T. Fouquet - Asahi glass AGC

Thierry Fouquet, PhD (JSPS fellow, AIST)

ASAHI GLASS CO. (AGC) – Innovative Technology Research Center, July 6

MS & Allied Techniques

for Fluoro(co)polymers

and EVA Copolymers

Biographical sketch

Thierry Fouquet (ティエリフーケ)

29 y.o.

French (officially), World citizen (deep down)

42 papers, 15 talks, h-index 9

2006 – Jun 2015:

Engineering School, MSc, PhD, Post-doc + R&D Eng.

Aix-Marseille University, Public Research Centre Tudor,

Luxembourg Institute of Science and Technology

(France + Luxembourg)

June – Aug 2015:

Wanderlust

Oct 2015 – Oct 2017

Post-doc (JSPS fellow), AIST, Japan

MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 62

Naha, Okinawa

もくじ

3

Part 1: MS & DSC for

plasma fluoropolymers

Part 2: MS and KMD

for plasma copolymers

Part 3: MS and KMD for EVA copolymers

Part 1

MS & DSC for a plasma fluoropolymer

Evaluation of MW

Luxembourg Institute of

Science and Technology (LIST)

Plasma…

5

« Plasma discharge » (b)

(a) C. Tendero et al, Spectrochim. Acta Part B 2006, 61, 2.(b) U. Kogelschatz, Plasma Chem. Plasma Process. 2003, 23, 1.

Plasma used as an active medium (a)

« More or less ionized gas »

Formed of electrons, ions, radicals & neutrals

Electrode

Electrode

MS & Allied techniques for fluoropolymers and EVA

copolymers – T. Fouquet, July 6

Electrode

Electrode

… & plasma polymers (PP)

6

Injection

of precursor

PFDA (perfluorinated)

Plasma-polymer

(a) J. Petersen et al, RSC Advances 2013, 3, 4416.

Plasma-polymerization (a)

(a) T. Fouquet et al, Encyclopedia of Plasma Technology, CRC Press, 2016

DSC (b)

XRD (b)

MALDI-MS

(soluble part) (b)

PP & pitfalls

7

ATRP

(controlled

radical

polymerization)

Plasma polymer

（soluble part, 25%)

T. Fouquet et al, Plasma Process. Polymer. 2014, 11, 931.

Dispersity

Low solubility

MW ?


MW varies anyway

8

Sample 1

Sample 2

Sample 1

Sample 2


Probably biased Tmelting seems to vary as well

Sample 2

ATRP standards

9 T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.

“monodisperse” standards

Calibration curve

10

Sample 1

Sample 2

From MALDI-MS


From DSC

ATRP standards


MW evaluation

11

Sample 1

Sample 2

“DSC corrected”


Sample 1

Sample 2

ATRP vs. PP

Same NMR

Same XRD

To go further

12

Sample 2

Controlled radical

polymerization

Free radical

polymerization

T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

To go further

13

Controlled radical

polymerization

Free radical

polymerization

Insoluble

part Soluble part (SEC + MS)


Sample 2

Part 2

MS & KMD for plasma (co)polymers

Evidence of a copolymerization

Collaboration

Luxembourg Institute of

Science and Technology (LIST)

Dr G. Mertz

([email protected])

mailto:[email protected]

Plasma (co)polymers

15

Plasma-(CO)polymer

Is it a bilayer ?

Is it a polymer blend ?

Is it a copolymer ?

Injection

of precursor

AND

PFDA (perfluorinated)

(Co-injection)

DOCA (long alkyl)

Electrode

Electrode


Co-injecting two precursors

16

Variation of the

melting temperature

+

One melting peak only

=

Copolymer

Evidence at a

molecular level ?

(a) T. Fouquet et al, Plasma Process. Polymer. 2016, 10.1002/ppap.201600053.

DSC, melting point (a)

Is MS the tool ?

17 (a) T. Fouquet et al, Plasma Process. Polymer. 2016, 10.1002/ppap.201600053.

Different composition of the feeding mixture →

Different MS fingerprint (a)

Tracking co-oligomers = tedious manual peak picking and assignments

Mass defect

• 1st-order mass: Kendrick mass(a)

18

KM(ion) =)𝑟𝑜𝑢𝑛𝑑(𝑚𝐼𝑈𝑃𝐴𝐶 𝑏𝑎𝑠𝑒 𝑢𝑛𝑖𝑡 , 0

𝑚𝐼𝑈𝑃𝐴𝐶 𝑏𝑎𝑠𝑒 𝑢𝑛𝑖𝑡∙ 𝑚𝐼𝑈𝑃𝐴𝐶 𝑖𝑜𝑛

IUPAC scale:

mass of C = 12.0000 (base unit)

mass of CH2 = 14.0157

Kendrick scale (base transformation)

mass of CH2 = 14.0000 (base unit)

mass of C = 11.9866

Esso Research and Engineering Company, New Jersey

(a) E. Kendrick, Anal. Chem. 1963, 35, 2146.

