HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization...

12
Polymer chemists and lab managers are challenged to achieve these analysis requirements: • Produce accurate and precise results with confidence when accepting or approving incoming raw material • Stay ahead of sample demand and increase productivity by eliminating the need for recalibrating systems and rerunning samples • Generate quality, reliable information from raw data in automated reporting formats HPLC/GPC SYSTEM SOLUTIONS: POLYMER CHARACTERIZATION Polymer technology presents great challenges to the analyst concerned with material properties and performance. Issues of consistency, processability and unexpected end-use behavior have to be dealt with. Fortunately, advances in analytical techniques now provide you with the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile analytical techniques available for understanding and pre- dicting polymer performance. It is the only proven technique for charac- terizing the complete molecular weight distribution of a polymer, which is required for predicting material properties and performance. As the pioneer of GPC, Waters continues to explore and develop new GPC applications and improve the instrumentation that makes GPC so powerful. Whether it is high performance at an affordable price or fully integrated performance with advanced multi-detection capabilities, Waters provides the system solutions for polymer charac- terization applications using room temperature GPC, gradient HPLC and high temperature GPC. Polyolefins Elastomers Copolymers Nylons/Polyesters Aqueous Polymers Polycarbonates Additives Polymer Blends

Transcript of HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization...

Page 1: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Polymer chemists and lab managers are challenged to achieve these analysis requirements:

• Produce accurate and precise results with confidence when accepting or approving incoming raw material

• Stay ahead of sample demand and increase productivity by eliminating the need for recalibrating systems and rerunning samples

• Generate quality, reliable information from raw data in automatedreporting formats

HPLC/GPC SYSTEM SOLUTIONS: POLYMER CHARACTERIZATION

Polymer technology presents great challenges to the analyst concernedwith material properties and performance. Issues of consistency,processability and unexpected end-use behavior have to be dealt with.Fortunately, advances in analytical techniques now provide you withthe tools you need to solve today’s polymer characterization problems.

Gel Permeation Chromatography (GPC) is one of the most powerfuland versatile analytical techniques available for understanding and pre-dicting polymer performance. It is the only proven technique for charac-terizing the complete molecular weight distribution of a polymer, whichis required for predicting material properties and performance.

As the pioneer of GPC, Waters continues to explore and developnew GPC applications and improve the instrumentation that makesGPC so powerful. Whether it is high performance at an affordableprice or fully integrated performance with advanced multi-detectioncapabilities, Waters provides the system solutions for polymer charac-terization applications using room temperature GPC, gradient HPLCand high temperature GPC.

• Polyolefins• Elastomers• Copolymers• Nylons/Polyesters• Aqueous Polymers• Polycarbonates• Additives• Polymer Blends

Page 2: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

ROOM TEMPERATURE GPC AND GRADIENT HPLC WITH ALLIANCE® SYSTEMS

Accuracy, precision and reliability.

Whether you are responsible for quality control of incoming raw materials, R&D support to the polymer synthesis group,or deformulating competitor materials, you have the ability to provide your customers with the most accurate, preciseand reliable polymer information. With the Alliance GPC System, you can be confident that the small differences yousee from batch-to-batch are real, and not due to instrument variability.

Waters Alliance HPLC System.

The 2695 Separations Module is based on an integrated configura-tion for solvent and sample management aimed at meeting the moststringent user expectations. The sophisticated, software-driven mech-anism produces pulse-free eluent delivery, compensates for changesin eluent viscosity and automatically adapts to eluent blending ratio,thereby enhancing performance for room temperature GPC or gradi-ent HPLC analysis of polymers and additives. Expectconsistent performance, unparalleled precision, high-er reproducibility and higher quality results withincreased uptime.

Adding Millennium®32 Software to yourAlliance System provides you with sys-tem control and results management withthe calibration, integration and flexibilityyou need. Millennium32 GPC Softwareeffectively collects, manages and reportsGPC data and is the most versatile soft-ware developed for polymer characteri-zation. When combined with the 2996detector, Millennium32 Software providesunlimited information about the structuralcomposition of polymers for advancedspectral analysis of copolymers, blends,alloys, as well as additives.

