Polymer Science U.S.S.R. Vol. 28, No: 10, pp.

2327-2335, 1986 Printed in Poland

0032*3950/86 $10.00+ .lO ~ 1987 Pergamon Journals Ltd.

ASPECTS OF THE COPOLYMERIZATION OF STYRENE WITH ACRYLONITRII,E IN SOLUTION IN THE PRESENCE OF DISPERSE FILLERS CONTAINING SILICA*
S. S. IVANCHEV, A. V. DMITRENKO, V. A. DEMIDOVA and N. YE. SHAORINA
"Plastpolimer" Scientific and Production Unit, Okhtinsk

(Received 18 February 1985)

Aspects of the copolymerization of styrene and aerylonitrile have been investigated in solution in the presence of Aerosil and of microfibrous Sivol, both unmodified and with the surface modified by the chemical grafting of (methacryloxymethyl) methyldiethoxysilane. An increase has been found in the rate of heterogeneous copolymerization, which occurs simultaneously with an increase in the molecular mass both of the copolymers grafted to the surface and also the ungrafted polymers; this is related to the gel-effect created by the filler in the reaction system. The modified Sivol surface has been found to have a selective effect on the composition of the styrene-acrylonitrile grafted polymer that is formed. It has been established that the relative reactivity of styrene in the graft copolymerization reaction is reduced as compared with that in the heterogeneous non-graft process and in the homogeneous process. The special features of polym:rization occurring in the presence of disperse fillers, which has been considered as a method of obtaining filled polymeric compositions, have been widely discussed in the literature in recent times. Features of polymerization in the presence of fillers modified by having (m:thacryloxym~thyl) methylsilane groups (MES), capable of polym~.rization, grafted to them hav~ b~en discussed previously [1, 2]. In view o f its simplicity and economy, there is also great interest in exploring the possibility o f localizing polymerization to the absorbed zone of filler particles using the natural functional groups of the filler without their surface modification. Since the monomer-surface interaction is determined both by the functional nature o f the surface and also by the structure of the monomer [3], it is of interest to investigate the selective effect o f the surface in the joint polymerization of monomers differing in their reactivity and polarity. The objective o f the present work has been to investigate features of the joint polymerization of styrene and acrylonitrile in the presence of unmodified fillers containing silica and also in the presence of such fillers modified hy the grafting of MES groups to the surface. It was, moreover, of interest to consider the effect of the specific surface area and the capillary structure of the filler on the occurrence of the process.

The application of MES groups on to the surface of Aerosil and Sivol [4l was carried out by the method given previously [2]. The presence of MES groups on the surface was confirmed by IR
* Vysokomol. soyed. A28: No. 10, 2095-2101, 1986. 2327

"2328

S.S. IVANCnEVet al.

spectroscopy (Fig. 1) from the reduction in the ~ntensity of the absorption band corresponding to free silane groups in the region of 3700 cm- ~ and also by the appearance of an increase in the intensity of the absorption band characteristic of carbonyl groups (1705 cm-~). The copolymerization of styrene with acrylonitrile was carried out in solution in D M F A in the presence of benzoyl peroxide (5-78x 10 -3 mole/L) as initiator: concentration of the monomer mixture, 5.5 mole/L; temperature, 70C; duration, 0.5-8 hr; acrylonitrile concentration in the monomer mixture varied from 10-90 mole 70. The reaction was carried out in the presence of MES-substituted fillers and also in the presence of unmodified fillers using the method given previously [2]. Copolymerization was also carried out under homogeneous conditions for comparison. The separation of the grafted from the ungrafted copolymer was carried out as in [2, 3]. The intrinsic viscosity of the copolymers was measured in solution in MEK. The molecular mass of copolymers with the azeotropic composition was calculated by use of the Mark-Houwink equation with the constants K=0.00025 and a=0-67 [5]. The compositions of the copolymers grafted to the surface and those of the ungrafted copolymers were determined by pyrolytic gas chromatography (PGC) in a current of helium at a temperature ,of 600 + 10C for 45 + 5 sec. The adsorption potential of the surface was assessed by the potentiometric method [6].

