Smart Polymeric Materials:

Dutch Polymer Research

Martien Cohen Stuart

IA seminar12 december 2012, The Hague

Pioneers of polymer research in The Netherlands (1960 - ….)

Companies: AKU cellulosics; fibres, resins DSM coal-derived chemistry: olefines polyolefines PE, PP

nitrogen binding: caprolactam polyamidesDOW GE various engineering plasticsWAVIN (PVC) processing

Universities: Leiden (Staverman, Hermans)Delft (Janeschietz-Kriegl, van der Vegt)Groningen (Challa, Pennings)Eindhoven (Heikens, German, Lemstra)Twente (Feijen, Smolders, Noordermeer)

Polymer chemistry & physics in the polder

1997:

launch of the ‘Dutch Polymer Institute’

for public-private collaboration in polymer science

(initiative Hans Wijers, minister of Economic Affairs)

From science to market:

Chemical R&D timeframes Industrial R&D

University

Business <3 months

3 months-2 years

2-5 years

DPI

Dutch Polymer Institute

5-10 years

>10 years

DPI: ‘Leading Technology Institute’

Missions

•To fill the gap in the Dutch knowledge infrastructure

•To operate at the interface between academia and industry

•To become a key instrument for innovation

The art of connecting….

Government

Universities

Industry Society

The art of connecting….

Government

UniversitiesIndustry

Society

Industrial partners2011

Academic partners2012

How does it work?

…bringing academia and industry together…..

$$$$$$$$$$

E = mc2

Participation InfrastructureInnovation budget

Portfolio 2012

Technology areas

•Functional Polymer Systems & Large-Area Thin-Film

Electronics

•Polyolefins

•Performance Polymers

•Coatings Technology

•Bio-Inspired Polymers

•Emerging Technologies: polymers for EOR

High-Throughput Experimentation

Corporate Research

Functional Polymer Systems

Largest area

Research topics:

conducting & light emitting polymer systems

OLEDs, organic solar cells

polymer systems with switching and actuation properties

Lighting and electronics

Globally leading research: Eindhoven, Delft, Groningen fast developments,

‘hot’ field

Side-chain Liquid Crystalline polymers

Light-induced shape and optical changes

display technology

Actuators, artificial flagella, surface morphology switching

Very innovative field (Eindhoven)

Polyolefines

2nd largest area; all major players participate

Mainly research on new catalysts and catalyticcontrol of material properties

Major breakthrough: unentangled UHMPE

New: mixed catalyst systems for controlled microstructure

Performance Polymers

Large area; many global players participate

Elastomers; engineering plastics

Research on processing & performance:

Toughness, fracturing, friction & wear, composites,

processing technology

Building and construction

Liquid Crystal Thermosets for Structural Materials

• Liquid crystalline polymers (LCPs) were recognized and introduced in

the 70’s:

+ excellent barrier properties (He, O2, H2O uptake < 0.03%)

+ high strength/stiffness

+ outstanding solvent resistance (Skydrol, jet fuel etc.)

+ low CTE, low mold shrinkage (V0 rating, also used in ablative

applications)

• The first generation LCPs had such properties

but were very difficult, if not impossible, to process.

CN

H O

n

poly(iminocarbonyl-1,4-phenylene)

Lyotropic, Tm>> 500 oC

CO

O

n

poly(oxy-1,4-phenylenecarbonyl)

"Thermotropic", Tm>> 500 oC

The challenge: how to make these intractable polymers tractable?

Good propertiesbut intractable

tractablebut poor properties

The solution: The solution:

use oligomers with (latent) reactive endgroups use oligomers with (latent) reactive endgroups

(Telechelic Oligomers)(Telechelic Oligomers)

PETI-5

1. Before cure: LC thermoplast

2. After cure: LC thermosetwith excellent performance High T organic materials

Solar cellsGas separation membranes

Space durability tests (MISSE 2005-2009)

Prof. Theo Dingemans

DPI fellow 2011

Coatings technology

Vital area, many participants, often market leaders

A diverse field, physics & chemistry:

(Sustainable) esin chemistry

Drying of water borne dispersions

Thickeners

Weathering chemistry

Corrosion protection

.......

Alkyd emulsion drying

crystallization

deformation

coalescence

Fresh paint

dry paint

?

(a) (b) (c)

(d) (f)(e)

Microscopic observations

two modes of coalescenceHigh [emulsifier]

Low [emulsifier]

‘top down’

‘random’

resinresin

resin resin

Marine coatings: sustainable biofouling control

Developing research field; very challenging

Bio-inspired Polymers

Developing field

sustainability & biomedical applications

New bio-based monomers

Enzymatic polymersation technology

Biosynthetic aminoacid polymers

Polysaccharide research

‘Bio Related Materials’ Programme (together with FOM and TIFN)

PHYSICAL CHEMISTRY AND COLLOID SCIENCE

Rational Design of Block Copolypeptides

C -SQ -K144 12 Triblocks

Molecular Biomimetics

Diblocks

++++ + + +++++

++++ + + +++++

-Binding of single DNA molecules- Reassembling cylindrical viruses

Hernandez-Garcia, Et. al. Small, 2012

PHYSICAL CHEMISTRY AND COLLOID SCIENCE

Mechanism of DNA Packing

Highly organized virus-like nanorod structures

2.5 kbp DNAScale is 780, 780, 625, 500 & 500 nm (left to right)

8 kbp2.5 kbp

Frustrations on packing

2.5 kbp

Time, concentration, salt…(pH, temperature)

More than one “growing” point

C -SQ -K104 12

Emerging: water soluble polymers for EOR

New area (2 participants)

development of water soluble polymersfor oil & gas industry

High throughput Experimentation

An extensive platform of

advanced equipment for

high throughput research

of new polymeric materials:

// synthesis, molecular characterization, phase behaviour

mixing & compounding, spotting

Corporate Research

Explorative research on new directions in polymer science

(thematic calls)

AND

Enabling technology (theory & simulation, polymer

characterization, chromatography,

neutron & synchrotron experiments)

DPI: workforce

Output (articles) Impact (citations)

Output and impact of DPI: web-of-science

start

Scientific quality: DPI Journal Impact Factor

Normalized impact Dutch chemical research:the highest in the world: 1.53

Steady improvement

Increasing internationalisationNew collaborations

European consortia

- CompNanoComp: Multiscale computational approach

for design of polymer-matrix nanocomposites

- SHINE: Self-Healing Innovative Elastomers

Other proposals in preparation

Outside Europe

• Brasil

- Collaboration between CNPq, TU/e and DPI

- seven projects; start January 2013

• China

- Programme within Coatings Technology and Bio-Inspired

Polymers

- approximately ten PhDs; start early 2013

DPI: quo vadis?

• New Dutch innovation policy (topsectoren) starting....

• Companies shift to new markets & activities

• Polymers remain important for Dutch economy

• Many creative polymer scientists in Dutch academia:

Groningen (Hermann, Loos)

Twente (Vancso)

Delft (Dingemans)

Eindhoven (Meijer, Huetter, Wyss, Noordover, van der Schoot)

Wageningen (Kamperman, Sprakel)

DPI strives to be(come)

worldwide connected polymer centre of excellence