EP1401895A2

EP1401895A2 - Polymerisation method and device for carrying out a polymerisation method

Info

Publication number: EP1401895A2
Application number: EP02743127A
Authority: EP
Inventors: Karl-Heinz Reichert; Annette Wittebrock; Kalle Kallio
Original assignee: Borealis Technology Oy
Current assignee: Borealis Technology Oy
Priority date: 2001-06-01
Filing date: 2002-05-29
Publication date: 2004-03-31
Also published as: WO2002098934A1; WO2003011919A3; AU2002344994A1; WO2003011919A2; US20040192866A1; WO2002098935A1; US7291655B2

Abstract

A polymerisation method with improved productivity, using a co-ordination catalyst, whereby electromagnetic radiation is applied during the polymerisation. The activity of the co-ordination catalyst is greatly enhanced by the irradiation with light.

Description

Polymerization process and device for carrying out a polymerization process

The invention relates to a polymerization process, in particular to a process for increasing the productivity of the polymerization process, and to the polymers produced by the process and to devices for carrying out the polymerization process.

In polymerization, a distinction is made between radical polymerization and coordination polymerization using coordination catalysts. The coordination catalysts, e.g. Metallocene catalysts are usually used together with a cocatalyst, such as alumoxane, since the catalytic activity of the coordination catalysts is often inadequate. New coordination catalysts are being developed which have higher activity, as a result of which the addition of cocatalysts can be avoided or at least reduced.

Another disadvantage of coordination polymerization is that the coordination catalysts are very sensitive to impurities, which can lead to a considerable reduction or even inactivation of the catalytic activity.

There is therefore a need to improve the catalytic activity of coordination catalysts in coordination polymerization.

The invention has for its object to provide a coordination polymerization process which is characterized by particularly high activity of the coordination catalyst and thereby high productivity.

The invention is based on the knowledge that this object can be achieved by supplying electromagnetic radiation during the coordination polymerization.

Surprisingly, it has been shown that in the case of coordination polymerization, that is to say a polymerization which does not take place according to a radical process, the use of electromagnetic radiation results in Increase in the activity of the catalyst or an increase in the productivity of the process can be achieved. Further advantages are that the amount of cocatalyst that is added to increase the catalyst activity can be reduced, or that no cocatalyst has to be added. Another advantage is that "weak" coordination catalysts can be used, which can be activated by radiation to a useful activity level.

The invention relates to a polymerization process using a coordination catalyst, the coordination catalyst and / or the monomer being exposed to electromagnetic radiation during the coordination polymerization process.

The invention further relates to a method for increasing the productivity of a coordination catalyst in a polymerization process, the coordination catalyst and the monomer being exposed to electromagnetic radiation during the polymerization process.

The invention further relates to a polymer which is produced by a coordination polymerization process using a coordination catalyst, the coordination catalyst and the monomer being exposed to electromagnetic radiation during the polymerization reaction.

Finally, the invention relates to a device for a polymerization process, which comprises devices for emitting electromagnetic radiation, the radiation being directed onto the coordination catalyst and the monomer.

Coordination polymerization is a polymerization in which the polymerization is initiated by catalysts such as Ziegler-Natta catalysts or metallocene catalysts, the newly emerging monomers being embedded between growing polymer chains and transition metal of the catalyst complex. Regarding the definition of coordination polymerization, express reference is made to Römpp, Lexikon der Chemie, 10th edition, page 2246 and George Odian, "Principles of Polymerization", 2nd Edition, John Wiley & Sons, USA, 1981. Ionic polymerization is also subsumed under the term coordination polymerization.

The polymerization reaction of the present invention takes place without the formation of free radicals. Furthermore, it is possible that impurities are present in the polymerization process, which can usually be contained in the raw materials.

Coordination catalysts are understood to mean all catalysts that can be used in a coordination polymerization, in particular transition metal compounds, such as Ziegler-Natta catalysts, metallocenes, so-called late transition metal catalysts, and also chromium catalysts, nickel catalysts, vanadium catalysts and Phillips catalysts.

