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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•

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Analytical Department, IntematiohaJ.8pecia/tYProtiUcts, 1361 A/psRoad, Wayne, New Jersey 07470

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

swellvolume data for a specific series of aQ8S-1iD1redpoly-

(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 ofvinyl pyrrolidone (i.e.

1-vinyl-2-pyrrolidone)(VP).1The two principal methods involve

either the heating ofVP above 100 °Cin the presence of an alkali

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

".

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.

situ, namely, 3-ethyliden~1.vinyJ-2-pyrrolidone(EVP) (~1.5%)and

3,3'-ethylidenebis(1-vinyl-2~pYriolidone)(EBvp) (~O.1%). The

principal cross-linker employedin the latter process is N,N-

divinylimidazolidone(or N,N-divinylethyleneurea) (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.

PVPPis primarilyused in two applicationsareas: as a beverage

clarifier and as a pharmaceutical tablet disintegrant, It has been

in use since 1961for the clarification of beer by the removal of

chill haze and precursorsf This results from the specificity of

PVPP hydrogen bonding to particular polyphenolic substances

known as anthocyanogens, which are responsible (together with

certain proteins) for the haze formation in refrigerated beer and,

hence, for reduced shelf llfe. 6 The material's use as a tablet

disintegrant dates back to ca. 1973. 7 ,8 In these and other applica-

tions, the fine structure ofthe polymer, particularly the degree of

chemical and physical cross-linking,plays a large role in determin-

ing whether the material's physical properties are suitable for the

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"

are all heavily influenced by the amount of cross-linker incorpo-

rated.

The determination ofthe degree ofcross-linkinghas long been

treated by physicochemical methods, particularly by swelling and

mechanical techniques. Flory and Rehner developed a relationship

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

.~ ,...••..

~."

..:1dullins

,0:0.-..

the lymer density.loAlternativel

po

,y,

developed aSimpl~relationship based upon stress-strain

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,

(10)

Wayne, NJ. 1997. F1ory, P. }.; Rehner. ].]. Chem. Phys. 1943, 11, 521.

.

  • 468 Analytical Chemistry, Vol. 71, No.2, January 15. 1999

10.1021/ac9804689 CCC: $18.00

e 1999 American Chemical Society Published on Web 1210411998

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modulus and the lengths ofthe dry and swollen polymer sample

(at equilibrium).'! Neither ofthese 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) filmsto determine the level of cross-

linker incorporated.P Infrared methods are not applicableto PVPP

because ofthe previously cited simi1arityin the functional groups

of the base pOlymerand the cross-linkers used. UVmethods ate

equally inapplicable owing'to the particulate nature ofthe material

and the lack ofUVchromophores 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 Asimilar technique,

thermogravimetry-GC/MS, has also been used to study the

composition of cured epoxy resins," -

Pyrolysis-GCwasfirst applied by Goetzet al.to pure PVPusing

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 ofsoluble

PVP in which an analyte concentration scheme' and a nitrogen

detector were employedto 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

PVPP2Were 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_

Dekker: New York, 1985.

(18) Ericsson, I.; IJunggren,1.J.

au TecJIJwlogJSeries4); Bore, P., Ed; Marcel

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 PVPPproducts 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 studywas a laboratory sample

of 99%purity. EBVPwas a laboratory sample synthesized accord-

ing to the procedure of Hort, Grosser, and Schwartz.25N,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 VPand 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%DVIwere also synthesized, but the amount of cross-

linker incorporated into the polymer could not be accurately

ascertained due to incomplete polymerization. Several standards

of PVPPcontaining the EBVPcross-linker were also synthesized.

These polymer samples were used for identificationpurposes only.

Kraton 1107,a styrene/isoprene/styrene block copolymer,was

obtained from CDSAnalytical 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-mlength, 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-1301column of 0.25-mmLd., 30-mlength 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, 1.0mUdivision,

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'

'·4

".0." 2 • o .. ... 20 o >0 •• 0 30 Time (Dlin) Time(min)
".0."
2
o
..
...
20
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>0
•• 0
30
Time (Dlin)
Time(min)

Figure 1. PyrogramofKraton1107at 722°Cpyrolysistemperature.

