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A spectrographic study of the products of polycondensation of diethylol terephthalate with various reactants
Products of polycondensation of diethylol terephthalate
1849
10. N. V. MIKHAILOV, D. N. SHIGORIN and S. P. MAKAR'EVA, Dokl. Akad. Nauk SSSt~ 87: 1009, 1952 11. O. Ya. FEDOTOVA and M. I. SHTIL'MAN, Vysokomol. soyed. 7: 312, 1965 (Translated in Polymer Sci. U.S.S.R. 7: 2, 290, 1965) 12. D. N. SHIGORIN, N. V. MIKHAILOV and S. P. MAKAR'EVA, Dokl. Akad. :Nauk SSSR 97: 711, 1954 13. T. TOKATA, Kobunshi kagaku 19: 653, 1962 14. T. TOKATA, J. HIROI and M. TANIJAMA, J. Polymer Sci. A2: 1573, 1964
A SPECTROGRAPHIC STUDY OF THE PRODUCTS OF POLYCONDENSATION OF DIETHYLOL TEREPHTHALATE WITH VARIOUS REACTANTS* 1). IV[. BUGAI, V. 1~. KOI~EL'SKAYA a n d N. M. TIMOSHEVSKAYA V. I. Lenin Polytechnical Institute, Khar'kov (Received 26 July 1965)
TH~ kinetics of p o l y c o n d e n s a t i o n of diethylol t e r e p h t h a l a t e h a v e been studied b y K o r s h a k and his collaborators [1, 2]. I n order to p r o d u c e polyesters of the L a v s a n t y p e with new c o m p o n e n t s we h a v e studied the p o l y c o n d e n s a t i o n of diethylol t e r e p h t h a l a t e ( D E T P ) in c o n j u n c t i o n with various r e a c t a n t s (hydroquinone, resorcinal a n d 4,4'-dihydrox y d i p h e n y l a m i n e ( D H P A ) ) , a d d e d at the synthesis stage. F o r investigation of the process we r e c o r d e d a b s o r p t i o n spectra of t h e initial a n d i n t e r m e d i a t e p o l y c o n d e n s a t i o n products. F o r d e t e r m i n a t i o n of specific viscosity and for spectrographic analysis we w i t h d r e w test samples e v e r y 2-2.5 hr during b o t h the transesterification a n d p o l y c o n d e n s a t i o n stages (3-4 samples in all). T h e transesterification process lasted up to 10 hr and p o l y c o n d e n s a t i o n in vacuo up to 2.5 hr. T h e specific viscosity of each test sample of resin was d e t e r m i n e d b y the conventional, p u b l i s h e d m e t h o d a n d the molecular weight of the p o l y m e r was calculated from this b y means of P e t u k h o v ' s formula [7]: M--
~/--0.01 1.37 x 10 -5 "
T h e ultraviolet, infrared a n d X - r a y spectra of D E T P and p o l y e t h y l e n e t e r e p h t h a l a t e ( P E T P ) h a v e been studied b y a n u m b e r of authors [3-6], b u t there * Vysokomol. soycd. 8: :No. 10, 1677-1680, 1966.
P.M. B u o ~ et al.
1850
are no spectroscopic data in the literature on the intermediate products of polycondensation of D E T P or the products obtained b y condensation of this with other reactants. It was for this reason that we undertook the present work. The spectra were measured in an SF-4 spectrophotometer in the 200-350 m/~ region, in concentrated sulphuric acid, which is a solvent for the polymer. Characteristic of the bands (2 and log e)" of D E T P and its polyeondensations products, i.e. of polymers of increasing molecular weight, are given in Table 1. TABLE
Curve No.
Compound
1. A B S O R P T I O N
S P E C T R A OF D E T P
Solution concentration, mole/1.
Mole w~.