The 2487 Dual λ Absorbance Detector provides unsurpassed sensitivity(≤0.35 x 10-5 AU @ 254 nm, 1-second filter time constant), achievingthe Limit of Detection (LOD) necessary to identify the smallest impurities.Lamp Optimization Software automatically manages detector performance to ensure consistent results over time.

The 2996 Photodiode Array (PDA) Detectorenables you to set up spectral libraries andcompare spectra obtained from unknown mate-rials to those stored in the library for compoundidentification. This library matching capabilityis useful for competitive product deformulation.

The 2414 Refractive IndexDetector’s design ensures stable andreproducible results. When com-bined with the 2695 SeparationsModule, the 2414 detector deliversreduced baseline noise, allowingyou to choose the polymer integra-tion region more consistently, whichin turn provides higher precisionmolecular weight determinations.

Page 3: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Figure 1C: Five MWD overlays each of the“Old” and “New” polyamide samples,showing the slightest differences that arereal, giving credence to the remarkablereproducibility of the Alliance System.

Figure 1A: Overlay of four molecular weight distribu-tions for 0.015% broad polystyrene sample.

Narrowbore GPC.

Narrowbore (also called solvent efficient) GPCcolumns are popular for use with certain solventssuch as Hexafluoroisopropanol (HFIP), a verygood, but expensive solvent for dissolvingpolyamides and polyesters at room temperature.With Waters solvent efficient columns (4.6 mmi.d.) and Alliance Systems, the cost of solvent pur-chase and disposal is alleviated.Figure 1C shows five molecular weight distributionoverlays, each of a polyether amide copolymer(“old” and “new”) medical plastic used in heartcatheterization. Note that the slight differences inthe overlays are reproducible, making it easier todiscern “good” from “bad”.

dwt

/d(l

ogM

)

Cum

ulat

ive

%

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

0

10

20

30

40

50

60

70

80

90

100

Slice Log MW3.84.04.24.44.64.85.05.25.45.65.86.06.26.4

Average MW’sMn = 111,000 1.2 % RSDMw = 255,300 0.6 % RSDMz = 454,000 1.0 % RSDMw/ Mn = 2.3 1.6 % RSD Average of 4 Injections

Quantitated againstPolystyrene Calibration

Eluent: THFSystem: Waters Alliance System with 2414 RI Detector at 40˚ CColumns: (2) Styragel®

HR5E + (1) HR2Column Temp: 40˚ CFlow Rate: 1.0 mL/minConcentration: 0.10%Inj. Volume: 100 µL

3.04.05.06.0 log MW

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

dW/d

(logM

W)

NewOld

New

Old

Overlay of New vs. Old

PolyetherAmide-Old

AverageN=5

%RSDN=5

Rt 18.952 min 0.066%Mn 14,953 1.296%Mw 40,061 1.039%Mz 154,462 3.440%

Mw/Mn 2.680 1.363%

PolyetherAmide-New

AverageN=5

%RSDN=5

Rt 18.923 min 0.113%Mn 14,855 0.564%Mw 44,177 1.119%Mz 150,880 4.990%

Mw/Mn 2.974 1.084%

Eluent: HFlP (hexafluoroisopropanol) with 0.05 M sodium trifluoroacetateSystem: Waters Alliance System with 2414 RI Detector at 40˚ CColumns: Narrowbore (1) Styragel®

HR2 + (1) HR3 + (1) HR4Column Temp: 30˚ CFlow Rate: 0.35 mL/minConcentration: 0.10%Injection Volume: 50 µL

Analysis of polystyrene, SBR and polyamides.

The Alliance System ensures analysis reproducibility with high performance instrumentation and highly efficient columns.Figure 1A shows four molecular weight distribution overlays of a broad polystyrene run at a concentration of only 0.015%,about ten times less than traditional methods. Low concentration means more available pore capacity, which results in a moreaccurate measurement. This analysis was developed using a Waters Alliance HPLC System, which includes the 2414Refractive Index Detector. Figure 1B shows twelve molecular weight distributions of SBR, an elastomer used extensively in thetire industry. Analysis precision provides you with confidence in your results, so rerunning samples is no longer necessary.

