Anda di halaman 1dari 7

Indian Journal of Chemical Technology

Vol. 5, May 1998, pp. 139-145

Effect of unsaturated acids on the properties of epoxy resins:


Syn.thesis and characterization
Pragyan Mohan & A K Srivastava'
Department of Chemistry, Harcourt.Butier Technological Institute, Kanpur 208 002 India
Received 4 September 1997; accepted 17 February 1998
The effect of unsaturated aliphatic and aromatic acids such as acrylic acid and cinnamic acid on the
properties of epoxy resins has been studied by synthesizing related resins in their presence at llO2"C.
These resins have been characterized by IR,IHNMR, spectroscopy by the thermal analysis. The reactions
follows first order kinetics with activation energy 53 and 92 kJ mol-I for resins containing cinnamic acid
and acrylic acid, respectively. The characteristic value, such as epoxide equivalent, specific viscosity
increased in the presence of acids due to formation of P-hydroxy ester of diglycidal ether of bisphenol A.
However, the hydroxyl content and hydrolyzable chlorine content decreased due to formation of diester
of propanol 2 and poly( acryloyl-chloride).

Epoxy resins, having good mechanical thermal and


electrical
properties,
are widely
used
as
engineering materials. It is important to investigate
and understand the relationship between structure
and properties of epoxy resins for their most
The present paper
appropriate applicationsl-9
highlights some aspects of synthesis of epoxy
resins in the presence of aliphatic and aromatic
unsaturated
acid covering structure-properties
relationship along with elucidation of mechanism.

Experimental Procedure
Materials

Epichlorohydrin,
dioxan, acetone, methanol
(Ranbaxy), pyridine (Nice), bisphenol A (Robert
Johnson) acrylic acid (Merck), acetyl chloride
(Qualigens), cinnamic acid (Loba) were obtained
from commercial source and used as received.

(3.6xloo2,

7.2xloo2,

1.45xlO-1
bisphenol

1.08xlO-I,

mol).Sodium hydroxide (0.15 mol.)


A(0.018 mol)
(3) Epichlorohydrin
(0.18mol),cinnamic
acid
(3.6xlOo2mol) sodium hydroxide (0.15 mol) and
bisphenol A(0.018 mol).
(4) Epichlorictrin
(0.18 mol), acrylic acid
(3.6xloo2 mol) and sodium hydroxide (0.15 mol).
The epoxy resins were characterized as below:

Epoxide equivalent (EE)-EE of various resins


was determined by the pyridinium
chloride
method, which include addition of pyridinium
chloride (0.2 N, 2.5 mL) solution of epoxy resins
(a.5 g). It was then stirred and retluxed for 25 min
followed by addition of 50 mL methanol through
condensor and titrated against methanolic NaOH
(0.5 M). Blank was used without epoxy resins. The
epoxide equivalent was calculated by following
formulall.

Method

Epoxy Resins Synthesis-The

epoxy resins were


synthesised at 1102 C according to the method of
Lee and Neville10 using the following amount of
reactants.
0

16 x weight of sample
Epoxide equivalent = ----------Weight of oxiran oxygen in sample
:The weight of ox iran oxygen sample=(A-B) (O.16)N

(1) Epichlorohydrin (0.18), bisphenol A .(0.018


mol) sodium hydroxide (0.15mol) and cinnamic
acid (3.6xlOo2, 7.2xlO-I, l.08xlO-1 mol)
(2) Epichlorohydrin (0.18 mol) and acrylic acid

A=mL of methanolic NaOH for blank


B=mL of methanolic NaOH for sample
N=Normality ofNaOH
0.OI6=Miliequivalent of oxygen in g.

*Forcorrespondence

Hydroxyl

content-Hydroxyl

content

was

140

INDIAN 1. CHEM. TECHNOL., MAY 1998

determined by Acetyl chloride method and using


the following formulae.l2
weight of sample
Hydroxyl ontent= Normality of NaOH (VI

- V2)

170

V]=thevolume of methanolic NaOH used for the


blank

Vi=the volume of the methanolic used for the


sample.

