copolymer microstructure determination by the click of a

-‐ 1 -‐

Supporting information belonging to the paper entitled:

Copolymer microstructure determination by the click

of a button; reactivity ratios of comonomers from a

single MALDI-ToF-MS measurement.

S. Huijser, G. D. Mooiweer, R. van der Hofstad, B. B. P. Staal,

J. Feenstra, A. M. van Herk, C.E. Koning, R. Duchateau*

-‐ 2 -‐

Content: Page:

Experimental Section 5

Figure S1a. Benchmark Dell PC, 1 CPU, 3GHz processor, 1 Gb RAM. 6

Figure S1b. Benchmark LIME PC, 4 CPUs parallel, 3 GHz processor, 8 Gb RAM. 6

Figure S2. Flowchart of procedure to determine reactivity ratios by MALDI-ToF-MS. 7

Table S1. Classification of reactivity ratios and microstructure. 8

The analytical form of the probability mass function 8

Table S2. Molecular weights of monomers. 11

Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of: Figure S3. Copolymer of styrene/methyl acrylate. 12

Figure S4. Copolymer of styrene/ethyl acrylate. 12

Figure S5. Copolymer of styrene/butyl acrylate. 13

Figure S6. Copolymer of styrene/methyl methacrylate. 13

Figure S7. Copolymer of styrene/ethyl methacrylate. 14

Figure S8. Copolymer of styrene/butyl methacrylate. 14

Figure S9. Copolymer of methyl methacrylate/ethyl methacrylate. 15

Figure S10. Copolymer of methyl methacrylate/butyl methacrylate. 15

Figure S11. Copolymer of methyl methacrylate/butyl acrylate. 16

Figure S12. Copolymer of methyl methacrylate/vinyl acetate. 16

Figure S13. Copolymer of butyl methacrylate/ethyl acrylate. 17

Figure S14. Copolymer of ethyl acrylate/vinyl acetate. 17

Figure S15. Copolymer of vinyl acetate/butyl acrylate. 18

Figure S16. Copolymer of ε-caprolactone/4-methylcaprolactone recorded in reflector mode with Na+. 19

Figure S17. Copolymer of ε-caprolactone/1,5-dioxepan-2-one recorded in reflector mode with K+. 19

Figure S18. Copolymer of δ-valerolactone/1,5-dioxepan-2-one recorded in reflector mode with K. 20

Figure S19. Copolymer of ε-caprolactone/trimethylene carbonate with 1,3-propanediol as initiator

recorded in reflector mode with K+. 20

Figure S20. Copolymer of lactide/1,5-dioxepan-2-one recorded in reflector mode with K+. 21

Figure S21. Copolymer of ε-caprolactone / lactide recorded in reflector mode with K+. 21

Chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution of: Figure S22. Copolymer styrene/methyl acrylate, chain length 20. 22

-‐ 3 -‐

Figure S23. Copolymer styrene/ethyl acrylate, chain length 20. 22

Content: Page:

Figure S24. Copolymer styrene/butyl acrylate, chain length 20. 23

Figure S25. Copolymer Styrene / Methyl methacrylate, chain length 20. 23

Figure S26. Copolymer styrene/ethyl methacrylate, chain length 16. 24

Figure S27. Copolymer styrene/butyl methacrylate, chain length 15. 24

Figure S28. Copolymer methyl methacrylate/ethyl methacrylate, chain length 17. 25

Figure S29. Copolymer methyl methacrylate/butyl methacrylate, chain length 15. 25

Figure S30. Copolymer methyl methacrylate/butyl acrylate, chain length 20. 26

Figure S31. Copolymer methyl methacrylate/vinyl acetate, 20:80 ratio, chain length 18. 26

Figure S32. Copolymer butyl methacrylate/ethyl acrylate, chain length 19. 27

Figure S33. Copolymer ethyl acrylate/vinyl acetate, chain length 15. 27

Figure S34. Copolymer butyl acrylate/vinyl acetate, chain length 30. 28

Figure S35. Copolymer ε-caprolactone/4-methylcaprolactone, 50:50 ratio, chain length 18. 29

Figure S36. Copolymer ε-caprolactone/4-methylcaprolactone, 30:70 ratio, chain length 18. 29

Figure S37. Copolymer ε-caprolactone/1,5-dioxepan-2-one, 50:50 ratio, chain length 20. 30

Figure S38. Copolymer ε-caprolactone/1,5-dioxepan-2-one, 70:30 ratio, chain length 18. 30

Figure S39. Copolymer δ-valerolactone/1,5-dioxepan-2-one, 50:50 ratio, chain length 15. 31

Figure S40. Copolymer ε-caprolactone/trimethylene carbonate, 50:50 ratio, chain length 15. 31

Figure S41. Copolymer lactide/1,5-dioxepan-2-one, 50:50 ratio, chain length 20. 32

Figure S42. Copolymer ε-caprolactone/lactide, chain length 30. 32

Composition vs. chain length of: Figure S43. Copolymer styrene/methyl acrylate, 50:50 ratio. 33

