# Patent

## Title
Preparation of long-chain branched isotactic polypropylene

## Abstract

The present invention discloses a method for preparing long-chain-branched isotactic polypropylene by first oligomerizing propylene with a suitable oligomerization catalyst system and then copolymerizing propylene and the oligomer obtained in situ with a mono-aryl-substituted methylene bridged catalyst system.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of PCT/EP2009/067062, filed Dec. 14, 2009, which claims priority from EP 08291192.6, filed Dec. 12, 2008.
The present invention relates to the field of long-chain branched isotactic polypropylene and to their method of preparation.
A major interesting property of isotactic polypropylene is its high crystallinity, which makes it a solid material that can be used for specific applications. This property also presents some pitfalls like the fact that isotactic polypropylene is a brittle and poorly processable polymer. To overcome this problem, one can envision preparing so-called Long-Chain Branched Isotactic Polypropylene (LCB-iPP). The introduction of long branches in the polypropylene backbone gives the polymer some new mechanical properties; it becomes both stiff and stress resistant. Also, crystallinity decreases and, as a consequence, the polypropylene becomes much more processable.
To date, the only way to prepare LCB-PP, either isotactic or syndiotactic or atactic, is to copolymerise propylene and a longer α-olefin. In some cases, the comonomer is introduced in the polymerisation medium before injecting the copolymerisation catalyst.
The copolymerisation of propylene and methyloctadiene (MOD) has been achieved in an atactic fashion using Cp*TiMe3/B(C6F5)3 (Cp*=C5Me5) and in an isotactic fashion using a metallocene catalyst system comprising the metallocene component {rac-C2H4(Ind)2}ZrCl2 (Ind=1-indenyl) and methylaluminoxane (MAO) as activating agent. This method is described in Fuquan Song, Daniela Pappalardo, Anthony F. Johnson, Bernhard Rieger, and Manfred Bochmann, J. Polym. Chem.: Part A: Polym. Chem., 2002, 40, 1484-1497. The comonomer incorporation was a linear function of the feed ratio.
The same trend was observed for the copolymerisation of propylene and other α-olefins (1-hexene and 1-octene) using either isospecific systems such as {rac-C2H4(Ind)2}ZrCl2, {rac-C2H4(2-MeInd)2}ZrCl2 or {rac-Me2Si(Ind)2}ZrCl2 activated with MAO as syndiospecific systems such as {Ph2C(Flu)(Cp)}ZrCl2 (Flu=9-fluorenyl) and {Me2C(Flu)(Cp)}ZrCl2 also activated with MAO. These methods are described in Raul Quijada, Juan Luis Guevara, Griselda B. Galland, Franco M. Rabagliati and Juan M. Lopez-Majada, Polymer, 2005, 1567-1574.
In some other cases the macromer was formed in situ with a first catalytic system before the copolymerisation catalyst was introduced in the reaction medium. The copolymerisation of propylene and ethylene-based macromers led to LCB-sPP as described in S. Rulhoff and W. Kaminsky, Macromol. Symp., 2006, 236, 161-167. First, macromers were synthesised using the metallocene catalyst system {Me2C(Cp)2}ZrCl2/MAO, and then the reactor was purged from ethylene gas, the second catalyst system {Ph2C(Cp)(Flu)}ZrCl2/MAO was injected and propylene was injected into the reaction medium to yield the copolymer.
It has been reported that in situ generation of atactic PP macromers by {[2-ArN=C(Me)]2C5H3N}FeCl2/MAO wherein Ar is 2,6-C6H3(Me)2 could be followed by its copolymerisation with propylene by injection of the isospecific {rac-Me2Si(2-MeBenz[e]Ind)2}ZrCl2/MAO catalyst system. Attempts to synthesise the copolymer in a one-step protocol, by injection of the two catalysts at the same time, has failed as described in Zhibin Ye and Shiping Zhu, J. Polym. Chem.: Part A: Polym. Chem., 2003, 41, 1152-1159.
There are no examples of one-step synthesis of LCB-PP. A “one-step process” is advantageous as there is no need of comonomer feed or of previous in situ comonomer synthesis thereby greatly simplifying the process. Such process has however been used for the copolymerisation of ethylene to end up with so-called Long-Chain Branched Polyethylene (LCB-PE).
Several catalyst combinations were found to be effective for synthesising LCB-PE by tandem catalysis. A mixture of {C5H5B-OEt}2ZrCl2/MAO, used for oligomerising ethylene, and of [(η5-C5Me4)SiMe2(η1-NCMe3)]TiCl2/MAO, used for copolymerising the macromers and ethylene, provided synthesis of LBC-PE with a quantitative incorporation of the macromer formed. The melting point of the polymer, reflecting the number of branches incorporated, was a function of the initial ratio of the two catalysts as described in Richard W. Barnhart and Guillermo C. Bazan, J. Am. Chem. Soc., 1998, 120, 1082-1083.
Another tandem catalyst system that proved to be efficient was the combination of {[(2-ArN=C(Me))2C5H3N]FeCl2}/MAO wherein Ar is 2-C6H4(Et) and of {rac-Me2Si(Ind)2}ZrCl2/MAO or {rac-C2H4(Ind)2}ZrCl2/MAO, respectively for macromer production and for copolymerisation as described in Raul Quijada, René Rojas, Guillermo Bazan, Zachary J. A. Komon, Raquel S. Mauler and Griselda B. Galland, Macromolecules, 2001, 34, 2411-2417.
The preparation of LBC-PE with two different lengths of branches has also been reported in Zachary J. A. Komon, Gary M. Diamond, Margarete K. Leclerc, Vince Murphy, Miho Okazaki and Guillermo C. Bazan, J. Am. Chem. Soc., 2002, 124, 15280-15285. In this case, the system was based on a triple catalysis.
There is a need for single-step catalysis of long-chained branched isotactic polypropylene.
It is an aim of the present invention to provide an effective process for the synthesis of LCB-iPP by tandem catalysis.
It is another aim of the present invention to provide isotactic polypropylene with an homogeneous distribution of long branches.
It is also an aim of the present invention to provide isotactic propylene polymers having good processability.
Any one of those aims is, at least partially, fulfilled by the present invention.
Accordingly, the present invention discloses a process to prepare long chain branched isotactic polypropylene (LCB-iPP) that comprises the steps of:

