2016-10-10
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HPLC Characterization of Polymers y
2016. 9. 27
Taihyun ChangDivision of Advanced Materials Science
and Department of ChemistryPohang University of Science and Technology (POSTECH)
http://tc.postech.ac.kr/
Various molecular heterogeneities in synthetic polymers
How well do we know the polymers we are working with?
Molar mass Chain ArchitectureChemical
CompositionFunctionality
Stereoregularity, Monomer sequence, etc.
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Reservoir containing
Chromatography separation
In a chromatographic separation, analyte molecules are subjected to consecutive equilibrium in the distribution between the mobile phase and stationary phase while they pass through the column.
Reservoir containingthe eluent (mobile phase)
Sample
Column packed with stationary phase
Time Time
The fastest moving substance eluted from columnfrom column
Mobile phase ⇔ Stationary phasecm cs
K = cs/cm
VR = Vm + K Vs
R
Sexp
RT
GexpK
SECo
SECo
SEC
Size Exclusion Chromatography (SEC)
Size Exclusion Chromatography
ow
Interstitial space Solid phase
Pore
1i
pSEC c
cKo
Development of the technique: J. Moore, Dow Chemical Company (1962)
First commercial instrument: Waters Associate (1963)
Flo
First paper: J. Moore, J. Polym. Sci., Part A 2 835 (1964)
Introduction of Q factor: L. E. Maley, J. Polym. Sci., Part C 8 253 (1965)
Universal calibration: Z. Grubisic; P. Rempp; H. Benoit, J. Polym. Sci., Part B 5 753 (1967)
Theoretical Interpretation: E.F. Casassa, J. Polym. Sci., Part B 5 773 (1967)
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Limitations in SEC analysis
1. SEC separates polymers by hydrodynamic size only2. Hydrodynamic size decreases with chain branching
Polymer Mixture Copolymer Non-linear Polymer
Intrinsic Band broadening –particularly serious in SEC
Linear Homopolymer
SEC vs. IC
Size Exclusion Chromatography
R
Sexp
RT
GexpK
SECo
SECo
SEC
ow
Interstitial space Solid phase
Pore
Interaction Chromatography
RRT
1i
pSEC c
cKo
Exclusion∆S
Flo
Interstitial space Solid phase
Exclusion
RT
H
R
Sexp
RT
GexpK
oIC
oIC
oIC
IC
m
sIC c
cKo
Flo
w
Stationary phase
Pore
Interaction∆H
Exclusion∆S
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Temperature & Solvent effect on HPLC retention
6 5 4
Column: Nucleosil C18, 5 μm, 100 Å , 250 x 4.5 mmEluent: CH2Cl2/CH3CN mixture at 0.5 mL/min
Eluent Effect (30.5oC) Temperature Effect (57/43)
1,2,3
2 13
6,5,4Temperature
50oC
45oC
40oC
35oC
30.5oC
A2
60 (
a.u
.)
6,5,4
3 21
59 %
57.5 %
57 %
62 %
65 %
CH2Cl
2 vol%
A26
0 (
a.u.
)
< Samples >
165,0004
29,0003
12,0002
2,5001
MWPS
0 10 20 30
32
1
54 28oC
25oC
20oC
tR (min)
0 10 20 30
43
21
53 %
55 %
57 %
tR (min)
1,800,0006
502,0005
Critical Adsorption Point (CAP)to
to
Chang, Adv. Polym. Sci. 163 1 (2003)
Three HPLC separation modes for polymersThree HPLC separation modes for polymers
SEC: Exclusion >> Interaction ~ 0
LCCC: Interaction ~ Exclusion
IC: Exclusion < Interaction
IC
LCCC
SEC
og M
SGIC/TGIC
VR
lo
Vi Vp
Vm or Vo
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Two Dimensional Liquid Chromatography (2D-LC)
Temperature effect in IC Separation
Column: Nucleosil C18, 3 μm, 100 Å
50 x 4.6 mm
Eluent: CH2Cl2/CH3CN = 57/43 (v/v)
1 0 mL/min
dT/dt = 8oC/min
30
40
1.0 mL/min
PS Samples: 5.1, 15.3, 30.9, 55.2,
98.9, 200, 648 (kg/mol)
• In TGIC, retention is controlled by changing the column temperature.
0 5 10 15
T ( oC
)
A2
60 (
a.u.
)
30
40
5.1kdT/dt = 2oC/min
10
20
• How does the temperature program affect the retention?
