- Email: [email protected]
On the mechanism of radical copolymerization of maleic anhydride with trans-stilbene
Copolymerization of maleic anhydride with ~'ans-stilbene
689
28. P.Ye. TULUPOV, Zh. fizieh, k]~imli 45: 1205, 1971 2 9 . K. M. S)tl.nADZE, A. B. PASHlgOV and V. 8. TITOV, Ionoobmennye vysokomol~kulyarnye soyedineniya (Ion Excb~m~ High Polymers). Izd. Goskhimizdat, 1960 30. V.D. BOROBYEVA, L. V. DMITRENKO and G. V. 8AMSONOV, Trans. Leningrad Chem. Pharm. Inst., No. 25, 11, 1968 31. A. 811. GENEDI and G. V . ~ A M S O N O V , I b i d e m , N o . 25, 164, 1968 32. Yu. I. TARASEVICH, V. P. TELTCHXUN and F. D. OVCHARENKO, Teoretich. i experim khimia 6: 804, 1970
Polymer Science U.S.S,R. Vol. 28, No. $, pp. 689-695. 1981 Printed in Poland
0082~3950/81/030689-07 $07.5010 O 1982 Pergamon l~mm Ltd.
ON THE. MECHANISM OF RADICAL COPOLYMERIZATION OF MALEIC ANHYDRIDE WITH TRANS-STILBENE* Z. M. RZAYEV, I. P. ZF~S~OV, L. V. MEDYAKOVA, A. I. BABAYEV a n d M. M. AOAYE¥ Institute for Organochlorine Synthesis, Az. S.S.R. Academy of S c i e n c e s (Received 7 J~vuary 1980) A study has been made of the radical copolymerization of maleic anhydride with ~rans-stilbene. It was found that irrespective of the make-up of the initial monomer mixture the resulting copolymers have an approximately equimolar composition. The formation of MA-stilbene charge-transfer complexes has been detected by PMR, and the equilibrium complexing constant has been determined. On the basis of kinetic analysis a "complex" mechanism is proposed for the formation of a copolymer of constant composition with a regularly alternating structure. The contribution of chargetransfer complexes to the propagation reaction has been determined quantitatively. INSUFFICIENT iS k n o w n a b o u t t h e m e c h a n i s m o f a l t e r n a t i n g radical copolymerization: two h y p o t h e s e s r e g a r d i n g t h e p r o p a g a t i o n m e c h a n i s m are largely c o n t r a d i c t o r y . According t o one h y p o t h e s i s chain p r o p a g a t i o n t a k e s place t h r o u g h a d d i t i o n o f free m o n o m e r s t o t h e macroradicals; t h e o t h e r assumes t h a t homop o l y m e r i z a t i o n o f d o n o r - a c c e p t o r complexes o f m o n o m e r s t a k e s ,place. Continuing earlier investigations [1-4] o f some features o f t h e radical copolym e r i z a t i o n o f maleic a n h y d r i d e (MA) w i t h electron-donor m o n o m e r s we t o o k i n t h e p r e s e n t w o r k t h e copolymerization o f MA w i t h trans-stilbene. I t is k n o w n * Vysokomol. soyed. A28: No. 3, 614-618, 1981.
690
z . M . RzAY~.v et ~.
