No. 2 POLYMER COMMUNICATIONS 1985 THE MECHANISM OF THE COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PROPYLENE* HAO Shuke (f4#}) JIANG Jian (% 4) and YU Dingsheng (444) (Department of Applied Chemistry, Beijing Institute of Chemical Technology, Beijiag) ABSTRACT The copolymerization of BF,-complexed ethyl acrylate with propylene in the presence of AIBN at 25°C was investigated. It was found that the rate of the copolymerization was propor- tienal to the square root of the initiator concentration. ‘The chain transfer agent CCl, greatly af fects the inherent viscosity of the resulting copolymer. The smaller the dielectric constant of the solvent, the greater the rate of copolymerization is. The equal concentration of the two monomers give the maximum copolymerization rate. The H-NMR and “C-NMR analysis indicated, when [EA-BF,]/[EA-BF,]+[P]>0.5, the resulting copolymer was the acrylate-rich random copoly: mer. Through the kinetic experiments we suggest that copolymerization follows the mechanism of the random copolymerization of the ternary complex with binary complex. When [EA-BF,]/ [EA-BF,]+[P] < 0.5, the resulting copolymer is always strictly alternating, and the alternating copolymerization follows the mechanism of the ternary complex homopolymerization. Using the homolog of the propylene, I-pentene, we found that BF,-complexed ethyl acrylate can form a ternary complex with 1-pentene identified by UV spectroscopy. This is a strong evidence for the mechanism of ternary complex homopolymerization, INTRODUCTION The radical copolymerization of an electron-accepting monomer with an electron- donating monomer can produce an alternating copolymer in the presence of Lewis acid. There have been a lot of researches on the mechanism of the alternating copolymerization of an electron-accepting monomer with an electron-donating monomer, especially on the copoly- merization system of styrene with methyl methacrylate complexed with alkylaluminum chlo- ride. However, there were little or no research on the alternating copolymerization mechanism of propylene, which is in gas form under standard condition, with acrylate in the presence of Lewis acid. Three different kinds of mechanism to explain alternating regulation have been postulated for alternating copolymerization of an electron-accepting monomer and an electron-donating monomer in the presence of Lewis acid. One is the cross-propagat- ing mechanism based on the conventional radical copolymerization scheme derived from ‘Lewis-Mayo equation in which the alternating regulation is attributed to the selective cross propagation reactions enhanced by the complex formation of the accepter monomer with the Lewis acid'), The second is the monomer complex mechanism in which a ternary mo- lecular complex between two monomers and the Lewis acid is involved and acts as if it were a single monomer and js selectively polymerized to give an alternating copolymer!?}, The * Received January 15, 1985158 POLYMER COMMUNICATIONS 1985 third one is the radical complex mechanism in which the charge transfer interaction between the growing chain end, the attacking monomer and Lewis acid governs the alternating regula- tion and the Lewis acid plays an important role on site'?!,_ In our experiments, the copoly- merization of BF,~complexed ethyl acrylate with propylene can produce an alternating copoly- mer and a random copolymer at the appropriate conditions, According to the experimental data, we suggest that when [EA+BF,]/[EA+BF,]+[P]>0.5, the copolymerization may follow the mechanism of the random copolymerization of the ternary complex with binary complex; when the (EA-BF,]/[EA-BF,]-+[P]<0.5, the alternating copolymerization fol- lows the ternary complex mechanism. EXPERIMENTAL 1. Materials Solvents: Analytical reagents dichloromethane, chloroform, carbon tetrachloride and toluene were used with drying. Initiator: Azobisisobutyronitrile (AIBN) chemical pure grade was used without purifica- tion. Monomers: Ethyl acrylate, supplied by Dong Fang Chemical Plant, was purified by using normal method. Propylene of polymerization grade and chemical pure 1-pentene were used. 2. Polymerization The copolymerization was carried out in a 250ml glass pressure bottle, in which 20 ml