6. Olefin polymerization by zirconium enolatoimine complexes
6.4.5. Ethylene or propylene polymerization
Ethylene and propylene, respectively, polymerization was carried out under atmospheric pressure in a thermostated 500 mL double-mantle glass reactor equipped with a mechanical stirrer. Toluene (200 mL) was introduced into the nitrogen-purged reactor and stirred vigorously (500 rpm). The toluene was kept at the desired polymerization temperature, and then the ethylene gas feed was started. After 15 min, polymerization was initiated by the addition of a
reactor, such that the total volume of toluene in the reactor was 250 mL. After the desired reaction time, ethanol (5 mL) was added to terminate the polymerization reaction, and the ethylene gas feed was stopped. The reaction mixture was added to acidified methanol (1 mL of concentrated HCl in 500 mL of methanol). Solid polyethylene was recovered by filtration, washed with methanol, and dried at 50 °C for 24 h in a vacuum oven.
6.4.6. 1-Hexene polymerization
In the glove box, 500 eq. MAO (145 mg) was added to 5g 1-hexene in a Schlenk flask.
To this solution was added a dichloromethane solution of 5 µmol of the catalyst precursor 1b (3.4 mg), and the reaction was allowed to proceed with continuous stirring for the desired period of time. The polymerization was quenched with 5 mL of acidified (HCl) methanol. The polymer was extracted with hexane and dried under vacuum.
6.4.7. X-ray crystal structure determinations
The data collection was performed at 100 K on a STOE IPDS-II diffractometer equipped with a graphite-monochromated radiation source (λ = 0.71073 Å) and an image plate detection system. A crystal mounted on a fine glass fibre with silicon grease was employed. The selection, integration and averaging procedure of the measured reflex intensities, the determination of the unit cell dimensions by a least-squares fit of the 2Θ values, data reduction, LP-correction and space group determination were performed using the X-Area software package of the diffractometer. A semiempirical absorption correction was performed. The structure was solved by direct methods (SHELXS-97), completed with difference Fourier syntheses, and refined with full-matrix least-squares using SHELXL-97 minimizing w(Fo2 – Fc2)2. Weighted R factor (wR) and the goodness of fit S are based on F2; the conventional R factor (R) is based on F. All non-hydrogen atoms were refined with anisotropic displacement parameters. All scattering factors
and anomalous dispersion factors are provided by the SHELXL-97 program. The hydrogen atom positions were located in the difference Fourier map and refined isotropically.
Table 6-3. Details of the crystal structure determination of d.
formula C17 H22 F3 N O
Table 6-4. Details of the crystal structure determination of 1a.
formula C22 H18 Cl2 F6 N2 O2 Zr
Fw 618.50
cryst. size, mm 0.4 x 0.383 x 0.35
space group C2/c
a, Å 9.7961(6)
b, Å 14.0461(8)
c, Å 18.3236(12)
α, deg. 90.00
β, deg. 95.011(5)
γ, deg. 90.00
V, Å3 2511.6(3)
Z 4
δcalc, g cm-3 1.636
T, K 100
µ, mm-1 0.717
F(000) 1232
Θmax, deg. 28.06
No. of rflns measd. 18366
No. of unique rflns 3015
No. of rflns I > 2σ(I) 2643
R1, I > 2σ(I) a 0.0394
R1, all data 0.0473
wR2a 0.0736
diff. Fourier peak min./ max., e Å-3 -0.50/ 0.45
a R1 = Σ||F0-Fc||/ Σ|F0|, wR2 = [Σ(w(F02
-Fc2
)2)/Σ(w(F02
)2)]1/2
Table 6-5. Details of the crystal structure determination of 1b.
formula C22 H14 Cl2 F10 N2 O2 Zr
Fw 690.47
cryst. size, mm 0.38 x 0.36 x 0.35
space group C2/c
a, Å 10.313(9)
b, Å 13.317(1)
c, Å 19.161(2)
α, deg. 90.00
β, deg. 95.468(9)
γ, deg. 90.00
V, Å3 2619.8(5)
Z 4
δcalc, g cm-3 1.751
T, K 100
µ, mm-1 0.719
F(000) 1360
Θmax, deg. 26.84
No. of rflns measd. 17115
No. of unique rflns 2789
No. of rflns I > 2σ(I) 2428
R1, I > 2σ(I) a 0.0301
R1, all data 0.0386
wR2a 0.072
diff. Fourier peak min./ max., e Å-3 -0.81/ 0.36
a R1 = Σ||F0-Fc||/ Σ|F0|, wR2 = [Σ(w(F02
-Fc2
)2)/Σ(w(F02
)2)]1/2
Table 6-6. Details of the crystal structure determination of 1d.