from [5-7] that MA and its derivatives copelymerize with stilbene to give copolymers with a regular alternating structure. The system selected for investigation of the mechanism of formation of alternative copolymers was suitable in t h a t no homopolymerization of the monomers takes place under the binary copolymerization conditions. Our aim in the present instance was to investigate the influence of complex formation on the kinetics and composition of the resulting copolymers and to estimate the quantitative contribution of charge-transfer complexes to the propagation reaction. Copolymerization of MA (m.p. 52.8°) and tra~.stilbene (m.p. 124"} was carried out in glass ampoules in an argon atmosphere in methyl ethyl ketone at 80° in the presence of benzoyl peroxide (0.5°~o). Weighed portions of the monomers, initiator and solvent were placed in ampoules, frozen with a dry-ice-acetone mixture, then evacuated and sealed, in an argon atmosphere. The ampoule~ were placed in an ultrathermostat, and retained up to 7-12o~o conversion. The eopolymer sel~rated from the reaction system by ultracentrifuging was purified, washed with several portions of hot benzene and dried under vacuum to constant weight. 92.5~ yield,' softening point 372*. The copolymerization kinetics were investigated dil~temetrically. The PMR spectra were recorded with a Tesla B-487-B apparatus operating at 80 MHz; the internal standard was hexamethyldlsiloxane, and the solvent was ethyl acetate. The formation of charge transfer complexes between MA and tra~-stilbene was verified b y an analysis of the P M R spectra of the pure monomers and of the monomer mixtures (1:1, see Fig. 1). It can be seen from the Figure that the maleie anhydride (acceptor) singlet has a strong field shift (Lte~=7.18-7.13=0.05 p.p.m), while a weak field shift appears for stilbene double bond protons (Aexp ~ 7 . 0 8 - 7 - 1 0 = 0 . 0 2 p.p.m). The change in the P M R spectra is associated with the formation of charge-transfer complexes 0
~!. o
~/
On t h e basis of changes in the chemical shifts of MA protons in the P M R spectra of the MA-stilbene mixtures we obtained the complexing equilibrium constant K, using a Beneshi-Hildebrand-Ketelaar equation [8] under conditions where [stilbene]>>[1VL~]. A value of K ~ 0 . 2 1 1./mole (at 354-0.5 °) was obtained from the plot shown in Fig. 2. I t is seen from the data in Table 1 that copolymerization of the monomers leads to the formation of copolymers of constant composition (close to an equimolar one), irrespective of t h e composition of the initial monomer mixtures.
Copolymorization of malei¢ anhydride with #ra~-stilbene
691
Since neither MA nor stilbene homopolymedze under ~ copolymeriz~tion conditions, the monomer system may be c h ~ by the following .elementary reactions of chain propagation allowing for free monomers and for those bound in a complex:
(1)
~bi;.-t-M= ~",~ ~M; ~M;+M1
kll
(2)
~ ~Mi
(3) (4)
=xp,(p.p.m.)
.
8O Z.175
40
I
8
7 FIG. 1
I
I
~ p,p.m. FIG. 2
FIG. I. PMR spectra of MA (1), tra~-stilbene (2) and the equimolar MA-tra~.stilbene mixture (3) in ethyl acetate. FIG. 2. Graphic method of determining the complexing constant K between MA (A) and stilbene (D): 1/Ac is t.he intercept on the ordinate axis, tan = ~ l / J j ~ , [D] is the donor concentration, ~ p is the difference in chemical shifts of free MA protons and those in systema oontainln~ MA and stilbene ([D]:~[A]).
,
692:
Z.M. RzAx,z~ e~ a/.
where M, is stilbene, M2 is MA, and [MI...M2] is the charge:transfer complex, k,s,/q~, kxo and kle are rate constants for addition of free and complexed monomers to the mseroradical. On the basis of the above scheme a eopolymer of constant composition and of regular alternating structure is obtainable only by reactions (1) and (2) (by a "free-monomer" mechanism), or by reactions (3) and (4) ("complex" mechanism). T~SL~ l. COPOLYM~.--*~.a~O~OF I~'~nS-STILBENE (M1) WiTH (Solvent--methyl ethyl ketone; initiator--benzoyl peroxide (0.5%) 80°; reaction time 45 rain) Yield, %
MI~
mole %
7.6 8.4
80 60 50 40 20
8.8 9.8 11.6
Analysis*, % c I H 79.05 78.11 77.41 77.86 76.92
5.69 5.54 5-32 5.46 4.75
ml,mole% 45.44 47.95 60.05 48"72 52.38
* Calculated for the copolymer of equimolar comi~sition, %: C 77.68; H 5.07.
