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1H and 13C NMR analysis of the synthesis of polyarylene sulphonoxides based on diphenylolpropane and dichlorodiphenylsulphone
IH and lsC NMR analysis of synthesis of Imlyarylene sulphonoxides
1183
ItH|ltEl~a~ I. Yu. A. M][IEHEYEV, L. N. GUSEVA, L. S. ROGOVA and D. Ya. TOFI'Y@IN, Vysokomol. soyed. 28: 386, 1981 (Translated in Polymer Sci. U.S.S.R. 28: 2, 431, 1981) 2. L. S. ROGOVA, L. N. GUSEVA, Yu. A. Mi3KHEYEV and D. Ya. TOPTYGIN, Vysokomol. soyed. A21: 1373, 1979 (Translated in Polymer Sci. U.S.S.R. 21: 6, 1508, 1979i 3. L. B. GAVRILOV, Ye. M. ZVONKOVA, Yu. A. MIKHEYEV, D. Ya. TOPTYGIN and M. L. KERBER, Vysokomol. soyed. 23: 1552, 1981 (Translated in Polymer Sci. U.S.S.R. 23: 7, 1715, 1981) 4. V. R. REGEL, A. I. SLUTSKER and E. Ye. TOMASHEVSKII, Kineticheskaya priroda prochnosti tverdykh tel (Kinetic l~ature of the Strength of Solid Bodies) pp. 501, 514, Nauka, 197~ 5. M. P. VERSHININA, V. R. REGEL and N. N. CHERNYI, Vysokomol. soyed. 6: 1450, 1964 (Translated in Polymer Sci. U.S.S.R. 6: 8, 1606, 1964) 6. G. V. VINOGRADOV and D. Ya. MALKIN, Reologiya polimerov (Polymer Rheology). p. 279, Khimiya, Moscow, 1977 7. V. A. KABANOV, Dokl. Akad. Iqauk SSSR 195: No. 2, 402 1970
PolymerScienceU.S.S.R.Vol. 24, lqo. 5, pp. 1183-119~, 1982 Printed in Poland
0032-3950]82/051183-12$07.50/0 © 1983 Pergamon Press Ltd.
1H AND 13C NMR ANALYSIS OF T ~ SYNTHESIS OF POLYARYLENE SULPHONOXIDES BASED ON DIPHENYLOLPROPANE AND DICHLORODIPHENYLSULPHONE * A. K ~ . BULAI, YA. G. URMAN, I. YA. SLONIM, L. M. BOLOTINA, L. YE, REITBURD, M. M. GOL'DER, A. 1~. SHAPOVALOVA a n d R. N. SIVAKOVA ',Plastmassy" Scientific & Industrial Resoareh Association
(Received 12 January 1981) The method of ~H and lsC NMR analysis has been used to investigate reaction mixtures formed in the synthesis of oligoarylene sulphonoxides from the sodium salt of diphenylolpropane and diehlorodiphenylsulphone. A quantitative study was carried out to determine the amount of different endgroups and of monomerie and "dimeric" products formed at some stages in the synthesis. Number-average molecular weights were determined for oligoarylene sulphonoxides in the reaction mixture.
A D E T A I L E D investigation of the synthesis of polyarylene sulphonoxides is called for as a necessary conditions in achieving maximum efficiency in the commercial production of these polymers. * Vysokomol. soyed. A$4: No. 5, 1047-1056, 1982.