.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

 

peak area ratio,

isoprene/dipentene

equivalentpyrolysis

temp,°C

  • 850 4.756

861

  • 800 3.509

769

~

2~

m

.700

2.366

-. 685..

  • 650 2.015

659

  • 600 1.686

635

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

flowrate 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) untilthe residual sample was completelyburned off.

Calibration ofPyroptobe Temperature. It is not necessary

to know the true pyrolysis temperature in order to perform this

analysis. However, pyrolysis temperature does affectthe 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

Figure 2. Pyrogramof PVP K-30obtained at 685 °Cpyrolysis

temperature. L1, mixtureof C~, CaH6.CaH8.and C 4 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 VPdimers 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

by the solids.

RESULTS AND:DISCUSSION

Pyrolysis of PvP. PVP K-30, a linear, non-cross-linked

polymer ofVP, was pyrolyzed to obtain the reference pyrogram.

Figure 2 shows the.GC pyrogram of PVP 100 obtained at the 685

DCequivalent pyrolysis temperature. Mass spectral inforiIiation

provided the identification of most of the peaks. The pyr~

can.be.divided into three regions. The low column temperature

r~l!p'!ith

..retention

times shorter than that of N-methy1-2-

.J?~WlM!lne(NMP) at 9.28min contains peaks 'iliat are m.ostly

from tl:!e~on

.of the polymer backbone. The middle

region. fromthe retention time of NMP to ~ 18 min contains

peakS that are mostlysubsti~ 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.pyrogramis 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 18min to the end ofthe 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

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Figure 3. Expanded pyrogram of PVP K-30

for the region between

9 and 16 min of the pyrogram identification.

in Figure 2. See Table 2 for peak

Table 2. Retention Times and Peak Identification

peak

no.

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

retention

time, min

9.281

10.095

10.443

10.522

10.759

11.230

11.656

11.708

12.237

12.939.

13.061

13.403

14.332

.

14.613

15.041

identification

1-methyl-2-pyrrolidon~ (or N-methyl-2-pyrrolidone, NMp)

2-pyrrolidone (2-Py)

1-Yinyl-2-pyrrolidone (VI') .

m/z = 125, probably

mlz = 125, probably

3-methyl-VP

4-methyl-VP

mlz = 125, N-CaHs-py

m/« == 123, N-C*py

m/z = 135, probably a substituted pyridine

mlz = 139, N-C#irP1

mlz = 139, N.:CJlrPY

mlz = 137, N-C#is-py

mlz = 151, unknown

mlz = 149, probably a quinoline or isoquinoline derivative

mlz = 137, N-C#is-py

mlz = 155, probably a quinoline or isoquinoline derivative

.0

Timc(min)

1<5

Figure S. Expanded pyrogram of PVPP 2 for the region between 9

and 16 min of the pyrogram in Figure 4. See Tables 2 and 3 for peak identification.

Table 3. New Peaks from the Pyrolysis of PVPP2

peak

no.

PI + peak 7

P2

P3 ..

P4

P5

retention

time, min

identification

11.631

mlz =123, C*py, peak 7 ofTable .2

spectrum similar to

12.468·-,. mlz=1-25;C~Pi

12~584mlz=

125,C~silY

12.700

14.038

mlz = 137, cU-EVP (or (Z)-EVP)

mlz = 137, tnJns-EVP (or (E)-EVP)

cls-EVP

trans-EVP

Figure &. Structures of cis-EVP and trans-EVP

o

10

'"'0

Time(min)

F'1gU~4. Pyrogram of PVPP 2. See for peaks in the low temperature and

Figure 2 for peak identification 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. 4 Figure 4 showsthe 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 ofauthentic compounds and their

retention times. The structures ofthese 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

.otherfhree new peaks in Table 3 are still unknown; The

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 EBVPis 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

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Figure 7 • Mass spectra of (A) cis-EVP, (B)tlans-EVP, and (e)

peak

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

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

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O~--~'0~--------'~2~------~~--------~,e

Time (min)

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

identification.

1.0.

'i?

o§e.o •

..

fe

o_ ..

$ .~ •. o.