Suitable Ziegler-Natta catalysts are, for example, those which combine a transition element from groups 4 to 6 of the Periodic Table (IUPAC Nomenclature of Inorganic Chemistry, 1989) as a procatalyst and a compound of a metal from Groups 1 to 3 of the periodic table contain the elements as a cocatalyst. They are preferably applied to a carrier, such as silicon dioxide. They can also contain other additives, such as electron donors. Ziegler-Natta catalysts are described, for example, in EP-A-0 261 130, the disclosure of which is expressly incorporated by reference. Further examples of Ziegler-Natta catalysts are described in EP-A-0 688 794, FI-A-974622, FI-A-86866, FI-A-96615, FI-A-88047 and FI-A-88048.

The organic transition metal compounds of the formula I represent a subgroup of the transition metal compounds:

(L) _m R _n MX _q (I)

wherein M is a transition metal from group 3 to 10, for example 3 to 7, such as 4 to 6, and each X is independently a monovalent anionic ligand, such as a σ ligand, each L is independently an organic ligand that coordinated to M, R a bridging group which two Ligand L connects, m is 1, 2 or 3, n is 0 or 1, q is 1, 2 or 3, and m + q is equal to the valence of the metal.

“Σ ligand” is understood to mean a group which is bonded to the metal at one or more points via a sigma bond.

According to a preferred embodiment, said organic transition metal compounds I are a group of compounds known as metallocenes. Said metallocenes carry at least one organic ligand, generally 1, 2 or 3, for example 1 or 2, which is η -bound to the metal, for example an η ^" ligand, such as an η ⁵ ligand. The metallocene preferably contains a transition metal from groups 4 to 6, and is suitably a titanocene, zirconocene or hafnocene which contains at least one η ⁵ ligand, which is, for example, an optionally substituted cyclopentadienyl, an optionally substituted indenyl, an optionally substituted tetrahydroindenyl or an optionally substituted fluorenyl ,

The metallocene compound can have the following formula II:

(Cp) _m R _n MX _q (II)

each Cp is independently an unsubstituted or substituted and / or fused homo- or heterocyclopentadienyl ligand, for example a substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl or substituted or unsubstituted fluoreneyl ligand; the optional one or more. Substituent / substituents are preferably from halogen, hydrocarbon residue (e.g. C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl or C7-C20-aryl-alkyl), C3- C12-Cycloalkyl which contains 1, 2, 3 or 4 heteroatoms in the ring component, C6-C20-heteroaryl, C1-C20-haloalkyl, -SiR " ₃ , -OSiR" ₃ , -SR ", -PR" ₂ or -NR " ₂ , where each R" independently represents a hydrogen or hydrocarbon radical, for example C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl; or, for example, in the case of -NR " ₂ , the two substituents R" can form a ring, for example a five- or six-membered ring, together with the nitrogen atom to which they are attached; R is a bridge of 1 to 7 atoms, for example a bridge of 1-4 C atoms and 0-4 hetero- atoms in which the heteroatom (s) can be, for example, Si, Ge and / or 0 atoms, where each of the bridging atoms can independently carry substituents, such as Cl-C20-alkyl, tri (Cl-C20alkyl) silyl, tri (Cl-C20alkyl) siloxy or C6-C20 aryl substituents; or a bridge of 1-3, for example one or two, heteroatom (s), such as silicon, germanium and / or oxygen atom (s), for example -SiR ^! ₂ , wherein each R ^{1 can} independently be a Cl-C20-alkyl, C6-C20-aryl or tri (Cl-C20-alkyl) silyl radical such as trimethylsilyl;

M is a Group 4 to 6 transition metal, such as Group 4, e.g. Ti, Zr or Hf,

each X is independently a sigma ligand such as H, halogen, C1-C20-alkyl, Cl-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl , C6-C20-aryloxy, C7-C20-arylalkyl, C7-C20-arylalkenyl, -SR ", -PR" ₂ , -SiR " ₃ , -OSiR" ₃ , or -NR " ₂ , each R" as above X is defined, and is preferably independently hydrogen or a hydrocarbon radical, for example C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or C6-C20-aryl; or, for example in the case of - NR " ₂ , the two substituents R" can form a ring, for example a five- or six-membered ring, together with the nitrogen atom to which they are attached;

and each of the above rings alone or as part of a radical as a substituent for Cp, X, R "or R ¹ can further be substituted, for example, with C1-C20-alkyl which contains Si and / or O atoms;

n is 0, 1 or 2, preferably 0 or 1,

m is 1, 2 or 3, e.g. 1 or 2,

q is 1, 2 or 3, e.g. 2 or 3,

m + q is equal to the valence of M.