• Can we predict the polymer retention with given T-program?
0 5 10 15
tR (min)
10
20
98.9k
648k200k
55.2k30.9k
15.3k
Ryu et al. J. Chromatogr. A 1075 145 (2005)
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5
6 experiment
5th order fitting
3rd order fitting
log
M
Temperature Gradient Interaction Chromatography (TGIC)A
260 (a
.u.)
T( oC
)
20
30
T
a.u.
)
20
30
0 3 6 9 12 15
4
tR (min)
15.9 k
30 9 k
55.2 k89 k
200 k 384 k
648 k
5 0
5.5
6.0
g M
calculated tR
experimental tR
0 4 8 12 16
A
tR (min)
10
0 5 10 15 20
( oC)
tR (min)
A2
60 (
a
0
10
30.9 k
Column: Nucleosil C18, 3 μm, 100Å, 50 x 4.6 mm
Eluent: CH2Cl2/CH3CN = 57/43 (v/v) at 0.7 mL/min
log M = 3.96619 + 0,0871 x tR
0 5 10 15 204.0
4.5
5.0
log
tR (min)
Ryu & Chang, Anal. Chem. 77 6347 (2005)
Advantage of TGIC over solvent gradient elution
Solvent gradient elution causes significant background signal drift that makes it difficult to use many useful detection methods for polymer analysis such as differential refractometer, light scattering, and viscometry. Temperature change also causes background signal drift, b t it i ll th l t di t d i i i l t tbut it is smaller than solvent gradient and, in principle, temperature can be readjusted at the detector.
6(a) RI
LS
2927252210
T (oC)
u.)
TGIC of PS with RI & LS detectionIsocratic Elution !!
0 10 20 30
2
4
LogM
n o
r R
(0)
(a.u
PS: 32.7k, 74.4k, 127k, 213k, 394k, 683k
VR (mL)
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Column: 4 DVB columns, 105, 104, 103 Å,
mixed, 250 x 10 mm
Eluent: THF
Column: 1 C18 silica column, 100 Å,
250 x 4.5 mm
Eluent: CH2Cl2/CH3CN (57/43)
Advantage of TGIC over SEC
Much lower band broadening and MW sensitive separation !
IC SEC
Mw/Mn = 1.005
Mw/Mn = 1.05
9 PS standards: 2.0 k,11.6 k, 30.7 k, 53.5 k, 114 k, 208 k, 502 k, 1090 k, 2890 k
Lee & Chang, Polymer 37 5747 (1996)
60 years of Anionic Polymerization
Szwarc et al. J.Am.Chem.Soc. 1956, 78, 2656
Szwarc, Nature 1956, 178, 1168
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Poisson Distribution
Flory, J. Am. Chem. Soc. 1940, 62, 1561
MWD of polymer of <DP>n = 1,000
How Narrow is really Narrow?
wi (
a.u.
)
Mw/Mn
1.0011.011.021.05
400 600 800 1000 1200 1400 1600
degree of polymerization
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TGIC Poisson distribution
SEC
MWD of Polystyrenes by SEC and TGIC
SEC: 2 x PL mixed C, THF
TGIC: 1 x Nucleosil C18 (100Å), CH2Cl2/CH3CN 57/43 (v/v)
Poisson
238s
wi (
a.u
.)
888s
1626s
2296s
3098s
Poissondistribution:
Poly’ntime
Mw/Mn (Mw)
SEC TGIC Poisson
238s 1.08 (4.3k) 1.06 (4.0k) 1.02
888s 1.04 (21.3k) 1.02 (21.0k) 1.003
)!1)(1(
1
i
eiW
i
i
0 200 400 600 800 10000 200 400 600 800 1000
i
14345s
4220s
1626s 1.05 (35.0k) 1.02 (34.4k) 1.002
2296s 1.05 (42.9k) 1.01 (43.4k) 1.002
3098s 1.05 (50.3k) 1.008 (50.2k) 1.002
4220s 1.05 (56.0 k) 1.006 (55.2k) 1.002
14345s 1.05 (62.0k) 1.005 (62.0k) 1.002
Lee et al. Macromolecules 33 5111 (2000)
6
7
2D-LC of PS standards (RP-TGIC x SEC)
(100
Å)
PS standards: 6 k, 15.3 k 30.9 k, 54 k, 93 k, 170 k, 384 k, 1160 kCalibration curve
RP-TGIC
RP
-TG
IC t
R(m
in)
0 50 100 150 200 250 300 350 4003
4
5
Lo
g M
tR (min)
6
7
1D R
P -
TG
ICN
ucle
osil
C18
150
×4.
