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Copolycondensation of diamines, dicarboxylic acid chlorides and aromatic disulphonylchlorides in amide solvents
J~olymer Science U.S,S.R. Yol. 25, :No. 8, pp. 1864-1~70, 1983 Printed in Poland
0032-3950/83 $10.00 + .00 4~ 198.t Pergamon l'ress Ltd.
COPOLYCONDENSATION OF DIAMINES, DICARBOXYLIC ACID CHLORIDES AND AROMATIC DISULPHONYLCHLORIDES IN AMIDE SOLVENTS* L. B. SOKOLOV ( d e c . ) , V. S. NAUbIOV and V. I. LOQU.~OVA All-Union Synthetic Resin Research Institute
(Received 22 December 1981) In solution in DMAA new all-aromatic polyanfidosulphamides have been obtained from disulphonylchlorides. The kinetics of the reaction of disulphochlorides with aniline and the patterns of the synthesis of polyamidosulphonmnides by twostage copolycondonsation have been studied. The main properties of the polymers obtained have been studied. ATTE~IVrs to rise disulphonylctflori(lcs to obtain all-aromatic polysulphonamides o r modify the aromatic polyamide,s remained unsuccessful for a long time o~ing to the low reactivity of the disulphonylchloride,s [ 1, 2]. l~econtly , e,ommunications have been published on the synthesis of quite high molecular weight all-aromatic polysulphomunides from the corresponding aromatic diamines and disulphonylchlorides in the" enmlsion system T H F - w a t e r .HCI accepter [3, 4] and also in solutiou iil tctramethylenesulphonc [5, 6]. However the amide solvents, in particular DSL~A, ve,ry widely used for synthesis with use of the dichloranhydrides of the carboxylic acids have so far not b ~ n employed to obtain polyst|lphonamide,s. In [1] despite" wide variation in the conditions of polycondensation of the aromatic disulphonylchlorides and diamines, only low molecular weight polymers were obtained in DMAA. The present work examine,s the possibility of synthesizing high molecular weight polymers in DMAA by copolycondensation of the aromatic diamines, disulphochlorides and acid chlorides of die,arboxylie acids. Study of the kinetics of model reactions. On the basis of the earlier findings [7] on the possibility of predicting the conditions for synthesizing high molecular weight polymers starting from the results of determination of the reactivity of the monomers in model reactions we sought the optimal conditions for polycondensation with the participation of the aromatic disulphonylchlorides as exemplified by the model reaction of the latter with aniline. Study of the kinetics showed that the rate of the sulphonamidation reaction in D5IAA is fairly high--in 1 rain 50% of the' SO2Cl-groups of the initial disulI)honylchloridcs enter the reaction with aniline (Fig. l). However a~s soon as the degree' of conversion reaches this value, the" reaction slows ~harply. * V~'sokomol. soyed. A25:No. 8, 1610-1614, 1983.
1864
C(~p(,lycon(h,ns~ltion of diammes
1865
From the reaction of 1,5-naphthalenedisulphonylchloride with excess dimethylamine it has been showu that the rate of the secondary reaction of the SOsCI groups with DMAA is low as compared with the COC1 groups [8] and cannot be the cause of the observed sharp slowing of the reaction of sulphonamidation. Thus, for example, the degree of conversion in the reaction with dimethylamine remained unchanged (99-100°/o) irrespective of the form in which the disulphonylchloride was loaded: solid or after keeping in solution in DMAA for 15 rain before the start of the reaction.
0
80
,
,0
0
ot
0"6
x 2
qo
02 a3 0
A. 5
O2
/0~ Time 7rain
["it:. I
1~20°
I 30
I
]
6O 80 Time, rain
I
120
FI(;. 2
Flu. l. Kinetic curves of the reaction of aniline with disulphonylchloridcs in DMAA: 1 1,3-benzene disulphonylchloride; 2--2,4-toluene disulphonylehloride; 3--1,5-naphthalene disuIphonylchloridc. Concentration of aniline 0.1)5mole/l, disulphonylchloride 0.025 mole/l., q--degree of conversi.n of SO=CI groups. F~o. 2. Logarithmic viscosity of polyamidosulphonamidc based on 4,4'-diaminodiphenylexido, 4,4"-diphenyldisulphonylchloride and isophthaloylchloride a.u a function of the duration of the first (1) and second (2) stages of synthesis (with a duration of 1-30 rain). It nfight have been supposed that the observed slowing of the reaction of sulphonamidation is linked with the formation of aniline hydroehloride with low reactivity in relation to the sulphonylchlorides. In fact, running the reaction with a two-fold excess of NH= groups despite the fact that this was done by lowering the concentration of disulphonylchloride helped to raise the overall reaction rate. The degree of con~crsion of tile SOsCl groups ill the reaction of 2,4-toluenedisulphonylchloride with aniline in 30 min was 80°.~, (the concentration of aniline 0.05 mole/1., the disulphonylchloride 0.0125 molc/l.) whereas for the e(luimolar ratio of the NH2 and S(),CI groups (concentration of aniline 0.05 mole/l., ([isulphonylt,hlori(h, 0.025 mole/l.) it. was 640/o. The low reactivity of the aromatic diamine hych'ochlorides in relation to tim disul]d~onylchlorides is also apparently the main reason why low molecular weight aromatic polysulphonamides are obtained in DSL~A.
