REACTION OF METHACRYLIC ACID WITH EPOXY COMPOUNDS

G. V. Leplyanin, L. Kh. Bikchurina, UDC 542.91~547.39!.3~541.64

I. A. Gailyunas, E. M. Tsyrlina,
V. Kh. Singizova, and Ao R. Derzhinskii

One of the methods for obtaining B-hydroxyethyl acrylates~ which are used in the syn-
thesis of water-soluble and water-swellable polymeric materials, is the reaction of epoxy
compounds with either acrylic (AA) or methacrylic (MAA) acid [1-3]. A method is known for
the synthesis of poly(8-hydroxyethyl acrylates) via the analogous transformations of the
homo- and copolymers of AA (~IAA), which are obtained in the presence of epoxides [4]. The
reactions for opening oxides also proceed during the curing of epoxide resins by multihydric
acids, and also of epoxide resin-unsaturated acid compositions and subsequent simultaneous
or prior polymerization of the acid. The kinetic rules for opening the a-oxide ring by acids
should be taken into account if these processes are to be run successfully. However, the
information on the reaction rate of epoxides with unsaturated acids is very scanty and data
are completely lacking on the reaction of cyclic epoxide compounds with unsaturated acids.
B-Hydroxyethyl acrylates are synthesized using either acid or basic catalysts [5],
although the uncatalyzed reaction of epoxide compounds with M~kA is also possible [6]. We
established that B-hydroxyethyl acrylates can be synthesized by the copol}~erization of vinyl
monomers with MAA in the presence of epoxide compounds [7]. Here, depending on the reactiv-
ity of the epoxide compounds, the reaction with MAA can proceed either in or before the poly-
merization step.
The reaction of equivalent amounts of epoxide compounds of variable structure with !~A_A
is described by a second=order equation, which follows from the linear dependence of the
values, reciprocal to the change in the MAA concentration, on the time. This reaction order
is in harmony with the literature data on the reaction of epoxy compounds with carboxylic
acids [8]. The values of the rate constant for the noncatalytic reactions of MAA with
epoxides depend on the nature of the epoxide compound (Table i). When discussing the reac-
tivity of the silacyclopentane oxides (I)-(IV) it can be seen that the reaction rate is
probably determined by steric factors, l,l-Dimethyl-3,4-epoxysilacyclopentane (I) exhibits
the greatest activity. When the bulky trimethylsi!oxy group is substituted on the Si atom
(IV) the rate constant drops to 0.48.10 -6 liter/mole.sec. The same rule was also observed
for epoxides that contain the cyclohexane ring: The rate of opening the epoxide in l-tri-
methoxysilyl-3,4-epoxycyclohexane (VI) is ~0.5 times slower than for the unsubstituted analog
(V). In exo-oxide (VII) [9] the shielding effect of the endo-methylene bridge causes an
even greater decrease in the rate constant.
When discussing the reactivity of epoxy compounds containing sulfur of variable degree
of oxidation in the molecule, it can be seen that the epoxy compound containing a sulfoxide
group in the substituent has the greatest value of the reaction rate constant with M ~ .
The high activity of 2,3-epoxypropyl octyl sulfoxide (IX) can be explained by the ability of
the sulfoxide group to complex with carboxylic acids [i0]. It was shown by IR spectroscopy
that the absorption band of the sulfoxide group in an equimolar mixture of 2,3-epoxypropyl
octyl sulfoxide and MAA is shifted by 15 cm -~ toward lower frequencies. It is possible that
complex formation activates the opening of the epoxide ring in the reactions of MAA with
epoxy alkyl sulfoxides.

EXPERIMENTAL
The ~iAA was purified by standard methods. The epoxy compounds had the characteristics
given in Table i.

Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Trans-
lated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, ppo 1432-1434~ June,
1984. Original article submitted ~ y 27, 1983.

0568-5230/84/3306-1319508.50 9 1984 Plenum Publishing Corporation 1319

 TABLE i. Characteristics of Epoxy Compounds and Effective
Rate Constants for Reaction of Epoxy Compounds with MAA (MAA:
epoxy = i:i)
Bp, ~ C (p, mm k, I0~ 9liteb/
Epoxy compound mole. sec
of rig}

0
/\
(I) t39(760) 1,4525 6,2_+0,7
\ /
SiMe,~
O
/\
(II) 37-38 (t) 1,4385 t,6•
\ /
Si (OEt),

0
/\ 0,92_+0,1
(III) 60-6t (t,5) 1,4339
\ /
Si (O-i-Pr):,~
0
/\ 0,48-•
(IV) 61-62(1) t,425i
\ /
Si [OSiMe~]_,

129-134 (760) 1,4460 13,8~I,5

Si (0Me)3
79-S0 (I) t,4455 5,8•

( ~,/Si(OM e)3
S5-S6(I) t,4490 3,9•

(vii)

C~ttl~SCH..CHCH~ (VIII) i30 (2) 4,2•

\/
O

CsH17SOCH2CHCH2 (IX) mp 44-45 16,1•

\/
0

C.~,HI=SO~CH2CHCH~ (X) mp 40-4i 1,65+0,2

\/
0

The rate of the noncatalytic reaction of M A A w i t h the epoxide compounds was studied at
85~ and a reactant ratio of epoxide:MAA = I:i. The reaction rate was followed by the change
in the MAA concentration using potentiometric titration. Hydroquinone (0.1%) was used as the
polymerization inhibitor. The rate constants for the reaction of the epoxy compounds with
MAA were calculated from the slope of the lines that were obtained by plotting the experimen-
tal curves in the coordinates: I/[MAA] vs. time.

CONCLUSIONS
The reaction rate of methacrylic acid with the studied epoxy compounds depends on steric
factors and the ability of the epoxy compounds to complex with methacrylic acid.

LITERATURE CITED
i. Masauki Murayama, U. S. Patent 3,441,599 (1969).
2. Richard L. Rowton, U. S. Patent 3,441,598 (1969).
3. M . F . Sorokin, R. I. Denisova, and G. S. Tishkova, Trudy Mosk. Khim.-Tekhnol. Inst. im.
D. I. Mendeleeva, No. 80, 42 (1974).

1320
4. N. A. Lavrov, V. M. Bondarenko, and A. F. Nikolaev, Filed as No. 1259/77 in ONIITEKhim,
Cherkassy (1977).
5. E. G. Stepanov, V. A. Podgornova, I. I. Ivanova, and E. F. Ustavshchikov, in: Basic
Organic Synthesis and Petrochemistry, Vol. i [in Russian], Yaroslavl (1974), po 62.
6. E. G. Stepanov, M. I. Belostotskaya, V. A. Podgornova, and E. F. Ustavshchikov, in:
Basic Organic Synthesis and Petrochemistry, Vol. 1 [in Russian], Yaroslavl (1974), po 77~
7. G. V. Leplyanin, L. Kh. Bikchurina, S. R. Rafikov, eta!., USSR Patent 579,2865 Byull.
Izobret., No. 41 (1977).
8. M. F. Sorokin and E. L. Gershanova, Kinet. Katal., 8, 512 (1967).
9. H. G. Kuivila and G. L. Grady, J. Organomet. Chem., 21~ 303 (1970).
I0. G. V. Gusakov and A. L. Smolyanskii, Opt. Spektrosk., 32, 509 (1972).

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