NBSIR 78-1463

Studies on the Photodegradation

of Poly(Methyl Methacrylate)

Mohamed Abouelezz

Structures and Materials Division

Center for Building Technology

National Engineering Laboratory

National Bureau of Standards

Washington, DC 20234

and

P. F. Waters

Chemistry Department

American University

Washington, DC 20016

May 1978

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

NBSIR 78-1463

STUDIES ON THE PHOTODEGRADATION

OF POLY(METHYl METHACRYLATE)

Mohamed Abouelezz

Structures and Materials Division

Center for Building Technology

National Engineering Laboratory

National Bureau of Standards

Washington, DC 20234

and

P. F. Waters

Chemistry Department

American University

Washington, DC 20016

May 1978

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary

Dr. Sidney Harman, Under Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS. Ernest Ambler, Director

CONTENTS

page

1. INTRODUCTION 1

1.1 Background 1

1.2 Scope 9

2. APPARATUS AND TEST SAMPLES 10

2.1 Polymer 10

2.2 Light Source 10

2.3 Actinometry 11

2.4 Molecular Weight Measurement H

2.5 Thermal Mechanical Analyzer 12

3. TEST PROCEDURES 12

3.1 Polymer Preparation *- 2

3.1.1 Purification of Polymer ^ 2

3.1.2 Film Casting ^- 2

3.1.3 Heat Treatments

3.2 Irradiation of the Polymer 13

3.3 Actinometry

3.4 Molecular Weights Measurements 14

3.5 Glass Transition Temperature 14

3.6 UV and IR Spectra 15

3.7 Volatile Loss of Polymer 15
4. RESULTS AND DISCUSSION 15

4.1 Molecular Weight Changes 15

4.2 Glass Transition Temperature 18

4.3 Spectral Changes 18

4.4 Volatile Loss of Polymer 19

5. CONCLUSION AND FURTHER STUDIES 20

6. REFERENCES 22

7. TABLES 24

8. FIGURES 36

i V
ABSTRACT

Although poly (methyl methacrylate), PMMA, is

known to degrade when exposed to ultraviolet radiation,

studies at wavelengths other than 253.7 nm have not

been done. The lack of knowledge about the mechanism

of degradation of PMMA at wavelengths other than 253.7

nm hinders efforts to develop short-term test methods

for predicting the long-term performance of PMMA in

applications in which it is exposed to sunlight. This

study was performed to determine the effect of ultraviolet

radiation on PMMA and to identify mechanisms of degradation

induced by the radiation.

Thin films of PMMA of two different molecular

weights were irradiated with radiation nominally of 253.7 nm

and 300 nm. The irradiations were conducted in air and

under vacuum. Exposure at 253.7 nm caused a rapid decrease

in molecular mass and loss of a small amount of volatile

products, which is a characteristic of random chain scission.

The quantum yield was greater in air than in vacuum. Changes

in the molecular mass and the glass transition temperature

as well as weight loss data indicating that wavelengths

bands at greater than 253.7 nm also cause degradation. The

data further indicate that the degradation at the longer

wavelengths may not be completely random scission.

V
ACKNOWLEDGMENT

The authors wish to acknowledge the contributions of the staff at

NBS and others who contributed to the success of this publication. In

particular, substantial contributions were made by members of the

Building Materials and Building Composites Programs of the Structures

and Materials Division. The authors thank Dr. P. Campbell and Mr. L. Masters

for their valuable contributions and Dr. G. Frohnsdorff and Dr. R. Steihler

for their editorial review. Also the authors wish to thank the members of

Stability and Standards Sections of the Polymers Division and Mr. W. L.

McLaughlen of the Center for Radiation Research for their valuable discussions.

The authors wish to acknowledge the Research Laboratory Division of the Rohm

and Hass Co. for supplying the polymer samples.

VI
1 . INTRODUCTION

1.1 Background

Poly (methyl methacrylate), PMMA, is an important polymer in the building

industry as well as in other industries. Typical applications are in architectural coatings and in glazing material of high impact resistance including

cover plates in solar energy systems. When exposed to sunlight, PMMA may

undergo changes which alter its properties. For this reason, it is essential

to study its long-term performance and to understand the mechanisms by which

its properties change.

The ultraviolet (UV) component is the most damaging part of sunlight

because of its high energy. The photon energy associated with it is of the

order of 0.3 to 0.4 MJ, which is in the range of carbon-carbon single bond

energy, uv radiation may cause carbon-carbon bonds to break, resulting in

a scission of the polymer chain. Other bonds, e.g. carbon-oxygen, carbonhydrogen, may also break. The most characteristic feature of random scission

of a polymer chain is a rapid decrease in the molecular mass. Molecular mass

changes, accompanied by changes in the physical and mechanical properties of a

polymer, may cause a reduction in its mechanical properties and its ability

to perform adequately in some applications.

Previous studies of the effect of UV irradiation on PMMA have been carried

out using 253.7 nm radiation sources from low and medium pressure mercury

(Hg) lamps. The techniques typically used to detect degradation include

determination of molecular mass change, quantum yield of scission, and UV, IR

and ESR (electron spin resonance) spectra. From the above measurements, the

rate of degradation can be determined.
The change in molecular mass is most often determined from viscosity

measurements [1-8]. The photodegradation of PMMA by 253.7 nm radiation results

in a rapid decrease in the viscosity average molecular weight and the formation

of small amounts of volatile products. Fox et al. [7] assumed that the number

of scissions occurring in the PMMA chain was proportional to the number of

quanta absorbed by the chain and they identified the proportionality constant

as the quantum yield of chain scission. They reported a quantum yield of

-2

random scission of 4 x 10 per absorbed quantum at a pressure of 2.7 m Pa

(2 x 10 ^ mm Hg) of air. A hundred fold increase in the air pressure did not

affect the resulting quantum yield while, at atmospheric pressure, the quantum

-2

yield was 1.7 x 10 . Charlesby et al. [6] reported a quantum yield of

-3

4 x 10 for the photolysis of thin films of PMMA in air and in nitrogen.

