ATRP up to High Pressure

ATRP of styrene (cf. chapter 5.1) catalyzed by chloro-substituted amine−bis(phenolate)iron complexes^86,87,241 (Figure 6.16) was investigated via online vis/NIR spectroscopy up to 6000 bar. Primary interest was directed toward the effect of pressure and temperature on KATRP and on the dispersity of the polymeric product.

As the catalyst is more readily handled in the higher Fe^III oxidation state, ATRPs of styrene were started in the reverse fashion (R-ATRP), as shown in Scheme 6.2, where alkyl halide and the Fe^II/L catalyst are produced in situ via decomposition of an azo initiator, R1N=NR1. The type of azo initiator was selected according to the targeted reaction temperature: 2,2'-azo-bis(4-methoxy-2,4-dimethyl valeronitrile) (V-70) was used for ATRPs between 70 and 90 °C, 2,2'-azo-bis(2,4-dimethyl valeronitrile) (V-65) at 100 and 110 °C, and 2,2′-azo-bis(2-methyl-propionitrile) (AIBN) at 120 °C. The differences in the temperature stability of these azo initiators thus provide rapid initiator decomposition at each polymerization temperature and allows for an immediate initiation of the chain-growth reaction.

The system under investigation consisted of the amine–

bis(phenolate)iron(III) chloride complex (Figure 6.16), Cl-Fe^III/L, and of 0.6 equiv of the azo initiator, R¹N=NR¹, in solution of styrene. The Cl-Fe^III/L concentration was monitored via the associated absorbance between 27 000 and 12 000 cm⁻¹ (Figure 6.17A). The spectra were

9 Reproduced with permission from Schroeder, H.; Buback, M.; Shaver, M. P. Macromolecules 2015, 48, 6114–6120, Copyright 2015 American Chemical Society.

Figure 6.16: Structure of the inves-tigated amine−bis(phenolate)iron(III) chloride catalyst.

6.4 Kinetics with Amine–bis(phenolate) Iron Complexes

135 Scheme 6.2: Reverse ATRP catalyzed by Cl-Fe^III/L and Fe^II/L complexes.

The starting materials are indicated in red. Polymerization is initiated by the decomposition of the thermal initiator, R1N=NR1. The structure of the primary radicals, R^1•, depends on the type of the thermal initiator and differs from the monomer-specific radicals, R^n•.

calibrated against the absorbance measured at known Cl-Fe^III/L content in the absence of the thermal initiator (dashed-dotted line in Figure 6.17A). After addition of the thermal initiator, this absorption almost entirely disappears due to the rapid reduction of Cl-Fe^III/L (fullred line). The initiator efficiency, i.e., the fraction of successful chain-initiation events, should be around 83 % at 120 °C, since 0.60 equiv of the azo initiator, i.e., 1.2 equiv of R¹ are required for the initial reduction of Cl-Fe^III/L. The formation of the reduced iron complex, Fe^II/L, was evidenced via Mössbauer spectroscopy as shown in chapter 5.1. During the subsequent polymerization, the Cl-Fe^III/L concentration increases with time according to the PRE.¹⁵⁵ Nine out of a multitude of recorded spectra are shown in Figure 6.17A for clarity.

The full Cl-Fe^III/L absorption band may be recorded via UV/VIS spectroscopy within the experiments at ambient pressure. The high-pressure equipment has been designed for FT-NIR spectroscopic studies and affords detection at wavenumbers up to 15 800 cm⁻¹ (cf. chapter 8.2), i.e., in the shaded area at wavenumbers below the one given by the dashed vertical line in Figure 6.17A. At 15 800 cm⁻¹, the Cl-Fe^III/L absorbance amounts to about one third of the intensity in the peak maximum, which is, however, sufficient to accurately determine Cl-Fe^III/L concentration in the high-pressure experiments, in particular, as increased optical path lengths were used to compensate for the

