25(6)-09().fmhttp://dx.doi.org/10.5806/AST.2012.25.6.395
Development of the testing method for vinyl chloride monomer (VCM) in polyvinyl chloride(PVC) samples
Deok-Jun Kweon, Ki-In Choi, Hui-Jeong Eom, Jae-In Lee and Zel-Ho Choi
Test & Standard Center, Korea Institute of Ceramic Engineering & Technology, Korea
(Received November 23, 2012; Revised December 6, 2012; Accepted December 6, 2012)
PVC
····

(2012. 11. 23. , 2012. 12. 6. , 2012. 12. 6. )
Abstract: This study presents a method for the quantitative analysis of residual vinyl chloride monomer (VCM)
in PVC products. In elution solvent, the extraction efficiency was similar by ethanol, THF, and acetone, but
using n-hexane, it indicated relatively low extraction efficiency. Measuring VCM in the pulverized PVC samples,
it showed reasonable results in both the direct injection method and headspace method with GC/MS. Regarding
analysis of VCM in the intermediate sponge samples, five laboratories showed good results, and from the results,
it was considered that VCM quantitative method in this study was reliable.
: PVC (VCM)
. , , THF, ,
. PVC VCM
VCM , GC/MS
. PVC VCM 5
,
VCM .
Key words: vinyl chloride monomer, polyvinyl chloride, plastics, test method
1.

.

.
Corresponding author
E-mail : kichoi@kicet.re.kr
396 Deok-Jun Kweon, Ki-In Choi, Hui-Jeong Eom, Jae-In Lee and Zel-Ho Choi
Analytical Science & Technology
, ,
(poly vinyl chloride, PVC),
(polystyrene, PS), (polypropylene, PP),
(polyethylene, PE), --
,
, .


.


.

,
.
(
) ,

,
.

.
, PVC
2,300
PE
. PVC , ,

(
)
, ,
, , , ,
, , , , 2
, , ,

. 1935 PVC 1.1
, 1950 22, 1980 1,100
1997 2,300 60
.
1966 11 PVC
,
110 .

-13.9 oC . Table 1 VCM
.1
, PVC VCM ,
VCM , ,
, , , , ,
,
. VCM ,
, , ,
,
(Occupational Safety and Health Administration,
OSHA) VCM
, (International Agency for
K 1 . ,
(European Community, EC) VCM 1
(R 45) ,
VCM
(A1) ,
,
. , FDA
PVC 10 ppb VCM
Table 1. Chemical characteristics of vinyl chloride monomer
Compound Synonym CAS No. Property Use Chemical structure
Vinyl chloride
material
Development of the testing method for vinyl chloride monomer (VCM) in polyvinyl chloride(PVC) samples 397
Vol. 25, No. 6, 2012
PVC
VCM .
Table 2 VCM
. VCM
,
,
.
VCM
PVC (THF)
0730 , KS K 0730
ASTM D 3680 2005
KS VCM
. , PVC
THF VCM (KS K 0730
), PVC THF column
PVC column
, FID
GC/MS (direct injection
VCM (head-space
.

, GC/MS

VCM .
2.
. PVC
PVC ,
. -20 oC VCM
(100 mg VCM/L) 1:9
VCM [1±0.01 mg
VCM/L] GC/MS
Table 2. Standard methods for the determination of vinyl chloride monomer
Method No. Title
KS K 07302 Test method for residual vinyl chloride monomer(VCM) content of poly(vinyl chloride) fiber and resins
EPA 50213 Volatile organic compounds in soils and other solid matrices using equilibrium headspace analysis
ISO 87624 Workplace-Determination of vinyl chloride (charcoal tube/gas chromatographic method
ASTM D 36805
(Withdrawn)
Standard Test Method for Residual Vinyl Chloride Monomer Content of Poly(Vinyl Chloride) Resins,
Compounds, and Copolymers by Solution Injection Technique
ASTM D 37496 Standard Test Method for Residual Vinyl Chloride Monomer in Poly(Vinyl Chloride) Resins by Gas Chro-
matographic Headspace Technique
Fig. 1. PVC grinded sample and PVC sponge sample.
398 Deok-Jun Kweon, Ki-In Choi, Hui-Jeong Eom, Jae-In Lee and Zel-Ho Choi
Analytical Science & Technology
VCM
VCM PVC

