NATIONAL BUREAU OF STANDARDS REPORTNBS PROJECT NBS REPORT

0708-20-07560 May 24, i960 6853

Progress Report

on

ANALYSIS OF PYROLYZATES OF POLYMERSBY GAS CHROMATOGRAPHY

I. Pyrolysis of Polystyrene andPoly(methyl methacrylate)

at 400 to 1100°C

by

Frank A . Lehmann*Alphonse F, Forziatl**

Gerhard M. Brauer ’

-

* Guest Worker, U, S. Army, Dental Research Section,National Bureau of Standards.

** Research Associate, American Dental AssociationResearch Division, National Bureau of Standards,

' Chemist, Dental Research Section, National Bureau ofStandards

.

This work is a part of the dental research program conduc-ted at the National Bureau of Standards in cooperationwith the Council on Dental Research of the American DentalAssociation, the Army Dental Corps,, the Dental SciencesDivision of the School of Aviation Medicine, USAF, theNavy Dental Corps, and Administration.

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Approved for public release by the

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Standards and Technology (NIST)

on October 9, 2015

ress accounting documents

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oduction, or open-literature

is obtained in writing from

h permission is not needed,

lared if that agency wishes

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

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ANALYSIS OF PYROLYZATES OP POLYMERSBY GAS CHROMATOGRAPHY

lo Pyrolysis of Polystyrene andPoly(methyl methacrylate)

at 400 to 1100®C

Abstract

Pyrolyzates of polystyrene and poly(methyl metha-

crylate) were studied at temperatures from 400 to 1100®C

using gas chromatographic techniques. A small Vycor

boat surrounded by a platinum heating coil was placed in

the inlet system of the chromatograph. The 2 to 3 nig

sample was degraded at a constant temperature which was

measured by means of a thermocouple placed in an inden-

tation at the bottom of the boat. Helium carried the

volatile products into the heated column of the chroma-

tograph.

Analyses of the products could usually be accom-

plished with a reproducibility of better than 1^.

Polystyrene degrades to monomer below 700® C and

poly(methyl methacrylate) behaves similarly below 450®C.

At higher temperatures some gaseous and liquid secondary

decomposition products are formed which were identified

by their characteristic retention times.

The technique uses inexpensive equipment and is

generally applicable for the study of the thermal

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stability of polymers and their pyrolyzates. Results

obtained are very helpful in identifying primary and

secondary reaction products and in the elucidation of

degradation mechanisms over wide temperature ranges* The

procedure is also useful in the rapid characterization and

quantitative estimation of the composition of complex

copolymer systems*

1* INTRODUCTION

The recent interest in developing polymers that are

heat stable at high temperatures has made it desirable

to obtain more information on the degradation reactions

and mechanisms of polymers. A great number of papers have

described the thermal behavior of polymers at moderately

high temperatures^ that is in the 200 to 500 ® C range [1^2].

However, relatively little information is available on

the reactions occurring at higher temperatures.

The application of gas chromatographic techniques

to the identification of polymers [3-5] and quantitative/

determination of the composition of copolymers [6-7]

offers a rapid means for the analyses of volatile

pyrolyzates. Until recently, such analyses could only be

made by time consuming separations or mass spectrometric

methods

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This investigation deals with the study of the pyrolysis

products of polystyrene and poly(methyl methacrylate) obtained

on degradation of these polymers at temperatures ranging from

400 to llOO^C.

2. EXPERIMENTAL PROCEDURES

2*1 Materials

The polystyrene was a thermally polymerized sample oft

number average molecular weight 233^000. The poly(methyl

methacrylate) was a Rohm and Haas No. 2 suspension polymer.

Eastman reagent grade liquids and reagent grade Matheson

compressed gases were used to identify pyrolysis products.

2.2 Apparatus

A Consolidated Electrodynamics Corp. type X-26-201

chromatograph with a redesigned inlet system differing

from that previously described [6] was used. Figure 1

shows the experimental set-up that was employed to pyrolyze

the polymeric material Inside the chromatograph. A 2 to 3

mg sample was placed in a weighed Vyco^* glass boat [3 nim

outside diameter^ 4 mm height) that was surrounded by a

34 gauge platinum heating coll having a total resistance

of about 0.2 ohms. The ends of the coil were silver

soldered to two copper wire leads connected to a series

of variable transformers by which the temperature of the

boat could be regulated. The pyrolysis temperature was

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measured by placing a chromel-alumel thermocouple (gauge

NOo 42 wire) In a small Indentation In the bottom of the

boat. The measurement of the pyrolysis temperature was

considered to be accurate within better than 10® C,

The copper wire leads were sealed into a standard

taper (14/35) Teflon plug which was inserted into a

female glass joint. This Joint was connected to the

metal inlet system by two glass-to-kpvar seals.

