The transformation of plastics from “ugly duckling” to ... · APAC IS 2015 | Gerry Wilson| Page...

CSIRO MANUFACTURING

The transformation of plastics from “ugly duckling” to “beautiful swan” Gerry Wilson| Research Program Director | Industrial Innovation

APAC IS 2015 | Gerry Wilson|

Megatrends Polymers Case History 1: RAFT Case History 2: Electroactive Polymers Case History 3: Flow Chemistry

Overview


CSIRO MEGATRENDS

More from less: A world of limited resources, needs better efficiency,

On the move: Transport, Urbanization, Global supply chains

iWorld: Increased electronic connection

A personal touch: Health care, products, platforms services

Divergent demographics: Economies shifting from Ag-based to Manufacturing-based

WAVES OF INNOVATION

Megatrends v2009 Cleaner, smarter and high performing

More from less

On the move

iWorld A personal touch

Divergent

Cleaner

Smarter

Service Oriented

High Performance


Megatrends v2009 Cleaner, smarter and high performing

ISBN: 9781486301409


Megatrends v2015 Shaping our 2020 strategy

More from less Efficient use of resources

Planetary pushback From Large (climate change) to Small (antibiotic resistance)

The silk highway Emerging and transitioning economies

Forever young Physical and mental healthspan,

Digital immersion Big data, IoT

Porous boundaries Agile, networked and flexible economies

Great expectations The ‘experience factor’


Megatrends v2015 Shaping our 2020 strategy


• Australia’s National Research Labs.

• Established in 1926

• CSIRO has over 5,000 employees

• Our income ($1.3B) has two main sources:

60% from the Australian Government,

40% from external collaboration

CSIRO Commonwealth Scientific and Industrial Research Organization


• >1,600 Australian companies

Big Australians and SMEs

• > 380 Multinationals

• >330 licences

• >$400M R&D work per annum

• >150 spinouts

• Interests in 34

>$1.4Bn market cap

>$450M in sales

>300 jobs

CSIRO Commonwealth Scientific and Industrial Research Organization


From ugly duckling to beautiful swan…


Polymer Age

1909 1946

? ? ?

2000

“1,001 uses” Nylon riots waste, waste, waste a new beginning…

http://en.wikipedia.org/wiki/File:Bakelite_radio.jpg

http://en.wikipedia.org/wiki/File:Bakelite_radio.jpg



Overview


Case History: RAFT Reversible Addition Fragmentation Chain Transfer

Free radical leaving group

R, must be able to reinitiate

polymerization Weak C-S bond;

monomer inserts here

Reactive C-S double bond

Z-group controls the

reactivity of the C-S

double bond; influences

the rate of radical addition

and fragmentation

RAFT Agent / Chain

Transfer Agent (CTA)

Polymeric RAFT Agent

(MacroCTA)

RAFT End Group enables

reactivation of polymer to add

a new block or cross-linker; or

post-polymerisation

functionalisation

R group can contain

functionality to enable

conjugation of actives or

targeting groups

RAFT agents are tailored

to different monomers to

provide an efficient

process and narrow

dispersisties

MW

A versatile way to create new materials

in a systematic way

A simple yet sophisticated form of

controlled free radical polymerisation

RAFT

---------- Free

Radical


S

C

R – S Z




Accessing Unique Architectures with Precision

RAFT offers the ability to design and manufacture complex, multi-functional

polymers with unique properties, tailored to their industrial application



Agriculture

Personal Care

Industrial Chem

Biomedical


Case History: RAFT Agriculture Agriculture

Personal Care

Industrial Chem

Biomedical

0

0.5

1

1.5

2

2.5

3

3.5

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

ug

/ml

Acti

ve I

ng

red

ien

t

sample point

A.I.:Polymer; quasiblocks

Spartan 4F

Control (A.I.)

Dispersion in water

“Solid Solutions”

No Surfactants Needed

RAFT improves solubility and bioavailability of active ingredients:

RAFT polymers offer a minimum 30 wt% loading (ca. 300g/L)

in final formulation

Current solubility limits: Metconazole (30mg/L) Pyraclostrobin (1.9mg/L)

RAFT reduces leaching of actives in soil:

CSIRO polymer provides better retardation than pure A.I. or commercial

A.I. formulations

Ref: US 2010/0047203, BASF Use of Block copolymers based on vinyl lactams and vinyl acetate as solubilisers

pVP pVAc 60:40 (13,900 Da)


Case History: RAFT for Cosmetics Agriculture

Personal Care

Industrial Chem

Biomedical

Adhesive block ethylenic copolymers, cosmetic compositions containing them and cosmetic use of these copolymers:

Design: Linear, block ethylenic copolymer of two very different Tg’s; Setting defined Tg parameters provides discrete properties Properties: Adhesive copolymer with an adhesion value > 3N. Thermoplastic polymer is soluble in cosmetic formulations, and provides superior adhesion properties

Uses:

• Hairspray – improved styling power and suppleness • Nail polish – increased resistance to shock • Improved strength of a wide variety of cosmetic compositions

L’Oreal

US7910120B2 (March 22nd 2011)


Case History: RAFT for Cosmetics Agriculture

Personal Care

Industrial Chem

Biomedical

Triblock copolymer, composition comprising it and cosmetic treatment process:

Design: • Combination of two different Tg blocks provides elastomeric and adhesive properties • Block copolymers have advantageous mechanical properties and may be used in large amounts

within the formulation, without having a substantial influence on gelation or thickening • Polymer is film forming on keratin materials

Uses: Care/makeup product for bodily or facial skin, lips and hair Anti-sun product Self tanning product Hair care product

L’Oreal/Arkema

US7951888B2 (May 31st 2011)


Case History: RAFT for Conditioners Agriculture

Personal Care

Industrial Chem

Biomedical

Cosmetic composition comprising a block copolymer:

Linear AB diblock with positively charged major block reduces amount of surfactant needed in final formulation

Provides: 1. Conditioning effect and enhances/triggers deposition of other compounds (silicone

emulsions or cationic conditioning polymers) 2. Stable emulsions (oil in water and triple emulsions) 3. Avoids phase separation of colloids

Rhodia

US7846423B2 (December 7th 2010)


Case History: RAFT Viscosity modifiers

RAFT improves additive performance via multifunctional

polymers:

‘Arm first’ approach for simpler

manufacturing

Replace complex formulation

with ‘just right’ multifunctional

polymer

Methacrylate based star polymer architecture required for improved

performance readily available using RAFT

Agriculture

Personal Care

Industrial Chem

Biomedical

Ref: WO 2012030616, Lubrizol, M Baum, JR Johnson, H Qin


Case History: RAFT Dispersants

US 2008/0268250, Dulux/Usyd Polymerisation Process and Polymer Product

P(AA) – P(Sty) P(MMA/BA)

Multi functional RAFT Polymer: AA10-b-St130-b-(MMA-co-BA)1100

RAFT improves pigment dispersion:

Dispersing TiO2 in water using RAFT

• Encapsulation of TiO2 particles

• 60 wt% dispersion in water

• Film formation

Film formation

Agriculture

Personal Care

Industrial Chem

Biomedical


Case History: RAFT Surface Initiated RAFT

Surface Initiated RAFT

Cross-platform methodology to graft polymers from various substrates

Meagher, L. et al. Acta Biomaterialia 2012, 8, 608; US 8795782 B2

Example Surfaces: Gold, Silica, Ceramics, Graphite, Polymers,

Perfluorinated EP films Surface is functionalised with anti-fouling polymers for use in biomedical implants that prevent protein adhesion

Agriculture

Personal Care

Industrial Chem

Biomedical

APAC IS 2015 | Gerry Wilson| Page 24

Case History: RAFT for Dental Coatings Agriculture

Personal Care

Industrial Chem

Biomedical

RAFT can generate biocompatible coatings to prevent tooth erosion under acidic conditions:

Binds to hydroxyapatite through bridging bidentate bonds, which are retained at low pH, preventing mineral loss due to acid corrosion

Incorporate into dentifrices and mouthrinses as alternative to non-fluoride

additives

Mimic of natural proteins casein phosphopeptide and amelogenin

which prevent tooth erosion

Example 1:

Example 2:

Polymer decreased the mineral loss of hydroxyapatite by 36–46% compared to the untreated control

Lei, Y. et al. J. Dent. Res. 2014, 93, 1264; RSC Adv. 2014, 4, 49053 (Colgate sponsored research)


Case History: RAFT Anti-Fouling Coatings

Anti-Fouling Coatings

Amphiphilic polymers which prevent protein and bacterial adhesion:

By combining hydrophilic PEG and hydrophobic Fluorine groups into one polymer architecture, bacteria, protein and cell adhesion can be prevented

Ober, C. K. et al. Biomacromolecules, 2006, 7, 1449; Langmuir, 2010, 26, 9772; Janczewski, D. et al. Langmuir 2014, 30, 288

Surface attachment block can be RAFT agent group, siloxane macroRAFT or styrene block

Agriculture

Personal Care

Industrial Chem

Biomedical



Overview


Case History: Electroactive polymers

C

H

H

C

H

H

( ) n

PA

Structural complexity

Fu

nctionalit

y


Why print solar cells? Solar energy

from everywhere

Light-weight

Semi-transparent

Diffuse light

Flexible


Why print solar cells?