DETP PETP Ditto
1 × 10 -5
254
1 × 1 0 -5
1610
1 × 10 -5
1750
))
1 × 10 -5
2500
))
1 × 10 -6
13130
))
1 × 10 -e
18900
AND PETP
Absorption band maxima I
2, mg ] Ioge 264 264 265 264 264 265
4.39 4-72 4.95 5.17 5.94 6.27
2, ma I log e 315 314 316 316 315 315
3.43 3.72 3.98 4-15 4.98 5.25
It is seen from Table 1 that the absorption spectra of D E T P (curve 1) and P E T P (curves 2-6) consist of two bands with maxima in the 264-265 nag and 314-316 m/~ regions. Comparison of the spectra of D E T P and P E T P of increasing molecular weight shows that the products of higher molecular weight preserve the spectrum of D E T P , b u t the intensity of the bands increases, especially of the band with a maximum at 264-265 m/~. For Lavsan of molecular weight 18,900 the intensity of the latter is 75 times greater than for D E T P . In addition to spectra of pure Lavsan spectra of products of polycondensation carried out in the presence of other reactants were also studied. The additional reactants were the aromatic, hydroxyl-containing compounds, hydroquinone, resorcinol and D H P A , which can react chemically with D E T P during the process. Table 2 gives data and characteristics of the absorption curves of hydroquinone (curve 1), D E T P (curve 2) and polymers of increasing molecular weight (curves 2-5). Comparison of the spectra of hydroquinone (curve 1) with the curves of D E T P and P E T P (curves 2-5) shows that in the curves of polymers of lower molecular weight a shortwave band appears, with a maximum at 222 m/l, attributable to the hydroquinone component. This band disappears with increase in the molecular weight of the polymer and the spectrum of the polymer of molecular weight 10,900 is similar to those of D E T P and Lavsan, i.e. it also consists of two bands with maxima at 264 and 312-315 ma, differing only in the intensity of absorption.
Products TABLE
2.
ABSORPTION
of polycondensation
SPECTRA
of diethylol terephthalate
O F HYDROQIUINOI~'E,
DETP
AND
PETP
1851 ] P R O D U C E D I N TRSE
P R E S E N C E OF H Y D R O Q U I N O N E
Curve :No.
Compound
Solution concentration, mole/1.
Mole wt.
Absorption 2, m z ] l o g e
band maxima
!2, m p [
loge
[2, m p
3.44 4.39 4.92 5.36 5.74
315 310 310 312
log
Itydro2 3 4 5
i quinone* DETP PETP Ditto Ditto
1 × 10 .4 1 × 10 .5 1 × 10 .5 1 × 10 .6
1 × 10 - s
110 254 1620 6750 10900
220 222 222
3-81 -4.70 5-06 --
290 264 262 262 264
3'43 3"80 4'80 5'05
* The quantity of hydroquinone added was 5% of the weight of the starting materials.
Table 3 gives data on the absorption curves of resorcinol and of polymers prepared in the presence of resorcinol. I t is seen from Table 3 that, as in the case of hydroquinone, polymers of low molecular weight prepared in the presence of resorcinol show a band contributed by the additional component (resorcinol), and this band, with the maximum at 248 m/~, is still present in the spectrum of a polymer of molecular weight 13,140. This band disappears at higher molecular weights and the spectrum of the polymer then acquires the characteristics of the spectrum of D E T P , with maxima at 264 and 314 mp. Here the intensity of the maxima exceeds t h a t for D E T P by a factor of 50 (see curves 2 and 5, Table 3). TABLE 3. ABSORPTION SPECTRA OF RESORCINOL, D E T P AND P E T P PRESENCE OF RESORCYNOL Curve
:No.
Compound
Solution concentration, mole/1.
Resorcinol* DETP
1 × 10 -4
PETP
1 × 10 -5
Ditto Ditto
1 × 10 -e
1 × 10 -5
1 × 10 -s
Mole wt.
110 254 2190 13140 15330
Absorption )~, rn/t
240 246 248
]PRODUCED IN THE
band
maxima I
I
l o g e ] 4, m g
loge
)., m]~
4.03 -5.15 5.84 --
-4"39 --6-10
300 315 310 310 314
-264 --264
I loge 3"45 3"43 4"33 4"90 5"08
* The quantity of resorcinol added was 5% of the weight of the starting materials.