Said metallocenes II and their representation are known from the prior art. Metallocenes are described in detail in EP 0 260 130, the disclosure of which is expressly incorporated by reference. Further literature which is referred to with regard to the metallocenes is as follows: WO 97/28170, WO 98/46616, WO 98/49208, WO 99/12981, WO 99/19335, WO 98/56831, WO 00/34341, EP-A-0 423 101 and EP-A-0 537 130 and "Metallocenes", vol. 1, Togni and Halterman (Eds.), Wiley-VCH 1998, and VC Gibson et al., In Angew. Chem. Int. Ed., Engl, vol. 38, 1999, pages 428-447, EP 576 970, EP 485 823, EP 785 821, EP 702 303.

Alternatively, in a further subgroup of the metallocene compounds, the metal carries a Cp group as defined above and additionally an η ¹ or η ² ligand, in which said ligands may or may not be bridged to one another. This subgroup includes so-called "scorpionate compounds" (with forced geometry) in which the metal is complexed by an η ligand, which is bridged by an η or η ligand, preferably by an η ^! Ligand (eg a σ-bonded ), for example a metal complex of a Cp group as defined above, for example a cyclopentadienyl group which, via a bridge member, bears an acyclic or cyclic group which contains at least one heteroatom, for example —NR " ₂ as defined above. Such compounds are described, for example, in WO-A-9613529, the content of which is incorporated herein by reference.

Another subgroup of the organic transition metal compounds of formula I that can be used in the present invention is known as "non-metallocenes" in which the transition metal (preferably a transition metal of groups 4 to 6, suitably Ti, Zr or Hf) has a coordination ligand other than the η ⁵ ligand (ie a different one than a cyclopentadienyl ligand.) As examples of such compounds, ie transition metal complexes with nitrogen-based, cyclic or acyclic aliphatic or aromatic ligands, for example like those described in the earlier application WO-A-9910353 or in the review article by VC Gibson et al., Angew. Chem. Int. Ed., engl., volume 38, 1999, 428-447 or with oxygen based ligands, such as Group 4 metal complexes, which carry bidental cyclic or acyclic aliphatic or aromatic alkoxide ligands, for example optionally substituted, bridged bisphenolic Li ganden (see the above-mentioned review by Gibson et al.). Other specific examples of non-η ⁵ ligands are amido, amide diphosphine, amidinate, aminopyridine, benzamidinate, triazacyclononane, allyl, hydrocarbon, beta-diketimate and alkoxide.

Other suitable catalysts are chromium catalysts, such as chromium oxide on silicon dioxide, chromocenes and in particular the catalysts described in EP-A-0 480 276, EP-A-0 533 156, EP-A-0 533 160, EP-A-0 100 879 and US 4,011,382, the disclosure of which is incorporated by reference; as well as nickel catalysts, especially those described in W099 / 62968, W098 / 47933, WO98 / 40420, W098 / 47933, WO00 / 06620 and WO96 / 23010, the disclosure of which is expressly incorporated by reference, and vanadium catalysts.

Phillips catalysts are also very suitable.

It is also possible to use different coordination catalysts together, so-called dual or multi-catalytic systems. These can consist of a combination of various of the aforementioned catalysts, e.g. a combination of two or more metal locenes, a metallocene and a non-metallocene, a Ziegler-Natta catalyst and a metallocene or a Ziegler-Natta catalyst and a non-metallocene.

Preferably the coordination catalysts comprise one or more cocatalysts, e.g. an organic aluminum compound, such as trialkyl aluminum and / or alumoxane compounds. Boron coactivators are also particularly suitable.

