The role of mother earth, water, air and fire in the development of new polymer materials

Cor Koning

DPI Annual meetingMaastricht, November 21, 2007

The role of mother earth, water, air and fire in the development of new polymer materials

or

‘The elements’ and materials development

Four examples

Novel bio-based polyesters: Synthesis, characterization and evaluation

TA Coating Technology, DPI project # 451

B.A.J. Noordover1, R. Duchateau1, C.E. Koning1, R.A.T.M. van Benthem2, Andreas Heise1, R. Koelewijn3, J. van Haveren3 and D.S. van Es3

1 Laboratory of Polymer Chemistry, Eindhoven University of Technology, The Netherlands

2 Laboratory of Materials and Interface Chemistry, Eindhoven University of Technology3 Agrotechnology and Food Innovations, Wageningen University and Research Centre

Renewable thermoset powder coatings

• general characteristics

• solvent-free coating systems• mixing of components (i.e. resin, cross-linker and additives) by extrusion• powder applied to substrate using electrostatic interactions• subsequent thermally induced flow and curing

• resin requirements

• storage stability and mechanical performance: Tg > 45 ºCalready for moderate Mn, 2000 – 6000 g/mol

• functionality f ≥ 2 (often: carboxylic acid or hydroxyl functionalities) • amorphous and colorless• appropriate flow properties at Tcure• UV stability aliphatic rather than aromatic polyesters

Why use renewables?

• building blocks with high functionality available from nature, suitable for polymer network formation

• decreasing fossil feedstock (and increasing oil prices)• rigid, high Tg providing aliphatic monomers readily available

for example: dianhydrohexitols

• available feedstock: starch (corn, potatoes etc.), cellulose, vegetable oils etc. ‘From corn to coatings’

Synthesis of 1,4:3,6-dianhydro-D-sorbitol (isosorbide) from sorbitol

sorbitol isosorbide

acid cat.- 2 H2O

OHOH

OH

OH

OHOH

O

OOH

OH

H

H

Monomers from biomass

isosorbide isomannide isoidide 2,3-butanediol 1,3-propanediol(IS) (IM) (II) (BD) PD)

OHOH

O

OOH

OH

H

HO

OOH

OH

H

HO

OOH

OH

H

H

OHOH

OHOH

O

O O

OOH

OH

glycerol sorbitol citric acid tartaric acid(GLY) (CA)

OH OHOH O

O

OHOH

OHOH

OH O

OH

O

OHO OHOH

OH

OH

OH

OHOH

succinic acid adipic acid(SA) (AA)

Melt polycondensation

• polyesterification under inert gas flux, followed by vacuum processing• typical temperatures: 180 – 230 ºC (not too long at 230 ºC !!!) • typical pressures (2nd stage): 1-5 mbar

O

OHO

OH

O

OO

O

H

H

O

O

O

O

O

m

n

RO

O

OOH

OH

H

H

OH R OH+ +m nΔT, Ti(OBu)4

Succinic acid Diol 2 Isosorbide

Succinic anhydride + Isosorbide + second diol

0

10

20

3040

50

60

70

50 60 70 80 90 100

isosorbide content [mol% of diols]

T g [º

C]

Diol 2▲ = 2,3-butanediol▲ = 1,3-propanediol

Molar mass can be controlled (2000-6000 g/mol

Enhancing OH functionality with glycerol

O

O

O

O

O

O

O Hp

O

O

O

O

O

O

OH

m O

O

OO

O

O O

Hn

OH groups can easily be transformed into COOH groups by reaction with citric acid