136 R-ATRP carried out at 90 °C and 1 bar starting with 14.5 mM Cl-Fe^III/L and 8.7 mM V-70 in solution of styrene/anisole (1:1, v/v). Cl-Fe^III/L concentration is measured between 27 000 and 12 000 cm⁻¹ at an optical path length of 0.5 mm. The initial spectrum (dashed-dotted line) was recorded in the absence of the thermal initiator. For better presentation, the intensity of this spectrum was reduced by a factor of three. (B) Styrene concentration monitored via the characteristic peak absorbance at around 6137 cm⁻¹ at an optical path length of 5 mm. The spectral series was recorded at 2000 bar

Monomer concentration was determined from the characteristic peak absorbance at around 6137 cm⁻¹, which is associated with the first overtone of the C–H stretching modes at an unsaturated carbon atom (Figure 6.17B). For clarity,only six out of a multitude of recorded spectra are shown in Figure 6.17B. The dashed line represents the reference spectrum for full conversion of styrene. A second autoclave104,166,167 with larger optical path length has been used for online NIR detection of ATRPs at pressures above 2000 bar. In this experimental setup, styrene concentration was monitored at around 8980 cm⁻¹ via the second overtone of C–H stretching modes at an unsaturated carbon atom.

The ln([M]⁰/[M]) vs time, t, traces for ATRPs of styrene carried out in bulk at 120 °C and pressures of 1, 1000, 2000 and 5000 bar are shown in

6.4 Kinetics with Amine–bis(phenolate) Iron Complexes

137 Figure 6.18: ln([M]0/[M]) vs t for ATRPs of styrene carried out at 120 °C and 1, 1000, 2000, and 5000 bar. The initial molar ratios of reagents were:

[Sty] : [Cl-Fe^III/L] : [R¹N=NR¹] = 1000 : 1.00 : 0.60 with the exception of the reaction at 5000 bar, where only 0.40 equiv R1N=NR1 have been employed.

Figure 6.18. The molar ratios of the reagents were: [Sty] : [Cl-Fe^III/L] : [R1N=NR1] = 1000 : 1.00 : 0.60, with the exception of the reaction at 5000 bar, where 0.40 equiv of R1N=NR1 relative to Cl-Fe^III/L were employed. After an initial reaction period, the increase in ln([M]⁰/[M]) vs t exhibits a straight-line behavior, which is indicative of a constant level of radical concentration.

At ambient pressure, radicals produced from styrene via self-initiation²⁸⁷ may compensate the loss of growing chains due to termination reactions, thus yielding linear ln([M]0/[M]) vs t traces over an extended time period (> 5h). Within the short duration of the high-pressure experiments, e.g., of about 40 min at 120 °C and 2000 bar, it was verified experimentally that the amount of radicals produced by self-initiation is negligible. Termination reactions and the simultaneous accumulation of Cl-Fe^III/L typically result in a slight curvature of ln([M]0/[M]) vs t such as seen for the data at 1000 bar. The observed linearity of the ln([M]0/[M]) vs t plots for 2000 and 5000 bar is thus assigned to the beneficial lowering of termination rate toward high pressure.^99-101

0 1 2 3 4 5

0.0 0.5 1.0

1.5 5000 bar

1 bar 1000 bar ln([M]0/[M])

time / h 2000 bar

138

ATRP is significantly accelerated toward higher pressure as is seen from the increase in the slope of the ln([M]0/[M]) vs t correlations, by about one order of magnitude, in passing from 1 to 2000 bar (cf.

