Polymer Degradation and Stability 37 (1992) 125-129

Spectroscopic study of the molecular structure

of a lignin-polymer system
A . M . A . N a d a , ~ M . Fadly b & M . D a w y ~
a Cellulose & Paper Department, National Research Centre, h Physics Department, Faculty of Science, Helwan University,
c Physical Chemistry Department, National Research Centre, Cairo, Egypt
(Received 15 May 1991; accepted 30 May 1991)

The molecular structure of phenol-lignin formaldehyde resin was studied by

means of infrared and electronic spectra. The effect of the phenol : lignin ratio,
temperature and the adduct (phenol-lignin):formaldehyde (PL:F) ratio on
the absorption spectra of the polymer produced were investigated. The new
band which appeared at 2850 cm-~ in the infrared spectra of P L - F resins was
assigned to the methoxyl group. More information about the molecular
structure was obtained from a qualitative study of the frequency and intensity
changes of the absorption bands.

INTRODUCTION

resins produced are lignin concentration, temperature and the phenol-lignin:formaldehyde

ratio.
Differential scanning calorimetry has shown
great promise in the characterization of thermoset resin cure. 8 Thus, the evaluation of the
structure-property relationships in lignin based
polymeric materials becomes
a technical
possibility. 9
In this present work, infrared (IR) and
ultraviolet (UV) spectroscopic studies are used to
obtain information about the molecular structure
and reactions of the phenol-lignin formaldehyde
resin.

Phenol-formaldehyde resins are widely applied

as insulating materials, foundry resins and wood
adhesives. Acid (novalac) or base (resol)
catalysed phenolic resins are the preferred
adhesives in plywood production.
The opportunity to incorporate lignin, an
abundant polyphenolic pulping residue, which is
very similar in structure to a phenolic resin, into
a phenol-formaldehyde adhesive has been of
interest. Most early attempts to incorporate
lignin into thermosetting phenolics ~ were limited
to small proportions. There has been great
interest in enhancing the chemical reactivity and
the physical properties of lignin fractions to be
used as prepolymers in phenolic resins. 2,3
In the pulping of rice straw, which is used in
many pulp mills at Rakta in Egypt, a large
amount of black liquor from soda pulping is
wasted. Most previous work in this area which
claims that phenol-lignin can be used as a raw
material for phenol-formaldehyde resins does
not mention reaction conditions. In our previous
studies 6'7 it was shown that the most important
factors affecting the yield and properties of the

EXPERIMENTAL

Lignin was precipitated from Rakta black liquor

by acidification with sulphuric acid. Phenollignin formaldehyde resin was prepared in two
stages. In the adduct stage, the lignin reacted
with phenol in the presence of oxalic acid as
catalyst, according to the condition used by
Vorher.10 The reaction was carried out in a small
autoclave. In the polymerization stage the
phenol-lignin (PL) or phenol (P) and formaldehyde (F) in the required ratio, with oxalic acid
as catalyst were heated under reflux in a

Polymer Degradation and Stability 0141-3910/92/$05.00

1992 Elsevier Science Publishers Ltd.
125

126

A. M. A. Nada, M. Fadly, M. Dawy

three-neck flask. The resin was then separated

and purified as stated elsewhere, n The resulting
novalac resin was dissolved in alcohol and
purified by reprecipitation.
IR spectra were obtained using a Beckman
4250 spectrophotometer and the KBr disc
technique. The frequencies of the bands are
reproducible to within + 1 cm-1. Electronic
spectra were obtained in methanol solution using
a Beckman 5260 spectrophotometer.

60
50
t~

4o

.o
.<

3O

2O
0

&

Time

(hr)

Fig. 2. Effect of heating time on the absorbance of (O) OH

phenolic and (O) OCH3 groups in the adduct (-) and
polymerization ( - - - ) stages of the formation of phenol
lignin-formaldehyde resins.

