SLIDE 1
Thierry Fouquet, PhD (JSPS fellow, AIST)
ASAHI GLASS CO. (AGC) – Innovative Technology Research Center, July 6
for Fluoro(co)polymers and EVA Copolymers Thierry Fouquet, PhD (JSPS - - PowerPoint PPT Presentation
for Fluoro(co)polymers and EVA Copolymers Thierry Fouquet, PhD (JSPS - - PowerPoint PPT Presentation
MS & Allied Techniques for Fluoro(co)polymers and EVA Copolymers Thierry Fouquet, PhD (JSPS fellow, AIST) ASAHI GLASS CO. (AGC) Innovative Technology Research Center, July 6 Additional slides Part 2 MS & KMD for plasma (co)polymers
SLIDE 2
SLIDE 3
Part 2 MS & KMD for plasma (co)polymers Evidence of a copolymerization
Collaboration
Luxembourg Institute of Science and Technology (LIST) Dr G. Mertz (gregory.mertz@list.lu)
SLIDE 4
A way of the Cross
4
ATRP polyDOCA (a) Gaussian shaped two sets of terminations only Plasma polymerized DOCA (PPDOCA)
(a) T. Fouquet et al, Plasma Process. Polymer. 2014, 11, 931.
SLIDE 5
A way of the Cross
5
Plasma polymerized DOCA (PPDOCA)
- 0.5
- 0.4
- 0.3
- 0.2
- 0.1
0.1 0.2 0.3 0.4 0.5 1000 2000 3000 4000 5000 6000
KMD NKM
ATRP PDOCA KMD
Base unit: DOCA
SLIDE 6
Plasma homopolymers
6
w
5
a Innumerable end-groups
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6
SLIDE 7
Beware: aliasing
7
PPDOCA (PFDA-based KMD) Mass defect / DOCA unit: -0.201 KMD = round(KM) – KM
- 0.5 / 0.5 range
SLIDE 8
Beware: aliasing
8
Origami-like KMD plot
SLIDE 9
Beware: aliasing
9
PPPFDA (DOCA-based KMD) Mass defect / PFDA unit: -0.567
SLIDE 10
Part 3 KMD for EVA copolymers Co-monomeric compositions and aging routes
EVA pellets EVA as encapsulant for photovoltaic modules
SLIDE 11
- 1. Pristine EVA
Offline SEC-MALDI
EVA 40 wt% VA EVA 25 wt% VA EVA 18 wt% VA MALDI-MS MALDI-MS MALDI-MS
11
- T. Fouquet et al, Rapid Commun. Mass Spectrom. 2016, 30, 973.
SLIDE 12
VA content
EVA 40 wt% VA EVA 25 wt% VA EVA 18 wt% VA
12
- T. Fouquet et al, Rapid Commun. Mass Spectrom. 2016, 30, 973.
- Calc. 25 wt% VA
- Calc. 29 wt% VA
m
- Calc. 42 wt% VA
n
SLIDE 13
Data mining
13
SEC MALDI SpiralTOF Mass defect
Strategy:
+
SLIDE 14
Direct application
- Crosslinked EVA sheets for photovoltaic modules
14
SEC MALDI SpiralTOF Soxhlet extraction
MALDI-MS Strategy: No chain scission MW reduction
+
Soxhlet soluble part
SLIDE 15
VA content
15
Pristine EVA Crosslinked EVA (180 deg) Soxhlet-extracted VA content: ~ 41 wt% (centroid) VA content: ~ 29 wt% (centroid) Crosslinking affects the VA units first
SLIDE 16
VA content
16
EVA 40 wt% VA Known end-groups Unknown end-groups (first approximation)
KMD centroid = KMD endgroups + ion + 𝐿𝑁𝐸𝐹 𝑊𝐵 ∙ 𝒐 𝑂𝐿𝑁 centroid = NKM endgroups + ion + 𝑂𝐿𝑁𝐹 𝐹 ∙ 𝒏 + 𝑂𝐿𝑁𝐹 𝑊𝐵 ∙ 𝑜
Relative DP %𝑛𝑝𝑚 = 𝒐 𝒏 + 𝒐 %𝑥𝑢 = 𝑂𝐿𝑁𝐹 𝑊𝐵 ∙ 𝒐 𝑂𝐿𝑁𝐹 𝑊𝐵 ∙ 𝒐 + 𝑂𝐿𝑁𝐹 𝐹 ∙ 𝒏
SLIDE 17
Untargeted KMD
17
- 0.5
- 0.4
- 0.3
- 0.2
- 0.1
0.1 0.2 0.3 0.4 0.5 750 850 950 1050 1150 1250 1350 1450 1550 1650
- 0.5
- 0.4
- 0.3
- 0.2
- 0.1
0.1 0.2 0.3 0.4 0.5 750 850 950 1050 1150 1250 1350 1450 1550 1650
EVA 25 t = 0 t = 1h @ 150 deg
SLIDE 18
Untargeted KMD
- 0.5