Figure 6.18). This effect significantly exceeds the expected rate enhancement associated with the pressure dependence of k^p.⁹⁷ The additional rate enhancement must be due to the increase in [Rn•] with pressure (cf. Equation 6.21, chapter 6.3.2). [Rn•] may be estimated by rearranging Equation 6.21 to [R_n^]dln[M]/(k_pdt). The measured rate data, together with the known k^p(p), suggest that, in passing from 1 to 1000 and to 2000 bar, [R^n•] increases from 1.4  10⁻⁸ to 2.5  10⁻⁸ and 4.8  10⁻⁸ molL⁻¹, respectively, with these numbers being determined at 33 % monomer conversion. The ln([M]0/[M]) vs t trace at 5000 bar was recorded at a reduced ratio of initiator to Fe concentration to counterbalance the otherwise enormous pressure-induced rate enhancement. The adjustment was necessary to maintain a low degree of monomer conversion during the time interval required for reaching the targeted pressure and temperature and to provide sufficient time for online reaction monitoring.

The increase in [Rn•] with pressure is assigned to the enhancement of KATRP. The online spectroscopic analysis of both Fe^III concentration and monomer conversion allows for analyzing KATRP according to Equation 6.21.³⁶ The time-dependent concentrations of Fe^II and Rⁿ-Cl during the R-ATRP may be calculated from the relationship:

[Fe^II] = [Rⁿ-Cl] = [Fe^III]⁰−[Fe^III]. The propagation rate coefficient is known from pulsed-laser polymerization experiments up to 2800 bar.⁹⁷ The reported activation volume, Δ^‡V(kp) = (−12.1 ± 1.1) cm³mol⁻¹,⁹⁷ was used for estimating k^p up to 6000 bar.

Plotted in Figure 6.19 are the so-obtained values of lg(KATRP) vs pressure (red symbols). According to Equation 6.20, the reaction volume, Δ^rV, was deduced from the slope of the straight line to be (−17 ± 2) cm³mol⁻¹, reflecting an increase in K^ATRP by a factor of 20 upon increasing pressure from 1 to 6000 bar. Due to the simultaneous increase in kp, ATRP rates increase by two orders of magnitude within this extended pressure range. The simultaneous pressure-induced lowering of the termination rate allows for a high living character of amine–

bis(phenolate)iron-mediated ATRP.

The large negative ΔrV(KATRP) is assigned to the stronger contraction of the ligand sphere¹⁰⁴ of the Cl-Fe^III/L complex in solution, which may

6.4 Kinetics with Amine–bis(phenolate) Iron Complexes

139 Figure 6.19: lg(K^ATRP) vs pressure, p, for ATRPs of styrene at 120 °C mediated by either the amine–bis(phenolate)iron(III) catalyst (upper part) or by [FeCl⁴]⁻ (lower part) with TBA-Cl (black symbols) or HCl (gray symbols) being added for catalyst formation. Straight lines were fitted to the data.

be understood in terms of Cl-Fe^III/L being a stronger Lewis acid than Fe^II/L. The reaction volume is similar to the numbers reported for Cu-ligand ATRP systems,^102-104 where high pressure also shifts the ATRP equilibrium toward the metal species of higher charge, i.e., to Fe^III or Cu^II, respectively. The only exception to this behavior was the iron bromide system (see chapter 6.3) complexed by bromide and solvent molecules: [Fe^IIBru(Solv)v]^(2−u), which is due to the pressure-induced rearrangement of the Fe^II species.

In order to check whether the iron chloride complexes [Fe^IIClu(Solv)v]^(2−u) exhibit the same behavior as the bromide complexes, and to enable a direct comparison of K^ATRP with the amine–

bis(phenolate)iron catalyst, ^Cl,Cl,NMe2[O²NN']FeCl, ATRPs of styrene were conducted with iron chlorides in the absence of a specific ligand. The reactions were carried out at 120 °C and pressures between 1 and 2500 bar with the following initial molar ratio of reagents in solution of DMF (33 vol%): [Sty] : [EClPA] : [FeCl²] : [TBA-Cl] = 200 : 1.00 : 1.00 : 1.00, where EClPA is ethyl α-chlorophenylacetate and TBA-Cl is tetrabutylammonium chloride. TBA-Cl provides the additional chloride for the formation of the catalyst species, [Fe^IICl3(Solv)]⁻ and [Fe^IIICl4]⁻,

0 1000 2000 3000 4000 5000 6000 -8

-7 -6 -5

w. TBA-Cl w. HCl 120 °C

lg (KATRP)

p / bar 120 °C

140 TBA-Cl and HCl, respectively. Based on relative KATRP, TBA-Cl seems to be the more effective chloride source than HCl in organic media.