formula C34 H42 Cl2 F6 N2 O2 Zr
Fw 786.82
cryst. size, mm 0.3 x 0.23 x 0.15
space group P-1
a, Å 11.652(3)
b, Å 11.781(2)
c, Å 13.684(2)
α, deg. 74.216(12)
β, deg. 82.723(17)
γ, deg. 86.135(17)
V, Å3 1791.9(6)
Z 2
δcalc, g cm-3 1.458
T, K 100
µ, mm-1 0.52
F(000) 808
Θmax, deg. 27.72
No. of rflns measd. 28369
No. of unique rflns 8067
No. of rflns I > 2σ(I) 6610
R1, I > 2σ(I) a 0.0364
R1, all data 0.0516
wR2a 0.0949
diff. Fourier peak min./ max., e Å-3 -0.69/ 0.74
a R1 = Σ||F0-Fc||/ Σ|F0|, wR2 = [Σ(w(F02
-Fc2
)2)/Σ(w(F02
)2)]1/2
Chapter 7
Synthesis and characterization of copolymers from ethylene and cyclopentene by an ortho-fluorinated
enolatoimine Ti complex
Abstract: The synthesis and characterization of ethylene/cyclopentene copolymers is reported.
Living polymerization of ethylene and cyclopentene with a catalyst derived from ortho-fluorinated bis(ketoenamine)titanium catalyst [(o-F2C6H3N=CMeCHC=CF3O)2TiCl2](1) yields copolymers with exclusive cis-1,2 cyclopentane units, high molecular weights and low polydispersities. The effects of cyclopentene concentration, ethylene pressure and reaction temperature on cyclopentene incorporation were determined; under appropriate reaction conditions up to 50 mol % cyclopentene were incorporated to afford a perfectly alternating iso-enriched copolymer ([rr]~ 0.51). The glass transition temperatures of the polymers were found to range from -26 °C (19 mol % cyclopentene) to 21 °C (50 mol % cyclopentene).
7.1. Introduction
Over the last two decades, the development of homogeneous catalysts for polymerization has rendered possible the synthesis of a broad range of macromolecules with tailored structures.
Catalysts are now accessible that allow control of polymer stereochemistry, molecular weight and composition.12a,39,134 However, it still remains challenging to synthesize ordered copolymers with e.g. block or alternating sequences, particularly in olefin polymerization. Living polymerization provides new routes to block copolymers by the sequential addition of monomer.94a One of the most appealing block copolymer structures are those with ‘‘hard’’ or semicrystalline end blocks (e.g. PE, iPP, sPP) and amorphous midblocks (e.g. aPP, poly (E-co-P), LLPE); triblock copolymers of this type have been shown to behave as thermoplastic elastomers.50,59,105,135
A generic route to alternating copolymers is polymerization with catalysts which are unable of homopolymerization of either monomers, but capable of cross-propagation.136 This method is rather rare owing to the little number of complexes known to feature such polymerization properties. An alternative for the synthesis of alternating polyolefins is the utilization of a catalyst where the rate of incorporation of one monomer is significantly greater than that of the other monomer. Increasing the concentration of the less readily polymerized monomer, alternating polymer is obtained in some cases provided that the consecutive insertion of the less favourable monomer is hindered or extremely slow.
Cycloolefin copolymers have been targeted as a new class of engineering plastics.137 According to the type of cycloolefin, the composition and sequence distribution of comonomers in the chain, polymers with various microstructures can be prepared. Random ethylene–
cycloolefin copolymers are amorphous glasses with a wide range of glass transition temperatures, from low to elevated temperatures. Therefore, these materials have promising characteristics as elastomers. Moreover, cycloolefin copolymers are of interest due to the
combination of thermal stability, good transparency, high refractive index, high stiffness or softness, chemical resistance and good processability.137a Although a number of cyclopentene-ethylene copolymerizations using several metallocene catalysts were performed recently, these copolymers have a mixed microstructure of 1,2- and 1,3-enchained cyclopentene units together with ethylene-ethylene and cyclopentene-cyclopentene monomer sequences.138
Recently, Coates and co-workers prepared and assigned the isotactic alternating ethylene–cyclopentene copolymer by an indirect route involving stereoselective ring-opening metathesis followed by hydrogenation; the observation of a melting point of 185 °C corroborates Natta’s assignment of this copolymer as the erythro-diisotactic alternating E–cP copolymer.139 More recently, highly alternating copolymers with isotactic 1,2-cyclopentene incorporation have been obtained employing a half-titanocene catalyst [Me2Si(Ind)(NtBu)]TiCl2. (Mn vs PS = 3.4 x 104 g mol-1, Mw/Mn = 1.9, TOF= 39 kg mol(Ti)-1 h-1).140
Given the established living nature of ethylene polymerization with fluorinated imineenolato-based titanium catalyst (chapter 4),105 the synthesis of alternating ethylene/cyclopentene copolymers with this catalytic system was studied.
7.2. Results and discussion
7.2.1. Cyclopentene/ethylene copolymerization
TiCl2 2 N
O F3C
F
F
+
MAO
1
Figure 7-1. Copolymerization of ethylene and cyclopentene using 1/MAO (polymer is
Copolymerization of cyclopentene and ethylene was carried out using 1 with MAO under a variety of conditions to yield ethylene/cyclopentene copolymers (Figure 7-1, Table 7-1).