Both homogeneous and heterogeneous catalyst systems can be used. In the case of a heterogeneous catalyst system, the coordination catalyst component, optionally together with the cocatalyst, is preferably applied to an inert support, such as, for example, silicon dioxide. The porous, particulate support is usually impregnated with the catalyst system. In this regard, reference is made to EP 678103 and PCT / GB01 / 01280. The coordination catalysts used do not decompose due to activation with electromagnetic radiation.

Suitable monomers for the process according to the invention are, in particular, olefins. Any olefin that can be polymerized by coordination polymerization is suitable.

Preferred olefins are ethylene and propylene and mixtures of ethylene and propylene with one or more α-olefins. Suitable co-monomers are C _2-12 olefins, preferably C ₄ . ₁₀ olefins, such as 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonen, 1-decene, and dienes such as butadiene, 1.7 -Octadiene and 1,4-hexadiene or cyclic olefins such as norbornene, and mixtures thereof. The amount of comonomer is generally from 0.01 to 50% by weight, preferably from 0.1 to 10% by weight and in particular from 0.3 to 3% by weight.

The process according to the invention is also suitable for the polymerization of long-chain α-olefins having 4 to 40 carbon atoms, which can be polymerized either alone or in combination, and also with short-chain α-olefins. Suitable examples are: 1-butenes, 1-pentene, 1-hexenes, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1- Pentadecene, 1-hexadecene, 1-heptodecene, 1-octodecene, 1-nonadecene, 1-eicosen, etc. to tetradecene. Alpha-olefins having 4 to 16 carbon atoms are preferred. Further suitable monomers are isomers of α-olefins with branched alkyl groups, such as 4-methyl-1-pentene.

Other suitable monomers are vinyl monomers such as alkyl and aryl vinyl monomers, e.g. Styrene, vinyl ether, vinyl ester, acrylic acid and its esters, methacrylic acid and its esters, acrylamides, acrylonitriles, vinyl amines, and the like.

The coordination polymerization according to the invention can be carried out in one or more polymerization reactors. Conventional polymerization techniques can be used, such as gas phase polymerization, solution polymerization, slurry polymerization, bulk polymerization, emulsion polymerization and precipitation polymerization. Different polymerization processes can be combined. Particularly suitable net is the combination of a slurry polymerization followed by a gas phase polymerization.

The polymerization processes can be carried out continuously or batchwise.

The process according to the invention is also particularly suitable for prepolymerization, i.e. a prepolymerization followed by the actual polymerization.

The process according to the invention is also suitable for oligomerization. This means that the oligomerization is subsumed under the term "polymerization".

The polymerization process is carried out in the presence of electromagnetic radiation. Electromagnetic radiation is an additional radiation to natural radiation or artificial room lighting.

The increase in the activity of the catalyst system or the increase in the productivity of the polymerization process depends on the intensity of the radiation. The higher the intensity, the higher the activity.

Irradiation can take place continuously, but also at intervals or pulsating or only for a short period at the start of the polymerization.

Radiations of different wavelengths can be used in the method according to the invention. The wavelength can be in any wavelength range of the electromagnetic spectrum, which ranges from gamma radiation to radio waves. Waves in the area between X-rays and microwaves are particularly suitable, the area between UV and infrared being preferred and short-wave visible light and UV light being particularly suitable.

In terms of wavelengths, the radiation can be in the range between 10 ^"12 and 10 ⁴ m. However, radiation between 10 ^{" 8} and 10 ^"2 m, in particular 10 ^{" 8} and 10 ^"6 m and especially radiation in the range is preferred. range between 100 and 800 nm. The radiation can have a uniform wavelength or consist of radiation with different wavelengths.

It has been shown in the attached examples that blue light has a particularly favorable effect on effective polymerization for the catalysts used there, i.e. for the example in question, a wavelength range from 300 to 480 nm.

According to a particularly preferred embodiment, the electromagnetic radiation of a wavelength that lies in the range of the absorption spectrum of the coordination catalyst is used. Radiation of a wavelength in the range of the maximum of the absorption spectrum of the coordination catalyst is preferred.

