Characterization of complex polymer systems by MALDI Mass - - PowerPoint PPT Presentation

Characterization of complex polymer systems by MALDI Mass Spectrometry”

Concetto Puglisi

National Research Council Institute of Polymers, Composites and Biomaterials Catania, Italy

Ions Separation Ions Production Ions Detection

Ion Detectors

Mass Spectrometry

Analytical Techniques based on the production of ions in the high vacuum of the MS source, separation as a function of mass to charge ratio (m/z) and detection.

Before ¡MALDI, ¡ ¡MS ¡ ¡analysis ¡of ¡polymers ¡was ¡restricted ¡to ¡addi:ves ¡or ¡low ¡ molecular ¡mass ¡products ¡obtained ¡from ¡pyrolisis ¡or ¡other ¡ ¡degrada:on ¡

• methods. ¡ ¡(DP-­‑MS, ¡PY ¡GC/MS, ¡FAB/MS). ¡

Chemistry Nobel Prize 2001

John B. Fenn Koichi Tanaka

R.Abate, ¡A. ¡Ballistreri, ¡G. ¡Montaudo, ¡D. ¡Garozzo, ¡G. ¡Impallomeni, ¡G. ¡Critchley, ¡ ¡K. ¡Tanaka, ¡ ¡ Rapid ¡Communica>on ¡in ¡ ¡Mass ¡Spectrometry, ¡vol. ¡7, ¡1033-­‑1036 ¡(1993) ¡

Ions Separation Ions Production Ions Detection

Ion Detectors

MALDI WI WITH H MALD LDI MACROM OMOLE OLECULE ULES ARE DESOR ORBED INT NTACT MALDI/TOF ¡HAS ¡ALLOWED ¡THE ¡MASS ¡JUMP. ¡ A ¡REVOLUTION ¡IN ¡THE ¡ANALYTICAL ¡CHEMISTRY ¡OF ¡MACROMOLECULES. ¡ TIME ¡OF ¡FLIGHT ¡(TOF) ¡ Matrix Assisted Laser Desorption Ionization (MALDI)

Matrix Assisted Laser Desorption Ionization (MALDI)

The MALDI process consists of the intimate mixing of the sample with a high molar excess (up to 104 fold) of a low molecular mass organic matrix compound; Conversion of this mixture to a solid deposit; Introduction to a high vacuum chamber; Bombardment with a pulsed UV laser light; and Collection and measurement of the ions desorbed by the laser. Separation and identification of the ions produced by a Time Of Flight (TOF) tube

Each laser pulse generates a plume of particles, including ions and neutrals, matrix and analyte, which expand at supersonic speed from the surface of the probe and particularly at right angles to the surface. The ionization of polymer occurs by the formation of adducts ions with H+ or with alcaline ions (litium, sodium or potassium) even they are not added to the solution

Most ¡Used ¡MALDI ¡Matrices ¡

Malononitrile DHB HABA IAA Ditranolo CHCA DEA-CHCA

The triple role of the matrix is to incorporate and isolate the analyte molecules, absorb and transfer the laser energy to form the microplasma, and finally, assisting in the formation of the macromolecular ions.

Modern Mass Spectrometry in Polymer Chemistry

MALD LDI-T

• TOF

OF OF OF POL OLYMERS

Ø Detection of Intact Molecules Ø Very High Sensitivity Ø High Resolution (> 20000 ppm) q Molar Mass Determination q Copolymer Analysis q End Groups Determination/Structure v Mechanisms of Polymer Degradation v Mechanisms of Synthesis

Main ain APPLI LICATIONS ONS Main ain FE FEATUR URES

MALD LDI-T

• TOF

OF OF OF POL OLYMERS

Ø Detection of Intact Molecules Ø Very High Sensitivity Ø High Resolution q Molar Mass Determination q Copolymer Analysis q End Groups Determination v Mechanisms of Polymer Degradation v Mechanisms of Synthesis

Main ain APPLI LICATIONS ONS Main ain FE FEATUR URES

Polystyrene, Narrow Distribution Mw 330,000; 600,000; 900,000

, ¡

0 ¡ 20 ¡ 40 ¡ 60 ¡ 80 ¡ 100 ¡ 120 ¡ 140 ¡ 160 ¡ 180 ¡ 200 ¡

counts/1000 ¡

m/z ¡

79160 ¡

156970 ¡

312530 ¡

Osmometry Mn= 153600 Viscosometry Mv=159770 Light Scattering Mw=158180 GPC (SEC) Mn= 152350 Mw= 156050 MALDI Mn = 152350 Mw= 156450

Pol

• lystyrene

ene (D=1.001)