To solve this problem we used a kinetic method based on the general alterhating copolymerization principles proposed in papers by Zubov and coworkers [9, 10]. Figure 3 shows the copolymerization rate vs. the composition of the initial monomer system with differing total monomer concentrations. It can be seen t h a t plots of the reaction rate vs. the monomer ratio go through maxima, and there is no displacement of the peaks. To determine the quantitative contribution of charge-transfer complexes to the propagation reaction we used the following equation for the copolymerization rate allowing for the constant of complex formation between the monomers: v
where F1---- [M1] - -
[M,] --
Assuming
v~a K(k2,kxeFZ+k12kzeF)
, V~n
[stilbene]
[MA]
that K ( k,x kleF ~~ - k12k,eF )
k~o
kxs~-k,lF k~
kla+k,~F
~b~
=a;
2kx~k~iF
Copolymerization o f maleic anhydride with tear~-stilbene
eg~
we m a y now rewrit~ e q u a t i o n (5) in t h e f o r m of v - -
-----a~[I]-Fb
Using t h e plot of [M~] ~ -, f[M2] (Fig. 4) w i t h different values of F we o b t a i n t h e values of a (tangent of the angle of slope of the curves) a n d b (intercept o n t h e Y-axis). I f a/b=f, we have
f= k(k,,lk,,F + k,,Ik,,)
or
2ftK=k,,!k,=F+k~lk=,
Table 2 gives t h e yalues of a, b, f a n d 2f/K for various values of F.
v. 1os,,,,ole/l.. 1.2
e.8 U MAJ ,10 ,sec-'
~E.
3-
o.q
I
ZO
60 ~t'IAJ,mole % Fie. 3
0
0.I.
O.Z 0.3 O.q [MA~ , rnole/l.
Fig. 4
FIO. 3. Rate of MA-stilbene copol'ymerization vs. make-up of the monomer mixture, w i t h total monomer concentrations of 0.4 (1), 0.5 (2), 0.6 (3) and 0.7 mole/1. (4). Fie. 4. Plot of v/EMA]vs. [MA] for definite values of a and b with differing ratios of initial monomers F=--[stilbene]/[MA]: F----0.82 (1), !'.0 (2), 1.22 (3), 1.67 (4), 3.0 (5) and 2-33 (6). Values of klc/k12, a n d k2c/k12 were d e t e r m i n e d from t h e d a t a in Fig. 5. On comparing values of klc/k12=437-5 a n d kit/ks1=300.0, it is seen t h a t ratios o f t h e rates of addition of complexed a n d free monomers to a growing chain e n d
~94
Z.~M. RzAY~V e~ a/.
~ r e o f t h e s a m e o r d e r o f m a g n i t u d e , a n d t h e a b s o l u t e v a l u e s o f t h e r a t i o s a r e so h i g h t h a t a " c o m p l e x " p r o p a g a t i o n m e c h a n i s m m a y he p r o p o s e d for t h e r a d i c a l c o p o l y m e r i z a t i o n o f M A w i t h trana-stilbene.
1200
400
.k /k2, f
I
I 2 F FIO. 5. Relations of 2f/K to F for determining quantitative contribution of MA .... stilbene charge-transfer complexes (klc/kxl=tan ~, kit/kit is tho intercept on the ordinate axis). TABLE 2. RESULTS OF .
