- Email: [email protected]
Reaction of polyvinylamine with benzaldehyde, salicylaldehyde and furfural
Reaction of polyvinylamine with benzaldehyde
2021
REFERENCES 1. S. R. RAFIKOV, Sb. Materialy seminara "Poliamidy" (Collection, Proceedings of the Seminar "Poliamides".) LDNTP, Leningrad, I, 14, 1963 2. T. L. CAIRNS, H. G. FOSTER, A. W. LARCHER, A. K. SCHNEIDER and R. S. SCHREIBER, J. Amer. Chem. Soe. 71: 651, 1949 3. K. N. VLASOVA and L. A. RODIVILOVA, Plast. massy 2: 19, 1960 4. S. M. RAIBURD, L. A. RODIVILOVA, K. N. VLASOVA, A. N. SHABADASH and L. A. IGONIN, Plast. massy 7: 20, 1960 5. H. GROHN, ttOANG HUI-BINH, Plaste u n d kautschuk 2: 3, 1961 6. S. KROZER, M. WEINREIB and L. SILINA, Vysokomol. soyed. 2: 1876, 1960 7. K. MEYER and K. SCHUSTER, Chem. ber. 55: 819, 1922 8. A. DORNOV and F. ISCHE, Chem. ber. 89: 870, 1956
REACTION OF POLYVINYLAMINE W I T H B E N Z A L D E H Y D E , SALICYLALDEHYDE AND F U R F U R A L * A. F. I~IKOLAYEV and V. M. B O N D A R E N K O Leningrad Technological I n s t i t u t e
(Received 8 December 1963)
THE polyvinylamines and their derivatives have still not been studied very much. The literature contains descriptions of a few salts and amides of polyvinylamines [1-5], copolymers of vinylalcohol with vinylamines [6] and ethylenes [7], products of the interaction of vinylamine copolymers with penicillin [8, 9] and formaldehyde [7], and of polyvinylamine with salicylic aldehyde [10]. Both theoretical and practical interest attaches to the high molecular compounds of poly-N-aryl (alkylidinevinylamine) (PAVA), which are polymeric Schiff bases. Some of them are able to undergo various different chemical conversions and form coordination polymers. Preparation of PAVA is based on reaction of aldehydes with polyvinylamines according to: O
z
E-c-rc--1
!
+
Rc( \
H
E--c-.--C---l. +
NH~
I
N
II
CH
I
R
The present work describes the polymers which were prepared by the interaction of polyvinylamines with benzoyl and salicylic aldehydes and with furfural. * Vysokomol. soyed. 6: No. 10, 1825-1828, 1964.
2022
A . F . NIKOLAYEV a n d V. M. BONDAREI~KO
Poly- N- benzylidenevinylamine (PBVA), poly- N- salicylidenevinylamine (PSVA) and poly-N-furfurylidinevinylamine (PFVA) are polymeric analogues of low-molecular Schiff bases. They are prepared by merging alcoholic solutions of equimoleeular amounts of polyvinylamines and the corresponding aldehydes. The experiments were performed at 65-70 ° for 1 hr, and at room temperature for 24 hr. After separation, purification and drying, the specimens were finely dispersed powders ranging from white to greenish yellow, insoluble in water but soluble in benzyl alcohol, dimethylformamide and glacial acetic acid. PBVA and PFVA were also soluble in ethyl alcohol and pyridene. Since it contains strong hydrogen intra- and intermoleeular bonds, PSVA dissolves in a small amount of the solvents. In solution in glacial acetic acid all three polymers show an anomalous tlsp./c dependence on c (Fig. 1), which is typical of polyelectrolytes and due to the Ah/h, 23
60
20
1.0 I
04
C,g/lO0ml FIG. 1.
0'8
f
40
120
200
Tempepatupe, °C FIG. 2.
F I e . 1. R e d u c e d viscosity as a f u n c t i o n of t h e c o n c e n t r a t i o n of p o l y m e r solutions in basal acetic acid: / - - p o l y - N - b e n z y l i d e n e v i n y l a m i n c ; 2 - - p o l y - N - f u r f u r y l i d e n e v i n y l a m i n e ; 3 -- poly-l~-salicylidenevinylamine. F I a . 2. T h e r m o - m e c h a n i c a l p e n e t r a t i o n c u r v e of p o l y m e r i c Schiff bases under const a n t load. 1, 2, 3 - - a s for Fig. 1.
