Chemical Composition and Microstructure Analysis of ... · 3 Chain Length End Group Block Length...
Transcript of Chemical Composition and Microstructure Analysis of ... · 3 Chain Length End Group Block Length...
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Chemical Composition and Microstructure Analysis of Complex
Polymers by Multidimensional Liquid Chromatography
Harald Pasch, Khumo Maiko, Pritish Sinha SASOL Chair of Analytical Polymer Science Department of Chemistry and Polymer Science Wolf Hiller, Mathias Hehn Faculty of Chemistry Technical University Dortmund, Germany
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Stellenbosch – South Africa
Darmstadt
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Chain Length End Group
Block Length Architecture
Molar Mass
Häu
figke
it Chain length
Chemical composition
Functionality Type
Molecular topology
Molecular Heterogeneity of Complex Polymers
SEC
LAC
LCCC
DC
D2C
DC
D2C
DC
D2C
DC* *
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D D
D
D
HC
H2C
HC
H2C
HC
H2C
HC* *
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
Isotactic
Atactic
Syndiotactic
*
H
H3COOCCH3
H H
H3COOC
CH3
H H
H3COOC
CH3
H
*
*
HH H
H3COOC
CH3
H H
H3C
COOCH3
H
*
H3CCOOCH3
*
HH H
H3C
COOCH3
H H
H3COOC
CH3
H
*
H3CCOOCH3
Isotopic composition H vs. D
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Liquid Chromatography of Polymers
S S
S
S S
S
SEC
Log
M
Elution volume or Kd
LC-CC LAC Gradient
Pore in stationary phase
Example: column: Nucleosil Si 100 mobile phase: THF / Hexane 80:20 PS PVAc PMMA S injection solvent
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The LEGO Approach
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Comprehensive 2D-LC for Maximum Selectivity
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Functional Polyethylene Oxides
Alk(Ar) OH +O
Alk(Ar) (OCH2CH2)n OH
secondary reactions additional functionality fractions
H (OCH2CH2)n OH
Alk(Ar) (OCH2CH2)n OAlk(Ar)
(OCH2CH2)n
Molar mass distribution Functionality type distribution Amount of cyclics
Washing formulations
Body care Dispersants
Emulsifiers
Paper chemicals
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Functionality separation by LC-CC Oligomer Separation by LAC stationary phase: RP-18 stationary phase: Si mobile phase: MeOH-water 80:20 mobile phase: i-PrOH-water 88:12
Functional Polyethylene Oxides
0
20
40
60
80
100
Elution Volume (mL) 1 2 3 4 5 6 7 8
PEG
C10
C12
C13
C14
C15
C16
C18
Nonylphenyl
0
20
40
60
80
100
Elution Volume (mL)
2 3 4 5 6 7 8
Det
ecto
r Sig
nal
16 14 15
11
12 13
8
9
10
6 7
Endgroup selectivity Chain length selectivity
J.-A. Raust, A. Bruell, P. Sinha, W. Hiller, H. Pasch. J. Sep. Sci. 33 (2010) 1-7
CnH2n+1O(CH2CH2O)xH CnH2n+1O(CH2CH2O)xH
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Degasser
Pump
Degasser
Pump Injector HPLC Column
2D Chromatography HPLC vs. SEC
Detector
Data Processing
Waste
1. Dimension: HPLC/LCCC
2. Dimension: GPC
SEC Column
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Endgroup and oligomer separation by 2D-LC (LC-CC x LAC)
C10 C9Φ C12 C13 C14 C15 C16 C18
Endgroup Length
Oligom
er Length
4-8 9 10 11 12 13
14
15
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Functional Polyethylene Oxides
C16H31O(CH2CH2O)14H