RESULTS A N D DISCUSSION

The IR absorption spectra of lignin (L),

phenol-formaldehyde (P-F) and phenol-lignin
formaldehyde (PL-F) in the region 2004000 cm -~ are shown in Fig. 1. Close comparison
of the spectra of lignin with those of PL-F and P-F
shows a new strong band at 755 cm -1 in the IR
spectra of both P-F and PL-F. Some bands show
detectable intensity changes such as methoxyl,
hydroxyl and the C------Cstretching vibration.
The integrated intensities of these bands for
the three samples are shown in Table 1. From
these data it is clear that the intensity of the

characteristic absorption bands of the methoxyl

of lignin at 2850 cm -1 is lower in PL-F resin than
in lignin itself. However, P-F does not absorb in
this region as shown by Fig. 1. The decrease in
the intensity of the methoxyl stretching vibration
of PL-F is attributed to the hydrolysis of this
group during the adduct and polymerization
stages. These results can be confirmed by
considering the effect of time and temperature on
the absorbance of the methoxyl and phenolic
hydroxyl groups, as shown in Figs 2 and 3. These
figures show that the intensity at 2850 cm-' of the
methoxyl group of the PL-F resin decreases with
increasing time and temperature of the adduct
and polymerization stages. On the other hand,
60
v

50

\
\

o 40
/o /

30

200

500

1000

1500

2000
Wave

2020

3000

number

60

/*000

100

1~,0

Teml~eralure (*C)

(cm -1)

Fig. 1. The IR absorption spectra of (1) lignin, (2)

phenol-formaldehyde, and (3) phenol lignin-formaldehyde
resins.

Fig. 3. Effect of temperature on the absorbance of (O) OH

phenolic and ( 0 ) OCH 3 groups in the adduct (-) and
polymerization ( - - - ) stages of the formation of phenol
lignin-formaldehyde resins.

Table 1. Integrated band intensity of various groups in lignin, phenolformaldehyde and phenol lignin-formaldehyde
Substance
L
P-F
PL-F

(25% L)

180

3300 cm-1

2850 cm 1

1600 cm-1

1200 cm-1

50
67
46

65
-39

43
39
38

34
50
37

755 cm
-16
11.5

Molecular structure of a lignin-polymer system

60
u
c

5O

z.O

.a

3O

20
0

,i
I0

20

30

40

50

60

Concent rat ion ('/o)

Fig. 4. Effect of lignin concentration on the absorbance of

(O) OH and (O) OCH3 groups in phenol ligninformaldehyde resins.
the intensity of the phenolic hydroxyl groups (at
1200cm -1) of the resin is increased. This
confirms the hydrolysis of the methoxyl group of
the lignin during the polymerization stage.
However, by increasing the lignin content of
the PL-F resin, the intensity of OCH3 group
absorption increases (Fig. 4), and that of OH
phenolic groups decreases. The intensity of the
phenolic OH band (at 1200cm -1) of lignin is
lower than that of phenol. This is attributed to

the lower molecular weight of phenol (94), which

has one phenolic hydroxyl group, than that of
lignin (324) with one phenolic hydroxyl group.
For this reason the band intensity of the phenolic
hydroxyl groups of the resin decreases with
increasing lignin concentration.
The new strong band, which appears at
755 cm ' in the IR spectra of PL-F and P-F, can
be assigned to a methylene group. The
appearance of this band is due to the reaction of
phenol in the ortho or para position (or its
phenolic hydroxyl group) with the ot-hydroxyl
group of the propane side chain on the aromatic
ring of the lignin molecule. The intensity of this
band increases with increasing time of the adduct
stage in which phenol is reacting with ligin. The
~ C stretching vibration of lignin at 1450cm -l
shows a detectable increase in intensity and
broadening in the spectra of P-F and PL-F resins.
The broadening and intensification of this band
may be due to the coupling of the vibrational
band of the CH2 group, produced from the
reaction between phenol or phenol-lignin with
formaldehyde, with the C--C stretching vibration, which can be represented as follows:

I
C
I
C
I

.C-

-C-

I
o:--C--OH

--OH

H ~ C -O / ~- O H .

H3CO/~
OH

OH

Phenol-lignin
I
C
I
C
I
cr--C--OH

t
Co~ CI- - C H 2 - - ~ O H

+ CH20

H3CO~ )

a3co

OH

OH

Phenol lignin-formaldehyderesin
OH

OH
+ CH20

127

~
Phenol-formaldehyderesin

CH2,~

128

A. M. A. Nada, M. Fadly, M. Dawy

_.~0.3
_o
u

50.2

--~ 0.1
o
:E
0

I
40

i
60

Lignin conc.(*l,)

Fig. 6. Effect of lignin concentration on the molecular

absorption coefficient of phenol lignin-formaldehyde resin.

