sec/gpc applications using conventional and advanced … · 2016. 6. 1. · 1 130k 560k 310k 200k...

Miroslav JANČO, Matt CROWE, Mark RICKARD, Jian WU and

Tianlan ZHANG

SEC/GPC Applications Using Conventional

and Advanced Detectors

The Dow Chemical Company, Core R&D, Analytical Sciences

Overview

1. Introduction

2. SEC/GPC Using “Conventional” Detectors

• SEC-UV-RI Coupling

3. SEC/GPC Using “Advanced” Detectors

• Off-line SEC-MALDI/MS

• On-line SEC-ESI MS and ESI/CR/MS

• On-line SEC-ICP/MS

• On-line SEC-FTIR

• On-line SEC-NMR

• On-line SEC-macroIMS

4. Conclusions

5. Acknowledgements

Molecular Heterogeneity of Polymers

Molar mass

distribution

Molecular Architecture

Stereoregularity

distributionEnd-functionality

type distribution

Chemical

composition

distribution

Liquid Chromatography and Its Modes

Retention time, [min]

SEC (GPC) LC CAP HPLC/UPLC

TG or EG

tR=A-B log M tR = constant tR=C+D exp M

1 1

30K

560K

310K

200K

120K

98K

66K

44K

30K

22K

11.6

K

7000

3250

1700

580 2

20 (

BH

T)

Advanced Polymer Chromatography (APC)

Run time: 40 minRun time: 6 minR

I d

ete

cto

r re

sp

on

se

, [m

V]

RI d

ete

cto

r re

sp

on

se

, [m

V]

SEC APC

Application technique for the size based separation of polymers using

columns packed with sub-3µm, rigid, high-pore-volume, hybrid particles

combined with a fully optimized low dispersion ACQUITY™ system

SPEED RESOLUTION PRECISION SUSTAINABILITY

Injection Mp Mw Mn Ɖ

20 2743 6143 3870 1.587

40 2753 6160 3884 1.586

60 2754 6156 3884 1.585

80 2745 6146 3870 1.588

100 2746 6151 3878 1.586

% RSD 0.18 0.11 0.18 0.08

Tetra Detector Array SEC with OmniSECTM software

GPCmax™

Integrated Degasser,

Pump and Autosampler

Tetra Detector Array (TDA)

Integrated Columns and Detectors

(UV, LALS/RALS, RI & VIS)

SEC of Halogenated Polymers using ELSD and TDA

79.70

97.22

81.00

82.00

83.00

84.00

85.00

86.00

87.00

88.00

89.00

90.00

91.00

92.00

93.00

94.00

95.00

96.00

20

04

-09

-30

_1

6;4

9;4

8_

Me

gu

mm

_1

12

0,_

lot#

20

21

10

37

_(c

on

tro

l)_

01

.v2

00

4-0

9-3

0_

16

;49

;48

_M

eg

um

m_

11

20

,_lo

t#2

02

11

03

7_

(co

ntr

ol)

_0

1.v

/ M

eth

od

: Y

-18

80

-00

00

.vcm

8.0 19.0

Retention Volume (mL)

9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0

Overlay Plot: Right Angle Light Scattering (mV) Vs. Retention Volume (mL)

Method: Y-1880-0000.vcm

2004-09-30_16;49;48_Megumm_1120,_lot#20211037_(control)_01.v2004-09-30_16;49;48_Megumm_1120,_lot#20211037_(control)_01.v : Y-1880-0000.vcm

2004-09-30_17;20;40_Y-1880,_lot#1006732_01.vdt : Y-1880-0000.vcm

2004-09-30_17;51;32_Megum_1120,_lot#20211037_(control)_2nd_i : Y-1880-0000.vcm

2004-09-30_18;22;24_Y-1880,_lot#1006732_01.vdt : Y-1880-0000.vcm

Sample ID

“Absolute” M data as determined by TDA

Mw Mn Mw/Mn Rh [nm]

Polymer A

350 000 68 000 5.1 7.2

Polymer B

200 000 49 000 4.1 8.4

Sample ID

“Apparent” M data as determined by ELSD using PS standards

Mw Mn Mw/Mn Rh [nm]