. VCM
100 oC VCM

.
“PVC ”
VCM .
40 oC
, VCM -14 oC
-20 oC VCM
. Fig. 1

.
, n-, THF
vinyl chloride gas 10 mL 10
-20 oC 24
VCM .
VCM 2.1
PVC GC/MS
.
, 0.5 g 0.1 mg
20 mL 10 mL
-20 oC 24
VCM . ,
0.5 g 0.1 mg 20
mL
10 mL ,
90 oC 1 -
. PVC
PVC
.
VCM
(splitless injection mode)
1.3 mL/min,
30 oC, initial time 5 min.
240 oC 20 oC/min .
EI 70 eV, Interface temp. 300 oC
GC/MS . Table
3 , VCM
Table 4 .
, VCM
VCM
. VCM (100 µg/
mL) ethanol 1, 2, 5, 10 20
µg/mL .
(response factor)
, (y=2289x-53991, r2=0.996)
,
Table 3. Analytical conditions for the determination of VCM
Gas
Column DB - 624 (30 m × 0.32 mm ID × 0.18 µm
film thickness)
20 oC/min to 240oC
5 min at 240 oC
Table 4. Retention time and selected molecular ion of VCM chromatogram
Compounds Retention time
Fig. 2. Calibration curve for vinyl chloride standard solution.
Development of the testing method for vinyl chloride monomer (VCM) in polyvinyl chloride(PVC) samples 399
Vol. 25, No. 6, 2012
. Fig. 2 VCM
.
. Table 5
, n-, THF
VCM GC/MS()
.
, VCM 329.4 mg/
L~412.1 mg/L ( 370.4 mg/L, 32.5 mg/
L) , THF
VCM 305.3 mg/L
~401.5 mg/L ( 352.8 mg/L, 33.1 mg/L)
. VCM
302.5 mg/L~388.7 mg/L ( 338.9 mg/L,
23.9 mg/L) . , n-
VCM 219.3 mg/L~288.1 mg/L ( 253.9
mg/L, 23.9 mg/L)
. , n-,
THF (/
, coefficient of variation) 0.07, 0.09, 0.09,
0.09 .
VCM ,
, THF
,
()
. , PVC
THF PVC
THF
VCM .
3.2.
1 mg/
kg VCM VCM
Table 5. Leaching concentrations of VCM in various solvents
Solvent VCM concentration (mg/L) Avg.
(mg/L)1 2 3 4 5 6 7 8 9 10
Acetone 324.5 346.7 332.8 329.4 318.1 388.7 356.9 302.5 336.8 352.2 338.9
n-hexane 252.4 288.1 219.3 282.6 220.7 272.8 263.3 251.4 233.6 255.1 253.9
EhOH 386.7 392.0 345.6 329.4 402.2 412.1 329.9 333.0 396.4 376.2 370.4
THF 305.3 321.4 381.2 365.8 392.4 354.2 345.2 312.5 348.2 401.5 352.8
Table 6. Comparison of direct injection and head-space methods with GC/MS
Injection
type
(mg/L)1 2 3 4 5 6 7 8 9 10
Direct injection 1.23 1.42 0.98 0.87 0.84 1.45 1.37 1.21 1.15 0.99 1.15
Head-space method 1.19 1.22 0.98 0.87 1.29 1.35 0.91 1.11 1.45 1.31 1.17
Fig. 3. GC/MS chromatogram of VCM.
400 Deok-Jun Kweon, Ki-In Choi, Hui-Jeong Eom, Jae-In Lee and Zel-Ho Choi
Analytical Science & Technology
. Fig. 3 ,
,
VCM
.
VCM
(selected ion monitoring) , Table
6
,
,
,
VCM
.
3.3. PVC
Table 7 PVC
GC/MS .
10 PVC VCM
8.0 mg/kg (7.1~8.9 mg/kg, 0.6
mg/kg) . ,
VCM

.
4 VCM
.

, PVC
Table 8 .
0.8018,
9.7315%
,
Table 8 Fig. 4 z-score
2 PVC
VCM

VCM
.

, , , ·, ,
, ,
. 2000
, 1
(2009 20
), (2011 166
37% )
.7
Table 7. VCM content in PVC sponge sample
Sample VCM concentration (mg/kg) Avg.
(mg/kg)1 2 3 4 5 6 7 8 9 10
PVC sponge 7.5 8.1 8.3 7.9 7.1 8.9 8.5 7.6 7.4 8.7 8.0
Table 8. Results of interlaboratory comparison test for deter- mination of VCM in PVC sponge sample
Code VCM content
Lab-1(A) 7.6 5.0 -0.49
Lab-2(B) 7.5 6.3 -0.61
Lab-3(C) 8.7 -8.7 0.86
Lab-4(D) 9.4 -17.5 1.72
Lab-5(E) 8.0 0.0 0.00
Fig. 4. Results of interlaboratory comparison test for determi- nation of VCM in PVC sponge sample (z-score).
Development of the testing method for vinyl chloride monomer (VCM) in polyvinyl chloride(PVC) samples 401
Vol. 25, No. 6, 2012


VCM

. , , THF,
. ,
PVC VCM
VCM ,
GC/MS
. PVC
VCM 5
,

VCM
.
vi_commitment2.html
2. KS K 0730, Test method for residual vinyl chloride
monomer(VCM) content of poly(vinyl chloride) fiber
and resins, Korean Agency for Technologys and Stan-
dards, 2009.
and other solid matrices using equilibrium headspace
analysis, US Environmental Protection Agency, 1996.
4. ISO 8762, Workplace-Determination of vinyl chloride
charcoal tube/gas chromatographic method, Interna-
tional Organization for Standardization, 1988.
5. ASTM D 3680, Standard Test Method for Residual
Vinyl Chloride Monomer Content of Poly(Vinyl Chloride)
Resins, Compounds, and Copolymers by Solution
Injection Technique, American Society for Testing and
Materials, 2005.
Vinyl Chloride Monomer in Poly(Vinyl Chloride) Res-
ins by Gas Chromatographic Headspace Technique,
American Society for Testing and Materials, 2008.
7. Ministry of Knowledge Economy, http://www.mctnet.
org/index.jsp