polymer characterization by temperature gradient ......2015-10-26 1 polymer characterization by...

2015-10-26

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Polymer Characterization by Temperature Gradient Interaction Chromatography:Temperature Gradient Interaction Chromatography:

SEC vs. TGIC

2015. 10. 20

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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Content

• IntroductionSize Exclusion Chromatography vs. Interaction Chromatography

• Temperature Gradient Interaction Chromatography• Temperature Gradient Interaction Chromatography

• Precision Analysis of Molecular Weight Distribution

• Nonlinear PolymersBranched polymer, Ring polymer

• Chemical CompositionMixture, Block Copolymer, Functionality

• Stereoregularity, Isotope

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/cmVR = Vm + K Vs

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SEM images of PS/DVB gel (top: 103, bottom: 106)

Cross-sectional TEM images of a silica particle for IC (pore diameter = 300 Å)

Porous packing materials for HPLC columns

3 ~ 5 m

1 m1 m1 m

10 ~ 20 m

200 nm200 nm

RSexp

RTGexpK SEC

oSEC

o

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


RSexp

RTGexpK SEC

oSEC

o

SEC

ow


Pore

Interaction Chromatography

RRT

1i

pSEC c

cKo

Exclusion∆S

Flo

Interstitial space Solid phaseExclusion

RTH

RSexp

RTGexpK

oIC

oIC

oIC

IC

m

sIC c

cKo

Flow

Stationary phase

Pore

Interaction∆H

Exclusion∆S

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Separation of Copolymers in terms of Chemical Composition

TLC : Inagaki et al. Macromolecules 1 520 (1968)Belenki et al. Akad.Nauk SSSR 186 857 (1969)

NPLC: Teramachi et al. Macromolecules 12 992 (1979)

IC Analysis of Polymers - History

( )Glöckner et al. Acta Polym. 33 614 (1982)

Separation of Homopolymers in terms of Molecular Weight

TLC : Inagaki & coworkers Polym. J. 1 518 (1970) Otocka & Hellman Macromolecules 3 362 (1970) Belenki et al. J. Chromatogr. 53 3 (1970)

RPLC: Armstrong & Bui Anal. Chem. 54 706 (1982)TGIC: Chang & coworkers Polymer 37 5747 (1996)

Lochmüller & coworkers, J. Chromotgr. Sci. 34 69 (1996)

Separation at Chromatographic Critical Condition (LCCC)

Belenki & coworkers, Dokl Acad Nauk USSR 231 1147 (1976)Vysokomol. Soedin. A19 657 (1977)

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

6,5,4 Temperature50oC

45oC

40oC

35oC

30.5oC

A26

0 (a.

u.)

6,5,43 2

1

59 %

57.5 %

57 %

62 %

65 %

CH2Cl2 vol%

A26

0 (a.

u.)

< Samples >

165,000429,000312,00022,5001

MWPS

0 10 20 30

32

1

54 28oC

25oC

20oC

tR (min)0 10 20 30

43

21

53 %

55 %

57 %

tR (min)

1,800,0006502,0005

Chromatographic Critical Conditionto to

Chang, Adv. Polym. Sci. 163 1 (2003)

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Three HPLC separation modes for polymersThree HPLC separation modes for polymers

SEC: Exclusion >> Interaction ~ 0

LCCC: Interaction ~ ExclusionIC: Exclusion < Interaction

IC

LCCC

SEC

og M

VR

lo

Vi Vp

Vm or Vo

Two Dimensional Liquid Chromatography (2D-LC)

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Martin’s rule: ,n : degree of polymerization

Then or

unito

polymo GnG

nunitpolym KK s

nunitmR VKVV

2

3 1400k

Martin’s Rule

RPLC of PS

Retention of polymer molecules changes exponentially with the degree of polymerization.

In order for a polymer sample with a wide molecular weight distribution to be eluted in a reasonableexperimental period, it is necessary to change K during the elution.

3.3 3.4 3.5 3.6 3.7

0

1

2

13.8k

ln k

1/T (x1000)

0

One way to control the retention is to change Go itself: Solvent gradient interaction chromatography

Alternative way to control the retention is to change T: Temperature gradient interaction chromatography (TGIC)

0 400 800 1200 1600-1600

-1200

-800

-400

Ho (

kJ/m

ol)

MW (kg/mol)

Kim et al. Anal. Chem. 81 14 (2009)

Content







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Column Temperature Control

Temperature effect in IC Separation

Column: Nucleosil C18, 3 μm, 100 Å50 x 4.6 mm

Eluent: CH2Cl2/CH3CN = 57/43 (v/v)1 0 mL/min

dT/dt = 8oC/min

30

40

1.0 mL/minPS 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)

A 260

(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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mSsmR ccK,KVVV KIC: solute distribution constantVR: retention volumeVm: mobile phase volumeVs: stationary phase volumec : solute concentration in MP

RS

RTHexpRTGexpK

ooo

Thermodynamics in IC separation

ooR tttlnkln

cm: solute concentration in MPcS: solute concentration in SP

msooR VVKtttk

RRT

k: retention factortR: retention time

tR = VR / flow rateto: solvent elution time

to = Vm / flow ratemsoo

VVRS

RTH

,lno mRRT

• Assuming that Vs and Vm are invariant, the solute retention is a function of the thermodynamic parameters, Ho and So, and temperature, T.

