Journal of Polymer Research 11: 203–209, 2004. © 2004 Kluwer Academic Publishers. Printed in the Netherlands.


Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate: Synthesis, Characterization, and Monomer Reactivity at High Conversions
Mohammad Taghi Taghizadeh & Maasumeh Foroutan∗
Department of Physical Chemistry, Faculty of Chemistry, Tabriz University, Tabriz, Iran (∗ Author fot correspondence; Fax: +98-411-3340191; E-mail:
Received 18 October 2003; accepted in revised form 2 February 2004

Key words: copolymerization, FTIR, NMR, N-vinylpyrrolidone, reactivity ratio, vinyl acetate, water-soluble polymers

Abstract Homogeneous copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) which form clear aqueous solutions were prepared by free radical polymerization in a solution of isopropanol alcohol, using 2,2-azobisisobutyronitrile as an initiator. They were characterized by FTIR, 1 H-NMR, and element analysis studies. The reactivity ratios of the monomer were computed by the Extended Kelen–Tüdós method at high conversions, using data from both 1 H-NMR and elemental analysis studies. The reactivity ratios of VP and VA in a homogenous copolymer were observed to be very different from that of a heterogeneous copolymer. Additional information was obtained by finding out the sequence length distribution for copolymers.

Introduction Copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) monomers are of significant utility in the pharmaceutical and cosmetic industries. For these uses, however, it is necessary that the copolymer is present as a clear aqueous solution. This property is characteristic of a copolymer having a substantially homogeneous structure. Homogeneity in copolymeric structure, i.e., the copolymer having a uniform distribution of VP and VA monomer units in its macromolecular chain structure, is highly desirable from the standpoint of water solubility. Depending on the method of synthesis, the hydrophobes (VA monomers) can be distributed anywhere in the copolymer, e.g., at each end of the backbone or within the chain in a random or blocky fashion. The synthesis of a homogeneous VP/VA copolymer is very difficult, because the VA monomer is less active than the VP monomer and will react later leading to formation of VA blocks during the copolymerization. Therefore, the presence of VA blocks in a heterogeneous copolymer will reduce its water solubility. The resultant copolymer thus will appear cloudy in water solution. In recent years, there has been an increasing interest in the synthesis and properties of VP/VA copolymers. Mathakiya et al. [1] have reported the synthesis of VP/VA copolymers that are soluble in non-aqueous solution. However, many published works describe the process of making homogeneous copolymers VP and VA that form a clear aqueous solution [2–9]. It is demonstrated that distribution of hydrophobic units along the chain affects the solution properties of the copolymer containing a hydrophobic monomer [10]. Also, from the theoretical aspect, the influ-

ence of distribution of monomer units along the chain on the phase behavior of statistical copolymers has been studied by Foroutan and Jafarizadeh [11, 12]. In this paper, VP/VA copolymers with different monomer ratios and different homogeneity in their backbone were prepared through the free radical copolymerization in the alcohol solution followed by solvent exchange to obtain the aqueous solution and freeze drying to obtain the final product in powder form. The process involves precharging VP and VA monomers in a predetermined ratio and then feeding VP and VA at a predetermined rate, the ratio of the components in the initial change and the feeding rates for the monomers being selected in accordance with the reactivity ratios of the monomers towards copolymerization as opposed to homopolymerization. Zhong et al. [9] described the above process of making homogenous VP/VA copolymers. They applied this method in the synthesis of the VP/VA copolymer, using Vazo 67 (2,2-Azobis-2-methylbutane nitrile) and Lup101(2,5-dimethyl-2,5-di(t-butylperoxy) hexan) as initiators. In this work, homogeneous VP/VA copolymers that form clear aqueous solutions are synthesized, using 2,2-azobisisobutyronitrile as an initiator for the first time, and their characterization and monomer reactivity are calculated by the EKT method. A comparative study concerning the homogeneous and heterogeneous copolymers will provide a clearer insight into the influence of the method for the synthesis of a copolymer and how it affects the homogeneity and reactivity ratios.