1184
A. K~. BULaI eta/.
Existing methods of chemical and spectroscopic analysis of the synthesis of polysulphones provide no means of estimating the amounts of different endgroups in the chain, and, in particular, cannot be used to solve the important problem of determining concentrations of monomers, dimers and n-mers in reaction systems. Such data must be available before a kinetic description of the synthesis can be attempted. This paper relates to our use of the 1H and 13C NMR as a means of resolving these problems. The study objects were oligoarylene sulphonoxides (OAS) prepared by a reaction of nucleophilic substitution under homogeneous conditions: to a solution of sodium salt of diphenylolprepano (P) in ]:)MSO, heated to the synthesis temperature (120 °) was added a solution dichlorodiphenylsulphone (D) in DMSO. Samples wore collected at the start of the process (after 1-2 rain) and at the end (after 15-20 min); the reaction was terminated b y decanting the latter into a solution of HC1 in DMSO (whereupon phenols were formed from the sodium salts). The mixtures containing the starting compounds and the condensation products of the general formula arts
L
"
~
I
C]-]s
(,, ~
- -
- -
J"
CH8 where B'--H-, CH3 were extracted with chloroform (to remove NaCI) and precipitated with isopropyl alcohol from solution in chloroform. The 1H (90 MHz) and 13C (22.63 MHz) NMR spectra of the oligoarylene sulphonoxides were recorded on a Brucker WH-90 type spectrometer, using a Fourier transformation method. Methylene chlorlde-dl was used as a solvent and hexamethyldisiloxane, whoso chemical shift was p u t at 2.4 p.p.m., was the internal standard. To assign signals in the 1H and lsC NMR spectra of the oligoarylene sulphonoxides we took the proton and carbon spectra of the monomeric products (P and D) a n d of primary products of the interaction of P with D - - t h e "dimer" (I, n----1, R ' ~ - H ; R"----CI) and "trimer" (I, n-~ 1, R'~-C1CsH,SO2CeH,--; R"=C1) and likewise of the model compound
.o-O-=o,-O_o_ 0 The "dimer" a n d "trlmer" were synthesized as follows. I n t o a glass thermostatted reactor fitted with a stirrer were placed 11.42 g of P, 2 g of sodium hydroxide (3.55 m] of a 56~o aqueous solution) and 150 ml of DMSO. Under a 532 P a vacuum a t 54° were distilled off 40 ml of DMSO which contained 2.45 g of water (Fischer), which is equal to the theoretical a m o u n t that ought to be evolved in the formation of monosodium salt P and to the a m o u n t of water introduced along with the sodium hydroxide solution. Next, ! 1.36 g of D were placed in the reactor, the reaction system was heated for 15 hr at 75-80 ° in a nitrogen atmosphere (a specially pure grade of N). The reaction products were decanted into water. F r o m a n alkali solution were filtered the unrea~ted D and a large part of the primary product of inter-
1H and x3C NMR analysis of synthesis of polyarylene sulphonoxides
1185
action of P with D. After acidification of the filtrate the unreacted P separated out, along ~xdth a small a m o u n t of the reaction product. The reaction products were fractionated on a chromatographic column (column diameter 15 ram, height 68 ram) filled with silica gel L 40/100 (Czechoslovakia). Chloroform was used as a n eluent. The "dimor" (m.p. 135-138 °) and "trimer" (re.l). 166--168.9 °) were separated.
The 13C N M R spectra of the OAS. For convenience let us consider separately the signal areas of C atoms of the residue of D (Fig. 1) and that of P (Fig. 2). Signal assignment for the OAS spectrum (see Tables 1 and 2) was carried out by using the spectra of the monomers, and of high molecular polysulphone [1] and of the model compounds ("dimer" and "trimer"), as well analysing changes in ~he carbon spectra of the reaction mixtures obtained at various stages in the synthesis. The 13C NMR chemical shifts of aromatic carbon atoms in residues of P and D in the polycondensation products be described by the additive scheme
X
,-- (X:=C(CI-Ia)~ or SO~) can
M ~OMO -yzJ M=-i- ~M=' -~/-JM#-i-/AM#,
where M~-P, D; i ~ 1 - 4 (position of the carbon atom in the aromatic ring);
cl m
t,,
1o6.2 IJ5"8 135.6 l,.~.J 135"0
•
b
d C
e
IM'2
163.0
162"8
lql.5
h
lql.O
lqO.~" ~,,Fp.m.
FIe. 1. Signals of dichlorodiphenylsulphone (D) residue in tile a*C NMR spectrum of t h e oligoarylene sulphonoxide based on diphenylolpropane a n d D. Solution in methylene-chloride-d2. Reaction time 10 rain. Xumber of accumulations 32,000.
1186
A, K~, Bur-~1 e~ ~.
~
~1~.~ ~~
1
u~
e
~
.
~H and ~sC NMR analysis of s~ynthesis of polyarylene sulphonoxides
i 0
I ~q
o 0
P~
~P
0
0
~
~
1187
1188
A. KH. B ~
et al.