J.-A. Raust, A. Bruell, P. Sinha, W. Hiller, H. Pasch. J. Sep. Sci. 33 (2010) 1-7
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Functional Polyethylene Oxides
Quantification of oligomer distributions and topology of endgroups by 2D-LC (LC-CC x LAC) – 1H-NMR
LC-CC– 1H-NMR for topology of endgroups LAC– 1H-NMR for oligomer distributions
W. Hiller, M. Hehn, P. Sinha, J. Raust, H. Pasch. Macromolecules 45 (2012) 7740-7748
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Functional Polyethylene Oxides
Quantification of oligomer distributions and topology of endgroups by 2D-LC (LC-CC x LAC) – 1H-NMR
W. Hiller, M. Hehn, P. Sinha, J. Raust, H. Pasch. Macromolecules 45 (2012) 7740-7748
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Separation According to Isotope Effects and Microstructure
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Separation of PS by Degree of Deuteration
45 oC
41 oC 54 oC
d-PS d-PS
d-PS
h-PS h-PS
h-PS
LCCC LCCC
LAC
LAC
SEC
stationary phase:
Nucleosil C18 300 Å
mobile phase:
THF-ACN 47:53 v/v
SEC Kd = exp (∆S/R - ∆H/RT)
VR = Vi + V Kd
P. Sinha, G. Harding, K. Maiko, H. Pasch, J. Chromatogr. A 1265 (2012) 95-104
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Separation of PS by Degree of Deuteration
Separation of similar molar masses and chemical structures the only difference being the deuteration
P. Sinha, G. Harding, K. Maiko, H. Pasch, J. Chromatogr. A 1265 (2012) 95-104
LC x LC: injection volume: 50µL 1st Dimension conditions: Hypercarb (150mmx4.6mm), 30°C; Flow rate: 0.044 mL/min (387 min); mobile phase: DCM/acetone gradient 2nd Dimension conditions: PL Mixed E (300mmx7.5mm); 25°C; loops :200µL; Flow rate: 2mL/min (4.5min); Detection: ELSD
0 1 2 3 4 5 6 7 8 9
0.00
0.01
0.02
0.03
0.04
0.05
0.06
ELS
D R
esp
onse
Elution volume (ml)
Vertical cut of 2D (SGIC)Syndio 4900 (S3)
Iso 4890 (I1)
0 1 2 3 4 5 6 7 8 9
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
Iso 4890 (I1)
ELS
D R
espo
nse
Elution volume (ml)
Horizontal cut of 2D (SEC)Syndio 4900 (S3)
0 2 4 6 8
0.00
0.02
0.04
0.06
0.08
0.10
0.12
ELS
D R
espo
nse
Elution volume (ml)
Vertical cut of 2D (SGIC)Syndio 4900 (S3)
Syndio 60150 (HS4)
0 2 4 6 8
0.00
0.02
0.04
0.06
0.08
0.10
0.12
ELS
D R
espo
nse
Elution volume (ml)
Horizontal cut of 2D (SEC)
Syndio 60150 (HS4)
Syndio 4900 (S3)
Microstructure Analysis of PMMA
K. Maiko, M. Hehn, W. Hiller, H. Pasch, Anal. Chem. 85 (2013) 9793-9798
2 4 6 8 10-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
0.020
ELSD
Sig
nal
SGIC Elution volume (ml)
2 4 6 8-0.002
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
ELSD
Sig
nal
SEC Elution volume (ml)
Microstructure Analysis of PMMA
K. Maiko, M. Hehn, W. Hiller, H. Pasch, Anal. Chem. 85 (2013) 9793-9798
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Hyphenation of Selective Separations with Spectroscopic Methods
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On-flow-Coupling of HPLC and 1H-NMR
Loop collector
Waste
HPLC System
NMR Console AVANCE 400
Magnet
Pump
Sampler
Detector
On-Flow
400 MHz
AGILENT 1100
5mm NMR tube
rf coils
rf coils
Flow cell
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HPLC-NMR Coupling: Experimental Challenges
Use of protonated solvents: overlapping of polymer and solvent signals Efficient solvent suppression techniques !
