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A. KUMAR* and A. SOOD, Department of Chemical Engineering, Indian Institute of Technology, Kanpur-208,016, India
The urea formaldehyde polymerization has been modeled using the functional group approach, which accounts for the formation of higher oligomers. The kinetic model involves four molecular species and three rate constants, as opposed to six as proposed in earlier studies. The experimental data of Price et al. have been curve fitted using our model, which is found to describe them very well in the entire range of temperature and urea formaldehyde ratio. Based on the activation energies, it has been argued that the reverse reaction step must involve the condensation product, water.
The polymerization of urea and formaldehyde is normally carried out by mixing water solution of formaldehyde (formalin) and urea and subjecting it to high temperature.'S2 Formaldehyde is highly reactive, and when it is present in large concentration it polymerizes into white powder called polyformaldehyde as fol10ws~-~
* O H ( - C H 2 0 ) , H + ( n - 1)HZO
where n is usually of the order of 10. Under alkaline conditions polyformaldehyde depolymerizes into formaldehyde, which exists mostly as methylene glyc01~-~ in aqueous solution. Formaldehyde can polymerize with phenol, cresol, urea, and melamine, and depending upon the reaction conditions, it can either form a linear polymer or a network."-14 In this study, we have analyzed the formation of urea formaldehyde polymer. The proposed kinetic model accounts for the addition as well as the condensation reactions and is completely general. This involves only three rate constants, as opposed to six used in earlier studies. The urea-formaldehyde resin is mainly used as an adhesive in plywood and particle board industries.'?'' The resin is prepared as prepolymer in the first stage. This is subsequently mixed with suitable hardener and catalyst and applied on sheets to be jointed. There is a gelation of the polymer leading to the formation of a network in the second stage.
* To whom correspondence should be addressed.
Journal of Applied Polymer Science, Vol. 40,1473-1486 (1990) CCC 0021-8995/90/9-l01473-14$04.00 0 1990 John Wiley & Sons, Inc.
thermal gravimetric analysis. ( 1) and ( 2 ) seem to indicate that the reversed step is unimolecular. eqs. In addition to this. Price et aL3' have experimentally measured the free formaldehyde in the reaction mass.. In addition. the progress in the studies of gelation has been relatively slow. If urea is in excess in the acidic medium. and there is a bond scission that may not occur at moderate tem- . They observed that the kinetic model of eq. The gelation of resins occurs at low pH. various additives.1474 KUMAR AND SOOD There have been several studies reported on the formation of prepolymer of urea and f ~ r m a l d e h y d e . we have rewritten the mechanism involving these species.23. l ~ Urea . and their concentrations upon the gelation time. U and F represent a urea and a formaldehyde molecule whereas UF. low molecular weight polymer is also formed. U -CH20H reacts with another U preferentially to give diurea methyl ether. and the process can be induced by any method that lowers the pH of the reaction mass. methylene linkages reduce. U -CH2-0 -CH2Uor methyl diurea U -CH2 -U. and nuclear magnetic resonance. OH -CH2-OH. and each of them has a different reactivity. As the pH increases.24. For high temperatures they proposed the following additional reaction: UF2 +F k5 UF3 The urea-formaldehyde polymer has been analyzed by Katuscak et al. Most of the analysis of the urea-formaldehyde system has been limited to the first stage. in water) there is a formation of U-CH20H. They have studied several samples and characterized them with a molecular weight distribution. and polydispersity index.23-32 This is called the addition step and a methylol bond is formed. ( 1) fits the experimental results for low temperature only. infrared spectroscopy. Based on the chemistry of polymer formation.3%34 Mayer' has discussed a t great length the effect of pH. differential thermal analysis. Price et aL3' have assumed the absence of the polycondensation step and only two of the sites of urea participate in the first stage as follows: In this. Three of its hydrogens are highly reactive compared to the fourth On reaction of urea with formaldehyde (existing as methylene glycol. and the primary products are methylols and ethers. we have used the functional group approach in which we follow the polymerization by defining four reactive species.~ ~ ( NH2 -CO -NH2 denoted by U ) has four reactive hydrogens. and the chain length of the polymer is limited to a small value. 29 who clearly show that it contains higher oligomers. In this study. The gelation has been followed using X-ray. and this is sometimes called the polycondensation step. Due to the difficulty of instrumental analysis. average molecular weight. and UF2are two of their substitution products.
