Appearance of individual spectra of relaxation times

1492

Yu. I..~ATVEYEV I..-~I"VEYEV and A. A. ASXADSXII Asx~vsg~

6. V. V. KORSHAK, T. M. FRUNZE, S. P. DAVTYAN, V. V. KURASHEV, T. V. VOLKOVA, V. A. KOTEL'NIKOV KOTEL'NIKOV and R. B. SHLEIFMAN, SHLEIFMAN, Vysokomol. Vysokomol. soyed. A21: 1960, 1960, 197~ 1979 (Translated in Polymer Sci. U.S.S.R. U.S.S.R. 21: 9, 2161, 1979) 1979) BEGISHEV, S. A. BOLGOV, MALKIN, N. L SUBBOTINA and V. G. FROLOV, 7. V. P. BEGISHEV, BOLGOV, A. Ya. MALKIN, I. SUBBOTINA

Vysokomol. soyed. B21: 714, 1979 (Not translated in Polymer Sci. U.S.S.R.) 8. V. P. BEGISHEV, S. A. BOLGOV, A. Ya. MALKIN, N. I. SUBBOTINA SUBBOTINA and V. G. FROLOV, FROLOV, Vysokomol. Vysokomol. soyod. soyed. B22: 124, 124, 1980 1980 (Not translated in Polymer Sci. U.S.S.R.) U.S.S.R.)

PolymerScience Polymer Science U.S.S.R. U.S.S.:R. Vol. Vol. 23, 23, ~,~o. ~o. 6, 6, pp. pp. 1492-1504, 1492-1504. 1981 1981 Printed Printed in la Poland Poland

0032-3950/81/061492-13507.50/0, 0032-3050/811061492-13507.50/0"

'D 1082 Pergamon Pergamon Press Press Ltd.

APPEARANCE OF INDIVIDUAL SPECTRA OF RELAXATION TIMES* Y Yr. u . I. I. MATVEY~V M:ATVEYEV and a n d A. A. A. ASKADSKII ASKADSKYI

All-Union Central Scientific Research Institute of Labour Protection

(Received (Received 9 April 1980) 1980) A non-linear model was proposed to describe relaxation properties of polymers and a mathematical analysis made of this model using the Van Vazl der Pole method. The model explains the appearance of a relaxation time spectrum, in whicll which there are two basic relaxation times, while the others are a combination of these values and elastic characteristics of the polymer. The approximation derived gives a satisfactory description of experimental results collcerning stress relaxation and transmits qualitatively the type of dependences of relaxation times on deformation. :NuMF.~tovs e x p e r i m e n t s o f stress r e l a x a t i o n aan(] n d p o l y m e r creep confirm t h a t tthe h e (creep) r e l a x a t i o n c u r v e consists of two clearly expressed expressed sections--the section of r a p i d stress r e d u c t i o n (rapid d e v e l o p m e n t o f d e f o r m maattiioonn)) aanndd the the section of slow stress r e d u c t i o n (slow d e v e l o p m e n t of d e f o r m a t i o n ) . T h i s is s c h e m a t i c a l l y showlt in Fig. 1. H o w e v e r , a t t e m p t s to describe these curves b y oonly n l y two r e l a x a t i o n t i m e s (delay) n o r m a l l y end in failure fitilure since tthe h e use of of o n l y two p a r a m e t e r s hinders the a~ccurate only c c u r a t e description d e s c r i p t i o n of the i n t e r m e d i a t ce section o f r e l a x a t i o n curves. F o r a more a c c u r a t e description d e s c r i p t i o n of thesc curves the rrelaxaelaxattion i o n t i m e (delay) s p e c t r u m is used, for e x a m p l e , a n iin(lividual n d i v i d u a l s p e c t r u m determ i n e d b y T o b o l s k y - M u r a k a m i [1]. I t should bc n o t e d t h a t the a p p e a r a n c e o f a r e l a x a t i o n t i m e s p e c t r u m was w~s p r o v e d b y K a r g i n a n d Slonimskii w h e n a n a lysing a m u l t i - e l e m e n t model of p o l y m e r s [2-4] p r o p o s e d b y t h e m . I n view of using a n iindividual n d i v i d u a l s p e c t r u m o f r e l a x a t i o n t i m e s a c c o r d i n g to T o b o l s k y - M u r a k a m i the question arises w h e t h e r these t i m c s are t y p i c a l o f tthe he p o l y m e r s y s t e m , or w h e t h e r t h e y are d e r i v a t i v e s of two basic r e l a x a t i o n t i m e s * Vysokomol. soyed. A23: No. 6, 1347-1357, 1981.

