GPC Consumables An Overview of Organic and Aqueous GPC ... · aqueous GPC • Different...

GPC Consumables

An Overview of Organic and

Aqueous GPC Column

Solutions

1

Agilent Technologies Total GPC Solution

• GPC Columns

– GPC Standards

• GPC Instrumentation

– GPC Software

• GPC Expertise

GPC/SEC Consumables

• GPC/SEC consumables based on

GPC products originally from Polymer

Laboratories, who were acquired by

Varian, Inc.

• These can be split into two areas

• First area is columns for liquid

chromatography containing mainly

polymer-based packing materials

(PS/DVB, coated materials, some other

co-polymers)

• Second business area are well-

characterised polymer standards for use

in GPC/SEC calibration procedures

Standards

17%

Organic

Cols

72%

Aqueous

Cols

11%

4

Synthesis of Porous Particles

High cross-link content

gives a rigid, low swelling

product with a well-

defined pore structure

• The column products can be divided into two application areas – organic GPC

and aqueous SEC

• PolarGel is a cross-over

Organic GPC

PLgel, PlusPore, Olexis

Aqueous SEC

PL aquagel-OH

Copolymers of styrene

and divinyl benzene Coated or now copolymerised

–OH functionalised materials

Column Ranges

----PolarGel----

Differentiation of Columns Products

• Like other LC columns, GPC/SEC columns are differentiated by particle

chemistry, pore size and particle size

• PS/DVB is used for organic solvents,

• Hydrophilic copolymers are used for aqueous compatible columns

• Pore size is carefully controlled to determine the resolving range of the column

– what range of polymer molecular weights can be separated by the column

• But the wider the resolving range of the column, the lower the resolution

• Products range from 50Å to 10E6Å (resolving range of the product line up to

100,000,000 g/mol)

• Particle size reflects the resolving range – large molecule samples need large

particle size column to stop shear degradation of samples on-column

• Particle size of product range from 3μm to 20μm

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Column Types

• The factor that principally controls which type of column is selected for a GPC

experiment is the solvent

• Many polymer dissolve in only very limited numbers of solvents

• The columns used must be compatible with the solvent of choice

• Most importantly, the size exclusion mechanism must be maintained

• Agilent have two main ranges of GPC column for organic solvents

• The properties of each range that must be considered when selecting them

for an application shall be presented

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Organic GPC

• The vast majority of commercially important polymers are only soluble in

organic solvents such as tetrahydrofuran, toluene or trichlorobenzene

• For these applications a column packed with material compatible with these

solvents must be chosen

• Almost universally columns packed with insoluble porous beads of

polystyrene cross-linked with divinyl benzene are used (PS/DVB)

• The majority of manufactures use columns of this type

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Styrene/Divinyl Benzene Columns - PLgel

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PLgel solvent Compatibility

• Columns can be used in a

wide range of solvents

• Transfer between solvents

is possible assuming care is

taken

• The column user guide

details the procedure

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PLgel Column Range

• The extensive range of

products has variation in pore

size, particle size and column

dimensions

• The packing materials are

identical in terms of surface

chemistry

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Or use PLgel MIXED Bed columns

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Individual Pore Size Combination Versus

MIXED Gel Columns - Polydisperse Sample

Eluent THF

Flow rate 1.0 ml/min

Detector UV 254nm

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PLgel MIXED Bed Calibrations

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PLgel MIXED Bed Application Guide

SMALL

MOLECULES

ULTRA-HIGH MW

POLYMERS

Organic GPC separations Across the Molecular weight Range

High MW polyethylene

Columns : 3 x PLgel 10um MIXED-B

Eluent : TCB + 0.0125% BHT

C12 to C36 hydrocarbons

Columns : 2 x PLgel 3µm 100Å

Eluent : THF

PLgel – Application Across the Molecular Weight

Range

Organic GPC separations across the solvent polarity range

NON-

POLAR POLAR

Polylactic acid analysis

Columns : 2 x PLgel 5um MIXED-D

Eluent : Chloroform

Starch analysis

Columns : 4 x PLgel 20µm MIXED-A

Eluent : DMSO + 5mM NaNO3

PLgel – Application Across the Polarity Range

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PLgel LS Columns

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PLgel LS Columns

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Special Case – Polyolefin Analysis

Requirements:

High mechanical stability, high temperature operation

Increased molecular weight resolving range to 100,000,000 g/mol

Larger particle size than 10µm to ensure no shear degradation

Smaller particle size than 20µm to ensure good efficiency

• Often, it is the inlet frit that

causes shearing

• PLgel Olexis columns have a

narrow particle size

distribution and so can employ

larger frits, reducing the

possibility of shearing

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• Maximum resolution with minimum shear degradation

