Document 5k8qQYe9veZD6wRE91wX4JbDz
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2
Supplemental Information for
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4
Elucidation of Targeted and Non-Targeted
5 Fluorinated Impurities in the manufacturing of
6 PTFE utilizing a Non-Fluorinated Polymerization
7
Aid
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9 John C. Sworen#,*, Peter A. Morken#, Michael C. Davis#, Adam P. Smith+, Jill E.
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Boyle#, Maria D. Cervantes Garcia#, and Jordyn Kramer#
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12 #The Chemours Company, 201 Discovery Blvd. Newark, DE.,
13 +The Chemours Company, 8480 DuPont Road, Washington, WV., *Corresponding Author.
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15 Text S1. PTFE Polymerization Conditions and Methods 16 17 METHODS 18 Standard Specific Gravity (SSG) provides an indirect measure of polymer molecular weight and 19 is obtained according to ASTM (American Society of Testing and Materials) D 792 and D 4894. 20 Traditionally, SSG is related to PTFE molecular weight using the equation of Sperati:1
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Mn = 0.597[log10(0.157)/(2.306-SSG)]-1 x 106
22 Polymerization - PTFE Fluoropolymer prepared with DOSS
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The following example illustrates a semi-batch process for making aqueous fluoropolymer
24 PTFE dispersion to produce an approximately 25 weight % solids batch. PTFE fine powder is
25 produced from the dispersion.
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To a nominally 10-gallon reactor was charged 600 g of paraffin wax, 5 mL of tert-butanol,
27 and 15 mL of a 20% (w/w) aqueous solution of perfluoroionomer particulate as disclosed in US
28 (United States) Patent 6,916,853.2 After adding 24.0 liters of water, the reactor was heated to 65
29 C then pressured to 400 PSIG with nitrogen and checked for leaks. After venting, the reactor was
30 purged with TFE and evacuated. After heating to 70 C, 600 mL of a 0.2% (m/v) solution of
31 ascorbic acid was added. The reactor was charged with TFE to a pressure of 390 PSIG then to start
32 the polymerization, 200 mL of a 0.5% (m/v) aqueous solution of tert-butyl hydroperoxide (TBHP)
33 was added. After this injection was complete, kickoff was declared and TBHP injection continued
34 until the end of the batch (by which time 505 mL additional TBHP solution was added). Also,
1 Sperati, C. A.; Starkweather Jr., H. W. Fortschr. Hochpolym.-Forsch. 1961, 2, 465. 2 Curtin, D. E; Howard, Jr. E.G. Compositions containing particles or highly fluorinated ion exchange polymer. US 6916853 B2, 2005.
35 after kickoff, additional TFE was fed to the reactor to maintain a constant pressure of 400 PSIG. 36 Also, after kickoff 1000 mL of a 3.0% (m/v) solution of dioctyl sulfosuccinate (DOSS) was added 37 at a rate of 40.0 mL/min. After a total of 8.2 kg of TFE were added since kickoff, the reactor was 38 vented. The resulting dispersion, containing 25.36% polymer, was discharged from the reactor.
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Polymer was coagulated by diluting the dispersion to about 14 wt. % solids and by adding
40 about 3.7% by mass (dry weight) of a 20 wt. % aqueous ammonium carbonate solution followed
41 by vigorous agitation until the polymer fully separated from the water. The polymer was dried at
42 150 C. The SSG of this polymer is 2.1917.
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45 46 47 48 49 50
51 Table S1: Additional LCMS parameters - LC Gradient Profile:
Time (min)
Aqueous Mobile Phase (%)
0.00
100
1.00
100
14.50
0
16.50
0
16.60
100
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53
Organic Mobile Phase (%) 0 0 100 100 0
54 Table S2: Additional LCMS parameters - MS Source conditions:
Gas Temp (C) Drying Gas (L/min)
Nebulizer (psig) Capillary voltage (V)
Fragmentor (V) Skimmer (V) Oct 1 RF Vpp
Mode 55
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325 12 45 3500 175 65 750 Negative
57 Table S3: Concentrations of diacids measured through targeted LC/QqQ. Since quantitative analytical
58 standards are not available for all analytes in the homolog series these diacids are quantified from a C8
59 or C10 diacid standard, i.e., two carboxylic acids ends with a perfluorinated C6 (CF2 = 6) or C8 (CF2 = 8),
60 standard.
