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PATHWAYS TOWARDS A 100 % RENEWABLE ELECTRICITY SYSTEM. Summary for policy makers
- Rudolph Bates
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1 PATHWAYS TOWARDS A 100 % RENEWABLE ELECTRICITY SYSTEM Summary for policy makers
2 Executive Summary Climate policy-makers are facing the challenge that greenhouse gas emissions in industrialized countries need to be reduced by 80 to 95 % in order to avert a rise in global temperature by more than 2 C against the pre-industrial level, which is widely regarded as dangerous. The European Council has politically endorsed this objective in October Not least because of this target level fixed at the time when the present special report was published, important strategic decisions for the future structure of electricity supply are being discussed and taken in Germany. Today, energy production accounts for almost 40 % of German greenhouse gas emissions. A considerable part of conventional power plants will have to be replaced over the next years. This situation provides an opportunity to take advantage of this change to develop a sustainable energy supply. In Germany, there is a broad consensus that in the long run, a sustainable development of the energy sector will require an electricity supply which, in a best-case scenario, is almost completely based on renewable energy sources. In this respect, the time period needed to achieve this goal and the costs of the required transformation of the system have been a subject of controversial discussions. The present special report by the German Advisory Council on the Environment (Sachverständigenrat für Umweltfragen SRU) is to make a scientifically supported contribution to forming opinions among politicians and the general public. It refers to the following issues: Is it possible to ensure security of supply at any hour of the target year 2050 on the sole basis of renewable energy sources? How much would a fully renewable energy supply cost? Are bridging technologies required for the transition to a renewable-energy age? The following abstract of the essential results of the special report will enable decision-makers to obtain a synoptic view of the answers to these questions. A 100 % fully renewable energy supply is possible, safe and affordable. A detailed analysis of the potential of renewable energy sources for electricity production in Germany, Europe and North Africa has shown that an energy supply based exclusively on renewable energy sources by 2050 will be possible while taking into account the stringent requirements of nature conservation and avoiding other conflicts of use. The target scenario computations commissioned by the SRU differ as to the level of electricity demand for the year 2050 (between 500 and 700 TWh/a for Germany) and the degree of exchange and networking with the neighbouring countries. They range from full German selfsufficiency without any exchange to the possibility of electricity exchange with 35 other countries in Europe and North Africa. In the latter scenario, a maximum net import of the national electricity generation of 15 % is assumed. Compared with the target scenarios based on service life extension for nuclear power plants under the energy concept of the German federal government, these assumptions are on the conservative side. These target scenarios are based on a clearly lower energy consumption of 410 to 430 TWh/a and a markedly higher dependency on electricity imports of 22 to 31 % in A synoptic view of the eight SRU scenarios calculated is given in Table. All calculations meet the condition that the respective region examined has to achieve a fully renewable energy supply in Which are the measures and instruments necessary to support the transition to a climate-friendly renewable energy supply? 2 German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system
3 Demand GE in 2050: 500 TWh Self-sufficiency Scenario 1.a GE 100 % Demand GE in 2050: 700 TWh Scenario 1.b GE 100 % Net self-sufficiency interchange with DK/NO Maximum 15 % net import from DK/NO Maximum 15 % net import from EUNA Scenario 2.1.a GE-DK-NO 100 % Scenario 2.2.a GE-DK-NO 85 % Scenario 3.a GE-EUNA 85 % Scenario 2.1.b GE-DK-NO 100 % Scenario 2.2.b GE-DK-NO 85 % Scenario 3.b GE-EUNA 85 % Table: Eight scenarios for a 100 % renewable electricity supply in 2050 (SRU/SG /Tab. 0-1) GE Germany, DK Denmark, NO Norway, EUNA Europe and North Africa, SS Self-sufficiency. Based on an appropriate expansion of storage and network facilities, the utilizable potential of renewable energies in Germany and Europe will allow to meet, at any hour, the foreseeable maximum demand for electricity. Thus, the security of supply can be ensured at any time, in spite of variations in energy production from renewable sources. The technologies available already today, particularly for the use of wind and solar energy, are sufficient to achieve this goal. For 2050, a portfolio of renewable energies being as cost-effective as possible was calculated in the different scenarios, taking into account a long-term TWh/a a: GE 100 % 2.1.a: GE-DK- NO 100 % 2.2.a: GE-DK- NO 85 % 3.a: GE-EUNA 85 % 1.b: GE 100 % 2.1.b: GE-DK- NO 100 % 2.2.b: GE 85 % 3.b: GE-EUNA 85 % PV Geothermal Solid biomass with combined heat and power (CHP) Storage hydroelectric Pump storage systems Onshore wind energy Geothermal with combined heat and power (CHP) Biogas Solar thermal electricity Compressed air energy storage (CAES) Offshore wind energy Solid biomass Run-of-river stations Biogas with combined heat and power (CHP) Net imported electricity Figure 1: Electricity production in Germany and net imports (2050) (Source: SRU/SG /Abb. 0-1) German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system 3
4 Ct/kWh a: GE 100 % 2.1.a: GE-DK- NO 100 % 2.2.a: GE-DK- NO 85 % 3.a: GE-EUNA 85 % 1.b: GE 100 % 2.1.b: GE-DK- NO 100 % 2.2.b: GE 85 % 3.b: GE-EUNA 85 % Figure 2: Electricity production costs in Germany (2050) (Source: SRU/SG /Abb. 0-2) decline in costs of renewable energies owing to the effect of learning curves. Based on such cost optimization, it has been found that wind energy, particularly offshore wind energy, will assume paramount importance by 2050 in all of the scenarios (Fig. 1). In the different scenarios, the level of solar energy used varies depending on energy demand and the amount of electricity imported. The share of biomass use in energy production does not exceed about 7 % in the network scenarios, mainly owing to possible land use conflicts and relatively high costs of this resource. The inflation-adjusted electricity production costs of a fully renewable supply in 2050 will altogether fall below those of a low-carbon conventional energy mix because increasing fuel costs and costs of emission allowances can be avoided. The total costs of full supply by renewables would be below 7 ct/kwh including the costs of international grid and storage capacity expansion. These costs will be the lower the more successful ambitious energy saving and efficiency policies and a use of cost-effective storage technologies, particularly of pumped-storage plants in Scandinavia or the Alpine region will be (Fig. 2). Transition to renewables would not require either a significant service life extension or the construction of new coal-fired power plants. Neither a service life extension for nuclear power plants nor the construction of new coal-fired power plants with carbon dioxide capture and storage are required. The capacity of existing conventional power plants, together with a minor expansion of gas turbine power plants will suffice as a bridge to renewable energy supply. This can be demonstrated even for the restrictive assumption of an average service life of 35 years for all conventional power plants and maintaining the current rate of renewable energy expansion (Fig. 3). The need for base load power plants will decrease in a system with a high share of renewable energies. The high volatility of renewable energies will require a 4 German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system