Under 1 bar of ethylene, complex 1 copolymerizes cyclopentene (0.67 M) with ethylene to a random amorphous copolymer with a cyclopentene content of 14 mol % over 1h at 25 °C (Table 7-1, Entry 1). The number-average molecular weight Mn is ca. 2.6 x 105 g/mol. Furthermore, the polydispersity is extremely narrow (Mw/Mn = 1.03), consistent with the aforementioned living character of polymerization with 1. The melting point (Tm = 131 °C) is slightly lower than that of the polyethylene obtained in the absence of cyclopentene under otherwise identical conditions (139 °C) as a consequence of the incorporation of cyclopentene. Complex 1 displays a remarkable catalytic activity of 105 g mol (Ti)-1h-1 and a high degree of incorporation at low cyclopentene concentration. However, the yield of polymer decreased with decreasing ethylene concentration and increasing cyclopentene incorporation. (Table 7-1, entries 5-7, 9). This is due to the higher insertion rate of ethylene than that of cyclopentene. Overall, molecular weight distributions of the cyclopentene/ethylene copolymers (Mw/Mn = 1.03-1.43) are much narrower than conventional polymers that were obtained by homogeneous catalysts such as metallocenes.138,140,141
Table 7-1: Results of ethylene/cyclopentene copolymerization experiments with 1.[a] polyethylene standard. e 20 µmol of catalyst 1, 250 mL glass reactor. f Determined by GPC vs. polystyrene standards. g 20 µmol of [{F5C6N=CHC6H2(tBu)2O}2TiCl2], 250 mL glass reactor.
All polymers studied contain isolated cyclopentene units exclusively, in accordance with the rate of cyclopentene homopolymerization being very low. In addition, the cyclopentene units are incorporated solely via cis-1,2-enchainment between 0 and 40 °C as determined by 13C NMR. 142 It is known that cyclopentene-ethylene copolymers derived from metallocene catalysts show a significant amount of 1,3-enchainment of cyclopentene.138a,139 Using metallocene catalysts, the polymerization must be carried out with appreciable ethylene concentration in order to observe perfect 1,2-enchainment of cyclopentene units in the copolymers; under these conditions, cyclopentene incorporation is low.139 Cyclopentene incorporation, again determined by 13C NMR, correlates with the molar fraction of the comomer in the reaction mixture. In 13C NMR spectrum (Figure 7-2) of the polymer synthesized by 1 at a relatively high ethylene
29.1-30.1 ppm are due to the ethylene-ethylene sequences.
Figure 7-2. 13C NMR spectrum (100 MHz) of the cyclopentene-ethylene copolymer synthesized by 1/MAO (Table 7-1, entry 1).
The cyclopentene content increased up to 50 mol % by decreasing the ethylene pressure.
When the ethylene pressure was 0.11 bar and the concentration of cyclopentene is increased to 7.90 mol L-1, perfectly alternating cyclopentene-ethylene copolymer was formed (Figure 7-3;
Table 7-1, entry 9). Under identical reaction conditions in a comparative experiment, poly(ethylene-co-cyclopentene) with 29 mol % incorporation rate of cyclopentene was formed with a fluorinated bis(phenoxyimine)titanium catalyst [{F5C6N=CHC6H2(tBu)2O}2TiCl2]. By comparison, an alternating copolymer (47 %) is obtained with the phenoxyimine system only at much higher cyclopentene/ethylene ratios, with a low activity of 30 g mol-1 h-1 (Mn vs PS = 2.1 x 104 g mol-1, Mw/Mn = 1.34). 143 On the basis of the microstructural assignments of these polymers (vide supra), the alternating copolymers made prepared by 1/MAO are slightly isotactic, which leads to a melting point of 149 °C. The Tm of linear PE prepared with 1/MAO is
around 139°C. Increasing the cyclopentene portion in the polymer gave rise firstly to a disappearance of a sharp melting peak, determined by DSC, and at higher cyclopentene incorporation (XCPE = 36 mol %)subsequently a recurrence of a melting peak at >110 °C. The higher the cyclopentene content, the higher the melting point which is due to the slight preference of isotacticity of the cyclopentene-ethylene units. The Tg increased as well by increasing the incorporation of cyclopentene.
Figure 7-3: 13C NMR spectrum (100 MHz) of alternating cyclopentene-ethylene copolymer synthesized by 1/MAO (Table 7-1, entry 9).
The molecular weight distribution was narrow (Mw/Mn = 1.22, Figure 7-4), indicative of living polymerization. Another hint of the livingness of the catalyst system is that the polymer molecular weight determined (Mn = 8 x 103 g/mol) agrees within experimental error with the theoretical value calculated from the amount of polymer obtained and catalyst precursor employed (Mn(calc) = 9 x 103 g/mol). This shows that the catalyst precursor is rapidly converted to a single type of active species, chains are initiated simultaneously, and essentially no chain
contrast, it was reported that the fraction of active chains, estimated by the polymer yield, catalyst amount and Mn of the polymer, in ethylene/cyclopentene copolymerization using a fluorinated bis(phenoxyimine)titanium catalyst is less than 0.5.143
Figure 7-4. GPC profile of poly(ethylene-co-cyclopentene) obtained with complex 1 at 25 ºC (Table 7-1, entry 7, Mn = 8×103 g mol-1, Mw/Mn = 1.22).