100 parts of the copolymer product and 600 parts of distilled water then were admixed at 1 atmosphere pressure. during the reaction.10 4. based on their consumption ratios. Merck). Distillation was continued until 300 parts of distillate was collected. After the addition of feed 1 had terminated.0358 IPA (cc) 9. Synthesis of a Copolymer 1-liter Buchi reactor was purged with nitrogen and the initial charge was pumped into the reactor. feed 3 was started immediately. Therefore each monomer feeding rate can be adjusted independently to keep the monomer conversion ratio constant. The mole fractions of the monomers in the copolymer were determined by elemental analysis. 2. Copolymerization First we describe Zhong’s copolymerization method [9] for the synthesis of a homogenous VP/VA copolymer.227. In this section.17 – – – – 0. was frozen and dried to provide the copolymer product in powder form. GC samples of the polymerization mixture were taken to determine the amounts of residual monomers present in the mixture. After feed 4 had been completed. The well-organized distribution of VP and VA units in the macromolecule chain maximized the copolymer’s aqueous solution solubility. although there is some difference between these values and the ones we will obtain later. we can obtain the following equation: (F1 − F2 ) + [(F2 − F1 )2 + 4F1 F2 r1 r2 ]1/2 f1 = . Then the reactor was cooled down and the intermediate product was discharged. The processes of copolymer number 4 as an example are summarized below: Initial feed Feed 1 Feed 2 Feed 3 Feed 4 Time (hour) – VP (cc) 13. Gradual addition of monomers and the initiator and concurrent raise of temperature of the reaction mixture were the important factors for the preparation of these substantially homogeneous VP/VA copolymers.2325 – – 1. As mentioned below. and the solvent feeding rate can be adjusted independently. f2 2F2 r1 (2) where F1 and F2 are the mole fractions of monomer 1 and monomer 2 in the copolymer. It should be noted that r1 and r2 are assumed to be equal to 1.6 AIBN (gr) 0. the temperature was held at 95 ◦ C for another 3 hours. we can decide the initial monomer composition (f1 and f2 ) to make up the initial copolymer having the instantaneous composition of F1 and F2 . in the reactor. After the addition of feeds 2 and 3 had been completed. 400 MHz 1 H-NMR spectrometer. Merck) was used as received. The batch then was maintained at 95 ◦ C for another 3 hours and feed 4 was added. the copolymerization of VP with VA in the IPA solution is studied for various mole fractions. Merck) and vinyl acetate (VA. Then feeds 1 and 2 were introduced simultaneously. Since the amounts of VP and VA added were known.2 – 14 5. the amounts and ratio of VP and VA react to the copolymer then could be calculated by differences. The mixture was held until the vapor temperature reached 100 ◦ C.01 24.33 7. Starting from the Flory copolymerization equation [13] F1 = 2 r1 f1 + f1 f2 2 r1 f1 + 2f1 f2 + r2 f22 (1) and the equivalent equation for F2 . Adjustment of the feeding rates of monomers was not enough for controlling f1 and f2 . Isopropanol alcohol (IPA.0 1. Therefore. N-vinylpyrrolidone (VP. r1 and r2 are the reactivity ratios for monomer 1 and monomer 2. The NMR of the copolymer solution in CDCl3 was recorded by a JEOL GSX. to maintain the instantaneous monomer composition to be constant at f1 and f2 . By using Equation (2) and that f1 + f2 = 1. the instantaneous copolymer composition can be maintained constant at F1 and F2 and equal to the cumulative copolymer composition. Therefore.89 and 0. The reactants were Results and Discussion By the general synthesis methods of VP/VA copolymers.5 – 11. Measurements FTIR spectra of the copolymers were recorded with FTIR Nicolet 520 on KBr pellets by a 4000–400 cm−1 range spectrometer. we synthesize the VP/VA copolymer by this method. Then the temperature was raised to 95 ◦ C to start a post-treatment stage.2 3. monomers should be supplemented continuously. each monomer and solvent should be added into the reactor separately. which contained about solids. i.. The aqueous solution after solvent exchange. Aldrich) was recrystallized from methanol. leading to the formation of VA blocks in the copolymer. The copolymer architecture is determined by the reactivity ratios and feed composition.204 Experimental Mohammad Taghi Taghizadeh and Maasumeh Foroutan stirred at 150 rpm and heated to 85 ◦ C. As the reaction progresses. the initial monomer concentration is established based on the monomer reactivity ratios (r1 and r2 ) and F1 and F2 . respectively.03 VA (cc) 4. respectively. the batch was held at 85 ◦ C for 2 hours.0 1.2-azobisisobutyronitrile (AIBN.5 20.e. VA will react later.8 Materials The monomers. the amounts of VP and VA unreacted. VP will react faster and go into the copolymer chains first as VP units. f1 and f2 are the mole fractions of unreacted monomer 1 and monomer 2. after derivation. were vacuum-distilled. according to the monomer feeding rates. The .