• In solvent gradient elution, retention is controlled by changing the mobile phase composition (thus changing Ho and So) while in TGIC, retention is controlled by changing the column temperature.

bTa

RS

RTH

tttk

oo

o

oR

lnlnln

At a fixed temperature, T

Definitionv(T): migration rate of polymer (T dependent)tR : retention time of polymerto : solvent elution time (T independent)T(t): column temperature at time tL: column length : column heating rate (K/min)

1 bTaexptt oR

1 bTaexptL

tLTv

oR LdtTvRt 0and

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For a linear T ramp with a gradient , T = T(0) + t.

dT = dt or dt = dT/ , and

At t = 0, T = T(0) and at t = tR, T = T(0) + tR.

RR tTt 10

LdTTvdtTv RR

tT

T

t

10

00

1 bTaexptLTv

o

Since

LdTbTat

LRtTT

0

0 1exp

• Using the integral equation above, we can calculate tR numerically if we know a and b, which depend on M.

o

tT

TtdT

bTaexpR

0

0 11

bTato 1exp

For a multistep linear T-ramp

T(t3) = T(0)+1(t2-t1)+ 2(t3-t2)

T(t2) = T(0) + 1(t2-t1)

T(0)

T(t2) T(0) 1(t2 t1)

time0 t1 t2 t3

3

2

2

11exp1exp10exp 21

1tT

tT

tT

tTo RSRTH

dTRSRTH

dTRSRTH

tt

• We can solve this integral equation numerically to obtain tR.

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Column: Nucleosil C18, 3m, 100Å, 50 x 4.6 mmEluent: CH2Cl2/CH3CN = 57/43 (v/v), 0.7 mL/min

Experimental verification

-600

-400

-200

0

Ho (

kJ/m

ol)

1

2

3

k

van’t Hoff plot of polystyrene

31k

55k

99k

113k

384k648k0 200 400 600

-1000

-800

Mp (kg/mol)

-1500

-1000

-500

0

(J/m

ol/K

)

0.0033 0.0034 0.0035 0.0036-2

-1

0

lnk

1/T (oC)

15k

First, the thermodynamic parameters are obtained by van’t Hoff plot.

0 200 400 600

-3000

-2500

-2000

-1500

Mp (kg/mol)

So +

Rln

5

6 experiment 5th order fitting 3rd order fitting

log

M

Temperature Gradient Interaction Chromatography (TGIC)

A26

0 (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 t

R

0 4 8 12 16

A

tR (min)

10

0 5 10 15 20

( oC)

tR (min)

A26

0 (a

0

10

30.9 k

Column: Nucleosil C18, 3 μm, 100Å, 50 x 4.6 mmEluent: CH2Cl2/CH3CN = 57/43 (v/v) at 0.7 mL/min

log M = 3.96619 + 0,0871 x tR0 5 10 15 20

4.0

4.5

5.0

log

tR (min)

Ryu & Chang, Anal. Chem. 77 6347 (2005)

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How polymers migrate inside the column?

Column: Nucleosil C18, 3 m, 100Å50 x 4.6 mm

Eluent: CH2Cl2/CH3CN = 57/43 (v/v)Flow rate: 0.7 mL/min

200 k 384 k

High MW polymers essentially do not move at all until it reaches a certain temperature.

Above the temperature, they start to move rapidly.

T-program: linear log MW vs. tR

15.9 k

30.9 k

55.2 k89 k

648 k

solvent

15.9 k 30.9 k 55.2 k 89 k 200 k 384 k 648 k

they start to move rapidly. It tells us that most of the separation of high MW polymers occurs in a short distance from the column inlet.

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 kLee & Chang, Polymer 37 5747 (1996)

Content







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2k50

Sample: 14 PS standardsColumn: C18 100 Å (Nucleosil, 250 x 2.1 mm)Eluent: CH2Cl2/CH3CN = 57/43(v/v)

TGIC separation of 14 Polystyrene Standards

Mw( Mw/Mn by SEC, Mw/Mn by TGIC )

2890k1530k

1090k(1.06, 1.007)

632k403k

228k(1.05, 1.005)

151k114k

81.9k53.5k

37.3k

22k(1.03, 1.010)

11.6k

A 260

(a.u

.)

10

20

30

40

T ( oC)

0 10 20 30 40

VR (mL)

0

10

Chang et al. Am. Lab. 34 39 (2002)

MWD of polymer of n = 1,000

How Narrow is really Narrow?

wi (

a.u.

)

Mw/Mn1.0011.011.021.05

400 600 800 1000 1200 1400 1600

degree of polymerization

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SEC and TGIC Characterization of Polystyrenes

3226181555

T (oC)

Styrene

Cyclohexane, 45 oC

Take out aliquots and terminate with i-propanol at different polymerization times.sec-BuLi

4.0

4.5

5.0

A26

0 (a.

u.)

logM

SEC PS1

PS2

PS3

PS4

TGIC

6.0x104

8.0x104

1.0x105

M

A26

0 (a.

u.)

