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94--_

Overview ofPolyolefinAdditive Analysis

R.C. Nielson - Waters Chromatography Division, Millipore CorporationA

WatersDivisionof MILLIPORE

Presentedat the 1989 InternationalGPCSymposium,October 1-4, 1989

OVERVIEW OF POLYOLEFIN ADDITIVE ANALYSIS

BY: Richard NielsonWaters Chromatography DivisionMilford, MA 01757

ABSTRACT: The extraction and subsequent separation and quantitation of polymeradditives in polyolefins has proven to be a challenge for the analytical chemist. Wehave investigated some ways to extract the additives from polyolefins, namely,microwave oven and ultrasonic bath techniques for high density polyethylene (HDPE)and polypropylene. We have concentrated on identifying and quantitating recoveriesfor typical polyolefin antioxidants, such as Irganox 1010, Irgafos 168, and Cyasorb UV

i 531. The extraction times are typically 20 minutes for the microwave oven and 30-60minutes for the ultrasonic bath with 90+% recoveries being obtained. Both normalphase isocratic (used when phosphites are present) and reverse phase gradient LCtechniques are discussed.

INTRODUCTION: The additive packages used for polyolefins can be quitecomplicated, containing several antioxidants, both primary (such as hindered phenols),and secondary (or also called "synergistic') antioxtdants, as well as antistats, slips,pigments, etc.

The slip agents tend to be long chain aliphatic amides, such as oleamide anderucamide. These compounds have limited solubility and UV absorption. Reversephase LC analysis (using conventional water/aceto or water/methanol C18 methods) isvery difficult due to the limited solubility of the amides. Methylene chloride does anexcellent job at extracting out these materials, but absorbs in the UV region (-205nm)required. The differential refractometer proves to be a good detector to use, but ourseparations with a normal phase (Si02 column) system failed as the slips eluted alltogether at the void volume. We will continue to look at other chromatographic modesof separation, but the analysis of choice at present seems to be a total nitrogenelemental analysis determination. We will concentrate on the analysis of antioxldantsfor this presentation. The following table lists the antioxidants that we have examinedand chromatographed successfully.

TABLE #1 - POLYOLEFIN ANTIOXIDANTS

ADDITIVE CHEMICAL NAME MANUFACTURER*

BHT Butylated Hydroxy Toluene ManyIrgafos 168 Tds (2,4-di-t-butylphenyl. Ciba-Geigy

phosphite)Irganox 1010 Tetrakis methylene (3,5-di-t Ciba-Geigy

butyl-4-hydroxyhydrocinnamate)methane

Irganox 1076 Octadecyl 3,5 di-t-butyl-4- Ciba-GeigyUltranox 276 hydroxyhydrocinnamate Borg-WarnerIrganox 1330 1,3,5-trimethyl-2,4,6-tris Ciba-GeigyGoodrite 1339 (3,5-di-t-butyl-4-hydroxybenzyl)- B.F. Goodrich

benzene

Irganox 3114 1,3,5-tris (3,5,dt-t-butyl-4- Ciba-Geigyhydroxybenzyl)-s-triazine 2,4,6(t H,3H,5H) trione

Tinuvin 328 2-(2'-hydroxy-3',5'-di-tert- Ciba-Geigyamylphenyl benzotriazole

Cyasorb UV 531 2-hydroxy-4-n-octobenzophenone American CyanamidUltranox 626 Bis(2.4-di-t-butylphenyl) Borg-Warner

pentaerythriotol diphosphiteAM 340 ? Ferro

* NOTE: There are other manufacturers that also provide many of the abovestabilizers that are not listed.

RESULTS: This paper will be broken up into two sections: the first will deal with theextraction and chromatographic analysis of three antioxidants compounded into a highdensity polyethylene (HDPE), and the second section will discuss the extraction andchromatographic analysis of antioxidants compounded into five different polypropyleneresins. We obtained a sample of high density polyethylene (HDPE) in pellet form towhich had been compounded 500 ppm each of BHT, Irganox 1010 and Irganox 1076.Four separate extraction solvents were utilized, the first being a 9:1 mixture ofcyclohexane and isopropanol, (IPA), which was from a proposed ASTM extractionmethod. The second choice (which proved to be more efficient) was a 50:50 mixture ofthe same two solvents. The third choice was a 75:25 mixture of methylene chlodde(MeCI2) and cyclohexane, and the fourth choice being a 98:2 methylene chloride/IPAmixture. Three different methods of extraction were tded using the first solventmixture, including Soxhlet, ultrasonic, (conventional laboratory sonic bath) andmicrowave oven, (highpowered, explosion proof microwave oven). Only the ultrasonicand microwave methods were usedwith the 50:50, 75:25 and 98:2 mixtures as theSoxhlet method proved to be too long and labor intensive.