Using the Figure 2. (3) 0.Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate 205 Figure 1. the carboxyl group band of VA was observed at 1734 cm−1 [16]. the concentration of VA and VP in the copolymers can be obtained. It is evident that with an increase in VA contents. This characteristic peak is the peak of stretching vibration absorption of carboxyl groups of VA in the copolymers.233.715. The calculation procedure has been reported in detail elsewhere [14. we can determine the concentration of VA and VP in the copolymers. Pure Poly N-vinylpyrrolidone (PVP) has a characteristic. By calculating the absorbance of this peak and the peak of carboxyl groups of VP at 1680 cm−1 . Absorbance peaks of carboxyl groups of VP and VA in the copolymers are shown in Figure 2. VP: peak 2). . Transmittance peaks of carboxyl groups of VP and VA in the copolymers (VA: peak 1. peak 1 rises correspondingly. FTIR spectra of VP/VA copolymers with different compositions (mol% of VA-unit): (1) 0. a characteristic peak appears around 1742 cm−1 . in contrast to the spectrum of PVP. On the other hand. Copolymerization was carried out under a high conversion condition in order to determine monomer reactivity ratios by elemental analysis and H-NMR data.485. copolymers were soluble in the aqueous solution. Copolymer Characterization The composition of copolymers for a wide range of monomer feed can be determined by Fourier transform infrared spectroscopy (FTIR) through recorded analytical absorption bands for comonomers. infrared band at 1682 cm−1 that is attributed to a mixed mode containing major contributions from the carbonyl and N–C stretching vibrations. a relatively broad.287. 15]. absorbance of carboxyl groups of VA and VP of all copolymers. Figure 1 shows the FTIR spectral band of VP/VA copolymers. Figure 1 demonstrates that. (4) 0. (2) 0.

17–2. The mole fractions of VP and VA in the copolymers of various compositions. are not visible because of picture compression). and 50.485. and 1.20. The weight conversion (%W) of the synthesized copolymers (1. Figure 3 shows the signals appropriate to the H-NMR spectra of the copolymers corresponding to protons of VP and VA in the copolymers. 49. in the H-NMR spectrum of copolymer number 1. in CDCl3 (more details of some peaks. Reactivity Ratio and Sequence Distribution of Copolymers The extended Kelen–Tüdós (EKT) [17] method considers the drift of comonomer and copolymer composition with conversion. it is possible to resonate a certain proton at different δ. protons (h). ζ = H /(α + H ). are listed in Table 1.89 ppm.233. 1 H-NMR spectra of VP/VA copolymers with different compositions (mol% of VA-unit): (1) 0. especially the smaller ones in the range of 4–5 ppm. Hmax and . η.43–1. (f). The results are in very good agreement with each other. X = fVP /fVA . respectively. and (g) resonate at δ = 3. I (−CH of VA) + I (−CH of VP) (3) where I (−CH of VP) and I (−CH of VA) represent the peak intensities of the −CH protons of VP and VA.01. The Finemann–Ross copolymer composition equation is: G = rVP H − rVA .98. H = X2 /Y . (3) 0. using the following relation: F1 = I (−CH of VP) .62–3. 2. 60. The intercept at ζ = 0 and ζ = 1 of the plot η versus ζ gives −rVA /α and rVP .20.04.01 ppm. and 4) was obtained 40. Repeat unit in the VP/VA copolymers. The H-NMR spectrum of this copolymer shows that the three peaks of the acetoxy proton signals resonate at 2. 2. respectively.52 ppm. 3. (4) where G = X(Y − 1)/Y .206 Mohammad Taghi Taghizadeh and Maasumeh Foroutan Figure 3. Figure 4.70. respectively.37. The mole fraction of VP (F1 ) in the copolymer was determined by H-NMR.287. ζ . As Figure 3 shows. Therefore it is suitable for the manipulation of our highly conventional data. (4) 0. and α: η= rVP + rVA rVA . methine backbone protons (b) resonate at δ = 4. (2) 0. respectively. Y = FVP /FVA . ζ− α α (5) where η = G/(α + H ). Also. Kelen and Tüdós apply these parameters in the linearized copolymerization. α = (Hmax Hmin )1/2 . Although the spectra of all the copolymers are similar.715. whereas methine backbone protons (e) appear as a broad peak at δ = 3. calculated by using 1 H-NMR and elemental analysis data. The constituent monomeric units of VP/VA copolymers are given in Figure 4. These shifts can be attributed to the different alternation of VP and VA monomers in each copolymer.

