Article

pubs.acs.org/JPCC

Mechanism of Propylene Polymerization with MgCl2Supported

ZieglerNatta Catalysts Based on Counting of Active Centers: The
Role of External Electron Donor
Xian-rong Shen, Zhi-sheng Fu, Jie Hu, Qi Wang, and Zhi-qiang Fan*
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang
University, Hangzhou 310027, China
*
S Supporting Information

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
isotactic polypropylene (PP) each year is based on catalyzed
propylene polymerization with MgCl2-supported Ziegler
Natta catalysts.1,2 Organic electron donors like esters, ethers,
and alkoxysilanes are widely used in the catalyst preparation
and polymerization processes, which play key roles in
enhancing isotacticity and regulating molecular weight
distribution of the PP products.311 The electron donor
added in the process of catalyst preparation is called the
internal electron donor (Di), and the electron donor added in
the polymerization process is called the external electron donor
(De). In recent decades, the most commonly used catalyst in
PP production contains phthalate as Di and alkoxysilane as De.
With such catalysts, PP with high isotacticity and controllable
molecular weight can be produced at very high catalysis
eciency.1
Since the discovery of TiCl4/Di/MgCl2AlR3/De type
propylene polymerization catalysts in the early 1980s, great
eorts have been paid to disclosing and understanding the
mechanism of electron donor eects, with an aim of further
improving the chain structure of PP by applying new Di/De
combinations.340 The main role of Di has been proposed to
control the amount and spacial distribution of TiCl4 adsorbed
on the MgCl2 crystallite surface.1214 When TiCl4/Di/MgCl2
type catalysts were treated with an AlR3/De mixture, most of
Di molecules in the catalyst were found to be quickly replaced
by De, implying that the De plays more important roles in the
polymerization system.4,14 The eects of De on stereoselectivity
of active centers have been ascribed to reversible adsorption of
donor on metal atoms (Mg or Ti) neighboring the central Ti
metal of the active center. Busico et al. proposed a three-site
model to explain the eects of De on catalyst eciency and
polymer stereoregularity.19 In this model, successive adsorption
of De on catalyst changes the stereochemical environment of
the active center, turning apsecic centers into isospecic
centers. A modied three-site model was proposed by Terano
et al.20 The mechanism of donor eects have also been studied
based on investigation of the polymerization kinetics, including
the eects of donor on the number and propagation rate
constant of active centers.2629 Terano et al. investigated the
eects of both Di and De on the number and propagation rate
constant of dierent type of active centers based on stopped-
ow polymerization experiments.26,27 By using a 14CO tagging
method, Bukatov et al. compared the number and propagation
rate constant of active centers of a series of catalysts containing
Received: May 4, 2013
Revised: June 29, 2013
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
dierent Di and De.28,29 According to this literature, addition of
an external donor in the propylene polymerization system with
MgCl2-supported ZieglerNatta catalysts causes a decrease in
the number of active centers ([C*]/[Ti]) and increase in the
chain propagation rate constant (kp). These results suggest that
deactivation of a part of active centers and properties alteration
of the remaining active centers happen in parallel when De is
added. However, because the changes of active centers number
and propagation rate constant with De/Ti molar ratio have not
been experimentally determined, a detailed evaluation of the
donor eects and quantitative comparisons between dierent
external donors have not been reported before.
On the other hand, many theoretical studies on the
mechanism of donor eects have been reported in the past
ten years, using density functional theory (DFT) calculations as
the main tool.4050 It has been proved by DFT calculation that
De molecules can coordinate on lateral cuts of MgCl2
crystallites in the catalyst. Adsorption of the donor molecule
on the adjacent positions of active sites increases their
stereospecicity and changes their intrinsic activity. However,
these conclusions are to be conrmed by more experimental
evidence.
In our previous works, we have developed a new method of
counting active centers in propylene or ethylene polymerization
with ZieglerNatta catalysts using 2-thiophenecarbonyl
chloride (TPCC) as a quenching agent.5153 The method
enables us to determine the number of active centers eciently.
Alkoxysilanes are widely used as De in industrial production of
isotactic PP with TiCl4/Di/MgCl2 type ZieglerNatta catalyst
containing diester type Di. Previous studies show that the size
of alkyl groups in alkoxysilane inuences the catalyst activity as
well as the microstructure and the molecular weight character-
istics of the PP product.19,54,55 However, inuence of De