DETERMIlqATIOlqS
OF kac/klt ~ D kzc/kzx ratios
~=[Md/[Md
a x 10~
b x 10'
2.333
10.909 9.333 6.476 7"692 5"000
0.08 0-08 0",08 0-08 0.08
1.666 1.000 1.222 0.818
j'=a/b 136.36 116.66 80.95 96.15 62-50
2ilk 1298.66 1111.05 770.95 915.71 595.24
T h u s one m a y conclude o n t h e basis o f e x p e r i m e n t a l results t h a t t h e r a d i c a l ~ o p o l y m e r i z a t i o n o f M_~ a n d stilbene t a k e s place p r e f e r e n t i a l l y a t t h e s t a g e o f i h o m o c o p o l y m e r i z a t i o n o f t h e M A . . . s t i i b e n e c h a r g e - t r a n s f e r complex. Trandated by R. J. A. I ~ I ~ B Y REFERENCES ]. S. I. SADYKi~-ZADE, Z. M. RZAYEV, L. V. BRYKSINA, Sh. K. KYAZIMOV and F. Ya. KASUMOV, Vysokomol. s0yed. BI$: 481, 1971 (Not translated in Polymer Sci. U.S.S.R.) 12. Z. M. RZAYEV, S. I. SADYIKH-ZADE and L. V. BRYKSINA, Vysokomol. soyed. BI6: 8, 1974 (Not translated in Polymer Sci. U.S.S.R.) 3. Z. M. RZAYEV, L. V. BRYKSINA and S. I. SADIK-ZADE, J. Polymer Sci., Polymer Syrup. 42: 5i9, 1973 4. Z. M. RZAYEV, Sh. K. KYAZIMOV, A. M~ GULIYEV and R. V. DZHAFAROV, Azerb. khimieh, zh., No. 4, 87, 1972 ~5. T. WABNER-JAUREGG, Ber. 63:3213, 1930 6. M.L. H#LLENSLEBEN, ~urop. Polymer J. 9: 227, 1973 7. Y A M ~ t T A HIRONI, and HAYAKAWA KIYOS=, J. Polymer Sci. 10, A-I: 2223. 1972
Synthesis of branched oligoarylates
695
8. J. A. A. Klg'ITJ,AA.K, Rec. Trs,v. Chim. 71: 1104, 1952 9. {~. 8. G E O ~ V , V. B~ GOLUBEV andV. P. ZUBOV, Vysokomol. soyed, A2O: 1608, 1978 (Tranalated in Polymer Sei. U.S.S.R. 20: 7, 1814, 1978) 10. G. S. GEORG1YEV and V. P. ZUBOV, Europ. Polymer J. 14: 93, 1978
Polymer Science U.S.8.R. Vol. 28, No. 3, pp.
695-703, 1981
0032-89501811030695-09507.5010 © 1982 PergamonPress Ltd.
Printed in Poland
SYNTHESIS OF BRANCHED 0LIGOARYLATES* S. V. V~OGRADOVA, V. A. VAS~EV, T. S. SIMONENKO,A. M. TARTAKOVSKAYA and V. V. K o v ~ q ~ Hetero-organic Compounds Institute, U.S.S.R. Academy of Sciences (Received 8 January 1980)
Branched oligoarylates having an average functionality offa v >~2, and terminal and side alcoholic hydroxyls have been synthesized by aceeptor-eatalytie polyesterification of terephthalic acid dichloride with phenolphthalein, 2-fl-hydroxycthyl3,3'-bis-(4-hydroxyphenyl)phthalimidine and ethylene glycol in dioxan at 30° in the presence of triethylamine. The structure of the products was determined by high resolution 1H NMR spectroscopy, and the number-average MW of the polymers have b e e n determined, as well as the main chain length, hydroxyl equivalent and average functionality. I t is shown that branched otigoarylates that dissolve in organic solvents may be prepared by introducing 2-fl-hydroxyethyL3,3'-bis-(4-hydroxyphenyl)phthalimidine (not more than 50 tool. % on total bisphenols). I t was found that higher softening points were obtainable by increasing the degree of branching of the oligoarylates.
PROMISn~Gmethods of preparing novel polymeric materials include the synthesis of block copotymers possessing good properties obtainable by combining qualities of various gypes of high polymers. On a previous occasion [1] we described features of the synthesis of type I linear oligoarylates having terminal alcoholic OH groups I
.
~x~/~. / \ )\/o
~
c=o CH~CH20H * Vysokomol. soyed. A23: No. 3, 619-625, 1981.