/#"~ /

III",l--

'7
1
E I

[f

38

34

30

IS

17 vxlO-~Zcm -t

Fio. 1. IR spectra of Sivol: 1 - i n the initial condition and 2, 3 - MES-substituted, the concentration of MES groups being 0"28 (2) and 0.98 (3) mmole/g. A.s is to be e x p e c t e d , the p o l y m e r i z a t i o n o f styrene a n d a c r y l o n i t r i l e in the presence o f u n m o d i f i e d fillers is n o t a c c o m p a n i e d by the f o r m a t i o n o f a c o p o l y m e r g r a f t e d to the filler surface: the p o l y m e r i c p r o d u c t is c o m p l e t e l y e x t r a c t e d by boiling M E K (Table 1). D u r i n g p o l y m e r i z a t i o n in the p r e s e n c e o f M E S - s u b s t i t u t e d fillers, c o p o l y m e r s b o t h u n g r a f t e d a n d also g r a f t e d to the surface a r e f o r m e d . I t m a y be seen f r o m Fig. 2 t h a t the g r a f t e d c o p o l y m e r is f o r m e d at a lower rate t h a n the u n g r a f t e d p o l y m e r , the f o r m a tion o f the g r a f t e d c o p o l y m e r slowing d o w n to a c o n s i d e r a b l e extent with time. This is c o n n e c t e d w i t h diffusional r e s t r i c t i o n s on the M E S g r o u p s because o f their b e i n g f i x e d o n the surface a n d also it is c o n n e c t e d with the e x h a u s t i o n o r p a r t i a l screening o f the M E S g r o u p s as the g r a f t e d p o l y m e r is formed. T h e use o f the m o r e d e v e l o p e d

Copolymorization of styrene with aerylonitrile in solution

2329

Sivol surface leads, as is to be expected, to a larger yield of the grafted copolymer and to a greater proportion of the grafted copolymer in the total yield of polymeric products than is the case when Aerosil is used with the same loading of the filler. This is caused by the higher concentration of MES groups on the Sivol particles. During the process, the rate of accumulation of the grafted copolymer and the efficiency of grafting decrease. When the conversion of the monomers reaches a value of approximately 50%, the efficiency of grating becomes approximately the same when either type of filler is used (Fig. 2, curves 5 and 6; Table 1). It is important to note that, in the presence of Sivol modified with MES, which has the more developed surface, the rate not only of grafted but also of ungrafted copolymerization is higher (Fig. 2). It may be seen from an analysis of the results of the copolymerization of styreneacrylonitrile mixtures having the azeot~opic composition (Table 1) and with various ratios between the monomers (Fig. 3) that, in the initial period of the reaction, the overall rate is practically the same in the presence of fillers, whether they are unmodified or modified: after 0.5 hr, the conversion of a filled and of an unfilled monomer mixture is approximately 5 ~o (experiments 1, 4, 9, 11, 12). Attention should, however, be given to the considerable increase in the copolymers' molecular mass (by a factor of 3-5) in the case of copolymers formed under heterogeneous conditions as compared with those obtained under homogeneous conditions (Table 1). It should be noted that we are referring to the molecular mass of the ungrafted copolymer since the grafted copolymer, separated from the filler by dissolving the latter in hydrofluoric acid, is insoluble in known solvents. Such a marked increase in the molecular mass of the polymers formed in the filled system whilst the overall rate of the process remains unchanged is evidence that the way in which the elementary reactions of propagation and especially termination occur is changed (the rate of initiation, because of the use of an oil-soluble initiator, namely benzoyl peroxide, should not be altered). The effects that have been revealed are connected with structural features of the polymerization system and with the possibility of the gel-effect appearing in early stages of polymerization because of the disperse filler. Modification of the Sivol surface by MES groups leads to the formation of ungrafted copolymers whose molecular mass in the initial period of the reaction is lower than that of copolymers obtained in the presence of unmodified Sivol, this effect becoming more marked as the concentration of surface MES groups is increased. In the present case it is clearly necessary to take account of the possibility that chains growing in the volume may transfer to the modified surface, which can lead either to their annihilation or to branching of the grafted copolymers. Chain transfer may be accomplished by capture of a mobile hydrogen atom from the methylene group of MES. Of course, the probability of this process increases as the concentration of MES groups on the surface is increased. Let us follow these relationships at higher conversions ( ~ 25 //ofor Aerosil or ,-~40 % for Sivol) when, to judge from Fig. 2, the surface MES groups have practically disappeared or are blocked by the grafted layer that has been formed. In the case of Aerosil, whether unmodified or modified, the overall rate of copolymerization hardly differs

2330

S . S . IVANCHEVe t al.