In terms of the influence of polymerization temperature on the polymer properties, polymerizations at 25 °C and 40 °C under otherwise exactly identical conditions have been carried out (cf. Table 7-1, entries 7-8). At higher temperature, the catalyst showed a higher activity, but the molecular weight distribution was broader. Otherwise, the copolymers obtained exhibited similar characteristics; namely a similar incorporation rate of cyclopentene and comparable molecular weight Mn.
7.3. Summary and conclusion
The catalyst system [(o-F2C6H3N=CMeCHC=CF3O)2TiCl2] 1 /MAO promotes living copolymerization of ethylene with cyclopentene. This provides access to copolymers which cover a wide range of crystallinities, and glass transition and melt temperatures, as previously demonstrated for ethylene/ cyclopentene copolymers prepared with other catalysts.140,141,143
The system studied here appears useful for the preparation of perfectly alternating copolymers. By
comparison to related N^O-chelated phenoxyimine-based catalysts, cyclopentene competes better with ethylene for incorporation, and alternating copolymer can be obtained at lower cyclopentene/ethylene ratios and with significantly high catalyst activity. Also, all metal sites are active during the formation of the alternating copolymer. The material formed is iso-enriched, what is reflected by a Tm= 149 °C.
7.4. Experimental section
7.4.1. Materials and general considerations
All manipulations of air- and/or water-sensitive compounds were carried out under an inert atmosphere using standard glove box or Schlenk techniques. All glassware was flame-dried under vacuum before use. Toluene was distilled from sodium under argon. Complex 1 and the fluorinated phenoxyimine Ti complex were prepared according to published procedures.105,143 Methylalumoxane (MAO), purchased from Crompton as a 10 wt.-% solution in toluene, was evaporated to dryness at room temperature in vacuo, and stored as a solid white powder.
High-temperature NMR spectra of copolymers were recorded on a Varian Unity INOVA 400 spectrometer in 1,1,2,2-tetrachlorethane-d2 at 130 °C. 1H and 13C NMR chemical shifts were referenced to the solvent signal. A small amount of [Cr(acac)3] was added as relaxation aid.
Differential scanning calorimetry (DSC) was performed on a Netzsch Phoenix 204 F1 at a heating/cooling rate of 10 K min-1. DSC data reported are from second heating cycles. Polymer crystallinities were calculated based on a melt enthalpy of 293 J g-1 for 100% crystalline polyethylene. Gel permeation chromatography (GPC) was carried out in 1,2,4-trichlorobenzene at 160 °C at a flow rate of 1 mL min-1on a Polymer Laboratories 220 instrument equipped with Olexis columns with differential refractive index, viscosity and light scattering (15° and 90°) detectors. Data reported were determined via linear PE calibration (Mw < 30 000 g/mol),
g/mol) employing the PL GPC-220 software algorithm. As the instrument records light scattering at only two angles, data analysis involves an iteration for the calculation of molecular weights and form factors for each measured interval. The instrument was calibrated with narrow polystyrene and polyethylene standards. Data given is referenced to linear polyethylene.
7.4.2. Synthesis of poly(ethylene-co-cyclopentene)
Ethylene-cyclopentene copolymerization was carried out under varied pressure of ethylene in a 500 mL or 250 mL glass reactor equipped with a mechanical stirrer. Toluene and cyclopentene were introduced into the nitrogen-purged reactor and stirred vigorously (250 rpm).
The mixture was kept at the desired polymerization temperature, and then the ethylene gas feed was started. After 15 min, polymerization was initiated by the addition of a toluene solution of MAO followed by a toluene solution of catalyst precursor 1 into the reactor. After the desired reaction time, ethanol (5 mL) was added to terminate the polymerization reaction, and the ethylene gas feed was stopped. The reaction mixture was added to acidified methanol (1 mL of concentrated HCl in 500 mL of methanol). Depending on the cyclopentene content, viscose to solid copolymers were recovered by filtration, washed with methanol, and dried at 50 °C for 24 h in a vacuum oven.
8. Zusammenfassung
Die potenziellen Anwendungen eines Polymers werden durch seine physikalischen und mechanischen Eigenschaften bestimmt, die von der Morphologie des Polymers abhängen. Die Morphologie ergibt sich weitgehend aus der Zusammensetzung und Architektur des Polymers.
Die Entwicklung von Polymerisationen, die unter Kontrolle der Stereochemie und des Molekulargewichts und auch direkt bei der Polymerisation gebildeter Morphologien, verlaufen, ist daher eine seit langem bestehende wissenschaftliche Herausforderung.