0_.oo _0_ o_1o.o_
689
28. P.Ye. TULUPOV, Zh. fizieh, k]~imli 45: 1205, 1971 2 9 . K. M. S)tl.nADZE, A. B. PASHlgOV and V. 8. TITOV, Ionoobmennye vysokomol~kulyarnye soyedineniya (Ion Excb~m~ High Polymers). Izd. Goskhimizdat, 1960 30. V.D. BOROBYEVA, L. V. DMITRENKO and G. V. 8AMSONOV, Trans. Leningrad Chem. Pharm. Inst., No. 25, 11, 1968 31. A. 811. GENEDI and G. V . ~ A M S O N O V , I b i d e m , N o . 25, 164, 1968 32. Yu. I. TARASEVICH, V. P. TELTCHXUN and F. D. OVCHARENKO, Teoretich. i experim khimia 6: 804, 1970
Polymer Science U.S.S,R. Vol. 28, No. $, pp. 689-695. 1981 Printed in Poland
0082~3950/81/030689-07 $07.5010 O 1982 Pergamon l~mm Ltd.
ON THE. MECHANISM OF RADICAL COPOLYMERIZATION OF MALEIC ANHYDRIDE WITH TRANS-STILBENE* Z. M. RZAYEV, I. P. ZF~S~OV, L. V. MEDYAKOVA, A. I. BABAYEV a n d M. M. AOAYE¥ Institute for Organochlorine Synthesis, Az. S.S.R. Academy of S c i e n c e s (Received 7 J~vuary 1980) A study has been made of the radical copolymerization of maleic anhydride with ~rans-stilbene. It was found that irrespective of the make-up of the initial monomer mixture the resulting copolymers have an approximately equimolar composition. The formation of MA-stilbene charge-transfer complexes has been detected by PMR, and the equilibrium complexing constant has been determined. On the basis of kinetic analysis a "complex" mechanism is proposed for the formation of a copolymer of constant composition with a regularly alternating structure. The contribution of chargetransfer complexes to the propagation reaction has been determined quantitatively. INSUFFICIENT iS k n o w n a b o u t t h e m e c h a n i s m o f a l t e r n a t i n g radical copolymerization: two h y p o t h e s e s r e g a r d i n g t h e p r o p a g a t i o n m e c h a n i s m are largely c o n t r a d i c t o r y . According t o one h y p o t h e s i s chain p r o p a g a t i o n t a k e s place t h r o u g h a d d i t i o n o f free m o n o m e r s t o t h e macroradicals; t h e o t h e r assumes t h a t homop o l y m e r i z a t i o n o f d o n o r - a c c e p t o r complexes o f m o n o m e r s t a k e s ,place. Continuing earlier investigations [1-4] o f some features o f t h e radical copolym e r i z a t i o n o f maleic a n h y d r i d e (MA) w i t h electron-donor m o n o m e r s we t o o k i n t h e p r e s e n t w o r k t h e copolymerization o f MA w i t h trans-stilbene. I t is k n o w n * Vysokomol. soyed. A28: No. 3, 614-618, 1981.
690
z . M . RzAY~.v et ~.