TABLE 1. COPOLYMERIZATION OF A $TYRENE-ACRYLONITRILE AZEOTROPIC MIXTURE IN THE PRESENCE OF A FILLER, UNMODIFIEDOR MODIFIED WITH MES Concentration o f acrylonitrile in monomer mixture, mole ~o grafted 0 0 0 39'6_+ 1"3 38.8_+ 1"3 40"1_+ 1.3 41.4_+ 1"3 0 0 50-4_+ 1"6 54"2 _+1"8 43'7_+ 1.4 40"4 _+1.3 ungraftod 37"8_+ 1"2 37"8 _+ 1"2 37"9 _ 1"2 38"8_ 1 "3 38"8_+1.3 40"1_+1.3 37"8_+1"2 40.3 _+ 1 "3 41"4_+ 1.3 40.3_+1-3 42.2 -+ 1"4 40.7-+ 1"3 34.9_+1.1

[MES]snrt,co Exp. No. Filler (65 l./g) mmole mole/kg m~ x [ 103

0"5 4 4 0"5 1 2 4 8 0"5 4 0"5 0'5 4 8

o~ d
O

E
e~

,
Q 0 0 X

8
~

Aerosil* ,, ,, ,, ,,
9~

0.47 0.47 0-47 0.47 0.47

2"0 2"0 2"0 2'0 2"0 -

Sivol t ,, ,, ,, ,, 0-28 0.98 0.98 0.98

0'6 2'6 2"6 2"6

5.0 27"8 27"2 5.4 5.5 13.8 25"6 45-5 5'4 45 '0 5"0 5"3 42"0 50"0

0.25 0-28 0.74 0.73 0.74 0-76 0"77 0"94 0.94 0"74 0.65 1.42

44 46 153 147 152 170 187 217 217 152 125 401

* Particle diameter. 15-35 rim. specific surface, s = 175 + 25 m2/g. t Microfibrous material, external diameter of fibres, 30-35 rim; diameter of central capiUary, 5-10 rim: S m . . , , , ~ = 4 7 0 m=/S (S.,~,. = 1000 ra21S).

q , g/g 3
o "

f
07

0.5

03
X

07
I I I I

q T/me, he

Fie. 2. Dependence of the yield, q, of: 1 and 2 - g r a f t e d ; 3 and 4 - u n g r a f t e d copolymers, together with the dependence o f the efficiency o f grafting J ( 5 and 6) on time in the presence o f the following: 1, 3 and 5 - A e r o s i l ; 2, 4 and 6 - S i v o l . The m o n o m e r mixture had the azeotropic composition,

Copolymerization of styrene with acrylonitrile in solution

2331

at all from that in a homogeneous system (experiments 2, 3 and 7). The products' molecular mass increases slightly as the conversion rises. In the ease of Sivol, the rate of the process and the molecular mass of the copolymers are substantially increased. Despite the fact that there is not a large difference between the values of the copolymerization rates on the modified and the unmodified Sivol (experiments 10 and 13), the molecular mass of the grafted copolymer obtained in the presence of the MESsubstituted Sivol is much the greater (by a factor of approximately 2).

L ~[ ltiSW[ % .~ A pt "
20 qo 60

..
80 N ~mole %

FIG. 3. Dependence of the overall rate of copolymerization of styrene with acrylonitrile on the concentration of acrylonitrile, M, in the monomer mixture in the presence of: 1-unmodified Sivol and 2-MES-substituted Sivol; 3 - i n the absence of a filler. These data may be taken as evidence that, in the presence of the two factors introduced by the filler and affecting the kinetics of the process, namely the chemical and the steric factor, the latter becomes dominant as the reaction proceeds. It follows from the results that the principal factor affecting the onset of the gel-effect in such a system is the existence of a highly developed surface separating the phases. In this respect it may be postulated that, during the chemical grafting of the polymer as distinct f r o m ungrafted copolymerization, there is a uniform distribution of the polymer on the surfaces of the individual particles and, as a result of this, the solid phase remains highly dispersed throughout the entire duration of the process and its effect on the kinetics of the process is retained to high degrees of conversion of the monomers. It was of interest to study the effect of the solid surface on the composition of the copolymer formed. The investigation was carried out with grafted and also ungrafted copolymers obtained with the composition of the comonomer mixture varied from 10 : 90 to 90 : 10, the degree o f conversion of the monomers being not greater than 5-10 ~ . The quantitative determination of the copolymer composition was carried out by internal normalization of the areas of the acrylonitrile and styrene peaks on the chromatograms of the volatile products of pyrolysis (Fig. 4), the relative coefficients of sensitivity of the components to be determined being taken into account [7]. It may be seen from Table 1 and Fig. 5 that the presence of an unmodified filler (either Aerosil or Sivol) in the reaction zone results in hardly any change in the copolymer composition as compared with the unfilled copolymer at all values o f the acrylonitrile-styrene ratio, that is, the adsorption interaction between the filler surface and the monomers has insufficient effect to substantially disrupt the copolymer composition.

