818

A . V . DMITRENKOet al.

15. V. A. BERSHTEIN and V. M. YEGOROV, Vysokomol. soyed. ,4,27: 2440, 1985 (Translated in Polymer Sci. U.S.S.R. 27: 11, 2743, 1985) 16. G. V. GUSAKOVA, G. S. DENISOV and A. L. SMOLYANSKII, Zhurn. prikl, spektroskopii, 16: 320; 502, 1972 17. G. V. GUSAKOVA, G. S. DENISOV and A. L. SMOLYANSKH, Teoret. i eksperim, khimiya 9: 387, 1973 18. G. S. DENISOV, G. V. GUSAKOVA and A. L. SMOLYANSKY, J. Molec, Struct. 15: 377, 1973 19. G. S. DENISOV and V. M. SHRAIBER, Dokl. AN SSSR 215: 841, 1974 20. A. I. KUL'BIDA and V. M. SHRAIBER, Dokl. AN SSSR 250: 889, 1980 21. G. S. DENISOV, A. I. KUL'BIDA, Z. Z, RECHAPOV, A. L. SMOLYANSKII and V. M. SHRAIBER, Khim. fizika 1: 221, 1982 22. G. V. G U S A K O V A , G. S. DENISOV and A. L. SMOLYANSKII, Khim. fizika 4: 534, 1985 23. A. I. KUL'BIDA, Khim. fizika 1: 802, 1982 24. N. S. KARDASH, V. A. KRONGANZ, V. L. ZAITSEV and A. B. MOVSHOVICH, Vysokomol. soyed. AI6: 390, 1974 (Translated in Polymer Sci. U.S.S.R. 16: 2, 453, 1974)

PolymerScienceU.S.S.R. Vol. 30, No. 4, pp. 818-826, 1988 Printed in Poland

0032-3950/88 $10.00+.00 1989PergamonPros pie

COPOLYMERIZATION OF STYRENE A N D ACRYLONITRILE INITIATED BY THE REDOX REDUCTION OF HYDROPEROXIDE GRAFTED TO THE SURFACE OF DISPERSED FILLERS *
A. V. DMITRENKO, S. S. IVANCHEV, V. A. DEMIDOVA a n d S. L. MOSKOVSKII "Plastolpolimer" Scientific Production Association, Okhtinsk
(Received 31 October 1986)

The eopolymerization of styrene and acrylonitrile initiated by redox degradation of hydroperoxide grafted to the surfaces of dispersed fillers of various structure and containing silicon dioxide i$ studied. It is established that coating of the filler particles with a grafted layer of considerable thickness results in the appearance of a gel effect even during the reaction stage. The presence of a grafted surface and a grafted capillary system on the microfibrillar filler Sivol, in contrast to Aerosil, results in a significant decrease in effectiveness of polymerization initiation, and also a certain enrichment of the grafted copolymer by the acrylonitrile units. The effective copolymerization constants are determined. A mathematical method of calculating the initiation effectiveness and the effective degradation constant of the grafted hydroperoxide as determined from radical formation data is proposed.
OF the m e t h o d s o f l o c a l i z i n g p o l y m e r i z a t i o n in the s u r f a c e zone o f t h e d i s p e r s e p h a s e

u s e d in t h e p r o d u c t i o n o f c o m p o s i t e m a t e r i a l s by the p o l y m e r i z e d film m e t h o d , the u s e o f a filler with p e r o x i d e g r o u p s c h e m i c a l l y g r a f t e d to its surface is p r o m i s i n ~ [1, p. * V}tsokom01. so~'ed. A30" No. 4, 807-813, ~[98~,

Copolymerization of styrene and acrylonitrile

819

216]. This a p p r o a c h provides a means, even without the filler modification stage, o f predicting the grafting density, and the macromolecule characteristics, and the corresponding properties o f the compositions. T h e use o f initiator-fillers which generate exclusively grafted radicals, and which ensure initiation only by graft polymerization [1, 2] is o f special interest. In this w o r k the special features o f graft copolymerization o f styrene with acrylonitrile and the effect o n the filler structure on the process is studied, with due allowance for the previously discovered laws governing the graft polymerization o f styrene initiated by redox decomposition o f grafted hydroperoxide ( G H P ) on an Aerosil surface [2]. Silicon dioxide containing two types of fillers was used, i.e. finely dispersed grains A-175 Aerosil of specific surface S,p= 175 m 2 and the microfibrillar material, Sivol. of specific surface Ssp=470 m~/g (where S,p was measured by the BET method). Sivol consists of fibrils obtained from surfaces wound into tubes, forming hollow capillaries of diameter 10-50 A (Fig. 1). The Aerosil and Sivol with grafted GHP were obtained in a two-stage method by treatment of the filler trichloronorbornenylsilane (TCNS), and its subsequent ozonization

