New New Aspects of Polyolefin Quantitative Analysis Using 1D and … · 2009. 8. 2. · New Aspects...
Transcript of New New Aspects of Polyolefin Quantitative Analysis Using 1D and … · 2009. 8. 2. · New Aspects...
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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
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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
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Outline
• nD NMR
• HC Double (Triple)
Resonance 3D NMR
• Polyolefins
• Quantitative nD NMR
• Conclusions
http://www.dow.com/
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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
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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)
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2D NMR Poly(EB*C)
Monwar et al., Anal. Bioanal. Chem., 378, 1414 (2004).
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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
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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
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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
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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).
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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).
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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).
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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).
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?Quantitation in nD NMR?
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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
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64% Octene
98% Octene
99% Octene
1D 13C NMR Spectra of Poly(EO)
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1D 13C Expansion of αα Region
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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)
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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).
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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
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Copolymer A Copolymer B Copolymer C
Expansions of gHMBC & gHSQCαα for of copolymer A,B and C
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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
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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
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Maybe There is Hope After All Copolymer C
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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
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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