In urea there are four hydrogens that can undergo reaction with the hydroxyl group of methylene glycol. A. B. Reactive species used for modeling reversible urea-formaldehyde polymerization. . At a given -N-C-N-H I 1 or OHCH2-N-C-N-H 0 H I 0 II I B -N-C-N-H II = ---N-C-N-H or O H C H 2 . we have defined four species. In view of this. C. In Figure 1. we have shown in this study that it was possible to describe the experimental data of Price et aL31 in the complete range. I I 0 -N-C-N-H = 0 II -N-C-N-H II \ 1 y20H or OHCH2-N-C-N-H I ! 0 d CH2OH CH20H or -N-C-N-H \ or -N-C-N-H I I 6 C . we have considered an additional kinetic model in which water was assumed to participate in the reverse step of polymerization.k . We have attempted to model the polymerization by using functional group approach. Using both these kinetic schemes.120H C. thus urea exhibiting a functionality of four.N . 1. it shows a functionality of two. OH-CH2-OH. In this we identify species in terms of which the formed polymer can be represented. the first methylene glycol molecule can react at four positions of a urea with equal likelihood.H 0 I I 0 I 8 CH2OH H -N-C II CH2OH H I or a H -N-H or OHCH2-N-C-N-H 8 --N-C-N-H 7 1 a 8 o r OHCH2-N-C-N-H H ? t CH2OH d 5HzOH -N-c-N-H or C~+OH-A--C-N-H I. KINETIC MODEL FOR THE FORMATION OF UREA-FORMALDEHYDE POLYMER Since formaldehyde exists in the aqueous medium as methylene glycol.H2OH or O H C H -N-c-N-H ~ or OHCHZ-A -c-N-H 6 0 II Fig. and D. In view of this.MODELING OF POLYMERIZATION 1475 peratures. H 20H I 8 CI.
The latter formed whenever two repeat units react. k3 = rate constant for the reverse reaction occurring between a reacted -CH2. the forward reaction can be written in terms of species A to D. Based on this chemistry of polymerization of urea and formaldehyde. For example. In defining these species. k2 = rate constant for the secondary or tertiary hydrogen of urea with the OH group. an effort is made here to determine the conversion of urea and formaldehyde in the reaction mass as a function of time. polymerization can be represented by . Also a t moderate reaction conditions. One plausible description of the progress of reaction would be to follow the concentration of species A to D in the reaction mass. CHzOH CH~OH-NH-CO-NH-CH~-NH-CO-N-CH~-N-CO-NH~ CHZOH-N-CO -NH-CHz-NH-CO I I -NHz (3) can be represented by C-D-B D-A Instead of attempting to find out the concentration of different isomers in a polymer. The overall polymerization represented by reaction of functional groups can be written in terms of the following rate constants: I (4) k1 = rate constant for the reaction of primary hydrogen of urea with the OH groups. whether it is part of a polymer chain or it is a freely existing molecule. When polymerization is carried out for some time starting with a feed consisting of urea and formaldehyde.1476 KUMAR AND SOOD time within the reactor. polymers of various lengths and structures are formed. Experimental work of de Jong" have shown that the reactivity of various hydrogens on urea is dependent upon the number of sites already reacted.bond or a -CHzOH group. Species A to D can be used to represent any polymer molecule. no distinction has been made whether the linkages at these reacted sites are a reacted -CH2. we have unreacted CHzOH groups on the polymer molecule formed during reaction as well as the reacted CH2 bond. there is little evidence of finding reacted tetrasubstituted urea.bond (denoted by Z ) and water molecule. Since there is no formation of tetrasubstituted urea. which also leads to formation of higher oligomers.