PMMA has a low absorption at 253.7 nm and the incident radiation can

penetrate into the polymer sample. Irradiation of the polymer cause the appearence of two new absorption bands in the UV region; one at 240 nm, which has been

assigned to conjugated unsaturation, and another at 285 nm, which is probably

due to carbonyl chromophores [7,9,10].

The IR spectrum of PMMA changes little on irradiation with 253.7 nm radiation

[7,9,10]. Only a broadening of the carbonyl band at 5.71 pm (1750 cm

and the formation of new bands at 6.19 pm (1615 cm '*") and 6.01 pm (1640 cm

were observed. The latter two bands are attributed to olefinic unsaturation

[7,9,10].

Electron spin resonance (ESR) spectra of PMMA irradiated with UV (253.7

nm) and y-rays are almost identical [11]. This indicates that the same

2
free radicals are formed during both kinds of irradiations. The following four

free radicals have been reported [6, 11, 12]:

CH

3 •CH

2

a) CH

2 — C. b) CH

2 CH

C00CI1

3

COOCH

3

c) CH

3 d) H — C - 0

Keto and Nishoka [13] determined that the half life of methyl radicals was

1.5 hours for both UV and y radiated PMMA samples at 77 K. Charlesby et al.

[14,15] compared the results obtained from UV and y irradiation of PMMA at

different temperatures. At high temperature (above 170 °C) , depolymerization

was much less with y radiation than with UV. This finding was interpreted as

indicating that UV radiation at high temperature is selectively absorbed at

unsaturated chain ends resulting in depolymerization [15].

The photodegradation of PMMA in 2-chloroethanol solution has been investigated

[15] as a function of irradiation time, polymer concentration, temperature

(25-159 °C) and intensity of the incident beam. The investigators reported

that the random chain scission initial reaction was dependent on polymer

concentration. They also added that, at elevated temperatures (54° to 159

°C), an absorption peak at 224 nm increased in intensity with irradiation

3
time. This increase was shown to be a measure of the amount of monomer formed

during photolysis Charlesby and his coworkers claimed that, under the

experimental conditions, thermal degradation was negligible. Only monomer has

been detected from the unzipping mechanism as a result of the thermal degradation

of PMMA.

Unzipping is a continuous release of monomer from the end of the polymer

chain once the scission of the chain has started. The decrease in the molecular

weight due to unzipping is slow in contrast to that resulting from photodegradation.

The kinetic chain lengths of PMMA, determined from the average number of

monomer molecules per main chain scission, were less than 14 at 25°C but

increased to 312 at a temperature of 159°C. Photolysis of PMMA in benzene

solution has also been investigated by Kardash and Krongeuz [17] and Charlesby

and Thomas [6]. The latter authors found the quantum yield for random scission

of PMMA in benzene solution to be independent of polymer concentration.

The photodegradation of PMMA may result in a random scission of the

polymer chain backbone by radical process [1-3,7,18-25]. The major reactions

thought to occur simultaneously are:

1) Random homolysis scission of main chain carbon-carbon bonds:

CH,

CH.

CH,

CH,

c iWW\*M

COOCH

3 COOCH3

vvw* CH,

CH,

C*

COOCH.

'CH;

CH,

C iMawvi

COOCH,

(a)

4
2) Photolysis of ester side group in three different ways:

CH,

^CH I

CH,

2 . aAMA + 'COOCH, (b)

CH,

I ^ -CUN* + * OCH,

COOCH,

(c)

(d)

3) Photodissociation of the methyl side chain group:

CH

3 C

CH,

/WW\ CH

2

‘ :h. AMfc

I

Z

I COOCH

3 COOCH3

CH,

I yvw\ CH 0 *C CH„ C

2

I 2I

+ * CH,

COOCH

3 COOCH3

(e)
The main volatile products of the photolysis of PMMA in vacuum are

methyl formate, methanol and methyl methacrylate with quantum yields of

0.14, 0.48 and 0.20, respectively. In air, additional products include methane,

hydrogen, carbon monoxide and carbon dioxide [7].

Monomer methyl methacrylate can originate in at least three ways during

PMMA degradation:

1)

End chain depolymerization (unzipping)

CH„ CH

|

I ,-WVH CH

2—C—CH2 c

’

C00CH

3 C00CH3

CH- CH

lA/VW* CH C* + CH -*-C

I I C00CH

3 C00CH3

2) Trapped residual monomer from the initial polymerization

3) Random thermal degradation

Monomer methyl methacrylate formed during UV irradiation is mainly due to

depolymerization after photolytic scission of the main chain as in (a)

A

maximum zip length of about 5 monomer units per scission at 25°C was indicated

[7]. With increasing irradiation temperature (up to 160°C) , a minimum kinetic

6
chain length of 220 monomer units per scission [1,2] and 312 at 159°C was

reported by Jellink [16]. No cross linking has been reported when PMMA is

irradiated as a film or in solution.

In contrast, the dominant product of thermal degradation of PMMA is

monomer which is liberated in high yield at 250°C. PMMA degradation was the

first polymer degradation reaction to be investigated in detail [27,28]. The

principal features were revealed by a combination of molecular weight and rate

of monomer formation measurements. The molecular mass changes which occur

during thermal degradation in PMMA of various molecular mass are illustrated

in Figure (1). Grassie [29] explained the fact that the molecular mass of low

molecular mass polymer does not change during degradation by demonstrating

that complete molecules are lost from the polymer. This suggested to him a

reaction mechanism which is the reverse of a radical polymerization. The

initiation process in this reaction involves scission of the molecule to

produce radicals, which unzip to produce monomer. The entire process,

called depolymerization, may be represented generally as the following:

Initiation M —» m: + m* . n J n-j

M >M* , + M- n n-1

Depropagation M*~-=

n-1 —» M* + M

n o n-2

M>

l

+ M; +

x-z M

z Transfer M>

J M. + M

J-z z

Mj + M- M + M*

n j n

Termination M:

J + M: • X 4 M.