1866
L.B.
SOKOLOV (dee.) et
al.
Paitern,~ of the formation of the polyamidosulphonamides. This peculiarity makes it possible to use on polycondensation of the disulphonylchlorides and diamines in DMAA only the first stage of the reaction when the free amino groups react with the SO.,CI groups. This may be done by obtaining copolymers using as iuitial monomer t()gether with the disulphonylchloride the diacid chloride of a carboxylic acid. From all this ~ metlmd of synthesizhlg polyamidosulphonamides was devised [9] with stepped loading of the acid chlorides in which the carboxylic diacid chloride was added to the reaction zone after completion of the reaction of the free diamine with disulphonylchloride. To complete the first stage rapidly the content of the latter in the total amount of acid chlorides must not exceed 50 mole%. In the first stage all the S02CI groups react chiefly with the free amino groups and the second sees the reaction of formation of the amide bonds 2nNH~ArNI-I~ nCISO:Ar'SO:CI-*nHCI. NH,ArNHSO2Aa"80~. • N H A r N H I- HCI
( 1)
nHCI.NH,ArNHSO,Ar'SO,NHArNH,. HCI-bnCOCIAr"COCI--, - * H - - ( - NHAr.NHSO~Ar'SO,N HArNHCOAr"CO- )-- .C1-t- (4n- I)HCI
(2)
The data on synthesis in the way described of polyamidosulphonamides on the basis of 4,4'-diaminod;phenyloxide, 4,4'-diphenyl disulphonylchloride and isophthaloyl chloride given in Table 1 show that increase in the content of disulphonylchloride in relation to the sum of the acid chlorides above 50 mole ~/o leads to sharp fall in the logarithmic viscosity of the copolymer, which m a y be compared with fall ill MW on deviation from equimolarity of the monomers on synthesis of the polyamides in DMAA [8], TABLE I . PROPERTIES OF COPOLYMERS
BASED ON 4,4'-DIA.'~INODIPH.ENYLOXIDE, I)HEN'YLDISULPHONYLCHLORIDE AND ISOPHTHALOYI, OHLOltlDE
Polymer No.
Content, mole %. ill relation to sum of acid chlorides 4,4'-dipheisophthanyldisulpholoylchloride nylchloride 100
5
0 25 50 75 90 95
0
100
75 50 25
10
l/log, dl/g
T~,rt
(~ 1
185* 250 265 273 287 290 300
23 0.98 1.05 1.34 1.45 1.38
4,4'-DI-
Solubility in mixture THF-water (90 : 10 by volume) Yes ,, ,, No ,,
.,
* ::~ofteningpoint for polymerwith logarithmic viscosity1.09obtained in syste~nTHF-water-Na2CO,.
Copolyeondensation of diamines TABLE
2.
PROPERTIES
OF THE
1867
ARO:~[ATIC I ' O L Y A 3 I I D O S I ) ' L P H ~ ) N k ) . I I D E S B A S E D
ON
ISOPHTHA-
LOYL CHLOI~.ID~.:AI~'D DIFFERENT DISULPHONYLCHLORIDI';S i
:
Polymor! Nr). i
1)isulf)h"lo'lehlrwide
T']lel t
i
'Ijo~, dl/g
i Solubility I. in mixture ] T H FT ~,,rt ' tw a t o r (90 : 10
:
)
i
i
i
by
vol-
ume)
Din mine-4,4'-diaminodiphonyloxido 1 .)
3 4 5 6
7 9
10
4,4'-Dil)honyhlisull)hoto'lehlori(h; 207.5-21)S' 0 I 1-27 4.4'-I)iphenyloxid,~ (li,~ulphonyl[I chh)ride 126.8-12.%o 0.35 4,4'-Diphenylsulphono disulphonyl- ~ 267.0 ] 0. 64 chloride i 3,3"-Diphcnylsulphone (limflphonyl-! chloride ]81"7 0'60 i ,5-Naphtlmlone disulpbonyl181"0--183-0 , 0-56 chloride 1,5.Nit ronal)ht halcne disulphonyl176-0-178.0 0-19 chloride 4,6-m-Xylene disulphonylchlorido 127.3-128.4 [ ff62 2,4-Toluene disulphonylchloride 52.5-53.0 I 0.93 ! ,3-Benzene (lisulphonylehloride 62.o-62.5 i ~81 141.0-142-0. 0.6:) 1,4-Benzene ,li~ulplmnylehlori(lo
265
Yo~
185
,,
250
,,
215
,,
240
,,
210 250 230 { 240 240
,, ,, ,, No
Diamine~n-phenylem~liamine II 12 13 14
4,4'-Diphenyl disulphonylchh)ride 4,4'-Dipheny]oxide disulphonylchlorido 1,5-~itronaphthalcno disulphonylchloride 2,4.Tohmn, disulphonylehloride
O. 35
207.5-208.0
245 [
Yes
(
/
126. 8-128. 0 [
I
O.36
0.4O 176. 0- ! 78- 0 52..5--53.0 ~ 0. 63
210 !
