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Synthesis of polymer crown ethers by cyclopolymerization of divinyl ethers of mono-, tri- and tetraethylene glycols
IP6IyIMer~¢imtm U.$.t.R. Vol. 25, No. I I , pp. 2576--2580, 1986 Printed in Poland
--
0032-$950186 $10.00+ .00 © 1987 Pergamon Journaht Ltd.
SYNTHESIS OF POLYMER CROWN ETHERS BY CYCLOPOLYMERIZATION OF DIVIN'YL ETHERS OF MONO-, TRI- AND TETRAETHYLENE GLYCOLS* V. V. STEPANOV,A. R. SIXPANOVA,S. S. SKOROKHODOV,V. [. LAVROVand B. A. TROFIMOV Institute of High Molecular Weight Compounds, U.S.S.R. Academy of Sciences Irkutsk Institute of Organic Chemistry, Siberian Divisior~, U.S.S.R. Academy of Sciences _
(Received
26 M a r c h 1985)
• It-hasbeen shown that cationic cyclopolymerization with formation of soluble polymers with the degree of cyclization above 95 ~o may be undertaken for divinyl ethers of mono-, tri- and tetraethylene glycol using BFa'O(CH=), as initiator. Favourable conditions for cyclopolymerization were created by lowering the initial concentration of the monomers to 0~1too!e/1, and below: The polymer analogues of the crown ethers obtained and containing in the main chain macrocycles of the crown-2, crown-4 and crown-5 types are soluble in the vast majority of organic solvents and in water. Tm~ gwi~r development of the chemistry of macrocyclic ligands for the ions o f metals Such as crownethers, Cryptands, etc. [1] has found due ref[exion in polymer chemistry. Quite a considerable amount of work has been published on the synthesi s of complexforming polymers, sorbents and macromolecular catalysts of phase transfer reactions [2]. Such polymers are synthesized either by polymerization or polycondensation of monomers containing a cylic complex-forming group or by reactions in polymer chains. Cyclopolymerization is a direct method for introducing cyclic structures into a polymer chain. The analysis made by Butler of the mechanism of cyclopolymerization leads to the conclusion that for the synthesis of polymers with cycles of large size cationic cyclopolymerization is preferable [3]. This predetermined our choice of test objects in favour of divinyl) ethers of polyethylene glycols. These monomers are readily accessible and their synthesis has been well researched [4] although polymerization of divinyl ethers has been insufficiently studied and still cannot serve as the basis for regulated effective polymer synthesis. Eailier the formation of cyclopolymers was observed on polymerization of divinyl ethers of ethylene- and diethylene-glycols initiated by iodine [5, 6]. The cyclopolymers obtained were of low molecular weight and coloured containing labile iodine as terminal group. The use of boron tritluoride etherats as initiator led the authors of the work quoted to synthesis of crosslinked polymers. The use of this intitiator in other studies either gave the same result or, in certain conditions, led to the synthesis of linear cyclopolymers [7]. Analysis of these findings and the direct experimental check made by us * Vysokomol. soyed. A28: No. II, 2318-2321, 1986.
2576
Synthesis of polymer crown ethers
257,7
showed that in the experimental conditions described only network p o l y m e r s with an undefined degree o f erosslinking be obtained. Their structure was not convincingly demonstrated. Y o k o t a et al. carried out cationic polymerization of diepoxides with formation o f polymers containing the benzo-16-crown-5 group [8]. The polymers either had very low intrinsic viscosity or higher (with use o f the van den Berg catalysts) but then lost solubility in the usual solvents. Earlier it was shown that cationic cyclopolymerization of the divinyl ether of diethylene glycol with synthesis o f soluble polymers o f high molecular mass and high degree o f cyelization (above 95 %) may be successfully carried out [9]. The cyclopolymers obtained represent the polymer analogues of crown-3. From the known data on the complexing capacity o f low molecular weight crown ether it follows that stronger and more selective complexing is observed in the case o f cycles o f large size [I0]. For this purpose in the present work the :range of objects was widened and the cyclopolymers (P-l, P-3 and P-4) based on the divinyl ethers of the mono-, tri- and tetraethylene glycols synthesized by the cationic mechanism.