B.A.J. Noordover et al, Biomacromolecules, 2007

Curing with petrochemical-based curing agents

N

N N

O

O

O

NH

O

NO

NH

ON

O

NH

O

N O

N

OCN

NN

O

OO

NCOOCN

N

NN

O

O

O

O

O

OO

O

NN

OH

OH

OH

OH

R OH OCN R1 RO

O

NR1

H

+ urethane

COOHRO

R1

O

R OR1

OH

COOHR OH R1

O

ORR1

+

+

ester

OH-functional

COOH-functional

Appearance, toughness and UV-stability

OH functional,cured withtriisocyanate

reference coating

weathered coating

COOHfunctional,cured withtri-epoxide

COOHfunctional,cured with Tetra-hydroxy

No yellowing under highintensity mercury lamp

Fully biobased polycondensate resins

Branched polyesters and polycarbonates based on the 1,4:3,6-dianhydrohexitols (notably: isosorbide and isoidide)Functionality enhanced by incorporation of, e.g., glycerol, citric acid

OH-functional polyesters / polycarbonates COOH-functional polyesters(based on isosorbide / isoidide) (obtained by citric acid modification

of linear OH-functional polymers)

fully biobased resins with Fn > 2

conventional curing agents:- OH-functional polymers: polyfunctional isocyanate compounds - COOH-functional polymers: epoxy / activated OH compounds

O

O

OHO

OO

O

O

O

H

H

H

O Om

O

O

n H

HO

O

RO

OHOOC

OH

COOH

O

OOH

COOHCOOH

Three novel, biobased, blocked diisocyanate compounds were developed by A&Ffor curing OH-functional polymers (I – III)A biobased bis(glycidyl ether) was prepared by A&F to cure COOH-functional polymers (IV)

Biobased curing agents

O

OO

OO

OH

H

ON

O

N

OO

N

O

N

O

N

OO

OO

O

ON

O

N

O

N

O

O

O

N

N

O

O

H

H

N

O

N

O

I II

III IV

I = bl-IPDFI, II = bl-IIDI, III = bl-FDEDI, IV = ISBGE

Glycerol-branched biobased resin + blocked diisocyanatesCitric acid-modified polyester + ISBGE

Coating results:bl-IIDI: - good solvent resistance

- good impact resistance- some discoloration

bl-IPDFI/: - moderate to good solvent resistancebl-FDEDI - moderate impact resistance

- strong discoloration

ISBGE: - moderate to good solvent and impact resistance- some discoloration

O

O

N

N

O

N

O

N

O

O

H

H

O ON N

O

O

NN

O

O

N

OO

OO

O

ON

O

N

O

N

O

O

OO

OO

OH

H

From bio-feedstock provided by mother earth high quality performance products can be

developed

Using enzymes for developing novel polymer materials

Core program DPI project #381,continued within TA-BI, project #608 , Inge v.d. Meulen

M. de Geus, B. van As, J. Peeters, A.R.A. Palmans, A. Heise, C.E. Koning

Laboratory of Polymer Chemistry

Laboratory of Macromolecular and Organic Chemistry

Technische Universiteit Eindhoven

enzymemonomer

polymer

These advantages can be utilized to make materials especially for biomedical applications in view of absence of metal residues,

not easily available from conventional techniques.

These advantages can be utilized to make materials especially for biomedical applications in view of absence of metal residues,

not easily available from conventional techniques.

Advantages of Enzymes

• Enzymes are very efficient catalysts.

• Enzymes act under mild conditions.

• Enzymes are environmentally acceptable and metal-free.

• Enzymes are not bound to their natural role.

• Enzymes can catalyze a broad spectrum of reactions.

• Enzymes are selective (chemo-, regio-, enantioselective).

Two questions

1. Can enzymes be used in combination with chemical catalysts e.g. for the synthesis of block copolymers, and can this be realized in one pot?

2. Can enzymes result in materials that cannot be made using chemical catalysts?

Two questions

1. Can enzymes be used in combination with chemical catalysts e.g. for the synthesis of block copolymers, and can this be realized in one pot?

2. Can enzymes result in materials that cannot be made using chemical catalysts?

Yes

Yes

Matthijs de Geus – DPI GTA presentation

eROP and Nitroxide Mediated LFRP

O

OH

N

OHn

O

O

NOm

O

O

Novozym 435,

13 14 15 16 17 18t (min.)