Gmf'tvd polymep

FIG. 1. Electron micrograph of an elementary Sivol fibre with a styrene-AN copolymer grafted to the surface (magnification 220 x 103) and diagram showing the distribution of grafted polymer along the fibre cross-section. [4]. According to lvanchev et aL [4] TCNS can be grafted from boiling solution in toluene (concentration 0.06 mole/l.) in the presence of 0.07 wt. % KOH, with subsequent vacuum distillation of the solvent and excess TCNS. After washing the filler with methanol it was ozonized in methanol. The extent of filler modification was determined by IR spectroscopy. During polymerization a filler containing (7-8) x 10-5 mole/g was used. The styrene and acrylonitrile (AN) were eopolymerized iO DMFA solution at a total monomgr concentration of .5.5 mole/g (GHP concentration 5"0 10 -~

820

'

A. V. DMrrRI~NKO et

aL

mole/L 50-70C), over 0.5 hr with variation of the A N content of the monomer mixture from 10 to 90 mole ~o. A reversible Fe (III) stearate-benzoin system was used as reducing agent. For comparison the reduction was conducted in the presence of modified fillers, and also under homogeneous conditions with initiation by benzoyl peroxide (5.8 10 -~ mole/l.). The grafted and ungrafted polymers were analyzed similarly [5]. The free radical yield was determined by the Bagdasaryan method [6, p. 34] with the aid of the free radical, 2,2,6,6-tetramethyl-4-hydroxypyridine-l-oxide. The morphology of the grafted polymer was studied under a type EA-100.L electron microscope.

In the given system the primary radicals are generated by the reaction of peroxide with the divalent Fe compound formed on the reduction of Fe(III) stearate by benzoin, in accordance with the scheme l;e (~t),~-}-L~lt, Fe (St,) ~+EH' "~ --ROOH + Fe01)--- ~ - - R O ' + O H - + Fe(]II), where St=CH,(CH2),0C(O) 0 - ; EH=C6HsCH (OH) C (0) Colt.~; EII'--zC~II~C(O)C(O)C6H~; ROOH: _~Si-----~ttO / OCH3

I_1 Ctt--OOII--.

The radicals, which are almost all fixed on the solid polymer surface, initiate the graft polymerization of monomers, i.e. ~ - - R O ' + n M I - I - mM 2 -~ ~ --RO[MI]a [M2}6 ~ -+- [M1]~,a IMply0 However, formation of a certain quantity of ungrafted product is also observed together with the grafted copolymer. This is because thermal polymerization makes a significant contribution in the copolymerization of styrene with AN over the given temperature range. Thus, it is established that in the presence of modified fillers the rate of copolymerization of these monomers at 70C is 2-3 ~o/hr. Introduction of the Fe(III)-benzoin system into the reaction mixture somewhat decreases the thermal polymerization rate, which is nevertheless about 1%/hr. The yield of grafted polymer formed on initiation with Aerosil surface (Fig. 2a) increases both with rise in temperature and with increase in reaction time. The grafted product formed has a high MM, the value of which is directly related to the reaction time, and attains a value of about l06. At a certain degree of conversion (7-8 ~ ) there is a rapid increase in rate, which is more noticeable at 70C (Fig. 2b). Acceleration of the reaction is accompanied by increase in the MM of the grafted copolymer (Fig. 2b). The above finding is associated with the gel effect, due to the presence of a highly developed phase interface in the system. It can be assumed that formation of a grafted polymer, uniformly distributed over the disperse phase surface promotes, as the grafted layer grows, physical hooking of and overlapping of the layers adjacent to specific parts of the filler, and the formation of a pseudo-structured system, with consequent

Copolymerization of Styrene and acrylonitrile

821

restriction of the termination reaction. During heterophase polymerization the reaotion mass thickens much more rapidly, and even at a conversion of o n l y 7-10 ~o has almost completely lost its mobility, The minimum content of grafted polymer required for

,,F o
0"8 o. -

v,/a,9/g

/
/. / ,
-

5 _ _

8"

u,*/./hr

~ M?,IO J

,
z

/j

-,oo

-2oo
2 4

Time, h,

"8

"

