Slurry process EP(D)M: New Grades obtained withan Innovative New Ziegler Natta Catalyst System.

Angelo Lucio SpeltaTS&D Manager

MANCHESTER POLYMER GROUP RUBBER SEMINAR in conjunction with RIEG Rubber and Elastomers sustainably meeting tomorrow’s challengesEMIRATES STADIUM, OLD TRAFFORD CRICKET GROUND – 15th MAY 2017

Summary

Introduction

Improvements achieved with the new catalyst system

Development of new grades Very high ENB (ethyliden-norbornene) grade for automotive sponge application Ultra high molecular weight grade for TPV application Tailored structure for solid profiles application (branching technologies)

Conclusions

2

5,200 employees

5 research centres >250 patents

71 production units5.3 Mt/y production

390 products

Intermediates Polyethylene Styrenics Elastomers

HeadquarterMilan

Plants

Commercial network

Licensing and strategic partnerships

Introduction : versalis at a glance

With an integrated industrial platform, versalis – the Italian leading chemical company – offers to the market an extensive portfolio of around 400 product grades and a new range of bio-based chemical products

12 plants(8 Italy, 4 Europe)

5.2 bln €turnover

Elastomers: product mix

High performance tyres for passenger cars (SSBR)

Europrene ® SBR Styrene Butadiene Rubber (SBR)

Adhesives

Europrene ® SOL T, THThermoplastic Rubber (SBS,SIS,SEBS)

Technical goods

Europrene ® NAcrylonitrile-Butadiene Rubber (NBR)

Europrene ®Neocis/InteneButadiene Rubber (BR)

Car/truck Tyres, Styrenics modif.

Dutral ®

Ethylene-Propylene Rubber (EP(D)M)

Automotive and Building

Europrene ® Latex Synthetic Latexes (HS, CBX)

Moulded foam and masking tapes

IMPROVEMENTS ACHIEVED WITH THE NEW CATALYST SYSTEM

5

The new catalyst system

Advantages in terms of:

Polymerization yield

Gel control

Co-monomers addition

6

EP(D)M DUTRAL® elastomers polymerizations

+

Ziegler Natta catalyst system

CH-CH3

CH 2

ENB

C

H

H

C

H

H

Ethylene C

H

H

C

CH

H

3Propylene

DUTRAL® CO(EPM)

DUTRAL® TER(EPDM)

(ENB content : 3 - 9 % wt)Co-Catalyst

Activator

Catalyst

7

Traditional Catalyst System: veryversatile, able to produce from very lowto very high Molecular Weight, fromlow to high Ethylene and ENB content

The New Catalyst System keeps the versatilityof the traditional one, significantly increasesthe polymerization yield, improves co-monomers addition to obtain betterdistribution inside the polymer chain, reducesundesired side reactions

DUTRAL®: development of a new catalyst systemAfter years of internal development Versalis is scaling up an improved Z-N catalyst

Co-Catalyst

ActivatorCatalyst

Co-Catalyst

ActivatorCatalyst

8

DUTRAL®: development of a new catalyst system

• Higher polymerization yield

• Cleaner products

• Better monomer distribution and side reactions control

• Lower up to no gel

• Better consistency

• Better curing efficiency

This new catalyst is currently used on industrial scale to produce all the new developed grades

Widening the polymer design

• New polymer structures• Improved processability

9

DUTRAL® : new catalyst system Cleaner Product

AluminumVanadium

-29%-31%

-56% -55%

Residual catalyst (V and Al)

100% 100%

44%

69% 71%

45%

Improved ZN Improved ZNTraditional ZN Traditional ZN

10

DUTRAL® : new catalyst system lower gel

Polymer dispersion in std rubber compound

Traditional ZN Improved ZN

Defects counted in std rubber compound strip

Very low gel level

Acceptance limit

11

DUTRAL® : new catalyst system better co-monomer C2 C3 addition

Crystallinity

Traditional ZN 4,3 0Improved ZN 0 3,3

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

Improved ZNTraditional ZN

∆H (joule/g) Semi-crystalline grade (identical composition)

12

Dutral TER

•High MW ML(1+4)125°C 65 MU

•Moderate Oil Extension 15%

•Amorphous grade C3 40%

•High ENB content 7%0123456789

10111213141516171819202122

0 1 2 3 4 5 6 7 8 9 10

Torq

ue, d

Nm

t, min

ASTM D3568 Compound Vulcanization @ 180 °C

Traditional ZN Catalyst Improved ZN Catalyst

DUTRAL®: new catalyst system better ENB addition better ENB addition

13

NEW CATALYST SYSTEM

DEVELOPMENT OF NEW GRADES

14

DUTRAL® : new grades development Automotive Sponge Grade

The ability to minimize the side reactions can be used to develop a new grade with very high thirdmonomer (ENB) content and high molecular weight, suitable for automotive sponge profilesapplications, finally filling the gap of the slurry technology versus the solution technology for suchapplication.

Sponge profile is probably the most demandingautomotive body sealing application. It requires:

• low Mooney compound to allow properexpansion,

• good collapse resistance,• high cure rate and• perfect surface.