In principle, there are two options for arranging the radiation source in the polymerization system. Either, and this is preferred, the radiation source is arranged in the interior of the polymerization reactor, optionally also in the feed line to the reactor. Alternatively, the radiation source can be arranged outside the reactor. This is then provided with a window that is transparent to the respective radiation. The window is preferably made of glass or quartz. A window can be omitted if the radiation can penetrate through the wall of the reactor.

Furthermore, it is also possible for a device for emitting electromagnetic radiation to be arranged outside the polymerization reactor or the feed line to the polymerization reactor and for the electromagnetic radiation to be able to reach the reactor via an optical conductor.

The amount of radiation depends on the size of the reactor system.

In a combined polymerization process, such as a slurry polymerization, which is preferably carried out in a loop reactor, and a subsequent gas phase reactor, the radiation can be introduced at one or more points in the loop system. Radiation can also be applied to the gas phase reactor. Alternatively, you can the feed lines to the reactors, optionally in addition to the reactors, are irradiated.

A suitable polymerization system is, for example, the following. The first reactor is a slurry reactor. This works at a temperature in the range of 60 to 110 ° C. The reactor pressure is in the range from 0.1 to 100 bar, preferably 5 to 80 bar and in particular 50 to 65 bar. The residence time is 0.1 to 5 hours, preferably 0.3 to 5 hours and in particular 0.5 to 2 hours. An aliphatic hydrocarbon is generally used as the diluent. The polymerization can be carried out under supercritical conditions. One or more gas phase reactors are subsequently connected. The reaction temperature is generally 60 to 115 ° C, preferably 70 to 110 ° C. The reactor pressure is 10 to 25 bar and the residence time is 1 to 8 hours. The gas used is generally a non-reactive gas such as nitrogen.

The reactor system described for example is particularly suitable for the polymerization of ethylene and propylene, or the copolymerization of ethylene and propylene with α-olefins.

Suitable devices for emitting the electromagnetic radiation are, for example, fluorescent lamps, incandescent lamps and halogen lamps. The amount of radiation in the UV or visible range should be at least one watt per 100 ml reaction volume.

The invention is described in more detail below with the aid of examples which show preferred embodiments. Example 1: Catalyst preparation

The catalyst was prepared by dissolving 11 mg of n-Bu-Cp ₂ ZrCl ₂ (Witco GmbH, Germany) with MAO / toluene containing 1.15 ml of 30% by weight of MAO (30% by weight of MAO in toluene, from Albemarle) and 0.35 ml of moisture and oxygen-free toluene. The metallocene / MAO / toluene solution was placed on a silicon dioxide carrier (SYLOPOL 55 SJ; Grace-Davison, calcined at 600 ° C. with a pore volume of 1.5 to 1.7 ml / g, surface 350 m ² / g) Given in such a way that the volume of the complex solution did not exceed the pore volume of the silicon dioxide (1.5 ml / g). The mixture was then dried and the drying was completed by passing moisture-free and oxygen-free nitrogen through the catalyst at room temperature.

Example 2: Catalyst production

The catalyst was prepared as described in Example 1, but 14 mg of n-Bu-Cp ₂ ZrCl ₂ (Witco GmbH, Germany) were used as the metal locene compound.

Example 3: Catalyst preparation

The catalyst was prepared as described in Example 1, but 17.5 mg of rac-ethylene-bis (2-butyldimethylsiloxyindenyl) zirconium dichloride (prepared according to WO 97 28170) were used as the metallocene compound.

Example 4: Polymerization with full light

The polymerization was carried out in a 20 ml mini-reactor, 7.08 mg of catalyst, prepared according to Example 1, being introduced into the reactor. The reactor was closed and connected to the ethylene source. The ethylene partial pressure was set at 5 bar. The polymerization temperature was 80 ° C and the polymerization time was 60 minute The ethylene consumption was followed by the pressure drop, namely in the range between 4980 and 5010 mbar. The reactor, provided with a glass window, was irradiated with a cold light source FLEXILUX 600 longlife with Phillips 14501 DDL, 20V / 150W halogen lamps. The highest light intensity was used. After a reaction time of 60 minutes, the polymerization was stopped by closing the ethylene feed and the ethylene pressure was released. The yield of the polymer was 0.888488 g and the activity of the catalyst was 125.5 gHDPE / g catalyst per hour.

