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Chemicals Company, ASAHl GLASS CO., LTD. Company sanitized.
04/07/05
ASAHI GLASS COMPANY
Does not contain TSCA CBI.
Asahi Glass Co., Ltd. 10,Goikaigan, Ichihara-shi, Chiba 290-8566, Japan
A 2 2 & -/8 o Sl
Characterization of a Polymeric Product (AAA) by Asahi Glass
Study director (Question to:)
Tsuguhide Isemura Senior Manager Analytical Technology Group Quality Assurance Office Chemicals Company, Asahi Glass Co., Ltd. 10, Goikaigan, Ichihara-shi, Chiba 290-8566 Japan Phone: +81-436-23-3183 Fax: +81-436-23-3126 E-mail: tsueuhide-isemura@agc.co.jp
July 05. 2004 Date
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Chemicals Company, ASAHI GLASS CO., LTD.
Summary
04/07/05
Asahi Glass conducted a characterization of a polymeric product which substance name is AAA and TRP identification # for NOACK shipment is BBB according to the method described in this report. The result of the characterization is listed below.
Measurement
Units
Weight % solids Mn (Num ber average m olecular w eight) M w (W eight average m olecular w eight) Molality o f 8-2 alcohol in product
T otal organic fluorine (W T )
Total inorganic fluoride T otal carbon
PFOA C7F15COOH
8-2 alcoh ol, C 8F17C 2H 40H M W 4 6 4 .il C 10H 5F17O 8-2 acrylate, C8F17C 2H 40C 0C H =C H 2 518,16 C13H7F1702 8 -2 ethyl iod id e, C 8F17C 2H 4I MW 574,01 C 10H 4F17I 8-2 olefine, C8F17CH=CH2 MW 446,10 C10H3F17 C8 iodide, C8F17I M W 545,95 C8F17I total sum o f PFOA and total C8 precursors
% Da Da m ol/k g as percentage (%} as m olality m ol F /k g polym er as concentration g F /k g polym er ppm (mg/kg) as percentage (% ) ppm (mg/kg) m ol/k g
ppm (m g/kg) m ol/kg
ppm (mg/kg) mol/kg
ppm (m g/kg) m ol/kg
ppm (mg/kg) mol/kg
ppm (m g/kg) m ol/kg m ol/k g
Results AAA
' "
Method
Drying SEC SEC
Calculated
Comments
A K -225G /T H F Solven t calibrated relative to PM M A calculated on the basis of specific polymer-recipe
C om bustion - ion chrom atography
ultrafiltration - ion chromatography C alculated
L C /M S
calculated on the basis o f sp ecific polym er-recipe Standard addition method
GC A b solu te calibration m ethod
GC Absolute calibration method
GC A bsolute calibration m ethod
GC Absolute calibration method
GC Calculated
A b solu te calibration m ethod
-2 -
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
1. Substance name and TRP Identification # (for Noack shipment) of the polymeric product Substance name: AAA Lot. XXXX (TRP Identification #: BBB) AAA Lot. XXXX was purified for biodegradation test and named AAA purified (TRP
Identification #. CCC). The purification process and characterization of AAA purified were detailed in the report1'.
2. Characterization of the polymeric product 2-1 Size exclusion chromatography (SEC)
SEC of the polymeric product for molecular weight analysis was conducted according to OECD guidelines2''3' and the result was shown in the previously submitted report1' inclusive of the comparison with the purified polymer. Here the analytical method and result are omitted except for the isolation and preparation of the polymer from the product.
2-1-1 Isolation of the polymer from the product At first, the polymeric product was shaken well for homogenization. 1 ml of the polymeric
product and 5 ml of isopropanol was mixed in a centrifuge tube and shaken well. The precipitated polymer was separated by centrifugation (6,000 rpm, 10 min) and following decantation. The precipitate was then dried in vacuum condition for 20 hours in room temperature. The isolated polymer was dissolved in the mobile phase by 0.75 wt% by shaking for several minutes and stand for overnight. The solubility of the polymer was sufficient: no precipitation or insoluble fraction was observed and the solution looks completely transparent.
