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2016 Material Science Series “Chemistry of Go: High Performance Elastomers”

Edmund Carnahan

Mark Jones

R&D Fellow, Dow Chemical

Executive External Strategy and Communications Fellow, Dow Chemical

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Chemistry of Go: High Performance Elastomers June 2, 2016 Olefin Block Copolymers by Chain Shuttling Catalysis

Edmund (Ted) Carnahan Research Fellow Performance Plastics R&D, Freeport TX Dow.com

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Polyolefins Are In Many Products

15

Why Polyolefins?

Customers Like Olefin Solutions • Polyolefin plastics are inexpensive, nontoxic, light weight, recyclable, and easy to process. • If an olefin solution meets performance needs, it is usually used.

How far can we push performance? 16

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5/31/2016

The Evolution of Polyethylene: An Evolution of Catalysis! LDPE

Radical mechanism (1933)

Highly Branched:

• High Temperature & Pressure • Many reactions possible • Kinetics complicated

LLDPE

Coordination catalysis (1950’s)

mPE

“Single Site” catalysts (1990’s)

Linear Backbone:

• Low Temperature & Pressure • Multiple catalytic sites • Nobel Prize Zielger & Natta 1963

• Molecular catalysts • Kinetics the same for each site

• Excellent flow properties • Fast extrusion rates • Poor mechanical properties

• PE homopolymer: crystalline • Copolymers: flexible and tough • Inhomogeneous

Homogeneous Polymers: • Narrow molecular weight distribution • Narrow comonomer distribution • New monomer combinations • Long chain branching 17

Polymer Properties Determined by Catalysis Composition of each chain determined by relative kinetic rates:

Branch=“defect” catalyst

Molecular structure of polymer chains determines bulk structure:

Lamella: long sequences of ethylene units fold into crystallites Interfacial regions: “defects” are excluded into amorphous regions Tie molecule: Bridge more than one lamellar crystallite Prog. Polym. Sci. 2011, 36, 793.

Catalysis

Molecular Structure

Bulk Structure

Properties 18

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Audience Survey Question

ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

Which of these is almost certainly does NOT contain polyethylene?

•

Kayak

•

Trash bag

•

Plastic water bottle

•

Athletic sneaker 19

Melting Peak Temperature (°C)

With “Perfect” Kinetics Properties are Correlated 140

120

Rigid High Tm Crystalline

Soft Low Tm Amorphous

100

80

60

ELASTOMERS

40 0.86

0.88

LLDPE 0.90

0.92

HDPE 0.94

0.96

Polymer Density (g/cc) More comonomer = lower density = less crystallinity = softer material = lower melting

What if you want a crystalline elastomer with a high melting point? 20

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OBCs can Decouple Melt and Modulus “Random” Semi-crystalline Copolymer

• High catalyst efficiency – low cost continuous process • Poor control of melting, other properties from random structure “Block” Copolymer - Linear

Hard

Soft

Hard

• Performance from a combination of linear and branched segments • Controlled placement of well-defined blocks • Stoichiometric initiators – batch process

Challenge: New olefin block copolymers and new methods for making them. 21

Introduce a new kinetic step: Chain Shuttling Catalyst 1

Makes “SOFT” polymer

Chain shuttling generates a HARD/SOFT multiblock copolymer via cooperative catalysis! Hard/Soft multiblock copolymer!

Chain Shuttling Agent

Catalyst 2

Makes “HARD” polymer Arriola, D. J.; Carnahan, E. M.; Hustad, P. D.; Kuhlman, R. L.; Wenzel, T. T. Science 2006, 312, 714. 22

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Kinetic Modeling Revealed Key Insights… 6.0

M w/M n

5.0

Cao=0

Cao=2

Cao=4

Cao=6

Cao=8

Cao=10

Cao=25

Cao=50

4.0

3.0 R

M R

2.0 2

4 6 Conversion (Xf)

8

10

50,000

40,000

Polymer!