Example 5: Polymerization without light

The polymerization was carried out as described in Example 4, but no light was irradiated. The amount of catalyst was 6.95 mg. After 60 minutes of polymerization, the yield of polymer was 0.13806 g. The activity of the catalyst was 19.9 gHDPE / g Kat h.

Example 6: Half light polymerization

The polymerization was carried out as described in Example 4, but using only half the light intensity. The amount of catalyst was 6.96 mg. After 60 minutes of polymerization, the yield of polymer was 0.7831 g. The activity of the catalyst was 112.5 gHDPE / g cat h.

Example 7: Polymerization with light

The polymerization was carried out as described in Example 4, but using the catalyst according to Example 2. The amount of catalyst was 7.32 mg. After 60 minutes of polymerization, the yield of polymer was 0.56008 g. The activity of the catalyst was 76.5 gHDPE / g Kat h. Example 8: Polymerization without light

The polymerization was carried out as in Example 7, but no light was used. The amount of catalyst was 7.31 mg. After 60 minutes of polymerization, the yield of polymer is 0.10527 g. The activity of the catalyst was 14.4 gHDPE / g Kat h.

Example 9: Polymerization with light

The polymerization was carried out as described in Example 4, but the catalyst from Example 3 was used. The amount of catalyst was 6.85 mg. After 60 minutes of polymerization, the yield of polymer was 0.74192 g. The activity of the catalyst was 108.3 gHDPE / g Kat h.

Example 10: Polymerization without light

The polymerization was carried out as described in Example 9, but no light was used. The amount of catalyst was 7.24 mg. After 60 minutes of polymerization, the yield of polymer is 0.18847 g. The activity of the catalyst is 26.0 gHDPE / g cat h.

Example 11: Blue light polymerization

The polymerization was carried out as described in Example 4, but using a blue filter which transmits at wavelengths in the range from 300 to 480 nm. The amount of catalyst was 7.24 g. After 60 minutes of polymerization, the yield of polymer is 1.06657 g. The activity of the catalyst was 149.6 gHDPE / g Kat h. Example 12: Polymerization with green / yellow light

The polymerization was carried out as described in Example 4, but with a green / yellow filter which transmits at wavelengths above 400 nm. The amount of catalyst was 7.1 mg. After 60 minutes of polymerization, the yield of polymer was 0.7225 g. The activity of the catalyst was 101.8 gHDPE / g Kat h.

Example 13: Red light polymerization

The polymerization was carried out as described in Example 4, but a red filter was used which transmits at wavelengths above 600 nm. The amount of catalyst was 6.93 mg. After 60 minutes of polymerization, the yield of polymer was 0.43305 g. The activity of the catalyst was 62.5 gHDPE / g Kat h.

The examples show that the activity of the catalyst increases dramatically when irradiated with light and that the activity depends on the intensity of the radiation. The examples further show that the wavelength of the light influences the increase in activity.

Example 14: Polymerization with a Ziegler-Natta catalyst

All starting materials were essentially free of water and air and all material additions to the reactor and at the different steps were carried out under inert conditions in a nitrogen atmosphere. The water content in the propylene was less than 5 ppm.

The polymerization was carried out in a 51 reactor, which was heated, evacuated and flushed with nitrogen before it was put into use. 213 μl TEA (triethylaluminum, from Witco, used without further purification / treatment), 36 μl donor D (dicyclopentyldimetoxysilane from Wacker, dried over molecular sieve) and 30 ml pentane (dried over molecular sieve and gassed with nitrogen) were mixed, and for 5 Leave minutes to react. Half of the mi Schung was added to the reactor and the other half was mixed with 14.2 mg of highly active and stereospecific Ziegler-Natta catalyst (ZN catalyst). The ZN catalyst was produced according to test example 3 in EP 591224 (Borealis) and had a Ti content of 2.1 percent by weight. After approximately 10 minutes, the ZN catalyst / TEA / donor D / pentane mixture was fed to the reactor. The Al / Ti molar ratio was 250 and the Al / Do molar ratio was 10. 100 mmol of hydrogen and 1400 g of propylene were added to the reactor. The lamp was turned on. The lamp was a halogen lamp, 50 watts, 12 volts. The temperature was raised from room temperature to 80 ° C over 19 minutes. After 30 minutes at 80 ° C, the reaction was stopped by letting out unreacted propylene.

