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GE CRD Engineering Thermoplastics Perspectives for the 21st Century Dr.Gregory R. Gillette Manager-Strategic Materials

GE CRD

Engineering Thermoplastics

Perspectives for the 21st Century

Dr.Gregory R. Gillette Manager-Strategic Materials Program

GE Corporate Research and Development Schenectady, NY

12309

Greg Gillette-GE CRD

Acknowledgments GE CRD Dan Brunelle-CRD Ray Naar-GEP Jon Rich-BF Goodrich Carolyn Warden-CRD Pam Northrop-CRD GE

Acknowledgments

GE CRD

Dan Brunelle-CRD Ray Naar-GEP Jon Rich-BF Goodrich Carolyn Warden-CRD Pam Northrop-CRD GE CRD

Greg Gillette-GE CRD

Outline GE CRD • Introduction - GE - GE Plastics • Definition of ETP •

Outline

GE CRD

Introduction

- GE

- GE Plastics

Definition of ETP

General Trends in ETP

Outlook for

Silicones

Polycarbonates

Crystalline Resins

Polyimides/High Temperature Resins

POSS in ETP

Discussion

Greg Gillette-GE CRD

GE CRD GGeneraleneral ElElectricectric CompanyCompany • • 1999 Revenues: $112 Billion 1999 Revenues: $112 Billion
GE CRD
GGeneraleneral ElElectricectric CompanyCompany
• • 1999 Revenues: $112 Billion
1999 Revenues: $112 Billion
Businesses:
Businesses:
— — GE Aircraft Engines
GE Aircraft Engines
— — GE Appliances
GE Appliances
— — GE Capital Services
GE Capital Services
— — GE Global Exchange Services
GE Global Exchange Services
— — GE Industrial Systems
GE Industrial Systems
— — GE Lighting
GE Lighting
— — GEMedical Systems
GEMedical Systems
— — GE Plastics
GE Plastics
— — GE Powe r Systems
GE Powe r Systems
— — GE Trans port ation Systems
GE Trans port ation Systems
— — NBC
NBC
Greg Gillette-GE CRD
5-00
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas
Global R&D: Speed and New Ideas
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)

GE CRD

Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)
Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)

France

Global R&D: Speed and New Ideas GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU)

The Netherlands

Aircraft Engines (SNECMA)

GE CRD France The Netherlands Aircraft Engines (SNECMA) EngineeringPlastics(AKU) EngineeringPlastics GreatBritain
EngineeringPlastics(AKU) EngineeringPlastics GreatBritain Canada Medical Systems Appliances (GDA) Motors, Hydro
EngineeringPlastics(AKU)
EngineeringPlastics
GreatBritain
Canada
Medical Systems
Appliances (GDA)
Motors, Hydro Generators
Lighting Systems
Russia
Protective Relays
Aircraft Engines Turbines (GE/VIAM, GE/IMSP)
Spain
Power Controls
Italy Gas Turbines (Nuovo PIgnone)
Hungary Lighting Systems (Tungsram)
Japan
EngineeringPlastics
Medical Systems (YMS)
Silicone Products (Tosil)
China
Aircraft Engines
(GE/BIAM, CSUT)
Medical Systems
(GE/NIM, BRIRE, SICCAS)
Mexico
Appliances
Ukraine
‘99 RD&E: $1.9B
Aircraft Engines
United States
Turbines
RD&E staff:
Aircraft Engines, Lynn, MA
Aircraft Engines, Evendale, OH
Medical Systems, Waukesha, WI
Lighting Systems, Hendersonville, NC
Nuclear Energy, San Jose, CA
Silicone Products, Waterford, N.Y.
India
— 7300 U.S.
Engineering
Plastics
Appliances, Louisville, KY.
Superabrasives, Worthington, OH
— 1800 non-U.S.
(GE/NCL)
Communications, Raleigh, N.C.
Transportation Systems, Erie, PA
Medical
CorporateR&D, Schenectady, N.Y.
Turbines, Schenectady, N.Y.
Many RD&E
Systems
Elec. Distribution Equipment,
Plainville,Ct.
Factory Automation, Lynchburg,
Information Systems, Rockville MD
approaches
Engineering Plastics, Pittsfield, MA
3-00
GE Plastics Business GE CRD Resin Business Plastics — Engineering Thermoplastics Worldwide Polymerland -- Plastics

