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Calculating glass temperatures of polymers containing phosphorus
Glass temperature of polymers containing phosphorus
162I
4. N. GRASSI, K h i m i y a protsessov destruktsii polimerov (Chemistry of Polymer Degradation). Izd. inostr, lit., 1959 5. E. BEER, (Ed.), K o n s t r u k t s i o n n y y e svoistva plastmass (Structural Properties of Plastics). Izd. " K h i m i y a " . 1967 6. J. B. YANNAS a n d A. V. TOBOLSKY, Europ. Polymer J. 4: 257, 1968 7. F. PAULIK, J. PAULIK a n d L. ERDEY, Z. analyt. Chem. 160: 241, 1959 8. J. PAULIK, H. MACSKASY, F. PAULIK and L. ERDEY, Plaste u n d Kautschuk 8: 588, 1961 9. J. B. YANNAS and A. V. TOBOLSKY, Nature 215: 509, 1967 10. I. F. KAIMIN', Plast. massy, No. 9, 62, 1966 11. T. KUBO and T. ADZUMI, Nippon nogei kagaku kaisi 39: 495, 1965 12. L. P. WITNAUER and A. WISNEWSKI, J. Amer. Leather Chem. Assoc. 59: 598, 1964 13. G. I. BURDYGINA, P. V. KOZLOV and V. A. KARGIN, Vysokomol. soyed. A14: 383, 1972 (Translated in Polymer Sci. U.S.S.R. 14: 2, 429, 1972) 14. J, B. YANNAS and A. V. TOBOLSKY, J. Maeromolec. Chem. 1: 723, 1966 15. B. A. DOLGOPLOSK, B. L. YERUSALIMSKII, Ye. B. MILOVSKAYA and G. P. BELONOVSKAYA, Dokl. AN SSSR 120: 783, 1958 16. Ye. N. KROPACHEVA, B. A. DOLGOPLOSK, V. F. OTTEN and K. G. GOLODOVA, Zh. organ, khim. 29: 1853, 1959 17. B. A. DOLGOPLOSK and Ye. I. TINYAKOVA, Khim. prom-st', No. 11, 52, 1961 18. N. GRASSIE and H. W. MELVILLE, Prec. Roy. Soc. A199: 14, 1949 19. Zh. F. MOTENEVA, T. I. BURDYGINA, I. M. FRIDMAN and V. P. KOZLOV, Vysokomol. soyed. A16: 1113, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 5, 1288, 1974) 20. V. V. DEREVYANKO, A. G. VASHAKIDZE, V. V. MAL'TSEV and B. A. GROMOV, Plast. massy, No. 3, 58, 1975
CALCULATING GLASS TEMPERATURES OF POLYMERS CONTAINING PHOSPHORUS* E. F. GUBANOV, S. V. SHULYNDIN,N. KH. BORISOVA and B. M. ZUYEV A. Ye. Arbuzov Institute of Organic a n d Physical Chemistry, U.S.S.R. Academy of Sciences
(Received 22 December 1975) A universal system is used for calculating the glass temperatures T I of organophosphorus polymers. Satisfactory agreement was found between experimental a n d calculated values of Tg. The quantitative analysis of the microstructure of diene polymers containing phosphorus, which was carried out using the method of calculation in question, is in satisfactory agreement with results of NMR of alp spectroscopy.
IT IS now possible to calculate glass temperatures T~ of linear amorphous polymers and copolymers from the structure of the recurrent unit [1, 2]
Eg, logTg=_ ~_, _ + A ~A'~'~V~ ' * Vysokomol. soyed. A18: No. 6, 1413-1419, 1976.
(1)
1622
E.F.
