Professional Documents
Culture Documents
pubs.acs.org/JPCC
ABSTRACT: Four R1R2Si(OMe)2 type compounds were added as an external electron donor (De) in propylene polymerization
with TiCl4/Di/MgCl2 type supported ZieglerNatta catalysts (Di = internal donor). Each polypropylene (PP) sample was
fractionated into three parts (atactic, medium-isotactic and isotactic PP), and the number of active centers ([C*]/[Ti]) in each
PP fraction was counted using 2-thiophenecarbonyl chloride as the quenching and tagging agent. The gradual decrease of [C*]/
[Ti] with De/Ti ratio is ascribed to competitive and reversible coordination of De on either central Ti of the active center or Mg
adjacent to the central Ti. The former coordination leads to deactivation of C*, and the latter one leads to still living C*. The
chain propagation rate constant (kp) of the active centers producing atactic, medium-isotactic and isotactic PP change with De/
Ti in dierent ways. Only the kp of active centers producing isotactic PP was evidently increased by De. Enhancement in
isotacticity of PP product is found to be a combined result of both deactivation of active centers by De and selective activation of
the active centers that produce isotactic PP. Changing the alkyl groups of R1R2Si(OMe)2 leads to an altered balance between the
deactivation and activation eects of De.
INTRODUCTION
The industrial production of more than 50 million tons of
type catalysts were treated with an AlR3/De mixture, most of
Di molecules in the catalyst were found to be quickly replaced
isotactic polypropylene (PP) each year is based on catalyzed by De, implying that the De plays more important roles in the
propylene polymerization with MgCl2-supported Ziegler polymerization system.4,14 The eects of De on stereoselectivity
Natta catalysts.1,2 Organic electron donors like esters, ethers, of active centers have been ascribed to reversible adsorption of
and alkoxysilanes are widely used in the catalyst preparation donor on metal atoms (Mg or Ti) neighboring the central Ti
and polymerization processes, which play key roles in metal of the active center. Busico et al. proposed a three-site
enhancing isotacticity and regulating molecular weight model to explain the eects of De on catalyst eciency and
distribution of the PP products.311 The electron donor polymer stereoregularity.19 In this model, successive adsorption
added in the process of catalyst preparation is called the of De on catalyst changes the stereochemical environment of
internal electron donor (Di), and the electron donor added in the active center, turning apsecic centers into isospecic
the polymerization process is called the external electron donor centers. A modied three-site model was proposed by Terano
(De). In recent decades, the most commonly used catalyst in et al.20 The mechanism of donor eects have also been studied
PP production contains phthalate as Di and alkoxysilane as De. based on investigation of the polymerization kinetics, including
With such catalysts, PP with high isotacticity and controllable the eects of donor on the number and propagation rate
molecular weight can be produced at very high catalysis constant of active centers.2629 Terano et al. investigated the
eciency.1 eects of both Di and De on the number and propagation rate
Since the discovery of TiCl4/Di/MgCl2AlR3/De type constant of dierent type of active centers based on stopped-
propylene polymerization catalysts in the early 1980s, great ow polymerization experiments.26,27 By using a 14CO tagging
eorts have been paid to disclosing and understanding the method, Bukatov et al. compared the number and propagation
mechanism of electron donor eects, with an aim of further rate constant of active centers of a series of catalysts containing
improving the chain structure of PP by applying new Di/De
combinations.340 The main role of Di has been proposed to Received: May 4, 2013
control the amount and spacial distribution of TiCl4 adsorbed Revised: June 29, 2013
on the MgCl2 crystallite surface.1214 When TiCl4/Di/MgCl2 Published: July 1, 2013
2013 American Chemical Society 15174 dx.doi.org/10.1021/jp404416n | J. Phys. Chem. C 2013, 117, 1517415182
The Journal of Physical Chemistry C Article
dierent Di and De.28,29 According to this literature, addition of were supplied by Linyi Lujing Chemical Co. (Shandong,
an external donor in the propylene polymerization system with China) and distilled before use.