6 m
m
CH
2Cl 2
/CH
3CN
= 5
7/43
(v/
v)0.
05 m
L/m
in
SEC
SEC tR (min)
0.8 1.0 1.2 1.43
4
5
6
Lo
g M
tR (min)
N C 0
2D SECPolyPore (250 ×4.6 mm)THF: 1.65 mL/min, T = 110 oC
Im et al. J. Chromatogr. A 1216 4606 (2009)
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Star-shaped PS by linking with divinyl benzene
DVB+ + + +
Highly Branched Species
Styrene + sec-BuLi PS Li
A
260 (
a.u
.)
R90
&
n (
a.u
.)
Light Scattering R.I.
SEC TGIC
1
0 10 20 30
tR (min)8 10 12 14 16
VR (mL)
R
Nucleosil C18 250 × 4.6 mm (500 Å)Eluent : CH2Cl2/CH3CN = 57/43 (v/v)Flow rate: 0.5 mL/min
2 x PL mixed C (300 x 7.5 mm)Eluent: THFFlow rate : 0.8 mL/min
2 3 4 5 6
1D RP - TGICNucleosil C18 250 × 4.6 mm (500 Å)Eluent: CH Cl /CH CN = 57/43 (v/v)
2D-LC of Star-shaped PS (RP-TGIC x SEC)
Eluent: CH2Cl2/CH3CN = 57/43 (v/v)Flow rate: 0.05 mL/min
RP
-TG
IC t
R(m
in)
2D SECBare Silica 150 × 4.6 mm (100 Å) + 50 × 4.6 mm (300 Å) +150 × 4.6 mm (1000 Å)Eluent : THFFlow rate : 1.8 mL/min at 130 oC
Im et al. J. Chromatogr. A 1216 4606 (2009)
SEC tR (min)
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Synthesis of H-shaped Polybutadiene
s-BuLi LiBenzene
RT20k (arm)
Si ClCl
CH3
Si
CH3
Butadiene
s-BuLi
Li
Titration
Jimmy Mays, Univ. of Tennessee
(CH3)2SiCl2Li
20k (star) 120k (H)HA20B40
SEC & TGIC characterization of H-shaped PBd
(b)
R90
,
n (a
.u.)
R90
, n
(a.u
.)
(a)(a) linear PBd arm (b) star PBd (½ H) (c) H-PBd (HA20B40).
SEC
16 18
R
14 16 18
R
tR
(c)
R90
, n
(a.u
.)
tR
(b)
R90
,
n (a
.u.)
R90
, n
(a.u
.)
(a)
31 18
20
22
T (
oC
)
2
TGIC
14 16 18
tR
0 2 4 6 8 0 10 20 30
tR (min)
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
(c)
tR (min)
R90
, n
(a.u
.)
1
2
3
4
tR (min)
T (
oC
)
14
16
18
20
22
24
26
28
30
32
(1)a+1/2b
(2)
a1/2b
aa
a
a
1/2b
a
a
b+a a
a
ab a ab
peak 1 peak 2 peak 3
peak 1 peak 2 peak 3 peak 4
a+b+a
(1)a+1/2b
(2)
a1/2b
a
a1/2b
aa
a
a
1/2ba
a
a
1/2b
a
a
b+aa
a
b+a a
a
aba
a
ab a aba ab
peak 1 peak 2 peak 3
peak 1 peak 2 peak 3 peak 4
a+b+a
Chen et al. Macromolecules,44, 7799 (2011)
2016-10-10
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polyisoprene
10
20
30
40
50
308 k
78.4 k35.1 k13.3 k
3.2 k
T ( oC
)
I ELS
D(a
.u.)
Column: C18 silica, 5 μm, 100 Å poreEluent: CH2Cl2/CH3CN = 80/20(v/v)
TGIC Separation of Various Polymers
0 10 20 30 40
0
10
20
30
40
polystyrene
2890 k1090 k502 k208 k
114 k53.5 k
30.7 k
11.6 k
2 k
T ( oC
)
A26
0(a
.u.)
