I!
Anal. Chem. 1999,71,468-475
Identification and Determination of Cross-Linkers
in Cross-Linked Poly(vinylpyrrolidone) by
Pyrolysis-Gas Chromatography/Mass Spectrometry
T~ M. H. Cheng* and Edward Q• ...,..,.;-.
Analytical Department, IntematiohaJ.8pecia/tYProtiUcts,
Pyrolysis-GC and pyrolysi8-'GC/MSwere U8elIto identify
and quantify specific nitrogen-oonmmhiif;~ 1iDker'
compounds incorporated intO the' strud:afei,~(J:rOOin:
mercially available cross-linked po1y(vhijtpyilctiione)
polymers which appear to be identical by Ff-IR ~
scopy. The pyrolyzer regenerates and yolatilia sPed6c
cross-linkers which can be distinguislied from other
pyrolysate compounds by either peak retE:ntion time or
mass spectral response. Individual compounds studied
included 3-ethylidene-l-vinyl-2-pyrroJidone, 3,3'-eth-
ylidenebis(1-vinyl-2-pyrrolidone), andN,N -diviuylimida-
zolidone. In general, the level of specific aoss-liDkers in
various commercial products ranged from 1.8 to 2.5%
w/w. The effect of pyrolysis temperature upon this level
varied with the cross-linkers studied. The aoss-Iinker
content obtained by this technique ootn!IaIed widl the
swell volume data for a specific series of aQ8S-1iD1red poly-
(vinylpyrrolidone) samples madewidl asDlJle auss-linker
and having similar particle size distributioos. The pyroly-
sis methodology cannot distinguish the level cI cross-
linker which is incorporated as a pendant functionality
from that portion which is incorporated through both vinyl
groups.
Cross-linked poly(vinylpyrrolidone) (PVP) or polyvinylpoly-
pyrrolidone (PVPP) is commercially produced by the free radical
proliferous (or popcorn) polymerization of vinyl pyrrolidone (i.e.
1-vinyl-2-pyrrolidone)(VP).1The two principal methods involve
either the heating of VP above 100 °C in the presence of an alkali mechanical techniques. Flory and Rehner developed a relationship
metal hydroxide and a small amount of water.:!or the heating of
an aqueous solution of VP above 100 °C with a small amount of
deliberately added bitunctional monomer.t Bothmethods produce
densely cross-linked structures whichare iriSohiplein ;;""Apd'
only slightly swellable as a result 6ftlietormation Qt' .
derived covalent bonds and physl(:at entanglement"of polamer ". ..:1dullins developed Simpl~relationship based upon stress-strain
chains. Haaf et al. have studied the mechanism of the former
method by quenching the free radical reaction at an early stage
in order to identify and quantify compounds formed.! They
demonstrated that this process generates several cross-linkers in
(1) Barabas. E. In E1ICyClopmia of Polymer Science and EngilUlmrig. 2nd ed.;
Kroschwi1z.]., ed.; John Wiley & Sons: New York, 1989;pp211-213.
(2) Grosser. F. U.S. Patent 2,938,017, 1960.
(3) Hoffmann, E.; Herrle. K U.S. Patent 3.759.880, 1973.
(4) Haaf, F.; Sanner. A; Straub. F. Polym.]. 1985. 17, 143.
468 Analytical Chemistry, Vol. 71, No.2, January 15. 1999
1361 A/psRoad, Wayne, New Jersey 07470 .1
I
'i
situ, namely, 3-ethyliden~1.vinyJ-2-pyrrolidone(EVP) (~1.5%)and I
3,3'-ethylidenebis(1-vinyl-2~pYriolidone) (EBvp) (~O.1%). The ,j
principal cross-linker employedin the latter process is N,N-
divinylimidazolidone(or N,N-divinylethylene urea) (DVI).Despite
the incorporation of 1-4% of cross-linker into the final popcorn
polymer, the infrared spectra of the final products of these
processes cannot be differentiated from one another or from that
of linear PVPl owing, undoubtedly, to the spectral similarity of
the functional groups ofthe aforementioned cross-linkers and VP. 1
PVPP is primarily used in two applicationsareas: as a beverage I l
clarifier and as a pharmaceutical tablet disintegrant, It has been
in use since 1961 for the clarification of beer by the removal of
chill haze and precursorsf This results from the specificity of )1
PVPP hydrogen bonding to particular polyphenolic substances I I
known as anthocyanogens, which are responsible (together with
certain proteins) for the haze formation in refrigerated beer and,
I I
hence, for reduced shelf llfe.6 The material's use as a tablet 1 1
I
disintegrant dates back to ca. 1973.7,8 In these and other applica- I
I
tions, the fine structure of the polymer, particularly the degree of \
chemical and physical cross-linking,plays a large role in determin- i