of CH,Cl, solution of ethyl acrylate (60 mmoles), and 6.0% 10-3 g of AIBN were added under the protection of nitrogen. The mixture was cooled in an ice bath, and BF, was bub- bled through the solution until it was saturated (60 mmoles). Then, the mixture was cooled in a dry ice-ethanol bath and 20m! of CH,Cl, solution of propylene (60 mmoles) was added, The bottle was put into water bath (25°C) with agitation, the polymerization took place immediately. After 3 hours the bottle was cooled and 10ml of ethanol was added to prevent fuming. The viscous polymer solution was poured into a large beaker and steam was passed through it to remove the solvent. The precipitated polymer was washed with an ethanol-water mixture and dried in vacuum oven at 80—90°C overnight. The conver- sion reached about 95% and the copolymer obtained had an inherent viscosity of 2—3, and through the analysis by H-NMR, the copolymer contained 50 mole% of propylene. 3. Kinetic experiments The kinetic experiment was carricd out with a dilatometer in a water—bath at 25°C. (After the dilatometer reached the constant temperature the conversion was calculated by fol- lowing the dilatometer volume scale) dry copolymer (g)x AV, : . al yildlg)x AV 100% where AV, is the contracted volume at time t, and 4V,. is the total contracted volume at the end of the reaction. Conversion X% =No. 2 COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PP 159 A. Analytical Inherent viscosities were determined at 304-0.1°C as 0.19% (wt./V) solution in CHCl, and are given in unit of dl/g. Composition analysis was obtained on EM-360 3H-NMR. The polymer composition was calculated from the expression Lx mole % propylene = 72 where T is the total integration and X is the integration of the CH, hydrogens of the ethyl ester groups. IR spectra was determined on a SHIMADZU-420 infrared spectrophotometer. 13C_NMR Fourier-transform spectra were obtained on a Q-90 C-NMR system with proton random-noise decoupling. RESULTS AND DISCUSSION 1. The radical feature of the copolymerization and copolymer composition EA-BF,-propylene copolymerization was run in the CH,Cl, solution with AIBN as initiator at 25°C. It is the same as radical polymerization, the lower the concentration of the initiator, the higher the molecular weight of copolymer is, however, the amounts of initia- tor used do not affect the polymer composition (Fig. 1). Plot the rate of copolymerization against the square root of initiator concentration, a straight line (Fig. 2) was obtained. It indicated that the order of initiating reaction is 1/2; Re {AIBN}? This behavior agreed with the feature of radical copolymerization. wo a By e 4 0 24 6 8 10 ° = 6 8 (AIBNJ/(EA-BFs) +(P}x 10" CATBN]!? 10% Fig. 1 Plot of initiator ratio versus [7] and Fig. 2. The relation between Rp and [AIB composition of copolymer Copolymerization condition: T= Copolymerization condition: T=25°C; S—CFACh, [EA-BF,I+[P]=3M; 1=60min; [EA-BF,]+[P]=2.59 4 (Q) BFEA=1.03 110; EA-BF, mole fraction=0.44 (2) BE JEA=0.91 1=20mia. From the data of Fig. 3, it can be seen that at the same molar ratio of BF,/EA, the co-160 POLYMER COMMUNICATIONS 1985 polymerization can produce the equimolar alternating copolymer as long as the monomer feed satisfies the condition of [EA-BF,] /[EA+BF,] + [P]<0.5. If the molar fraction of ethyl acrylate in the monomer feed is greater than that of propylene, the copolymer obtained is the acrylate-rich. 33C-NMR analysis also proves the above results, and they are consistent with that of Logothetis''22), 10 EAMole fraction in polymer 02-01 06.. 08 10 EAMole fraction in monomer Fig. 3 Ethyl acrylate content in copolymer as a function of the monomer con- centration in P-EA copolymerization Copolymerization condition: 1=25°C; =CHiCh; conv. <20% 2. Random copolymerization mechanism ‘As shown above, the propylene with BF,-complexed ethyl acrylate copolymerization can produce the acrylate-rich random copolymer, when the monomer feed [EA+BF,]/[EA+ BF,]+[P] >0.5. Now, if we assume that the random copolymerization js run in the me- chanism of ternary complex with binary complex. Hence P ay Here Kis the formation equilibrium constant of ternary complex, B stands for binary com- plex and T for ternary complex. K EA-BF, +P = EA+BF,... B