4,4'-Dihydroxydiphenylamine was also used as an additional reactant. Characteristics of the absorption spectra of the polymers and of D H P A are given in Table 4. I t is seen from the spectra (Table 4) t h a t even polymers of low molecular weight (730-1620) prepared in the presence of D H P A give spectral curves and
1852
P.M. BUOAI et al.
absorption maxima of the same nature as D E T P and Lavsan. I t is evident t h a t D H P A participates in the polycondensation reaction more rapidly than resoreinol and hydroquinone. F r o m our investigations it is seen t h a t in the production of pure Lavsan extensive polycondensation already occurs during the transestcrification stage (before the reaction is conducted in vacuo), to produce a resin with a molecular weight of 13,130. W hen other reactants are added however different molecular weights are obtained under the same conditions. When hydroquinone is added the molecular weight is 6570 and with resorcinol it is 13,140, whereas with D H P A the molecular weight is only 1680. T A B L E 4. A B S O R P T I O N S P E C T R A OF
Curve
No.
Compound •DHPA*
DttPA, D E T P AND PETP oF DHPA
Solution concentration, mole/1. 1 × 1 0 -4
DETP PETP
1 × 1 0 -5
Ditto Ditto
1 × 10 -° 1 × 10 -s
1 × 1 0 -5
Mole wt.
201 254 730 1680 15400
PRODUCED I N T H E PRESENCE
Absorption band maxima 2, m~
log e
275 264 264 264 264
2.98 4.39 4.67 4.99 5"94
)~, m/2
log
315
3.43
314 315 315
3.62 3.90 4.96
* ]From 1% to 5% of DHPA, calculated on the weight of starting materials, was added.
Thus D H P A has the greatest retarding effect on the polycondensation, hydroquinone occupies an intermediate position and resorcinol does not show this effect. The final polycondensation pr oduc t with the highest molecular weight is pure Lavsan, at 18,900. The final product of lowest molecular weight is the one containing hydroquinone, for which the figure is 10,900, and the products with the other two additional compounds have a molecular weight of 15,400. Characteristics of starting materials: Dimethyl terephthalate, m.p. 141-142° (colourless crystals). Ethylene glycol, (99'9~o) d 1.1087, b,p. 197°. Diethylol terephthalate, m.p. 112° (eolourless crystals). Hydroquinone, chemically pure, m.p. 170'4° (colourless crystals). Resorcinol, chemically pure, m.p. 110° (colourless crystals). 4,4'.Dihydroxydiphenylamine, m.p. 169° (colourless crystals). CONCLUSIONS
(1) I t is shown t h a t polycondensation of diethylol terephthalate (D E T P) occurs to a considerable e xt e nt during the transesterification stage. (2) Products of the polycondensation of D E T P of different molecular weight give spectra and absorption m axi m a similar to those of D E T P , but the intensity of absorption increases with increase in molecular weight.
The mechanism of polymerization of aliphatic diazo compounds
1853
(3) On t h e basis of t h e n a t u r e of t h e a b s o r p t i o n s p e c t r a of p o l y c o n d e n s a t i o n p r o d u c t s o b t a i n e d in t h e presence of a d d i t i o n a l r e a c t a n t s it can be seen t h a t t h e s p e c t r a a t first p r e s e r v e b a n d s c h a r a c t e r i s t i c of t h e a d d i t i o n a l c o m p o n e n t s , b u t these b a n d s d i s a p p e a r as t h e m o l e c u l a r w e i g h t increases. T h e r e is a s h a r p in-crease in t h e i n t e n s i t y of t h e m a i n b a n d s of t h e i n t e r m e d i a t e a n d final p r o d u c t s . (4) T h e stage of p o l y c o n d e n s a t i o n of D E T P a n d t h e e x t e n t of r e a c t i o n of t h e a d d i t i o n a l c o m p o n e n t s can be followed to s o m e e x t e n t b y m e a n s of t h e n a t u r e of t h e a b s o r p t i o n s p e c t r a a n d i n t e n s i t y of t h e b a n d s of t h e p r o d u c t s of p o l y c o n d e n s a t i o n in the presence of a d d i t i o n a l r e a c t a n t s .
