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Synthesis and properties of sulphur-containing oligodiamines and epoxide polymers on their basis
Synthesis a n d properties of sulphur-oont~iningoligodiamines
1523
12. L. V. ZUBAKOVA, A. S. TEVLINA a n d A. B. DAVANKOV, Sinteticheskiye ionoobmennyye materialy (Synthetic Ion-exchange Materials), p. 149, Khimiya, Moscow, 1978 13. G. I. MIGACHEV, N. G. GREKHOVA and N. S. DOKUNIKHII~, Zh. organ, khimii 14: 2380, 1978
Polymer Science U.S.S.R. Vol. 25, ~o. 6, pp. 1523-1529, 1983 Printed in Poland
0032-3950183 $10.00q-.O0 ~) 1984 Pergamon Press Ltd.
SYNTHESIS AND PROPERTIES OF SULPHUR-CONTAINING OLIGODIAMINES AND EPOXIDE POLYMERS ON THEIR BASIS* V. A. SE~G~YnV, V. I. ~NT:EDEL'KINand V. U. NovIKov A. N. Nesmeyanov I n s t i t u t e of Itetero-organic Compounds, U.S.S.R. Academy ,Jr Scie~,~e(,s All-Union Correspondence Polytechnic
(Received 14 March 1982) A study was made of properties of oligo-l,4-phenylenesulphide sulphone-~,e~diamhms and sulphur-containing polyepoxides synthesized from them. I t was shown to be possible to regulate properties of thes¢~ preparations b y changing t h , molecular weight of oligodiamine.
~LROMATIC diamines with groups linked between benzene rings are widely us,~d as curing agents of epoxide oligomers [1]. Polyepoxides formed in the case of using diamine with an ether or sulphide bond have increased flexibility, while polyepoxides based on 4,4'-diaminodiphenylsulphone--have high heat stability [2]; increasing the distance between amino-groups on transition from bi-nuclear diamines to tetra-nuclear diamines, 4,4'-bis-(4"-aminophenoxy)diphenylsulphone containing sulphone and ether bonds simultaneously, is accompanied by an increase in the strength, heat- and chemical-resistance of poly-epoxides [3]. Poly-epoxides containing linked 0, S or SO~ groups in the diglycidyl fragment [4] have increased elastic and thermal properties [4]. It is therefore advisable to obtain oligomer aromatic diamines with varying distance between amino end groups and sulphide, sulphonic and ether groups contained simultaneously in the chain and use these for the controlled variation of the structure and properties of epoxide polymers. Oligomer a,w-diamines based on polyarylene sulphoxides have been kno~ul previously, which had been used for the synthesis of poly-amidoimides [5, 6], polyimides [7] and as crosslinking agents of chlorine-containing aliphatic polymers * Vysokomol. soyed. A25" No. 6, 1311-1315, 1983.
1524
V . A . SE~to~.YEv et al.
TABLE 1.
C01~DITIONS OF SYNTHESIS AND PROPERTIES
OF
OLIGO-1,4-
pHE1WlrLENE S U L P H I D E S U L P H O N E - ~ 0 ~ - D I A M I N E S
Time of synthesis before the addition of sodium 4-aminophenate, br
o
Tsof t
N,* %
3-70
M
0.5
130
1.0
140
2.0
160
3.0
160
1.72 1.67
1620
5"0
I60
1.10 -1.05
2540
4.12 2.50 2.38 2.03
1.96
Average degree of polyeondensation
870
1120
1380
"4
* Calculated f or average degree of polycondensatlon (value found tn the numerator, that calculated, in denominator).
[8]. However, there is no information available in the literature about their use as curing agents of epoxypolymers. By polycondensation of 4,4'-dichlorodiphenylsulphone with sodium sulphide in the presence of a mono-functional agent interrupting the propagation of a sodium 4-aminophenate chain aromatic oligomer a,o)-diamines were obtained with a ~ e l d of 50-70%, containing S, S02 and 0 bridge groups simultaneously in the chain between 1,4-disubstituted phenylene units [9]. In order to control MW of oligo-l,4-phenylenesnlphide sulphone-a,w-diamines, the agent interrupting chain propagation was introduced some time after the start of polycondensation of 4,4'-dichlorodiphenylsulphone with sodium sulphide. Results of investigation are shown in Table 1, which indicate that on introducing an agent interrupting chain propagation 30 min after the start of polycondensation of 4,4'-dichlorodiphenylsulphone with sodium sulphide, nitrogen content in oligomers is 3.7%. With an increase in the time of polycondensation of monomers before the introduction of sodium 4-aminophenate, nitrogen content in oligomers decreases and is 1-1% after 5 hr synthesis. In I R spectra of oligomers obtained (Fig. 1) the following absorption bands were identified (em-1): 820--out-of-plane deformation vibrations of G--H bonds of 1,4-disubstituted benzene rings; 1080 and 1240--bond-stretching vibrations of phenyl--sulphur and phenyl--oxygen bonds, respectively; 1110, 1160 and 1320--bond-stretching vibrations of sulphone groups; 1480, 1580--skeletal
Synthesis and properties of sulphur-containing oligodiaanhms
1525
~ibrations of O--C bonds of aromatic rings and 3090--bond-stretching vibrations of C--H bonds of these rings. :FurShermore, there are absorption bands of lower intensity in the range of 1620 and 3380 corresponding to shearing vibrations of N - - H bonds and bond-stretching vibrations of primary amino-groups [10].