Figure 1B: Twelve molecular weight distri-bution (MWD) overlays of a bimodalStyrene-Butadiene Rubber (SBR) samplein toluene. The molecular weight averageRSD’s are better than 0.70%. ThreeStyragel® HR columns were used for thecolumn set. Narrow polybutadiene stan-dards were used for the calibration.

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

3.0

4.24.44.64.85.05.25.45.6

dwt/

d(lo

gM)

Log Mol Wt

Mn = 72,000 0.68% RSD

Mw = 88,300 0.47% RSD

Mz = 105,600 0.67% RSD

Average MW‘s

Overlay of 12 injections

40° C

Eluent: Toluene

System: Waters Alliance System with 2414 RI Detector at

Columns: (2) Styragel® HR5E + (1) HR2

Column Temp.: 75° C

Flow Rate: 1.0 mL/min

Concentration: 0.10%

Injection Volume: 300 µL

Quantitated againstPolybutadiene Calibration

Page 4: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Analysis of polymer additives.

In addition to GPC and gradient analysis of your polymersamples, you should analyze your (and your competitors’)polymer additive package, which is perhaps more impor-tant than the quality of the polymer. Premature failure ofmaterial is often the result of an incorrect additive oramount of additive in the formulation.The separation shown in Figure 3 was performed by theAlliance System with PDA, a Symmetry® C8 column, andan acetonitrile/water gradient with a 2.0 - 3.0mL/minute flow program—started at 6.0 minutes. Theremarkable precision of the 2695 Separations Moduleshows what looks like one chromatogram, not twelve.

Standard UV Detection at 230nm

2.0 4.0 6.0 8.0

Minutes

0.00

0.10

0.20

0.30

0.40

0.50

AU

Tinuvin P

MD 1024

BHT

BHEB UV 531

Isonox 129 Irganox3114

Irganox 1010

Irganox 1076

Irgafos 168

Figure 3: Shown are twelve overlaid chromatograms ofcommon antioxidants and UV stabilizers used in the poly-olefin industry. The gradient and flow program repro-ducibility, as well as the injector reproducibility for heightand area, provide you with confidence in your results.

mV

28303234363840424446485052545658

Minutes

13 14 15 16 17 18 19 20 21 22 23 24 25 26 27

Styrene-Butadiene Rubber(50% Styrene)

Polystyrene

Styrene-Acrylonitrile

(25% Acrylonitrile)

SBR/PS/SANBlend

Columns: (2)Styragel® HR5E, (1)HR2

System: Waters Alliance System with 2414 RI Detector

Flow Rate: 1.0 mL/minInjection Volume:100 µL

Figure 2A: Conventional GPC analysis of three polymers(PS, SBR, SAN) and the analysis of all three (equalamounts of each). You can obtain the MWD of the blend,but there is no compositional information provided.

Polystyrene

% THF

0

10

20

30

40

50

60

70

80

90

100

Minutes0 2 4 6 8 10 12 14 16

Column: SymmetryShield™ C8 (3.9 x 150 mm)Eluent: 100% CH3CN to 100% THF over 20 minutes

Detection: ELSD Styrene-ButadieneRubber

(50% Styrene)

Styrene-Acrylonitrile

(25%Acrylonitrile)

Figure 2B: Reversed phase HPLC separation of thethree polymers using a SymmetryShield™ C8 columnand a 100% acetonitrile/100% THF linear gradient.Suitable modes of detection include UV, PDA orEvaporative Light Scattering.

GRADIENT HPLC FOR POLYMER COMPOSITION

Showing you the entire picture.

Sometimes when performing just the GPC analysis to find molecular weight, you only see part of the picture. You don’t getany information on composition. What is underneath that broad GPC chromatogram? Is it a pure polymer, blend or alloy?Many times you need to look further to get compositional information. Using a binary gradient HPLC technique—continuously changing the solvent composition and using a reversed phase column—you can now separate multiple polymers by chemistry and gain important compositional information. Informationthat GPC alone could not provide. Both critical analyses—binary gradient HPLC and GPC—can be performed by theAlliance System. The HPLC analysis allows quantitation of each polymer present in the blend.