.:sa.o. Ii

2.0e

.1 ..0.

4

os

'"

p

'4

YO••

10

O+---~~------~'~2~------~~~----~

Time (Dun)

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

identification. E1, E2, and E3 are unidentifledsubstituted pyrrolidones.

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

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

EVP and EBVP in PVPP.

I

.~

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

(A) 350000 G) o 100000 U US i asoaoo "0 !:: 6 zooooo -c 150000 12
(A)
350000
G)
o
100000
U
US
i
asoaoo
"0
!::
6
zooooo
-c
150000
12
100000
9'
50000
0
30
40
rnJZ
20100
(B)
G)
U
15000
~
!::
6
n
10001
<:
125
"
sooo
,.
II
..
"i
II
It,0
13"
,. 10
iAo 110
0 30
40
CO
'0
laG
130
100
SO
rnJz
110000
(C)
110000
G)
U
140000
i
120000
"0 !::
::s
1.00000
,D
US
<:
u
80000
.0000
.0000
20000
0
]0
rnJz
Figure 10. Mass spectra of (A) peak 6, (8) peak P2, and (C) peak

P3.

structure o.fpeak 6 is more or less known. It is present

in the

pyrogram of PVP; therefore, the C31Isgroup is attached to the

nitrogen atom in the pyrrolidone ring.The P2 and P3 peaks appear

to be stereoisomers that may assume one of the two structures:

(I) the ~H5 group is attached to the carbon next to the carbonyl

group in the pyrro.lido.nering (i.e., the C3 carbon); (2) A CRa

group. is attached to the nitrogen atom and a ~H3 group is

attached to the C3 carbon. The third possible structure which is

3-methyl-I-viny1-2-pyrro.lido.ne(or briefly, 3-methyl VP) is ruled

out because it is known to be eluted as peak 4 in the pyro.gram.

Of the above two structures, thedisubstitution structure is less

probable because it can be generated in pyrolysis by both EVP

and EBVP in PVPP.

Ifit is assumed that the structure ofP3 is ~Hs-2-pyrrolidone,

then it is a rather polar compound with respect to GC analysis

due to the hydrogen atom attached to the nitrogen atom in the

2.0 -.----------_--"

 

y • 0.1723 + 0.4080x

r'2 • 0.9951

 

...

••

~

1.5

a: iD

e,

~

..

co

g 1.0

!i

a;

a:

as

CD

<

-= 0.5

CD

e,

0.0

 

0.0

1.0

2.0

3.0

4.0

 

% (EVP I VP)

FiguJe 11. Calibration curve for EVP in PVPP. Peak 14 is the

reference peak fer the calculation of peak area ratio.

pyrrolidone ring. The compound should be eluted slightly earlier

(i.e., P3 being shifted awayfrom the P4 peak) on a less polar GC

column. The pyrogram of PVPP 2 obtained with a nonpolar

column (e.g.,po.ly(dimethylsi1oxane)type such as DB-IfromJ&W

Scientific)did confirmthat the P3 peak was eluted ~0.5 min earlier

than the P4 peak under approximately the same GC conditions,

The DB-I column was actually the first column tried for the

analysis of cross-linkers in PVPP in this study: It was found that

a brand new DB-l column did not completely separate a minor

interfering peak from trans-EVP. Only with a used Dfs-lcolumn

was trans-EVP separated fromthe interfering peak ADB-5column

wo.uldmake the separation worse. However, the cross-linker data

obtained from DB-l and DB-1S0l agree with each other to within

experimental error. Therefore, either column may be used for this

analysis.

Peak 14 was chosen as the internal reference peak for EVP

analysis. This compound has the same molecular weight as EVP

and is eluted very close to the trans-EVP peak. The cis-EVP peak

is not used for quantitative arialySisbecause it is a smaller peak

with more area fluctuation due to integration error. The calibration

curve is quite linear over the range from 0.5%to 4%EVP,and is

shown in FIgUI"e11.A simple calculation will convert the value of

percent. (EVPIVP) obtained from Figure 11 tc percent EVP in

PVPP. A sample of PVPP 2 was analyzed seven times and was

found to contain 2.52%cross-linker. The standard deviation of

analysis was 0.066%.A sample of PVPP 1was also analyzed seven

times and was found to contain 1.72%cross-linker. The standard

deviation of analysis was 0.050%.

