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CHEMISTRY
Corresponding Member of the Academy of Sciences of the USSR M. M. KOTON and F. S. FLORINSKII
SYNTHESIS OF POLYMERIZABLE ORGANOANTIMONY ACRYLATES AND METHACRYLATES
Recently, derivatives of acrylic and methacrylic acids containing atoms of mercury (^1), lead (^1,^2), tin (^3–^5), and germanium (^6) have been synthesized. In continuation of these studies, we have for the first time synthesized organoantimony derivatives of acrylic and methacrylic acids.
The following were synthesized: diphenylstibine acrylate
$\mathrm{CH_2{=}CHCOOSb(C_6H_5)_2}$
and diphenylstibine methacrylate
$\mathrm{CH_2{=}C(CH_3)COOSb(C_6H_5)_2}$.
The synthesis of unsaturated organoantimony compounds was carried out by the interaction of diphenylstibine oxide and acrylic (methacrylic) acid in methanol solution, according to the equation:
\[
((\mathrm{C_6H_5})_2\mathrm{Sb})_2\mathrm{O}
+ 2\mathrm{CH_2{=}CRCOOH}
\rightarrow
2\mathrm{CH_2{=}CRCOOSb}(\mathrm{C_6H_5})_2
+ \mathrm{H_2O},
\]
\[
\mathrm{R}=\mathrm{H},\ \mathrm{CH_3}
\]
These substances are colorless crystalline compounds, soluble in organic solvents. They readily polymerize in bulk and in solution, and also form copolymers with various vinyl monomers.
Experimental Part*
Diphenylchlorostibine was obtained by the interaction of tetraphenyltin with antimony trichloride, converted into the corresponding acetate, which was transformed into diphenylstibine oxide with m.p. 78° (^7).
Diphenylstibine acrylate was obtained as follows. To a boiling solution of 5.7 g (0.01 mole) of diphenylstibine oxide in 50 ml of methanol was added a solution of 2.1 g (0.03 mole) of acrylic acid in 15 ml of methanol; the reaction mixture was heated on a water bath for 1 hr. After removal of the methanol, the residue was treated with n-hexane, and upon cooling a crystalline precipitate separated from the solution. After two recrystallizations from n-hexane, colorless crystals with m.p. 115–117° were obtained. Yield 5.1 g (74% of theory).
Found, %: C 51.80; 52.12; H 4.24; 4.26; Sb 35.00; 35.43
$\mathrm{C_{15}H_{13}O_2}$. Calculated, %: C 51.87; H 3.74; Sb 35.15
Diphenylstibine methacrylate was obtained by an analogous method, using, per 5.7 g (0.01 mole) of diphenylstibine oxide, 2.6 g (0.03 mole) of methacrylic acid. 5.5 g of colorless crystals were obtained after two recrystallizations from n-hexane, m.p. 113–115°.
Found, %: C 53.47; 53.14; H 4.81; 4.75; Sb 33.80; 33.57
$\mathrm{C_{16}H_{15}O_2}$. Calculated, %: C 53.18; H 4.15; Sb 33.79
* With the participation of S. V. Troitskii.
Diphenylstibine acrylate and methacrylate have an irritating effect on the upper respiratory tract, causing sneezing.
The monomers obtained polymerize readily in bulk and in solution (toluene) upon heating in the presence of azobisisobutyronitrile (as initiator).
The polymers obtained are insoluble in organic solvents and have a high softening temperature. They readily copolymerize with methyl methacrylate and styrene, forming hard, colorless thermoplastic masses.
Institute of Macromolecular Compounds
Academy of Sciences of the USSR
Received
20 I 1961
REFERENCES
- M. M. Koton, T. M. Kiseleva, F. S. Florinsky, Vysokomolek. soed., 2, 1639 (1960).
- D. A. Kochkin, DAN, 135, 857 (1960).
- J. Montermoso, T. Andrews, L. Marinelli, J. Polym. Sci., 32, 523 (1958).
- M. M. Koton, T. M. Kiseleva, V. A. Paribok, DAN, 125, 1263 (1959).
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