1626s

2296s

888s

238s

13 14 15 16 17 18 19 202.5

3.0

3.5

A

tR (min)

PS7

PS5

PS6

0.0

2.0x104

4.0x104

0 20 40 60 80 100

A

tR (min)

3098s

4220s

14345s

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) 1.02888s 1.04 (21.3k) 1.02 (21.0k) 1.003

)!1)(1(

1

ieiW

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) 1.0022296s 1.05 (42.9k) 1.01 (43.4k) 1.0023098s 1.05 (50.3k) 1.008 (50.2k) 1.0024220s 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)

2015-10-26

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6

7

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-

TGIC

t R(m

in)

0 50 100 150 200 250 300 350 4003

4

5

Log

M

tR (min)

6

7

1D R

P -T

GIC

Nuc

leos

il C

18 1

50 ×

4.6

mm

C

H2C

l 2/C

H3C

N =

57/

43 (v

/v)

0.05

mL/

min

SEC

SEC tR (min)

0.8 1.0 1.2 1.43

4

5

6

Log

MtR (min)

N C 02D SECPolyPore (250 ×4.6 mm)THF: 1.65 mL/min, T = 110 oC

Content







2015-10-26

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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 30tR (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-

TGIC

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 Exact PB combs

Nikos Hadjichristidis, Univ. of Athens

Column: Polypore(300 x 7.5mm, 5μm) 2EAEluent: THF, 0.8mL/min

SEC & TGIC analysis of comb-shaped Polybutadiene

Column: Lunasil C18, 150×4.6 (i.d.) mm, 500Å, 7μmEluent : 1,4-dioxane , 0.5mL/min

580k

48586kAs-preparedAs-prepared

12 14 16 18 20

n,

R90

(a.u

.)

tE (m in)

89k

195k

9 18 27 36 45

n,

R90

(a.u

.)

tE (min)

36

39

42

45

T ( oC)

67k

165k214k

48After fractionation

After fractionation

12 14 16 18 20

n,

R90

(a.u

.)

tE (min)9 18 27 36 45

n, R

90 (a

.u.)

tE (min)

36

39

42

45

T ( oC)

Ratkanthwar et al. Polym. Chem. 4 5645 (2013)

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Synthesis of H-shaped Polybutadiene

s-BuLi LiBenzene

RT20k (arm)

Si ClCl

CH3

Si

CH3

Butadienes-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 (o

C)

2

TGIC

14 16 18

tR

0 2 4 6 8 0 10 20 30tR (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 (o

C)

14

16

18

20

22

24

26

28

30

32

(1) a+1/2b

(2)

a1/2b

aa

a

a

1/2b

a

ab+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

ab+a

a

ab+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)

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Styrene + sec-BuLi Li Isoprene + sec-BuLi Li

PSPI3 Miktoarm Star Copolymer

Li + SiCl4 (excess) SiCl3 + excess SiCl4

SiCl3 + Li (excess)

+ side products (fractionation)

Possible side products: PSPI2SiOR, PSPISi(OR)2, HomoPI, etc.

J. Mays, Univ. of Tennessee

C)

(a.u

.)

50

60F1

F4

F5

F6

SEC and TGIC Analysis of PSPI3

high MW PI

PI

SEC TGIC unfractionated mother

F6

F7

0 10 20 30 40 50 60 70

)

a.u.

)

50

60

T (o C

A 260

,235

(

20

30

40F2

F3

F6

F7

PSPI3

PSPI2

PS2PI

PSPI

PSPI

PSn

(a.u

.)

fractionated mother

F1

F2

F3

F4

F5

F5

0 10 20 30 40 50 60 70

T (o C

)

A 260

,235

(a

tR (min)

20

30

40

9 10 11 12 13 14 15

Unfractionated mother

Fractionated mother

vR (mL)

F4F2

F7

Park et al. Macromolecules 36, 5834 (2003)

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Relative Molar Mass

1D RP-TGICC18 100 x 2.1mm, 5 μm, 100 ÅEluent: 1,4 Dioxane, 0.015 mL/min

PIUV 230 nm

PSPI3 mikto arm star copolymer (RP-TGIC x SEC)

RP-

TGIC

t R(m

in)

T ( oC)

PS2PI

PSPI

PSPI2

PSPI3

UV 260 nm

SEC tR (min)2D SECPolyPore 250 ×4.6 mmEluent : THF, 1.7 mL/minTemperature : 110 oC

PS

2


Content







2015-10-26

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Synthetic scheme of Ring PS

LCCC separation of Rings from Linear Precursors

(1) (CH3)2SiCl2(1) (CH3)2SiCl2extreme dilution

(2) CH3OH

Possible byproducts

J. Roovers, NRC-Canada

LCCC for linear PSColumn: Nucleosil C18ABEluent: CH2Cl2/CH3CN=57/43Column temperature: 42 oC

SECColumn: 2 x PL mixed-CEluent: THFColumn temperature: 40 oC

LCCC separation of Rings from Linear precursors

Precursor(linear)

Precursor(linear)Ring

(a.u

.)

86.9k

73.3k

48.0k

.161k

.198kRing

ecu so ( ea )

A26

0 (a.

u.)

Ring

86.9k

73.3k

48.0k

.161k

.198k

14 16 18 20 22

n

tR (min) Lee et al. Macromolecules, 33 8129 (2000)

16.9k

23.4k

18.0k

12.1k

3 5 7 9 11

A

tR (min)

16.9k

23.4k

18.0k

12.1k

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SEC

Fractionation results by SEC & MALDI-TOF MS

MALDI-TOF MS

ensi

ty (a

.u.)

: As-received Ring PS : Fractionated Ring PS

n

(a.u

.)