Y . F1 and F2 are the mole fractions of VP and VA in the copolymer. EKT method for determining monomer reactivity ratios in the copolymerization of VP and VA by using NMR spectroscopy data.420 0.233 N (%) 8.285 0. and µ is the ratio of the molecular weight of VA to that of VP. G = (Y − 1)/Z. Table 2. Hmin are the highest and the lowest values of H . Composition of VP(1) and VA(2) in the feed and copolymers Copolymer number Monomer feed (mol %) Copolymer composition (mol %) By NMR analysis f1 1 2 3 4 0.044 0. ζVP .640 3.250 0.806 0.360 4. The EKT plots for copolymer samples are given in Figures 5 and 6. The partial molar conversion of VP is: ζVP = ζVA Then.102 0.920 13. .650 0.194 0. where η = G/(α + H ).720 0. F1 and F2 are the mole fractions of VP and VA Figure 6.576 0.560 6.040 2.092 0. The effect of conversion is considered in the extended Kelen–Tüdós equation. Z= Y .423 0.169 9.28 0. ζVA .480 3. (11) 1 + [(2F1 − 1)2 + 4r1 r2 F1 F2 ]1/2 where r1 and r2 are the reactivity ratios of VP and VA.750 0. 2–2. The statistical distributions of the monomer sequence 1–1. and 1–2 are calculated using the following relations: S1–1 = F1 − S2–2 S1–2 2F1 F2 .793 0.287 1.Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate Table 1.144 0.110 0. EKT parameters are calculated from the above equations using data in Table 1 and are summarized in Tables 2 and 3. Z. the parameters X. (10) 1 + [(2F1 − 1)2 + 4r1 r2 F1 F2 ]1/2 4F1 F2 = . H = Y/Z 2 .080 3. ζ = H /(α + H ). H .088 207 By nitrogen analysis F1 0.890 0.582 5. X (7) log(1 − ζVP ) .430 0.287 0.189 0. ζ and η have been mentioned in the text through Equations (6) to (8).767 f2 0. µ+Y (6) where W is the weight conversion of polymerization.390 6.713 0.361 2.182 0.061 2.207 0. The partial molar conversion of VA is defined as: ζVA = W (µ + X) .136.91 F1 0.912 F2 0. EKT method for determining monomer reactivity ratios in the copolymerization of VP and VA by using elemental analysis data.065 0.220 0.610 0.185 0.940 Hmax Hmin = 0. EKT parameters for VP and VA using elemental analysis data Copolymer number 1 2 3 4 α= √ X Y ζVA ζVP Z G H ζ η 0.485 0.496 1. log(1 − ζVA ) (8) Figure 5. G.02 10.62 11.908 0.68 11. (9) 1 + [(2F1 − 1)2 + 4r1 r2 F1 F2 ]1/2 2F1 F2 = F2 − .424 0.715 0.577 0.399 1. Table 4 shows the reactivity ratios rVA and rVP obtained by the EKT method.340 5. respectively.750 0.240 0.070 f1 and f2 are the mole fractions of VP and VA in the feed.730 0.930 F2 0.515 0.

