Process for the preparation of polyethylene having a broad molecular weight distribution
Abstract
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Expired 10 September 2017, 9 years ago.
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14 claims: 14 independent, 0 dependent
- 1Method of preparing polyethylene by the homopolymerisation of ethylene or by the copolymerisation of ethylene and at least one alpha-olefin comonomer having 3 to 10 carbon atoms, in two liquid phase polymerisation loop reactors connected in series in the presence of a chromium catalyst, characterised in that the ethylene and the chromium catalyst are first introduced into the first reactor at a temperature of between 95 and 110°C to produce an ethylene homopolymer of low molecular weight with a melt-flow index MI2 of at least lg/10 minutes and in that the ethylene homopolymer thus obtained is then transferred into the second reactor to which is added ethylene and possibly the alpha-olefin comonomer at a temperature of between 80 and 90°C in order to obtain an ethylene homopolymer or copolymer of high molecular weight. Procédé de préparation de polyéthylène par l'homopolymérisation d'éthylène ou par la copolymérisation d'éthylène et d'au moins un comonomère alpha-oléfinique comportant de 3 à 10 atomes de carbone, dans deux réacteurs de polymérisation à boucle en phase liquide connectés en série en présence d'un catalyseur au chrome, caractérisé en ce que l'éthylène et le catalyseur au chrome sont d'abord introduits dans le premier réacteur à une température de 95 à 110°C pour produire un homopolymère d'éthylène de bas poids moléculaire d'un indice de fusion MI2 d'au moins 1 g/10 minutes et en ce que l'homopolymère d'éthylène ainsi obtenu est ensuite transféré dans le second réacteur auquel est ajouté de l'éthylène et éventuellement le comonomère alpha-oléfinique, à une température de 80 à 90°C pour obtenir un homopolymère ou un copolymère d'éthylène de haut poids moléculaire. Verfahren zur Herstellung von Polyethylen durch Homopolymerisation von Ethylen oder durch Copolymerisation von Ethylen und von mindestens einem Alphaolefincomonomer mit 3 bis 10 Kohlenstoffatomen, in zwei in Serie geschalteten Polymerisationsreaktoren, die im Kreislauf in flüssiger Phase arbeiten, in Anwesenheit eines Chromkatalysators, dadurch gekennzeichnet, dass das Ethylen und der Chromkatalysator zuerst in den ersten Reaktor bei einer Temperatur von 95 bis 110°C eingeführt werden, zwecks Herstellung eines Ethylenhomopolymers mit niedrigem Molekulargewicht und einem Schmelzindex MI2 von mindestens lg/10 Minuten, und dass das so hergestellte Ethylenhomopolymer alsdann in den zweiten Reaktor überführt wird, in welchen Ethylen und gegebenenfalls das Alphaolefincomonomer bei einer Temperatur von 80 bis 90°C hinzugefügt wird, um ein Homopolymer oder ein Copolymer des Ethylens mit hohem Molekulargewicht zu erzeugen.
- 2Method according to claim 1, characterised in that the chromium catalyst is a chromium catalyst on a carrier, activated. Procédé suivant la revendication 1, caractérisé en ce que le catalyseur au chrome est un catalyseur au chrome sur support, activé. Verfahren gemäß dem Patentanspruch 1, dadurch gekennzeichnet, dass der Chromkatalysator ein sich auf einem Träger befindlicher Chromkatalysator ist und aktiviert worden ist.
- 3Method according to claim 2, characterised in that the catalyst contains 1% chromium and its carrier is based on silica and titanium oxide. Procédé suivant la revendication 2, caractérisé en ce que le catalyseur contient 1 % de chrome et son support est à base de silice et d'oxyde de titane. Verfahren gemäß dem Patentanspruch 2, dadurch gekennzeichnet, dass der Katalysator 1 % Chrom enthält und sein Träger auf der Basis von Kieselerde und Titanoxid beruht.
- 4Method according to claim 3, characterised in that the catalyst has a specific surface area of between 300 and 750 m2/g and a pore volume of between 1 and 3 cm3/g. Procédé suivant la revendication 3, caractérisé en ce que le catalyseur a une surface spécifique de 300 à 750 m2/g et un volume poreux de 1 à 3 cm3/g. Verfahren gemäß dem Patentanspruch 3, dadurch gekennzeichnet, dass der Katalysator eine spezifische Oberfläche von 300 bis 750 m2/g und ein Porenvolumen von 1 bis 3 cm3/g aufweist.