7
I
1'
II
II
1
i
15"
I
I"
18
1~ 0
I
1
[
3q
v', 10-z, crn q
FIG. 1. IR spectrum of oligo-l,4-phenylenesulphide sulphone-a,~o-diambw. Since according to results of elemental analysis, all oligomers were free from chlorine and furthermore, according to IR spectra, were free from free hydroxyl and thiol groups, aminophenylene oxide groups are, apparently, their end groups. MW of oligomers calculated from amino end groups, are 900-2500, which corresponds to a degree of polycondensation of 1 t~3 9. The system of formation of oligo-l,4-phenylenesulphide sulphone-a, oJ-diamines thus obtained may be presented o~: .
+
-3.-cl =-=J
(31_[_~---~_SO.z_,~%--S--]--(~-~/--SO.,--~--~/--CI
.N.,S
-.
NaO--<--)--NI-I~+
~ raN_ (Y'-~ _ 0 _ [_ (--~--SO,-- (Y~/--S--l--
where n~- 1-9. All oligomer diamines obtained are amorphous (according to results of X-ray analysis) powders light gray in colour, soluble in the cold in DMSO, DMF, N-methylpyrrolidone and other high-boiling organic polar solvents, but are insoluble in alcohol, benzene and aliphatic hydrocarbons. According to results of thermo-mechanical tests, oligodiamines soften at 130--160° (Table 1). They are soluble in epoxide oligomers, which enabled them to be mixed with each other. A study was made initially of the effect of temperature and the duration of hardening on the degree of completion of the reaction of epoxy-diane oligomer
1526
V . A . SERGEYEV et al.
the structure of which corresponds to oligo-=,~o-diamines, b u t without a sulphide bond (n=0). This system was regarded as a model system, which enables conditions of solidification of epoxides b y oligomer a,op-diamines to be selected. A s t u d y of solidification of the model system b y the acoustic method, I R spectroscopy and gel-analysis shows that highest structure formation is achieved with a gradual increase of temperature to 200 °. I~esults of the temperature dependence of the velocity of sound and the coefficient of mechanical loss for systems with n = 0 indicates that with an increase in the duration of solidification at 140 °, the temperature of mechanical glass transition increases from 108 (2 hr) to 133 ° (12 hr). Crosslinking density increases at the same time, which is confirmed b y a reduction in MW of the chain segment between crosslink units Mg from 102 kg/kmole in 2 hr to 98 kg/kmole in 12 hr, while elastic properties at room temperature change slightly (Fig. 2). An increase in the temperature of hardening to 160 somewhat lowers Mg and increases the temperature of glasstransition (Fig. 2, curve d). Hardening of epoxides b y oligomer diamines was therefore carried out b y a gradual mechanism with a final temperature of 200 °. with 4,4'-bis-(4"-aminophenoxy)diphenylsulphone,
(a) (J) (z) izI 12- 1Z ~.