Column: C18 silica, 5 μm, 100 Å poreEluent: CH2Cl2/CH3CN = 57/43(v/v)
0 10 20 30 40 50 60 70
0
poly(methyl methacrylate)
0 10 20 30 40 50 600
20
40
60
1350 k500 k183 k68.4 k
31.1 k9.4 k
T ( oC
)
A23
5(a
.u.)
VR (mL)
Column: C18 silica, 5 μm, 100 Å poreEluent: CH3CN 100%
Size Exclusion Chromatography
Fractionation of Mixture by Simultaneous SEC/IC
SOLVENT
FLOW
Interaction Chromatography
SEC condition
FLOW
tR
IC condition
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Temperature Dependence of PS/PMMA Retention
SEC IC
Column : 3 Nucleosil C18, 5 μm 100Å, 500Å, 1000Å pore
Eluent : CH2Cl2/CH3CN = 57/43 (v/v)SEC diti f PMMA
.0℃
SEC condition for PMMAIC condition for PS
R
S
RT
GK
SECo
SECo
SEC expexp
T i itiA
235
(a.u
.)
10℃
20℃
30℃
40℃
T- insensitive
RT
H
R
S
RT
GK
oIC
oIC
oIC
IC expexp
T- sensitive
0 5 10 15 20 25
VR (mL)
50℃
5 PMMA standards: 2k ~1,500k 11 PS standards: 1.7k ~2,890k
50
Simultaneous SEC/TGIC fractionation of PS/PMMA mixture
code PolymerMw
(kg/mol)Mw/Mn (SEC)
1 PMMA 1500 1.11
2 PMMA 501 1.09
3 PMMA 77 5 1 06
Column: 3 Nucleosil C18, 5 μm 100Å, 500Å, 1000Å pore
Eluent: CH2Cl2/CH3CN = 57/43 (v/v)
PMMA PS
A
235
(a.
u.)
20
30
40
T (
oC)
3 PMMA 77.5 1.06
4 PMMA 8.5 1.14
5 PMMA 2.0 1.10
a PS 1.7 1.06
b PS 5.1 1.05
c PS 11.6 1.03
d PS 22.0 1.03
e PS 37.3 1.04
12
3
45
S
PMMA PS
a
b
cd e
f
g
h
i
jk
0 10 20 30 40 50 60
VR (mL)
0 10 20 30 40 50 60
0
10f PS 68.0 1.03
g PS 114 1.05
h PS 208 1.05
i PS 502 1.04
j PS 1090 1.08
k PS 2890 1.09
Lee & Chang, Macromolecules 29 7294 (1996)
2016-10-10
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30
40
543
21
PIPS
(a)
T
Column : Nucleosil C18, 250 x 4.6 mm1000, 500, 100 Å pore
Eluent : CH2Cl2/CH3CN = 80/20(v/v)
Simultaneous SEC/TGIC Fractionation of Polymer Mixtures
0
10
205
4321
521
T ( oC
)
3PIPMMA
(b)I EL
SD (
a.u
.)
TGICSEC
SEC condition for PS and PMMATGIC condition for PI
Code PI PS PMMA
1 2,700 2,890,000 2,130,000
2 10 400 501 500 365 000
0 10 20 30
54
321
421
VR (min)
Lee et al. Macromol. Chem. Phys. 201 320 (2000)
2 10,400 501,500 365,000
3 28,100 140,000 78,700
4 56,800 15,300 17,900
5 199,000 3,600
NP-TGICColumn : Nucleosil bare silica
100 Å pore, 250 x 2.1 mmEluent : i-octane/THF = 55/45(v/v)
G C
NP- and RP-TGIC of PS
NP-TGIC
20
30
40
T( oC
)
A2
60(a
.u.)
RP-TGICColumn : Nucleosil C18 bonded silica
100 Å pore, 250 x 2.1 mmEluent : CH2Cl2/CH3CN = 57/43(v/v)
RP-TGIC
0 2 4 6 8 10 12 14
30
35
40
0
10
VR (mL)PS
(kg/mol)
Mw (kg/mol) Mw/Mn
NP RP NP RP
32.7
68 1 68 1 68 5 1 006 1 008
0 1 2 3 4 5 6 710
15
20
25
A2
60(a
.u.)