Page 5: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

ROOM/HIGH TEMPERATURE GPC WITH ALLIANCE GPC 2000 SERIES SYSTEMS

A series of fully integrated instruments capable of advanced detection and providing room temperature to hightemperature operation—the Waters Alliance GPC 2000 Series Systems are not only easy to use and maintain,but offer new levels of safety and performance.

Built on the proven Alliance technology for HPLC and room temperature GPC, the Alliance GPC 2000 System’s solventmanager includes the same independently-driven, dual pistons that deliver a smooth, pulseless flow of solvent with anunprecedented precision of <0.075%, eliminating the need for flow marker peaks. Pulseless flow equals noise-free base-lines—particularly important for obtaining high signal-to-noise—making peak integration much easier and more repro-ducible. As a result of this remarkable flow precision, molecular weight results can be obtained using only a single 7.8mm x 30 cm GPC column.The Alliance GPCV 2000 System is a fully integrated GPC system that is capable of operating up to 180˚ C. You maychoose RI detection alone, or RI with the triple capillary viscometer.Another molecular weight sensitive detection option that the Alliance GPC 2000 Series Systems can accommodate is light scattering. The Alliance GPC 2000 Series Systems come light scattering-ready with a removable panel that can utilizePrecision Detectors’ PD2040, or Wyatt Technology’s High Temperature miniDAWN® (HTmD) and Dawn EOS®.

Page 6: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Figure 4A: Overlay (2 injections each) of apolyurethane sample before and after heat treatment.Note the significant change in the MWD of the heatedmaterial. There is a long, low MW tail, indicative ofmolecular weight degradation, as well as some forma-tion of higher MW material. The polydispersityincreased from ~2.1 to ~5.3.

Sample Name Vial Injection Mn Mw Mz Mz+1 Polydisp.NO HEATNO HEATHEATHEAT

1122

1212

37864362841592115759

78738768738427584888

132887131117812344809180

206495208569

24227652299026

2.082.125.295.39

Chromatographic Conditions: DMF, 80˚ C, 3 Styragel HT Columns

dwt/

d(lo

gM)

Rete

ntio

n tim

e

0.00

0.20

0.40

0.60

0.80

1.00

1.20

18.00

20.00

22.00

24.00

26.00

Log MW

3.50 4.00 4.50 5.00 5.50 6.00 6.50

UnheatedHeated

Calibration Curve

Figure 4B: Crystalline polypropylene sample wasdissolved at 170˚ C for two hours; one samplesolution with Santonox antioxidant and the othersample without. Sample was in carousel at 145˚ Cfor 12 hours prior to injection. Analysis was per-formed on the Alliance GPCV 2000 System usingthree Styragel® HT columns, TCB as eluent. Samplemanagement compartment and column oven weremaintained at 145˚ C. Note the significant thermaldegradation for the unprotected sample solution.

dwt/

d(lo

gM)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Log M

3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0

Sample Name Conditions Santonox Mn Mw MzIntrinsic

Viscosity

PPPP

170 ̊/ 2hours

170 ̊/ 2hoursYesNo

80,70013,530

390,62048,230

1,267,400100,100

2.140.31

With SantonoxWithout Santonox

Thermal degradation studies.

GPC is an excellent technique for monitoring polymerdegradation. Figure 4A shows molecular weight distribu-tion overlays provided by Waters Alliance GPCV 2000System. These overlays (two each) were obtained beforeand after heat treatment in an environmental chamber for apolyurethane used in an automotive application. There is alarge shift in the molecular weight distribution to lowermolecular weight, indicative of severe thermal degradation.

Sample preparation is extremely important for polymers thatare run at high temperature, such as polyolefins. It is neces-sary to protect the sample with an antioxidant to preventdegradation.

Figure 4B illustrates what happens to polypropylene whenit is analyzed with and without Santonox antioxidant pro-tection. The polypropylene sample was in the samplecarousel twelve hours prior to the injection.

Page 7: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

SampleName g' g' LCB g' SCB B B_NMRNIST 1476 0.608 0.732 0.831 1.334 1.41

Bran

chin

g Fr

eque

ncy

g'

0.00

2.00

4.00

6.00

8.00

10.00

12.00

14.00

16.00

18.00

20.00

22.00

24.00

26.00

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

Log M3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00

g'LCBg'

B

g'SCB

Figure 5A: Molecular weight distribution and branchinginformation (both LCB and SCB) for NIST 1476. Shownare the long chain, short chain and overall branchingindices (g’LCB, g’SCB, g’, respectively), and B, the branch-ing frequency (number of branches per 1,000 C atoms).