J + M.

X or M. ,

.

i+J

7
where

n: is the kinetic chain length of the starting material

M...

i J i+J

M^, M : , M-

,

represent dead polymer molecules

etc. are chain radicals

(have no radical)

Grassie [28] reported the formation of the monomer through the

unzipping process as follows:

CH„ CH0

I 3

|

3

AA/W CH? C CH

2 Ccooch

3 cooch

3

CH^ c* +

C00CH

3

CH,

cooch

3

8
Grassi [29] stated that the unchanging molecular mass in low molecular

mass PMMA suggested that there was a high probability that the depropagation

would reach the end of the molecule before the termination process, which

would stabilize the radicals, could intervene. Otherwise, the average molecular

mass would decrease with volatilization. As the initial molecular mass of PMMA

is increased, the probability that the degrading radicals will be stabilized

by mutual interaction of pairs, as in radical polymerization, is increased.

The resulting residual low molecular weight material causes the decrease in

molecular weight to occur progressively earlier in the reaction as the molecular

weight of the initial PMMA is increased.

The photodegradation of PMMA has been studied using a 253.7 nm

source, while the spectrum of natural sunlight at the earth’s surface

cuts off at about 292 nm. However, when PMMA is exposed to sunlight

for long periods of time, it is known to degrade. For this reason, there

is a need to study the effects of UV and visible radiation on the polymer

degradation. Such studies should emphasize identification of the mechanisms

of the degradation under these conditions. The results of photodegradation

studies, combined with those of simulated natural weathering of PMMA, are

urgently needed to permit prediction of long-term performance in building

applications by short-term testing.

1.2 Scope

Because of the wide use of PMMA in coating and other building material

this study was proposed to have the following three objectives:

1. To investigate the effect of different bands of UV and visible

light as well as combination of these bands on the photodegradation

of PMMA.

9
2. To study the mechanism of the photodegradation caused by

the individual or combination bands.

3. To investigate the effect of simulated natural weathering

on the photodegradation of PMMA using a xenon-arc accelerated

weathering machine.

2. MATERIAL AND APPARATUS

2.1 Polymer

Test samples of poly (methylmethacrylate) were provided by the Research

* Laboratory Division of the (Rohm and Haas Co.) Two different molecular

weight products were provided. The weight average molecular weight of the

first was stated to be 190,000 while that for the second was 240,000. The

two polymers have been designated PMMA I and II, respectively. They were

reported by the supplier to contain UV stabilizer and ca. 1% residual monomer

and to have 75% syndiotactic character.

2.2 Light Source

* The photochemical reactor was a Rayonet Model RPR-100, obtained from

the Southern New England Ultra-violet Company, Middletown, Connecticut. The

apparatus is shown in Figures 2 and 3. It consists of a sheet metal housing

and a bank of 16 tubular UV lamps. Within the housing, the 285 mm length

lamps were mounted vertically around a circle of 235 mm diameter. Surrounding

the cyclinder of lamps is a polished cylindrical reflector, 390 mm in height

*DISCLAIMER: Certain trade names and company products are identified in order

to adequately specify the experimental procedure. In no case does such

identification imply recommendation or endorsement by the National Bureau of

Standards, nor does it imply that the products are necessarily the best available

for the purpose.

10
and 260 mm in diameter. A fan in the base of the reactor blows air through

the irradiation space to cool the material being irradiated. The interior of

the reactor is shown in Figure 3.

Three sets of lamps are available commercially, with spectral distribution peaking at 253.7 run, 300 nm and 350 nm. The spectral distribution of

the three sets of lamps were measured and shown in Figures 4 through 6,

respectively

.

2.3 Actinometry

Actinometry was performed during the exposure tests to measure the

amount of radiation the samples received. These measurements were necessary

to permit comparison of the fluxes for different lamps and to permit a

determination of the quantum efficiency of the degradation. The procedure

employed was that of McLaughlin et al. [30,31]. In this method, the colorless

pararosaniline cyanide becomes deeply colored upon irradiation with ultraviolet

radiation. Its quantum efficiency is 0.96 mol/photon up to 340 nm [30,31].

2.4 Molecular Mass Measurement

The molecular mass was measured by gel permeation chromatography using a

Water Associates chromatograph. The columns used were packed with Microstyrogel

.

Six columns was used, four of pore size .01 mm, one each of .1 and 10 pm. The

diluent used, tetrahydrofuran , was degassed daily during the measurements.

The differential refractometer was a Waters Associates model R401. The

resulting chromatographic data were analysed by computer to give number and

weight average molecular mass.

11
2 . 5 Thermal Mechanical Analyzer (TMA)

The glass transition temperature for the original and the degraded

polymer was measured using a Dupont Model No. 941 Thermal Mechanical Analyzer.

Figures 7 and 8 show the TMA apparatus used.

3. TEST PROCEDURES

3.1 Polymer Preparation

3.1.1 Purification of PMMA

The polymer samples were dissolved in methylene chloride (analytical grade)

by boiling the methylene chloride solution until complete dissolution was

obtained. The solution was then cooled to about 10°C, and the PMMA precipitated

by adding cold methyl alcohol (also at about 10°C) . The precipitated solid

was filtered under suction. This process was done twice to insure the

removal of most of the residual monomer and all the UV absorber originally

present the UV spectra of the treated polymer show no presence of the UV

absorber

3.1.2 Film Casting

After purification, the polymer was dissolved in methylene chloride and

cast on polished black glass using a draw down blade. The blade, made of

cold-rolled steel, had a wide U-shape. The filmflow opening of the one edge

used had a clearance of 254 micrometer and a width of 139.7 mm. After evaporation

of the solvent, the film was released by immersing the glass plate in water.