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, i i ~ , . . i , - , , i , i i ~ - i , ~ , ~ , i i
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q-I and 13CNMR analysis of synthesis of polyarylenc sulphonoxides
1189
$~o~-- chemical shifts of carbon atoms in monomers; a, fl are increments for OH or C1 group substitution by D or P units on the part of an aromatic ring whose carbon atoms are numbered; a', fl' are increments for OH or C1 group substitution by D or P units on the part o f an aromatic ring whose carbon atoms have n o t been numbered.* Tim chemical shift of a bridge carbon atom $(a) in a P residue likewise obeys the additivity rule; ~(5) in a P_D sequence is equal to a middle value between $(5) in free P and 5(s) in a DPD sequence. The increments calculated by least squares using a computer are given in Table 3; the chemical shifts of aromatic carbon atoms in residues of D and P, calculated on the basis of increments a, ~' and fl, fl' are given in Tables 1 and 2 respectively. An analysis of the data in Tables 1 and 2 shows t h a t calculated values of $cal are in good agreement with 5~xp, which supports the tabulated assignments. I t should be noted t h a t for all the C atoms in the P residue and in the D residue there is only one value of 5cal corresponding to one 5exp. The exception is carbon a.tom C-3 in the P residue: here there are two calculated chemical shifts (&al -----118"32 and 118.44 p.p.m) corresponding to one signal o (~exp~llS"40 p.p.m). This is because in the ~sC NMR spectrum of the OAS an overlap of C-3 signals occurs in sequences P D and DPD; a widening of signal o, and in some spectra a splitting of the signal can be seen. T A B L E 3. 1)A-RAMETERS OF T H E A D D I T I V E SCHEME FOR CALCU:LATII~G 1He CHEMICAL SHIFTS OF AROMATIC CARBON ATOMS I1~ R E S I D U E S OF P A!~D
Monomer residues P
D
Increments (see oqn. (1))
Carbon atom C-1 C-2 C-3 C-4 C-1 C-2 C-3 C-4
D MOal~
p,
square error
+ 5"93 ÷0.78 ~- 2"83 -- 2-02 --5-55 --0.61
--9.60 +22-70
--0.88 0 ÷0.12 -~ 0.30
+0.12 0 0 +0.10
--0.78 4- 0"42 -~0-30 --0.31
+0.16 0 0 --0-11
0 0 0 0 --
0.003 0 0 0
o"
0"05 0 0"17 0"007 0-32 0.38
0"23 0"10
I n P and in the "dimer" it was found t h a t for the carbon atom adjoiuiug the OH group (C-4) there is a discrepancy between chemical shifts in the 0AS spectrum and in the spectra of the individual compounds (a discrepancy amounting to 0.16 p.p.m, for P and 0.41 p.p.m, for the "dimer"). This is probably due to the influence of the concentration and p i t of the medium on the chemical ahift of C-4, and so care is needed when using the spectra of model compounds for signal assignment in 0AS spectra. * Example: P D P D P.
1190
A. I ~ . Buz~AI eta/.
It was found that signals of quaternary aromatic carbon atoms of the P residue (C-l, C-4, see Table 2) and the D residue (C-4, see Table 1) are split into six peaks; the signal of the C atom adjoining the sulpho group was found to be the most sensitive (as in the case of the blended polyarylene sulphonoxide in [1]) to the influence of oligomer chain structure, and is split into eight peaks (see Table 1). Thus it appears that chemical shifts of quaternary aromatic carbon atoms are influenced not only by the adjacent unit, but also by the preadjacent one. The a3C NMR spectra are an excellent source of information, and provide a basis for a quantitative analysis of reactio~ systems. The number of free, terminal and central units of P (per P residue) may be determined from ratios of the peak areas: St, Ss and Sr (C-5 signal); S~, ZSa,y, e and ZSc,~ (C-4 signal); S~; ~Sg,~,z and ZS~,j (C-1 signal); S~; S# and S O (C-3 signal) (see Fig. 2 and Table 2). Similarly, the number of free, terminal and central units of D (per D residue) was calculated by using the peak areas: Sg, ZSa,~,~ and ZSc, d (C-4 signal); SI; ZSe, m,~ and ZS~,j,~,I (C-1 signal) (see Fig. 1, Table 1). In addition, the spectrum may be used to determine the "dimer" concentration in the reaction mixture: to do so, we use peak areas Sa (C-4 signal) and S~ (C-1 signal) in sequence D P (see Fig. 1, Table 1); S! (C-4 signal) and S¢ (C-1 signal) in sequence P D (see Fig. 2, Table 2). It must be said that in all calculations signal areas were compared for monotype carbon atoms only; in this way one may avoid errors due to differing relaxation, and to signal intensification due to an Overhauser effect. Some of the above data on the composition of the reaction mixture can also be obtained from the ~H NMR spectra. ~H N M R spectra of the OAS. The proton spectrum is shown in Fig. 3. Signal assignments may be carried out (Tables 4 and 5) by comparing the latter with the spectra of the high molecular polysulphone and the free P and D and with the aH NMR spectra of reaction mixtures obtained at the start and the end of processes. The data in Tables 4 and 5 show that the ~H NMR spectra also provide a good deal of information. The latter spectra enable us to determine the number o~ffree, terminal and central units of P from the ratio of signal areas S~, Sy and Sz (H-5 signal); ZSu, w ZSt, w (H-4 signal) and ZSa, ~ (H-3' signal); ZSe, ~ (H-3 signal) (see Fig. 3, Table 5), and likewise the number of free, terminal and central units of D from the ratio of the signal areas ZSc, e (H-2 signals); ZS4,I (H-2 signal) aud ZSa, b (H-1 signal) (see Fig. 3, Table 4). However, while it is true that aH NMR is more sensitive than the ~8C NMR, calculations based on signals of aromatic protons a-w are eoml~lieated by the overlap of AA'BB' quadruplets. OAS characteristics. Knowig the number of terminal and central P units (per P residue) and the number of terminal and central D units (per D residue), without counting the free P and D or the molar ratio of P : D in the OAS (R),
~H and ~sC NMR analysis of synthesis of polyaryleno sulphonoxides 0
119~
¢,11
o 0
o
~
0
g~Ze
I 0
0
o
N
o
N W 0 N
0 N N
0 ¢g
r~ r~
4 N o
1192
A. K m
B ~
et ~.
