Thermodynamic investigation of the swelling of filled interpenetrating polymeric networks based on a polyurethane and a styrene-divinylbenzene copolymer

THERMODYNAMIC INVESTIGATION OF THE SWELLING OF FILLED INTERPENETRATING POLYMERIC NETWORKS BASED ON A POLYURETHANE AND A STYRENE-DIVINYLBENZENE COPOLYMER* Y r . S. LIPATOV, L. V. KARABAI~'OVAand L. M. SERGEYEVA High Polymer Chemistry Institute, Ukr. S.S.I%. Academy of Sciences

(Received 24 September 1976) The method of sorption of organic solvent vapours was used to investigate a system of filled interpenetrating networks containing a polyurethane and styrenedivinylbenzene copolymer. Thermodynamic parameters calculated on the basis of the experimental results included changes in the partial free energies of the solvent and the network system during swelling as well as in the free energy of swelling and the swelling entropy and enthalpy. It was found that the addition of an inorganic filler to polymeric network systems increases the heterogeneity of the latter, and influences processes taking place during their formation. In addition to the transition region tha~ appers also in unfilled interpenetrating networks a surface layer is formed on an inorganic filler. This has a marked effect on thermodynamic properties, influencing the flexibility of chain segments in the network as well as the thermodynamic stability of polymer-solvent systems. CONSIDERABLE interest has recently been shown by authors in the synthesis o f interpenetrating polymeric networks (IPN) and in investigations of systems of this t y p e [1-6] which, in view of t he conditions of their preparation, are micro heterogeneous system [7]. Taking as an example networks containing a polyu reth an e and a styrene-divinylbenzene copelymer [5] we found t h a t the properties of these systems were non-additive in character. This non-additivity is due to th e fact t h a t the influence which one of the network components (in particular, t h a t of the polyurethane) exerts upon the other (the styrene-divinylbenzene copolymer) in the process of network formation is analogous to t he action of a solid polymeric filler. I n view of this the properties of the s t y r e n e divinylbenzene copolymer network formed in presence of the polyurethane, and in particular the effective network density, packing density, and other properties, differ considerably from the properties of an individual network of a similar nature. I n addition, an analysis of the t h e r m o d y n a m i c behaviour of interpenetrating polymeric networks showed t h a t a transitional region [4] exists in systems of the t y p e in question, and t h a t the properties of the transition region differ considerably from those of the individual components. * Vysokomol. soyed. A19: No. 5, 1073-1081, 1977. 1237

1238

Y~. S. Ln~ATOVet al.

I t seemed appropriate t h a t a study should be made of the structure and properties of systems of this type formed in the presence of inorganic fillers, t h e addition of which to polymers has a considerable effect on their properties because o f the formation of boundary layers of polymer in the vicinity of the filler, and it is known t h a t these differ structurally from the polymer in the volume [8]. I n this paper we present the results of a thermodynamic analysis of interpenetrating polymeric networks based on a styrene-divinylbenzene copolymer a n d a polyurethane, some of these networks being filled with glass micro spheres, and the others unfilled. The study objects were filled interpenetrating networks, the first of the latter being a crosslinkod polyurethane .prepared from an oligocthyleno glycol adipato (M~2000), and an adduct of trimethylolpropane with toluenodiisocyanate, and the second network, formed within the first, a copolymer of styrene with divinylbonzene. As a filler we used glass micro spheres of diameter 40/2. The systems wore investigated whilst varying the weight ratio of the networks W,/W1 from 0.044 to 0.133 and increasing the percentage filling with glass spheres from 0.5 to 7%. The filler was added to the systems at the stage of polyurethane preparation. Otherwise the method of preparation was identical to that, described in [5]. The diffusion of benzene vapour in the filled systems was investigated by a sorption method. The specimens used for the sorption tests were films of thickness 0.3 mm. Weighb changes in a specimen during sorption wore determined on a MacBain balance with molybdenum helices of sensitivity 3-4 rag/ram. The temperature in the sorption cell was main. rained with an accuracy of ~0"1 °. Sorption was investigated at 30 and 40°. The sorption isotherms for benzene vapours (30 °) appearing in Fig. 1 relate to the individual (polyurethane) component of the interpenetrating polymeric networks (isotherm 1), and to the unfilled system, and to the system filled with differing amounts of glass spheres, with W2/W1 varying from 0.037 to 0.044 (isotherms 2-6). The benzene vapour sorption by the unfilled system exceeds t h a t of the individual network, and agrees with results reported in [9] which were explained in terms of ideas relating to interpenetrating polymeric networks regarded as a filled system: in this case the second network (styrene-divinylbenzene copolymer) formed in the presence of the first (polyurethane) is, as it were, a filler for the latter. I t is known t h a t the structure of the second network is marked by the presence of network defects formed as a result of a reduction in the number of chemical network points and also as a result of "free" ends appearing in the network for the reasons discussed in [8, 10]. In addition we showed t h a t a transitional region appears in systems of this type, and t h a t the structure is looser in this region compared with the network components. All the above factors give rise to increased sorption of the systems compared w i t h the individual components. An analysis of isotherms 3-6 in Fig. 1 shows t h a t vapour sorption by t h e specimens of interest in the presence of an inorganic filler is reduced proportionally with the filler content in the system. Only in the case of the highest (7%) filler content does the sorption rise slightly in comparison with the preceding specimen t h a t has a 5% filler content (isotherms 5, 6).