    
    
        a) oligomerising propylene with a first metallocene or post-metallocene catalyst system suitable for producing macromers having vinyl-terminated chains or providing “molecular” alpha-olefins;
        b) copolymerising the macromers obtained in step a) with propylene using a metallocene catalyst system comprising a catalyst component of formula

{R′(Rb2-Flu) (RcRdC5H2)}MQ2 

        having C1symmetry or C2 symmetry wherein R′ is a mono-aryl-substituted methylene bridge, preferably a mono-phenyl-substituted methylene bridge, and wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to 12 carbon atoms, or aryl groups having up to 12 atoms, or silyl groups substituted or unsubstituted
        wherein M is a metal Group 4 of the Periodic Table and wherein Q is halogen or alkyl having from 1 to 12 carbon atoms and an activating agent having an alkylating and ionising action;
        c) retrieving a long-chain-branched isotactic polypropylene (LCB-iPP)
    
    


Preferably, the copoymerisation catalyst component has C1 symmetry.
In a preferred embodiment according to the present invention, the fluorenyl group is substituted in positions 3 and 6 with a bulky substituent. The preferred subsituent is tert-butyl.
Preferably the cyclopentadienyl group is substituted in a position distal to the bridge with a bulky substituent, at least as bulky as tert-butyl, and in a position vicinal to the bridge but not vicinal to the distal susbstituent with a small substituent, smaller than tert-butyl. The bulky substituent may be selected from tert-butyl, ethyl or phenyl and the small substituent is preferably methyl.
The oligomerisation catalyst system is not particularly limited as long as it produces vinyl-terminated chains. Amongst the preferred catalyst components, one can cite Cp*2MQ2 wherein Cp* is a cyclopentadienyl substituted with 5 alkyl groups, preferably with 5 methyl groups, and wherein M is a metal group 4 of the Periodic Table, preferably Zr or Hf and Q is halogen or alkyl, preferably Cl. Other preferred oligomerisation catalyst components can be selected from {R′(2-R′′3Si-Ind)2}MQ2 wherein R′ is a one- or two-atom (C, Si) bridge between the two indenyl moieties and R′′ is alkyl having from 1 to 6 carbon atoms, preferably methyl, or from iron complex of formula {2,6-(ArN=C(Me))2Pyr}FeCl2, wherein Ar is 2,6-Me2C6H3 and Pyr is pyridine (see below):