The HDPE (for all extraction methods) was ground using the Wiley Mill to a 20 mesh,with 5 grams + or - 0.10 mg. being added to exactly 50 mls of the solvent mixture.After the desired extraction time pedod, the HDPE is removed by filtration, and thesolvent mixture allowed to evaporate (without any heat applied, however) to dryness.The additives are resolubilized with acetonltrile, and brought to mark in a volumetdcflask. The LC analysis consists of a reverse phase gradient with 3:2 water/acetonitdleto 100% acetonitrile (5 minute linear gradient) over a Nova-Pak C18 column, (15cm).Figure #1 shows a typical chromatogram of the extracted antioxidants; in this case,after two hours extraction using the ultrasonic bath. The BHT, Irganox 1010, andIrganox 1076 (respectively), peaks are observed. UV detection (@ 254nm in this case)was used for all of the chromatographic analyses. The table below shows therecoveries at three different time periods for the Soxhlet extraction using the 9:1mixture:

TABLE #2SOXHLIET EXTRACTION - HDPE

9:1 CYCLOHEXANE/ISOPROPANOL

ADDITIVES Con_c_=_Lopm) Conc._(ppm) Conc. (ppm) % Recovery3 hrs. 7 hrs. 24 hrs. (Total)

BHT 406 427 437 87IRG. 1010 369 429 464 93IRG. 1076 421 463. 469 94

The table shows that in order to get the majority of the 1010 out, 24 hours of Soxhletextraction may be necessary. The BHT levels are a little on the low side, perhapsbecause of the tendency of BHT to sublime under excess heating. The next tableshows the recovedes obtained for the ultrasonic bath extraction, again with the 9:1cyclohexane/IPA mixture.

TABLE #3ULTRASONIC EXTRACTION - HDPE9:1 CYCLOHEXANE/ISOPROPANOL

ADDITIVES Conc. (ppm) Conc. (ppm) Conc. (ppm) % Recovery1hr. 2hrs. 3 hrs. (Total)

'1BHT 443 450 454 91IRG.1010 423 440 458 92IRG. 1076 453 470 477 95

The relative standard deviations for both the Soxhlet and ultrasonic extractiontechniques were -2%, (result lrom six different extractions and subsequentchromatographic analyses). The microwave oven was also used, heating the HDPE for60 minutes in the oven. After -40 minutes, however, the polymer completelydissolved, and formed a thick suspension upon cooling which was impossible tohandle. It appeared as though the HDPE had formed a mass of "gel", which madesample filtering and reproducible recovedes impossible.

It was next decided to repeat the microwave and ultrasonic extractions on the HDPEsample, but using a 50:50 mixture of cyclohexane and IPA. This would cut down onthe amount of non-polar solvent, and presumably, decrease the chance of "gelation" ofthe polymer. It was found that only a 20 minute heating of the solution in themicrowave oven at 50% power (and vigorous stirring every 5 minutes) was required toextract out the additives. The HDPE was ground to a 20 mesh with a Willey Mill for thisexperiment as well. The 98:2 MeCI2/IPA mixture was also used for the microwaveoven method (20 minutes at 25% power with stirring every 5 minutes). The results forthe microwave extraction are as follows:

TABLE #4MICROWAVE EXTRACTION RESULTS- HDPE

ADDITIVE Concentration (ppm) Concentration (ppm)1:1 Cyclohexane/IPA 98:2 MeCI2/IPA

BHT 451 (90%) 455 (91%)1010 454 (91%) 459 (92%)1076 480 (95%) 474 (95%)

