Heterochain polyesters—LX. Polyarylates based on phenolphthalein anilide

Hotorochain polyestors -- LX

1549

REFERENCES

1. V. V. KORSHAK, A. M. SLADKOV and A. G. MAKHSUMOV, Uzbekskii khim. zhurnal, No. 12, 643, 1963 2. Fc~t. Get. Rcpub. Pat. No, 871004; Chem. Abs., 50, 8712, 1956; RZhKhim, No. 22, 288, 1957

HETEROCHAIN POLYESTERS--LX. POLYARYLATES BASED ON PHENOLPHTHALEIN ANILIDE*t S. V. VINOGI¢ADOVA, V. V. KORSHAK, S. N. SALAZKIN and S. V. BEREZA Institut(; of Elmnontary Organic Compounds, U.S.S.R. Academy of Scioncos (Received 13 August 1963) x,~,'F HAVE already rcported about polyarylates based on phcnolphthalein [1, 2]. Besides retaining the high heat resistance which is typical of the polyarylates of aromatic dicarboxylie acids, these polymers have good solubility in a number of readily available organic solvents. Phenolphthalein polyarylatc films prepared by casting from the melt retain their good dielectric properties at higher temperatures than lavsan, polyearbonate diane or the polyarylatcs based oll diane [3]. But the disadvantage of using phenolphthalein as the bifunctional phenol for the, synthesis of polyarylates is t h a t high molccular weight polyarylates cannot be produced from it by interracial polycondcnsation [2]. This is because it tends to rearrange in an alkaline medium. On the basis of the data published for the stability of 2-pheuyl-3,3-bis-(4-hydroxyphenyl)phthalimidine (phenolphthalcin anilide) in alkaline medium [4], HO

OH

,%, ,% \c,/ ,/L,, / (,, lie/ \ = / "%/ ' ~ o it was to bc expected t h a t this difunctional phenol could bc successfully used to synthcsis polyarylates, not only by equilibrium but also by interracial poly* Vysokomol. soyod. 6: No. 8, 1403-1406, I964. ? L. L. Reshotnikov took part in tho oxporimontal work.

S . V . V I N O G I t A D O V A et al.

1550

condensation. Its structure (large number of aromatic rings, with a polar group and nitrogen atom) suggests that it would be reasonable to expect valuable properties of polyarylates derived from it. The aim of the present work was to synthesize and study the properties of homogeneous and mixed polyarylatcs of phenolphthalein (PPA) base. Table 1 gives the data for the homogeneous polyarylates of P P A base which we synthesized. It can bc seen that they have quite high softening temperatures despite the fact that the original bifunctional phenol has quite a large number of phenyl side groups. These should promote a lowering of the softening point due to the considerable break up of the packing density of the polymeric chain. T A B L E 1. P O L Y A I t Y L A T E S OF P H E N O L P H T H A L E I N ANILIDE Softoning

tomporaturo,

°C, dotorminod

Dicarboxylic acid

4,4'-diphonyldiear boxylic Torophthalic Isophthalie Diphonyl Fumaric* Sobacic

r/r in I from tricrosol I (0"5 g/lO0 ral) thormomochanical curvet 0'74 0"64 0'60 0"22 0"20 0'20

350 310 275 235 215 130

in a capillary tubo 370 350 280 240 230

Films¢

kg/cm2

~,%

900 960 860

26 3.9 3.6

140

*Produced by lnterfactal polycondeasation. ¢Is the tensllo strength of an unoriented film, the elongation in tension. Sin this and the following Tables the softening temperatuxe from the thermomechanical curve is taken as t h a t which corresponds to the point where the tangents to the thermomechanical curve intersect at the beginning of the flow.

The fact that P P A polyarylates with the more flexible (as compared with aromatic) aliphatic dicarboxylic acids have higher softening points than the corresponding phenolphthalein polyarylates (130 and 100 ° respectively in the case of polysibacates, and 215 and 180 ° for polyfumarates) could be due to the fact that the polymeric chain contains the more rigid P P A residues which have polar groups. The polyarylates of P P A and the rigid aromatic dicarboxyl!c acids (4,4'diphenyldicarboxylic, terephthalic, isophthalic and diphenyl) have softening temperatures which are very close to one another as compared with the corresponding phenolphthalein polyarylates (310 and 320 ° respectively for polyterephthalates, 350 ° for 4,4'-diphenyldicarboxylic acid polymers, 275 and 265 ° respectively for polyisophthalates and 235 and 227 ° respectively for the diphenyl earboxylic acid polymers).