After flushing the chromatograph with helium for

3 minutes an electric current was passed through the

heating coll. The voltage of the transformers was

preset to heat the boat to the desired temperature

within 3 to 5 seconds. The helium passing over the

sample carried away the vaporized products into the

column. The coluimn material and temperature were varied

until chromatograms with sharp peaks that did not overlap

and suitable retention times were- obtained, A summary

of the experimental conditions including the column materials

and temperatures as well as the carrier gas flow rate

and pressure are given in Table I. The column was

considered to be purged of pyrolytic products when no

further peaks on the chromatogram were obtained for 10

minutes. The boat was removed from the chromatograph,

cooled and weighed to determine the presence of any non-

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volatile residue,

3. RESULTS

3,1 Polystyrene

Typical chromatograms obtained on pyrolyzing poly-

styrene at 400®C^ 800®C and 1000®C are shown in Figure 2.

Whereas styrene monomer is the only product at 400® C,

secondary products are formed at 800®C, These secondary

reactions are even more important at a temperature of

1000®C. Identification of the compounds from the

various peaks was made by comparing their retention

times with those obtained from chromatograms of known

compounds

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At temperatures above 1000®C the polymer was probably

flash-pyrolyzed completely before the boat reached an

equilibrium temperature. Hence, the composition was

not altered appreciably on Increasing the temperature

from 1000® to 1100®C as evidenced by the nearly identical

chromatograms for the pyrolyzates. The initial peak for

the gaseous products could not be resolved by Aplezon L or

Chlorowax 70 columns. Chromatograms with a silica gel

column showed the presence of ethylene, acetylene and some

carbon dioxide. The amount of each product in the

pyrolyzate was calculated from the ratio of the area

under the peak to the sum of the areas under all the

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peaks. Results at various pyrolysis temperatures are shown

In Table II. Duplicate runs usually agreed within 1%.

Substitution of an Aplezon L for the Chlorowax 70 column

gave chromatograms with peaks at different retention

times > but did not change appreciably the results of the

chromatographic analyses. The Aplezon L column, however,

separated the ethylbenzene-toluene single peak obtained

with Chlorowax 70. In all degradations at temperatures

above 350®C no residue was foiind on rewelghlng the boat

after cooling.

Percentage of styrene monomer In the pyrolyzate

versus pyrolysis temperature Is shown In Figure 4. Below

700® C the polyrolyzate was nearly all monomer under the

experimental conditions employed. Secondary reactions

leading to the formation of ethylbenzene, toluene,

benzene, ethylene and acetylene occurred at higher

temperatures.

Variations of the flow rate of the carrier gas

between 45 ml/mln and 75 ml/mln did no't alter the comp-

position of the degradation products. At lower flow rates

(less than 45 ml/mln) the primary products were not

immediately carried away from the hot zone and secondary

reactions took place. Thus, the percentage of benzene

(a secondary reaction product) was Increased more than

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twofold in the pyrolysis at 1000® C when the flow rate was

reduced from 60 to 10 ml/mlno

Comparison of the chromatographic results with mass

spectrometrlc analyses of polystyrene degraded In a

helium atmosphere by Modorsky and Strauss [8] indicates

that consistently smaller quantities of secondary products

are obtained by the chromatographic procedure. The high

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and Strauss on the other hand is quite large, and the

primary products are kept at the elevated temperature

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undergo secondary decompositions

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3«2 Poly(methyl methacrylate)

Chromatograms obtained from pyrolyzing poly(methyl

methacrylate) at 400® and 1000®C using a dinonyl phthalate

column are shown in Figure 5. Only monomer is formed

at 400®C whereas a number of compounds are detected

at 1000® Co The gaseous products which appear as a

single peak on the chromatograms are separated and

identified with a silica gel packed column (Figure 6),

Tables III and IV give the composition of the pyrolyzates

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at degradation temperatures from 400 to 1000®Ce Figure 7

shows the percentage of monomer product as a function of

degradation temperature. Below 400®C monomer is formed

nearly exclusively. The percentage of methyl methacrylate

monomer in the pyrolyzate decreases to about 20^ at

850®C and remains constant at higher temperatures.

Gaseous products predominate at 800® C and above. On

raising the temperature from 800®C to 1000®C the quantities

of carbon monoxide > methane and ethane decrease rapidly.

Secondary reactions may partially convert these compounds

to carbon dioxide and acetylene.