- 5Method according to claim 4, characterised in that the catalyst has a specific surface area of between 400 and 600 m2/g and a pore volume of between 1 and 3 cm3/g. Procédé suivant la revendication 4, caractérisé en ce que le catalyseur a une surface spécifique de 400 à 600 m2/g et un volume poreux de 1 à 3 cm3/g. Verfahren gemäß dem Patentanspruch 4, dadurch gekennzeichnet, dass der Katalysator eine spezifische Oberfläche von 400 bis 600 m2/g und ein Porenvolumen von 1 bis 3 cm3/g aufweist.
- 6Method according to any one of claims 1 to 5, characterised in that the quantity of polymer formed in the first reactor is between 45 and 55 % by weight of the total polymer. Procédé suivant l'une quelconque des revendications 1 à 5, caractérisé en ce que la quantité de polymère formé dans le premier réacteur est de 45 à 55 % en poids du polymère total. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 5, dadurch gekennzeichnet, dass die Menge des in dem ersten Reaktor gebildeten Polymers sich auf 45 bis 55 Gew.-% des gesamtem Polymers beläuft.
- 7Method according to any one of claims 1 to 6, characterised in that the alpha-olefin comonomer, if used, is selected from the group comprising 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-heptene and 1-octene. Procédé suivant l'une quelconque des revendications 1 à 6, caractérisé en ce que le comonomère alpha-oléfinique, si utilisé, est choisi dans le groupe comprenant le 1-butène, le 1-pentène, le 1-hexène, le 4-méthyl 1-pentène, le 1-heptène et le 1-octène. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 6, dadurch gekennzeichnet, dass das Alphaolefincomonomer, wenn es zum Einsatz kommt, ausgewählt wird aus der Gruppe bestehend aus 1-Buten, 1-Penten, 1-Hexen, 4-Methyl-1-Penten, 1-Hepten und 1-Okten.
- 8Method according to any one of claims 1 to 7, characterised in that the polymerisation temperature in the first reactor is between 104 and 109°C and the polymerisation temperature in the second reactor is between 84 and 86°C. Procédé suivant l'une quelconque des revendications 1 à 7, caractérisé en ce que la température de polymérisation dans le premier réacteur est de 104 à 109°C et la température de polymérisation dans le second réacteur est de 84 à 86°C. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 7, dadurch gekennzeichnet, dass die Polymerisationstemperatur in dem ersten Reaktor bei 104 bis 109°C liegt und die Polymerisationstemperatur in dem zweiten Reaktor bei 84 bis 86°C liegt.
- 9Method according to any one of claims 1 to 8, characterised in that the polymerisation pressure in the first reactor and in the second reactor is between 30 and 50 bar. Procédé suivant l'une quelconque des revendications 1 à 8, caractérisé en ce que la pression de polymérisation dans le premier et le second réacteur est de 30 à 50 bars. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 8, dadurch gekennzeichnet, dass der Polymerisationsdruck in dem ersten und in dem zweiten Reaktor bei 30 bis 50 Bar liegt.
- 10Method according to any one of claims 1 to 9, characterised in that a cocatalyst of the alkyl metal, alumoxane or boroxane type is added to the second reactor. Procédé suivant l'une quelconque des revendications 1 à 9, caractérisé en ce qu'un cocatalyseur du type alkylmétal, alumoxane ou boroxane est ajouté au second réacteur. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 9, dadurch gekennzeichnet, das ein Katalysator vom Typ eines Alkylmetalls, Alumoxan oder Boroxan in den zweiten Reaktor hinzugefügt wird.
- 11Method according to claim 10, characterised in that the cocatalyst is an alkylaluminium such as triethylaluminium. Procédé suivant la revendication 10, caractérisé en ce que le cocatalyseur est un alkylaluminium tel que du triéthylaluminium. Verfahren gemäß dem Patentanspruch 10, dadurch gekennzeichnet, dass der Katalysator ein Alkylaluminium ist, wie etwa Triethylaluminium.