ing whether the material's physical properties are suitable for the I
i
intended use. Such parameters as the swell volume, the amount
of residual soluble PVP, and the adsorptive capacity (i.e., the
relative ability to adsorb a model phenolic compound, catechinj"
I
are all heavily influenced by the amount of cross-linker incorpo- j
rated.
The determination of the degree of cross-linking has long been
treated by physicochemical methods, particularly by swelling and
for the molecular weight between cross-links for a cross-linked
polymer swollen in a good solvent (at equilibrium) which depends
on knowledge of the volume fraction of polymer in the swollen
.'!Ja~the~po1ar~ol~~ of the solvent, the polymer-solvent
mtlirtidion;""~'.;·i~\and
.~ ,...••.. ~." ,0:0.-.. the polymer density.loAlternativel
,y,
a
measurement for the cross-link density as a function of Young's
(5) McFarlane, W. D.; Bayne, P. D. Proc. Congr. Ear. BreII!. Conu. 1961. 8.
278-285.
(6) Dadic, M.; Lavallee 1. G.]. Am. Soc. BfflQ, Chem. 1983. 41. 141-147,
(J) Kornblum, S. S.; Stoopak, S. B.J l'ftann. Sci. 1973.62,43-49.
(8) Strom,]. G. In Handbook of Phar1tll.lUUtiCIJ/ &cipi8llts, 2nd ed.; Wade. A;
Weller, P. J. Eds.; The Pharmaceutical Press: London. UK. 1994.
(9) Polyclar Super R product specification. International Specialty Products,
Wayne, NJ. 1997. .
(10) F1ory, P. }.; Rehner. ].]. Chem. Phys. 1943, 11, 521.
10.1021/ac9804689 CCC: $18.00 e 1999 American Chemical Society
Published on Web 1210411998
IIIF""'---------------~------------.-
modulus and the lengths of the dry and swollen polymer sample
(at equilibrium).'! Neither of these classical, nonspecific methods
apply to PVPP, however, as both require a continuous specimen
whose dimensions are known while PVPP exists as an irregular
particulate powder.
A wide variety of instrumental analytical methods have been
employed to measure specific cross-linkers in cross-linked sys-
tems. For example, Sherinski employed infrared laser spectro-
scopy to measure a cross-linker in a silicone processing unit on-
line based upon its unique and strong carbonyl group absor-
bance.P Barrall et al. performed ultraviolet spectroscopy analyses
upon poly(dimethylsiloxane) films to determine the level of cross-
linker incorporated.P Infrared methods are not applicable to PVPP
because of the previously cited simi1arityin the functional groups
of the base pOlymer and the cross-linkers used. UV methods ate
equally inapplicable owing'to the particulate nature of the material
and the lack of UVchromophores in these cross-linkers. Pyrolysis-
gas chromatography (or pYrolysis-gas chromatography/mass
spectrometry) has been applied to the specific analysis of cross-
linkers in cured materials for many years.14,15 A similar technique,
thermogravimetry-GC/MS, has also been used to study the
composition of cured epoxy resins," -
Pyrolysis-GCwas first applied by Goetz et al. to pure PVP using
a Curie-point pyrolyzer and a flame ionization detector (FID) and
found that the principal compounds produeed were VP and
2-pyrrolidone (2-Py).17Ericsson and IJunggren inV'~ted the
possibility of using pyrolysiS'GCto deterininetrace levels ofPVP
in poly(ethylene oxide) filmS.18Cheng and MaIawerintroduced a
pyrolysis-GCmethod to test commercial'beers for traces of soluble
PVP in which an analyte concentration scheme' and a nitrogen
detector were employed to increase sensitivity.19As in the Ericsson
and IJunggren work, the method relied upon the unique retention
time of VP as a PVP signature compound. In the present work,
pyrolysis-GCwith FID detection and pyrolysis-GC/MS are applied
to pure PVPPin order to identify and quantify the cross-linker(s)
employed' in manufacture in several commercial samples. The
method. relies on the regeneration of volati1izable cross-linker
compounds (such as EVP, EBVP, and DVI) upon pyrolysis which
can be distinguished from other compounds in the pyrolysate by
either GC separation or distinct mass spectral response.
EXPERIMENTAL SECnoN
Ma1Erials~ PVP K-30 (average MW ~57 000 amu) was ob-
tainedfrom International Specialty Products; Inc. PVPP1 and
PVPP2 Were commercial PVPP products made by an alkali metal
hydroxide process. 20-22 PVPP 3, PVPP 4, and PVPP 5 were
(11) Mullins,.!,; J.APPL Po/ym. Sci. 1959,2, 257.
(12) Sherinski, 1. R U.S. Patent, 4,227,083, 1980.