~0
Q
0
©
~D
!0 Q
1H and 13CNMR analysis of synthesis ofpolyarylenc sulphonoxides
1193
we obtain the number-average MW of the oligomers from the formula * l]~oAs----2 2 7 . n ~ 210.np-~ 251.5.n~ ~- 232.nD,
(2)
where ntp and m) are numbers of terminal P (mass 227) and D (mass 251.5) units in the OAS molecule; np and riD--numbers of central P (mass 210 and D (mass 232) units in the OAS molecule.
Y
P CL
b /.70
~'~
7.S
1"60
[ /'50
7"3
7"0
a7 ~p.p.m
Fia. 3. 1H NMR spectrum of solution of oligoarylono sulphonoxido based on diphonylolpropane and dichlorodiphenylsulphono. Solution in methylene chloride-d2. Reaction time 10 rain. Number of accumulations 25. Knowing the amount of monomeric products in the reaction mixture we determine the number-average MW of the reaction mixture b y the formula
.~[mix~- ml~/ioAs--l-m2228-~ m3287 ,
(3)
where ml, m s and ma are mole fractions of OAS, free P (mass 228) and D (mass" 287) in the mixture, respectively. From the lsC N M R spectra we also obtain the amount (in wt.%) of OH and C1 groups in the reaction mixture O H : (W134/228~- W=17ntp/.~loAs)lO0
(4)
C1----(W,7 t / 2 8 7 + W~35.Sn~)/~loAs)tO0,
(5)
where W1, W2 and Wa are weight fractions of free P, OAS and free D in t h e reaction mixture, respectively; 17--the mass of the OH group, and 35.5, that of t h e C1. * The sensitivity of the method does, of course, restrict limit of measurable molecular w e i g h t s at the level of ~/oAs to ~ 5 × l 0 s.
1194
¥U. G. Y~OVSX~ 6t a/.
Table 6 gives the results of determin~ions of the characteristics of some OAS specimens. On comparing data on the composition of the reaction mixtures obtained at the same time at temperatures 110 and 120 ° it is seen that a 10 ° rise in temperature leads to a marked reduction in the concentration of initial compounds (3 fold reduction) and "dimer" (~ 2.2 fold reduction); the number of terminal P and D units (in fi-mers, where fi~2) varies only slightly, but the concentration of central P and D units is doubled, and the M-W is increased accordingly. The ltTmlx values and degrees of conversion are in good agreement with the results obtained by other methods (chemical analysis, ebullioscopy), which points to the trustworthiness and reliability of the analytical procedures developed on the basis of NMR spectroscopy. Translated by R. J. A. ~-IENDRY REFERENCES 1. I. Ys. SLONIM, L. M. BOLOTINA, Ira. G. URMAN, L. Ye. REITBURD, A. Kh. BULAI a n d M. M. GOL'DER, Vysokomo]. soyed. B22: 644, 1980 (Not translated in Polymer Sci. U.S.S.R.)
PolymerScienceU.S.S.R.Vol. 24, No. 5, pp. 1194-1204,1982 Printed in Poland
0082-8950182/051194-11$07.50/0 © 1983 Pergamon Pros Ltd.
VISCO-ELASTIC PROPERTIES OF LINEAR POLYMERS AND THEIR MIXTURES WITH NARROW MOLECULAR WEIGHT DISTRIBUTION * Yu. G. ¥A~OVSKII, G. V. VINOGRADOVand L. I. IvA~ovA A. V. Topchiyev Institute of Petrochemical Synthesis, U.S.S.R. Academy of Sciences
(Received 14 Jmu~ry 1981) A study was made of visco-elastic, dynamic characteristics of mixtures based on 1,4-polybutadiencs of narrow molecular weight distribution (MWD) with different molecular weights of the matrix a n d additive (from 104 to 106) in the range of low concentrations of the high molecular weight component. Concentration dependences were determined for initial viscosity, the initial coefficient of high-elasticity a n d equilibrium oompliance. I t v ~ s shown t h a t the relative variation of components of the dynamic modulus of the initial mstrix increases with a n increase in MW of the additive and decreases with an increase in MW of the matrix. I t was established that for m i n i m u m
* Vysokomol. coyed. A~4: No. 5, 1057-1065, 1982.