Swelling of filled interpenetrating polymeric networks

12394

In earlier investigations we found that during the formation of individual networks (of a polyurethane and a styrene-divinylbenzene eopolymer) in the presence of dispersed inorganic fillers [10, 11] the sorption of organic solvent vapours generally exceeds the sorption observed for unfilled network polymers. This was attributed to defective network formation due to the fact that a well developed filler surface leads to a higher rate of termination of reactive chains at the surface with the result that the number of network points is reduced. ~//z, % 2q ~-

18

1li ,3

,t/ 1Z

7,]

10

~'I

o.~

FIG. 1

o.7

1"o PlP~

0.!

O.q

0.7

i.g p/'/~

Fro. 2

FIG. 1. Isotherms of the sorption of benzene at 30 ° by the filled and unfilled interpenetrating networks and the polyurethane: /--polyurethane; 2--IPl~, W2/Wl=O'044; 3--IPN, W~/WI=O.043, 0.5% filler; IPN, W2/W,=O.044, 1.5% filler, 5--IPN, WJWI~O'041, 7% filler; 6--IPN, W~/W~-O.037, 5% filler. FIG. 2. Sorption isotherms at 40 ° for the filled and unfilled interpenetrating polymeric systems: 1--IPN, Ws/WI~--O'04, 3~o filler; 2--IPN, W2/Wl=O'07, 3% filler, 3--IPN, W~/WI=O'04; 4--IPN, W~/WI=O.07. To a c c o u n t for t h e r e d u c e d sorption of solvents b y specimens o f systems c o n t a i n i n g i n t e r p e n e t r a t i n g p o l y m e r i c n e t w o r k s filled with glass spheres one has t o consider certain m a t t e r s relating to p r e p a r a t i o n of t h e networks. I n t h i s

YU. S. LIPATOV et al.

1240

~HA_NGES I N THERMODYNA.MIC F U N C T I O N S D U R I N G SORPTIOI~" B Y TRATING

Specimoil

Polymer

W2

No.

FILLED

INTEI%PElqE

zJ]12,

Agm,

cal/g

cal/g

] i

AH~, eal/g

T AS,, eal/g

0.9844 0.9756 0.9654 0.9533 0.9436 0.9355 0-9296 O.9252

--0.0944 --0.1580 --0.2243 --0.2989 --0.3750 --0.4516 --0.5284 --0-5998

--0-2943 --0"3884 --0.4693 --0.5426 --0"5836 --0.6059 --0"6165 --0-6178

2.9521 4.1333 5.3387 6-4301 7.5458 8"9865 10.9075 14.0745

3.047 4.291 5-563 6.654 7.921 9.438 11.436 14.674

IPN, W~/W1----O'043;

