Effect of cyclization on the topological structure and properties of polymeric networks based on diglycidyl ethers and aromatic amines

Polymeric networks based on diglycidyl ethers and aromatic amines

1873

5. T. B. BOROVRIKII, K. P. GUROY, I. D. MARCHUKOVA and Yu. E. UGASTE, Protsessy vzaimnoi diffuzii v splavakh (Joint Diffusion Processes in Alloys) p. 359, Nauka, Moscow, 1973 6. R. B. BIRD, W. E. STEWART and E. N. LIGHTFOOT, Yavleniya perenosa (Transfer Phenomena). Khimiya, Moscow, 1974 7. J. FERRY, Vyazkouprugiye svoistva polimerov (Viscoelastic Properties of Polymers). Izd. inostr, lit., Moscow, 1963 8. A. Ya. M/tLKIN and A. Ye. CHALY~H~ Diffuziya i vyazkost' polimerov (Diffusion and Viscosity of Polymers). p. 302, Khimiya, Moscow, 1979 9. V. V. AFANAS'YEV, A. A. EL'BERT, T. A. VITMAN and L. A. SERAFIMOV, Zh. fiz. khimii 49: 1,231, 1975

Polymer Science U,S.S.R. Vol. 24, No. 8, pp. 1873-1883, 1982 Printed in Poland

0032-~950/82 $7.50 ÷.00 ~) 1983 Pergamon Prem Ltd.

EFFECT OF CYCLIZATION ON Tiq~. TOPOLOGICAL STRUCTURE AND PROPERTIES OF POLYMERIC NETWORKS BASED ON DIGLYCIDYL ETHERS AND AROMATIC AMINES* L. M. CHEPF~L',V. A. TOPOLWARAYEV,A. N. ZELEN~TSKII, E. V. PRUT,

G. M. Tao~zMOvA, D. D. N o v ~ o v and AL. AL. BF,Rr~X Institute of Chemical Physics, U.S.S.R. Academy of Sciences

(Received 9 .May 1981) The dependence of ring-formation on the structure of diglycidyl ethers in re. actions with aromatic amines is discussed. The structure of the network polymer and the conformational tendency to cyclization in the oligomers under consideration are analysed on the basis of a statistical model. An interconneetion between the probability of ring-formation and the equilibrium elasticity of the network systems is demonstrated. The tendency towards the formation of ring structures in systems based on diglyeidyl ortho-ethers has been established experimentally, a fact which is in agreement with the theoretical calculations. T h e s t r u c t u r e of a n e t w o r k p o l y m e r is k n o w n to be closely r e l a t e d to t h e process of g e l - f o r m a t i o n . E v e n a c o m p l e t e l y u n i f o r m n e t w o r k s t r u c t u r e c u r e d to tlm m a x i m u m e x t e n t is f a r f r o m ideal a n d a considerable n u m b e r of defects, which d e p e n d o n t h e m o l e c u l a r n a t u r e o f t h e initial r e a c t a n t s a n d t h e m e c h a n i s m a n d conditions of n e t w o r k f o r m a t i o n , is p r e s e n t [1]. Especial difficulties of b o t h a c o m p u t a t i o n a l a n d also a n e x p e r i m e n t a l n a t u r e arise in a t t e m p t s to assess t h e p r o p o r t i o n of ineffective loops in a n e t w o r k s y s t e m a n d t h e p a r t p l a y e d b y such s t r u c t u r e s in t h e elastic b e h a v i o u r o f a n e t w o r k p o l y m e r . I t m u s t be s t a t e d * Vysokomol. soyed. A24: l~o. 8, 1646--1653, 1982.