MWD

[η]

Log

[η]

[η]

lin

g' g'

3.0

2.0

1.0

0.0

-1.0

3.0 4.0 5.0 6.0 7.0

1.0

0.8

0.6

0.4

0.2

0.0

Log M

Sample Mn Mw Mz g' K oc λ

LDPE 25937 162658 624498 0.571 0.000370 0.725 0.0000313

Branching Frequency: 1.406

Figure 5B: Molecular weight distribution and branching infor-mation for the metallocene catalyzed LDPE. In addition to theMW averages and Mark-Houwink constants, the overallbranching index (g’), branching frequency and also thebranching probability (λ, defined as the number of branchpoints per unit of MW) are shown.

GPCV FOR STRUCTURE ANALYSES

Branching information for accurate MW averages.

In many instances, more than just molecular weight or composition information is required for polymer characterization.Structural information, such as the presence of short chain and long chain branching, greatly influence the processing char-acteristics and physical properties of the polymer as compared with a linear counterpart of the same molecular weight.Only by using a combination of refractive index (RI) and viscometry detection can we obtain both short and long chainbranching information, as well as accurate molecular weight averages. Seamlessly integrated with this detection is the mostsophisticated data reduction package available for polymer scientists—Millennium32 Software offering patented algorithmsfor RI/viscometry data reduction.

The broad polyethylene standard, NIST 1476, (Figure 5A) contains both short chain (< 6 carbons) and long chain (> 6carbons) branches that have been verified by NMR. NMR provides information on the average, or overall branchinglevel, whereas the Alliance GPCV 2000 System provides short chain and long chain branching information at eachmolecular weight slice across the entire distribution.

Figure 5B shows an analysis of metallocene catalyzed low density polyethylene run on the Alliance GPCV 2000 System.This is a highly branched polymer, as seen in the branching index plot (g’).

Page 8: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

HIGH SPEED GPC

Accuracy and precision…even faster.

Increased workloads, limited staff and the demand for high-er throughput in less time have become the edict of today’spolymer analysis labs. To meet these challenges, Watersoffers new High Speed GPC Columns that will increaseyour sample throughput, without compromising accuracy orprecision. Now you can process a sample in triplicate inless time than it currently takes to complete a single analysis.And better still, these High Speed GPC Columns will helpyou save on solvent purchase and disposal.

High speed analysis of broad polystyrene.

A conventional column set provides the expected molecu-lar weight distribution values, in a run time of ~40 min-utes. The high speed column enabled analysis in lessthan 7 minutes (Figure 7A). However, the high speed rungives incorrect number average and z-average molecularweight values, using a narrow standard polystyrene cali-bration curve. The high speed chromatogram is shownagain in Figure 7B from ~2.5 to 5.5 minutes.

Figure 7A: Broad polystyrene sample run (overlay of4 injections) on the conventional 3-column set and thesingle high speed column. The molecular weight aver-ages are as expected for this sample. Total run time is40 minutes for the 3-column set, and only 7 minutesfor the high speed column.

MV

-20

-10

0.

10

20

30

40

Minutes

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

40 Minute RunTraditional GPC

7 Minute RunHigh Speed GPC

Eluent: THF (stabilized) at 0.6 mL/minSystem: Waters Alliance System with

2414 RI DetectorColumn: Waters High Speed GPC

Column (1) 6.0 mm x 150 mm Column Temp: 35˚ CSample: Broad PolystyreneInjection Volume: 5 µL

Eluent: THF (stabilized) at 1 mL/minSystem: Waters Alliance System with

2414 RI DetectorColumns: Waters (2) Styragel® HR5E,

1 HR2 column; 7.8 x 300 mm Column Temp: 35˚ CSample: Broad PolystyreneInjection Volume: 50 µL

HIGH TEMPERATURE GPC FOR FAST MOLECULAR WEIGHT SCREENING

Many polymer characterization chemists track system reproducibility over days or even weeks. As seen in Figures 6A and 6B,exceptional RSD’s are obtainable over weeks of analysis—using only a single mixed-bed column. The advantage is excellentreproducibility and more confidence in your results with shorter analysis time.

