Abstract Generated abstract
This study examines the synthesis of polyesters containing conjugated triple bonds by joint oxidative dehydropolycondensation of propargyl and dipropargyl esters with p-diethynylbenzene. The authors selected aromatic, bisphenol, fluorinated bisphenol, benzoate, phenoxy, and quinizarin derivatives to test whether incorporation of p-diethynylbenzene into the chain could modify properties absent in earlier dipropargyl ester polymers. The reactions yielded mainly insoluble yellow to brown polymers, which were characterized by elemental analysis and infrared spectroscopy. The spectral and analytical data indicate formation of polymers in which conjugated acetylene units alternate with ether or ester-containing fragments, while bands associated with p-disubstituted phenyl nuclei vary with the amount of p-diethynylbenzene incorporated.
Full Text
A. M. SLADKOV, Corresponding Member of the USSR Academy of Sciences, V. V. KORSHAK, Yu. P. KUDRYAVTSEV,
A. G. MAKHSUMOV
SYNTHESIS OF POLYESTERS CONTAINING TRIPLE BONDS IN THE CHAIN
In the present work, investigations are continued \((^{1,2})\) on the synthesis and study of the properties of polyesters obtained by joint oxidative condensation of mono- and dipropargyl esters with \(p\)-diethynylbenzene.
As starting products we used dipropargyl esters of 4,4′-dioxydiphenyl, 4,4′-dioxydiphenyl-2-propane, hexafluoro-2,2-bis-(4-oxyphenyl)-propane, and propargyl esters of benzoic acid, phenol, and quinizarin. The choice of the above-mentioned esters is due to the fact that preliminary investigations of the polymers obtained on the basis of dipropargyl esters showed the absence of certain electrophysical properties (for example, photo-e.m.f.) characteristic of conjugated polyynes. We hoped, by introducing a molecule of \(p\)-diethynylbenzene into the polyester chain, to alter the electrophysical properties of the polyesters.
It had previously been shown \((^3)\) that introduction of terminal groups (using phenylacetylene and \(p\)-diethynylbenzene as examples) into the polyyne chain leads to the formation of a polymer of crystalline structure.
As a result of joint oxidative dehydropolycondensation of dipropargyl esters with \(p\)-diethynylbenzene, mainly insoluble products were obtained. The experimental data are summarized in Table 2.
Table 1
Data from the IR spectra of the copolymers
| Polymer based on | \(-\langle\!\!=\!\!\rangle-\) | \(\equiv \mathrm{CH}\) | \(-\mathrm{C}\equiv\mathrm{C}-\) | \(-\mathrm{C}-\mathrm{O}-\mathrm{C}-\) | \(\mathrm{C}=\mathrm{O}\) | \([\mathrm{CH}_3]_2\mathrm{C}<\) | \(-\mathrm{CH}_2-\) | \(\begin{matrix}\mathrm{CF}_3\\ \vert\\ -\mathrm{C}-\\ \vert\\ \mathrm{CF}_3\end{matrix}\) | |
|---|---|---|---|---|---|---|---|---|---|
| \(p\)-Diethynylbenzene | 830 960 1020 1100 |
1500 1800 1900 |
3300 1250 |
2200 | — | — | — | — | — |
| \(p\)-Diethynylbenzene and propargyl benzoate | 835 963 1020 1095 |
3300 | 2235 2315 |
1110 | 1725 | — | 1460 | — | |
| \(p\)-Diethynylbenzene and propargyl ether of quinizarin | 835 950 1020 |
3270 | 2105 2140 2210 |
1110 | — | — | 1440 | — | |
| \(p\)-Diethynylbenzene and dipropargyl ether of dioxydiphenyl | 835 977 1020 |
3280 | 2125 | 1110 | — | — | 1460 | — | |
| \(p\)-Diethynylbenzene and dipropargyl ether of dioxydiphenylpropane | 835 1020 1090 |
3290 | 2200 2235 2340 |
1110 | — | 1188 | 1450 | — | |
| \(p\)-Diethynylbenzene and dipropargyl ether of hexafluoropropane | 830 980 1020 |
3300 | 1130 | — | — | 1440 | 1310 1170 1130 |
For the synthesized polymers, IR spectra* were recorded. In all samples there remain absorption bands characteristic of the IR spectrum of the product of oxidative polydehydrocondensation of \(p\)-diethynylbenzene \((^4)\).
* The IR spectra were recorded in the optical laboratory of INEOS, Academy of Sciences of the USSR, by N. A. Chumaevskii, to whom the authors express their deep gratitude.