The experiments at elevated pressure demonstrate that the

Cl,Cl,NMe2[O2NN']FeCl catalyst does not undergo any competing solvent coordination or undesirable complex rearrangements. The amine–

bis(phenolate) ligand affords Fe catalysis with enhanced K^ATRP. It was found that ATRP using this catalyst system may be carried out in bulk and in anisole solutions without any effect on KATRP. The reaction enthalpy of ATRP with ^Cl,Cl,NMe2[O2NN']FeCl is 25 ± 5 kJ mol⁻¹ (Figure 6.20) and thus considerably below the enthalpy of 58 kJ mol⁻¹ measured for ATRP of MMA with iron halides.¹⁰⁵ The temperature and pressure dependence of K^ATRP for ^Cl,Cl,NMe2[O²NN']FeCl deduced from the styrene polymerization experiments is given by Equation 6.22.

 

( /bar 1)

The effect of pressure on the dispersity of the polymeric product is also of interest. For this purpose, another series of ATRP experiments were carried out using a simultaneous reverse & normal initiation (SR&NI) principle: In addition to alkyl halide formation by in situ reduction of Cl-Fe^III/L with a thermal initiator, the alkyl halide initiator, EClPA, was added to the system. ATRPs were conducted at 120 °C in solution of anisole (25 vol%) with an identical initial molar ratio of reagents at all investigated pressures: [Sty]:[Cl-Fe^III/L]:[EClPA]: [R¹N=NR¹]=300:1.00:1.00:0.13. The SR&NI methodology was used because the small amount of thermal initiator means that only about

6.4 Kinetics with Amine–bis(phenolate) Iron Complexes

141 Table 6.10: Equilibrium constants, K^ATRP, at 1 bar and 120 °C, reaction enthalpy, ΔrH, and reaction volumes, ΔrV, for styrene ATRP mediated by the indicated catalyst.

entry Fe^III catalyst KATRP ΔrH / ΔrV / at 120 °C / 1 bar kJ mol⁻¹ cm³ mol⁻¹

1 ^Cl,Cl,NMe2[O2NN']FeCl 6.8 × 10⁻⁷ 25 ± 5 −17 ± 2

2 [TBA][FeCl⁴] 1.5 × 10⁻⁷ - 17 ± 3

3 [H³O][FeCl⁴] 3.5 × 10⁻⁸ - 18 ± 3

Figure 6.20: lg(KATRP) vs T⁻¹ for the ATRP of styrene at 120 °C mediated by ^Cl,Cl,NMe2[O²NN']FeCl. A straight line was fitted to the data with the slope yielding the reaction enthalpy, Δ^rH = 25 ± 5 kJmol⁻¹.

20 % of Cl-Fe^III/L is converted to Fe^II/L. This provides a high Cl-Fe^III/L deactivator concentration throughout the entire ATRP reaction. The excess of EClPA as compared to Fe^II/L essentially yields polymer with a high degree of chain-end functionality. Listed in Table 6.11 are the experimental and theoretical molar masses, M^n,SEC and M^n,theo, respectively, and the dispersity, Ɖ, of polystyrene samples produced between 1 and 6000 bar. The experimental molar masses are in

0.0026 0.0027 0.0028 0.0029 -6.7

-6.6 -6.5 -6.4 -6.3

-6.2 _rH = (25 5) kJmol^1

lg (K ATRP)

