Some correlations in the formation of poly(amidearylates) from polycyclic bisphenols by low-temperature polycondensation

SOMECORRELATIONSINTHEFORMATIONOFPOLY(AMIDEARYLATES)FROMPOLYCYCLIC BISPIXENOLS BYLOWTEMPERATURE POLYCONDENSATION* V. V. KORSHAK,S. V. VINO~RADOVA,G. SH. PAPAVA,R. P. TSISKARIS~~ILJ and P. D. TSISKARISEMIJ P. G. Melikishvili Institute

of Physical and Organic Chemistry, Georgian S.S.R. Academy of Sciences Institute of Hetero-organic Compounds, U.S.S.R. Academy of Sciences (Received 10 November 1970)

POLY(AMIDE-ARYLATES) obtained by .interfacial polycondensation of bisphenols of the ordinary type (diphenylolpropane, hydroquinone etc.) with diamines and acid chlorides of dibasic acids are well known [l-5]. Recently the method of synthesis of polymers by low-temperature polycondensation in solution has been used extensively [6-71, but there is no information in the literature on the preparation of poly(amide-arylates) by this method. The aim of the present paper is to study some correlations in low-temperature polycondensation leading to formation of poly(amide-arylates). By the examples of polycondensation of sebacyl chloride with 4,4’-(hexahydro-4,7_methyleneindan5ylidene) diphenol and hexamethylene diamine, and of the same diphenol and diamine with terephthalyl chloride, we have studied the effect of such factors as temperature, the nature of the solvent and t.ertiary amine, reaction time and the ratio of the reactants. DISCUSSION

Since in the co-polycondensation with dicarboxylic acid chlorides substances with end groups of different nature were used (bisphenols and diamines), it was first necessary to make certain whether under the given conditions copolymers (poly(amide-arylates) or a mechanical mixture of homopolymers is formed. For this purpose polymers obtained by polycondensation of sebacyl or terephthalyl chlorides with 4,4’-(hexahydro-4,7-methyleneindan-5-ylidene)~phenol and hexamethylene diamine, taken in the molar ratio of 1 : O-5 : 0.5 respectively, were treated with chloroform. It had been shown by previous experiment that a mechanical mixture of the corresponding polyarylate and polyamide can be separated quantitatively by treatment with chloroform, because the polyarylates from 4,4’-(hexahydro-4,7-methyleneindan-5-ylidene)diphenol and sebacyl or terephthalyl chlorides are readily soluble in chloroform, whereas the corresponding polyamides from hexamethylene diamine are insoluble. * Vysokomol. soyed. A14: No. 8, 1699-1703, 1899

1972.

V. V. KORSHA~

1900

et al.

Table 1 presents the results of elementary analysis of the polymers before treatment with chloroform and of the fractions soluble and insoluble in that solvent. It may be concluded from the figures in Table 1 that polymers of composition close to the composition that should be obtained from the reactants in the given ratio, are obtained by this reaction. At the same time it is seen that these polymers are not of uniform composition. The elementary compositions of the fractions soluble and insoluble in chloroform are different. TABLE 1. NITROUEN CONTENT OFPOLY(AMIDE-ARYLATES)FROM 4,4’-(HEXAHYDRO-4,7-METHYLEEEIEDAN-5-YLIDENE)DIFHENOL,

~E~~METHYIE~

DIAMINE AND SERACYL 0~ TICREPHTEALYL

CHLORIDES (Molar ratio of acid chloride ’Quantity Acid chloride

: bisphenol : d&nine=

of polymer,

%

1

: 0.5 : 0.5)

Nitrogen

content, %

in originS1 polymer

soluble in

insoluble

chloroform

C&lC.

/ found

1 ;z;$Ez;!r

/

/

Sebwyl

1

Terephthttlyl

ii::

1

ii::

1 2::;

;:;i

;:;;

/

::i;

The fact that the chloroform-soluble fractions contain nitrogen and that in the insoluble fractions the nitrogen content is lower than is required for the corresponding homopolyamides (the nitrogen content of polyhexamethylenesebacamide TABLE 2. EFFECT OF THE NATURE OF THE SOLVENT ON THE YIELD AND

REDUCED

(Experiments :06);

vD3COSITY OF POLY(AMIDE-ARYLATES)

1-4, sebacylchloride

experiments 5-8, terephthslyl (1

: bisphenol : diamine (1 : 0.6 : chloride : bisphenol : diamine

: 0.5 : 0.5)). -

Expt. No.