1.001) Ver ery Nar Narrow Dis istribut ibution ion

M+ M++ 2M+

200 400 600 800 1000 1200 1400 1600 1800

C

• u

n t s 2000 4000 6000 8000 10000 12000 14000 16000 18000 m/z

4000 4500 m/z

CH3 CH3 O O O C O

n

CH3 CH3 CH3 CH3 CH3 O O C CH3 A= CH3 CH3 O O O C O

n

CH3 CH3 CH3 H B= CH3 CH3 O O O C O

n

H CH3 CH3 OH C=

CH3 CH3 O O O C O

n

D=

D14 D15 D16 D17 A13 A14 A15 A16 B14 B15 B16 B17 C14 C16 D9 A17 D12 D8 D15 A14 A21 A25 A33 A42 A50

Bisphenol ¡A ¡Polycarbonate, ¡Mw ¡50.000 ¡by ¡SEC ¡

Coupling «off-line» SEC with MALDI

MALDI as absolute mass detector for GPC

A.U

10 20 30 40 Vr ¡(ml)

m/z m/z m/z m/z

310000 190000 49000 2400

3.5 4.0 4.5 5.0 5.5 log(Mw) 20 21 22 23 24 25 26 27 28 29 30 31

Ve (mL)

Mw PMMA standards by MALDI Mw PMMA Standards by Supplier Mw of PMMA Fractions by MALDI

3.5 4.0 4.5 5.0 5.5 log(Mw) 20 21 22 23 24 25 26 27 28 29 30 31

Ve (mL)

Mw PMMA standards by MALDI Mw PMMA Standards by Supplier Mw of PMMA Fractions by MALDI

3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8

log ¡Mw

28 29 30 31 32 33 34 35 36 37 38 39

Ve(mL)

Y ¡= ¡13.99 ¡-­‑ ¡0.4498X ¡+ ¡0.004456X

2

10 20 30 40 50 60 70 80

A r b i t r a r y U n i t s

10 20 30 40 50

Ve(ml)

ULTEM 1000

Determinazione di pesi molecolari assoluti

Ve (mL) Mw Log Mw

28.8 52500 4.72016 29.03 49150 4.69152 29.5 40500 4.60745 29.74 5700 4.55267 30.44 26900 4.42975 31.38 19000 4.27875 32.08 14000 4.14613 33 10250 4.01072 33.254 8950 3.95182 33.72 7920 3.89873 34.43 6620 3.82086 35.56 3780 3.57634 36.77 2970 3.47276 37.7 2360 3.37291 38.64 1890 3.27646 Volume di eluizione e Mw di ciascuna frazione analizzata mediante MALDI

TABLE 1 Molar Mass Distribution of PC calculated from SEC curves obtanined at different concentrations (wt%).

SEC/MALDI Polystyrene Conc. Solvent Mw

a Mn a Mp a

Mw

b Mn b Mp b

0.3 CHCl3 22200 10300 22400 55800 23600 58400 0.5 CHCl3 22000 10200 21900 55600 23400 56700 1 CHCl3 18350 10250 18500 50150 21850 22400 2 CHCl3 17500 9700 17000 46100 20000 42100

3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2

l

• g

M w

50 100

a r b i t r a r y u n i t s

25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

Ve (mL)

PC

Polycarbonate

MALD LDI-T

• TOF

OF OF OF POL OLYMERS

Ø Detection of Intact Molecules Ø Very High Sensitivity Ø High Resolution q Molar Mass Determination q Copolymer Analysis q End Groups Determination v Mechanisms of Polymer Degradation v Mechanisms of Synthesis

APPLI LICATIONS ONS FE FEATUR URES

Structure Characterization of Copolymers

NMR (1H – 13C) MALDI Mass Spectrometry

Copolymers microstructure

§ Copolymer Composition

§ Average sequence length § Degree of randomness § The weight fraction of copolymers with respect to homopolymers

MODELING PROCESS BASED ON CHAIN STATISTICS

• 1. CHOICE OF DISTRIBUTION MODELS

A NUMBER OF DIFFERENT DISTRIBUTION MODELS CAN BE CONSIDERED, OLIGOMERS ABUNDANCES CAN BE GENERATED ACCORDING TO EACH MODEL (BERNOULLIAN, MARKOFFIAN 1° AND 2°, SEQUENTIAL)

2 THEORETICAL NMR OR MASS SPECTRA

GENERATE THEORICAL NMR OR MASS SPECTRA FOR A SPECIFIC

COPOLYMER SEQUENCE BY ASSUMING PEAKS INTENSITIES EQUAL TO RELATIVE OLIGOMER ABUNDANCES, AND APPLYING THE APPROPRIATE CONVOLUTION AND MULTIPLICITY RULES

3 ITERATION AND BEST FIT MINIMIZATION

A SERIES OF THEORETICAL MASS SPECTRA ARE ORIGINATED AND,

COMPARING THE EXPERIMENTAL MS INTENSITIES WITH THOSE CALCULATED FOR A SPECIFIC MODEL, THE MOST LIKELY COPOLYMER MICROSTRUCTURE AND COMPOSITION CAN BE DETERMINED