The oligomerisation catalyst system further comprises an activating agent based on aluminium or boron. The most preferred activating agent is methylaluminoxane (MAO).
The preferred copolymerisation catalyst component can be selected from {CHPh (3,6-tBu2-Flu) (3-tBu,5-MeC5H2)}ZrCl2,{CHPh (3,6-tBu2-Flu) (3-tBu,5-EtC5H2)}ZrCl2 or {CHPh (3,6-tBu2-Flu) (3-tBu,5-PhC5H2)}ZrCl2, the most preferred being {CHPh (3,6-tBu2-Flu)}(3-tBu,5-EtC5H2) ZrCl2.
The copolymerisation catalyst component must also be activated with an activating agent, preferably the same as that used with the oligomerisation catalyst component, more preferably MAO.
The relative amounts of first and second catalyst components is not particularly limited and must be adjusted according to the number of branches sought, the nature of the oligomerisation and copolymerisation catalyst components and the desired composition of the final polymer. The ratio of the copolymerisation to oligomerisation catalyst components can range from 1:1 to 100:1.
In a first step, the oligomerisation of propylene with the Cp*2ZrCl2/MAO (Cp*=C5Me5) system was investigated and the obtained oligomers were studied in order to determine their vinyl-end content and chains length.
Then the ability of the {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)}ZrCl2/MAO catalyst system to copolymerise propylene with “molecular” α-olefins was investigated.
Alternatively, instead of being polymerised in situ, the macromers can be prepared independently and added to the reactor. Such “molecular” α-olefins or macromers can be selected for example from 7-methyl-1,6-octadiene (MOD), 8-trimethylsilyl-1-octene (TMS-octene)).
Preferably, they are macromers issued from the oligomerisation of propylene for example with the Cp*2ZrCl2/MAO system.
The oligomerisation and copolymerisation can be carried out sequentially with isolation of the macromer between the two steps. Alternatively and preferably, both oligomerisation and copolymerisation can be carried out in one step by inserting both catalyst components and the activating agent simultaneously in the same reactor.
All the polymerisations were performed at a temperature of from 20 to 150° C., preferably 50 to 100° C., under a pressure of from 1 to 30 bars, preferably from 3 to 15 bars and for a period of time of from 2 minutes to 2 hours, in a single reactor either in two successive steps of oligomerisation followed by copolymerisation or in a single step wherein both catalyst components were introduced simultaneously into the reactor.


EXAMPLES
All polymerisations were performed according to the following procedure: A 300 mL glass reactor was purged under vacuum and then filled with argon. The reactor was charged under argon with 150 mL of dry toluene, an appropriate amount of MAO and the comonomer, when not generated in situ. The reactor was pressurised at 5 atm with propylene and thermostated to a temperature of about 60° C. via circulation of water in the double mantle. When the reactor had reached the required temperature, propylene was vented, the metallocene pre-catalyst was injected in by syringe and the reactor was pressurised at 5 bars with propylene. After the desired reaction time period, the reactor was depressurised and the polymerisation was quenched by addition of a protic compound. For the oligomerisation process, the solvent was removed and the residue was dried under vacuum. For the copolymerisation process, methanol was added and the polymer that precipitated was filtered, washed with methanol and dried under vacuum.
Examples 1 and 2
Oligomerization of Propylene Cp*2ZrCl2/MAO System.
First, the oligomerisation described in Janiak et al. (Christoph Janiak, Katharina C. H. Lange and Peter Marquardt, in J. Mol. Catal A: Chem., 2002, 180, 43-58) (Scheme 1). The catalyst used was Cp*2ZrCl2 with 1000 equivalents of MAO vs Zr, and 10 min of pre-activation. 150 mL of toluene were used as solvent. The amount of oligomers obtained in 1 h was the same as that described in the latter article. Oligomers were analysed by 1H NMR and proved to be 90% vinyl-ended. They had a number average molecular weight Mn of 280 g.mol−1. Slightly different conditions were also tested in example 2, resulting in similar oligomers (Mn=320 g.mol−1, 90% vinyl-ended). In both cases, the remaining 10% are vinylidene-ended oligomers. Thanks to the 90% of vinyl-ends, these oligomers were used for further copolymerisations. The oligomerisation results are displayed in Table 1.


















TABLE 1






[Zr]

T
t
activity
Mn
vinyl-ends


Example
(μmol · L−1)
[Al]/[Zr]
(° C.)
(min)
(Kg · mol−1 · h−1)
(g · mol−1)
(%)






















1
70
1000
50
60
1070
280
90


2
35
1500
60
30
400
320
90









Examples 3-8
Copolymerization of Propylene and Preliminarily-prepared Comonomers by the {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)}ZrCl2/MAO system.
The metallocene catalyst system {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)}ZrCl2/MAO was used to copolymerise propylene and higher α-olefins (Scheme 2). Three different comonomers were used for this purpose: 8-trimethylsilyl-1-octene (TMS-octene), 7-methyl-1,6-octadiene (MOD) and propylene oligomers previously obtained with the Cp*2ZrCl2/MAO system in example 1.




