Production and Analysis of Highly Monodisperse Oligomeric ... · Crystal growth rates vs T c and...

Production and Analysis of Highly Monodisperse Oligomeric Poly(Ethylene Oxide)

Junjie Yin

Adam Raegen

James Forrest

IPR SymposiumMay 09 2018

Production and Analysis of Highly Monodisperse Oligomeric PEO PAGE 2

Introduction PEO and sample information

Review of PEO crystallization

Technique and Products

Production technique

MALDI-TOF results of products

Analysis on Crystallization

DSC measurements

Crystal growth rates

Conclusions Work done

Future work

Outline

Introduction

MALDI spectrum of neat sample


Mn=587.7 Mw=606.3 PDI=1.032

Poly(Ethylene Oxide) (PEO) structure

linear structure

easily crystallizes

How does N affect crystallization behaviours?

(Matrix-Assisted Laser Desorption/Ionization - Time Of Flight mass spectrometry)

300

500

700

900

1100

1300

1500

1700

400 500 600 700 800 900 1000

inte

nsi

ty (

a.u

.)

molecular weight

polymer crystallization

Review of PEO Crystallization


lamella structure

Folded chain model

Gibbs Thomson relation

𝑇𝑚 = 𝑇𝑚∞(1−

2𝜎𝑒𝑙∆ℎ

)

σe: interfacial energy between amorphous and crystalline phases𝑇𝑚∞ = 342K for PEO

polymer crystallization



ideal: 𝑇𝑚 = 𝑇𝑚∞

lamella structure

Folded chain model


𝑇𝑚 = 𝑇𝑚∞(1−

2𝜎𝑒𝑙∆ℎ

)


polymer crystallization PEO crystallization

Review of PEO CrystallizationMakromol. Chem. 185,1559- 1563 (1984)

Tm vs N for PEO oligomers.


● monodisperse

◻ polydisperse

lamella structure

Folded chain model


𝑇𝑚 = 𝑇𝑚∞(1−

2𝜎𝑒𝑙∆ℎ

)


J. POLYMER SCI.: Symposium No. 50, 283-325 (1975)

polymer crystallization PEO crystallization


Crystal growth rates vs Tc and MW.


lamella structure

Folded chain model


𝑇𝑚 = 𝑇𝑚∞(1−

2𝜎𝑒𝑙∆ℎ

)


Production Technique


PEO

heat

top substrate

bottom substrate

in N2

P ~ 847 mbar

0

2

4

6

8

10

12

0 2 4 6 8 10 12 14 16 18 20 22 24 26

inte

ns

ity

(a

.u.)

N (degree of polymerization)

MALDI Spectrum of Products

300

500

700

900

1100

1300

1500

1700

7 9 11 13 15 17 19

inte

nsi

ty (

a.u

.)


MALDI Spectrum of Neat Sample

MALDI-TOF Results

T=413K


T=423K

T=433K

T=443K

T=453K

T=463K

T=473K

T=483K

T=483K

T=493K

leftover

MALDI-TOF Resultsneat

neat

neat

ഥ𝑁


0

2

4

6

8

10

12

0 2 4 6 8 10 12 14 16 18 20 22 24 26

inte

ns

ity

(a

.u.)


MALDI Spectrum of Products

T=413K

T=423K

T=433K

T=443K

T=453K

T=463K

T=473K

T=483K

T=483K

T=493K

leftover

0100200300400500600700

0 5 10 15 20

Mn

0100200300400500600700

0 5 10 15 20

Mw

1

1.01

1.02

1.03

1.04

0 5 10 15 20

PD

I

MALDI-TOF Results


Evolution of n(N) with respect of evaporation time

0

1

2

3

4

5

6

7

8

9

230 250 270 290 310

hea

t fl

ow

(a

.u.)

T (K)

some DSC curves on heating

DSC Measurements


(Differential Scanning Calorimetry)

neat sample

someisolatedfractions

250

255

260

265

270

275

280

285

290

295

300

8 10 12 14

Tm (K) Tm1

Tm2

ഥ𝑁

250

255

260

265

270

275

280

285

290

295

300

8 10 12 14

Tm (K)Tm1

Tm2

Tm (extended)

0

1

2

3

4

5

6

7

8

9

230 250 270 290 310

hea

t fl

ow

(a

.u.)

T (K)


DSC Measurements



neat sample

Colloid and Polymer Science, 254(8), 695-715

European Polymer Journal, 44(12), 4146-4150

Blaine, R. L. (2002). Texas Instruments.

(Ɣamo = 98.4mJ/m2)

Ɣends = 275.1mJ/m2

ഥ𝑁


250

255

260

265

270

275

280

285

290

295

300

8 10 12 14

Tm (K)

Tm1

Tm2

Tm (extended)

Tm (once folded)

0

1

2

3

4

5

6

7

8

9

230 250 270 290 310

hea

t fl

ow

(a

.u.)

T (K)


DSC Measurements



neat sample

(Ɣamo = 98.4mJ/m2)

Ɣends = 275.1mJ/m2

Ɣ1-fold

= (Ne*Ɣamo + 2*Ɣends)/(Ne+2)= 162.1mJ/m2

Colloid and Polymer Science, 254(8), 695-715

European Polymer Journal, 44(12), 4146-4150


Ne = 3.5

ഥ𝑁


DSC Measurements



00.20.40.60.8

1

250 260 270 280 290 300 310hea

t fl

ow

(a

.u.)