10 MWD Overlays of a Bimodal HDPE0.60

0.55

0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.002.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0

dwt/

d(lo

gM)

Column: (1) 7.8 mm X 30 cm, 10 µMobile Phase: 1,2,4-TrichlorobenzeneFlow Rate: 1.0 mL/minSystem Temp: 145° CDetectors: Alliance GPCV SystemRun Time: 12 minutes

Log MW

Figure 6A: Ten overlays of a Bimodal HDPE obtained overa four-week period using the Alliance GPCV 2000 System.

32 MWD Overlays of NIST 14751.20

0.10

1.00

0.95

0.80

0.70

0.60

0.50

0.40

0.30

0.20

0.10

0.00

2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4

dwt/

d(lo

gM)

Column: (1) 7.8 mm X 30 cm, 10 µMobile Phase: 1,2,4-TrichlorobenzeneFlow Rate: 1.0 mL/minSystem Temp: 145° CDetectors: Alliance GPCV SystemRun Time: 12 minutes

Log MW

Figure 6B: Thirty-two overlays of NIST 1475 (broad, linear PE standard) obtained over a two-week periodusing the Alliance GPCV 2000 System. Mw RSD is <2%.

Page 9: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Log

Mol

Wt

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

5.4

5.6

5.8

6.0

6.2

6.4

Retention Time

2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0

6.0 mm X 15 cm Column0.6 mL/min

5th Order FitR 2= 0.99998

Broad Standard Cumulative Matching Calibration

Figure 8A: The cumulative matching calibration curvegenerated using a broad polystyrene standard under thehigh speed conditions. The entire calibration curve isobtained in less than 4 minutes.

Figure 8B: The broad polystyrene sample run (4 overlays)using the high speed conditions. Note that the MW aver-ages are now nearly identical to the values obtained forthe conventional column set. The RSD’s, however, areeven better—all 0.8% or less.

The combination of Waters Alliance technology,Millennium32 Software and High Speed GPC Columnsgives you the ability to obtain accurate, reproduciblemolecular weight average information in under 7 minutes.

Minutes2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4

1925

50Eluent: THFColumn: Waters High Speed

(1) 6.0 mm x 150 mmColumn Temp: 40˚ CFlow Rate: 0.60 mL/minConcentration: 0.10%Injection Volume: 5 µL

Overlay of four injectionsof Broad Polystyrene Sample

Figure 7B: Broad polystyrene sample run (overlayof 4 injections) on the 6.0 mm x 15 cm highspeed column. The precision is outstanding, butthe MW accuracy is poor for Mn, Mz and Mz+1,as compared with the known values.

Conventional GPCMn Mw Mz Polydispersity

Mean: 105,000 233,600 396,600 2.23% RSD: 0.8% 0.2% 0.4% 0.6%

High Speed GPC With Cumulative Matching Calibration

Mean: 103,600 232,300 390,600 2.24% RSD: 0.8% 0.3% 0.5% 0.9%

% Variance: 1.33% 0.56% 1.51% 0.45%

In Figure 7B, the reproducibility is remarkable due tothe outstanding flow precision of the Alliance System’ssolvent manager.

To improve the MW accuracy, a narrow standard cali-bration was replaced with a broad standard calibrationmethod that is available with Millennium32 Softwareknown as cumulative matching. A well-characterized(i.e. the MWD is known) broad polystyrene standard isrun on the high speed column and the cumulativematching calibration curve is generated; 100 datapoints at 1% peak area increments, Figure 8A.

The same polystyrene sample was run once more usingthe same high speed GPC conditions and the cumulativematching calibration curve.

When the molecular weight averages are re-calculatedusing the cumulative matching broad standard calibra-tion, it is now possible to correct the molecular weightaverage errors. As show in Figure 8B, the molecularweight averages for the high speed analysis are in closeagreement with the 3-column conventional GPC analysis.Note that the molecular weight RSD’s for both the con-ventional and high speed analyses are all under 1%.