2-2 Determination ofPFOA in the polymeric product
The method validation and determination in this section was conducted according to the Attachment 1 of this report.
2-2-1 Test and control substances The test substance, perfluorooctanoic acid (PFOA, 98.9 %, lot. C17001401), and the surrogate
standard, 9-hydrohexadecafluorononanoic acid (9H-PFNA, 97.8%, lot. C58002501), were purchased from Daikin Fine Chemical (Osaka, Japan). Distilled water was produced in-house and checked for contaminants by LC/MS before use. Distilled water was filtered through a pre-column, Preclean-ORG (GL Sciences Inc. (Tokyo, Japan)) placed between HPLC pump and auto-sampler. HPLC grade methanol (MeOH), reagent grade ethanol (EtOH) and isopropanol (IPA), and reagent grade ammonium acetate were purchased from Kanto Chemical Co., Inc.
In order to avoid contamination, disposable lab ware (tubes, pipettes, etc) was used. 2 mmol/L ammonium acetate solution was prepared by weighing 154 mg of ammonium acetate and dissolving in 1 L of distilled water.
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
2-2-2 Preparation of fortification standards 50 pg/ml and 100 pg/ml PFOA solution was prepared using a solvent ( 2 / 8 (wt) mixture of
distilled water / ethanol). 10 mg/ml 8-2 alcohol solution was prepared using isopropanol (IPA) for solvent
for the use of latter section (2-3).
2-2-3 Preparation of a surrogate standard 100 ng/ml 9H-PFNA solution was prepared using a solvent (1 /1 (wt) mixture of distilled water /
ethanol).
2-2-4 Preparation of calibration standards 0, 0.1, 0.2, 0.4 ml of the 100 pg/ml PFOA solution was diluted by IPA up to 5 ml. 100 pi of the
each solution and 9ml of 100 ng/ml 9H-PFNA solution was mixed in a vial. About 1 ml of each solution was filtered through a 0.2 pm filter, Millex-LG (MILL1PORE, U.S.A), into an auto-sampler vial and injected twice into LC/MS conditioned as follows.
2-2-5 Extraction of PFOA from the polymeric product Before the sampling of the polymeric product they were shaken well without generating bubbles
to homogenize the polymeric product. 1 ml of the polymeric product was put in each of four centrifugation vials. Fortification of PFOA and 8-2 alcohol were conducted as listed in Table 1. Fortification of 8-2
alcohol was conducted for the use of latter section (2-3). IRA was added into all vials until total amount
with fortification solution was 5 ml. After putting a lid, each of five vials (with the blank) was shaken vigorously and the precipitation was separated by centrifugation at 6000 rpm for 10 minutes. About 3 ml of each supernatant was dealt out for 8-2 alcohol determination by GC.
100 pi of the each supernatant and 9ml of 100 ng/ml 9H-PFNA solution was mixed in a vial. About 1 ml of each solution was filtered through the 0.2 pm filter into an auto-sampler vial and injected into LC/MS conditioned as follows. These procedures were repeated once again for the verification of the reproducibility.
Table 1 Fortification of C8 precursors and PFOA
Sample
Fortification
10 mg/ml 8-2 alcohol
PFOA
A 0 pi 0 pi
B
50 pi
100 pi X 50 pg/ml
C
100 pi
100 pi X 100 pg/ml
D
200 pi
200 pi X 100 pg/ml
2-2-6 LC/MS analysis LC/MS analysis was conducted with the conditions listed below.