(13) Barrall, E. M., D; Hawkins, R; Fukushima, A A; Johnson, J. F. J. Po/ym.
Sci.: Po/ym. Sytnp. 1984, 71,l89-:w2.
(14) Prob~ J{./{w1lSlstl1/fe 1976, 66, 379-380.
(15) Karino, 1; Amaniura, T.;Enomoto, J. MiIssdJisJriDe1Iki GiIto 1978,52, 910-
-914.
(16) Okino, T.; Takahashi, 5.; Harigai, T.; Shiratsuchi, K SJaimadzu Hyorrm 1987,
44, 213- 217.
(17) Goetz, N.; Lasserre, P.; Kaba, G. In Co.smeticAMlysis: SelectedMeIhodsand
- Tedcfliqlus (Cosmdic Sci_ au TecJIJwlogJSeries4); Bore, P., Ed; Marcel
Dekker: New York, 1985.
(18) Ericsson, I.; IJunggren,1.J. AMI. APPl Pyrol. 1990,17,251-260.
(19) Cheng,T. M. H.; Malawer, E. G.I.Am. Soc. Brew. CMm. 1996,54,85-
90. . . . .
(20) Grosser, F.; Park, M.; Hart, E. V.: Schwartz, A U.S. Patent 3,277,066, 1966.
commercial PVPP products made by a DVI-based process.23,u cis-
EVP, 95.8% pure, was obtained by fractional distillation of a
laboratory sample of EVP, which was isolated from the reaction
products of VP arid NaOH. cis-EVP was used only for peak
identification.trans-EVP used in this study was a laboratory sample
of 99%purity. EBVP was a laboratory sample synthesized accord-
ing to the procedure of Hort, Grosser, and Schwartz.25 N,N-
divinylimidazolidone (DVI)was produced by BASF.
PVPP standards containing 0.5%,1.0%,2.0%,and 4.0%(w/w)
EVP (from trans-EVP) were prepared by reacting VP and EVP in
an aqueous solution at 100 °C without any initiator. PVPP
standards containing 1.96%,2.91%,and 3.85% (w/w) DVI were
prepared similarly. PVPP standards containing less than 2% or
more than 4%DVI were also synthesized, but the amount of cross-
linker incorporated into the polymer could not be accurately
ascertained due to incomplete polymerization. Several standards
of PVPP containing the EBVP cross-linker were also synthesized.
These polymer samples were used for identificationpurposes only.
Kraton 1107,a styrene/isoprene/styrene block copolymer, was
obtained from CDS Analytical Ine. (Oxford, PA).
Apparatus. The pyrolysis-GC system consisted of 'a CDS
Pyroprobe2000 (CDS Analytical Inc., Oxford, PA) coupled to a
HP5890 GC (Hewlett-Packard Co., Palo Alto, CA) with a flame
ionization detector. The pyrolyzer was a coil probe with a quartz
boat sample holder. The quartz boat \vas a commercial product
available Irl)m CDS. It is more convenient to weigh a powder
sample into a quartz boat than into a quartz tube. A heating tape
was wrapped around the exposed portion between the pyrolyzer
interface and the GC injector to prevent cold spot condensation.
A HP597Lmass detector was connected to the same HP5890 GC
for pyrolysis-GC/MS analysis. The capillary GC column used for
the pyrolysis-GC work, DB-1301, 30-m length, O.53-mmi.d, and
1.O-llm film thickness O&W Scientific, Folsom, CA)was coated
with poly(94%dimethylsilo~e-6% cyanopropylphenylsiloxane).
A DB-1301 column of 0.25-mm Ld., 30-m length and 1.O-llm film
thickness was used in the GC/MS study. An analytical balance
capable. of weighing to 0.01 mg was used to weigh each sample
into a quartz boat
The particle size distribution ofPVPP was measured with a
Microtrac SRA,series 9200 laser, diffraction type particle size
analyzer with sample reclrculator.and dry powder feed (Honeywell
Inc., Austin, TX). A 100-mLgraduated cylinder, 1.0 mUdivision,
with ground glass stopper was used to measure the Swellvolume
of PVPP in water.
Pyrolysis and Chromatographic Conditions. The sample
size used for this study was kept between 0.2 and 0.3 mg for
pyrolysis-GC and 0.1-0.2 mg for pyrolysis-GC/MS;Though the
sample weight was not used for calculating the cross-linker level
in PVPP, a sample size too large .or too small could affect the
precision of analysis.
The sample was placed in the center of a quartz boat A pair
of tweezers with sharp tips was used to transfer a small amount
of PVPP to the -sample boat The pyrolyzer· temperature was
calibrated to be -685 °C and the sample waspyrolyzed for 20 s.
(21) Grosser, F.; Park, M.; Hort, E. V.; Schwartz,A U.S. Patent 3,306,886, 1967.
(22) Shih, J. S~ Tseng, S. Y. U.S. Patent 5,286,826, 1994.
(23) Hoflinann, E.; Herrle, K U.S. Patent 3,759,880, 1973.
(24) Denzinger, W.; Hoffmann, E.; Herrle, K U.S. Patent 3,992,562, 1976.
(25) Hart, E. V.; Grosser, F.; Schwartz, A U.S. Patent 3,294,765, 1966.
Analytical Chemistry, Vol. 71, No.2, January 15, 1999 469'