TM

Page 10: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

ROOM TEMPERATURE GPC WITH BREEZE™ SYSTEMS

Simplicity, performance and reliability.

Reliable, easy-to-use and affordable, the Waters Breeze System delivers the same world-class technology and perform-ance that Waters is known for. From teaching university students to providing analytical support for manufacturing, theBreeze System’s rugged and robust features strike a balance of simplicity, performance and reliability, making it the idealpolymer characterization system for any organization with a limited budget and minimal chromatography experience.

Log

Mol

Wt

3.00

4.00

5.00

6.00

7.00

Elution Volume

16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00 25.00 26.00 27.00 28.00 29.00 30.00 31.00

Each point overlay of 5 injectionsFigure 9: Breeze HPLC Systemsdeliver flow reproducibility of 0.10%which results in GPC calibrationsand calculations that represent accu-rate and reproducible molecularweights. This polystyrene calibrationcurve was generated by injectingeach standard five times.

Figure 10: Breeze software calculates molecular weight(MW) for broad unknown polymers based on either nar-row or broad standard (including universal) calibration.Hardware performance delivers precise chromatographyfor reproducible results. Here is an example of five molec-ular weight distributions for a broad polystyrene.

dwt

/d(l

ogM

)

Cum

ulat

ive

%

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

0

10

20

30

40

50

60

70

80

90

100

Slice Log MW

4.004.505.005.506.006.50

Mn

Average MW’sMn = 104,300 1.6 % RSDMw = 244,700 0.7 % RSDMz = 427,500 0.9 % RSDMw/ = 2.3 1.1 % RSD Average of 5 Injections

Quantitated againstPolystyrene Calibration

Eluent: THFSystem: Waters Breeze SystemColumn: (2) Styragel® HR5E + (1) HR2Temp: 40˚ CFlow Rate: 1.0 mL/minConcentration: 0.10%Injection Volume: 50 µL

With a Breeze System, you will experience:

• World-class GPC/HPLC technology and performance• Intuitive interface in an award-winning design• Reduced training costs• Minimal investment, maximum GPC/HPLC performance

Page 11: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Analysis of PVC, polycarbonate and PMMA.

The Breeze System delivers highly accurate and reproducible molecular weight information as well as characterizationfor polymer blends and additives via gradient HPLC. It provides excellent molecular weight distribution reproducibility fora variety of polymers-—thanks to its 0.10% flow precision. Figures 11A, 11B and 11C demonstrate this remarkable reproducibility.

dwt

/d(l

ogM

)

Cum

ulat

ive

%

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

1.20

1.30

0

10

20

30

40

50

60

70

80

90

100

Slice Log MW

3.63.84.04.24.44.64.85.05.25.45.65.86.06.2

Quantitated againstPolystyrene Calibration

Average MW’sMn = 67,300 0.7 % RSDMw = 130,600 0.8 % RSDMz = 213,300 1.3 % RSDMw/ Mn = 1.9 0.6 % RSD Average of 5 Injections

Eluent: THFSystem:Waters Breeze System with 2414 RI DetectorColumn: (2) Styragel® HR5E + (1) HR2Temp: 40˚ CFlow Rate: 1.0 mL/minConcentration: 0.10%Injection Volume: 50 µL

Figure 11A: Overlay of five poly(vinylchloride) molecularweight distributions.

dwt

/d(l

ogM

)

Cum

ulat

ive

%

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

0

10

20

30

40

50

60

70

80

90

100

Slice Log MW

3.003.504.004.505.005.50

Quantitated againstPolystyrene Calibration

Average MW’sMn = 15,800 1.4 % RSDMw = 45,500 0.9 % RSDMz = 72,100 1.1 % RSDMw/ Mn = 2.9 1.5 % RSD Average of 5 Injections

Eluent: THFSystem: Waters Breeze System with 2414 RI DetectorColumn: (2) Styragel® HR5E + (1) HR2Temp: 40˚ CFlow Rate: 1.0 mL/minConcentration: 0.10%Injection Volume: 50 µL

Figure 11B: Overlay of five polycarbonate molecularweight distributions.

dwt

/d(l

ogM

)