Appearance of individual spectra of relaxation times

1493.

(delay) as a consequence of a more complex mechanism of deformatiofl than t h a t described by conventional two-element models. Since in real polymers in addition to a displacement of structural elements in deformation, considerable importance is attached to the rotation of these elements in relation to each other, this condition shouht be considered when examining a meeh~Lnical model of the polymer. Since rotation of structural elements, particularly with considerable deformations results in non-linear effects, it is clear t h a t even on considering the model in the form of two simple elements joined at a certain angle with each other, we obtain a system of nonlinear differential equations, the solution of which produces the relaxation time spectrum. Both relaxation times typical of elements of the model and times appearing as a result of the non-linearity of equations, which will depend either on deformation (if stress relaxation is ex~tmined), or on stress (if creep is examined), will be present in the spectrum as relax.~tion times typical of elements of the model. This study therefore seeks to show, using a model consisting of two Aleksandrov-Lazurkin elements [5] joined at angle u how experimental results of stress relaxation ~md creep m a y be described. Two basic relaxation times, which are typical of these elements of the model and further relaxation times (spectrum) are obtained, depcrtdent on main relaxation times (delay) and on deformation (stress).

0",

a

b

e~

/, t

Z"

:Fro. 1. Schematic layout of curves of stress relaxation and creep: I--section showing rapid stress r(,duction (increase in defi)rmation), II--scction showing slow stress reduction (increase in deformation).

Let us examine deformation of the model shown in Fig. 2. Equations of deformation of Aleksandrov-Lazurkin elements take the form

,2,

1494

Yrr. I. M~TV~.rEV and A. A. As~AnS~I~

,Considering the d i s p l a c e m e n t o f the p o i n t o f j u n c t i o n of elements (Fig. 2b) we write 2

2

2

1 ----/i.o-{-12.o--2ll.o/2.o cos a0 .2

2

2

----(/~.0÷Ax~) +(12.0+Ax2) --2(l~.0+Ax~) (l~.0+Ax~) cos 1 I,.o

sin ao

lz.o

s i n ` 8 = -~- sin ao

-- - -

sin ,8

sin `8'----

/2.o+Axz . l

sin a

x o = l l . o sin ]7

x--(lt.o-F,d:~i) sin fl' , d x - - x - - x o ,or

Ax----

~--ll.ol2.o sin ao

(ll.o-[-Ax,) (li.o~-Ax,) sin

(3)

4 l ) . o + / ~ . o - - 21~.o l,.o cos ~o

a

b

.i//i/I////////////.///////.'///.////////~

I//..////.'///

,

c

l

/

~.y.4/////,'/[

.i

: ;///./..~///////I///////////.

117"

FIo. 2. Model of polymer deformation: a--general appearance of the model, b--displacement ~f the point of joining elements of the model, c--forces acting on the point of joining elements of the model. where values of all p a r a m e t e r s are clearly seen in Fig. 2b. F r o m the e q u a l i t y o f l values with different ~ angles we o b t a i n a n o t h e r ratio

cos ~ =

(ll.o+Axl)2+(12.o+Ax2)2--1~.o--l~.o+211.ol~.ocos ~o 2 (11.o+ ~ x l ) ( / , . o + A X , )

F o r force f we h a v e 2

2

2

f --~fl ~ f * - - 2 f J , cos (~--a)'

(4)

Appearance of individual spectra of relaxation times

1495

f l cos fl'-----fzcos (rt--a--fl') cos ( l t - - g - - f l ' ) = - - c o s ( a + f l ' ) - - --cos g cos i f + s i n g sinfl'

(,5)

cos fl' (fl+f2 cos g ) = f 2 sin g sin fl' 1We denote by y=

12.o ztX2slng "

)'

(fx+foeos~)=f2sin~gl,.o-t-Ax, 1

la'o+ Ax2 .

sm g and solve the previot[s e q u a t i o n iit relation

1

1o y. T h e n

Y= (fl+f~ cos g)/f or

l~.o+ Ax,z -2

Z + f 2 cos g

sine=

2

.......