1183
ItH|ltEl~a~ I. Yu. A. M][IEHEYEV, L. N. GUSEVA, L. S. ROGOVA and D. Ya. TOFI'Y@IN, Vysokomol. soyed. 28: 386, 1981 (Translated in Polymer Sci. U.S.S.R. 28: 2, 431, 1981) 2. L. S. ROGOVA, L. N. GUSEVA, Yu. A. Mi3KHEYEV and D. Ya. TOPTYGIN, Vysokomol. soyed. A21: 1373, 1979 (Translated in Polymer Sci. U.S.S.R. 21: 6, 1508, 1979i 3. L. B. GAVRILOV, Ye. M. ZVONKOVA, Yu. A. MIKHEYEV, D. Ya. TOPTYGIN and M. L. KERBER, Vysokomol. soyed. 23: 1552, 1981 (Translated in Polymer Sci. U.S.S.R. 23: 7, 1715, 1981) 4. V. R. REGEL, A. I. SLUTSKER and E. Ye. TOMASHEVSKII, Kineticheskaya priroda prochnosti tverdykh tel (Kinetic l~ature of the Strength of Solid Bodies) pp. 501, 514, Nauka, 197~ 5. M. P. VERSHININA, V. R. REGEL and N. N. CHERNYI, Vysokomol. soyed. 6: 1450, 1964 (Translated in Polymer Sci. U.S.S.R. 6: 8, 1606, 1964) 6. G. V. VINOGRADOV and D. Ya. MALKIN, Reologiya polimerov (Polymer Rheology). p. 279, Khimiya, Moscow, 1977 7. V. A. KABANOV, Dokl. Akad. Iqauk SSSR 195: No. 2, 402 1970
PolymerScienceU.S.S.R.Vol. 24, lqo. 5, pp. 1183-119~, 1982 Printed in Poland
0032-3950]82/051183-12$07.50/0 © 1983 Pergamon Press Ltd.
1H AND 13C NMR ANALYSIS OF T ~ SYNTHESIS OF POLYARYLENE SULPHONOXIDES BASED ON DIPHENYLOLPROPANE AND DICHLORODIPHENYLSULPHONE * A. K ~ . BULAI, YA. G. URMAN, I. YA. SLONIM, L. M. BOLOTINA, L. YE, REITBURD, M. M. GOL'DER, A. 1~. SHAPOVALOVA a n d R. N. SIVAKOVA ',Plastmassy" Scientific & Industrial Resoareh Association
(Received 12 January 1981) The method of ~H and lsC NMR analysis has been used to investigate reaction mixtures formed in the synthesis of oligoarylene sulphonoxides from the sodium salt of diphenylolpropane and diehlorodiphenylsulphone. A quantitative study was carried out to determine the amount of different endgroups and of monomerie and "dimeric" products formed at some stages in the synthesis. Number-average molecular weights were determined for oligoarylene sulphonoxides in the reaction mixture.
A D E T A I L E D investigation of the synthesis of polyarylene sulphonoxides is called for as a necessary conditions in achieving maximum efficiency in the commercial production of these polymers. * Vysokomol. soyed. A$4: No. 5, 1047-1056, 1982.
1184
A. K~. BULaI eta/.
Existing methods of chemical and spectroscopic analysis of the synthesis of polysulphones provide no means of estimating the amounts of different endgroups in the chain, and, in particular, cannot be used to solve the important problem of determining concentrations of monomers, dimers and n-mers in reaction systems. Such data must be available before a kinetic description of the synthesis can be attempted. This paper relates to our use of the 1H and 13C NMR as a means of resolving these problems. The study objects were oligoarylene sulphonoxides (OAS) prepared by a reaction of nucleophilic substitution under homogeneous conditions: to a solution of sodium salt of diphenylolprepano (P) in ]:)MSO, heated to the synthesis temperature (120 °) was added a solution dichlorodiphenylsulphone (D) in DMSO. Samples wore collected at the start of the process (after 1-2 rain) and at the end (after 15-20 min); the reaction was terminated b y decanting the latter into a solution of HC1 in DMSO (whereupon phenols were formed from the sodium salts). The mixtures containing the starting compounds and the condensation products of the general formula arts
L
"
~
I
C]-]s
(,, ~
- -
- -
J"