MgCl2-supported ZieglerNatta catalysts causes a decrease in General Procedures of Polymerization. Propylene
the number of active centers ([C*]/[Ti]) and increase in the polymerizations were performed in a 150 mL Schlenk ask
chain propagation rate constant (kp). These results suggest that containing about 80 mL of n-heptane at 60 C under N2
deactivation of a part of active centers and properties alteration atmosphere. The reagents were added in the order of solvent,
of the remaining active centers happen in parallel when De is TEA, external electron donor (when needed), and the catalyst
added. However, because the changes of active centers number with [Ti] = 0.8 mmol/L and Al/Ti = 100 (mol/mol). After the
and propagation rate constant with De/Ti molar ratio have not catalyst was precontacted with TEA for 30 min, propylene gas
been experimentally determined, a detailed evaluation of the of 1 atm pressure was bubbled into the Schlenk ask for 4.5
donor eects and quantitative comparisons between dierent min. Then a TPCC toluene solution (in TPCC/Al = 2) was
external donors have not been reported before. injected into the reactor to quench the polymerization and
On the other hand, many theoretical studies on the stirred at 60 C for 5.5 min. Subsequently an ethanol/HCl
mechanism of donor eects have been reported in the past mixture (95/5) was added to decompose the catalyst, and the
ten years, using density functional theory (DFT) calculations as polymer was precipitated with excess of ethanol.
the main tool.4050 It has been proved by DFT calculation that Polypropylene was treated by reuxing the quenched
De molecules can coordinate on lateral cuts of MgCl2 polymer in excess of ethanol/HCl mixture for 60 min. Then
crystallites in the catalyst. Adsorption of the donor molecule the polymer was isolated, washed, dried and weighed. Each
on the adjacent positions of active sites increases their polymer sample was then thoroughly puried by one
stereospecicity and changes their intrinsic activity. However, dissolutionprecipitation operation, extracted with fresh
these conclusions are to be conrmed by more experimental ethanol in a Soxhlet extractor for 12 h, and then dried in
evidence. vacuum at 60 C.
In our previous works, we have developed a new method of Polymer Fractionation. Each puried polypropylene
counting active centers in propylene or ethylene polymerization sample was fractionated into three fractions in two steps. (1)
with ZieglerNatta catalysts using 2-thiophenecarbonyl About 2 g of PP was fully dissolved in 200 mL of boiling n-
chloride (TPCC) as a quenching agent.5153 The method octane, and then the solution was cooled to room temperature.
enables us to determine the number of active centers eciently. After the polymer was fully crystallized, the suspension was
Alkoxysilanes are widely used as De in industrial production of separated into the solution part and solid part by centrifuging.
isotactic PP with TiCl4/Di/MgCl2 type ZieglerNatta catalyst Polymer recovered from the solution part was named as n-
containing diester type Di. Previous studies show that the size octane soluble part (C8-sol). (2) The solid part was rst dried
of alkyl groups in alkoxysilane inuences the catalyst activity as in vacuum and then extracted with boiling n-heptane for 12 h in
well as the microstructure and the molecular weight character- a Soxhlet extractor. The boiling n-heptane soluble part (C7-sol)
istics of the PP product.19,54,55 However, inuence of De was recovered from the solution, and the n-heptane insoluble
structure on the active center distribution is scarcely reported. part (C7-ins) was collected from the sample holder. All three
In this paper, four dierent alkoxysilanes were used as De in fractions were dried in vacuum and weighed. Sulfur content of
TiCl4/Di/MgCl2Al(CH2CH3)3 catalyst for propylene poly- the fractions was also measured to count the number of active
merization. The changes of active centers number with the centers in each fraction. As proved by 13C NMR and DSC
addition of dierent alkoxysilanes in systems of propylene analysis, the C8-sol, C7-sol and C7-ins fractions are composed
polymerization with a TiCl4/Di/MgCl2 type ZieglerNatta of atactic PP (aPP), medium-isotactic PP (miPP), and isotactic
catalyst were determined. The eects of De on the catalytic PP (iPP) chains, respectively (see the Supporting Information
activity, isospecicity and the distribution of active centers will for the results of 13C NMR and DSC analysis on the fractions).
also be investigated. The aims of this work are to disclose the Characterization Methods. The sulfur content of the
details of donor eects and give more precise evaluation on the quenched polymer was measured in a GLC-200 micro-
performances of dierent De. A mechanistic model of the coulometry sulfur analyzer with a lower detection limit of
donor eect will be proposed. 0.05 ppm (Jiangyan Yinhe Instrument Co., Jiangyan, China).
