Agilent GPC Solutions

Polymer Labs Is Now Part Of Agilent Technologies

Agilent PL-GPC 220

Fully integrated, high-temperature dedicated GPC system

• Operates from ambient to 220 ºC, covering all GPC applications

• All sample carrying components heated to required temperature

– Eliminates sample precipitation

• High temperature detectors housed

inside the oven

– Refractive Index (Included)

– Viscometer (Optional)

– Light Scattering (Optional)

• Powered by Agilent 1260 pump

– Includes degasser

• Dedicated control software

– PL-GPC 220 Control

• Cirrus GPC software for data analysis

Accurately controlled column

oven with integrated injection

system, columns and detector(s)

Temperature controlled

solvent delivery module

with solvent reservoirs,

Agilent pump and degasser

Dual temperature

zone autosampler

prevents sample

degradation

PL-GPC 220

High precision

Agilent pump

ensures

reproducible

results even

in viscous

solvents

Sample is heated from injection to waste to maintain sample solubility & stability

Solvent Delivery

-56c.005 -56c.009 -56c.007 -56c.008 -56c.006

0

50

0 15

The flow rate reproducibility has been verified

by experimentation and reflect the total system

performance. The value quoted has been

calculated from analyses performed in THF at

40°C and TCB at 160°C

Type Specification

Hydraulic system Dual piston in series pump with proprietary servo-controlled

variable stroke drive, floating pistons

Flow precision ≤0.07 % RSD, or ≤ 0.02 min SD whatever is greater, based on

retention time at constant room temperature

Flow accuracy ± 1 % or 10 μL/min whatever is greater

Built-in Degasser 4-channel degasser

Injection point Hot Zone

Warm Zone

50

100

200

Te

mp

era

ture

(C

)

-20 -10 0 10 20

Vial Position

Carousel Motion

Injection Point

Agitated

PL-GPC 220 Autosampler

Dual Zone Autosampler

40 vial position carousel

2 ml glass vials with crimped aluminum caps

Sample can be slowly stirred prior to injection

Two zone heating, minimized risk of sample degradation

PL-GPC 220 Autosampler

Effect of Autosampler Temperature

2009 Agilent Innovations Seminar

Analysis of commercial polypropylene samples held in carousel for prolonged

period of time

Without dual zone heating, significant degradation of the sample can occur

over extended periods in the autosampler

By controlling the temperature profile, degradation can be minimised

Oven To Injection

Valve Injection system

Vial is transported up to the column oven

Vial equilibration time in the oven is

programmable

Excess solution returned to vial

No risk that the polymer will precipitate

out of solution and cause a system

blockage

Injection precision RSD <1% with no

cross contamination

PL-GPC 220 Autosampler

Hot

Cold

Columns

Pump

Injection System

Electrically actuated injection valve

Flushed fixed loop injection Interchangeable loop volume, 5 - 500 µl

Loop and valve in oven Eliminates sample precipitation and blockages

No contact between solvent

and syringe

Avoids sample carryover and contamination of syringe

Extends lifetime and reduces maintenance required

Jul14.011 Jul14.007 Jul14.008 Jul14.009 Jul14.010 Jul14.006 Jul14.012

Response

Minutes

0

30

5 8 11 14 17 20 23 26 29 32

Djul14.012 Djul14.006 Djul14.007 Djul14.008 Djul14.009 Djul14.010 Djul14.011 Djul14.005

dw

/dlo

gM

logM

0.0

0.1

0.2

0.3

0.4

0.5

2 3 4 5 6 7

Overlaid raw data

chromatograms

Overlaid molecular weight

distributions

Repeatability of GPC (polyethylene)

Injection No. Mn Mw Peak Area

1 17,289 76,818 333851

2 16,988 77,434 335496

3 17,248 77,514 332616

4 17,251 77,052 335635

5 17,348 76,520 334212

6 17,487 77,728 333511

7 16,898 77,578 335642

8 17,457 77,288 334923

Mean 17,302 77,241 334485

s.d. 220 687 1048

% variance 1.3 0.5 0.3

Column Oven

Multi-heater (x8), forced air oven

Rack mounted GPC columns

Up to 6 x 30cm columns

Injection valve

DRI detector

Vapour sensor

High temperature, precise column oven

Easy access for simple column change and routine maintenance

Fully enclosed system, complete outer surface of unit at safe temperature

Temperature range of ambient to 220 °C

Temperature stability: ≤0.05 °C/hour

Space for integrated Viscometer and

Dual Angle Light Scattering detectors

DRI

Viscometer

Light scattering detector

Injection valve, columns and up to three detector modules

through to waste can be heated to 220 °C in the same oven

• Critical to maintain sample solubility throughout the analysis

• Only available system on market that is fully integrated

Temperature stability is key, and the PL-GPC 220 is maintained

at ≤0.05 °C/hour

Triple detection within the PL-GPC 220

Open oven environment

allows easy access

Built in vapour sensors

maintain high safety levels for

the operator

Maintaining sample solubility to the end

2009 Agilent Innovations Seminar

Solvent Delivery Module

Heated Transfer Line from oven to waste bottle

Enclosed system to prevent solvent fumes escaping

Full extraction from rear of unit

Solvent leak sensor with automatic system shut-down

Safety Features

2009 Agilent Innovations Seminar

Solvent Delivery Module

Heated Transfer Line from oven to waste bottle

Enclosed system to prevent solvent fumes escaping

Full extraction from rear of unit

Solvent leak sensor with automatic system shut-down

Dual Angle Light Scattering Detector

detector response directly proportional to weight average

molecular weight (Mw) of the polymer

no column calibration required

scattered light intensity measured at more than one angle

permits determination of radius of gyration (Rg)

