Polysulphones from allyl esters of phosphorus acids

Polysulphones from allyl esters of phosphorus acids

2743

REFERENCES

1. N. V. KIJM~NTOVA, V. M. ZHULIN, A. P. SUPRUN and V. V, KORSHAK, Vysokomol. soyed. BI0: 415, 1968 (Not translated in Polymer Sci. U.S.S.R.) 2. V. 1YI.ZHUIA~, N. V. ]~LEVI~_~TOVA,A. P. SUPRUI~, 1K. G. GONI~RERG and V. V. KORSHAK, Vysokomol. soyed. AU: 101, 1969 (Translated in Polymer Sci. U.S.S.R. 11: 1, 111, 1969) 3. V. IV[.ZHULIN, 1~. G. GONIKBERG and V. N. ZAGORBININA, Izv. Akad. Nauk SSSR, ser. khim., 827, 997, 1966 4. V. M. ZHULIN, R. I. B~IKOVA, M. G. GONIKBERG and G. P. SHAKHOVSKOI, Vysokomol, soyed. AI3: 1071, 1971 (Translated in Polymer Sci. U.S.S.R. 18: 5, 1205, 1971) 5. A. H. EWALD, Disc. Faraday Soc., N22, 138, 1956 6. B. S. EL'YANOV and 1~. G. GONIKBERG, Izv. Akad. Nauk SSSR, set. khim., 1044, 1967 7. V. M. ZHUIA~, Dissertation, 1971 8. A. A. ZHAROV, Dissertation, 1967 9. C. WALLING and J. PELLON, J. Amer. Chem. Soc. 79: 4782, 1957 10. M. M. ROMANI and K. E. WEALE, Trans. Faraday Soc. 62: 2264, 1966 11. N. V. KLIMENTOVA, A. S. SHASHKOV, G. L. BERESTNEVA, V. V. KORSHAK and A. P. SUPRUN, Vysokomol. soyed. B10: 656, 1968 (Not translated in Polymer Sci. U.S.S.R.) 12. G. L. SLONIMSKII, A. A. ASKADSKII and A. L KITAIGORODS~II~ Vysokomol. soyed. AI2: 494, 1970 (Translated in Polymer Sci. U.S.S.R. 12: 3, 556, 1970)

POLYSULPHONES FROM ALLYL ESTERS OF PHOSPHORUS ACIDS* I. N. FAIZULT~r~, T. M. MAKSUDOVA, E. M. SHAGIAKHMETOVa n d D. I. I~ABIEVA,

(Received 23 A ~ u a t 1971) Polysulphones containing phosphorus have been obtained by reacting allyl-alkyl methylphosphonates or allyl-aryl fl-chloroethylphosphonates with sulphur dioxide. The reaction temperature limits have been determined. The effect of the structure of the phosphorus acid allyl esters on the temperature of the polysulphone-formation reaction was studied. I t is shown that branching of the monomer lowers the limiting temperature. Deviation from this effect occurs in the case of allyl esters of chloroalkylphosphonic acids. I t was found that change in the position of a substi~uent on the aromatic ring does not affect the limiting temperature substantially. THE f o r m a t i o n of p o l y s u l p h o n e s (PS) b y r e a c t i o n o f s u l p h u r dioxide w i t h u n s a t u r a t e d organic [1] a n d o r g a n o p h o s p h o r u s [2-6] c o m p o u n d s occurs o n l y if c e r t a i n t e m p e r a t u r e conditions are observed. The yield a n d properties of t h e P S d e p e n d to a considerable e x t e n t o n t h e r e a c t i o n t e m p e r a t u r e [3-6]. T h e f o r m a t i o n o f a P S has a characteristic limiting r e a c t i o n t e m p e r a t u r e (Tl~), * Vysokomol. soyed. A15: No. 11, 2424-2428, 1973.