GUBANOV et ~l,
where ~ K~ is an additive value of volumetric dimensions; ~A V~, the van der Waals volume of the recurrent unit; A - - a constant and NA--the Avogadro number. Use of the universal system proposed is particularly promising in those cases when for some reason it is dii~icult to determine Tg. This refers in particular to organo-phosphorus polymers which, in view of specific reaction conditions of chain transfer [3] are normally of low molecular weight and as a result, the limiting temperature of thermal stability of polymer homologues of a given structure, i.e. Tg cannot be determined. In order to use ratio (1) to calculate Tg of polymers containing phosphorus, the unknown increment K~ has to be found for the phosphorus atom. Other values of K~ may be taken from previous studies [1, 2]. The numerical value of K~ was obtained from equation (1) derived for several polymers containing phosphorus and copolymers with four coordinated phosphorus atoms in the side chain, the Tg values of which had previously been determined experimentally. In calculating Tg the average value of K~ used was 12-1. Volumetric increments ~ V~ needed for calculation of individual atoms and atomic groups by methods previously described [4], are shown in Table 1. Table 2 indicates experimental Tg values and Tg values calculated from ratio (1) for several polymers containing phosphorus and eopolymers synthesized by us and previously described [5] (polymers V and VI). Except for polymer IX, which will be dealt with later, the discrepancy between calculated and experimental values is not more than 5%. As an example we ~alculate ~ K~, ~A V~ and Tg for polymer V. The additive value of ~K~ contains increments of C, H, O, P atoms and increments of dipoledipole interaction K~, the number of which (3) is taken according to the rule that applies for vinyl derivatives [1]: K s -----18Kc-~ 19K~ ~-4Ko.4-Kp~-3K a =219.6. The molecular volume is easily found by the summation of volumetric increments of atoms and atomic groups ([1] in Table 1) AV~304.2 A3; N A ~ AV~=6.023 × 10~3× 304'2 × 10-24=183.2 cm3; log Tg--~219.6/183.2-~ 1-435~2.6337; Tgo,,o~430°K. The deviation from the experimental value of Tg is 7°. Results of calculations by a universal system, if analysed together with structural details of macromoleeules, enable some specific feature of organo-phosphorus polymers to be explained. Properties of organo-phosphorus polymers containing a polar-~P--~O-- group are largely determined by the environment of this group. It has been shown [6] that the carbony] group ~ C ~ O is excluded
Glass temperature
1623
of polymers containing phosphorus
TABLE 1. VOLUMETRIC INCREMENTS OF SOME ATOMS AND ATOMIC GROUPS Atom or atomic group C 1'34 r~ - - 1.1 1.54 i iC i
A V~, A a
Atom or atomic group
A Y~, A '
~1'81
C
9"25
18"85
P
c!.34F :-i:.6~-,~-] i~..
r~ I
~J~.gl. . . . J
N
C tl.54
15"3
18"2
P t_ . . . .
.'~1 "77
CI
/i.si
C |1.8i
20"4 L . . . . .
J
~:~.0_ ___ _ .J
O
1.61F~-I.~-~,] I r = v
L-~i:.sT--J
O
23"2
C P
11.s~
11-8o
23"4
r -T- EA~--- --1
oI.61, ~, -.~ o I
~-~'I.~E--'~
/
H
C
P
N
p.el
11-65
18"4
'
i l.~
23 "4
J
CI
N O
P
Ii.si
/ i-sl
17"3 ]'1.54
c i.sl FT-~-4~-'~, ,p = O i
C
O
P 11.81
C
11.8i
11"3
c 18~
-~
rI z-7.E,,-] r , = v I "fi:sr---
P
1"61 tm - - 1 , ,0 I
1"50 c
1...__ J
8"9 "~C
O
c 1.54f ~ ] i.~6 .J
P
c
|11-28
/
20"8
C
P
L._J
25"6
--'-~
rC t- J-t.~l C
C~ ~
23"2
14"3
1.61
j,--~
jO I
1.38
l__J
1.37 7 j ]
l s7 c
L't:l.Js
C
3"15 2"4
1"55
P
from molecular interaction if it is between aromatic nuclei. The role of the - ~ P = O group in molecular interaction is minimized in exactly the same way if it is between two hydroxyphenyl radicals. The calculated value of T~ in this case
1624
E.F.
GUBA~OV
e~ ~ .
i' I11 0 0 0
0 0
O
8 I i @ 0
II ~n r~
L
0
r
1
t
&
4
d .v..
=
I o
I o
=
=
o
o
0 09
L
N
o =~"
o =~"
=
I
I
¢
.
r? ~r..3 ~r,.J rj
rj
rj
I I
rD
r~
I
t
'
i,-I 1"-4
0
r.D
L J
I
r~
I I
I
] •
XlII
XII
XI
X
IX
VIII
VII
Polymer, No.
-,,//
....
P
/ - -
-CIl:--CII--
'i"" ,
[
[
CH~,--C 0 ii ,' CH-- Ih C, tt
I I
-).~-~o * ,
/ k
CI
O=C--NHCH~ -F(()C~Hp)a-lo.~t k ~ (11 I
--ClI..--~--
l-
o.~s
-
()=:=P(OC,H~L
.1o.09
I
II:-- 1
a .... O -P(OC21 I:,)2 {
l--[-cm-,i=c-c
I--[":"-'-?'-
CIt--P(OC:H~ a .... L
[-~:,,r?,-
0 ~ C -' - OCII-.--O O " (OC.~IH): J0.~. | L CII,--~; o,~ Pl il CH--P[N(C~H~) ]t
--CH:--C--
-~.~-~=~-~,,:_
/ | ~o~ / o=~(OC,H0~.:~o.:~ "/~ -,o., III -,.k
- L < " < O=C--- OCt-[aJo.4a iO=P(OC~II~)~iJo.sr
....
