BA as a Model for AA to estimate C CTAt by EPR

5 Acrylic Acid

5.1 Model development for Non-ionized Acrylic Acid

5.1.5 BA as a Model for AA to estimate C CTAt by EPR

In previous work,^[147] a retardation of the AA polymerization by ME as CTA has been found for low concentrations of CTA, which was explained by a higher

k

_t resulting from reducted of chain length. However, at even higher concentrations of CTA, an enhancement of rate of polymerization was found relative to the expected value considering CLDT, i.e., in going from no to high concentration of CTA, r_polym passes through a minimum. One explanation could be that at higher CTA concentration a significant amount of MCRs undergo transfer to CTA with subsequent reinitiation of

q t

the CTA radical that the rate enhancing effect of transforming MCRs into SPRs notably compensates retardation by enhancement of termination.

The polymerization kinetics of BA (butyl acrylate) has been investigated with focus on propagation, termination, backbiting and high-temperature reactions.

[40-43,49,101,107,176-181] BA polymerizations have been successfully modeled for different conditions.^[42,43] Overall BA is one of the best examined monomers. BA and AA show a similar general kinetic behavior and even kinetic coefficients are of similar size.

The main difference arises from solvent, because BA is polymerized in organic solvents, while AA polymerization takes place in aqueous solution. For many monomers including AA, the rate coefficient of propagation becomes a function of monomer concentration (see subchapter 2.4.2 and 5.1.2) when polymerized in water, thus making kinetics more complex. This does not affect the comparison made in this chapter, because C_CTA is a good constant even in aqueous systems (subchapter 4.1.1).

In this subchapter investigation into the chain transfer of MCRs to CTA are described and an approximate value for C_CTA^t is determined. On the one hand, chain-transfer constants of thiols to both methacrylate and acrylate monomers are close to each other, i.e., between 0.5 and 2. On the other hand, it was found by Junkers et al.^[176] via mass spectrometry that the amount of -scission products is reduced a great deal even in case that small amounts of CTA (0.01 mol mol^¹) were added to the reaction mixture. The authors concluded that the CTA reacted so fast with MCRs that transfer becomes the main reaction pathway of MCRs, i.e. the CTA “patches”

MCRs thus reducing branching. So far, no experimental procedure has been developed to measure chains-transfer of MCRs to CTA directly.

Agirre et al. polymerized BA with tetrabromomethane added as CTA.^[182]

Tetrabromomethane was chosen, because in contrast to thiols this CTA transfers a bromine atom instead of a hydrogen atom, and thus the “patching” product is different from the backbone of the polymer. Mass spectrometry confirmed that the amount of -scission products was reduced, the “patching” product could not be found via¹³C-NMR analysis, which strongly suggests that C_CTA^t is rather low.

As the two types of radicals, SPRs and MCRs, show different hyperfine splitting, they can be easily distinguished by EPR. In addition, absolute radical concentrations can be obtained. Unfortunately, EPR measurements of aqueous solutions are difficult and can only be carried out using special equipment (see chapter 3.4.3).

Water has a rather high dipole moment of 1.855 D.^[183] In contrast, toluene is an almost ideal solvent for EPR experiments, with a dipole moment of 0.357 D.^[183] This led to the idea of using BA as a model to get a better understanding of AA kinetics.

In previous work by Sergeeva et al. polymerization of 1.52 mol L^¹ BA polymerization in toluene was investigated by EPR.^[101] Polymerization took place under constant UV initiation. Both absolute radical concentration and the fraction of MCRs were determined as a function of temperature in the range of 50 to 90 °C. As the aim of this investigation was to fathom the effect of chain transfer on MCR kinetics, the same setup and experimental procedure as in the earlier work was used, with the exception of adding different levels of ME as CTA.

20 G

68.7 %

3-line 7-line 4-line

Figure 5-12 The simulated 3-line spectrum and the 7-line spectrum assigned to MCRs and the 4-line assigned to SPRs are given in the upper part. The double integrals of the 3-line, the 7-line, and the 4-line spectrum account for 10.9, 68.7, and 20.4 %, respectively, of the double integral of the combined spectrum, which best represents the measured spectrum. Conditions: 1.52 mol L^¹ BA in toluene, 0.02 eq. ME, 30 °C.