Polymer A

50 000 22 000 2.2 N/A

Polymer B

78 000 26 000 3.0 N/A

Halogen Content of Polymer A and B by TDA SEC

-1.62

0.17

-1.50

-1.40

-1.30

-1.20

-1.10

-1.00

-0.90

-0.80

-0.70

-0.60

-0.50

-0.40

-0.30

-0.20

-0.10

0.00

0.10

20

04

-09

-30

_1

6;4

9;4

8_

Me

gu

mm

_1

12

0,_

lot#

20

21

10

37

_(c

on

tro

l)_

01

.v2

00

4-0

9-3

0_

16

;49

;48

_M

eg

um

m_

11

20

,_lo

t#2

02

11

03

7_

(co

ntr

ol)

_0

1.v

/ M

eth

od

: Y

-18

80

-00

00

.vcm

4.4 6.8

Log Molecular Weight

4.5 4.6 4.7 4.8 4.9 5.0 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7

Overlay Plot: Log Intrinsic Viscosity Vs. Log Molecular Weight

Method: Y-1880-0000.vcm

2004-09-30_16;49;48_Megumm_1120,_lot#20211037_(control)_01.v2004-09-30_16;49;48_Megumm_1120,_lot#20211037_(control)_01.v : Y-1880-0000.vcm

2004-09-30_17;20;40_Y-1880,_lot#1006732_01.vdt : Y-1880-0000.vcm

2004-09-30_17;51;32_Megum_1120,_lot#20211037_(control)_2nd_i : Y-1880-0000.vcm

2004-09-30_18;22;24_Y-1880,_lot#1006732_01.vdt : Y-1880-0000.vcm

Polymer A

Polymer B

Lo

g I

V

Log M

Distribution of UV Absorbing Co-monomer

SEC using “conventional” (RI, UV, ELSD, LS, VIS) detectors:

1. “Relative” MW

2. “Absolute” MW

3. Hydrodynamic radius – Rh

4. Radius of gyration – Rg

5. Conformation/branching information

6. chemical composition distribution within MW (some instances)

MALDI-TOF Mass Spectroscopy

For M+ of 1000 Da @U=15 KV, L=1.5 m

t = 2.792 X 10-5 S

q

m

U

Lt

2

OH

CO2H

HO

CO2HH3CO

OCH3

HO

MW=154.03 Da MW=224.07 Da

Sinapinic acid2,5-dihydroxybenzoic acid =337 nm

UV Absorption MatricesMatrix Assisted Laser Desorption Ionization

Time of Flight Mass Spectrometer

Flight Time vs. m/q

MW Determination of Polymers by MALDI-TOF-MS

10

50

1 BO-EO-BO 2013-115.0 0:P14 MS Raw

50

100

150

200

250

300

Inte

ns.

[a.u

.]

11

82

8 BO-EO-BO 2013-115.1 0:N14 MS Raw

50

100

150

200

250

300

Inte

ns.

[a.u

.]

11

95

9 BO-EO-BO 2013-115.2 0:L14 MS Raw

50

100

150

200

250

Inte

ns.

[a.u

.]

8000 9000 10000 11000 12000 13000 14000m/z

P, batch #1

P, batch #2

P, batch #3

Structural Elucidation by MALDI-TOF-MS

16

70

.4

15

26

.3

15

98

.4

16

42

.4

15

70

.3

17

14

.5

14

54

.2

13

82

.1

14

98

.2

17

86

.5

17

42

.5

16

86

.4

16

14

.4

17

58

.5

14

26

.2

15

54

.3 18

58

.6

14

82

.3

18

14

.6

13

38

.1

12

66

.1

11

94

.0

10

49

.9

13

10

.1

97

7.8

11

21

.9

19

02

.6

19

30

.7

12

38

.0

18

74

.6

19

74

.7

12

82

.0

20

02

.7

19

46

.7

13

98

.1

11

65

.9

20

46

.8

12

10

.0

11

37

.9

20

18

.8

20

74

.8

21

18

.8

200

400

600

800

1000

Inte

ns. [a

.u.]