Figure S44. Copolymer styrene/ ethyl acrylate, 50:50 ratio. 33

Figure S45. Copolymer styrene/ butyl acrylate, 50:50 ratio. 34

Figure S46. Copolymer styrene/ methyl methacrylate, 50:50 ratio. 34

Figure S47. Copolymer styrene/ethyl methacrylate, 50:50 ratio. 35

Figure S48. Copolymer methyl methacrylate/ethyl methacrylate, 50:50 ratio. 35

Figure S49. Copolymer methyl methacrylate/butyl methacrylate, 50:50 ratio. 36

Figure S50. Copolymer methyl methacrylate/vinyl acetate, 20:80 ratio. 36

Figure S51. Copolymer butyl methacrylate/ethyl acrylate, 50:50 ratio. 37

Figure S52. Copolymer ethyl acrylate/vinyl acetate, 50:50 ratio. 37

Figure S53. Copolymer butyl acrylate/vinyl acetate, 50:50 ratio. 38

Figure S54. Copolymer ε-caprolactone/4-methylcaprolactone, 50:50 ratio. 39

-‐ 4 -‐

Figure S55. Copolymer ε-caprolactone/4-methylcaprolactone, 30:70 ratio. 39

Content: Page:

Figure S56. Copolymer ε-caprolactone/1,5-dioxepan-2-one, 50:50 ratio. 40


Figure S58. Copolymer δ-valerolactone/1,5-dioxepan-2-one, 50:50 ratio. 41

Figure S59. Copolymer ε-caprolactone/trimethylene carbonate, 50:50 ratio. 41

Figure S60. Copolymer lactide/1,5-dioxepan-2one, 50:50 ratio. 42

Figure S61. Copolymer ε-caprolactone/lactide, 50:50 ratio. 42

Homo-probabilities versus chain length (Most abundant chain lengths) of: Figure S62. Copolymer styrene/methyl acrylate. 43

Figure S63. Copolymer styrene/ethyl acrylate. 43

Figure S64. Copolymer styrene/butyl acrylate. 44

Figure S65. Copolymer styrene/ethyl methacrylate. 44

Figure S66. Copolymer styrene/ethyl methacrylate. 45

Figure S67. Copolymer methyl methacrylate/ethyl methacrylate. 45

Figure S68. Copolymer methyl methacrylate/butyl methacrylate. 46

Figure S69. Copolymer methyl methacrylate/butyl acrylate. 46

Figure S70. Copolymer vinyl acetate/methyl methacrylate. 47

Figure S71. Copolymer ethyl acrylate/butyl methacrylate. 47

Figure S72. Copolymer ethyl acrylate/vinyl acetate. 48

Figure S73. Copolymer ε-caprolactone/4-methyl caprolactone, 50:50 ratio. 49



Figure S76. Copolymer δ-valerolactone/1,5-dioxepan-2-one, 50:50 ratio. 50

Figure S77. Copolymer ε-caprolactone/trimethylene carbonate. 51

Figure S78. Copolymer lactide/1,5-dioxepan-2one. 51

Figure S79. Copolymer ε-caprolactone/lactide. 52

-‐ 5 -‐

Experimental Section

Reagents. Free radical: Monomers were purified by conventional methods. 2,2’-azobis(isobutyronitrile)

(AIBN) was recrystallized from methanol. 1-Dodecanethiol (DDT) was used without further purification and

purchased from Aldrich. Ring opening: 1,5- dioxepan-2-one and 4-methylcaprolactone were prepared

according to literature procedures.1,2 D-Lactide was a gift from Purac. ε-Caprolactone, δ-Valerolactone and

Tin (II) 2-ethylhexanoate (Sn(Oct)2) was purchased from Aldrich. The data of the copolymerization of

trimethylene carbonate and ε-caprolactone are reported elsewhere.3

Synthesis. Free radical: A mixture of comonomers (6 mmol) in required molar ratio, initiator AIBN and

chain transfer agent DDT (in a molar ratio of 500:10:1 respectively) was reacted in a 1.5 mL crimp lid vial

placed in an aluminium heating block at 60 or 70 oC. Crude samples were taken with an interval of 30 s to

undergo immediate MALDI-ToF-MS analyses. Ring opening: A mixture of comonomers (10 mmol) in

required molar ratio and a drop of Sn(Oct)2 was reacted in a 1.5 mL crimp lid vial placed in an aluminium

heating block at 130 oC. Crude samples were taken with an interval of 5 minutes to undergo immediate

MALDI-ToF-MS analyses.

MALDI-ToF-MS Analysis. MALDI-ToF-MS analysis was performed on a Voyager DE-STR from Applied

Biosystems equipped with a 337 nm nitrogen laser. An accelerating voltage of 25 kV was applied. Mass

spectra of 1000 shots were accumulated. The polymer samples were dissolved in THF at a concentration of 1

mg mL-1. The cationization agent used was potassium trifluoroacetate (Fluka, >99%) dissolved in THF at a

concentration of 5 mg mL-1. The matrix used was trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-

propenylidene]malononitrile (DCTB) (Fluka) and was dissolved in THF at a concentration of 40 mg mL-1.

Solutions of matrix, salt and polymer were mixed in a volume ratio of 4:1:4, respectively. The mixed solution

was hand-spotted on a stainless steel MALDI target and left to dry. The spectra were recorded in the reflectron

mode as well as the linear mode.