A B

• Chemoenzymatic block copolymersynthesis was achieved in one pot.

• Method to synthesize block copolymers in a metal free fashion.

First example of a one-pot chemo-enzymatic cascade polymerization!

Polypentadecalactone:

biodegradable polyethylene?

Polycaprolactone - PCL

Polyethylene

Polypentadecalactone – PPDL(100% linear)

OHO

OH

O

O n /2

OH O

O

H

n

n

Properties ‘enzymatic’ PPDL (Mw= 190 kg/mol)

60

>1200

εbreak

[%]

163504254-60PCL

184208195-20PPDL

σyield

[MPa]E

[MPa]Tc

[oC]Tm

[oC]Tg

[oC]

Non-oriented samples

Chemically catalyzed synthesis of PPDL: Mw,max = 40.000 g/molEnzymatically (literature) : Mw,max = 80.000 g/molAfter careful drying the enzyme (this study): Mw,max = 190.000 g/mol→ (Biomedical) fiber applications come within reach (Evaluation with Bert Joosten, Marco Marcus and Ronald Deumens of AZM Maastricht)

First results fiber spinning from melt

Melt spinning of highest molecular weight PPDL, followed by

drawing/elongation results in fibers with strength of

0.6-0.7 GPa (Commercial Nylon fibers: ca. 1 GPa)

Solution spinning is expected to yield even higher strength

(experiments in progress in collaboration with Lemstra)

Degradability needs optimization if biomedical applications

are targeted (copolymers with more hydrophilic comonomers

and reduced crystallinity)

Inge van der Meulen (DPI # )

[1] C.M. Byrne et al, J. Am. Chem. Soc., 126, 11404-11405 (2004)

Chiral polyester particles for drug release

O

O

OOO

O

Hn

O

O

Hm

*racemic mixture

1 2 3

1: poly((S)-4-methyl caprolactone)2: poly((R,S)-4-methyl caprolactone)3: poly((R)-4-methyl caprolactone)

**

O

O

O

O

OO

O

n

Om

**O

O

O

O

OO

O

n

Om

**

O

Cl

N(Et)3

Jenny Xiao, Andreas Heise, Anja Palmans ‘Biomade’

0 5 10 15 20 250

10

20

30

40

poly (S) MCL poly (R,S)MCL poly(R) MCL

time (h)

conv

ersi

on B

A (%

)

0 5 10 15 20 250

10

20

30

40

poly (S) MCL poly (R,S)MCL poly(R) MCL

time (h)

conv

ersi

on B

A (%

)

Novozym 435 catalyzed degradation of chiral and racemic PMCL

UV-cured poly(4-Methyl CL) particles

Mother earth provides bio-catalysts suitable for development of high quality

performance products

CarbonCarbon--NanotubeNanotube/Polymer Composites: /Polymer Composites:

Starting Wetter, Conducting Better Starting Wetter, Conducting Better

A latex-based concept to develop electrically conductivePolymer/carbon nanotube composites

TAs EP/RT + FPS, projects 416 and 529

• Nadia Grossiord, Marie-Claire Hermant, Bert Klumperman, Junrong Yu, Kangbo Lu, Joachim Loos, Jan Meuldijk, Alex van Herk, Paul van der SchootEindhoven University of Technology, The Netherlands

• Oren RegevBen-Gurion University of the Negev, Israel

• Hans Miltner, Bruno Van MeleFree University of Brussels, Belgium

Single vs. Multi-Wall Nanotube

vs.