Hydrolyzable chlorine content-Dehydrohalogenation method is used for determination of


chlorine content of various resins using the
following formulal2 :
HydrolY7.able chlorine content (%)=
355xl0-4

x N of KOH x volume of KOH neutralized by epoxy resins


weight of sample

Infrared Spectra-The
IR spectrum
was
recorded on a Perkin Elmer Spectrophotometer
(model 377).
Spectra-'HNMR
spectra
were
IHNMR
recorded on varian EM 390 spectrophotometer.
Viscosity-Ubbelohde
viscometer and Abbe
Refractometer were used to determine viscosity (in
dioxan
40%
w/v)
and
refractive
index,
respectively.
Results and Discussion
No reaction occurred between epichlorohydrin
and acrylic acid. However, the reaction of
epichlorohydrin with bisphenol A in the presence
of cinnamic acid/acrylic acid yielded epoxy resin
along with a white solid as single component
product. The solid was separated from epoxy resins

by filtration and identified as poly(acryloyl


chloride) on the basis of following data:
It contains chlorine (37.02% in acrylic acid and
20.70% in cinnamic acid) and decolourised
Baeyer's reagent. It does not melt upto 250'C. On
the basis of IR and 'H NMR spectral analysis
following structure may be assigned to the solid:
-(R-CH-CH,\,.

-(RCH-C ~-

II

Cl-C=O

CI-C-OH

(Keto form)
(enol form) enol
Fig I shows the characteristic band position of
white solid by IR spectroscopy:
770 cm-l (C-CI), 1580 cm-I (C-C, phenyl
group),
1650 cm-' (C=C), 2900-3000
cm-1
.
,
(methylene
group), 3020 cm- (C-H, phenyl
group), 1780 cm-1 (C=C-CI), 1100-1350 cm-l
(OH, primary alcohol) The following band
positions have been observed in IHNMR spectrum
(Fig 2)
2.0 8 (m, methylene, protons), 4.0 8 (8,OH
proton) 7.0-8.58 (m, aromatic protons).
Table 1 shows that the blank epoxy resins as
well as those containing acrylic acid/cinnamic acid
are amber coloured. The refractive indices of
epoxy resins derived from cinnamic acid, and
acrylic acid are marginally higher as compared
with the blank epoxy resins. Table 1 further reveals
that the epoxide epuivalent of epoxy resins is in the
order ER(i) > ER(ii) > ER(iii) > epoxy resins
containing
propionic
acidl3
> epoxy resins
containing benzoic acidl3 > blank, which may be
due to formation of f3 hydroxyester of diglycidal
ether of bisphenol A [B) (Reaction Scheme A)

80!

I
V
~_~_~I_"_

1400

WAVENUMBER,

Fig. 1-IR

II" Il~
II

III'

1200

.._,--L.....~~

1000

em'

spectrum of poly (acryloyl chloride)

II

800
O,ppm

Fig. 2_IH NMR spectrum of poly (acryloyl chloride)

MOHAN

& S RW ASTAV

141

A: EFFECT OF UNSA 1URA TED ACIDS ON EPOXY RESINS

Reaction SCheme
.ttecbanisl'A
'A'
for etJoxy resin
acid and acrylic acid.
Step

I:

Bisphenol A react
X,~ and Z product.

formation
with

in the presence

epichlorohydrin

and

of cinnamic

acid

to

give

Bisphenol A
(BA)

F;pich10rohydrin
(ECH)

Acid(R=H
or C6HS)
( A)

naOH( Aq)

[Z)

[Y)

Step

II:

Product
[X) give
formed
in Step ether
I either
react withA e~ichlorohydiglycidal
of bis~henol
[AJ or
drin or [Y]
hydroxy eSer of diylycidal ether of bispheno1 A [B)

Diglycida1 ether of
bispheno1 A[A)

A 1\'0-<=:>1'-<':::>-01/\
L.Y
~

AA
U/lf'"