2744

I . N . FA~ULLI~ et al.

the value of which is mainly dependent on the structure of the organophosphorus monomer (PM). The present paper discusses the reaction of sulphur dioxide with allyl-alkyl esters of methylphosphonic acid and with allyl-aryl esters of p-cMoroethylphosphonic acid, to form phosphorus~ontaining PS's as follows:

n~H,CH---CH'H'~ J --~H--CHs--S0, i ] --

I + n SO~ --, O I R--P(O)OR' LR--P(O)OR"

-~"

where R = C H 8 and R'----C2H6, n-C3H7 or n-C4Hg, or R-~C1CH~CH2 and R ' = C e H s , o-, m- or p-C1C6H v p-CHsCeH 4 or p-BrC6H4. T A B L E 1. C H A R A C T E R I S T I C S OF P O L Y S U L P H O N E S F R O M ~ r ~ E D ACIDS

PS No.

II III IV V VI VII VIII IX

R

R'

CH8 CH3 CHs C1CH,CH2 CICH2CH2 CICH,CH, CICH2CHs C1CH,CH2 C1CH~CH2

C,H~ n-CsH~ n-C4H9 C6H5 o-C1CeH~ ~n-C1C,H~ p-C1C6H~ p-CHsC6H, p-BrC6H,

E S T E R S OF A L K Y I , P H O S P H O N I C

I

P,% M.p., °C " found calculated 85-87 I 13.06 12.66 92-94 95-97 12.37 65-67 8.64 7.97 857.87 8.07 78-83 85-87 7.97 8-18 75-76 -98-100

13.62 12.81 12.22 9.55 8.64 8.64 8.64 9.19 7.79

S, % found

calculated

14.12 13.50 12.57 10.37 8"97 8.93 9.38 9"40 8.80

14.03 13.22 12.50 9-86 8'91 8.91 8-91 9"40 7-92

Yield, % 96 94 73 78 87 70 74 70 68

The structure of these polysulphones is confirmed by elementary analysis (Table 1) and infrared spectroscopy. The infrared spectra of PS's prepared a t --60 ° contain absorption bands characteristic of S02 groups (1145 and 1330 cm -1) an d P ~- O groups (1250 cm-1). The results obtained in the present work and information published previously [2-6] permit more general conclusions to be drawn about the effect of t he structure of the PM on the process of formation and properties of the polysulphones.

Polysulphones from allyl esters of phosphorus acids

2745

T h e s t r u c t u r e of t h e i n d i v i d u a l radicals in t h e PM molecule a n d t h e presence a n d n a t u r e of s u b s t i t u e n t in t h e m , h a v e a s u b s t a n t i a l effect on Tmn. I t is seen f r o m T a b l e 2 t h a t increase in t h e size o f t h e a l i p h a t i c radical att a c h e d d i r e c t l y or t h r o u g h o x y g e n to t h e p h o s p h o r u s a t o m brings a b o u t a reducTABLE 2. EFFECT OF THE STRUCTUREOF THE PM oN Tlim (R-- P(O)(O-- CH2-- CH = CH2)OR') R'

R

Turn, °C

C9H6

CH. CH3 CH3 CH 3

15-20 10-15 5-10 40-45

n-CsH~ n-C4H,

C.Hs

R' C3H5 CsHs C.H5 C.Hs CeH~

R

Tnm, °C

CH2C1CH2CH~CI CHs CH2C1 CH~CH~C1

25-30 10-15 5-0 5-10 15-20

t i o n in Tl~n. T h u s t h e general p a t t e r n of t h e effect of t h e s t r u c t u r e of t h e u n s a t u r a t e d c o m o n o m e r on t h e v a l u e of Tnm in f o r m a t i o n of a PS, which is c o m m o n t o olefins, applies also to P M ' s [7]. R e p l a c e m e n t of a n aliphatic or allyl radical a

fO0 ,~.Br

I 50

~

2O i

t

i

.o

,o

i

i

r

d

g

ii

iu g

0

f0

!