T In the copolymerization mixture due to ternary complex and binary complex coexist when the mole fraction of BF,-complexed ethyl acrylate is greater than that of propylene, the propagation reaction of copolymerization can be expressed by eqs. (2) to (5) Kopp P-EA++T—> | BF, Ts Q) Kop P-EA+ +B—> | BF, (3)No. 2, COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PP 161 Kon EA+-+T-—> Ts “@ | BF, Koy WEAF Bonn Be oy BF, under the steady state KeoglT] [B]=kolB-] [1] © Equation (7) is derived by assigning y to be the molar ratio of the P—EA sequences (derived from T) to the EA unit (derived from B) in the copolymer and x is the ratio of T to B in the reaction mixture, thus we get Kool T+] (T+ kyl Be} (T] Keo T] [B] + yplB*] [B] @ using eq. (6), we can reduce eq. (7) to ryxt fox y= tn ® here rp = kyy/kop and ty = kyp/Kur From eq. (1) (TI X= BPD o where [P], is the charged concentration of propylene, If K&1, [P]>{T] and x=[T]/[B]~KIP], (10) substituting x into eq. (8), we obtain eq. (11) ry K[P]5 +P) y=, + JK ay or [P]LO-Diy=reKTPliy ry (12) The molar fraction of ethyl acrylate in copolymer Fy, is expressed by definition as yl (3) If the above assumption is true, the straight line relation between the [P], (y—Ljy and [P]?/ should be present. The actual plot of the data in Fig. 3 is shown in Fig. 4, we can get rpK=9.281 I/M and r,/K = 0.63 M/l from the slope and the intercept respectively. The experimental data are quite in agreement with the theoretical assumption, so we suggest that the copoly- merization of propylene with BF,-complexed ethyl acrylate runs in the mechanism of ran- dom copolymerization of ternary complex with binary complex when the [EA-BF,] /[EA+ BF,]+[P] > 0.5.162 POLYMER COMMUNICATIONS 1985, 0 04} os ° sa a ay z& = -04 -o8 Fig. 4 Plot of [Ply (y-D/y versus [Pist/¥ 3. The mechanism of alternating copolymerization (1) The effect of chain transfer agent Mckenna and Logothetis‘? got a result that the CCI, did not affect the copolymeriza~ tion of BF,-complexed ethyl acrylate with ethylene). They postulated a complexed ra~ dical mechanism for the copolymerization of BF,-complexed etnyl acrylate with ethylene ‘or propylene as shown in eqs. (14) and (15) K ~ EAs P= ~[EA+ +P] (14) I | BF, BF, k “LEAs essP]-PEA > EA (is) | | I BF, BF, BF, according to this mechanism, the terminal radical is capped by an electron~donating mo- nomer so that this complexed radical does not react with a weak chain tranfer such as toluene and CC. Oo ae ea (eck) On Fig. 5 Dependence of the amount of CC1, on the inherent viscc of P-EA alternating copolymer Copolymerization condition: 7=25°C; S=CH;Ch; BF,/EA=0.83; t=Timin, [EA-BF,]+[P]=3M; [AIBN]=4.57 x 10M Jn our experiment, it was found that the CCl, can strongly affect the [7m] of the copolymer 4Fig. 5). After adding 1.7 M CCI, to the copolymerization mixture, the inherent viscosity ity and Cl contentNo. 2 COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PP 163 of copolymer has been fallen to 1/3 of the original value and the chlorine content of copoly- mer increases strongly. This phenomenon indicated that the chain transfer must have occurred in the copolymerization. The possible chain transfer reaction is as follows om PEAY + CC, —> P—EA—C1++CCh (16) i BF, BF, OLC+"¢ Pm FA > CLC—PEAL ay | BF, BF, “FA—COl (18) BF, If only the reaction (16) and (17) take place, the inherent viscosity of the copolymer decreases with the increment of CCI,.. Where equation (18) is a termination of residue of chain transfer agent, if this reaction occurs, the rate of copolymerization will decrease with the increment of CCl, The data shown in Fig. 5 indicated that the inherent viscosity and con- version of copolymerization were decreasing strongly with the increment of CCl, the Cl content of resulting copolymer was also increasing with the increment of CCl,. This results not only verify the existence of the chain transfer to CCl,, but also rule out the possibility of complexed-radical mechanism. (2) The effect of dielectric constants of solvents on the rate of copolymerization It is assumed that if the alternating copolymerization follows the mechanism of ternary complex, the ternary complex must exist in the copolymerization system K EA-BF,-+-P—=EA-BF,--P (19) B T = EA-BF, ~~ P = [EA-BFsI[P] (20) Because the charge transfer complex is generally more polar than the component mo- nomers, the equilibrium constant and, therefore, the rate of copolymerization should decrease with increment of the dielectric constant of solvents, The rate of copolymerization deter- mined in the different solvents are shown in Fig. 6. 