The polymer was analyzed and the results are shown in Table 1. The activity was 22.6 kg of propylene per gram of catalyst.

Comparative Example 15:

This example was carried out according to Example 14, but no light treatment was carried out during the polymerization. Details and results are shown in Table 1. The activity was 19.9 kg propylene per gram of catalyst.

The example of this patent thus gives about 15% higher activity than the comparative example. The table also shows that the light treatment has no significant effect on the polymer properties.

Example 16: Comparison of the polymerization with light from a halogen lamp and with light from a mercury lamp

The polymerization was carried out in a 20 ml mini reactor, with catalyst prepared according to Example 1 in the amounts given in Table 2 being introduced into the reactor. The reactor was closed and connected to the ethylene source. The ethylene partial pressure was set at 4.5 bar. The polymerization temperature was 80 ° C and the polymerization time was 60 min. The ethylene consumption was followed by the pressure drop, namely in the range between 4980 and 5010 mbar. The reactor, provided with a glass window, was irradiated with a cold light source FLEXILUX 600 longlife with Phillips 14501 DDL, 20V / 150W halogen lamps. The highest light intensity was used. After a reaction time of 60 minutes, the polymerization was stopped by closing the ethylene feed and the ethylene pressure was released.

The halogen lamp had a very broad spectrum of the emitted visible light with wavelengths from 350 to 750 nm. Three light filters were used which transmit light of three different wavelengths. Ren. The blue filter transmitted wavelengths between 300 and 480 nm, the green / yellow filter transmitted wavelengths above 400 nm and the red filter transmitted wavelengths above 600 nm. The filtered light has only a fraction of the total intensity of the light source. This must be taken into account when comparing the results.

Table 2 below shows the influence of the longitudinal wave of light on the polymerization activity.

Table 2: Effect of light on the polymerization activity with a halogen lamp:

The activity of the catalyst was highest when the filter transmitted light with a wavelength of 300 to 450 nm. The activity decreased when the irradiation was carried out at a higher wavelength.

Was the absorption spectrum of the catalyst n-Bu-Cp ₂ ZrCl ₂ / MAO; Al / Zr = 200 mol / mol compared with the transmitted light, there was a clear overlap of the absorbed light and the transmitted light. It can be seen that the highest activity is achieved at a radiation frequency which corresponds to that of the absorption of the active metallocene / MAO complex. The more the radiation frequency is removed from the absorption spectrum of the catalytic converter, the less the activation effect. FIG. 1 shows the comparison of the absorption spectrum of the metallocene complex (gray area) in comparison with the emission ranges of the three filters.

Additional polymerizations were carried out as described above in this example 16, but instead of a halogen lamp, a mercury lamp was used which emitted in the range from 300 to 550 nm. Compared to the halogen lamp, which has a wide emission spectrum, the mercury lamp has a few individual, very strong emissions. The result of these polymerizations is shown in Table 3:

Table 3: Effect of light on the polymerization activity with a mercury lamp:

Claims

claims

1. A polymerization method using a coordination catalyst, wherein the coordination catalyst and the monomer are exposed to electromagnetic radiation during the coordination polymerization method.

2. A method for increasing the productivity of a coordination catalyst in a polymerization process, wherein the coordination catalyst and the monomer are exposed to electromagnetic radiation during the polymerization process.

3. The method according spoke 1 or 2, characterized in that the electromagnetic radiation has a wavelength in the range between infrared and ultraviolet.

4. The method according to any one of claims 1 to 3, characterized in that the electromagnetic radiation has a wavelength in the range between 800 and 100 nm.

5. The method according to any one of claims 1 to 4, characterized in that the electromagnetic radiation has a wavelength of the absorption region of the coordination catalyst.

6. The method according to any one of claims 1 to 5, characterized in that the electromagnetic radiation has a wavelength in the range of the maximum of the absorption spectrum of the coordination catalyst.