- 0.4
- 0.3
- 0.2
- 0.1
0.1 0.2 0.3 0.4 0.5 750 850 950 1050 1150 1250 1350 1450 1550 1650
18
- 0.5
- 0.4
- 0.3
- 0.2
- 0.1
0.1 0.2 0.3 0.4 0.5 750 850 950 1050 1150 1250 1350 1450 1550 1650
EVA 25 t = 0 Too much data No centroidization available (different end-groups) t = 6h @ 150 deg
SLIDE 19
Hand-picking
19
- 0.1
- 0.05
0.05 0.1 0.15 0.2 0.25 0.3 750 800 850 900 950 1000 1050
C H2 C H O C CH3 O C H2 C H2 CH CH O C O
- CH4
Lactone (La) VA t = 0 Base unit: CH4 E18VA6 E33VA1 E24VA4
SLIDE 20
- 0.1
- 0.05
0.05 0.1 0.15 0.2 0.25 0.3 750 800 850 900 950 1000 1050
20
C H2 C H O C CH3 O C H2 C H2 CH CH O C O
- CH4
Hand-picking
t = 1h Base unit: CH4 E18VA6 E33VA1 E24VA4 E24VA1La3 Lactone (La) VA
SLIDE 21
- 0.1
- 0.05
0.05 0.1 0.15 0.2 0.25 0.3 750 800 850 900 950 1000 1050
21
C H2 C H O C CH3 O C H2 C H2 CH CH O C O
- CH4
Hand-picking
t = 6h Base unit: CH4 Lactone (La) VA
SLIDE 22
Part 4 The need for resolution & Other mass defect plots
SLIDE 23
Alternative plots
23
(a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
4 sets of terminations
- “Remainder of NKM (RKM)” (a)
SLIDE 24
Alternative plots
24
(a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
4 sets of terminations = 4 lines KMD plot (KMD vs. NKM)
- “Remainder of NKM (RKM)” (a)
SLIDE 25
Alternative plots
25
(a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
𝑺𝑳𝑵 𝐩𝐦𝐣𝐡𝐩𝐧𝐟𝐬 = 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 − 𝒈𝒎𝒑𝒑𝒔 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 , 𝟏 KMD plot (KMD vs. NKM)
- “Remainder of NKM (RKM)” (a)
SLIDE 26
Alternative plots
- “Remainder of NKM (RKM)” (a)
26
(a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
𝑺𝑳𝑵 𝐩𝐦𝐣𝐡𝐩𝐧𝐟𝐬 = 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 − 𝒈𝒎𝒑𝒑𝒔 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 , 𝟏 KMD plot (KMD vs. NKM) KMD vs. RKM*NKM(repeating unit)
SLIDE 27
Alternative plots
- “Remainder of NKM (RKM)” (a)
27
(a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
𝑺𝑳𝑵 𝐩𝐦𝐣𝐡𝐩𝐧𝐟𝐬 = 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 − 𝒈𝒎𝒑𝒑𝒔 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 , 𝟏 KMD vs. RKM*NKM(repeating unit) End-group profiling for a homopolymer
SLIDE 28
Remainder of NKM
28
(a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
- A few examples
Application to PCL (ROP with different catalysts)
SLIDE 29
Alternative plots
29
- A few examples
Application to PO with fluorinated end-groups
(a) 柿内俊文 et al,包括的2次元LC-MALDI/TOFMSによるRf基末端修飾ポリオールの構造解析, MSSJ 2016
SLIDE 30
…
30
- 0.1
0.1 0.2 0.3 50 100 150 200
- A few examples
KMR KMR by 240 (NKM of DOCA) KMD Plasma polymerized DOCA (See part 1)
SLIDE 31
Higher-order mass defects
31
- C2H4O- (44.026 u), -C2F4O- (115.989 u),
- CF2- (49.997 u), -CF2O- (65.992 u).
multiblock copolymer
- I. Ken Dimzon, J. Am. Soc. Mass Spectrom. 2016, 27, 309.
SLIDE 32
Higher-order mass defects
32
- I. Ken Dimzon, J. Am. Soc. Mass Spectrom. 2016, 27, 309.
Points cluster in single point Survey of different repeating units Need for high resolution