Copolymers from propylene and each of these macromers were synthesised. As a reference test, homopolymerisation of propylene (example 3) was carried out under the same conditions of temperature, propylene pressure, [Zr], [Al]/[Zr], . . . as those used for copolymerisations. Copolymers formed with TMS-octene (examples 4 and 5) and MOD (examples 6 and 7) were analysed by 1H NMR in C2D2Cl4 at a temperature of 373 K to determine the comonomer incorporation amount, by integration of characteristic signals CH=CMe2 and Si(CH3)3. Example 8 was obtained with the oligomers obtained in example 1. The melting temperatures were determined by DSC measurements and the molecular weights and molecular weight distributions were determined by GPC (at room temperature, in THF, vs polystyrene standards). Some of the samples were also analysed by dynamic rheology. The results are reported in Table 2.














TABLE 2






comonomer
comonomer
t
activity
Tm
Mw



Example
(nature)
(mg)
(min)
(Kg · mol−1 · h−1)
(° C.)
(×103 g · mol−1)
PDI






















3
—
—
30
5940
156
200
2.6


4
TMS-octene
265
10
8035
149
187
n.d.


5
TMS-octene
505
10
21695
146
n.d.
n.d.


6
MOD
280
10
2325
146
n.d.
n.d.


7
MOD
510
10
7635
145
n.d.
n.d.


8
OligoPP
400
10
20830
151
n.d.
n.d.





The polymerization conditions were as follows:


toluene (150 mL),


[Zr] = 10 μmol · L−1, MAO (5000 equiv. vs Zr), in situ activation,


P(propylene) = 5 bars,


T = 60° C.






As evidenced by the lower Tm values, the obtained copolymers were less crystalline than the isotactic homopolypropylene obtained with no comonomer. Interestingly and unexpectedly, an improvement of the catalytic activity, as a direct function of the comonomer feed, was observed.
Examples 9-15
Long-chain Branching Polymerization by Tandem Catalysis.




For the one-pot synthesis of LCB-iPP represented in Scheme 3, two different protocols were used. The first protocol consists in a sequential polymerisation, in which the Cp*2ZrCl2/MAO system, pre-activated for 10 min, was reacted with propylene for a 30 minutes time period to produce vinyl end-capped propylene oligomers, after which time period {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)}ZrCl2 was further injected in the reactor and the reaction was pursued for a 30 minutes time period in order to achieve copolymerisation. Results for examples 9 and 10 are reported in Table 3.














TABLE 3a






[Zr1]
[Zr2]
[Al]/
[Al]/
activityb
Mw



example
(μmol · L−1)
(μmol · L−1)
[Zr1]
[Zr2]
(Kg · mol−1 · h−1)
(×103 g · mol−1)
PDI






















9
35
 10
1500
5000
 0c
0.296c
n.d.


10
35
100
1500
500
181d
126 (66 wt - %)
1.46/








 1.3 (34 wt - %)
1.08





aThe polymerisation conditions were as follows: [Zr1] = Cp*2ZrCl2, [Zr2] = {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)}ZrCl2; Polymerization conditions: toluene (150 mL), P(propylene) = 5 bars, T = 60° C.,


bactivity calculated vs [Zr2]


conly oligomers were obtained in this run; their molecular weight was determined by 1HNMR.


dThe final product obtained in this run was an oily product, which showed two very distinct and separated distributions in GPC. No melting point was measured.






The second protocol used was a direct (co)polymerization by tandem catalysis, with introduction of the two catalysts components at the same time. The reaction time was of 30 min. The results for examples 11 to 13 are reported in Table 4.















TABLE 4a






[Zr1]
[Zr2]
[Al]/
[Al]/
activityb
Tm
Mw



example
(μmol · L−1)
(μmol · L−1)
[Zr1]
[Zr2]
(Kg · mol−1 · h−1)
(° C.)
(×103 g · mol−1)
PDI























11
35
10
1500
5000
105
101
n.d.
n.d.


12
17
50
3000
1000
195
129
77
2.3


13
6
50
8000
1000
285
131
n.d.
n.d.





aThe polymerisation conditions were as follows: [Zr1] = Cp*2ZrCl2 and [Zr2] = {(3-tBu-5-MeCp)CHPh(3,6-ditBuFlu)}ZrCl2; toluene (150 mL), P(propylene) = 5 bars, 60° C.


bactivity calculated vs [Zr2]






From these results, it appears that the copolymerisation activity of the {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)}ZrCl2/MAO catalyst system was diminished, as compared to its activity observed for homopolymerisation of propylene or its copolymerization with higher α-olefins preliminarily prepared (see Table 2).
Finally, the use of the {(3-tBu-5-EtCp)CHPh(3,6-tBu2Flu)}ZrCl2/MAO system was evaluated for the tandem catalysis. The results for example 14 are given in Table 5.