Fio. 2. Copolymer yield (a), and also ~'~ (1, 2) and the overall process rate fb) asa function of process time: 1-4, 1'2"-in the presence of Aerosil; 5,5', 6 - i n the presence of Sivol; 1,2,5-grafted, l',2",S-tmgrafted copolymer; 1,1,3-50 C, 2,2,4,5,5,6-70 C, DMFA; [MI + M2]=5.5 mole/l.; [filler]=65 g/I.; [GHP]=5.0x 10-3; [benzoin]= 1.65 x 10-3; [Fe stearate] = 3.8 x 10-4 mole/l.
, o , / o

establishing such a three-dimensional network and the appearance of the gel effect, as judged from Fig. 2, is about 3 x 10-3/m 2 in the case of Aerosil. It can be assumed that the gel effect will be significant in the case of Sivol, which has a more developed surface than-Aerosil. However, it is found that on initiation of styrene copolymerization with A N using a Sivol, surface (at the same surface concentration of G H P ) the gel effect does not occur. On the other hand, the reaction rate is low and gradually decreases during the reaction (Fig. 2a). One reason for this difference compared with a system filled with Aerosil could be the low rate of initiation.

822

A. V. DMITRENKO et el.

To explain this problem, the yield of free radicals on polymerization initiation o f G H P with Aerosil and Sivol surfaces was compared, using the polymerization o f styrene in chlorobenzene solution as an example. It is observed (Fig. 3) that the free
,

-ln (1-'~o3-=~

CROl.

[Ro:],1o~,,,,ole/t.
10 ~

[Ro'.l.lO%oZe/t.
1"6

- 10

//
,1 xZ
I

,-

0.8

/
8

Z
1

100

200 300 Time, rain

16 tO-J,sec

FIG. 3 FIG. 4 FIG. 3. Yield of primary radicals as a function of time at 70C, 1 -initiation with an Aerosil surface, [ROOH]o=0.5 x 10-2; 2-initiation with a Sivol surface, [ROOH]o=0.46 x 10-z. [FeSt3]=3.8 x x 10 -* mol/l.; [benzoin= 1.65 x 10-3 mole/1. ln~l [RO'I ~ FIG. 4. - \ - [--R--6~-]]as a fm~tion of time. GHP on Aerosil (1) and Sivol (2); IROOH]o 10z =0.5 (1) and 0.46 mote/1. (2). radical yield with the Sivol surface is significantly lower than with the Aerosil surface for the same G H P concentration. It is interesting to calculate the value of the initiation efficiency in the given systems. However, determination of this parameter by traditional methods is difficult in practice. It is thus proposed to c a l c u l a t e f b y mathematical treatment of the results given in Fig. 4. The differential equation describing the initiator degradation is
d [ROOH]/dt = - k [FeSt2] [ R O O H ]

(1")

and can be solved for the initial condition [ROOH]

=

[ROOH]0

at

t= 0

(2)

(where [ROOH] is the initial initiator concentration and k is the effective degradation rate constant). The actual yield of primary radicals is described by the equation
/

d [ R O ' ] / d t = f k [FeSt2] [ R O O H ]

for the initial conditiorts [RO']=0, t = 0 ,

~x)polymet'izatiOtiof styrene arid act'ylonitrile The solution of the giveB equation is

t

8~):~

[RO'] (t) =fk ~ [ROOH] (t) dr o

The function [RO'] (t) is determined by solution of (1) under the initial conditions
(2) [ROOH] = [ROOH]o exp -k', and on allowing for this
t

[RO']

=fk [ROOH]o ~ exp-k'dt

o

On integrating it is found that [RO']=f[ROOH]o(l-exp-kt). The last equation shows that the concentration of primary radicals tends to the limiting value [RO']=f[ROOH]o, at t-~o% from which it is possible to find f If this relation is given in the form ln(1

'~ [[RO'] -~j:k t,

on treating this (Fig 4) at a known value of f i t is possible to determine the value of k, When f=0.26, on initiation with an Aerosil surface and f=0.02 on initiation with a Sivol surface (these values give the best approximation to the experimental curve), the value k : l . 1 x 10 -4 sec -1 was obtained The reason for such a sharp fall in the effectiveness of initiation when the hydroperoxide groups are fixed on the Sivol surface to all appearances must be sought in the structural features of the given filler. It can be assumed that the fixation of GPH takes place over the whole surface of the micro fibre, including the internal surfaces of the capillaries. The closeness of the adjacent GHP, which is determined by the unfavourable radius of curvature of the capillaries can, in the authors' opinion, result in increased probability of recombination of the primary radicals and chain termination at these radicals. As a result of the decrease in efficiency of polymerization initiation the growth of the grafted layer at parts of the Sivol is hindered and does not exceed (as can be seen from Fig. 2) 0.25-0.3 g per 1 g of filler, which amounts to about 1.8 x 10- a g/m 2, which is almost half the value for the polymer coating of Aerosil particles in which a gel effect appears. Probably this amount is insufficient for coating of the fibre surfaces and for maintaining their degree of dispersion during the process and for the formation of pseudo-structured systems. It is interesting to show the effect of surface modification by hydroperoxide groups on the relative reactivity of monomers, with due allowance for previous studies on the copolymerization of styrene and AN on Aerosil and Sivol with natural = SiOH and methyl methacrylate functional coatings [5].

