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

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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)

A way of the Cross Plasma polymerized DOCA ( PP DOCA) ATRP polyDOCA (a) Gaussian shaped two sets of terminations only (a) T. Fouquet et al, Plasma Process. Polymer. 2014 , 11 , 931. 4

A way of the Cross Plasma polymerized DOCA ( PP DOCA) NKM 0 1000 2000 3000 4000 5000 6000 0.5 0.4 ATRP 0.3 PDOCA 0.2 0.1 0 KMD KMD -0.1 -0.2 -0.3 Base unit: DOCA -0.4 -0.5 5

Plasma homopolymers w a 5 Innumerable end-groups MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6 6

Beware: aliasing PPDOCA (PFDA-based KMD) Mass defect / DOCA unit: -0.201 KMD = round(KM) – KM -0.5 / 0.5 range 7

Beware: aliasing Origami-like KMD plot 8

Beware: aliasing PPPFDA (DOCA-based KMD) Mass defect / PFDA unit: -0.567 9

EVA as encapsulant for photovoltaic modules Part 3 KMD for EVA copolymers Co-monomeric compositions and aging routes EVA pellets

1. Pristine EVA Offline SEC-MALDI MALDI-MS EVA 40 wt% VA MALDI-MS MALDI-MS EVA 25 wt% VA EVA 18 wt% VA 11 T. Fouquet et al, Rapid Commun. Mass Spectrom. 2016 , 30 , 973.

VA content EVA 40 wt% VA m n Calc. 42 wt% VA EVA 25 wt% VA Calc. 29 wt% VA EVA 18 wt% VA Calc. 25 wt% VA 12 T. Fouquet et al, Rapid Commun. Mass Spectrom. 2016 , 30 , 973.

Data mining MALDI SEC Strategy: SpiralTOF + Mass defect 13

Direct application • Crosslinked EVA sheets for photovoltaic modules Soxhlet MALDI + Strategy: SEC extraction SpiralTOF Soxhlet soluble part No chain scission MALDI-MS MW reduction 14

VA content Crosslinked EVA (180 deg) Pristine EVA Soxhlet-extracted VA content: ~ 41 wt% (centroid) VA content: ~ 29 wt% (centroid) Crosslinking affects the VA units first 15

VA content EVA 40 wt% VA Known end-groups Unknown end-groups KMD centroid = KMD endgroups + ion + 𝐿𝑁𝐸 𝐹 𝑊𝐵 ∙ 𝒐 (first approximation) 𝑂𝐿𝑁 centroid = NKM endgroups + ion + 𝑂𝐿𝑁 𝐹 𝐹 ∙ 𝒏 + 𝑂𝐿𝑁 𝐹 𝑊𝐵 ∙ 𝑜 Relative DP 𝑂𝐿𝑁 𝐹 𝑊𝐵 ∙ 𝒐 𝒐 %𝑥𝑢 = %𝑛𝑝𝑚 = 𝑂𝐿𝑁 𝐹 𝑊𝐵 ∙ 𝒐 + 𝑂𝐿𝑁 𝐹 𝐹 ∙ 𝒏 𝒏 + 𝒐 16

Untargeted KMD 750 850 950 1050 1150 1250 1350 1450 1550 1650 0.5 EVA 25 0.4 0.3 t = 0 0.2 0.1 0 -0.1 t = 1h -0.2 @ 150 deg -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 -0.1 -0.2 -0.3 -0.4 -0.5 17

Untargeted KMD 750 850 950 1050 1150 1250 1350 1450 1550 1650 0.5 EVA 25 0.4 0.3 t = 0 0.2 0.1 0 -0.1 t = 6h -0.2 @ 150 deg -0.3 -0.4 -0.5 750 850 950 1050 1150 1250 1350 1450 1550 1650 0.5 Too much data 0.4 0.3 No centroidization 0.2 available 0.1 0 (different end-groups) -0.1 -0.2 -0.3 -0.4 -0.5 18

Hand-picking H Lactone (La) H 2 C C C C H 2 H 2 CH CH O VA - CH 4 C O O C O CH 3 750 800 850 900 950 1000 1050 0.3 E 18 VA 6 0.25 Base unit: 0.2 CH 4 0.15 E 24 VA 4 0.1 0.05 t = 0 0 E 33 VA 1 -0.05 -0.1 19

Hand-picking H Lactone (La) H 2 C C C C H 2 H 2 CH CH O VA - CH 4 C O O C O CH 3 750 800 850 900 950 1000 1050 0.3 E 18 VA 6 0.25 Base unit: 0.2 CH 4 0.15 E 24 VA 1 La 3 E 24 VA 4 0.1 0.05 t = 1h 0 E 33 VA 1 -0.05 -0.1 20

Hand-picking H Lactone (La) H 2 C C C C H 2 H 2 CH CH O VA - CH 4 C O O C O CH 3 750 800 850 900 950 1000 1050 0.3 0.25 Base unit: 0.2 CH 4 0.15 0.1 0.05 t = 6h 0 -0.05 -0.1 21

Part 4 The need for resolution & Other mass defect plots

Alternative plots • “Remainder of NKM (RKM)” (a) 4 sets of terminations (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014 , 25 , 1346. 23

Alternative plots • “Remainder of NKM (RKM)” (a) 4 sets of terminations = 4 lines KMD plot (KMD vs. NKM) (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014 , 25 , 1346. 24

Alternative plots • “Remainder of NKM (RKM)” (a) KMD plot (KMD vs. NKM) 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑺𝑳𝑵 𝐩𝐦𝐣𝐡𝐩𝐧𝐟𝐬 = 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 − 𝒈𝒎𝒑𝒑𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 , 𝟏 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014 , 25 , 1346. 25

Alternative plots • “Remainder of NKM (RKM)” (a) KMD vs. RKM*NKM(repeating unit) KMD plot (KMD vs. NKM) 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑺𝑳𝑵 𝐩𝐦𝐣𝐡𝐩𝐧𝐟𝐬 = 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 − 𝒈𝒎𝒑𝒑𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 , 𝟏 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014 , 25 , 1346. 26

Alternative plots • “Remainder of NKM (RKM)” (a) KMD vs. RKM*NKM(repeating unit) End-group profiling for a homopolymer 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑶𝑳𝑵(𝒑𝒎𝒋𝒉𝒑𝒏𝒇𝒔 𝑺𝑳𝑵 𝐩𝐦𝐣𝐡𝐩𝐧𝐟𝐬 = 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 − 𝒈𝒎𝒑𝒑𝒔 𝑶𝑳𝑵 𝒔𝒇𝒒𝒇𝒃𝒖𝒋𝒐𝒉 𝒗𝒐𝒋𝒖 , 𝟏 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014 , 25 , 1346. 27

Remainder of NKM • A few examples Application to PCL (ROP with different catalysts) (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014 , 25 , 1346. 28

Alternative plots • A few examples Application to PO with fluorinated end-groups 29 (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

… • A few examples Plasma polymerized DOCA (See part 1) KMR by 240 (NKM of DOCA) 0 50 100 150 200 0.3 0.2 KMR KMD 0.1 0 -0.1 30

Higher-order mass defects -C 2 H 4 O- (44.026 u), -C 2 F 4 O- (115.989 u), -CF 2 - (49.997 u), -CF 2 O- (65.992 u). multiblock copolymer 31 I. Ken Dimzon, J. Am. Soc. Mass Spectrom. 2016 , 27 , 309.

Higher-order mass defects Points cluster in single point Survey of different repeating units Need for high resolution 32 I. Ken Dimzon, J. Am. Soc. Mass Spectrom. 2016 , 27 , 309.