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Calibration Standard
Analyte
MRM Transition
Concentration On Total Sample (ppbw)
Concentration on Polymer Basis (ppbw)
CF2=6
CF2=4
288.9 -> 181.0
6.24
24.6
CF2=6
CF2=5
338.9 -> 231.0
< 4.76
< 18.8
CF2=6
CF2=6
388.9 -> 281.0
28.1
111
CF2=6
CF2=7
438.9 -> 331.0
< 4.76
< 18.8
CF2=8
CF2=8
488.9 -> 381.0
27.6
109
CF2=8
CF2=9
538.9 -> 431.0
< 4.76
< 18.8
CF2=8
CF2=10
588.9 -> 481.0
12.2
48.2
CF2=8
CF2=11
638.9 -> 531.0
< 4.76
< 18.8
CF2=8
CF2=12
688.9 -> 581.0
< 4.76
< 18.8
CF2=8
CF2=13
738.9 -> 631.0
< 4.76
< 18.8
CF2=8
CF2=14
788.9 -> 681.0
< 4.76
< 18.8
CF2=8
CF2=15
838.9 -> 731.0
< 4.76
< 18.8
CF2=8
CF2=16
888.9 -> 781.0
< 4.76
< 18.8
CF2=8
CF2=17
938.9 -> 831.0
< 4.76
< 18.8
CF2=8
CF2=18
988.9 -> 881.0
< 4.76
< 18.8
Totals
74.2
293
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65 Table S4: Concentrations of H-cap carboxylic acids measured through targeted LC/QqQ. Since
66 quantitative analytical standards are not available for all analytes in the homolog series these acids are
67 quantified from C5 (5H-acid), C7 (7H-acid), C9 (9H-acid), or C11 (11H-acid) standards.
68
Calibration Standard
Analyte
MRM Transition
Concentration On Total Sample (ppbw)
Concentration on Polymer Basis (ppbw)
5H-acid
5H-acid
245.0 -> 180.9
< 2.38
< 9.38
7H-acid
6H-acid
295.0 -> 230.9
1527
6020
7H-acid
7H-acid
345.0 -> 280.9
< 2.38
< 9.38
8H-acid
8H-acid
395.0 -> 330.9
2079
8199
9H-acid
9H-acid
445.0 -> 380.9
< 2.38
< 9.38
9H-acid
10H-acid
495.0 -> 430.9
1274
5025
11H-acid
11H-acid
545.0 -> 480.9
< 2.38
< 9.38
11H-acid
12H-acid
595.0 -> 530.9
1764
6955
11H-acid
13H-acid
645.0 -> 580.9
< 2.38
< 9.38
11H-acid
14H-acid
695.0 -> 630.9
1847
7283
11H-acid
15H-acid
745.0 -> 680.9
< 2.38
< 9.38
11H-acid
16H-acid
795.0 -> 730.9
2359
9303
11H-acid
17H-acid
845.0 -> 780.9
< 2.38
< 9.38
11H-acid
18H-acid
895.0 -> 830.9
1272
5017
11H-acid
19H-acid
945.0 -> 880.9
< 2.38
< 9.38
11H-acid
20H-acid
995.0 -> 930.9
96
378
Totals
12218
48179
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72 Table S5: Concentrations of H-cap sulfonic acids measured through targeted LC/QqQ. Since quantitative
73 analytical standards are not available for these analytes an analytical standard of PFOS is used for
74 calibration.
75
Calibration Standard
Analyte
MRM Transition
Concentration On Total Sample (ppbw)
Concentration on Polymer Basis (ppbw)
PFOS 499 Adduct 281
281.0 -> 80.0
37.3
147
PFOS 499 Adduct 381
381.0 -> 80.0
252.2
994
PFOS 499 Adduct 481
481.0 -> 80.0
422.9
1668
PFOS 499 Adduct 581
581.0 -> 80.0
381.6
1505
PFOS 499 Adduct 681
681.0 -> 80.0
294.9
1163
PFOS 499 Adduct 781
781.0 -> 80.0
104.6
412
PFOS 499 Adduct 881
881.0 -> 80.0
102.1
403
PFOS 499 Adduct 981
981.0 -> 80.0
43.5
172
PFOS 499 Adduct 1081 1081.0 -> 80.0
10.6
42
PFOS 499 Adduct 1181 1181.0 -> 80.0
< 4.76
< 18.8
Totals
1650
6505
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77 78