EXPERIMENTAL SECTION
Chemicals. A commercial MgCl2-supported ZieglerNatta
The polymer sample for analysis was solid powder (24 mg,
weighed to 0.01 mg), and the average value of three parallel
measurements was taken as the sulfur content.
catalyst (MgCl2/Di/TiCl4, Ti content = 2.7 wt %, produced by Propagation rate constant (kp) of polymerization was
SINOPEC) containing a diol ester type Di was used for calculated according to the equation
polymerization. Propylene (polymerization grade, supplied by R p = k p[C*][M]
Yangzi Petrochemical Co., Nanjing, China) was puried by
passing through columns of molecular sieve and manganese- where Rp is the rate of polymerization calculated by dividing the
based deoxygen agent in a gas purication system made by polymer yield with polymerization time, [C*] is the
Dalian Samat Chemicals Co., Ltd. 2-Thiophenecarbonyl concentration of active center, and [M] is propylene
chloride (TPCC) was purchased from Alfa Aesar Co. and concentration.
distilled before use. Triethylaluminum (TEA, purchased from Thermal analysis of the PP fractions was performed on a TA
Albemarle Co.) was used as received and diluted in n-heptane Q100 thermal analyzer. The polymer (about 4 mg) was sealed
before use. n-Heptane was rst dried over 4A molecular sieves in aluminum pan, heated to 180 C at 10 K/min, kept at that
under dry N2 and then reuxed over Na before use. temperature for 5 min, and then cooled to 40 C at 10 K/min
Diisobutyldimethoxysilane (DIBDMS), cyclohexylmethyldime- and kept for 5 min. Then the sample was scanned from 40 to
thoxysilane (CHMDMS), dicyclopentyldimethoxysilane 180 C at a heating rate of 10 K/min, and the DSC trace was
(DCPDMS), and diisopropyldimethoxysilane (DIPDMS) recorded.
15175 dx.doi.org/10.1021/jp404416n | J. Phys. Chem. C 2013, 117, 1517415182
The Journal of Physical Chemistry C Article
Table 2. Inuence of De on the Number of Active Centers and Chain Propagation Rate Constants of Three Groups of Active
Centersa
atactic PP medium-isotactic PP isotactic PP
De [Ca*]/[Ti] (mol %) kpa (L/mol s) [Cm*]/[Ti] (mol %) kpm (L/mol s) [Ci*]/[Ti] (mol %) kpi (L/mol s)
none 0.21 68 0.79 80 1.12 304
DIBDMS 0.12 76 0.33 74 0.64 468
CHMDMS 0.10 59 0.35 69 0.70 365
DCPDMS 0.10 82 0.34 86 0.75 624
DIPDMS 0.12 49 0.27 62 0.35 661
a
Polymerization conditions of the PP samples are the same as those in Table 1.
a
Equilibrium constant K1 of De coordination on Ca*, Cm*, or Ci*; bEquilibrium constant K2 of De coordination on Ca*, Cm*, or Ci*.
Scheme 1. Coordination of De Molecule on a Mono-Ti Active Site Located on the (110) Lateral Cut of MgCl2 Crystallite
on the results of this work, the improvement of the polymer fractionated into three parts (aPP, miPP, and iPP) in the order
isotacticity (percentage of iPP fraction) by an external donor of increasing stereoregularity by simple dissolution and
can be largely attributed to the increase in kpi at a relatively high extraction. The number of active centers ([C*]/[Ti]) in all
De/Ti ratio. three fractions decreased with increasing De/Ti molar ratio
Considering the coordination of De molecule on a mono-Ti from 0 to 15, and the plateau value of [C*]/[Ti] that was
active site located on (110) lateral cut of MgCl2 crystallite, the
higher than 0 exists in all cases. Such a change in [C*] with
model of Scheme 1 may be plausible. In this model, the external
donor R2Si(OMe)2 can either coordinate to the central Ti and De/Ti can be reasonably depicted by a mechanistic model that
its adjacent Mg in chelate form, leading to deactivated center includes competitive and reversible coordination of a De
(b), or coordinate to two adjacent Mg in chelate form, leading molecule on either the central Ti of the active center or the Mg
to active center (c). These two kinds of De coordinated active adjacent to the central Ti. In this model, the former
centers are relatively stable because both of the two methoxy coordination leads to deactivation of C*, the latter one leads
groups of De have been xed. When a second De molecule to still active centers with altered kp values and isospecicity,
coordinates with Ti in active center (c), only the monodentate and coordination of another De on active centers that already
complex (d) can be formed. This monodentate De will be have an adsorbed De can be neglected. The equilibrium
easily removed by the cocatalyst. Therefore, formation of (d) constants of De coordination on either Ti (K1) or Mg (K2) for
can be neglected when the De concentration is not very high. three groups of active centers in polymerizations using four
There is another question concerning the above-mentioned
types of De were determined. The K1 values of all three groups
mechanistic model: why the stereoselectivity of Ci* can be
further improved by De, as Ci* already has high stereo- of active centers are larger than the K2 values, excepting the
selectivity in the absence of De? One possible reason is that equilibrium constants of De coordination on C*i when
diethylaluminum chloride (DEAC) formed by the reactions of DCPDMS was used as De. It means that De has a stronger
titanium species and TEA may coordinate on Mg adjacent to tendency to coordinate on the central Ti than the adjacent Mg,
the central Ti of active centers, and turning them into as the former has a larger Lewis acidity than the latter. The
isospecic centers (Ci*).20 When De is introduced in the much larger K2 value on Ci * of the DCPDMS system can be
system, it may replace the coordinated DEAC. Because the ascribed to a strong protection eect of the bulky cyclo-pentyl
coordination of De on Ci* is more stable than that of DEAC, groups on the adsorbed De.