Promising fillers for polymer composites

• Low loading can give percolation

because of high aspect ratio

• Strong and stiff

• Good electrical conductivity

A bundle of nanotubes

Bundled (SW) or entangled (MW)

Production of the composite

1st step Make stable aqueous CNT dispersion1. Bring the NTs in contact with SDS (sodium

dodecyl sulphate) surfactant solution

2. Sonication for debundling (15 min, 20W, 20kHz)

3. Centrifugation of catalyst residues (30 min, 4000 rpm) and continue with supernatant

2nd step: Mixing of the NTs solution with

the polymer latex

3rd step: Freeze drying of the mixture

4th step: Melt Processing of the powder obtained

Step 2Mix NTs and latex

Both NTs and PS latex particles stabilized by SDS

Φav,latex = 70 nm

PS-SWNT composite

1.00E-12

1.00E-11

1.00E-10

1.00E-09

1.00E-08

1.00E-07

1.00E-06

1.00E-05

1.00E-04

1.00E-03

1.00E-02

1.00E-01

1.00E+00

0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60

concentration nanotubes (wt%)

Con

duct

ivity

[S/c

m]

Con

duct

ivity

(S/c

m)

Concentration nanotubes (wt%)

Percolation threshold ~

0.3wt%

1.E-12

1.E-10

1.E-08

1.E-06

1.E-04

1.E-02

1.E+00

0.0 0.5 1.0 1.5 2.0 2.5 3.0SWNT loading (wt%)

Con

duct

ivity

(S/c

m)

SWNT-PS1SWNT-PS2

4-point measurements. Addition of 2-3 wt% ‘PS’ with DP=5 to nanocomposite PS-2 with 1 wt% SWNT roughly raises conductivity by a factor 10 (2-point)

Nadia Grossiord et al., Chem. Mater., 2007

Question

How versatile is the latex concept?

Question

How versatile is the latex concept?

It works for PS, ABS, PMMA, PP, PE, PUR, PS/PPE, and PVC latexes.

So, virtually all polymer latex particles can be applied.

Polypropylene/CNT nanocomposites (semi-crystalline)

1, E- 07

1, E- 06

1, E- 05

1, E- 04

1, E- 03

1, E- 02

1, E- 01

1, E+00

1, E+01

0 0, 5 1 1, 5 2 2, 5CNTs concent r at i on ( wt %)

Cond

ucti

vity

(S/

m)

SWCNTs/ PP composi t es

MWCNTs/ PP composi t es

2-point conductivity measurements of Priex 801 + HiPCO SWNTs and Priex 801 + thin MWNTs of Nanocyl.

Four-point conductivity measurements as a function of the SWCNT concentration for: ( ) SWCNT/Priex®801 and ( ) SWCNT/PS nanocomposites.

1.E-10

1.E-08

1.E-06

1.E-04

1.E-02

1.E+00

1.E+02

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

SWCNT concentration (wt%)

Con

duct

ivity

(S/m

Hans Miltner, Kangbo Lu, Joachim Loos

Where and what can we improve?

Improving dispersion is difficult or even impossible.

Therefore we focused on- Quality of the tubes- Reduction of amount of CNTs by making foams- Reduction contact resistivity by replacing surfactant SDS by conducting surfactants

as methods to reduce percolation thresholds.

a

b

Scale bars: (a): 250 μm; (b): 50 μm

Vertically grown MWNTs (John Hart, MIT)

b

a

(a): picture of a vertically-grown MWNT (MIT)

(b): commercially available MWNT (Nanocyl)

Scale bar valid for both photos: 20 nm

HRTEM (High Resolution

TEM) photos

Long NTs vertically grown

1.E-10

1.E-08

1.E-06

1.E-04

1.E-02

1.E+00

1.E+02

1.E+04

0 0.5 1 1.5 2 2.5 3

CNT concentration (wt%)

Con

duct

ivity

(S/m

)

Four-point conductivity of MWNT-PS compositeas a function of MWNT concentration.

CNTs dispersed in the same PS matrix, under similar conditions.