Translated by E. O. PHILLIPS REFERENCES
1. V. V. KORSHAK and S. V. VINOGRADOVA, Geterotsepnye poliefiry (Heterochain Polyesters (ethers)), Izd. Akad. Nauk SSSR, Moscow 1958 2. V. V. KORSHAK, N. I. BEKASOVA and V. A. ZAMYATINA, Izv. Akad. Nauk SSSR, Otd. khim. nauk, 486, 1958 3. L. E. AMBORSKI and D. W. FLIERL, Ind. Engng. Chem. 45: 2294, 1953 4. I. M. WARD, Chem. Ind., 905, 1956 5. R. J. QUYNN and R. STEELE, Nature 173: 1240, 1954 6. Yu. A. ZUBKOV, G. S. MARKOVA and V. A. KARGIN, Vysokomol. soyed. 5: 1171, 1963 (Translated in Polymer Sci. U.S.S.R. 5: 2, 1964) 7. B. V. PETUKttOV, Poliefirnoe volokno (Polyester Fibre), Goskhimizdat Moscow, 1960
THE MECHANISM OF POLYMERIZATION OF ALIPHATIC DIAZO COMPOUNDS* M. G. KI~AKOVYAK, Y:E. V. AI~I:FRIYEVA a n d S. S. SKOROKHODOV Institute of Macromolecular Compounds, U.S.S.R. Academy of Sciences
(Received 26 July 1965) THE c a t a l y t i c d e c o m p o s i t i o n of diazoalkanes, w i t h e v o l u t i o n of n i t r o g e n a n d f o r m a t i o n of p o l y m e t h y l e n e or p o l y a l k y l i d e n e s is a special case of c o o r d i n a t i o n ionic p o l y m e r i z a t i o n . T h e m e c h a n i s m of p o l y m e r i z a t i o n has b e e n s t u d i e d e x t e n s i v e l y in t h e case of d i a z o m e t h a n e , w i t h c a t a l y s t s of t h e BX3 t y p e , where X is halogen, alkyl, aryl, a l k o x y l or acyl [1-3]. A t t h e p r e s e n t t i m e t h e following t w o basic schemes for t h e m e c h a n i s m of p o l y m e r i z a t i o n are considered: * Vysokomol. soyed. 8: No. 10, 1681-1685, 1966.
1849
10. N. V. MIKHAILOV, D. N. SHIGORIN and S. P. MAKAR'EVA, Dokl. Akad. Nauk SSSt~ 87: 1009, 1952 11. O. Ya. FEDOTOVA and M. I. SHTIL'MAN, Vysokomol. soyed. 7: 312, 1965 (Translated in Polymer Sci. U.S.S.R. 7: 2, 290, 1965) 12. D. N. SHIGORIN, N. V. MIKHAILOV and S. P. MAKAR'EVA, Dokl. Akad. :Nauk SSSR 97: 711, 1954 13. T. TOKATA, Kobunshi kagaku 19: 653, 1962 14. T. TOKATA, J. HIROI and M. TANIJAMA, J. Polymer Sci. A2: 1573, 1964
A SPECTROGRAPHIC STUDY OF THE PRODUCTS OF POLYCONDENSATION OF DIETHYLOL TEREPHTHALATE WITH VARIOUS REACTANTS* 1). IV[. BUGAI, V. 1~. KOI~EL'SKAYA a n d N. M. TIMOSHEVSKAYA V. I. Lenin Polytechnical Institute, Khar'kov (Received 26 July 1965)
TH~ kinetics of p o l y c o n d e n s a t i o n of diethylol t e r e p h t h a l a t e h a v e been studied b y K o r s h a k and his collaborators [1, 2]. I n order to p r o d u c e polyesters of the L a v s a n t y p e with new c o m p o n e n t s we h a v e studied the p o l y c o n d e n s a t i o n of diethylol t e r e p h t h a l a t e ( D E T P ) in c o n j u n c t i o n with various r e a c t a n t s (hydroquinone, resorcinal a n d 4,4'-dihydrox y d i p h e n y l a m i n e ( D H P A ) ) , a d d e d at the synthesis stage. F o r investigation of the process we r e c o r d e d a b s o r p t i o n spectra of t h e initial a n d i n t e r m e d i a t e p o l y c o n d e n s a t i o n products. F o r d e t e r m i n a t i o n of specific viscosity and for spectrographic analysis we w i t h d r e w test samples e v e r y 2-2.5 hr during b o t h the transesterification a n d p o l y c o n d e n s a t i o n stages (3-4 samples in all). T h e transesterification process lasted up to 10 hr and p o l y c o n d e n s a t i o n in vacuo up to 2.5 hr. T h e specific viscosity of each test sample of resin was d e t e r m i n e d b y the conventional, p u b l i s h e d m e t h o d a n d the molecular weight of the p o l y m e r was calculated from this b y means of P e t u k h o v ' s formula [7]: M--
~/--0.01 1.37 x 10 -5 "
T h e ultraviolet, infrared a n d X - r a y spectra of D E T P and p o l y e t h y l e n e t e r e p h t h a l a t e ( P E T P ) h a v e been studied b y a n u m b e r of authors [3-6], b u t there * Vysokomol. soycd. 8: :No. 10, 1677-1680, 1966.