".0."
..•
..
Time (Dlin)
...
Figure 1. Pyrogramof Kraton1107at 722°C pyrolysistemperature.
.Peak: 1, isoprene;2. styrene; 3. 1.4-dimethyl-4-vinyl-i-cyclohexene;
5. i-methyl-4-(i-methylethenyl)cyclohexene(dipentene).
Table 1. Temperature Calibration of CDS 2000 Coil
Probe with Quartz Boat Sample Holder
set probe peak area ratio, equivalentpyrolysis
temp, °C isoprene/dipentene temp, °C
850 4.756
800 3.509
~ 2~
.700 2.366 -. 685..
650
600
2.015
1.686
The pyrolysis temperature ramp was 20 °C/IDS.. 'l.'he:Gtiiiijector
and detector temperatures were set to 240 and 260 OC; 'te!!peC-
tively, and the interface temperature was set to 24C)'''C;'l'he GC
oven was held at 50 DCfor 1 min and then programmed·at 10
°C/min to 240 DCand held for 20 min. The helium carrier gas
flow rate was set at 8 mUmin, and the split ratio was ~6.
After each GC analysis was completed, the coil probe was
withdrawn from the interlace, and the quartz boat was cleaned in
the air at an 850°C probe temperature (not the true pyrolysis
temperature) until the residual sample was completely burned off.
Calibration ofPyroptobe Temperature. It is not necessary
to know the true pyrolysis temperature in order to perform this
analysis. However, pyrolysis temperature does affect the relative
responses of the cross-linkers and thus the slopes of calibration
curves. The pyrolysis temperature of the CDS·,2000coil probe
used in this study was calibrated according to the' "model
molecular thermometer" of levy and WaIker.26Figure 1 shows
the pyrolysis chromatogram (pyrogram) of Kratonl107.at722
°C pyrolysis temperature. The peak area ratio of isoprene
(2-methyl-1,3-butadiene)to dipentene (l-methyl-4-(l-methylethen-
yl)cyclohexene) was used for temperature calibration. The cal-
culated equivalent temperatures of the probe are listed in Table
1. It can be seen that the probe temperature does not correlate
linearly with the equivalent pyrolysis temperature. Most of the
data discussed in this paper were obtained at the pyrolysis
temperatures of either 685 or 722 DC.
Swell Volume of PVPP. The test was performed by placing
10.0 g of PVPP in a lOQ-mLgraduated cylinder~About 50 mL of
(26) Levy. E. J; Walker, J. Q. J. Chromatogr. Sci. 1984, 32, 49-54.
470 Analytical Chemistry, Vol. 71, No.2, January 15, 1999
'·4
20 o >0
Time(min)
•• 0 30
Figure 2. Pyrogram of PVP K-30 obtained at 685 °Cpyrolysis
temperature. L1, mixtureof C~, CaH6.CaH8.and C4 hydrocarbor)s;
L2. CHaCN;L3. benzene; L4, mixture;LS,toluene; L6.2-methylpy-
ridine;L7, styrene and 2-methylpyrrole;LB,benzaldehyde. Hi, H2,
H3, H4, and HSare VP dimers and related compounds.
water was added, and then the contents were mixed thoroughly.
The solution was diluted to 100 mL, stoppered, and allowed to
stand for 24 h. The swell volume was the total volume attained
861 by the solids.
769 1
m
RESULTS AND:DISCUSSION 1
Pyrolysis of PvP. PVP K-30, a linear, non-cross-linked
659
635
polymer of VP, was pyrolyzed to obtain the reference pyrogram.
Figure 2 shows the.GC pyrogram of PVP 100 obtained at the 685
,i l
DCequivalent pyrolysis temperature. Mass spectral inforiIiation 1
provided the identification of most of the peaks. The pyr~ 1
1
can.be.divided into three regions. The low column temperature
r~l!p'!ith ..retention times shorter than that of N-methy1-2- ,j
,
.J?~WlM!lne (NMP) at 9.28min contains peaks 'iliat are m.ostly
from tl:!e~on
region. from
.of the polymer backbone. The middle
the retention time of NMP to ~ 18 min contains
lI
peakS that are mostly substi~ pyrrolidones. The most common
structures are unsaturated' hydrocarbon chains attached to the
nitrogen in the pymindcmerillg. Since the cross-linker peaks are
also eluted in this region. 1;he.pyrogram is further expanded in .
Figure 3 and the Peaks are identified in Table 2. The peaks of
identical molecular weights may appear in more than one place
due to the structural and cis/trans isomers thai-are separated by
the GC column. The majority of the very small JXiaksnot listed
in Table 2 are also pyrrolidone-type compounds: It.should be
pointed out that the 2-pyrrolidone peak (peak 2) in T~le-,4 (and
Figure 3) was due to residual 2-pyrrolidone in PVP. In addmpn.
pyrolysis did generate an additionalamount of 2-pyrrolidonewhich
was buried under the large VP peak. an Table 2,"py" stands for
the pyrrolidone ring.) ,
The high (column) temperature region of the pyTogram in
Figure 2 (i.e., from 18 min to the end of the pyrogram) contains
the peaks ofVP dimers and related compounds. Ifa higher column
final temperature were used for analysis, then trimers and even
tetramers could also be observed. The intensities of these high-
molecular-weighthomologues were relativelysmall, and therefore,
no further information concerning the cross-linkers is gained by
studying peaks in this region.
Pyrolysis ofPVPP 1 and PVPP 2. Both polymers are made
by the in situ generation of cross-linkers using the aqueous alkali
 1.0.