1000 1200 1400 1600 1800 2000 2200 2400m/z

HO-(C4H8O)m-H

p-BO/EO

GPC-RI/MS

100

1000

10000

100000

1000000

11.5 12.5 13.5 14.5 15.5 16.5 17.5 18.5 19.5

Elution Vol. (ml)

Mo

l. M

ass (

g/m

ole

)

0

2000

4000

6000

8000

10000

RIU

Off-line SEC – RI/MALDI-TOF-MS of Polymers

4000 6000 8000 10000 12000 14000 m/z

MALDI-MS of the SEC fraction 14.0-14.5 ml

900 1100 1300 1500 m/z900 1100 1300 1500 m/z900 1100 1300 1500 m/z

MALDI-MS of the SEC fraction 16.5-17.0 ml

MMA

What we can learn from SEC-RI/MALDI-MS:

1. “Absolute MW ”

2. Composition/structure of polymer

3. End group information

SEC-RI Chromatogram

Why Oligomer Fraction Is Important

1. Product Status Information Worksheet (PSIW)

2. Polymer Exemption (PE) Submissions

Average Mn Fraction <1000 Fraction < 500

<10 K <25% <10%

>10 K <5% <2%

3. Pre Manufacturing Notice (PMN) Submissions

4. Good Laboratory Practice (GLP) Submissions

5. Food Contact Applications

Off-line SEC – MALDI-TOF-MS Hyphenation

10 11 12 13 14 15 16 17

0

100

200

300

400

500

fr.#

10

fr.#

9

fr.#

8

fr.#

7

fr.#

6

RI d

ete

cto

r re

sp

on

se, [m

Vxs

-1]

Retention time, [min]

3253

.3

3108

.8

3396

.7

2964

.6

3541

.1

2820

.6

3757

.8

* Fr7\0_B14\1\1Ref

0

100

200

300Inte

ns. [

a.u.

]

1882

.3 2026

.4

1738

.2

2170

.5

1594

.1

2314

.6

2458

.6

1450

.0

2602

.9

1305

.8

2746

.8

2890

.8

1161

.7

3035

.5

3179

.3

1017

.5

3323

.3

3467

.6

3611

.7

3755

.7

* Fr8\0_C14\1\1Ref

0

500

1000

1500Inte

ns. [

a.u.

]

1000 1500 2000 2500 3000 3500 4000 4500 5000

m/z

Sample ID

Molar Mass characteristics

determined by SEC-RI/MALDI-MS

Percentage of fraction below

Mw# Mn# Ɖ# <1000# <500#

P#1, B#1 2 400 1 500 1.6 15.7 2.0

P#1, B#2 2 400 1 500 1.6 15.5 1.9

P#2, B#1 2 100 1 500 1.4 15.3 1.9

P#2, B#2 2 100 1 500 1.4 15.1 1.9

Challenge: Determination % of fractions below 1000 and 500 g/mol but no standards

SEC – MALDI/MS Hyphenation

From Shimadzu Web page

Tetrapolymers: An Analytical Challenge

17

# of each monomer indicated by:

(a/b/c/d)a = # A, b = # B, c = # C, d = # D

Hydrophilic

Hydrophobic

Structure & Nomenclature

Tetrapolymer Analysis with ESI/MS

18

884.34

1088.46

1214.38

1384.44

1588.56

1758.62

1928.69

2132.80

2506.98

-MS, 0.0-5.0min #(1-149)

0

1000

2000

3000

Intens.

750 1000 1250 1500 1750 2000 2250 2500 2750 m/z

1/2/0/1_X,Y

2/2

/0/1

_X

,Y

1/1

/1/1

_X

,Y 1/2

/1/1

_X

,Y

2/2

/1/1

_X

,Y

2/3

/1/1

_X

,Y

2/4

/1/1

_X

,Y

3/4

/1/1

_X

,Y2302.87

3/5

/1/1

_X

,Y

4/5

/1/1

_X

,Y

2711.08

5/5

/1/1

_X

,Y

2881.16

5/6

/1/1

_X

,Y

MWmax = ~3000 u

+ Can hypothesize chemical composition of observed components

- Spectra dominated by singly charged, low MW species

- Congested mass spectra

- Unknown extent of ion suppression

- Unknown instrument response versus molecular weight & chemical composition

UPLC/ESI-MS of Tetrapolymers

19

Accurate mass analysis Bruker MicrOTOF-Q II

ESI-/MS

External m/z calibration

HighVoltage

Electrospray

IonizationTime of Flight (TOF) Mass Analysis

Ion

Source

Detector

Refle

ctro

n

ESI/TOF Accurate Mass MS Identifies Eluting Compounds

C4

UHPLC

column

Compounds

elute

over time,

according to

their polarity

Specific Goals:

Reduce mass spectral complexity

Lessen ion suppression

Increase mass range

Solution: LC/MS!