Viscosity detector

detector response proportional to the intrinsic viscosity [ ] of

the polymer

generate molecular weight values for a variety of polymer

types via Universal Calibration approach

permits determination of branching in polymers

Molecular weight sensitive detectors for GPC

LS 90•

LS 15°

Visc

DRI

Retention time / min

Polystyrene standards

Mp = 520,000 and

Mp = 9,680 g/mol

Retention time / min

LS 90•

LS 15°

Visc

DRI

Polyethylene NBS 1475

(2.29 mg/ml, 200 µl)

Triple detection

Filtration of Samples at High Temperature

Ideally samples for high temperature analysis are prepared with no

filtration step

• Get the full picture of your polymer constituents

• Most accurate way to use advanced detection

However,the presence of insoluble material in polymer solutions for GPC

analysis can cause major problems by blocking the column frits, resulting

in high back-pressure which degrades column performance

• Remove insoluble material before introduction to system

Many commercial polymers contain insoluble fillers such as carbon black

which must be removed from solution prior to analysis

• Remove fillers before introduction to system

However, many crystalline polymers are only soluble at high temperatures

• Filter polymer solutions at high temperature to avoid precipitation

Shaker / Agitator

Thermostated

Sample Blocks

Hand Pipettor

/ filter

Temperature and

Shaker Controls

PL-SP 260 VS Sample Preparation System

High temperature dissolution and filtration of polymer samples

PL-SP 260VS Sample Preparation System

Developed to allow routine, reproducible sample dissolution,

agitation, and filtration at elevated temperatures.

Compatible with a wide range of solvents.

Suitable for hot solvents up to 260 °C including DMF, DMSO,

DMAc, TCB, o-DCB, and m-Cresol.

Filtration of solutions using either stainless steel frit or glass

fibre membrane filters.

Range of filter porosities available, allows filtration of polymers

containing fillers such as carbon black

PL-SP 260VS Hand Pipettor

DISPLACEMENT

BUTTON

SLOT FOR FILTER CARTRIDGE

CLAMPING LEVER

FILTER CARTRIDGE

4 Frit/filters per cartridge

Colour coded to indicate porosity

Clear centre hole for cleaning and for

transfering samples without filtration

A. Sample unfiltered and transferred by pipettor

B. Sample filtered through 1 µm glass fibre membrane

C. Sample filtered through 2 µm Stainless Steel Frit

D. Sample filtered through 0.5 µm Stainless Steel Frit gives

high resistance, and very little carbon is filtered out

A B C D

Filtering Carbon Filled PE

PL-GPC 220 Applications

– Polystyrene

– Polybutylene Terephthalate (PBT)

– Polyethylene (PE)

– Polyethylene High Molecular Weight

– Polyethylene Ultra High Molecular Weight (UHMWPE)

– Ethylene - Vinylacetate copolymers (EVA)

– Poly(ethylene -co - norbornene)

Summary

The PL-GPC 220 and Agilent PL column technology provides unmatched

accuracy, flexibility and performance for HT-GPC

The advanced design of the PL-GPC 220 allows Conventional GPC

coupled with Viscosity and LS detectors to provide a more thorough

characterization of polymers such as polyolefins

Variability in sample preparation procedures can be eliminated by using

the PL-SP 260VS Sample Preparation System, whilst also providing a

unique mechanism for analysing polymer solutions requiring high

temperature sample filtration

Agilent Technologies provides a complete solution for the difficult

analyses demanding High Temperature GPC

Agilent has the portfolio to offer a world leading complete

GPC solution

• GPC Instrumentation

− Including advanced detectors

• GPC Software

• GPC Columns

− Including specialist columns for polyolefins

• GPC Standards

• GPC Expertise

Agilent Technologies Complete GPC Solution

PL-GPC220 Analysis of Commercial Polystyrene

Column: 2x10µm MIXED-B, 300x7.5mm

Flow Rate: 1.0ml/min

Eluent: THF

Temp: 40°C

Polyester/Polyamide Applications

PET

Nylon 6,6

Nylon 6

HFIP is an alternative solve

nt, viscous but low boiling p

oint

Column: 2xPL HFIPgel, 250x4.6mm

Eluent: HFIP + 20mM NaTFAc

Temp: 40°C

Flow Rate: 0.3 ml/min

Detector: DRI

Ethylene - vinyl Acetate Copolymer Samples

Column: 3xPLgel 10µm MIXED-B, 300 x 7.5mm

Eluent: TCB + 0.00125% BHT

Flow Rate: 1.0ml/min

Temp: 160°C

Sample A

Sample B

2009 Agilent Innovations Seminar