IAmBn = f(PAA, PAB, PBA, PBB) AF = qΣi(Ii

exp - Ii calcd)2

i n t e n s . ( a r b . u . )

300 400 500 600 700 800 900 1000 1100

m/z

AB AB4 A4B

Number of MS peaks (n+1) random AB copolymer (1:1)

A2 B2 A3 B3 A4 AB2 B4 A2B A2B3 A2B2 A3B A5 AB3 A3B2 B5

Oligomer Oligomers For

• rmula

mula Monomers

C1

A

I(A) / { I(A) + I(B) }

Dimers

C2

A

{2I(A2) + I(AB)} / {2I(A2) + 2I(AB) + 2I(B2)}

Trimers

C3

A

{3I(A3) + 2I(A2B) + I(AB2)} / {3I(A3) + 3I(A2B) + 3I(AB2) + 3I(B3)}

Tetramers

C4

A

{4I(A4) + 3I(A3B) + 2I(A2B2) + I(AB3)}/ {4I(A4) + 4I(A3B) + 4I(A2B2) + 4I(AB3) 4I(B4)}

Composition for a AB copolymer (Composition Estimates Method)

Oligomers AB ABC ABCD

2-mers 3 6 10 3-mers 4 10 20 4-mers 5 15 35 5-mers 6 21 56 6-mers 7 28 84 7-mers 8 36 120 8-mers 9 45 165 9-mers 10 55 220 10-mer 11 66 286 11

• mers

12 78 364 12

• mers

13 91 455 13

• mers

14 105 560 14

• mers

15 120 680 15

• mers

16 136 816 16

• mers

17 153 969

Number Number of

• f peaks

peaks expect xpected ed for

• r two,

, thr hree ee ad ad four

• ur

component components copol copolymer mers

200 400 600 800 1000 2000 3000 4000 5000 6000 7000 8000 9000

m/z

2600 2700 2800 2900 3000 3100 m/z

A6B6 A7B5 A5B7 A4B8 A3B9 A8B5

A9B4

A8B4 A4B7 A5B6 A6B5 A7B4 A3B7 A8B3

A2B8 A9B3 A3B8 A2B9 A10B3

a.i.

A6B6 A6B7 A6B5 A5B6 A7B7 A7B8 A8B7 A5B5 A8B8 A8B9 A9B9 A9B10 A10B10 A10B11 A11B11

MALDI-TOF spectrum of butylene adipate (A)/sebacate (B) copolymer.

MODELING PROCESS BASED ON CHAIN STATISTICS

• 1. CHOICE OF DISTRIBUTION MODELS

A NUMBER OF DIFFERENT DISTRIBUTION MODELS CAN BE CONSIDERED, OLIGOMERS ABUNDANCES CAN BE GENERATED ACCORDING TO EACH MODEL (BERNOULLIAN, MARKOFFIAN 1° AND 2°, SEQUENTIAL)

2 THEORETICAL NMR OR MASS SPECTRA

GENERATE THEORICAL NMR OR MASS SPECTRA FOR A SPECIFIC

COPOLYMER SEQUENCE BY ASSUMING PEAKS INTENSITIES EQUAL TO RELATIVE OLIGOMER ABUNDANCES, AND APPLYING THE APPROPRIATE CONVOLUTION AND MULTIPLICITY RULES

3 ITERATION AND BEST FIT MINIMIZATION

A SERIES OF THEORETICAL MASS SPECTRA ARE ORIGINATED AND,

COMPARING THE EXPERIMENTAL MS INTENSITIES WITH THOSE CALCULATED FOR A SPECIFIC MODEL, THE MOST LIKELY COPOLYMER MICROSTRUCTURE AND COMPOSITION CAN BE DETERMINED

IAmBn = f(PAA, PAB, PBA, PBB) AF = qΣi(Ii

exp - Ii calcd)2

m/z (b) (a)

MALD LDI-T

• TOF

OF Spect pectra a of

• f a

a thr hree ee component components copol copolymer mer (BSu-B u-BAd-B d-Bse) e) Theor heoret etical ical Exper xperiment imental al

Application of MALDI in Reactive Melt Mixing of Polymers Containing Functional Groups (Esters, Carbonates, Amides) Understand the Exchange Mechanisms