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
<Instruments> (1) LC/MS
HPLC Mass spectrometer (2) LC column (3) PC (4) Software (5) LC/MS vial
Agilent Technologies, Model 1100 Agilent Technologies, Model 1100MSD (SL) Imtakt (Tokyo, Japan), cadenza CD-C18 2 mm (diameter) X 100 mm Hewlett Packard Kayak PC Workstation OS: MS-Windows NT 4.0 LC/MSD ChemStation, Rev. A. 08. 03 2ml vial for auto-sampler, Chromatography-Convenience 400-C80, Tomsic (Tokyo, Japan)
<Analytical conditions> (1) Column temp. (2) Mobile phase
(3) Gradient condition
(4) Flow rate (5) Injection volume (6) Retention time
35 C A: 2 mmol/L ammonium acetate B: Methanol time/min 0 2 5 15 15.01 B/% 57 -> 57 -> 100 100 -> 57 0.3 mL/min 5 pL PFOA (4.3 min), 9H-PFNA (2.5 min)
25 57
<MS operating parameters>
(1) Ionization mode
Electrospray (ESI) (negative ion mode)
(2) Fragmentor voltage 100 V
(3) Ion monitored
m/z = 413 (C7F15COO ), 445 (CF2H(CF2)7COO )
(4) Desolvation temperature 350 C
(5) Nebulizer gas
N2
(6) Desolvation
N2 12 L/min
2-2-7 Results Two calibration curves for standard addition method are plotted and shown in Fig. 1 for the ratio
of (peak area of m/z = 413) / (peak area of m/z = 445) as a vertical axis against the amount of PFOA fortification (pg) as a horizontal axis. The coefficients of correlation are more than 0.9990 for both curves, and the amounts of PFOA determined in the polymeric product are (CBI) ppm and (CBI) ppm (average (CBI) ppm). (CBI) ppm is equivalent to (CBI) mol/kg (specific gravity of AAA is (CBI)).
Two calibration curves for PFOA calibration standards are shown in Fig. 2 for the same axis with Fig. 1. PFOA is not detected (zero count) for 0 pg standard (blank). The coefficients of correlation are more than 0.9995, and the recovery defined as (the slope for the standard addition) / (the slope for the
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
calibration standards) was 95%. All the linearity of the calibration curve, reproducibility of the result, and recovery satisfied the criteria stipulated in the attachment 1.
(CBI)
(CBI)
Fig. 1 Calibration curves for AAA by standard addition method
Fig. 2 Calibration curves for PFOA calibration standards
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
2-3 Determination of 8-2 alcohol and C8 precursors in the polymeric product
The method validation and determination was conducted according to the Attachment 1 of this report for 8-2 alcohol. C8 precursors other than 8-2 alcohol were determined by absolute calibration method using 4 calibration standards, and not evaluated by standard addition method.
2-3-1 Test and control substances
The test substances used in this section are listed in Table 2. These substances were used without
further purification process.
Table 2 The test substances used in 2-3
Standards
Origin
Purity by GC
8-2 alcohol
Reagent grade, purchased from Daikin fine chemical (A-1820 lot. A18202601)
8-2 acrylate
Received from Seimi Chemical Co., Ltd. (Kanagawa, JAPAN)
99.71 (FID area)%
8-2 olefin
Prepared in-house
99.75 (FID area)%
C8 ethyl iodide
Reagent grade, purchased from Daikin fine chemical (1-1820 lot. I18200Z01)
C8 iodide
Prepared in-house
89.77 (FID area)%
2-3-2 Preparation of fortification and calibration standards Mixture solutions of 8-2 alcohol and C8 precursors were prepared using IPA as a solvent as
listed in Table 3.
Table 3 Preparation of 8-2 alcohol and C8 precursor standard solutions
(xg/ml IPA solution
Standard 8-2 alcohol 8-2 acrylate 8-2 olefin C8 ethyl iodide C8 iodide
A 10 10 10 10 1
B 50 50 50 50 5
C 500 500 500 500 50
D
3000
3000
3000
3000
300
2-3-3 Extraction of C8 precursors from the polymeric product Extraction procedures of 8-2 alcohol and C8 precursors are explained in 2-2-5.
2-3-4 GC analysis GC analysis was conducted with the conditions listed below.
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
<Instruments> (1) GC/MS
GC Integrator (2) GC column (5) Auto-sampler vial
HP 5890 series II with auto-injector HP 3396C (CBI) 2ml vial for auto-sampler, Chromatography-Convenience 400-C80, Tomsic (Tokyo, Japan)
<Analytical conditions>
(1) Injector temp.