CH8 where B'--H-, CH3 were extracted with chloroform (to remove NaCI) and precipitated with isopropyl alcohol from solution in chloroform. The 1H (90 MHz) and 13C (22.63 MHz) NMR spectra of the oligoarylene sulphonoxides were recorded on a Brucker WH-90 type spectrometer, using a Fourier transformation method. Methylene chlorlde-dl was used as a solvent and hexamethyldisiloxane, whoso chemical shift was p u t at 2.4 p.p.m., was the internal standard. To assign signals in the 1H and lsC NMR spectra of the oligoarylene sulphonoxides we took the proton and carbon spectra of the monomeric products (P and D) a n d of primary products of the interaction of P with D - - t h e "dimer" (I, n----1, R ' ~ - H ; R"----CI) and "trimer" (I, n-~ 1, R'~-C1CsH,SO2CeH,--; R"=C1) and likewise of the model compound
.o-O-=o,-O_o_ 0 The "dimer" a n d "trlmer" were synthesized as follows. I n t o a glass thermostatted reactor fitted with a stirrer were placed 11.42 g of P, 2 g of sodium hydroxide (3.55 m] of a 56~o aqueous solution) and 150 ml of DMSO. Under a 532 P a vacuum a t 54° were distilled off 40 ml of DMSO which contained 2.45 g of water (Fischer), which is equal to the theoretical a m o u n t that ought to be evolved in the formation of monosodium salt P and to the a m o u n t of water introduced along with the sodium hydroxide solution. Next, ! 1.36 g of D were placed in the reactor, the reaction system was heated for 15 hr at 75-80 ° in a nitrogen atmosphere (a specially pure grade of N). The reaction products were decanted into water. F r o m a n alkali solution were filtered the unrea~ted D and a large part of the primary product of inter-
1H and x3C NMR analysis of synthesis of polyarylene sulphonoxides
1185
action of P with D. After acidification of the filtrate the unreacted P separated out, along ~xdth a small a m o u n t of the reaction product. The reaction products were fractionated on a chromatographic column (column diameter 15 ram, height 68 ram) filled with silica gel L 40/100 (Czechoslovakia). Chloroform was used as a n eluent. The "dimor" (m.p. 135-138 °) and "trimer" (re.l). 166--168.9 °) were separated.
The 13C N M R spectra of the OAS. For convenience let us consider separately the signal areas of C atoms of the residue of D (Fig. 1) and that of P (Fig. 2). Signal assignment for the OAS spectrum (see Tables 1 and 2) was carried out by using the spectra of the monomers, and of high molecular polysulphone [1] and of the model compounds ("dimer" and "trimer"), as well analysing changes in ~he carbon spectra of the reaction mixtures obtained at various stages in the synthesis. The 13C NMR chemical shifts of aromatic carbon atoms in residues of P and D in the polycondensation products be described by the additive scheme
X
,-- (X:=C(CI-Ia)~ or SO~) can
M ~OMO -yzJ M=-i- ~M=' -~/-JM#-i-/AM#,
where M~-P, D; i ~ 1 - 4 (position of the carbon atom in the aromatic ring);
cl m
t,,
1o6.2 IJ5"8 135.6 l,.~.J 135"0
•
b
d C
e
IM'2
163.0
162"8
lql.5
h
lql.O
lqO.~" ~,,Fp.m.
FIe. 1. Signals of dichlorodiphenylsulphone (D) residue in tile a*C NMR spectrum of t h e oligoarylene sulphonoxide based on diphenylolpropane a n d D. Solution in methylene-chloride-d2. Reaction time 10 rain. Xumber of accumulations 32,000.
1186
A, K~, Bur-~1 e~ ~.
~
~1~.~ ~~
1
u~
e
~
.
~H and ~sC NMR analysis of s~ynthesis of polyarylene sulphonoxides
i 0
I ~q
o 0
P~
~P
0
0
~
~
1187
1188
A. KH. B ~
et al.
l~l~II
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~S~~q~
r.2
, i i ~ , . . i , - , , i , i i ~ - i , ~ , ~ , i i
~2
+ .
.
.
.
.
.
.
.