5 GW Aggregate hydro power Onshore wind Offshore wind Aggregate biomass Photovoltaic Figure 3: Expansion of electricity production capacities for the transition to a fully renewable energy supply in 2050 (Szenario 2.1.a) (Source: SRU/SG /Abb. 0-3) substantially higher level of flexibility on the part of all conventional power plants. To cope with the residual load, the number of shutdowns required and of rapid shutdown and startup procedures will considerably rise. Thus, a permanently available and consistent base load is no longer required. As a result, both the service life extension for nuclear power plants and the additional construction of coal-fired power plants will increase the risk of surplus capacities in the system over increasingly longer periods. Recommendations for action by energy policy For energy and climate policies, key approaches to a transformation of electricity supply include: Energy efficiency is the most suitable bridging technology for a transformation to fully renewable energy supply and hence, should be vigorously promoted. To form the basis and create important economic incentives for such a transformation, statutory European and national climate protection and decarbonization targets for 2050 should be set and translated into emissions trading policies. In addition, the conditions for supporting renewable energies have to be enhanced both on the European and national levels in order to pave the way for a secure and efficient future electricity supply fully relying on renewables. No new power plants should be constructed which, for technical and economic reasons, fail to meet the requirements for a highly flexible electricity production and are incompatible with long-term climate protection objectives. Moreover, the envisaged service life extension for nuclear power plants is likewise incompatible with the flexibility requirements to be met for the transition to renewables. Flanking measures required to ensure security of supply during the expansion of renewable energies will include an accelerated and sufficiently dimensioned network expansion and German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system 5
6 above all, network conversion. To this aim, investment incentive and network planning modalities have to undergo fundamental changes. From the national perspective, Germany s cooperation with the countries bordering the North Sea is of strategic interest regarding energy policy in order to advance the connection and development of Scandinavia s considerable and comparably cost-effective pumped storage potentials. Based on the considerations outlined above, the SRU has formulated eight central recommendations for action for German and European energy policies. 1 Climate and energy concept: sectoral climate protection target 2050 and commitment to 100 % renewable energies The yardstick for the medium-term German and European climate protection policies should consist in a reduction of greenhouse gas emissions by 80 to 95 % by 2050 in order to avert dangerous anthropogenic interference with the climate system. Even for a less ambitious climate protection target of up to 80 %, a climate-neutral electricity supply is required to be achieved by For electricity supply, the goal of climate neutrality can be achieved at lower costs than in other sectors such as mobility, heating, agriculture and industry. Simultaneously, the objective of a sustainable electricity supply by means of full transformation to renewable energy sources by 2050 should be stipulated in high-ranking programme documents. 2 Energy efficiency by means of household electricity accounts Saving electricity may be regarded as the most important bridging technology on the way to a fully renewable supply. This is why the German federal government should set an absolute electricity consumption target. A suitable instrument to strengthen market incentives for such a target could consist in the introduction of household electricity accounts. Household electricity accounts are upper kwh sales limits for energy suppliers calculated on the basis of the number of households served by these companies. Similar to a cap-and-trade system, these limits are tradeable and may be harmonized with a national consumption target. In this way, energy efficiency would become a strategic business objective of energy suppliers. 3 Continuity and reform for the EEG The Renewable Energy Sources Act (Erneuerbare- Energien-Gesetz EEG) has proved to be successful as a potent and comparatively efficient instrument. The EEG s two fundamental pillars, i.e. the priority feed-in for renewables (Einspeisevorrang) and the guaranteed feed-in compensation for non-adjustable renewable energies should be maintained as a basic structure. During the transition period, the conventional power plant fleet should be used for load management in a flexible way and thus, make an essential contribution to the integration of renewables into the system. An onward development of the EEG should be aimed at long-term cost efficiency and portfolio optimization and, where meaningful, promote the system integration of renewable energies. For offshore wind energy, tendering models should be considered in the future where companies offer the construction and operation of such facilities at guar anteed feed-in tariffs that are as low as possible. Such approach could improve the linking with grid expansion. In addition, this could strengthen the competition for cost-effective electricity supplies. For wind energy in rural areas, the EEG should be maintained in its current form. Due to considerable prognostic uncertainties with regard to the future demand for photovoltaics (PV) in a cost-effective energy mix, PV support should aim at a minor but stable growth and avoid the development of inefficient excess capacities. In addition to compensation tariffs orienting towards cost reduction, another reasonable measure would consist in an absolute maximum limit for the PV capacities supported. Biomass support should be increasingly aimed at a balancing of power services and the use of residual materials and therefore, paid as a market price premium. The amount of such premium should increase with the proportion of residual material in the substrate mass 6 German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system
7 used. However, the bonus for energy from renewable raw materials (NAWARO-Bonus) should be abolished because of its negative environmental impacts. For other technologies that are still being developed at present, a first option could consist in project promotion from government funds which could be transferred to funding according to EEG principles if such technologies proved to be successful. 4 National plan to develop the electricity transmission grid by 2030 The SRU suggests the development of a national plan entitled Stromübertragungsnetz 2030 (The Electricity Transmission Grid 2030). It should, at a high level, establish the needs, define transmission line corridors and discuss alternatives with a 2030 target horizon. This plan should take into account the planning of transmission grid operators, the requirements set by trans-european energy networks and a model of future demand elaborated by the Federal Network Agency (Bundesnetzagentur). The plan is to define the required grid expansion on the basis of a transparent and open participation procedure that integrates the Strategic Environmental Assessment and the applicable nature conservation law. It is to concentrate the superordinate elements of a two-stage technical planning. Detailed planning and project approval will continue to be performed by means of administrative plan approval procedures. In addition to the grid expansion by transmission grid operators, central lines should be tendered in order to be able to safeguard the construction of required connections. 5 No service life extension for nuclear power plants During the period of transition to energy supply from renewable sources, there is no need to extend the service life of nuclear power plants. The expansion of renewables and the flexibility reserves of the existing conventional power plant fleet will suffice to meet the electricity demand, i.e. there is no reason to fear that a gap in electricity supply might arise. Due to their limited flexibility, nuclear power plants are unsuitable to serve as a bridging technology to complement renewables. As a result of the envisaged service life extension, the system conflict between high proportions of volatile renewables and poorly adjustable base load energy will considerably intensify during the 2020ies, eventually leading to high economic costs and risks for investment in renewable energies. 6 Planning the phasing-out of conventional power plants An integrated energy policy should synchronize the phasing-out of conventional capacities with the expansion of renewables. It will be helpful that the further expansion of renewables and a more stringent European emissions trading regime will result in a decreasing economic attractiveness of new coal-fired power plants. Nevertheless, flanking regulatory measures should be considered that would allow, if required, a control of the construction of new coal-fired plants. In the view of the SRU, an amendment to the Federal Control of Pollution Act (Bundes-Immissionsschutzgesetz BImschG) establishing CO 2 emission limit values is possible under European law. Special measures to accelerate the shutting-down of old power plants will not be needed since due to the priority feed-in for renewables, the latter will serve anyway only to cover the residual load, to an increasing extent. Owing to the long transition periods, there is a considerable scope for planning a socially acceptable structural change of energy supply. In addition, such change should be supported by regional policy. 7 European roadmap for renewable energies with a 2030 target horizon The 2009 Renewable Energy Directive (2009/28/EC) has contributed to a perpetuation of renewables expansion on the European level and thus, to a convergence of promotion strategies adopted by the Member States. Moreover, new initiatives for an expansion of the electricity grid have emerged owing to the certainty of orientation associated with the targets and national action plans. This is why the definition of expansion targets should be updated soon, initially with a 2030 horizon. By 2030, a proportion of renewables in energy supply clearly exceeding 50 % may be achieved on the European level. The Directive s instruments should be proactively used by the German federal govern- German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system 7