Insbesondere was die Kontrolle des Molekulargewichts (ermöglicht durch lebende Polymerisation), der Verzweigungsstruktur und auch der Bildung nanoskaliger Polymerkristalle in wässrigen Systemen anbelangt, wurden in jüngster Zeit bedeutende Fortschritte mit Salicylaldiminato-Metallkomplexen erzielt.
In dieser Dissertation wurden die Polymerisationseigenschaften der strukturell verwandten chelatisierend koordinierender Enolatoimine (N^O) untersucht, welche elektronenziehende CF3C(O)-Gruppen tragen.
Im Kapitel 3 werden definierte Ni (II) Methyl Komplexe [(N^O)NiMe(L)] beschrieben, welche aufgrund sulfonierter oder Polyethylenglykol-substituierter labilen Liganden wasserlöslich sind. In wässrigen Systemen sind diese Komplexe Vorstufen für sehr stabile Katalysatoren, welche Ethylen bei erhöhten Temperaturen (70 °C) zu Dispersionen von Nanokristallen (≤ 30 nm) polymerisieren. Der Verzweigungsgrad und die daraus resultierende Kristallinität kann über das Substitutionsmuster der Enolatoimin-Liganden variiert werden.
Kapitel 4 berichtet über die Polymerisationseigenschaften von Titan-Komplexen [(N^O)2TiCl2]. Mit einem geeigneten ortho-F substituierten Enolatoimin-Liganden konnte lineares Polyethylen mit einer bislang unerreicht engen Molekulargewichtsverteilung von Mw/Mn = 1.01 und gleichzeitig einem hohen Molekulargewicht von > 105 g mol-1 erhalten werden. Darüber hinaus wurden engverteilte Blockcopolymere mit ataktischem Polypropylen
Komplexen geht mit der ineffizienten Aktivierung mit MAO einher.
Kapitel 5 handelt von der Synthese, der Strukturaufklärung und der Reaktivität der in Kapitel 4 beschriebenen Katalysator-Vorstufen. Für die hier verwendeten Enolatoimin-Liganden scheint die Reaktion der entsprechenden Ketoenamine mit [Ti(NMe2)2X2] zu den Amido-Komplexen [(N^O)2Ti(NMe2)X] (X= NMe2 oder Cl) eine besser geeignete Darstellungsmethode zu sein als die traditionelle Komplexierungsroute durch Reaktion eines deprotonierten N^O-Liganden mit TiCl4.
Kapitel 6 beschreibt die Darstellung, die Struktur und die Reaktivität der analogen Zirkonkomplexe [(N^O)2ZrCl2]. Nach der Aktivierung durch MAO polymerisieren diese Ethylen mit hoher Aktivität in einer „nicht-lebenden“ Weise. Sterisch anspruchsvolle Substituenten am N-aryl Rest der Enolatoiminliganden behindern die Aktivierung und/oder das Kettenwachstum in beträchtlichem Maße und in noch größerem Maße die Kettenübertragungstransfer, so dass Polymere mit sehr hohem Molekulargewicht erhalten werden.
Im Kapitel 7 werden die Synthese und die Charakterisierung der Copolymeren von Ethylen und Cyclopenten durch katalytische Polymerisation mit einem ortho-fluorinierten Enolatoimin-Ti Komplex und deren Mikrostruktur beschrieben. Copolymere mit hohem Molekulargewicht und ausschließlichem cis-1,2-Cyclopenten Einbau sowie sehr enger Molekulargewichtsverteilung konnten erhalten werden. Unter geeigneten Reaktionsbedingungen konnten 50 mol % Cyclopenten eingebaut werden unter Bildung eines alternierenden Copolymers mit leichter Präferenz für Isotaktizität.
9. Addendum
Chapter 3
Figure S1. GPC profile of polyethylene obtained with complex 1a at 30 °C (Table 3-1, entry 6).
Figure S2. DSC traces of isolated bulk polymer obtained with complex 1a at 30 °C (Table 3-1, entry 6, heating/cooling rate 10 K/min).
Figure S3. DSC traces of polyethylene dispersion obtained with complex 1a at 30 °C (Table 3-1, entry 6, heating/cooling rate 10 K/min).
Figure S4. DLS traces of polyethylene dispersion obtained with 1a at 30 °C (750 mg SDS, 40 bar ethylene, 10 µmol 1a), size average particle diameter (average of 4 runs) = 29 nm.
Figure S5. GPC profile of polyethylene obtained with complex 2b at 50 °C (Table 3-1, entry 12).
Figure S6. DSC traces of isolated bulk polymer obtained with complex 2b at 50 °C (Table 3-1, entry 12, heating/cooling rate 10 K/min).
Figure S7. DLS trace of polyethylene dispersion obtained with 2b at 50 °C (750 mg SDS, 40 bar ethylene, 10 µmol 2b), size average particle diameter (average of 5 runs) = 18 nm.