The 50:50 cyclohexane/IPA and 75:25 MeCI2/Cyclohexane mixturesproved to workexremely well with the ultrasonic method of-extraction. The groundHDPE wasextracted for just one hour in the sonic bath, with the solution being stirred every 10minutes vigorously for at least 30 seconds. The extraction was carded out for only 30minutes using the MeCI2/cyclohexane mixture (again, stirring every 10 minutes). Thetable below illustrates the recoveries obtained for each additive:

TABLE 15ULTRASONIC EXTRACTION RESULTS - HDPE

ADDITIVE Concentration (ppm) Concentration (ppm)1:1 Cyclohexane/IPA 75:25 MeCI2/(60 Min) Cyclohexane (30 Min)

aNT 454 (91%) 449 (90%)

1010 457 (91%) 458 (92%)

1076 475 (95%) 481 (96%)

In all cases, the separations were carried out using a 15cm Nova-Pak C18 column, witha gradient of 60:40 water/acetonitrile to 100% CH.gCN (5 minute linear gradient). Forthe first experiment (9:1 solvent ratio), the flow rat_ was 2.0ml/min., an(:l for the 50:50solvent mixture extractions, the eluent flow rate was 1.5 ml/min. The column temp.should be held above room temp., such as 40c. We also used a 7.5cm NovaPakcolumn, which will bring the 1010 and 1076 retention time down significantly. Theshorter column can be used when the additive package is relatively simple (threecomponents or less, for example), with the same water/acetonltrilegradient. If theadditive package is much more complicated (i.e., contains several additives that elutevery closely), than the 15cm NovaPak should be used. In summary, the 50:50cyclohexane/IPA mixture works very well with both the ultrasonic bath extractionmethod (1 hr. with stirring every 10 minutes), and the microwave oven (only 20 minutesat 50% power, vigorous stirring every 5 minutes). The stirring is very important, asagitation will facilitate the extraction of the additives out of the polymer matrix. The

small amount of IPA added to the MeCI 2 mixture for the microwave extraction isnecessary as MeCI 2 alone heats up very slowly in the microwave, and the IPA(because of the polar OH group), heats up very quickly. The addition of only 2% wasenough to heat up the solution and extract the additives successfully. The 75:25MeCI2/cyclohexane mixture used with the ultrasonic bath worked very well also. Anyone o-fthese three methods may be used to efficiently extract out the additive packagefor HDPE.

The next step was to investigate the ultrasonic and microwave extraction proceduresand determine recoveries for polypropylene. Several polypropylene resvns weresubmitted to us that contained a variety of additive packages. The additives were

resent at various levels, with the precision of the compounding being + or - 35 ppm.he polypropylene formulations consisted of antistats, pigments, fillers, slip agents, and J

antioxidants/UV degradants. For the purposeof this Work, we will concentrate on the "Iextraction, identification and quantitat,on of the antioxidants, including the phosphiteesters. Each of the resins was said to possibly contain an unknown (but low) amountof Irganox 1076 which was compound into the resin initially. The 1076 can beobserved at times in some of the chromatograms for the resins. In addition to theusual hindered phenolic type antioxidants such as Irganox 1010, 1076, and 3114, manyof the resins contained phosphite esters such as Irgafos 168 and Ultranox 626. Thesephosphite esters are referredto as secondary antioxidants, or synergistic antioxidants.One of their primary functions is to react with the hyroperoxide (°OOH) group which isthe last step prior to chain scission. Where reverse phase separation techniquesrequire water as part of the gradient elution scheme, the phosphite esters are prone tohydrolysis. We, therefore, examined normal phase chromatographic techniques, usinga Resolve silica column (51.1.particle size) when the phosphites were present. Severalsolvent combinations were tried, as well as many gradient and isocratic methods. Thebest chromatographic system consisted of a 70:30 mixture of n-butylchloride�methylene chloride.

The same methylene chloride/IPA, methylene chloride/cyclohexane andcyclohexane/IPA solvent mixtures that were used for the HDPE extractions were alsoinvestigated for the polypropylene resins.