In view of this. therefore it is assumed not to react anymore. . the -CH. A + H 2 0 2 U + F . in the second one (model 11) the linkage of species A to D have all been assumed to be mainly reacted -CH2bonds.OH + H 2 0 k2 A + CHzOH B + H2O + Z A + F 2 C + CH20H + H2O A + CH20H 2 C + H 2 0 + Z C + F 2 D + CH20H + H 2 0 C + CH20H 2 D + H 2 0 + Z B +F D + CH2OH + H20 B + CHzOH 3 D + H 2 0 + Z U + (5g) (5h) (5i) (5j) 2k2 + In writing these reactions it has been assumed that the overall reactivity of a given reaction is completely governed by the site involved. ~ In the first one (model I ) the various linkage of species A to D have all been assumed to be mainly CH20H groups.Lastly. Reverse Reaction for Model I All linkage are assumed to be reacted - CH20H groups. Since in species A to D. It is assumed that model I would be a better representation of the situation in the initial phases of polymerization whereas model I1 would give a better description in the final stages of polymerization. species D does not have any reactive site left. (5a). As opposed to this. and the overall reactivity is 8 k I .MODELING OF POLYMERIZATION 1477 (5a) (5b) (5c) (5d) (5e) ( 5f) + F 2 A + CH20H + H20 U + CH20H 2 A + H 2 0 + Z A + F 2 B + CH. Therefore when urea consisting of four hydrogens reacts with formaldehyde (or methylene glycol) having two -OH groups.bond and the CH20H linkage have not been distinguished.(CH20H) B + H20 2 A + F (CH20H) (CH20H) C + H20 2 A + F - + HzO 2 B + F D + H 2 02 C + F D (CH20H) (CH20H) . For these two models the mechanism of polymerization is given next. it forms species A as in eq. ~ . two extreme possibilities have been p r o p o ~ e d . it is not possible to write the mechanism of the reverse reaction exactly.
Z The mole balance relation for various species in batch reactors can now be easily written for both these mechanisms.OH]) . and these are considered next.1478 KUMAR AND SOOD Reverse Reaction for Model I1 All linkage are assumed to be -CH2-. Model I and I1 -d[A1 - dt (2[F] + [CH. A + H 2 0 2 U + (CHzOH) . It may be observed that the mole balances for species A to D and water are identical for both these models.Z C + H20 2 A + (CH2OH) Z + H 2 0 2 B + ( C H 2 0 H ).Z D D + H 2 0 2 C + (CH20H) .Z - (7a) (7b) (7c) (7d) (7e) B + H20 2 A + (CHZOH) .
there are two equilibrium constants. = 1: 1.[CH20H](2kl(2[U] (18) dt + [A] + [ B I ) + k2([Al + 2 I C l ) ) RESULTS AND DISCUSSION Price et aL3' have carried out polymerization of urea and formalin (37% formaldehyde in water by weight) in a special shaped sealed reactor. Experimental data of Price et al?' for U / F of this article. In the kinetic model proposed in this work.MODELING OF POLYMERIZATION 1479 Model I1 + k. depending upon the temperature of the reaction mass.([A] + z [ C ] ) } + k3[H20]( [A] + 2[B] + 2[C] + 3 [ D ] } -d [ Z 1 . 31 reveals that the concentrations of free formaldehyde in the reaction mass falls very rapidly for short times. it attains an equilibrium.33 curve fitted by the kinetic model . However. K 1and K2 defined as - Without water _ _ _ .With water Fig. for large times. A careful examination of the experimental data reported in ref. 2.
We have already observed that de Jong et a1.33 and 1 : 2.31 assumed that the reversed reaction was unimolecular. It is thus seen that the kinetic model proposed in this work describes the experimental data very well. . and determined k2 and k3 from the asymptotic levels of free formaldehyde in the reaction mass. while we have shown results . We first kept k2 = k3 = 0 and determined kl .2 are shown in Figures 2 and 3. we modified the mechanism in eqs. ( 6 ) and ( 7 ) and the mole balance relations in eqs.W i t h o u t water _ _ _ _ _ W i t h water -100% 0-160'C Fig. Experimental data of Price et al?' for U / F = 1 : 2. Even for these. These were similarly simulated on computer.which would give the same initial fall as observed experimentally. We have summarized rate constants in Table I for comparison. It is found that for the U :F ratio of 1 : 2. and on the same plots the experimental results of Price et aL31have been shown. the initial rate of fall and the eqililibrium value are lower than that for 16OoC. and it was possible to determine the rate constants similarly. (8). This is found to have the opposite trend from that seen in the rest of the data.20 and a temperature of 100°C.1480 KUMAR AND SOOD This clearly means that the initial fall in F is largely affected by the choice of kl and k2 while for large times asymptotic level of F is controlled by Kl and K2 . 3. (8)-( 16) for model I on a computer. we simulated eqs.l' and Price et al. it is possible to find the set of rate constants to fit the data in the entire range.( 16). The final simulation for U : F ratio as 1 : 1.2 curve fitted by this kinetic model. Assuming the breakage of bonds to occur this way. With this background.