3.1 q
q-
l qI
I
50
I
I
100
150
I
ZOO 7==
Fxo. 2. Temperature dependence of the velocity of soun4 in oligoepoxide (ED-20), h a rde ned wit h 4,4' -bis-(4" -aminoph enoxy)dip11enylsulph ono: 1-- 140°,2 hr ; 2--140 °, 6 hr, 3, 4--140 °, 12 hr; 4--140 °, 12 hr+160 °, 3 hr. Figure 3 shows the temperature dependence of the velocity Of sound C and the t a n g e n t of mechanical loss angle tan 5 for epoxydiane oligomer samples hardened with oligo-l,4-phenylenesulphide sulphone-a, op-diamines with a degree of polycondensation of 3, 5 and 9. For curves of C (T) and tan ~ (T) the presence in the range of segmental mobility of several transitions is typical. These, apparently, reflect the structural heterogeneity of the oligomer-oligomer system, which is due to the presence of oligophenylenesulphide sulphone and oligoepoxide fragments of different structure in the hardened polymers. With an in-
Synthesis and properties of sulphur-containingoligodiamines
1527
crease in MW of oligodiamine, these transitions are observed at higher temperatures, while Mg and the maximum value of tan 5 increases in the a-transition (Table 2). TABLE
2. E F F E C T OF T H E D E G R E E OF POLYCOI~IDENSATIOI~ OF O L I G O - 1 , 4 - P H E N Y L E N E S U L P H I D E SULPHOI~E-~,(0-DIAJYrINE O1~ P R O P E R T I E S OF S O L I D I F I E D P O L Y E P O X I D E S
Degree of polycondensation of oligodiamine
o
tan 5
Tg
M-g, kg/kmole
Velocity of sound, C X 10 -'~,
Esoo, MPa
eln/s(~c 107 135 143 156
0"71 0"87 0"93
127 130 148 142
59 154 206 331
1"22
1973 2067 2679 2467
Table 2 indicates that the glass-transition temperature of hardened polymers increases with an increase in MW of a,e)-diamine with a simultaneous reduction in crosslinldng density. This is, apparently, due to an increase in the weight fraction of sulphone-containing aromatic polar sections between network units in the polyepoxides, resulting in an increase in chain interaction and therefore, an increase in the glass-transition temperature, although crosslinking density decreases. This is also confirmed by results in Fig. 4 concerning the dependence of the glass temperature of hardened polymers on the content of sulphone groups in initial oligomer diamines, according to which the glass temperature of polyepoxide increases with an increase in the proportion of sulphone groups. Therefore, heat-resistant, sulphur-containing crosslinked polyepoxides were obtained from oligo-l,4-phenylenesulphide sulphone-a,e)-diamines synthesized; t,heir structure and physical properties may be controlled within wide limit,s by changing MW of oligodiamine.
C,lO-,%m/~ec 15
b
tan8
a
t'an~
0'6
1"2
O,q
0.8
70
5
m-
0"2 I
50
I
lOO
I
fSO
......
"I
---
ZOO
100
150
o.q
200 T °
FIG. 3. Temperature dependence of the velocity of sound (a) and the tangent of mechanical loss angle (b) for hardened polyepoxide samples. Degree of polymerization of ~,c3-diamine n - - 3 (1), 5 (2), 9 (3).
V . A . S~a~G~.Y~v et al.
1528
r~ y ~ Of oligo-l,4-phenylenesulphide sulphone.a,eo-diamines. 57-4 g (0.2 mole) 4,4"4ichlorodiphenylsulphone, 45.6 g (0.19 mole) nona-hydrate crystal o f sodium sulphide, 250 ml DMSO and 50 ml tohmne were placed in a four-neck vessel of 500 ml volume, provide4 with a mechanical stirrer, thermometer, a D e a n - S t a r k headpiece and inlet for argon. The content of the flask was heated, while stirring, i~l argon over an oil bath up to 120°; the water-toluene azeotrope was first distilled, followed by pure tohmne. Temperature was then increased to 170 ° and the reaction mass stirred for 0. 5 to 5"0 hr according to t h e time of synthesis mltil the introdnction of the agent interrupting chain propagation (Table 1}. The content of the flask was cooled to 145 °, 13. l g (0.1 mole) sodium 4-aminophenate was added, temperature raised to 170 ° and retabmd while stirring for 4 hr. After cooling to room temperature, the oligomer solution was filtered to remove sodium chloride and precipitated by slow dropwise addition to 1500 ml l~o dilute solution of sodium sulphite whihstirring vigorously. The oligomer precipitated into residue was filtered, rinsed with water to remove traces of chlorine ions (m~mples tested with silver nitrate) and dried at 100 ° in v a c u u m at 765 Pa to constant weisht. Yield and some properties of oligomers are shown in Table 1.
40i/ 100 I:-I
Ii I 23
I 25
80z,%
Fro. 4. Dependence of the glass temperature of hardened polyepoxides on the content of SO~ groups in the curing agent.