~4

A.V.

][)MITI~I~NKO et at.

TABLE 1. YIELD AND COMPOSITION OF A COPOLYMER AS A FUNCTION OF THE COPOLYMERIZATION COND|TIONS OF AN AZEOTROPIC MIXTURE OF STYRENE AND A N IN THE PRESENCE OF FILLER ( D M F A , [ s t y r e n e + A N ] = 5 . 5 mole/l., [Fe stearate]=4.2 10 -4 m o l e / l , [ b e n z o i n ] = l . 6 5 x 10 -a mole/l.) [ G H P , ur] x x 10 3, mole/l. 0 0 0'08 0'08 0'08 0.08 0'08 0'08 0'08 0 0 0.07 0.07 0"07 0'07 0 0 Conversion,. A N content of copolymer, mole~ grafted copolymer ungrafted copolymer 35'1 36.7 28.8 36.7 36'7 36"7 34.0
m

Test No.

Filler

Time, hr

%
27"6 27"2 4'5 10"5 20"7 8"9 8'8 11"6 38.0

2* 3 4 5 6 7 8 9 I0" 11" 12 13 14 15 16" 17"

Aerosil

70 70 50 50 50 70 70 70 70 70 70 70 70 70 70 70 70 0.5 4 0.5 2 4
8" '

29'8 36'7 36.7 34-3 34"3 36'7 35.9 45'91.3 0 45'9+_1.3 44'1l.3 45"4+_1.3 45~4 +_ 1 '3 0 0

34"0 42.6 +_ 1 '4 41'4+_1.3 45.2+_1.4 44.5 :[: 1 '4 45-7 +_ 1 "4 45"4~_ 1.4 37.8 ~ 1 '2 37.8 +_ 1"2

Sivol

0'5 4

5'2 45-0 3'8 5.2 6-8 8-7 5"0 27"6

* Benzoyl l~roxide concentration 5.8 x 10 -a mole/I. Note. In te~ts 1-9 the composition of the copolymers was determined from elemental analysis, and in tests 10-17 from pyrolytic chromatography data.

TABLE 2. COPOLYMERIZATION CONSTANTS OF A N (rl) AND STYRENE (r2) IN HOMOGENEOUS AND HETEROGENEOUS PROCESSES

( D M F A , 70C, [benzoyl peroxide] = 5.8 x 10- a mole/l., [GHP] = ~.0 x 10- amole/I.,[styrene + AN] = 5.5 mole/l.)
rt I r2 I rlF2 rl [ r2 [ FIr2

Filler --* Unmodified Sivol* Sivol with G H P (grafted copolymer)

as calculated from the F i n e m a n - R o s e equation 0.023+_0"010 0.026+_0.005 0"831 +_0"260 0.636+_0.120 0'019 I 0'017

as calculated from the K e l e n - T y d o s h equation 0+0'030 0+0"020 0.631 +_0-070 0-552 +_0.060 0 0

0.043 +_0.003

0.580 _+0.060

0'024

0.036+_0.011

0.554+_0.040 I 0'019

* Benzoyl peroxide filler.

A s c a n b e s e e n f r o m t h e d a t a i n T a b l e I, t h e p r e s e n c e o f A e r o s i l w i t h G H P reaction zone has hardly any effect on the changes in composition polymer compared with the unfilled copolymer, the formation of which was

in the

of the grafted coinitiated

Copolymerlzatlonof styrene and acrylonitrile by benzoyl peroxide. When Sivol and GHP are in the reaction zone, grafted and ungrafted copolymers are formed only slightly enriched with AN (Table 1, Fig. 5). The introduction of a mixture of unmodified Sivol with a silane surface coating into the
m I

