Journal of Polymer Research 11: 203209, 2004. 2004 Kluwer Academic Publishers. Printed in the Netherlands.

203

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: m.foroutan@tabrizu.ac.ir)
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 KelenTds 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 nding out the sequence length distribution for copolymers.

Introduction Copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) monomers are of signicant 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 difcult, 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 [29]. 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 inu-

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 nal 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 rst 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 inuence of the method for the synthesis of a copolymer and how it affects the homogeneity and reactivity ratios.

204 Experimental

Mohammad Taghi Taghizadeh and Maasumeh Foroutan stirred at 150 rpm and heated to 85 C. Then feeds 1 and 2 were introduced simultaneously. After the addition of feed 1 had terminated, feed 3 was started immediately. After the addition of feeds 2 and 3 had been completed, the batch was held at 85 C for 2 hours. Then the temperature was raised to 95 C to start a post-treatment stage. The batch then was maintained at 95 C for another 3 hours and feed 4 was added. After feed 4 had been completed, the temperature was held at 95 C for another 3 hours. Then the reactor was cooled down and the intermediate product was discharged. 100 parts of the copolymer product and 600 parts of distilled water then were admixed at 1 atmosphere pressure. The mixture was held until the vapor temperature reached 100 C. Distillation was continued until 300 parts of distillate was collected. The aqueous solution after solvent exchange, which contained about solids, 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, i.e., the amounts of VP and VA unreacted. Since the amounts of VP and VA added were known, the amounts and ratio of VP and VA react to the copolymer then could be calculated by differences. 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) 13.03 VA (cc) 4.6 AIBN (gr) 0.0358 IPA (cc) 9.2 3.5 20.33 7.2 14 5.0 1.0 1.5 11.17 0.2325 1.10 4.01 24.8

Materials The monomers, N-vinylpyrrolidone (VP, Merck) and vinyl acetate (VA, Merck), were vacuum-distilled. 2,2-azobisisobutyronitrile (AIBN, Aldrich) was recrystallized from methanol. Isopropanol alcohol (IPA, Merck) was used as received. Measurements FTIR spectra of the copolymers were recorded with FTIR Nicolet 520 on KBr pellets by a 4000400 cm1 range spectrometer. The mole fractions of the monomers in the copolymer were determined by elemental analysis. The NMR of the copolymer solution in CDCl3 was recorded by a JEOL GSX, 400 MHz 1 H-NMR spectrometer. Copolymerization First we describe Zhongs copolymerization method [9] for the synthesis of a homogenous VP/VA copolymer. 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 , after derivation, we can obtain the following equation: (F1 F2 ) + [(F2 F1 )2 + 4F1 F2 r1 r2 ]1/2 f1 = , f2 2F2 r1 (2)

where F1 and F2 are the mole fractions of monomer 1 and monomer 2 in the copolymer; r1 and r2 are the reactivity ratios for monomer 1 and monomer 2, respectively; f1 and f2 are the mole fractions of unreacted monomer 1 and monomer 2, respectively, in the reactor. It should be noted that r1 and r2 are assumed to be equal to 1.89 and 0.227, although there is some difference between these values and the ones we will obtain later. By using Equation (2) and that f1 + f2 = 1, we can decide the initial monomer composition (f1 and f2 ) to make up the initial copolymer having the instantaneous composition of F1 and F2 . Therefore, the initial monomer concentration is established based on the monomer reactivity ratios (r1 and r2 ) and F1 and F2 . As the reaction progresses, monomers should be supplemented continuously, based on their consumption ratios, to maintain the instantaneous monomer composition to be constant at f1 and f2 . Therefore, the instantaneous copolymer composition can be maintained constant at F1 and F2 and equal to the cumulative copolymer composition. Synthesis of a Copolymer 1-liter Buchi reactor was purged with nitrogen and the initial charge was pumped into the reactor. The reactants were