.198k

73.3k

48.0k

Linear precursor

16.9k

Ring PSAs-received

2000 3000 4000 5000 6000 7000 8000 9000 100002000 3000 4000 5000 6000 7000 8000 9000 100002000 3000 4000 5000 6000 7000 8000 9000 10000

Inte

m/z15 16 17 18 19

tR (min)

18.0kRing PSFractionated by LCCC

Si

CH3

CH3

Before and After LCCC Fractionation

Before After

DP =38

4244.7

4155.7

4124.4

4124.5

4000 4100 4200 4300

4000 4100 4200 4300

Si

CH3

CH3

Si

CH3

CH3

OCH3H3COSi

CH3

CH3

OCH3H

Cho et al. Macromolecules 34 7570 (2001)

2015-10-26

24

400

Property of Purified Ring PS – 4.6 kg/mol

103Tg

Segmental RelaxationTime

3840

300

350

PS ringPS ring (theory)linear PS

T g (

K)

100

101

102

(s

)

6.4

90

3840

Ring

1 10 100 1000

250

figure 1

Mn (kg/mol)2.6 2.7 2.8 2.9

10-1

10

figure

1000 / T (K-1)

Santangelo et al. Macromolecules 34 9002 (2001)

3.7 kg/mol

Stress Relaxation of Entangled Polymers

Δ R198▲ Linear □ R161■ Linear

103

104

105

106

GNd

G(t)

(Pa

)

e

R198

.u.)

198,000 g/mol

10-7 10-6 10-5 10-4 10-3 10-2 10-1 100 101 102

102

103

d

t (s)

R161

n (a

.

VR (mL)

161,000 g/mol

Kapnistos et al. Nature Mater. 7 997 (2008)

2015-10-26

25

Content







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 k114 k

53.5 k30.7 k

11.6 k

2 k

T ( oC)

A 260

(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)

A 235

(a.u

.)

VR (mL)

Column: C18 silica, 5 μm, 100 Å poreEluent: CH3CN 100%

2015-10-26

26


Fractionation of Mixture by Simultaneous SEC/IC

SOLVENT

FLOW


SEC condition

FLOW

tRIC condition

Temperature Dependence of PS/PMMA RetentionSEC 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

RS

RTGK SEC

oSEC

o

SEC expexp

T i iti

A23

5 (a.

u.)

10℃

20℃

30℃

40℃

T- insensitive

RTH

RS

RTGK

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

2015-10-26

27

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)

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

205432

1

521

T ( oC)

3PIPMMA

(b)I ELS

D (a

.u.)

TGICSEC

SEC condition for PS and PMMATGIC condition for PI

Code PI PS PMMA1 2,700 2,890,000 2,130,0002 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 10,400 501,500 365,0003 28,100 140,000 78,7004 56,800 15,300 17,9005 199,000 3,600

2015-10-26

28

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 PSNP-TGIC

20

30

40

T( oC)

A 260

(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/MnNP RP NP RP

32.768 1 68 1 68 5 1 006 1 008

0 1 2 3 4 5 6 710

15

20

25A 2

60(a

.u.)

VR (mL)

T ( oC)

68.1 68.1 68.5 1.006 1.008112 112.3 113.0 1.005 1.006213 205.7 200.3 1.004 1.004394 395.5 385.4 1.003 1.004683 653.4 648.3 1.006 1.0061530

Lee et al. J. Chromatogr. A. 910 51 (2001)

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-6

PS-5PS-4PS-3

oC)A 2

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-1A23

0(a

.u.

VR (mL)

0

10

20

30Solvent

T( oC)

Lee et al. J. Chromatogr. A 910 51 (2001)

2015-10-26

29

Content







MW & Composition Distribution in Block Copolymers

Effects of MW and composition distributionon the BCP phase behavior.

Various structures of diblock copolymer

Body Centered Cubic Hexgonally Packed Cylinder

MW

(BCC)

Lamella(LAM) Double Gyroid

(DG)

g y y(HEX)

CompositionModulated Lamella

(MLAM)Hexagonally Perforated Lamella

(HPL)

2015-10-26

30

SOLVENT

FLOW


Fractionation of Homopolymer from BCP

SEC condition


FLOW

tRIC 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

Column : Bare Silica (100 22 mm)Eluent : THF/isooctane = 60/40 (v/v)Flow rate : 1 5 mL/min

Multiple Injection

Column : Bare Silica (100 22 mm)Eluent : THF/isooctane = 65/35 (v/v)Flow rate : 1 5 mL/min

NPLC separation of PS-b-PMMA

Fractionation of homo-PS (Multiple injection)

A 260

(a.u

.)

40

60

80

T( oC)

PS Precursor

PS-b-PMMA

Flow rate : 1.5 mL/minFlow rate : 1.5 mL/min

PS-b-PMMA

PS

A26

0 (a.

u.)

0 50 100 150 200 250 300 350

tR (min)

A

0

20

(10 injections)

Park et al. J. Am. Chem. Soc 126 8906 (2004)

0 10 20 30 40 50 60

A

tR (min)

2015-10-26

31

P

Fractionation of individual block of BCP

PS block length

PI block length

RPLC

Composition

MW

PS block PI block

PS block lengthNPLC

Composition

NP & RPLC Separation of Low MW PS-b-PI

PS-b-PI 2.4 kg/mol, 30.4 wt% PIColumn: Diol bonded silica 7.8 mm ID, 100ÅEluent: i-Octane/THF = 97/3 (v/v)

0.7 mL/min

PS

Reflection mode MALDI-TOF MSMatrix: dithranolSalt: AgTFA

Column: LUNA C18 4.6 mm ID, 100ÅSolvent: CH2Cl2/CH3CN = 53/47 (v/v)

0.5 mL/min, 20OC

Matrix: dithranolSalt: AgTFADetection: Reflection mode

Molar mass (DPPS, DPPI)

T( OC)

f6

f11

f9

f7f5

f3

f1

A 260

(a.u

.)