,,
210 --
..
T h e m a i n palt.e, r n s o f s y n t h e s i s o f ttle p o l y a m i d o s u l p h o n a m i d e s in t h e D M A A m e d i u m w e r e s t u d i e d in t h e l i g h t o f s y n t h e s i s o f the c o p o l y m e r f r o m t h e a b o v e m o n o m e r s for a n e q u i m o l a r r~tio o f acid chlorides. F r o m Fig. 2 it will b e seen t h a t t h e r a t e o f p o l y c o n d o n s a t i o n o f the, a r o m a t i c d i a m i n e s w i t h d i s u l p h o n y l c h l o r i d e s in t h e w a y d e s c r i b e d is fairly h i g h a n d c o m p a r a b l e w i t h t h a t o f t h e s e c o n d s t a g e o f t h e r e a c t i o n o f t h e s e d i a m i n e s w i t h t h e dit~cid chlorides o f e a r b o x.vlic acids. I t t a k e s n o t m o r e t h a n 15 m i n to c o m p l e t e e a c h s t a g e o f s y n t h e s i s . S t u d y o f t h e influence o f t h e r a t i o o f t h e bfitial m o n o m e r s on t h e M W r e v e a l e d t h e usual r e l a t i o n c h a r a c t e r i s t i c o f p o l y c o n d e n s a t i o n in s o l u t i o n [8]: excess o f a c i d chloride b o t h in t h e first a n d s e c o n d st t~ges r e d u c e s t h e l o g a r i t h m i c v i s c o s i t y of the polymer. T h e d e p e n d e n c e o f the M W on t h e , ' o n c e n t r a t i o n o f t h e initial m o n o m e r s is d e s c r i b e d (Fig. 3 , ) b y a c u r v e w i l h ~ m a x i m u m . Shift o f this m a x i m u m t o th!s
L. B. SOKOLOV(dec.) et el.
1868
or that side is due to the structure of the monomer. :Fall in the logarithmic viscosity of the polymer at high concentration results from rise in the viscosity of the reaction mass, which hinders passage of the reaction to the required depth. Change in the temperature of the first stage of polycondensation from -- 10 to -t-60°C makes little difference to the MW of the polyamidosulphonamides formed (Fig. 3b). Evidently, the ratio of the rates of the main and secondary reactions remains constant. Appreciable fall in the logarithmic viscosity of the polymers is observed only at 80-100°C.
~09,di/9 I'0 ~6
CL
1~'~
2
1.0~
~2
~5
1"0
1"5
C~mole/[.
0
#0
80T°
lho. 3. Logarithmic viscosity of polyamidosulphonamides based on 4,4'-diphcnyld~ulphonylchloride (1), 2,4-toluene disulphonylchloride (2) and 3,3'.diphenylsulphone disulphonylchloride (3) as a function of concentration of monomers (a) and also temperature of firs~ stage of synthesis of 4,4'-diphenyldisulphonylchloride (b). Thus, a peculiarity of the behaviour of the disulphonylchlorides on polycondensation in DMAA is their lower reactivity in relation to the aromatic diamine hydrochlorides and less proneness to secon(lary reactions. The main properties of polyamidosulphonamides. Table l shows that in the series polyamides-polyamidosulphonamides-polysulphonamides the softening point of the polymers falls while the solubility improves: for a content of the sulphonamide groups below 25% the polymer loses solubility in the T H F - w a t e r mixture. To study the influence of the structure of the disulphonylchloride on the properties we synthesized various polyamidosulphonamide~s for an equimolar ratio of disulphonylchloride and carboxylic diacid chloride on the basis of iso- and terophthaloyl chlorides and various disulphonylchlorides and diamines indicated in Table 2. From the results of X-ray structural analysis all the polymers obtained are amorphous. The softening point of the polyamidosulphonamides, based on isophthaloyl chloride the properties of which are indicated in Table 2, lies within the limits 185-265°C; most of the polymers based on terephthaloyl chloride do not soften on heating to 500°C. T h e polvamidosulphonamides like the aromatic
Copolycon,h,nsation of diamines
1869