As mentioned above, the. peaks P3 and 14 may be used to

estimate the relative amount of EBVPincorporated into PVPP 2.

The ratio.of (P3/I4) from PVPP made with EVPwas found to be

1.467,whereas avalue of 1.437was obtained for a sample ofPVPP

2. The standard deviation of analysis was 0.028. Therefore, the

. Table 4. Effect of Pyrolysis Temperature on EVP

probe temp, °C

cis-EVPltrans-EVP

trans-EVP/peak 14

.850

0,433

0.882

  • 750 1.020

0.352

  • 650 1.136

0.305

  • 550 1.449

0.287

1.e_~

  • 1 •••

!!I-

L1

H2

  • 1 .2."

_

1 ..0_5

.~

c::

~ e ,0.4-

of

os

~e.o _.

H ••

/

L2

1f

..

3

L

/ L"

'"

.!! .••.0 ••

.

.5

Le

I L'"

2.0.4

j

1

l.

~

J

. Table 4. Effect of Pyrolysis Temperature on EVP probe temp, °C cis-EVPltrans-EVP trans-EVP/peak 14 .

I

H1

I

><3

H~
H~

./0' 1 ..

0

0

10

20

Time(min)

FIgUre 12. PyrogramofPVPP 3. SeeFigure2 forpeak1ttii1lilitaliOh for peaks in the low temperature and higbtempetaluie~.~

amount of EBVP present in pvpp 2 was too low to hIrtJf>1"~

tiP.o.

~"".oe

§ ".0.

..

;

,!e .oe

.~

V2 -e . 0.

'"

.E3 .0.

••

D1

1.

e

10

'z

TlIDe(min)

Figure 13. Expanded pyrogram of PVPP 3 for the region between 9 and 16 min of:thepyrogram in Figure 11. See Tables 2 and 5 for

peak identification.

T.ble 5. New Peaks from Pyrolysis of PVPP3

peak no.

D1 + peak 7

D2

retention

time, min

11.650

13.815

identification

m/z = 123, CaHa-py, spectrum

peak pl of Table 3

m/z = 138, DVI

identical to

Table &. Effect of Pyrolysis Temperature 011 DVI

by this method.

.."

..

probe temp, ·C

DVI/peak14

The temperature of pyrolysis does affect the cisltranS);yp

ratio as well as the slope of calibration curve. The resultsmiJiSred

850

0.715

750

0.723

asa function of probe temperature

(not true

pyrolysis ~-

 

650

0.764

attire) in Table 4. The change of cis/trans EVP ratio' wiJh

550

0.920

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

analyzed six times, and the cross-linker level was found tPbe 2.04%

with a standard deviation of 0.023%. A sample of PVPP 4 was also

cross-linker content if the same calibration curve is used. Thus

analyzed six times, and the Cross-linker level was

found to~ 1.87%

the pyrolysis temperature should be maintained constant to within

with a

standard deviation, of 0.Q78%' Therefore, these two DVI

about 2-3 °C for quantitative analysis,

values are equivalent wllhiD eXperimental error.

Pyrolysis of PVPP 3 and PVPP 4. These polymers are

The ratio of (DVl/peak.14)

was not affected as much by

manufactured

using an externally added cross-linker, DVI, to the

pyrolysis temperature as was tli~ratiR pf (EVP/peak 14). The

VP monomer solution. The pyrogram of a sample ofPVPP 3 which

results are listed

in Table 6. Except rort'iie lowest

temperature at

was obtained in November

1991 is shown in Figure 12, and the

550 °C, the ratio

is almost constant This

implies

that as long as

.expanded pyrogtain for the middle temperature regiOn is shown

the true

pyrolysis temperature is above 700 °C,a variation in

in Figure 13. Comparing the latter to the pyrogram ofPW shown

pyrolysis

temperature of up to 10°C from run to run Willonotaffect

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.

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.