•• t .. '"
"7 "3
.."
,-..

.~
§
7.0

".0_
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.. 14

14·

.0
.!!, ~.O •

.~
~ ..•.
0.

i 3.0.

2.0_

10 . .2 .0 1<5

Time(min) Timc(min)
Figure 3. Expanded pyrogram of PVP K-30 for the region between Figure S. Expanded pyrogram of PVPP 2 for the region between 9
9 and 16 min of the pyrogram in Figure 2. See Table 2 for peak and 16 min of the pyrogram in Figure 4. See Tables 2 and 3 for peak
identification. identification.

Table 2. Retention Times and Peak Identification Table 3. New Peaks from the Pyrolysis of PVPP2
peak retention peak retention
no. time, min identification no. time, min identification

1 9.281 1-methyl-2-pyrrolidon~ (or N-methyl-2-pyrrolidone, PI + peak 7 11.631 mlz =123, C*py, spectrum similar to
NMp) peak 7 ofTable .2
2 10.095 2-pyrrolidone (2-Py) P2 12.468·-,. mlz=1-25;C~Pi
3 10.443 1-Yinyl-2-pyrrolidone (VI') . P3 .. 12~584mlz= 125,C~silY
4 10.522 m/z = 125, probably 3-methyl-VP P4 12.700 mlz = 137, cU-EVP (or (Z)-EVP)
5 10.759 mlz = 125, probably 4-methyl-VP P5 14.038 mlz = 137, tnJns-EVP (or (E)-EVP)
6 11.230 mlz = 125, N-CaHs-py
7 11.656 m/« == 123, N-C*py
8 11.708 m/z = 135, probably a substituted pyridine
9 12.237 mlz = 139, N-C#irP1
10 12.939. mlz = 139, N.:CJlrPY
11 13.061 mlz = 137, N-C#is-py
12 13.403 mlz = 151, unknown
13 14.332 . mlz = 149, probably a quinoline or isoquinoline
derivative
14 14.613 mlz = 137, N-C#is-py
15 15.041 mlz = 155, probably a quinoline or isoquinoline
derivative cls-EVP trans-EVP
Figure &. Structures of cis-EVP and trans-EVP

.otherfhree new peaks in Table 3 are still unknown; The
o 10
'"'0
Time(min)
F'1gU~4. Pyrogram of PVPP 2. See Figure 2 for peak identification
for peaks in the low temperature and high temperature regions.
hydroxide process. It was reported that two cross-linkers, EVP
and EBVP, were present in the aqueous VP solution just before
the start ofpopcorn polyinerization.4Figure 4 shows the pyrogram
of PVPP 2 and Figure 5 shows the expanded pyrogram of.the
middle (column) temperature region. Comparing Figure 4 to
Figure 2, the peaks eluted in the low-temperature region are very
similar. Only the peak 18, which is benzaldehyde, is missing. In
fact, PVPP samples made by other processes also did not show
this 18 peak in their pyrograms.
In Figure 5,the peaks corresponding to those found for PVP
in Figure 3 are labeled with the same peak numbers. The new
peaks are labeled with "P" prefixes and are listed in Table 3.
Peaks P4 and P5 are the cross-linker EVP.Their identities are
confirmed by the mass spectra of authentic compounds and their
retention times. The structures of these two EVP are depicted in
Figure 6, and their mass spectra are displayed in figure 7. The
cis-EVP was present at "'30% of trons-EVP ..The structures ()fthe
significance of the peak 1'3, which is the largest new peak in
Figure 5, will become clear later when the pyrogram of PVPP
made with EBVP is discussed.
.To analyze both EVP and EBVP in PVPP 2, two polymers of
various cross-linker levels were prepared. One was PVPP made
with trons-EVP, and the other was made with EBVP. The
pyrogram for the middle column temperature region of PVPP
made with 4%trans-EVP is shown in Figure 8. Comparing this
pyrogram to Figure 5 for PVPP 2, the two pyrograms are
essentially identical except that the peaks related to the cross-
linker appear in greaterintensity, Alarger sample size was also
used to obtain the pyrogramin Figure 8. Even with an analytical
Analytical Chemistry, Vol. 71, No.2, January 15, 1999 471
 •••

4)
o
20000
(A) Q.O. .,.
Pl
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m1z
O~--~'0~--------'~2~------~~--------~,e
u, Time (min)
4)
o a_o (B)
"0
a Figure 8. Expanded pyrogram of PVPP made 'with 4% ~r;vP
for the region between 9 and 16 min. See Tables 2 and 3 for'~eak
s::: ltOIO identification.
=:s
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1.0.

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O+---~~------~'~2~------~~~----~
s:: n f1
=:s
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-< 200. t. 122
Figure 9. Expanded pyrogiam of PVPP made with 2.5% EBVP for
the region between 9 and 16 min. See Tables 2 ahd 3 for peak
~ooo identification. E1, E2, and E3 are unidentifledsubstituted pyrrolidones.