8 ment for a regional cross-border cooperation to promote expansion. In contrast, a European harmonization of such promotion would constitute an inappropriate objective for the foreseeable future and rather could thwart instrumental innovations. 8 Action plan for offshore connection and cooperation in the North Sea region The North Sea wind energy belt extending from Scotland to Denmark plays an essential strategic role for the further development of renewables in the EU. Its exploitation will require a coordination of grid planning in the North Sea region and an integration of the Scandinavian pump storage potential in the planning. The federal government should launch clear and binding initiatives and incentives for such integrated capacity and grid planning for the North Sea region. Grid operators should be encouraged to become involved in cooperative projects required to this aim. Outlook: Future Europeanization of energy and climate policies By means of the energy and climate protection package adopted in 2008, an important boost has been given to the Europeanization supporting national policies for the expansion of renewable energies. Forward-looking key initiatives such as the Decarbonization and Energy Roadmaps 2050 to be published in 2011, the pan-european high-capacity long distance electricity transmission grid, as well as the further development of the emissions trading system and the Renewable Energy Directive offer further opportunities for a continued support of national policies by means of the European climate and energy policies. A European energy strategy placing particular emphasis on climate protection and renewable energies would have numerous advantages: It would level the playing field in terms of market competition, it would provide access to cheaper energy sources and storage facilities, and it would open up new markets for all enterprises involved in the renewable energy value chain. Imprint Published by: German Advisory Council on the Environment (SRU) Secretariat: Luisenstraße Berlin Phone: +49 (030) Fax: +49 (030) Internet: Images: p. 1: DOTI (1), Bernd Müller (2, 3), B. Hiss (4), Bernd Müller (5), Regenerative Modellregion Harz (6) Design BLOCK DESIGN Kommunikation & Werbung Printing Komag mbh An electronic version of this report and further information are available online at The Advisory Council on the Environment (SRU) was founded in 1971 to advise the German government. The Council is made up of seven university professors from a range of different environment-related disciplines. This ensures an encompassing and independent evaluation from a natural scientific and technical as well as from an economic, legal and political science perspective. The Council has currently the following members: Prof. Dr. Martin Faulstich (Chair), Technische Universität München Prof. Dr. Heidi Foth (Vice Chair), Universität Halle-Wittenberg Prof. Dr. Christian Calliess, Freie Universität Berlin Prof. Dr. Olav Hohmeyer, Universität Flensburg Prof. Dr. Karin Holm-Müller, Rheinische Friedrich-Wilhelms-Universität Bonn Prof. Dr. Manfred Niekisch, Goethe Universität Frankfurt and Zoologischer Garten Frankfurt Prof. Dr. Miranda Schreurs, Freie Universität Berlin 8 German Advisory Council on the Environment l Pathways towards a 100 % renewable electricity system
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text:
I enjoy the outdoors, i love art history, science and math. im silly, i have fantastic dreams and high hopes of makeing all of them a reality.
oh and I can't spell.... but i like to pretend that i can.
I like to build sand sculptures at the beach, I hate mosquitoes and cold weather. I think pachouli is sexy, but musk is not. i love flowers but im slightly allergict to them. I will always tell the truth, but not always the whole story- unless i feel that you need to know.
I have developed a short patience for those who are not willing to put effort or time into getting to know me.
I am amiable, off the beaten path, and an art lover
Movies: KUNGFU,master with crippled fingers (early jackie chan) the Sisters of Magdelene- the funny kind the ones I haven't seen yet... beleive you me there are a lot of those.
Music:bluegrass, folk, jazz, assthumping booty music. irish, greg brown spider john koerner.
Food: the yummy kind. and chocolate cake
something that happens to be part of a stimulating conversation.
ninjas. they rock. Pirates rock more.WHEN i have time to sleep how I can make a lot of money so I can afford my rock and roll lifestyle.PUPPETS giant marionettes how to create social change through puppetry- how I can live like a rockstar and still make puppets.

subset: commoncrawl


text:
Burt's Buzz is an in-depth and personal look at the life of Burt Shavitz, known to millions around the world as the 'Burt' of the Burt's Bees natural product brand. The documentary explores what it means to be marketed as an icon, and how that life differs from the one of the man behind the logo.
This is Burt's Buzz and you are watching MovieZion
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If the above stream is offline (saying We are sorry!),
please click on the "Refresh Link" to get a new streaming link. Don't worry it'll just take a second.


text:
The Wicked Wheelie a action vehicle which is part of Kenners The Real Ghostbusters Toy Line's line. This is one of the two Haunted Vehicles released, the other being Air Sickness.
Toy DescriptionsEdit
Wicked Wheelie
with Motorcycle monster
Back of Card InstructionEdit
Here comes a motorcycle and rider you can roll into action. But watch out! They convert into...
Wicked Wheelie! It's a ghostly motorcycle monster and his creepy companion!
The Real Ghostbusters Heroes will be astounded when they meet Wicked Wheelie!
Booklet DescriptionEdit
Description from Action Toy Guide
Here's a motorcycle and rider that change into a ghostly motorcycle monster and his creepy companion!
- On page nine of Ghostbusters Issue #12, the Wicked Wheelie is parked outside of KBIB.
External LinksEdit
- Ecto-Containment.com »Kenner »Vehicles »Wicked Wheelie page which has instructions for the Wicked Wheelie toy.


text:
The important and overarching issue for Bobby Johnson's team--and it always will be so unless or until it is definitively addressed--is that it must change the culture that has pervaded Vandy football for so long. The extremely close losses to Alabama and Arkansas were nothing other than failures of nerve. In games where the Dores battled gamely and competed on very even terms with their opposition, victory was lost for no other reason than the simple fact that Vandy--perpetuating a pattern witnessed in every year after 1982--could not make enough big plays in key situations. VU football teams under several coaches--with Johnson being the latest one--have repeatedly made modest plays in non-critical situations, and quality plays in semi-critical situations, but rarely huge plays in game-defining situations. Pure talent--which the Dores have much more of this year--is not the issue; the issue is about bringing that talent to bear when a game's outcome hangs in the balance. That is the goal for Bobby Johnson and Vanderbilt's program: changing the culture so that VU can rise--and opposing teams can fall--when all the cards are on the table and victory is waiting to be claimed.
With all this in mind, then, the signs can't be terribly encouraging in the wake of the 29-point win over a Temple team that lost by more than twice as much in previous games against Louisville and Minnesota.