GE Plastics Business

GE CRD

Resin

Business

Plastics — Engineering Thermoplastics Worldwide

Polymerland -- Plastics distribution, resource recovery

Structured Products -- Thermoplastic sheet and film

Silicones -- Adhesives, Sealants, Coatings, Elastomers

Superabrasives -- Man-made diamonds

Specialty Chemicals -- Impact modifiers, Stabilizers

Petrochemicals -- Ethylene, Styrene, Phenol

Electromaterials -- Printed Circuit Boards

Stabilizers Petrochemicals -- Ethylene, Styrene, Phenol Electromaterials -- Printed Circuit Boards Greg Gillette-GE CRD

Greg Gillette-GE CRD

Engineering Thermoplastics-Definition GE CRD • Engineering Plastics defined as materials which can be used

Engineering Thermoplastics-Definition

GE CRD

Engineering Plastics defined as materials which can be used structurally, typically replacing metals, wood, glass, or ceramics. Can maintain mechanical and dimensional stability above 100 o C and below 0 o C.

About 7% of all Plastics production, but nearly 10% of Plastics Sales Dollars.

Do not include films, thermosets, phenolics, epoxies, etc.

For this Discussion we will include Silicones as well typical ETP’s

Many other types of injection-molded materials (styrenics, acrylics, poly(vinyl chloride), polyolefins and polyurethanes are not typically considered in this category.

Greg Gillette-GE CRD

Engineering Thermoplastics (ETP’s) -Definition GE CRD Greg Gillette-GE CRD

Engineering Thermoplastics (ETP’s) -Definition

GE CRD

Engineering Thermoplastics (ETP’s) -Definition GE CRD Greg Gillette-GE CRD

Greg Gillette-GE CRD

ETP- Sales by Polymer Type GE CRD Engineering Plastics Sales In US Dollars Polyamide 26%

ETP- Sales by Polymer Type

GE CRD

Engineering Plastics Sales In US Dollars Polyamide 26% Polyester 38% PPS 4% PPO 7% PES
Engineering Plastics Sales In US Dollars
Polyamide
26%
Polyester
38%
PPS
4%
PPO
7%
PES
PEI
1%
1%
PC
Acetal
10%
13%
2000 Sales to Reach $22 Billion Worldwide

Greg Gillette-GE CRD

ETP-Business Trends GE CRD • Forces Driving Reduced Time to ROI •High investor expectations (Stock

ETP-Business Trends

GE CRD

Forces Driving Reduced Time to ROI •High investor expectations (Stock Performance) •E-commerce (Rapid Information Exchange) •Global competition (Cost Pressure/Commoditization)

Time Scale for Technology Innovation Static

How does the Industry Accelerate Innovation •Reorganizations, restructuring, mergers •Growth Through Acquisition vs Organic Growth •Joint Venturing/Resource pooling •Tilt to life sciences and/or Core Business

(DuPont, Hoescht/ Ticona)

(Shell, BP Amoco)

•Specialized vs. Diversified Portfolios ? •Globalization •Combi Chem

Time Scale of Technology Innovation vs Time to ROI

Greg Gillette-GE CRD

ETP-- Technology Trends GE CRD High Perf. Engineering Thermoplastics Commodity Thermoplastics Polyimides,

ETP-- Technology Trends

GE CRD

High Perf. Engineering Thermoplastics Commodity Thermoplastics
High
Perf.
Engineering
Thermoplastics
Commodity
Thermoplastics

Polyimides, Polysulfones, PEEK, LCP’s, etc

Squeeze Play on the Traditional Engineering Thermoplastics

Nylons, Polyesters, Acetal, Polycarbonate, PPO/PS, Ultem, Polyarylates.

Polyolefins (PE, PP, PS, PMMA, PVC), ABS, etc.

Cost Becomes the Key Driver for Those in the Middle

Greg Gillette-GE CRD

ETP -R&D Trends GE CRD 1900-1960 The Age of Discovery . New theories of polymeric

ETP -R&D Trends

GE CRD

1900-1960 The Age of Discovery. New theories of polymeric materials developed. Polymers which account for 98% of the engineering thermoplastic market discovered, developed, and commercialized.

1960-1985 The Research Years. Advanced material developments in liquid crystalline polymers high heat materials; pushing the envelope. Multitude of high-tech materials invented; only a few niche materials commercialized. Blends get commercialized.