/ ...
r
/
/ L
"(,
]I--CH.--CH
,,o
CHg.=CII--(O--CIt~--ClI2)r~--O--Ctt-:CHz -'~ CH2
\
\
tit--l--
'/
- -
\ \
w h e r e n = = t , 3, 4. The d!vinyl ethers of the diols were obtained by direct vinylation of the corresponding diols at raised or atmospheric pressure [4]. Before use in cationic polymerization the monomers were further purified by successive distillation over metallic sodium and LiAIH, and again over sodium (5 % of the weight of the monomer each) into a Schlenk vessel. Divinyl ether of ethylene glycol: BP 126°C, n~° 1"4350;divinyl ether of diethylene glycol: BP 85-87°C (14 mm Hg), n~° 1"4430;divinyl ether of triethylene glycol: BP 85-87°C (1 mm Hg), n~° 1"4533; divinyl ether of tetraethylene glycol; BP 121-122°C (2 nun Hg), n~° 1.4585. Toluene was purified by the standard technique and distilled three times over metallic sodium. BF3. O(CH3)2 was used freshly distilled in an argon current. Polymerization was carried out with use of the syringe technique in an atmosphere of dry argon. The process was stopped with methanol, the polymers precipitated with petroleum ether and stabilized by adding before precipitation phenyl-/~-naphthylamine (0.5 wt. % inrelation to 100% polYmer yield). The IR spectra were recorded with the UR-20 spectrometer and the PMR spectra with the JNM-3 spectrometer (60 MHz) in a solution in dimethylformamide-dT. The intrinsic viscosity of the polymers was measured in solution in chloroform at 20°C. Favourable conditions for cyclopolymerization were created by lowering the initial concentration o f monomers and temperature. Using boron trifluoride etherate as initiator we obtained samples with fairly high values o f the characteristic viscosity. The
Synthesis of polymer crown ethers TABLE 1.
2579
CONDITIONS AND RESULTS OF EXPERIMENTS ON POLYMERIZATION OF DIVINYLETHERS
(Solvent: toluene; initiator BFa.O (CH3)2, [C]K-----10-3 m o l e / l , 15 ° C) Monomer (n)
[M], mole/l, 0"05 0"I0 0"05 O~ 12 0"05 0"I0 0"05 0"I0
1 1
2* 2* 3 3 4 4
Time of polymerization, hr
Yield, ~
1
28 34 90 95 55 77 47 49
I
2 20 1 1
1"5 3
Iv/], dl/g 0"19 0"18 0'56 0"53 0"75 1"50 0"48 0"37
* Data of reference [9].
TABLE 2. Solvent Acetone Methanol Water Diethyl ether Dimethylformamide Acetonitrile Tetrahydrofurane Ethanol Ethyl acetate Carbon tetrachloride Chloroform Toluene
SOLUBILITY OF CYCLOPOLYMERS
Solubility of polymer P-1
P-3
-
+
-
+
+(58 °)
+(64 °)
+ -
+
+ + + + + +
+ + + + + +
P-4
+ + + (68 °) + + + + + + + +
Note: " + "-soluble; " - " - i n s o l u b l e . In parentheses temperature at which the polymer falls out of solution.