--CH.~--C=C--CH:-- / - - / - - C H , - - C H / -
Recurrent unit
73.1
177-0
110.7
166.0
128.9
124.85
128.1
ZK~ I
69.5
169"6
112-5
156.3
107-5
125.8
127.3
N.A" Z A Vf, c m 3
316
296
255
315
358
280
277
experimentM
307
300
262
314
430
268
276
cMculated
Tg ~ OK
to
o
o
E
¢b o
o
O
g
Q_
E.
t626
F. G U B A N O V et al.
considerably exceeds the experimental value (polymer IX, Table 2). However, in contrast to the carbonyl group, the phosphoryl group in the surrounding two phenyl radicals is not subject to steric hindrance (polymer V). This is confirmed b y results of an earlier study [7] and the Stuart-Brigleb models. The steric position of the groups mentioned takes the form 0
115°71!
0
(Y' 0 O,
0
0
In the structure of 1-phosphouisoprenc polymers (polymers I - I I I , Table 2) units may be contained as a result of the addition of the monomer in position 1,4 CH~
I --CH=,--CIt=:C--CH-I
O=PX~ a n d in position 3,4 --CH~--CII--
C 0 / %, 1I CH3 CH--PX~. (The absence of 1,2 structures from polymers was shown by IR spectroscopy [8]). To establish quantitatively the microstructure of polymers, we used .of alp spectroscopy which enables the position of phosphorus at the saturated, vinyl or allyl group to be distinguished according to chemical shifts of alp nuclei ~9]. Two signals are present in the spectrum of polymer I with a chemical shift gp~---16 p.p.m, which corresponds to the resonance of phosphorus nuclei in 1-alkenephosphonates and indicates 3,4-polymerization of the monomer and the signal 5 p = - - 2 5 p.p.m, corresponds to the resonance of alp nuclei in allyl phosphonates, which points to the presence of 1,4-structure in polymers. Two ,signals with ~p=--38 and --50 p.p.m, corresponding to similar structures of polymes I are also present in the spectrum of polymer II. A comparison of signal intensities shows that the contents of units with 3,4- and 1,4-structure of both polymers are 70 and 30%, respectively. In the spectrum of polymer I I I there is one signal with ~p=--24 p.p.m, which corresponds to the resonance of phosphorus nuclei in 1-alkene amide phosphonates. This indicates that 3,4-addition only takes place in this case. The absence of 1,4-structure is, apparently, due to steric hindrance of volumetric diethylamide groups. Copolymers of symmetrical 2fl-diphosphone butadienes (polymers VII-IX, Table 2) are formed by 1,4-addition [8, 10], which is indicated by an intense ~ignal with ~ p = - 14 p.p.m.
Glass temperature of polymers containing phosphorus
1627
The effect on molecular interaction of 1,4- and 3,4 chain fragments varies and this forms the basis for determining the microstructure of polydiene polymers from the Tg value [11]. The calculation of the content of each type of unit of organophosphorus diene polymers from experimental values of Tg using the increment obtained for the phosphorus atom Kp--12.1 showed satisfactory agreement with results of NMR spectroscopy of 3xp (Table 3). TABLE 3. MICROS~UCTURE OF POLYDIENES CONTAINING P H O S P H O R U S Ratio of 3,4- and 1,4- units Polymer I II III
according to Tg 73 : 27 73 : 27 100
I according to NMR of 31p 70 : 30 70 : 30 100
The system of calculation therefore ensures satisfactory accuracy in determining glass temperature and in some cases, the structure of organo-phosphorus polymers and copolymers containing phosphorus in the side chain and may also be used to calculate Tg of polymers containing tetraeoordinated phosphorus a t o m in the main chain. Polymers and eopolymers c o n t a i n ~ g phosphorus were obtained by radical p01ymorization in bulk or solution [8, 10]. The polymers were purified b y triple reprecipitation from solution in benzene or acetone in diethyl other and dried in v a c u u m to constant weight. T , was determined from temperature/deformation curves. NI~IR spectra of ~lp in the form o f concentrated polymer solutions were obtained in a NMR KGU-4 spectrometer in relation to a 85% solution of I-I3PO, at an operating frequency of 10.2 Mc/s. The authors are grateful to A. A. Askadskii for his advice and discussion.
