Real World
Challenges in
Plastic
Analysis
Presented By:
D J
Dr. Jack
kHHubball
bb ll
A
AccuStandard
St d d
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Why Is There a Need for a
Industrial Additive Standards?
Good Science
• Analytical work relies on a comparison
that is made with well-characterized
well characterized
standards
• Whether a laboratory prepares their
standards in-house, or buys them from
y the
an outside source, there is always
need to know that they are prepared and
identified correctly
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Why Is There a Need for a Industrial
Additi Standards?
Additive St d d ? (cont.)
( t)
• Regulatory requirements
– ASTM – Method D6042-96
Determination of Phenolic Antioxidants & Erucamide Slip
Additives in Polyproylene Homopolymer Formulations
Using Liquid Chromatography
– ASTM – Proposed Method D7065-06
P-tert-Octylphenol, Nonylphenol Monoethoxylate &
Nonophenol Diethoxylate and Tech Nonylphenol, Mono-
and Di
Di-ethoxylate
ethoxylate
– FDA
– EU Directives
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Categories of Polymer Additives
• Antifoams • Lubricants and
• Antioxidants Related Additives
• Antistatic Agents • Plasticizers
• Blowing Agents • Retarders
• Coupling Agents • UV stabilizers
• Cross-Linking • Colorants
Agents • Release agents
• Flame Retardants
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Chemical Additive Standards are
different…
• Typically we think of a Chemical
Reference Standard as a single pure
analyte
• Typically a Reference Standard has a
traceability link to a NIST SRM or other
Primary Standard
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Chemical Additive Standards are
different… (cont.)
• Chemical Additives are often technical
mixes of several different chemicals
• Purity may be less than 90%
• Characterization in a real world sample
can be
b challenging
h ll i
• Traceability can be dubious
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Extraction Methods
• Solvent Extraction • Super Critical
– Native material Fluid Extraction
– Pulverized • Microwave
Polymer
• Thermal
• Soxhlet Extraction D
Desorption
ti
– Native material
– Pulverized
P l i d
Polymer
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Polymer Sample in GC Inlet
AccuStandard
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Polymer Sample in GC Inlet with
Aluminum Foil Plug
AccuStandard
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Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Analysis
• LC/MS
– Higher molecular weight capability
– No thermal degradation
– Poor resolution
• GC/MS
– Better resolution
– Possible thermal degradation
– Lower molecular weight capability
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
You can ID a compound by the
Representative Fragments
Ethanox 310
– Penterythritol tetrakis (3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate
OH
MW = 1177.65
C73H108O12
O
O C
4
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Ethanox 310 GC and Mass
Spectrum of the Major Fragment
Scan 2127 (18.762 min): ETHAN310A.D 277
Abundance TIC: ETHAN310A.D Abundance
18.76
6
2e+07 3500000
1.8e+07
3000000
1.6e+07
2500000
1.4e+07
1.2e+07
2000000
1e+07
1500000 292
8000000 147
57
6000000 1000000 219
4000000
203
500000 161
91 128
2000000 115 185
77
103 173 235 249 261
45
0
Time-->5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 m/z--> 40 60 80 100 120 140 160 180 200 220 240 260 280
AccuStandard
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Insulators containing PBDEs
AccuStandard
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Abundance TIC: PBB.D
1600000
1400000
1200000
1000000
800000
600000
400000
200000
Time--> 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00
Abundance Scan 3049 (26.553 min): PBB.D
110000 406
100000
90000 564
74
80000
70000
60000
50000
40000
30000 137
223 297
20000
10000 325
110 170 251 484
45 377 455 522 609 655
0
m/z--> 50 100 150 200 250 300 350 400 450 500 550 600 650
Pharmaceutical Delivery Systems
• Plastics in medical devices are not
currently regulated
• Unknown compounds may be added
from raw material to finished product
• These
Th additives
dditi can be
b detrimental
d ti t l to
t the
th
product and to the consumer
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Gelled Product
AccuStandard
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Conclusion
• A complete analysis of a polymer is
possible with efficient extraction and a
suitable analytical technique
• An array of properly characterized
Chemical Reference Standards is
required for the true determination of the
additives contained a polymeric material
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Questions
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287