Ultra-High Performance Liquid Chromatography Waters Acquity UPLC

Waters Acquity UPLC BEH300 C4 1.7 μm 1.0 x 100 mm

3

1090.4950

1260.5560

1605.5714

0

100

200

300

400

800 1000 1200 1400 1600 1800 2000 2200 2400 2600 m/z

UHPLC/ESI/MS of Tetrapolymer #1

3

5/b/2/1 (b = 3-11)

MWmax =

~4200 u

714.27731-

959.36501-

0

1000

2000

3000

4000

5000

200 600 1000 1400 1800 m/z

1

2

680.22001-

0

200

400

600

800

1000

Inte

nsity

200 600 1000 1400 1800 m/z

0/2/0/1

1 21/1/0/1

0/3/0/1

6000

+ Reduced mass spectral

complexity

+ Increased MW range

20

Further Understand Capabilities of LC/MS

Column: Shodex X-linked PS/DVB, 300x8.0 mm

Solvent: 5% formic acid in THF

Flow Rate: 1.0 mL/min.

Detector: RI

1 2 3 4 5 6 7 8 9

10,000 g/mol 2900 g/mol

#1

To Answer These Questions:

• Size Exclusion Chromatography vs. PS standards

• SEC Fractionation followed by UHPLC/MS and UHPLC/ELSD of fractions

Tetrapolymer #1, SEC Fraction 3

UHPLC/ELSD

1 2 3 4 5 6 7 8 9 1

0

UHPLC/ESI-/MS

• SEC Fraction 3: Polymer present by RI

• UHPLC/ELSD: signal from 8-12 min

• UHPLC/MS: no signal

+ Polymer eluting from UHPLC column over entire MW

range

- High MW polymer NOT detected by ESI/MS

- Similar results for SEC Fraction 4

22

#1, SEC Fraction 5 (3600-5400)

2 D1 D

0 D

1 2 3 4 5 6 7 8 9 1

0

UHPLC/ELSD

UHPLC/ESI-/MS

• SEC Fraction 5:

successful detection

w/ both ELSD and

ESI/MS

• Relative RTs support

hypothesized

monomer

composition

23

1551.5257

-MS, 8.9-9.0min #(529-538)

0

50

100

150

200

250

Intens.

1000 1500 2000 2500 m/z

1832.2701 1835.6339

-MS, 8.9-9.0min #(529-538)

20

40

60

80

100

Intens.

1828 1830 1832 1834 1836 1838 1840 m/z

#1, SEC Fraction 5; Example MS Data

MW: 3600-5400 u

6/13/3/23-

2 D

1 D

0 D

MWmax = 5500 u

3-

2-

4-

+ MWmax increased to ~5500 g/mol!!

+ MWmax agrees with SEC results for this fraction

24

#1, SEC Fraction 6; MS Data

25

MW: 1700-3800 u

1069.3327

1541.0418

-MS, 11.8-12.1min #(703-722)

0

100

200

300

400

Intens.

500 750 1000 1250 1500 1750 2000 2250 m/z

3/8/2/02-

3/9/2/02-1010.2982

1430.9355

-MS, 7.3-7.5min #(435-445)

0

200

400

600

Intens.

800 1000 1200 1400 1600 1800 2000 2200 m/z

1298.8999

1962.7183

-MS, 8.5-8.8min #(509-526)

0

500

1000

1500

2000

Intens.