P.M. B u o ~ et al.
1850
are no spectroscopic data in the literature on the intermediate products of polycondensation of D E T P or the products obtained b y condensation of this with other reactants. It was for this reason that we undertook the present work. The spectra were measured in an SF-4 spectrophotometer in the 200-350 m/~ region, in concentrated sulphuric acid, which is a solvent for the polymer. Characteristic of the bands (2 and log e)" of D E T P and its polyeondensations products, i.e. of polymers of increasing molecular weight, are given in Table 1. TABLE
Curve No.
Compound
1. A B S O R P T I O N
S P E C T R A OF D E T P
Solution concentration, mole/1.
Mole w~.
DETP PETP Ditto
1 × 10 -5
254
1 × 1 0 -5
1610
1 × 10 -5
1750
))
1 × 10 -5
2500
))
1 × 10 -6
13130
))
1 × 10 -e
18900
AND PETP
Absorption band maxima I
2, mg ] Ioge 264 264 265 264 264 265
4.39 4-72 4.95 5.17 5.94 6.27
2, ma I log e 315 314 316 316 315 315
3.43 3.72 3.98 4-15 4.98 5.25
It is seen from Table 1 that the absorption spectra of D E T P (curve 1) and P E T P (curves 2-6) consist of two bands with maxima in the 264-265 nag and 314-316 m/~ regions. Comparison of the spectra of D E T P and P E T P of increasing molecular weight shows that the products of higher molecular weight preserve the spectrum of D E T P , b u t the intensity of the bands increases, especially of the band with a maximum at 264-265 m/~. For Lavsan of molecular weight 18,900 the intensity of the latter is 75 times greater than for D E T P . In addition to spectra of pure Lavsan spectra of products of polycondensation carried out in the presence of other reactants were also studied. The additional reactants were the aromatic, hydroxyl-containing compounds, hydroquinone, resorcinol and D H P A , which can react chemically with D E T P during the process. Table 2 gives data and characteristics of the absorption curves of hydroquinone (curve 1), D E T P (curve 2) and polymers of increasing molecular weight (curves 2-5). Comparison of the spectra of hydroquinone (curve 1) with the curves of D E T P and P E T P (curves 2-5) shows that in the curves of polymers of lower molecular weight a shortwave band appears, with a maximum at 222 m/l, attributable to the hydroquinone component. This band disappears with increase in the molecular weight of the polymer and the spectrum of the polymer of molecular weight 10,900 is similar to those of D E T P and Lavsan, i.e. it also consists of two bands with maxima at 264 and 312-315 ma, differing only in the intensity of absorption.
Products TABLE
2.
ABSORPTION
of polycondensation
SPECTRA
of diethylol terephthalate
O F HYDROQIUINOI~'E,
DETP
AND
PETP
1851 ] P R O D U C E D I N TRSE
P R E S E N C E OF H Y D R O Q U I N O N E
Curve :No.
Compound
Solution concentration, mole/1.
Mole wt.