mole%

60

2 0 -

"2 I00

I 2 0 N 6 I,mole %0

FIG. 5. Compositionof ungrafted(1, 2) and grafted copolymer(3) as a function of the composition of the monomericmixture(M t denotesacrylonitrile):1 - under homogeneousconditions; 2 - in the presenceof tmmodified$ivol; 3 - in the presenceof $ivol with grafted hydroperoxide groups. DMFA, [Mt + M2]=5"5, mole/l, 70C. reaction mixture gives approximately the same results. In our view, the reasons for the observed disturbance of copolymer composition must be a redistribution of local concentrations of AN in the monomer mixture when there is a developed capillary system in the filler. To confirm this assumption, copolymers formed in the bulk of a heterogeneous system and directly in Sivol capillaries were compared. The tests showed that on initiation by free benzoyl peroxide, the copolymer formed in the capillaries is about 3 ~o enriched in AN, in contrast to the copolymer formed on initiation by free benzoyl peroxide. This, it can be assumed that functionalization of the filler surface by GHP has little effect on the relative reactivity of the monomers, and a certain deviation in composition of the grafted copolymers is due to the structural features of the filler. Figure 1 indicates that polymerization takes place in certain internal regions of the fibre. As can be seen from the electron micrographs, a layer under the external surface of the fibre is formed together with the external grafted polymer layer. Table 2 shows the values of the effective copolymerization constants for AN (rl) and styrene (r2), as calculated with a computer using two iinearization methods, i.e. with the aid of the Fineman-Ross and Kelen-Tydosh equations. It can be seen from the given data that rt and r2 as calculated from the composition of the grafted copolymer and the copolymer formed in the presence of unmodified Sivol differ somewhat

82~

P. ~E. |L~MENE~et at.

f r o m the values o f r l a n d r2 for a n unfilled system: t h e r e is a c e r t a i n t e n d e n c y t o w a r d s a d e c r e a s e in the relative activity o f styrene a n d a n i n c r e a s e in the relative activity o f A N . T h e results thus indicate t h a t the s t r u c t u r a l features o f the filler have a significant effect on the kinetics o f c o p o l y m e r i z a t i o n o f styrene a n d A N , a n d also in the relative r e a c t i v i t y o f the c o m o n o m e r s , as a result o f r e d i s t r i b u t i o n o f their local c o n c e n t r a t i o n s in the surface zones o f the solid particles. Translated by N. STANDEN REFERENCES 1. S. S. IVANCHEV, Radikalnaya polimerizatsiya (Radical Polymerization). Leningrad, 1985 2. S. S. IVANTSCHEV and A. W. DMITRENKO, Plaste und Kautschuk B32: 31, 1985 3. V. P. PRYANISHNIKOV, V. F. GUSYNIN, A. F. SOROKIN and K. L CHEPIZHNY, Russian Pat. 579246, ByulL Izobret. No. 41, 80, 1977 4. S. S. IVANCHEV, N. S. YENIKOLOPYAN, B. V. POLOZOV, A. A. SYROV, O. N. PRIMACHENKO and Z. N. POLYAKOV, Russian Pat. 787411, Byull. Izobret. No. 46, 97, 1980; Current West German Pat. No. 2852778; U.S. Pat. No. 421914; French Pat. No. 7834134; and Japanese Pat. No. 1029500. 5. S. S. IVANCHEV, A. V. DMITRENKO, V. A. DEMIDOVA and N. Ye. SHADRINA, Vysokotool. soyed. A28: 2095, 1986 (Translated in Polymer Sci. U.S.S.R. 28: 10, 2327, 1986) 6. Kh. S. BAGDASARYAN, Teoriya radikalnoi polimerizatsii (Theory of Radical Polymerization), Moscow, 1966

PolymerScienceU.S.S.R.Vol. 30, No. 4, pp. 826-834, 1988 Printed in Poland

0032-3950/88 $10.00+.00 1989PergamonPressplc

FEATURES OF EMULSION POLYMERIZATION OF STYRENE USING SLIGHTLY SOLUBLE INITIATORS *

P. YE. [L'MENEV, G . I. LITVINENKO, V. A. KAMINSKII a n d 1. A. GRITSKOVA L. Ya. Karpov Physicochemical Research Institute M. V. Lomonosov Institute of Fine Chemical Technology, Moscow
(Received 2 November 1986)

The emulsion polymerization of styrene in the presence of slightly soluble initiators is studied. A relation is observed between the polymerization rate and the initiator solubility in the aqueous phase. A mathematical model of the process is constructed for determining the concentration of the latex particles formed in the system. It is shown that the main contribution to particle formation is provided by the radicals arising on decomposition of the initiator dissolved in water. * Vysokomol. soyed. A30: No. 4, 814-820, 1988.