structure on the active center distribution is scarcely reported.
In this paper, four dierent alkoxysilanes were used as De in
TiCl4/Di/MgCl2Al(CH2CH3)3 catalyst for propylene poly-
merization. The changes of active centers number with the
addition of dierent alkoxysilanes in systems of propylene
polymerization with a TiCl4/Di/MgCl2 type ZieglerNatta
catalyst were determined. The eects of De on the catalytic
activity, isospecicity and the distribution of active centers will
also be investigated. The aims of this work are to disclose the
details of donor eects and give more precise evaluation on the
performances of dierent De. A mechanistic model of the
donor eect will be proposed.
EXPERIMENTAL SECTION
Chemicals. A commercial MgCl2-supported ZieglerNatta
catalyst (MgCl2/Di/TiCl4, Ti content = 2.7 wt %, produced by
SINOPEC) containing a diol ester type Di was used for
polymerization. Propylene (polymerization grade, supplied by
Yangzi Petrochemical Co., Nanjing, China) was puried by
passing through columns of molecular sieve and manganese-
based deoxygen agent in a gas purication system made by
Dalian Samat Chemicals Co., Ltd. 2-Thiophenecarbonyl
chloride (TPCC) was purchased from Alfa Aesar Co. and
distilled before use. Triethylaluminum (TEA, purchased from
Albemarle Co.) was used as received and diluted in n-heptane
before use. n-Heptane was rst dried over 4A molecular sieves
under dry N2 and then reuxed over Na before use.
Diisobutyldimethoxysilane (DIBDMS), cyclohexylmethyldime-
thoxysilane (CHMDMS), dicyclopentyldimethoxysilane
(DCPDMS), and diisopropyldimethoxysilane (DIPDMS)
15175
Article
were supplied by Linyi Lujing Chemical Co. (Shandong,
China) and distilled before use.
General Procedures of Polymerization. Propylene
polymerizations were performed in a 150 mL Schlenk ask
containing about 80 mL of n-heptane at 60 C under N2
atmosphere. The reagents were added in the order of solvent,
TEA, external electron donor (when needed), and the catalyst
with [Ti] = 0.8 mmol/L and Al/Ti = 100 (mol/mol). After the
catalyst was precontacted with TEA for 30 min, propylene gas
of 1 atm pressure was bubbled into the Schlenk ask for 4.5
min. Then a TPCC toluene solution (in TPCC/Al = 2) was
injected into the reactor to quench the polymerization and
stirred at 60 C for 5.5 min. Subsequently an ethanol/HCl
mixture (95/5) was added to decompose the catalyst, and the
polymer was precipitated with excess of ethanol.
Polypropylene was treated by reuxing the quenched
polymer in excess of ethanol/HCl mixture for 60 min. Then
the polymer was isolated, washed, dried and weighed. Each
polymer sample was then thoroughly puried by one
dissolutionprecipitation operation, extracted with fresh
ethanol in a Soxhlet extractor for 12 h, and then dried in
vacuum at 60 C.
Polymer Fractionation. Each puried polypropylene
sample was fractionated into three fractions in two steps. (1)
About 2 g of PP was fully dissolved in 200 mL of boiling n-
octane, and then the solution was cooled to room temperature.
After the polymer was fully crystallized, the suspension was
separated into the solution part and solid part by centrifuging.
Polymer recovered from the solution part was named as n-
octane soluble part (C8-sol). (2) The solid part was rst dried
in vacuum and then extracted with boiling n-heptane for 12 h in
a Soxhlet extractor. The boiling n-heptane soluble part (C7-sol)
was recovered from the solution, and the n-heptane insoluble
part (C7-ins) was collected from the sample holder. All three
fractions were dried in vacuum and weighed. Sulfur content of
the fractions was also measured to count the number of active
centers in each fraction. As proved by 13C NMR and DSC
analysis, the C8-sol, C7-sol and C7-ins fractions are composed
of atactic PP (aPP), medium-isotactic PP (miPP), and isotactic
PP (iPP) chains, respectively (see the Supporting Information
for the results of 13C NMR and DSC analysis on the fractions).
Characterization Methods. The sulfur content of the
quenched polymer was measured in a GLC-200 micro-
coulometry sulfur analyzer with a lower detection limit of
0.05 ppm (Jiangyan Yinhe Instrument Co., Jiangyan, China).
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.
Propagation rate constant (kp) of polymerization was
calculated according to the equation
R p = k p[C*][M]
where Rp is the rate of polymerization calculated by dividing the
polymer yield with polymerization time, [C*] is the
concentration of active center, and [M] is propylene
concentration.
Thermal analysis of the PP fractions was performed on a TA
Q100 thermal analyzer. The polymer (about 4 mg) was sealed
in aluminum pan, heated to 180 C at 10 K/min, kept at that
temperature for 5 min, and then cooled to 40 C at 10 K/min
and kept for 5 min. Then the sample was scanned from 40 to
180 C at a heating rate of 10 K/min, and the DSC trace was
recorded.
dx.doi.org/10.1021/jp404416n | J. Phys. Chem. C 2013, 117, 1517415182
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Table 1. Polymerization Results in the Presence of Dierent External Donorsa