- 12Method according to any one of claims 1 to 11, characterised in that the polymer formed in the first reactor has a melt-flow index of at least 2g/10 minutes. Procédé suivant l'une quelconque des revendications 1 à 11, caractérisé en ce que le polymère formé dans le premier réacteur a un indice de fusion d'au moins 2 g/10 minutes. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 11, dadurch gekennzeichnet, dass das in dem ersten Reaktor gebildete Polymer einen Schmelzindex von mindestens 2 g/10 Minuten aufweist.
- 13Method according to any one of claims 1 to 12, characterised in that the final polymer has a melt-flow index MI2 lower than 0.1 g/10 minutes. Procédé suivant l'une quelconque des revendications 1 à 12, caractérisé en ce que le polymère final a un indice de fusion MI2 inférieur à 0,1 g/10 minutes. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 12, dadurch gekennzeichnet, dass das endgültige Polymer einen Schmelzindex MI2 aufweist der geringer ist als 0,1 g/10 Minuten.
- 14Method according to any one of claims 1 to 13, characterised in that it is carried out continuously. Procédé suivant l'une quelconque des revendications 1 à 13, caractérisé en ce qu'il est réalisé en continu. Verfahren gemäß irgendeinem der Patentansprüche 1 bis 13, dadurch gekennzeichnet, dass es auf kontinuierliche Weise durchgeführt wird.
Independent claims14
32 paragraphs, as filed
The present invention relates to a process for preparing polyethylene having a broad molecular weight distribution. More particularly, the present invention relates to the preparation of high density polyethylene, medium and low density having a broad or bimodal molecular weight distribution.
Particularly for high density polyethylene, the distribution of molecular weight distribution (MWD) is a fundamental properties determines the properties of the polymer and thus its applications.
Although it may be difficult to assess the influence of each of property taken independently, it is generally recognized that the molecular weight mostly determines the properties mechanical while the molecular weight dispersion determines mainly the rheological properties.
As an increase in molecular weight normally improves the physical properties of the resins, there is a strong demand for the high molecular weight polyethylene. However it is the highest molecular weight which render the polymers more difficult to transform. On the other hand, an increase in the MWD tends to improve flow high shear rate during the transformation. Thus, in applications requiring a rapid transformation in fairly high die swell as in blow molding techniques and extrusion, broadening the MWD improves the high weight polyethylene processing molecular (= low flow index to melt or low MID<sub>2</sub>)
It is believed that when the polyethylene has both a high weight molecular and a wide distribution of molecular weight, transformation is made easier by the low weight section molecular while the high molecular weight portion contributes to good impact resistance of the film. A polyethylene of this type can be transformed into less energy with yields higher.
The MWD may be described completely by the curve obtained by gel permeation chromatography. However, the MWD is generally described by a value that is a fair assessment, also called the polydispersity index, and which has the ratio between the average molecular weight and weight number average molecular. Depending on the application, the MWD required will vary from 10 to 30.
In order to obtain the advantages of a broad distribution was first proposed to prepare polyethylene having a broad MWD by mixing polyethylenes having different molecular weights. However, results are not proven satisfactory because a simple mixture not behave like an intimate blend of polyethylene prepared in if you. reactions have also been proposed to use two-step in a reactor. Examples of such methods are described in the patent publications GB-A-1174542, GB-A-2020672 and BE-A-883 687.
It was also proposed to use several reactors connected in series. In this respect, there is known a method for preparing a polymodal ethylene polymer in which ethylene is polymerized in the two stages in the presence of an organoaluminum compound containing a halogen, a transition metal compound and different amounts hydrogen in each stage (British Patent No. 1,233,599).