4c DISCUSSION

Products obtained on pyrolysis of polystyrene and

poly(methyl methacrylate) between 400®C and 1000®C can be

readily analyzed by chromatographic techniques. Table V

shows the comparison of the percentages of carbon^ hydrogen,

and oxygen in the polymer sample and in the jproducts of

the pyrolysis. The satisfactory agreement of the material

balance indicates that little if any of the products are

retained in the column.

The chromatograph employed a filament type katharometer

for measuring the thermal conductivity of the effluent gas

„

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of the vaporized liquid components of .the pyrolysis mixture

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appear unnecessaryo Results accurate within 1% were

obtained for synthetic mixtures having the same composition

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ring after the retention times of the pyrolysis products.

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position of the pyrolyzateo To study degradation of

these polymers below 350®C the material should be

pyrolyzed in another apparatus and after collection^ the

pyrolyzate should be introduced into the chromatograph.

The procedure is also limited by excessive depolymeri-

zation rates at elevated temperatures. Thus^ the

polymers investigated are degraded nearly instantaneously

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above 1000®C whereas the equilibriimi temperature of the boat

Is reached only after the sample is completely pyrolyzed.

Analyses of the decomposition products of polystyrene

show that faster carrier gas flow rates and therefore more

rapid removal of the products from the hot reaction zone

produces Increased proportions of monomer. It appears

that even at the higher temperatures polystyrene and poly-

(methyl methacrylate) degradation is initiated at the

chain ends and results in the formation of monomer. Since

the secondary reactions do not proceed to equilibrium

their extent depends on the initial reaction temperature .

1

and is also influenced by the rate of cooling of the

products. The latter variable is Influenced by the

temperature and rate of flow of the carrier gas as well

as the geometry and thermal properties of the pyrolysis

vessel.

It is not possible to state the complex secondary

reactions which lead to the products observed without

detailed kinetic studies. Inspection of Tables II, III

and IV shows that secondary reaction products were found

in increasing amounts as the temperature of the pyrolysis

was increased. Undoubtedly, the C5H5 - C bond of

styrene and the bonds adjacent to the C = C in methyl

methacrylate are most susceptible to chain scission.

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The resulting free radicals may imdergo a variety of re-

actions- such as disproportionation, further cleavage

of bonds or recombination with other fragments o Free

radicals formed on scission of the C5H5 - C bond will

yield benzene and acetylene o Some of the acetylene as

well as some of the remaining styrene will react with

hydrogen, another product, to form ethylene and ethyl-

benzene « Secondary decomposition reactions of methyl

methacrylate are even more complex and much work remains

to be done to clarify the intermediate steps

•

5o SUMMARY

Analysis of the composition of the pyrolyzates of

polystyrene and poly(methyl methacrylate) degraded at

temperatures ranging from 400®C to 1100®C was accomplished

by gas chromatography o The procedure in which the

polymer is pyrolyzed inside the chromatograph and the

vaporized components are carried directly into the

column is rapid, uses relatively inexpensive equipment

and is applicable to degradation studies of other polymers.

Identity of the products was established from their

retention times and the quantitative composition from

the peak areas on the chromatograms , Below 700®C poly-

styrene degrades to monomerj poly(methyl methacrylate)

shows a similar behavior below 450®Co Gaseous auid liquid

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products are formed at higher temperatures. The method

is very useful for the Identification of primary and

secondary reaction products, aids in the investigation

of the mechanisms of degradation and shows the relative

Importance of various pyrolytic reactions over a wide

range of temperatures. The procedure also gives

valuable information about the structure of polymers

and copolymers by comparison of the chromatograms of the

pyrolysis products obtained at different degradation

temperatures. The method can, therefore, be used for

the rapid detection and determinations of polymers and

constituents of copolymers.

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REFERENCES

1. Jellinek^ H. Ho^ Degradation of Vinyl Polymers ,

Academic Press Incorporated, New York, 1955.

2. Grassle, N,, Chemistry of High Polymer Degradation

Processes , Interscience Publishers, New York, 1956.

3. Davison, W. H. T., Slaney, S., and Wragg, A. L.,

Chem. and Ind . 1136 (195^).

4. Haslam, J,, and Jeff, A, R., Analyst 7.^ 24 (1957).

5. Radell, E. A„, and Strutz, H, C., Anal. Chem. 31 ^

1890 ( 1959 ).

6. Lehrle, R. S. and Robb, J. C., Nature I83 , I 67 I

(1959).

7 . Strassburger, J., Brauer, G. M., Tryon, M. and

Porzlatl, A. F,, Anal. Chem. 32 , 454 (i960 ).

8. Madorsky, S. L. and Straus, S., J. Research Nat.

Bur. Standards 63 A, 26l (1959).

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