Absorption 2, m z ] l o g e
band maxima
!2, m p [
loge
[2, m p
3.44 4.39 4.92 5.36 5.74
315 310 310 312
log
Itydro2 3 4 5
i quinone* DETP PETP Ditto Ditto
1 × 10 .4 1 × 10 .5 1 × 10 .5 1 × 10 .6
1 × 10 - s
110 254 1620 6750 10900
220 222 222
3-81 -4.70 5-06 --
290 264 262 262 264
3'43 3"80 4'80 5'05
* The quantity of hydroquinone added was 5% of the weight of the starting materials.
Table 3 gives data on the absorption curves of resorcinol and of polymers prepared in the presence of resorcinol. I t is seen from Table 3 that, as in the case of hydroquinone, polymers of low molecular weight prepared in the presence of resorcinol show a band contributed by the additional component (resorcinol), and this band, with the maximum at 248 m/~, is still present in the spectrum of a polymer of molecular weight 13,140. This band disappears at higher molecular weights and the spectrum of the polymer then acquires the characteristics of the spectrum of D E T P , with maxima at 264 and 314 mp. Here the intensity of the maxima exceeds t h a t for D E T P by a factor of 50 (see curves 2 and 5, Table 3). TABLE 3. ABSORPTION SPECTRA OF RESORCINOL, D E T P AND P E T P PRESENCE OF RESORCYNOL Curve
:No.
Compound
Solution concentration, mole/1.
Resorcinol* DETP
1 × 10 -4
PETP
1 × 10 -5
Ditto Ditto
1 × 10 -e
1 × 10 -5
1 × 10 -s
Mole wt.
110 254 2190 13140 15330
Absorption )~, rn/t
240 246 248
]PRODUCED IN THE
band
maxima I
I
l o g e ] 4, m g
loge
)., m]~
4.03 -5.15 5.84 --
-4"39 --6-10
300 315 310 310 314
-264 --264
I loge 3"45 3"43 4"33 4"90 5"08
* The quantity of resorcinol added was 5% of the weight of the starting materials.
4,4'-Dihydroxydiphenylamine was also used as an additional reactant. Characteristics of the absorption spectra of the polymers and of D H P A are given in Table 4. I t is seen from the spectra (Table 4) t h a t even polymers of low molecular weight (730-1620) prepared in the presence of D H P A give spectral curves and
1852
P.M. BUOAI et al.
absorption maxima of the same nature as D E T P and Lavsan. I t is evident t h a t D H P A participates in the polycondensation reaction more rapidly than resoreinol and hydroquinone. F r o m our investigations it is seen t h a t in the production of pure Lavsan extensive polycondensation already occurs during the transestcrification stage (before the reaction is conducted in vacuo), to produce a resin with a molecular weight of 13,130. W hen other reactants are added however different molecular weights are obtained under the same conditions. When hydroquinone is added the molecular weight is 6570 and with resorcinol it is 13,140, whereas with D H P A the molecular weight is only 1680. T A B L E 4. A B S O R P T I O N S P E C T R A OF
Curve
No.
Compound •DHPA*
DttPA, D E T P AND PETP oF DHPA
Solution concentration, mole/1. 1 × 1 0 -4
DETP PETP
1 × 1 0 -5
Ditto Ditto
1 × 10 -° 1 × 10 -s
1 × 1 0 -5
Mole wt.
201 254 730 1680 15400
PRODUCED I N T H E PRESENCE
Absorption band maxima 2, m~
log e
275 264 264 264 264
2.98 4.39 4.67 4.99 5"94
)~, m/2
log
315
3.43
314 315 315
3.62 3.90 4.96
* ]From 1% to 5% of DHPA, calculated on the weight of starting materials, was added.
Thus D H P A has the greatest retarding effect on the polycondensation, hydroquinone occupies an intermediate position and resorcinol does not show this effect. The final polycondensation pr oduc t with the highest molecular weight is pure Lavsan, at 18,900. The final product of lowest molecular weight is the one containing hydroquinone, for which the figure is 10,900, and the products with the other two additional compounds have a molecular weight of 15,400. Characteristics of starting materials: Dimethyl terephthalate, m.p. 141-142° (colourless crystals). Ethylene glycol, (99'9~o) d 1.1087, b,p. 197°. Diethylol terephthalate, m.p. 112° (eolourless crystals). Hydroquinone, chemically pure, m.p. 170'4° (colourless crystals). Resorcinol, chemically pure, m.p. 110° (colourless crystals). 4,4'.Dihydroxydiphenylamine, m.p. 169° (colourless crystals). CONCLUSIONS
(1) I t is shown t h a t polycondensation of diethylol terephthalate (D E T P) occurs to a considerable e xt e nt during the transesterification stage. (2) Products of the polycondensation of D E T P of different molecular weight give spectra and absorption m axi m a similar to those of D E T P , but the intensity of absorption increases with increase in molecular weight.