500 750 1000 1250 1500 1750 2000 2250 m/z

2/5/2/12-

2/6/2/12-3/4/2/22-

3/5/2/23-

1/b/2/1 4/b/2/1

3/b/2/12/b/2/1

5/b/2/1

3/b/2/0

4/b/2/02/b/2/0

5/b/2/0

1/b/2/2

2/b/2/2

0/b/2/2

3/b/2/2

1 2 3 4 5 6 7 8 9 1

0

• RTs reflect

monomer

composition

• “3D” Separations

• LCCC of “B”

Summary of UHPL/ESI/MS Experiments

UHPLC/ESI-/MS developed for tetrapolymer characterization

Can observe up to ~4000 g/mol

Results dominated by low MW species

SEC Fractionation followed by UHPLC/ESI-/MS and UHPLC/ELSD of tetrapolymers

Material eluting off UHPLC column over entire MW range

Can observe up to ~5500 g/mol with UHPLC/ESI-/MS

Simplifies MS data, facilitates interpretation

Cannot observe >5500 g/mol, upper ~40% of MWD

Low MW trends don’t necessary represent entire MWD

SEC/UHPLC/ESI-/MS with PolymerixTM data analysis to explore differentiation of polymer samples

Limited to < 5500 g/mol

Limited to ions generated by ESI-/MS

26

+MS, 5.2-7.0min #(310-417), Background Subtracted

0

2

4

6

Intens.

500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 m/z

LC/MS & LC/CR/MS: PEG 5000

27

PEG5000_8499.d

0

1000

2000

3000

Intens.

0 1 2 3 4 5 6 Time [min]

ESI+/MS

ESI+/CR/MS

UHPLC/ESI+/MS TIC

1+

[M+nNH4]n+

[M+NH4]+

784.5019

+MS, 1.7-2.0min #(99-116)

0

500

1000

1500

2000

2500

Intens.

1000 2000 3000 4000 5000 m/z

6+

5+

4+

3+

On-line LC-UV-RI-ICP/MS Hyphenation

Key outcomes:

• Demonstrated feasibility of

ICP/MS as an on-line LC

detector

•Separation modes: HDC,

SEC/GPC and HPLC

• Solvents:

• Aqueous volatile buffers

• Organic solvent used for

the first time

• Extended range of

organic solvents

compatible with ICP/MS

• Elements: All that are

detectable by ICP/MS

HDC cartridge

SEC column set

HPLC column

Shodex RI detector

Agilent 1100 LC system

Agilent 7700x

ICP/MS

UV detector

ICP/MS Schematics

Sample ID

M data determined using PMMA standards and RI detection

% of fractions below

Mw Mn Mw/Mn <1000 <500

batch# 21 10 000 3 700 2.7 4.2 3.0

lot#811002 9 500 3 200 3.0 5.2 3.8

lot#810078 10 000 3 500 2.9 3.6 2.6

lot#96640-46 9 000 3 400 2.6 4.6 3.1

batch#5 9 000 3 300 2.7 4.9 3.5

ZW7105P# 5 400 2 000 2.7 9.8 5.8

lot#PC-B400004710, 30K Lb

10 000 3 200 3.1 n/d n/d

On-line SEC-RI-ICP/MS of Polyester Resins

On-line SEC-RI-ICP/MS of Polyester Resins

0 100 200 300 400 500

0

50

100

150

200

250

300

350

400

y=796.6

6441x (R

=0.99986)

H3PO

4

ICP

/MS

resp

on

se [

x10

3 c

ou

nts

]

Concentration, [ppm]

Sample name

Heteroatom Containing Monomer Content and Its Distribution by SEC-ICP/MS

Polymer

ResidualHeteroatom containing monomer

UnknownTotal

[%]

batch# 21 1 0.05 0.25 1.3

lot#811002 0.9 0 0.2 1.1

lot#810078 0.9 0.03 0.2 1.1

lot#96640-46 1 0.1 0.3 1.4

batch#5 2 0.1 0.5 2.5

ZW7105P 0.9 0.3 0.2 1.3

lot#PC-B400004710, 30K Lb 1.0 0.05 0.35 1.4

Heteroatom Containing

Monomer

Heteroatom Response

From Polymer

Characterization X-Polymer in Polymer FormulationR

I d

ete

cto

r re

sp

on

se,

[mV

]

Retention Time, [min]

PS Foam 2290

Neat FR-63

Neat FR-63 at 2% load

X-Polymer and Polymer Formulation co-elute

Amount of X-Polymer in Formulation is low (~2-3%)

Polymer Formulation

Neat X-Polymer

Next X-Polymer at 2% load

Impact:

1. Broadening of X-Component in Polymer Formulation revealed with high

sensitivity

First clear evidence of

broadening of X-Polymer

as result of processing

High M

Species

ICP

/MS

dete

cto

r re

sp

on

se,

[co

un

ts]