from [5-7] that MA and its derivatives copelymerize with stilbene to give copolymers with a regular alternating structure. The system selected for investigation of the mechanism of formation of alternative copolymers was suitable in t h a t no homopolymerization of the monomers takes place under the binary copolymerization conditions. Our aim in the present instance was to investigate the influence of complex formation on the kinetics and composition of the resulting copolymers and to estimate the quantitative contribution of charge-transfer complexes to the propagation reaction. Copolymerization of MA (m.p. 52.8°) and tra~.stilbene (m.p. 124"} was carried out in glass ampoules in an argon atmosphere in methyl ethyl ketone at 80° in the presence of benzoyl peroxide (0.5°~o). Weighed portions of the monomers, initiator and solvent were placed in ampoules, frozen with a dry-ice-acetone mixture, then evacuated and sealed, in an argon atmosphere. The ampoule~ were placed in an ultrathermostat, and retained up to 7-12o~o conversion. The eopolymer sel~rated from the reaction system by ultracentrifuging was purified, washed with several portions of hot benzene and dried under vacuum to constant weight. 92.5~ yield,' softening point 372*. The copolymerization kinetics were investigated dil~temetrically. The PMR spectra were recorded with a Tesla B-487-B apparatus operating at 80 MHz; the internal standard was hexamethyldlsiloxane, and the solvent was ethyl acetate. The formation of charge transfer complexes between MA and tra~-stilbene was verified b y an analysis of the P M R spectra of the pure monomers and of the monomer mixtures (1:1, see Fig. 1). It can be seen from the Figure that the maleie anhydride (acceptor) singlet has a strong field shift (Lte~=7.18-7.13=0.05 p.p.m), while a weak field shift appears for stilbene double bond protons (Aexp ~ 7 . 0 8 - 7 - 1 0 = 0 . 0 2 p.p.m). The change in the P M R spectra is associated with the formation of charge-transfer complexes 0
~!. o
~/
On t h e basis of changes in the chemical shifts of MA protons in the P M R spectra of the MA-stilbene mixtures we obtained the complexing equilibrium constant K, using a Beneshi-Hildebrand-Ketelaar equation [8] under conditions where [stilbene]>>[1VL~]. A value of K ~ 0 . 2 1 1./mole (at 354-0.5 °) was obtained from the plot shown in Fig. 2. I t is seen from the data in Table 1 that copolymerization of the monomers leads to the formation of copolymers of constant composition (close to an equimolar one), irrespective of t h e composition of the initial monomer mixtures.
Copolymorization of malei¢ anhydride with #ra~-stilbene
691
Since neither MA nor stilbene homopolymedze under ~ copolymeriz~tion conditions, the monomer system may be c h ~ by the following .elementary reactions of chain propagation allowing for free monomers and for those bound in a complex:
(1)
~bi;.-t-M= ~",~ ~M; ~M;+M1
kll
(2)
~ ~Mi
(3) (4)
=xp,(p.p.m.)
.
8O Z.175
40
I
8
7 FIG. 1
I
I
~ p,p.m. FIG. 2
FIG. I. PMR spectra of MA (1), tra~-stilbene (2) and the equimolar MA-tra~.stilbene mixture (3) in ethyl acetate. FIG. 2. Graphic method of determining the complexing constant K between MA (A) and stilbene (D): 1/Ac is t.he intercept on the ordinate axis, tan = ~ l / J j ~ , [D] is the donor concentration, ~ p is the difference in chemical shifts of free MA protons and those in systema oontainln~ MA and stilbene ([D]:~[A]).
,
692:
Z.M. RzAx,z~ e~ a/.
where M, is stilbene, M2 is MA, and [MI...M2] is the charge:transfer complex, k,s,/q~, kxo and kle are rate constants for addition of free and complexed monomers to the mseroradical. On the basis of the above scheme a eopolymer of constant composition and of regular alternating structure is obtainable only by reactions (1) and (2) (by a "free-monomer" mechanism), or by reactions (3) and (4) ("complex" mechanism). T~SL~ l. COPOLYM~.--*~.a~O~OF I~'~nS-STILBENE (M1) WiTH (Solvent--methyl ethyl ketone; initiator--benzoyl peroxide (0.5%) 80°; reaction time 45 rain) Yield, %
MI~
mole %
7.6 8.4
80 60 50 40 20
8.8 9.8 11.6
Analysis*, % c I H 79.05 78.11 77.41 77.86 76.92
5.69 5.54 5-32 5.46 4.75
ml,mole% 45.44 47.95 60.05 48"72 52.38
* Calculated for the copolymer of equimolar comi~sition, %: C 77.68; H 5.07.