external donor activity (kg PP/gTi h) C7-ins (wt %) C7-sol (wt %) C8-sol (wt %) [C*]/[Ti] (mol %) kp (L/mol s)
none 3.30 81.3 15.3 3.4 2.12 197
DIBDMS 2.63 90.0 7.4 2.6 1.09 306
CHMDMS 2.26 89.5 8.4 2.1 1.15 249
DCPDMS 3.97 92.6 5.8 1.6 1.18 425
DIPDMS 2.02 91.3 6.5 2.2 0.74 348
a
The conditions of the polymerization and quenching reaction are described in the experimental part. The external donor was added in Si/Ti = 5.

RESULTS AND DISCUSSION

Eect of External Electron Donors on Behavior of
Propylene Polymerization. The results of propylene
polymerization catalyzed by MgCl2-supported ZieglerNatta
catalysts with dierent external electron donors are shown in
Table 1. The introduction of De caused a decrease in
polymerization activity excepting DCPDMS. All four external
donors enhanced the isotacticity (percentage of boiling n-
heptane insoluble fraction) of PP. The isotacticity of PP
decreased in the order of DCPDMS (92.6%) > DIPDMS
(91.3%) > DIBDMS (90.0%) and CHMDMS (89.5%). It
means the bulkier the alkyl substituents of alkoxysilane are, the
higher the isotacticity is. It is still dicult to explain such
relationship between the bulkiness of De and its ability to
improve isotacticity. A generally accepted mechanism is that
alkoxysilane can complex with both the active sites and the
cocatalyst (TEA in this work). Bulky substituents on
alkoxysilane are required to prevent the De from leaving the
catalyst surface through complexation with the cocatalyst.
Bearing two bulky cyclopentyl groups, DCPDMS caused the
largest extent of isotacticity improvement among the four
external donors.
The inuence of external donor on the productivity of three
PP fractions is shown in Figure 1. The activity of centers that
Figure 1. Inuence of De on the activity of three groups of active
centers (conditions of polymerization are the same as Table 1).
produce iPP was enhanced by addition of DCPDMS, whereas
in other cases, the productivities of the PP fractions were all
lowered by De. The deactivation eect of De may be attributed
to a marked decrease in the number of active centers (see Table
1). It can be seen that quite a large portion of active centers are
deactivated by the added De.
By measuring sulfur content of the PP fractions, the number
of active centers that produce iPP, miPP, and aPP chains were
determined, and the chain propagation rate constants of the
three groups of active centers were calculated (see Table 2). It
is clear that number of all the three groups of active centers was
more or less reduced by addition of De, among which the active
center that produces miPP (Cm*) experienced the largest
extent of reduction. On the other hand, the propagation rate
constant (kp) of the active center that produces iPP (Ci*) was
markedly enhanced by De, meanwhile kp of the other two
groups of active centers (Cm* and Ca*) were unchanged or
only slightly lowered. The three groups of active centers show
dierent responses to addition of De in the polymerization
system. The behavior of Ci* is especially dierent from that of
Cm* and Ca*.
Eects of De Concentration on Propylene Polymer-
ization. To further disclose the mechanism of external donor
eects, detailed studies on the inuences of Si/Ti molar ratio
on propylene polymerization were conducted. Figure 2a shows
