New Aspects of Polyolefin Quantitative Analysis Using

1D and 2D NMR

A. Nuamthanom & P. L. Rinaldi

University of Akron, Akron, OH 44325-3601

D. Baugh, A. Taha, D. Vanderlende & D. Redwine

Dow Chemical Co., Freeport TX & Midland MI

PeterRinaldi@uakron.edu

Acknowledgments

• Funding• Dow Chemical• NSF (DMR-0073346, DMR-0330816,)• Kresge Foundation, Donors to Kresge Challenge Program at UAkron• Ohio Board of Regents, Research Challenge• University of Akron• Dupont

StudentsM. MonwarA. Al-HamriD. SavantA. Nuamthanon

StaffV. DudipalaS. StakleffT. WaglerJ. Massey

PostdocsS. Sahoo

StudentsR. Medsker

H. Latz

• Senior• D. Redwine• D. Baugh• A. Taha• D. Vanderlende

• E. McCord• M. Buback

Outline

• nD NMR

• HC Double (Triple)

Resonance 3D NMR

• Polyolefins

• Quantitative nD NMR

• Conclusions

http://www.dow.com/

A B CC C C

H H HHcHAHB

t1 t2

COSYa

decprep t1 t2Δ ΔC

H

HMQC

b

decprep t1 t2Δ Δ t3C

H

HMQC- COSY

c

1D, 2D & 3D NMR Spectra

CA

CCCB

E-centered B-centered C-centered

EEEEEB

BEB(2)CEECEC

BEC/CEB

BBB(3)EBB(2)

EBECBB(2)/BBC(2)

CBCEBC/CBE

CCCECCECE

BCC/CCBBCB(2)

ECB/BCE

E = ethylene C = carbon monoxide B* = 13C-n-butylacrylate72 B-centered pentad sequences

Possible Triads of Poly(EB*C)Poly(ethylene-co-butylacrylate*-co-carbon monoxide)

2D NMR Poly(EB*C)

Monwar et al., Anal. Bioanal. Chem., 378, 1414 (2004).

Biological 3D-NMR Pulse Sequences

H

N C

H

C N

H

C

H

C

O O

a H N C

H

C N

H

C

H

C

O O

b

H

N C

H

C N

H

C

H

C

O O

c H N C

H

C N

H

C

H

C

O O

d

H

N C

H

C N

H

C

H

C

O O

e

R1 R2

R1 R2

R1 R2

R1 R2

R1 R2

HNCO HNCA

HCACO

HCA(CO)N

15N-TOCSY-HMQC

Clore & Gronenborn, Progress NMR Spectoscopy, 23, 43 (1991).Griesinger et al., J. Magn. Resonance, 84, 14 (1989).

Biomolecular NMR Spectroscopy. J. Evans. Oxford University Press, New York, 1995.

C C N

H O H

αC C N

H O H

α

R1 R2

1D 13C NMR of Labeled Poly(EBC)

200 180 160 140 120 100 80 60 40 20 ppm

Unlabeled

O

13C

OBuO

13CH

OBuO13C

X A

A B C D E GF

gt1 gt2 gt3 gt4 gt5 gt7 gt8

t313Caliph

t1/2 t1/2

T T T-t1/2

GARP

T+t1/2

Gz gt6

∆ ττ

∆ ∆∆ ∆ ∆Waltz-16 Waltz-161H

Waltz-16

Grzsiek and Bax, J. Magn. Resonance, B102, 103 (1993). Xia et al., J. Magn. Resonance, 143, 407 (2000).Sahoo et al., Macromolecules, 36, 6695 (2003).

13CC=O

13C

H

X

C

(C)(D)

(D)

(B)(F)

(E)

(G)

t1

t3

t2

1JCH

1JCC

H2C

HCACX 3D Pulse Sequence

R1 C

X

R1

C

H

H

C

R

H

C

H

H

C

H

R

1 42 3

3D Slices HCACO Poly(EB*C)

e

ab c

d

47 4447 44

42 3942 39

46 45 41 40δC ppm

δ H p

pm

δC ppm

δC ppm

HSQC

HC

AC

X

1.5

2.5

f1= 174.1

174176

f1= 174.6f1= 174.8

((( )) )p q r

f1= 175.3

Sahoo et al., Macromolecules, 36, 6695 (2003).

13C

H

O OBu

C(C)

(D)

(D)

(B)(F)

(E)

(H)

t1

t3

t2

1JCH

1JCC

H2C

A B C D E F H

gt1 gt3 gt4 gt5 gt7 gt8gt2

t313C

t1/2 t1/2

T T T-t1/2

GARP∆ ∆ ∆ ∆

T+t1/2

Gz gt6

∆ ττ

∆ ∆∆ ∆ ∆1H

DIPSI-2

G

(G)

gt9

HCACX-HH-TOCSY 3D Pulse Sequence

Waltz-16 Waltz-16Waltz-16

R1 C

X

R1

C

H

H

C

R

H

C

H

H

C

H

R

1 42 3

Sahoo et al., J. Magn. Reson, 168, 352 (2004).