Results and Discussion By the general synthesis methods of VP/VA copolymers, VP will react faster and go into the copolymer chains rst as VP units. VA will react later, leading to the formation of VA blocks in the copolymer. As mentioned below, we synthesize the VP/VA copolymer by this method; during the reaction, each monomer and solvent should be added into the reactor separately. Therefore each monomer feeding rate can be adjusted independently to keep the monomer conversion ratio constant, and the solvent feeding rate can be adjusted independently, according to the monomer feeding rates. 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. Adjustment of the feeding rates of monomers was not enough for controlling f1 and f2 . The well-organized distribution of VP and VA units in the macromolecule chain maximized the copolymers aqueous solution solubility. The copolymer architecture is determined by the reactivity ratios and feed composition. In this section, the copolymerization of VP with VA in the IPA solution is studied for various mole fractions. The

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate

205

Figure 1. FTIR spectra of VP/VA copolymers with different compositions (mol% of VA-unit): (1) 0.715; (2) 0.485; (3) 0.287; (4) 0.233.

copolymers were soluble in the aqueous solution. Copolymerization was carried out under a high conversion condition in order to determine monomer reactivity ratios by elemental analysis and H-NMR data. 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. The calculation procedure has been reported in detail elsewhere [14, 15]. Pure Poly N-vinylpyrrolidone (PVP) has a characteristic, a relatively broad, infrared band at 1682 cm1 that is attributed to a mixed mode containing major contributions from the carbonyl and NC stretching vibrations. On the other hand, the carboxyl group band of VA was observed at 1734 cm1 [16]. Figure 1 shows the FTIR spectral band of VP/VA copolymers. Figure 1 demonstrates that, in contrast to the spectrum of PVP, a characteristic peak appears around 1742 cm1 . This characteristic peak is the peak of stretching vibration absorption of carboxyl groups of VA in the copolymers. By calculating the absorbance of this peak and the peak of carboxyl groups of VP at 1680 cm1 , we can determine the concentration of VA and VP in the copolymers. Absorbance peaks of carboxyl groups of VP and VA in the copolymers are shown in Figure 2. It is evident that with an increase in VA contents, peak 1 rises correspondingly. Using the

Figure 2. Transmittance peaks of carboxyl groups of VP and VA in the copolymers (VA: peak 1; VP: peak 2).

absorbance of carboxyl groups of VA and VP of all copolymers, the concentration of VA and VP in the copolymers can be obtained.

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Mohammad Taghi Taghizadeh and Maasumeh Foroutan

Figure 3. 1 H-NMR spectra of VP/VA copolymers with different compositions (mol% of VA-unit): (1) 0.715; (2) 0.485; (3) 0.287; (4) 0.233, in CDCl3 (more details of some peaks, especially the smaller ones in the range of 45 ppm, are not visible because of picture compression).

Figure 4. Repeat unit in the VP/VA copolymers.

Figure 3 shows the signals appropriate to the H-NMR spectra of the copolymers corresponding to protons of VP and VA in the copolymers. The constituent monomeric units of VP/VA copolymers are given in Figure 4. As Figure 3 shows, in the H-NMR spectrum of copolymer number 1, methine backbone protons (b) resonate at = 4.52 ppm, whereas methine backbone protons (e) appear as a broad peak at = 3.623.89 ppm. The H-NMR spectrum of this copolymer shows that the three peaks of the acetoxy proton signals resonate at 2.01 ppm. Also, protons (h), (f), and (g) resonate at = 3.20, 2.172.37, and 1.431.70, respectively. Although the spectra of all the copolymers are similar, it is possible to resonate a certain proton at different . These shifts can be attributed to the different alternation of VP and VA monomers in each copolymer. Reactivity Ratio and Sequence Distribution of Copolymers The extended KelenTds (EKT) [17] method considers the drift of comonomer and copolymer composition with

conversion. Therefore it is suitable for the manipulation of our highly conventional data. The mole fractions of VP and VA in the copolymers of various compositions, calculated by using 1 H-NMR and elemental analysis data, are listed in Table 1. The results are in very good agreement with each other. The weight conversion (%W) of the synthesized copolymers (1, 2, 3, and 4) was obtained 40.01, 49.98, 60.20, and 50.04, respectively. The mole fraction of VP (F1 ) in the copolymer was determined by H-NMR, using the following relation: F1 = I (CH of VP) , 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, respectively. The FinemannRoss copolymer composition equation is: G = rVP H rVA , (4) where G = X(Y 1)/Y ; H = X2 /Y ; Y = FVP /FVA ; X = fVP /fVA . Kelen and Tds apply these parameters in the linearized copolymerization; , , and : = rVP + rVA rVA , (5)

where = G/( + H ); = H /( + H ); = (Hmax Hmin )1/2 . The intercept at = 0 and = 1 of the plot versus gives rVA / and rVP , respectively. Hmax and