Yes, one could acknowledge that Vanderbilt might have soft-pedaled things just a bit against a severely overwhelmed and outmanned opponent. But one must counter by saying that a program with Vandy's particular subculture hasn't earned the benefit of the doubt when it treads lightly upon a grossly inferior opponent. Good programs will trample Temple by 40, 50 or 60 points, and while Bobby Johnson certainly got extra work in for a lot of players on the roster--a legitimate need before the teeth of the SEC schedule still to come--it remains that a team with a better internal subculture would display the kind of killer instinct that would decimate Temple on the scoreboard. The 280 rushing yards was extremely impressive, a sign that Vanderbilt brought the hard hats to the Owls for much of the evening. But the allowance of 14 points, combined with an ineffective passing game, has to concern Coach Johnson before the road trip to Oxford to face Ole Miss next week. One small lapse against Brent Schaeffer could produce more 78-yard touchdown plays like the one Tim Brown of Temple (no, not the Notre Dame and Oakland Raider star) popped off in Nashville on Saturday night.
You get the point. A 29-point win is a 29-point win, so there shouldn't be grumbling in the Commodore locker room. But just the same, this team has a long way to go in the attempt to finally change and overturn the current culture of Vanderbilt football. This Temple game will have meaning if it awakens the Dores and drives them to play in a more ruthless and unrelenting manner. If VU wins at the Grove next Saturday, this breather on the Commodores' 2006 schedule will ultimately prove to be beneficial. Bobby Johnson can only hope so.


text: You are pointing out a lot of teams that are on there second string center already, which really doesn't accurately back up your argument that Johnson is a an above average STARTING center. This is really a judgment argument that have very few stats that one can point to single out Johnson as not very good. The only one I can point to is 3.5/yrds (28th in the league) yet to be fair, the young tackle have contributed to that as well. I can only judge what I have seen as I have re-watched the line play in some games in slow motion this season. Based on my judgment, he is soft and a blow average run blocker, even with two veteran past -all-pro gaurds next to him. Taking into consideration he didn't even play his first season, I would say that Johnson Sucks. If you want to put together a reel and show me how he has dominated opposing NG on a constant bases this season or even point to a game that he has ( if i have a copy). I will be glad to watch it and I am open to changing my opinion. Until then I will stick with Johnson sucking bad.


text:
The idea of boots as an autumn/winter man-staple is hardly an earth-shattering realisation, even if said trend does arrive slap-bang in the middle of August. Hefty boots – think extreme sole and a hint of the hikers or bikers – were seen stomping about on various men's new season catwalks. Of course, if you're a brogues-are-the-new-brogues kind of chap, just buy a booted version of those and carry on regardless.
Clockwise from top
Brogues £85, by Bertie
Brown slouch £518, by Dolce & Gabbana, from matchesfashion.com
Navy lace-up £150, by Cos
Suede £145, by Russell & Bromley
Claret lace-up £130, by Asos
Black leather with fringe tongue £100, by Aldo


text:
Greenwich Green Party is growing everyday! And there's never been a better time to get involved. Come and join us!
Any help you can give us - from a setting up a regular donation to working on the doorstep - will make a real difference to getting more Greens elected, where we can create a fairer, cleaner, more affordable future for everyone.
Greens are making a difference on local councils across the country, and have their first MP. Want to be part of the future? Join us.
As a member, you can be as active as you like - from armchair and online support to standing as a candidate for election. Or why not make a donation?
Your donation will help us stand more candidates for more elections, and help the party do more to support the work of our members in Greenwich, as well as across London and nationwide.
Our monthly meetings at Mycenae House, Blackheath, are open to both members and supporters. They are held on the first Wednesday of each month at 7.30pm.
Next Greenwich Events
PLEASE NOTE: The next meeting is on WEDNESDAY 7 June 2017 at 7.00pm at Mycenae House.
Rob Stead. Get in touch if you notice any problems or would like to help: www.robstead.co.uk/contact
E: firstname.lastname@example.com
If you're a member go to the My Local Party page for individual contact details, minutes and other resources.


text:
|Publication number
|Publication type
|Application number
|Publication date
|May 26, 1998
|Filing date
|Oct 17, 1996
|Priority date
|Oct 19, 1995
|Fee status
|Also published as
|Publication number
|Steven A. Cohen
|Original Assignee
|Amoco Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (6), Referenced by (36), Classifications (30), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This application claims benefit under 35 USC 119(e) of U.S. Provisional Application Ser. No. 60/005,598, filed Oct. 19, 1995, incorporated by reference herein.
This invention relates to metallocene-based homogeneous olefin polymerization catalysts, and more particularly relates to an increased activity catalyst system especially suited for producing crystalline polymers of propylene.
Alpha-olefin polymerization using Ziegler-Natta catalysts is well known. Typically, the solid component of these catalysts is based on a titanium halide such as titanium tetrachloride or titanium trichloride which may be supported on a solid magnesium-containing compound. The co-catalyst component used in such heterogeneous systems typically is an aluminum alkyl such as triethylaluminum or diethylaluminum chloride. Recently, a homogeneous catalyst system has been described to polymerize alpha olefins, such as ethylene, propylene, butene, and hexene, which is based on a transition metal arene (metallocene) complex and an anion component such as derived from an aluminoxane or a boron-containing material.
Synthesis of polyolefins with metallocene/aluminoxane homogeneous catalysts is reviewed by Kaminsky in History of Polyolefins, pp.257-270, R. B. Seymour and T. Cheng (ed.), D. Reidel Publishing Co. (1986) and by Kaminsky et al in Makromol. Chem. Macromol. Symp., Vol. 3, 377-387 (1986). Metallocene/aluminoxane homogeneous catalyzed polymerization of ethylene also is reviewed by Giannetti et al in J. Poly. Sci., Vol 23, 2117-2137 (1985). Homogeneous polymerization and copolymerization of ethylene and other alpha-olefins was reported by Kaminsky and Sinn using an aluminoxane oligomer and cyclopentadienyl titanium and zirconium complexes in Proc. IUPAC Macromol. Symp. Vol. 28, 247 (1982). Copolymers of ethylene and hexene as well as low molecular weight amorphous polyhexenes have been prepared using homogeneous catalysts as reported by Kaminsky in the Proceedings of the International Symposium on Future Aspects of Olefin Polymerization (1986). This report also describes making pure isotactic polypropylene using a racemic mixture of {bis(indenyl)ethane}zirconium dichloride, while Ewen et al describe polymerization of propylene using corresponding hafnium complexes in J.Am.Chem Soc., Vol. 109, 6544-6545 (1987). Ewen describes ligand effects of metallocene/aluminoxane catalyst systems to make both atactic and isotactic polypropylene and copolymers of propylene with ethylene in Stud. Surf. Sci. & Cataly., Vol. 25, 271-292 (1986). 1-Butene was reported to be polymerized using a zircocene/methylalumoxane catalyst by Kaminsky et al in Angew. Chem. Int. Ed. Engl., Vol. 24, 507-508 (1985). All of the above-identified articles are incorporated by reference herein.