the stereoselectivity of Ci* and its chain propagation rate The change in the kp value by De also disclosed important
constant will be further enhanced. information on the external donor eects. The kp values of
In summary, experimental data on changes of [C*] and kp
active centers producing atactic (Ca*) and medium-isotactic PP
with [De] disclose the coexistence of deactivation and
activation eects of De on the active centers. Enhancement (Cm*) only slightly changed with De/Ti ratio, but kpi increased
in the isotacticity of PP is a combined result of both temporary with De/Ti evidently. Meanwhile, the isotacticity of the iPP
elimination of three groups of active centers by De and fraction was increased by De, but those of the aPP and miPP
selective activation of the active centers that produce isotactic fractions were slightly lowered. It means that the catalysis
PP. properties of Ci * are inuenced by De in much larger extent
Article
ASSOCIATED CONTENT (11) Lou, J. Q.; Tu, S. T.; Fan, Z. Q. Polypropylene Chain Structure
Regulation by Alkoxysilane and Ether Type External Donors in TiCl4/
*
S Supporting Information
DIBP/MgCl2-AlEt3 Ziegler-Natta Catalyst. Iran. Polym. J. 2010, 19,
Experimental procedures of polymer purication and sulfur 927936.
content determination, conditions of 13C NMR analysis of (12) Busico, V.; Corradini, P.; Martino, L. D.; Proto, A.; Savino, V.;
polypropylene fractions, experiment data of fraction distribu- Albizzati, E. Polymerization of Propene in the Presence of MgCl2-
tion of the PP product and sulfur content of the fractions, Supported Ziegler-Natta Catalysts, 1. The Role of Ethyl Benzoate as
experimental data of the number and chain propagation rate Internal and External Base. Makromol. Chem. 1985, 186, 1279
constants of three groups of active centers, and results of DSC 1288.
and 13C NMR analysis on the three kinds of PP fractions. This (13) Albizzati, E.; Giannini, U.; Morini, G.; Galimberti, M.; Barino,
material is available free of charge via the Internet at http:// L.; Scordamaglia, R. Recent Advances in Propylene Polymerization
pubs.acs.org. with MgCl2 Supported Catalysts. Macromol. Symp. 1995, 89, 7389.
(14) Sacchi, M. C.; Tritto, I.; Shan, C. J.; Mendichi, R. Role of the
Pair of Internal and External Donors in Magnesium Chloride-
AUTHOR INFORMATION
Supported Ziegler-Natta Catalysts. Macromolecules 1991, 24, 6823
Corresponding Author 6826.
*E-mail: fanzq@zju.edu.cn. (15) Sacchi, M. C.; Fan, Z. Q.; Forlini, F.; Tritto, I.; Locatelli, P. Use
Notes of Different Alkoxysilanes as External Donors in MgCl2-Supported
Ziegler-Natta Catalysts to Obtain Propene/1-Butene Copolymers with
The authors declare no competing nancial interest.
(28) Bukatov, G. D.; Zakharov, V. A. Propylene Ziegler-Natta (45) Vanka, K.; Singh, G.; Iyer, D.; Gupta, V. K. DFT Study of Lewis
Polymerization: Numbers and Propagation Rate Constants for Base Interactions with the MgCl2 Surface in the ZieglerNatta
Stereospecific and Non-Stereospecific Centers. Macromol. Chem. Catalytic System: Expanding the Role of the Donors. J. Phys. Chem. C
Phys. 2001, 202, 20032009. 2010, 114, 1577115781.