To solve this problem we used a kinetic method based on the general alterhating copolymerization principles proposed in papers by Zubov and coworkers [9, 10]. Figure 3 shows the copolymerization rate vs. the composition of the initial monomer system with differing total monomer concentrations. It can be seen t h a t plots of the reaction rate vs. the monomer ratio go through maxima, and there is no displacement of the peaks. To determine the quantitative contribution of charge-transfer complexes to the propagation reaction we used the following equation for the copolymerization rate allowing for the constant of complex formation between the monomers: v
where F1---- [M1] - -
[M,] --
Assuming
v~a K(k2,kxeFZ+k12kzeF)
, V~n
[stilbene]
[MA]
that K ( k,x kleF ~~ - k12k,eF )
k~o
kxs~-k,lF k~
kla+k,~F
~b~
=a;
2kx~k~iF
Copolymerization o f maleic anhydride with tear~-stilbene
eg~
we m a y now rewrit~ e q u a t i o n (5) in t h e f o r m of v - -
-----a~[I]-Fb
Using t h e plot of [M~] ~ -, f[M2] (Fig. 4) w i t h different values of F we o b t a i n t h e values of a (tangent of the angle of slope of the curves) a n d b (intercept o n t h e Y-axis). I f a/b=f, we have
f= k(k,,lk,,F + k,,Ik,,)
or
2ftK=k,,!k,=F+k~lk=,
Table 2 gives t h e yalues of a, b, f a n d 2f/K for various values of F.
v. 1os,,,,ole/l.. 1.2
e.8 U MAJ ,10 ,sec-'
~E.
3-
o.q
I
ZO
60 ~t'IAJ,mole % Fie. 3
0
0.I.
O.Z 0.3 O.q [MA~ , rnole/l.
Fig. 4
FIO. 3. Rate of MA-stilbene copol'ymerization vs. make-up of the monomer mixture, w i t h total monomer concentrations of 0.4 (1), 0.5 (2), 0.6 (3) and 0.7 mole/1. (4). Fie. 4. Plot of v/EMA]vs. [MA] for definite values of a and b with differing ratios of initial monomers F=--[stilbene]/[MA]: F----0.82 (1), !'.0 (2), 1.22 (3), 1.67 (4), 3.0 (5) and 2-33 (6). Values of klc/k12, a n d k2c/k12 were d e t e r m i n e d from t h e d a t a in Fig. 5. On comparing values of klc/k12=437-5 a n d kit/ks1=300.0, it is seen t h a t ratios o f t h e rates of addition of complexed a n d free monomers to a growing chain e n d
~94
Z.~M. RzAY~V e~ a/.
~ r e o f t h e s a m e o r d e r o f m a g n i t u d e , a n d t h e a b s o l u t e v a l u e s o f t h e r a t i o s a r e so h i g h t h a t a " c o m p l e x " p r o p a g a t i o n m e c h a n i s m m a y he p r o p o s e d for t h e r a d i c a l c o p o l y m e r i z a t i o n o f M A w i t h trana-stilbene.
1200
400
.k /k2, f
I
I 2 F FIO. 5. Relations of 2f/K to F for determining quantitative contribution of MA .... stilbene charge-transfer complexes (klc/kxl=tan ~, kit/kit is tho intercept on the ordinate axis). TABLE 2. RESULTS OF .