U.S. Pat. No. 4,542,199 describes use of a homogeneous catalyst system for polymerization of alpha-olefins composed of a bis(cyclopentadienyl)zirconium chloride and an aluminoxane. U.S. Pat. No. 4,544,982 describes production of normally-solid isotactic stereoblock polypropylene using a metallocene-aluminoxane catalyst. U.S. Pat. No. 4,530,914 describes polymerization of ethylene or higher alpha-olefins having a broad molecular weight distribution using a catalyst system comprising two or more metallocenes in combination with alumoxane. U.S. Pat. No. 5,324,800 describes various metallocene components, including substituted cyclopentadienyls and bridged cyclopentadienyls, in combination with aluminoxane useful in olefin polymerization. U.S. Pat. No. 4,794,096 describes a catalyst system containing an aluminoxane and a chiral stereorigid hafnium metallocene containing a structural bridge between cyclopentadienyls. The bridge includes silicon and hydrocarbon radicals. U.S. Pat. No. 4,931,417 describes a silyl or hydrocarbyl bridged metallocene component in which the metal is zirconium or hafnium and the arene is a substituted or unsubstituted cyclopentadienyl group. U.S. Pat. No. 5,241,025 describes an olefin polymerization catalyst system which is an organometallic additive compound and the reaction product of a bis(cyclopentadienyl) Group IV-B metal compound with an activator comprising a cation which irreversibly reacts with at least one ligand of the Group IV-B metal compound and a labile, bulky anion which is a single coordination complex having a plurality of lipophillic radicals or a plurality of boron atoms covalently coordinated to and shielding a central charge-bearing metal or metalloid atom. Examples of activators include substituted borane and alkyl ammonium salts of substituted borate compounds. U.S. Pat. No. 5,314,973 describes silicon-bridged metallocene compounds used as catalysts for stereoregular alpha-olefin polymerizations.
U.S. Pat. No. 5,198,401 describes metallocene-containing catalyst systems incorporating aluminium alkyls and a protic salt of a non-coordinating anion. In this reference, excess of aluminum alkyl is shown to be advantageous, in contrast to this invention in which aluminum alkyl optimally is minimized.
U.S. Pat. Nos. 5,444,134 and 5,498,582 describe metallocene-based catalyst systems supported on a carrier in which triisobutylaluminum is one of several aluminum alkyls used as co-catalysts. However, the polymerization activities reported using TIBA for such supported systems do not show the substantial activity increase as demonstrated in this invention using homogeneous catalysts.
Irrespective of the metallocene system, there is a need to increase activity of a metallocene-based olefin polymerization catalyst, to form crystalline polymers of propylene or propylene in combination with other monomers. An substantial increase in activity especially is advantageous if costly bridged metallocenes are used as a catalyst component.
An olefin homogeneous polymerization catalyst demonstrating increased activity is formed from a cyclopentadienyl metallocene component, a salt of a compatible cation and a non-coordinating anion, and a C3 -C6 trialkylaluminum, preferably triisobutylaluminum. A homogeneous polymerization process comprises controlling polymerization activity with such catalyst by controlling the aluminum/transition metal (Al/M) molar ratio to a minimal level within the effective range of Al/M ratios.
The catalyst system and process of this invention incorporate a transition metal containing metallocene component in combination with a non-coordinating borate anion and a C3 -C6 trialkylaluminum, preferably triisobutylaluminum (TIBA). The source of the non-coordinating anion typically is a salt of the non-coordinating anion and a compatible cation which has either an active proton or its equivalent such as a Lewis acid capable of extracting an anion. An aspect of the invention is that olefin, especially propylene, homogeneous polymerization activity is increased using this catalyst system in contrast with comparable systems using other anions, such as derived from aluminoxanes or boranes, or other aluminum alkyls. Also, surprisingly, use of TIBA to increase polymerization activity is observed only in homogeneous polymerization systems and not in metallocene catalyst systems in which the metallocene component is supported on a carrier. Another aspect of this invention is that higher catalytic activity is promoted by controlling the concentration of metallocene catalyst component and anion component at minimal concentrations. This effect is unexpected based on prior studies using aluminoxanes or boranes alone which indicate that catalyst activity is increased in metallocene/aluminoxane systems by increasing component concentrations. Further, the large effect of using TIBA in homogeneous polymerization, in contrast to conventional trimethylaluminum, is unexpected and unpredictable.
The transition metal-containing component of the catalysts useful in this invention is based on transition metal arene complexes referred to as metallocenes in which typically, a Group 4b, 5b, or 6b transition metal is complexed with one or more cyclopentadienyl moieties together with one or more other ligands. In the metallocene components useful in this invention, cyclopentadiene or a substituted cyclopentadiene is complexed with a transition metal which preferably is a Group 4b metal such as titanium, zirconium or hafnium. In addition, this invention is especially beneficial for bridged metallocene compounds in which two cyclopentadiene moieties are structurally joined by a bridging group such as a hydrocarbyl or silyl radical.
Suitable metallocenes useful in this invention include those having a formula Zm CPn Y4-n M, wherein CP is cyclopentadienyl a substituted cyclopentadienyl; Y is a C1 -C20 hydrocarbon radical such as alkyl, aryl, alkenyl, alkylaryl, or arylalkyl radical or a halogen; Z is a bridging group between the CP's; n is 1 or 2; and m is 0 or 1, provided that if n=1, m=0.
More particularly, suitable metallocenes of this invention include those having a formula ZCP2 Y1 Y2 wherein CP is cyclopentadienyl or a substituted cyclopentadienyl, Y1 and Y2 may be the same or different and may be an alkyl, aryl, alkenyl, arylalkyl, or alkylaryl group or a halogen, Z is a bridging group between the CP's.
A typical bridged biscyclopentadienyl complex useful in this invention may be represented as: ##STR1## wherein Y1 and Y2 =C1 -C20 hydrocarbyl or silahydrocarbyl radicals or halogen; M=Ti, Zr, or Hf; Z=a C1 -C6 hydrocarbyl, silahydrocarbyl, or silyl bridge radical; and the cyclopentadienyls may be substituted with hydrogen, halogens, or C1 -C20 hydrocarbon or silahydrocarbyl radicals and may be multi-ring including substituted indenyl.
The bridging radical, Z, typically contains 1 to about 5 carbon or silicon atoms in the bridging chain structure, which may be substituted further with C1 -C6 hydrocarbon or C1 -C6 /Si1 -Si3 silahydrocarbon. Typical bridging radicals include ethylene, propylene, trimethylene, vinylene, and SiR2, wherein R is a C1 -C8 hydrocarbon group such as methyl, ethyl, propyl, or phenyl. Preferable bridging radicals include dimethylsilyl, diphenylsilyl, and ethylene.
The ligands, Y1 and Y2, attached to the transition metal include C1 -C20 hydrocarbyl or silahydrocarbyl radicals and halogens such as chloride, fluoride, or bromide. Typical radicals are C1 -C12 hydrocarbyl radicals including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, isopentyl and the like. Preferable ligands include methyl and chloride.
The cyclopentadienyls (CP's) useful in this invention may be substituted with C1 -C20 hydrocarbyl or silahydrocarbyl groups or halogens and may contain multi-ring systems such as indenyls. Hydrocarbyl groups include alkyl, aryl, alkenyl, arylalkyl, and alkylaryl radicals. Typical substituent groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, isopentyl and the like. Preferable substituents include trimethylsilyl and C1 -C4 lower alkyls and most preferably is methyl.
Other examples of a bridged cyclopentadienyl metallocene component useful in this invention includes structures similar to: ##STR2## wherein R1 and R2 are C1 -C8 hydrocarbyl groups, including alkyls and aryls; Y1, Y2 and M are defined as above; and the cyclopentadienyl moieties can be substituted with C1 -C20 hydrocarbyl or silahydrocarbyl radicals, multi-ring, halogens, or hydrogen.