phenyl-flrnaphthylamine was added to the polymer solution as stabilizer. The stabilized samples remained soluble and held unchanged the value of the intrinsic viscosity for a long time. Thus, in the present work on the basis of readily accessible divinyl ethers of the polyethylene glycols a method is proposed for synthesizing cyclopolymers with a high degree of cyclization containing in their structure crown ether cycles of different sizes. From the known published findings [2, 19, 20] such polymers may be proposed for use as complexants for metal ions and organic compounds and as macromolecular catalysts. Translated by A. CROZY REFERENCES 1. J. M. LEHN, Pure Appl. Chem. 50: 871, 1978 2. E. BLASIUS and K. P. J A N Z E N , Ibid. 54: 2115, 1982 3. G. B. BUTLER, J. Polymer Sci. Polymer Syrup. 64: 71, 1978
2580
T , GANctrev~ et al. "
4. M. F. SHOSTAKOVSKII, A. S. ATAVIN and B. A. TROFIMOV, Zh. 0bshch. khim. 34" 2112, 1964 5. T. NISHIKUBA, T. TIZAWA, A. ZOSHINAGA and M. NITTA, Makromolek. Chem. 183: 789, 1982 6. S . L . N . SUENG and R. N, YOUNG, Polymer Lett. 16: 367, 1978 7. L. J. MATHIASS, J. B. CANTERBERRY and M. SOUTH, Ibid 20: 473, 1982 8, K. YOKOTA, H. HASHIMOTO, T. KAKUCHI and Y. TAKADA, Macromolek. Chem. Rapid Commun. 5: I15, 1984 9. V. V. STEPANOV, A. R. BARANTSEVA, S. S. SKOROKHODOV, V. I. LAVROV and B. A. TROFIMOV, Vysokomol. soyed. B26: 741, 1984 (Not translated in Polymer Sci. U.S.S.R.) 10. Yu. A. OVCHINNIKOV, V. T. IVANOV and A. M. SHKROB, Membranoaktivnye kompleksony (Membrane Active Complexones). p. 64, Nauka, Moscow, 1974 11. K. YOKOTA, T. KAKUCHI, T. JIYAMA and Y. TAKADA, Polymer J. 16: 145, 1984 12. M.L. ILLUMINATI and B. MASCI, J. Amer. Chem. Soc. 103: 4142, 1981 13. B. A. TROFIMOV, Geteroatomnye proizvodnye atsetilena (Heteroatomic Acetylene Derivatives), p. 31, Nauka, Moscow, 1981 14. G. B. BUTLER, Accounts Chem. Res. 15: 370, 1982 15. Ye. V. ANUFRIYEVA, M. V. VOL'KENSHTEIN, Yu. Ya. GOTLIB, M. G. KRAKOVYAK, V. D. PAUTOV and V. V. STEPANOV, Dokl. Akad. Nauk SSSR 207: 1379, 1972 16. V.I. KLENIN, L. G. LEBEDEVA, S. S. SKOROKHODOV, V. V. STEPANOV, S. M. KLENIN and S. Ya, FRENKEL', Vysokomoi. soyed..4,21: 520, 1979 (Translated in Polymer Sci. U.S.S.R. A21: 3, 569, 1979) 17. S. S. SKOROCHODOV, J. Polymer Sci. Polymer Syrup. 42: 1583, 1973 18. T. MAEDA, B. OUCHI, K. KIMURA and T. SHONO, Chem. Lett. 11, 1573, 1981 19. G. MANECKE, A. KRAMER, H. -J. WINTER and P. R E ~ ! Nouveau •J. Chim. 6: 623, 1982 20. Host-Guest Complex Chemistry I (Edited by F. Boschke). p. 163, Berlin, 1982
Polymer S~ienc4e U.S.S.R. Vol. 28, No. II, pp. 2580-2586, 1986 Printed in Poland
0032-3950/86 $10.00+ .00 O 1987PergamonJournals Ltd.
•DYNAMIC MECHANICAL PROPERTIES O F POLYVINYL CHLORIDE CONTAINING STRUCTURE-REGULATING ADDITIVES* T. GANCH~VA, A. MARINOVA a n d M. M ^ T ~ v Lenin VIEM, Sofia, Bulgaria (Received 26 March 1985)
The influence of small additions of a number of low molecular weight substances on the mechanical properties of PVC is described. I t i s shown that in some cases the main change in the modulus of elasticity and mechanical losses is observed for a content of additives not exceeding 1 ~o. The mechanism of the phenomenon described is discussed. ~ * Vysokomol. soyed. A28: No. 11,232-2322, 1986.