The fraction of MCRs is obtained by fitting the simulated spectra to the measured ones. The EPR spectrum of SPRs actually consists of six lines, but due to line broadening a 4-line spectrum is observed. The 7-line MCR spectrum consists intrinsically of nine lines resulting from coupling with two non-equivalent groups of

two -protons. The 3-line spectrum results from slow rotation of macromolecules, as discussed in detail in ref.^[101]

In Figure 5-12, the three-component fit is shown consisting of the 4-line, 7-line, and 3-line species. All three simulated spectra (top) are combined to best represent the measured spectrum. The comparison between simulated and measured spectrum (bottom) demonstrates good accuracy of the simulation. Most of the small deviation results from the baseline of the experimental spectrum being somewhat tilted. The ratio of the double integrals yields the ratio of radical concentrations and thus the fraction of MCRs is given by:

Shown in Figure 5-13 is, to which extent MCRs are observed as a 3-line spectrum depending on temperature for different CTA concentrations. The 3-line specrum is associated with a hindered rotation of the macroradical.^[101] It is not observed with model species consisting of a few monomer units only. A reduction of the fraction of the 3-line spectrum may indicate that chain length is reduced into the oligomeric region. The 3-line spectrum is observed for polymerizations with 0.02 mol mol^¹ CTA^XXIV to the same extent as without CTA. For 0.05 mol mol^¹ CTA this is approximately true as well even though the fraction of the 3-line spectrum appears to some extent reduced. On the other hand, this deviation is within experimental uncertainty.

Figure 5-14 shows the mole fraction of mid-chain radicals for BA polymerizations from low temperature, where SPRs predominate, to high temperature, where MCRs predominate. Depending on temperature, the mole fraction of MCRs is reduced slightly by CTA. For both 0.02 mol mol^¹ and 0.05 mol mol^¹ the reduction can only be observed between 0 and 60 °C.

XXIV CTA content is given relative to monomer content.

MCR

-60 -30 0 30 60 90 0.0

0.2 0.4 0.6 0.8 1.0

 / °C

 3- li ne / (  3- li ne +  7- li ne)

Figure 5-13 The share of the 3-line spectrum is given as a function of temperature. Comparing polymerizations without CTA (squares) taken from ref.^[101] to those with addition of 0.02 mol mol^¹ CTA (circles) the 3-line spectra indicate no effect of CTA. Comparison with polymerizations, where 0.05 mol mol^¹ CTA (triangles) have been added, does not fully support this; there appears to be a slight lowering towards less 3-line signal.

Other than with PLP, continuous initiation ensures that radical concentration is (pseudo) stationary. Thus, eq. (2.18) can be used to analyze polymerization without CTA. For polymerizations with CTA, a transfer term, k_tr,CTA^t c_CTA, has to be added yielding eq. (5.25). Transfer to monomer may be ignored. Transfer to polymer was negligible because

x

_MCRdid not show any conversion dependence.

Backbiting as well as propagation of MCRs are independent of CTA. There are two effects of CTA that influence

x

_MCR. First, even small amounts of CTA reduce

MCR bb

MCR t t tt st

SPR MCR p M tr,CTA CTA 2 t MCR 2 t SPR bb

c k

x ^c c ^ k c k c  k c  k c k ^(5.25)

average chain length dramatically, which leads to higher k_t^st and k_t^tt. At this, the former coefficient is much higher, and thus crosstermination is the dominant reaction. Second, a new reaction pathway is opened. MCRs can transfer to the CTA, which initiates as follow-up reaction, thereby converting MCRs into SPRs.

-60 -30 0 30 60 90

0.0 0.2 0.4 0.6 0.8 1.0



/ °C

x

MCR

Figure 5-14 The mole fraction of mid-chain radicals during polymerization of BA (1.52 mol L^¹ in toluene) under continuous photoinitiation is shown as a function of temperature. The CTA reduces the fraction of MCRs; this effect increases with the amount of CTA, but the effect is small and not seen for every temperature. All data points are averages of multiple measurements. Squares: no CTA, circles: 0.02 mol mol^¹, triangles:

0.05 mol mol^¹. Statistical error is calculated as corrected sample standard deviation.