7. The method according to any one of claims 1 to 6, characterized in that the electromagnetic radiation is applied continuously during the polymerization process.

8. The method according to any one of claims 1 to 7, characterized in that the electromagnetic radiation is applied at intervals during the polymerization process.

9. The method according to any one of claims 1 to 8, characterized in that the coordination catalyst is not decomposed by the activating with electromagnetic radiation.

10. The method according to any one of claims 1 to 9, characterized in that the polymerization proceeds without the formation of free radicals.

11. The method according to any one of claims 1 to 10, characterized in that impurities are present in the polymerization process.

12. The method according to any one of claims 1 to 11, characterized in that olefins are polymerized in the polymerization process.

13. The method according to any one of claims 1 to 12, characterized in that in the polymerization process ethylene or ethylene and comonomers are polymerized.

14. The method according to any one of claims 1 to 13, characterized in that in the polymerization process, propylene or propylene and comonomers are polymerized.

15. The method according to any one of claims 1 to 14, characterized in that a Ziegler-Natta catalyst is used as the coordination catalyst.

16. The method according to any one of claims 1 to 14, characterized in that a metallocene catalyst is used as the coordination catalyst.

17. The method according to any one of claims 1 to 16, characterized in that only coordination catalysts with or without cocatalysts are used.

18. The method according to any one of claims 1 to 17, characterized in that a mixture of coordination catalysts is used.

19. The method according to any one of claims 1 to 18, characterized in that a coordination catalyst is used together with a cocatalyst.

20. The method according to claim 19, characterized in that alumoxanes are used as cocatalyst.

21. The method according to claim 19, characterized in that boron catalysts are used as cocatalyst.

22. The method according to any one of claims 1 to 21, characterized in that the polymerization is a solution polymerization.

23. The method according to any one of claims 1 to 22, characterized in that the polymerization is a slurry polymerization.

24. The method according to any one of claims 1 to 23, characterized in that the polymerization is a gas phase polymerization.

25. The method according to any one of claims 1 to 21, characterized in that the polymerization is a slurry polymerization followed by a gas phase polymerization.

26. The method according to any one of claims 1 to 21, characterized in that the polymerization is a supercritical ethylene polymerization.

27. The method according to any one of claims 1 to 21, characterized in that the polymerization is a pre-polymerization.

28. The method according to any one of claims 1 to 21, characterized in that the polymerization is an oligomerization.

29. A polymer produced by a coordination polymerization process according to any one of claims 1 to 28 using a coordination catalyst, wherein the coordination catalyst and the monomer are exposed to electromagnetic radiation during the polymerization reaction.

30. Apparatus for a polymerization process, which comprises means for emitting electromagnetic radiation, the radiation being directed onto the coordination catalyst and the monomer.

31. The device according to claim 30, characterized in that the device for emitting electromagnetic radiation is arranged within the polymerization reactor.

32. Apparatus according to claim 30, characterized in that the device for emitting electromagnetic radiation is arranged within the feed line to the polymerization reactor.

33. Device according to claim 30, characterized in that the device for emitting electromagnetic radiation is arranged outside the polymerization reactor and a window is provided in the wall of the polymerization reactor through which the electromagnetic radiation can get into the reactor.

34. Device according to claim 33, characterized in that the window is made of glass or quartz.

35. Apparatus according to claim 30, characterized in that the device for emitting electromagnetic radiation is arranged outside the feed line to the polymerization reactor and a window is provided in the feed line through which the radiation passes into the line.

36. Device according to claim 35, characterized in that the window is made of glass or quartz.

37. Device according spoke 30, characterized in that the device for emitting electromagnetic radiation is arranged outside the polymerization reactor and the electromagnetic radiation can reach the reactor via an optical conductor.

38. Device according to claim 30, characterized in that the device for emitting electromagnetic radiation is arranged outside the feed line to the polymerization reactor and is electromag- netic radiation can reach the line via an optical conductor.

39. Device according to one of claims 30 to 38, characterized in that the device for emitting electromagnetic radiation emits radiation in the range between infrared and ultraviolet.