Specific examples of a bridged cyclopentadienyl metallocene component useful in this invention include structures similar to: ##STR3## wherein the cyclopentadienyl moieties can be substituted with C1 -C20 hydrocarbyl or silahydrocarbyl radicals, multi-ring, halogens, or hydrogen.
Specific examples of a suitable metallocene component include {bis(2,3,5-trimethylcyclopentadienyl)dimethylsilane} hafnium dichloride, {bis(2,4-dimethylcyclopentadienyl)dimethylsilane} hafnium dichloride, {bis(2-methyl-4-t-butylcyclopentadienyl)dimethylsilane} hafnium dichloride, and their respective zirconium analogues.
Other examples of suitable cyclopentadienyl complexes are bridged indenyl structures such as {bis(indenyl)ethane}zirconium dichloride: ##STR4##
Indenyl-based metallocenes used in this invention typically may be substituted with C1 -C20 hydrocarbyl or silahydrocarbyl groups, halogens, or hydrogen. Preferable substituents include aryl and C1 -C4 lower alkyls and most preferably is methyl, ethyl, and phenyl. Examples of indenyl-based metallocenes include {bis(2-methylindenyl)dimethylsilane}zirconium dichloride and {bis(2-alkyl-4-arylindenyl)dimethylsilane}zirconium dichloride and their hafnium analogs.
The preferable metallocene component used in this invention contains a substituted single-ring CP.
Anions especially useful in the metallocene catalyst systems of this invention are derived from salts of compatible cations and non-coordinating anions such as borates and, typically, include bulky borate anions such as anilinium salts of perfluorophenylborate. Compatible cations have either active protons or their equivalent such as a Lewis acid capable of extracting an anion. Compatible cations include triethylammonium, N,N-dimethylanilinium, and triphenylcarbenium. Suitable anions include tetra(hydrocarbyl) derivatives of boron and aluminum, such as tetraphenylborate, tetrakis{3,5-bis(trifluoromethyl)phenyl}borate, tetrakis(pentafluorophenyl)borate, and tetrakis(pentafluorophenyl)aluminate. A specific example is derived from dimethylanilinium perfluorophenylborate. Other examples of suitable species are listed on pages 6 and 7 of EP 0 277 004, incorporated by reference herein.
Triisobutylaluminum (TIBA) has been found to be most effective in promoting increased activity in metallocene/borate catalyst systems used in homogeneous polymerizations. Other possible aluminum alkyls include C3 -C6 trialkylaluminum compounds such as tri-s-butylaluminum, tri-t-butylaluminum, tri-isopentylaluminum, isopropyidiisobutylaluminum, and the like.
Although not preferred in all applications, the TIBA/borate system of this invention may incorporate other materials such as aluminoxanes and boranes.
The amount of catalyst to be employed varies depending on choice of polymerization technique, reactor size, monomer to be polymerized, and other factors known to persons of skill in the art, and can be determined on the basis of the examples appearing hereinafter and routine experimentation. Typically the metallocene catalyst component of this invention is used in amounts ranging from about 0.0001 to 10 milligrams, preferably about 0.1 to about 0.001 milligrams, of catalyst to gram of polymer produced.
The molar ratio of non-coordinating (such as borate) anion to transition metal typically ranges from about 0.1 to about 100 and preferably ranges from about 1 to about 20.
The molar ratio of aluminum alkyl/transition metal typically ranges from about 10 to 10000, preferably ranges from about 50 to about 1000, and more preferably ranges from about 100 to about 600. Increased activity is observed if the aluminum/transition metal (Al/M) ratio is controlled to a minimal level within the effective range of Al/M ratios. The optimal ratio may be determined by routine experimentation by those skilled in the art.
Also in the process of this invention, increased activity (kg of PP/g of catalyst/hr) typically is observed if the concentration of catalyst in the polymerization medium is minimized within effective polymerization concentration ranges. Optimal concentrations also may be determined by routine experimentation known to the art.
Aluminoxanes are oligomeric aluminum/oxygen-containing compounds containing the structure: ##STR5## wherein R is a suitable alkyl or aryl substituent group.
More specifically, aluminoxanes are represented as linear or cyclic compounds with structures: ##STR6## wherein R is a C1 -C5 alkyl group and n=2 to about 20.
R is methyl or ethyl and n equals about 5 to about 15 and the most typical aluminoxane is methylaluminoxane wherein n is about 10.
Typically, mixtures of linear and cyclic aluminoxanes are prepared by reacting an aluminum trialkyl with water in a suitable organic solvent such as toluene. In one suitable method, a solution of trimethyl aluminum in toluene is reacted with the water of hydration of copper sulfate pentahydrate. Methods to prepare aluminoxanes are described in U.S. Pat. Nos. 4,542,199, 4,544,762, and 4,665,047 and by Herwig and Kaminsky in Polymer Bulletin, Vol 9, 464-469 (1983) and in J.Poly.Sci., Vol 23, 2117-2132 (1985), all incorporated by reference herein.
Typical conventional catalyst compositions have been formed by combining the transition metal metallocene compound and an aluminoxane compound with typical aluminum-to-transition metal atomic ratios of about 10 to about 10,000 and preferably about 100 to about 1000.
Irrespective of the polymerization or copolymerization process employed, polymerization or copolymerization should be carried out at temperatures sufficiently high to ensure reasonable polymerization or copolymerization rates and avoid unduly long reactor residence times, but not so high as to result in the production of unreasonably high levels of stereorandom products due to excessively rapid polymerization or copolymerization rates. Typically, polymerization temperatures from about--20� to about 150� C., preferably from about 10� C. to about 120� C., are suitable from the standpoint of attaining good catalyst performance and high production rates. More preferably, polymerization according to this invention is carried out at temperatures ranging from about 20� C. to about 100� C.
Alpha-olefin polymerization or copolymerization according to this invention is carried out in a solution at reactor pressures of about atmospheric or above. Typically, reactor pressures range from about 20 to about 600 psi (140 to 4000 kPa).
The polymerization or copolymerization time will generally range from about 1/2 to several hours in batch processes with corresponding average residence times in continuous processes. Polymerization or copolymerization times ranging from about 1 to about 4 hours are typical in autoclave-type reactions.
Diluents suitable for use in homogeneous polymerization or copolymerization processes include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane; alkylaromatics such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyl toluene, n-propyl-benzene, diethylbenzenes, and mono- and dialkylnaphthalenes; halogenated and hydrogenated aromatics such as chlorobenzene. Chloronaphthalene, ortho-dichlorobenzene, tetrahydro-naphthalene, decahydronaphthalene; high molecular weight liquid paraffins or mixtures thereof, and other well-known diluents. It often is desirable to purify the polymerization or copolymerization medium prior to use, such as by distillation, percolation through molecular sieves, contacting with a compound such as an alkylaluminum compound capable of removing trace impurities, or by other suitable means.
Polymerization according to this invention also may be performed using bulk monomer, such as propylene, as the diluent. In such a system, preferably, a minor amount of a solvent such as toluene is incorporated to solubilize the metallocene component in the monomer.