40 1 s > 20) 3 ° 40, 80, 120 190 Hai) Fig. 6 The yield of copolymer at any reaction time Copolymerization condition: T=25°C; BF,/EA=0.89, {EA-BF,]+ [P]=3M; EA-BF, molar fraction =0.25 (1) Toluene e=2.379, R,=6.25x10- g/min: 2) CHCl, Re=4.0%10-? gimin; @) CH:Cle 2=9.08, R,=3.0X10-® gimin,164 POLYMER COMMUNICATIONS 1985 The rate of copolymerization is the greatest when in the toluene solution, followed by that is in chloroform solution and the lowest when in the dichloromethane solution. It shows that the rate of copolymerization decreases indeed with increasing dielectric constants of the solvents as the theoretical prediction. This result indicates that the ternary complex homopolymerization mechanism is consistent with the alternating copolymerization. (3) The effect of the monomer feed on the rate of copolymerization In the case of the alternating copolymerization via a ternary complex, the rate of copolymerization should be proportional to the concentration of the ternary complex, hence Rea] ely From the eq. (20), we get [1] = K [EA-BF,) [P] (22) If K <1, then (T] = K [EA-BF,], [Plo (23) Substituting eq. (23) into eq. (21) yields Rpak [EA-BF,], [P], (24) in all above equations, Kis an equilibrium constant of complex formation and [T] is the con- centration of ternary complex, [EA+BF,], and [PJ], are the charged concentration of monomers, respectively. 0 80 nO 160 t(min) Fig. 7 The yield of copolymer as the function of monomer feed under different reaction times in the CHCl, solution Copolymerization condition: T=25°C; [AIBN]=9.13x10-'M; BF,/EA=1.02; firs are (1) 0.25; (2).0.375; (3) 0.53 (4) 0.625; (5) 0.75. According to eq. (24), the rate of copolymerization should be proportional to the pro- duct of the original concentrations of two monomers, it follows that the rate of copolymeriza~ tion should be maximized when the molar ratio of two monomers is 1:1 in monomer feed'"?. This is observed by changing the monomer feed in the CH,Cl, solution (Fig. 7 and Fig. 8).No. 2, COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PP 165 a x = 0 02 OF 06 08 EAMole fraction in monomer Fig. 8 The relation between the Rp and monomer feed Copolymerization condition: the same as in Fig. 7 1 in the CHC}, solution 2 in the CHCl, solution As shown in the Fig. 7 and Fig. 8, the rate of copolymerization is maximized at the EA-BF, molar fraction of just 0.5 in monomer feed. This fact strongly supports that ternary complex mechanism. (4) Kinetic evidence If the alternating copolymerization follows the mechanism of ternary complex when the monomer feed [EA+BF,|/[EA+BF,]+-[P]<0.5, the elementary reactions of copolymerization are as follows initiation, AIBN->2R+ 25) Re ot oat. (26) propagation, Moat ee 7) termination, mM. ‘sp (28) where R- is the primary radical and Me is the polymer chain radical. The corresponding rate equations of initiation, propagation and termination are written as follows: R, = 2fks [AIBN] (29) Rp=ke[Me] [T] 30) R=KIM+P G1) where R,, Rp and R, are the rates of initiation, propagation and termination, respectively, ‘f stands for the initiator efficiency and kg is the rate constant of the initiator decomposition, kp is the propagation rate constant and k, is the termination rate constant. Under steady state, R166 POLYMER COMMUNICATIONS 1985" 0, 2fk{ATBN]=k,[M-? (2) IM-]}(2fka/k,)"* [ATBN}** (G3 Substituting eq. (33) into eq. (30) Ry=k(2fka/k,{AIBNP UT] Gay or Rp=kpK(2fka/k,)!"AIBN]!"[EA -BF,] [P] G5) let k=kpK(2fka/ k,)!