presence in the polymeric units of an electron-accepter nitrogen atom capable of catching mobile hydrogen ions in proton-donor solutions, and charging the macromolecular chains. Figure 2 shows the thermomechanical curve of the penetration of the polymer specimens at a constant load of 0.57 g/ram ~, which were taken on dynamometer scales [11], and the Table gives the properties of the polymers. The specimens were prepared by compacting the powder at 180-200 ° at a pressure of 150 kg/cm ~. Comparing the curves in Fig. 2 we can see that they are similar to those for amorphous polymers.
l~eaction of polyvinylamine with benzaldehyde
2023
P S V A has a higher glass t e m p e r a t u r e (Tg) a n d flow p o i n t (Tf) 80 a n d 200 °, t h a n P B V A (60 a n d 180 °) for P F V A (70 a n d 190°). PROPERTIESOF POLYMERICSCHIFFBASES Properties
PBVA
Colour
White
[~] 25 ° in benzylalcohol, dl/g Density, g/cm a Yield point, °C Glass temperature, °C Vicar he~t resistance Vickcrs hardness, kg/mm ~ Dinstat unit impact toughness, kg. cm/cm 2 Ash content, %
1-02 1"09 180 60 162 18.0 2.0-2-5 0.20
PFVA
PSVA
Light -yellow Greeny-yiellow 1"22 1.09
190 70 164 19.0 2.2-2.5 0.23
1.45
1.11 20O 80 187 19"3 2.5-3.0 0-25
The high-elasticity r a n g e was p r a c t i c a l l y the same for all t h e polymers, covering 120 °. B u t in P F V A , a p p a r e n t l y due t o t h e a p p e r a n c e of t h e h y d r o g e n bonds, the horizontal section of t h e curve was shorter a n d t h e m a g n i t u d e of the d e f o r m a t i o n less. A t 140 ° for instance, in t h e high elasticity range t h e def o r m a t i o n was 13~oo for P S V A , 20 ~ for P F V A a n d 26~o for P B V A . The shape of t h e t h e r m o m e c h a n i c a l p e n e t r a t i o n curves a n d their position on the t e m p e r a t u r e scale, t o g e t h e r w i t h the slope of the c u r v e where t h e y change over f r o m the glasslike t o t h e high-elasticity state, suggest t h a t t h e rigidity of t h e molecular chains increases in t h e following order: P B V A - - P F V A - - P S V A . Like t h e low-molecular a z o m e t h a n e [12], t h e p r o d u c t p o l y m e r s are easily h y d r o l y z e d w i t h dilute mineral acids via t h e - - N = C H - b o n d b a c k to their original c o m p o n e n t s ( p o l y v i n y l a m i n e a n d aldehyde), a n d less easily w i t h dilute alkalis. F o r instance, w i t h 0.1 N HC1 h y d r o l y s i s t a k e s 90-120 rain at r o o m t e m perature, while with 0.1 N N a O H it t a k e s 16 h r at 75-80 °.
EXPERIMENTAL
Poly-N-benzylidenevinylamine (PBVA). Stirring all the time, 4.4 g benzaldehyde dissolved in 20 ml ethyl alcohol are added to 2 g polyvinylamine [4] dissolved in 100 ml ethyl alcohol. The reaction mixture is heated at 65-70 ° for 1 hr. cooled to room temperature and poured into excess ethyl ether. The polymer is precipitated as white flakes. After washing and reprecipitation from an alcoholic solution, the polymer is dried to constant weight at 50-60 ° (5 ram); yield 97-98%. Experimental, %: CgHgN Theoretical, %:
C 81.49; H 7-50; N 10.67 C 81.40; H 7.0; N 10-68
Poly-N-furfurylidenevinylamine (PFVA). Stirring constantly, 2 g furfural dissolved in 10 ml ethyl alcohol are added to 1 g polyvinylamine dissolved in 50 ml ethyl alcohol. The reaction mixture is brought up to 65-70 ° in the course of an hour, cooled to room temperature
2024
A . F . NXKOLAYEVand V. M. BONDARENKO
and poured into excess ethyl ether. The polymer is precipitated as flakes light yellow in colour. After washing and reprecipitation the polymer is dried to constant weight at 50-60 ° (5 ram); yield 98-99%. Experimental, %: C 68.0; H 5.4; N 11.10 CTHTNO Theoretical, %: C 69.4; H 5.8; N 11.57
Poly-N-sallcylldenevinylamine (PSVA). Stirring all the time, 1 g polyvinylamine dissolved in 50 ml ethyl alcohol is added to 3.2 g salicylic aldehyde dissolved in 100 ml ethyl ether. The product is precipitated as a bright yellow powder. After reprecipitation and washing the polymer is dried to constant weight at 50-60 ° (5 ram); yield 99%. Experimental, %: C~HoN0 Theoretical, %:
C 72.9; H 7.0; :N 9.44 C 73.4; H 6.7; N 9.52
CONCLUSIONS (l) Poly-N-benzylidenevinylamine, poly-N-furfurylidenevinylamine and polyN-salicylidenevinylamine have been synthesized and their properties studied. (2) T h e r e a c t i o n m e c h a n i s m o f p o l y v i n y l a m i n e w i t h a r o m a t i c a l d e h y d e s has been found to be similar to the mechanism of the formation of low-molecular Schiff bases (azomethenes). Translated by V. ALFORD
REFERENCES 1. 2. 3. 4.