--
0032-$950186 $10.00+ .00 © 1987 Pergamon Journaht Ltd.
SYNTHESIS OF POLYMER CROWN ETHERS BY CYCLOPOLYMERIZATION OF DIVIN'YL ETHERS OF MONO-, TRI- AND TETRAETHYLENE GLYCOLS* V. V. STEPANOV,A. R. SIXPANOVA,S. S. SKOROKHODOV,V. [. LAVROVand B. A. TROFIMOV Institute of High Molecular Weight Compounds, U.S.S.R. Academy of Sciences Irkutsk Institute of Organic Chemistry, Siberian Divisior~, U.S.S.R. Academy of Sciences _
(Received
26 M a r c h 1985)
• It-hasbeen shown that cationic cyclopolymerization with formation of soluble polymers with the degree of cyclization above 95 ~o may be undertaken for divinyl ethers of mono-, tri- and tetraethylene glycol using BFa'O(CH=), as initiator. Favourable conditions for cyclopolymerization were created by lowering the initial concentration of the monomers to 0~1too!e/1, and below: The polymer analogues of the crown ethers obtained and containing in the main chain macrocycles of the crown-2, crown-4 and crown-5 types are soluble in the vast majority of organic solvents and in water. Tm~ gwi~r development of the chemistry of macrocyclic ligands for the ions o f metals Such as crownethers, Cryptands, etc. [1] has found due ref[exion in polymer chemistry. Quite a considerable amount of work has been published on the synthesi s of complexforming polymers, sorbents and macromolecular catalysts of phase transfer reactions [2]. Such polymers are synthesized either by polymerization or polycondensation of monomers containing a cylic complex-forming group or by reactions in polymer chains. Cyclopolymerization is a direct method for introducing cyclic structures into a polymer chain. The analysis made by Butler of the mechanism of cyclopolymerization leads to the conclusion that for the synthesis of polymers with cycles of large size cationic cyclopolymerization is preferable [3]. This predetermined our choice of test objects in favour of divinyl) ethers of polyethylene glycols. These monomers are readily accessible and their synthesis has been well researched [4] although polymerization of divinyl ethers has been insufficiently studied and still cannot serve as the basis for regulated effective polymer synthesis. Eailier the formation of cyclopolymers was observed on polymerization of divinyl ethers of ethylene- and diethylene-glycols initiated by iodine [5, 6]. The cyclopolymers obtained were of low molecular weight and coloured containing labile iodine as terminal group. The use of boron tritluoride etherats as initiator led the authors of the work quoted to synthesis of crosslinked polymers. The use of this intitiator in other studies either gave the same result or, in certain conditions, led to the synthesis of linear cyclopolymers [7]. Analysis of these findings and the direct experimental check made by us * Vysokomol. soyed. A28: No. II, 2318-2321, 1986.
2576
Synthesis of polymer crown ethers
257,7
showed that in the experimental conditions described only network p o l y m e r s with an undefined degree o f erosslinking be obtained. Their structure was not convincingly demonstrated. Y o k o t a et al. carried out cationic polymerization of diepoxides with formation o f polymers containing the benzo-16-crown-5 group [8]. The polymers either had very low intrinsic viscosity or higher (with use o f the van den Berg catalysts) but then lost solubility in the usual solvents. Earlier it was shown that cationic cyclopolymerization of the divinyl ether of diethylene glycol with synthesis o f soluble polymers o f high molecular mass and high degree o f cyelization (above 95 %) may be successfully carried out [9]. The cyclopolymers obtained represent the polymer analogues of crown-3. From the known data on the complexing capacity o f low molecular weight crown ether it follows that stronger and more selective complexing is observed in the case o f cycles o f large size [I0]. For this purpose in the present work the :range of objects was widened and the cyclopolymers (P-l, P-3 and P-4) based on the divinyl ethers of the mono-, tri- and tetraethylene glycols synthesized by the cationic mechanism.