F/me, rain

2O

i

¢0

i

00

FIG. 1. Dependence on the yield of PS's on reaction time at --40 ° (I-IV, VII-IX), --60 ° (I') and --20 ° (I') with 5~/o (a, b, d) and 2"5~o by weight (c) of initiator (isopropylbenzene hydroporoxide). b y a n a r o m a t i c r a d i c a l leads to d e v i a t i o n f r o m t h e general r e l a t i o n s h i p (Table 2). I n this case Tl~n increases w i t h increase in t h e degree of b r a n c h i n g of t h e PM. T h i s is p r o b a b l y due to difference in t h e s t a b i l i t y o f t h e radicals f o r m e d in t h e course of p o l y m e r i z a t i o n , w h i c h in t u r n is d e p e n d e n t on t h e configuration of t h e P M molecule. B r a n c h i n g of t h e P M molecule b y i n t r o d u c t i o n o f s u b s t i t u e n t s on t h e a r o m a t i c

2746

I.N.

FAIZ~LLU~ e$ al.

rings as a rule causes a r e d u c t i o n in T l ~ (Table 3). T h e value o f Tnm is t h e n d e p e n d e n t on t h e size of t h e substituent, the more b u l k y it is t h e lower is T I ~ . The position of t h e s u b s t i t u e n t on the a r o m a t i c ring does not e x e r t a substantial effect on Tmn (Table 3). TABLE 3. EFFECT OF SUBSTITUENTS ON THE'AROMATIC RING OF THE P M ON

Turn XC6H,OP(O)(R)OCsHs R

OCsH6

X

H o-C1 o-Sr o-CHs m-CH s p-CHs

Turn, °C

R

23-28 12-17 0-5 18-23 5-10 15-20

CH,CHIC1

X

Turn, °C

14-19 18-23 10-15 8-13 15-20 10-15

H

p-CHa p-Br p-Cl m-C] o.Cl

6O 0"/J

0"0J -40

r,°C

/00

0

FIG. 2

200 7"oc

J00

Fro. 3

Fro. 2. Dependence of the specific viscosity on reaction temperature for a reaction time of 30 rain.

Fio. 3. Thermomechanical curve of PS IV prepared at --60 ° in 30 min. Decrease in t h e n u m b e r of aUyl groups in t h e molecule, i.e. passing from a triallyl p h o s p h a t e to the di- or mono-derivative, brings a b o u t a r e d u c t i o n in Tmn. PM O-~P(OC~ts) s CHaP(O)(OCsHs), CeHsOP(O)(OCsHs)s

Turn, °G

55-60

40-45

23-28

CHs O C6HaO O

Y

Y

15-20

10-15

T h e s t r u c t u r e o f t h e P M also has some effect on t h e yield o f t h e polysulphone. T h e yield of p o l y m e r decreases in t h e series of polysulphones based on

Polysulphones from allyl esters of phosphorus acids

2747

allyl alkyl methylphosphonates as the number of methylene groups in the alkyl group is increased, and also in the case of polysulphones from allyl aryl fl~hloroethylphosphonates when there is chlorine or bromine attached to the aromatic ring (Fig. l a and b). TABLE 4. A L L Y L

ESTERS OF ALKYT~ PHOSPHONIC ACIDS

OR'

/ R P ~ R ~H3

R'

n~

°C/for 49"5-51/1-2

n-C3H, n-C,H 9

66-67/2 79-81/0.2

~ICH,CH~ Cell5 o-C1C6H, m-C1C6H, p-C1C6Ha p-CHsC6H4 p-BrC6H,

MRD

B . p.~

C21~ 5

OCHs---CH=CHz

150/0"06

152-155/0"06 145-148/0.08 158/0.06 144/0.02 147/0.07

d~°

P,%

found calcu- found calcu lated lated

Yield %

1-4330 1.0598 40.22 40-31 18"51 18.89 1,4407 1.0460 44.91 44"93 17"50 17-41 1.4390 1-0269 49.51 49.54 16"32 16.14