15

30

45

60

f7

f5

f3

f1

PS-b-PI

PS precursor

Inte

nsity

(a.u

.)

(9,11)(9,10)

(7,11)(7,10)

(5,11)(5,10)

(3,11)(3,10)

1784.1 1852.1

1576.1 1644.2

1368.2 1436.2

1160.1 1228.2

Molar mass(DPPS, DPPI)

f7

f5

f3

f1

A 230

(a.u

.)

Inte

nsity

(a.u

.)

1748.2 (8,11)

1680.1 (8,10)

1612.1 (8,9)

1544.1 (8,8)

1475.9 (8,7)

frac 5

frac 4

frac 3

frac 2

frac 1

1816 4 (8 12)

Molar mass (DPPS, DPPI)

0 20 40 60 80tR (min)

0

NPLC ⇒ fractionation of PS blockNear LCCC for PI and IC for PS

1000 2000 3000 40001000 2000 3000 40001000 2000 3000 40001000 2000 3000 40001000 2000 3000 40001000 2000 3000 40001000 2000 3000 40001000 2000 3000 4000

f11

f9

f7

2269.72201.6

2060.4

m/z

(13,11)(13,10)

(11,11)(11,10)1992.4

RPLC ⇒ fractionation of PI blockNear LCCC for PS and IC for PI

0 10 20 30 40tR (min)

Park et al. Macromolecules 35 5974 (2002)

1400 1600 1800 2000 22001400 1600 1800 2000 22001400 1600 1800 2000 22001400 1600 1800 2000 22001400 1600 1800 2000 22001400 1600 1800 2000 22001400 1600 1800 2000 22001400 1600 1800 2000 2200m/z

frac 8

frac 7

frac 6

1952.3 (8,14)

1884.1 (8,13)

1816.4 (8,12)

2015-10-26

32

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 250×7.8 mm Eluent : isooctane/THF = 97/3 (v/v) Flow rate : 0.05 mL/min

C18 silica, 150×4.6 mmEluent : CH2Cl2/CH3CN=53/47 (v/v)Flow rate : 1.5 mL/min

Im et al. Anal. Chem. 79, 1067 (2007)

2015-10-26

33

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)

A 235

(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

SLIHSMIH SHIH

SLIM SMIM SHIM

PI block leR

PLC

0.60 0.62 0.64 0.66 0.68 0.70 0.72 0.7410

12

14

fPI

SLIL SMILSHIL

engthC

PS block lengthNPLC

Park et al. Macromolecules 36 4662 (2003)

2015-10-26

34

PS-b-PMMA at Air/Water Interface - surface micelles

Top viewSide view

Structure of surface micelles of amphiphilic block copolymers at PS

PSPMMA PMMA

Water

Homo-polymer free PS-b-PMMA mother:

block copolymers at air/water interface

PS

PMMA

Water

53.1k - 19.7k, wtPS = 0.73, Mw/Mn = 1.05

3 x 3 m

Chung et al. Macromolecules 38 6122 (2005)

Morphology of PS-b-PMMA Surface Micelles

ML MM MH

SH

PS-b-PMMA mother: 72.8 kg/mol wtPS = 0.73 M /M = 1 05 (SEC)

SM

67 7k/0 76/1 01

72.3k/0.77/1.01

69 5k/0 72/1 01

77.6k/0.74/1.01

71.3k/0.70/1.01

79.5k/0.71/1.01

Fra

ctio

nate

d b

y R

Mw/Mn 1.05 (SEC)

SHML

SMMM

PS b

lock

RPL SMML

SHMM SHMH

SMMH

63.1k/0.73/1.01

SL

67.7k/0.76/1.01

64.8k/0.69/1.01

69.5k/0.72/1.01

65.3k/0.67/1.01

71.3k/0.70/1.01

3 x 3 mFractionated by NPLC

RPLC

k length

LC

PMMA block length

NPLC

SLML SLMM SLMH

Chung et al. Macromolecules 38 6122 (2005)

2015-10-26

35

Content







OH end-functional PSSEC2 x PL-mixed BEluent: THFFlow rate: 1.5 mL/min


(1) Ethyleneoxide

(2) i-propanoli-propanol

PS,PS-OH 10K

PS,PS-OH 100KA26

0 (a.

u.)

PS Li

H CH2CH2OH

10 11 12 13 14 15 16

PS,PS-OH 500K

VR (mL)

2015-10-26

36

PS-OH 10k

PS 10k

T( OC

A 260

(a.u

.)

20

30

40

50

NP-TGIC

Column: Nucleosil bare silica100 Å 250 2 1

NP- vs. RP-TGIC: Separation by a single -OH end group

NP-TGIC

0 1 2 3 4 5 6 7

PS-OH 100kPS 100k

C)A

VR (mL)

0

10

20

30

35

100 Å pore, 250 x 2.1 mmEluent: i-octane/THF = 55/45(v/v)

RP-TGICRP-TGIC

0 1 2 3 4 5 6

PS, PS-OH 100k

PS, PS-OH 10k

T( OC)

A 260

(a.u

.)