220 C
(2) Oven temp.
40 C (2 min) 10 C/min - 170 C (0 min) - 30 C/min
-> 250 C (10 min)
(3) Transfer line temp.
250 C
(4) Column top pressure 15 psi constant
(5) Split flow
50 ml/min
(6) Injection volume
lp l
(7) Carrier gas
He (>99.99%)
(8) Retention time (Rt, min)
Rt: 12.2 min (8-2 alcohol)
Rt: 14.4 min (8-2 acrylate)
Rt: 5.4 min (8-2 olefin)
Rt: 13.0 min (C8 ethyl iodide)
Rt: 7.4 min (C8 iodide)
2-3-5 Results Calibration curves for determination of 8-2 alcohol in AAA by standard addition method are
plotted and shown in Fig. 3. Two curves from different runs, which include the different pretreatment runs, are reproducible. Surrogate standard is not used in this section, therefore, the vertical axis is for GC FID peak area (%) and the horizontal axis is for the amount (pg) of 8-2 alcohol fortified to the 1ml polymeric product.
Three calibration curves for 8-2 alcohol calibration standards are shown in Fig. 4 for the equivalent axis with Fig. 3. That is, the horizontal axis of Fig. 4 shows the amount in 5ml IPA, which is equal to the amount in 1ml polymeric product supposing that the recovery is 100%. In the same way, calibration curves for calibration standards for C8 precursors are shown in Figs. 5-8.
The results are arranged in Table 4. All the reproducibility and recovery satisfied the criteria provided in the Attachment 1.
Chemicals Company, ASAHI GLASS CO., LTD. (CB1)
04/07/05
Fig. 3 Calibration curves of 8-2 alcohol by standard addition method
0.12 y = 0.0000073 * + O0009B2
0.10 .
R* = 09999987 ' y=00000073*+ 00001999
2nd i n e
0.9999702
0.08
#I
y = 0.0000072* +
S 0.06 -
---------t s .
m-''~ nvr-\ ffrtfTf&r-T*
1st time 2nd time * 3rd time
76. '
-J ;
0 2000 4000 6000 8000 10000 12000 14000 16000 8-2 alcohol concentration (jig/5 ml IPA)
Fig. 4 Calibration curves of 8-2 alcohol calibration standards
1st time 2nd time A 3rd time
0 2000 4000 6000 8000 10000 12000 14000 16000 8-2 acrylate concentration (pg /5 mi IPA)
Fig. 5 Calibration curves of 8-2 acrylate calibration standards
FID area (%)
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
FID area (%)
FID area (%)
0 2000 4000 6000 8000 10000 12000 14000 16000 8-2 olefin concentration (gg /5 ml IPA)
Fig. 6 Calibration curves of 8-2 olefin calibration standards
8-2 ethyl iodide concentration (|ig /5 ml IPA)
1st time 2nd time * 3rd time
0 200 400 600 800 1000 1200 1400 1600 C8 iodide concentration (ug /5 ml IPA)
Fig. 8 Calibration curves of C8 iodide calibration standards
FID area (%)
Chemicals Company, ASAH1 GLASS CO., LTD.
04/07/05
Table 4 Result of determination for 8-2 alcohol and C8 precursors
Component Retention time (min)
8-2 alcohol
8-2 acrylate
8-2 olefin C8 ethyl iodide C8 iodide
run
MoJecular weight (g/mol)
Absolute calibration method (ppm)
1 2
average (ppm)
average (mol/kg)
Standard addition method (ppm)
1 2
Recovery (%)
\ 2
2-4 Weight % solids
Before the analysis, weighing bottles were dried in a oven set at 120 C for more than 30 minutes and left for cooling in a desiccator for 15 minutes. About 1 g of polymeric product was weighed precisely into a weighing bottle after mixing well. This bottle was put in the oven for 4 hours, and after that left in a desiccator for 15 minutes. The weighing bottle was weighed and the solid content was calculated. The result was (CBI)%.