it is k2. and results have been plotted in Figures 4 and 5 . 0X l o ' 9.3 X 2. 0x 10-3 4. We have curve-fitted experimental data for both these sets.0 x 10-6 5 .0X 4 . 2 . We have already observed that for 100 and 120°C and U : F ratio as 1 : 2.0 5 . In Figure 4 we assume that water affects the depropagation reaction.0X l o ' 2. 3 3 kZ for U/F = 1/2.25 X l 1 .25X l o ' (b)Kinetic Model Assuming the Reverse Step Involving Water 25 4 0 6 0 8 0 100 3 .33 k3 for U/F = 1/2.0 x lo-' Indicates that rate constants are for U/F Indicates that rate constants are for U/F 1/1. for U/F = k2 for U / F = kl for U/F = 1/1.0 x l o ' 4 .5X 3. 0X l o ' 8 . 0 x 10-6 = = 9.5 x 10-6 8. 7 5X 3 . 0 x lo-' - - 8 . 5 x 10-6 8 .2. 0X 9. Consequently.5 X l o ' 1.22 - k3 for U/F = 1/1. 0x - 4.0X 3 . in contrast to that found in earlier kinetic models .0 x 4 . 0 x lo-* 3. If these are ignored. 0X 3.0 x l o ' 3 . 0x l o ' - - 8 .0 X l o ' 4. 5X 3 . 3 ) while activation energies are affected only negligibly. 3x 2 . 0X 10" 8. by dotted lines on Figures 2 and 3. 5X 3. 0x 4. 5X l o ' 1 .0 x lo-' 120 160 2 .25X lod 4 .0 X l o ' 4.0 X 7 . 7 5X l o ' 4. 2 5 X lo-' 8 . 1/2. and k3as seen.22 25 4 0 6 0 8 0 100 120 3. These figures give rate constants that are temperature dependent only. the rate constants needed to fit these are higher than those for 160°C as the reaction temperature. 0X l o ' 1. 6 x 10-3 4.0 x 1.0X l o ' 4. We have prepared Arrhenius plots for these in Figure 4.9 X 160 8 . the experimental data have different trends from those observed for the rest of the data.0X lo-' 8.0 X l o ' 1 . the filled legends have been used for U :F as 1 : 2. 0x l o ' 4. 7 5X 8 .3 X l o ' 1.0X l o ' 2.2. while in generating Figure 5.0X l o ' 2 .25X lo-" 1 . 5X 3. In both these figures.33 1/22 - 1 / 1 .0X l o ' 1 . 0x l o ' 4 . 0X l 5.3X l o ' 1 . 0X o ' 4.20. Price et aL31have presented experimental data for two different U : F ratios. and we find that the choice of inclusion of water in the reverse step has an effect only on kio (i = 1.5 X 5.0 x l o ' 2. 0X l o ' 1 . we assume that it does not. 0 X lo-' 9. is independent of the U / F ratio. It is seen that the two simulations almost overlap for all cases. 0X o ' 4 . 5 X lo-' 3. indicating a relative insensitivity of these models to the concentration of water in the reaction mass.75X l o ' 4. 0x 1 0 6 x lo-' 3.33.25 X l o ' 1.25 X l o ' 1 .0 X l o ' 4 .MODELING OF POLYMERIZATION TABLE I Rate Constants Needed to Fit the Experimental Data of Price et al?' (a) Kinetic Model Assuming the Reverse Step as Unimolecular 1481 Rate Constant Temperature ("C) k.0 X l o ' 2. This is found because in formalin there is already a large amount of water present and its concentration changes only by a small amount due to polymerization. 0X 8 . which possible to draw a decent single straight line for kl.
The activation energy of rate constant k 3 is found to be small compared to the degradation reaction. step. Arrhenius plots of rate constants k. With increasing reaction temperature. ultimately leveling at the equilibrium value. the former gives the unreacted urea in the reaction mass as a function of time a t different temperatures.2 I$O*C 2 ._ - x c -11 - -13 -15 - EJ 2000 -16 '2. With the rate constants so found. 32 34 18lT (%-'I Fig. it is found that the rate of fall in the initial region increases while the equilibrium . Comparison of Figures 4 and 5 shows smaller scatter of data in the latter. Figures 6 and 7 give some results. water. 6 28 60 3 .1482 Or KUMAR AND SOOD 4 - 5Case1 Case 2 -7- kl k2 k3 O A O 6 -9. which suggests that water must be playing some role in the reverse reaction. It is very difficult to conclude from the limited data of Price et aL31as to whether the condensation product. The unreacted urea decreases rapidly in the initial region. participates in the reverse reaction. 4. we have simulated the urea-formaldehyde polymerization in batch reactors. to k3assuming water having no effect on the reverse proposed in the literature. 4 1 2 0 1 0 0 80 2 . 0 4p 2.