Also known is a process for the preparation of polymers olefin by a two stage polymerization, in which process the high molecular weight polymer is prepared in the first step H with a report<sub>2</sub>/ C<sub>2</sub>H<sub>4</sub> low and the low molecular weight polymer is prepared in the second step with a ratio H<sub>2</sub>/ C<sub>2</sub>H<sub>4</sub> high (demand EP-A-57 352). The catalyst used is, inter alia, a organoaluminum compound containing a halogen and the product of reacting an organomagnesium compound containing oxygen, a organotitanium compound containing oxygen (both compounds being in solution) and a halide of aluminum. A similar process is described in patent application EP-A-57 420. It was also suggested a process for polymerizing ethylene in two steps wherein pressure in the second reactor is maintained smaller than the first reactor; the polymerization is carried out in the presence of a Ziegler-Natta catalyst usual such as a metal catalyst transition supported on a solid carrier and a compound organoaluminum. Examples of such methods are described in the US-A-4414369 and US Patent 4,338,424. However, the polymers ethylene obtained by these methods do not bear long side chains, which is unfavorable for their ability to be processed. This is why the Applicant has developed polyethylene production processes by copolymerizing ethylene and one or more alpha-olefin comonomers having 3 to 10 carbon atoms, in two reactors loop polymerization liquid phase connected in series, presence of a catalytic system consisting of the reaction product an organomagnesium compound with a titanium compound, a compound organoaluminum and optionally one or more donors of electrons, a metallocene catalyst with an aluminoxane cocatalyst or a chromium catalyst, which is the subject of Patent Applications EP-A-580 930 and 649 860.
However, these two processes have the major drawback of being based on the production of very high molecular masses copolymerized in the first reactor and of low mass molecular in the second reactor. This configuration is necessary by the fact that the molecular weight is regulated by Hydrogen additions and difficult in two reactors loop polymerization liquid phase connected in series to produce low molecular weight initially and generate hydrogen surplus between the two reactors. In addition, the comonomer not incorporated into the polymer chains produced in the first reactor is driven in the second where it can react and incorporate in low molecular weights.
The object of the present invention is therefore to remedy the aforesaid drawbacks and to provide ethylene polymers high, medium and low density with good aptitude for processing, good physical properties including mechanical and in which there is no incorporation of the comonomer in the low molecular weights.
To this end, there is provided, according to the present invention, a method of polyethylene prepared by the homopolymerization of ethylene or by copolymerizing ethylene and at least one alpha-olefin comonomer having 3 to 10 carbon atoms, in two reactors polymerization in liquid phase loop connected in series presence of a chromium catalyst. The ethylene and the chromium catalyst are first introduced into the first reactor at a temperature of 95 to 110 ° C to produce a ethylene homopolymer of low molecular weight of an index MI fusion<sub>2</sub> at least 1 g / 10 minutes. The homopolymer of ethylene thus obtained is transferred into the second reactor in which is added ethylene and optionally an alpha-olefinic comonomer at a temperature of 80 to 90 ° C for obtain a homopolymer or a high weight ethylene copolymer molecular.
Advantageously, the chromium catalyst is a chromium catalyst on a support, activated, said catalyst preferably containing 1% chromium and its support being preferably based on silica and oxide titanium.
According to an advantageous embodiment of the invention, the catalyst has a surface area of 300 to 750 m<sup>2</sup>/ G, preferably from 400 to 600 m<sup>2</sup>/ G and a pore volume of 1 to 3 cm<sup>3</sup>/ G, preferably of 1.3 to 2.7 cm<sup>3</sup>/ G.
According to another advantageous embodiment of the invention, the amount of polymer formed in the first reactor is from 45 to 55% by weight of the total polymer and when alpha-olefinic comonomer is injected, it is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-heptene and 1-octene.
The invention also relates to the broad distribution of polyethylene molecular weight and very good homogeneity obtained.
As was already mentioned, the ethylene supply, chromium catalyst and optionally hydrogen are injected in the first loop reactor in the liquid phase at a temperature of polymerization of from 95 to 110 ° C, preferably from 104 to 109 ° C for produce an ethylene homopolymer. These loop reactors are known in the art and are described, for example, in the patents US-A-3,152,872, 3,242,150 and 4,613,484.