Heterochain polyesters-- LX TABLE

2. M I X E D

POLYAItYLATES

1551

OF PIIENOLPIITltALEIN

AN1LIDE AND DIANE WII'H TEREPHTHALI('

Molar ratio

PPA : diano : torophthalyl chloride

1-0 0.5 0.4 0.3 0.2 0.15 0.1 0.0

TABLE

:0.0 : 0.5 : 0.6 :0.7 : 0.8 : 0.85 :0-9 : 1-0

:1.0 : 1.0 : 1.0 :1.0 : 1.0 : 1.0 : 1.0 : 1.0

3. M I X E D

qr in tricresol (0"5 g/lO0 ml)

Softoning temporaturo (dotormined from tho thormomochanical curvo), °C 310 255 260 260 235 240 250 350

0.60 0.56 0.44 0.38 0.70 0.88 0.70 060

POLYARYLATES

A(:II)

OF PHENOLPWJ'HALEIN

A N D I)IANF V¢ITH TEREPIITIIALIC A C I D

Molar ratio phenolphthaloin : diano : lorophthalyl Ühlorido

1"0

:0"0

: 1"0

0'5 0"2 0-15 0.1 0"0

:0'5 :0'8 : 0'85 :0'9 :l'0

:1'0 : 1.0 : 1'0 : i'0 : l'0

r/r in tricrosol (0.5 g/lO0 ml)

0'8 0'68 0'58 1 '06 0"54* 0'60

Softoning tomporaturo (dotorminod from tho thormomoehanical eurvo), °C 320 280 247 235 :340

350

*The viscosity was determined ia a tetrachloroethane : phenol (3:1 b y weight) m i x t u r e .

In many of the rcadily available organic solvents PPA polyarylates retain t h e e x c e l l e n t s o l u b i l i t y w h i c h is t y p i c a l o f t h e p h e n o l p h t h a l e i n p o l y a r y l a t e s . F o r i n s t a r t c e , t h a t o f t c r e p h t h a l i c a c i d a n d P P A ( F - 7 ) is s o l u b l e i n m e t h y l e n e chloride, chloroform, dichloroethane, tetrachloroethane, tctrahydrofuran, cycloh c x a n e , d i m e t h y l f o r m a m i d e a n d o t h e r o r g a n i c s o l v e n t s . I t is s u g g e s t e d t h a t , like the phenolphthalein polyarylatcs, the good solubility of those on PPA base is d u e t o t h e l a r g e p o l a r s i d e g r o u p i n g in t h e b i f u n c t i o n a l m o l e c u l e . We also synthesized mixcd polyarylates of PPA base, and base on diane and t e r e p h t h a l i c a c i d ( T a b l e 2). A s a c o m p a r i s o n , T a b l e 3 g i v e s t h e p r o p c r t i c s o f t h e

S.v. VINOGRADOVA

1552 T A B L E 4.

MIXED

a ~.

AND HOMOGENEOUS POLYARYLATES OF P H E N O L P H T H A L E I N A N I L I D E AND FUM_ARIC ACID

I

Polymor, No.

Diearboxylic acids

qr in triercsol (0.5 g/100 ml)

Softening tompora.ture, °C dotorminod ,. . . . . . . . . . . . . . . . . . . . . . from thcrmoin a capillary iI mechanical tubo !

curvo

I

1

2

Fumaric Fumaric and torophthalic (0.5 : 0.5) Fumaric and torophthalic (0.2 : 0.8)

0.20

215

0.26

230 270

0.54

280

270

T A B L E 5. T E N S I L E STRENOTH (o') AND ELONGATION IN TENSION (~) OF A FILM OF POLYARYLATE

Tomporature, oC

a, kg/cm z i .

20 150 180 25O

.

.

.

.

.

.

.

.

.

.

720 540 400 430

.

.

.

.