r1 = 0. in the copolymer. (N1 )j = (p11 )(j −1) p12 .220 0.357 0.285 0.743 5.320 1.178 0.485 0.159. using the NMR spectroscopy data in Table 4.822 0. Similarly (N2 )j .928 0. (14) r1 f1 + f2 where (N1 )j is the sequence length of monomer 1.930 F2 0.935 0. .168 0.750 0.044 0. Homogenous and Heterogeneous Copolymers Mathakiya et al.116 0. ζ and η have been mentioned in the text through Equations (6) to (8).423 0.828 0.916 0.220 0. EKT parameters for VP and VA using NMR data Copolymer number 1 2 3 4 α= √ X Y ζVA ζVP Mohammad Taghi Taghizadeh and Maasumeh Foroutan Z G H ζ η 0.202 0.480 3. a From elemental analysis data. The distribution of the sequence length is determined by using the r1 and r2 information along with the following equations.233 0.399 1. p22 .092 4.968 0.217 0. Sequence length distribution for VP and VA units in the copolymerization of a VP/VA homogeneous copolymer (number 1): N-vinylpyrrolidone (white).493 1. S2–2 . Monomer reactivity in the copolymerization of VP and VA By elemental analysis VP(r1 ) VA(r2 ) r1 r2 5. The sequence length distribution is a statistical representation of the probability of monomer 2 to be attached to monomer 2.360 Table 5. 2–2 and 1–2 sequences are shown by S1–1 .713 0.422 0.005 Alternationb (mole fraction) S1–2 0.767 0. and for r1 = 4.025 0. Z. Table 6.830 8.032 0.253 0. They have observed a different reactivity than that in our work.072 0.366 0.360 3. The values of r1 and r2 are obtained by the EKT method. The transition probabilities are given in Table 6.719 0. In order to understand the relationship between the VP/VA copolymer structure and its solubility. we have: r1 .357 and r2 = 0.394 2.037 0.314 0. Y .577 0.974 By NMR spectroscopy 4. H .718 0. and S1–2 .208 Table 3.730 0.824 0. b Statistically calculated using reactivity ratios.285/0.194 0. and p21 can be described.908 0. The mole fractions of the 1–1.975 0. the mole fraction of 1–1 and 2–2 sequences decreases as the mole fraction of VA decreases.634 0.142. which are soluble in non-aqueous solutions.715 VP/VA.065 f1 and f2 are the mole fractions of VP and VA monomers in the feed.170 0.065 0. As Table 5 shows.622 0. transition probabilityp11 is the probability of monomer 1 to be attached to monomer 1. it is important to determine the sequence distribution of the copolymer. These structural data are given in Table 5. under solution conditions. G.182 0.490 0.960 3.130 0. Transition probability data for the copolymers of VP(1) with VA(2) Copolymer number 1 2 3 4 f1 f2 p22 p21 p11 p12 Table 4.312 0. This figure shows the probability of having the VP and VA segments of the given monomer unit length carried to a unit length of 14 VP and VA segments. the parameters X. ζVA .083 0.092 0.084 0.100 10.070 Blockinessb (mole fraction) S1–1 0.199 0. [1] have reported the synthesis of heterogeneous VP/VA copolymers in methanol. and p12 is the probability of monomer 1 to be attached to monomer 2.574 5.182 and r2 = 0.331 0. vinyl acetate (black).649 0.178 0.008 Hmax Hmin = 0.36 0.515 0.083. respectively.287 1.715 0. Structural data for the copolymers of VP(1) with VA(2) Compositiona (mole fraction) Copolymer number 1 2 3 4 F1 0.560 5. Figure 7 shows the number-average sequence length distribution for both VP and VA.172 0.865 S2–2 0. obtained from the elemental analysis data. (12) Figure 7.573 0.793 2.806 0. Assuming that only the ultimate monomeric unit affects the rate constants of copolymerization (ultimate effect or firstorder Markov chain) [18]. initial mole ratios of 0. (13) p11 = r1 + (f2 /f1 ) f2 p12 = .287 0. ζVP .061 2.783 0.008 0.