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate

Table 1. 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 0.285 0.515 0.713 0.767 f2 0.715 0.485 0.287 0.233 N (%) 8.02 10.62 11.68 11.91 F1 0.576 0.793 0.890 0.912 F2 0.424 0.207 0.110 0.088

207

By nitrogen analysis F1 0.577 0.806 0.908 0.930 F2 0.423 0.194 0.092 0.070

f1 and f2 are the mole fractions of VP and VA in the feed. F1 and F2 are the mole fractions of VP and VA in the copolymer. Table 2. EKT parameters for VP and VA using elemental analysis data Copolymer number 1 2 3 4 = X Y VA VP Z G H

0.399 1.061 2.480 3.287

1.360 4.169 9.920 13.28

0.220 0.185 0.182 0.144

0.750 0.730 0.720 0.582

5.560 6.390 6.340 5.610

0.065 0.496 1.040 2.189

0.044 0.102 0.250 0.420

0.240 0.430 0.650 0.750

0.361 2.080 3.640 3.940

Hmax Hmin = 0.136; the parameters X, Y , VA , VP , Z, G, H , and have been mentioned in the text through Equations (6) to (8).

Hmin are the highest and the lowest values of H . The effect of conversion is considered in the extended KelenTds equation. The partial molar conversion of VA is dened as: VA = W ( + X) , +Y (6)

where W is the weight conversion of polymerization, and is the ratio of the molecular weight of VA to that of VP. The partial molar conversion of VP is: VP = VA Then, Z= Y . X (7)

log(1 VP ) , log(1 VA )

(8)
Figure 5. EKT method for determining monomer reactivity ratios in the copolymerization of VP and VA by using elemental analysis data.

where = G/( + H ); = H /( + H ); G = (Y 1)/Z; H = Y/Z 2 . EKT parameters are calculated from the above equations using data in Table 1 and are summarized in Tables 2 and 3. The EKT plots for copolymer samples are given in Figures 5 and 6. Table 4 shows the reactivity ratios rVA and rVP obtained by the EKT method. The statistical distributions of the monomer sequence 11, 22, and 12 are calculated using the following relations: S11 = F1 S22 S12 2F1 F2 , (9) 1 + [(2F1 1)2 + 4r1 r2 F1 F2 ]1/2 2F1 F2 = F2 , (10) 1 + [(2F1 1)2 + 4r1 r2 F1 F2 ]1/2 4F1 F2 = , (11) 1 + [(2F1 1)2 + 4r1 r2 F1 F2 ]1/2

where r1 and r2 are the reactivity ratios of VP and VA, respectively. F1 and F2 are the mole fractions of VP and VA

Figure 6. EKT method for determining monomer reactivity ratios in the copolymerization of VP and VA by using NMR spectroscopy data.

208
Table 3. EKT parameters for VP and VA using NMR data Copolymer number 1 2 3 4 = X Y VA VP

Mohammad Taghi Taghizadeh and Maasumeh Foroutan

0.399 1.061 2.480 3.287

1.360 3.830 8.100 10.36

0.220 0.199 0.220 0.182

0.750 0.719 0.718 0.574

5.560 5.743 5.092 4.253

0.065 0.493 1.394 2.202

0.044 0.116 0.312 0.573

0.217 0.422 0.622 0.783

0.320 1.793 2.960 3.008

Hmax Hmin = 0.159; the parameters X, Y , VA , VP , Z, G, H , and have been mentioned in the text through Equations (6) to (8). Table 6. 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. Monomer reactivity in the copolymerization of VP and VA By elemental analysis VP(r1 ) VA(r2 ) r1 r2 5.730 0.170 0.974 By NMR spectroscopy 4.357 0.083 0.360