We will use as a catalyst any type of catalyst but the chrome chromium catalysts activated carrier suitable particularly well for this purpose. Thus was obtained the Particularly interesting polyethylene yields with Catalysts containing 1% chromium on silica support and titanium oxide, previously activated before being introduced into the reactor in air at a temperature of 500 to 900 ° C, preferably about 650 ° C and optionally reduced Monoxide carbon at a temperature of 300 to 500 ° C. Be used as catalysts supported catalysts with a surface area of 300 750 m<sup>2</sup>/ G and preferably from 400 to 600 m<sup>2</sup>/ G and a pore volume of 1 to 3 cm<sup>3</sup>/ G and preferably from 1.3 to 2.7 cm<sup>3</sup>/ G. The residence time of ethylene and the chromium catalyst in the first reactor is preferably adjusted to produce 45 to 55% by weight of total polymer.
As was already stated, the first reactor is heated to a temperature of 95 to 110 ° C and preferably at a temperature of 104 to 109 ° C to give a product consisting homopolymer essentially of low molecular weight, high density, and MI melt index<sub>2</sub> at least 1 g / 10 minutes and preferably greater than 2 g / 10 minutes.
According to the invention, the ethylene homopolymer stream obtained in the first polymerisation reactor is then transferred to the second loop reactor, eg via one or more settling legs of the first reactor, as described in Patent Application EP-A-649 860. At this time, the second reactor is also fed with ethylene and optionally with comonomer alpha-olefin such as, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-heptene, 1-octene or a mixture thereof. The reaction in this second reactor is carried out at a temperature 80 to 90 ° C, preferably 84 to 86 ° C, preferably in the presence of an inert diluent such as, for example, a aliphatic or cycloaliphatic hydrocarbon such as butane, pentane, hexane, heptane, cyclohexane, methylcyclohexane or an aromatic hydrocarbon such as benzene or toluene. A metal alkyl co-catalyst type, preferably aluminum alkyl, such as triethylaluminum, or alumoxane or boroxane or alkylboron is preferably added to reaction product of the second polymerization reactor to lower the melt index of the copolymer product obtained.
The operating conditions in the second reactor are adapted to the homopolymer or the copolymer of ethylene has a high weight molecular and melt index and the desired density. It is and the final polymer will preferably have a melt index MID<sub>2</sub> less than 0.1 g / 10 minutes.
Although the polymerization pressure in the first reactor is slightly higher than that of the second reactor, to be used a Generally a pressure of from 30 to 50 bar and a time of stay of the reactants in each reactor between 25 and 90 minutes. Thus it advantageous to use a pressure about 40 bar in the second reactor and slightly higher, such as, for example, 42 bar in the first reactor. In fact, it At a minimum the inert diluent containing dissolved ethylene remains liquid and pressure we could increase if the cost of reactor materials did not become prohibitive.
The process is generally carried out continuously, that is to say ethylene homopolymer composed of low molecular weights and containing the active catalyst is transferred in a continuous manner in the second reactor through a transfer line such as, for example, a settling leg of the first reactor, connecting two reactors.
The major advantage of the method of the invention is that by adapting The operating conditions of polymerization in the first and second reactor, such as in particular the temperature and the pressure of polymerization, the choice of chromium catalyst, the amount of ethylene injected, the addition of the cocatalyst, a polymer was obtained final ethylene of melt index, density, and distribution of desired molecular weight.
The production of low molecular weight ethylene homopolymer in the first reactor solves the problem encountered in patent applications EP-A-580 930 and EP-A-649860 where the production of high molecular weight polyethylene is in the first reactor; the latter arrangement inevitably causes The drive into the second reactor, the unincorporated comonomer in the polymer chains formed in the first reactor.
The following provides two non-limiting examples describing the preparation polyethylene according to the process of the present invention and two comparative examples.
<u>Examples 1 and 2</u>
The copolymerization of ethylene was carried out with 1-hexene in two loop reactors in liquid phase connected in series, following the polymerization process written above, under the conditions specified in Table 1 below. Isobutane was used as diluent. The concentration of triethylaluminum (Teai) is given by based on the amount of isobutane. The catalyst is a catalyst containing 1% chromium on silica carrier and titanium oxide (4% titanium), activated at 650 ° C. It has the following features:<tables><table><tgroup cols="2"><tbody><row><entry align="left">specific surface</entry><entry align="left">443 m<sup>2</sup>/ G;</entry></row><row><entry align="left">pore volume</entry><entry align="left">1.4 cm<sup>3</sup>/ G;</entry></row><row><entry align="left">average pore diameter</entry><entry align="left">125 Å.</entry></row></tbody></tgroup></table></tables>
The physical properties such as melt index (MI<sub>2</sub>), The index under high load melt (HLMI), the ratio of these indexes HLMI / MI<sub>2</sub>(SR) and the density and the mechanical properties (resistance to stress cracking) of the final product are also given in Table 1.