• The packing material is the same as the PL ‘LS’ product line, and so is

especially suited for light scattering applications

PLgel Olexis Columns

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PS/DVB miniMIX Columns

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miniMIX Solvent Consumpsion

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PS/DVB Preparative Columns

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Comparative Preparative Separations

• Preparative columns give

identical chromatography to

analytical columns under the

right conditions

• Method development can

be performed on the

analytical columns, reducing

the risk of damage to

expensive preparative

columns

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Polar and Aqueous SEC Columns

• There are a wide variety of columns available for polar and aqueous GPC

• This presentation shall introduce the most common types of column

• This information can act as a reference

• Applications on the various columns shall also be discussed

• We have performed many applications on our columns, so even if your

application is not shown here, we’ve probably done it!

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Aqueous GPC

• A growing number of polymers are water soluble

• Interest in recycling, renewable resources and biomedical applications has led

to increased interest in this area

• There are lots of different chemistries of packing materials employed for

aqueous GPC

• Different manufacturers use different column types

• Columns are available as individual or MIXED type and in a range of pore,

particle and column dimensions, just like the organic GPC columns

• We shall also discuss a new packing material that can be used in organic and

aqueous solvents

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PL Aquagel-OH Columns

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PolarGel Columns

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PolarGel Columns

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PolarGel-M Calibrations

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Peak Shapes of Polar Compounds

• High purity

• Very narrow polydispersity

• Extremely well characterised

Most commonly used polymer calibrants

Polystyrene - THF, toluene, chloroform, TCB

Polymethyl methacrylate - MEK, ethyl acetate, acetone,

DMF

Polyethylene oxide/glycol - aqueous eluents, DMF, DMSO

Calibration Standards for Conventional GPC

Narrow standards

Polystyrene

PMMA

PEG/PEO

Polysaccharide

Polyacrylic Acid

Polyethylene

GPC Calibrants in different polymers

EasiCal pre-prepared calibrants for GPC/SEC

EasiCal PS-1 separation on

3 x PLgel 10µm MIXED-B

Spatula A Spatula B

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EasiVial pre-weighed standards for GPC/SEC

Vial Mp Mass (mg)

RED 6,035,000 0.8

483,000 1.6

19,720 2.4

1,260 3.2

YELLOW 3,053,000 0.8

184,900 1.6

8,450 2.4

580 3.2

GREEN 915,000 0.8

60,450 1.6

3,370 2.4

162 3.2

Narrow Standards Available

Mn - number average molecular weight

Mw - weight average molecular weight

Mv - viscosity average molecular weight

Mp - peak molecular weight by GPC

For GPC calibration Mp must be used

Characterisation of Narrow Polydispersity

Polymer Standards

CERTIFICATE OF ANALYSIS

Polystyrene Batch Number 20132-4 Mp 30,300

GPC Light scattering Viscometry

Mp (g/mol) 30,300

Mn (g/mol) 29,800

Mw (g/mol) 30,150 30,400

Mv (g/mol) 30,100 29,630

Mw/Mn =1.02 rg = 2.9 nm [ ] = 0.1795

Mp, Mn, Mw & Mv are the respective peak, number, weight and viscosity molecular weight averages

Mw/Mn = molecular weight distribution or polydispersity ratio

rg = radius of gyration [ ] = Intrinsic viscosity

Full details of analytical conditions are described overleaf

The above characterisation data has been measured according to

Polymer Laboratories Quality Assurance procedures

N.W.Titley P.J.Scott

Quality Assurance Dept.QCFQ120

Issue 02 08/03/99

Gel Permeation Chromatography Light Scattering

Viscometry

Summary

table

MWD from

GPC

Light

scattering

(Zimm plot)

Dilute

solution

viscometry

Batch

number for

traceability

Assigned

Mp

Organic

Aqueous

Polar Organic

Let’s take a look at some applications…

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Applications in General Polymers

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Applications in Elastomers Analysis

Elastomers Butyl rubber in Hexane

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Oil Extended rubber Styrene-butadiene rubbers

Applications in Elastomers Analysis

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Applications in Polyolefin Analysis

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Applications in Polyolefins

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Applications in Engineering Polymers

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Applications in Engineering Polymers

GPC Consumables An Overview of Organic and Aqueous GPC ... · aqueous GPC • Different...

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