Table 5. Structural data for the copolymers of VP(1) with VA(2) Compositiona (mole fraction) Copolymer number 1 2 3 4 F1 0.577 0.806 0.908 0.930 F2 0.423 0.194 0.092 0.070 Blockinessb (mole fraction) S11 0.331 0.649 0.824 0.865 S22 0.178 0.037 0.008 0.005 Alternationb (mole fraction) S12 0.490 0.314 0.168 0.130

0.285 0.515 0.713 0.767

0.715 0.485 0.287 0.233

0.172 0.072 0.032 0.025

0.828 0.928 0.968 0.975

0.634 0.822 0.916 0.935

0.366 0.178 0.084 0.065

f1 and f2 are the mole fractions of VP and VA monomers in the feed.

a From elemental analysis data. b Statistically calculated using reactivity ratios.

in the copolymer, obtained from the elemental analysis data. The mole fractions of the 11, 22 and 12 sequences are shown by S11 , S22 , and S12 , respectively. These structural data are given in Table 5. As Table 5 shows, the mole fraction of 11 and 22 sequences decreases as the mole fraction of VA decreases. In order to understand the relationship between the VP/VA copolymer structure and its solubility, it is important to determine the sequence distribution of the copolymer. The sequence length distribution is a statistical representation of the probability of monomer 2 to be attached to monomer 2. The distribution of the sequence length is determined by using the r1 and r2 information along with the following equations. (N1 )j = (p11 )(j 1) p12 . (12)

Figure 7. Sequence length distribution for VP and VA units in the copolymerization of a VP/VA homogeneous copolymer (number 1): N-vinylpyrrolidone (white); vinyl acetate (black).

Assuming that only the ultimate monomeric unit affects the rate constants of copolymerization (ultimate effect or rstorder Markov chain) [18], we have: r1 , (13) p11 = r1 + (f2 /f1 ) f2 p12 = , (14) r1 f1 + f2 where (N1 )j is the sequence length of monomer 1, transition probabilityp11 is the probability of monomer 1 to

be attached to monomer 1, and p12 is the probability of monomer 1 to be attached to monomer 2. Similarly (N2 )j , p22 , and p21 can be described. The transition probabilities are given in Table 6. The values of r1 and r2 are obtained by the EKT method, using the NMR spectroscopy data in Table 4. Figure 7 shows the number-average sequence length distribution for both VP and VA, under solution conditions, initial mole ratios of 0.285/0.715 VP/VA, and for r1 = 4.357 and r2 = 0.083. This gure 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. Homogenous and Heterogeneous Copolymers Mathakiya et al. [1] have reported the synthesis of heterogeneous VP/VA copolymers in methanol, which are soluble in non-aqueous solutions. They have observed a different reactivity than that in our work, r1 = 0.182 and r2 = 0.142,

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate making the elemental analysis by the KT method, while we have calculated r1 = 5.730 and r2 = 0.17 for homogeneous VP/VA copolymers by the EKT method. By comparing the reactivity ratios of homogenous and heterogeneous VP/VA copolymers, it can be seen that, if the copolymer is homogenous, the reactivity ratio of the VA monomer is very low. In the ideal situation, the result of multiplication of the reactivity ratios is a unity. For the heterogeneous VP/VA copolymer r1 r2 = 0.026, while for the homogeneous copolymer, at a high conversion in the present work, r1 r2 = 0.974. The latter is closer to 1 and hence more similar to the ideal system. Conclusion A series of the VP and VA copolymers with different monomer ratios and homogeneity in backbone distribution are synthesized. By applying the EKT methodology to the copolymerization data obtained by the elemental analysis and NMR, the reactivity ratios of VP(1) and VP(2) are found to be r1 = 5.73 and r2 = 0.17. The differences in reactivity ratios are explained on the basis of quite different properties of VP and VA monomers. The formation of a homogeneous (or alternating) copolymer is demonstrated by the formation of a clear aqueous solution [10]. Additional information can be obtained by nding out the sequence length distributions for the copolymers. This monomer sequence distribution is directly related to the experimental condition used in the copolymer synthesis. 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. The results presented in this paper illustrate that the distribution of VA units along the backbone is an important

209

parameter. The comparison of the reactivity ratios of homogenous and heterogeneous copolymers is also discussed.

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