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CHEMISTRY
A. N. PUDOVIK, E. I. KASHEVAROVA, and Yu. P. RUDNEV
PHOSPHORUS-CONTAINING ESTERS OF ACRYLIC AND METHACRYLIC ACIDS
(Presented by Academician B. A. Arbuzov, May 8, 1961)
In recent years, in addition to esters of acrylic and methacrylic acids containing hydrocarbon radicals, great interest has been shown in esters whose radical also contains various elements. The synthesis of a number of complex esters of acrylic and methacrylic acids and nitro alcohols has been carried out \((^{1,2})\); acrylates and methacrylates containing sulfur \((^3)\), fluorine \((^4)\), tin \((^{5-8})\), lead \((^9)\), silicon \((^{10-13})\), mercury \((^{14})\), and other elements are being widely studied. Polymers and copolymers obtained on their basis possess, in a number of cases, interesting properties: increased hardness and heat resistance, good adhesion to glass and metal, low permeability to X-rays, reduced flammability, and others.
In the present work we set ourselves the task of synthesizing esters of acrylic and methacrylic acids containing phosphorus in the ester radical, and of studying some of their properties. Reactions of acrylic and methacrylic acid chlorides with oxoalkylphosphine esters were carried out. The reactions were conducted in ethereal solution in the presence of triethylamine. Cuprous chloride was used as inhibitor:
\[
\mathrm{CH_2{=}CR{-}COCl + R'CHOHP(OR'')_2 \rightarrow CH_2{=}CR{-}COOCHR'{-}P(OR'')_2,}
\]
\[
\begin{array}{cc}
& \overset{\mathrm{O}}{\Vert} \qquad\qquad\qquad\qquad\qquad\qquad \overset{\mathrm{O}}{\Vert}
\end{array}
\]
where \(R = H\) or \(CH_3\); \(R' = H\) or \(CH_3\); \(R'' = CH_3, C_2H_5 \ldots\)
The reactions proceed smoothly; in most cases the esters were obtained in yields of 60–70%.
The characteristics of the acrylic acid esters obtained are given in Table 1, and those of the methacrylic acid esters in Table 2.
All esters are readily soluble in methyl and ethyl alcohols, ether, acetone, benzene, and carbon tetrachloride. Esters of acrylic and methacrylic acids containing methyl and ethyl radicals in the phosphono group are soluble in water.
On polymerization of α-(dimethylphosphono)ethyl methacrylate in the presence of 0.3 mole % benzoyl peroxide (9 hr at \(80^\circ\)), a hard, transparent polymer was formed, which swells considerably in water, alcohol, benzene, acetone, and carbon tetrachloride. The polymer burns with a smoky flame; when removed from the flame it is immediately extinguished.
Polymerization of α-(diethylphosphono)ethyl methacrylate was carried out at \(100^\circ\) for 30 hr with 0.5 mole % benzoyl peroxide in the reaction mixture. The polymer, a soft, transparent, plastic mass, dissolves readily in methyl and ethyl alcohols and in acetone. From benzene and acetone solutions it is precipitated by petroleum ether. Copolymerization of methyl methacrylate and α-(dimethylphosphono)ethyl methacrylate (ratio by weight percent 83:17, respectively) was carried out at \(75^\circ\) for 1.5 hr. The copolymer is a transparent, hard product, soluble in acetone and benzene.
After reprecipitation from an acetone solution with petroleum ether and drying in vacuum, the copolymer was obtained as a solid, white, opaque product. The phosphorus content in it was 2.2%. The copolymer burns with a sooty flame; when it is removed from the flame, combustion continues.
Experimental Part
Esters of α-hydroxyalkylphosphinic acids were prepared by the reaction of formaldehyde and acetaldehyde with dialkylphosphorous acids in the presence of sodium alcoholate (15). The acid chlorides of acrylic and methacrylic acids were prepared from the acids and phosphorus trichloride (16).