1 Mathisen, T., Masus, K. & Albertsson, A.-C Macromolecules 22, 3842-3846 (1989).

2 Trollsås, M. Kelly, M.A. Claesson, H., Siemens R. & Hedrick, J.L. Macromolecules 32, 4917-4924 (1999).

3 Henry, G.R.P., Huijser, S., Heise, A. & Koning, C.E. manuscript in preparation.

-‐ 6 -‐

Benchmark tests

Benchmark tests were performed to determine the number of time, ‘d’, a single chain requires to be simulated

by MC to obtain an acceptable absolute error. These tests were performed for a Bernoullian distribution since

the analytical expression for the probability density function is known, enabling direct comparison with the

chemical composition distribution determined by MC. Evidently, the computer’s processor time increases but

the absolute error decreases with increasing sample size as shown in Figure S1. In the case of a quad core

processor the time required to simulate a chain 3·106 times is 5 s with an accuracy that allows for three digits.

5 5.5 6 6.5 7-4.2

-4

-3.8

-3.6

-3.4

-3.2

-3

-2.8

-2.6

-2.4

log10(Sample size)

log 10

(Max

abs

err

or)

Max abs error versus binomial distribution

5 5.5 6 6.5 7-0.5

0

0.5

1

1.5

2

2.5

log10(Sample size)

log 10

(Req

uire

d C

PU ti

me

[sec

])

Plot of required CPU time (sec)

Figure S1a. Benchmark Dell PC, 1 CPU, 3GHz processor, 1 Gb RAM.

-‐ 7 -‐

5 5.5 6 6.5 7-4.2

-4

-3.8

-3.6

-3.4

-3.2

-3

-2.8

-2.6

-2.4

log10(Sample size)

log 10

(Max

abs

err

or)

Max abs error versus binomial distribution

5 5.5 6 6.5 7-1

-0.5

0

0.5

1

1.5

log10(Sample size)

log 10

(Req

uire

d C

PU ti

me

[sec

])

Plot of required CPU time (sec)

Figure S1b. Benchmark LIME PC, 4 CPUs parallel, 3 GHz processor, 8 Gb RAM.

-‐ 8 -‐

Flow chart of procedure to determine r-values.

Figure S3. Flowchart of procedure to determine reactivity ratios by MALDI-ToF-MS.

Polymerization

MALDI-ToF-MS

Extract chemical composition distribution per chain length

Deconvolution MALDI-ToF-MS spectrum into matrix

Check if measured distribution fits MC simulated distribution by LSSQ

NO YES Change P11 and P22 in order to minimize

LSSQ and simulate new 1st order Markov Chain by MC

MATLAB

MC simulation of 1st order Markov chain for chain length ‘n’ starting with

P11+P22=1

Calculate r-values from feed ratios and P-values

Copolymer analysis software by B.B.P. Staal

-‐ 9 -‐

Classification of reactivity ratios according to topology. Table S1 is given here as a support to how the reactivity ratios relate to the expected microstructure of the

copolymer. Table S1. Classification of reactivity ratios and microstructure. Ratios Topology

r1 = 1/r2, r2 = 1/r1 (r1r2 = 1) Random copolymer

r1 << 1, r2 << 1 (r1r2 → 0) Alternating copolymer

r1 >> 1, r2 < 1 (r1r2 < 1) Tends to homopolymer of M1

r1 >>1, r2 >>1 Tends to block copolymer

The analytical form of the probability mass function:

The probability mass function of the number of monomers of type 1 (= monomer B), in a copolymer consisting of monomers A and B with a length n is given.

( )( )mnNPa =1 (1)

Where n is the chain length, m the number of B units in the chain and aP is the probability distribution.

In order compute a probability mass function, the Fourier theory shall be used. It is already mentioned in an internal memo that the Fourier theory can be very convenient to compute such mass functions. Let :f N→ R

( ) ( ) ( ) ( ) ( ) ( )xfkxixfkxxfekfxxx

ikx ∑∑∑∞

=

∞

=

∞

=

+==000

sincosˆ (2)

And for the Fourier inverse:

( ) ( )π

π

π 2ˆ dkkfexf ikx∫

−

−= (3)

Now we would like to apply these to formulas to calculate our mass probability function. The characteristic function of ( )nN1 is now given by:

(4) ( ) ( )( )∑

=

==n

ma

ikma mnNPekf

01

ˆ

-‐ 10 -‐

In order to help the reader we shall apply these formulas for a polymer with chain length equals three (n=3).Therefore we go back to “tree” of probabilities as depicted below.

R is our starting group (e.g. a radical). Every time a chain end reacts there will be 2 possibilities, simply an attachment of repeat unit A or B. All probabilities are now given by all the possible paths we can take. In this case at a chain length of m=3, 8 possible routes could have been taken. The probability for each route is given by the product of the probabilities. For example, the probability of 3 A units in a row is ( )( )( )papapa0 etc. The next step is that we write the sum of probabilities for chains which have the same number of B monomers (m) for a given chain length (n).

R

pa0

R-b

R-a

pa R-aa

R-ab

R-aaa

R-aab

R-aba

R-abb

R-ba

R-bb

R-baa

R-bab

R-bba

R-bbb

pb0

1-pa

pa

1-pa

1-pb

pb

1-pb

pb

pb

1-pb

pa

1-pa

Number of b-units in the polymer chain

m=0

m=1

m=1

m=2

m=1

m=2

m=2

m=3

n=3

m=0

m=1

m=2

m=3

( )( )20 papa

( )( )( ) ( )( )( ) ( )( )( )papbpbpbpapapapapa −+−−+− 1011010

( )( )( ) ( )( )( ) ( )( )( )pbpbpbpapbpbpbpapa −+−−+− 1011010

( )( )20 pbpb

-‐ 11 -‐

Applying the following formula, we obtain:

(5)

This result can be written in a more compact and general way by introducing it in a matrix form.