R.Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate making the elemental analysis by the KT method. 5. New York. while we have calculated r1 = 5. the reactivity ratios of VP(1) and VP(2) are found to be r1 = 5. Y. B. 1992). M. assigned to ISP Investments. I. 6. Cho. Physica A.S.. I. Wiley.. Additional information can be obtained by finding out the sequence length distributions for the copolymers. assigned to GAF Corporation. Sanner. Patent 5. E. S. A. Wel and Z. the reactivity ratio of the VA monomer is very low. Spectroscopic Identification of Organic Compounds.041 (June 7. C.. 15.506. Kelen. N. E. Germany. Schenck and W. Appl. 329. 16. Sci.730 and r2 = 0.103. H. 337 (2003). while for the homogeneous copolymer. Terry. Barabas and J. Roland and D. Motoc et al.520. M. J. Jafarizadeh. S. Pekel et al. Inc. r1 r2 = 0. Patent 4.582 (June 16. assigned to ISP Investments. K. Rakshit. G. Springer Verlag. Sanner. The formation of a homogeneous (or alternating) copolymer is demonstrated by the formation of a clear aqueous solution [10]. S. Wetzel. Flory. 3. The latter is closer to 1 and hence more similar to the ideal system. 12.904 (March 5. U. P. Lecture Notes in Chemistry 27. W. Dong. Macromol. Patent 5. H.. 1996).122. S. 1980). 10. Zhong. 74. The differences in reactivity ratios are explained on the basis of quite different properties of VP and VA monomers. 13. if the copolymer is homogenous. 1985). Patent 5. S. A.17 for homogeneous VP/VA copolymers by the EKT method.179 (May 28. Morril. Y. Physica A. Barabas and J. W. Schwarz. J. Eur. 91 (1998). The comparison of the reactivity ratios of homogenous and heterogeneous copolymers is also discussed. 17. Wolf. Nuber. The results presented in this paper illustrate that the distribution of VA units along the backbone is an important 209 parameter.026.S. U. J. 345 (1999). at a high conversion in the present work. 2. 1994). New York. 10. Inc. Monte Carlo Applications in Polymer Science. References 1. Zhong. Zhang.. J. 4th Edit. Hinz and A. A. Blankenburg. Parikh et al. Bessler and T. 221 (2002). C. R. By comparing the reactivity ratios of homogenous and heterogeneous VP/VA copolymers. (A).. 11. This monomer sequence distribution is directly related to the experimental condition used in the copolymer synthesis. Polym. J. U. Zhong and P. F.. H. Tüdós. 1981. assigned to BASF Aktiengesellschaft.311 (November 19. Spoor. J. U. Silverstien. Appl. Turcsanyi. M. Potthoff-Karl.851 (January 8. Cho. in Principles of Polymer Chemistry. the result of multiplication of the reactivity ratios is a unity.S. Sci.. By applying the EKT methodology to the copolymerization data obtained by the elemental analysis and NMR. Patent. 4. Y. Y.395. 307.. 9. Patent 5. J. Straub. assigned to BASF Aktiengesellschaft. F. Polym. Cornell University Press. 2443 (2001). Conclusion A series of the VP and VA copolymers with different monomer ratios and homogeneity in backbone distribution are synthesized. T. Inc.182. For the heterogeneous VP/VA copolymer r1 r2 = 0. assigned to Air Products and Chemicals. .554. 1707 (1976). Bruns. 37.S. Sci. 1995). Foroutan and M.318 (April 9. Polym. 8. U. Foroutan and M.974. 516 (1999). assigned to GAF Corporation. 18. Parikh et al. Kothrade and A. Sci. R. 1985). U. R. 2000). 14. The reactivity ratios of the VP and VA in homogeneous structure of VP/VA copolymer were observed to be very different from those in heterogeneous structure. Patent 6.17. U. Mathakiya and A.319.S. Foldes-Berezsnich and B.S.820 (August 15. In the ideal situation. 7. 1st Edit. it can be seen that. 74. U. T. 4.73 and r2 = 0. M. Jafarizadeh. Chem. Patent 4. 1953. assigned to BASF Aktiengesellschaft. Polym. 68.S. Thorpe.S. R. Appl. 1981. H.

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