1.E-10

1.E-08

1.E-06

1.E-04

1.E-02

1.E+00

1.E+02

1.E+04

0 0.5 1 1.5 2MWCNT concentration (wt%)

Con

duct

ivity

(S/m

)

NOTE: extremely high conductivity (>1000 S/m) for 1.5-2.0 wt% MWNT

Blue: Nanocyl MWNTsPink/green: vertically grown MWNTs

Vertically grown tubes are longerafter incorporation into PS, and contain less amorphous carbon

Reduction of required wt% CNTs by ‘foaming’

Continuous styrene/divinyl benzene phase is polymerizedSWNTs are dispersed in water droplets

WaterOil

High internal phase emulsion derived PS foam

SWNTs embedded in polyHipe walls

Percolation threshold reduced by factor 3 - 4

0.0 0.4 0.8 1.2 1.61E-12

1E-10

1E-8

1E-6

1E-4

0.01

1

polyHIPE - SWNT foam: 75/25 (w/o) polyHIPE - SWNT foam 84/16 (w/o) PS - SWNT films

Con

duct

ivity

(S/m

)

SWNT loading (wt%)in PS phase

Conductive surfactants replacing SDS and lowering contact resistivity

0.0 0.4 0.8 1.2 1.6

10-7

10-6

10-5

10-4

10-3

10-2

10-1

100

0 2 4 6

Control - PS BaytronP SWNT C

ondu

ctiv

ity (S

/m)

SWNT wt%

Baytron wt%

Control - PS + Baytron

Water plays a crucial role inthe development of polymer/carbon nanotubes nano-composites with well-dispersed CNTs

New coating resins based on the New coating resins based on the copolymerization of copolymerization of epoxidesepoxides with with

carbon dioxide carbon dioxide

Rob Rob DuchateauDuchateau WouterWouter van Meerendonkvan MeerendonkSaskia Saskia HuijserHuijser Maurice Maurice FrijnsFrijnsBart Bart NoordoverNoordover WiebWieb KingmaKingmaMarion van Marion van StratenStraten

TA-CT, DPI projects # 451 and 607

CoCo--polymerization of COpolymerization of CO22 and oxiranesand oxiranes

First discovery in 1969 by Inoue.First discovery in 1969 by Inoue.

Most frequently used catalysts are based on Zn, Al and Cr.Most frequently used catalysts are based on Zn, Al and Cr.

Frequently used monomers: cyclohexene oxide (CHO), propylene Frequently used monomers: cyclohexene oxide (CHO), propylene

oxide (PO) and ethylene oxide (EO).oxide (PO) and ethylene oxide (EO).

AliphaticAliphatic polycarbonatespolycarbonates

C2 bridge

O

OO

R

R

O

RRO C O +

[cat]

n

O

CO2

O

O

O n

+n n

Development of catalystsDevelopment of catalysts

ZnEt2 + H2O1969

ORR

OZn

R

ROR R

O Zn

R

R

O

O

1995

R3R3

R3

NM

N

R2R1

X

R3

M = Zn, Y, La

1998N N

N

N

M

X

PhPh

Ph Ph

M = Al, Cr

1978

N

R

N

R

O OMX

M = Al, Cr, Mn, Co

2002

NN O

Ph OPh

OPh

PhM M

O

R

M = Zn, Mg

2005

2004

R3R3

R3

NZn

N

R2R1

X

R3

R3R3

R3N

ZnN

R2R

X

R3

Typical reaction kinetics of Typical reaction kinetics of ββ--diiminate zinc catalystsdiiminate zinc catalysts

0 5 10 15 20 25 30 35 400

5000

10000

15000

20000

25000

30000

35000

Mn (g

/mol

)

Conversion (%)0 5 10 15 20 25

05

10152025303540

050001000015000200002500030000350004000045000

Con

vers

ion

(%)

Time (h)

Conversion (%) Mw (g/mol)

Mw

(g/m

ol)

MonomerCatalyst

ON

ZnN

OMe

MacromolMacromol. Rapid Commun. . Rapid Commun. 20042004, , 2525, 382., 382.