Translated by E. SEMEHV, REFERENCES 1. A. A. ASKADSKII and G. L. SLONIMSKII, Vysokomol. soyed. AI3: 1917, 1971 (Translated in Polymer Sci. U.S.S.R. 13: 8, 2158, 1971) 2. G. L. SLONIMSKII and A. A. ASKADSKII, Mekhanika polimerov 4 7 : 1 9 7 5 3. B. Ye. IVANOV, Ya. A. LEV1N a n d S. V. ZHULYNDIN, Sb. Problemy organicheskoi i fizicheskoi khimii (Problems of Organic Chemistry). Kazan, 1971 4. G. L. SLONIMSKII, A. A. ASKADSKII and A. I. KITAIGORODSKII, Vysokomol. soyed. A12: 494, 1970 (Translated in Polymer Sei. U.S.S.R. 12: 3, 556, 1970) 5. Yu. N. KARGIN, A. N. SMIRNOV and A. P. KHARDIN, Tr. Volgogradskogo politekhn. in-ta, F u n k t s i o n a l ' n y y e organieheskiye soyedineniya i polimery (Functional Organic Compounds and Polymers). Volgograd, 1973 6. A. A. KUL'KOV, S. N. SALAZKIN, G. L. SLONIMSKII, A. A. ASKADSKII, K. A. BYCttKO, S. V. VINOGRADOVA and ¥. V. KORSttAK, Vysokomol. soyed. A16: 1543, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 7, 1787, 1974) 7. L. S. KI-IAIKIN a n d L. V. VILKOV, Uspekhi khimii 40: 2174, 1971 8. S. V. SHULYNDIN, N. Kh. BORISOVA, E. F. GUBANOV and B. Ye. IVANOV, Vysokotool. soyod. B17: 752, 1975 (Not translated in Polymer Sci. U.S.S.R.)
1628
I. L. STOYACHENKO et a~.
9. V. MARK, C. H. DUNGAN, M. CRUTCHFIELD and J. R. VAN WASER, Topics Phosphor. Chem. 5: 227, 1967 10. S. V. SHULYNDIN, V. Sh. GURSKAYA, M. K. IL'INA, V. A. BYL'YEV, Ye. F. GUBANOV and B. Ye. IVANOV, Vysokomol. soyed. A16: 992, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 6, 1146, 1974) t 11. A. P. SUPRUN, I. I. VOINTSEVA, T. A. SOBOLEVA, A. S. SHASHKOV, A. A. ASKADSl~II a n d G. L. SLONIMSKII~ Vysokomol. soyed. A16: 1106, 1974 (Translated in P o l y m e r Sci. U.S.S.R. 16: 5, 1280, 1974)
MECHANISM OF ALTERNATING COPOLYMERIZATION OF SULPHUR DIOXIDE WITH DONOR MONOMERS* I. L. STOYACHENKO,YE. I. SHKLYXROVA,A. Y[. KAPLA~, V. B. GOLUBEV, V. P. ZUBOVand V. A. KABA~OV M. V. Lomonosov State University, Moscow I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences
(Received 5 May 1974) A s t u d y was made of. copolymerization of d i m e t h y l b u t a d i e n e a n d vinyl acetate w i t h sulphur dioxide, in order to examine the mechanism of formation of alternating copolymers, which remains debatable up to the present time. Polymerization was carried out b y slowly heating a frozen glassy monomer m i x t u r e exposed to ~ and U V radiation a t --196% The t e m p e r a t u r e ranges of post-polymerization taking place under these conditions were determined colorimetrieally. A s t u d y was also made of low t e m p e r a t u r e post-polymerization of these systems in the presence of quinones-- inhibitors of radical reactions. Copolymer yield and the overall thermal effect of copolymerization decreases with an increase in inhibitor content in the initial mixture. A signal in E P R spectra of samples during softening at given temperatures is interp r e t e d as a signal corresponding to the product of addition of a quinone molecule to an active radical. I t is concluded from these results t h a t radical copolymerization takes place in these systems. I t was shown t h a t copolymerizatiou of SOj and d i m e t h y l b u t a diene and, apparently, SOs a n d vinyl acetate takes place b y a mechanism of addition of b i n a r y monomer complexes to the end of a growing chain.
COPOLYMERIZATIONresulting in products with accurate alternation of monomer units has specific properties, which differ noticeably from those of conventional statistical copolymerization. In spite of extensive studies in this direction, the mechanism of alternating copolymerization remains up to the present time open to discussion. Although the fact that donor-accepter interactions between reacting particles are of decisive significance, it is beyond any doubt that there are two extreme points of view concerning the mechanism of chain extension. * Vysokomol. soyed. A18: No. 6, 1420-1427, 1976.