polyamides and polysulphonamides are insoluble in hydrocarbons and chlorinated hydrocarbons, in aliphatic alcohols, acotonitrile, acetic acid and in 80% aqueous ethanol. To obtain concentrated solutions of most of the polyamidosulphonamides based on isophthaloyl chloride most suitable are solvents of the amide type, I)MSO, cyclohexanone, 0.5-10°~) aqueous T H F and 5-10°/o aqueous dioxane. The polyamidosulphonamidcs based on terephthaloyl chloride dissolve only in solvents of the amide type and some of them in DMSO. Study of hydrolytic stal)ility showed that. in concentrated sulphuric acid not only is there dissolution of the polymer but also degradation of the S02NH bonds, which leads, as in the c~se of aromatic polysulphonamides [3] to fall in MW. In 10% KO]t solution the polyamidosulphonamidcs hydrol,'se: slowly at 22°C (heterogeneously) and rapidly at 100°C (with dissolution). The water and moisture abso,])tion of the synthesized l)olyamidosulphonamidos like the polysulphonanfidcs [3] is less than for the armm~tic polyamidos [8]. Thus on 1)oiling in w,~ter to saturation the. monolithic pellets of polymers 1, 5* and 8' absorb respectively 5, 2.5 and 2.5% w a ~ r while when kept in air at 28°0 fihns of the polymers 5* and 8t absorb 1% water. Better solubility and ability to soften at lower temperatures as compared with the polyamidos fit cilitate the processing of the l)olyamidosulphonamides. From solution of the polymers based on 4,4-diphcnyl disulphonylchloride and 2.4-toluene (lisulphonylchloride (polymers l and 8) in I)MAA we obtained transparent films the properties of which arc given below. Polymer I),med on Disruptive stress on stretching, MPa Relative elongation at rupture, °o Dielectric eonstnnt Tangent of Iho nn~]' of dieh,et.ric losses, tan J × I0 2 Specific volmnelric ch,etrieal resislance, .Q. en~ Electrical stwngt.h, kV/mm
4,4'-diphenyl 2,4-toluene disulphonylehhwide disulphonylehloride 83 9
58 5
4-8
4.0
2"5
I-7
I ' S x 101~ 130
2'5)< 1011 110
The samples of polymer 1 obtained by direct pressing had a resilience lq0 N.cm/cm". Starti~,ff substance.,.. For synthesi.~ we used disulphonylehlorides with the melting points indicated in "]?able 2, p-toluene sulphonylehh)ride melting at 67.5-68°C, m-phenylenediamine of grade pure fi)r analysis, 4,4'-diaminodiphenyloxide (MRTU B-09-2665-65) and aniline grade " p u r e " twice distilled at 1.33 kPa. * On the basis of terephthaloyl chloride', t Composition of pnlymers is indicated in Table 2,
1870
L. B. SOKOLOV (dee.) et el.
Kinetic measuremenSs. Tile rate of acylation of aniline with sulphonyl chlorides in DMAA at 25°C was studied b y determining the ongoing concentration of aniline bromometrically with iodometrie indication of the titration end point at 2-3°C. Sulphonylehlorido in the form of a finely crushed powder was rapidly introduced into the solution of aniline in DMAA; the reaction was arrested with dilute hydrochloric acid. Synthesis of the polyamidosulphonamide~,. To the diamine dissolved in DMAA a t 22°C was a d d e d with agitation the solid disulphonylclfloridc. After a certain time (I hr) the solution was cooled to 0-5°C and the solid diaeid chloride of the carboxylie acid added. Synthesis was carried out for 1 hr at 22°C, the concentration of the monomers was ~ 5 mole/l. The polymer was separated out with water, washed, dried and the logarithmic viscosity in DMAA at 25°C determined (concentration of p,)lymer 0.Sg/100ml). Translate~l by A. CRozY REFERENCES 1. F. E. ARNOLD, 8. CANTOR and C. 8. MARVEL, J. Polymer Sci. A - l , 5: 553, 1967 2. P. U. MORGAN, Polikondensatsionnye protsessy sinteza polimerov (Polycondensation Processes of Polymer Synthesis). Khimiya, Moscow, 1970 3. V. I. LOGUNOVA and L. B. SOKOLOV, Vysokom,fl. soycd. A22: 321, 1980 (Translated in P o l y m e r Sei. U.S.S.R. 22: 2, 357, 1980) 4. V. I. LOGUNOVA, L. B. SOKOLOV, V. M. SAZINOV and L. M. VESELOVA, U.S.S.R. Pat. 522205, Byull. izobr., No. 27, 78, 1976 5. S. 1"._KW0LI~K, U.S.A. Pat. 3591559, Publ. in RZhKhim. 5S434P, 1972 6. Y. IMAI, M. UED& a n d T. I I Z A W A , Polymer Letters 17: 1483, 1979 7. L. B. SOKOLOV and V. I. LOGUNOVA, Vysokomol. soyed. A21: 1075, 1!}79 (Translated in P o l y m e r Sci. U.S.S.R. 21: 5, 1177, 1979) 8. L. B. SOKOLOV, V. D. GERASIMOV, V. M. SAZINOV and V. K. BELYAKOV, Termostoikiye aromatieheskiye poliamidy (Heat Stable Aromatic Polyamides). Khimiya, Moscow, 1975 9. V. S. NAUMOV, L. B. SOKOLOV and A. A. SPRYS:KOV, U.S.S.R. Pat. 451339, Byull. izobr., :No. 41,238, 1978
0032-3950/83 $10.00 + .00 4~ 198.t Pergamon l'ress Ltd.