The middle part of the film was used in the tests to insure a uniform thickness

of 20 + 5 micrometer.

12
3.1.3 Heat Treatment

Each film was heated to 100°C for 8-16 hours, then at 80°C under

vacuum for 16 hours. This treatment removed the residual solvent and any

stresses developed in the film during casting.

3.2 Irradiation of the Polymer.

After the PMMA film was freed from the residual solvent, it was

weighed and attached with clips to a quartz microscope slide (7.5 x 2.5 mm)

The microscope slide with the film was mounted vertically inside a quartz

tube in the center of the photochemical reactor. The polymer samples were

irradiated, using either the 253.7 or 300 nm lamps, in air and under a vacuum of

.07 K Pa (0.5 mm mercury) for various intervals of time. After a few exposure

trials the polymer film was exposed to the 253.7 nm lamps for 1/2, 1, 1-1/2,

2, 3, 4, 5, 6 and 8 hour intervals, and to the 300 nm lamps for 2, 4,

8, 16 24, 32, 48 and 64 hour intervals.

3.3 Actinometry

3

A solution of pararosaniline cyanide of 1.136 mg/m gm/ml concentration

in isopropyl alcohol (spectro grade) was used for actinometry. Its molar

extinction coefficient was measured at its absorption maximum (549nm) to be

1.31 x 10

7 mol ^ m \ McLaughlin [30] determined the value to be 1.39 x

in 7 t _1 "I

10 mol m

13
In order to duplicate exposure conditions of the PMMA irradiations,

actinometry was performed as follows:

A quartz cell of 1 mm path length was filled with pararosaniline

3 cyanide (0.35 cm capacity) and placed vertically in the center of the

reactor inside a quartz tube and irradiated for certain intervals of time

(e.g. 3,5 and 7 seconds). The absorbance (A) at 549 nm was measured using

a spectrophotometer. By measuring the absorbance the intensity of the

UV light received by the pararosaniline cyanide per second (I) , could be

calculated, and the intensity of irradiation absorbed by the PMMA sample (la)

could be calculated.

3.4 Molecular Mass Measurements

The original and degraded PMMA were dissolved in tetrahydrofuran to

give concentrations ranging between 0.25 and 1.0 % by mass. The

solution was filtered twice under pressure through Teflon filters. A

3 100-200 nm sample of the solution was then injected into the chromatograph.

The diluent (tetrahydrofuran) was degassed daily during the measurements by

filtering through a fretted glass suction funnel. The resulting chromatographic

data were analyzed by computer to give number and mass average molecular

masses

.

3.5 Glass Transition Temperature (Tg)

The glass transition temperature, Tg, for the original and degraded

PMMA was measured using a thermal mechanical analyzer (TMA) (Figures 6

and 7). The round tip probe was used, and the instrument conditions were

14
as follows:

Temperature scale 0 to 200°C

Probe displacement .14 ym/mm

Loading on Tray 10 g

Heating Rate 10°C/min.

Three measurements were made for each sample and the average calculated to

the nearest degree.

3.6 UV and IR Spectra

The transmissions of the original and degraded PMMA films were scanned

from 210 - 360 nm using a Beckman DK1 spectrophotometer. The IR spectra

were measured for the PMMA films using a Perkin Elmer Model 467 spectrophotometer between 2-5 and 40 ym.

3.7 Volitile Loss of Polymer

The percentage of mass loss (as volatile products) during the

irradiation of PMMA I and II was determined by weighing , to 10 ^ gram,

the film before and after exposure.

4. RESULTS AND DISCUSSION

4.1 Molecular Mass Changes

The results of the changes in mass average and number average

molecular mass for the original and degraded PMMA I and II during

15
irradiation with 253.7 nm lamps in air and under vacuum are shown in

Tables 1 through 4. (The mass average molecular mass was in consistant

with that reported by the supplier.) Changes during irradiation with 300 nm

lamps are shown in Tables 5 through 8. It is clear from these results that

the effect of irradiation is a rapid decrease in the molecular mass of both

PMMA I and II. The 253.7 lamps are more effective in inducing degradation

than the 300 nm lamps; i.e. for the same amount of degradation it took a

longer time of exposure using the 300 nm lamps.

A comparison of the changes in the number average molecular mass

with the intensity of the absorbed irradiation between PMMA I and II

is shown in Figures 9 through 12. The graphs illustrate that the behavior

of PMMA I and II were similar although they were originally different in

molecular mass. Another observation is that the rate of degradation

under all the different conditions of exposures (air or vacuum also with

253.7 nm and 300 nm lamps) is greater initially, than during the latter

stages

The quantum yield for chain scission (0 ) calculated from the

molecular mass changes during irradiation, is tabulated in Tables 1 through 8

according to the following equation:

16
where

is the density of PMMA mg/m'

Avogadro ’ s number

M and M

n n

o p

Ia

original and degraded number average molecular mass

respectively.

3 intensity of absorbed radiation (photon/cm sec)

t time of exposure in seconds.

For PMMA irradiated with 253.7 run lamps, the quantum yield was calculated

-2 -2 -2

to be between 3.0 x 10 and 4.55 x 10 in air and between 2.45 x 10

( -2

and 3.46 x 10 in vacuum. For PMMA irradiated with 300 nm lamps, the quantum

-2 -2 -2

yield was between 0.64 x 10 and 1.21 x 10 in air and between 0.51 x 10

-2

and 1.06 x 10 in vacuum.

Two important observations follow from the above results. First, the

rate of degradation in air is higher than in vacuum for PMMA I and II, which

is opposite to the finding of Fox et al. [7]. The higher quantum yield in

air may be attributed to the result of simultaneous photooxidation and photo*

degradation. Secondly, at the same intensity the rate of degradation for

PMMA irradiated with the 300 nm lamps is much less than that observed with

the 253.7 nm lamps (about one fourth). It is apparent from Figs. 4 and 5

that the intensity of the 253.7 nm output from the 300 nm lamps was determined

17
to be one tenth of that from the 253.7 nm lamps. It can be concluded that

the irradiation by the bands longer than 253.7 nm (311, 365, 436 nm) , which

are of greater intensity in the 300 nm lamps, can play an important role in

the photodegradation of PMMA.