Interestingly.the mass spectrum of peak

D1 is identical to that

Correlation to Swell Voltune.'Theswell

volume of PVPP in

of peak P1 inFigure 5. At)pareJitlythis peakis caused by the

water is routinely measured by manufacturers to indirectl¥ monitor

presence of EVP or

DVIin PVPP which' alters the conformation

the cross-link density of PVPP. Swell volume is

affected by cross-

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

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

peak. The calibration CUrve obtained in a 'WaY-similar: to

Figure

volume, the mean volume particle size, and cross-linker level

11 using peak 14 as the internal referenctHvas also 'llnear

from 0

determined by pyrolysis-GC for a few PVPP samples are listed.

to 4%DVI, described by the

equation, y~ 0.0961 + 0.3262X,

and

These results indicate that fairly good correlation was obtained

a correlation 'coefficient of 0.9937. The sample of PVPP 3 was

  • 474 Aria/yticaJ Chemistry, Vol. 71, No.2, January 15, 1999

between the swell volume and the cross-linker level of PVPP 4

Table 7. Swell Volume, Particle Size, and Cross·Linker Level

There is no sample preparation, and sample size is not used in

data analysis.

sample

PVPP1

PVPP

2, sample

1

PVPP

2, sample

2

PVPP

4, sample

1

pvpp 4, sample

2

PVPP

5, sample

1

PVPP

5, sample

2

particle

size,pm

%

cross-linker

swellvol,

mL

However, the response factor is somewhat dependent on

pyrolysistemperature, particularly for the analysis ofEVP.Unless

32.8

115

1.72

2.47

55

50

a pyrolyzer ofthe same configuration is used and its temperature

is calibrated, it is not recommended to use the response factors

  • 107 2.37
    1.87

    • 52 reported in this paper

(i,e., the slope of calibration curve in Figure

  • 14.1 10 for EVP, or the slope of equation for DVI mentioned above)

51

  • 14.9 15.1 for general application. A standard of PVPP containing a known

2.04

1.68

45

78

1.70

  • 14.0 amount of cross-linker is stillneeded to obtain the actual response

73

factor for sample analysis. Thus, this method is probably most

useful for comparing relative cross-linker levelsin a qualitycontrol

and PVPP 5 which have similar particle size distribution. There

is no correlation between the samples of PVPP 1 and PVPP 2,

apparently due to the large difference in particle size distribution

for these two products. Furthermore, pyrolysis-GCdetermines the

total amount of cross-linker present in a polymer. It cannot

distinguish between a cross-linker which has only one end

participating in free radical reaction from one which has both ends

incorporated into the polymer backbone. Onlythe cross-linker of

the latter type may affect the polymer swell volume.

CONCLUSIONS

Pyrolysis-GC and pyrolysis-GC/MS have been used to char-

acterize the decomposition fragments of PVPP and to determine

cross-linker levels in these products. PVPP 1 and PVPP 2 were

found to contain about 1.8% and 2.5% total cross-linkers, respec-

tively, that are mainly EVP. PVPP3, 4, and 5 samples were found

to contain about 1.7-2.1% DVI.

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

of a cross-linker is known, determination ofthe level ofthat cross-

laboratory. For that application, no PVPP standard is needed.

There was only fair correlation between the cross-linker level

determined by pyrolysis and the swell volume of polymer. If

particle size distribution of two samples was much different, no

correlation was found. In addition, it is possible that a fraction of

the cross-linker in PVPP may have only one end incorporated into

the polymer backbone. This type of cross-linker would not

contribute to the swell volume of the popcorn polymer.

ACKNOWLEDGMENT

The authors thank S. Tseng and P. Wolf for preparing PVPP

standards cross-linked with EVP; ]. Shih and J. Chuang for

preparing PVPPcross-linked with DVI;K Plochocka for preparing

PVPP cross-linked with EBVP; and M. Wrinkle, R Geise, M.

Krass, and J. O'Reillyfor providingdata on particle size distribution

and swell volume of commercial PVPP. The authors also thank

International Specialty Products for permission to publish this

work.

Received for review April 28, 1998. Accepted October 27,

1998.

linker in PVPPsamples by pyrolysis-GCis rather straightforward.

AC9804689

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

475