COPOLYCONDENSATION OF DIAMINES, DICARBOXYLIC ACID CHLORIDES AND AROMATIC DISULPHONYLCHLORIDES IN AMIDE SOLVENTS* L. B. SOKOLOV ( d e c . ) , V. S. NAUbIOV and V. I. LOQU.~OVA All-Union Synthetic Resin Research Institute
(Received 22 December 1981) In solution in DMAA new all-aromatic polyanfidosulphamides have been obtained from disulphonylchlorides. The kinetics of the reaction of disulphochlorides with aniline and the patterns of the synthesis of polyamidosulphonmnides by twostage copolycondonsation have been studied. The main properties of the polymers obtained have been studied. ATTE~IVrs to rise disulphonylctflori(lcs to obtain all-aromatic polysulphonamides o r modify the aromatic polyamide,s remained unsuccessful for a long time o~ing to the low reactivity of the disulphonylchloride,s [ 1, 2]. l~econtly , e,ommunications have been published on the synthesis of quite high molecular weight all-aromatic polysulphomunides from the corresponding aromatic diamines and disulphonylchlorides in the" enmlsion system T H F - w a t e r .HCI accepter [3, 4] and also in solutiou iil tctramethylenesulphonc [5, 6]. However the amide solvents, in particular DSL~A, ve,ry widely used for synthesis with use of the dichloranhydrides of the carboxylic acids have so far not b ~ n employed to obtain polyst|lphonamide,s. In [1] despite" wide variation in the conditions of polycondensation of the aromatic disulphonylchlorides and diamines, only low molecular weight polymers were obtained in DMAA. The present work examine,s the possibility of synthesizing high molecular weight polymers in DMAA by copolycondensation of the aromatic diamines, disulphochlorides and acid chlorides of die,arboxylie acids. Study of the kinetics of model reactions. On the basis of the earlier findings [7] on the possibility of predicting the conditions for synthesizing high molecular weight polymers starting from the results of determination of the reactivity of the monomers in model reactions we sought the optimal conditions for polycondensation with the participation of the aromatic disulphonylchlorides as exemplified by the model reaction of the latter with aniline. Study of the kinetics showed that the rate of the sulphonamidation reaction in D5IAA is fairly high--in 1 rain 50% of the' SO2Cl-groups of the initial disulI)honylchloridcs enter the reaction with aniline (Fig. l). However a~s soon as the degree' of conversion reaches this value, the" reaction slows ~harply. * V~'sokomol. soyed. A25:No. 8, 1610-1614, 1983.
1864
C(~p(,lycon(h,ns~ltion of diammes
1865
From the reaction of 1,5-naphthalenedisulphonylchloride with excess dimethylamine it has been showu that the rate of the secondary reaction of the SOsCI groups with DMAA is low as compared with the COC1 groups [8] and cannot be the cause of the observed sharp slowing of the reaction of sulphonamidation. Thus, for example, the degree of conversion in the reaction with dimethylamine remained unchanged (99-100°/o) irrespective of the form in which the disulphonylchloride was loaded: solid or after keeping in solution in DMAA for 15 rain before the start of the reaction.
0
80
,
,0
0
ot
0"6
x 2
qo
02 a3 0
A. 5
O2
/0~ Time 7rain
["it:. I
1~20°
I 30
I
]
6O 80 Time, rain
I
120
FI(;. 2
Flu. l. Kinetic curves of the reaction of aniline with disulphonylchloridcs in DMAA: 1 1,3-benzene disulphonylchloride; 2--2,4-toluene disulphonylehloride; 3--1,5-naphthalene disuIphonylchloridc. Concentration of aniline 0.1)5mole/l, disulphonylchloride 0.025 mole/l., q--degree of conversi.n of SO=CI groups. F~o. 2. Logarithmic viscosity of polyamidosulphonamidc based on 4,4'-diaminodiphenylexido, 4,4"-diphenyldisulphonylchloride and isophthaloylchloride a.u a function of the duration of the first (1) and second (2) stages of synthesis (with a duration of 1-30 rain). It nfight have been supposed that the observed slowing of the reaction of sulphonamidation is linked with the formation of aniline hydroehloride with low reactivity in relation to the sulphonylchlorides. In fact, running the reaction with a two-fold excess of NH= groups despite the fact that this was done by lowering the concentration of disulphonylchloride helped to raise the overall reaction rate. The degree of con~crsion of tile SOsCl groups ill the reaction of 2,4-toluenedisulphonylchloride with aniline in 30 min was 80°.~, (the concentration of aniline 0.05 mole/1., the disulphonylchloride 0.0125 molc/l.) whereas for the e(luimolar ratio of the NH2 and S(),CI groups (concentration of aniline 0.05 mole/l., ([isulphonylt,hlori(h, 0.025 mole/l.) it. was 640/o. The low reactivity of the aromatic diamine hych'ochlorides in relation to tim disul]d~onylchlorides is also apparently the main reason why low molecular weight aromatic polysulphonamides are obtained in DSL~A.