Different polymer structures are suitable for theapplication including the one below reported

DUTRAL® : new grades development Automotive Sponge Grade

Dutral TX reference composition for sponge application

•High MW ML(1+4)125°C 68 MU

•Moderate Oil Extension 17,5 %

•Amorphous grade C3 39 %

•Very High ENB content 8,5 %

0

20

40

60

80

100

120

140

160

180

200

1 2 3 4 5 6 7 8 9 10 11 12 13

Gel C

ount

progressive control sample

Gel Count in a reference compound

Gel Count BEST Accettable limit for application

As known the slurry process has advantages versus the solution process in the production of very high molecular weight grades. These grades are typically oil extended to facilitate their processability.The new catalyst system allows to reach molecular weights not possible with the traditional one.A growing application were these type of grades are desirable is the TPV application.

TPV (Thermoplastic Vulcanized)

DUTRAL® : new grades development TPV Grade

Traditional ZN Catalyst highest MW currentportfolio

Improved ZN Catalyst new highest MW grade

kDal

ton

ZN Slurry Process Very High Molecular Weight

TPV greatly contributed to the grow of theThermoplastic Elastomer Family (TPE) atwhich belongs together with (H)SBC, TPOetc.The reason of this success is its superiorelasticity combined with the recyclability.

DUTRAL® : new grades development TPV Grade

TPV (Thermoplastic Vulcanizate) is arubber/thermoplastic blend (plusfillers/plasticizers/other additives) wherethe rubber phase is cross-linked (dynamicvulcanization) and finely dispersed in thecontinuous matrix of the thermoplastic(typically PP).Being a blend of a rubber in a plastic, inorder to reach the desired hardness, ahigh amount of oil is required. Toemphasize the elastic and mechanicalproperties ultra-high molecular weightEP(D)M are preferred

TPVbuilding

Car interior appliances

Dutral TX reference composition for TPV application

•Very High MW - ML(1+4)125°C 47 MU•Extension with White Oil 50 %•Amorphous grade C3 36 %•Medium ENB content 4,5%

DUTRAL® : new grades development TPV Grade

-60

-40

-20

0

20

40

60

80

Injection moulding comp.

D.TER D.TX

C.S. 22h 100 °C TR 10

%

°C

BRANCHING TECHNOLOGY

20

DUTRAL® : new catalyst system branching technology

The new catalyst system is particularly suitable to introduce branching technology in a slurry process, toget easy processable grades and to keep a negligible gel content.To evaluate the effect of branching technology another grade was designed starting from a standardreference grade. The two grades are characterized by a high molecular weight, medium third monomercontent, amorphous composition.Being the only difference the presence of branching, it is possible to focus just on that characteristic. Theinduced branching present is evaluated by Mooney slope and Mooney relaxation area. The higherelasticity obtained allows improving the workability in internal mixing without sacrificing the finalproperties of the vulcanizates.

TER BTR

High MW ML (1+4) 125°C 76 76

Amorphous grade Propylene Content 40% 40%

Medium ENB ENB Content 4,5% 4,5%

Molecular Structure Linear Tailored

DUTRAL® : new catalyst system branching technology

New and standard amorphous grades comparison - basic data

MAIN PROPERTIES linear tailored

Propylene cont. / ENB cont. %wt 40 / 4,5 40 / 4,5

Polymer Mooney - ML (1+4) a 125 °C MU 78 78

Slope lg M/lg s -0,942 -0,529

Area 175,3 608,8

Area/ML 2,3 7,8

Performance evaluation in compact profile (Composition in phr - total: 379,1)

Polymer 100 100

C.B. N550 - Paraffinic Oil - CaCO3 140 - 90 - 30 140 - 90 - 30

ZnO: 5; Stearic Acid: 1; PEG 4000: 5; Structol WB 16: 3; Sulphur 80: 1,5; MBTS 1; ZBOP/S 1,2; ZBEC 0,7; TBzTD 0,5; Vulcalent E80: 0,2

Compound Mooney - ML (1+4) a 100 °C MU 61 51

Δ ML (1+4)125°C - ML(1+4)100 °C 16 27

DUTRAL® : new catalyst system branching technology

0

2

4

6

8

10

12

0 50 100 150 200 250 300 350

Garv

ey R

ate

mixing time sec.

Garvey Rate vs mixing time (at 40 rpm)

Branched

0

2

4

6

8

10

12

0 10 20 30 40 50 60 70

Garv

ey ra

te

rpm

Branched

Extrusion properties: Garvey rate vs. mixing time/extr. speed (ASTM D 3568 – cpd)

Linear

Garvey rate vs. extrusion speed (at 200’’ mix time)

DUTRAL® : new catalyst system branching technology

62

64

66

68

70

72

74

50 100 150 200 250 300 350

ML(

1+4)

@10

0°C

[MU

]

Time, s

Mooney compounds vs mixing time

9

9,5

10

10,5

11

11,5

12

12,5

13

13,5

50 100 150 200 250 300 350

T.S.

[MPa

]

Time, s

Cured compounds T.S. vs mixing time

Mooney compound and Tensile Strength vs. mixing time (ASTM D 3568 – cpd)

Linear

Branched Linear

Branched

With the adoption of an improved ZN catalyst, in a slurry process, it is possible to

obtain EP(D)M grades with low catalyst residual and very low gel content. The

new ZN catalyst is also able to improve the co-monomers addition and minimize

undesired side reactions to allow the adoption of technics for obtaining tailored

polymer structures with improved processability.

Consequently it is now possible to overcome the limits of the traditional catalyst

used in a slurry process and to obtain new EP(D)M grades suitable for a wider

range of applications.

Conclusions

thank you for your attention