'It

>

M-<::;;;;;>-c~ '"
~~~

Step

III:

Product

[Y) formed in Step

&M+M

&.3
' 1ycida l'ether
ster of d~gA [B)
I
react wo~
ithbisphenol
ac~'d and gl.
P hydroxy
.ve 1,3

diester of Pfiopanol-2 [C)

~
~
[C)

Step IV: Acryloyl chloride [Z) formed in Ste~ I exist in keto and enol
form was ~olymerized at l50nC to give ~oly(acrYloyl Chloride)

polymerization
150'"(.
)
f CHR -

. 0=

n
+

-Cl"

fCHR:-:fH+n
HG-~-Cl
poly(acryloy1 chloride)

142

INDIAN 1. CHEM. TECHNOL., MAY 1998

However, the higher value of EE for ER (i) in increasing the molar concentration of acid (S)
comparison to ER (ii) may be attributed the greater during resinification. It is probably due to the
acidic nature of cinnamic acid than acrylic acid. In reaction between epichlorohydrin and acidl4 rather
both cases ER (i) and ER (ii) the EE decreases on than less acidic bisphenol A. Which results the
formation of more 1, 3 diester of propanol 2 in
Mechanism 'B': epoxy reslns have been forllHtd by the
reaction
of cinnamic
acid and eplchlorohydrin.
comparison to 13 hydroxydiester of DGEBA and

DGEBA. The formation of these products were


+ L::V"-CI
~OH
confirmed by thin layer chromatography.
Epichlorohydrin

Cinnomic acid

NoOH

vV\

IECH)

OPLA.{'CI
ONo

OH

Table 2 shows a comparative chart of epoxy


resins containing unsaturated/saturated acids13, The
lower value of hydroxyl content of epoxy resins
containing cinnamic acid/acrylic acid/propionic
acidl3/benzoic acid13, also supported the formation

1 NoCl

~o~
ECH

-NoCI
INoOH

Q-ALo/'..("o~
OH
, ,3-Dill stllr (3-pheny lproponotll-l)
propanol 2 (b)
90

c~
~
'f

'"

c
o

1200 -1000

Fig. 3-IR

.900

Fig. 4-IH

spectrum of epoxy resins containing 0.07 mol


cinnainic acid (ERA2)

Amber
Blank
1.552
0.041
1.135
1.13
0.0845
1.582
0.001
1.12
1.139
0.091
0.1035
0.072
1.141.037
1.137
1.02
1.173
889
2.5
1.589
1.549
1535
0.15
O.ll
0.0021
0.0011
Amber
2.0
2.4
0.0775
1.512
1.591
0.07
0.04
1.563
1210
1451
0.0016
0.0008
0.0006
2.5
2.2
2.3
0.067
0.060
1.554
0.150.04
0.0017
1651
1697
Amber
0.0008
1.581
E
R cinnamic
+Cinnamic
acid
0.0
0.12
0.5
1.5695
acid
3028
998
1.6
1.9
1.08
194
1.58
ERA1
ERA2
ER83
ER82
ERB1
ERB4
ERA3
Epichlorohydrin+BisphenoIA+
ER(iii)
ER(ii)
ERA4
Epichlorohydrin
E~crylic
pichlorohydrin+Bisphenol
Table I--characteristicA
acid
Hydroxyl ER(i)
content (eq/IOO)

'Ii

II' I '~

I, p

'I

"

NMR spectrum of epoxy resins' containing 0.07


mol cinnamic acid (ERA2)

of epoxy resin

"'''11'11

MOHAN & SF. IV AST AV A: EFFECT OF UNSATURATED

of [B] and [C] product (Reaction Scheme A)


during sYI\thesis. Similarly, the lower value of
hydrolyzable chlorine content of epoxy resins
containing acrylic acid/cinnamic acid confirms the
formation of acryloyl chloride, which undergoes
polymerization at 150C after distillation.
However, the hydrolyable chlorine content of ER
(iii) is greater than that of blank which indicates
the possibility of side reaction of epichlorohydrin.
Table 2--Comparative
Properties
Molar concentration
of acid
Colour
Refractive index
Epoxide equivalent
Hydroxyl content