1866
L.B.
SOKOLOV (dee.) et
al.
Paitern,~ of the formation of the polyamidosulphonamides. This peculiarity makes it possible to use on polycondensation of the disulphonylchlorides and diamines in DMAA only the first stage of the reaction when the free amino groups react with the SO.,CI groups. This may be done by obtaining copolymers using as iuitial monomer t()gether with the disulphonylchloride the diacid chloride of a carboxylic acid. From all this ~ metlmd of synthesizhlg polyamidosulphonamides was devised [9] with stepped loading of the acid chlorides in which the carboxylic diacid chloride was added to the reaction zone after completion of the reaction of the free diamine with disulphonylchloride. To complete the first stage rapidly the content of the latter in the total amount of acid chlorides must not exceed 50 mole%. In the first stage all the S02CI groups react chiefly with the free amino groups and the second sees the reaction of formation of the amide bonds 2nNH~ArNI-I~ nCISO:Ar'SO:CI-*nHCI. NH,ArNHSO2Aa"80~. • N H A r N H I- HCI
( 1)
nHCI.NH,ArNHSO,Ar'SO,NHArNH,. HCI-bnCOCIAr"COCI--, - * H - - ( - NHAr.NHSO~Ar'SO,N HArNHCOAr"CO- )-- .C1-t- (4n- I)HCI
(2)
The data on synthesis in the way described of polyamidosulphonamides on the basis of 4,4'-diaminod;phenyloxide, 4,4'-diphenyl disulphonylchloride and isophthaloyl chloride given in Table 1 show that increase in the content of disulphonylchloride in relation to the sum of the acid chlorides above 50 mole ~/o leads to sharp fall in the logarithmic viscosity of the copolymer, which m a y be compared with fall ill MW on deviation from equimolarity of the monomers on synthesis of the polyamides in DMAA [8], TABLE I . PROPERTIES OF COPOLYMERS
BASED ON 4,4'-DIA.'~INODIPH.ENYLOXIDE, I)HEN'YLDISULPHONYLCHLORIDE AND ISOPHTHALOYI, OHLOltlDE
Polymer No.
Content, mole %. ill relation to sum of acid chlorides 4,4'-dipheisophthanyldisulpholoylchloride nylchloride 100
5
0 25 50 75 90 95
0
100
75 50 25
10
l/log, dl/g
T~,rt
(~ 1
185* 250 265 273 287 290 300
23 0.98 1.05 1.34 1.45 1.38
4,4'-DI-
Solubility in mixture THF-water (90 : 10 by volume) Yes ,, ,, No ,,
.,
* ::~ofteningpoint for polymerwith logarithmic viscosity1.09obtained in syste~nTHF-water-Na2CO,.
Copolyeondensation of diamines TABLE
2.
PROPERTIES
OF THE
1867
ARO:~[ATIC I ' O L Y A 3 I I D O S I ) ' L P H ~ ) N k ) . I I D E S B A S E D
ON
ISOPHTHA-
LOYL CHLOI~.ID~.:AI~'D DIFFERENT DISULPHONYLCHLORIDI';S i
:
Polymor! Nr). i
1)isulf)h"lo'lehlrwide
T']lel t
i
'Ijo~, dl/g
i Solubility I. in mixture ] T H FT ~,,rt ' tw a t o r (90 : 10
:
)
i
i
i
by
vol-
ume)
Din mine-4,4'-diaminodiphonyloxido 1 .)
3 4 5 6
7 9
10
4,4'-Dil)honyhlisull)hoto'lehlori(h; 207.5-21)S' 0 I 1-27 4.4'-I)iphenyloxid,~ (li,~ulphonyl[I chh)ride 126.8-12.%o 0.35 4,4'-Diphenylsulphono disulphonyl- ~ 267.0 ] 0. 64 chloride i 3,3"-Diphcnylsulphone (limflphonyl-! chloride ]81"7 0'60 i ,5-Naphtlmlone disulpbonyl181"0--183-0 , 0-56 chloride 1,5.Nit ronal)ht halcne disulphonyl176-0-178.0 0-19 chloride 4,6-m-Xylene disulphonylchlorido 127.3-128.4 [ ff62 2,4-Toluene disulphonylchloride 52.5-53.0 I 0.93 ! ,3-Benzene (lisulphonylehloride 62.o-62.5 i ~81 141.0-142-0. 0.6:) 1,4-Benzene ,li~ulplmnylehlori(lo
265
Yo~
185
,,
250
,,
215
,,
240
,,
210 250 230 { 240 240
,, ,, ,, No
Diamine~n-phenylem~liamine II 12 13 14
4,4'-Diphenyl disulphonylchh)ride 4,4'-Dipheny]oxide disulphonylchlorido 1,5-~itronaphthalcno disulphonylchloride 2,4.Tohmn, disulphonylehloride
O. 35
207.5-208.0
245 [
Yes
(
/
126. 8-128. 0 [
I
O.36
0.4O 176. 0- ! 78- 0 52..5--53.0 ~ 0. 63
210 !