/ ...
r
/
/ L
"(,
]I--CH.--CH
,,o
CHg.=CII--(O--CIt~--ClI2)r~--O--Ctt-:CHz -'~ CH2
\
\
tit--l--
'/
- -
\ \
w h e r e n = = t , 3, 4. The d!vinyl ethers of the diols were obtained by direct vinylation of the corresponding diols at raised or atmospheric pressure [4]. Before use in cationic polymerization the monomers were further purified by successive distillation over metallic sodium and LiAIH, and again over sodium (5 % of the weight of the monomer each) into a Schlenk vessel. Divinyl ether of ethylene glycol: BP 126°C, n~° 1"4350;divinyl ether of diethylene glycol: BP 85-87°C (14 mm Hg), n~° 1"4430;divinyl ether of triethylene glycol: BP 85-87°C (1 mm Hg), n~° 1"4533; divinyl ether of tetraethylene glycol; BP 121-122°C (2 nun Hg), n~° 1.4585. Toluene was purified by the standard technique and distilled three times over metallic sodium. BF3. O(CH3)2 was used freshly distilled in an argon current. Polymerization was carried out with use of the syringe technique in an atmosphere of dry argon. The process was stopped with methanol, the polymers precipitated with petroleum ether and stabilized by adding before precipitation phenyl-/~-naphthylamine (0.5 wt. % inrelation to 100% polYmer yield). The IR spectra were recorded with the UR-20 spectrometer and the PMR spectra with the JNM-3 spectrometer (60 MHz) in a solution in dimethylformamide-dT. The intrinsic viscosity of the polymers was measured in solution in chloroform at 20°C. Favourable conditions for cyclopolymerization were created by lowering the initial concentration o f monomers and temperature. Using boron trifluoride etherate as initiator we obtained samples with fairly high values o f the characteristic viscosity. The
Synthesis of polymer crown ethers TABLE 1.
2579
CONDITIONS AND RESULTS OF EXPERIMENTS ON POLYMERIZATION OF DIVINYLETHERS
(Solvent: toluene; initiator BFa.O (CH3)2, [C]K-----10-3 m o l e / l , 15 ° C) Monomer (n)
[M], mole/l, 0"05 0"I0 0"05 O~ 12 0"05 0"I0 0"05 0"I0
1 1
2* 2* 3 3 4 4
Time of polymerization, hr
Yield, ~
1
28 34 90 95 55 77 47 49
I
2 20 1 1
1"5 3
Iv/], dl/g 0"19 0"18 0'56 0"53 0"75 1"50 0"48 0"37
* Data of reference [9].
TABLE 2. Solvent Acetone Methanol Water Diethyl ether Dimethylformamide Acetonitrile Tetrahydrofurane Ethanol Ethyl acetate Carbon tetrachloride Chloroform Toluene
SOLUBILITY OF CYCLOPOLYMERS
Solubility of polymer P-1
P-3
-
+
-
+
+(58 °)
+(64 °)
+ -
+
+ + + + + +
+ + + + + +
P-4
+ + + (68 °) + + + + + + + +
Note: " + "-soluble; " - " - i n s o l u b l e . In parentheses temperature at which the polymer falls out of solution.