• ]0
mlz
Figure 7 • Mass spectra of (A) cis-EVP, (B)tlans-EVP,
14 in Figure 3 and Table 2.
balance readable to O;01mg, accurate weighing ofaO.2~mg powder
sample for pyrolysis analysis was still very difficult Thtisquanti1a-
tive analysis for 'cross-linkers in PVPP requires, using. an .internal
reference peak.
The peak.arearatioof cis-EVP to tt'uIU-EVP found in Figure 8
,."
for PVPP which was made with tnBI&-EVP was 0.346. This
compares to 0.342 found for PVPP 2m FJgUre 5. This is expected
since the original cis/trans isomers' identities ofEVP'monomers
should be lost after the cross-linker is incorporated into polymer;
The particular ratio of cis/tt'u1lS-EVP detected in a pyrogram
should reflect the thermal stability of these two isomers at the
110
pyrogram to Figure 8, it is immediately seen that PI is relatively
small in this pyrogram. Furthermore, P2 and P3 are absent Peak
9·is also relatively small as compared to peak 9 in Figures 5 and
and (e) peak 8. The cis/trans ratio of the EVP peaks was found to be 0.362,
which is only slightly greater than the value of 0.346 reported
above for PVPP made with EVP. The difference is within
experimental error.
The above pyrograms indicate that the .EBVP cross-linker leVel
in PVPP can also be analyzed using the EVP peaks in the
pyrogram. The results of analysisfol' cross-linkers in PVPP 2
based on the EVP peaks will. therefore, represent the total amount
of cross-linkers EVP and EBVP present in the polymer. The
absence of the P3 peak in FIgure 9 enables the pyrolysis-GC
method to distinguish betweenPvf'P made from EVP or EBVP.
The ratio ofP3 to P5 may also be used to estimate the amounts
of these two polymers ill a mixture, or the relative amounts of
I
EVP and EBVP in PVPP. .~

given pyrolysis temperature.
The pyrogram of the PVPP standard made with 2.5% EBVP is
shown in Figure 9 for the middle-temperature region. Again the
peaks of interest are labeled the same way as before. However,
three small peaks in Figure 9 are labeled E1, E2, and E3 which
are also present in Figures, 5 and, 8. These three peaks are too
small to be, identified by mass spectrometry. Comparing this
472 Analytical Chemistry, Vol. 71, No.2, January 15, 1999
Since P3 is absent in Figure 9"and it is the largest new peak
in the pyrogram of PVPP made with EVP, the exact structure of
this compound is of some interest to the understanding. of the
fragmentation mechanism of EVP. cross-linker in PVPP under
pyrolysis conditions. The mass spectra of peak 6, P2 and P3 in
Figure 5 are displayed in Figure 10. They are all isomers of the
compound with molecular weight 125 and one double bond. The
 400000
2.0 -.----------_--"
350000
(A)
G) y • 0.1723 + 0.4080x
o 100000 U
US
r'2 • 0.9951
i
"0 asoaoo
...••
..6!:: zooooo ~ 1.5
-c 150000 iD
a:
12
100000 9' e,

50000

0
..
~
gco 1.0
30 40
!i
rnJZ a;
a:
as
CD

<
-=
CD
0.5
20100 e,
G) (B)
U
15000
~
..6!:: n
0.0
10001
<: 125
0.0 1.0 2.0 3.0 4.0
sooo " % (EVP I VP)

0
II..
CO
II
,.
"i ,.
iAo
It,0

110 130
13"

100
FiguJe 11. Calibration curve for EVP in PVPP. Peak 14 is the
reference peak fer the calculation of peak area ratio.
30 40 SO 10 '0 laG

rnJz
pyrrolidone ring. The compound should be eluted slightly earlier
(i.e., P3 being shifted away from the P4 peak) on a less polar GC
110000 column. The pyrogram of PVPP 2 obtained with a nonpolar
110000 (C) column (e.g., po.ly(dimethylsi1oxane)type such as DB-I fromJ&W
G)
U 140000 Scientific)did confirm that the P3 peak was eluted ~0.5 min earlier
i
"0
120000 than the P4 peak under approximately the same GC conditions,
!::
::s 1.00000
US
The DB-I column was actually the first column tried for the
,D
<: 80000 u analysis of cross-linkers in PVPP in this study: It was found that
.0000
a brand new DB-l column did not completely separate a minor
.0000
interfering peak from trans-EVP. Only with a used Dfs-lcolumn
20000
was trans-EVP separated from the interfering peak A DB-5column
0
]0 wo.uldmake the separation worse. However, the cross-linker data
obtained from DB-l and DB-1S0l agree with each other to within
rnJz experimental error. Therefore, either column may be used for this
Figure 10. Mass spectra of (A) peak 6, (8) peak P2, and (C) peak analysis.
P3.
Peak 14 was chosen as the internal reference peak for EVP
analysis. This compound has the same molecular weight as EVP
structure o.fpeak 6 is more or less known. It is present in the and is eluted very close to the trans-EVP peak. The cis-EVP peak
pyrogram of PVP; therefore, the C31Isgroup is attached to the is not used for quantitative arialySisbecause it is a smaller peak
nitrogen atom in the pyrrolidone ring. The P2 and P3 peaks appear with more area fluctuation due to integration error. The calibration
to be stereoisomers that may assume one of the two structures: curve is quite linear over the range from 0.5%to 4%EVP,and is
(I) the ~H5 group is attached to the carbon next to the carbonyl shown in FIgUI"e11.A simple calculation will convert the value of
group in the pyrro.lido.nering (i.e., the C3 carbon); (2) A CRa percent. (EVPIVP) obtained from Figure 11 tc percent EVP in
group. is attached to the nitrogen atom and a ~H3 group is PVPP. A sample of PVPP 2 was analyzed seven times and was
attached to the C3 carbon. The third possible structure which is found to contain 2.52%cross-linker. The standard deviation of
3-methyl-I-viny1-2-pyrro.lido.ne(or briefly, 3-methyl VP) is ruled analysis was 0.066%.A sample of PVPP 1 was also analyzed seven
out because it is known to be eluted as peak 4 in the pyro.gram. times and was found to contain 1.72%cross-linker. The standard
Of the above two structures, thedisubstitution structure is less deviation of analysis was 0.050%.
probable because it can be generated in pyrolysis by both EVP As mentioned above, the. peaks P3 and 14 may be used to
and EBVP in PVPP. estimate the relative amount of EBVP incorporated into PVPP 2.
If it is assumed that the structure of P3 is ~Hs-2-pyrrolidone, The ratio.of (P3/I4) from PVPP made with EVP was found to be
then it is a rather polar compound with respect to GC analysis 1.467,whereas avalue of 1.437was obtained for a sample ofPVPP
due to the hydrogen atom attached to the nitrogen atom in the 2. The standard deviation of analysis was 0.028. Therefore, the
Analytical Chemistry, Vol. 71, No. 2,January 15, 1999 473
. Table 4. Effect of Pyrolysis Temperature on EVP
D1