,,
210 --
..
T h e m a i n palt.e, r n s o f s y n t h e s i s o f ttle p o l y a m i d o s u l p h o n a m i d e s in t h e D M A A m e d i u m w e r e s t u d i e d in t h e l i g h t o f s y n t h e s i s o f the c o p o l y m e r f r o m t h e a b o v e m o n o m e r s for a n e q u i m o l a r r~tio o f acid chlorides. F r o m Fig. 2 it will b e seen t h a t t h e r a t e o f p o l y c o n d o n s a t i o n o f the, a r o m a t i c d i a m i n e s w i t h d i s u l p h o n y l c h l o r i d e s in t h e w a y d e s c r i b e d is fairly h i g h a n d c o m p a r a b l e w i t h t h a t o f t h e s e c o n d s t a g e o f t h e r e a c t i o n o f t h e s e d i a m i n e s w i t h t h e dit~cid chlorides o f e a r b o x.vlic acids. I t t a k e s n o t m o r e t h a n 15 m i n to c o m p l e t e e a c h s t a g e o f s y n t h e s i s . S t u d y o f t h e influence o f t h e r a t i o o f t h e bfitial m o n o m e r s on t h e M W r e v e a l e d t h e usual r e l a t i o n c h a r a c t e r i s t i c o f p o l y c o n d e n s a t i o n in s o l u t i o n [8]: excess o f a c i d chloride b o t h in t h e first a n d s e c o n d st t~ges r e d u c e s t h e l o g a r i t h m i c v i s c o s i t y of the polymer. T h e d e p e n d e n c e o f the M W on t h e , ' o n c e n t r a t i o n o f t h e initial m o n o m e r s is d e s c r i b e d (Fig. 3 , ) b y a c u r v e w i l h ~ m a x i m u m . Shift o f this m a x i m u m t o th!s
L. B. SOKOLOV(dec.) et el.
1868
or that side is due to the structure of the monomer. :Fall in the logarithmic viscosity of the polymer at high concentration results from rise in the viscosity of the reaction mass, which hinders passage of the reaction to the required depth. Change in the temperature of the first stage of polycondensation from -- 10 to -t-60°C makes little difference to the MW of the polyamidosulphonamides formed (Fig. 3b). Evidently, the ratio of the rates of the main and secondary reactions remains constant. Appreciable fall in the logarithmic viscosity of the polymers is observed only at 80-100°C.
~09,di/9 I'0 ~6
CL
1~'~
2
1.0~
~2
~5
1"0
1"5
C~mole/[.
0
#0
80T°
lho. 3. Logarithmic viscosity of polyamidosulphonamides based on 4,4'-diphcnyld~ulphonylchloride (1), 2,4-toluene disulphonylchloride (2) and 3,3'.diphenylsulphone disulphonylchloride (3) as a function of concentration of monomers (a) and also temperature of firs~ stage of synthesis of 4,4'-diphenyldisulphonylchloride (b). Thus, a peculiarity of the behaviour of the disulphonylchlorides on polycondensation in DMAA is their lower reactivity in relation to the aromatic diamine hydrochlorides and less proneness to secon(lary reactions. The main properties of polyamidosulphonamides. Table l shows that in the series polyamides-polyamidosulphonamides-polysulphonamides the softening point of the polymers falls while the solubility improves: for a content of the sulphonamide groups below 25% the polymer loses solubility in the T H F - w a t e r mixture. To study the influence of the structure of the disulphonylchloride on the properties we synthesized various polyamidosulphonamide~s for an equimolar ratio of disulphonylchloride and carboxylic diacid chloride on the basis of iso- and terophthaloyl chlorides and various disulphonylchlorides and diamines indicated in Table 2. From the results of X-ray structural analysis all the polymers obtained are amorphous. The softening point of the polyamidosulphonamides, based on isophthaloyl chloride the properties of which are indicated in Table 2, lies within the limits 185-265°C; most of the polymers based on terephthaloyl chloride do not soften on heating to 500°C. T h e polvamidosulphonamides like the aromatic
Copolycon,h,nsation of diamines
1869