(6)

Now the Fourier inverse rather easy:

( )( ) ( )( ) ( )( ) ( ) π

π

π 211

001

1dk

epbpbepapa

epbpaemnNPn

ik

ikikikm

a ∫ ∑−

−

−

⎟⎟⎠

⎞⎜⎜⎝

⎛

−

−== (7)

This is finally the general formula that is used to perform all other calculations and more over this formula is explicit!

Note that 11Ppa = , 22Ppb = , 00 11Ppa = and 022Ppb =

( )( )( ) ( )( )( ) ( )( )( ) ( )( )232 01011010 pbpbepbpbpbpapbpbpbpapae ikik +−+−−+−

( )( ) ( )( )( ) ( )( )( ) ( )( )( )+−+−−+−+= papbpbpbpapapapapaepapae ikik 10110100 120

( ) ( )( )∑=

==3

01 3ˆ

ma

ikma mNPekf

( ) ( )( ) ( )( ) ( )∑

−

⎟⎟⎠

⎞⎜⎜⎝

⎛

−

−=

1

11

00ˆn

ik

ikik

a epbpbepapa

epbpakf

-‐ 12 -‐

MALDI-ToF-MS spectra

The MALDI-ToF-MS spectra recorded in the reflector mode and the matching isotope patterns for end group

determination are given in the following section. First, the spectra of the free radical copolymers and second

the spectra of the ring opening copolymers will be shown. Table 2 is given as support to explain the difference

between peaks in the spectra.

Table S2. Molecular weights of monomers.

Abbreviation Name Mw (g mol−l) BA Butyl Acrylate 128 MA Methyl Acrylate 86 EA Ethyl Acrylate 100 nBMA n-Butyl Methacrylate 142 MMA Methyl Methacrylate 100 EMA Ethyl Methacrylate 114 Sty Styrene 104 VAc Vinyl Acetate 86 CL ε-Caprolactone 114 D-LA D-Lactide 144 DXO 1,5-dioxepan-2-one 116 MCL 4-Methylcaprolactone 128 TMC Trimethylene carbonate 102 VL δ-Valerolactone 100

-‐ 13 -‐

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ity

1740 1779 1818 1857 1896 1935

Mass (m/z)

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% In

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1740 1779 1818 1857 1896 1935

50

100Experimental

C12H25S-(STY)n-(MA)m-H

Δm/z = 18 Δm/z = 104

1250 3000 4750 6500 8250 10000Mass (m/z)

50

100

% In

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ity

1250 3000 4750 6500 8250 10000Mass (m/z)

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1740 1779 1818 1857 1896 1935

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1740 1779 1818 1857 1896 1935

50

100Experimental

C12H25S-(STY)n-(MA)m-H

Δm/z = 18 Δm/z = 104

Figure S3. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of styrene/methyl acrylate.

2780 2811 2842 2873 2904 2935

Mass (m/z)

50

100

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2780 2811 2842 2873 2904 2935

50

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1250 3000 4750 6500 8250 10000

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Experimental

C12H25S-(STY)n-(EA)m-H

Δm/z = 104

2780 2811 2842 2873 2904 2935

Mass (m/z)

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ity

2780 2811 2842 2873 2904 2935

50

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1250 3000 4750 6500 8250 10000

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Experimental

C12H25S-(STY)n-(EA)m-H

Δm/z = 104

Figure S4. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of styrene/ethyl acrylate.

-‐ 14 -‐

1000 2800 4600 6400 8200 10000

Mass (m/z)

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ity

1670 1718 1766 1814 1862 1910Mass (m/z)

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1670 1718 1766 1814 1862 1910

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C12H25S-(STY)n-(BA)m-H

Experimental

Δm/z = 24 Δm/z = 104

1000 2800 4600 6400 8200 10000

Mass (m/z)

50

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% In

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ity

1670 1718 1766 1814 1862 1910Mass (m/z)

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1670 1718 1766 1814 1862 1910

50

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C12H25S-(STY)n-(BA)m-H

Experimental

Δm/z = 24 Δm/z = 104

Figure S5. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of styrene/butyl acrylate.

1000 2800 4600 6400 8200 10000

Mass (m/z)

50

100

% In

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ity

2435 2471 2507 2543 2579 2615

50

100

2435 2471 2507 2543 2579 2615

50

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Experimental

C12H25S-(STY)n-(MMA)m-H

C12H25S-(STY)n-(MMA)m-C4H6N

2435 2471 2507 2543 2579 2615Mass (m/z)

50

100

% In

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ity

1000 2800 4600 6400 8200 10000

Mass (m/z)

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2435 2471 2507 2543 2579 2615

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2435 2471 2507 2543 2579 2615

50

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Experimental

C12H25S-(STY)n-(MMA)m-H

C12H25S-(STY)n-(MMA)m-C4H6N

2435 2471 2507 2543 2579 2615Mass (m/z)

50

100

% In

tens

ity

Figure S6. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS

spectrum of the copolymer of styrene/methyl methacrylate.