4.2 Glass Transition Temperature

The effect of irradiation on the glass transition temperature (Tg)

,

of PMMA I and II is shown in Tables 9 and 10 and Figures 13 through 16. The

results are accurate to + 2°C. As with the changes in molecular weight, the

samples irradiated with 253.7 lamps showed a greater decrease in the glass

transition temperature than those irradiated with the 300 nm lamps. Also the

rate of change of T^ is less in vacuum than in air. Another similarity

between T and the molecular mass data is that the decrease of T with

g g

irradiation is faster at the beginning of irradiation than at the end. This

similarity between changes in molecular weight (number average) and glass

transition can be clearly seen in the linear relationship shown in Figures

17 and 18. These figures also illustrate that the two polymers behave

similarly in T changes during irradiation,

g

4.3 Spectral Changes

UV irradiation of PMMA causes an increase in the absorption of the thin

film, as shown in Figures 19 and 20. A new band at 285 nm, previously

observed by Shultz [4], Frolova [9,10] and Fox et al. [7] was also observed

in this work. This band is in the region usually associated with carbonyl

18
chromphores and is believed to result from carbonyl groups in the polymer

chain itself rather than from low molecular mass photolysis products.

The only changes in the IR spectrum of PMMA during the irradiation were

a broadening of the carbonyl band at 5.71 ym (1750 cm’

1

) and the appearance

of small new bands at 6.19-6.10 ym (1610-1640 cm”

1

). The latter bands are

attributed to olefinic unsaturation produced during the photolytic chain

scission

As for changes in molecular mass and glass transition temperature

changes, the spectral changes are much greater following irradiation with

253.7 nm lamps than with 300 nm lamps.

4.4 Loss of Volatiles from Polymer

The percentage mass loss during the irradiation of PMMA I and II are

shown in Tables 11 and 12. At the end of 8 hours of exposure to 253.7 nm

lamps, the mass losses were 1.39% and 1.55% in air and under vacuum,

respectively. For PMMA I and II irradiated with 300 nm lamps, the mass

losses after 64 hours of exposure were 3.68% in air and 4.3 % under vacuum.

From the above data, the mass losses in vacuum are higher than in air.

This could be explained by the fact that in vacuum there is more diffusion of

the volatile products out of the film than in air. Another observation is

that the mass loss of PMMA irradiated with 253.7 nm lamps is much lower than

that obtained with 300 nm lamps at equivalent levels of degradation.

19
5. CONCLUSIONS AND FURTHER STUDIES

The test data show that UV irradiation of PMMA caused a rapid decrease

in the molecular mass accompanied by small amount of volatile products. This

observation is characteristic of random scission degradation. Molecular mass

and Tg data further show that, while the intensity of the 300 nm lamps at

253.7 nm was about one tenth than that of 253.7 nm lamps, the quantum yield

was only about one fourth. This suggests that UV wavelengths greater than

253.7 nm play a role in the degradation and that the longer wavelength

radiation results in a different degradation mechanism than for 253.7 nm.

The mechanism at the longer wavelength may be at least in part a thermal

degradation, (unzipping).

Mass losses data show that exposure to 300 nm lamps results in a greater

weight loss than exposure to 253.7 lamps. These data provide a further

indication that the mechanism of degradation is a combination of thermal and

random scission, with thermal degradation being primarily induced at wavelengths

greater than 253.7 nm.

Additional research on the degradation of PMMA is needed to study

the effect of UV light greater than 253.7 nm in wavelength and visible

light (separately or in combination) . Specifically, it is proposed that

the following exposure studies be done to meet the initial objectives:

1) exposure to 300 nm lamps with filters to remove the 253.7 nm

wavelength light

2) exposure to 350 nm lamps

20
3) exposure to a combination of UV-visible light (300-700 run)

4) exposure to 546 nm (green) light and 436 nm (blue) light

separately

Such studies, combined with studies of simulated natural weathering are

needed to more fully characterize the mechanisms of degradation under

these different conditions. Once the degradation mechanisms are

characterized, the feasibility of utilizing accelerated aging (weathering)

tests to predict long-term performance of the polymer can be determined.

21
6. REFERENCES

[1] P. R. E. J. Cowley and H. W. Melville; Proc. Roy. Soc. A 210,

461 (1952)

[2] Ibid, A211, 320 (1952)

[3] Ibid., Nat. Bur. Std. Circ. No. 525, 59 (1953).

[4] A. Shultz, J. Phys. Cham. 65, 967 (1961).

[5] D. G. Gardner, J. Chem. Phys. 34, 1653 (1961).

[6] A. Charlesby and D. K. Thomas, Proc. Roy. Soc. A 269, 104, (1962).

[7] R. B. Fox, L. G. Isaacs and S. Stokes, J. Polym. Sci., Al, 1, 1079

(1963)

[8] V. Ya. Shlyapintokh and V. I. Goldengerg, EUROP. Polym. J., 10,

679 (1974).

[9] M. I. Frolova and A. V. Riabov, Tr. Khim,i Khim. Tekhnol. , 2, 161 (1959).

[10] M. I. Frolova L. I. Efimov and A. V. Riabov, Tr. Khim,i Khim. Tekhnol.,

7, 304 (1964).

[11] R. E. Michel F. W. Chapman and T. J. Mao, J. Chem. Phys. 45, 4604 (1966).

[12] V. K. Milinshuk and S. Ya Pshezhetskii, Vysokomol. Soedin.,

6, 1605 (1964).

[13] Y. Kato and A. Nishioka, Rep Progr. Polym. Phys. Japan 9, 477

(1966)

[14] A. Charlesby, D. Libby, and M. G. Ormerod, Pro, Roy. Soc A 262,207 (1961).