5.
6. 7. 8. 9. 10. 11. 12.
D. D. REYNOLDS and W. O. KENYON, J. Amer. Chem. Soc. 69: 911, 1947 R. HART, J. Polymer Sci. 29: 629, 1958 M. L. W O L F R A M a n d A. CHANEY, J. Organ. Chem. 4: 1319, 1961 A. F. NIKOLAYEV and V. M. BONDARENKO, Sb. khim. svoistva i modifikatsiya polimerov. (Collection: Chemical Properties and Modification of Polymers.) Izd. Nauka, 146, 1964 A. F. NIKOLAYEV, N. V. DANIEL and T. B. DROZDOVA, Sb. Karbotsepn. vysokomol. soyed. (Collection: Carboehain Macromoleeular Compounds.) Izd. Akad. l~auk SSSR, 114, 1963 A. F. NIKOLAYEV, S. N. USHAKOV, L. P. VISHNEVETSKAYA and N. A. VORONOVA, Vysokomol. soyed. 5: 547, 1963 D. D. COFFMAN, H. H. HOEHN and Y. G. MAYNARD, J. Amer. Chem. Soc. 76, 6394, 1954 S. N. USHAKOV and Ye. F. PANARIN, :Dokl. Akad. N a u k SSSR 147: 1102, 1962 S. N. USHAKOV and Ye. F. PANARIN, Dokl. Akad. Nauk. SSSR 149: 334, 1963 G. DECOENE a n d P. H. TEYSSIE, J. P o l y m e r Sci. 57: 121, 1962 V. A. KARGIN and T. I. SOGOLOVA, Zh. fiz. khim. 23: 530, 1949 B. A. PORAI-KOSHITS, E. M. POZNANSKAYA, V. S. SHEVCHENKO and L. A. PAVLOVA, Zh. obshch, khim. 17: 1774, 1947
2021
REFERENCES 1. S. R. RAFIKOV, Sb. Materialy seminara "Poliamidy" (Collection, Proceedings of the Seminar "Poliamides".) LDNTP, Leningrad, I, 14, 1963 2. T. L. CAIRNS, H. G. FOSTER, A. W. LARCHER, A. K. SCHNEIDER and R. S. SCHREIBER, J. Amer. Chem. Soe. 71: 651, 1949 3. K. N. VLASOVA and L. A. RODIVILOVA, Plast. massy 2: 19, 1960 4. S. M. RAIBURD, L. A. RODIVILOVA, K. N. VLASOVA, A. N. SHABADASH and L. A. IGONIN, Plast. massy 7: 20, 1960 5. H. GROHN, ttOANG HUI-BINH, Plaste u n d kautschuk 2: 3, 1961 6. S. KROZER, M. WEINREIB and L. SILINA, Vysokomol. soyed. 2: 1876, 1960 7. K. MEYER and K. SCHUSTER, Chem. ber. 55: 819, 1922 8. A. DORNOV and F. ISCHE, Chem. ber. 89: 870, 1956
REACTION OF POLYVINYLAMINE W I T H B E N Z A L D E H Y D E , SALICYLALDEHYDE AND F U R F U R A L * A. F. I~IKOLAYEV and V. M. B O N D A R E N K O Leningrad Technological I n s t i t u t e
(Received 8 December 1963)
THE polyvinylamines and their derivatives have still not been studied very much. The literature contains descriptions of a few salts and amides of polyvinylamines [1-5], copolymers of vinylalcohol with vinylamines [6] and ethylenes [7], products of the interaction of vinylamine copolymers with penicillin [8, 9] and formaldehyde [7], and of polyvinylamine with salicylic aldehyde [10]. Both theoretical and practical interest attaches to the high molecular compounds of poly-N-aryl (alkylidinevinylamine) (PAVA), which are polymeric Schiff bases. Some of them are able to undergo various different chemical conversions and form coordination polymers. Preparation of PAVA is based on reaction of aldehydes with polyvinylamines according to: O
z
E-c-rc--1
!