-‐ 15 -‐

1250 2317 3384 4451 5518 6585Mass (m/z)

50

100

% In

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ity

1605 1653 1701 1749 1797 1845

Mass (m/z)

40

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1605 1653 1701 1749 1797 1845

40

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C12H25S-(STY)n-(EMA)m-H

Δm/z = 104Δm/z = 10

1250 2317 3384 4451 5518 6585Mass (m/z)

50

100

% In

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ity

1605 1653 1701 1749 1797 1845

Mass (m/z)

40

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% In

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1605 1653 1701 1749 1797 1845

40

100 Experimental

C12H25S-(STY)n-(EMA)m-H

Δm/z = 104Δm/z = 10

Figure S7. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of styrene/ethyl methacrylate.

100

1250 3000 4750 6500 8250 10000Mass (m/z)

50

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1855 1882 1909 1936 1963 1990

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C12H25S-(STY)n-(BMA)m-H

100

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1250 3000 4750 6500 8250 10000Mass (m/z)

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1855 1882 1909 1936 1963 1990

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C12H25S-(STY)n-(BMA)m-H

Figure S8. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of styrene/butyl methacrylate.

-‐ 16 -‐

1245 2615 3985 5355 6725 8095

Mass (m/z)

50

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1900 1941 1982 2023 2064 2105Mass (m/z)

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1900 1941 1982 2023 2064 2105

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C12H25S-(EMA)n-(MMA)m-H

Δm/z = 114Δm/z = 14

1245 2615 3985 5355 6725 8095

Mass (m/z)

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ity

1900 1941 1982 2023 2064 2105Mass (m/z)

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1900 1941 1982 2023 2064 2105

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C12H25S-(EMA)n-(MMA)m-H

Δm/z = 114Δm/z = 14

Figure S9. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of methyl methacrylate/ethyl methacrylate.

1455 2481 3507 4533 5559 6585

Mass (m/z)

50

100

% In

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ity

2170 2202 2234 2266 2298 2330Mass (m/z)

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2170 2202 2234 2266 2298 2330

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C12H25S-(BMA)n-(MMA)m-H

Δm/z = 42 Δm/z = 100

1455 2481 3507 4533 5559 6585

Mass (m/z)

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ity

1455 2481 3507 4533 5559 6585

Mass (m/z)

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2170 2202 2234 2266 2298 2330Mass (m/z)

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ity

2170 2202 2234 2266 2298 2330

50

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C12H25S-(BMA)n-(MMA)m-H

Δm/z = 42 Δm/z = 100

Figure S10. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of methyl methacrylate/butyl methacrylate.

-‐ 17 -‐

1000 2800 4600 6400 8200 10000

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1900 1924 1948 1972 1996 2020

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C12H25S-(MMA)n-(BA)m-H

Δm/z = 100Δm/z = 28

1000 2800 4600 6400 8200 10000

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1900 1924 1948 1972 1996 2020

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C12H25S-(MMA)n-(BA)m-H

Δm/z = 100Δm/z = 28

Figure S11. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of methyl methacrylate/butyl acrylate.

1250 2000 2750 3500 4250 5000

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1465 1505 1545 1585 1625 1665

Mass (m/z)

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1465 1505 1545 1585 1625 1665

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C12H25S-(VAc)n-(MMA)m-H

Δm/z = 100Δm/z = 14

1250 2000 2750 3500 4250 5000

Mass (m/z)

50

100

% In

tens

ity

1250 2000 2750 3500 4250 5000

Mass (m/z)

50

100

% In

tens

ity

1465 1505 1545 1585 1625 1665

Mass (m/z)

50

100

% In

tens

ity

1465 1505 1545 1585 1625 1665

50

100 Experimental

C12H25S-(VAc)n-(MMA)m-H

Δm/z = 100Δm/z = 14

Figure S12. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of methyl methacrylate/vinyl acetate.

-‐ 18 -‐

995 2375 3755 5135 6515 7895

Mass (m/z)

50

100

% In

tens

ity

1625 1681 1737 1793 1849 1905

Mass (m/z)

50

100

% In

tens

ity

1625 1681 1737 1793 1849 1905

50

100Experimental

C12H25S-(EA)n-(BMA)m-HΔm/z = 42 Δm/z = 100

995 2375 3755 5135 6515 7895

Mass (m/z)

50

100

% In

tens

ity

1625 1681 1737 1793 1849 1905

Mass (m/z)

50

100

% In

tens

ity

1625 1681 1737 1793 1849 1905

50

100Experimental

C12H25S-(EA)n-(BMA)m-HΔm/z = 42 Δm/z = 100

Figure S13. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS

spectrum of the copolymer of butyl methacrylate/ethyl acrylate.

1565 1605 1645 1685 1725 1765Mass (m/z)

50

100

% In

tens

ity

1565 1605 1645 1685 1725 1765

50

100

1250 3000 4750 6500 8250 10000

Mass (m/z)

50

100

% In

tens

ity

Experimental

C12H25S-(VAc)n-(EA)m-H

Δm/z = 100Δm/z = 14

1565 1605 1645 1685 1725 1765Mass (m/z)

50

100

% In

tens

ity

1565 1605 1645 1685 1725 1765

50

100

1250 3000 4750 6500 8250 10000

Mass (m/z)

50

100

% In

tens

ity

1250 3000 4750 6500 8250 10000

Mass (m/z)

50

100

% In

tens

ity

Experimental

C12H25S-(VAc)n-(EA)m-H

Δm/z = 100Δm/z = 14

Figure S14. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of ethyl acrylate/vinyl acetate.