VR (mL)

5

10

15

20

25

Lee et al. J. Chromatogr. A 910 51 (2001)

Column: Nucleosil C18 bonded silica100 Å pore, 250 x 2.1 mm

Eluent: CH2Cl2/CH3CN = 57/43(v/v)

1D NPLCBare silica 50 × 2.1 mm (100 Å)Eluent : isooctane/THF = 55/45 (v/v)Temperature : 34.2 oCFlow rate : 0.015 mL/min

End group analysis by 2D-LC

PS 2k, 10k, 110kPS-OH 2k, 10k, 110k

PS OH

NPL

C t R

(min

)

PS-OH

PSPS

PS-OHPS-OH

2D SECPolyPore 250 ×4.6 mmEluent : THFTemperature : 110 oCFlow rate : 1.7 mL/min

Switching valve loop : 30 μL

SEC tR (min)

2 k110 k 10 k


PS PS

2015-10-26

37


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)



K. Lee, Kumho Petrochemical Ltd.

Highly branched species

SEC and TGIC separation of branched PS

BS 87: CDMSS/sec-BuLi = 0.87



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

V R (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)

2015-10-26

38

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)

A26

0

tR (min)

10

20BS49

PS precursor BS65

2 4 6 8tR (min)


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

34

RP-

TGIC

VR

(mL

) Molecular W

eight

1


LCCC VR (mL)

t

Branch number

2015-10-26

39

Content







SEC vs. TGIC of the three different tactic PEMAs

SECColumn: PL-mixed C 2Eluent: THFFl t 0 8 L/ i

RPLCColumn: LUNA C18 4.6 mm ID, 100ÅSolvent: CH3CN/CH2Cl2 = 70/30 (v/v)Fl t 0 45 L/ i

1530k 384k 113k 31k 11.6k 3250 580

h- PEMA

s- PEMA

PS stds

A 235

(a.u

.)

Flow rate: 0.8mL/min

f3f4

f2f1

i-PEMAf3

f2

f2f1

h-PEMA

s-PEMA

A23

5 (a.

u.)

40

48

T( OC)

Flow rate: 0.45 mL/min

8 12 16 20

i- PEMA

VR (mL)0 10 20 30 40 50

tR (min)

32

T. Kitayama, Osaka Univ.

2015-10-26

40

MALDI-TOF MS Spectra of mother PEMAs & Fractions

MALDI-TOF (Reflection mode)Matrix: IAA (indoleacrylic acid)Solvent: THFSalt: NaI

s - f 2

s - f 1

s - P E M A

Inte

nsity

(a.u

.)

i - f2

i - f1

i - PEMA

Inte

nsity

(a.u

.)

h - f 2

h - f 1

h - P E M A

Inte

nsity

(a.u

.)

4000 8000 12000 16000 20000

s - f 3

m / z6000 9000 12000 15000

i - f3

m/z4000 8000 12000 16000 20000

h - f 4

h - f 3

m / z

SEC vs. TGIC of the three different tactic PEMAs

SECColumn: PL-mixed C 2Eluent: THFFl t 0 8 L/ i

RPLCColumn: LUNA C18 4.6 mm ID, 100ÅSolvent: CH3CN/CH2Cl2 = 70/30 (v/v)Fl t 0 45 L/ i

1530k 384k 113k 31k 11.6k 3250 580

h- PEMA

s- PEMA

PS stds

A 235

(a.u

.) f3f4

f2f1

h-f3s-f2

i-PEMAf3

f2

f2f1

h-PEMA

s-PEMA

A23

5 (a.

u.)

40

48

T( OC)

Flow rate: 0.8mL/min Flow rate: 0.45 mL/min

8 12 16 20

i- PEMA

VR (mL)0 10 20 30 40 50

h-f4s-f3

i-f3h-f2

tR (min)

32

Cho et al. Anal. Chem. 74 1928 (2002)

2015-10-26

41

4.4

PS stds s-PEMAh1 PEMA

SEC calibration curve of stereoregular PEMA

Column: PL mixed C 2Eluent: THFFlow rate: 0.8 mL/min

3 8

4.0

4.2

h1-PEMA h2-PEMA i-PEMA

log

M

17.0 17.5 18.0 18.5 19.0 19.5 20.0

3.6

3.8

tR (min)

Cho et al. Macromolecules 35 5974 (2002)

Content







2015-10-26

42

PS Comb - Synthetic Scheme

h-styrene + sec-BuLih-PS bar (200k)

Bu

chloromethylation

Cl Cl Cld-styrene + sec-BuLi

d-PS arm (85k)

Bu

d-PS d-PS d-PS

C.M. Fernyhough, Univ. of Sheffield

PS Comb Mw/Mn = 595 k / 540 k

SEC & Light scattering detection

A b h b

SECPL mixed C×2, THFLight scattering detection (Viscotek TDA 300)

83 k

374 k

186 k

BackboneMw/Mn = 200 k / 190 k

n

& R

90 (a

.u.)

Average branch number

= 4.2 branchn

backbonencombnnbr M

MMN

,

,,

0.6

0.8

1.0

ght F

ract

ion

6 8 10 12 14

160 kBranchesMw/Mn = 85 k / 83 k

VR (mL)

4.0x105 6.0x105 8.0x105 1.0x106 1.2x106 1.4x106

0.0

0.2

0.4

Molar Mass (g/mol)

Cum

ulat

ive

Wei

g

2015-10-26

43

Column: Bare, 7 μm , 500 Å, 250×2.1 mm Eluent: Hexane/THF = 57/43 (v/v)Flow rate: 0.3 mL/min

NP-TGIC Chromatogram of PS Comb

1.2x106 50321414

T (oC)

6.0x105

8.0x105

1.0x106

0 &

n (a

.u.)