Chlorine content
Viscosity (130C)
Specific grants

143

ACIDS ON EPOXY RESINS

Based on the above discussion two spectualation


mechanism can be proposed for (i), (ii) and (iii)
cases.
Structural evidence for epoxy resins-IR spectra
(Figs 3 and 4) of epoxy resins containing acid
(cinnamic acid and acrylic acid) are reported
below.
900-950 em-I (epoxy group), 1250 em-I (ether
group), 1650-1670 cm-I (carboxylic group), 1580-

"chart of epoxy resins containing unsaturated/saturated acids. 13_"


Blank
Unsaturated acid
Saturated acid
0.0

Acrylic acid
0.04

Cinnamic acid
0.04

Propionic acid
0.036

Benzoic acid
0.036

Amber
1.5695
194
0.12
0.5
1.58
1.173

Amber
1.512
1651
0.0006
0.0775
2.3
1.13

Amber
1.552
3028
0.001
0.1035
2.5
1.12

Amber
1.4354
819
0.0015
0.023

Amber
1.4215
568
0.0013
0.018

1.l034

1.l07-

l.l

0.8

80

-: 60
13

~
"~

401

r~
20'

1
WQvenumbcl:r, em'

Fig. 5--IR spectrum of epoxy resins containing 0.041 mol


.
acrylic acid (ERB1)

03000

1800

1600
Wavenumber, em'

1000

Fig. 7--1R spectrum of epoxy resins derived from cinnamic


acid and epichlorohydrin (ERjjj)

Fig. 6-IH

4
&,ppm

NMR spectrum of epoxy resins containing 0.041 .


mol acrylic acid (ERat)

Fig. &-IH NMR spectrum of epoxy resins derived from


cinnamic acid and epichlorohydrin (ER;u)

800

144

INDIAN 1. CHEM. TECHNOL., MAY 1998

1600 em'] (C-C, phenyl group), 2900-3000 cm-I


(methyl and methylens group), 3000-3020 cm-I (CH, phenyl group), 3500 cm-I (OH, alcoholic group)
IR spectra of epoxy resins containing acid (S) show
the virtually additional absorption band due to
carboxylic group at 1650-1670 cm-I showing
thereby the formation of l3-hydroxy ester of
deglycidal ether of besphenol A (B) and 1, 3 diester
ofpropanol-2 (C) (Reaction scheme A).
Figs 5 and 6 show the IH NMR spectra of epoxy
resins containing acrylic acid and cinnamic acid.
The following band position has been noticed
IHNMR spectra:
2.0-3.0 () (m, epoxy protons), 3.5-4.0 8 (m,
methylene and CH=CH2 conjugated protons), 5.76.58 (m,hydroxy protons) 6.9 - 8.0 <5(m,aromatic
protons). The peak area ratio about 5.7-6.58 due to
hydroxyl protons in ERA2 (3.1 cm) and ERB1(1.8
em) is lower than that of blank (6.1 cm)6 cpoxy
resins. This observation supported the lower value
of hydroxyl content in the presence of acid(s)
calculated by acetyl chloride method .
-66
The presence of a bond at 900 cm-I in the IR

TGA (Fig. 9). The epoxy resins containing


cinnamic
acid (280 C) is more stable in
comparison of blank epoxy resins7,8 (130C)and
resins containing acrylic acid (285C). The rapid
decomposition was observed around 300 to 500C
and almost total volatilization occurred above
500C temperature in E~i)' However, in the case of
E~iii) the rapid decomposition
was observed
around 385 to 56s"C and almost total volatilization
occurred above 565C. These data confirm that the
incorporation of the selected acids in the reactants
and consequent modification of epoxy resins
system by them resulted in increase in thermal
stability of the epoxy resins.

Kinetics
The activation energy (~