0 100 200 300 400 500 600
0,00 0,02 0,04 0,06 0,08 0,10 0,12 0,14 0,16 0,18 0,20 0,22 0,24 0,26 0,28 0,30 0,32 0,34 0,36
Consumption of ethylene [g/min]
time [min]
Figure S8. Mass-flow trace of the polymerization of ethylene with 2b at 50 °C and 40 bar ethylene pressure (Table 3-1, entry 12).
ppm (t1) 35.0 30.0 25.0 20.0 15.0
39,767 38,269 37,598 37,085 34,953 34,647 34,171 33,708 33,306 30,495 30,394 30,000 27,463 27,361 26,847 20,133 11,314
1B2
Figure S9. 13C NMR spectrum of polyethylene obtained with complex 1a at 30 °C (Table 3-1, entry 6, 100 MHz, solvent C2D2Cl4, T = 130 °C).
Figure S10. 13C NMR spectrum of polyethylene obtained with complex 2c at 50 °C; (Table 3-1, entry 13, 100 MHz, solvent C2D2Cl4, T = 130 °C).
Figure S11. Cryo-TEM images of polymer particles obtained with 1a at 50 °C (Table 3-1, entry 1).
Chapter 4
Figure S12. GPC profile of PE obtained with complex 3a at 25 °C; 15 min polymerization time (Table 4-1, entry 2, Mn = 2.7×105, Mw/Mn = 1.01).
Figure S13. DSC diagram of PE obtained with complex 3a at 25 °C; 1 h polymerization time (Table 4-1, entry 7, Mn = 9.9×105, Mw/Mn = 1.17).
0 3 6 9 12 15
Figure S14. Plots of Mn and Mw/Mn versus polymerization time for ethylene polymerization at a) 25 °C and b) 50 °C with complex 3a (reaction conditions:1atm ethylene pressure, 2 µmol for a) and 1 µmol for b) of 3a, 250 mL of toluene, 2000 eq. MAO (molar ratio)).
Figure S15. DSC diagram of PE-aPP-PE obtained with complex 3a at 25 °C (Table 4-2, entry 5, Mn = 3.0×105, Mw/Mn = 1.17).
Figure S16. DSC diagram of PE-EPR obtained with complex 3a at 25 °C (Table 4-2, entry 6, Mn = 7.3×105, Mw/Mn = 1.24).
Figure S17. DSC diagram of PE-EPR obtained with complex 3a at 25 °C (Table 4-2, entry 6, Mn = 7.3×105, Mw/Mn = 1.24).
Chapter 5
Figure S18. 1H NMR spectrum of 2d.
Table S1. Atomic coordinates (x 104) and equivalent isotropicdisplacement parameters (A2 x 103) for 1g.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________
x y z U(eq) ________________________________________________________________
F(1) 4230(3) 3470(1) 1402(1) 27(1) F(2) 350(3) 3666(1) 218(1) 29(1) F(3) 6942(2) 2259(1) 1161(1) 26(1) F(4) 5571(3) 2270(1) 2241(1) 29(1) F(5) 6105(3) 1008(1) -357(1) 29(1) F(6) -732(3) -1774(1) 1978(1) 42(1) O(1) -583(3) -165(1) 855(1) 19(1) F(7) 390(4) -539(2) 2793(1) 64(1) F(8) -3051(3) -410(2) 2161(1) 55(1) C(1) 3216(4) 2318(2) -52(1) 15(1) N(1) 2383(4) 1548(2) 480(1) 16(1) C(2) 4951(4) 2392(2) 1506(1) 19(1) C(3) 270(4) 35(2) 1506(1) 16(1) C(4) 3014(4) 1551(2) 1223(1) 15(1) C(5) 5087(4) 2038(2) -475(1) 18(1) C(6) 2181(4) 3374(2) -187(1) 19(1) C(7) 2060(4) 851(2) 1727(1) 17(1) C(8) 2955(5) 4135(2) -695(2) 24(1) C(9) 5920(5) 2765(2) -990(2) 21(1) C(10) 4854(5) 3817(2) -1093(2) 23(1) C(11) -774(5) -659(2) 2121(2) 22(1) ________________________________________________________________
Table S2. Bond lengths [Å] and angles [deg] for 1g.
C(9)-C(10)-C(8) 121.1(2) F(8)-C(11)-F(7) 109.0(2) F(8)-C(11)-F(6) 105.2(2) F(7)-C(11)-F(6) 105.3(2) F(8)-C(11)-C(3) 110.9(2) F(7)-C(11)-C(3) 114.2(2) F(6)-C(11)-C(3) 111.7(2)
_____________________________________________________________
Table S3. Anisotropic displacement parameters (A2 x 103) for 1g.
