SBS

Styrene-Butadiene
block copolymers
Proprietary
process technology
POLIMERI EUROPA PRODUCTION TECHNOLOGIES NOW AVAILABLE
FOR LICENSING

Polimeri Europa Licensing

Polimeri Europa – the petrochemical Proprietary process technologies
company of Eni – manages the production Phenol and derivatives
and marketing of Basic Chemicals, PBE-1 Zeolite catalyst based Cumene *
Polyethylene, Elastomers and Styrenics. Phenol, Acetone, Alphamethylstyrene *
Isopropyl Alcohol Acetone hydrogenation *
With its 17 production sites throughout Isopropyl Alcohol to Cumene *
Europe and a widespread sales network, PBE-1 Zeolite catalyst
Polimeri Europa can present itself TS-1 Titanium silicalite catalyst based
to the intermediates, thermoplastic resins Ammoximation
and elastomers market as a sound and DMC and derivatives
comprehensive supplier whose key strength Dimethylcarbonate
is its integration. From raw materials to via Carbon Monoxide and Methanol *
production plants, from research laboratories Dimethylcarbonate / Diphenylcarbonate *
to technology, through to the interface with Polyethylene
the market which can turn to a single source LDPE
with the certainty of finding solutions to its HDPE
requirements not only in terms of products, EVA
but also in terms of assistance and service. Styrenics
Thanks to the definition of the e-commerce PBE-1 and PBE-2 Zeolite catalyst based
and the logistic portal express, Polimeri Europa Ethylbenzene
can offer to its customers the opportunity Styrene monomer
to use their tailored made e-shopping GPPS
and logistics. HIPS
Saving time and money. EPS
ABS continuous mass polymerization
On the basis of its first hand experience, SAN
Polimeri Europa can also license its proprietary Elastomers
production technologies aiming to satisfy e-SBR
the even more specific customers needs. s-SBR
SBS / SB / LCBR
Polimeri Europa’s commitment to quality, Polybutadiene
improvement and innovation continues, Proprietary catalyst technologies
as does its pledge to promote sustainable Titanium silicalite
growth with regard to the community PBE-1 Zeolite
and the environment. PBE-2 Zeolite

* Co-licensing in cooperation with Lummus Technology

Introduction to Polimeri Europa Versatile tuning of final product properties
SBS technology can be easily obtained by mixing with other
SBS copolymers made by styrene and polymers, oil and fillers allowing wide
butadiene linked homopolymer blocks product applications, ranging from enhancer
belong to the class of thermoplastic of bitumen performance in road paving
elastomers (TPE) whose elastic behaviour and roofing applications (particularly under
– the properties to change and recover the extreme weather conditions), through
shape when a force is first applied and then adhesives, sealants, coatings, footwear
removed – and thermoplastic behaviour – up to compounds able to enhance grip,
the property to become soften, viscous feel, and appearance properties in toys,
and free-flowing like a liquid when heated automotive, personal hygiene, and
and return solid when cooled at room packaging goods market.
temperature – are joined together in the Polimeri Europa SBS technology is
same material. well-known for its high flexibility in tailoring
The elastic/rubbery and thermoplastic/viscous the different product grades required by
behaviours are displayed at room and high the SBS market which is characterized
temperatures respectively allowing the by a continuous product innovation
fabrication of TPE goods having the same to meet new application requirements.
rubbery feeling than traditional vulcanized Polimeri Europa SBS technology allows
rubbers, but considerably less expensive then competitive production of the most
in manufacturing process due to the full common SBS grades, as well as additional
recyclability of scraps, the shorter cycle time grades for special applications.
and the easier process automation/robot Such portfolio of products is continuously
assistance. This balance between properties improved by our R&D centers through
and processability leads SBS based material market feedback.
focusing on unique applications instead
of only replacing general-purpose rubber.
TECHNICAL DATA

Material balance and process economics

Per MT of Oil Extended SBS

Butadiene + Styrene + Paraffinic oil extensor 1,003 kg
Solvent make up 10 kg
Electricity 510 kWh
Steam (medium pressure + low pressure (1)) 4,500 kg
Cooling water (delta T + 8 °C) 200 m3
Per MT of Dry SBS
Butadiene + Styrene 1,001 kg
Solvent make up 10 kg
Electricity 510 kWh
Steam (medium pressure + low pressure (1)) 5,000 kg
Cooling water (delta T + 8 °C) 200 m3
(1)
10 barg and 6 barg respectively.