PDI < 1.2

Properties of polycyclohexene carbonateProperties of polycyclohexene carbonate

Thermal stabilityThermal stability

O OHO

O

Pol

OHPolO O

O

O

O

OO

H

Pol+ +

250250ooCC

OPol O

O

OO

OHO

Thermal stability is Thermal stability is significantly increased by significantly increased by endend--cappingcapping

SuccinicSuccinic anhydride endanhydride end--cappedcapped

330330ooCC

GlassGlass TransitionTransition temperaturetemperature PCHCPCHC: T: Tgg = 116 = 116 ººC C –– rather low rather low Tg prevents broad application as Tg prevents broad application as engineering plasticengineering plastic

0.0 0.2 0.4 0.6 0.8 1.00

20

40

60

80

100

120

X

True

stre

ss (M

Pa)

True strain (-)

A' B' C'

X

Initial break point

PCHCPCHC

bisphenolbisphenol--A polycarbonateA polycarbonate

Compression molding tests on high MW PCHCCompression molding tests on high MW PCHC

Properties of polycyclohexene carbonate (PCHC)Properties of polycyclohexene carbonate (PCHC)

Too brittle for engineering Too brittle for engineering plastic applications, plastic applications, butbutlow molar mass PCHC mightlow molar mass PCHC mightbe suitable for coatingsbe suitable for coatings→→ controlled breakdowncontrolled breakdown((TgTg high enough for powderhigh enough for powdercoating applications) coating applications)

Controlled breakdown of high MW PCHC

O

O

O R2R1 OHR1 R2O

O

OOH

OH

OH

OH

OH+ +

TMP-mediated break-down of high MW PCHC through alcoholysis affords OH-functional polycarbonate, curable with trifunctional isocyanate (glycerol also possible). R1 and R2 are polymer chain fragments.

Controlled degradation of high MW PCHC with TMP

0

2000

4000

6000

8000

10000

12000

14000

16000

0 100 200 300 400 500 600

t [min]

Mn [g

/mol

]

1

1.5

2

2.5

PDI [

-]

This works, but:Preferred route: chain transfer agents furnishing OH end groups in living polymerization

The resins obtained after hydrolysis of high Mw The resins obtained after hydrolysis of high Mw polycarbonates using TMP afford highly glossy, chemically polycarbonates using TMP afford highly glossy, chemically inert and tough coatings after crossinert and tough coatings after cross--linking.linking.

N N

N OO

OC6H12NCO

C6H12NCO

OCNC6H12

R2O

O

OOH

OH

An example of fully renewable, biodegradable polymers.An example of fully renewable, biodegradable polymers.

Extraction

[O]Fermentation

+

OOO O

O OO

O

n

OC O+ 2

CO2O O

O

n

Catalytic routes to renewable (biodegradable) polymersCatalytic routes to renewable (biodegradable) polymers

Maurice Frijns, Saskia Huijser

C.M. Byrne et al, J. Am. Chem. Soc., 126, 11404-11405 (2004)

One of the components of the air is a promisingraw material for the manufacturing of novel, high

performance coating materials

One of the components of the air is a promisingraw material for the manufacturing of novel, high

performance coating materials

But we cannot solve the ‘greenhouse’ problem by polymerizing all carbon dioxide present in the air !

All four examples illustrate DPI ‘chain-of-knowledge’ philosophyand have a flavor of important aspects of DPI’s future strategy

• SustainabilityWhere possible use biomass as feedstockEnhance lifetime by e.g. enhancing coatings UV stability

• Alternative (bio)catalytic routes to existing bulk and new specialty polymers. Full understanding of catalysis mechanisms is required. Join forces with modelling groups

• Upgrade existing polymers with ‘smart additives’• Environment deserves priority #1

Cleaner processes (in water or carbon dioxide). More focus on process development is required.Compostable, CO2-neutral polymers

The elements help making the DPI dream to come true

• Natural resources for new polymers• Biocatalysts from nature furnishing new

materials

• ‘Greenhouse’ gas from the air as feedstock for new polymers

• Water as an environmentally benign medium for the manufacturing of nanocomposites

• Fire (heat) for taking the chemistry ‘over the top’

DPI, congratulations with your 10th anniversary !