the change of polymerization activities with increase of De
concentration. With increase in Si/Ti molar ratio, the activity
decreased when CHMDMS, DIBDMS, and DIPDMA were
added as De, whereas that of activity containing DCPDMS
slightly increased. Similar deactivation eects of other types of
De have been reported in literatures,21,56 and activation of
propylene polymerization by DCPDMS has also been reported
in literature.23
Figure 2b shows the change of active center concentration
with the Si/Ti ratio. It is seen that each kind of De caused
marked reduction of [C*], and the extent of [C*] reduction
tends to level o when a large amount of De is added. Among
the four types of external donors, DCPDMS caused the
smallest extent of [C*] reduction. For the other three donors,
more than one-half of active centers were killed when the Si/Ti

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.

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Figure 2. Changes of polymerization activity (a) and the number of

active centers (b) with Si/Ti in the presence of dierent external
donors.
Figure 3. Inuence of CHMDMS and DCPDMS on fraction
distribution of the PP product.
ratio was larger than 15. It seems that the disappearance of a
part of the active centers is the main reason for Des
deactivation eects on propylene polymerization.
In addition to the decrease of the total polymerization
activity with Si/Ti ratio, the productivity of iPP was found to
increase with an increase in the Si/Ti ratio (see Figure 3). Each
De showed similar trends of enhancing iPP productivity with
rising Si/Ti ratio, meanwhile lowering the productivities of
miPP and aPP chains (see the Supporting Information for the
data of fraction distribution when DIBDMS and DIPDMS were
the De). Among the four donors, DCPDMS showed the
strongest ability to improve isotacticity of PP.
Changes of the number of three groups of active centers
(Ci*, Cm*, and Ca*) with donor concentration have also been
determined. Figure 4 shows the inuences of Si/Ti ratio on
[Ci*]/[Ti], [Cm*]/[Ti], and [Ca*]/[Ti] when CHMDMA and
DCPDMS are used as De. Data of the systems containing
DIBDMS and DIPDMS can be found in Supporting
Information. The number of all three groups of active centers
decreased with increase of external donor concentration. There
are similarities between the [Cm*]/[Ti] vs Si/Ti and [Ca*]/
[Ti] vs Si/Ti curves of systems containing dierent De, but the
[Ci*]/[Ti] vs Si/Ti curve of the systems containing CHMDMS
and DCPDMS is quite dierent. CHMDMS caused a much
larger reduction in [Ci*] than DCPDMS. It means that the
active centers producing isotactic PP are more sensitive to the
molecular structure of the external donor.
Using the data of [Ci*], [Cm*], and [Ca*] and activity of Figure 4. Inuence of CHMDMS and DCPDMS on the number of
three groups of active centers, chain propagation rate constants three groups of active centers ([C*] = [Ci*], [Cm*], or [Ca*]; dots:
of each group of active centers were calculated. Figure 5 shows experimental data, lines: tting of the experimental data).
changes of kpi, kpm, and kpa with Si/Ti ratio for the systems
containing CHMDMA and DCPDMS. Data of the systems
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the survived active centers is also changed by the added donor,