162I
4. N. GRASSI, K h i m i y a protsessov destruktsii polimerov (Chemistry of Polymer Degradation). Izd. inostr, lit., 1959 5. E. BEER, (Ed.), K o n s t r u k t s i o n n y y e svoistva plastmass (Structural Properties of Plastics). Izd. " K h i m i y a " . 1967 6. J. B. YANNAS a n d A. V. TOBOLSKY, Europ. Polymer J. 4: 257, 1968 7. F. PAULIK, J. PAULIK a n d L. ERDEY, Z. analyt. Chem. 160: 241, 1959 8. J. PAULIK, H. MACSKASY, F. PAULIK and L. ERDEY, Plaste u n d Kautschuk 8: 588, 1961 9. J. B. YANNAS and A. V. TOBOLSKY, Nature 215: 509, 1967 10. I. F. KAIMIN', Plast. massy, No. 9, 62, 1966 11. T. KUBO and T. ADZUMI, Nippon nogei kagaku kaisi 39: 495, 1965 12. L. P. WITNAUER and A. WISNEWSKI, J. Amer. Leather Chem. Assoc. 59: 598, 1964 13. G. I. BURDYGINA, P. V. KOZLOV and V. A. KARGIN, Vysokomol. soyed. A14: 383, 1972 (Translated in Polymer Sci. U.S.S.R. 14: 2, 429, 1972) 14. J, B. YANNAS and A. V. TOBOLSKY, J. Maeromolec. Chem. 1: 723, 1966 15. B. A. DOLGOPLOSK, B. L. YERUSALIMSKII, Ye. B. MILOVSKAYA and G. P. BELONOVSKAYA, Dokl. AN SSSR 120: 783, 1958 16. Ye. N. KROPACHEVA, B. A. DOLGOPLOSK, V. F. OTTEN and K. G. GOLODOVA, Zh. organ, khim. 29: 1853, 1959 17. B. A. DOLGOPLOSK and Ye. I. TINYAKOVA, Khim. prom-st', No. 11, 52, 1961 18. N. GRASSIE and H. W. MELVILLE, Prec. Roy. Soc. A199: 14, 1949 19. Zh. F. MOTENEVA, T. I. BURDYGINA, I. M. FRIDMAN and V. P. KOZLOV, Vysokomol. soyed. A16: 1113, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 5, 1288, 1974) 20. V. V. DEREVYANKO, A. G. VASHAKIDZE, V. V. MAL'TSEV and B. A. GROMOV, Plast. massy, No. 3, 58, 1975
CALCULATING GLASS TEMPERATURES OF POLYMERS CONTAINING PHOSPHORUS* E. F. GUBANOV, S. V. SHULYNDIN,N. KH. BORISOVA and B. M. ZUYEV A. Ye. Arbuzov Institute of Organic a n d Physical Chemistry, U.S.S.R. Academy of Sciences
(Received 22 December 1975) A universal system is used for calculating the glass temperatures T I of organophosphorus polymers. Satisfactory agreement was found between experimental a n d calculated values of Tg. The quantitative analysis of the microstructure of diene polymers containing phosphorus, which was carried out using the method of calculation in question, is in satisfactory agreement with results of NMR of alp spectroscopy.
IT IS now possible to calculate glass temperatures T~ of linear amorphous polymers and copolymers from the structure of the recurrent unit [1, 2]
Eg, logTg=_ ~_, _ + A ~A'~'~V~ ' * Vysokomol. soyed. A18: No. 6, 1413-1419, 1976.
(1)
1622
E.F.