4,4'-Bis (4"-aminophenoxy)diphenyIaulpho~ was prepared by condensation of 4,4'-diehiorodiphenylsulphone with sodium 4-aminophenate b y methods previously d e ~ % e d [11]. M.p. 192 ° (results in the literature give 191-192 ° [11]). Orosalinkedepoxidepolym~rs were obtained by interemtion of oligo-l,4-phenylsulphid¢, sulphone-a,eo-diamines with ED-20 epoxide oligomer in a molecular ratio of 1 : 2 using the following conditions of hardening: 70 ° - 1 hr, 85 ° -- 1 hr, 100°--2 hr, 140 ° - 2 hr and thc.t~ under a pressure o f 5 MPa in a mould; 160°--4 hr, 180°--2 hr and 200°--2 hr. lnvestiqation o,f polymers. The temperature dependence of acoustic properties (velocity of sound an d coefficient o f mechanical losses) was studied by the method of resonant vibrations [12] of an overhanging sample (1 × 5 × 70 ram), the rate of temperature increase being I deg/min. Softening point was determined from temperature/deformation curves plotted usin~ samples 4. 5 m m in diameter and 2 ram high. The rate of temperature increase was 1 deg/min. The gel-fraction was determined by extremtion of powdered samples using boiling acetone in a Soxblet apparatus. I R spectra were obtained using a UR-20 device and K B r pellets an d diffractmn curves were obtained using a DRON-1 device with GuK, radiation. Translated by E. SI~ERE
Mech~ll dsm of conformation change-overs in 1)olymor chains
1529
REFERENCES 1. Kh. LI a n d K. NEVILL, Spravochnoye rukovodstvo po epoksidr~ym .~mobm~ (Han4book on Epoxide Resins), p. 98, Energiya, Moscow, 1973 2. V. A. LAPITSKII, N. A. DURMANENKO, T. I. PILIPENKO and P. A. PRUDKAI, (book): Khimicheakaya tekhnologiya (Chemical Technology). p. 31, :Naukova dumka, Kiev, 1.f}73 3. V. A. LAPITSKII, T. I. PILIPENKO, L. K. POPOV and B. M. USHAKOVA, A.e. 476296 (U.S.S.R.), Publ. in Buyll. izobr., No. 25, 79, 1975 4. N. K. RED'KINA, E. A. DZHAVADYAN, T. I. PONOMAREVA, E. V. PRUT, L. A. DUBINA a n d B. A. ROZEN'BERG, Vysokomol. soyed. B23: 777, 1981 (Not trans!~te(1 in Polymer Sci. U.S.S.R.) 5. G. T. :KWIATKOWSKI, G. L. BRODE, L. M. ROBENSON, Pat. 3658938 (U.S.A.), P~bl. in RZhKhim., 4C557P, 1973 6. G. T. K W I A T K O W S K I , G. L. B R O D E , J. H. KAWAKAMI a n d A. W. B E D W I N . J. Polymer Sci., Polymer Chem. Ed. 12: 589, 1974 7. G. T. K W I A T K O W S K I , L. M. R O B E N S O N , G. L. BRODE and A. W. BEDWLN', .1. Polymer Sci., Polymer Chem. Ed. 13: 961, 1975 8. S. INAGAKI, Y. ONOUCHI, H. OKAMOTO a n d J. FURUKAWA, :Nippon Gomi KXo~:,kaishi 58: 177, 1980 9. V. A . S E R G E Y E V , V. I. N E D E L ' K I N , V.-Ya. LEPILIN and V. D. V O R O B ' Y E V , A.c. 676597 (U.S.S.R.), Publ. in Buyll. izobr., No. 28, 93, 1979 10. R. SIL'VERSTEIN, G. BASSLER and T. MORHff,~ Spektrometricheskaya identifikatsiya organieheskikh soyedinenii (Spectrometric Identification of Organic Compou~ds), p. 125, Mir, Moscow, 1977 11. J. N. K A W A K A M I , G. T. K W I A T K O W S K I , G. L. BRODE a n d A. W . B E D W I N , J. Polymer Sci., Polymer Chem. Ed. 12: 565, 1974 12. I. I. PEREPECH]KO, Akusticheskiye metody issledovaniya polimerov (Acoustic Methods of Investigating Polymers), p. 229, Khimiya, Moscow, 1973
Polvmer Science U.S.8.I~, Vet. 25, l~o. 6, pp. 1529-1538, 1983
0032-3950/83 $10.00+ .00 © 1984 Pergamon Pre~ Ltd.
Printed in Poland
MECHANISM OF CONFORMATION CHANGE-OVERS IN POLYMER CHAINS* L. S. PRISS a n d Y r . A. GAMLITSKII Scientific Research I n s t i t u t e of the Tyre I n d u s t r y
(Received 23 March 1982) :New ideas are p u t forward about the mechanism of conformation change-overs ill polymer chains which take pla~e in sections exter.~;" ': to five or six lmits. After trmlsition through the potential barrier rotal T isomei~ of the section m a y appear dis* Vysokomol. soyed. A~5: No. 6, 1316-1323, 1983.