TABLE 5a






[Zr1]
[Zr2]
[Al]/
[[Al]/
Activityb
Tm
Mw



example
(μmol · L−1)
(μmol · L−1)
[Zr1]
[Zr2]
(Kg · mol−1 · h−1)
(° C.)
(×103 g · mol−1)
PDI







14
12
40
4000
1300
250
n.d.
n.d.
n.d.





aThe polymerisation conditions were as follows: [Zr1] = Cp*2ZrCl2 and [Zr2] = {(3-tBu-5-EtCp)CHPh(3,6-tBu2Flu)}ZrCl2; toluene (150 mL), P(propylene) = 5 bars, T = 60° C.


bactivity calculated vs [Zr2]






The activity of the {(3-tBu-5-EtCp)CHPh(3,6-tBu2Flu)}ZrCl2/MAO catalyst system was slightly higher than that of the {(3-tBu-5-MeCp)CHPh(3,6-tBu2Flu)]ZrCl2/MAO system for this tandem catalysis application.

## Claims

1. A method for preparing long-chain-branched isotactic polypropylene that comprises the steps of:
a) feeding propylene into a reactor;
b) providing an oligomerisation catalyst system capable of producing macromers of propylene having vinyl-terminated chains;
c) providing a metallocene catalyst system to copolymerise the macromers of step b) with propylene wherein said metallocene catalyst system comprises a catalyst component of formula


{R′(Rb2-Flu) (RcRdC5H2)}MQ2 



having C1-symmetry or C2-symmetry wherein R′ is a mono-aryl-substituted methylene bridge, and wherein Rb ,Rc and Rd are each independently selected from H or alkyl having from 1 to 12 carbon atoms, or aryl groups having up to 12 carbon atoms, or silyl groups substituted or unsubstituted
wherein M is a metal Group 4 of the Periodic Table and
wherein Q is halogen or alkyl having from 1 to 12 carbon atoms
and an activating agent having an alkylating and ionising action, wherein the oligomerisation and copolymerisation are carried out in one step by inserting both catalyst components and the activating agent simultaneously in the reactor;
d) retrieving polypropylene product.

2. The method of claim 1 wherein the oligomerisation catalyst system is selected from Cp*2MQ2 or R′(2-R′′3Si-Ind)2MQ2 or iron complex of formula {2,6-(ArN=C(Me))2Pyr}FeCl2, wherein Cp* is cyclopentadienyl substituted with 5 alkyl groups, M is a metal group 4 of the periodic table, Q is halogen or alkyl having at most 6 carbon atoms, R′ is a one- or two-atom (C, Si) bridge linking the two indenyl moieties, R′′ is alkyl having from 1 to 6 carbon atoms, Ind is 1-indenyl group, Ar is 2,6-Me2C6H3 and Pyr is pyridine.

3. The method of claim 2 wherein the oligomerisation catalyst is selected from Cp*2ZrCl2 or Cp*HfC2 or rac-C2H4(2-Me′′3Si-Ind)2ZrCl2.

4. The method of claim 1 wherein the copolymerisation catalyst component has C1-symmetry;
wherein substituent Rc is at least as bulky as tert-butyl and at a position distal to the bridge; and wherein Rd is at a position vicinal to the bridge, non vicinal to Rc and is less bulky than tert-butyl.

5. The method of claim 4 wherein the copolymerisation catalyst component is selected from {CHPh(3,6-tBu2Flu)(3-tBu,5-MeC5H2)}ZrCl2, {CHPh(3,6-tBu2Flu)(3-tBu,5 -EtC5H2)}ZrCl2 or {CHPh(3,6-tBu2Flu)(3-tBu,5-PhC5H2)} ZrCl2.

6. The method of claim 1 wherein the activating agent is the same for both catalyst components and is methylaluminoxane.

7. The method of claim 1 wherein the ratio of copolymerisation to oligomerisation catalyst components is from 1:1 to 100:1.

8. The method of claim 1, wherein R′ is a mono-phenyl-substituted methylene bridge.

9. The method of claim 4, wherein the copolymerisation catalyst component is {CHPh (3,6-tBu2Flu)(3-tBu,5-EtC5H2)}ZrCl2.