GUBANOV et ~l,
where ~ K~ is an additive value of volumetric dimensions; ~A V~, the van der Waals volume of the recurrent unit; A - - a constant and NA--the Avogadro number. Use of the universal system proposed is particularly promising in those cases when for some reason it is dii~icult to determine Tg. This refers in particular to organo-phosphorus polymers which, in view of specific reaction conditions of chain transfer [3] are normally of low molecular weight and as a result, the limiting temperature of thermal stability of polymer homologues of a given structure, i.e. Tg cannot be determined. In order to use ratio (1) to calculate Tg of polymers containing phosphorus, the unknown increment K~ has to be found for the phosphorus atom. Other values of K~ may be taken from previous studies [1, 2]. The numerical value of K~ was obtained from equation (1) derived for several polymers containing phosphorus and copolymers with four coordinated phosphorus atoms in the side chain, the Tg values of which had previously been determined experimentally. In calculating Tg the average value of K~ used was 12-1. Volumetric increments ~ V~ needed for calculation of individual atoms and atomic groups by methods previously described [4], are shown in Table 1. Table 2 indicates experimental Tg values and Tg values calculated from ratio (1) for several polymers containing phosphorus and eopolymers synthesized by us and previously described [5] (polymers V and VI). Except for polymer IX, which will be dealt with later, the discrepancy between calculated and experimental values is not more than 5%. As an example we ~alculate ~ K~, ~A V~ and Tg for polymer V. The additive value of ~K~ contains increments of C, H, O, P atoms and increments of dipoledipole interaction K~, the number of which (3) is taken according to the rule that applies for vinyl derivatives [1]: K s -----18Kc-~ 19K~ ~-4Ko.4-Kp~-3K a =219.6. The molecular volume is easily found by the summation of volumetric increments of atoms and atomic groups ([1] in Table 1) AV~304.2 A3; N A ~ AV~=6.023 × 10~3× 304'2 × 10-24=183.2 cm3; log Tg--~219.6/183.2-~ 1-435~2.6337; Tgo,,o~430°K. The deviation from the experimental value of Tg is 7°. Results of calculations by a universal system, if analysed together with structural details of macromoleeules, enable some specific feature of organo-phosphorus polymers to be explained. Properties of organo-phosphorus polymers containing a polar-~P--~O-- group are largely determined by the environment of this group. It has been shown [6] that the carbony] group ~ C ~ O is excluded
Glass temperature
1623
of polymers containing phosphorus
TABLE 1. VOLUMETRIC INCREMENTS OF SOME ATOMS AND ATOMIC GROUPS Atom or atomic group C 1'34 r~ - - 1.1 1.54 i iC i
A V~, A a
Atom or atomic group
A Y~, A '
~1'81
C
9"25
18"85
P
c!.34F :-i:.6~-,~-] i~..
r~ I
~J~.gl. . . . J
N
C tl.54
15"3
18"2
P t_ . . . .
.'~1 "77
CI
/i.si
C |1.8i
20"4 L . . . . .
J
~:~.0_ ___ _ .J
O
1.61F~-I.~-~,] I r = v
L-~i:.sT--J
O
23"2
C P
11.s~
11-8o
23"4
r -T- EA~--- --1
oI.61, ~, -.~ o I
~-~'I.~E--'~
/
H
C
P
N
p.el
11-65
18"4
'
i l.~
23 "4
J
CI
N O
P
Ii.si
/ i-sl
17"3 ]'1.54
c i.sl FT-~-4~-'~, ,p = O i
C
O
P 11.81
C
11.8i
11"3
c 18~
-~
rI z-7.E,,-] r , = v I "fi:sr---
P
1"61 tm - - 1 , ,0 I
1"50 c
1...__ J
8"9 "~C
O
c 1.54f ~ ] i.~6 .J
P
c
|11-28
/
20"8
C
P
L._J
25"6
--'-~
rC t- J-t.~l C
C~ ~
23"2
14"3
1.61
j,--~
jO I
1.38
l__J
1.37 7 j ]
l s7 c
L't:l.Js
C
3"15 2"4
1"55
P
from molecular interaction if it is between aromatic nuclei. The role of the - ~ P = O group in molecular interaction is minimized in exactly the same way if it is between two hydroxyphenyl radicals. The calculated value of T~ in this case
1624
E.F.
GUBA~OV
e~ ~ .
i' I11 0 0 0
0 0
O
8 I i @ 0
II ~n r~
L
0
r
1
t
&
4
d .v..
=
I o
I o
=
=
o
o
0 09
L
N
o =~"
o =~"
=
I
I
¢
.
r? ~r..3 ~r,.J rj
rj
rj
I I
rD
r~
I
t
'
i,-I 1"-4
0
r.D
L J
I
r~
I I
I
] •
XlII
XII
XI
X
IX
VIII
VII
Polymer, No.
-,,//
....
P
/ - -
-CIl:--CII--
'i"" ,
[
[
CH~,--C 0 ii ,' CH-- Ih C, tt
I I
-).~-~o * ,
/ k
CI
O=C--NHCH~ -F(()C~Hp)a-lo.~t k ~ (11 I
--ClI..--~--
l-
o.~s
-
()=:=P(OC,H~L
.1o.09
I
II:-- 1
a .... O -P(OC21 I:,)2 {
l--[-cm-,i=c-c
I--[":"-'-?'-
CIt--P(OC:H~ a .... L
[-~:,,r?,-
0 ~ C -' - OCII-.--O O " (OC.~IH): J0.~. | L CII,--~; o,~ Pl il CH--P[N(C~H~) ]t
--CH:--C--
-~.~-~=~-~,,:_
/ | ~o~ / o=~(OC,H0~.:~o.:~ "/~ -,o., III -,.k
- L < " < O=C--- OCt-[aJo.4a iO=P(OC~II~)~iJo.sr
....