/1.o+/2.o-- 2/I.o/2.o cos eo

F o r simplicity we will f u r t h e r assume w r i t t e n in the f o r m

that

(6)

f

ll.o=12.o=lo. T h e n , (3)-(6) ~re

AX21o sin ao = (lo+Axi)(lo-4-Ax2) s,n . g--lo~.. s,n go

(7)

2

(zix~--Ax2)* = 41o*sin 2 go - - 4 (lo+,~x~)(/o+Zlx2) sin z ~-~

2

2

(8)

g

f ~ - - (L +f2)2-- 4 L A sin2 - 2

(9)

f(lo-4-Ax2) sin g----(fl A-f~ cos g) 2/o sin _a_o 2

(10)

L e t us consider the case w h e n a 0 = 0 . T h e n , (7)-(10) t a k e the form:

(lo+dXl)(lo+Ax2) sing----0;

g=0

ll)

Ax, --Ax 2 - 0

(12)

f =fl-4-f~

(13)

T r a n s f o r m i n g (7) using e q u a t i o n (10) we o b t a i n

A x = (lo-4-zlxl) A + f 2 c o s g I

l 0 c o s -go -

2

Since when g o = 0 , g = 0 , the e q u a t i o n for Ax takes the form

A x : l o + A x l-lo~-Ax 1 Therefore, the mtknown s y s t e m of e q u a t i o n s (1), (2), (7)-(10) as m a x i m u m

1496

Y~. :. MA.zv~.z~'V and A. A. A~r*nsx.~

transition provides the case when both Aleksandrov-Lazurkin models are parallel. This case is examined in detail in a separate study [6]. Let us examine the case of high deformations, when lo/ztx<>lo and Axz~lo and equations (7)-(10) take the form: 2/o sin -~

z~xl--Ax2:

d X = A X 1 d X 2 sin

sm

f = (fxq-A)

(14)

a

Axldx2 sin

2

- 2-

i 4f, f2sin,2 (f,-4-f,)' 1--.

fdx2sin a= (f~ ~f2_ 2f2sin~2 ) 21oSin ao2

(15)

(16) (17)

Let ns" examine the case of these deformations />> lo, when an is determined from the condition (as--angle after instantaneous definition of deformation) ~2

•

ao - z i x l d x l sin~-~ -

2 ao

o sm ~

o

Then sin an

2

lo sin -ao -<<1

-dxl

2

In this case (16) may be written in the form 2fLf' ( j '° sin - ~ ) ~

f~fx+f'--fx---~

xx

(18)

and (14) using formula (17) in the form

f,-]-f.--2fz(~- sin-~) z dx = ,#xl f

(19)

We then assume in all calculations that ao=½n (although this may also be different). Denoting small parameter (lo/dx)Z=p, we write (19), (15) and (18) in the form

dz:ztzr(1-- ~.~- l.L) A/, dx1--,Jx,---~ 0

(20) (21)

1497

Appearance of individual speotra of relaxation times

I t is easy to see t h a t in zero approximation (/~=0) the model examined changes into two Aleksanclrov-Lazurkin models joined in parallell Let us now examine the effect of the variation of angle a during stress relaxation on initial relationships. Let a = a n + A ~ and and (Aa/~n)<
Since (Aa/an)<
1 4 ] Ale, or

Aot'=--

f ,dx,

2

--

f \~-'zJ

or

(23) Substituting in equation (23) formula (15), we derive

x/

'o

f \ztx,2)

ax~, ,~ ,1

f i!

,=>

Therefore, bearing in mind variations of angle a, we obtain equation (24) in the form I I f then we assume that the Aleksandrov-I~zurkin element with index 1 is more flexible t h a n the element with index 2, ,and t h i s m a y be due to the fact t h a t element 1 depends on molecular interaction, the plus sign m a y be used in equation (25). Therefore, when (10/Ax)l<
,1~98

Yu. I. MATVE~'EV and A. A. A s ~ s ~

d

fl

(2o) (27)

£h

(28)

f=ft+f2--f,+fa'/~

(29)

AXl:AX2+2Ax./ f2. p fl -~-f2 W e t r a n s f o r m the u n k n o w n s y s t e m in relation to

(30)

Zxl,fl

a n d fu

(lc2+~hd)(Ax---~):f,'l~(k:b~iud'~ fu Ax \ I/l-J-f2

(31)

(k't-r/'d~)(Ax---~3):f'-t-Prkflq-f,f' -t-(k.-I-~.--~) f2 d

d

~-j .f,.x~] × :-f'f~- +2/Ix \ks(f,+f.) fxfg}-f2 fx-Ff2)_[

×

(32)