Irrespective of polymerization or copolymerization technique, polymerization or copolymerization is carried out under conditions that exclude oxygen, water, and other materials that act as catalyst poisons. Preferably, olefin monomers and other chemicals used in this invention should be purified of known catalyst poisons before use. Also, according to this invention, polymerization or copolymerization can be carried out in the presence of additives to control polymer or copolymer molecular weights. Hydrogen is typically employed for this purpose in a manner well known to persons of skill in the art. Although not usually required, upon completion of polymerization or copolymerization, or when it is desired to terminate polymerization or copolymerization or at least temporarily deactivate the catalyst or catalyst component of this invention, the catalyst can be contacted with water, alcohols, acetone, or other suitable catalyst deactivators in a manner known to persons of skill in the art.
The polymerization process used in this invention is referred to as homogeneous. In homogeneous polymerization, the catalyst components, including the transition metal-containing component, initially are contained in solution in the polymerization medium. As polymerization of olefin progresses, particles of solid polymer form in the medium.
In one aspect of this invention, a solid catalytically active particle may be formed using the catalyst system described in this invention by polymerizing an olefin monomer, such as propylene, in solution using a metallocene-based catalyst system. Such particles can be recovered from a polymerizing solution without substantially affecting catalyst activity and used as a transition metal-containing catalyst component in a further polymerization which may be in bulk, slurry, or gas-phase. The co-catalyst systems and conditions used in such polymerizations may be selected from those known in the art. Typically, such catalytically active particles made according to this invention would contain polymer in a weight ratio to metallocene-containing component of about 1:1 to 1,000:1 and preferably 5:1 to 500:1.
The products produced in accordance with the process of this invention are normally solid, predominantly isotactic polyalpha-olefins. Homopolymer or copolymer yields are sufficiently high relative to the amount of catalyst employed so that useful products can be obtained without separation of catalyst residues. Further, levels of stereorandom by-products are sufficiently low so that useful products can be obtained without separation thereof. The polymeric or copolymeric products produced in the presence of the invented catalyst can be fabricated into useful articles by extrusion, injection molding, and other common techniques.
The invention described herein is illustrated, but not limited, by the following Examples and Comparative Runs. All procedures were performed under an inert atmosphere. Propylene polymerizations were performed at 30� C. in toluene solution under 80 psig (550 kPa) propylene pressure in "six-ounce" (175-milliliter) Fischer-Porter pressure bottles.
The racemic isomer of {bis(2,3,5-trimethylcyclopentadienyl) dimethylsilane} hafnium dichloride (Catalyst A), produces highly isotactic polypropylene in low yield using the methylaluminoxane (MAO) cocatalyst. An alternate cocatalyst system is desired to overcome the low activity, high cost, and high aluminum residues associated with the MAO. Preparation of Catalyst A is described in T. Mise, S. Miya, H. Yamazaki, Chem.Letters (1989), 1853-56, incorporated by reference herein.
Catalyst systems were prepared using {bis(2,3,5-trimethylcyclopentadienyl)dimethylsilane} hafnium dichloride (Catalyst A) from the metallocene component (97% racemic isomer) incorporated into toluene (distilled from sodium/benzophenone) stock solutions of dimethylanilinium perfluorophenylborate (Akzo), MAO (Sherex, 5.9% Al), modified MAO (MMAO, Akzo type 3A), tri(isobutyl)aluminum (TIBA, Albemarle), tris(perfluorophenyl)borane (Akzo, 3.15 wt % in aliphatic hydrocarbons), diethylzinc (DEZ), triethylaluminum (TEA, Aldrich, 1M in hexane), and dibutylmagnesium (DBM, FMC, 15 wt % in heptane). The metal alkyl (MAO, TIBA, TEA, DBM, MMAO, and/or DEZ) was added to a pressure bottle containing magnetic stir bar, followed by toluene and the stock solution of catalyst. After the components were allowed to react for 15 minutes, the boron containing reagent(s) was added and the bottle was closed. The final solution volume in each pressure bottle was 70 milliliters. A group of pressure bottles was removed to a constant temperature bath, stirring was begun, and gaseous propylene was introduced. The reactions were terminated by removing the bottles from the bath, excess propylene pressure was vented, and 30 vol. % isopropanol in hexane was added to deactivate the metal alkyl species. The resin samples were recovered by filtration and dried at 50� C. to constant weight under vacuum.
The effects of various cocatalyst systems on the activity of the metallocene catalyst are provided in Table 1.
TABLE 1______________________________________ ActivityRun Catatyst MAO Metal (M') Borate Borane kg PP/gNo. (mg) Al/Hf Alkyl M'/Hf B/Hf B'/Hf cat/h______________________________________1 0.30 500 0.072 0.30 1000 0.23 0.30 2000 0.314 0.30 5000 0.375 0.20 500 2.0 18.6 0.50 50 2.0 20.7 0.50* 50 TIBA 400 1.0 26.8 0.50* 0 TIBA 400 1.0 45.9 0.20* 0 TIBA 400 1.0 77.10 0.50* 0 TIBA 400 20.0 66.11 0.20* 0 TIBA 400 5.0 128.12 0.20* 0 TIBA 1000 5.0 55.13 0.20* 0 TIBA 600 5.0 123.14 0.20* 0 TIBA 200 5.0 182.15 0.07 0 TIBA 400 5.0 326.16 0.07 0 TIBA 300 5.0 341.17 0.07 0 TIBA 200 5.0 408.18 0.07 0 TIBA 150 5.0 67.19 0.07 0 TIBA 100 5.0 0.420 0.07 0 TIBA 50 5.0 0.421 0.07 0 TIBA 300 1.0 397.22 0.07 0 TIBA 300 2.0 393.23 0.07 0 TIBA 300 4.0 393.24 0.07 0 TIBA 300 6.0 304.25 0.07 0 TIBA 300 8.0 366.26 0.07 0 TIBA 300 10.0 398.27 0.20* 0 MMAO 200 5.0 44.28 0.20 0 TEA 200 5.0 3.129 0.20 0 DBM 200 5.0 2.230 0.20 0 DEZ 200 5.0 0.431 0.20 500 5.0 0.3832 0.07 0 TIBA 300 5.0 0.033 0.07 0 TIBA 300 1.0 4.0 365.______________________________________ *Activity may be limited by excess catalyst
The following observations regarding Catalyst A were made:
Runs 1-4 illustrate that when MAO is used at large Al/Hf values between 500 and 5000, increasing the Al/Hf ratio increased polymer yield, although catalyst activity remained very low (0.1-0.4 kg PP/g cat/h).
Use of borate (B(C6 F5)4) with MAO increased catalyst activity (Run 5). The activity gain was maintained as the MAO/Hf ratio was reduced to a very low level (Run 6). Additional aluminum alkyl scavenger (TIBA) had a small positive effect on the activity achieved with the low MAO+borate cocatalyst system, (Run 7). Substitution of the MAO with MMAO (modified methylaluminoxane) produced the highest activity observed with the MAO/borate system, 44 kg PP/g cat/h (Run 27).