o
m
q-I and 13CNMR analysis of synthesis of polyarylenc sulphonoxides
1189
$~o~-- chemical shifts of carbon atoms in monomers; a, fl are increments for OH or C1 group substitution by D or P units on the part of an aromatic ring whose carbon atoms are numbered; a', fl' are increments for OH or C1 group substitution by D or P units on the part o f an aromatic ring whose carbon atoms have n o t been numbered.* Tim chemical shift of a bridge carbon atom $(a) in a P residue likewise obeys the additivity rule; ~(5) in a P_D sequence is equal to a middle value between $(5) in free P and 5(s) in a DPD sequence. The increments calculated by least squares using a computer are given in Table 3; the chemical shifts of aromatic carbon atoms in residues of D and P, calculated on the basis of increments a, ~' and fl, fl' are given in Tables 1 and 2 respectively. An analysis of the data in Tables 1 and 2 shows t h a t calculated values of $cal are in good agreement with 5~xp, which supports the tabulated assignments. I t should be noted t h a t for all the C atoms in the P residue and in the D residue there is only one value of 5cal corresponding to one 5exp. The exception is carbon a.tom C-3 in the P residue: here there are two calculated chemical shifts (&al -----118"32 and 118.44 p.p.m) corresponding to one signal o (~exp~llS"40 p.p.m). This is because in the ~sC NMR spectrum of the OAS an overlap of C-3 signals occurs in sequences P D and DPD; a widening of signal o, and in some spectra a splitting of the signal can be seen. T A B L E 3. 1)A-RAMETERS OF T H E A D D I T I V E SCHEME FOR CALCU:LATII~G 1He CHEMICAL SHIFTS OF AROMATIC CARBON ATOMS I1~ R E S I D U E S OF P A!~D
Monomer residues P
D
Increments (see oqn. (1))
Carbon atom C-1 C-2 C-3 C-4 C-1 C-2 C-3 C-4
D MOal~
p,
square error
+ 5"93 ÷0.78 ~- 2"83 -- 2-02 --5-55 --0.61
--9.60 +22-70
--0.88 0 ÷0.12 -~ 0.30
+0.12 0 0 +0.10
--0.78 4- 0"42 -~0-30 --0.31
+0.16 0 0 --0-11
0 0 0 0 --
0.003 0 0 0
o"
0"05 0 0"17 0"007 0-32 0.38
0"23 0"10
I n P and in the "dimer" it was found t h a t for the carbon atom adjoiuiug the OH group (C-4) there is a discrepancy between chemical shifts in the 0AS spectrum and in the spectra of the individual compounds (a discrepancy amounting to 0.16 p.p.m, for P and 0.41 p.p.m, for the "dimer"). This is probably due to the influence of the concentration and p i t of the medium on the chemical ahift of C-4, and so care is needed when using the spectra of model compounds for signal assignment in 0AS spectra. * Example: P D P D P.
1190
A. I ~ . Buz~AI eta/.
It was found that signals of quaternary aromatic carbon atoms of the P residue (C-l, C-4, see Table 2) and the D residue (C-4, see Table 1) are split into six peaks; the signal of the C atom adjoining the sulpho group was found to be the most sensitive (as in the case of the blended polyarylene sulphonoxide in [1]) to the influence of oligomer chain structure, and is split into eight peaks (see Table 1). Thus it appears that chemical shifts of quaternary aromatic carbon atoms are influenced not only by the adjacent unit, but also by the preadjacent one. The a3C NMR spectra are an excellent source of information, and provide a basis for a quantitative analysis of reactio~ systems. The number of free, terminal and central units of P (per P residue) may be determined from ratios of the peak areas: St, Ss and Sr (C-5 signal); S~, ZSa,y, e and ZSc,~ (C-4 signal); S~; ~Sg,~,z and ZS~,j (C-1 signal); S~; S# and S O (C-3 signal) (see Fig. 2 and Table 2). Similarly, the number of free, terminal and central units of D (per D residue) was calculated by using the peak areas: Sg, ZSa,~,~ and ZSc, d (C-4 signal); SI; ZSe, m,~ and ZS~,j,~,I (C-1 signal) (see Fig. 1, Table 1). In addition, the spectrum may be used to determine the "dimer" concentration in the reaction mixture: to do so, we use peak areas Sa (C-4 signal) and S~ (C-1 signal) in sequence D P (see Fig. 1, Table 1); S! (C-4 signal) and S¢ (C-1 signal) in sequence P D (see Fig. 2, Table 2). It must be said that in all calculations signal areas were compared for monotype carbon atoms only; in this way one may avoid errors due to differing relaxation, and to signal intensification due to an Overhauser effect. Some of the above data on the composition of the reaction mixture can also be obtained from the ~H NMR spectra. ~H N M R spectra of the OAS. The proton spectrum is shown in Fig. 3. Signal assignments may be carried out (Tables 4 and 5) by comparing the latter with the spectra of the high molecular polysulphone and the free P and D and with the aH NMR spectra of reaction mixtures obtained at the start and the end of processes. The data in Tables 4 and 5 show that the ~H NMR spectra also provide a good deal of information. The latter spectra enable us to determine the number o~ffree, terminal and central units of P from the ratio of signal areas S~, Sy and Sz (H-5 signal); ZSu, w ZSt, w (H-4 signal) and ZSa, ~ (H-3' signal); ZSe, ~ (H-3 signal) (see Fig. 3, Table 5), and likewise the number of free, terminal and central units of D from the ratio of the signal areas ZSc, e (H-2 signals); ZS4,I (H-2 signal) aud ZSa, b (H-1 signal) (see Fig. 3, Table 4). However, while it is true that aH NMR is more sensitive than the ~8C NMR, calculations based on signals of aromatic protons a-w are eoml~lieated by the overlap of AA'BB' quadruplets. OAS characteristics. Knowig the number of terminal and central P units (per P residue) and the number of terminal and central D units (per D residue), without counting the free P and D or the molar ratio of P : D in the OAS (R),
~H and ~sC NMR analysis of synthesis of polyaryleno sulphonoxides 0
119~
¢,11
o 0
o
~
0
g~Ze
I 0
0
o
N
o
N W 0 N
0 N N
0 ¢g
r~ r~
4 N o
1192
A. K m
B ~
et ~.