Figure 5. Inuence of CHMDMS and DCPDMS concentration on
chain propagation rate constants of three groups of active centers (kp
represents kpi, kpm or kpa).
containing DIBDMS and DIPDMS as De can be found in the
Supporting Information. It is seen that kp of the active centers
producing atactic and medium-isotactic PP only slightly
changed with an increase in the Si/Ti ratio, but kpi markedly
increased with the Si/Ti ratio. It also means that the active
centers producing isotactic PP are more sensitive to the
interaction of external donor than the active centers producing
atactic and medium-isotactic PP. By comparing Figure 5 to
Figures 4 and 3, one can nd that the increase in kpi is the main
reason for the increase of iPP content with De concentration.
Mechanism of External Donors Interaction with
Active Centers. Summing up the results presented above, it
can be found that the external donor interacts with the active
centers in a rather complicated way. All three groups of active
centers are partly deactivated by the donor, but the extent of
deactivation rises with De concentration rather slowly.
Considering that the concentration of De is 50 times higher
than that of the active centers, it means that the donor cannot
deactivate the active centers eciently. The intrinsic activity of
which might be correlated with the disappearance of
deactivated centers. To simplify the situation, the law of active
center deactivation with De concentration will be analyzed rst.
To explain the eects of De in improving isospecicity of the
catalyst, Busico et al. proposed a three-site model, in which
reversible adsorption of De molecules on Mg atoms adjacent to
Ti atoms of the active centers can turn aspecic centers into
isospecic ones.19 However, this model cannot explain the
deactivation eect of De on a part of active centers as reported
in this work. To include Des deactivation eect in the
mechanistic model, we propose the following competitive
equilibriums which occur in catalyst system containing external
donor:
K1 K2
De C1* De + C* De C2*
Inactive Active (1)
In these equilibrium equations, C* is active center that has not
been coordinated by a De molecule, DeC1* is active center
that is deactivated by De, and DeC2* is active center that is
coordinated by a De molecule but remain active. Considering
that an active center has at least one vacant position for
monomer coordination, there should be high tendency of De
coordination at these vacant positions. On the other hand,
coordination of De on Mg atoms adjacent to the central Ti of
an active center may retain or enhance its activity, meanwhile
improve its stereospecicity. If the coordinated active centers
DeC2* cannot be deactivated by coordination of another De
molecule, the equilibrium constants of the two reversible
coordination of De on C* in eq 1 can be expressed as follows:
[De C1*] [De C2*]
K1 = K2 =
[De][C*] [De][C*] (2)
As DeC1* is unable to form a propagation chain, it is
reasonable to assume that [DeC1*] is not included in the
experimentally determined active center concentration ([C*]e).
Both the uncoordinated active centers (C*) and DeC2*
produce polymer chains and can be counted into [C*]e
measured by the quenching experiment, namely
[C*]e = [C*] + [De C2*] (3)
According to this model, [DeC1*] should equal to the reduced
active center concentration in the presence of De
[De C1*] = [C*]o [C*]e (4)
([C*]o is the measured active center concentration in the
absence of De). When eqs 24 are combined, the following
equations can be obtained:
[C*]e
[C*] =
1 + K 2[De] (5)

Table 3. Equilibrium Constants of De Coordination on Three Groups of Active Centers

Ca* Cm * Ci *
De K1aa (L/mol) K2ab (L/mol) K1ma (L/mol) K2mb (L/mol) K1ia (L/mol) K2ib (L/mol)
DIBDMS 310 390 1730 900 350 170
CHMDMS 310 245 695 500 350 180
DCPDMS 310 260 685 350 670 1050
DIPDMS 310 290 1680 530 860 180

a
Equilibrium constant K1 of De coordination on Ca*, Cm*, or Ci*; bEquilibrium constant K2 of De coordination on Ca*, Cm*, or Ci*.