1523
12. L. V. ZUBAKOVA, A. S. TEVLINA a n d A. B. DAVANKOV, Sinteticheskiye ionoobmennyye materialy (Synthetic Ion-exchange Materials), p. 149, Khimiya, Moscow, 1978 13. G. I. MIGACHEV, N. G. GREKHOVA and N. S. DOKUNIKHII~, Zh. organ, khimii 14: 2380, 1978
Polymer Science U.S.S.R. Vol. 25, ~o. 6, pp. 1523-1529, 1983 Printed in Poland
0032-3950183 $10.00q-.O0 ~) 1984 Pergamon Press Ltd.
SYNTHESIS AND PROPERTIES OF SULPHUR-CONTAINING OLIGODIAMINES AND EPOXIDE POLYMERS ON THEIR BASIS* V. A. SE~G~YnV, V. I. ~NT:EDEL'KINand V. U. NovIKov A. N. Nesmeyanov I n s t i t u t e of Itetero-organic Compounds, U.S.S.R. Academy ,Jr Scie~,~e(,s All-Union Correspondence Polytechnic
(Received 14 March 1982) A study was made of properties of oligo-l,4-phenylenesulphide sulphone-~,e~diamhms and sulphur-containing polyepoxides synthesized from them. I t was shown to be possible to regulate properties of thes¢~ preparations b y changing t h , molecular weight of oligodiamine.
~LROMATIC diamines with groups linked between benzene rings are widely us,~d as curing agents of epoxide oligomers [1]. Polyepoxides formed in the case of using diamine with an ether or sulphide bond have increased flexibility, while polyepoxides based on 4,4'-diaminodiphenylsulphone--have high heat stability [2]; increasing the distance between amino-groups on transition from bi-nuclear diamines to tetra-nuclear diamines, 4,4'-bis-(4"-aminophenoxy)diphenylsulphone containing sulphone and ether bonds simultaneously, is accompanied by an increase in the strength, heat- and chemical-resistance of poly-epoxides [3]. Poly-epoxides containing linked 0, S or SO~ groups in the diglycidyl fragment [4] have increased elastic and thermal properties [4]. It is therefore advisable to obtain oligomer aromatic diamines with varying distance between amino end groups and sulphide, sulphonic and ether groups contained simultaneously in the chain and use these for the controlled variation of the structure and properties of epoxide polymers. Oligomer a,w-diamines based on polyarylene sulphoxides have been kno~ul previously, which had been used for the synthesis of poly-amidoimides [5, 6], polyimides [7] and as crosslinking agents of chlorine-containing aliphatic polymers * Vysokomol. soyed. A25" No. 6, 1311-1315, 1983.
1524
V . A . SE~to~.YEv et al.
TABLE 1.
C01~DITIONS OF SYNTHESIS AND PROPERTIES
OF
OLIGO-1,4-
pHE1WlrLENE S U L P H I D E S U L P H O N E - ~ 0 ~ - D I A M I N E S
Time of synthesis before the addition of sodium 4-aminophenate, br
o
Tsof t
N,* %
3-70
M
0.5
130
1.0
140
2.0
160
3.0
160
1.72 1.67
1620
5"0
I60
1.10 -1.05
2540
4.12 2.50 2.38 2.03
1.96
Average degree of polyeondensation
870
1120
1380
"4
* Calculated f or average degree of polycondensatlon (value found tn the numerator, that calculated, in denominator).
[8]. However, there is no information available in the literature about their use as curing agents of epoxypolymers. By polycondensation of 4,4'-dichlorodiphenylsulphone with sodium sulphide in the presence of a mono-functional agent interrupting the propagation of a sodium 4-aminophenate chain aromatic oligomer a,o)-diamines were obtained with a ~ e l d of 50-70%, containing S, S02 and 0 bridge groups simultaneously in the chain between 1,4-disubstituted phenylene units [9]. In order to control MW of oligo-l,4-phenylenesnlphide sulphone-a,w-diamines, the agent interrupting chain propagation was introduced some time after the start of polycondensation of 4,4'-dichlorodiphenylsulphone with sodium sulphide. Results of investigation are shown in Table 1, which indicate that on introducing an agent interrupting chain propagation 30 min after the start of polycondensation of 4,4'-dichlorodiphenylsulphone with sodium sulphide, nitrogen content in oligomers is 3.7%. With an increase in the time of polycondensation of monomers before the introduction of sodium 4-aminophenate, nitrogen content in oligomers decreases and is 1-1% after 5 hr synthesis. In I R spectra of oligomers obtained (Fig. 1) the following absorption bands were identified (em-1): 820--out-of-plane deformation vibrations of G--H bonds of 1,4-disubstituted benzene rings; 1080 and 1240--bond-stretching vibrations of phenyl--sulphur and phenyl--oxygen bonds, respectively; 1110, 1160 and 1320--bond-stretching vibrations of sulphone groups; 1480, 1580--skeletal
Synthesis and properties of sulphur-containing oligodiaanhms
1525
~ibrations of O--C bonds of aromatic rings and 3090--bond-stretching vibrations of C--H bonds of these rings. :FurShermore, there are absorption bands of lower intensity in the range of 1620 and 3380 corresponding to shearing vibrations of N - - H bonds and bond-stretching vibrations of primary amino-groups [10].