T (K)

DSC curve of N=12.3 on heating

0

0.2

0.4

0.6

0.8

1

250 260 270 280 290 300 310hea

t fl

ow

(a

.u.)

T (K)

lamella thickening?

150

250

350

450

T (K)

time

treatment

24h

250

255

260

265

270

275

280

285

290

295

300

8 10 12 14

Tm (K)

Tm1

Tm2

Tm (extended)

Tm (once folded)

ഥ𝑁

250

255

260

265

270

275

280

285

290

295

300

8 10 12 14

Tm (K) Tm1

Tm2

DSC Measurements



Makromol. Chem. 185,1559- 1563 (1984)

Tm vs N for PEO oligomers.

● monodisperse

◻ polydisperse

ഥ𝑁

DSC Measurements

Production and Analysis of Highly Monodisperse Oligomeric PEO

0.00%

20.00%

40.00%

60.00%

80.00%

100.00%

8 9 10 11 12 13 14

Degree of Crystallinity Xc

European Polymer Journal, 39(8), 1721-1727.


-25 -15 -5 5 15 25 35

T (℃)

∆𝐻𝑓(𝑇𝑚)

∆𝐻𝑓∞(𝑇𝑚) = 197J/g,

enthalpy of melting of PEO with 100% crystallinity ഥ𝑁

PAGE 8

DSC Measurements


0.00%

20.00%

40.00%

60.00%

80.00%

100.00%

8 9 10 11 12 13 14

Degree of Crystallinity Xc

ഥ𝑁250

255

260

265

270

275

280

285

290

295

300

8 10 12 14

Tm (K) Tm1

Tm2

ഥ𝑁

PAGE 8

Crystal Growth


Crystal Growth


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 20 40 60 80 100 120

cry

sta

l si

ze (

mm

)

time (s)

0

1

2

3

4

5

6

255 265 275 285 295

log

G (

nm

/s)

Tc (K)

N = 9.6

N = 10.9

N = 12

N = 12.5

Crystal Growth


Growth rates vs Tc (vertical lines: Tm)

extended-chain crystals

Journal of Polymer Science: Polymer Symposia (Vol. 59, No. 1, pp. 31-54).

bars: Tm

Conclusions

▪ Work done:

1. Evaporative purification achieved PDI ~6 times better

2. DSC measurements (Tm difference between mono- and poly-disperse)

3. Crystal growth rate measurements

▪ Future work

1. Even lower PDI (larger scale, shorter collection intervals)

2. Crystal growth rate measurements (near Tm)

3. X-ray measurements (lamella information)


References

▪ Yeates, S. G., Teo, H. H., Mobbs, R. H., & Booth, C. (1984). Ethylene glycol oligomers. Macromolecular Chemistry and Physics, 185(8), 1559-1563.

▪ Kovacs, A. J., Gonthier, A., & Straupe, C. (1975, January). Isothermal growth, thickening, and melting of poly (ethylene oxide) single crystals in the bulk. In Journal of Polymer Science: Polymer Symposia (Vol. 50, No. 1, pp. 283-325). Wiley Subscription Services, Inc., A Wiley Company.

▪ Buckley, C. P., & Kovacs, A. J. (1976). Melting behaviour of low molecular weight poly (ethylene-oxide) fractions. Colloid and Polymer Science, 254(8), 695-715.

▪ Blaine, R. L. (2002). Thermal applications note polymer heats of fusion. Texas Instruments, New Castle Google Scholar.

▪ Spěváček, J., & Baldrian, J. (2008). Solid-state 13C NMR and SAXS characterization of the amorphous phase in low-molecular weight poly (ethylene oxide) s. European Polymer Journal, 44(12), 4146-4150.

▪ Kovacs, A. J., Straupe, C., & Gonthier, A. (1977, January). Isothermal growth, thickening, and melting of polyethylene oxide) single crystals in the bulk. II. In Journal of Polymer Science: Polymer Symposia(Vol. 59, No. 1, pp. 31-54). Wiley Subscription Services, Inc., A Wiley Company.


THANK YOU!


Vapor Pressure Calculation

Sanchez-Lacombe Lattice-Fluid Model

J. Phys. Chem. 80(21), 2352-2362

-4

-2

0

2

4

6

8

0 50 100 150 200 250 300

logP (Pa)

T (ºC )

n=1

n=2

n=3

n=4

n=5

n=6

n=7

n=8

n=9

n=10

Plot of logPv vs T for PEO from N=1 to N=10


G

ρgas0 ρmax ρliq 1

Plot of free energy vs mass density

Vapor Pressure Calculation

-4

-2

0

2

4

6

8

0 50 100 150 200 250 300 350

logP (Pa)

T (ºC)

n=1

n=2

n=3

n=4

n=5

n=6

n=7

n=8

n=9

n=10

Plot of logPv vs T for PEO from n=1 to n=10


-10

-8

-6

-4

-2

0

2

4

6

0 50 100 150 200 250 300 350

logP(Pa)

T(ºC)

n=2

n=3

n=4

n=5

n=6

n=7

n=8

n=9

Plot of logPv vs T for PS from n=2 to n=9

PHYSICAL REVIEW MATERIALS 1, 025605 (2017)

Production and Analysis of Highly Monodisperse Oligomeric ... · Crystal growth rates vs T c and...

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