1985-1995 The Retrenching Years. Improvements in production processes

to take costs out.

Steady growth of plastics sales at steadily decreasing cost.

1995-?? Research years Phase 2. Upper management recognizes the need to develop new markets in order to continue growth. Engineering plastics become commodities and commodity plastics become engineering plastics.

Greg Gillette-GE CRD

ETP-Market Trends GE CRD Cost, Cost, Cost System Cost Analysis is the Key for New

ETP-Market Trends

GE CRD

Cost, Cost, Cost System Cost Analysis is the Key for New Technology Performance Differentiation Aesthetics-Visual, Touch, Smell (personalization) Weatherability, Modulus/Ductility Balance Optical Properties-Data Storage/Transmission ECO Friendly Materials Processes-Environmental vs. Economic Products-Biodegradability, FR Recyclability Key Technologies Driving Innovation Combi Chem-Catalysis/ Low Cost Monomers Nanomaterials Process Innovations-Thin Walls

Innovation Combi Chem-Catalysis/ Low Cost Monomers Nanomaterials Process Innovations-Thin Walls Greg Gillette-GE CRD

Greg Gillette-GE CRD

ETP-Major Markets GE CRD • Automotive-30 to 40 Lbs./car-Mirror Shells, Underhood •

ETP-Major Markets

GE CRD

Automotive-30 to 40 Lbs./car-Mirror Shells, Underhood

Electrical-Connectors/Switches/Sockets

Building and Construction-Windows/Glazing/Siding

Electrical Equipment-Pagers/Cell Phones/PC’s

Business Equipment-Copiers/Printers

Appliances

Data Storage Media-CD’s/DVD’s

Greg Gillette-GE CRD

Polycarbonate Chemistry GE CRD Melt Process HO OH MeOH + CO O + PhO OPh

Polycarbonate Chemistry

GE CRD

Melt Process

HO

OH MeOH + CO
OH
MeOH + CO

O

+ PhO OPh PhOH O MeO OMe
+
PhO
OPh
PhOH
O
MeO
OMe

catalyst

HO OH MeOH + CO O + PhO OPh PhOH O MeO OMe catalyst 150-320 o

150-320 o C

Advantages:

Environmentally acceptable, no solvent or phosgene. Product cleanliness (low lows), MW control for OQ grades.

Interfacial Process

HO OH
HO
OH

+

Cl

O

control for OQ grades. Interfacial Process HO OH + C l O + ArOH R 3

+

ArOH

R 3 N

grades. Interfacial Process HO OH + C l O + ArOH R 3 N Cl CH

Cl CH 2 Cl 2 / NaOH

Advantages:

Simple, fast reactions, ability to make high MW with complete end-capping.

Greg Gillette-GE CRD

H

O
O

O

O n
O
n

OPh

Research Areas:

Catalysis, process engineering, Monomer purification, Activated Carbonates, end-capping, Quenching and stabilization.

Ar O O
Ar
O
O
O n
O
n

OAr

Research areas:

New monomers, end-cappers, Process Engineering

ETP’s-Emerging PC Application Needs GE CRD Needed- Materials with PC Properties (Ductility/Transparency) With: •

ETP’s-Emerging PC Application Needs

GE CRD

Needed-Materials with PC Properties (Ductility/Transparency) With:

• Barrier Properties

• More Flow-Reduced Cycle Time/Thinner Walls

• Better Optical Properties-Reduced Birefrigence/Higher RI/Lower Absorbance

• Better Dimensional Stability-Higher Heat

• Better FR Properties-PC/Silicone hybrids(Idemitsu)

• Improved Weatherability

• Improved Scratch Resistance

• Reduced Surface Static

• Improved Mold Release

• Improved Hydrolytic Stability

Key Issue: Who is Willing to Pay for Improved Performance?