+
Rc( \
H
E--c-.--C---l. +
NH~
I
N
II
CH
I
R
The present work describes the polymers which were prepared by the interaction of polyvinylamines with benzoyl and salicylic aldehydes and with furfural. * Vysokomol. soyed. 6: No. 10, 1825-1828, 1964.
2022
A . F . NIKOLAYEV a n d V. M. BONDAREI~KO
Poly- N- benzylidenevinylamine (PBVA), poly- N- salicylidenevinylamine (PSVA) and poly-N-furfurylidinevinylamine (PFVA) are polymeric analogues of low-molecular Schiff bases. They are prepared by merging alcoholic solutions of equimoleeular amounts of polyvinylamines and the corresponding aldehydes. The experiments were performed at 65-70 ° for 1 hr, and at room temperature for 24 hr. After separation, purification and drying, the specimens were finely dispersed powders ranging from white to greenish yellow, insoluble in water but soluble in benzyl alcohol, dimethylformamide and glacial acetic acid. PBVA and PFVA were also soluble in ethyl alcohol and pyridene. Since it contains strong hydrogen intra- and intermoleeular bonds, PSVA dissolves in a small amount of the solvents. In solution in glacial acetic acid all three polymers show an anomalous tlsp./c dependence on c (Fig. 1), which is typical of polyelectrolytes and due to the Ah/h, 23
60
20
1.0 I
04
C,g/lO0ml FIG. 1.
0'8
f
40
120
200
Tempepatupe, °C FIG. 2.
F I e . 1. R e d u c e d viscosity as a f u n c t i o n of t h e c o n c e n t r a t i o n of p o l y m e r solutions in basal acetic acid: / - - p o l y - N - b e n z y l i d e n e v i n y l a m i n c ; 2 - - p o l y - N - f u r f u r y l i d e n e v i n y l a m i n e ; 3 -- poly-l~-salicylidenevinylamine. F I a . 2. T h e r m o - m e c h a n i c a l p e n e t r a t i o n c u r v e of p o l y m e r i c Schiff bases under const a n t load. 1, 2, 3 - - a s for Fig. 1.
presence in the polymeric units of an electron-accepter nitrogen atom capable of catching mobile hydrogen ions in proton-donor solutions, and charging the macromolecular chains. Figure 2 shows the thermomechanical curve of the penetration of the polymer specimens at a constant load of 0.57 g/ram ~, which were taken on dynamometer scales [11], and the Table gives the properties of the polymers. The specimens were prepared by compacting the powder at 180-200 ° at a pressure of 150 kg/cm ~. Comparing the curves in Fig. 2 we can see that they are similar to those for amorphous polymers.
l~eaction of polyvinylamine with benzaldehyde
2023
P S V A has a higher glass t e m p e r a t u r e (Tg) a n d flow p o i n t (Tf) 80 a n d 200 °, t h a n P B V A (60 a n d 180 °) for P F V A (70 a n d 190°). PROPERTIESOF POLYMERICSCHIFFBASES Properties
PBVA
Colour
White
[~] 25 ° in benzylalcohol, dl/g Density, g/cm a Yield point, °C Glass temperature, °C Vicar he~t resistance Vickcrs hardness, kg/mm ~ Dinstat unit impact toughness, kg. cm/cm 2 Ash content, %
1-02 1"09 180 60 162 18.0 2.0-2-5 0.20
PFVA
PSVA
Light -yellow Greeny-yiellow 1"22 1.09
190 70 164 19.0 2.2-2.5 0.23
1.45
1.11 20O 80 187 19"3 2.5-3.0 0-25
The high-elasticity r a n g e was p r a c t i c a l l y the same for all t h e polymers, covering 120 °. B u t in P F V A , a p p a r e n t l y due t o t h e a p p e r a n c e of t h e h y d r o g e n bonds, the horizontal section of t h e curve was shorter a n d t h e m a g n i t u d e of the d e f o r m a t i o n less. A t 140 ° for instance, in t h e high elasticity range t h e def o r m a t i o n was 13~oo for P S V A , 20 ~ for P F V A a n d 26~o for P B V A . The shape of t h e t h e r m o m e c h a n i c a l p e n e t r a t i o n curves a n d their position on the t e m p e r a t u r e scale, t o g e t h e r w i t h the slope of the c u r v e where t h e y change over f r o m the glasslike t o t h e high-elasticity state, suggest t h a t t h e rigidity of t h e molecular chains increases in t h e following order: P B V A - - P F V A - - P S V A . Like t h e low-molecular a z o m e t h a n e [12], t h e p r o d u c t p o l y m e r s are easily h y d r o l y z e d w i t h dilute mineral acids via t h e - - N = C H - b o n d b a c k to their original c o m p o n e n t s ( p o l y v i n y l a m i n e a n d aldehyde), a n d less easily w i t h dilute alkalis. F o r instance, w i t h 0.1 N HC1 h y d r o l y s i s t a k e s 90-120 rain at r o o m t e m perature, while with 0.1 N N a O H it t a k e s 16 h r at 75-80 °.