The anisotropic displacement factor exponent takes the form: -2 π2 [ h2 a*2 U11 + ... + 2 h k a*
b* U12 ]
_______________________________________________________________________
U11 U22 U33 U23 U13 U12 _______________________________________________________________________
F(1) 37(1) 15(1) 28(1) -4(1) 1(1) -2(1) F(2) 31(1) 27(1) 31(1) 2(1) 13(1) 13(1) F(3) 18(1) 33(1) 26(1) -3(1) 4(1) -4(1) F(4) 36(1) 36(1) 15(1) 1(1) -3(1) -14(1) F(5) 34(1) 21(1) 33(1) 6(1) 11(1) 15(1) F(6) 58(1) 27(1) 45(1) 9(1) 21(1) -3(1) O(1) 22(1) 21(1) 15(1) -1(1) 1(1) -1(1) F(7) 86(2) 83(2) 20(1) 14(1) -8(1) -54(1) F(8) 37(1) 64(1) 69(1) 38(1) 35(1) 24(1) C(1) 17(1) 15(1) 12(1) 0(1) 2(1) -3(1) N(1) 20(1) 14(1) 13(1) 1(1) 1(1) -3(1) C(2) 22(1) 21(2) 13(1) 1(1) 1(1) 1(1) C(3) 16(1) 15(1) 17(1) 2(1) 4(1) 3(1) C(4) 16(1) 14(1) 16(1) -1(1) 2(1) 5(1) C(5) 22(1) 15(1) 17(1) 1(1) 1(1) 3(1) C(6) 17(1) 22(1) 17(1) -3(1) 4(1) 5(1) C(7) 19(1) 18(1) 14(1) 1(1) 3(1) 1(1) C(8) 37(2) 16(1) 20(2) 1(1) 4(1) 4(1) C(9) 21(1) 25(2) 17(1) -1(1) 7(1) 0(1) C(10) 36(2) 20(1) 15(1) 1(1) 4(1) -6(1) C(11) 23(1) 21(2) 21(2) -1(1) 1(1) 0(1) _______________________________________________________________________
Table S4. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2 x 103) for 2b.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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Table S5. Bond lengths [Å] and angles [deg] for 2b.
N(4)-Ti(1)-N(3) 97.24(7)
N(2)-C(17)-C(18) 122.36(16)
Table S6. Anisotropic displacement parameters (A2 x 103) for 1g.
C(29) 27(1) 14(1) 26(1) -1(1) 10(1) -4(1) C(3) 19(1) 19(1) 19(1) 2(1) 4(1) 7(1) C(7) 20(1) 17(1) 16(1) -1(1) 4(1) 1(1) F(4) 35(1) 14(1) 33(1) 1(1) 11(1) -6(1) F(6) 33(1) 17(1) 45(1) -7(1) 20(1) 3(1) F(5) 30(1) 24(1) 31(1) -6(1) -4(1) -7(1) F(3) 29(1) 31(1) 27(1) 7(1) 4(1) 18(1) F(2) 38(1) 81(1) 54(1) 49(1) 24(1) 25(1) F(1) 62(1) 51(1) 31(1) -13(1) -22(1) 27(1) C(2) 14(1) 14(1) 20(1) 2(1) 1(1) 1(1) C(1) 25(1) 30(1) 20(1) 5(1) 5(1) 12(1) C(14) 20(1) 16(1) 24(1) -2(1) 6(1) -1(1) C(5) 31(1) 31(1) 18(1) 0(1) 9(1) 12(1) C(27) 17(1) 30(1) 30(1) -4(1) -3(1) 2(1) C(28) 25(1) 25(1) 21(1) 7(1) 4(1) 9(1) _______________________________________________________________________
Table S7. Atomic coordinates (x 104) and equivalent isotropicdisplacement parameters (A2 x 103) for 2b_Zr.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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Table S8. Bond lengths [Å] and angles [deg] for 2b_Zr.
N(3)-Zr(1)-N(4) 99.45(11)
C(9)-C(10)-C(11) 121.3(3) C(21)-C(26)-C(25) 117.5(3) C(21)-C(26)-C(28) 121.6(3) C(25)-C(26)-C(28) 120.9(3) C(10)-C(11)-C(6) 118.0(3) C(10)-C(11)-C(13) 119.8(3) C(6)-C(11)-C(13) 122.2(3) C(11)-C(6)-C(7) 122.2(3) C(11)-C(6)-N(1) 118.7(3) C(7)-C(6)-N(1) 119.1(3) C(9)-C(8)-C(7) 121.2(3) C(24)-C(23)-C(22) 121.2(3) O(1)-C(2)-C(3) 127.3(3) O(1)-C(2)-C(1) 112.7(3) C(3)-C(2)-C(1) 120.0(3) C(2)-C(3)-C(4) 125.2(3) F(1)-C(1)-F(3) 107.3(3) F(1)-C(1)-F(2) 106.5(3) F(3)-C(1)-F(2) 106.4(3) F(1)-C(1)-C(2) 111.4(3) F(3)-C(1)-C(2) 114.0(3) F(2)-C(1)-C(2) 110.9(3) F(6)-C(16)-F(5) 107.0(3) F(6)-C(16)-F(4) 107.4(3) F(5)-C(16)-F(4) 106.6(3) F(6)-C(16)-C(17) 113.9(3) F(5)-C(16)-C(17) 110.9(3) F(4)-C(16)-C(17) 110.8(3)
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Table S9. Anisotropic displacement parameters (A2 x 103) for 2b_Zr.