Molar m

ass (g/

Chambon et al. Macromolecules 41 5869 (2008)

0 20 40 60 80 100

2.0x105

4.0x105

R90

Elution time(min)

/mol)

0 4

0.6

0.8

1.0

ve W

eigh

t Fra

ctio

n

Assumption - Backbone: 200 kBranch: 85 k

NP-TGIC Analysis of PS comb

3-branch

2.0x105 4.0x105 6.0x105 8.0x105 1.0x106 1.2x106

0.0

0.2

0.4

Cum

ulat

iv

Molar Mass (g/mol)

15

20

Wt fraction of 3-branch

PS Comb

1 2 3 4 5 6 7 8 9 100

5

10%

Arm number

PS Comb

From average MW 4.1

From distribution 4.0

nbrN

2015-10-26

44

Column: C18, 7 μm , 500 Å, 150×4.6 mm Eluent: CH2Cl2/CH3CN=57/43 (v/v)Flow rate : 0.5 mL/min

RP-TGIC Analysis of PS comb

342624 T (oC)

24

107

342624

& A

260 (

a.u.

)

24

LogM

1.2x106 50321414

T (oC)

0 5 10 15 20106

R90

&

tR (min)0 20 40 60 80 100

2.0x105

4.0x105

6.0x105

8.0x105

1.0x106

R90

&

n (a

.u.)

Elution time(min)

Molar m

ass (g/mol)

SEC NP-TGIC RP-TGIC

Column: PL mixed C×2Eluent: THFFlow rate: 0.8 mL/min

Bare silica 250×2.1 mm, 5 μm, 500 ÅEluent : i-octane/THF=57/43 (v/v)Flow rate: 0.3 mL/min

Kromasil C18 150×4.6 mm, 5 μm, 100 ÅCH2Cl2/CH3CN=57/43 (v/v) Flow rate: 0.5 mL/min

Isotope effect in IC separation

60 (a

.u.)

60 k10 k

h-PS

20

25

30

35

T ( oC)

260 (

a.u.

)

60 k

10 k

h-PS

16

18

20

22

T ( oC)

60 k

10 k

A26

0 (a.

u.)

10 12 14 16 18tR (min)

A26

d-PS

0 3 6 9 12 15 18 215

10

15

A2

tR (min)

d-PS

0 5 10 15 20

10

12

1460 k

d-PS

tR (min)

h-PS

2015-10-26

45

Nucleosil C18 150 × 4.6 mm (500 Å)Eluent: CH2Cl2/CH3CN = 57/43 (v/v)Flow rate: 0.05 mL/min 34

0 0 0 2 0 4 0 6 0 8 1 0 1 2 1 4 1 60 0 0 2 0 4 0 6 0 8 1 0 1 2 1 4 1 6

A26

0(a

.u.)

RP-TGIC× SEC of comb PS

A260TG

IC t R

(min

)

T ( oC)

26

24

PolyPore 250 ×4.6 mmEluent : THF, 1.7 mL/minTemperature : 110 oC

RP-

T

SEC tR (min)

24

R90 & A260

40F6 F8F3F1

RP-TGIC & NP-TGIC analysis of PS comb

RP-TGIC

T (oC)32175 5

0 2 4 6 8 10 12 14 16 18 20

0

20

R90

& A

260 (

a.u.

)

tR (min)

T ( oC)

T (oC)

F1

F6

F5

F4

F3

F2

A26

0 (a.

u.)

Mother

R ( )

0 5 10 15 20106

107

342624T (oC)

R90

& A

260 (

a.u.

)

tR (min)

24

LogM

0 10 20 30 40 50

F8

F6

F7

tR (min)

NP-TGIC

2015-10-26

46

2D NP2D NP--TGIC x RPTGIC x RP--SGIC setSGIC set--upup

Things need to be considered:

1. Eluent compatibilty: NPLC first, trapping and eluent exchange

Switching valve conditionSwitching valve conditionPre-column: Diol, 50×4.6 mm, 100 Å, 7 μm

Diol, 50×4.6 mm, 100 Å, 7 μmLoop : 100 μl

2. Speed: Solvent gradient elution of 2nd - RPLC

CH3CN (with 4% iso-octane)

Initial state

…Time (min)B

con

tent

(%)

Re-stabilization timeSeparation time

5min 3min 5min 3min 5min 3min

32

A 260

(a.u

.)

NP-TGICNucleosil bare silica, 50 × 4.6 mm, 500 ÅEluent: THF/iso-octane = 48/52 (v/v)Flow rate: 0.05 mL/min

RPLCNucleosil C18 150 ×4.6 mm (500Å)Eluent: CH2Cl2/CH3CN = 57/43 (v/v) 59/41 (v/v)Flow rate: 1.5 mL/min

NP-TGIC x RPLC of comb PS

T ( oC)

min

)

Triple backbone !