Industrial applications
Polimeri Europa is currently one of the
major industrial producer of SBS polymer.
Two industrial units worldwide, in Italy
and US, are currently based on proprietary
SBS technology.
The Italian plant is on stream since 1970
based on a current 90 kt/y capacity,
which has been reached throughout two
plant revampings, in 1991 and in 2001.
The US plant is on stream since 1992
based on a current 45 kt/y capacity;
since 2003 this plant is no longer property
of Polimeri Europa.
Expected properties

Oil Extended Types

Block Oil % Diblock Melt flow Hardness (3)
styrene % w/w Mw/1000 content % index (2) Shore A Physical
Grades ASTM D5775 ASTM D5774 Structure MA 02225 (1) MA 02225 (1) ASTM 1238 ASTM D2240 form (4) Main applications

Europrene® SOL T 172 30 31 Radial 165 <10 9 43 PL Footwear, polymer modification and
plastic recycling, technical goods
Europrene® SOL T 177 50 28,5 Radial 145 <10 15 86 PL Footwear, high hardness
sheets and soles
Dry Types
Block Diblock Brookfield Melt flow Hardness (3)
styrene % content % Mw/1000 viscosity index (2) Shore A Physical
Grades ASTM D5775 MA 02225 (1) Structure MA 02225 (1) cPs (5) ASTM 1238 ASTM D2240 form (4) Main applications

Europrene SOL T 161 B

®
30 10 Radial 240 20,000 <1 82 G, P Bitumen modification for roofing
and road paving
Europrene® SOL T 166 30 10 Linear 70 1,300 6 72 PL Moulded and extruded goods,
polymer modification, adhesives
Europrene® SOL T 6302 30 12 Linear 110 4,000 <1 80 G, F, P Bitumen modification for roofing
and road paving, compounding
(1) (3) (5)
Internal method. Values obtained on compression moulded specimen. Toluene solution, 25% by weight.
(2) (4)
Modified P conditions (5 kg, 190 °C). PL = pellets; G = granules; F = fluffy granule; P = powder.
Basics of SBS polymerization Alternatively the addition of a coupling agent
Styrene butadiene triblock copolymers having a functionality of three or more leads
are obtained by anionic polymerization to the formation of radial triblock SBS
initiated by lithium alkyls in cycloaliphatic copolymer, whose number of SB arms
media as solvent; main features of this depends on the structure of the
class of anionic chain polymerization polyfunctional coupling agent. When styrene
is the livingness, i.e. the ability of polymeric is added instead of the coupling agent we
chain ends to survive even when monomer refer to SBS three stages polymerization
is completely depleted and to reinitiate leading always to linear SBS copolymer.
the polymerization reaction when monomer Finally a terminating agent must be added
is newly added. in order to terminate the active chain-ends.
Due to the absence of termination reactions, The chemical residuals from terminating or
polymer active chain-ends do not inherently coupling reactions must be inactive towards
terminate, continuously growing up to the antioxidant in order to avoid yellowness
complete monomers depletion, which in of SBS copolymer. Based on the above it
turn means that average polymer molecular comes that linear SBS can be obtained from
weight can be really predicted from the both the three stages one polymerization
amount of starting material and the quantity process as well as from the two stages,
of initiator. while radial SBS can be only obtained from
Flexibility is the peculiar aspect the two stages polymerization process.
of this polymerization technique which When polymerization reaction of butadiene
allows, under appropriate conditions, and styrene is carried out at the same time
the production of thermoplastic elastomers in batch reactor, a SB type copolymer is
differentiated by composition (in styrene), obtained. In this case polibutadiene and
molecular weight and structure, ranging polystyrene blocks join together through
from pure triblock, both linear and star a portion of polymeric chain (tapered
copolymers, to tapered diblock. junction) in which a progressive variation
Three main synthetic methods are employed. of composition is observed.
In the two stages polymerization the living The consequent lack of the second block
styrene-butadiene diblock copolymer of polystyrene does not allow the mechanical
becomes a linear triblock SBS copolymer properties of pure triblock copolymers,
by subsequent addition of a difunctional but enhances other useful properties
coupling agent, whose relative amount for adhesives applications and bitumen
can be varied to obtain different yields of modifications.
coupled SBS and uncoupled SB polymers.
 Amount of Styrene in S-B-Blockcopolymers