T^1 / K^1

142

Table 6.11: Experimental and theoretical molar masses, M^n,SEC and Mn,theo, respectively, and dispersity, Ɖ, of polystyrene produced at different pressures and up to the indicated degree of monomer conversion.^[a]

p / bar

conv. /

%

Mn,SEC / gmol⁻¹

Mn,theo /

gmol^{−1 [a]} Ɖ

1 38 9400 9880 1.18

2000 37 9100 9620 1.21

3000 39 9300 10140 1.20

4000 45 10000 11700 1.22

5000 38 8600 9880 1.24

6000 54 11400 14040 1.28

[a] Conditions: [Sty] : [Cl-Fe^III/L] : [EClPA] : [R¹N=NR¹] = 300 : 1.00 : 1.00 : 0.13, styrene : anisole = 3:1 (v/v), 120 °C. M^n,theo = [Sty]⁰ / ([EClPA]⁰ + [R¹N=NR¹]⁰ × 1.7) × M(Sty) × conversion + M(EClPA).

reasonable or even excellent agreement with the theoretical values. It is particularly gratifying to note that, despite the enormous rate enhancement toward higher pressure, ATRP may still be operated in a well-controlled fashion at 6000 bar with the dispersity being Ɖ = 1.28.

Nevertheless dispersity increases from 1.18 to 1.28 in passing from 1 to 6000 bar (Figure 6.21). The associated broadening of the molar-mass distribution is illustrated in Figure 6.22. This effect is attributed to a relative lowering of deactivation to propagation rate toward higher pressure. The situation may be similar to the one with Cu-based ATRP systems, for which the activation volume, Ea(kdeact), was found to be close to zero,²⁷ whereas propagation rate is strongly enhanced. The consequences of such relative changes in deactivation to propagation rate are more vigorous at lower Cl-Fe^III/L content: An ATRP started with 2 mM Cl-Fe^III/L occurs in a controlled fashion (Ɖ < 1.3) at ambient pressure, whereas the dispersity in ATRP at 5000 is significantly affected by lowering initial Cl-Fe^III/L concentration from 22 mM to 8 mM and 2 mM, which yields an increase in dispersity from Ɖ = 1.24 to 1.50 and to

> 2.5, respectively.

6.4 Kinetics with Amine–bis(phenolate) Iron Complexes

143 Figure 6.21: Dispersity as a function of pressure of polystyrene synthesized via ATRP (see text). The dashed line serves the purpose of guiding the eye.

Figure 6.22: SEC-derived molar-mass distributions (MMDs) of polystyrene produced via ATRP (see text) at 120 °C and pressures from 1 to 6000 bar. The MMDs were scaled to identical area under the curves.

Applying high pressure turns out to be helpful once

Cl,Cl,NMe2[O²NN']FeCl is used at further optimized conditions: To reach higher degrees of polymerization and thus higher molar masses, the concentration of growing chains and thus of ATRP initiator needs to be reduced. Such ATRPs are more feasible under high pressure due to the

0 1000 2000 3000 4000 5000 6000 1.0

1.2 1.4

p / bar

Ð

10³ 10⁴ 10⁵

6000 bar 1 bar 4000 bar

molar mass 2000 bar

144

beneficial lowering of termination rate. E.g., a number-average molar mass Mn = 103,000 g mol⁻¹ (Ɖ = 1.4) was obtained after only 1 h by carrying out an R-ATRP of styrene at 120 °C and 5000 bar with 2 mM AIBN as the single initiator.

After this detailed kinetic study into styrene ATRP mediated by

Cl,Cl,NMe2[O²NN']FeCl, other monomers should be investigated along the same lines. The reported reaction volumes for a variety of Cu–ligand systems were found to be almost independent of the type of propagating radical and of the associated alkyl halide,^102-104 despite the differences in absolute KATRP.44,102,103,201,233

Im Dokument Metal-Catalyzed Radical Polymerization up to High Pressure (Seite 138-148)