[15] Ibid, Int. J. Appl. Radiation and Isotopes 15, 703 (1954).

[16] H. H. G. Jellinek and J. C. Wang; Kolloid Z.Z. Polym., 202,1 (1965).

[17] N.S. Kardash and V. A. Krongauz, Vysokomol Soedin, B, 10, 271 (1968).

[18] R. B. Fox, L. G. Isaacks and S. Stokes, U.S. Naval Res. Lab. Report,

No. 5720 (1961).

22
[19] C. Forgacs and W. G. Hodgson J. Polym. Sci Al, 2, 1275 (1964).

[20] J. P. Allison, J. Polym. Sci, Al , 4, 1209 (1966).

[21] D.G. Gardner and G. A. Henry, J. Polym. Sci. B, 5, 101 (1967).

[22] J. R. MacCallum and C.K. Schoffs Trans. Faraday Soc. 75, 2383

(1971).

[23] K. Morimoto and S. Suzuki, J. Appl. Polym. Sci, 16, 2947 (1972).

[24] J. R. Shelton, In Polymer Stabilization [Ed. W.L. Hawkin] , WileyInterscience , New York (1972).

[25] E. Bystritskaya, v. I. Goldenberg, G. R. Pariskii, L. V. Samson and

V.Ya. Slya Pinto Klug, Visokomol Soedin A, 14, 1727 (1972).

[26] C. David, D. Fuld, G. Geusken and A. Charlesby, Europ. Polym. J.,

5 641 (1969).

[27] N. Grassie and H. W. Melville Proc. Roy. Soc. A 199, (1949).

[28] N. Grassie, The Chemistry of High Polymer Degradation Process,

London, Butterworth (1956).

[29] N. Grassie, Polymer Science [Ed. AD Jenkins American Elsevier (1972)].

[30] W. L. McLaughlin, Intrn. J. of Appl. Rad. and Iso., 17, 85 (1965).

[31] W. L. McLaughlin et al. in press.

23
Table 1. Molecular Weight Changes, Quantum Yield for PMMA I Irradiated with 253.7 nm in Air

Exposure Time

in Hours

-19

I a

-T x 10^

Photon/ cm"

M„ x

10" 3 Mn x 10“ 3 ^no

Mnp

Quantum Yield

4>cs x 10^

0.0 0.0 189 152 0.0 0.0

0.5 1.285 168 135 0.126 4.53

1.0 2.57 156 127 0.197 3.55

1.5 3.855 142 116 0.310 3.72

2.0 5.14 137 111 0.369 3.32

3.0 7.71 119 98 0.551 3.31

4.0 10.28 107 89 0.708 3.19

5.0 12.85 92 77 0.974 3.51

6.0 15.42 82 68 1.235 3.71

8.0 20.56 58 50 2.040 4.59

24
Table 2. Molecular Mass Changes and Quantum Yields for PMMA I During Irradiation with 253.7 nm Lamps in Vacuum

Exposure Time

in Hours

-19

I a-T x 10"

Photon/cm'

% x 10

3 Mn x 10~ 3

S

^no “1

Mnp

Quantum Yield

4>cs x 10^

0.0 0.0 189 152 0.0 0.0

0.5 1.285 173 139 0.092 3.31

1.0 2.57 158 127 0.197 3.55

1.5 3.855 151 121 0.256 3.07

2.0 5.14 143 116 0.310 2.79

3.0 7.71 135 103 0.476 2.86

4.0 10.28 113 92 0.652 2.93

5.0 12.85 109 88 0.727 2.62

6.0 15.42 97 78 0.949 2.85

8.0 20.56 90 72 1.111 2.5

25
Table 3. Molecular Mass Changes and Quantum Yields for PMMA II

During Irradiation with 253.7 nm Lamps in Air

Exposure Time

in Hours

-19

I a

-T x 10~

Photon/ cm^

Mw

x 10' 3 Mn x 10

-3

s

^no ~1

Mnp

Quantum Yield

<|>cs x 10^

0.0 0.0 248 197 0.0 0.0

0.5 1.285 214 171 0.152 4.31

1.0 2.57 201 157 0.255 3.57

1.5 3.855 176 140 0.407 3.80

2.0 5.14 167 135 0.459 3.21

3.0 7.71 150 120 0.642 3.00

4.0 10.28 126 102 0.931 3.26

5.0 12.85 109 89 1.2 3.40

6.0 15.42 94 77 1.56 3.64

8.0 20.56 67 55 2.58 4.51

26
Table 4. Molecular Mass Changes and Quantum Yields for PMMA II

During Irradiation with 253.7 nm Lamps in Vacuum

Exposure Time

in Hours

-19

la'T x 10^

y Photon/cm^

^ x 10

3 Mn x 10

3

s

Mno “1

Mnp

Quantum Yield

4>cs x 10^

0.0 0.0 248 197 0.0 0.0

0.5 1.285 219 177 0.113 3.16

1.0 2.57 197 158 0.247 3.46

1.5 3.855 190 151 0.305 2.86

2.0 5.14 173 141 0.397 2.78

3.0 7.71 152 122 0.615 2.87

4.0 10.28 133 108 0.824 2.88

5.0 12.85 126 102 0.931 2.60

6.0 15.42 112 89 1.213 2.83

8.0 20.56 102 82 1.40 2.45

27
Table 5. Molecular Mass Changes and Quantum Yields for PMMA II

During Irradiation with 300 nm Lamps in Air

Exposure Time

in Hours

-19

I a

-T x 10,

Photon/cm''