. Role of Funcional Groups

. Role of Catalysts

Controlled Synthesis of Copolymers by

Intermolecular Exchange Reactions

Main ¡Goals ¡

random copolymers

A-A-B-A-B-B-A-A-B-B-B-A-A-A-B-B-A-B B-B-A-B-A-A-B-B-A-A-A-B-B-B-A-A-B-A

+

diblock copolymers

A-A-A-A-A-A-A-A-A-A-A-A-A-A-B-B-B-B B-B-B-B-B-B-B-B-B-B-B-B-B-B-A-A-A-A

+

interchange

A-A-A-B-B-A-A-A-A-A-B-B-B-A-A-A-A-A B-B-B-A-A-B-B-B-B-B-A-A-A-B-B-B-B-B

+

multiblock copolymers

interchange interchange

A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B

+

homopolymers

Block Copolyamide

Random Copolyamide

O O HOC (CH2)4 C NH (CH2)6 NH

y

O O OH C (CH2)4 C

x

O O NH (CH2)6 NH C (CH2)8 C

Ny6,10 Ny6,6

+ C (CH2)8 C NH (CH2)6 NH

p

HO

Ny6,10

O O

Further reaction

m

C (CH2)4 C C (CH2)4 C NH (CH2)6 NH

n

O O O O O O NH (CH2)6 NH C (CH2)8 C + NH (CH2)6 NH C (CH2)8 C n O O

Ny6,10

OH C (CH2)4 C C (CH2)4 C NH (CH2)6 NH

n

Ny6,6

O O O O

AMMIDE/AMMIDE (Ny66/Ny610)

Mixing ¡Temp ¡290°C ¡

13C-NMR spectra of Ny6,6-COOH and Ny6,10 equimolar mixtures

(ppm) 178 179 180 43.5 44.5 33 33.5 34 194 195

a’’ a’ a b c d e f e’ e’’ A B C physical blend 290°C for 3h 310°C for 1h

n C CH2 (CH2)2 CH2 C HO OH n NH CH2 (CH2)4 CH2 NH C CH2 (CH2)2 CH2 C O e' e'' a' c a e O a'' O O O NH CH2 (CH2)4 CH2 NH C CH2 (CH2)6 CH2 C d b f O

Ny6,6-COOH Ny Ny6,10 6,10

AMMIDE/AMMIDE (Ny66/Ny610)

50 100 1000 2000 3000 4000 5000 I% m/z

(a) A4 £ A8 £ A6 £ A10 £ A20 £ A12 £ A15 £ A HO CO-(CH2)4-COOH

y x

B £ = A = Ny66 B = Ny610

50 100 1000 2000 3000 4000 5000 I% m/z

(b) A2B2 £ AB3 £ AB2 £ A3B3 £ A4B4 £

0 ¡min ¡of ¡mixing ¡ 30 ¡min ¡of ¡mixing ¡

50 100 1000 1200 1400 1600 1800

I% m/z

A4

A3

A5 A6 A7 A3

A3B2 A2B3 A5B A4B2 A3B3 A4B AB3 A3B A2B2 A2B AB2 B3 A6B

290°C 10 min

50 100 50 100 1000 1200 1400 1600 1800 1000 1200 1400 1600 1800 1000 1200 1400 1600 1800

I% m/z m/z I% m/z

A4

A4B AB3 A2B2 A3B B3 AB2 A2B

B4 A3 A3 A7 A6 A5 A4

A2B2 A3B AB4 AB3 A2B3 A4B A3B2 AB2 AB3 B3 A5B A2B A4B2 A3B3 A2B4 AB5 A3B2 A2B3 A5B A4B2 A3B3 A6B

290°C 15 min 290°C 30 min

tetramers trimers pentamers hexamers

50 100

Tetrameri

AMMIDE/AMMIDE (Ny66/Ny610)

290 °C

30 min 60 min 180 min

50 100 50 100 50 100 1000 m/z 1000 1000 I% I% m/z m/z

(a) (c)

I% m/z

(b) AB2 A2B 1014 B3 958 AB2 B3 A3 902 A2B B3 B3 B3 B3 AB2 AB2 AB2 AB2 A2B A2B A2B A2B A3 A3 Δ Δ Δ Δ Δ Δ Δ Δ Δ

MALD LDI-T

• TOF

OF OF OF POL OLYMERS

Ø Detection of Intact Molecules Ø Very High Sensitivity Ø High Resolution q Molar Mass Determination q Copolymer Analysis q End Groups Determination v Mechanisms of Polymer Degradation v Mechanisms of Synthesis

APPLI LICATIONS ONS FE FEATUR URES

MALDI ¡–TOF ¡Mass ¡Spectrum ¡of ¡ ¡ULTEM, ¡Mw ¡about ¡25,000 ¡

10000 ¡ 15000 ¡ 20000 ¡ 0 ¡ 5000 ¡

Counts ¡ 2000 ¡ 3000 ¡ 4000 ¡ 5000 ¡ 6000 ¡ 7000 ¡ 8000 ¡ 9000 ¡ 10000 ¡ 11000 ¡

Mass (m/z) ¡

A ¡ A ¡ A ¡ A ¡ A ¡ B ¡ B ¡ B ¡ B ¡ B ¡ B ¡ D ¡ D ¡ D ¡ D ¡

C ¡ C ¡ F ¡ E ¡

2200 ¡ 2400 ¡ 2600 ¡ 2800 ¡ 3000 ¡ 3200 ¡ Mass (m/z) ¡

2761 ¡ 2939 ¡ 2169 ¡ 2393 ¡ 2541 ¡ 2554 ¡ 2986 ¡ 3147 ¡ 3132 ¡ 2926 ¡

A ¡ D A ¡ D B ¡ B ¡

n CH3 CH3 O N O O N O O O

Mw=25 000 (SEC)