1874

L. M° CHEPEL' ~ ~l.

t h a t , in a n u m b e r o f specific cases and, in p a r t i c u ] a r , in t h e s y n t h e s i s b y p o ] y c o n d e n s a t i o n o f e p o x i d e n e t w o r k s f r o m s h o r t e p o x i d e oligomers which are, h o w ever, c o n f o r m a t i o n a l l y p r o n e to cyclization, t h e f o r m a t i o n o f ineffective ]oop~ will be a p r i n c i p a l cause for loss in n e t w o r k d e n s i t y of t h e s y s t e m . Initial substances. Aniline was dried with K,COs and distilled in vacuum (moisture content, not greater than 0.01%). Diaminodiphenylsulphone (DADPS) was recrystallized from hot alcohol (Tm~ 175-176°C). m-Phenyldiamine (MPDA) was distilled in a current of argon in vacuum (Tm~ 63-64°C). The diglyeidyl ether of pyrocatechol (DGEP) was obtained as in [2], T~11~ 132-140°C/26 •6 Pc. The diglycidyl ether of resorcinol (DGER), the diglycidyt ether of diphenylolpropane (DGEDPP) and the digiycidyl ester of hexahydrophthalic acid (DGEHHPA) were purified by distillation in vacuum; epoxide number (e.n.), 38.2, 24-9 and 29.8 respectively (theoretical e.n.; 38.7, 25.3 and 30.3). According to the data from thin-layer chromatography (TLC), GPC, I R spectroscopy and mass spectroscopy, the starting materials were single compounds. The reaction between the diglycidyl ethers and aniline was carried out with a stoichiometric ratio between the starting substances, in bulk at 60°C, as well as in solutions of benzene and toluene of different concentrations at the boiling point of the solvent, until the starting substances disappeared (as monitored by TLC). I t had been shown beforehand that the rate of hydrolysis of the epoxide groups under the experimental conditions was small and the concentration of products of hydrolysis in a control experiment was below the limit of sensitivity of the TLC method (I<0.01%). TLC was carried out on AlIO8 of I I I r d degree of activity; eluent, chloroform-acetone, 96 : 4; identifier, 0"3% aqueous solution of KMnO4. Gel-chromatograms were recorded with a Waters Associates instrument having five columns filled with Microstyrogel having pore sizes of 250, 250, 500, 1000 and 3000 A; eluent, THF; rate of feed of the eluent, 1 ml/min. The nature of the non-functional part in the products was confirmed by comparing the gel-chromatogram with the ehromatogram of specially hydrolysed products and by comparing the chromatograms of reaction products obtained with various times of he~ting with the chromatograms of products obtained in solution. The I R spectra were recorded with a UR-20 spectrometer. The molecular weight was determined by ITEC in MEK. The molecular weight of the polymers obtained was calculated from the curve showing the dependence of Mn on c (where c is the concentration of the solution}, it being selected in that region of the curve where it was independent of the concentration of the solution. The e.n. were determined by chemical and by potentiometric titration using the well known methods. Specimens for the dynamic tests, 60>( 10× 1 m m in size, were obtained from plates cured between fiat parallel glass plates coated with an anti-adhesive (dimethyldichlomilane)o The dynamic shear modulus G and the glass temperature Tg were determined by the inverted torsional pendulum method in the temperature range 20-250°C.

I t has b e e n f o u n d to be v e r y useful to use t h e s t a t i s t i c a l m o d e l of t h e s t r u c t u r e of a n e t w o r k p o l y m e r (~MSNP) in a n a l y s i n g t h e effect o f t h e c o n d i t i o n s ' o f n e t w o r k f o r m a t i o n on t h e topological s t r u c t u r e of the n e t w o r k a n d on its elastic b e h a v i o u r [1, 3-5]. T h e idea o f a n e t w o r k as a set o f r a n d o m l y linked rings w i t h a certai~l d i s t r i b u t i o n w i t h r e s p e c t to size lies a t t h e basis o f t h e model, so t h a t all the rings m a y be quite s i m p l y classified. T h u s rings o f t h e t y p e 1,0 a n d 1,1 which we h a v e called " m o n o - r i n g s " for short, are considered to be ineffective f r o m t h e poin~

Polymeric networks based on diglyeidyl ethers and aromatic amines

1875

•of view of the connectivity of the network. The first members of the series of ring :structures are shown below.