Solvent

-

mer, %,

qred

-

in trioresol

at 200, dl/g

Diohloroethsne

83

0.36

Acetone

70

0.28

Benzene

93

0.80

68

0.26

Dichloroethane

80

0.40

Acetone

90

0.62

Benzene

68

0.28

Petroleum

Petroleum

-

Yield of poly-

ether

ether

80

0.36

-

is 9.92% and of polyhexamethyleneterephthalamide 11.38%) shows that poly(amide-arylates) are formed in co-polycondensation of the above bisphenol, diamine and acid chlorides. Infrared spectroscopic evidence and thermomechanical studies

Some correlations in formation

of poly(amide-arylates)

1901

also confirm this. For example the infrared spectra of the chloroform-soluble fractions contain a band (3400 cm-‘), assigned to amide groups [S, Q] (Fig. 1). Since polyamides from hexamethylene diamine and terephtha~~ or sebacic acids are insoluble in chloroform the presence in the infrared spectrum of the chloroform-soluble fractions of a band characteristic of the --CONH-group shows that poly(a~de-arylates) are formed in the low-temperat~e polycondensation process.

Fm.

1. Infrared

spectra of the chloroform-soluble on s&a&

fractions

(ct) and terephthalic

of poly(emide-arylates)

based

(6) acids.

We studied the polycondensation of sebacyl and terephthalyl chlorides with the polycyclic bisphenol 4,4’-(hexahydro-4,7-methylene~dan-5-y~dene~~phenol and hexamethylene diamine at -30” to 50’in dichloroethane in the first instance, and at -70° to 50” in acetone in the second. The molar ratio of the reactants was 1 : 05 : 05. The tertiary amine used was triethyla~ne. It is seen from Fig. 2a that the best yield and highest reduced viscosity were obtained for polymers prepared at 20-30”. Any increase or decrease in temperature outside this range worsens the yield and reduces the molecular weight of the polymer. In a previous study of the laws of the low-temperature polycondensation it was shown that the organic medium in which it is carried out has a large effect on the process [lo]. We investigated the effect of the organic medium on the formation of poly(amide-arylates) in the reaction of sebacyl chloride with 4,4’-(hexahy~o-4,7-methyleneindan-5ylidene)diphenol and hexamethylene diamine at 30”, and of terephthalyl chloride and the same bisphenol and diamine at 20”. In both instances the reaction was carried out in the presence of triethylamine at a molar ratio of the reactants of 1 : 0.5 : 05 : 2. As organic media we used dichloroethane, acetone, benzene and petroleum ether. It is seen from Table 2 that with sebacyl chloride the best results are obtained when the polycondensation is carried out in benzene. With terephthalyl chloride the polymer with the highest viscosity and yield is obtained in acetone.

1902

v. v. KoasHag

et al.

The effect of the nature of the tertriary amine on the polycondensation process was studied with triethylamine and pyridine as examples. These experiments showed that triethylamine gives the best yield and highest reduced viscosity, and consequently triethylamine was used in all subsequent experiments.

3

4

5 6 7 A, mde/mole

8

FIQ. 2. Dependence of the reduced viecosity (I, 2) and yield (I’, 2’) of poly(amide-arylates) on reaction temperature (a), quantity of triethylamine (b) and ratio of bisphenolfdiamine (0.6 : 0.6): aoid ohloride (0): 1-poly(amide-arylato) from sebacyl chloride, Z-from torephth-

alyl chloride. A-Number of moles of triethylamine per mole of acid chloride; B-molar retie of biaphenol+diamine (045 : 0.6) : acid chloride.

As in other instances of low-temperature polycondensation [ll] the systems under teat here are not insensitive to the quantity of tertiary amine used or to the ratio of the reactants. Figure 2b shows our results on the variation in the reduced viscosity of poly(amide-arylates) with change in the quantity of tertiary amine, Best results are obtained with 2 moles of tertiary amine per mole of acid chloride. The effect of the ratio of acid chloride to the mixture of polycyclic bisphenol and hexamethylene diamine was studied in benzene at 30” in the case of sebacyl chloride, and in acetone at 20” for terephthalyl chloride. In both instances the tertiary amine was triethylamine. It was found that any deviation from the equivalent ratio of the acidic component to the d&nine-bisphenol mixture causes a marked reduction in the

molecular weight and yield of the polymer (Fig. 2~).

Some correlationsin formation of poly(amide-arylates)

Polycondensation

of the above bisphenol with hexamethylene,

1903

diam.ine and

the given acid chlorides is very rapid, and there is little change in the yield and reduced viscosity

of the polymer after 5 min from the beginning of the reaction. EXPERIMENTAL

4,4’-(Hexahydro-4,7-methyleneindan-5-ylidene)diphenol was synthesized as in reference [12]. After three or four recrystallizationsfrom acetic acid it was obtained as a white, crystalline substance with m.p. 219-221” (according to the literature, m.p. 221-223’). The other starting materials and the solvents were purified by methods described in the literature [7, 10, 13, 141. Polycondensation was carried out in a three-necked flask fitted with a stirrer, calcium chloride tube and thermometer. To a mixture of the bisphenol (0.001 mole), diamine (0.001 mole), solvent (2.6 ml) and tertiary amine (0.004 mole) the acid chloride (0.002 mole) was added, with stirring, after the bisphenol and diamine had dissolved. The reaction time was 90 min. The polymer formed was precipitated by pouring the reaction mixture into petroleum ether, the precipitated polymer was filtered off, washed with acetone, water and ether, and dried for 6-8 hr, in vacua at 106-120”. The reduced viscosity was determined with a 0.5% solution of the polymer in tricresol at 20”. CONCLUSIONS (1) A study

has been made of some correlations in the low-temperature polycondensation of 4,4’-(hexahydro-4,7-methyleneindan-5-ylidene) diphenol and hexamethylene diamine with sebacyl and terephthalyl mation of poly(amide-arylates).