7
I
1'
II
II
1
i
15"
I
I"
18
1~ 0
I
1
[
3q
v', 10-z, crn q
FIG. 1. IR spectrum of oligo-l,4-phenylenesulphide sulphone-a,~o-diambw. Since according to results of elemental analysis, all oligomers were free from chlorine and furthermore, according to IR spectra, were free from free hydroxyl and thiol groups, aminophenylene oxide groups are, apparently, their end groups. MW of oligomers calculated from amino end groups, are 900-2500, which corresponds to a degree of polycondensation of 1 t~3 9. The system of formation of oligo-l,4-phenylenesulphide sulphone-a, oJ-diamines thus obtained may be presented o~: .
+
-3.-cl =-=J
(31_[_~---~_SO.z_,~%--S--]--(~-~/--SO.,--~--~/--CI
.N.,S
-.
NaO--<--)--NI-I~+
~ raN_ (Y'-~ _ 0 _ [_ (--~--SO,-- (Y~/--S--l--
where n~- 1-9. All oligomer diamines obtained are amorphous (according to results of X-ray analysis) powders light gray in colour, soluble in the cold in DMSO, DMF, N-methylpyrrolidone and other high-boiling organic polar solvents, but are insoluble in alcohol, benzene and aliphatic hydrocarbons. According to results of thermo-mechanical tests, oligodiamines soften at 130--160° (Table 1). They are soluble in epoxide oligomers, which enabled them to be mixed with each other. A study was made initially of the effect of temperature and the duration of hardening on the degree of completion of the reaction of epoxy-diane oligomer
1526
V . A . SERGEYEV et al.
the structure of which corresponds to oligo-=,~o-diamines, b u t without a sulphide bond (n=0). This system was regarded as a model system, which enables conditions of solidification of epoxides b y oligomer a,op-diamines to be selected. A s t u d y of solidification of the model system b y the acoustic method, I R spectroscopy and gel-analysis shows that highest structure formation is achieved with a gradual increase of temperature to 200 °. I~esults of the temperature dependence of the velocity of sound and the coefficient of mechanical loss for systems with n = 0 indicates that with an increase in the duration of solidification at 140 °, the temperature of mechanical glass transition increases from 108 (2 hr) to 133 ° (12 hr). Crosslinking density increases at the same time, which is confirmed b y a reduction in MW of the chain segment between crosslink units Mg from 102 kg/kmole in 2 hr to 98 kg/kmole in 12 hr, while elastic properties at room temperature change slightly (Fig. 2). An increase in the temperature of hardening to 160 somewhat lowers Mg and increases the temperature of glasstransition (Fig. 2, curve d). Hardening of epoxides b y oligomer diamines was therefore carried out b y a gradual mechanism with a final temperature of 200 °. with 4,4'-bis-(4"-aminophenoxy)diphenylsulphone,
(a) (J) (z) izI 12- 1Z ~.