I

i

F-7*

o 13 14 6.6 5'1

*Produced by interracial polycondensation: ~r of a solution of the polymer In tricresol 0'60.

m i x e d p o l y a r y l a t e s of phenolphthalein, d i a n e a n d terephthalic acid. I f the figures in these two Tables are compared, it can be seen t h a t there is a m i n i m u m on the softening t e m p e r a t u r e versus composition curves for both series, the same as is well known for m a n y series of m i x e d polyesters. E x c e p t for those containing 0.9 mole diane, all the m i x e d p o l y a r y l a t e s of both series showed good solubility in chloroform. We also synthesized m i x e d p o l y a r y l a t c s of P P A a n d phenolp h t h a l e i n w i t h t e r e p h t h a l i c and isophthalic acids (~Sth a molar ratio of 0.5 : 0.5 for the biatomic phenols). The softening t e m p e r a t u r e s of these p o l y a r y l a t e s were 310 a n d 365 ° respectively. T a b l e 4 shows the properties of homogeneous a n d m i x e d u n s a t u r a t e d polya r y l a t e s on P P A base with fumaric acid. A film was cast from a solution of polymer 3 (Table 4) in chloroform. T h e tensile s t r e n g t h was 640 kg/cm 2 and the percentage elongation 2 . 9 ~ . Table 5 gives the d a t a for the s t r e n g t h characteristics of an u n o r i e n t e d film of p o l y a r y l a t e F-7 at different t e m p e r a t u r e s (produced b y casting from a solution in chloroform). I t can be seert t h a t p o l y a r y l a t e F-7 retains considerable s t r e n g t h at 250 °.

Heterochain polyesters -- LX

1553

EXPERIMENTAL Phonolphthaloin anilido (PPA) was synthesized by the interaction of phonolphthalein with a mixture of aniline and aniline hydrochlorido by the method which has been described by Albert [4]. The PPA was purified a~ follows. After distilling off the aniline with the vapour, it was rinsed in water and then twice in methanol; the solution of the product in ethyl alcohol was boiled several times, then it was treated with carbon dust and r(~rystallizod from the aqueous ethanol; m.p. 280 ° (279 ° according to [4]). The equilibrium polycon(Ionsation of the polyarylatos w~q conducted accor(iing to the method which we have already d(*saribed [1]. Instead of ditolylmothano, we use(l sovol (chlorinated biphenyl). A polyaryiate wa.q prepared from sebacic acid base I)y polycondensation in the molt using the method described in [1 ]. The int(~rfacial polycondonsation synthesis of th(, l)olyarylates wa.~ ,~ follows. To an a(lUOOUS alkaline solution of PPA (0.1 molo/l.) containing 0.9 to 1~) Nokal (by weight of the aqu(,~us phase) we added a 0.1 .~I solution of dicarboxylic chloride in benzene, stirring vigorously for l0 min (in the ca,~o of the homogeneous and mixed polyarylatos with fumaric acid) and in p-xylono (in the case of polyarylate F-7), then the reaction mixture was stirred for another 20 rain. The resulting polymer was precipitated in methanol an(l w,mhad in methanol, hot water, again in methanol and drie(t in a vacuum at 80 :~.

CONCLUSIONS (1) H o m o g e n e o u s a n d m i x e d p o l y a r y l a t c s h a v e b e e n s y n t h e s i z e d f r o m p h e n o l p h t h a l c i n anilide a n d their proi)crtics havc been studied. (2) T h e p o l y a r y l a t e s of p h e n o l p h t h a l e i n a n i l i d e a n d a r o m a t i c d i c a r b o x y l i c a c i d s a r e e a s i l y s o l u b l e in a n u m b e r of r e a d i l y a v a i l a b l e o r g a n i c s o l v e n t s a n d also have high softening t e m p e r a t u r e s . (3) H o m o g e n e o u s a n d m i x e d 1 ) o l y a r y l a t c s of p h e n o l p h t h a l e i n a n i l i d e e a s i l y f o r m t r a n s p a r e n t h e a t r e s i s t a n t films f r o m a s o l u t i o u . A film of t h e p o l y a r y l a t e of p h e n o l p h t h a l e i n a n i l i d e a n d t e r e p h t h a l i c a c i d has high m e c h a n i c a l p r o p e r t i e s a t 250 ° . Translated by V. ALFOItD REFERENCES I. V. V. KORSHAK, S. V. VINOGRAJDOVA an(] S. N. SAJ~AZKIN, Vysokomol. soye(l. 4: 339, 1962 2. V. V. KORSHAK, S. V. VINOGRADOVA, S. N. SALAZKIN and T. A. SIDOROV, Izv. Akad. Nauk SSSR, Otd, khim. n, 1416, 1962 3. T.S. KNYAZEVA, V. V. KORSHAK, M. S. AKUTIN, M. M. KULEVA, S. V. VINOGRADOVA, L. A. RODIVILOVA, G. P. NEDOPEKINA, P. M. VALETSKII, S. A. MOROZOVA and S. N. SALAZKIN, Plast. massy, No. 12, 37, 1962 4. R. ALBERT, Bet. 26: 3077, 1893