/

/

/

R1 /\

\

\

\

N

N

c/ \

C \

/

C

",,C / C

/ C \

e tin 9 t" 1

N I R1 I C--N-

,, C I C--O--R~--O--C Pi. 9 1.0

C--C~C--O--R,~--O--C--C--C N__RI__N\/

C\

\ N~RI--N

C--N--RI--N--C I t C C I

c - c - c - 0 - R, - c - c - c /

I

C

C

ring 2' 0

RI

/

N--C--C--C--O--R ~--O--C--C--C_N \

\

/ N--C--C--C--0--R2--O_C_C_C_N nin9 2.2

R1

I I R~. R2 I I 0 0 I C C I I C--C--N--C--C I R1 r~n9 2. t

T h e possibility of forming such structures has been experimentally demon:strated as a result of a detailed spectroscopic and chromatographic analysis of :systems formed by the diglyeidyl ether of diphenylolpropane and aliphatic diamines having hydrocarbon chains of various lengths [6]. The effect of monocyelization on the network's topology has been taken into a c c o u n t [1] by introducing an appropriate probability parameter into the calculations. In general, the probability of such reactions is determined b y rate constants for bimolecular, /co, and for intramolecular, kin, linking and m a y be determined from model experiments. The ratio of these rates for the continuation and termination of network growth depends, in its turn, on the conformational .disposition of the initial monomers towards monocyclization, as well as on the conditions under which the reaction takes place. A topological diagram of a network obtained with the assumption that a = k i , / k ~ 5 is shown in Fig. 1. It m a y be seen from this Figure that monoeyeli~ation leads to the formation of a considerable number of ineffective loops in

1876

L.M. Cn~rffi~.'~ a/.

the network system. Figure 2 shows how the proportion of single rings in the network system depends on the effective probability of monoeyclization, the result obtained being based on SMSNP. An increase in the number of single rings leads to pronounced opelfing-up of the network and to a decrease in th~ connectivity of the system (Fig. 1 and 2).

FIG. 1. Topological diagram of a network with a relative probability of monoeyeligatio~

A theoretical calculation of the equilibrium elasticity Eequjl made on t h e basis of the SMSNP [3] showed that Eecuil decreased roughly as the connectivity o f the system was reduced and that it was possible to use the values of F ~ u ~ as a parameter characterizing the topology of real network systems. In connection with what has been said, it was of interest to analyse t h e process of single-ring formation and its effect on the equilibrium modulus of a number of real compositions formed by an epoxy-containing oligomer and an aromatic amine, the compositions differing in their molecular structure of the, oligomeric block. The conformational predisposition towards cyclization of the various diglycidyl ethers had been assessed beforehand. Elementary ring structures o f type 1,0 and 1,1 were constructed from various diepoxides and diamines by means of Bridge-Stewart molecular models, the following compounds being used: DGER, DGEDPP, DGEP, DA.DPS and MPDA. It was found that the predisposition of the system to single-ring formation depends on the chemical structure of the diepoxide and diamine or, more exactly, on the set of conformations that they have.

Polymeric networks based on diglyvidyt ethers and aromatio amines

1877

The following conclusions m a y be made on the basis of the analysis: 1) in the. reaction between D G E R and D A D I ~ , the formation of single rings is improbable since the ring 1,1 is highly stressed and 1,0 does not occur because of the geometry of the chains; 2) the ring 1,1 is less stressed in the system D G E R ~ M P D A ; 3) the systems DGEP-I-I)AI)PS and D G E P + M P I ) A are conformationally disposed to the formation of the ring 1,1, b u t the ring 1,0 is stressed; 4) the ring 1,1 is characterized b y a large number of conformations in the case of the system DGEDPP~DADPS.

2L 2 n ~ing

2

I

0

I

I

2

FxG. 2

I

l_

q

=

07

O.J

0.5"

0.7

?/nl

FIG. 3

FIe. 2. Dependence of the fraction of single rings in the network on the relative frequency of monocyclization. FIG. 3. Radial distribution function for the length vector of chains of the following molecules: /--DOER; 2--I)GEP and $--DGEDPP. The chain conflagrations leading to monoeyeliz~tion are shown for the following systenm: a--DGER-MPDA; b--DGEP-MPDA; e-- DGEDPP-DADPS and d-- DGEP-DADPS.