(29) Bukatov, G. D.; Zakharov, V. A.; Barabanov, A. A. Mechanism of (46) Stukalov, D. V.; Zakharov, V. A.; Zilberberg, I. L. Adsorption
Olefin Polymerization on Supported Ziegler-Natta Catalysts Based on Species of Ethyl Benzoate in MgCl2-Supported ZieglerNatta
Data on the Number of Active Centers and Propagation Rate Catalysts. A Density Functional Theory Study. J. Phys. Chem. C
Constants. Kinet. Catal. 2005, 46, 166176. 2010, 114, 429435.
(30) Singh, G.; Kaur, S.; Makwana, U.; Patankar, R. B.; Gupta, V. K. (47) Taniike, T.; Terano, M. Coadsorption Model for First-Principle
Influence of Internal Donors on the Performance and Structure of Description of Roles of Donors in Heterogeneous ZieglerNatta
MgCl2 Supported Titanium Catalysts for Propylene Polymerization. Propylene Polymerization. J. Catal. 2012, 293, 3950.
Macromol. Chem. Phys. 2009, 210, 6976. (48) Credendino, R.; Pater, J. T. M.; Liguori, D.; Morini, G.; Cavallo,
(31) Makwana, U.; Naik, D. G.; Singh, G.; Patel, V.; Patil, H. R.; L. Investigating Alkoxysilane Coverage and Dynamics on the (104)
Gupta, V. K. Nature of Phthalates as Internal Donors in High and (110) Surfaces of MgCl2-Supported ZieglerNatta Catalysts. J.
Performance MgCl2 Supported Titanium Catalysts. Catal. Lett. 2009, Phys. Chem. C 2012, 116, 2298022986.
131, 624631. (49) Wondimagegn, T.; Ziegler, T. The Role of External Alkoxysilane
(32) Kissin, Y. V.; Liu, X. S.; Pollick, D. J.; Brungard, N. L.; Chang, Donors on Stereoselectivity and Molecular Weight in MgCl2-
M. Ziegler-Natta Catalysts for Propylene Polymerization: Chemistry of Supported ZieglerNatta Propylene Polymerization: A Density
Reactions Leading to the Formation of Active Centers. J. Mol. Catal. A: Functional Theory Study. J. Phys. Chem. C 2012, 116, 10271033.
Chem. 2008, 287, 4552. (50) Cheng, R. H.; Luo, J.; Liu, Z.; Sun, J. W.; Huang, W. H.; Zhang,
(33) Heikkinen, H.; Liitia, T.; Virkkunen, V.; Leinonen, T.; Helaja, M. G.; Yi, J. J.; Liu, B. P. Adsorption of TiCl4 and Electron Donor on
T.; Denifl, P. Solid State 13C NMR Characterisation Study on Fourth Defective MgCl2 Surfaces and Propylene Polymerization over Ziegler-
Generation ZieglerNatta Catalysts. Solid State Nucl. Magn. Reson. Natta Catalyst: A DFT Study. Chinese J. Polym. Sci. 2013, 31, 591600.
2012, 4344, 3641. (51) Shen, X. R.; Hu, J.; Fu, Z. S.; Lou, J. Q.; Fan, Z. Q. Counting the
(34) Lu, L.; Niu, H.; Dong, J. Y. Propylene Polymerization over Number of Active Centers in MgCl2-Supported ZieglerNatta
MgCl2-Supported TiCl4 Catalysts Bearing Different Amounts of a Catalysts by Quenching with 2-Thiophenecarbonyl Chloride and
Diether Internal Electron Donor: Extrapolation to the Role of Internal Study on the Initial Kinetics of Propylene Polymerization. Catal.
Electron Donor on Active Site. J. Appl. Polym. Sci. 2012, 124, 1265 Commun. 2013, 30, 6669.
1270. (52) Xia, S. J.; Fu, Z. S.; Liu, X. Y.; Fan, Z. Q. Copolymerization of
(35) Alshaiban, A.; Soares, J. B. P. Effect of Hydrogen and External Ethylene and 1-Hexene with TiCl4/MgCl2 Catalysts Modified by 2,6-
Donor on Propylene Polymerization Kinetics with a 4th-Generation Diisopropylphenol. Chin. J. Polym. Sci. 2013, 31, 110121.