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
2-5 Determination o f total inorganic fluoride
Total inorganic fluoride, the amount of fluoride containing in the polymeric product without such treatment as combustion, is determined by ultrafiltration of the polymeric product and subsequent determination using ion chromatography. At first, 2 ml of the polymeric product was filtered using ultrafiltration membrane. After filtration, 1 ml of the polymeric product (containing practically no polymer) was diluted by 4 ml of distilled water and injected into an ion chromatograph conditioned below.
2-5-1 Apparatus and conditions
<Ultrafiltration>
Membrane
ADVANTEC
Ultra Filter Unit USY-1
<Ion Chromatography>
Ion chromatograph
Dionex DX-500
Column
Ionpack AG11HC x 2
Mobile phase
KOH aq
Flow rate
1.0 ml/min
Gradient condition
time/min 0 -> 5 7 -> 17 20 30
B/mM 2 -> 2 -> 60 60 2 2
Injection volume
50 L
Suppressor
ASRS
Detector
Conductive Detector
2-5-2 Procedure of determination Absolute calibration curve of fluoride was generated for calibration standards consist of
potassium fluoride. Fluoride content of the polymeric product was determined using this calibration curve by absolute calibration method.
2-5-3 Result Fluoride was determined to (CBI) ppm in AAA.
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
2-6 Determination of total organic fluorine (TOF)
TOF was obtained by combustion-pyrohydrolysis, fluoride trap into aqueous alkaline, followed by determination by ion chromatography. At first, about 20 mg of the polymeric product was heated on a hot plate set at 120 C for 30 minutes. Then, known amount (2 ~ 3 mg) of the polymeric product was introduced into a combustion-F ion analyzer conditioned below.
< Apparatus and conditions >
Instrument
(CBI)
Combustion conditions (CBI)
Ion chromatography conditions Column Mobile phase Injection volume Suppressor Detector
lonpack AG12+AS12 (Dionex) 2.7mM Na2C 0 3+ 0.3 mM-NaHCOj 10 pJL ASRS Conductive Detector
<Procedure of determination> Calibration curve of fluoride was generated using an ion chromatography for calibration
standards consist of potassium fluoride. TOF of standard poly(tetrafluoroethylene) (PTFE, prepared in-house) was obtained and compared with the theoretical value of 76 wt%. TOF of the polymeric product were determined using the calibration curve by absolute calibration method and corrected by the recovery of standard PTFE.
<Result> TOF of standard PTFE was 71.1%. Therefore the recovery of the combustion was calculated to
93.5%. TOF of AAA was (CBI)% and corrected to (CBI)% using the recovery of standard PTFE. TOF calculated from the composition of the polymeric product (theoretical amount) were (CBI)%. Empirical and theoretical values were in good agreement for the polymeric product.
Chemicals Company, ASAHI GLASS CO., LTD.
04/07/05
2-7 Calculation of total carbon
Total carbon in the polymeric product is estimated by calculation based on the sample calculation of Attachment 2. Carbon content is calculated to (CBI)%.
2-8 Calculation of Molality of 8-2 alcohol
Molality of 8-2 alcohol in the polymeric product is estimated by calculation based on the sample calculation of Attachment 3. Molality of 8-2 alcohol is calculated to (CBI) mol/kg.
3. References 0 Purification and characterization of purified Telomer polymer by Asahi Glass, submitted to EPA on May 07, 2004, contains TSCA CBI 2) OECD guidelines 118 ("Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography") 3) OECD guidelines 119 ("Determination of Low Molecular Weight Content of a Polymer using Gel Permeation Chromatography") 4) Isemura, T. et. al.; J. Chromatogr., Vol 1026/1-2, pp 109-116 (2004)
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Attachment 1 - Validation Example
A simple validation method to determine PFOA in the purified polymer is proposed. Equivalent method can be employed for the determination of C8 precursors and for the determination of PFOA and C8 precursors in polymer products.