My X 10

3 Mn x 10“3

Mno -1

Mnp

Quantum Yield

4>cs x 10^

0.0 0.0 189 152 0.0 0.0

2.0 2.57 178 143 0.063 1.13

4.0 5.14 168 135 0.126 1.13

8.0 10.28 157 124 0.226 1.02

16.0 20.56 138 108 0.407 0.91

24.0 30.84 130 102 .490 0.80

32.0 41.12 118 92 0.652 0.79

48.0 61.68 101 80 0.90 0.68

64.0 82.24 88 69 1.203 0.68

28
Table 6. Molecular Mass Changes and Quantum Yields for PMMA II

During Irradiation with 300 run Lamps in Vacuum

Exposure Time

in Hours

-19

I a

-T x 10,

Photon/ cm'

Mw x 10

3 Mn x 10~ 3

t

^no “I

Mnp

Quantum Yield

4>cs x 10^

0.0 0.0 189 152 0.0 0.0

2.0 2.57 183 144 0.056 1.01

4.0 5.14 178 138 0.101 0.91

8.0 10.28 166 128 0.188 0.94

16.0 20.56 143 117 0.299 0.67

24.0 30.84 130 104 0.462 0.69

32.0 41.12 116 96 0.583 0.66

48.0 61.68 104 84 0.810 0.61

64.0 82.24 90 73 1.082 0.61

29
Table 7. Molecular Mass Changes and Quantum Yields for PMMA II

During Irradiation with 300 nm Lamps in Air

Exposure Time

in Hours

-19

I a-T x 10^

Photon/ cm^

My X 10

3

Mj, x 10

3

s

^no “1

Mnp

Quantum Yield

<J>cs x 10^

0.0 0.0 248 197 0.0 0.0

2.0 2.57 232 183 0.077 1.08

4.0 5.14 216 168 0.173 1.21

8.0 10.28 192 150 0.313 1.10

16.0 20.56 166 131 0.504 0.88

24.0 30.84 151 116 0.698 0.81

32.0 41.12 141 110 0.791 0.69

48.0 61.68 119 94 1.096 0.64

64.0 82.24 101 79 1.494 0.65

30
Table 8. Molecular Mass Changes and Quantum Yields for PMMA II

During Irradiation with 300 nm Lamps in Vacuum

Exposure Time

in Hours

-19

I a

*T x 10,

Photon/ cm'" My x 10" 3 Mn x 10‘ 3

3

^no “1

Mnp

Quantum Yield

4>cs x 10^

0.0 0.0 248 197 0.0 0.0

2.0 2.57 234 185 0.065 0.91

4.0 5.14 216 171 0.152 1.06

8.0 10.28 202 161 0.224 0.78

16.0 20.56 181 145 0.359 0.63

24.0 30.84 162 130 0.515 0.60

32.0 41.12 141 113 0.743 0.65

48.0 61.68 126 102 0.931 0.54

64.0 82.24 112 91 1.165 0.51

31
Table 9. Glass Transition Temperatures of PMMA I and II

During Irradiation with 253.7 nm Lamps

Exposure Time

in Hours

-19

I a

-T x 10

Photon/ cm

GLASS TRANSITION TEMPERATURE P C

IN AIR UNDER VACUUM

PMMA //I PMMA #2 PMMA #1 PMMA #2

0.0 0.0 115 116 115 116

0.5 1.285 113 114 113 113

1.0 2.57 110 110 111 111

1.5 3.855 108 108 110 109

2.0 5.14 106 106 108 108

3.0 7.71 104 104 106 106

4.0 10.28 103 103 105 104

5.0 12.85 101 100 102 102

6.0 15.42 99 99 100 101

8.0 20.56 96 96 98 98

32
Table 10. Glass Transition Temperatures of PMMA I and

II During Irradiation with 300 nm Lamps

Exposure Time

in Hours

-19

I a

*T x 10 3 Photon/ cm

GLASS TRANSITION TEMPERATURE 9 C IN AIR UNDER VACUUM

PMMA //I PMMA it 2 PMMA ttl PMMA it 2

0,0 0.0 115 116 115 116

2.0 2.57 113 114 114 114

4.0 5.14 111 111 112 112

8.0 10.28 109 110 110 110

16.0 20.56 108 108 109 109

24.0 30.84 107 107 108 109

32.0 41.12 105 106 107 107

48.0 61.68 104 105 105 106

64.0 82.24 103 103 104 105

33
Table 11. Percent Weight Loss in PMMA I and II During

Irradiation with 253.7 nm Lamps

Exposure Time

in Hours

-19

I a

*T x 10 3 Photon/ cm

% WEIGHT LOSS

IN AIR UNDER VACUUM

PMMA //I PMMA 112 PMMA //I PMMA 1t2

0.0 0.0 0.0 0.0 0.0 0.0

0.5 1.285 0.0 0.0 0.0 0.0

1.0 2.57 0.0 0.0 0.0 0.0

1.5 3.855 0.0 0.0 0.0 0.0

2.0 5.14 0.15 0.21 0.22 0.25

3.0 7.71 0.40 0.40 0.45 0.42

4.0 10.28 0.62 0.61 0.70 0.66

5.0 12.85 0.85 0.90 0.95 0.96

6.0 15.42 1.01 1.09 1.18 1.15

8.0 20.56 1.36 1.42 1.52 1.59

34
Table 12. Percent Weight Loss in PMMA I and II During

Irradiation with 300 nm Lamps

Exposure Time

in Hours

-19

I a

-T x 10

Photon/ cm

% WEIGHT LOSS

IN AIR UNDER VACUUM

PMMA if 1 PMMA it 2 PMMA if 1 PMMA it

2

0.0 0.0 0.0 0.0 0.0 0.0

2.0 2.57 0.0 0.0 0.0 0.0

4.0 5.14 0.22 0.20 0.25 0.29

8.0 10.28 0.41 0.37 0.52 0.55

16.0 20.56 0.69 0.59 0.78 0.82

24.0 30.84 0.78 0.72 1.22 1.35

32.0 41.12 1.64 1.67 1.97 1.73

48.0 61.68 2.56 2.63 3.11 2.94

64.0 82.24 3.72 3.66 4.24 4.35
Fig. 1. Grassie [29]

.