probe temp, °C cis-EVPltrans-EVP trans-EVP/peak 14

tiP.o.
•• 1.

.850 0,433 0.882

~"".oe
750 0.352 1.020
650 0.305 1.136 § ".0.
550 0.287 1.449 ..;
10
,!e.oe
e
.~-e .
V2 0.

.E'"
1.e_~
3.0.
H2
1 •••• !!I- L1

1.2."

H ••
_ 1..0_5
/
.~
c:: L2 'z
TlIDe(min)
~ e ,0.4-
of 1f..3
os
~e.o_.
L Figure 13. Expanded pyrogram of PVPP 3 for the region between
/ L" 9 and 16 min of:thepyrogram in Figure 11. See Tables 2 and 5 for
'"
.!! .••.0 •• . peak identification.
.5 ><3

J
Le H~
I L'" H1
2.0.4

0
j 1 l. ~ I I ./0'..1 T.ble 5. New Peaks from Pyrolysis of PVPP3
retention
peak no. time, min identification
0 10 20

Time(min) D1 + peak 7 11.650 m/z = 123, CaHa-py, spectrum identical to

peak pl of Table 3
FIgUre 12. PyrogramofPVPP 3. SeeFigure 2 forpeak1ttii1lilitaliOh
D2 13.815 m/z = 138, DVI
for peaks in the low temperature and higbtempetaluie~.~

