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Mecanismos Curado Epoxy Anhidrido
Mecanismos Curado Epoxy Anhidrido
Mecanismos Curado Epoxy Anhidrido
Institute of Rock Structure and Mechanics, Academy of Sciences of the Czech Republic, v.v.i.,
V Holešovičkách 41, 182 09 Prague 8, Czech Republic
*Corresponding author‘s e-mail: kolar@irsm.cas.cz
not proved. As the author reports, his results did not 3. RESULTS AND DISCUSSION
prove the conclusions of Tanaka and Kakiuchi (1963, ALCOHOLYSIS
1964), or Fischer (1960). Indeed, he found that the The generation of monoester was modeled by the
anhydride depleted during the reaction substantially reaction of maleic anhydride with isopropyl alcohol.
faster than the epoxy compound. This agrees with the The reactions provided at temperatures of 52, 65 and
experiments of Fisch and Hofmann (1954, 1961). 78 ºC. The course of the reactions was monitored by
Sorokin considers the reaction of the epoxy determining the concentrations of anhydride and
compounds with monoester to be the crucial step. This monoester by double titration after Smith and Bryant
reaction is of the 1st order with respect to the epoxy (details in Jureček (1955)). The sigmoid shape of time
compound and catalyst, and of the zero order with dependence of the maleic anhydride conversion for
respect to monoester. The author does not mention systems without DMA indicates that the reaction was
how the tertiary amine works under alcoholysis, catalyzed by a reaction product (see Fig. 1). The
referring the reader to the paper of Gold and Jefferson generation of diester was not observed under the given
(1953). At present is cure kinetics of epoxy resin conditions.
studied in general by the help of physical methods as The active substance is evidently the proton
thermogravimetric analysis (Wang and Shi, 2005), produced by the dissociation of the generated
DSC (Chen et al., 2004; Kim and Lee, 2002), monoester. The proton is first bound to the anhydride
dielectric analysis (Chen et al., 2004) or Raman molecule under generation of an oxonium cation,
spectroscopy (Rocks et al., 2004). which then reacts with alcohol and monoester
In this paper we study the mechanism and originates (Ernest et al., 1959).
kinetics of epoxy resins cured via anhydrides on The dissociation of monoester is very fast in both
model reactions. The changes in the concentration of ways so that, soon after the beginning of the reaction,
reaction components were monitored by chemical equilibrium sets up. The control step, therefore, is the
methods. reaction of the oxonium cation with alcohol. The
7
2. EXPERIMENTAL
DGEBA (CHS Epoxy 15 (present name is CHS 6
Epoxy 520), epoxy group content 5.193, OH groups
0.610 mol kg-1, SpolChemie, a.s. Czech Republic) 5
was used as the initial resin. Maleic anhydride purris,
isopropyl alkohol anhydrous (Sigma-Aldrich),
CA (mol kg )
-1
4
N,N-dimethyl aniline purris. (Sigma-Aldrich).
Mono(isopropyl) maleic ester was prepared by non- 3
catalyzed reaction of maleic anhydride and isopropyl 52
alcohol in equimolar amount as described in Ernest et 2
al. (1959). All reactions took place in closed flasks at 65
temperatures of 65 to 100 ºC under mixing with a 1 78
magnetic mixer. Samples collected in the course of the
reaction were dissolved in benzene, and the content of 0
epoxy groups was determined by HBr titration in 0 5000 10000 15000 20000 25000
acetic acid Durbetaki (1956). The contents of time (s)
anhydride and monoester were determined
simultaneously by natrium hydroxide and natrium Fig. 1 Alcoholysis of maleic anhydrid by
methanolate titration described in Jureček (1955). The isopropyl alcohol without DMA,
concentration of hydroxyl groups in the initial resin numbers at curves are reaction
was determined by acetylation after Chachapuridze temperature in oC.
(1969).
KINETICS AND MECHANISM OF CURING EPOXY/ANHYDRIDE SYSTEMS 87
(A*)
At the beginning of the reaction the rate of the
alcoholysis is very low, hence the inequality Scheme 1: Strukture of the MA (DMA)
k1 << k4′ K 3 . Equation (1) was solved by numerical
integration using the Runge-Kutta method. Constants
k4′ and K 3 were optimized using Marquardt’s method. the positive partial charge on the carbon neighboring
to nitrogen. Let us assume a reversible reaction, in
The values of the constants found are given in Table
which the initial substances and the product are in
1. Figure 1 shows the time dependence of anhydride
scheme 2.
concentration fitted with integrated function (1). The
The system of equations, describing the kinetics
temperature dependence of the constants was
of these reactions, can be simplified if one assumes
determined using Arrhenius’ and van Hoff’s relations.