Effect of thermal degradation on the

molecular mass of PMMA of various initial molecular

mass; o 44000, ® 94000, © 179000, ® 650000,

• 725000

36
Fig. 2 . Photochemical reactor.

37
Fig. 3. Interior view of the photochemical reactor.

38
A1ISN31NI 3AI1V13H

39

Figure

4.

Spectral

distribution

of

253.7

nm

lamp

used

in

the

reactor.
AilSN3J.NI 3AI1V13U

40

Figure

5.

Spectral

distribution

of

300

nm

lamp

used

in

the

reactor.
A1ISN31NI 3AI1V13H

41

Figure

6.

Spectral

distribution

of

350

nm

lamp

used

in

the

reactor.
Fig. 7 Thermomechanical Analyzer (TMA)

A - sample area and probe

B - recorder and controls

H - heater

L - load

42
Fig. 8 Thermomechanical Analyzer (Detail)

Close-up view of probe and samples with heater

P - probe

S - sample

B - base

H - heater

43
20

18

16

14

12

10

8

6

4

2

I

. c

\

^ °v

4 8 12 16 20 24

iDIATION ABSORBED |l a t x lO " 19 Photon/cm3

)

anges in the number average molecular mass of PMMA during

idiation with 253.7 nm lamps in air; o PMMA I, • PPMA II.

44
20

18

16

14

12

10

8

6

4

2

I

10.

4

1DIATI0N

8 12 16 20 24

ABSORBED (l a t * 10" 19 Photon/cm3

) Change in the number average molecular mass of PMMA during

irradiation with 253.7 lamps under vacuum; • PMMA I, o PMMA II.

45
20

18

16

14

12

10

8

6

4

2

i.

o

\

o

20 40 60 80 100 120

iDIATION ABSORBED |l a t * lO ' 19 Photon/cm 3

)

changes in the number average molecular mass of PMMA during

radiation with 300 nm lamps in air; • PMMA I, o PMMA II.

46
Figure 12. Changes in the number average molecular mass of PMMA during

irradiation with 300 nm lamps under vacuum; $ PMMA I, o PMMA II.

47
118

94

90

4 8 12 16 20 24

RADIATION ABSORBED (l a t * 10" 19 Photon/cm 3

)

Figure 13. Changes in the glass transition temperature, Tg, of PMMA during

irradiation with 253.7 nm lamps in air;o PMMA I, • PMMA II.

48
RADIATION ABSORBED (l a t x 10-' 9 Photon/cm3

)

Figure 14. Changes in the glass transition temperature Tg, of PMMA during

irradiation with 253.7 nm under vacuum;o PMMA I, • PMMA II.

49
Figure 15. Changes in the glass transition temperature, Tg, of PMMA during

irradiation with 300 nm lamps in air; o PMMA I, • PMMA II.

50
RADIATION ABSORBED (l a t x lO " 19 Photon/cm 3

)

Figure 16. Changes in the glass transition temperature, Tg, of PMMA during

irradiation with 300 nm lamps under vacuum; o PMMA I, © PMMA II.

51
cz>

0o

3

i 3amva3dW3i NouiSNvai ssvia

52

Figure

17.

Glass

transition

temperature

vs

number

average

molecular

mass

for

PMM

AI

irradiated

with

253.7

nm

lamps;

o

in

air,

•

under

vacuum.
120

p

CD OD oo r-->

0o 3

i 3MniVa3dW3i NOIllSNVai SSV19

53

Figure

18.

Glass

transition

temperature

vs

number

average

molecular

mass

for

PMMA

II

during

irradiation

with

253.7

nm

lamps;

o

in

air, e

under

vacuum.
JLl I 1. L_

210 240 270 300 330 360

WAVE LENGTH (nm)

Figure 19. Changes in the ultraviolet spectrum of PMMA II during irradiation

with 253.7 nm lamps.

54
J I

I I I 210 240 270 300 330 360

WAVE LENGTH (nm)

Figure 20. Changes in the ultraviolet spectrum of PMMA II during irradiation

with 300 nm lamps.

55

NBS-1 14A (REV. 7-73)

U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NBSIR 78-1463

2. Gov't Accession

No.

3. Recipient’s Accession No.

4. TITLE AND SUBTITLE

Studies on Photodegradation of Poly(Methyl Methacrylate)

5. Publication Date May 1978

6. Performing Organization Code

7. AUTHOR(S) ' Mohamed Abouelezz, P. F. Waters

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No.

11. Contract/Grant No.

12. Sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

Same as 9 above.

13. Type of Report & Period Covered

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

This work is done in partial fulfillment of requirements for Doctoral research. The

work was performed at the National Bureau of Standards where the author is participating in an IPA Fellowship.

16. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.) Although poly(methyl methacrylate), PMMA, is known to degrade when exposed to ultraviolet radiation, studies at wavelengths other than 253.7 nm have not been done. The

lack of knowledge about the mechanism of degradation of PMMA at wavelengths other than

253.7 nm hinders efforts to develop short-term test methods for predicting the longterm performance of PMMA in applications in which it is exposed to sunlight. This

study was performed to determine the effect of ultraviolet radiation on PMMA and to

identify mechanisms of degradation induced by radiation.

Thin films of PMMA of two different molecular weights were irradiated with radiation

nominally of 253.7 nm and 300 nm. The irradiations were conducted in air and under

vacuum. Exposure at 253.7 nm caused a rapid decrease in molecular mass and loss of a small amount of volatile products, which is a characteristic of random chain scission.

The quantum yield was greater in air than in vacuum. Changes in the molecular mass

and the glass transition temperature as well as weight loss data indicating that wavelengths bands at greater than 253.7 nm also cause degradation. The data further

indicate that the degradation at the longer wavelengths may not be completely

random scission.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons)

Degradation; photodegradation; poly (methyl methacrylate); UV.

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