2332

S.S. IVANCHBV et al.

COPOLYMERIZATION CONSTANTS FOR STYRENE AND ACRYLONITRILE I N THE HOMOGLtNEOUS AND HETEROGENEOUS PROCESS ! 0 ! 1"2

TABLE 2.

rl

Irlr2

r2

/'1

J rl f2

Fillex
grafted copolymer

ungrafted copolymer

,~-~

8
Unmodified Sivol MES-substituted Sivol* 10-90 10-90 10-90 10-40 40-90
0.023 0.013 0.831-4- 0.26 0.026 0.005 0.636+0.12 0.030 0-008 0.682 + 0.12

0"019 [ no grafted 0"020 0"020 0.085_+0.005 0_+0.004 0.087_+0.005

copolymer 0.380+0.11 0.032 0.119+0.03 0 0.471 _+0.18 0.041

* IMlSSlffi0.28mole/kg.

2 4 l

20

Time, re.in

tO

FIG. 4. Chromatogram obtained from the volatile products of the pyrolysis of a styrene aerylonitrile grafted copolymer. 1, 3-low-boiling point components formed in the degradation of the modified Sivol; 2-acrylonitrile; 4-styrene. The presence o f MES-substituted Sivol in the copolymerization zone leads to the formation of a grafted copolymer considerably enriched in acrylonitrile links (Fig. 5, Table 1); the enrichment gradually becomes less as the conversion increases. The deviation o f the composition o f the grafted copolymer from that o f the ungrafted copolymer was observed not only when Sivol with a high concentration o f MES groups on its surface was used (0.98 mole/kg; Table 1) but also when the concentration o f these groups was three times less (0.28 mole/kg, Fig. 5). It should be noted that, when ungrafted copolymerization occurred simultaneously with grafted copolymerization, the selective effect of the surface on the monomers was hardly observed at all.

Copolymerization of styrene with acrylonitrilein solution

2333,

The copolymerization constants for styrene, r,, and acrylonitrile, r2, were calculated from the Fineman-Ross equation using a computer method to linearize the curves. Table 2 indicates that rl and r2 during ungrafted copolymerization in the presence of both the modified and also the unmodified Sivol surfaces hardly differ from the corresponding values characterizing the unfilled system. During grafted copolymerization, however, r2 increases by a factor of almost three whereas rl decreases slightly. To judge from the increase in the value of rl r2, the degree of disorder in the distribution ofthe links increases in the grafted chains. The change in the monomers' copolymerization constants for grafted polymerization may be evidence of a change in the monomers" reactivity in the presence of MES groups, or it may be connected with an increase in the local concentration of acrylonitrile in a surface zone.
re,mole%
100-

50-

,g
I I

/el"

50

M ~rnole %

100

FIG. 5. Dependence of the composition of 1 - the grafted and 2 - t h e ungrafted copolymer on the composition of the monomer mixture in the presence of I and 2 - unmodified Sivol, and 3 - MESsubstituted Sivol; 4 - in the absence of Sivol.

In considering the results, it is, however, necessary to note two factors. Firstly, an assessment of the adsorption potential of the fillers showed that MES-substituted Sivol has a potential that is lower than that of the unmodified Sivol (Fig. 6), that is, in this case it is impossible to relate the selective effect of the filler to its adsorption activity. Secondly, the use of Aerosil with a concentration of MES groups of 0.47 mole/kg as the filler does not lead to any disruption of the composition of the grafted copolymer, that is, modification of the filler surface with MES groups is a necessary condition,

2334

S . S . IVANCHEV e t al.

but not a sufficient condition, for the surface to exert a selective action on the comonomers. F r o m all t h e indications, the reason for the observed change in the composition of the grafted copolymer is concealed in an overall factor which has contributions from the chemical effect o f the MES groups on the monomers' reactivity as well as contributions from structural features of Sivol. If we take account of the principal structural difference between Sivol and Aerosil, namely, the presence of a developed capillary system in the latter, we can assume that the enrichment of the grafted copolymer in acrylonitrile is a consequence o f the capillary effect, which leads to an increase in the local concentration o f acrylonitrile and to an enhanced probability o f interaction between the reactive pair of comonomers, namely acrylonitrile and MES: in the final analysis, the calculated copolymerization constants are effective constants and depend on the concentration of the comonomers. In order to confirm this, the values o f rx and r 2 were calculated for monomer mixtures with various ranges o f acrylonitrile concentration. It may be seen from the data in Table 2 that the values o f rt and r2 during grafted copolymerization depend on the degree o f saturation of the monomer mixture with acrylonitrile; in the case o f polymerization of a monomer mixture enriched in acrylonitrile the probability of forming a copolymer with a more regular structure~is increased (rlr2--~O).