--CH.~--C=C--CH:-- / - - / - - C H , - - C H / -
Recurrent unit
73.1
177-0
110.7
166.0
128.9
124.85
128.1
ZK~ I
69.5
169"6
112-5
156.3
107-5
125.8
127.3
N.A" Z A Vf, c m 3
316
296
255
315
358
280
277
experimentM
307
300
262
314
430
268
276
cMculated
Tg ~ OK
to
o
o
E
¢b o
o
O
g
Q_
E.
t626
F. G U B A N O V et al.
considerably exceeds the experimental value (polymer IX, Table 2). However, in contrast to the carbonyl group, the phosphoryl group in the surrounding two phenyl radicals is not subject to steric hindrance (polymer V). This is confirmed b y results of an earlier study [7] and the Stuart-Brigleb models. The steric position of the groups mentioned takes the form 0
115°71!
0
(Y' 0 O,
0
0
In the structure of 1-phosphouisoprenc polymers (polymers I - I I I , Table 2) units may be contained as a result of the addition of the monomer in position 1,4 CH~
I --CH=,--CIt=:C--CH-I
O=PX~ a n d in position 3,4 --CH~--CII--
C 0 / %, 1I CH3 CH--PX~. (The absence of 1,2 structures from polymers was shown by IR spectroscopy [8]). To establish quantitatively the microstructure of polymers, we used .of alp spectroscopy which enables the position of phosphorus at the saturated, vinyl or allyl group to be distinguished according to chemical shifts of alp nuclei ~9]. Two signals are present in the spectrum of polymer I with a chemical shift gp~---16 p.p.m, which corresponds to the resonance of phosphorus nuclei in 1-alkenephosphonates and indicates 3,4-polymerization of the monomer and the signal 5 p = - - 2 5 p.p.m, corresponds to the resonance of alp nuclei in allyl phosphonates, which points to the presence of 1,4-structure in polymers. Two ,signals with ~p=--38 and --50 p.p.m, corresponding to similar structures of polymes I are also present in the spectrum of polymer II. A comparison of signal intensities shows that the contents of units with 3,4- and 1,4-structure of both polymers are 70 and 30%, respectively. In the spectrum of polymer I I I there is one signal with ~p=--24 p.p.m, which corresponds to the resonance of phosphorus nuclei in 1-alkene amide phosphonates. This indicates that 3,4-addition only takes place in this case. The absence of 1,4-structure is, apparently, due to steric hindrance of volumetric diethylamide groups. Copolymers of symmetrical 2fl-diphosphone butadienes (polymers VII-IX, Table 2) are formed by 1,4-addition [8, 10], which is indicated by an intense ~ignal with ~ p = - 14 p.p.m.
Glass temperature of polymers containing phosphorus
1627
The effect on molecular interaction of 1,4- and 3,4 chain fragments varies and this forms the basis for determining the microstructure of polydiene polymers from the Tg value [11]. The calculation of the content of each type of unit of organophosphorus diene polymers from experimental values of Tg using the increment obtained for the phosphorus atom Kp--12.1 showed satisfactory agreement with results of NMR spectroscopy of 3xp (Table 3). TABLE 3. MICROS~UCTURE OF POLYDIENES CONTAINING P H O S P H O R U S Ratio of 3,4- and 1,4- units Polymer I II III
according to Tg 73 : 27 73 : 27 100
I according to NMR of 31p 70 : 30 70 : 30 100
The system of calculation therefore ensures satisfactory accuracy in determining glass temperature and in some cases, the structure of organo-phosphorus polymers and copolymers containing phosphorus in the side chain and may also be used to calculate Tg of polymers containing tetraeoordinated phosphorus a t o m in the main chain. Polymers and eopolymers c o n t a i n ~ g phosphorus were obtained by radical p01ymorization in bulk or solution [8, 10]. The polymers were purified b y triple reprecipitation from solution in benzene or acetone in diethyl other and dried in v a c u u m to constant weight. T , was determined from temperature/deformation curves. NI~IR spectra of ~lp in the form o f concentrated polymer solutions were obtained in a NMR KGU-4 spectrometer in relation to a 85% solution of I-I3PO, at an operating frequency of 10.2 Mc/s. The authors are grateful to A. A. Askadskii for his advice and discussion.