The analysis that has been carried out has shown that it is necessary to assess the proportion of chain c o n l ~ r a t i o n s for the various diepoxides that are capable to leading to the formation of single rings of the t ) T e 1,1, that is, cor~figurations having a distance between the chain bends approximating to the distance between the rftrogen atoms in the corresponding molecules of the diamine. The eonfigurational behaviour of the chains has been modelled b y the Monte-Carlo method as proposed in [4]. Figure 3 shows the radial distribution functions for the vector chain length of three glycidyl ethers: D G E R , I ) G E D P P and I)GEP. The numerical distribution functions were obtained using a [~ompurer. The batched areas of the Figure are, in fact, proportional to the fraction1 of the configurations of the particular diepoxide that are favourable to the for-

L.M. C-~.PEL'e~ aL

1878

mation of type 1,1 single rings with the specified amine. The relationships shown in Fig. 3 confirm the proposal that the systems D G E I ) P P ~ D A D P S and DGEP ~-MPDA are conformationally disposed to the formation of 1,1 rings whereas the formation of such rings is less probable for DGER. Table 1 gives the principal physieo-meehanical properties of the compositions determined by tho inverted torsional pendulum method [7]. It may be seen from the Table that the modulus of rubber-elasticity Ee,uiz is found to be the property most sensitive to the molecular structure of the network systems Kequll

0"5

0"3 -

U

b

0"I 0"5

1"5

2"5

o~

Fro. 4. Theoretical dependence of the network's topological-elasticity modulus on the probability of monocyclization. Experimental data: a--DGER-MPDA; b--DGEDPPDADPS and c--DGEP-MPDA. considered. Figure 4 shows the theoretical dependence of the topological elasticity of the networks reduced to a value of unit rigidity of the intermodal chain {the use of the method is described in [8]) on the probability of monocycli~ation in the system. A comparison of the theoretical calculations with the reduced values E r =

Eeq~l!.. for real networks enables the probability of monoeycliza~chaln~/N tion in those systems under consideration to be assessed (Table 1). It should be noted that the relative values of ~K/gDGEDPP obtained from the correlation relationship (Fig. 4) conflict with those based on the eonformational analysis (Table 1) for diepoxides based on DGEDPP and DGEP. The reason for the observed discrepancy clearly lay in the complexity of the calculation in the statistical analysis of the chain configurations with very small values of r/nl (Fig. 3), corresponding to rings of type 1,0. In a real system, because of specific interactions characteristic of the compounds considered, the probability of such configurations may be substantially increased. To throw light on this problem, special model experiments were set up with .systems formed by a diglycidyl ether and a monofunctional amine:

Polymeric networks based on digtycidyl etllers and aromatio amines 0

1879

0

/ \

/

C H , -- C H - - C H = - - O - - B - - O - - C H ~ - - C H - - 4 3 H .N,,

q-~*¢--~--NH~

.--+

DflE

--, CH~-- C H - - CHo--O--R--O--CH.,--CH--CH2--NH

\/

I

o,

•

f

0

0

/\

/\

0

--+ CH.,--CH--CH2--O--R--O--CH2CHCH~--N--CH2CHCH2--O--R--O--CHo--CIt--CH~--,

1

/ / - - - % - xI-I2 \__/ --"

J

T

H etc.

5N--[--CII,,--CH--CH.,--O--R--O--CH.,--CH--N--

l--

on i¢ ~ --C Ha-- C t t - - C I t 2 - - O - - R - - O - - C I t 2 - - C I ] - - C t I., OtlI

\o /

II

/

CH2--O--R--O--CH~

",,

I --, ItOCH

CH--OII / CH~

"\ CHa--N

I

0 .in 9 t. 0 !