Standard addition method to determine PFOA in the purified polymer a. Known amount of PFOA (p*q) mg is added to the purified polymer by addition of p ml of q mg/ml PFOA ethanol solution. A zero addition sample and two samples containing varied concentrations should be prepared (three concentrations in all). The amount of the addition should be in the range of 0 - 5 times of expected amount in the purified polymer.
b. For example, if 1 ppm PFOA is expected in the purified polymer, 0.0, 1.0, 2.0 pg PFOA is added to the 1 g purified polymer.
c. PFOA is extracted by ROH (MeOH or EtOH) addition, ultrasonication, and centrifugal separation. Soxhlet extraction by ROH may also be available. Final volumes for all samples must be identical.
d. Extracted ROH is introduced into the LC/MS(/MS) after the dilution if necessary. Dilution solvent may contain water to prevent band broadening in the HPLC column. Internal standard may be added into the extracted solution for the compensation of the fluctuation of injection volume and MS sensitivity.
e. The standard addition calibration curve is plotted against the added PFOA weight. The vertical axis is PFOA area (count) or (PFOA area (count)) / (internal standard area (count)).
f. If the calibration curve (a*x + b) satisfied the criteria of R2 > 0.99, it is valid.
g. PFOA content is obtained from the calibration curve where PFOA content = b/a or y-intercept.
h. Example calculations are shown below.
Chemicals Company, ASAHI GLASS CO., LTD.
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PFOA added to the lg purified polymer
Fg 0.0 1.0 2.0
PFOA concentration after extraction and dilution based on 100 % recovery
pg/ml 0.00 0.02 0.04
PFOA area
count 30,300 68,500 113,000
PFOA content = 0.71 pg/g = 0.71 ppm
Reproducibility of the method and homogeneity of the purified polymer a-g is repeated once more (2 times in all) for subsamples of the same purified polymer. If the two PFOA values are within the 15% of their average value, both the reproducibility of the method and homogeneity of the purified polymer are sufficient, and the PFOA value is the average value.
Recovery criteria Calibration curve for the standards Four concentrations of PFOA solutions containing a solvent blank (not extracted solution but pure standard solutions) are injected into LC/MS. The composition of ROH and water in the solvent should be identical with that injected in the standard addition method (d). Internal standard should be added by similar method. The concentration range should be equivalent to the standard addition range conducted in (a). The PFOA should not be detected or less than 20% of the count of the lowest standard concentration for the solvent blank. The calibration curve for the standards is plotted. If the calibration curve (c*x + d) satisfied the criteria of R2 > 0.99, it is valid. Recovery is defined as (the slope for the standard addition) / (the slope for the standards). If the recovery satisfied the criteria of 70-120%, it is valid.
Example calculations are shown below.
Chemicals Company, ASAHI GLASS CO., LTD.
Calibration curve for the standards> PFOA concentration pg/ml 0.00 0.01 0.03 0.05
04/07/05
PFOA area count 100 27,000 75,000 130,000
Recovery:
2067500 2574746
= 0.80 = 80%
Recovery is affected by both the matrix effect and extract efficiency. Recovery does not mean the value (PFOA determined) / (amount of PFOA in the purified polymers), but the value (PFOA recovered) / (PFOA added into the purified polymers). The recovery based on the former definition is practically impossible to obtain because all PFOA in the purified polymers must be extracted. Generally, the recovery is determined based on latter definition.
Chemicals Company, ASAHI GLASS CO., LTD.
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Example method details The amount of the purified polymer: Ig Expected PFOA in the purified polymer: lppm
<Standard addition method: 1 0.00, 0.10, 0.20 ml of 0.01 mg/ml PFOA EtOH solution is added to the 1 g purified polymer. 2 4.80 - 5.00 ml EtOH is added to the each polymer (total 5 ml EtOH) 3 PFOA is extracted by ultrasonication and centrifugal separation. 4 0.1 ml of extracted ROH is taken out into a vial and 0.9 ml of (EtOH:water = 1:1 (wt)) is
added and mixed well. 5 The mixture is introduced into the LC/MS(/MS). 6 The standard addition calibration curve is plotted against (PFOA weight added) / lg. The
vertical axis is PFOA area (count).