Translated by E. SEMEHV, REFERENCES 1. A. A. ASKADSKII and G. L. SLONIMSKII, Vysokomol. soyed. AI3: 1917, 1971 (Translated in Polymer Sci. U.S.S.R. 13: 8, 2158, 1971) 2. G. L. SLONIMSKII and A. A. ASKADSKII, Mekhanika polimerov 4 7 : 1 9 7 5 3. B. Ye. IVANOV, Ya. A. LEV1N a n d S. V. ZHULYNDIN, Sb. Problemy organicheskoi i fizicheskoi khimii (Problems of Organic Chemistry). Kazan, 1971 4. G. L. SLONIMSKII, A. A. ASKADSKII and A. I. KITAIGORODSKII, Vysokomol. soyed. A12: 494, 1970 (Translated in Polymer Sei. U.S.S.R. 12: 3, 556, 1970) 5. Yu. N. KARGIN, A. N. SMIRNOV and A. P. KHARDIN, Tr. Volgogradskogo politekhn. in-ta, F u n k t s i o n a l ' n y y e organieheskiye soyedineniya i polimery (Functional Organic Compounds and Polymers). Volgograd, 1973 6. A. A. KUL'KOV, S. N. SALAZKIN, G. L. SLONIMSKII, A. A. ASKADSKII, K. A. BYCttKO, S. V. VINOGRADOVA and ¥. V. KORSttAK, Vysokomol. soyed. A16: 1543, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 7, 1787, 1974) 7. L. S. KI-IAIKIN a n d L. V. VILKOV, Uspekhi khimii 40: 2174, 1971 8. S. V. SHULYNDIN, N. Kh. BORISOVA, E. F. GUBANOV and B. Ye. IVANOV, Vysokotool. soyod. B17: 752, 1975 (Not translated in Polymer Sci. U.S.S.R.)
1628
I. L. STOYACHENKO et a~.
9. V. MARK, C. H. DUNGAN, M. CRUTCHFIELD and J. R. VAN WASER, Topics Phosphor. Chem. 5: 227, 1967 10. S. V. SHULYNDIN, V. Sh. GURSKAYA, M. K. IL'INA, V. A. BYL'YEV, Ye. F. GUBANOV and B. Ye. IVANOV, Vysokomol. soyed. A16: 992, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 6, 1146, 1974) t 11. A. P. SUPRUN, I. I. VOINTSEVA, T. A. SOBOLEVA, A. S. SHASHKOV, A. A. ASKADSl~II a n d G. L. SLONIMSKII~ Vysokomol. soyed. A16: 1106, 1974 (Translated in P o l y m e r Sci. U.S.S.R. 16: 5, 1280, 1974)
MECHANISM OF ALTERNATING COPOLYMERIZATION OF SULPHUR DIOXIDE WITH DONOR MONOMERS* I. L. STOYACHENKO,YE. I. SHKLYXROVA,A. Y[. KAPLA~, V. B. GOLUBEV, V. P. ZUBOVand V. A. KABA~OV M. V. Lomonosov State University, Moscow I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences
(Received 5 May 1974) A s t u d y was made of. copolymerization of d i m e t h y l b u t a d i e n e a n d vinyl acetate w i t h sulphur dioxide, in order to examine the mechanism of formation of alternating copolymers, which remains debatable up to the present time. Polymerization was carried out b y slowly heating a frozen glassy monomer m i x t u r e exposed to ~ and U V radiation a t --196% The t e m p e r a t u r e ranges of post-polymerization taking place under these conditions were determined colorimetrieally. A s t u d y was also made of low t e m p e r a t u r e post-polymerization of these systems in the presence of quinones-- inhibitors of radical reactions. Copolymer yield and the overall thermal effect of copolymerization decreases with an increase in inhibitor content in the initial mixture. A signal in E P R spectra of samples during softening at given temperatures is interp r e t e d as a signal corresponding to the product of addition of a quinone molecule to an active radical. I t is concluded from these results t h a t radical copolymerization takes place in these systems. I t was shown t h a t copolymerizatiou of SOj and d i m e t h y l b u t a diene and, apparently, SOs a n d vinyl acetate takes place b y a mechanism of addition of b i n a r y monomer complexes to the end of a growing chain.
COPOLYMERIZATIONresulting in products with accurate alternation of monomer units has specific properties, which differ noticeably from those of conventional statistical copolymerization. In spite of extensive studies in this direction, the mechanism of alternating copolymerization remains up to the present time open to discussion. Although the fact that donor-accepter interactions between reacting particles are of decisive significance, it is beyond any doubt that there are two extreme points of view concerning the mechanism of chain extension. * Vysokomol. soyed. A18: No. 6, 1420-1427, 1976.