phenyl-flrnaphthylamine was added to the polymer solution as stabilizer. The stabilized samples remained soluble and held unchanged the value of the intrinsic viscosity for a long time. Thus, in the present work on the basis of readily accessible divinyl ethers of the polyethylene glycols a method is proposed for synthesizing cyclopolymers with a high degree of cyclization containing in their structure crown ether cycles of different sizes. From the known published findings [2, 19, 20] such polymers may be proposed for use as complexants for metal ions and organic compounds and as macromolecular catalysts. Translated by A. CROZY REFERENCES 1. J. M. LEHN, Pure Appl. Chem. 50: 871, 1978 2. E. BLASIUS and K. P. J A N Z E N , Ibid. 54: 2115, 1982 3. G. B. BUTLER, J. Polymer Sci. Polymer Syrup. 64: 71, 1978
2580
T , GANctrev~ et al. "
4. M. F. SHOSTAKOVSKII, A. S. ATAVIN and B. A. TROFIMOV, Zh. 0bshch. khim. 34" 2112, 1964 5. T. NISHIKUBA, T. TIZAWA, A. ZOSHINAGA and M. NITTA, Makromolek. Chem. 183: 789, 1982 6. S . L . N . SUENG and R. N, YOUNG, Polymer Lett. 16: 367, 1978 7. L. J. MATHIASS, J. B. CANTERBERRY and M. SOUTH, Ibid 20: 473, 1982 8, K. YOKOTA, H. HASHIMOTO, T. KAKUCHI and Y. TAKADA, Macromolek. Chem. Rapid Commun. 5: I15, 1984 9. V. V. STEPANOV, A. R. BARANTSEVA, S. S. SKOROKHODOV, V. I. LAVROV and B. A. TROFIMOV, Vysokomol. soyed. B26: 741, 1984 (Not translated in Polymer Sci. U.S.S.R.) 10. Yu. A. OVCHINNIKOV, V. T. IVANOV and A. M. SHKROB, Membranoaktivnye kompleksony (Membrane Active Complexones). p. 64, Nauka, Moscow, 1974 11. K. YOKOTA, T. KAKUCHI, T. JIYAMA and Y. TAKADA, Polymer J. 16: 145, 1984 12. M.L. ILLUMINATI and B. MASCI, J. Amer. Chem. Soc. 103: 4142, 1981 13. B. A. TROFIMOV, Geteroatomnye proizvodnye atsetilena (Heteroatomic Acetylene Derivatives), p. 31, Nauka, Moscow, 1981 14. G. B. BUTLER, Accounts Chem. Res. 15: 370, 1982 15. Ye. V. ANUFRIYEVA, M. V. VOL'KENSHTEIN, Yu. Ya. GOTLIB, M. G. KRAKOVYAK, V. D. PAUTOV and V. V. STEPANOV, Dokl. Akad. Nauk SSSR 207: 1379, 1972 16. V.I. KLENIN, L. G. LEBEDEVA, S. S. SKOROKHODOV, V. V. STEPANOV, S. M. KLENIN and S. Ya, FRENKEL', Vysokomoi. soyed..4,21: 520, 1979 (Translated in Polymer Sci. U.S.S.R. A21: 3, 569, 1979) 17. S. S. SKOROCHODOV, J. Polymer Sci. Polymer Syrup. 42: 1583, 1973 18. T. MAEDA, B. OUCHI, K. KIMURA and T. SHONO, Chem. Lett. 11, 1573, 1981 19. G. MANECKE, A. KRAMER, H. -J. WINTER and P. R E ~ ! Nouveau •J. Chim. 6: 623, 1982 20. Host-Guest Complex Chemistry I (Edited by F. Boschke). p. 163, Berlin, 1982
Polymer S~ienc4e U.S.S.R. Vol. 28, No. II, pp. 2580-2586, 1986 Printed in Poland
0032-3950/86 $10.00+ .00 O 1987PergamonJournals Ltd.
•DYNAMIC MECHANICAL PROPERTIES O F POLYVINYL CHLORIDE CONTAINING STRUCTURE-REGULATING ADDITIVES* T. GANCH~VA, A. MARINOVA a n d M. M ^ T ~ v Lenin VIEM, Sofia, Bulgaria (Received 26 March 1985)
The influence of small additions of a number of low molecular weight substances on the mechanical properties of PVC is described. I t i s shown that in some cases the main change in the modulus of elasticity and mechanical losses is observed for a content of additives not exceeding 1 ~o. The mechanism of the phenomenon described is discussed. ~ * Vysokomol. soyed. A28: No. 11,232-2322, 1986.