L e t us e x a m i n e the solution o f the linear s y s t e m

d

f l : AXkl_~_k2e

-J- -kl-{-Ic, ,Jx,

~1-- kl + k,~

f2=AXka+ka e

+ k-~4A x,

~2: ka+ka

We now e x a m i n e the solution of the non-linear e q u a t i o n using the Van d e r P o l e method. We therefore writc

k2

klk2

f~= Ax_ ~1_ a{t)e-t/,,.j_ ~ A x , kl + kz kl + k2 k2

f ~* = A

X

-t',

ksk,

~_,+k . - - -a- b(t)e "" + k---~-~ zjx

(33)

1499

Appearance of individual spectra of relaxation times

We substitute fl* and f2* in equations (31) and (32). An equation system is t h e n derived for a(t) and b(t) kx _ ~k,---4k--~ ~-t/,,-X ="L[k ' ~f;

k3 e_u, db (~

' fi'.fl--fl7;'~ ~-~ ~ )

[- f~*f*

**

(

•

\ $(J1 "1-Jg*)

~ fl + f *

d)

f* fl -{-fl

)_1

Right-hand sides of the unknown equation system may be transformed as follows:

k,

t/, k ~

•

+ ~(ae

e

_t/,da[

dr- =/~ ¢°(ae-t/"

be_t~,.)_

~°'(ae-t/"

be_t/,.)da_~_: at

-tl,, be-t/,.)db] , atJ

kse-t/"db [ ~tt db] Axq, k3+k4 d-tt: --~ ~°(ae-q"' be-t~")+~]x + ~-dt Solving the equation system derived in relation to da/dt and db/dt and being confined in the solutions only to terms of first-order for p, we obtain

d a _ p q~o(ae_t/,,' be_t/,,)et/,, dt k,rl db /a ~o(ae-t/',, be-t/'.)e */*,, dt Axksr2

(34)

where _ _ vxlv2f~(fa--f2.o)--f2(f~--f~.o) ~o(ae-t/', .oe-t:,,.) : / g.2 - - -f2- - --(kl+k2)

f,+f2

~o(ae-t/',, be-t/,,):

(fl+f2) 2

f ,f 2 + k, :

fl--~

flh

/

f2

~,k~(~+A)+ 2 ~ ~ fl+A

f2

:I+A

Ax.'~

]

',,

~, f2 1))flfZ ~!"Ol Let kl ~ks, k2 ~ k , and only ~I<> 1 and (t/v,)<< 1, a..~b (will examine the solution of system

1500

Y~y. I. M+_~nrEY~V a n d A. A. As~ransK~

(34) in the middle of the interval studied, in the position where the effect of further relaxation times is observed experimentally) ¢o-~'-t - ~ a e_~/,, /¢sb and

We take averages of the righ-hand sides of system (34) in the interval T<<~<
11\

$ ]

(35)

We take the values of a = l - F a , b=l-Ffl, where ~<<1, fl<
(36) - - ~ = ~ol a -

da de

__

kxk8 r~

p-l-1

_=--(o1~-]-~1~----o91

(37)

We find relaxation times rz and rn from the equation of variability _

_

Solving this equation we derive formulae for relaxation times

1

(I+~/5) ~-~:

TI

(-1+~/~)

or 7

~---- --0.62 ~ 8~ri

TH~ 1"63~k8 8~ l

Appearance of individual spectra of relaxation times

1501

I t is easy to see that ~ and fl, satisfying this system (37), take the form: ~ ~o-~~, e-th: + ~2e-Urn

(38)

.~=&+&e -u~'+&e-'''

I f the solution derived (38) is substituted in equation (33) it appears that, in addition to basic relaxation times r: and T2, new relaxation times vt appear, which depend on ~, and r2 and on deformation ~ as follows:

1

1

--

Tk

1

2l-

Ti

--

%.i+r,

TI,H

TI~'I

"t'i %.I

T(

T(

1 +%.~/rl

r2((+,) = vi-F'r~

vs~+:----1 -F%.i/rII

T~

%.t T,I,~+,

1-- 1"63--

--

1 +0"62--

k~: %.,

--

k~ 2 %.1

Therefore, %.1 T4=

T, ~1

T3=

1--1"63-I¢~2

kl"

1+0"62 - kae 2

(39) %.6~-

l'S

%'2 ~'5~

k, %.2 l - - 1"63 kae-~ T-~

1+0"62 k-~12T2 k3e %.,

Ratios (39) are valid with high e values, the lower boundary of which is determined from the condition e2>>1.63 k~.%.2. J~8 T1

