GPC/SEC/GFC basics Webinar: GPC Basics PSS Polymer Standards Service GmbH presentation for January 20, 2016 Dr. J. Preis 1 and Dr. D. Lohmann 2 1 Polymer Standards Service (PSS) GmbH; Mainz, Germany; 2 Polymer Standards Service (PSS) USA; Amherst, MA; USA
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PSS Webinar GPC/SEC/GFC basics · GPC/SEC/GFC basics Webinar: GPC Basics PSS Polymer Standards Service GmbH presentation for January 20, 2016 Dr. J. Preis1 and Dr. D. Lohmann2 1 Polymer
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GPC/SEC/GFC basics
Webinar: GPC Basics
PSS Polymer Standards Service GmbH presentation for
January 20, 2016
Dr. J. Preis1 and Dr. D. Lohmann2
1 Polymer Standards Service (PSS) GmbH; Mainz, Germany; 2 Polymer Standards Service (PSS) USA; Amherst, MA; USA
About PSS
Provides instruments and turn-key systems for the efficient and
comprehensive characterization of macromolecules.
Manufactures high-resolution GPC/SEC columns and
develops new stationary phases.
Develops compliant software for real-time data
acquisition and powerful and easy-to-use data evaluation.
Manufactures reference materials and validation kits.
Offers contract analysis, method development, validation services, training
courses and webinars.
PSS Headquarter with production facility and R&D center is located in Mainz,
Germany.
Webinar: GPC Basics Page 2
Outline
• Introduction
• Fundamentals
• Principle of separation
• Hydrodynamic volume and intrinsic viscosity
• Molar mass average values Mw and Mn
• Calibration and resolution
• Method development
• Detection
• Concentration detectors
• Molar mass sensitive detectors
Webinar: GPC Basics Page 3
Introduction
Webinar: GPC Basics Page 4
Macromolecules are everywhere
Automotive
Construction
Cosmetics
Feed & Food
Packaging
Paper & Wood
Pharma
Introduction
Webinar: GPC Basics Page 5
Synthesis of macromolecules
One or more different monomers form chains
Molar mass distribution (MMD)
Chemical composition distribution (CCD)
Molecular architecture distribution (MAD)
Structural type distribution (STD)
Functionality type distribution (FTD)
Introduction
Webinar: GPC Basics Page 6
Solution Molar mass distr.(MMD) Molecular architecture distr. (MAD)
Separation GPC/SEC GPC/SEC
Detection RI, UV, ELSD, MS,
Viscometer/LS + RI/UV
Viscometer/LS + RI/UV
Webinar: GPC Basics Page 7
Polystyrene
SDV, 3μm,
3 x 100, 3 x 1000,
THF, 0.25ml/min
W (
log M
)
molar mass
Question:
• What is the molar mass of
such a polymer?
• How can it be quantified?
Molar mass average values
Molar mass average values
How can we describe a polymer chain distibution
What is the molar mass of a polymer?
What are molar mass average values?
Webinar: GPC Basics Page 8
> 1
Number average molar mass Weight average molar mass
Polydispersity index
Molar mass distribution (MWD)
GPC offers the opportunity to detect the whole molar mass or molecular
weight distribution (MWD) of a polymer
MWD tells you the “true story” about the polymer
Mn and Mw are only single values
Webinar: GPC Basics Page 9
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
Molar mass [Da]
1*105
5*105
1*106
W(log
M)
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PC
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ity, B
uild
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PNBMA UV 230nm
PNBMA RI
0
10
20
30
40
50
60
70
80
90
100
molar mass [Da]
1*102
1*103
1*104
1*105
norm
. W
(log M
)
PS
S W
inG
PC
Un
ity, L
AB
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, In
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Example: MWD of Polymers
Low molar mass tailing
bimodal distribution
Difference between GPC/SEC and LAC
GPC/SEC
GPC/SEC is a pore size
limited, diffusion controlled,
partition chromatography
A pure GPC/SEC
mechanism has no
interaction with the matrix
GPC/SEC needs a polarity
balanced system.
Webinar: GPC Basics Page 10
LAC
• Interaction chromatography
(LAC) uses the
differences in the chemical
(polarity) or
structural nature of the
sample for the
separation
Polymer Interaction I
Homopolymer A
Webinar: GPC Basics Page 11
Homopolymer B
Adsorption of homopolymer
B on the matrix
Polymer Interaction II
Webinar: GPC Basics Page 12
Webinar: GPC Basics Page 13
GPC/SEC
different size = different hydrodynamic radius different color = different chemistry
GPC/SEC Column
Separation by Size
How does GPC/SEC work?
GPC = Gel permeation chromatography
SEC = Size exclusion chromatography
GPC/SEC Basics
GPC/SEC Separation is based on the size of a molecule in solution
RI reflects injected mass; Visco/LS injected mass and molar mass
Webinar: GPC Basics
Webinar: GPC Basics Page 34
column viscometer RI
visco [ ]·c RI c
visco/RI [ ] + universal calibration
curve log([ ]·M)
column LS RI
LS (dn/dc)2 ·M·c RI c
LS/RI (dn/dc)2 ·M
M
M
Molar Mass Sensitive Detection
and Applications
PSS Webinar Series 2013
Webinar: GPC Basics Page 35
Light Scattering
zylindrische Meßzelle
Lichtwellenleiter
(Eluat ein/aus: unter/über Ebene)
(Winkelpos ition)
LASER
cylindrical cell
(solvent in/out:
under/above
plane)
optical fibre
(angle position)
Cell design 7 angle SLD7000
Webinar: GPC Basics Page 36
Application Example Viscometer:
In combination with RI used to measure the intrinsic viscosity [ ]
PSS DVD1260
Viscometer bridge design :
2 signals from viscometer:
Delta pressure
Inlet pressure
Differential pressure
Inlet pressure
R2
R4
B
R1
A
R3
From Columns
Waste/concentration detector
Sample path Solvent path
Viscometer
Webinar: GPC Basics Page 37
Visco/LS
Advantages Light Scattering
- Absolute method: measures directly M at every elution volume
- No calibration standards required
Ideal for (homopolymer) high molar mass samples, and proteins where
absolute molar masses are required. Advantages Viscometry
Measures intrinsic viscosity directly
Independent of refractive index increment dn/dc
Absolut molar mass for copolymers
Branching information
Universal calibration required Ideal for homopolymers , copolymers and branched samples
PSS live Webinar : June 8 , 2016
PSS live Webinar: September 14 , 2016
Summary
GPC/SEC is a well established method for polymer characterization
GPC/SEC is relative method, calibration is required
True molar masses only if polymer and calibration standards are the same polymer type
Mw, Mn and Mp and any other molar mass average value and PDI can be determined
Mechanism is purely entropic, no interactions
Separation according to the size of the molecule, Vh not the molar mass
Porosity and particle size of the columns have to be chosen according to the separation task
GPC/SEC in combination with hyphenated coupling techniques provide deeper inside into polymer properties (branching, composition or absolute molar mass)
Webinar: GPC Basics Page 38
PSS GPC/SEC Training Cource (Theory and Praxis) in Mainz/Germany: September 19-20 , 2016