<15%

15-35%

The Europrene® SBS block copolymer The Polimeri Europa proprietary SBS
properties and portfolio technology allows the production of
Material properties are mainly dictated by the many grades of Dry and Oil Extended
ratio between polystyrene and polybutadiene polymers, mainly characterized by a
amounts as well as by the molecular weight different percentage of styrene block as
of the homopolymer blocks. At microscopic well as by different linear or radial
scale, low styrene content elastomers show molecular structures.
a morphology of spheres with dimensions The following tables give to our potential
35-65%
of 300-350 angstrom dispersed in a rubbery customers a picture of different typical
matrix while the progressive increase of properties and applications for some
styrene content leads polystyrene spheres to Dry and Oil Extended product grades
change into cylinders and then into lamellae. affordable by using Polimeri Europa
A further increase in styrene content turns proprietary SBS technology.
the material into a plastic matrix in which All polymer grades are stabilized with
the dispersed elastomer gradually changes a specifically designed antioxidant
from cylinders up to spheres. package.
The material then behaves as a vulcanised
elastomer at low styrene content, when
65-85%
the elastomeric phase is the continuous
one, while impact resistance properties
predominate at low butadiene content,
when the polystyrene phase becomes
the continuous one.
A proper pre-definition of both molecular
weights and molecular weight distribution
of the blocks, as well as their purity, avoids
the progressive worsening of the mechanical
characteristics due to poor phase separation.
>85%
Prevention of unwanted broadening of
molecular weight distributions is guaranteed
by using highly purified and dried monomers
preventing uncontrolled termination of
“living” chain-ends.

0.5 µm
PROCESS DESCRIPTION

The Polimeri Europa SBS technology Process design advanced features

is based on a sequential process through • High reactor volume (50 m3).
a “living” anionic polymerization reaction Capacity up to 50 kt/y for single reaction
of styrene and butadiene leading to polymer line is then afforded by using three batch
structures composed of styrene blocks reactors, lowering the investment cost.
at each end (hard phase), connected Capacity up to 30 kt/y per single finishing
by polybutadiene blocks (soft phase). line is available.
Dry solvent (cyclohexane or cyclopentane), • Technology does not have proprietary
styrene, initiator, butadiene and coupling/ items.
terminating agent are loaded batchwise to • Special design of solvent and monomer
the polymerization reactor, based on a purification columns allows the removing
sequence defined by a specific procedure of light and heavy components by one
depending on type of polymer to be produced. equipment.
Solvent and monomers distillation and • Cyclopentane, cyclohexane or blend,
adsorption operations before loading, as well highly compatible with all different
as blanketing with dry nitrogen of all polymer compositions, can be used
chemical mix and feed tanks, keep impurities as solvent depending on local climate
at the lowest level, preventing polymerization conditions.
poisoning. When polymerization reaction is • Proper solvent/monomer ratio in batch
completed, the polymer solution is pumped polymerization beside a defined solvent
to a blend tank operating at slight pressure. blend lead to lower steam consumption
Portion of solvent together with unreacted in stripping operation. Up to 30 % saving
monomers are flash vaporised. in steam consumption by using
The vapours are condensed and recycled cyclopentane instead of cyclohexane.
to the wet solvent tank. • Special design of die plate in dryer system
The blended solution with the antioxidant and proper operating condition lead
agents is fed to the stripping section where to regular shape of crumb rubber with
the solvent is removed by steam stripping different density.
in the presence of a dispersing agent for • High purity linear and radial triblock
controlling the crumb size. polymers, with four arms, are allowed
The vapours leaving the stripping section by the proper selection of halosilane
are then condensed and the solvent, structure as coupling agent.
separated from water in a decanter, is sent • High plant capability as well as easy
to the wet solvent tank. operability due to both specifically
The crumb slurry is pumped to the finishing designed feeding system for chemicals
unit, where the crumb is dewatered on a and batch automation.
shaker screen, from which water is partly • Proper selection of antioxidant package
recirculated to the strippers and partly sent as well as of packaging material avoids
to waste water treatment. damages to the marketed crumb or
The dewatered crumbs are dried in two powder final product, even if incorrectly
mechanical extruders in series, cooled with stored.
air, weighed and finally bagged.
 Suspending agent

Styrene

Butadiene

Chemicals

Steam
Raw materials

Process sections

Products

By products

Dry solvent

Batch polymerization

Solvent purification Flash

Blending

Stripping
Water

Finishing

Packaging
Water

SBS
 Polimeri Europa SpA
A subsidiary of Eni SpA
Sole shareholder company

Head Office
Piazza Boldrini, 1
20097 San Donato Milanese (Milano) – Italy
t +39 02 520.1
[email protected]
www.polimerieuropa.com

Licensing
Piazza Boldrini, 1
20097 San Donato Milanese (Milano) – Italy
t +39 02 520.32883
f +39 02 520.32077
[email protected]

Responsible Care

07/2009