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[C*]o [C*]e in isospecicity of Ci* by coordination of De on Mg adjacent to

K1 = (1 + K 2[De]) the central Ti. As the Si/Ti ratio increases, fraction of the active
[De][C*]e (6)
centers with higher isospecicity increases, leading to higher
[C*]e 1 chain propagation constant. Chain propagation constant of -
= + K 2/K1 olen polymerization with supported Z-N catalyst has been
[C*]o [C*]e K1[De] (7) found to be roughly proportional to the isotacticity of
Checking eq 7 using the experimental data of [C*]o, [C*]e, polymer.57 The much higher propagation rate constant of Ci*
and [De], a good linear relationship between [C*]e/([C*]o than Ca* and Cm* (see Figure 5) is also an evidence for this
[C*]e) and 1/[De] has been observed. This means that the correlation. Such positive correlation between k p and
gradual decreases of [C*]e with Si/Ti ratio in Figure 4 is very isotacticity should be related with slower chain propagation
likely to be the result of the above-mentioned competitive two- after a stereochemical mistaken insertion. As an evidence to this
way coordination of De on the active centers. By tting the explanation, melting temperature of the iPP fraction was found
experimental data according to eq 7, the two equilibrium to be higher in the presence of De (see Table 4), namely, the
constants K1 and K2 of each group of active centers were isospecicity of Ci*was improved.
determined and listed in Table 3.
The data in Table 3 show that in most cases the equilibrium Table 4. Thermal Properties of PP Fractions Obtained in the
constant K1 representing the ability of De to deactivate active Presence of Dierent External Donora
centers is larger than K2 representing the ability of De to
medium-isotactic
modify stereospecicity of the active centers. Considering that atactic PP PP isotactic PP
the central Ti atoms bearing coordination vacancies are more
H Tm H Tm H Tm
electron decient than their adjacent Mg atoms, such a De (J/g) (C) (J/g) (C) (J/g) (C)
phenomenon is quite expectable. It means that deactivation of a none 26.7 114.0 85.7 144.3 97.8 159.7
part of active centers by De is inevitable even if only a small DIBDMS 12.7 103.2 79.7 141.2 98.7 164.0
amount of De is added in the system. CHMDMS 13.8 100.9 78.7 142.2 98.5 163.7
Judging by the equilibrium constants, DCPDMS, the external DCPDMS 7.7 98.5 80.8 142.0 102.6 163.9
donor bearing the bulkiest alkyl substituents, still shows DIPDMS 8.4 101.0 82.5 142.4 95.7 165.0
unusual properties as compared to the other three donors. a
The K2i value of catalyst system containing DCPDMS is The PP samples in this table are synthesized in the same conditions
as those of Table 1.
evidently higher than the K1i value, meaning that its active
centers Ci* can be more eciently protected through
coordination of De on their adjacent Mg atoms, resulting in With regard to the aPP and miPP fractions, their propagation
lower extent of reduction in [Ci*]. This may be related with the rate constants are slightly lowered or nearly unchanged by the
ability of bulky cyclopentyl groups to shield the coordinated added De (see Figure 5). Meanwhile their isotacticity becomes
DCPDMS from leaving the active center through coordination lower as compared to that of the sample produced without De
with TEA. Complexation of De with the cocatalyst has been (see Table 4). This could mean that coordination of De on Ca*
well recognized and considered in explaining the external donor or Cm* cannot lead to improvement in their isospecicity.
eects.6 It is interesting to nd that bulky R groups in However, there is another possible reason. As mentioned
R2Si(OMe)2 type De also enhanced the K1i value. Both previously, active center with low steric hindrance has relatively
DCPDMS and DIPDMS show much higher K1i than those of smaller K1 value. It is highly possible that either Ca* or Cm* is
DIBDMS and CHMDMS. Though the K1i value of DIPDMS is composed of more than one types of active center. When they
even higher than that of DCPDMS, its K2i value is still low. It meet the De molecules, those centers with relatively bulkier