M+ R

Mw (g/mol)

35,000

2.2

2.0

P

M+

M+ R

H

M w/M n

1.8

Ca=2

Ca=4

Ca=6

Ca=8

Ca=10

1.6

t

Bu O N Zr N BnO Bn

30,000

t

1.5

+ ZnEt2

1.4

Bu

25,000

1.3

20,000 1.2

15,000

P

1.6 Ca=0

Mw Mn Mw/Mn

45,000

P

10,000

M+

1.1

1.4

1.2

Ca=25

5,000 0

Ca=50

1.0 0

1

2 3 Conversion (X f)

4

Mw/Mn

0

1.0 0

C6 H 13

5

0.05

0.1

0.15

0.2

0.25

0.3

Polymer Yield (g)

…but many, many experiments were required For details of kinetic modeling see: Macromolecules, 2008, 41(12), 4081. 23

High Throughput Experimentation

Add reagents

Dry Samples

Make polymers

Weigh Samples Robotically

Library Design

PPR (48 cell parallel pressure reactor) -Computer controlled temperature, pressure, and quench -Robotic injection of catalysts into equilibrated system -Real-time monitoring of pressure, temperature, uptake

High Temp Robot Transfers Samples dissolved in hot TCB

Rapid Iteration Data Analysis High temp. rapid GPC®

rapid serial FT-IR

-Molecular weight & PDI

-Comonomer Incorporation

>3000 polymerization experiments, including full analytical, in several weeks! 24 ® Registered trademark of Symyx Technologies

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5/31/2016

Continuous Polymerization in Pilot Plant GPC Molecular Weight Without Chain Shuttling Agent t

Bu

i

t

Bu

Me Me Hf

O N Zr N Bn Bn O t

Pr

N

N

Without CSA Mw/Mn = 13.8

i

i

Pr

Pr

Bu

t

Bu

High Mw amorphous

Low Mw crystalline

2.0

2.5

3.0

3.5

4.0

4.5 log M w

5.0

5.5

6.0

6.5

7.0

25

Continuous Polymerization in Pilot Plant Same Experiment with Added Chain Shuttling Agent t

Bu

i

t

Bu

Me Me

With CSA Mw/Mn = 1.97

O

Hf

N

N

N Zr N Bn Bn O t

Pr

i

i

Pr

Pr

Bu

t

Bu

2.0

2.5

3.0

3.5

4.0

4.5 log M w

5.0

5.5

6.0

6.5

7.0

Statistical multiblock olefin block copolymer made in a continuous reactor! 26

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Controlled Microstructure via Catalysis

More and shorter blocks

No chain shuttling

High chain shuttling

• All samples have the same composition (E/O), same density, same melt index! • Block architecture allows for a new level of performance from an olefin solution 27

INFUSE™ Olefin Block Copolymers ● Outstanding flexibility-high temperature resistance balance

130 120

OBC

110 Melting Temperature (C)

● Fast set-up in processing (shorter cycle time) – soft compounds!

100 90 80 70

Random

60

OBCs Random Copolymers

50 40 0.865

● Excellent elastic recovery properties

TM Trademark

of The Dow Chemical Co

Compression set @ 70 C

● Good compression set performance at room and elevated temperatures

100

0.875

0.885 Density (g/cc)

0.895

Excellent Compression Set@70C!

80 60 40 20 0 OBC

SEBS 28

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Photonic Polyethylene! OBCs that Scatter Light Soft block

Hard block

8.75 Phase separated

7.00 cN*

5.25 3.50 1.75

INFUSE™ OBCs

0 14

17

20

23

26

29

D mole% octene N*: Mn = 40 kg/mol 50% hard segment

29

Hustad, Marchand, Garcia-Meitin, Roberts, Weinhold Macromolecules 2009, 42, 3788 ®™Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow

Polyolefins with Nano-Scale Morphology

Drive polyolefin ordered morphologies to the nanometer-scale.

High Crystallinity Block Low Crystallinity Block

Gen 1

• iPP-EP block copolymers!

ethyleneoctene

Relative Solubility Parameter (cal/cm3)0.5

Approach: choose monomers with a larger solubility parameter difference to drive microphase separation.

Gen 2 Meso-phase ethyleneoctene

Gen 3 propyleneethylene

0.6 0.5 0.4 0.3 0.2 0.1 0

30

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Coordinative Chain Transfer Polymerization 40

Bu

2.0 Mn

35

t

Bu

Et2Zn as CSA EO Copolymer

Mw/Mn 1.8

30 M n (kg/mol)

O N Zr N BnO Bn

25

1.6 M w/M n

t

20 1.4

15 10

1.2 5 0 0.00

0.05

0.10

0.15

0.20

0.25

1.0 0.30

Polymer yield (g)

•

Fast, reversible chain transfer extends the life of an individual polymer chain from milliseconds to minutes or longer.