I I --+ ~ q - - [ - - C H , - - C H - - C H 2 - - O - - B - - O - - C H . - - C H - - C H , - - N - - ] - - C H 2 - - C H - - C I { o - J\

I

/

[

l

l

OH

OH

~

I

/ 7 % Jr,

"

r

OH

--O--R--O--CII.a--CH--CII..,

I

OH ping n + 1~0 0 /

~

CHa

--

~

I ~--; CI-I3

C

/\ F--N \,./ C

NN 0

1880

L.M. CHF-a~L'et al.

I f cyclization does n o t occur in such a system, p o l y a d d i t i o n leads to th(; f o r m a t i o n of linear polymers. T h e t y p e of end groups in the p o l y m e r s m a y be d e t e r m i n e d b y spectroscopic a n d b y chemical methods. A comp.arison of the molecular weights d e t e r m i n e d b y chemical analysis o f the end groups, Mnl, w i t h ~rn enables the p r o p o r t i o n o f ring molecules in t h e s y s t e m to be assessed. TABLE 1. PHYSICO-MECHANICALPROPERTIESOF COMPOSITIONSBASEDON DGER, DGEP AN[) DGEDPP (STOICHIOMETmCPROPERTIES)* I

Composition

DGER + DADPS DGER+MPDA DGEDPP + DADPS DGEP + MPDA

aK/~DGEDPP

p× lO-a, i N × 10-sa, G~s× IO-L Tg kg/m 3 ! 1/em s MPa

1.340 1.291 1.238 1.299

1.166 1.408 0.803 1.420

1.5 1.8 1-7 1.6

Gequil~

172 1 120 ] 110 115

3G~uil

MPa ~

23.0 17.0 3-0 5.8

0"58 0.42 0.18 1~12

confer, from marion the cot calcu- relation lation curve 0 0.2 1.0 0.3

0 0-3 l-0 1-3

* p--Denslty of eomlaosition,N--densityof nodes;G-shear modulus; kch.~--rlgidltyof the chain of dlepoxide molecules;3(~.~u..= E,quit;~ - calculatedprobability of monocyclizationof the compositionin relative units To--glass transitions temperature. The s t r u c t u r e of t h e amine determines t h a t , if cyclization occurs, it will be o f t h e t y p e n, 0. I t m a y be seen from Table 2 t h a t o-glycidyl ethers give a substantial p r o p o r t i o n of ring products. W i t h the reaction between d i g l y c i d y l ethers a n d a m y l alcohol in the presence of diethylaniline as an example, the ethers acting as models of the o x y a m i n e f o r m e d as a result of the reaction, it was shGwn t h a t t h e c o n c e n t r a t i o n of the epoxide groups in t h e diglycidyl ethers r e m a i n e d practically u n c h a n g e d in 16 hr at t e m p e r a t u r e s up to 130°C so t h a t it is possible to exclude hydrolysis a n d alcoholysis of the epoxide g r o u p as a TABLE 2. ESTIMATE OF T H E P R O P O R T I O N OF L I N E A R MOLECULES I N T H E PRODUCTS OF T H E R E A C T I O N B E T W E E N D I G L Y C I D I L E T H E R S A ~ D A N I L I N E

Initial epoxide compound

DGEDPP DGER DGEP DGEHHPA l ~ h e a t e d for 20 hr 10% solution in benzene 10~/o solution in toluene

Average No. of g-moles in 1 g of polymer, ex 104 calculated calculated from -~n from e.n. 10-0 7.2 18.2 8.1 8.1 9.0 7.2

I

10-0 7.1 16.1 6.2 6-2 4.1 5.3

Proportion of linear molecules* 1

1 0.89 0.75 0.75 (~44 (~71

* Relative errorin the determination of the proportionoflinear molectdes,7%.