Greg Gillette-GE CRD

ETP’s-New Materials- PC-like properties GE CRD New Transparent High Temperature Resins     Laboratory

ETP’s-New Materials- PC-like properties

GE CRD

New Transparent High Temperature Resins

   

Laboratory

Development

Pilot

Commercial

 

P(Cyclo-

PCHE

PCXA

Appear

Optorez

Topas

Arton

Zeonex

cene Y)

   

Material

Ethyl/phenyl

Hydrogen’d

P(cyclo-

(Substituted)

Methyl/

Ethylene/

Norbornyl

Norbornyl

norbornene

Polystyrene

hexane)

norbornene

norbornyl

norbornene

adduct

adduct

copolymer

copolymer

methacrylate

copolymer

(polar)

Process

Metallocene

Fr. Radical + H 2

Anionic + H 2

Cationic

Fr. Radical

Metallocene

ROMP + H2

ROMP + H2

 

OPTATECH

DOW

ASAHI

BF GOODRICH

HITACHI

HOECHST

JSR

NIPPON

Producer

   

ZEON

intrinsic

?

<PC

<PC

<PC

<PC

<<PC

<<PC

<<PC

birefringence

     

% Water

<<PC

<<PC

<<PC

<<PC

0.2

<PC

<PC

<<PC

absorption

     

Tg( C)

113

145

to 235

to 330(390)

143

to 170

171

140

Impact

25 kJ/m2

“good”

<<PC

Elongation break = 20%

<PC

<<PC

<<PC

<<PC

Charpy, notch

   

Others:

ICI

-- acrylate/maleimide copolymer

Tosoh -- isobutene/maleimide copolymer

New Transparent.doc

Greg Gillette-GE CRD

Crystalline Resins--New Materials GE CRD • “New” Performance Attributes: High flow (DuPont, Hoechst) Low warp,

Crystalline Resins--New Materials

GE CRD

“New” Performance Attributes:

High flow (DuPont, Hoechst) Low warp, low density (DuPont --> SAN, SMA ??)) ASA-containing (BASF, DuPont) Lower cost LCPs (eventually) ECO-label -- intense development (Toray - - commercial, others) Weatherables

• “New” Polyester Polymers:

PTT (Shell, DuPont, Asahi --> fiber strategy ) Thermx PCT (Eastman, new nucleation package)

“New” Materials with Similar Performance:

sPS (Dow Questra, Idemitsu Xarec) Dow: sPS/nylon blends, p-methyl styrene

Greg Gillette-GE CRD

Crystalline--New Developments GE CRD Monomers: Functional cycloolefins -- diacids and diols (Teijin, Mitsubishi Rayon)

Crystalline--New Developments

GE CRD

Monomers:

Functional cycloolefins -- diacids and diols (Teijin, Mitsubishi Rayon)

Cyclobutane diols (Shell)

Crystalline to Amorphous polyesters

Alkane diols from ethylene oxide (new catalysts Shell) Process:

DuPont developments:

Polymerization under Nitrogen sweep -- no vacuum

Solid state -- micropellets

Additives

Nanocomposites-Commercially used in Nylon for HDT

Greg Gillette-GE CRD

High Temperature ETP’s-Market View GE CRD High Temperature Thermoplastics 1997 & 2002 Global Market Volume

High Temperature ETP’s-Market View

GE CRD

High Temperature Thermoplastics 1997 & 2002 Global Market Volume vs Price

300 1997 Data 250 PPE 2002 Data 200 1997 Fit 2002 Fit 150 100 PPS
300
1997
Data
250
PPE
2002
Data
200
1997
Fit
2002
Fit
150
100
PPS
PSO
50
PEA
PES
PEI
0
0
2
6
8
Price 4 $/lb
Total Market
MM lbs

High Temperature Resins: Volume is Controlled by Price.

Greg Gillette-GE CRD

Polyetherimides-Market Breakdown GE CRD Packaging 14% 18% 7% 16% 14% 31% Houseware Medical E /

Polyetherimides-Market Breakdown

GE CRD

Packaging

14% 18% 7% 16% 14% 31%
14%
18%
7%
16%
14%
31%

Houseware

Medical

E/E

Other

Automotive

1998 Sales: 26MM lbs.

Houseware

25% 7% 12% 13% 43%
25%
7%
12%
13%
43%

Other

CEIS

E/E

Automotive

2005 Sales: 70MM lbs.

Growth Platforms

10% 40% 10% 40%
10%
40%
10%
40%

Cookware

Metallizing

All Other

Dimensional

Stability

Greg Gillette-GE CRD

ETP’s- Perspectives for POSS GE CRD Higher Performance Standards Create Opportunity for POSS •ECO FR-PWB’s

ETP’s- Perspectives for POSS

GE CRD

Higher Performance Standards Create Opportunity for POSS

•ECO FR-PWB’s

•Higher Heat/Modulus/ Nanotechnology

•Control of Surface Architecture-Nanopatterning

•High Performance Silicone Resins-PSA/Controlled Release

•Nanostructured Composites-Fillers

•Catalyst Supports Current Themes/Opportunities

ECO

Biodegradable

Recyclable

Weatherable

}

But Who Will Pay More for it??