seems that larger R groups are needed to eectively protect environment will be deactivated more than those having smaller
Des coordination on the adjacent Mg than on the central Ti steric hindrance. As a result, the survived centers are those
atom. having lower isospecicity.
It can be seen that the K1m value is larger than K1a and K1i As mentioned in the Introduction, the widely accepted three-
values for all four De systems in Table 3. It implies that among site model suggests that the stereochemical environment of the
the three groups of active centers the one that produces active centers are changed by successive adsorption of De on
medium-isotactic PP chains can be deactivated by De most catalyst, leading to transformation of the apsecic centers into
easily. This can be explained by the medium steric hindrance in isospecic centers.19 If this mechanism applies to the systems
the chemical environment of Cm* among the three groups of studied in this work, Ca* will be turned into Cm* and Cm* be
active centers. When the steric hindrance is low (the situation turned into Ci* as the De/Ti ratio increases. In other words,
of Ca*), though De can access the central Ti easily, there will be [Ci*] should decrease with De/Ti ratio much more slowly than
still plenty of space for TEA to access the inactive DeC1* and [Ca*] and [Cm*], because most of Cm* will join the Ci* group
remove the adsorbed De. In the case of Ci*, its large steric in the presence of De. However, as seen in Figure 4, the
hindrance will prevent the De molecule from approaching the decreases of [Ca*], [Cm*], and [Ci*] with Si/Ti ratio are
central Ti, leading to lower a K1i value. The dierences between roughly parallel with each other. In fact, when CHMDMS is
K1 values of Ca*, Cm*, and Ci* cause a quicker decrease in the used as De, the decrease of [Ci*] at De/Ti = 15 is even larger
amount of miPP fraction with Si/Ti than that of aPP fraction than that of [Cm*] (see Figure 4). Therefore, it is more
(see Table 1 and Figure 3). reasonable to say that transformations of Ca* into Cm* and
The change of propagation rate constant with De Cm* into Ci* did not happen in large scale. However, the
concentration can also be rationalized based on the competitive possibility of active center transformation by De in small scale
two-way coordination model. The marked increase of kpi with cannot be ruled out, as partial transformation of Ca* and Cm*
De concentration (Figure 5) can be attributed to improvement will not signicantly change the [C*] De/Ti proles. Based
15179 dx.doi.org/10.1021/jp404416n | J. Phys. Chem. C 2013, 117, 1517415182
The Journal of Physical Chemistry C
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
isotacticity (percentage of iPP fraction) by an external donor
can be largely attributed to the increase in kpi at a relatively high
De/Ti ratio.
Considering the coordination of De molecule on a mono-Ti
active site located on (110) lateral cut of MgCl2 crystallite, the
model of Scheme 1 may be plausible. In this model, the external
donor R2Si(OMe)2 can either coordinate to the central Ti and
its adjacent Mg in chelate form, leading to deactivated center
(b), or coordinate to two adjacent Mg in chelate form, leading
to active center (c). These two kinds of De coordinated active
centers are relatively stable because both of the two methoxy
groups of De have been xed. When a second De molecule
coordinates with Ti in active center (c), only the monodentate
complex (d) can be formed. This monodentate De will be
easily removed by the cocatalyst. Therefore, formation of (d)
can be neglected when the De concentration is not very high.
There is another question concerning the above-mentioned
mechanistic model: why the stereoselectivity of Ci* can be
further improved by De, as Ci* already has high stereo-
selectivity in the absence of De? One possible reason is that
diethylaluminum chloride (DEAC) formed by the reactions of
titanium species and TEA may coordinate on Mg adjacent to
the central Ti of active centers, and turning them into
isospecic centers (Ci*).20 When De is introduced in the