Calibration curve for the standards 7 0.00, 0.01, 0.03, 0.05 pg/ml PFOA (EtOH:water = 1:1 (wt)) solutions (not extracted solution
but pure standard solutions) are injected into LC/MS(/MS). 8 The calibration curve is plotted. 9 On the same graph, standard addition curve is plotted by PFOA concentration for the
extracted and diluted solution as horizontal axis. 10 If the "recovery" is 100 %, the slopes of two calibration curves are expected to be identical.
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Attachment 2 -Example Calculations of Carbon Content
The example is based on the estimation that the purified polymer is based on e.g. 4 different monomers used in the following weight percent
60%
35% 2.5% 2.5%
RfC2H4OCOCH=CH2 (the Rf chain distribution average may be equivalent for C9Fi9) C18H37OCOCH=CH2 HOC2H4OCOC(CH3)=CH2 HOCH2NHCOC(CH3)=CH2
Monomer type
Rf(= C9F19)C2H4OCOCH=CH2 Ci8H37OCOCH=CH2 HOC2H4OCOC(CH3)=CH2 HOCH2NHCOC(CH3)=CH2
Formula
C14F19H702 C21H40O2 C6H10O3 C5H9N02
MW [g/mol] 568,2 324,5 130,1 115,1
C-content [%] 29,6 77,2 55,4 52,2
On that basis the C-content of such a polymer will be 17.76% (29.6x 0,6) for RfC2H4OCOCH=CH2 (for Rf-average C9F19) 27.02% (77.2x0,35) for C18H37OCOCH=CH2
1.385% (55.4x0,025) for HOC2H4OCOC(CH3)=CH2 1.305% f52.2x0.025') for HOCH,NHCOaCHA=CH, 47.47% Sum
The carbon content in such a polymer will be approximately 47.5%.
Chemicals Company, ASAHI GLASS CO., LTD.
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Attachment 3 - Example Calculations of Molality of 8-2 TB alcohol in polymer
In order to compare the 8-2 TBA content in the different polymer types in addition to a mass based approach (e.g. 8-2 TBA/kg polymer) the content of 8-2 TBA also is needed on a molar basis (moles of 8-2 TBA/kg polymer). The 8-2 TBA content on a molecular basis will also allow a correct interpretation of the test results with respect to the potentially formed transformation products that have different molecular weights in comparison to 8-2 TBA.
In table 1, an example calculation is given for a pure 8-2 acrylate homopolymer.
Table 1. No. Description 1 8-2 TBAlcohol (MW) 2 8-2 acrylate (MW) 3 Repeating group in homopolymer (MW) 4 Molality of homopolymer 5 Molality of 8-2 TBAlcohol in homopolymer 6 Concentration of 8-2 TBAlcohol in homopolymer 7 Massfraction of 8-2 TBAlcohol in polymer
Values 464.11 g/mol 518.16 g/mol 518.16 g/mol 1.93 mol/Kg 1.93mol/Kg
896 g/Kg 89.6 % w/w
Remarks
= 8-2 acrylate [10001/518.16 mol/Kg
[11*[S] [61/10
In the table 2 an example calculation is given for an 8-2 acrylate co-polymer. The co-polymer's repeating group consists in this case of one molecule of 8-2 acrylate and two molecules of Methyl methacrylate.
Table 2. No. Description 1 8-2 TBAlcohol (MW) 2 8-2 acrylate (MW) 3 Methyl methacrylate (MW) 4 Repeating group in co-polymer (MW) 5 Molality of co-polymer 6 Molality of 8-2 TBAlcohol in co-polymer 7 Cone, of 8-2 TBAlcohol in co-polymer 8 Mass fraction of 8-2 TB Alcohol in polymer
Calculations 464.11 g/mol 518.16 g/mol 100.12 g/mol 718.40 g/mol 1.39 mol/Kg 1.39 mol/Kg 646 g/Kg 64.6 % w/w
Remarks CAS No. 678-39-7 CAS No. 27905-45-9 CAS No. 80-62-6 [2] + 2*[3J [10001/718.40 mol/Kg
[1M6] [6J/10