C(8) 32(2) 18(2) 14(2) 5(1) 10(1) 2(2) C(23) 21(2) 14(2) 28(2) 0(1) 12(1) 1(1) F(6) 36(1) 13(1) 28(1) 2(1) 9(1) -5(1) F(5) 38(1) 15(1) 48(1) -5(1) 24(1) 3(1) F(4) 36(1) 22(1) 26(1) -5(1) -5(1) -9(1) F(2) 56(2) 48(2) 25(1) -11(1) -20(1) 23(1) F(1) 33(1) 72(2) 45(1) 42(1) 16(1) 17(1) C(2) 15(2) 11(2) 16(2) 2(1) 0(1) 1(1) C(3) 15(2) 18(2) 17(2) 1(1) 1(1) 9(1) C(1) 22(2) 30(2) 18(2) 5(2) 2(1) 14(2) C(29) 32(2) 15(2) 31(2) -3(2) 13(2) -5(2) C(14) 19(2) 31(2) 29(2) -2(2) -4(1) 1(2) C(5) 30(2) 29(2) 15(2) 0(1) 9(1) 11(2) C(15) 24(2) 26(2) 20(2) 5(1) 3(1) 11(2) C(16) 22(2) 16(2) 23(2) 1(1) 7(1) -1(2) F(3) 25(1) 29(1) 24(1) 7(1) 1(1) 17(1) _______________________________________________________________________
Table S10. Atomic coordinates (x 104) and equivalent isotropicdisplacement parameters (A2 x 103) for 3b.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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Table S11. Bond lengths [Å] and angles [deg] for 3b.
O(2)-Ti(1)-O(1) 84.36(10)
F(5)-C(14)-F(6) 107.1(3)
F(4)-C(14)-F(6) 106.6(3) F(5)-C(14)-C(15) 113.2(3) F(4)-C(14)-C(15) 111.0(3) F(6)-C(14)-C(15) 111.2(3) C(6)-C(7)-C(8) 117.5(3) C(6)-C(7)-C(12) 122.7(3) C(8)-C(7)-C(12) 119.7(3) C(9)-C(10)-C(11) 121.5(4) N(2)-C(17)-C(16) 122.8(3) N(2)-C(17)-C(18) 121.9(3) C(16)-C(17)-C(18) 115.3(3) C(7)-C(6)-C(11) 121.6(3) C(7)-C(6)-N(1) 119.8(3) C(11)-C(6)-N(1) 118.5(3) C(15)-C(16)-C(17) 124.4(3) C(21)-C(22)-C(23) 120.0(4) C(9)-C(8)-C(7) 121.9(4) C(22)-C(21)-C(20) 121.6(4) C(8)-C(9)-C(10) 119.5(4) C(23)-C(24)-C(19) 118.2(3) C(23)-C(24)-C(26) 120.1(3) C(19)-C(24)-C(26) 121.7(3) C(22)-C(23)-C(24) 120.7(4)
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Table S12. Anisotropic displacement parameters (A2 x 103) for 3b.
Table S13. Atomic coordinates (x 104) and equivalent isotropicdisplacement parameters (A2 x 103) for 3c.
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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Table S14. Bond lengths [Å] and angles [deg] for 3c.
O(2)-Ti(1)-O(1) 165.93(10)
O(2)-C(13)-C(12) 112.6(3) C(14)-C(13)-C(12) 121.0(3) C(10)-C(9)-C(8) 121.0(3) F(3)-C(1)-F(1) 107.1(3) F(3)-C(1)-F(2) 107.3(2) F(1)-C(1)-F(2) 106.4(3) F(3)-C(1)-C(2) 111.3(3) F(1)-C(1)-C(2) 112.1(2) F(2)-C(1)-C(2) 112.3(3) F(9)-C(18)-C(19) 118.7(3) F(9)-C(18)-C(17) 117.4(3) C(19)-C(18)-C(17) 124.0(3) C(18)-C(17)-C(22) 114.7(3) C(18)-C(17)-N(2) 122.6(3) C(22)-C(17)-N(2) 122.6(3) C(22)-C(21)-C(20) 118.4(3) F(7)-C(12)-F(6) 107.3(3) F(7)-C(12)-F(8) 107.7(3) F(6)-C(12)-F(8) 106.5(3) F(7)-C(12)-C(13) 112.8(3) F(6)-C(12)-C(13) 111.8(2) F(8)-C(12)-C(13) 110.5(3) C(19)-C(20)-C(21) 120.1(3)
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Table S15. Anisotropic displacement parameters (A2 x 103) for 3c.
Chapter 6
0 5 10 15 20 25 30
0 5 10 15
ethylen flow (in ml/min)
time (in min)
Figure S19. Mass-flow traces for the polymerization of ethylene with 1c (Table 6-2, entry 10) in
Figure S19. Mass-flow traces for the polymerization of ethylene with 1c (Table 6-2, entry 10) in