Breakthrough In Cost Needed to Fuel Application Growth

Greg Gillette-GE CRD

Parting Thoughts GE CRD • Search for new ideas, new products, new markets . mutual

Parting Thoughts

GE CRD

• Search for new ideas, new products, new markets

.

mutual interaction between technology & commercial .Don’t underestimate unknown markets for new materials

.

Keenly aware of competition at our doors; must differentiate

• The future will not reflect the past

. willingness to think and operate outside our comfort zone

Metals have been around for 5000 years

Polymers have only been around for 70 years

The 21st century will bring many new things; expect surprises

Greg Gillette-GE CRD

Resin Types GE CRD Polyphenylene ether alloys O n n High temperature amorphous material. PPO

Resin Types

GE CRD

Polyphenylene ether alloys

O n
O
n
n
n

High temperature amorphous material. PPO with Tg ~260 o C blends with PS to lower HDT and processing temperature. Must be impact modified to obtain high strength. Excellent dimensional and hydrolytic stability, but no solvent resistance. Blends with nylons give materials for large parts for automotive applications. Markets of 100-160,000 t/yr with growth ~9%/yr.

Polysulfones

Markets of 100-160,000 t/yr with growth ~9%/yr. Polysulfones O O S O O n O S

O

O S O O
O
S
O
O

n

O S O O
O
S
O
O

n

Several types of polysulfones (PSO, PES, PPSO) are sold as amorphous materials with low flammability and good electric properties. Excellent hydrolytic stability and high HDT for high temperature use. Markets include electrical, electronic, and medical, with sales of 13,000 t/yr. Relatively high prices.

Greg Gillette-GE CRD

Resin Types GE CRD Acetals -(CH 2 O) n -, copolymers with ethylene oxide fast

Resin Types

GE CRD

Acetals

-(CH 2 O) n -, copolymers with ethylene oxide

fast crystallizing, solvent resistant; use temperature up to 135 o C, brittle, self-lubricating, low moisture absorption, but high shrinkage (25%). Used for small parts. Processibility and thermal stability main advantages. Worldwide capacity ~ 250,000 t/yr; Growth 2-10%/yr.

Nylons

O O R' N R N n H H
O
O
R'
N R
N
n
H
H
O N R n H
O
N
R
n
H

Nylon 6 and Nylon 6,6 largest volumes (~600,000 t/yr non-fiber), with modest growth (5-8%/yr). Amorphous nylons only ~1000 t/yr,but with higher growth. Fast-crystallizing polymer with HDT 194 o C (6,6) and 129 o C (6). from mp of 270 o C and 228 o C, respectively. Poor impact strength. Good hydrolytic stability but high water absorption (10%) and mold shrinkage. Small parts, electrical, building construction applications, under-the hood automotive.

Greg Gillette-GE CRD

Resin types GE CRD Polyesters O O (CH 2 ) n O n = 2,3,4

Resin types

GE CRD

Polyesters

O O (CH 2 ) n O n = 2,3,4 n
O
O
(CH 2 ) n O
n = 2,3,4
n

O

Both crystalline and amorphous products. Melt processing and solid-state polymerization are used. Largest applications are blow-molded bottles, films, and extrusions. PBT crystallizes fast, PET slower. PBT has Tm 225 o C, PET 265 o C. Both have low moisture absorption, poor impact strength. Glass-filled products are common. Market about 800,000 t/yr with a growth rate of 7-12%. Aromatic polyesters have much smaller niche in high temp materials which have high impact and are photostable.

Polycarbonates

O
O

O

O n
O
n

Transparent, very high impact strength, amorphous material with low moisture absorption, Tg of about 150 o C. Made interfacially via phosgene and by melt process. Poor solvent resistance. Markets include sheet products, optical applications, consoles and cabinets, power tools, automotive, etc. Market about 300,000t/yr with growth ~ 10%/yr

Greg Gillette-GE CRD