0.9901 0.9797 0.9690 0-9590 0-9471 0.9354 0.9240 0.9144

--0.0700 --0.1475 --0.2273 --0.3091 --0.3941 --0.4788 --0.5707 --0.6652

--0"2510 --0.4049 --0.5179 --0.5960 --0-6656 --0.7110 --0.7435 --0.7606

0.696 1.499 2.124 2.747 3.255 3.618 4.320 5.304

0-766 1-647 2.351 3.057 3.649 4.097 4.891 5.969

0.9923 0.9841 0.9754 0.9641 0.9525 0.9387 0-9265 0-9158 0.9053

--0.0400 --0.1043 --0.1693 --0.2393 --0-3145 --0.3964 --0.4805 --0.5739 --0.6589

--0.1810 --0.3066 --0.4013 --0.4930 --0.5621 --0.6218 --0.6542 --0.6754 --0.6761

3.796 4.934 6.088 6.869 7.545 7.949 7.955 8-944 8.033

3.836 5.038 6.257 7.108 7.859 8-346 8.435 9.517 8.692

I P N , W~/Wl=O'044; 3 % filling with glass spheres

0.9938 0.9850 0.9742 0.9621 0-9486 0.9346 0.9215 0.9125

--0.0350 --0-0921 --0.1577 --0.2307 --0.3116 --0-4029 --0-4989 --0.5936

--0.1486 --0.2832 --0.4013 --0.4989 --0-5797 --0-6429 --0.6830 --0.6974

1-913 3.156 4.149 4.782 5.348 5.589 5.861 6.271

4"306 5"012 5"659 5.992 6.359 6-865

I P ~ , Wa/Wl=O'077; 3 ~o filling with glass spheres

0.9864 0.9749 0.9637 0.9511 0.9379 0.9235 0.9096 0.8984

--0.0950 --0.1995 --0-2973 --0.3955 --0"4950 --0.6000 --0.7121 --0.8193

--0.3433 --0.5165 --0.6350 --0.7334 --0.8075 --0.8657 --0.9048 --0.9169

0.877 0.522 0"482 0-543 0.367 0.456 0.236 0.406

0.973 0-721 0.779 0"938 0"862 1-056 0"948 1"225

IPN, W,/W,=O.044; 1.5% filling with glass spheres

5

THE

(IPN)

Polyurethane

0.5% filling with glass spheres

4

NETWORK

1.948

3.~49

Swelling of filled interpenetrating polymeric networks

1241

TABLE (COnt.) Speei- I men No. 6

w,

A/I,, eal/g

zig , cal/g

zlH,, cal/g

0.9919 0.9831 0-9738 0.9627 0.9495 0.9368 0-9256 0.9142 0.9016

--0.0600 --0.1284 --0.1980 --0.2714 --0.3496 --0-4330 --0.5233 --0.6196 --0.7132

--0.2082 --0.3260 --0.4434 --0.5338 --0.6111 --0-6630 --0.6978 --0-719.1 --0.7257