3.1 q
q-
l qI
I
50
I
I
100
150
I
ZOO 7==
Fxo. 2. Temperature dependence of the velocity of soun4 in oligoepoxide (ED-20), h a rde ned wit h 4,4' -bis-(4" -aminoph enoxy)dip11enylsulph ono: 1-- 140°,2 hr ; 2--140 °, 6 hr, 3, 4--140 °, 12 hr; 4--140 °, 12 hr+160 °, 3 hr. Figure 3 shows the temperature dependence of the velocity Of sound C and the t a n g e n t of mechanical loss angle tan 5 for epoxydiane oligomer samples hardened with oligo-l,4-phenylenesulphide sulphone-a, op-diamines with a degree of polycondensation of 3, 5 and 9. For curves of C (T) and tan ~ (T) the presence in the range of segmental mobility of several transitions is typical. These, apparently, reflect the structural heterogeneity of the oligomer-oligomer system, which is due to the presence of oligophenylenesulphide sulphone and oligoepoxide fragments of different structure in the hardened polymers. With an in-
Synthesis and properties of sulphur-containingoligodiamines
1527
crease in MW of oligodiamine, these transitions are observed at higher temperatures, while Mg and the maximum value of tan 5 increases in the a-transition (Table 2). TABLE
2. E F F E C T OF T H E D E G R E E OF POLYCOI~IDENSATIOI~ OF O L I G O - 1 , 4 - P H E N Y L E N E S U L P H I D E SULPHOI~E-~,(0-DIAJYrINE O1~ P R O P E R T I E S OF S O L I D I F I E D P O L Y E P O X I D E S
Degree of polycondensation of oligodiamine
o
tan 5
Tg
M-g, kg/kmole
Velocity of sound, C X 10 -'~,
Esoo, MPa
eln/s(~c 107 135 143 156
0"71 0"87 0"93
127 130 148 142
59 154 206 331
1"22
1973 2067 2679 2467
Table 2 indicates that the glass-transition temperature of hardened polymers increases with an increase in MW of a,e)-diamine with a simultaneous reduction in crosslinldng density. This is, apparently, due to an increase in the weight fraction of sulphone-containing aromatic polar sections between network units in the polyepoxides, resulting in an increase in chain interaction and therefore, an increase in the glass-transition temperature, although crosslinking density decreases. This is also confirmed by results in Fig. 4 concerning the dependence of the glass temperature of hardened polymers on the content of sulphone groups in initial oligomer diamines, according to which the glass temperature of polyepoxide increases with an increase in the proportion of sulphone groups. Therefore, heat-resistant, sulphur-containing crosslinked polyepoxides were obtained from oligo-l,4-phenylenesulphide sulphone-a,e)-diamines synthesized; t,heir structure and physical properties may be controlled within wide limit,s by changing MW of oligodiamine.
C,lO-,%m/~ec 15
b
tan8
a
t'an~
0'6
1"2
O,q
0.8
70
5
m-
0"2 I
50
I
lOO
I
fSO
......
"I
---
ZOO
100
150
o.q
200 T °
FIG. 3. Temperature dependence of the velocity of sound (a) and the tangent of mechanical loss angle (b) for hardened polyepoxide samples. Degree of polymerization of ~,c3-diamine n - - 3 (1), 5 (2), 9 (3).
V . A . S~a~G~.Y~v et al.
1528
r~ y ~ Of oligo-l,4-phenylenesulphide sulphone.a,eo-diamines. 57-4 g (0.2 mole) 4,4"4ichlorodiphenylsulphone, 45.6 g (0.19 mole) nona-hydrate crystal o f sodium sulphide, 250 ml DMSO and 50 ml tohmne were placed in a four-neck vessel of 500 ml volume, provide4 with a mechanical stirrer, thermometer, a D e a n - S t a r k headpiece and inlet for argon. The content of the flask was heated, while stirring, i~l argon over an oil bath up to 120°; the water-toluene azeotrope was first distilled, followed by pure tohmne. Temperature was then increased to 170 ° and the reaction mass stirred for 0. 5 to 5"0 hr according to t h e time of synthesis mltil the introdnction of the agent interrupting chain propagation (Table 1}. The content of the flask was cooled to 145 °, 13. l g (0.1 mole) sodium 4-aminophenate was added, temperature raised to 170 ° and retabmd while stirring for 4 hr. After cooling to room temperature, the oligomer solution was filtered to remove sodium chloride and precipitated by slow dropwise addition to 1500 ml l~o dilute solution of sodium sulphite whihstirring vigorously. The oligomer precipitated into residue was filtered, rinsed with water to remove traces of chlorine ions (m~mples tested with silver nitrate) and dried at 100 ° in v a c u u m at 765 Pa to constant weisht. Yield and some properties of oligomers are shown in Table 1.
40i/ 100 I:-I
Ii I 23
I 25
80z,%
Fro. 4. Dependence of the glass temperature of hardened polyepoxides on the content of SO~ groups in the curing agent.