-‐ 19 -‐

1000 4800 8600 12400 16200 20000

Mass (m/z)

50

100

% In

tens

ity

1665 1685 1705 1725 1745 1765

Mass (m/z)

50

100

% In

tens

ity

1665 1685 1705 1725 1745 1765

50

100 Experimental

C12H25S-(VAc)n-(BA)m-H

Δm/z = 42

1000 4800 8600 12400 16200 20000

Mass (m/z)

50

100

% In

tens

ity

1000 4800 8600 12400 16200 20000

Mass (m/z)

50

100

% In

tens

ity

1665 1685 1705 1725 1745 1765

Mass (m/z)

50

100

% In

tens

ity

1665 1685 1705 1725 1745 1765

50

100 Experimental

C12H25S-(VAc)n-(BA)m-H

Δm/z = 42

Figure S15. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of vinyl acetate/butyl acrylate.

-‐ 20 -‐

Mass (m/z)

900 1720 2540 3360 4180 5000

Mass (m/z)

50

100

% In

tens

ity

1590 1639 1688 1737 1786 1835

50

100

% In

tens

ity

1590 1639 1688 1737 1786 1835

50

100 Experimental

O

O

O

OHOH

Δm/z = 14 Δm/z = 114

Mass (m/z)

900 1720 2540 3360 4180 5000

Mass (m/z)

50

100

% In

tens

ity

1590 1639 1688 1737 1786 1835

50

100

% In

tens

ity

1590 1639 1688 1737 1786 1835

50

100 Experimental

O

O

O

OHOH

Δm/z = 14 Δm/z = 114

900 1720 2540 3360 4180 5000

Mass (m/z)

50

100

% In

tens

ity

1590 1639 1688 1737 1786 1835

50

100

% In

tens

ity

1590 1639 1688 1737 1786 1835

50

100 Experimental

O

O

O

OHOH

Δm/z = 14 Δm/z = 114

Figure S16. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of ε-caprolactone/4-methylcaprolactone recorded in reflector mode with Na+.

900 1420 1940 2460 2980 3500

Mass (m/z)

50

100

% In

tens

ity

O

OO

O

OHOH

1740 1779 1818 1857 1896 1935Mass (m/z)

40

100

% In

tens

ity

1740 1779 1818 1857 1896 1935

40

100 Experimental

Δm/z = 116Δm/z = 2

900 1420 1940 2460 2980 3500

Mass (m/z)

50

100

% In

tens

ity

900 1420 1940 2460 2980 3500

Mass (m/z)

50

100

% In

tens

ity

O

OO

O

OHOH

1740 1779 1818 1857 1896 1935Mass (m/z)

40

100

% In

tens

ity

1740 1779 1818 1857 1896 1935

40

100 Experimental

Δm/z = 116Δm/z = 2

Figure S17. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of ε-caprolactone/1,5-dioxepan-2-one recorded in reflector mode with K+.

-‐ 21 -‐

1005 1383 1761 2139 2517 2895

Mass (m/z)

50

100

% In

tens

ity

1315 1339 1363 1387 1411 1435Mass (m/z)

50

100

% In

tens

ity

1315 1339 1363 1387 1411 1435

50

100Experimental

O

OO

O

OH

n m

OH

1005 1383 1761 2139 2517 2895

Mass (m/z)

50

100

% In

tens

ity

1315 1339 1363 1387 1411 1435Mass (m/z)

50

100

% In

tens

ity

1315 1339 1363 1387 1411 1435

50

100Experimental

1005 1383 1761 2139 2517 2895

Mass (m/z)

50

100

% In

tens

ity

1005 1383 1761 2139 2517 2895

Mass (m/z)

50

100

% In

tens

ity

1315 1339 1363 1387 1411 1435Mass (m/z)

50

100

% In

tens

ity

1315 1339 1363 1387 1411 1435

50

100Experimental

O

OO

O

OH

n m

OH

Figure S18. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of δ-valerolactone/1,5-dioxepan-2-one recorded in reflector mode with K.

750 1155 1560 1965 2370 2775Mass (m/z)

50

100

% In

tens

ity

1275 1320 1365 1410 1455 1500Mass (m/z)

50

100

% In

tens

ity

1275 1320 1365 1410 1455 1500

50

100

O O

O

O O

OOH

O

O O

O

OH

m n m n

Experimental

Δm/z = 12 Δm/z = 114

750 1155 1560 1965 2370 2775Mass (m/z)

50

100

% In

tens

ity

750 1155 1560 1965 2370 2775Mass (m/z)

50

100

% In

tens

ity

1275 1320 1365 1410 1455 1500Mass (m/z)

50

100

% In

tens

ity

1275 1320 1365 1410 1455 1500

50

100

O O

O

O O

OOH

O

O O

O

OH

m n m n

Experimental

Δm/z = 12 Δm/z = 114

Figure S19. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum of the copolymer of ε-caprolactone/trimethylene carbonate with 1,3-propanediol as initiator recorded in reflector mode with K+.