0.686 0.604 0"586 0-590 0.597 0.412 0.402 --0.419 --0.242

0.746 0.733 0-784 0"862 0.947 0.845 0.927 0.200 0.472

I P N , W,/Wl=O'037; 7 % filling with glass spheres

0.9888 0.9801 0.9701 0.9589 0.9473 0-9346 0.9236 0.9109 0.8974

--0-0700 --0.1514 --0.2293 --0.3077 --0.3936 0.4766 --0.5668 --0.6588 --0-7480

--0.2748 --0.4037 --0.5095 --0-5953 --0.6641 --0.7118 --0.7408 --0.7587 --0.7575

0.696 0.621 0.733 0.934 0.835 0.902 0-739 0-606 0-592

0.766 0.772 0.963 1.241 1.229 1.379 1-306 1-264 1.339

I P N , W,/Wl=0"133; 7 % filling with glass spheres

0.9875 0.9775 0-9671 0.9553 0.9432 0.9293 0.9165 0.9034 0.8887

--0.0800 --0.1736 --0.2618 --0.3514 --0.4475 --0.5436 --0.6463 --0.7541 --0.8579

--0.3084 --0.4583 --0.5690 --0.6623 --0.7360 --0-7931 --0.8298 --0.8532 --0.8560

0.080 --0.443 --0.612 --0.775 --1.074 --1.353 --1.708 --2.348 --2.654

0.160 --0.269 --0.349 --0.424 --0.626 -- 0.809 -- 1-061 -- 1-594 --1-796

IPN, W,/Wl=O'044

0-9919 0-9857 0.9792 0.9661 0.9502 0.9395 0.9351 0.9320

--0"1231 --0.1926 --0.3005 --0.4234 --0.5914 --0.7001 --0.7112 --0-8046

--0.3122 --0.4432 --0-5826 --0.7029 --0.8105 --0-8652 --0.8819 --0.9612

Polymer

IPlq, WJW,=O.041; 5% filling with glass spheres

1.9234 3.1746 4.8762 5.6341 6.2349 8-0327 9.2561 12.0663

T AS,, cal/g

2.005 3.583 4.592 6.153 8.754 11.351 12.702 13.763

connection an individual (polyurethane) network that has first been filled with g l a s s s p h e r e s is s u b j e c t e d t o s w e l l i n g i n s t y r e n e c o n t a i n i n g d i v i n y l b e n z e n e . I n t h e s w e l l i n g o f f i l l e d p o l y m e r s t h e s o l v e n t (or i n o u r c a s e t h e m o n o m e r ) d i f fuses both into the polyurethane and also to the polyurethane-glass interface. Published data and our results show that in some cases regions filled with solvent a p p e a r a r o u n d t h e filler p a r t i c l e s . I t s e e m s f a i r t o a s s u m e t h a t l i k e w i s e i n t h e

1242

'

Y u . S. L~eATOV e t a / .

case of a filled polyurethane swelling in styrene the latter will collect at tho filler-polymer interface. I t is probable that the effect of the solid surface will give rise to the orientation of monomer molecules in the thin layer at the interface, which will facilitate the formation, after polymerization, of a surface layer in which the molecules, or rather chain segments between network points, are arranged in an ordered manner relative to one another, i.e. a compact surface layer consisting almost entirely of the second network is formed. As was demonstrated in [9] the" sorption of benzene vapours b y the individual second network is much less marked compared with that of the polyurethane in the network system. I n view of the proposed concentration of monomers at the interface with the inorganic filler the effective fraction of the second network in a network system formed in the presence of glass spheres will be smaller in comparison with an unfilled system with the same W2/W1 ratio. Accordingly, we shall have a similar reduction in the transitional region fraction which has a looser structure compared with individual components of the network system. As the filler content rises, these effects, i.e. the appearance of a compact surface layer formed on the inorganic filler and consisting of the second network will become more marked, as will the reduction in the effective fraction of the second network in the network system. All these considerations are involved in the less marked sorption of solvent by the filled interpenetrating polymeric networks compared with the unfilled. I f the inorganic filler content in the polymeric network system is keptconstant, but the amount of the second network in the system is increased, the sorption of benzene vapour will increase, as can be soen from Fig. 2 (curves 1, 2). This is because in the case in question the reduction in the effective fraction of the second network, and consequently the reduction in the transition layer fraction take place to an equal extent in both cases during formation of the network system in presence of the filler. It should be noted that changes in the vapour sorption as the W2/WI ratio rises are more marked in the presence of the filler t h a n the change observed for the unfilled systems with identical W2/W~ ratios. On the basis of the sorption isotherms at two temperatures we calculated changes in some thermodynamic parameters with a view to estimating changes in the thermodynamic flexibility of the chains in the polyurethane network accompanying the addition of the styrene-divinylbenzene copolymer and the inorganic filler to the network, and also with a view to determining the thermodynamic stability of systems containing interpenetrating polymeric networks and a solvent. Free energy of swelling. To find the free energy of swelling we used data on the relative solvent vapour pressure PJPo and the equation 1