Data of polymerizations without ME is taken from ref.^[101]

At lower temperatures, backbiting and crosstermination are controlling for

x

_MCR. As the activation energy of the former is by 27.1 kJ mol^¹ higher, the fraction of MCRs increases with temperature. The higher rate of termination for polymerizations with CTA leads to the reduction of MCRs. The difference in

x

_MCR first increases then decreases again and disappears at ca. 60 °C. At higher temperature, termination loses importance compared to propagation of MCRs due to its 23.3 kJ mol^¹lower activation energy.[144,184,185] Moreover, at high temperature crosstermination

additionally loses importance, as there are only few SPRs left for termination with MCRs.

CCTA is approximately unity. In the system BA with thiols C_CTA^s is 1.5 and temperature independent.^[180] In general, chain-transfer constants exhibit no or very low activation energy. That means transfer becomes important when propagation becomes important. Hence, at high temperature, a reduction of

x

_MCR caused by increased transfer should be notable. This is not observed; the graphs merge at high temperature.

This phenomenon needs to be discussed in further detail. The two pathways reducing MCR concentration by transfer to CTA and by propagation are given by eq. (5.26) and eq. (5.27), respectively.

In order to estimate whether transfer is significant one has to look at the ratio of the two reaction rates. Doing so leads to eq. (5.28). With 0.01 mol mol^¹ CTA, the chain-transfer constant has to be 100 to get a chain-transfer rate as fast as propagation, which would be an uncommon value. To make transfer the dominant reaction an even higher value is needed.

Under the assumption that the long-chain approximation holds, eq. (5.29) is used to calculate the fraction of MCRs for 70 °C, a temperature, which lies in the region

The following Arrhenius parameters are used for calculation:^[144]

In Table 5-3 the difference between

x

_MCRwithout transfer to CTA and

x

_MCRwith transfer to CTA is given in percentage points. The log-chain approximation was used for calculation and, due to shorter chains, termination is higher for polymerization with CTA further decreasing

x

_MCR. Thus, the differences are only a minimum value.

In the experiment with the higher CTA concentration, a stronger effect is predicted.

As the effect is reduced by conversion, values at zero and 50 % conversion are given. . Within experimental accuracy, no conversion effect could be observed. Without transfer, a degree of monomer conversion of 0.9 would result in one percent point increase of

x

_MCR, eq. (5.29), which is within error range of

x

_MCR measurement.

At 70 °C, the measured difference of

x

_MCR between polymerization without CTA and with 0.02 mol mol^¹ CTA is 0.61 percentage points and between polymerization without CTA and with 0.05 mol mol^¹ CTA is 3.1 percentage points. Adding experimental error of 2 percentage points, which is more than twice the corrected sample standard deviation, gives 2.6 and 5.1, respectively. These values are already very close to 1.87 and 4.53, the calculated differences for C_CTA^t 10 and below 2.77 and 6.62, the calculated values for C_CTA^t 15. Besides, if the latter value of the constant were right, a notable conversion dependence would apply. Thus, C_CTA^t seems to be below 10 and is certainly below 15.

MCR t t bb

Table 5-3 The difference between xMCR without transfer to CTA to xMCR with transfer at 70 °C is given in percentage points. Long-chain approximation is made, thus calculated numbers are the minimum values. The initial value and the one at 50 % is given, because the value is a function of conversion (both monomer and CTA)

0.02 mol mol CTA^1 0.05 mol mol CTA^¹ X

CCTA ⁰ ^0.5 ⁰ ^0.5

1 0.19 0.11 0.47 0.27

5 0.94 0.53 2.32 1.31

10 1.87 1.05 4.53 2.59

15 2.77 1.57 6.62 3.83

100 15.72 9.57 31.09 20.76

200 26.74 17.37 46.13 34.03

300 34.88 23.86 54.99 43.25

By calibration with TEMPO, absolute radical concentrations can be obtained from the double integral of the EPR signal. The overall absolute radical concentrations for different conditions are given in Figure 5-15. Throughout the polymerization reaction, high stationary radical concentrations are observed. Addition of CTA causes a reduction of the radical concentration by about a factor of 3. The reduction does not increase linearly with CTA content. From 0.02 mol mol^¹ to 0.05 mol mol^¹ the reduction is only about 30 %.