The mechanism of polymerization of aliphatic diazo compounds
1853
(3) On t h e basis of t h e n a t u r e of t h e a b s o r p t i o n s p e c t r a of p o l y c o n d e n s a t i o n p r o d u c t s o b t a i n e d in t h e presence of a d d i t i o n a l r e a c t a n t s it can be seen t h a t t h e s p e c t r a a t first p r e s e r v e b a n d s c h a r a c t e r i s t i c of t h e a d d i t i o n a l c o m p o n e n t s , b u t these b a n d s d i s a p p e a r as t h e m o l e c u l a r w e i g h t increases. T h e r e is a s h a r p in-crease in t h e i n t e n s i t y of t h e m a i n b a n d s of t h e i n t e r m e d i a t e a n d final p r o d u c t s . (4) T h e stage of p o l y c o n d e n s a t i o n of D E T P a n d t h e e x t e n t of r e a c t i o n of t h e a d d i t i o n a l c o m p o n e n t s can be followed to s o m e e x t e n t b y m e a n s of t h e n a t u r e of t h e a b s o r p t i o n s p e c t r a a n d i n t e n s i t y of t h e b a n d s of t h e p r o d u c t s of p o l y c o n d e n s a t i o n in the presence of a d d i t i o n a l r e a c t a n t s .
Translated by E. O. PHILLIPS REFERENCES
1. V. V. KORSHAK and S. V. VINOGRADOVA, Geterotsepnye poliefiry (Heterochain Polyesters (ethers)), Izd. Akad. Nauk SSSR, Moscow 1958 2. V. V. KORSHAK, N. I. BEKASOVA and V. A. ZAMYATINA, Izv. Akad. Nauk SSSR, Otd. khim. nauk, 486, 1958 3. L. E. AMBORSKI and D. W. FLIERL, Ind. Engng. Chem. 45: 2294, 1953 4. I. M. WARD, Chem. Ind., 905, 1956 5. R. J. QUYNN and R. STEELE, Nature 173: 1240, 1954 6. Yu. A. ZUBKOV, G. S. MARKOVA and V. A. KARGIN, Vysokomol. soyed. 5: 1171, 1963 (Translated in Polymer Sci. U.S.S.R. 5: 2, 1964) 7. B. V. PETUKttOV, Poliefirnoe volokno (Polyester Fibre), Goskhimizdat Moscow, 1960
THE MECHANISM OF POLYMERIZATION OF ALIPHATIC DIAZO COMPOUNDS* M. G. KI~AKOVYAK, Y:E. V. AI~I:FRIYEVA a n d S. S. SKOROKHODOV Institute of Macromolecular Compounds, U.S.S.R. Academy of Sciences
(Received 26 July 1965) THE c a t a l y t i c d e c o m p o s i t i o n of diazoalkanes, w i t h e v o l u t i o n of n i t r o g e n a n d f o r m a t i o n of p o l y m e t h y l e n e or p o l y a l k y l i d e n e s is a special case of c o o r d i n a t i o n ionic p o l y m e r i z a t i o n . T h e m e c h a n i s m of p o l y m e r i z a t i o n has b e e n s t u d i e d e x t e n s i v e l y in t h e case of d i a z o m e t h a n e , w i t h c a t a l y s t s of t h e BX3 t y p e , where X is halogen, alkyl, aryl, a l k o x y l or acyl [1-3]. A t t h e p r e s e n t t i m e t h e following t w o basic schemes for t h e m e c h a n i s m of p o l y m e r i z a t i o n are considered: * Vysokomol. soyed. 8: No. 10, 1681-1685, 1966.