Use of HPLC quality solvents: Solvent impurities cause strong signals Solvents with NMR purity !
styrene-ethylacrylate copolymer
Solvent mixture THF-ACN
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Microstructure Analysis of Polyisoprene
R1 CH2 C R2
CH3
HC CH2
n
C CH
CH3
CH2 R2CH2R1n
R1 CH2 CH R2
C CH3
CH2
n
1,2-PI
1,4-PI
3,4-PI LCCC of 1,4-PI
mobile phase: butanone/cyclohexane ■ 70:30, ● 92:8, ▲97:3 stationary phase: 3 x C18 (100-5, 300-5, 1000-7)
W. Hiller, P. Sinha, M. Hehn, H. Pasch, T. Hofe. Macromolecules 44 (2011) 1311-1318
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Microstructure Analysis of Polyisoprene: LCCC-NMR
On-flow LCCC-NMR of blend of 1,4-PI (20.7 kg/mol) and 3,4-PI (72.8 kg/mol) at critical conditions of 1,4-PI, 100 µL injection, flow rate 0.5 mL/min
Normalized NMR intensities and chemical composition distributions of 1,2-, 1,4- and 3,4-isoprene units
W. Hiller, P. Sinha, M. Hehn, H. Pasch, T. Hofe. Macromolecules 44 (2011) 1311-1318
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Microstructure Analysis of PI-PMMA Block Copolymers
W. Hiller, H. Pasch, P. Sinha, T. Wagner, J. Thiel, M. Wagner, K. Müllen Macromolecules 43 (2010) 4853-4863
.
LCCC for PI stationary phase: Nucleosil C18 300-5 + 1000-7
mobile phase: 1,4-dioxane
LCCC for PMMA stationary phase: Nucleosil Si 300-5 + Si 1000-7
mobile phase: ethyl acetate
In both cases single mobile phases, adjustment of critical conditions through temperature variations
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Microstructure Analysis of PI-PMMA Block Copolymers
W. Hiller, H. Pasch, P. Sinha, T. Wagner, J. Thiel, M. Wagner, K. Müllen Macromolecules 43 (2010) 4853-4863
Separation of PMMA-PI blends at critical conditions for PMMA (left) and PI (right)
PMMA (Mp=22700)
PMMA (Mp=22700) 1,4-PI (Mp=20500)
1,4-PI (Mp=95000)
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Microstructure Analysis of PI-PMMA Block Copolymers
W. Hiller, H. Pasch, P. Sinha, T. Wagner, J. Thiel, M. Wagner, K. Müllen Macromolecules 43 (2010) 4853-4863
Separation of 3,4-PI-PMMA copolymer (52 kg/mol)
at critical conditions for PMMA (left) and PI (right)
PI Homopolymer
Copolymer
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Microstructure Analysis of PI-PMMA Block Copolymers
W. Hiller, H. Pasch, P. Sinha, T. Wagner, J. Thiel, M. Wagner, K. Müllen Macromolecules 43 (2010) 4853-4863
Chemical composition analysis of 3,4-PI-PMMA copolymer (52 kg/mol) at critical conditions for
PMMA (left) and PI (right)
PI Homopolymer Copolymer
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MS as a Detector for Liquid Chromatography
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Aliphatic Polyesters: Background
Paint/Coatings
Polymer/Binder
Pigments
Additives
Multi-vesiculated polyester particles
Main constituents of UPR: Maleic anhydride Phthalic anhydride Propylene glycol
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Aliphatic Polyesters: Chemistry
Simple monomer structures… … but complex rearrangements during polymerization
Chain Length End Group
Block Length Architecture
Molar Mass
Häu
figke
it
Chain Length Functional Groups
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Aliphatic Polyesters: Molar Mass Analysis by SEC
Size exclusion chromatography
Fraction 2
Fraction 3
Fraction 4
Fraction 5
Fraction 6
Fraction 7
Fraction 8
n = 7
n = 6
n = 5
n = 4
n = 3
n = 2
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MALDI-TOF analysis of SEC fractions
Aliphatic Polyesters: End Group Analysis by SEC-MALDI
Chemical structure Abbreviation m/z(exp) values for n
2 3 4
A.