Both a variable wavelength UV detector (@ 225nm and the photodiode array detectorwere used for the analysis. The following additives were chromatographed as part ofthe normal phase separation study:

AM 340 Irganox 1330BHT Irganox 3114Irgafos 168 (phosphite) Tinuvin 328Irganox 1010 Cyasorb UV 531Irganox 1076 Ultranox 626 (phosphlte)

The Irgafos 168, Irganox 1010, 1076 and 3114 can all be separated in under 7 minutesat a 1.5 ml/min flow rate. The first extraction procedure consisted of a microwave oven

ocedure, heating 5 grams (+ or - .10mg.) of resin that were previously ground in theiley Mill to 20 mesh in 50 mls. of a 98:2 methylene chloride/2-propanol mixture. The

IPA is added to allow for heating of the mixture in the microwave.The resins wereextracted in the microwave oven for 20 minutes at 25% power, with vigorous stirringevery 5 minutes. After the extraction period, the solutions were allowed to cool, (thesolvent temperature (48c) was above the boiling point of MeCI 2 (-40c) in the sealedsample containers), then filtered and dnsed with MeCI 2. The additive solutions arethen brought to mark in a volumetric flask, (10 or 25 mE depending on the amount ofadditives present in the resin), then chromatographed by the normal phase, isocraticseparation procedure. The normal phase separation is recommended only when apbosphlte ester is present in the formulation, or if the formulation is relatively simple. Acomplicated formulation containing several antioxidants (but no phosphite) would bestbe separated by reverse phase techniques, which will be discussed later on. Figure #2shows the normal phase isocratic separation of four antioxidant standards: Irgafos168, Irganox 1076, Irganox 3114, and Irganox 1010. Figure #3 shows the samechromatogram, but with the photodiode array detector instead of the UV detector. Thechromatogram is a 3-D picture, with retention time (X direction), absorbance (Ydirection) and wavelength (Z direction) all being shown. The table

below lists the recoveries obtained for four o! the resins, two of which contain aphosphite ester, using the microwave oven and the 98:2 methylenechlonde/isopropanol mixture (20 minutes):

TABLE #6MICROWAVE EXTRACTION RESULTS - POLYPROPYLENE

98:2 METHYLENE CHLORIDEJISOPROPANOL

RESIN "D*

Additive Amount Amount % RecoveryRecovered (ppm) Present (ppm)

+ or - 35

Irganox 31 t 4 565 600 94

Cyasorb UV 531 442 500 88

RESIN "E"

Irgafos 168 521 500 100+

Irganox 1010 986 1000 99

RESIN _G"

Ultranox 626 709 800 89

Irganox 3114 635 800 89

RESIN "1"

BHT 513 500 100+

Irganox 1010 931 1000 93

*Note: The "D" resin also contained 2,000 ppm of AM 340, but the normal phaseseparation results were not as good as for the reverse phase analysis, to be discussedlater on, for this antioxidant.

The recoveries are excellent for all of the additives except the Irganox 3114, which wasrecovered at only 79%. The two phosphites perhaps showed some signs ofdegradation, with a minor peak being observed next to the major one. This peak,however, eluted very closely to where Irganox 1076 elutes, and identification wasimpossible. Some of the resins were reported to contain an unknown amount of 1076.The 1010 was recovered in the two resins at better than 92%, which is veryencouraging. This is one of the more difficult antioxidants to remove, and the resinmust be ground in the Wiley Mill for extraction to be successful. During the grindingprocedure, one must be careful not to force the resin too quickly, as the heat buildupmay cause the polymer to melt. Addition of carbon dioxide or liquid nitrogen willprevent this from happening. Some of the resins were extracted "as is" (pellets, notground), and recoveries were excellent using the microwave technique except for 1010,which could be extracted at no better than -40% recovery without grinding. The nextstep was to microwave extract the "E" resin and perform the chromatographicseparation six times in order to determine the reproducibility of the technique. Thetable below shows the results:

TABLE #7"E" RESIN EXTRACTION REPRODUCIBILITY STUDY

Extraction # Conc. Irgafos 168 Conc. Irganox 1010(ppm) (ppm)

1 521 9862 485 10343 509 9814 476 10195 489 9786 496 970

[R.S.D. -- 3.3%] [R.S.D. = 2.6%]

This results in a value of 496 + or - 16 ppm, or 3.3% for Irgafos 168, and a value of 995+ or - 26 ppm, or 2.6% for the Irganox 1010 W_ wm,ld expect the Irgafos (phosphite)to not be quite as good precision-wise, as this material has more of a tendency todegrade more rapidly, and the peak height/area variance from run to run was greaterthan for the 1010.