VR (mL)
T ( oC
)
68.1 68.1 68.5 1.006 1.008
112 112.3 113.0 1.005 1.006
213 205.7 200.3 1.004 1.004
394 395.5 385.4 1.003 1.004
683 653.4 648.3 1.006 1.006
1530
Lee et al. J. Chromatogr. A. 910 51 (2001)
2016-10-10
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NP-TGICColumn : 3 Nucleosil bare silica
100, 500, 1000 Å pore, 250 x 4.6 mmEluent : i-octane/THF = 55/45(v/v)
NP- vs. RP-TGIC: Simultaneous SEC and TGIC of PS and PI
NP-TGIC
20
30
40
Solvent
PS-1
PI's
T ( o
0(a
.u.)
RP-TGICColumn : 3 Nucleosil C18 bonded silica
100, 500, 1000 Å pore, 250 x 4.6 mm)Eluent : CH2Cl2/CH3CN = 80/20 (v/v)
Samples (kg/mol)PS : 10.3, 32.7, 68.1, 112, 213, 394, 683, 1530PI : 2 7 11 9 53 0 199
0
10
20
0 10 20 30 40 50
PS-2
PS-8PS-7PS-6PS-5PS-4
PS-3
oC)
A2
30
VR (mL)
)
30
40
S l t
RP-TGIC
PI : 2.7, 11.9, 53.0, 199
0 10 20 30 40 50
PS's PI-7
PI-4
PI-2
PI-1A2
30(a
.u.
VR (mL)
0
10
20
30Solvent
T( oC
)
Lee et al. J. Chromatogr. A 910 51 (2001)
MW & Composition Distribution in Block Copolymers
Effects of MW and composition distributionon the BCP phase behavior.
Various morphology of diblock copolymer
MW
Body Centered Cubic(BCC)
Lamella(LAM) Double Gyroid
Hexgonally Packed Cylinder(HEX)
Composition
( )
Modulated Lamella(MLAM)
Hexagonally Perforated Lamella(HPL)
Double Gyroid(DG)
2016-10-10
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SOLVENT
FLOW
Size Exclusion Chromatography
Fractionation of Homopolymer from BCP
SEC condition
Interaction Chromatography
FLOW
tR
IC condition
PS b PMMA/PS Mi t
SEC for PS / IC for PMMA
SEC IC
PS
PSPMMA
PS PS
PMMA
PS-b-PMMA/PS Mixtures SOLVENT
FLOW
tR
P
Fractionation of individual block of BCP
PS block length
PI b
lock len
gth
RP
LC
Composition
MW
PS block PI block
PS block length
NPLC
Composition
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2D NP-TGIC & RPLC Separation set-up
Im et al. Anal. Chem. 79, 1067 (2007 )
PS-b-PI (NP-TGIC x RPLC)
Diol bonded silica 250 x 7.8 mm Eluent: isooctane/THF = 97/3 (v/v) Flow rate: 0.05 mL/min
C18 silica, 150 x 4.6 mmEluent: CH2Cl2/CH3CN=53/47 (v/v)Flow rate: 1.5 mL/min
Im et al. Anal. Chem. 79, 1067 (2007)
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Fractionation of High MW PS-b-PI
NPLC fractionationPS-b-PI 12k/24k (21k/12k)Column :Diol, 100Å (4.6mm ID) Eluent: isooctane/THF (75/25, 70/30)T = 5oC (16oC)
RPLC fractionationPS-b-PI 12k/24k (21k/12k)Column :C18, 100Å (4.6mm ID)Eluent: CH2Cl2/ACN (80/20, 74/26)T = 2oC (3oC)
A2
35(a
.u.)
A26
0(a
.u.)
0 5 10 15 20 25 30tR(m in)
0 5 10 15 20 25 30 35 40
tR(m in )
Fractionation according to PI block Fractionation according to PS block
100 nm100 nm 100 nm 100 nm 100 nm
SLIHSHIL MotherSMIMSMIH
16
18
20
22
24 LAM HPL G HEX ODT mean-field
N
SLIH
SMIH SHIH
SLIM SMIM SHIM
PI b
lock le
RP
LC
0.60 0.62 0.64 0.66 0.68 0.70 0.72 0.7410
12
14
fPI
SLIL SMILSHIL
eng
thC
PS block lengthNPLC
Park et al. Macromolecules 36 4662 (2003)
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Styrene + sec-BuLi PS Li
Synthetic Scheme of Branched PS with CDMSS
slow
PS Li
CDMSS (less than 1 eq.)
fast
branching point
Exp 1 : CDMSS/sec-BuLi = 0.87 (BS 87)
Exp 2 : CDMSS/sec-BuLi = 0.65 (BS 65)
Exp 3 : CDMSS/sec-BuLi = 0.45 (BS 45)
K. Lee, Kumho Petrochemical Ltd.
Highly branched species
SEC and TGIC separation of branched PS
BS 87: CDMSS/sec-BuLi = 0.87
BS 65: CDMSS/sec-BuLi = 0.65
BS 45: CDMSS/sec-BuLi = 0.45
SEC TGIC
(a.u
.)