\\
\
'~

0.4

x~.

t-

~ o.3
_~ 0.2
u
0
0.1

200

400
600
Wave number (nm)

B00

I
I
2
3
4
Polymerizotion time(hour)

Fig. 5. The electronic absorption spectra of (. . . . . )

lignin, ( . . . . ) phenol, (-) phenol-formaldehyde, and
( - - - ) phenol lignin-formaldehyde resins.

Fig. 7. Effect of polymerization time at 94C on the

oscillator strength (e) of phenol lignin-formaldehyde resin.

The electronic absorption spectra of lignin,

phenol, P-F and PL-F in the spectral region
900-200 nm are shown in Fig. 5. It is clear that a
strong absorption band appears at 280 + 5 nm.
This band can be assigned to a locally excited
n - n transition.
The effect of substitution of phenol with lignin
in the final resin product was studied. The effect
of various parameters in the adduct and
polymerization stages on the U V spectra will be
discussed.
The oscillator strengths per mole of the n-~r
transition of the samples were calculated and are
shown in Table 2. These data show that the

oscillator strength per mole of the n-~r transition

decreases with increasing lignin concentration in
the PL-F resin, as shown in Fig. 6.
This indicates the increasing lignin substitution
of low molar absorption coefficient (0.19) in
place of phenol of high molar absorption
coefficient (0.82). Figures 7-10 show that the
oscillator strength (e) of the resin increases with
increasing time and temperature as well as with
the ratio of formaldehyde in the polymerization
stages. This is attributed to the increase in
cross-linking between phenol-lignin and formaldehyde, which is confirmed by the increase in the
viscosity of the polymer on increasing the
0.3

Table 2. Oscillator strength (t) of the n - ~

transition (280_.+5 nm) of the samples
investigated

Substance
L
P
P-F
PL-F (25% L)
PL-F (40% L)
PL-F (50% L)

Oscillatorstrength (e)
0-19
0-82
0.55
0.23
0-19
0-18

0.2

"6

=_ 0.1

Adduct

time ( h o u r )

Fig. ft. Effect of adduct time at 155C on the oscillator

strength (e) of phenol lignin-formaldehyde resin.

Molecular structure of a lignin-polymer system

These results show that both IR and UV

spectroscopic studies give clear information
about the reaction which occurs between phenol,
lignin and formaldehyde.

0.4

tO

0.3
"6

02

129

oi

6o

70

80

90

100

Poly merizQtion ternp.(~)

Fig. 9. Effect of polymerization temperature for 3 h on the

oscillator strength (e) of phenol lignin-formaldehyde resin.

~0,6
c

-'~ o.4

.--_ o2
0

o
05

0.6

0.7

0.8

0.9

PL:F r a t i o

Fig. 10. Effect of phenol lignin:formaldehyde ratio on the

oscillator strength (e) of the resin produced.

temperature
stage .6

and time of the polymerization

REFERENCES
1. Nimz, H. H., Lignin-based wood adhesive. In Wood
Adhesive, ed. A. Pizzi. Marcel Dekker, New York,
1983, pp. 247.
2. Clarke, M. R. & Dolenko, A., US Pat. 4113675
(1978).
3. Enkvist, T. V. E., US Pat. 3 864 891 (1975).
4. Rieche, A. & Redmger, L., Plaste Kautsch, 9 (1962)
131.
5. Shinjo, H., Japan Pat, 13 797 (62) (1959).
6. EI-Saied, H., Nada, A. M. A., Ibrahem, A. A. &
Yousef, M. A., Angew. Makromol. Chem., 122 (1984)
169.
7. Nada, A. M. A., EI-Saied, H., Ibrahem, A. A. &
Yousef, M. A., J. Appl. Polym. Sci., 33 (1987) 2915.
8. Cassel, B., Characterization of Thermosets. PerkinElmer Thermal Analysis Application Study, 1977 p. 47.
9. Glasser, W. G., Barnett, C. A. & Sano, Y., Appl.
Polym. Symp., 37 (1983) 441.
10. Vorher, W., Schweers, W. H. M., Appl. Polym. Symp.,
28 (1975) 277.
11. US Department of Commerce, Off. Tech. Serv. PB
Rep., 25 (1945) 642.