Assuming monosubstitution of formaldehyde on urea. they have relaxed the earlier as- . value falls. they evaluated the rate constants. As the temperature is increased. At a given temperature. Arrhenius plots of rate constants k . In Figure 7. the peak height falls. and the kinetic model proposed by them completely neglected the formation of higher oligomers. and after passing through a maximum. The behavior observed is similar to those of intermediate species in a set of consecutive reactions.MODELING OF POLYMERIZATION 1483 -4 - Case 1 Case2 kl k2 0 A C I A k3 m Fig. 5. Earlier studies of de Jong and de Jong12were carried out a t low temperatures. it falls to the equilibrium value. we have plotted the concentration of species A as a function of time with temperature. Price et aL3' have performed their experiments a t much higher temperatures when the formation of higher oligomers cannot be ignored. and its position shifts to smaller times as seen. the concentration of species A first rises. to k3 assuming bimolecular reaction between water and reacted bonds. In fact in their kinetic model.
6.___ With water -25'C -at 1 bU 1LU 6 --__ 0 I t 1 - 1 a0 3$0 t (min) Fig.Without water _. . Concentration of species A versus reaction time. .1484 KUMAR AND SOOD \ -Without water __ . 7._ With water Fig. Concentration of unreacted urea versus reaction time.
Molhave. 4. Katuscak et al. 1929 (1982). Laeg. and B. Walker. As opposed to this. one finds that it is not possible to distinguish them from each other. Urea Formldehyde Resins. 1979. Tech. This accounts for the formation of higher oligomer and is found to be extremely suitable for the correlation of experimental data a t high temperatures. Ugeskr.6287 (1979). Kumar. On comparison of experimental data of Price et aL3' with computed results.' and he observed that it was possible to divide the polymer formation into two stages for low temperatures only. 141. 3. p. K. Interscience. Lindquist. and hence water must have some role to play. Polymer. as opposed to other models reported in literature that use at least six rate constants." have subjected this to GPC studies and shown that it has a polydispersity index more than unity. The kinetic model proposed in this work serves as a basis for determining the MWD of the polymer formed using the kinetic approach. Addison-Wesley. the polymer formed in the first stage is available as a syrup. New York. It is found that the model fits in the entire range and the rate constants. and L. It was argued in this article that this way of representation is similar to chain degradation and therefore should have high activation energy. 1st ed. F.. thus indicating the formation of higher oligomers. which already has large amount of water.. and a second-order kinetic for the reverse step is a better representation. in the second stage most of the chain growth occurs through the condensation mechanism.. Gupta. I. 1966.MODELING OF POLYMERIZATION 1485 sumption of monosubstitution and included reactions given in eq. They observe the insufficiency of their kinetic model in fitting the experimental data a t high temperatures. References 1. 10. London. it was felt that the activation energy of rate constant k3 is small. A. 2.. addition is the predominent reaction. ( 2 ) . In the first stage. 23. Meyer.. R. in Kirk-Othmer Encyclopedia of Chem. Kumar. J. Industrially. We have also examined a kinetic model in which the reverse step was assumed to be a bimolecular reaction involving the condensation product. However. This is due to the fact that polymerization has been carried out with formalin. The kinetic model proposed in this work involves fewer rate constants (only three as opposed to six) and accounts for the formation of higher oligomers. Anderson. so determined. can be represented by a suitable Arrhenius relation. according to Meyer. CONCLUSIONS A kinetic model for reversible urea-formaldehyde polymerization based upon functional group analysis has been proposed. G. 2nd ed. B. The model proposed in this work involves only three rate constants.31the reverse reaction was shown to be a unimolecular reaction. . Polymerization of urea-formaldehyde has been reviewed by Meyer. In the earlier kinetic models of de Jong12 and Price et al. 77. The kinetic model proposed in this work has been computer simulated and experimental data of Price et al?l have been curve fitted using rate constants as the parameters. S. even though small amount of condensation reaction also occurs. Vol.
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