functional polyolefins maleated polyolefins as versatile ... · functional polyolefins maleated...

FUNCTIONAL POLYOLEFINS

Maleated polyolefins as versatile HFFR coupling agents

Benoit SAVIGNATArkema CERDATO

AMI Cables 2015 Cologne2

Summary

ARKEMA at glance

HFFR compounds in cable

Case study:● Brucite based compound● NEW OREVAC® 18341 for better compound properties

Conclusion


30% 37% Coating Solutions

High Performance

Materials

Sales by segment*

Arkema in a snapshot

Industrial Specialties

33%

41% 34%

Sales by region*

25%

Europe

Asia and Row

North America

Global producer of specialty chemicalsSales of € 6.1 bn* Worldwide no1 to no3 on 90% of our portfolio14,000 employees in 40 countries90 industrial plants10 research centers3 Business segments :• High Performance Materials

• Industrial Specialties

• Coating Solutions

* 2013 figures


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≈€150 m allocated to R&D

1,200 researchersCoating Solutions

Carling

Coating Solutions

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Coating Solutions

Cary


High Performance Materials


King of Prussia



Serquigny


Kyoto



HFFR compounds in cables

•HFFR cables sheathing are growing thanks to very low smoke release properties

•HFFR cables are pushed by regulation (CPR,….)

•HFFR cables face PVC competition

PVC cables:

HFFR cables:

PVC cables:

HFFR cables:

PVC cables:30 seconds 3 minutes 6 minutes


HFFR compounds in cables

HFFR growth in W&C will induce:

Increase of technical requirement (cables air and water ageing, mechanical properties)

Price gap decrease with PVC to further develop the market

PVC cable HFFR cable


Filler acceptance/ Flexibility

Flame Retardancy

Cohesion / Mechanical properties

Main polyolefins :

• Ethylene copolymers (EVA, EMA, EBA)

• Polyethylene (VLD,LD, LL, HD) , Polypropylene

• Coupling agents : maleated polyolefins

Ethylene copolymer+

Mineral filler +

Coupling agent

HFFR compounds typical components


Copolymers

Terpolymers

Ethylene – Alkyl Acrylate

Ethylene – Vinyl Acetate

Ethylene – Alkyl Acrylate – MAH/GMA

GraftedPolyolefins MAH - Grafted

Main Polymers in HFFR

Ethylene copolymer

matrix

PE (LD, LLD, HD)PPEVA

Coupling agent


Filler Acceptance

200

LOI* (%)

*LOI: Limiting Oxygen Index = minimum amount of oxygen in atmosphere to maintain combustion

ATH content (wt%)

40 60 70

0

5

10

15

20

25

30

35

40

LDPE

EVA, EBA, EMA

28% comonomer

0

PVC

EMA/EBA/EVA vs. PE: Fire properties

Better LOI with Evatane® or Lotryl® resins compared to all kind of PEIntroduce +/- 65% of mineralfiller to match PVC LOI

Ethylene copolymer

+Filler

+ Coupling agent


Specific link for the 65% mineral filler with the polymer matrix is mandatory

Most of the mineral fillers for HFFR have hydroxyl functions available:• Aluminium hydroxide (precipitated ATH)

• Magnesium hydroxide (precipitated MDH )

• Brucite (Natural ground MDH)

• ….

High content MAH grafted polymers or MAH Terpolymers, reactive in presence of hydroxyl function, can play as coupling agent

FillerPolymer matrix

Coupling agent

Role of coupling agentsCoupling Agent = THE link between filler (sand-like) and polymerMechanical properties improvement

Ethylene copolymer+

Filler+

Coupling agent


Al

OH

OH OH

Lotader®: MAH –based Reactive Polyolefins (Terpolymers)

A bond is formed by reaction between MAH and hydroxyl groups present of the filler

Good efficiency with both ATH and MDH

Compatibility with the base polymer(EVA, EMA, EBA, PE)

Ethylene – Acrylic Ester – Maleic Anhydride (MAH)(CH2 - CH2 -)x (CH2 - CH - )y (CH2 - CH2 -)z (CH - CH - )t