•

Allows OBCs to be prepared by 2 reactors in series under different reactor conditions. 31

Statistical Diblocks by Coordinative Chain Transfer Polymerization

•

Chains shuttling between two catalysts in a single reactor produces statistical multiblocks with polydisperse block lengths.

•

CCTP produces statistical diblocks. Ideally every chain contains exactly two blocks, but the blocks have Mw polydispersity. Hustad, Kuhlman, Arriola, Carnahan, Wenzel, T. T. Macromolecules, 2007, 40, 7061.

32

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Morphology of PE/PP Blends PP OBC PE/PP 50/50

PP OBC, Blend High of HDPE Magnification and iPP 50/50 wt./wt.

10 mm

Segments of Crystalline PE and Crystalline iPP 33

Audience Survey Question

ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

Catalysts used in making olefin block copolymers are: •

recovered for reuse using a magnetic separator

•

so efficient that catalysts residues are left in the final product

•

heterogeneous catalysts that stay in the reactor and are reused

•

highly colored so that robots pick out the polymer pellets containing the catalyst

34

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Applications of Olefin Block Copolymers PE-Based

PP-Based

Flexibility + Heat Resistance

Compatibilization

New-to-the-world combinations of performance advantages that addresses unmet needs for a wide range of global market applications

35

INFUSE™ Olefin Block Copolymers

Adhesives

Footware Health & Hygiene

Flooring Wire & Cable

Infrastructure

36

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5/31/2016

Enabling A Broad Range of Possibilities

Multi-layer Structures

Polyolefin Blends

Bonding PP to PE,EVOH, PA , EVA

“Stiff Elastomer”

Retort Tie Layer

High Clarity Consumer Labels BOPP/ Cast PP

Clear Tough Storage

Muni Waste Containers

Kayaks

37

A New Level of Performance Catalysis to tailor the molecular structure of polyethylene drives the product morphology, and thus the properties and performance in applications. Meso-phase separated E/O copolymers Random copolymers

Granular

Statistical Multiblocks

Lamellar

PE-EO statistical diblocks

Lamellar Ordering

Ultra-efficient Blend Compatibilizers

Nano-domain Ordering 38

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Acknowledgments Catalyst

Process Jan Bazen Curvel Hypolite Tom Karjala

Dan Arriola Phil Hustad Roger Kuhlman Tim Wenzel Dow Elastomers Harold Boone Karen Fennessy-Ketola Yushan Hu Colin Li Pi Shan Gary Marchand

Analytical Eddy Garcia-Meitin Zhe Zhou Core R&D Jeff Weinhold

… and many more. 39


Edmund Carnahan

Mark Jones





40

20

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2016 Material Science Series http://bit.ly/2016MaterialScienceSeries Upcoming Material Science Series Webinars… Topics and Speaker suggestions welcome! The Chemistry of Comfort

The Chemistry of Life

Humans have ventured from the depths of the ocean to the highest peaks of the Himalayas. Discover the materials that made it possible to survive the inhospitable in all types of threating environments.

New materials are having a major, positive impact on human health. Learn about recent technological advancements that are spawning biomedical devices and other tools that are helping people live longer, healthier, happier lives.

The 2016 Material Science Series is co-produced with ACS Industry Member Programs, C&EN, and the ACS POLY Division

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Edmund Carnahan

Mark Jones





How has ACS Webinars benefited you?

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ACS Member 48 Years Strong! “Having seen snippets on the news from time to time, it was very helpful to get a more in-depth close-up on the project. The presentation was not too technical, but it nevertheless was very informative. It seems to me that we are witnessing an event in the history of aviation, comparable in magnitude to the first ground-breaking flight recorded by the Wright brothers at Kitty Hawk, NC, in 1903. Earthbound flight seems to be taking off in a new and exciting direction.” Quote in reference to: http://bit.ly/SolarPoweredFlight

Douglas E. Zabel, Ph. D. Professor of Chemistry, Semi-Retired College of Southern Maryland

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NEW! Free Access to ACS Presentations on Demand® ACS Member only access to over 1,000 presentation recordings from recent ACS meetings and select events.

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ACS Webinars does not endorse any products or services. The views expressed in this presentation are those of the presenter and do not necessarily reflect the views or policies of the American Chemical Society.


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