The next procedure consisted of an ultrasonic extraction of the "E" resin, (again ._roundwith the Wiley Mill), using a 75:25 MeCI2/cyclohexane solvent mixture. The firstextraction was done for thirty mlnutes. As the table below indicates, an additional 30minutes (or one hour total) was required to extract out the 1010 at 98+ % recovery.Each extraction was done in triplicate, with the results being as follows:

TABLE #8ULTRASONIC EXTRACTIONS - 75:25 MeG12/CYCLOHEXANE

ADDITIVE Conc. (ppm) Conc. (ppm)30 min. 60 min.

Irgafos 168-1 522/500 492/500Irgafos 168-2 494/500 516/500Irgafos 168-3 513/500 503/5001010-1 929/1,000 982/1,0001010-2 882/1,000 998/1,0001010-3 921/1,000 980/1,000

The above table indicates that all of the Irgafos 168 is extracted in only 30 minutes,with -88% (worst case) of the 1010 being extracted out. We can "squeeze out" a littlemore of the 1010 if we choose to extract in the ultrasonic bath for afull hour. Figures#4 and #5 show the UV and photodiode array chromatograms, respectively, for theultrasonic extract residue trom the "E" polypropylene resin. The small peak just undertwo minutes was not quantitated as 1076, as we did not know how much 1076 (if any)was present in this resin, (as discussed previously). All of the above chromatographywas carried out using the normal phase isocratic separation with the Resolve Si02column and the 70:30 BuCI2/MeCI 2 mixture. This procedure proved to be excellent forseveral of the resins that containei:l the phosphite esters, with no evidence of anyhydrolysis or other severe degradation of the phosphites having taken place.

The last procedure consisted of a reverse phase analysis, using a 3:2 water/acetonitrileto 100% acetonttrile 5 minute linear gradient across a Nova-Pak C18 column. Theeluent flow rate was 1.5 ml/minute, with column temperature being maintained at 40°c.The reverse phase separations afford much better selectivity than does the normalphase separations, but the retention times are longer. Note, however, the excellentseparation power of the mix of the 7 standards, eluting, in order: BHT, Cyasorb UV531, Irganox 3114, Tinuvin 328, Irganox 1010, Irganox 1330, and Irganox 1076, (seeFigures #6 and #7). The PDA chromatogram (Fig. #7) shows five of the antioxidantstandards for sake of clarity. These are all baseline separated in just about 20minutes. Three resins (not containing a phosphite) were extracted in both themicrowave oven and in the ultrason!c bath using, a 50:50 mixture of cyclohexane and2-propanol. The mwcrowave extraction was carried out for lust 20 minutes at 25%power, with vigorous stirring for 30 seconds at 5 minute intervals. The ultrasonicextraction was carded out for 1 hour with vigorous stirring every 15 minutes.

The 5 grams of PP resin were ground as usual on the Wiley Mill. Figure #8 shows thereverse phase gradient chromatogram for resin "D". Just for curiosity's sake, the "E"resin was also extracted, but the Irgafos 168 could not be detected. The 1010 wasrecovered, however. The results are as follows:

TABLEMICROWAVE EXTRACTIONS; REVERSE PHASE LC

50:50 CYCLOHEXANE/ISOPROPANOL - 20 MIN.

RESIN "D"

ADDITIVE AMOUNT RECOVERED/PRESENT (ppm)

Irganox 3114 604/600 (100%)Cyasorb UV 531 511/500 (100%)AM 340 1770/2000 (89%)

RESIN "E"

Irgafos 168 Not QuantitatedIrganox 1010 986/1000 (99%)

RESIN "I"

BHT 484/500 (97%)1010 947/1000 (95%)

RESIN "K"

BHT 1274/1400 (91%)1010 961/1000 (96%)

TABLE #10ULTRASONIC EXTRACTION RECOVERIES

50:50 CYCLOHEXANE/ISOPROPANOL - 60 MIN.