Precursor2.1k
BS8715.2k
BS658.3k BS45
4.7k
PS 2.1k CDMSS/sec-BuLi = 0.45 CDMSS/sec-BuLi = 0.65 CDMSS/sec-BuLi = 0.87
T (
a.u.
)
25
30
35
40
45
12 arms!
PL mixed Cⅹ2Eluent : THFFlow rate : 0.8 mL/min
Luna C18, 100 Å, 5 mm, 250ⅹ4.6 mmEluent : CH2Cl2/CH3CN = 55/45 (v/v)Flow rate : 0.6 mL/min
13 14 15 16 17
n
VR (m L)
0 20 40 60 80 100
( OC)
A26
0 (
a
tR (m in)
0
5
10
15
20
Im et al. Anal. Chem. 76 2638 (2004)
2016-10-10
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Star-shaped PS with arms of broad MWD
RP-TGICKromasil C18, 150×4.6 mm (100Å)Eluent : CH2Cl2/CH3CN = 53/47 (v/v)
LCCC ( T = 53.3oC)Kromasil C18, 150 × 4.6 mm, 5 m, 100 ÅEluent : CH2Cl2/CH3CN = 53/47 (v/v) Flow rate : 0.5 mL/min
BS 65: CDMSS/n-BuLi = 0.65
BS 49: CDMSS/n-BuLi = 0.45
T (
oC
0 (
a.u
.)
30
40
50
60
BS65
Eluent : CH2Cl2/CH3CN 53/47 (v/v) Flow rate : 0.5 mL/min
BS49
PS precursor
A26
0(a
.u.)
0 10 20 30 40 50 60 70
C)
A2
60
tR (min)
10
20BS49
PS precursor BS65
2 4 6 8
tR (min)Im et al. J. Chromatogr. A 1103 235 (2006)
Kromasil C18, 150 × 4.6 mm, 100 ÅEluent : CH2Cl2/CH3CN = 53/47 (v/v)
2-D LC (TGIC x LCCC) analysis of MW & branching
2
3
4
RP
-TG
IC V
R(m
L) M
olecular W
eight
1
Im et al. J. Chromatogr. A 1103 235 (2006)
LCCC VR (mL)
t
Branch number
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Summary
Size Exclusion Chromatography Interaction Chromatography
w
Interstitial space Solid phase
Pore
Interstitial space Solid phase
PoreExclusion
∆S
LCCCMW
vs.
SECExclusion >> Interaction ~ 0
Exclusion∆S
Flo
w
Stationary phase
Interaction∆H
VV
SECIC
Elution volume
log
M c us o te act o 0
ICExclusion < Interaction
LCCCInteraction ~ Exclusion
Chang, J. Polym. Sci. B 43 1591 (2005)
PS 2.1k CDMSS/sec-BuLi = 0.45 CDMSS/sec-BuLi = 0.65 CDMSS/sec-BuLi = 0.87
T (
OC)
A2
60 (
a.u
.)
15
20
25
30
35
40
45
Summary
Mw
( Mw/M
n by SEC, M
w/M
n by TGIC )
1530k
1090k(1.06, 1.007)
632k403k
228k(1.05, 1.005)
151k114k
81 9k53.5k
22k(1.03, 1.010)
11.6k
2k
26
0 (a.
u.)
20
30
40
50
T (
oC)
High Resolution Branched Polymer
0 20 40 60 80 100
A
tR (m in)
0
5
10
15
0 10 20 30 40
2890k81.9k37.3kA2
VR (mL)
0
10
)
Linearprecursor
Ring
40
50
k
j
i
a
S
3 5 7 9 11 13
A2
60
(a.u
.)
tR (min)
Cyclic PolymerMixture
Block copolymer
0
10
20
30
0 10 20 30 40 50 60
T ( oC
)
i
h
g
fedc
b
54
32
1
A23
5 (a
.u.)
VR (mL)
2016-10-10
22
Multivariate distribution in synthetic polymersMol. Wt., Composition, Branching, Functionality, etc.
2D-LC helps!
Summary