DETERMIlqATIOlqS
OF kac/klt ~ D kzc/kzx ratios
~=[Md/[Md
a x 10~
b x 10'
2.333
10.909 9.333 6.476 7"692 5"000
0.08 0-08 0",08 0-08 0.08
1.666 1.000 1.222 0.818
j'=a/b 136.36 116.66 80.95 96.15 62-50
2ilk 1298.66 1111.05 770.95 915.71 595.24
T h u s one m a y conclude o n t h e basis o f e x p e r i m e n t a l results t h a t t h e r a d i c a l ~ o p o l y m e r i z a t i o n o f M_~ a n d stilbene t a k e s place p r e f e r e n t i a l l y a t t h e s t a g e o f i h o m o c o p o l y m e r i z a t i o n o f t h e M A . . . s t i i b e n e c h a r g e - t r a n s f e r complex. Trandated by R. J. A. I ~ I ~ B Y REFERENCES ]. S. I. SADYKi~-ZADE, Z. M. RZAYEV, L. V. BRYKSINA, Sh. K. KYAZIMOV and F. Ya. KASUMOV, Vysokomol. s0yed. BI$: 481, 1971 (Not translated in Polymer Sci. U.S.S.R.) 12. Z. M. RZAYEV, S. I. SADYIKH-ZADE and L. V. BRYKSINA, Vysokomol. soyed. BI6: 8, 1974 (Not translated in Polymer Sci. U.S.S.R.) 3. Z. M. RZAYEV, L. V. BRYKSINA and S. I. SADIK-ZADE, J. Polymer Sci., Polymer Syrup. 42: 5i9, 1973 4. Z. M. RZAYEV, Sh. K. KYAZIMOV, A. M~ GULIYEV and R. V. DZHAFAROV, Azerb. khimieh, zh., No. 4, 87, 1972 ~5. T. WABNER-JAUREGG, Ber. 63:3213, 1930 6. M.L. H#LLENSLEBEN, ~urop. Polymer J. 9: 227, 1973 7. Y A M ~ t T A HIRONI, and HAYAKAWA KIYOS=, J. Polymer Sci. 10, A-I: 2223. 1972
Synthesis of branched oligoarylates
695
8. J. A. A. Klg'ITJ,AA.K, Rec. Trs,v. Chim. 71: 1104, 1952 9. {~. 8. G E O ~ V , V. B~ GOLUBEV andV. P. ZUBOV, Vysokomol. soyed, A2O: 1608, 1978 (Tranalated in Polymer Sei. U.S.S.R. 20: 7, 1814, 1978) 10. G. S. GEORG1YEV and V. P. ZUBOV, Europ. Polymer J. 14: 93, 1978
Polymer Science U.S.8.R. Vol. 28, No. 3, pp.
695-703, 1981
0032-89501811030695-09507.5010 © 1982 PergamonPress Ltd.
Printed in Poland
SYNTHESIS OF BRANCHED 0LIGOARYLATES* S. V. V~OGRADOVA, V. A. VAS~EV, T. S. SIMONENKO,A. M. TARTAKOVSKAYA and V. V. K o v ~ q ~ Hetero-organic Compounds Institute, U.S.S.R. Academy of Sciences (Received 8 January 1980)
Branched oligoarylates having an average functionality offa v >~2, and terminal and side alcoholic hydroxyls have been synthesized by aceeptor-eatalytie polyesterification of terephthalic acid dichloride with phenolphthalein, 2-fl-hydroxycthyl3,3'-bis-(4-hydroxyphenyl)phthalimidine and ethylene glycol in dioxan at 30° in the presence of triethylamine. The structure of the products was determined by high resolution 1H NMR spectroscopy, and the number-average MW of the polymers have b e e n determined, as well as the main chain length, hydroxyl equivalent and average functionality. I t is shown that branched otigoarylates that dissolve in organic solvents may be prepared by introducing 2-fl-hydroxyethyL3,3'-bis-(4-hydroxyphenyl)phthalimidine (not more than 50 tool. % on total bisphenols). I t was found that higher softening points were obtainable by increasing the degree of branching of the oligoarylates.
PROMISn~Gmethods of preparing novel polymeric materials include the synthesis of block copotymers possessing good properties obtainable by combining qualities of various gypes of high polymers. On a previous occasion [1] we described features of the synthesis of type I linear oligoarylates having terminal alcoholic OH groups I
.
~x~/~. / \ )\/o
~
c=o CH~CH20H * Vysokomol. soyed. A23: No. 3, 619-625, 1981.
0_.oo _0_ o_1o.o_