Real World
Challenges in
Plastic
Analysis
Presented By:
D J
Dr.
Jack
kH
Hubball
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, Monoand 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
Antioxidants
Antistatic Agents
Blowing Agents
Coupling Agents
Cross-Linking
Agents
• Flame Retardants
• Lubricants and
Related Additives
• Plasticizers
• Retarders
• UV stabilizers
• Colorants
• Release agents
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
– Native material
– Pulverized
Polymer
• Soxhlet Extraction
• Super Critical
Fluid Extraction
• Microwave
• Thermal
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
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Polymer Sample in GC Inlet with
Aluminum Foil Plug
AccuStandard
125 Market Street • New Haven, CT 06513
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-4hydroxyphenyl)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
Abundance
18.76
6
2e+07
277
Abundance
TIC: ETHAN310A.D
3500000
1.8e+07
3000000
1.6e+07
2500000
1.4e+07
1.2e+07
2000000
1e+07
292
1500000
8000000
147
57
6000000
1000000
219
4000000
203
500000
91
2000000
115
128
161
185
77
173
103
45
235
249 261
240
260
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
280
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
Insulators containing PBDEs
AccuStandard
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
TIC: PBB.D
Abundance
1600000
1400000
1200000
1000000
800000
600000
400000
200000
Time--> 6.00
Abundance
110000
8.00
10.00 12.00
14.00
16.00 18.00
20.00
22.00
24.00
26.00
28.00
Scan 3049 (26.553 min): PBB.D
406
100000
90000
564
74
80000
70000
60000
50000
40000
30000
137
10000
0
m/z-->
45
50
170
110
100
150
297
223
20000
200
325
251
250
377
300
350
400
455
450
484
500
522
550
609
600
655
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
125 Market Street • New Haven, CT 06513
Phone No: (203) 786-5290 • Fax No: (203) 786-5287
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