~0
Q
0
©
~D
!0 Q
1H and 13CNMR analysis of synthesis ofpolyarylenc sulphonoxides
1193
we obtain the number-average MW of the oligomers from the formula * l]~oAs----2 2 7 . n ~ 210.np-~ 251.5.n~ ~- 232.nD,
(2)
where ntp and m) are numbers of terminal P (mass 227) and D (mass 251.5) units in the OAS molecule; np and riD--numbers of central P (mass 210 and D (mass 232) units in the OAS molecule.
Y
P CL
b /.70
~'~
7.S
1"60
[ /'50
7"3
7"0
a7 ~p.p.m
Fia. 3. 1H NMR spectrum of solution of oligoarylono sulphonoxido based on diphonylolpropane and dichlorodiphenylsulphono. Solution in methylene chloride-d2. Reaction time 10 rain. Number of accumulations 25. Knowing the amount of monomeric products in the reaction mixture we determine the number-average MW of the reaction mixture b y the formula
.~[mix~- ml~/ioAs--l-m2228-~ m3287 ,
(3)
where ml, m s and ma are mole fractions of OAS, free P (mass 228) and D (mass" 287) in the mixture, respectively. From the lsC N M R spectra we also obtain the amount (in wt.%) of OH and C1 groups in the reaction mixture O H : (W134/228~- W=17ntp/.~loAs)lO0
(4)
C1----(W,7 t / 2 8 7 + W~35.Sn~)/~loAs)tO0,
(5)
where W1, W2 and Wa are weight fractions of free P, OAS and free D in t h e reaction mixture, respectively; 17--the mass of the OH group, and 35.5, that of t h e C1. * The sensitivity of the method does, of course, restrict limit of measurable molecular w e i g h t s at the level of ~/oAs to ~ 5 × l 0 s.
1194
¥U. G. Y~OVSX~ 6t a/.
Table 6 gives the results of determin~ions of the characteristics of some OAS specimens. On comparing data on the composition of the reaction mixtures obtained at the same time at temperatures 110 and 120 ° it is seen that a 10 ° rise in temperature leads to a marked reduction in the concentration of initial compounds (3 fold reduction) and "dimer" (~ 2.2 fold reduction); the number of terminal P and D units (in fi-mers, where fi~2) varies only slightly, but the concentration of central P and D units is doubled, and the M-W is increased accordingly. The ltTmlx values and degrees of conversion are in good agreement with the results obtained by other methods (chemical analysis, ebullioscopy), which points to the trustworthiness and reliability of the analytical procedures developed on the basis of NMR spectroscopy. Translated by R. J. A. ~-IENDRY REFERENCES 1. I. Ys. SLONIM, L. M. BOLOTINA, Ira. G. URMAN, L. Ye. REITBURD, A. Kh. BULAI a n d M. M. GOL'DER, Vysokomo]. soyed. B22: 644, 1980 (Not translated in Polymer Sci. U.S.S.R.)
PolymerScienceU.S.S.R.Vol. 24, No. 5, pp. 1194-1204,1982 Printed in Poland
0082-8950182/051194-11$07.50/0 © 1983 Pergamon Pros Ltd.
VISCO-ELASTIC PROPERTIES OF LINEAR POLYMERS AND THEIR MIXTURES WITH NARROW MOLECULAR WEIGHT DISTRIBUTION * Yu. G. ¥A~OVSKII, G. V. VINOGRADOVand L. I. IvA~ovA A. V. Topchiyev Institute of Petrochemical Synthesis, U.S.S.R. Academy of Sciences
(Received 14 Jmu~ry 1981) A study was made of visco-elastic, dynamic characteristics of mixtures based on 1,4-polybutadiencs of narrow molecular weight distribution (MWD) with different molecular weights of the matrix a n d additive (from 104 to 106) in the range of low concentrations of the high molecular weight component. Concentration dependences were determined for initial viscosity, the initial coefficient of high-elasticity a n d equilibrium oompliance. I t v ~ s shown t h a t the relative variation of components of the dynamic modulus of the initial mstrix increases with a n increase in MW of the additive and decreases with an increase in MW of the matrix. I t was established that for m i n i m u m
* Vysokomol. coyed. A~4: No. 5, 1057-1065, 1982.