,dp~= ~ RT lnp/po

(1)

and calculated changes in the partial free energy of the solvent ZJ~l (M is the

Swelling of filled interpenetrating polymeric networks

1243

molecular weight of the solvent). To find the partial free energy for the network system we used the Gibbs-Duhem equation which, for specific values, is written as ~1 W1 -

awl

~2 -~-W 2 -

aWl

:0,

(2)

where wl and w2 are weight fractions of the solvent and of the polymeric component respectively. A clear expression of the dependence of Ap~ on Apl is given by the relation

A~= -~" _wid (~m)

(3)

-ooW 2

Since no accurate solution is obtainable for equation (3) the Simpson formula [12] was used to find the approximate value of the integral A~ z Wl

A~/2:--

~ / •

\

J - - ~(z]~/1) , A~ W2 '

where A#~ is the minimum calculated partial free energy value equal to the minimum sorption measured experimentally. Next, we used a graphic method to determine the correction A for the area unaccounted for [13] AI~2=Ap~ + A The average free energy of mixing for solutions of varying concentration was given by the formula A~m=wIAJIIAVW2Ap2 The Table gives t h e calculated values of Ap2 and Ag m for all the specimens. The concentration dependence of the partial free energies A#~ and Ap2 is displayed in Fig. 3. As can be seen from the Figure, the A p ~ f ( w ~ ) curves (w2 being the weight fraction of the polymeric network system in solution) are identical for all the specimens: at w~-~l the value of A#~ tends to - - ~ , and with a w~ value corresponding to a maximum degree of swelling, A#I-~0. It is clear from Fig. 4 t h a t the shape of the Agm=f(w2) curve is characteristic of systems that well only to a limited extent. The curves for all the specimens O~Agm "~re concave at the bottom, i . e . - - > 0 . This means that all the systems con-

aw~

raining interpenetrating polymeric networks and a solvent are thermodynamic~lly stable systems [14]. According to [15], the thermodynamic stability of a polymer-solvent system is determined by the negative value of Ag~ (the spontaneous process of dissolution), and the lower the position of the Agr'~=f(w2) curve, the more stable is the system. As can be seen fi'om Fig. 4, the addition of an inorganic filler is reflected in lower thermodynamic stability of systems containing poly-

Yu. S. L[PATOV et al.

1244

merie networks and a solvent (Agm becoming less negative as the filler content rises). This %allies with considerations stated above in regard to the mechanism of formation of interpenetrating polymeric networks in the presence of an inorganic filler: reductions in the effective fraction of the second network and at the same time in the loose transitional layer, and the formation of a compact surface layer on the inorganic filler--all these factors lead to reduced thermod y n a m i c stability of polymer-solvent systems as the filler content rises. 0"81

0"90

0.93

I

I

l

!

z

0"95

04g Wz I

3

_

-0.St~ I

0.92 I

t

I

0.98 I

I

O. '

'

wz

[

-O'Z '

~

-0.!

~\

3

-12

-18

-L7.6 5

ZO -1.0 "V, , c . zlg

~

-1.0 g "/ c. llg

, , ca /le

FIG. 3

FIG. 4

FIG. 3. Concentration dependence of the partial specific free energies of mixing

for the solvent A/~, and for the system A~=: /--IPN, Wj/W,=0.043, 0.5% filler, 2--IPN, W,/W,=0.077, 3~o filler; 3--IPN, Ws/Wl=0"133, 7~o filler. FzG. 4. Plots of the free energy of mixing zigm at 30° vs. the weigh~ fraction of

IPN w, in the IPN-solvent system: 1--IPN, W=/W~=O.044; 2--IPN, W=/W, =0.043, 0.5% filler; 3--IPN, W,/Wl=O'044, 1.5% filler; 4--IPN, W=/WI=O.041, 5% filler; 5--IPN, W,/Wl=O.037, 7% filler.