3D-NMR Planes Poly(EB*C)

2.5

1.5

2.5

1.5

46 45

a b

41 40

dc

HSQC

HMBC

δC ppm

δ H p

pm

176 174

a

b cd

ppm

47 44 47 4442 39 42 39

F1=175.31 F1=174.8F1=174.14F1=174.56

HC

AC

X

a bc

d

a b c d

HC

AC

X-H

H-T

OC

SYF2 (ppm)

( (() ) )p q r

poly(ethylene-co-n-butylacrylate*-co-carbon monoxide)

Sahoo et al., J. Magn. Reson, 168, 352 (2004).

Poly(EB*C) 3D Planes at δCO=175.3, 174.8

M. Monwar et al., Macromolecules, 38, 2886 (2006).A. Al-hamri et al. Macromolecules, 38, 5768 (2006).

?Quantitation in nD NMR?

Quantitative nD NMR Complications

• Relaxation times – range• J Coupling range• Multiplicity (C, CH, CH2, CH3)• Resonance offset effects

Koskela,H.; Väänänen,T. Magn.Reson.Chem 2002,40,705

Koskela,H; Kilpeläinen,I; Heikkinen,S. J.Magn.Reson 2005,174,237

64% Octene

98% Octene

99% Octene

1D 13C NMR Spectra of Poly(EO)

1D 13C Expansion of αα Region

1012023030

13C NMR of (poly(ethylene-co-octene)

45 40 35 30 25 20 15 10 5 (ppm)

0 51 01 52 02 53 03 5

1H NMR of poly(ethylene-co-octene)

3.5 3.0 2.5 2.0 1.5 1.0 0.5 (ppm)

1D NMR Poly(EO)

13C

1H

decouple

at

d1 d2 d3 d3 d4 d4

180° 90° 180°

180° 90° 180° 90° 180°

13C Detected 1H T1’s

αα 1H T1’s ca. 200 ms

D.P. Burum , R.R. Ernst, J. Magn. Resonance, 39(1), 163-168 (1980). Brown. et al., J. Magn. Resonance, Series A, 110(1), 38-44 (1994).

In the m-centered configuration, the magnetic environments for geminal methylene protons are different from each other thus have different chemical shifts

In the r-centered configuration, both methylene protons have similar the magnetic environments and similar chemical shifts.

= R group

Chemical Shift Patterns

Copolymer A Copolymer B Copolymer C

Expansions of gHMBC & gHSQCαα for of copolymer A,B and C

F1 (ppm)40.040.240.440.640.841.041.241.441.641.842.042.2

F2(ppm)1.15

1.20

1.25

1.30

1.35

1.40

1.45

321

gHSQC

1D & 2D Quantitative Data for Copolymer A

1JCH = 125 HzRD = 1 sec

Copolymer A Copolymer B

Quantitative analysis of copolymers A and B by 1D 13C and 2D gHSQC NMR

1D & 2D Quantitative Data for Copolymer A & B

Maybe There is Hope After All Copolymer C

Copolymer A (~ % 64 Octene) mostly syndiotactic.

Copolymer B (~ % 99 Octene) mixture of meso and racemic dyadspredominantly syndiotactic,approximately 75 % racemic dyads and 25 % meso dyads.

Copolymer C (~ % 98 Octene) complex cross peaksmixture of meso and racemic diadsapproximately 48 % racemic dyads and 52 % meso dyads.

Quantitative 2D NMR can give reliable results under the right conditions

Perhaps there is even hope for extracting quantitative data from 3D NMR Spectra

Conclusions

http://www.uakron.edu/colleges/artsci/depts/chemistry/magnet/presentations.p

New Aspects of Polyolefin Quantitative Analysis Using 1D and 2D NMRAcknowledgmentsOutline 1D, 2D & 3D NMR SpectraPossible Triads of Poly(EB*C)��Poly(ethylene-co-butylacrylate*-co-carbon monoxide)2D NMR Poly(EB*C)Biological 3D-NMR Pulse Sequences1D 13C NMR of Labeled Poly(EBC)HCACX 3D Pulse SequenceHCACX-HH-TOCSY 3D Pulse Sequence3D-NMR Planes Poly(EB*C)Poly(EB*C) 3D Planes at δCO=175.3, 174.8?Quantitation in nD NMR?Quantitative nD NMR Complications