17

5

5A260(a.u.)N

P-TG

IC t R

(m

RPLC tR (min) Ahn et al. Anal. Chem. 83 4237 (2011)

2015-10-26

47

Column: Polypore (300 x 7.5mm, 5μm) 2EAEluent: THF at 0.8mL/minDetector: Viscotek (Triple detector)

SEC analysis of fractionated hPS-b-dPS

n,

A26

0, R

90 (a

.u.)

PrecursorhPS 18k

hPS-b-dPS18k-17k

hPS-b-dPS18k-38k

10 12 14 16 18 20

tE (min)

hPS-b-dPS18k-80k

Lee et al. Macromolecules. 46 9114 (2013)

Elution of hPS-b-dPS at CC of hPS

Lunasil C18, 150×4.6 mm, 100Å, 5µm; CH2Cl2/CH3CN = 57/43 (v/v), 0.5 mL/min

.u.)

Temp : 40˚ChPS 11khPS 27khPS 48k

u.) 5

6

7

Precursor hPS 18k

hPS-b-dPS

2 3 4 5

A26

0 (a.

tE (min)

dPS - Mp (g/mol)

Expected M Measured Mp( )

2.0 2.5 3.0 3.5 4.0 4.5 5.0

A26

0 (a.

u

tE (m in)

2

3

4

LogM

18k-17k

hPS-b-dPS18k-38k

hPS-b-dPS18k-80k

Calibration with homo-dPS Expected Mp p(error)

Precursor - -

hPS-b-dPS18k-17k 16.9 k 10.1 k (40.2%)

hPS-b-dPS18k-38k 37.7 k 33.5 k (11.4%)

hPS-b-dPS18k-80k 80.2 k 74.8 k (6.7%)

At CC of hPS, hPS-b-dPS elutes in the decreasing order of MW while they elute before the solvent peak (SEC region).

MW of dPS block (homo-dPS calibration) deviates significantly from the true value, particularly for low MW dPS block.

2015-10-26

48

Elution of hPS-b-dPS at CC of dPS.)

Temp : 33.6˚CdPS 6kdPS 25kdPS 46k

)

4

5

Precursor hPS 18k

hPS-b-dPS

Lunasil C18, 150×4.6 mm, 100Å, 5µm; CH2Cl2/CH3CN = 57/43 (v/v), 0.5 mL/min

3.0 3.5 4.0 4.5 5.0 5.5 6.0

tE (min)

A26

0(a.u

.

3 4 5 6

A26

0(a.u

.)

tE (min)2

3

LogM18k-17k

hPS-b-dPS18k-38k

hPS-b-dPS18k-80k

hPS - Mp (g/mol)Calibration with homo-hPS

Expected MpMeasured Mp

(error)

Precursor 17.8k -

hPS-b-dPS18k-17k 17.8k 15.6k (12.4%)

hPS-b-dPS18k-38k 17.8k 14.0k (21.3%)

hPS-b-dPS18k-80k 17.8k 8.2k (53.9%)

At CC of dPS, hPS-b-dPS elutes in the decreasing order of MW while they elute after the solvent peak (IC region).

Again, the MW of hPS block (homo hPS calibration) deviates significantly from the true value, particularly at high MW dPS block.

1st D (RP-TGIC)Lunasil C18, 150×4.6 (i.d.) mm, 100 Å, 5 μmCH2Cl2/CH3CN (57/43) at 0.05mL/min

18k-160k-18k(Coupled 18k-80k)


Solvent peak

2D-LC (RP-TGIC x RP-LCCC) of hPS-b-dPS

2nd D (RP-LCCC)Lunasil C18, 150×4.6 (i.d.) mm, 100 Å, 5 μm CH2Cl2/CH3CN (57/43) at 1.5 mL/min, 33.6oC

RP-

TGIC

tE

(min

)

18k-17k

18k-80k

18k-38k


36k(Coupled 18k)

As expected, hPS is retained more strongly than dPS in the RPLC separation

RP -LCCC tE (min)

18k

strongly than dPS in the RPLC separation.

At CC of dPS, hPS-b-dPS elutes in the order of decreasing MW while they elute after the solvent peak (IC region).

Full resolution of 3 hPS-b-dPS and a number of byproducts is realized by 2D-LC.

Lee et al. Macromolecules. 46 9114 (2013)

2015-10-26

49

Summary

Size Exclusion Chromatography Interaction Chromatography

w


Pore


PoreExclusion

∆S

LCCCMW

vs.

SECExclusion >> Interaction ~ 0

Exclusion∆S

Flow

Stationary phase

Interaction∆H

VV

SECIC

Elution volume

log

M c us o te act o 0ICExclusion < 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)

A26

0 (a.

u.)

15

20

25

30

35

40

45

Summary

Mw( Mw/Mn by SEC, Mw/Mn 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

260 (

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

ia

S

3 5 7 9 11 13

A26

0 (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)

2015-10-26

50

Multivariate distribution in synthetic polymersMol. Wt., Composition, Branching, Functionality, etc.

2D-LC helps! Even isotope effect can help!

Summary

32

A 260

(a.u

.)

T ( oC)

17

5

5A260(a.u.)

PohangChina Japan

N. Korea

S. Korea

2015-10-26

51

ChemistryPAL

Library

Pohang University of Science and Technology (POSTECH)

POSTECH was ranked 1st in Times Higher Education 100 under 50 Rankings for last 3 consecutive years, 2012-2014.

4th generation light source (x-ray free electron laser) is under construction to be operational in 2016.

polymer characterization by temperature gradient ......2015-10-26 1 polymer characterization by...

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