From the solution of heterogeneous system (37) we find values of ~0 and rio. It is easy to see that they are -- 1 and 0, respectively. Instead of six there are only five relaxation times. Values of el, as, fit and f12 are determined using properties of the function f*--flin. As it has zero and maximum values in certain typical points (there are three such points (Fig. 3)), f*--fnn----0, for t, and t.~, O/Ot(f*--flin)=O, for t2. Another condition is that t = 0 , by which the value of function f*--flin may be determined from static conditions. Of course, real dependences of relaxation times will be somewhat different, since a number of approximations were used when solving the initial equation system. The solution derived enables us also to determine the dependence of equilibrium stress on deformation. It follows from equation (28) (when t-,oo) that

f=(E~+E4)

sAx lo

E2E4sl o (Ef{-E4)Ax'

(40)

wh('re s is the cross-sectional area of the sample. Then, tile dependence of stress

1502

Yu. I. MATVEYEV and A. A. ASKADSKn

~o, calculated for the initial section, on ~ takes the form

E2E4 1 no= (E2+E4) ().-- 1 )-- E.,~-E------4").-- l '

(41)

where ). is the extension ratio. The dependence of stress a, calculated for the initial cross section of the sample is described as

a-= (E2+E4),t ().-- l )

E2E4 ). E2%E4 ).-- 1

(42)

The derived ((41) and (42)) differ from all well-known equations of deformat ion of e]astomers, although under appropriate conditions they may take .a form, which corresponds to an equation of the classical theory of high-elasticity, or (under different conditions) to Moouey-Rivlin, etc. type formulae. As fitr as the form of relaxation curves is concerned (dependences of force f on time t), it is determined from equation (28) with substitution in it of

f l ~-zixkl(ale-t/"a2e-t/")e-t/'~ + k2Ax and

(43) f2 ~- ~Xk3( 1 -~-flle-t/r' -~-f12e-t~'' )e -t/r' -~- k4~x

It is easy to show t h a t when studying the relaxation time spectrum the

115 " ~1 involves small corrections iu relaxation times. Consequently, value of f~-~2 this value may be ignored when calculating kinetics of the rclaxation process. Then, the dependence of force f on time t should be written in the form

f = Lfxkl (~l e -t/" ~-Of2e-t/'' - l )e -t/~' -~-zixks(flle -t/~' ~ fl2e-t/")e-t/" ~ f o ,

(44)

where fo-~(k2%k4)Ax is the equilibrium force. Therefore, five relaxation time values are contained in equation (44), two of which (r~ and r2) are typical of t h e model while the remaining ones are derivatives of these values. The relaxation times indicated, apart from r~, are characterized by times ~3-r6 which are determined from ratios (39). Therefore, relaxation times dependent on non-linearity (rs-r6) vary with a variation in deformation, according to the regularities derived (39), while baoic relaxation times are independent of deformation. Figure 4 shows schematically the dependence of relative relaxation times on deformation (rk----~/~, where i = 1 , 2; k=3-6). For the, experimental verification of the ratios derived relaxation time spectra wcre calculated for a PS-polybutadiene block-copolymer sample with a PS content of 62~o. Experiments were carried out with different high deformations. Results of calculation are tabulated. It can be seen t h a t with a duration of the relaxation process of 180 min experimental cm'ves are described by five relaxation times. Times v~ and r2 are practically independent of deformation ~ and are on.

Appearance of individual spectra of r~,laxation times

1503

RELAXATION 'rIMES FOR BLOCK-COPOLYI~mI~ SAMPLES OF PS-POLYB-UTADIENE

Relaxation times, see

Deformation.

%

r6X 10 -4

r2X 10 -3

200 40O 60(}

10-0

1"4

7.4 7.0

1.3 1-4

r,, X I 0 - ~"

rl X

4'6 4.8 4.7 .

10 -I 12-3 12.9 11.9

8.4

74) 6.5 .

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

average (rl)=12.3 sec a n d ( r 2 ) = 1 - 3 4 × 1 0 a so(,. O t h e r r e l a x a t i o n t i m e s a r e in q u a l i t a t i v e a g r e e m e n t w i t h d e p e n ( l e n c e s f o u n d (29), a l t h o u g h a m a r k e d q u a n t i t a t i v e d i f f e r e n c e is o b s e r v e d . T h i s is Cxl)htinc(I b y t h e a s s u m p t i o n s m a d e when deriving these formulae and by the simplifications of initial differential ( ' q u a t i o n s . T h e r e t b r c , t h e s o l u t i o n i n d i c a t e s t h a t t h e p~'oposed m o d e l g i v e s

f, l

a

I

t,

I

t

f

ta

Fie. 3

Fro. 4

Fro. 3. Schematic layout of the curve of stress rclax~tjon, for linear (1) and non-linear aasos (2) (a) ~md dependence o f f * - - f u . ,m time (b). FIo. 4. Schematic layout of the dependence of times r~. on doformat.ion ~: 1-- r~, 2-- rz~+