and order of reaction

/1

-10

-J

64

spectrum (Fig.7) of epoxy resins synthesised by


cinnamic acid and epichloride (ERiii) confirms the
presence of epoxy rings. The band at 1250 cm-I
due to presence of the ether group and an
additional band at 1600-1650 cm-) due to
carboxylic group confirm the presence of cinnamic
acid in resins. The IHNMR spectrum of E~iji)
(Fig.8) shows peak in region 8=2.Qppm. Which
could be attributed to the epoxide protons. The
spectra show aromatic signals at <5=1-2ppm.
Thermogravimetric analysis-The
effect of
unsaturated aliphatic and aromatic acid on the
thermal stability of epoxy resins was studied by
-- ----- ---- ..

..

-6,0

,5

,6

,7

"8

x=+-.,03

Fig. lOa-A plot of log [log (I-a)/T2] versus IITxlO3 for


epoxy resins containing 0.041 mol cinnamic acid (ERA.)

,,

"

,,,
,

\\

,\
.....

---5-5

,,3
Temperature.

Fig. 9-TGA curve of epoxy resins containing 0.041 mol (~)


acrylic acid (ERB2) and (---) cinnamic acid (ERAl)

I II'

l~

,-4

1-6

1.
.'03
T

100

I'

""""11'

i"l

"I'

Fig. lOb-A plot of log [log (1-a)/T2] versus IITxIO~ for


expoxy resins containing 0.041 mol acrylic acid (ERa.)

"

,'HI

I'll

MOHAN & SRIV ASTA VA: EFFECf OF UNSATURATED

was calculated by Coats and Redfenn equationlS


accord~ to which
IoglO
.[ -Tga2 ]

=---+I~o-2.3RT
pAE.!i.E
l1E
ZR ( 1--2RT} ...

g = (-.Jog(I-ai/I!]

The plot of

10+ ~~]verws

[:

x 10' ] gives

a linear cUJVe.It's slope is equal to AE /2.3RT and


I S

mtercept gives

"r "

oglO --

---

f1!i.E
!i.E
ZR (I 2RT)

Where AE = Apparent activation energy


P = linear heating rate
Z = pre-exponential factor
n = order of reaction
The activation energy, calculated from the slope
of the linear ~ph plotted between log g(a) versus
lI1XloJ (Fig.l Oa,b). The activation energy of
modified epoxy resins containing 0.36 mol of
cinnamic acid and acrylic acid is higher (53, kJmorl
and 92 kJ mol-I respectively) than that of blank

ACIDS ON EPOXY RESINS

145

epoxy resins (34 kJ morl). The overall reaction for


both blank7 and llJodified resins follows first order
kinetics.
Reference
1 Fukami A & Moriwaki T, J Macromol Sci Chem A. 26
(1986) 877.
2 Thangamathesvaran P M & Jain R S, J Polym Sci Part A
Polym Chem."26 (1991) 261.
3 Chen C S, Bulkin B J & Pearce E M, J Appl Polym Sci. 26
(1982) 1177.
4 Jain R K & ChandraR S, Acta Po/ym, 42 (1991) 668.
5 Yamada Y & Kaji M, ChemAb8l, 118 (1993) 816494.
6 Mohan P & Srivastava A K, Macromol Reports. A32,
(1995) 1213.
7 Anand M & Srivastava A K, J Appi Polym Sci. 51, (1992).
203.
8 Anand M & Srivastava A K, Die Angew Makro Chem. 216
(1994) 1.
9 Anand M & Srivastava A K, High Pref Po/ym. 4 (1992) 97.
10 Lee H & Neville K Hand Book of Epoxy Resin, (Me Graw
Hill New York) Chap 2-4 (1969).
11 Anand M & Srivastava A K, Polymer, 34 (1993) 2860.
12 Mohan P & Srivastava AK. Polym.Material (1997) (in
press).
13 Mark HF, Bikales NM, Overberger C.G. & Menges G,
Encyclopedia of Polymer Science & Engineering, (John
Willey & Son) (6) (1985) 341.
14 Coa!S A W & Redfern J R. Nahlre (London). 68 (1964) 201.