system, it may replace the coordinated DEAC. Because the
coordination of De on Ci* is more stable than that of DEAC,
the stereoselectivity of Ci* and its chain propagation rate
constant will be further enhanced.
In summary, experimental data on changes of [C*] and kp
with [De] disclose the coexistence of deactivation and
activation eects of De on the active centers. Enhancement
in the isotacticity of PP is a combined result of both temporary
elimination of three groups of active centers by De and
selective activation of the active centers that produce isotactic
PP.
CONCLUSIONS
Adding an R1R2Si(OMe)2 type external electron donor (De) in
TiCl4/Di/MgCl2 type supported ZieglerNatta catalysts
caused either decreases or increases the propylene polymer-
ization activity, which is a combined result of the reduction in
the number of active centers and enhancement in the chain
propagation rate constant (kp). The PP product can be
15180
Article
fractionated into three parts (aPP, miPP, and iPP) in the order
of increasing stereoregularity by simple dissolution and
extraction. The number of active centers ([C*]/[Ti]) in all
three fractions decreased with increasing De/Ti molar ratio
from 0 to 15, and the plateau value of [C*]/[Ti] that was
higher than 0 exists in all cases. Such a change in [C*] with
De/Ti can be reasonably depicted by a mechanistic model that
includes competitive and reversible coordination of a De
molecule on either the central Ti of the active center or the Mg
adjacent to the central Ti. In this model, the former
coordination leads to deactivation of C*, the latter one leads
to still active centers with altered kp values and isospecicity,
and coordination of another De on active centers that already
have an adsorbed De can be neglected. The equilibrium
constants of De coordination on either Ti (K1) or Mg (K2) for
three groups of active centers in polymerizations using four
types of De were determined. The K1 values of all three groups
of active centers are larger than the K2 values, excepting the
equilibrium constants of De coordination on C*i when
DCPDMS was used as De. It means that De has a stronger
tendency to coordinate on the central Ti than the adjacent Mg,
as the former has a larger Lewis acidity than the latter. The
much larger K2 value on Ci * of the DCPDMS system can be
ascribed to a strong protection eect of the bulky cyclo-pentyl
groups on the adsorbed De.
The change in the kp value by De also disclosed important
information on the external donor eects. The kp values of
active centers producing atactic (Ca*) and medium-isotactic PP
(Cm*) only slightly changed with De/Ti ratio, but kpi increased
with De/Ti evidently. Meanwhile, the isotacticity of the iPP
fraction was increased by De, but those of the aPP and miPP
fractions were slightly lowered. It means that the catalysis
properties of Ci * are inuenced by De in much larger extent
than those of Ca* and Cm*. Enhancement in the isotacticity of
the PP product is a combined result of both reversible
deactivation of three groups 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
and an altered PP chain structure and polymerization kinetic
parameters as consequences.
dx.doi.org/10.1021/jp404416n | J. Phys. Chem. C 2013, 117, 1517415182
The Journal of Physical Chemistry C
ASSOCIATED CONTENT
*
S Supporting Information
Experimental procedures of polymer purication and sulfur
content determination, conditions of 13C NMR analysis of
polypropylene fractions, experiment data of fraction distribu-
tion of the PP product and sulfur content of the fractions,
experimental data of the number and chain propagation rate
constants of three groups of active centers, and results of DSC
and 13C NMR analysis on the three kinds of PP fractions. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: fanzq@zju.edu.cn.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
Support by the National Natural Science Foundation of China
(Grant No. 21074108) and the Major State Basic Research
Programs (Grant No. 2011CB606001) is gratefully acknowl-
edged.
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