;m accurate picture of experimental curves and enables the regular appearance of relaxation time spectra to be explained. The behaviour of the system m a y really be describe(I by two basic relaxation time values. The other times are a combination of these two basic times and depcml on (h'fc)rmation and ou elastic characteristics of the polymer. We note finally that fbr the accurate qletermination of times rl and z2 and values of lh-k ~ it is ¢le~irable to solv(, the initial system of differential equations (3)-(6), which can only be done using a computer. r

Tran.slate~l by E. 8EMEI~,E REFERENCES I. A . V. T O B O L S K Y a n d K . M I Y R A K A M I , J . P o l y m e r Sei. 40: N o . 137, 443, 1959 2. G. L. SLONIi~glCIT, Tcoriya deformatsii lineinykh polimerov (Theory of Deformation of Linear Polymers). Dis. na soiskaniye uch. st. dokt. nauk, N I F K h I ira. L. Ya. K a r p o v a , Moscow, 355, 1947

L. S. S~Im~CA et al.

1504

3. 4. 5. •6.

V. A. KARGIN and G. L. SLONIMSKII, Dokl. AN SSSR 62: 239, 1948 V. A. KARGIN and G. L. SLONIMSgH, Zh. fiz. khimii ~ : 563, 1949 A. P. ALEKSANDROV and Yu. S. LAZURKIN, Zh. tekhn, fiziki 9: 1249, 1939 P. I. ZUBOV, Yu. I. MATVEYEV, A. A. ASKADSKII and T. A. ANDRYUSHCHENKO, Vysokomol. soyed. A22: 1347, 1980 (Translated in Polymer Sci. U.S.S.R. 22: 6, 1478, 1980)

PolymerScienceU.S.S.R. Prated in Polaad

Vol. 23, No. 6, pp.

1504-1511,1981

0032-$9501811061~4--4)~07.5010 1982PergamonPlea Ltd.

EFFECT OF SURFACE-ACTIVE SUBSTANCES ON THE. FORMATION OF CROSSLINKED POLYURETHANES* L. S. SHEINII~A,T. E. LIPATOVA, SH. G. VENGEROVSKAYA,A. Y~.. N~.s~aov and YE. V. LEB~D~V Institute of Organic Chemistry, Ukr.S.S.R. Academy of Sciences Institute of the Chemistry of High-Molecular Weight Compounds, Ukr.S.S.R. Academy of Sciences (Received 11 April 1980)

~Vhen using a number of methods to study kinetics and structural features of the formation of crosslinked polyurethanes in a system containing surface-active substances (SAS) it was found that the presence of the latter causes a marked change in reaction rate, the size of microheterogeneities formed during solidification, degrees of conversion at which crosslinked gel-formation begins and an polymer morphology. Results of investigations suggest that the effect of SAS on erosslinking is observed at the initial stage of gel-formation and involves the localization of SAS in the intcrfaeial range, which separates microvolumes with a developed three-dimensional network from the overall reactions .mass. SPECIFIC properties o f SAS a t t r a c t the a t t e n t i o n o f chemists working in various b r a n c h e s of chemistry, including chemists specializing in polymers. This interest ranges from properties of surface layers of p o l y m e r s [1, 2], including also the p o l y m c r o p h i l i z a t i o n of the surface of inorganic fillers [3, 4] u p to the use o f SAS in adhesive compositions [5]. F r o m our p o i n t of view considerable interest is a t t a c h e d to a t t e m p t s of t r y i n g to c h a n g e m a c r o - p r o p e r t i e s of p o l y m e r s b y r e g u l a t i n g processes of s t r u c t u r e - f o r m a t i o n b y SAS. A u t h o r s of a n o t h e r s t u d y [6] f o u n d t h a t for p o l y m e r s w i t h a m o r p h o u s s t r u c t u r e there is a relation between the p o l a r i t y of r u b b e r and t h e effect of the i o n o g e n e i t y of SAS, as shown for crystalline polymers. Results of these i n v e s t i g a t i o n s enable SAS t o * Vysokomol. soyod. A28: No. 6, 1358-1364, 1981.