Ziegler-Natta Catalyst. Macromol. React. Eng. 2012, 6, 265274. (53) Hu, J.; Han, B.; Shen, X. R.; Fu, Z. S.; Fan, Z. Q. Probing the
(36) Marques, M. F. V.; da Silva Cardoso, R.; da Silva, M. G. Roles of Diethylaluminum Chloride in Propylene Polymerization with
Preparation of MgCl2-Supported ZieglerNatta Catalyst Systems with MgCl2-Supported Ziegler-Natta Catalysts. Chin. J. Polym. Sci. 2013, 31,
New Electron Donors. Appl. Catal. A 2010, 374, 6570. 583590.
(37) Harding, G. W.; van Reenen, A. J. Polymerisation and (54) Harkonen, M.; Seppala, J. V.; Vaananen, T. Effects of the
StructureProperty Relationships of ZieglerNatta Catalyzed Iso- Structure of External Alkoxy Silane Donor in High Activity Ziegler-
tactic Polypropylenes. Eur. Polym. J. 2011, 47, 7077. Natta Catalyst on the Microstructure of Polypropylene. Stud. Surf. Sci.
(38) Vestberg, T.; Denifl, P.; Parkinson, M.; Wilen, C. E. Effects of Catal. 1990, 56, 87105.
External Donors and Hydrogen Concentration on Oligomer (55) Harkonen, M.; Seppala, J. V. External Silane Donors in Ziegler-
Formation and Chain End Distribution in Propylene Polymerization Natta Catalysis. An Approach to the Optimum Structure of the Donor.
with Ziegler-Natta Catalysts. J. Polym. Sci., Part A: Polym. Chem. 2010, Makromol. Chem. 1991, 192, 28572863.
48, 351358. (56) Gupta, V. K.; Satish, S.; Bhardwaj, I. S. Magnesium Dichloride
(39) Thushara, K. S.; Gnanakumar, E. S.; Mathew, R.; Jha, R. K.; Supported Titanium Catalyst System: Dimethoxypropane as an
Ajithkumar, T. G.; Rajamohanan, P. R.; Sarma, K.; Padmanabhan, S.; External Lewis Base. Eur. Polym. J. 1992, 28, 12691272.
Bhaduri, S.; Gopinath, C. S. Toward an Understanding of the (57) Fan, Z. Q.; Zhang, L. T.; Xia, S. J.; Fu, Z. S. Effects of Ethylene
Molecular Level Properties of ZieglerNatta Catalyst Support with as Comonomer on the Active Center Distribution of 1-Hexene
and without the Internal Electron Donor. J. Phys. Chem. C 2011, 115, Polymerization with MgCl2-Supported Ziegler-Natta Catalysts. J. Mol.
19521960. Catal. A 2011, 351, 9399.
(40) Brambilla, L.; Zerbi, G.; Piemontesi, F.; Nascetti, S.; Morini, G.
Structure of Donor Molecule 9,9-Bis(Methoxymethyl)-Fluorene in
Ziegler-Natta Catalyst by Infrared Spectroscopy and Quantum
Chemical Calculation. J. Phys. Chem. C 2010, 114, 1147511484.
(41) Yao, S.; Tanaka, Y. Theoretical Consideration of the External
Donor of Heterogeneous ZieglerNatta Catalysts Using Molecular
Mechanics, Molecular Dynamics, and QSAR Analysis. Macromol.
Theory Simul. 2001, 10, 850854.
(42) Seth, M.; Ziegler, T. Polymerization Properties of a
Heterogeneous Ziegler-Natta Catalyst Modified by a Base: A
Theoretical Study. Macromolecules 2003, 36, 66136623.
(43) Correa, A.; Piemontesi, F.; Morini, G.; Cavallo, L. Key Elements
in the Structure and Function Relationship of the MgCl2/TiCl4/Lewis
Base ZieglerNatta Catalytic System. Macromolecules 2007, 40, 9181
9189.
(44) Liu, B. P.; Cheng, R. H.; Liu, Z.; Qiu, P. Y.; Zhang, S. L.;
Taniike, T.; Terano, M.; Tashino, K.; Fujita, T. Experimental and
Computational Approaches on the Isospecific Role of Monoester-
Type Internal Electron Donor for TiCl4/MgCl2 Ziegler-Natta
Catalysts. Macromol. Symp. 2007, 260, 4248.