Reactions of the acid chlorides of acrylic and methacrylic acids with esters of α-hydroxyalkylphosphinic acids. Into a three-necked flask equipped with a stirrer and a reflux condenser were placed 0.13 mole of the dimethyl ester of α-hydroxyethylphosphinic acid, 0.13 mole of triethylamine, 100 ml of dry ether, and 0.75 g of cuprous chloride. With stirring, an ethereal solution of 0.13 mole of methacryloyl chloride was gradually added to the reaction mixture. The—
Table 1
| Values | Values | Yield, % | B.p., °C (pressure, mm) | $d_4^{20}$ | $n_D^{20}$ | $MR_D$ found | $MR_D$ calc. | Phosphorus content, % found | Phosphorus content, % calc. |
|---|---|---|---|---|---|---|---|---|---|
| $R$ | $R'$ | ||||||||
| Dialkylphosphonomethyl and dialkylphosphonoethyl esters of acrylic acid | |||||||||
| \multicolumn{10}{c}{$\mathrm{CH_2{=}CHCOOCHRP(=O)(OR')_2}$} | |||||||||
| H | $\mathrm{C_2H_5}$ | 67.2 | 114 (3) | 1.1451 | 1.4430 | 51.42 | 51.20 | 14.02 13.84 |
13.96 |
| $\mathrm{CH_3}$ | $\mathrm{CH_3}$ | 70 | 86–87 (1) | 1.1816 | 1.4458 | 46.96 | 46.58 | 15.10 14.80 |
14.88 |
| $\mathrm{CH_3}$ | $\mathrm{C_2H_5}$ | 55.1 | 129–130 (6) | 1.1102 | 1.4391 | 55.90 | 55.82 | 13.25 13.35 |
13.11 |
| $\mathrm{CH_3}$ | iso-$\mathrm{C_3H_7}$ | 65 | 102.5–103 (1) | 1.0526 | 1.4340 | 65.28 | 65.05 | 11.98 11.85 |
11.72 |
| $\mathrm{CH_3}$ | n-$\mathrm{C_3H_7}$ | 63.4 | 136–138 (5) | 1.0599 | 1.4409 | 65.75 | 65.05 | 11.61 11.59 |
11.72 |
| $\mathrm{CH_3}$ | n-$\mathrm{C_4H_9}$ | 65.3 | 140–141 (3) | 1.0423 | 1.4430 | 74.32 | 74.29 | 10.76 10.83 |
10.60 |
| Dialkylphosphonomethyl and dialkylphosphonoethyl esters of methacrylic acid | |||||||||
| \multicolumn{10}{c}{$\mathrm{CH_2{=}C(CH_3)COOCHRP(=O)(OR')_2}$} | |||||||||
| H | $\mathrm{C_2H_5}$ | 55 | 104.5–105 (2) | 1.1156 | 1.4416 | 56.32 | 55.82 | 13.12 13.24 |
13.14 |
| $\mathrm{CH_3}$ | $\mathrm{CH_3}$ | 64 | 104–105 (3) | 1.1551 | 1.4472 | 51.37 | 51.20 | 13.93 14.00 |
13.97 |
| $\mathrm{CH_3}$ | $\mathrm{C_2H_5}$ | 54.5 | 91–92 (0.6) | 1.0866 | 1.4405 | 60.69 | 60.43 | 12.06 12.22 |
12.38 |
| $\mathrm{CH_3}$ | iso-$\mathrm{C_3H_7}$ | 61.3 | 117 (2) | 1.0380 | 1.4367 | 70.18 | 69.67 | 11.11 11.01 |
11.15 |
| $\mathrm{CH_3}$ | n-$\mathrm{C_3H_7}$ | 60.8 | 121–123 (2) | 1.0479 | 1.4411 | 70.04 | 69.67 | 11.07 11.08 |
11.15 |
| $\mathrm{CH_3}$ | iso-$\mathrm{C_4H_9}$ | 60 | 119–120 (3) | 1.0159 | 1.4385 | 79.17 | 78.91 | 10.24 10.11 |
10.13 |
| $\mathrm{CH_3}$ | n-$\mathrm{C_4H_9}$ | 66.6 | 136–138 (3) | 1.0270 | 1.4440 | 79.12 | 78.91 | 10.25 9.99 |
10.13 |
The precipitated triethylamine hydrochloride was filtered off, the ether was distilled off under a slight vacuum, and, after hydroquinone had been added to it, the residue was distilled in vacuum with an oil pump. The constants and yields of the products obtained are given in the tables.
Thus, esters of acrylic and methacrylic acids containing phosphorus in the ester radical have been synthesized: dialkylphosphonomethyl and α-(dialkylphosphono)ethyl esters of acrylic and methacrylic acids. Their ability to form polymers and copolymers has been established.
Kazan State University
named after V. I. Ulyanov-Lenin
Received
5 May 1961
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