Swelling enthalpy and entropy. I f Apl and A#= are known a t two temperatures, we m a y find how the partial specific entropy of a polymeric network system changes b y using the formula [16]:

AH==

T~A#, (T~)--T,A#, (T,) T,--T,

Swelling of filled interpenetrating polymeric networks

1245

The change in the partial specific entropy was calculated b y the formula

TAS~----AH2--Ap2 The Table gives the values obtained for all the interpenetrating polymeric network specimens.

Z-A Sz , cal/g

"II

1I°

T,4 Sz ,cal/ff lg

Z-

~O 1

g.85

0.gz Fro. 5

0.98 ~Jz

1

I

1

i

3

Filling, %

l

5

I

7

FI~. 6

Concentration dependence of TAS2: /--polyurethane; 2--IPN, W2/WI ~0.044; 3--IPN, W2/Wl-~O.044, 0.5% filler; 4--IPN, W2/W1----O'044, 1.5% filler; 5--IPN, W2/WI=O.044, 3% filler; 6--IPN, W~/Wl=O'037, 7% filler.

FI(~. 5.

FIc. 6. Plot of TAS2 vs. percentage filling of the IPN with w2~0.94. As m a y be seen from the Table (AH2 values) the sorption of benzene by the filled systems, and likewise by the polyurethane, is accompanied by heat absorption, which is characteristic of the dissolution of polymers that are in the high elastic state. The only exception is specimen 8, where there is a considerable proportion of the second network which, under the conditions of the experiment, is in the glass-like state. Here AH2~O, which points to heat evolution during the sorption process. On comparing the AH2 values for specimens 4 and 5, and also for 7 and 8, it can be seen t h a t an increased amount of the second network leads to greatly reduced heat absorption during sorption (specimens 4, 5), or even to hea~ evolution (specimens 7, 8). I t is known [17] t h a t the dissolution of polar polymers in polar solvents (styrene-divinylbenzene copolymer in benzene) is most frequently accompanied

1246

~

Yu. S. LrrATOVet a~.

by a positive thermal effect. I f this is so, then it is quite understandable t h a t an increase in the amount of the styrene-divinylbenzene copolymer in polymeric network systems will have precisely this effect on the value of AH~. On the basis of the data on the change in T A S 2 the extent to which the flexibility of polymer chains changes m a y be surmised [18]: the higher the value of TASk, the greater is the flexibility of the chains. It is apparent from the TAS2 versus w2 plot (Fig. 5) t h a t as the inorganic filler content in the system is increased, TAS2 is reduced, and the flexibility of chain segments in the polyurethane network is consequently lessened. This is due to the formation of a compact surface layer on the filler in which the molecular mobility, and also the flexibility of the polymer chains, is normally lower in comparison with t h e polymer molecules in the volume. I t should be noted t h a t against the background of a general limitation of the mobility of polymer chains accompanying introduction of the filler, changes in the flexibility of the chains as the filler content rises are nonuniform in character, as m a y be seen in Fig. 6. On an earlier occasion we investigated changes in other parameters due to the influence of a filler, particularly the effect of the latter on the average internodal molecular weight Mc, and it was likewise found t h a t changes in the latter parameter accompanying a rise in the filler content are nonmonotonic in character [11]. It could well be t h a t the great variety of processes which were referred to above, and which take place during the formation of systems of polymeric networks, both unfilled and, particularly, filled systems, m a y give rise to this complex dependence of TAS2 on the filler content. Thus is appears from the results presented above t h a t if an inorganic filler is introduced into a system of interpenetrating polymeric networks the filler increases the heterogeneity of systems of this type and thereby influences processes occurring in the formation of the latter. This means that in the filled systems we will have not only a transitional region which likewise appears in unfilled interpenetrating networks also, but there will be in addition a surface layer consisting almost entirely of a single individual network appearing on the inorganic filler. Formation of the surface leads to a change in the effective amount of one of the networks in systems consisting of these networks. All these factors have a considerable effect on thermodynamic properties: the flexibility of chain segments in the network is affected, as is the thermodynamic stability of the polymer-solvent system. Translated by R. J. A. HE~RY