54 50 40

11.53 11.90 10.35 I 10"50 10.04 10"50 10.45 10.50 11-13i 11.20

58 59 39 46 41 18

1"5173 1"5285 1"5048 1"5268 1"5090 1"5190

1"2149 1"2933 1"2513 1"3304 1"1836 1"4283

64"45 69"91 69"56 68"79 69"11 72.21

64"66 69"53 69"53 69"53 69"28 72"43

9.84 ~ 9"11

The rate of formation of PS's is high from the beginning, the maximal yield being reached in 10-20 rain. The induction period characteristic of radical processes is not observed in formation of the polysulphones (Fig. Iv). The structure of the PM does not affect the way in which the reaction proceeds. The reaction temperature affects both the rate of formation of the PS and its molecular weight. Increase in temperature reduces the reaction rate (Fig. ld), but the nature of the process is identical at all the temperatures studied. The molecular weight (viscometric) of the PS varie~ in mverse proportion to the reaction temperature (Fig. 2). Polysulphones of low molecular weight are formed at temperatures close to TlunThe thermal stability of the PS's was determined by thermogravimetric analysis (Fig. 3). They all have similar thermal stability and withstand heating without appreciable decomposition up to 175-200 ° . The loss in weight is then 8-90/0 . Further increase in temperature brings about vigorous decomposition and the loss in'weight is 50-60%. The main gaseous degradation product is sulphur dioxide. EXPERIMENTAL

The allyl-alkyl and allyl-aryl esters were prepared in two stages [8]. Acid chloride-esters of the alkylphosphonic acids were first prepared by reacting the diacid chlorides of the alkylphosphonic acids with the appropriate alcohol, then these were condensed with allyl alcohol. The characteristics of the PM's, after repeated redistfllation, are given in Table 4.

2748

I.N. FA*ZULLn~ et al.

The polysu/phones were prepared as in reference [3]. I n the preparation of PS's from allyl-alkyl methylphosphonates diethyl ether was used as the solvent and toluene was used in the case of allyl-aryl fl-chloroethylphosphonates. F o r purification the end products were washed several times with the appropriate solvent. The polysulphones are soluble in DMSO and T H F , a n d those without an aromatic nucleus are soluble also in I ) M F and alcohols. The limiting polymerization temperature was found as in references [2-6]. Specific viscosities were determined with 2 ~o solutions of the polymers in D M F a t 20 °, in an Ubbelohde viseometer. The thermogravhnetric curves were obtained in a derivatograph, with a sample weight of 180 mg and a rate of rise in temperature of 7 deg/min. The inert substance was alumininm oxide. The infrared spectra were recorded with suspensions of the PS samples in liquid parafl~m in a UR-20 spectrometer. Translated by E. O. PHILLIPS REFERENCES 1. C. H. BAMFOR]D, W. G. BARB, A. D. JENKINS and P. F. ONYON, Kinetika radikal'noi polimerizatsii viniIovykh soyedinenii (The Kinetics of Vinyl Polymerization b y Radical Mechanisms). p. 217, Foreign Literature Publishing House, 1961 (Russian translation) 2. Ye. V. KUZNETSOV, I. N. FAIZULLIN and A. A. GUSEV, Vysokomol. soyed. A9: 1440, 1967 (Translated in Polymer Sci. U.S.S.R. 9: 7, 1611, 1967) 3. I. N. F A I Z U L U N , T. M. LAZAREVA, E. IV[.SHAGIAKH3/IETOV and Ye. V. KUZNETSOV, Vysokomol. soyed. BI3: 9, 1971 4. I. N. FAIZULLTN, T. M. MAJKSUDOVA and I. F. GARITOVA, Vysokomo]. soyed. B13: 554, 1971 5. I. N. FAIZULLIN, T. M. MAKSUDOVA and I). A. FAIZUTJ.INA, Vysokomol. soyed. A12: 430, 1970 (Translated in Polymer Sci. 12: 2, 491, 1970) 6. I. N. FAIZULT.IN, T. M. MAKSUDOVA, I. F. GABITOVA, A. V. DYUL'DEVA and D. A. FAIZULLINA, Vysokomol. soyed. BI3: 147, 4971 7. N. GRASSIE, K h i m i y a protsessov destruktsii polimerov (Chemistry of Polymer Degradation Processes). p. 83, Foreign Literature Publishing House, 1959 (Russian translation) 8. I. N. FAIZULT.IN, E. M. SHAGIAKHMETOV, D. A. FAIZULLINA and D. I. NARIEVA, Zh. obshch, khim. 41: 2112, 1971