Retention Time, [min]

Low M

species

(polymer chain

scission)

Neat X-Polymer

X-Polymer in PF

X-Polymer Distribution Before and After Processing

On-line SEC-FTIR Hyphenation

Fourier-transform infra-red (FTIR) spectroscopy is a well-established

laboratory analytical technique

Very sensitive to functional groups, ideal for ‘fingerprinting’ of

compounds

Typically used to obtain a ‘batch’ type static measurement using the

spectrometer and a sample holding system, e. g. pressed pellets,

windows or ATR crystals

Interfacing the FTIR spectrometer with a liquid flow system via a flow

cell historically difficult due to sensitivity and data handling issues

With increasing sensitivity of detectors and development of new data

handling routines FTIR detection coupled to chromatographic systems is

now possible

SEC-FTIR hyphenation allows direct measurement of chemical

composition distribution within molecular weight using one detector

On-line SEC – FTIR Hyphenation

Overview

Operating principle:

Nebulize and desolvate LC

eluent

Deposit particle stream onto

a cooled, rotating ZnSe disk

Analyze deposited track with

FT-IR in real-time, can

rescan deposited track Compatible with most LC

solvents

Can desolvate 100% H2O

and trichlorobenzene

Automatically adjusts for

gradient conditions Minimal peak broadening on

deposition → ~ few seconds Good sensitivity → ~ 0.1 to 1 μg

Courtesy of Spectra Analysis

Bulk Infrared Spectra of PMMA and PEMA

Unique

band

in PEMA

Poly(methyl methacrylate)

PMMA

Poly(ethyl methacrylate)

PEMA

C=O

stretch

SEC-IR Data Analysis

SEC-IR Chromatograms EMA Content

SEC-FTIR of P(MMA-EMA) Copolymers

0%

25%

50%

75%

100%

0

1

2

3

4

5

6

7

8

3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0

EMA

Co

nte

nt

(wt

%)

Int.

Ab

s. (

CO

Str

etc

h)

log (Molecular Weight)

SP-1, CO Stretch SP-2, CO Stretch SP-1, EMA Content SP-2, EMA Content

SP-1

SP-2

Heterogeneity PMMA-EMA Copolymers

Suspension Polymerization Emulsion Polymerization

Applications:

competitive analysis

polymer composition as a function of MW

polymer grafting/blending

block copolymer vs. random copolymer

impurity and metabolite analyses

On-line SEC/GPC-NMR Hyphenation

CryoFit ™ (30µL Flow cell)

Four-time signal enhancement

comparing to conventional NMR

Operation modes: Stop-flow and On-flow

NMR experiment: 1H, 2D

1mL/min

20-100µL (HPLC)

100 µL (SEC)

Separation modes:

1. Size (SEC)

2. Composition (HPLC) L= 15’ , ID=0.2mm

Mixture of p(BA-b-MMA) and p(MMA)

Peak 1 Peak 2

Peak 1: pBA-b-MMA (~87k)

Peak 2: pMMA (~14k)

SEC

Mobile phase: THFDetector: ELSD

Sample Concentration: 10mg/g/component

Column set: 2PLgel Mixed D (300x7.5 mm ID) plus guard (50x7.5mm ID)

THF THF

2I

2H2S

3

1

1

3

45 6

7

2S

2H

P(B

A-b

-MM

A)

MW

~ 8

7k

P(M

MA

)

MW

~14

k

On-line SEC-NMR Hyphenation

Macroion Mobility Spectrometer

Large size range: 2.5 to 150 nm

∝ 8 kDa to 600 MDa

Wide variety of analytes

Non-covalent complexes

Quantitative

Resolve complex mixtures

Size distribution (not average)

High throughput: minutes

Hyphenation: SEC-IMS ; LC-IMS

Size and Abundance of High MW Analytes

Courtesy of TSI Inc.c

MacroIMS System Operation

analyzer

voltage

blowerfilter saturated

vapor in

Condenser

light

beam

detector

+ HV -

Air + CO2

Soft x-ray

source

+1

ions

Charge-reduced

ESI Source

Ion Mobility

Drift CellMacroion Detector

Generation of singly-charged

macroions in the gas-phase

Separation of macroions at atmospheric

pressure based on ion mobility

Condensation growth of macroions

followed by laser photometer detection

Electrospray solution >> Ion mobility separation >> Detection

Courtesy of TSI Inc.