amount of EBVP present in pvpp 2 was too low to hIr tJf>1"~
by this method. .." ..
The temperature of pyrolysis does affect the cisltranS);yp
ratio as well as the slope of calibration curve. The resultsmiJiSred
asa function of probe temperature (not true pyrolysis ~-
attire) in Table 4. The change of cis/trans EVP ratio' wiJh
temperature is interesting. As expected, more energy is needed
to generate the cis isomer. Due to the change of ratio of tm1tS-
EVP to the reference peak with temperature, a 10°C drift in
pyrolysis temperature wouldresuh in 3.5%change in the calculated
cross-linker content if the same calibration curve is used. Thus
the pyrolysis temperature should be maintained constant to within
about 2-3 °C for quantitative analysis,
Pyrolysis of PVPP 3 and PVPP 4. These polymers are
manufactured using an externally added cross-linker, DVI, to the
VP monomer solution. The pyrogram of a sample ofPVPP 3 which
was obtained in November 1991 is shown in Figure 12, and the
.expanded pyrogtain for the middle temperature regiOn is shown
in Figure 13. Comparing the latter to the pyrogram ofPW shown
in Figure 3, only twon'ew"tnajor peaks are present in Figure 13.
The new peaks are labeled tit and D2 in Figure 13,anci their
identities are listed in Table 5.
Interestingly.the mass spectrum of peak D1 is identical to that
of peak P1 inFigure 5. At)pareJitlythis peakis caused by the
presence of EVP or DVIin PVPP which' alters the conformation
of PVP polymer backbone. In the case of tllePVPP standard cross-
linked with EBVP, no new polymer backbone conformation is
produced and this peak is missing in the pyrogra:m.
The DVI peak was eluted in a relatively clear region of the
PVPpyrogram although it is Still interfered with by a very Small
peak. The calibration CUrve obtained in a 'WaY-similar: to Figure
11 using peak 14 as the internal referenctHvas also 'llnear from 0
to 4% DVI, described by the equation, y~ 0.0961 + 0.3262X, and
a correlation 'coefficient of 0.9937. The sample of PVPP 3 was
474 Aria/yticaJ Chemistry, Vol. 71, No.2,
Table &. Effect of Pyrolysis Temperature 011 DVI
probe temp, ·C DVI/peak14
850 0.715
750 0.723
650 0.764
550 0.920
analyzed six times, and the cross-linker level was found be 2.04% tP
with a standard deviation of 0.023%. A sample of PVPP 4 was also
analyzed six times, and the Cross-linker level was found to~ 1.87%
with a standard deviation, of 0.Q78%' Therefore, these two DVI
values are equivalent wllhiD eXperimental error.
The ratio of (DVl/peak.14) was not affected as much by
pyrolysis temperature as was tli~ ratiR pf (EVP/peak 14). The
results are listed in Table 6. Except rort'iie lowest temperature at
550 °C, the ratio is almost constant This implies that as long as
the true pyrolysis temperature is above 700 °C,a variation in
pyrolysis temperature of up to 10°C from run to run Willonotaffect
the result of analysis. Still, it is prudent to analyze a nitet:ence
sample or standard afterevery 10;.-15 sample runs to check fot
any unexpected temperature drift of thepyrolyzer.
Correlation to Swell Voltune.'Theswell volume of PVPP in
water is routinely measured by manufacturers to indirectl¥ monitor
the cross-link density of PVPP. Swell volume is affected by cross-
linker level, particle size, and, probably, particle morphology. Thus
swell volume may not correlate to cross-linker level in PVPP
samples Unless they base-similar particle size distributions. If all
other parametetsanddentical,a'scUnple with a higher cross-link
densitywil]' have a ,lower swell volume. In Table 7 the. swell
volume, the mean volume particle size, and cross-linker level
determined by pyrolysis-GC for a few PVPP samples are listed.
These results indicate that fairly good correlation was obtained
between the swell volume and the cross-linker level of PVPP 4
January 15, 1999
Table 7. Swell Volume, Particle Size, and Cross·Linker There is no sample preparation, and sample size is not used in
Level data analysis.
particle However, the response factor is somewhat dependent on
% swellvol,
sample size,pm cross-linker mL pyrolysis temperature, particularly for the analysis of EVP. Unless
1.72
a pyrolyzer of the same configuration is used and its temperature
PVPP1 32.8 55
PVPP 2, sample 1 115 2.47 50 is calibrated, it is not recommended to use the response factors
PVPP 2, sample 2 107 2.37 52 reported in this paper (i,e., the slope of calibration curve in Figure
PVPP 4, sample 1 14.1 1.87 51
pvpp 4, sample 2 15.1 2.04
10 for EVP, or the slope of equation for DVI mentioned above)
45
PVPP 5, sample 1 14.9 1.68 78 for general application. A standard of PVPP containing a known
PVPP 5, sample 2 14.0 1.70 73 amount of cross-linker is still needed to obtain the actual response
factor for sample analysis. Thus, this method is probably most
useful for comparing relative cross-linker levels in a quality control
and PVPP 5 which have similar particle size distribution. There laboratory. For that application, no PVPP standard is needed.
is no correlation between the samples of PVPP 1 and PVPP 2, There was only fair correlation between the cross-linker level
apparently due to the large difference in particle size distribution determined by pyrolysis and the swell volume of polymer. If
for these two products. Furthermore, pyrolysis-GCdetermines the particle size distribution of two samples was much different, no
total amount of cross-linker present in a polymer. It cannot correlation was found. In addition, it is possible that a fraction of
distinguish between a cross-linker which has only one end the cross-linker in PVPP may have only one end incorporated into
participating in free radical reaction from one which has both ends the polymer backbone. This type of cross-linker would not
incorporated into the polymer backbone. Only the cross-linker of contribute to the swell volume of the popcorn polymer.
the latter type may affect the polymer swell volume.
ACKNOWLEDGMENT
The authors thank S. Tseng and P. Wolf for preparing PVPP
CONCLUSIONS
Pyrolysis-GC and pyrolysis-GC/MS have been used to char- standards cross-linked with EVP; ]. Shih and J. Chuang for
acterize the decomposition fragments of PVPP and to determine preparing PVPP cross-linked with DVI; K Plochocka for preparing
cross-linker levels in these products. PVPP 1 and PVPP 2 were PVPP cross-linked with EBVP; and M. Wrinkle, R Geise, M.
found to contain about 1.8% and 2.5% total cross-linkers, respec- Krass, and J. O'Reillyfor providing data on particle size distribution
tively, that are mainly EVP. PVPP 3, 4, and 5 samples were found and swell volume of commercial PVPP. The authors also thank
to contain about 1.7-2.1% DVI. International Specialty Products for permission to publish this
work.
The pyrolysis-GC method for cross-linker analysis is based
upon the peak area ratio of cross-linker to an internal reference
peak generated in the same pyrogram. Once the response factor Received for review April 28, 1998. Accepted October 27,
of a cross-linker is known, determination of the level of that cross- 1998.
linker in PVPP samples by pyrolysis-GCis rather straightforward. AC9804689

Analytical Chemistry, Vol. 71, No.2, January 15, 1999 475