HO-[PA-PG]n-PA 602 808 1014
B.
HO-[PA-PG]n-H 453 660 866
C.
PG-[PA-PG]n-H 512 718 924
D.
cyclic of
[PA-PG]n
434 640 847
E.
cyclic of
PG-[PA-PG]n
492 698 904
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Aliphatic Polyesters: End Group Analysis by HPLC
12 16 20 24 2812 16 20 24 280.0
0.2
0.4
0.6
0.8
1.0
12 16 20 24 28Elution volume (ml)
s28
% THF
5 7
5
64
4
3
3
3
2
2
1
1
2
Norm
alize
d EL
SD s
igna
l
Elution volume (ml)
s23
Elution volume (ml)
s25
40
50
60
70
80
90
100
1
14 16 18 20 22 24 260.0
0.2
0.4
0.6
0.8
1.0
7
6
5
4
3
2
Nor
mal
ized
ELS
D s
igna
l
Elution volume (ml)
zoomedin
1
peak splitting 20 21 22 23 24 25 26
0.00
0.05
0.10
0.15
10
8
9
Analysis conditions: Stationary phase: SupelcoCN 100Å, 5μm, Mobile phase: THF/Hexane, Temp: 30⁰C, Flow rate: 1.00 mL/min, Detector: ELSD, Injection vol: 20 μL
Solvent Gradient HPLC
Significantly improved separation Oligomer/functional group formation as a function of polymerization time
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Aliphatic Polyesters: HPLC Fractionation and MALDI-ToF
0
20
40
60
80
100 %Int.
1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 Mass/Charge
1954.39
1541.56 1970.76 2160.48
1557.86
1896.09 2177.40
1912.54 1690.31 2012.97
1499.87
2102.30 2218.61
1747.73
1615.83
1763.96
1295.39 2367.04 1927.62
1521.57 1294.00
1714.15 1839.83 1465.91
CNa
CNa
CNa
CNa CK
CK CK CK
BNa
BNa
BNa
BK
BK CNa
BK
BK fraction 9
fraction 10
BNa
m/z
0
20
40
60
80
100
%Int.
600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600
Mass/Charge
718.05
659.96
924.39
641.04
866.29
681.78
1130.86
1072.89907.36
866.73
940.95
1954.39
1541.56
1088.90
1970.76 2160.481557.861896.09
1072.80
2177.401912.54
1335.03
1690.311351.30
1499.87
2218.61
1747.73
1763.96
1483.871295.39
1277.66
2367.04
1521.57
1839.83 2070.86
fraction 5
fraction 6
fraction 7
fraction 8
fraction 9
fraction 10
CNa
CNa
CNa
CNa
CNa
CK
CK CKCK
CNaCNa
BNa
BNa
BNa
BNaBNa
BNa
BK
CNa
CK
m/z
BK
BK
BK
B. HO-[PA-PG]n-H/Na+ : m/z 866 (n=4); 1896 (n=9)
C. PG-[PA-PG]n-H/Na+ : m/z 718 (n=3); 2160 (n=10)
MALDI-ToF spectra of fractions 5 to 11 collected from the gradient elution HPLC separation of sample s28 from PA-PG batch.
OCH
CH3
CH2HO
G: PG-PG-[PA-PG]n-H/Na+: m/z 1615 (n=7) ; m/z 2218 (n=10)
Zoomed-in MALDI-ToF MS spectra of fractions 9 to 11 to indicate the presence of an additional oligomeric structure.