RESIN "D"

Irganox 3114 583/600 (97%)Cyasorb UV 531 491/500 (98%)AM 340 1788/2000 (89%)

RESIN "E"

Irgalos 168 Not detectedIrganox 1010 977/1000 (98%)

RESIN "1"

BHT 469/500 (94%)1010 953/1000 (95%)

RESIN "K"

BHT 1242/1400 (89%)1010 938/1000 (94%)

The recoveries are obviouslyvery good. The microwaveoven providesa very fastmeans of extractingthe additives from the groundresin. This techniquecan be doneon unground resins as well, depending upon the components present in theformulation. If 1010 is present, for example, the resin must be ground, otherwisethe1010 will not be recovered at better than 50%. The ultrasonic bath provides aninexpensive and relativelyfast way of extractingthe additives. The Soxhlet method ofextraction was not tried out on these polypropyleneresins, as we wouldassume that itwould take at lease seven hours to extract out the majodty of the additives, andperhaps as muchas 16 hoursto recover 1010, for example.

CONCLUSIONS: There are many other means of extraction of polyolefinadditivessuch as "superheating"a solvent mixturein a sealed vial to as much as 30 degrees Cabove the boiling point. We have demonstrated two quick ways to extract andquantitate the levels of typicalantioxidantspresent in high density polyethyleneandpolypropylene. Most analytical laboratoriP__have At their disposal an ultrasonicbathcleaner that will work very well at extracting out the antioxidants. The only othermaterials required are 250 ml. beakers and watch glasses. The microwaveoven allowsthe extraction to be done more quickly,but at a much higher initialcost. Up to twelvesamples can be extracted at once in the oven, and sample handlingis quiteeasy. Bothtechniques afford a great time savings when compared to conventionalSoxhletextraction. It is difficultto set up more than four Soxhlet condensersin a hood, so thesample throughputis obviouslymuch lessthan for the othertwo techniques.

kig, t¢.t

Chromatogram of Ultrasonic ExtractedHDPE

Acquisition method 990 Quantitation method 990Units System number 1Channel I Manual injectorInjection 1 Total injections 1Run time 25.00 min Sample rate 1.00 per sec

Injection volume I00 uL Rode AnalysisAcquisition version 840/6.2 Quantitation version 860/B01.37

484 UV, 254nm

CHARACTERIZATION ACROSS A NOVAPAK C18 COLUMN. GRADIENT

SEPARATION WITH 3:2 H20/CH3CN TO I00% CH3CN AS ELUENT.DETECTION WITH 484 UV (254 nm) AND 990 PDA.

#i, 2HRS. ULTRASONIC

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c_._

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Fig, #2

Antioxidant Standards

l Normal Phase SeparationII CONDITIONS:

" H ELUENT:II n-Butyl Chloride/Methylene Clfloride :70/30II @1.50 ml/min, IsocraticII CoLuMN:II Resolve Silica 5p Column

oc II I_ UV DETECTION: @ 225nm

#-

It

XlnuteI

Fig, #3

PDA of Polyolefin Standards

Separated by Isocratic Normal Phase LC

Fig, #4

Ultrasonic Extract from Polypropylene Resin "E"

Irgafos 168 (Phosphite)Irganox 1010 and 1076

CONDITIONS:Isocractic Normal Phase LC Separationwith 70:30 n-Butyl n-BuCI2/MeCI2 @1.5 ml/min, over a 51LResolve

_ Silica Column.DETECTION with UV @ 225 nmU3

c-O

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n"

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O

m ,

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Fig, #5

PDA Chromatogram of Ultrasonic Extract from Resin "E"

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• 107_ I010 -I

Fig, #6

Polyolefin Standards - Reverse Phase Gradient Separation

ELUENT: 3:2 H20/CH3CN- CH3CN- 5 Minute Gradient at

1.50 ml/minCOLUMN: Nova-Pak CI8

m

DETECTION: 490 UV @ 225nm i_It'/

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Fig #7

PDA 3D Chromatogram of 5 Polyolefin Additive Standards

Fig #8

Microwave Extract from Polypropylene Resin "D"

BOO CONDITIONS: Reverse Phase Gradient: 3:2 H20/CH3CNto CH3CN @ 1.50 ml/min

COLUMN: Nova-Pak C18DETECTION: 490 UV @ 225 nm

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100

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