Cum

ulat

ive

%

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

0

10

20

30

40

50

60

70

80

90

100

Slice Log MW

4.004.505.005.506.006.50

Average MW’s Mn = 172,700 3.2 % RSDMw = 446,300 1.4 % RSDMz = 865,700 1.0 % RSDMw/ Mn = 2.6 2.1 % RSD Average of 5 Injections

Quantitated againstPolystyrene Calibration

Eluent: THFSystem: Waters Breeze System with 2414 RI DetectorColumn: (2) Styragel® HR5E + (1) HR2Temp: 40˚ CFlow Rate: 1.0 mL/minConcentration: 0.10%Injection Volume: 50 µL

Figure 11C: Overlay of five poly(methylmethacrylate) molecularweight distributions.

Waters Breeze System includes the 1525 Binary Pump,the 2414 RI Detector, the 717plus Autosampler andBreeze Software.

Page 12: HPLC/GPC SYSTEM SOLUTIONS: POLYMER …the tools you need to solve today’s polymer characterization problems. Gel Permeation Chromatography (GPC) is one of the most powerful and versatile

Sales Offices:AUSTRIA AND EXPORT (CENTRAL EUROPE,CIS, MIDDLE EAST, INDIA AND INDIASUBCONTINENT) 43 1 8771807

AUSTRALIA 2 9933 1777

BELGIUM AND LUXEMBOURG 02 7261000

BRAZIL 55 11 543 7788

CANADA 800 252 4752 X2205

CIS 095 336 7000

CZECH REPUBLIC 02 617 11384

DENMARK 46 59 8080

FINLAND 90 506 4140

FRANCE 1 3048 7200

GERMANY 06196 40 06 00

HONG KONG 29 64 1800

HUNGARY 1 350 5086

INDIA 80 837 1900

ITALY 02 274211

JAPAN 3 3471 7191

KOREA 82 2 3284 1300

MALAYSIA 3 704 8600

MEXICO 525 524 8383

THE NETHERLANDS 076 508 7200

NORWAY 0 638 46 050

PEOPLES REPUBLIC OF CHINA – BEIJING 10 6526 0828

POLAND 0 22 833 4400

PUERTO RICO 787 747 8445

SINGAPORE 65 278 7997

SPAIN 93 600 9300

SWEDEN 08 594 69 200

SWITZERLAND 62 889 2030

TAIWAN 2 2543 1898

UK AND IRELAND 02 082 38 6100

U.S.A. AND ALL OTHER COUNTRIES: WATERS CORPORATION U.S.A.34 Maple St.Milford, MA 01757 U.S.A.T: 508 478 2000F: 508 872 1990www.waters.com

FOR YOUR THERMAL ANALYSIS NEEDS:T.A. Instruments Corporate Headquarters109 Lukens DriveNew Castle, DE 19720 U.S.A.T: 302 427 4000F: 302 427 4001www.tainst.com

Waters, Alliance, Millennium, Styragel, Symmetry and Connections are registered trademarks of Waters Corporation.Breeze and SymmetryShield are trademarks of Waters Corporation.MiniDAWN and DAWN EOS are registered trademarks of Wyatt Technology.©2002 Waters Corporation Printed in the U.S.A. January 2002 720000386EN LR-UL

WORLD-RENOWNED SERVICE AND SUPPORTWaters Connections® provides the solutions you need to maintain maximum uptime fromyour Waters systems:

• Analytical Instrumentation and Software Services include Total Assurance Plans thatextend and enhance the original warranty you receive when you buy a Watersproduct. These plans minimize the level of insurance investment and deliver thevalue you need to avoid costly and time-consuming system downtime.

• Connections Compliance Services provide you with timely and cost-efficient solutionsto your regulatory compliance challenges. You can use our Compliance Services toeffectively train and certify personnel in equipment and regulatory requirements forcGMP/GLP compliance, significantly reducing operating costs.

• Connections University is the center of our Educational Services, providing extensiveHPLC, GPC and LC/MS training and education at your site, at our corporate head-quarters or at our local offices around the world.

• Representatives of our global Customer Assurance Organization—trained and certi-fied in all our products and current in HPLC and LC/MS applications—are availablein person, on the phone, via FAX or at www.waters.com to answer questions and pro-vide you with around-the-clock support and information services.