N O O O CH3 CH3 O CH3 O O N N O O O CH3 CH3 O N O O CH3 n

F ¡

O O O CH3 CH3 O O O N N O O O H n

C ¡

O O O CH3 CH3 O O O N N O O O CH3 CH3 O N O O CH3 O n

E ¡

N O O O CH3 CH3 O N N O O O O N O O

n

B ¡

CH3 CH3 O N O O N O O O

n

A ¡

N O O O CH3 CH3 CH3 O N N O O O O

n

D ¡

0 ¡ 5000 ¡ Counts ¡

B ¡ B ¡

Mass ¡(m/z ¡

) ¡

2000 ¡ 3000 ¡ 4000 ¡ 5000 ¡ 6000 ¡ 7000 ¡ 8000 ¡ 9000 ¡ 10000 ¡ 10000 ¡ 15000 ¡

B ¡ B ¡ B ¡ B ¡

B ¡

2559 ¡ 2541 ¡ 2581 ¡ 2761 ¡ 2169 ¡ 2393 ¡ 2986 ¡ 3151 ¡ 3132 ¡ 2777 ¡

B ¡ A ¡ A ¡ C ¡ C ¡

2184 ¡ 2200 ¡ 2409 ¡ 3167 ¡ 2646 ¡ 2690 ¡ 3002 ¡ 2895 ¡ 2913 ¡ 2320 ¡ 2945 ¡

H ¡ L ¡

K ¡

R ¡ U ¡

W ¡

U ¡ B1 ¡ B2 ¡ A1 ¡ I ¡ B1 ¡ H ¡ H1 ¡

2200 ¡ ¡ 2400 ¡ ¡ 2600 ¡ ¡ 2800 ¡ ¡ 3000 ¡ ¡ 3200 ¡ ¡ Mass ¡(m/z) ¡

E ¡ E ¡ O ¡

2661 ¡ N ¡ 2676 ¡

¡MALDI-­‑TOF ¡Mass ¡Spectrum ¡of ¡PEI ¡Sample ¡Photo-­‑oxidised ¡at ¡60°C ¡for ¡216 ¡hours ¡

Photo-Oxidation

not-oxidized chains C ¡ C ¡ F ¡ E ¡

2200 ¡ 2400 ¡ 2600 ¡ 2800 ¡ 3000 ¡ 3200 ¡ Mass (m/z) ¡

2761 ¡ 2939 ¡ 2169 ¡ 2393 ¡ 2541 ¡ 2554 ¡ 2986 ¡ 3147 ¡ 3132 ¡ 2926 ¡

A ¡ D ¡ A ¡ D ¡ B ¡ B ¡

B

2559 2541 2581 2761 2169 2393 2986 3151 3132 2777

B A A C C

2184 2200 2409 3167 2646 2690 3002 2895 2913 2320 2945

H L

K

R U

W

U B1 B2 A1 I B1 H H1

2200 2400 2600 2800 3000 3200 Mass (m/z)

E E O

2661 N 2676

Photo-Oxidation

CH3 CH3 O N O O N O O O

CH3

P1

COCH3 O COOH O CH2COCH3 O OH O CH2OH O CH2COOH O

N H O O O O O O O

O H O H

H2 O hν,O

2

P2 P3 P4

OH CH3 O O CH2

Overall Photo-Oxidation Processes of Polyethereimide (ULTEM).

hν,O

2

1 2 3 4 5 6 Relative Amount % 5 10 15 20 25 30 100 200 300 400 500 600 700 800 900 1000 1100 Exposure time (Hours)

N O O O CH2OH CH3 O N O O N O O

N

O O O CH3 CH3 O N O O N O O

X=0,1,2,3

n

¡Rela:ve ¡amount ¡vs ¡exposure ¡:me ¡of ¡linear ¡oligomers ¡B, ¡B1, ¡B2, ¡and ¡B3 ¡as ¡

• btained ¡from ¡the ¡MALDI ¡spectra ¡of ¡photoxidized ¡ULTEM ¡sample ¡

B ¡ B1 ¡ B2 ¡ B3 ¡

CH H NH CO CO (CH2)4 CH2 CH2 CH2 CH2 CH2 NH CO

H abstraction NorrishI Norrish II

CO (CH2)4 NH CHO CO (CH2)4 NH COOH CO (CH2)4 NH CH3

(B)

(CH2)5 CO NH2 (CH2)5 CO NH CHO CO (CH2)3 NH CH CH2 CO (CH2)3 NH CH3 CO (CH2)2 NH CH CH2 (CH2)5 CO NH CO CH3

(C) (A)