Polymeric networks based on diglyoidyl ethers and aromatic amines

1881'

side reaction reducing the functionality of the polymer formed. Evidence that we are dealing with cyclization rather than with hydrolysis of the functional groups also comes from the fact that, when the system is diluted, the proportion of nonfunctional products increases and, if the temperature of the reaction in solution is raised b y 30°C, the proportion decreases. Gel-chromatographic analysis of the reaction systems showed the presence of modality in the molecular mass distributions of the polymers obtained with the (Fig. 5). /k comparison with the gel-chromatograms of" the initial others showed that they appear in the outflow at high eluent volumes. Thus the modality is not determined by contamination with the hydrolysed monomers. As the reaction time is increased, the maximum of the curves is found to be displaced towards higher masses but the position of the maximum corresponding to the non-functional part of the polymer is not changed (Fig. 5). The proportion of ring products calculated from the areas of the peaks on the gel-chromatograms agree with the data in the Table for reactions in bulk and in solution but the total concentration of rings calculated from the chromatograms is rather lower than that obtained from functional analysis of the systems (Fig. 6). ~ I t should be admitted that there are also type n, 0 rings present of largo size, where n > l , the peaks for which are not resolved.

ortho-ethers

;

!!I

t

) I

a

Li,,

\~

t I=

I

1

I

lO0

12g

150

Fie.5

b

175 V, ml

Z

I,

I,

ceg

~so Fro.

6

I

lzs V,ml-

FIG. 5. Gel-ehromatograms of reaction products: a--DGEDPP-aniline and b--DGEP-aniline. Stoichiometric quantities of the reactants; temperature of reaction, 60°C; /--dLtration of reaction, 280 hr; 2-- 600 hr. FIG. 6. Gel-ehrornatograms of the products of the reaction between equivalent quantities of DGEHHPA and aniline: /--reaction in bulk, 60°C, duration of reaction 6 hr (until the starting substances had disappeared); 2--reaction in a 10% solution in benzene, 80°C~ 90 hr; 3--reaction in bulk, 60°C, 20 hr.

188~

L.M. CHEP~.L'e2al.

The chemical functional-group analysis was carried out directly after the initial substances had disappeared, that is, at comparatively low degrees of conversion. There is thus the highest probubility of forming low polymers and correspondingly, the rings smallest in s'ze. It follows from the data shown in Table 2 that ortho-systems have a clearly expressed tendency to form the smallest rings. Pars- and meta-systems do not exhibit the same tendency. A comparison of the Mn and/17~ in the early stages of the reaction does not rule out the possibility that any of the diglycidyl ether-aniline pairs considered may form large ring systems. Figure 5 compares the changes'in the gel-chromatograms of the systems DGEDPP-aniline (a) and DGEP-aniline (b); th.~s clearly shows that when the reaction mixture of the first system is heated for long times, the change in the chromatogram corresponds to an increase i n the molecular weight of the polycondensation system, in particular, through the disappearance of lower polymers whereas, in the second system, ring products continue to be formed (the proportion of the low-molecular weight constituent incresses) and the high-molecular weight part is simultaneously displaced towards lower element volumes. These data give evidence that it is also possible to form the h;gher rings from ortho-ethers. We suggest that the closing of such type 1,0 rings, in reactions both in bulk and also in solution is probably determined by an intramolecular hydrogen bond between an epoxide and a hydroxyl group:

/

0

CH~--CH t\

OH CH~ //

N°\

t

H

/\ l

R'

C H ~ - - C H -- C H z

The association constant for such a bond at 25°G is approximately 0.1-~0.& Amongst the intra- and intermolecular bonds the numbers of the hydrogen bond mentioned arc small [9] but it has been shown previously [10] that the OH--epoxide bond markedly raises the activity of the epoxide ring and, because of the favourable positioning of the nueIeophilie and the eleetrophilic centres in a chelate compound of this type, the probability of an intramolecular interaction involving a substituted N atom and the Co) atom of the oxirane ring obviously increases. It had been found previously [11] that the reactivity of the second epoxide group of DGEP is greater than that of the first group in reactions with aniline; this was explained by the presence of an intramolecular hydrogen bond of the type discussed. Analysis of Bridge-Stuart models qualitatively confirms the validity of this suggestion. Tra~6d