-‐ 22 -‐

2240 2302 2364 2426 2488 2550

Mass (m/z)

50

100

% In

tens

ity

2240 2302 2364 2426 2488 2550

50

100

1345 1976 2607 3238 3869 4500Mass (m/z)

50

100

% In

tens

ity

Experimental

OO

OO

O

OH

n m

OO

H

Δm/z = 28 Δm/z = 144

2240 2302 2364 2426 2488 2550

Mass (m/z)

50

100

% In

tens

ity

2240 2302 2364 2426 2488 2550

50

100

1345 1976 2607 3238 3869 4500Mass (m/z)

50

100

% In

tens

ity

Experimental

OO

OO

O

OH

n m

OO

H

Δm/z = 28 Δm/z = 144

Figure S20. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum the copolymer of lactide/1,5-dioxepan-2-one recorded in reflector mode with K+.

1930 2886 3842 4798 5754 6710Mass (m/z)

50

100

% In

tens

ity

3000 3051 3102 3153 3204 3255

Mass (m/z)

50

100

% In

tens

ity

3000 3051 3102 3153 3204 3255

50

100 Experimental

OO

OO

OH

n m

OO

H

Δm/z = 30 Δm/z = 144

1930 2886 3842 4798 5754 6710Mass (m/z)

50

100

% In

tens

ity

1930 2886 3842 4798 5754 6710Mass (m/z)

50

100

% In

tens

ity

3000 3051 3102 3153 3204 3255

Mass (m/z)

50

100

% In

tens

ity

3000 3051 3102 3153 3204 3255

50

100 Experimental

OO

OO

OH

n m

OO

H

Δm/z = 30 Δm/z = 144

Figure S21. Experimental (full and zoomed in, top) and simulated (bottom) MALDI-ToF-MS spectrum the copolymer of ε-caprolactone / lactide recorded in reflector mode with K+.

-‐ 23 -‐

Chemical composition distribution An example of a recorded chemical composition distribution for a certain chain length will be shown for each comonomer pair treated in this paper along with the fitted distribution for that chain length.

Figure S22. Copolymer styrene/methyl acrylate, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S23. Copolymer styrene/ethyl acrylate, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 24 -‐

Figure S24. Copolymer styrene/butyl acrylate, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S25. Copolymer Styrene / Methyl methacrylate, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 25 -‐

Figure S26. Copolymer styrene/ethyl methacrylate, chain length 16, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S27. Copolymer styrene/butyl methacrylate, chain length 15, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 26 -‐

Figure S28. Copolymer methyl methacrylate/ethyl methacrylate, chain length 17, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S29. Copolymer methyl methacrylate/butyl methacrylate, chain length 15, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 27 -‐

Figure S30. Copolymer methyl methacrylate/butyl acrylate, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S31. Copolymer methyl methacrylate/vinyl acetate, 20:80 ratio, chain length 18, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 28 -‐

Figure S32. Copolymer butyl methacrylate/ethyl acrylate, chain length 19, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S33. Copolymer ethyl acrylate/vinyl acetate, chain length 15, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 29 -‐

Figure S34. Copolymer butyl acrylate/vinyl acetate, chain length 30, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 30 -‐

Figure S35. Copolymer ε-caprolactone/4-methylcaprolactone, 50:50 ratio, chain length 18, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S36. Copolymer ε-caprolactone/4-methylcaprolactone, 30:70 ratio, chain length 18, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 31 -‐

Figure S37. Copolymer ε-caprolactone/1,5-dioxepan-2-one, 50:50 ratio, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S38. Copolymer ε-caprolactone/1,5-dioxepan-2-one, 70:30 ratio, chain length 18, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 32 -‐

Figure S39. Copolymer δ-valerolactone/1,5-dioxepan-2-one, 50:50 ratio, chain length 15, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S40. Copolymer ε-caprolactone/trimethylene carbonate, 50:50 ratio, chain length 15, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

-‐ 33 -‐

Figure S41. Copolymer lactide/1,5-dioxepan-2-one, 50:50 ratio, chain length 20, chemical composition distribution fitted using Monte Carlo simulations and measured chemical composition distribution.

Figure S42. Copolymer ε-caprolactone/lactide, chain length 30, chemical composition distribution fitted using MC and measured chemical composition distribution.

-‐ 34 -‐

Composition versus chain length

Figure S43. Composition vs. chain length of copolymer styrene/methyl acrylate, 50:50 ratio.

Figure S44. Composition vs. chain length of copolymer styrene/ ethyl acrylate, 50:50 ratio.

-‐ 35 -‐

Figure S45. Composition vs. chain length of copolymer styrene/ butyl acrylate, 50:50 ratio.

! Figure S46. Composition vs. chain length of copolymer styrene/ methyl methacrylate, 50:50 ratio.

-‐ 36 -‐

Figure S47. Composition vs. chain length of copolymer styrene/ethyl methacrylate, 50:50 ratio.

Figure S48. Composition vs. chain length of copolymer methyl methacrylate/ethyl methacrylate, 50:50 ratio.

-‐ 37 -‐

Figure S49. Composition vs. chain length of copolymer methyl methacrylate/butyl methacrylate, 50:50 ratio.

!

-‐ 38 -‐

Figure S50. Composition vs. chain length of copolymer methyl methacrylate/vinyl acetate, 20:80 ratio.

Figure S51. Composition vs. chain length of copolymer butyl methacrylate/ethyl acrylate, 50:50 ratio.

-‐ 39 -‐

Figure S52. Composition vs. chain length of copolymer ethyl acrylate/vinyl acetate, 50:50 ratio.

Figure S53. Composition vs. chain length of copolymer butyl acrylate/vinyl acetate, 50:50 ratio.