58 Da
Fraction 9
Fraction 10
Fraction 11
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Aliphatic Polyesters: Comprehensive 2D-LC
To Waste
LC-CC or
Gradient-HPLC
Quaternary Pump, Degasser HPLC system
Binary Pump, Degasser HPLC system
SEC
ELSD
UV Detector
Oligomer length and endgroups
1st dimension: solvent gradient HPLC 2nd dimension: SEC
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Aliphatic Polyesters: SEC-SFC-ESI-QToF
ELSD
PDA
Column
Sample manager
Solvent manager Size exclusion chromatography
Supercritical fluid chromatography
Analysis conditions: Stationary phase: Acquity UPC2 BEH Mobile phase: CO2 (A) and 1% formic acid in ACN (B). Temp: 30°C, Pressure:150bar.
SFC of SEC fraction 2
SFC of SEC fraction 3
SFC of SEC fraction 5
SFC of s28
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Aliphatic Polyesters: ESI-QToF Analysis of SFC Fractions
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Annual production of polyolefins
> 100 million tons
Fractionation of polyolefins does not work at ambient temperatures
Chain Length End Group
Block Length Architecture
Molar Mass
Häu
figke
it
Chain length (MMD)
Chemical composition (CCD)
ABBBAAAABB
BBBBBAABAA
AAAAABBBBB
Molecular topology (MTD) Long Chain Branching Short Chain Branching
LDPE
LLDPE
HDPE
CRYSTAF
TREF
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EVAc Copolymers
0 5 10 15 20
0
2
4
6
8
10
12
0
20
40
60
80
100
Dete
ktor
signa
l ELS
D [V
]
Elutionsvolumen [ml]
EVA 5% VA EVA 12% VA EVA 14% VA EVA 19% VA EVA 28% VA EVA 45% VA EVA 50% VA EVA 60% VA EVA 70% VA PVAc-St. 164KD PVAc-St. 32KD PE-St. 126KD
% C
yclo
hexa
non
PVAc PE
PP by Tacticity
0 5 10 15 20 25
0,0
0,2
0,4
0,6
0,8
1,0
isotactic PP
linear PE
syndio-tactic PP
responseof ELSD[Volts]
elution time [minutes]
atactic PP
Start of gradient
Polyolefin Separation by Composition or Microstructure
stationary phase: silica gel mobile phase: gradient of decaline-cyclohexanone
stationary phase: Hypercarb mobile phase: gradient of 1-decanol to TCB
T. Macko, H. Pasch. Macromolecules 42 (2009) 6063-6067 A. Albrecht, R. Brüll, T. Macko, H. Pasch. Macromolecules 40 (2007) 5545
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The LEGO Approach for Polyolefins: HT-SEC-FTIR-DSC
Stage: 160°C
Nebulizer 150°C
Vacuum line
Hper DSC
S. Cheruthazhekatt, T.F.J. Pijpers, G.W. Harding, V.B.F. Mathot, H. Pasch. Macromolecules 45 (2012) 2025−2034
HT-SEC
TREF Fractionation of IPC
30 40 50 60 70 80 90 100 110 120 1300
10
20
30
40
50
60
Wi% Wi%/∆T
Wi%
TREF elution temperature (ºC)
0
10
20
30
40
50
EP Rubber
iPP
Segmented EPC
Controlled cooling
(1 °C/h)
1. Slow crystallization
Dissolved polymer +
support
Most crystalline, More crystalline
Less crystalline, Least crystalline
2. Elution
Increasing temperature
T1 T2 T3 T4 T5
Fractionation according to crystallizability
IPC: complex mixture of various (E/P) components - amorphous EP rubber - semi-crystalline EPC ?????? - crystalline iPP - aPP + hPE ??????
