% Fatty acid gives faster curing and high tensile properties. The emulsifier system is then usually a blend of Fatty and Rosin acid.

Industrial applicationsPolimeri Europa is one of the majorindustrial producer of Emulsion SBR with two industrial units, in Italy and UK.The Italian plant is on stream since 1957based on a 120 kt/y capacity of Europrene®

while the one in UK reaches a 75 kt/ycapacity of Intol®.SBR latices, low – and high solids, havebeen producing in Italy based on a 25 kt/ycapacity, of Europrene Latice® and in U.K.based on a 40 kt/y capacity of Intex®, bothon a dry basis. HSR (High Styrene Resins)are also produced in Italy as Europrene HS®.

950 kg430 kWh2,400 kg

290 m3

930 kg470 kWh3,000 kg

350 m3

related to reaction, monomer recovery and finishing sections only.

Mooney viscosity OilML (1+4) 100°C Type p.h.r.

ASTM D1646 ASTM D5774 Emulsifier Coagulant Stabilizer Main applications

51 Highly 37.5 Fatty-rosin Acid + Non staining Tyres, retreading, conveyor belts, Aromatic acid chemical hoses, mechanical goods

aids

49 Naphthenic 37.5 Fatty-rosin Acid + Non staining Footwear, flooring, acid chemical microcellular articles, hoses,

aids light coloured goods

Mooney viscosityML (1+4) 100°C

ASTM D1646 Emulsifier Coagulant Stabilizer Main applications

52 Rosin Acid + Non staining Tyres, retreading, conveyor belts, hoses, acid chemical mechanical goods

aids

52 Fatty-rosin Acid + Non staining Tyres, footwear, sheeting, light coloured mechanical goods, acid chemical flooring, adhesives, pharmaceutical and food contact articles

aids

33 Fatty-rosin Acid + Non staining Footwear, microcellular soles, acid chemical injection moulding, carpet underlay,

aids extruded and calendered goods

Process descriptionThe Polimeri Europa e-SBR technology isbased on a continuous polymerization reactioncarried out through a series of reactors up tothe desired reactants conversion is reached.Butadiene and Styrene monomers and demiwater are first emulsified and pre-cooled, thensolutions of catalyst, modifier and activatorare added to the mixture before entering thefirst reactor. Each reactor is equipped withevaporating ammonia cooling coils allowingthe selection of polymerization temperatureaccording to the desired product grade.Reaction is stopped in the last working reactorby shortstopper addition (catalyst & chemicalsused are all available in the open market). The emulsion is then discharged into laticeblow down drums and unreacted Butadiene isrecovered through a two steps flash – the firstone at atmospheric pressure and the next oneunder vacuum – submitted to compressionand condensation and then recycled to themonomer storage section. Latice is first pumpedto the styrene stripping tower – whereunreacted styrene is recovered by directinjection of L.P. steam – recovered as bottomproduct and then pumped to finishing section.OVHD vapours are condensed and sent to thewater/styrene decanter. Styrene is first cooledand then recycled to recycle styrene tanks.The uncondensed vapours containing mainlybutadiene are sent to liquid ring vacuum pumpsto be recovered while water from decanter isfully recycled to reaction, greatly reducing the environmental impact of the process. Storage and blending tanks for Latice displaysufficient hold up to allow stopping thefinishing section when product grade changes.Finishing section is then fed by Latice,antoxidant and extended oil (in case) whichcoagulate in a series of stirred vessels with a vibrating screen which separates rubbercrumbs from water, sending them to thewashing tank and then to the dewatering unit.Water content in SBR is reduced by means ofa continuous hot air belt dryer (Apron dryer)and air is recycled by means of air blowers.The rubber is then fed to the balers, passesthrough a metal detector and finally the balesare wrapped by a PE film. It is worth to note that a secondary ammoniaservice can be added to the plant to producechilled water for the plant cooling devices.

Process design advanced features• High polymerization conversion reduces

monomers and utilities consumptionsleading to both high productivity andprocess capability.

• Lower dimensions of recovery sectionleads to lower capital investment.

• Rejected monomer quantity is reducedthanks to a specific section design,integrated with upstream plants, allowingreduction of slop quantity. Polimeri Europais able to design this recovery sectionbased on both client needs as well as siteconditions. Possible technical options arethe recycle to butadiene extraction unit,new recovery/distillation section or LPsteam generation.

• The wide range of products grades coupledwith a real process know-how enablesmeeting the specific needs of the customer.

• High capacity and flexibility allowproduction, in the same continuousreactors train, of base Latices blendablewith batch or semibatch latices to producea HSR/HSL grades (1) and SBR latices.

• All the enviromental issues coming fromgaseous effluents, liquid effluents, waterconsumption and solids effluents havebeen deeply considered in the design baseof each process stage, according to thebest available technologies as well as to theIISRP suggestions to the E.U. Authorities.Significative examples are given below:Water recycle All the watery phaserecovered after the Latice stripping arerecycled to reaction, no water streams fromreaction or monomer recovery to CWWT.VOC captation Vapour streams fromreaction and recovery areas are connectedto flare system also for maintenanceoperations (low emission factors).

• High valuable technical assistance is givento the customer by Polimeri Europa R&Dstructure, whose long experience and knowhow on small, medium and large size pilotplants really supports new e-SBR Producerentering the market.

(1) Polimeri Europa can offer Hot Latices technology (batch or semibatch) whose products are blendable with e-SBR Latices giving High Solids Latices (HSL) and High Styrene Resins (HSR) materials with increasedstyrene content.

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By products

Products

Polimeri Europa SpAA subsidiary of Eni SpASole shareholder company

Head Office Piazza Boldrini, 120097 San Donato Milanese (Milano) – Italyt +39 02 520.1info@polimerieuropa.comwww.polimerieuropa.com

Licensing Piazza Boldrini, 120097 San Donato Milanese (Milano) – Italyt +39 02 520.32883f +39 02 520.32077info.licensing@polimerieuropa.com

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