REFERENCES L D. KLEMPNER, H. L. FRISCH and K. C. FRISCH, J. Elastoplast. 3: 2, 1971 2. K. C. FRISCH, D. KLEMPNER, S. MIGDAL and H. L. FRISCH, J. Polymer Sci. Po, lymer Chem. Ed. 12: 885, 1974 3. V. HUELCK, D. A. THOMAS and L. H. SPERLING, Macromolecules 5: 340, 1972

Symthes~ of ~igophenylenes

1247

4. Yu. S. LIPATOV, A. Ye. NESTEROV, L. M. SERGEYEVA, L. V. KARABANOVA and T. D. IGNATOVA, Dokl. AN SSSR 220: 637, 1975 5. Yu. S. LIPATOV, L. M. SF_~GEYEVA, L. V. MOZZHUKHINA and N. P. APUILHTINA, Vysokomol. soyed. A16: 2290, 1974 (Translated in Polymer Sei. U.S.S.R. 16: 10, 2658, 1974) 6. Yu. S. LIPATOV, L. M. SERGEYEVA, L. V. KARABANOVA, A. Ye. NESTEROV and T. D. IGNATOVA, Vysokomol. soyed. A18: 1025, 1976 (Translated in Polymer Sci. U.S.S.R. 18: 5, 1175, 1976) 7. Yu. S. LIPATOV, Vysokomol. soyed. A17: 2358, 1975 (Translated in Polymer Sci. U.S.S.R. 17: 10, 2717, 1975) 8. Yu. S. LIPATOV, Fiziko-khimiya napolnennykh polimerov (Physico-chemistry of Filled Polymers). Izd. "Naukova dumka", 1967 9. Yu. S. LIPATOV, L. V. KARABANOVA, L. M. SERGEYEVA and A. Ye. F ~ M A N , Sbornik. Sintez i fiziko-khimiya polimerov (Synthesis and Physico-chemistry of Polymers). +No. 18, Izd. "Naukova dumka", 1976 10. Yu. S. LIPATOV and L. lYI. SERGEYEV, Vysokomol. soyed. 8: 1895, 1966 (Translated in Polymer Sci. U.S.S.R. 8: 11, 2093, 1966) 11. L. lVl. SERGEYEVA, T. T. SAVCHENKO, Yu. S. LIPATOV and L. A. KOPTSEVA, Kauehuk i rezina, No. 6, 17, 1969 12. I. N. BRONSHTEIN and K. A. SElVIF~NDYAYEV, Spravoehnik po matematike (Mathematical Handbook). Izd. tekhn, lit., 1953 13. A. A. TAGER, T. J. SHOLOKHOVICH and Ju. S. BESSONOV, Europ. Polymer J. 11: 321, 1975 14. I. PRIGOZHIN and R. DEFEI, Khimieheskaya termodinamika (Chemical Thermodynamics). Izd. "Nauka", 1966 15. A. A. TAGER, Vysokomol. soyed. A14: 2690, 1972 (Translated in Polymer Sei. U.S.S.R. 14: 12, 3129, 1972) 16. F. DANIELS and R. ALBERT[, Fizieheskaya khimiya (Physical Chemistry). p. 127, Izd. "Vysshaya shkola", 1967 17. S. S. VOYUTSKII, Kurs kolloidnoi khimii (Colloid Chemistry Course). 1964 18. A. A. TAGER and K. S. DOMBEK, Kolloidn. zh. 15: 69, 1958

THE SYNTHESIS OF OLIGOPHENYLENES CONTAINING VINYL CHLORIDE GROUPS* V. A. SERGEYEV, Y u . 2~k. CHERNOlVl:ORDIK, YE. YA. KHARAS, I. V. ZHURAVLEVA a n d V. V. K O R S H A K

Hetero-organic Compounds Institute,U.S.S.R. Academy of Sciences (Received 6 October 1976) Oligophenylenes have been synthesized from diethinylberazene, phenylacetylene and ethinylehlorovinylbonzene, and some properties of the products have been investigated. The vinyl chloride group of ethinylchlorovinylbonzono is preserved in * Vysokomol. soyed. A19: No. 5, 1082-1086, 1977.