I I IC = O O = C C = OI \ / O O IR

R=Methyl CH3, Ethyl C2H5, Butyl C4H9

Ethylene – Acrylic Ester Maleic Anhydride+

Coupling agents: maleated copolymersEthylene copolymer

+Filler

+ Coupling agent


Orevac®: MAH based Reactive Polyolefins (Grafted Polyolefins)

Ethylene –Grafted Maleic Anhydride (MAH)Broad choice of grafted polymer :HDPE, LLDPE, VLDPE,

Grafted Maleic Anhydride key features in HFFR :Plays a key role in the mechanical propertiesGives polarity and high reactivity to polymer chains Higher filler acceptance

Strongly interacts with OH (hydroxyl) of mineral filler (ATH,MDH,..)

Enables large processing window thanks polymer choice

Coupling agents: MAH-grafted copolymersEthylene copolymer

+Filler

+ Coupling agent

High reactivity of GRAFTED MAH


5

10

15

20

0 50 100 150 200 250Elongation at Break (%)

Tens

ile S

treng

th (M

Pa)

5

10

15

20

0 50 100 150 200 250Elongation at Break (%)

Tens

ile S

treng

th (M

Pa)

Effect of a Coupling Agent

Coupling Agents improve mechanical propertiesElongation ↑++ , Tensile strength ↑+

Without Coupling Agent

With 5% of Grafted LLDPEOrevac® 18341

Role of coupling agentsEthylene copolymer

+Filler

+ Coupling agent


Hydrated mineral filler is more than 60% of the recipe

Natural ground product like brucite (natural MDH) is of interest.

Main issue known with brucite is to obtain good mechanical, good FR(LOI) and not too viscous compound.

Key properties to succeed with brucite are purity and size distribution.

Case study: Brucite as mineral filler


Internal mixerRoll calender Hot press

compression

Mineral filler cross-check

Goal 63%(+/-1)

Formulation & test method


Mechanical/LOI/MFI


Technical request:

Tensile strength (TS) ≥ 10 MPa

Elongation @ break (EB) ≥140%

LOI ≥ 34%

MFI (150°C/21.6kg) ≥ 2.5



ARKEMA approach for this new HFFR compound is to start from our knowledge e.g. in formulation

Goal

- Identify the difference induced on the compound by replacing precipitated ATH (63%) by ground brucite (63%)

Product %wt

EVA / EMA / EBA 23

PE (LD, HD, LL,VLD) 9

Maleated polyolefins

Lotader®/Orevac® resins

5

Mineral flame retardant filler

Al(OH)3 or Mg( OH)2

63

Stabilizer, processing aid <1



Mechanical properties: Tensile & Elongation



MFI & LOI :

Ground brucite highlyviscous

LOTADER® 3210 dramatically reducesviscosity



With standard recipe unsufficient coupling between natural MDH and EVA/PE polymer matrix.

Viscosity => MFI to be increased without reducing other properties

Elongation at break => to be increased

We should play on both directions :

Replace LLDPE by VLDPE to increase the mechanicals while keeping the coupling agent at same level

Introduce EVATANE® 28-800 (VA 28%, MFI 800) very high fluidity EVA to reduce the compound viscosity

NOTA: working in a sole way (VLDPE usage or fluid EVA usage) would lead to unbalanced compound properties.



Brucite as mineral filler : Phase II recipe

Product %wt

EVATANE® 28-03 23

EVATANE® 28-800 2

PE-g-MAH OREVAC® 5

VLDPE 7

Brucite 63



Mechanical properties: Tensile & Elongation

VLDPE and EVATANE® 28-800 increase coupling efficiency

Brucite as mineral filler : Phase II mechanical


MFI & LOI

VLDPE & EVATANE®

28-800 decrease viscosity (MFI x2)

Brucite as mineral filler : Phase II


Brucite as mineral filler : Conclusion

Product %wt

EVATANE® 28-03 23

EVATANE® 28-800 2

PE-g-MAH OREVAC® 5

VLDPE 7

Brucite 63


This specific recipe meets requirement (TS>10MPa, EB>140%)


Maleated coupling agent :

Commercial polymer (PE, PP, EVA,…)

Maleic Anhydride (MAH) grafted or terpolymers

Polymer selected to match the polymer matrix

%MAH and his influence ?