Complete replacement of costly MAO cocatalyst by TIBA and borate substantially increased activity of Catalyst A. The advantageous effects of the TIBA/borate were further improved by decreasing the catalyst charge from 0.50 mg to 0.20 mg and by increasing the B/Hf ratio (Runs 8-11). Large excesses of TIBA significantly reduced the catalyst activity (Runs 11-14). Propylene polymerization activity of Catalyst A with the TIBA/borate system achieved 400 kg PP/g cat/h by further reducing the catalyst charge from 0.20 to 0.07 mg and by optimizing the TIBA/Hf ratio to between about 200 and 400 (Runs 11-20). At the lowest catalyst concentration, however, variations in the B/Hf ratio (Runs 21-26) appeared to have minimal effect on activity.
Compared to the modified MAO and TIBA, triethylaluminum, dibutylmagnesium, and diethylzinc gave low catalyst activity when used with the borate anion (Runs 28-30).
A cocatalyst system (Run 31) containing MAO and tris(perfluorophenyl)borane improved activity of Catalyst A over that using MAO alone, but the results are far below those achieved using the borate anion. Catalyst A was inactive with a TIBA/borane cocatalyst package (Run 32), although the TMH/TIBA/borate system remained highly active in the presence of the borane (Run 33).
Use of TIBA and the perfluorophenylborate anion with Catalyst A gave an extremely active polymerization catalyst system, 400 kg PP/g cat/h. Even higher polymerization activities are expected under conditions or higher temperature, higher propylene pressure, and better agitation. The activity also could be increased by lowering the level of catalyst poisons, since the large excesses of TIBA, which were found to suppress activity, could be reduced.
Total catalyst costs would be affected significantly by use of the cocatalyst described in this invention. Use of costly MAO is eliminated or significantly reduced. Further, substantial activity increases (˜200 fold) using the co-catalyst system of this invention with bridged metallocene catalyst components, such as Catalyst A, offset the increased cost of using such bridged components. Since large excesses of MAO are not needed in the catalyst system of this invention, catalyst residues in the product also typically were low.
Polymerization procedures and reagents as described in Procedure 1 were used in the evaluation of {bis(2-methylindenyl)dimethylsilane}zirconium dichloride (Catalyst B), except that polymerizations were performed at 15� or 20� C. as indicated in Table 2. The metallocene sample was reported to be >90% racemic isomer. Catalyst B is prepared in accordance with U.S. Pat. No. 5,145,819, incorporated by reference herein.
TABLE 2______________________________________EVALUATION OF THE POLYMERIZATION ACTIVITY OFCATALYST BRun Catalyst MAO TIBA Borate Temp ActivityNo. mg Al/Zr Al/Zr B/Zr �C. kg PP/g cat/h______________________________________34 0.05 1000 0 0 20 2.35 0.10 0 600 2.0 15 390.36 0.07 0 600 2.0 15 680.37 0.07* 0 600 2.0 15 520.37A 0.5* 1500 0 0 15 29.38 0.07 0 600 2.0 20 410.39 0.05 0 600 2.0 20 400.40 0.06 0 400 2.0 20 310.______________________________________ *{bis(indenyl)ethane} zirconium dichloride, prepared according to W. Kaminsky, K. Kuper, H. H. Brintzinger, F. R. W. P. Wild, Angew. Chem., Int.. Ed. Engl., 24 (1985), 507-8.
Propylene polymerizations carried out with Catalyst B demonstrated the following:
Use of MAO cocatalyst at 1000 Al/Zr ratio resulted in low polymerization activity, 2 kg PP/g cat/h, at 20� C. in toluene solution. The activity reported for Catalyst B for a polymerization conducted at 50� C. in bulk propylene with 3300 Al/Zr is 84 kg PP/g cat/h. (W. Spaleck, et al, Angew. Chem. Int. Ed. Engl. (1992), 31, 1347-1350.)
Replacement of the MAO cocatalyst with TIBA/borate substantially increased the activity of Catalyst B. Lowering the catalyst concentration from 0.10 to 0.07 mg improved the activity to 680 kg PP/g cat/h. The activity of {bis(indenyl)ethane}zirconium dichloride under the same conditions was 520 kg PP/g cat/h. Increasing the temperature to 20 � C. results in a lower activity (Run 38 versus Run 36). Further reducing the catalyst charge to 0.05 mg had no effect, although reducing the Al/Zr value lowered the polymerization activity.
Qualitatively, the polymerization reactions using the highly reactive Catalyst B/TIBA/borate system experienced greater agitation problems than either those using {bis(indenyl)ethane}zirconium dichloride or Catalyst A.
The polymerization procedures and reagents described in Procedure 1 were used in the evaluation of {bis(cyclopentadienyl) hafnium dichloride (Catalyst C) obtained from Aldrich, except that the polymerizations were performed at temperatures indicated in Table 3. These runs demonstrate that the co-catalyst system of this invention preferably is used with bridged metallocene systems.
TABLE 3______________________________________EVALUATION OF THE POLYMERIZATION ACTIVITY OFCATALYST CRun Catalyst MAO TIBA Borate Temp. ActivityNo. mg Al/Hf Al/Hf B/Hf �C. kg PP/g cat/h______________________________________41 0.50 0 2000 1.0 15 0.242 0.50 0 800 1.0 15 0.143 0.50 0 500 1.0 15 0.144 0.50 4000 0 1.0 15 6.345 0.50 2000 0 1.0 15 8.546 0.50 400 0 1.0 15 10.847 0.50 200 0 1.0 15 12.248 0.50 100 0 1.0 15 12.749 0.50 75 0 1.0 15 14.750 0.50 50 0 1.0 15 16.051 0.50 40 0 1.0 15 15.9______________________________________
|Cited Patent
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|Chevron Phillips Chemical Company Lp
|Oligomerization of alpha olefins using metallocene-SSA catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends
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|Polymerization catalysts
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|Catalyst system and its use in a polymerization process
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|Patrick Brant
|Polymacromonomer And Process For Production Thereof
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|Patrick Brant
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|Patrick Brant
|Functionalized High Vinyl Terminated Propylene Based Oligomers
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|Olefin Functionalization By Metathesis Reaction
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|Chevron Phillips Chemical Company Lp
|Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends
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|Oligomerization of olefin waxes using metallocene-based catalyst systems
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|Process for the polymerization of an olefin, metallocene catalyst therefor and cocatalyst for activating a metallocene procatalyst
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|U.S. Classification
|526/127, 526/904, 502/108, 502/117, 502/129, 526/153, 502/153, 502/124, 526/151, 502/132, 502/118, 526/351, 526/132, 526/943, 502/128, 526/160, 526/133
|International Classification
|Cooperative Classification
|European Classification
|Nov 22, 1996
Owner name: AMOCO CORPORATION, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:COHEN, STEVEN A.;REEL/FRAME:008240/0076
Effective date: 19961016
|Feb 2, 1999
|Certificate of correction
|Sep 28, 2001
|Fee payment
Year of fee payment: 4
|Dec 14, 2005
|Maintenance fee reminder mailed
|May 26, 2006
|Lapse for failure to pay maintenance fees
|Jul 25, 2006
|Expired due to failure to pay maintenance fee
Effective date: 20060526


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