-‐ 40 -‐

Figure S54. Composition vs. chain length of copolymer ε-‐caprolactone/4-‐methylcaprolactone, 50:50 ratio.

Fig

ure S55. Composition vs. chain length of copolymer ε-‐caprolactone/4-‐methylcaprolactone,

30:70 ratio.

-‐ 41 -‐

! Figure S56. Composition vs. chain length of copolymer ε-‐caprolactone/1,5-‐dioxepan-‐2-‐one, 50:50 ratio.

-‐ 42 -‐

Fig

ure S57. Composition vs. chain length of copolymer ε-‐caprolactone/1,5-‐dioxepan-‐2-‐one, 70:30

ratio.

Figu

re S58. Composition vs. chain length of copolymer δ-‐valerolactone/1,5-‐dioxepan-‐2-‐one, 50:50

ratio.

-‐ 43 -‐

Figu

re S59. Composition vs. chain length of copolymer ε-‐caprolactone/trimethylene carbonate,

50:50 ratio.

!

-‐ 44 -‐

Figure S60. Composition vs. chain length of copolymer lactide/1,5-‐dioxepan-‐2one, 50:50 ratio.

! Figure S61. Composition vs. chain length of copolymer ε-‐caprolactone/lactide, 50:50 ratio.

Homo-‐probabilities versus chain length

‘Most abundant chain lengths’

-‐ 45 -‐

Figure S62. Homo-‐probabilities vs. chain length of copolymer styrene/methyl acrylate.

!

Figure S63. Homo-‐probabilities vs. chain length of copolymer styrene/ethyl acrylate.

-‐ 46 -‐

Figure S64. Homo-‐probabilities vs. chain length of copolymer styrene/butyl acrylate.

Figure A3-45. Homo-probabilities vs. chain length of copolymer styrene / methyl methacrylate.

Figure A3-46. Homo-probabilities vs. chain length of copolymer styrene / ethyl methacrylate.

Appendix Chapter 3

probabilities vs. chain length of copolymer styrene / methyl methacrylate.

probabilities vs. chain length of copolymer styrene / ethyl methacrylate.

Appendix Chapter 3

3-30

probabilities vs. chain length of copolymer styrene / methyl methacrylate.

probabilities vs. chain length of copolymer styrene / ethyl methacrylate.

Figure S65. Homo-‐probabilities vs. chain length of copolymer styrene/ethyl methacrylate.

-‐ 47 -‐

Figure S66. Homo-‐probabilities vs. chain length of copolymer styrene/ethyl methacrylate.

Figure S67. Homo-‐probabilities vs. chain length of copolymer methyl methacrylate/ethyl methacrylate.

-‐ 48 -‐

Figure S68. Homo-‐probabilities vs. chain length of copolymer methyl methacrylate/butyl methacrylate.

Figure A3-47. Homo-probabilities vs. chain length of copolymer methyl methacry

Figure A3-48. Homo-probabilities vs. chain length of copolymer methyl methacrylate / butyl acrylate.

Appendix Chapter 3

probabilities vs. chain length of copolymer methyl methacrylate / butyl methacrylate.

probabilities vs. chain length of copolymer methyl methacrylate / butyl acrylate.

Appendix Chapter 3

3-31

late / butyl methacrylate.

probabilities vs. chain length of copolymer methyl methacrylate / butyl acrylate.

Figure S69. Homo-‐probabilities vs. chain length of copolymer methyl methacrylate/butyl acrylate.

-‐ 49 -‐

Figure S70. Homo-‐probabilities vs. chain length of copolymer vinyl acetate/methyl methacrylate.

! Figure S71. Homo-‐probabilities vs. chain length of copolymer ethyl acrylate/butyl methacrylate.

-‐ 50 -‐

Figure S72. Homo-‐probabilities vs. chain length of copolymer ethyl acrylate/vinyl acetate.

-‐ 51 -‐

Figure S73. Homo-‐probabilities vs. chain length of copolymer ε-‐caprolactone/4-‐methyl caprolactone, 50:50 ratio.

!

-‐ 52 -‐

Figure S74. Homo-‐probabilities vs. chain length of copolymer ε-‐caprolactone/1,5-‐dioxepan-‐2-‐one, 50:50 ratio.

Figure S75. Homo-‐probabilities vs. chain length of copolymer ε-‐caprolactone/1,5-‐dioxepan-‐2-‐one, 70:30 ratio.

Figure A3-53. Homo-probabilities vs. chain length of copolymer

Figure A3-54. Homo-probabilities vs. chain length of copolymer

Appendix Chapter 3

probabilities vs. chain length of copolymer -caprolactone / trimethylene carbonate.

probabilities vs. chain length of copolymer -valerolactone / 1,5-dioxepan

Appendix Chapter 3

3-34

caprolactone / trimethylene carbonate.

dioxepan-2-one.

-‐ 53 -‐

Figure S76. Homo-‐probabilities vs. chain length of copolymer δ-‐valerolactone/1,5-‐dioxepan-‐2-‐one, 50:50 ratio.

Figure S77. Homo-‐probabilities vs. chain length of copolymer ε-‐caprolactone/trimethylene carbonate.

Figure S78. Homo-‐probabilities vs. chain length of copolymer lactide/1,5-‐dioxepan-‐2one.

-‐ 54 -‐

Figure S79. Homo-‐probabilities vs. chain length of copolymer ε-‐caprolactone/lactide.

copolymer microstructure determination by the click of a

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