Table 2
| Starting substances | Quantity, g | Quantity, mol | Reaction duration, h | Polymer yield, g | Polymer color | Polymer structure | Calculated, % C | Calculated, % H | Found, % C | Found, % H | Other found value, % |
|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. \( \mathrm{HC{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: fused aromatic system]]\(\mathrm{{-}O{-}CH_2{-}C{\equiv}CH}\) DEB* |
0.4 0.6 |
0.043 0.048 |
3 | 7.5 | yellow | \(\mathrm{{-}C{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: aromatic fragment]]\(\mathrm{{-}O{-}CH_2{-}C{\equiv}C{-}C{\equiv}C{-}}\)[[structural formula: phenylene fragment]]\(\mathrm{{-}C{\equiv}C{-}}\) | 87.50 | 4.16 | 79.77 | 4.58 | 8.32 |
| 2. \(\mathrm{HC{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: \(p,p'\)-substituted diphenylisopropylidene fragment, \(\mathrm{C(CH_3)_2}\)]]\(\mathrm{{-}OCH{-}C{\equiv}CH}\) DEB |
1.0 1.0 |
0.38 0.08 |
4 | 1.2 | yellow | \(\left[\mathrm{{-}C{\equiv}C{-}CH_2{-}O{-}}\right.\)[[structural formula: \(p,p'\)-substituted diphenylisopropylidene fragment, \(\mathrm{C(CH_3)_2}\)]]\(\left.\mathrm{{-}O{-}CH_2{-}C{\equiv}C{-}}\right]_n\left[\mathrm{{-}C{\equiv}C{-}}\right.\)[[structural formula: phenylene fragment]]\(\left.\mathrm{{-}C{\equiv}C{-}}\right]_m\), where \(n=2,\ m=1\) | 85.71 | 5.49 | 85.30 | 4.51 | — |
| 3. \(\mathrm{HC{\equiv}C{-}CH_2{-}O{-}C(O){-}}\)[[structural formula: phenyl fragment]] DEB |
1.6 1.0 |
0.089 0.08 |
3 | 1.6 | light yellow | [[structural formula: phenyl ester fragment]]\(\mathrm{{-}C(O)O{-}CH_2{-}C{\equiv}C{-}}\left[\mathrm{{-}C{\equiv}C{-}}\right.\)[[structural formula: phenylene fragment]]\(\left.\mathrm{{-}C{\equiv}C{-}}\right]_n\mathrm{{-}C{\equiv}C{-}CH_2{-}O{-}C(O){-}}\)[[structural formula: phenyl fragment]], where \(n=2,\ldots\) | 84.80 | 3.88 | 85.06 | 3.86 | 7.60 |
| 4. \(\mathrm{HC{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: hydroxyanthraquinone fragment]] DEB |
1.2 0.2 |
0.095 0.007 |
6 | 0.6 | brown | [[structural formula: anthraquinone fragment with \(\mathrm{OH}\) and \(\mathrm{O{-}CH_2{-}C{\equiv}C{-}}\) substituents]]\(\left[\mathrm{{-}C{\equiv}C{-}}\right.\)[[structural formula: phenylene fragment]]\(\left.\mathrm{{-}C{\equiv}C{-}}\right]_n\mathrm{{-}C{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: hydroxyanthraquinone fragment]], where \(n=1\) | 77.87 | 3.25 | 75.11 | 4.30 | 2.83 |
| 5. \(\mathrm{HC{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: phenyl fragment]] DEB |
0.5 1.0 |
0.04 0.075 |
1 | 1.0 | yellow | [[structural formula: phenoxypropargyl fragment]]\(\left[\mathrm{{-}C{\equiv}C{-}}\right.\)[[structural formula: phenylene fragment]]\(\left.\mathrm{{-}C{\equiv}C{-}}\right]_n\mathrm{{-}C{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: phenyl fragment]], where \(n=1\) | 87.04 | 4.63 | 81.33 | 4.85 | 4.66 |
| 6. \(\mathrm{HC{\equiv}C{-}CH_2{-}O{-}}\)[[structural formula: \(p\)-substituted phenylene–\(\mathrm{C(CF_3)_2}\)–phenylene fragment]]\(\mathrm{{-}OCH_2{-}C{\equiv}CH}\) DEB |
0.8 0.5 |
0.02 0.02 |
2 | 0.8 | light yellow | \(\left[\mathrm{{-}C{\equiv}C{-}CH_2{-}O{-}}\right.\)[[structural formula: \(p\)-substituted phenylene–\(\mathrm{C(CF_3)_2}\)–phenylene fragment]]\(\left.\mathrm{{-}OCH_2{-}C{\equiv}C{-}}\right]_n\left[\mathrm{{-}C{\equiv}C{-}}\right.\)[[structural formula: phenylene fragment]]\(\left.\mathrm{{-}C{\equiv}C{-}}\right]_m\), where \(n=1,\ m=4\) ** | 80.77 F = 12.58 |
3.10 | 80.68 F = 9.74 |
3.57 |
* DEB — \(p\)-diethynylbenzene.
** Isolated 0.5 g of soluble polymer with melting point 160° and fluorine content 20.9%.
Fig. 1. IR spectrum of the copolymer of dipropargyl ether of 4,4′-dihydroxydiphenyl with p-diethynylbenzene
Fig. 2. IR spectrum of the copolymer of dipropargyl ether of 4,4′-dihydroxydiphenylol-2-propane with p-diethynylbenzene
Fig. 3. IR spectrum of the copolyester of propargyl ether of benzoic acid with p-diethynylbenzene
Fig. 4. IR spectrum of the copolymer of dipropargyl ether of hexafluoro-2,2-bis(4-hydroxyphenyl)propane with p-diethynylbenzene
Depending on the ratio of the p-diethynylbenzene taken into the reaction, the intensities of the absorption bands characteristic of p-disubstituted phenyl nuclei change correspondingly. The data from the IR spectra are summarized in Table 1. At the same time, absorption bands characteristic of ether bonds appear in the polymer. On the basis of the spectral data, as well as the data of elemental analysis, it may be asserted that, as a result of the joint oxidation of p-diethynylbenzene with the ethers listed, polymers have been obtained that contain in their chain conjugated triple bonds alternating with ether groups.
Institute of Organoelement Compounds
Academy of Sciences of the USSR
Received
29 X 1963
REFERENCES
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