Solar energy for everyone

Low-cost

Fast payback

Remote or developing

communities

Why print solar cells?



Solar energy for Australian

manufacturing

Low-cost infrastructure

Drive local PV industry

Builds on existing processes


A D A

Traditional approach A

D

electron poor (acceptor)

electron rich (donor)

Tune molecular orbitals to:

Modify HOMO to max Voc

Lower band gap to max Jsc

Tune substituents to:

Modify solubility

Modify microstructure

Donor – Acceptor approach



Tianshi Qin et al., JACS, 136 (2014) 6049

Intermediate (A-D-A) Regioselectivity

Second donor (D2)

Improved ordering

Side-chain flexibility Improved solubility

A-D1-A-D2 polymers



ITO/PEDOT:PSS/polymer:PC61BM/PFN/Al

Structural control Better π-stacking Improved performance

Tianshi Qin et al., JACS, 136 (2014) 6049

A-D1-A-D2 polymers



Jegadesan Subbiah et al., submitted

Molecular weight

Polydispersity

Inverted geometry

Interlayers

(a) (b)

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2-16

-12

-8

-4

0

4

8

PBDT-BT:PC71

BM (1:2)

ZnO

ZnO/PCBE-OH

Voltage (V)

Cu

rren

t D

en

sit

y (

mA

/cm

2)

300 400 500 600 700 800

0

20

40

60

80

Wavelength (nm)

ZnO

ZnO/PCBE-OHEQ

E

Mn, Interlayers Jsc (mA/cm2) Voc (V) FF (%) PCE (%)

19 kDa, ZnO 9.5 0.92 50 4.4

78 kDa, ZnO 13.6 0.92 60 7.6

112 kDa, ZnO 14.5 0.92 64 8.5

136 kDa, ZnO 13.4 0.90 53 6.4

112 kDa, ZnO/PCBE-OH 15.4 0.92 66 9.4

A-D1-A-D2 polymers: From 2% PCE to 10% in 2 years!



Effi

cien

cy (

%)




Overview


Case History: Flow Chemistry

Conventional Organic Synthesis: The Paradigm

work-up

Batch reactor

Crudeproduct

Purification

Catalyst in batch reactor

work-up Crudeproduct

Purification

Cleanproduct

Scale-up

Laboratory Scale Pilot Scale

Conventional Chemical Manufacture: The Paradigm



A

B

Reactant feed tanks

Pump

Pump

Flow reactor

C

Pump Product

tank

In-line purification

In-line analysis

Mixer

Reactant/quench tank

Back pressure regulator

Mixer



Increased MW

improves device PCE

R Coffin, J Peet, J Rogers, G Bazan Nature Chemistry, 1, 2009, 657

Other reports show there are "sweet spots",

bigger is not always better but control is important



H Seyler, DJ Jones, AB Holmes, WWH Wong Chem Comm 2012, 48, 1598

PFO

PCDHTBT



Shorter reaction times and better yields

AND

completely scalable (without additional effort)




H Seyler, WWH Wong, DJ Jones, AB Holmes, J Org Chem 2011, 76, 3551

15g per day



H Seyler, WWH Wong, DJ Jones, AB Holmes, J Org Chem 2011, 76, 3551

RAFT

20600

22100

4570

23600

24800

21300

20500

15900

19500

16600

19800

22200

24900

4620

0

5000

10000

15000

20000

25000

1 2 3 4 5 6 7

Mn [

g/m

ol]

90 °C70 °C 80 °C 80 °C100 °C 100 °C

F B

8)7)5)4)3)2)1)

80 °C

NIPAM NIPAM DMANIPAMNIPAM VAc

F F F

F

F

B B B

B

B

nBA

Flow = Batch (yield and quality)

Good reproducibility

Efficient scale-up of a highly oxygen

sensitive process


Take away messages

Plastic ‘Renaissance’ following the ‘Dark Ages’

Functionality = Complexity + Control

New Chemistries deliver Functional Polymers

New Manufacturing Processes deliver Scale

Thank you CSIRO Manufacturiung Gerry Wilson t +61 3 9545 2205 E [email protected] w www.csiro.au

The transformation of plastics from “ugly duckling” to ... · APAC IS 2015 | Gerry Wilson| Page...

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