by G. F. M o D I ~

Polymerization of vinyl monomers

1888

1. V. A. TOPOL~ARAYEV, V. G. 08HMYAN, V. N. NISI~JH[ENKO, A. N. ZELENIgTffl~I, E. V. PRUT, A1. AI. B~T.U~I and N. S. YENIKOLOPYAN, Vysokomol. soyed. A21: 7, 1515, 1979 (Translat~i in Polymer Sci. U.S.S.R. 21: 7, 1663, 1979) 2. O. J. STEPHENSON, J. Chem. Soc., 5, 1571, 1954 3. V. A. TOPOLKARAYEV, V. G. OSHMYAN, A. V. DOBRODUMOV, A. M. Y~L~YASEV I i i , E. V. PRUT, A. N. ZELENETgKII, AI. AI. BERLIN and N. S. YEN~KOLOPYAN, Dokl. AN SSSR 226: 4, 880, 1976 4. V. A. TOPOLKARAYEV, S. N. RUDNEV, V. G. OSHMYAN, AI. AL BERLIN, E. F. OLEINIK and E. V. PRUT, Vysokomol. soyed. A22: 5, 1013, 1980 (Translated in Polymer Sci. U.S.S.R. 22: 5, 1117, 1980) 5. V. A. TOPOLKARAYEV, L. A. ZHORINA, L. V. VLADIbflROV, AI. AI. BERLIN, A.N. Zi~I.i~.NETSKU, E. V. PRUT and N, S. YENIKOLOPYAN, Vysokomol. soyed. A21: 7, 1655, 1979 (Translated in Polymer Sci. U.S.S.R. 21: 7, 1823, 1979) 6. S, ORE and O. G. TJUGMAN, Acta chem. Scand. 24: 2397, 1970 7. L I. PERRPEC.HlgO, Akusticheskiye metody issledovaniya polimerov (Acoustic Methods of Investigating Polymers). p. 110, Khimiya, Moscow, 1973 8. V. A. TOPOLKARAYEV, Diszert~tion for the Degree of Candidate of Physical and Mathematical Sciences, p. 91, MFTI, Moamow, 1977 9. L. A. ZHORINA, M. L KNUNYANTS, M~ A. STAKHOVSKAYA, A. N. ZELENI~SKII, V. V. IVANOV, E. V. PRUT, O. B, SA]kbMATINA, L. V. VLADIMHtOV, G. M. T R O ~ MOVA ~mi N. S, YENI]KOLOPYAN, In: Tez, dokl. I I Vses. Konf. 13o khlmii i flzikokhimfi oligomerev (Reports of the Proeeedings of I I n d All-Union Conference on Chemistry and Physical Chemistry of Oligomers) p. 85, OIKhF AN SSSR, Chornogolovka, 1979 10. N. S. VEDENYANINA, V. V. IVANOV, A. N. ZELENETSKII, L. A. PLOKHOTSKAYA, G. V. R A K O V A , A. T. PONOMARENKO, V. G. SHEVCHENKO and N. S. YENIKOLOPYAN, Izv. AN SSSR, Set. khim., 9, 1956, 1976 11. O. B. SALAMATINA, G. M. TARASOVA and V. V. IVANOV, Izv. AN SSSR, Ser. khim., 6, 1289, 1978

PolymerScienceU.S.S.R.Vol.24, No. 8, pp. 1888-1889,1982 Printed in Poland

0082-3950/82 $7.50~-.00 1988 Pergamon Prom Ltd.

POLYMERIZATION OF VINYL MONOMERS ON THE SURFACE OF CHALK ACTIVATED BY DICARBOXYL-CONTAIN1NG PEROXIDE* V. A. Porov, Yr. A. Zv~g~vA, A. N. G~mHn~, T. V. PAv,AYEVA and V. A. F o m ~

(Received 13 April 1981) The radical polymerization of methylmethacrylate and acrylonitrile in the presence of chalk containing chemisorbed peroxydisuccinie acid has been investigated. It has been shown that the chemical bond between the peroxide and the surface of the solid phase substantially affects both its initiating activity and also the elementary reactions in polymerization occurring at the interphase boundary, * Vysokomol. soyed. A24: 1~o. 8, 1654-1658, 1982.