CH NH O OH CO (CH2)4 (CH2)4 CO CHO (CH2)4 CO COOH NH CO NH2 (CH2)5 NH (CH2)4 CO CO CO

hν hν hν

A

B C

CH H NH CO CO (CH2)4 CH2 CH2 CH2 CH2 CH2 NH CO

H abstraction NorrishI Norrish II

CO (CH2)4 NH CHO CO (CH2)4 NH COOH CO (CH2)4 NH CH3

(B)

(CH2)5 CO NH2 (CH2)5 CO NH CHO CO (CH2)3 NH CH CH2 CO (CH2)3 NH CH3 CO (CH2)2 NH CH CH2 (CH2)5 CO NH CO CH3

(C) (A)

CH NH O OH CO (CH2)4 (CH2)4 CO CHO (CH2)4 CO COOH NH CO NH2 (CH2)5 NH (CH2)4 CO CO CO

hν hν hν

A

B C

Overall Photo-oxidation Processes in Ny6.

O CH3 CH2 O O H O OH O CH2COCH3 O COCH3 O CH2OH O CH2COCH3 O CH2COOH O

O2

CH2OH O

O2

COOH O CH2 O C CH3 O OH

+ +

1'

SCHEME ¡3b. ¡Photo-­‑degradaGon ¡mechanisms ¡of ¡Bisphenol-­‑A-­‑ ¡moiety ¡

N H O O N CH3 O O

hν ¡

O2 ¡

SCHEME ¡3a. ¡Photo-­‑degradaGon ¡mechanisms ¡of ¡Bisphenol-­‑A-­‑ ¡moiety ¡

O2 R.

CH2 CH3 O CH3 CH3 O O O CH2 CH3 O O CH2OH CH3 O O

O2

O CH3 CH2 O O H O CH3 CH2 O O O O H CH2 O C CH3 O OH

1' O2 rearrangement

.

Further Decomposition (Scheme 3 b) 1 + H.

.

+ H.

n NH O H C 2 H 2 H C 2 H C 2 H C C C 2

Nylon 6

Remarkable information on the photo oxidation of Nylon 6 and Nylon 66 has been provided, in the past, mainly by UV and IR spectroscopy and by wet chemistry methods

CH H NH CO CO (CH2)4 CH2 CH2 CH2 CH2 CH2 NH CO

H abstraction NorrishI Norrish II

CO (CH2)4 NH CHO CO (CH2)4 NH COOH CO (CH2)4 NH CH3

(B)

(CH2)5 CO NH2 (CH2)5 CO NH CHO CO (CH2)3 NH CH CH2 CO (CH2)3 NH CH3 CO (CH2)2 NH CH CH2 (CH2)5 CO NH CO CH3

(C) (A)

CH NH O OH CO (CH2)4 (CH2)4 CO CHO (CH2)4 CO COOH NH CO NH2 (CH2)5 NH (CH2)4 CO CO CO

hν hν hν

A

B C

CH H NH CO CO (CH2)4 CH2 CH2 CH2 CH2 CH2 NH CO

H abstraction NorrishI Norrish II

CO (CH2)4 NH CHO CO (CH2)4 NH COOH CO (CH2)4 NH CH3

(B)

(CH2)5 CO NH2 (CH2)5 CO NH CHO CO (CH2)3 NH CH CH2 CO (CH2)3 NH CH3 CO (CH2)2 NH CH CH2 (CH2)5 CO NH CO CH3

(C) (A)

CH NH O OH CO (CH2)4 (CH2)4 CO CHO (CH2)4 CO COOH NH CO NH2 (CH2)5 NH (CH2)4 CO CO CO

hν hν hν

A

B C

Overall Photo-oxidation Processes in Ny6.

3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.0 4.1 4.2 4.3

log log Mv

10 20 30 40 50 60 70 80 90 100 110 120

Expos xposit ition ion Time ime (hour hours) Molar mass of photo-oxidised Ny6 samples as a function of exposition time

Counts 10000 20000 30000 1000 2000 3000 4000 5000 6000 Mass (m/z)

MALDI-TOF mass spectrum of Ny6

CO (CH2)5 9 NH

A

O H CO (CH2)5 9 H NH

B

OH

8

CO (CH2)5 CO NH

C

1040 1045 1065 1020 1025 1030 1035 1050 1055 1060

1050 1050 CNa +

+

1019 1019 1020 1020 1041 1042 1043 ANa + AH+

+

1037 1037 1059 1059 1060 1060 BNa Na +

+

BH+

MALD LDI-T

• TOF

OF mas mass spect pectrum um of

• f Ny

Ny6 6 in in the he range ange 2800-3100 2800-3100

2853 2862 2872 2967 2976 2985 3080 3090 3098 2850 2900 2950 3000 3050 3100 Mass (m/z)