EXPERIMENTAL
Poly-N-benzylidenevinylamine (PBVA). Stirring all the time, 4.4 g benzaldehyde dissolved in 20 ml ethyl alcohol are added to 2 g polyvinylamine [4] dissolved in 100 ml ethyl alcohol. The reaction mixture is heated at 65-70 ° for 1 hr. cooled to room temperature and poured into excess ethyl ether. The polymer is precipitated as white flakes. After washing and reprecipitation from an alcoholic solution, the polymer is dried to constant weight at 50-60 ° (5 ram); yield 97-98%. Experimental, %: CgHgN Theoretical, %:
C 81.49; H 7-50; N 10.67 C 81.40; H 7.0; N 10-68
Poly-N-furfurylidenevinylamine (PFVA). Stirring constantly, 2 g furfural dissolved in 10 ml ethyl alcohol are added to 1 g polyvinylamine dissolved in 50 ml ethyl alcohol. The reaction mixture is brought up to 65-70 ° in the course of an hour, cooled to room temperature
2024
A . F . NXKOLAYEVand V. M. BONDARENKO
and poured into excess ethyl ether. The polymer is precipitated as flakes light yellow in colour. After washing and reprecipitation the polymer is dried to constant weight at 50-60 ° (5 ram); yield 98-99%. Experimental, %: C 68.0; H 5.4; N 11.10 CTHTNO Theoretical, %: C 69.4; H 5.8; N 11.57
Poly-N-sallcylldenevinylamine (PSVA). Stirring all the time, 1 g polyvinylamine dissolved in 50 ml ethyl alcohol is added to 3.2 g salicylic aldehyde dissolved in 100 ml ethyl ether. The product is precipitated as a bright yellow powder. After reprecipitation and washing the polymer is dried to constant weight at 50-60 ° (5 ram); yield 99%. Experimental, %: C~HoN0 Theoretical, %:
C 72.9; H 7.0; :N 9.44 C 73.4; H 6.7; N 9.52
CONCLUSIONS (l) Poly-N-benzylidenevinylamine, poly-N-furfurylidenevinylamine and polyN-salicylidenevinylamine have been synthesized and their properties studied. (2) T h e r e a c t i o n m e c h a n i s m o f p o l y v i n y l a m i n e w i t h a r o m a t i c a l d e h y d e s has been found to be similar to the mechanism of the formation of low-molecular Schiff bases (azomethenes). Translated by V. ALFORD
REFERENCES 1. 2. 3. 4.
5.
6. 7. 8. 9. 10. 11. 12.
D. D. REYNOLDS and W. O. KENYON, J. Amer. Chem. Soc. 69: 911, 1947 R. HART, J. Polymer Sci. 29: 629, 1958 M. L. W O L F R A M a n d A. CHANEY, J. Organ. Chem. 4: 1319, 1961 A. F. NIKOLAYEV and V. M. BONDARENKO, Sb. khim. svoistva i modifikatsiya polimerov. (Collection: Chemical Properties and Modification of Polymers.) Izd. Nauka, 146, 1964 A. F. NIKOLAYEV, N. V. DANIEL and T. B. DROZDOVA, Sb. Karbotsepn. vysokomol. soyed. (Collection: Carboehain Macromoleeular Compounds.) Izd. Akad. l~auk SSSR, 114, 1963 A. F. NIKOLAYEV, S. N. USHAKOV, L. P. VISHNEVETSKAYA and N. A. VORONOVA, Vysokomol. soyed. 5: 547, 1963 D. D. COFFMAN, H. H. HOEHN and Y. G. MAYNARD, J. Amer. Chem. Soc. 76, 6394, 1954 S. N. USHAKOV and Ye. F. PANARIN, :Dokl. Akad. N a u k SSSR 147: 1102, 1962 S. N. USHAKOV and Ye. F. PANARIN, Dokl. Akad. Nauk. SSSR 149: 334, 1963 G. DECOENE a n d P. H. TEYSSIE, J. P o l y m e r Sci. 57: 121, 1962 V. A. KARGIN and T. I. SOGOLOVA, Zh. fiz. khim. 23: 530, 1949 B. A. PORAI-KOSHITS, E. M. POZNANSKAYA, V. S. SHEVCHENKO and L. A. PAVLOVA, Zh. obshch, khim. 17: 1774, 1947