chlorides, resulting in for-

(2) The highest yield and molecular weight of the polymers are obtained when equivalent quantities of the acidic component and triethylamine with respect to the mixture

of diamine and bisphenol are used, the reaction being carried out

at 30” in benzene in the case of sebacyl chloride and at 20” in acetone in the case of terephthalyl chloride. Tran&&d by E. 0. PHILLIPS REFERENCES 1. V. V. KORSKAK, 5. V. VlNOGRABOVA, T. M. FRUNZE, A. B. KOZLOV and U BANYUAN, Vysokomol. soyed. 4: 1457, 1962 (Not translated in Polymer Sci. U.S.S.R.) 2. V. V. KORSHAK, S. V. VINOGRADOVA and U BAN-YUAN, Vysokomol. soyed. 5: 969, 1963 (Translated in Polymer Sci. U.S.S.R. 5: 1,18, 1963) 3. V. V. KORSHAK, S. V. VINOGBADOVA and U BAN-YUAN, Vysokomol. soyed. 5: 1765, 1963 (Translated in Polymer Sci. U.S.S.R. 5: 6, 886, 1964) 4. V. V. KORSHAK, S. V. VINOGRABOVA and U BAN-YUAN, Izv. Akad Nauk SSSR, ser. khim., 2492, 1964 5. S. V. VINOGRADOVA, V. V. KORSHAK, T. M. FRUNZE, L. V. KOZLOV and U BANYUAN, Rus. Pat. (Authors’ Certificate). 139, 823; Byull. izobretenii, No. 14, 47, 1961 6. P. W. MORGAN, Condensation Polymerization by Interfacial and Solution Methods, International Publications, New York-London-Sydney, 1965 7. S. V. VINOGRADOVA, V. A. VASNEV and V. V. KORSHAK, Vysokomol. soyed. B9: 522, 1967 (Not translated in Polymer Sci. U.S.S.R.) 8. R. E. RICHARDS and H. W. THOMPSON, J. Chem. Sot. 1248, 1947

1904

I. M.

1\6IRKAMIL ovetal.

9. W. T. ASTBURY, C. E. DALGLIESH, 5. E. DARMON end 6. B. B. M. SUTHERLAND, Nature 162: 696, 1950 10. V. V. KORSHAK, S. V. VINOGRADOVA and V. A. VASNEV, Vysokomol. soyed. AlO: 1329, 1968 (Transleted in Polymer Sci. U.S.S.R. 10: 6, 1543, 1968) 11. V. V. KORSEAK, V. A. VASNRV, S. V. VINOGRADOVA and T. I. MITAISHVILI, Vysokomol. soyed. AlO: 2182, 1968 (Translated in Polymer Sci. U.S.S.R. 10: 9, 2641, 1968) 12. 8. V. VINOGRADOVA, V. V. KORSHAK, 6. Sh. PAPAVA, N. A. MAISIJRADZE and P. D. TSISKARISHVILI, Izv. Akad. Neuk SSSR, ser. khim., 434, 1969 13. K. AUWBRS and M. SCBMIDT, Ber. 46: 457, 1913 14. C. LIEDERMAN and M. KARDOS, Ber. 46: 211, 1913

RADIATIONGRAFTGOPOLYMERIZATIONOFMETJiIYL METHACRYLATE ON CELLULOSE FROM THE VAPOUR PEASE* I. M. MIR~AMILOV, U. AZIZOV, M. U. SADYKOV and KH. U. USMANOV Research Institute of the Chemistry and Technology of Cotton Cellulose (Receiwd 18 Nowernber 1970) AT the present time radiation graft copolymers of cellulose are obtained by

irradiation of the latter in solutions of monomers or in monomer vapour, and also by treating previously irradiated cellulose with various monomers [l-5]. It has been shown in numerous papers by ourselves and by authors in other countries that much homopolymer is formed when cellulose is irradiated in monomer solutions. In some instances the consumption of monomer in homopolymerization is as much as 7040% [6]. It has been demonstrated by a number of authors that when certain polymers are grafted on to synthetic and cellulose fibres from the vapour phase hardly any formation of homopolymer takes place P, 7, 91. The grafting to cellulose of a readily available, cheap monomer such as methyl methacrylate (MMA) from the vapour phase has not however been studied. Meanwhile it is known that grafting of MMA from the liquid phase brings about an improvement in a number of properties of cellulosic materials (especially with respect to resistance to rotting and water repellance). The present paper reports a study of grafting of MMA from the vapour phase, one of the main tasks being to find grafting conditions that avoid formation of homopolymer

.

* Vysokomol. soyed. A14: No. 8, 17OP1708, 1972.