4,4'-Bis (4"-aminophenoxy)diphenyIaulpho~ was prepared by condensation of 4,4'-diehiorodiphenylsulphone with sodium 4-aminophenate b y methods previously d e ~ % e d [11]. M.p. 192 ° (results in the literature give 191-192 ° [11]). Orosalinkedepoxidepolym~rs were obtained by interemtion of oligo-l,4-phenylsulphid¢, sulphone-a,eo-diamines with ED-20 epoxide oligomer in a molecular ratio of 1 : 2 using the following conditions of hardening: 70 ° - 1 hr, 85 ° -- 1 hr, 100°--2 hr, 140 ° - 2 hr and thc.t~ under a pressure o f 5 MPa in a mould; 160°--4 hr, 180°--2 hr and 200°--2 hr. lnvestiqation o,f polymers. The temperature dependence of acoustic properties (velocity of sound an d coefficient o f mechanical losses) was studied by the method of resonant vibrations [12] of an overhanging sample (1 × 5 × 70 ram), the rate of temperature increase being I deg/min. Softening point was determined from temperature/deformation curves plotted usin~ samples 4. 5 m m in diameter and 2 ram high. The rate of temperature increase was 1 deg/min. The gel-fraction was determined by extremtion of powdered samples using boiling acetone in a Soxblet apparatus. I R spectra were obtained using a UR-20 device and K B r pellets an d diffractmn curves were obtained using a DRON-1 device with GuK, radiation. Translated by E. SI~ERE
Mech~ll dsm of conformation change-overs in 1)olymor chains
1529
REFERENCES 1. Kh. LI a n d K. NEVILL, Spravochnoye rukovodstvo po epoksidr~ym .~mobm~ (Han4book on Epoxide Resins), p. 98, Energiya, Moscow, 1973 2. V. A. LAPITSKII, N. A. DURMANENKO, T. I. PILIPENKO and P. A. PRUDKAI, (book): Khimicheakaya tekhnologiya (Chemical Technology). p. 31, :Naukova dumka, Kiev, 1.f}73 3. V. A. LAPITSKII, T. I. PILIPENKO, L. K. POPOV and B. M. USHAKOVA, A.e. 476296 (U.S.S.R.), Publ. in Buyll. izobr., No. 25, 79, 1975 4. N. K. RED'KINA, E. A. DZHAVADYAN, T. I. PONOMAREVA, E. V. PRUT, L. A. DUBINA a n d B. A. ROZEN'BERG, Vysokomol. soyed. B23: 777, 1981 (Not trans!~te(1 in Polymer Sci. U.S.S.R.) 5. G. T. :KWIATKOWSKI, G. L. BRODE, L. M. ROBENSON, Pat. 3658938 (U.S.A.), P~bl. in RZhKhim., 4C557P, 1973 6. G. T. K W I A T K O W S K I , G. L. B R O D E , J. H. KAWAKAMI a n d A. W. B E D W I N . J. Polymer Sci., Polymer Chem. Ed. 12: 589, 1974 7. G. T. K W I A T K O W S K I , L. M. R O B E N S O N , G. L. BRODE and A. W. BEDWLN', .1. Polymer Sci., Polymer Chem. Ed. 13: 961, 1975 8. S. INAGAKI, Y. ONOUCHI, H. OKAMOTO a n d J. FURUKAWA, :Nippon Gomi KXo~:,kaishi 58: 177, 1980 9. V. A . S E R G E Y E V , V. I. N E D E L ' K I N , V.-Ya. LEPILIN and V. D. V O R O B ' Y E V , A.c. 676597 (U.S.S.R.), Publ. in Buyll. izobr., No. 28, 93, 1979 10. R. SIL'VERSTEIN, G. BASSLER and T. MORHff,~ Spektrometricheskaya identifikatsiya organieheskikh soyedinenii (Spectrometric Identification of Organic Compou~ds), p. 125, Mir, Moscow, 1977 11. J. N. K A W A K A M I , G. T. K W I A T K O W S K I , G. L. BRODE a n d A. W . B E D W I N , J. Polymer Sci., Polymer Chem. Ed. 12: 565, 1974 12. I. I. PEREPECH]KO, Akusticheskiye metody issledovaniya polimerov (Acoustic Methods of Investigating Polymers), p. 229, Khimiya, Moscow, 1973
Polvmer Science U.S.8.I~, Vet. 25, l~o. 6, pp. 1529-1538, 1983
0032-3950/83 $10.00+ .00 © 1984 Pergamon Pre~ Ltd.
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MECHANISM OF CONFORMATION CHANGE-OVERS IN POLYMER CHAINS* L. S. PRISS a n d Y r . A. GAMLITSKII Scientific Research I n s t i t u t e of the Tyre I n d u s t r y
(Received 23 March 1982) :New ideas are p u t forward about the mechanism of conformation change-overs ill polymer chains which take pla~e in sections exter.~;" ': to five or six lmits. After trmlsition through the potential barrier rotal T isomei~ of the section m a y appear dis* Vysokomol. soyed. A~5: No. 6, 1316-1323, 1983.