No pic available


MS + mass defect

• Mass defect (KMD)

19

)KMD 𝑖𝑜𝑛 = 𝑟𝑜𝑢𝑛𝑑(KM ion , 0) − KM(ion

Congeners varying by a number of base units only = same KMD

→ KMD plot: KMD vs. NKM

Nominal Kendrick Mass NKM

Horizontal alignment

a-(X)n-w + Y+

KMD

Base unit = Ｘ

NKM

KM

D

Application to polymers(a)

20 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.

a-(PO)n-w + Y+

a-(PO)n-y + Y+

KMD



Base unit = PO

Application to polymers(a)

21 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.

a-(PO)n-w + Y+

a-(EO)n-w + Y+

Base unit = PO



Plasma homopolymers

22

w5a

KMD

KMD analysis is robust enough

KMD

Plasma homopolymers

23 MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

Of lines…

24 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

… and alignments


26

Sum = blend

KM

D

NKM

Blend…

…Or Copolymer

27

KM

D

NKM

Convolution = copolymer

Back to MS…


…But adding the KMD dimension


The more the merrier


Beyond all doubts…


…it’s a copolymer

33

It’s not flawless:

- Limited to the soluble part of the deposits (< 25-50 wt%)

- No quantitative data (co-monomeric composition)

But: definitive evidence of a plasma copolymerization

T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

Part 3

KMD for EVA copolymers

Co-monomeric compositions and aging routes

EVA pellets

EVA as encapsulant

for photovoltaic

modules

Ethylene Vinyl Acetate

• EVA copolymers

• Top industrial importance

• Depending on the VA content :

– Hot melt adhesives

– Drug delivery

– Padding

– Solar cells encapsulating materials

35 MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

MS for EVA: a main pitfall

36

Low molecular weight oligomers

High resolution MS analyzer

SECMALDI

SpiralTOFStrategy:

EmVAn

13C

13C2

13C2

13C3 13C4

13C3

13C0.06 Da

+

2 Da

3 x E = 84 Da

Em-3VAn+1

Mass defect+

KMD for EVA

37

EVA

40 wt% VA

EVA

25 wt% VA

EVA

18 wt% VA

1.

Easy comparison

2.

Evaluation of the

VA content with no

peak assignment

T. Fouquet, S. Nakamura, H. Sato, Rapid Commun. Mass Spectrom. 2016, 30, 973.

A foretaste of aging

38

• Hydrolysis of EVA (under basic conditions)

Terpolymer EVAVOH


More pitfalls…

39

Solubility

SECMALDI

SpiralTOFMass defectHydrolysisStrategy:

Isobaric issues

«in vial hydrolysis»

SEC-hydrolysis-MALDI-MS

40

IRRAS MALDI

higher m/z2 min hydrolysis

T. Fouquet, H. Sato, Rapid Commun. Mass Spectrom. 2016, XXX.

41

higher m/z

20 min hydrolysis

T. Fouquet, H. Sato, Rapid Commun. Mass Spectrom. 2016, XXX.

SEC-hydrolysis-MALDI-MS

Data mining. The big picture

42

• Base unit ?

E: poorly informative alignments

VA / VOH: interdependent

VA-VOH (CH2CO)

= marker of the hydrolysis

Hydrolysis

VA

VOH

2 min

43

20 min


Hydrolysis

degree

(centroid)Hydrolysis

VA

VOH

44

Untargeted plot


Hand-picked data could also

enhance the visualization


Data mining. Hand-picking

45

Handpicked data

Hydrolysis

VA

VOH

t=0

(pristine)



46

Hydrolysis

VA

VOH

t=0

(pristine)

2 min


47

Hydrolysis

VA

VOH

20 min

t=0

(pristine)

Another example

48

EVA 25

t = 0

t = 6h

@ 150 deg

• Thermo-oxidative aging of EVA

(hot plate, open air)

MALDI

EVA25 t=0

t = 6h

Before/after thermo-oxidation

49

EVA 25

t = 0

t = 1h

@ 150 deg

KMD

Too much

50

EVA 25

t = 0

Acetic acid loss

Oxidation

Chain scission

Cyclization (lactones)

…Too much data

No centroidization

available

(different end-groups)

t = 1h

@ 150 deg

Acetic acid loss - Hand-picking

51

CH2

CH

O

C

CH3

O

CH

CH- CH

3COOH

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

750 800 850 900 950 1000 1050

E18VA6

E33VA1

Acetylene (A)

VA

t = 0

Base unit:

CH3COOH

E24VA4

52

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

750 800 850 900 950 1000 1050

CH2

CH

O

C

CH3

O

CH

CH- CH

3COOH

- CH3COOH

E18VA3A3

E24VA2A2

E18VA6

E33VA1

E24VA4t = 1h

Base unit:

CH3COOH


Acetylene (A)

VA

53

-0.25

-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

750 800 850 900 950 1000 1050

CH2

CH

O

C

CH3

O

CH

CH- CH

3COOH

E18VA6

E33VA1

E18VA2A4

E24VA1A3E24VA4t = 6h

Base unit:

CH3COOH


Acetylene (A)

VA

Next step(s) ?

54

• EVA

– Aging of used PV modules (with NMR)

• Plasma copolymers

– Block copolymers & terpolymers (to be defined)

– KMD and higher-order mass defects (cf. MSSJ talk, June 23rd)

• MS & DSC

– So far, case closed


ありがとうございます！

[email protected]

LinkedIn

Researchgate

Hinode, Fuji-san,

July 3rd 4:30

T. Fouquet - Asahi glass AGC

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