polyamides and polysulphonamides are insoluble in hydrocarbons and chlorinated hydrocarbons, in aliphatic alcohols, acotonitrile, acetic acid and in 80% aqueous ethanol. To obtain concentrated solutions of most of the polyamidosulphonamides based on isophthaloyl chloride most suitable are solvents of the amide type, I)MSO, cyclohexanone, 0.5-10°~) aqueous T H F and 5-10°/o aqueous dioxane. The polyamidosulphonamidcs based on terephthaloyl chloride dissolve only in solvents of the amide type and some of them in DMSO. Study of hydrolytic stal)ility showed that. in concentrated sulphuric acid not only is there dissolution of the polymer but also degradation of the S02NH bonds, which leads, as in the c~se of aromatic polysulphonamides [3] to fall in MW. In 10% KO]t solution the polyamidosulphonamidcs hydrol,'se: slowly at 22°C (heterogeneously) and rapidly at 100°C (with dissolution). The water and moisture abso,])tion of the synthesized l)olyamidosulphonamidos like the polysulphonanfidcs [3] is less than for the armm~tic polyamidos [8]. Thus on 1)oiling in w,~ter to saturation the. monolithic pellets of polymers 1, 5* and 8' absorb respectively 5, 2.5 and 2.5% w a ~ r while when kept in air at 28°0 fihns of the polymers 5* and 8t absorb 1% water. Better solubility and ability to soften at lower temperatures as compared with the polyamidos fit cilitate the processing of the l)olyamidosulphonamides. From solution of the polymers based on 4,4-diphcnyl disulphonylchloride and 2.4-toluene (lisulphonylchloride (polymers l and 8) in I)MAA we obtained transparent films the properties of which arc given below. Polymer I),med on Disruptive stress on stretching, MPa Relative elongation at rupture, °o Dielectric eonstnnt Tangent of Iho nn~]' of dieh,et.ric losses, tan J × I0 2 Specific volmnelric ch,etrieal resislance, .Q. en~ Electrical stwngt.h, kV/mm
4,4'-diphenyl 2,4-toluene disulphonylehhwide disulphonylehloride 83 9
58 5
4-8
4.0
2"5
I-7
I ' S x 101~ 130
2'5)< 1011 110
The samples of polymer 1 obtained by direct pressing had a resilience lq0 N.cm/cm". Starti~,ff substance.,.. For synthesi.~ we used disulphonylehlorides with the melting points indicated in "]?able 2, p-toluene sulphonylehh)ride melting at 67.5-68°C, m-phenylenediamine of grade pure fi)r analysis, 4,4'-diaminodiphenyloxide (MRTU B-09-2665-65) and aniline grade " p u r e " twice distilled at 1.33 kPa. * On the basis of terephthaloyl chloride', t Composition of pnlymers is indicated in Table 2,
1870
L. B. SOKOLOV (dee.) et el.
Kinetic measuremenSs. Tile rate of acylation of aniline with sulphonyl chlorides in DMAA at 25°C was studied b y determining the ongoing concentration of aniline bromometrically with iodometrie indication of the titration end point at 2-3°C. Sulphonylehlorido in the form of a finely crushed powder was rapidly introduced into the solution of aniline in DMAA; the reaction was arrested with dilute hydrochloric acid. Synthesis of the polyamidosulphonamide~,. To the diamine dissolved in DMAA a t 22°C was a d d e d with agitation the solid disulphonylclfloridc. After a certain time (I hr) the solution was cooled to 0-5°C and the solid diaeid chloride of the carboxylie acid added. Synthesis was carried out for 1 hr at 22°C, the concentration of the monomers was ~ 5 mole/l. The polymer was separated out with water, washed, dried and the logarithmic viscosity in DMAA at 25°C determined (concentration of p,)lymer 0.Sg/100ml). Translate~l by A. CRozY REFERENCES 1. F. E. ARNOLD, 8. CANTOR and C. 8. MARVEL, J. Polymer Sci. A - l , 5: 553, 1967 2. P. U. MORGAN, Polikondensatsionnye protsessy sinteza polimerov (Polycondensation Processes of Polymer Synthesis). Khimiya, Moscow, 1970 3. V. I. LOGUNOVA and L. B. SOKOLOV, Vysokom,fl. soycd. A22: 321, 1980 (Translated in P o l y m e r Sei. U.S.S.R. 22: 2, 357, 1980) 4. V. I. LOGUNOVA, L. B. SOKOLOV, V. M. SAZINOV and L. M. VESELOVA, U.S.S.R. Pat. 522205, Byull. izobr., No. 27, 78, 1976 5. S. 1"._KW0LI~K, U.S.A. Pat. 3591559, Publ. in RZhKhim. 5S434P, 1972 6. Y. IMAI, M. UED& a n d T. I I Z A W A , Polymer Letters 17: 1483, 1979 7. L. B. SOKOLOV and V. I. LOGUNOVA, Vysokomol. soyed. A21: 1075, 1!}79 (Translated in P o l y m e r Sci. U.S.S.R. 21: 5, 1177, 1979) 8. L. B. SOKOLOV, V. D. GERASIMOV, V. M. SAZINOV and V. K. BELYAKOV, Termostoikiye aromatieheskiye poliamidy (Heat Stable Aromatic Polyamides). Khimiya, Moscow, 1975 9. V. S. NAUMOV, L. B. SOKOLOV and A. A. SPRYS:KOV, U.S.S.R. Pat. 451339, Byull. izobr., :No. 41,238, 1978