ANa+ BNa+ CNa+ ANa+ BNa+ CNa+ ANa+ CNa+ BNa+

CO (CH2)5 9 NH

A

O H CO (CH2)5 9 H NH

B

OH

8

CO (CH2)5 CO NH

C

5000 10000 15000 20000 25000 30000 1000 2000 3000 4000 5000 6000 7000 8000 10000 20000 30000 40000

1041 1041 1057 1057 1045 1045 1073 1073 1029 1029 1086 1114 1126 1126 1100 1114 1100 1086 1020 1040 1060 1080 1100 1120 Mass (m/z) 1013 1013

a b c

1059 1050 1041 1019 1132

48 h 289 h 0 h

MALD LDI-T

• TOF

OF mas mass spect pectrum um of

• f Ny

Ny 6 6 af after er the he deis deisot

• toping
• ping pr

procedur

• cedure.

e.

1020 1025 1030 1035 1040 1045 1050 1055 1060

m/z 1050

CNa+

1037 1059

BNa+

BH+ H+ 1019 1041

ANa+ AH+ H+ 1040 1045 1065 1020 1025 1030 1035 1050 1055 1060 Mass (m/z)

1050 1050

1019 1020 1041 1042 1043

1037 1037 1059 1059 1060 1060

1010 1020 1030 1040 1050 1060 1070 1080 1090 1100 1110 1120

1041 1043 1045 1055 1057 1069 1072 1073 1083 1085 1086 1100 1101 1114 1113 1013 1029

Deisotopized MALDI-TOF Mass Spectrum, in the mass range 1010-1120Da of Ny6 sample photo-oxidized for 289 hours.

m/z

(CH2)4 CO CHO (CH2)4 CO COOH

+

N H2 CO (CH2)4

CO

(CH2)5 NH NH (CH2)5 CO CH H NH CO (CH2)4

CO

(CH2)5 NH NH (CH2)5 CO CH NH

.

n n

CO (CH2)4

CO

(CH2)5 NH NH (CH2)5 CO CH NH

n

O OH CO (CH2)5 NH NH (CH2)4 CO O C CO (CH2)4 NH CH OH NH

n n

(CH2)2 CO CHO CH CH CO (CH2)5 NH

R. hν O2 H.

• H2O
• OH.

H. O2 2H.

(CH2)4 CO CHO (CH2)4 CO COOH

+

N H2 CO (CH2)4

CO

(CH2)5 NH NH (CH2)5 CO CH H NH CO (CH2)4

CO

(CH2)5 NH NH (CH2)5 CO CH NH

.

n n

CO (CH2)4

CO

(CH2)5 NH NH (CH2)5 CO CH NH

n

O OH CO (CH2)5 NH NH (CH2)4 CO O C CO (CH2)4 NH CH OH NH

n n

(CH2)2 CO CHO CH CH CO (CH2)5 NH

R. hν O2 H.

• H2O
• OH.

H. O2 2H.

Degradation via Hydroperoxide

chain ends

A

1040 1050 1060 1070 1080 1090 1100 1110 1120 1130 1140 1150

M/z

1041 1055 1050 1058

1059 1132

1057 Cycle+ Na+ 1041 1055 1050 1058

1059 1132

1057 Cycle+H+ 1057 1057

1048 1050 1052 1054 1056 1058 1060

Exposure Time (Hours)

1050 1055 1050 1055 1058 1059

A-E A-A A-A

Deisotopized MALDI-TOF Mass Spectrum, in the mass range 1010-1120Da of Ny6 sample photo-oxidized for 11 hours.

11 11 hour hours

E-E E-E

1010 1020 1030 1040 1050 1060 1070 1080 1090 1100 1110 1120

1041 1043 1045 1055 1057 1069 1072 1073 1083 1085 1086 1100 1101 1114 1113 1013 1029

Expos xposit ition ion Time ime 289 289 h h

A-A A-A A-A A-A A-E E-A-A E-A-A E-A

NH (CH2)5 CO COOH (CH2)5 CO NH2

+

CO CH2 (CH2)4

CO

NH (CH2)5 NH NH (CH2)5 CO CO (CH2)4 NH C H3 n

.

CO (CH2)4 NH CH2 NH (CH2)5 CO CHO

O2

• CO2

+H. +H.

O2

PH

CO (CH2)4 NH CH2 O OH

• H20

CO (CH2)4 NH OHC

O2

CO (CH2)4 NH HOOC

• H

.

NH (CH2)5 CO CO

.

• 2H.

CO (CH2)2 NH CH OHC HC CO (CH2)3 NH CH C H2

hν

NH (CH2)5 CO COOH (CH2)5 CO NH2

+

CO CH2 (CH2)4

CO

NH (CH2)5 NH NH (CH2)5 CO CO (CH2)4 NH C H3 n

.

CO (CH2)4 NH CH2 NH (CH2)5 CO CHO

O2

• CO2

+H. +H.