Alcoholysis of anhydrides is catalyzed by stationary concentrations CA* , CM* and constant
tertiary amines. Whereas the product of the reaction of concentration of active DMA particles:
acetic anhydride with pyridine was not proved [10]
the reaction of maleic anhydride with N,N-dimethyl dCA k K Co C C
= − 7 6 DMA A OH + ro (4)
aniline undoubtedly takes place. Evidence of this is dt 1 + K 6 CA + K 8 CM
the intensively orange coloration appearing after the
two substances have been mixed. Neither maleic where ro is the rate of non-catalyzed reaction
anhydride, nor N,N-dimethyl aniline absorb in the (Equation (1)).
visible part of the spectrum. Let us assume the Equation (4) can be conveniently approximated
reaction: by a 1st-order equation, to which it will transfer, if
K6
K 6 CA >> 1 + K8CM :
MA + nDMA MA(DMA) n (2)
dCA
= − k7 CDMA
o
COH + ro (5)
The equilibrium concentration MA(DMA)n dt
depends on the molar fraction DMA as:
The time dependences of maleic anhydride for
various amounts of catalyst at a temperature of 65 ºC
{ }
⎡⎣ MA ( DMA )n ⎤⎦ = K 6 C o (1 − X DMA ) − ⎡⎣ MA ( DMA )n ⎤⎦ are shown in Fig. 2. Rate constants k7 determined by
Marquardt’s method are given in Table 1.
{C X }
n
o
DMA − n ⎡⎣ MA ( DMA )n ⎤⎦ (3)
6
concentrations.
Maximum of function (3) is at X DMA = n (n + 1) . 4
C A (mol kg )
-1
O O
C C O
K6
O + R3N
C C NR3
O O
(A*)
O O
C O δ δ C O R3NH
k7
+ R'O H
C NR3 C OR'
O O
(A*)
O O
C O R3NH C OH
K8-1
+ R3N
C OR' C OR'
O O
(M*)
REACTION OF CHS EPOXY 15 RESIN WITH kinetics observed correspond to the data reported in
MONO(ISOPROPYL) MALEIC ESTER the literature. According to (Ernest et al., 1959) the
The reaction of monoester (generated by epoxy groups react with weak acids mostly with the
alcoholysis) with epoxy groups was studied on the SN2 mechanism. Kinetics of the second order in
model reaction of CHS Epoxy 15 resin with general was also observed by Sorokin, when he
Mono(isopropyl) maleic ester (M). The reactions took studied the non-catalyzed reaction of phenyl glycidyl
place in present DMA catalyst as well as without a ether with caproic acid (Sorokin, 1968).
catalyst, at temperatures of 65, 78, 89 and 100 ºC. The
reactions were monitored by measuring the 3
O O OH
C OR' O C OR'
O O
(M*)
3.0
Epoxy
1,0
C A, C E, C M (mol kg ) Anhydride
-1
Epoxy
0,6 Anhydride
2.0
C A, C E , C M (mol kg -1)
Monoester
0,4
1.5
0,2
0,0 1.0
0 5000 10000 15000 20000 25000
time (s)
0.5
groups and hydroxyls is comparable, the depletion of Fisch, W. and Hofmann, W.: 1961, Plastics
anhydride is faster than that of the epoxy groups. The Technology, 28, 8, 29.
time dependence of monoester has a form typical for Fischer, R.F.: 1960, J. Polym. Sci., 44, 155.
the subsequent reactions. A relatively short time after Gold, V.E. and Jefferson, CJ.: 1953, J. Chem. Soc.,
the beginning of the reaction, the anhydride vanishes 1049.
from the reaction mixture and only the reaction of Hagnauer, G.L. and Pearce, P.J.: 1992, ACS Symp.
epoxides with the monoester continues. In terms of Ser., 221, 193.
kinetics this reaction is of the first order. The low Jureček, M.: 1955, Organic Analysis, Prague,
concentration of OH groups restricts the rate of Czechoslovak Academy of Sciences.
alcoholysis as well as the reaction of monoester with Kim, W.G. and Lee, J.Y.: 2002, Polymer, 43, 5713–
the epoxy groups. It appears that the discrepancies in 5722.
curing kinetics and mechanism are related to the Kraus, W., Schneider, P. and Beránek, L.: 1978,
different content of OH groups in the resins studied. Chemical kinetics for engineers, Prague, SNTL.
Lee, H. and Neville, K.: 1967, Handbook of epoxy
ACKNOWLEDGEMENT resins, New York, McGraw-Hill.
This study has been supported by the Institute May, C.A.: 1988, Epoxy resins, New York, Marcel
Research Plan of the IRSM CAS CZ Dekker.
No. AVOZ30460519. Morgan, R.T.: 1985, Adv. Polym. Sci., 72, 1.
Rocks, J., Rintoul, L., Vohwinkel, F. and Georgie, G.:
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