Conclusions

• SEC/GPC using “conventional” detector(s) including RI, UV, ELSD,

MALS, and VIS is very robust and cost effective analytical tool but

provides limited information on analyzed samples

•SEC/GPC hyphenated techniques using “advanced” MALDI-TOF-

MS, ESI-MS, ICP/MS, FTIR and NMR detector capabilities deliver

significantly richer information on analyzed samples but add to

complexity of the experimental set-up and data processing resulting

in higher cost

•Further improvements/advances in both instrument and software

technologies are required to minimize the complexity of experiment

using “advanced” detectors so SEC/GPC hyphenated techniques

become “routine” analytical approaches for polymer characterization

in both academic and industrial setting

Acknowledgements

Jim ALEXANDER

Lu BAI

Michael BENDER

Michael CLARK

Matt CROWE

Wei GAO

Towhid HASAN

Samir JULKA

David MEUNIER

Mark RIKARD

John STUTZMAN

Scott WILLS

Jian WU

Wen-Shine YOUNG

Tianlan ZHANG

Zhe ZHOU

Dow Chemical

• Founded in 1897 by Herbert H. Dow in Midland, Michigan

• Combine the power of science and technology to

passionately innovate what is essential to human

progress

• Deliver a broad range of

technology-based products

and solutions to customers in

approximately 160 countries

• Manufacture more than

5,000 products at 197 sites in

countries across the globe

• Employ approximately 52,000 people worldwide

Business R&D • 80% people & resources

• Customer-centric

• Application development

Core R&D

• 20 % people & resources

• Discovery research

• Deep technical expertise

Dow R&D

$ 1.7 Billion ~6,300 Staff

Freeport, TX

(27)

Midland, MI

(104)Collegeville, PA

(50)

Terneuzen, Netherlands

(17)Shanghai, China

(31)

~230 people globally

5 Major Sites

Globally integrated delivery

Comprehensive analytical capability

>$100 million Installed Capital

Analytical Sciences - Global Footprint

Mumbai, India

(3)

Horgen, Switzerland

(3)

Kawasaki, Japan

(1)

Process

DevelopmentApplication

OptimizationMaterials Discovery

Conventional Size Exclusion Chromatography (SEC)

Polymer is prepared as a dilute solution in the

eluent and injected into the SEC system

The SEC column is packed with porous beads

of controlled porosity and particle size

Large molecules are not able to permeate all

of the pores and have a shorter residence

time in the column

Small molecules permeate deep into the

porous matrix and have a long residence time

in the column

Polymer molecules are separated according

to molecular size, eluting largest first, smallest

last

Column set of 2 or 3 columns (300x7.5-8.0

mm ID)

Typical Flow rates: 1-2mL/min in order not to

damage column bed by exceeding its back

pressure limit

Typical run times: 30-60 min

Molar ratio: PEO/PPO/Si-CH3/Propyl-linker ~69/10.4/19.4/1

On-line SEC-2D NMR of PDMS/EO/PO Polymer Mixture

SEC

PDMS/PEO/PPO PEO/PPO

Column set: 2PLgel Mixed D

(300x7.5 mm ID)

Mobile phase: CHCl3

Proposed

Grafting

Chemistry

The CryoFit ™ / CHCl3 provides excellent

sensitivity for 2D NMR experiment

The SEC-2D NMR generates both 13C

and 1H NMR data plus their correlation.

This enables detailed structural

elucidation at the molecular level.

Objective: To understand how the Polyol is grafted to PDMS

On-flow SEC-NMR of Block Copolymer Mixture

This data shows that the EO/BO ratio changes as a function of MW, with low MW polymers containing mostly pBO.

EOBO

EO/BO molar ratio ~1.0/0.30

~1.0/0.28

~1.0/0.31

~1.0/0.38

~1.0/0.53

~1.0/0.96

~1.0/2.53

~1.0/5.38

High Mw

Low Mw

sec/gpc applications using conventional and advanced … · 2016. 6. 1. · 1 130k 560k 310k 200k...

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