* hence R 5=K{AIBN}[EA-BF,] [P] (36) We have proved that the copolymerization of propylene and BF,-complexed ethyl acrylate: is a kind of radical copolymerization and the rate of copolymerization is proportional to the square root of the initiator concentration. When the charged concentrations of two monomers. are equal, then the equation (36) becomes to Rp=K{AIBN]!? [M}? G7) so the reaction order of the monomer is 2. From the integration of eq. (37) we get; 1/M—1/M,=k[AIBN]"t (38) if we assume that x is the conversion at any reaction time t, so, M=M,(1—x) then 1/(1—x)=K[AIBN} 2M t-41 G9), where M, is the charged monomer concentration and ¢ is reaction time. Fig. 9 is the curve of the conversion against reaction time at the different monomer feeds. Plotting 1/(1—x) against r using the data of Fig. 9, we get good linear relationship (Fig. 10). ° ‘The copolymerization data satisfy the second order reaction relationship within 90 % conversion. This result aiso demonstrates that the ternary complex mechanism of the alternating copoly- merization is reasonable. If the alternating copolymerization would follow the cross-propagation mechanism, the following kinetic equation (40) is derived. Re=k'[ly? [M] (40) Here the reaction order of monomer is 1. However, we have proved in this alternating copolymerization, the reaction order of the monomer is 2. So the cross-propagation mecha- nism is ruled out through the kinetic experiment. In a word, we have come to the conclusion that the copolymerization follows the ternary complex mechanism at the monomer feed [EA+BF,]/[EA+BF,] +[P]<0.5. (5) Observation of ternary complex The strong evidence of the ternary complex mechanism will be that the ternary complex. is directly determined. Because propylene is in gas form at the normal temperature and normal pressure, we have determined the ternary complex by using 1-pentene instead of‘No, 2 COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PP 167 00) oy a Oo a0 80120160200 2403807 Amin) Fig. 9 Plot of conversion (x%) versus reaction time (1) Copolymerization condition: 7T=25°C; $=CH,Chs (1) fna=0.286; (2) fna=0.43 1’) 6 6 min) Fig. 10 Plot of 1/(1-x) versus Copolymerization condition: the same as in Fig. 9 Absorbance O00 S00 600700 com) Fig. 11 UV spectrum of different monomers T=25°C; S=CH.C, 1, I-pentene C=1.5M; 3. EA-BF,+Pe 2. EA-BF, C=1.5M; SM168 POLYMER COMMUNICATIONS 1985 propylene, a homologue of propylene, to complex with BF,-complexed ethyl acrylate. In the CH,Cl, solution, at first we determined 1-pentene and BF,-complexed ethyl acry- late at 25°C respectively. It was found that no absorbing bands were observed at 370 nm to 400 nm. However, when the solution of I-pentene and BF,-complexed ethyl acrylate were mixed together, the strong absorption band appeared at 380 nm (Fig. 11). This is an absorp- tion band of ternary complex composed of 1~pentene and BF,-complexed ethyl acrylate according to the position of absorption band. When the concentration of BF,-complexed ethyl acrylate equals to that of 1-pentene, the absorption band at 380 nm and 390 nm are maximized by changing the monomer con- This proved that it follows the ternary complex of BF,-complexed ethyl centration (Fig. 12). From these determinations we can deduce a conclusion that pro- acrylate and 1-pentene. pylene also can form a ternary complex with BF,~complexed ethyl acrylate. Absorbance ° 0.5 1.0 EA Mole fraction in monomer Fig. 12. Absorbance versus monomer feed S= CHCl; [FA-BF,]+(P)]=3M 1 390mm; 2 380nm CONCLUSION The copolymerization of BF,-complexed ethyl acrylate with propylene in the presence of AIBN at 25°C is a radical polymerization. When the monomer feed EA+BF,]/[EA +BF,] + [P] >0.5, we can get an acrylate-rich random copolymer of P-EA, the copolymerization follows the mechanism of random copolymerization of ternary complex with binary complex; when the monomer feed of [EA+BF,]/[EA+BF,]+[P] <0.5, the copolymerization of propylene with BF,-complexed ethyl acrylate runs through the mechanism of ternary complex and produce the alternating copolymer of P-EA.No. 2 COPOLYMERIZATION OF BF,-COMPLEXED ETHYL ACRYLATE WITH PP 169 REFERENCES: {1] Golubev V. P., Zubov ¥. P., Georgiev G. S., Stoyachenco I. L., and Kabanov V. A., J. Polym. Sci. Polym. Chem. Ed., 1973, 11, 2463. (21 Ikegami T. and Hirai H., J. Polym. Sci., 1970, A-I(8), 195, [3] Hirooka M., J. Polym. Sci., 1972, BIO, 171. {3a} Logothetis A. L. and Mckenna J. M., J. Polym. Sci., Polym. Chem. Ed., 1978, 16, 2797. (4] Mckenna J. M. and Logothetis A. L., Polym. Preprints, Amer. Chem. Soc., Div. Pol ne "olym. Chem., 1975, {5] Logothetis A. L. and Mckenna J. 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