The difference in radical concentration between the three reaction mixtures may, to some extent, be explained by the difference in

k

_t resulting from different chain lengths. GPC analysis of a sample from polymerization without CTA at 20 °C gave an M_n of 3.61 10 g mol ⁴ ^¹ (Ð = 2.2). Applying the Mayo equation, eq. (2.12), and assuming C_CTA^s 1.0, the addition of 0.02 mol mol^¹ CTA reduces chain length from 282 to 50. With _l 0.2 the composite model, eq. (2.34), yields an associated reduction of

k

_t by a factor of 1.4. According to eq. (2.6) steady-state radical concentration is proportional to the reciprocal square root of

k

_t. Thus, the reduction of

c

_R is by a factor of 1.2. Further reduction of the radical concentration may arise

from termination by CTA radicals. For polymerizations with a smaller rate of initiation and therefore a lower rate of termination leading to longer chains the impact of a CTA would be stronger. It would be interesting to do the same experiment with low radical concentration (10 mol L )^⁸ ^¹ , but these conditions are at present beyond EPR measuring range.

-60 -30 0 30 60 90

0 2 4 6

 / °C c

/ 1 0

6

mol L

1

Figure 5-15 Overall radical concentrations (SPRs and MCRs) of polymerizations with different concentrations of CTA are shown as a function of temperature. Black squares: no CTA, red circles: 0.02 mol mol^¹, blue triangles: 0.05 mol mol^¹. Data of polymerizations without ME is taken from ref.^[101]

The radical concentrations in the three reaction mixtures exhibit exactly the same temperature dependency. The radical concentration slightly increases with higher temperature. Then it increases from 0 to 30 °C, and afterwards decreases again, but slowly or stays constant.

The rate of initiation is the same, because in case of photoinitiation the energy for decomposition of initiator is not supplied thermally. Termination increases with temperature, but only slightly, as the activation energy of

k

_tis as low as

5.6 kJ mol .^1 [144,184,185] Hence, with a constant fraction of MCRs a slight decrease of the radical concentration with higher temperature would be expected, but this is not the case. In the temperature region under investigation a dramatic shift in

x

_MCR

takes place. Due to MCRs terminating more slowly, a higher fraction of MCRs allows for a higher radical concentration. The fact that the inflection points of the curves in Figure 5-14 and Figure 5-15 are at the same temperature also supports MCRs function of temperature scaled to the radical concentration at 20 °C. For comparison the fraction of midchain radicals is plotted in pink. (upper half filled squares: no CTA, right half filled circles: 0.02 mol mol^¹, lower half filled triangles: 0.05 mol mol^¹)

In order to better visualize both the relationship between radical concentrations during polymerization with different CTA content and how they are related to the fraction of MCRs, both quantities are plotted together in Figure 5-16. At this, radical concentration is scaled to the value at 20 °C which is near the inflection point. The radical concentration curves of the three reaction mixtures are on top of each other

and they are also (though somewhat more scattered) on top of the curves fir the MCR fraction.

The fact, that the three curves have, within experimental error, the same shape even though chain length of both MCRs and SPRs are quite different points towards MCRs and SPRs showing the same chain-length dependency of

k

_t.

In this subchapter it has been shown that the chain-transfer constant of MCRs cannot be significantly higher than the chain-transfer constant of SPRs.

Even without considering higher termination rate for polymerizations with CTA,

CCTA still cannot be above 15, which would be too low to make transfer of MCRs a major reaction pathway. Thus, effects so far attributed to high transfer of MCRs to CTA have to be explained differently, e.g., a reduction of -scission products may be the result of increased termination. Moreover, an enhancement of rate of polymerization may result from additional initiation by the thiol-ene reaction.

Furthermore, it was demonstrated how termination increases and overall radical concentration drops by a factor of three upon addition of 0.02 mol mol^¹ CTA.

However, the reduction of the fractions of MCRs by higher crosstermination is only small.

Im Dokument Kinetics and Modeling of the Radical Polymerization of Acrylic Acid and of Methacrylic Acid in Aqueous Solution (Seite 172-183)