O2

PH

CO (CH2)4 NH CH2 O OH

• H20

CO (CH2)4 NH OHC

O2

CO (CH2)4 NH HOOC

• H

.

NH (CH2)5 CO CO

.

• 2H.

CO (CH2)2 NH CH OHC HC CO (CH2)3 NH CH C H2

hν

Photodegradation via Norrish I reaction. chain ends

B

CH2 NH CH2 CH CH2 CO NH (CH2)5 CO C H3

+

CH2 NH CH2 CH2 CH3 CO (CH2)5 NH NH CH2 CO CH2 CH CH2 CH2 H NH CH CH2 CH2 H C H2 CH2 O C NH CO (CH2)5

hν

Photodegradation via Norrish II reaction chain ends

C

1010 1020 1030 1040 1050 1060 1070 1080 1090 1100 1110 1120

1041 1043 1045 1055 1057 1069 1072 1073 1083 1085 1086 1100 1101 1114 1113 1013 1029

Expos xposit ition ion Time ime 289 289 h h

A-A A-A A-A A-A E-A E-A-A E-A-A A-E B-E B-E C-C B-E B-C A-C C-E

B-A-C B-A-C

A-B E-C B-E B-A B-C

• 1.0

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0

I %

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 10 20 30 40 50

Exposition Time

O H CO (CH2)5

9 H

NH

Decompos ecomposit ition ion via ia Hy Hydr droper

• peroxide

xide

Relative amount vs exposition time of species at m/z 1058 and 1059, as obtained from the MALDI spectra of photo-oxidized Ny6 sample N H2 CO (CH2)5

9 CO

NH (CH2)4 CHO

E-A E-E

• 1

1 2 3 % R e l a t i v e A m

• u

n t 5 10 15 20 25 30 35 40 45 50

Exposure Time

• 0.1

0.0 0.1 0.2 0.3 0.4 0.5 0.6

% R e l a t i v e A m

• u

n t

5 10 15 20 25 30 35 40 45 50

Exposure Time (Hours)

Induction Period Induction Period

Norrish II Norrish I

CO (CH2)5 NH HN (CH2)4 OHC H 8 O H CO (CH2)5 NH CO CH3 9

Relative amount vs exposition time of species at m/z 1029 and 1100, as obtained from the MALDI spectra of photo-oxidized Ny6 sample

CH H NH CO CO (CH2)4 CH2 CH2 CH2 CH2 CH2 NH CO

H abstraction NorrishI Norrish II

CO (CH2)4 NH CHO CO (CH2)4 NH COOH CO (CH2)4 NH CH3

(B)

(CH2)5 CO NH2 (CH2)5 CO NH CHO CO (CH2)3 NH CH CH2 CO (CH2)3 NH CH3 CO (CH2)2 NH CH CH2 (CH2)5 CO NH CO CH3

(C) (A)

CH NH O OH CO (CH2)4 (CH2)4 CO CHO (CH2)4 CO COOH NH CO NH2 (CH2)5 NH (CH2)4 CO CO CO

hν hν hν

A

B C

CH H NH CO CO (CH2)4 CH2 CH2 CH2 CH2 CH2 NH CO

H abstraction NorrishI Norrish II

CO (CH2)4 NH CHO CO (CH2)4 NH COOH CO (CH2)4 NH CH3

(B)

(CH2)5 CO NH2 (CH2)5 CO NH CHO CO (CH2)3 NH CH CH2 CO (CH2)3 NH CH3 CO (CH2)2 NH CH CH2 (CH2)5 CO NH CO CH3

(C) (A)

CH NH O OH CO (CH2)4 (CH2)4 CO CHO (CH2)4 CO COOH NH CO NH2 (CH2)5 NH (CH2)4 CO CO CO

hν hν hν

A

B C

Overall Photo-oxidation Processes in Ny6.

30 40 50 60 70 80 90 100 (°C)

a b c d e f g h Figure 7. DSC curves in the range 25-100°C (recorded at 10°C/min in heating mode) of (a) Ny6,10, (b) Ny6,6-COOH, and Ny6,6-COOH/Ny6,10 reacted at 290°C for: (c) 0 min, (d) 5 min, (e) 10 min, (f) 15 min, (g) 30 min, and (h) 60 min. Endo

Ny6,10 Ny6,6-COOH Ny6,6-COOH/ Ny6,10 at 290°C 0 min 5 min 10 min 15 min 30 min 60 min

3.5 4.0 4.5 5.0 5.5 log(Mw) 20 21 22 23 24 25 26 27 28 29 30 31

Ve (mL)

Mw PMMA standards by MALDI Mw PMMA Standards by Supplier Mw of PMMA Fractions by MALDI

3.5 4.0 4.5 5.0 5.5 log(Mw) 20 21 22 23 24 25 26 27 28 29 30 31

Ve (mL)

Mw PMMA standards by MALDI Mw PMMA Standards by Supplier Mw of PMMA Fractions by MALDI