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Impact PP Copolymers (IPC); TREF Fraction at 80 oC
S. Cheruthazhekatt, T.F.J. Pijpers, G.W. Harding, V.B.F. Mathot, H. Pasch. Macromolecules 45 (2012) 2025−2034
complex mixture (1) amorphous EP rubber, (2) semi-crystalline EPC, (3) crystalline iPP, (4) aPP, (5) hPE
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Impact PP Copolymers (IPC); TREF Fraction at 80 oC
0 1 2 3 4 5 6 7 80.00
0.01
0.02
0.03
0.04
3V 80
ELSD
Res
pons
e (V)
Elution volume (mL)
Star
t of g
radi
ent
Ethy
lene
rich
EPC
an
d PE
EPC
iPP
HT-HPLC stationary phase: Hypercarb
Mobile phase: gradient 1-decanol/TCB
HT-2D-LC 1st dimension: HT-HPLC
2nd dimension: HT-SEC in TCB
S. Cheruthazhekatt, T.F.J. Pijpers, G.W. Harding, V.B.F. Mathot, H. Pasch. Macromolecules 45 (2012) 2025−2034
43 43
20 40 60 80 100 120 140 160 180
-2.4
-1.6
-0.8
0.0
0.8
1.6
Heat
Flo
w (W
/g)
Temperature (°C)
2nd Heating 1st Cooling
3V A - 130
115.8 °C
110.9 °C
164.0 °C
123.9 °C
0.0
0.1
0.2
0.0
0.1
0.2
0.3
0.0
0.2
0.4
0.6
1000 1500 2000 2500 3000
Linked spectrum at Elution volume 6.3 mL
Linked spectrum at Elution volume 3.5 mL
Linked spectrum at Elution volume 1.85 mL
Wavenumbers (cm-1)
Abso
rban
ce
3V A - 130
Impact PP Copolymers (IPC); TREF Fraction at 130 oC
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Limitations of SEC/HPLC
Problems of SEC:
Limited towards higher molar masses
Shear degradation (mechanical stress due to stationary phase
Separation of linear and branched molecules
Adsorption on the stationary phase
Field Flow Fractionation
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Coupling of FFF and 1H-NMR
Temperature Field
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ThFFF-NMR of PI, PS and PMMA
Universal calibration
ThFFF SEC
Same molar masses but different elution volumes
for PI and PS/PMMA
W. Hiller, W. van Aswegen, M. Hehn, H. Pasch, Macromolecules 46 (2013) 2544-2552
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ThFFF-NMR of Block Copolymers
Uniform chemical composition as a function of molar mass
Clear indication for fractions of different chemical compositions
W. Hiller, W. van Aswegen, M. Hehn, H. Pasch, Macromolecules 46 (2013) 2544-2552
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ThFFF of Block Copolymers
selective towards chemical composition
N
Ph PhH
OOy zx
Separation according to block copolymer composition based on differences in DT
Block DT (cm2/s.K) polybutadiene 0.25 x 10-7
Poly(2-vinyl pyridine)
Still to be determined
Poly (tert-butyl methacrylate)
1.074 x 10-7
B830V180T1350 255 800 g/mol
RM
S R
adiu
s (n
m)
Mol
ar M
ass
(g/m
ol)
?
size
W. van Aswegen, W. Hiller, M. Hehn, H. Pasch, Macromol. Rapid Commun. 34 (2013) 1098-1103
Summary
Interaction LC is a perfect tool for the chemical composition and microstructure analysis of complex polymers
Comprehensive 2D-LC provides maximum selectivity regarding chemical composition/microstructure/molar mass separation
On-flow LC-1H-NMR provides microstructure as a function of molar mass or chemical composition
High-temp multidimensional LC has become a feasible tool for polyolefin analysis
If LC does not work – use field-flow fractionation
Vr
1
2
1
2
50
Multidimensional HPLC of Polymers Springer International Publishing Switzerland, 2013
Authors: Harald Pasch, Bernd Trathnigg ISBN: 978-3-642-36079-4 (Print) 978-3-642-36080-0 (Online)
Thank you for your attention
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