Case study Nr2: MAH level and properties


LLDPE-g-MAH medium grafted : Recipe A

LLDPE-g-MAH highly grafted (reference): Recipe B

OREVAC® 18341 highly grafted: Recipe C

RECIPE A %wt

EVATANE® 28-03 23

LLDPE 9

LLDPE-g-MAH medium

5

ATH 63

MAH level and properties: PE-g-MAH comparison

RECIPE B %wt

EVATANE® 28-03 23

LLDPE 9

LLDPE-g-MAH High

5

ATH 63

RECIPE C %wt

EVATANE® 28-03 23

LLDPE 9

OREVAC® 18341 5

ATH 63


LLDPE-g-MAH medium grafted : Recipe A


OREVAC® 18341 highly grafted: Recipe C

RECIPE A

Tensile strength 11

Elong. @ break 195

MFI(150°/21.6kg) 3,3

LOI 38

Water Resistance

Fail

MAH level and properties: PE-g-MAH comparison

RECIPE B

Tensile strength 14

Elong. @ break 185

MFI(150°/21.6kg) 3,7

LOI 38

Water Resistance

Pass

RECIPE C OREVAC® 18341

Tensile strength 15

Elong. @ break 190

MFI(150°/21.6kg) 5,8

LOI 38

Water Resistance

Pass

Water aging: 7days 70°C; variation <40%, TS>9Mpa, EB >100%



OREVAC® 18341 3% highly grafted: Recipe D

OREVAC® 18341 2,5% + LOTADER® 2,5%: Recipe E

MAH level & properties: highly grafted & Terpolymers

RECIPE B %wt

EVATANE® 28-03 23

LLDPE 9

LLDPEg-MAH High 5

ATH 63

RECIPE D %wt

EVATANE® 28-03 25

LLDPE 9

OREVAC® 18341 3

ATH 63

RECIPE E %wt

EVATANE® 28-03 23

LLDPE 9

OREVAC® 18341LOTADER® 3210

2,5 2,5

ATH 63



OREVAC® 18341 3% highly grafted: Recipe D

OREVAC® 18341 2,5% + LOTADER® 2,5%: Recipe E

RECIPE B

Tensile strength 14

Elong. @ break 185

MFI(150°/21.6kg) 3,7

LOI 38

Water Resistance

Pass

RECIPE E

Tensile strength 14

Elong. @ break 185

MFI(150°/21.6kg) 7

LOI 38

Water Resistance

Pass

RECIPE D

Tensile strength 14

Elong. @ break 200

MFI(150°/21.6kg) 6

LOI 38

Water Resistance

Pass


MAH level & properties: highly grafted & Terpolymers


Water aging: highly grafted & Terpolymers



OREVAC® 18341 alone at different %wt pass the requirement and offer good performance/cost ratio.

OREVAC® 18341 + LOTADER® 3210 is a solution for stringent technical request.

MAH level & properties: Conclusion


NEW Orevac® 18341Versatile coupling agentGood combination of elongation at break and tensile strength Building HFFR cables

OREVAC® 18507 HDPE basedHigher resistance to chemical and abrasionGood temperature stability XL Automotive HFFR Cables

OREVAC® OE808 VLD/LLDPEFlexibility at low temperature while maintaining high temperature performance Soft cables, high-end HFFR

LOTADER® 3210 Terpolymer BA/MAHLow melting Temperature low mixing Temperature internal mixerLow viscosity, good water resistance Blend in OREVAC® resins

OREVAC® 18302N LLDPE basedHigh Elongation at break

OREVAC® CA100 HOMO PP based For PP-based HFFR formulations higher Temperature MDH compounds without cross linking

Arkema HFFR coupling agents portfolio


Acknowledgements to: Dr Sébastien QUINEBECHE, Elisabeth LOERCH, Dominique BAILLEUL among others ARKEMA CERDATO colleagues.

Thank you for your kind attention

More information :www.evatane.com

www.lotryl.com

www.lotader.com

www.orevac.com

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