/6 /
9

/2[- "
I

" . /
I

,~
I I

2
I.

Q.lOa q

FIG. 6. Dependence of the failer's absorption potential, A/t, on the degree of occupancy by iron (HI) hydroxo-aquo complexes: Q.lFe3+]=4xl0 -7 g-ion/1, room temperature: /-unmodified Sivol; 2-MES-substituted Sivol. The results obtained this give evidence that not only the nature of the functional covering o f the filler but also its structural characteristics play a major part in the creation o f the gel-effect in the filled polymerization system as well as in producing the change in the composition of the copolymer formed directly in the surface zone and in affecting the regularity o f the distribution o f monomeric links in the macromolecules.
Translated by G. F. MODLEN

REFERENCES
1. S. S. IVANCHEV and A. V. DMITRENKO, Uspekhi khimii 51: 7, ] ]78, 1982 2. S. S. IVANCHEV, A. V. D M 1 T R E ~ O , B. V. POLOZOV, V. A. DEMH)OVA, A. K. DABAGOVA and N. V. SERGIYENKO, Plast. massy, 10, 20, 1982

Polyamides with benzimMazole links included symmetrically in chain

2335

3. S. S. IVANCHEV, A. V. DMITRENKO, V. A. DEMIDOVA and A. K. DABAGOVA,Vysokoreel. soyed. A27: 5, 1086, 1985 (Translated in Polymer Sci. U.S.S.R. 27: 5, 1217, 1985) 4. V. P. PRYANISHNIKOV, N. F. GUSYNIN, N. F. SOROKIN and K. I. CHEPIZHNYI, U.S.S.R. Pat. 579246. Byull izobr., No. 41, 80, 1977 5. V. P. BUDTOV, L. F. DOKUKINA, E. F. DAVYDOVA, T. N. PAVLOVA, G. P. FRADKINA and N. G. PODOSENOVA, Manuscript deposited at the All-Union Institute of Scientific and Technical Information (VII'4ITI) Moscow, Dep. 14o. 1242-77 6. Opredeleniye aktivnosti tverdykh veshchestv potentiometricheskim metodom. Metodicheskoye ukazaniye k laboratornym rabotam (Determination of the Activity of Solids by the Potentiometric Method. Instructions Regarding the Procedures for Laboratory Work), Lensovet Technical institute, Leningrad, 1980 7. N. CRASSIE, Developm. Polymer Degradation, 214 pp, Appl. Sci. Publ., 1979

PolymerScience U.S.S.R. Vol. 28, No. I0, pp. 2335-2342, 1986

Printed in Poland

0032-3950186 $10.00 + .00 1987 Pergamon Journals Ltd.

HYDRODYNAMIC AND OPTICAL PROPERTIES OF POLYAMIDES WITH BENZIMIDAZOLE LINKS INCLUDED SYMMETRICAIJ,Y IN THE CHAIN*
P. N. LAVRENKO,L N. SttTENNIKOVA,T. I. GARMONOVA, O. I. MIKRYUKOVA,M. M. GEL'MONTand L. S. EFROS Institute for High-Molecular Compounds, U.S.S.R. Academy of Science,

(Received 18 February 1985)

Forward diffusion, intrinsic viscosity and flow birefringence in acetic acid solutions have been investigated for polyamide benzimidazoles differing in the way in which the benzimidazole rings are incorporated in the molecular chain. It is shown that an increase in the proportion of benzimidazole rings orientated one to another in the "head-to-head" position from 2/3 to 1 does not give rise to any appreciable change in the equilibrium rigidity of the polyamide-benzimidazole molecules in solution or to the optical anisotropy of unit chain length.

Trm methods o f molecular hydrodynamics and optics in solution have been used [1, 2] to investigate the properties o f polyamide-benzimidazole (PABI) and it has been showm that the introduction of the benzimidazole ring into the poly-p-phenyleneterephthalamide chain leads to a reduction in the equilibrium rigidity o f the macromolecule by a factor o f approximately 1.5. The chemical structure of the PABI chain consists o f a r a n d o m sequence o f three types of links [3]. * Vysokomol. soyed. A28: No. 10, 2102-2107, 1986.