<u>Comparative Examples 3 and 4</u>
Copolymerization of ethylene with 1-hexene was carried out in a single reactor under reaction conditions indicated in the Table 1. monomodal resin obtained properties are Also described in this table.
It is found that the polyethylene resins produced by the process of the invention have a given density, a resistance to the stress cracking (ESCR bell) and a much better value SR much higher. <tables><table><tgroup cols="5"><tbody><row><entry align="left">Examples</entry><entry align="center">(1)</entry><entry align="center">(2)</entry><entry align="center">(3)</entry><entry align="center">(4)</entry></row><row><entry namest="1" align="center" /><entry namest="2" nameend="3" align="center">Two reactors in series</entry><entry namest="4" nameend="5" align="center">One reactor</entry></row><row><entry align="left">first reactor</entry><entry align="left">70</entry><entry align="left">70</entry><entry align="left">70</entry><entry align="left">70</entry></row><row><entry align="left">Volume (L)</entry></row><row><entry align="left">Catalyst</entry><entry namest="2" nameend="5" align="left"> Cr / Support activated at 650 ° C</entry></row><row><entry align="left">T (° C)</entry><entry align="left">106</entry><entry align="left">106</entry><entry align="left">105</entry><entry align="left">103</entry></row><row><entry align="left">TEAL (ppm)</entry><entry align="left">0</entry><entry align="left">0</entry><entry align="left">0</entry><entry align="left">0</entry></row><row><entry align="left">Ethylene (kg / hr)</entry><entry align="left">3.1</entry><entry align="left">3.1</entry><entry align="left">9.3</entry><entry align="left">10</entry></row><row><entry align="left">1-Hexene (cc / h)</entry><entry align="left">0</entry><entry align="left">0</entry><entry align="left">75</entry><entry align="left">87</entry></row><row><entry align="left">H<sub>2</sub> (Nl / h)</entry><entry align="left">0</entry><entry align="left">0</entry><entry align="left">10</entry><entry align="left">10</entry></row><row><entry align="left">Isobutane (Kg / h)</entry><entry align="left">thirty</entry><entry align="left">thirty</entry><entry align="left">26</entry><entry align="left">26</entry></row><row><entry align="left">Residence Time (min)</entry><entry align="left">71</entry><entry align="left">71</entry><entry align="left">68</entry><entry align="left">66</entry></row><row><entry align="left">Gas output</entry></row><row><entry align="left">Ethylene (wt%)</entry><entry align="left">1.9</entry><entry align="left">1.8</entry><entry align="left">4.3</entry><entry align="left">4</entry></row><row><entry align="left">1-Hexene (wt%)</entry><entry align="left">0</entry><entry align="left">0</entry></row><row><entry align="left">H<sub>2</sub> (% in volume)</entry><entry align="left">0</entry><entry align="left">0</entry><entry align="left">0.08</entry><entry align="left">0.12</entry></row><row><entry align="left">MID<sub>2</sub> (G / 10 min.)</entry><entry align="left">2.1</entry><entry align="left">2.4</entry><entry align="left">0.09</entry><entry align="left">0.09</entry></row><row><entry align="left">Density (g / cc)</entry><entry align="left">0.964</entry><entry align="left">0.964</entry></row><row><entry align="left">% Polymer produced in the first reactor</entry><entry align="left">51</entry><entry align="left">52</entry></row><row><entry align="left">second reactor</entry></row><row><entry align="left">Volume (L)</entry><entry align="left">35</entry><entry align="left">35</entry></row><row><entry align="left">T (° C)</entry><entry align="left">85</entry><entry align="left">84</entry></row><row><entry align="left">TEAL (ppm)</entry><entry align="left">0.5</entry><entry align="left">1.0</entry></row><row><entry align="left">Ethylene (kg / hr)</entry><entry align="left">4.0</entry><entry align="left">4.1</entry></row><row><entry align="left">1-Hexene (cc / h)</entry><entry align="left">393</entry><entry align="left">1073</entry></row><row><entry align="left">H<sub>2</sub> (Nl / h)</entry><entry align="left">0</entry><entry align="left">0</entry></row><row><entry align="left">Isobutane (kg / h)</entry><entry align="left">7</entry><entry align="left">7</entry></row><row><entry align="left">Residence Time (min)</entry><entry align="left">28</entry><entry align="left">28</entry></row><row><entry align="left">Gas output</entry></row><row><entry align="left">Ethylene (wt%)</entry><entry align="left">5.8</entry><entry align="left">6.1</entry></row><row><entry align="left">1-Hexene (wt%)</entry><entry align="left">0.46</entry><entry align="left">1.0</entry></row><row><entry align="left">MID<sub>2</sub> (G / 10min)</entry><entry align="left">0.07</entry><entry align="left">0.09</entry><entry align="left">0.29</entry><entry align="left">0,295</entry></row><row><entry align="left">HLMI</entry><entry align="left">13.2</entry><entry align="left">18.6</entry><entry align="left">25.3</entry><entry align="left">26.9</entry></row><row><entry align="left">SR</entry><entry align="left">189</entry><entry align="left">207</entry><entry align="left">86</entry><entry align="left">91</entry></row><row><entry align="left">Density (g / cm<sup>3</sup>)</entry><entry align="left">.9584</entry><entry align="left">.9567</entry><entry align="left">.9581</entry><entry align="left">0,958</entry></row><row><entry align="left">Bell ESCR F<sub>50</sub> (Hrs)</entry><entry align="left">175</entry><entry align="left">F<sub>0</sub>> 350</entry><entry align="left">57</entry><entry align="left">54</entry></row><row><entry align="left">50 ° C - 100% Antarox</entry></row></tbody></tgroup></table></tables>
Every citation, both ways
| Document | Relation | Office |
|---|---|---|
| EP0057352A | Cites | European Patent Office (EPO) |
| EP0570051A | Cites | European Patent Office (EPO) |
| EP0572003A | Cites | European Patent Office (EPO) |
| EP0580930A | Cites | European Patent Office (EPO) |
| EP0603935A | Cites | European Patent Office (EPO) |
| EP0649860A | Cites | European Patent Office (EPO) |
| US5284613A | Cites | United States of America |
7 members in 4 offices
Priority claims10
| Document | Office | Kind | Date |
|---|---|---|---|
| 96114683 | European Patent Office (EPO) | A | |
| 96114683 | European Patent Office (EPO) | – | |
| 97101976 | European Patent Office (EPO) | A | |
| 97101976 | European Patent Office (EPO) | – | |
| 97115713 | European Patent Office (EPO) | A | |
| 96114683 | – | – | – |
| 97101976 | – | – | – |
| EP19960114683 | – | – | – |
| EP19970101976 | – | – | – |
| EP19970115713 | – | – | – |
Members7
| Document | Office | Kind | |
|---|---|---|---|
| EP0829495A1 | European Patent Office (EPO) | A1 | |
| EP0832905A1 | European Patent Office (EPO) | A1 | |
| US6063878A | United States of America | A | |
| EP0832905B1This record | European Patent Office (EPO) | B1 | |
| AT201886T | Austria | T | |
| DE69705096D1 | Germany | D1 | |
| DE69705096T2 | Germany | T2 |
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| Event | Code | Office | |
|---|---|---|---|
| Lapsed because of non-payment of the annual feeLapsedMM | MM | BE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Notification of lapseLapsedST | ST | FR | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal feeWithdrawnR119 | R119 | DE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fee paymentPLFP | PLFP | FR | |
| No opposition filedOpposition26N | 26N | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| European patent in force as of 2002-01-01IF02 | IF02 | GB | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents actLapsedNLV1 | NLV1 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| European patents granted designating irelandGrantedFRENCHFG4D | FG4D | IE | |
| Corresponds to:REF | REF | EP | |
| Designated contracting statesAK | AK | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Corresponds to:REF | REF | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Designation fees paidAT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SEAKX | AKX | EP | |
| Designated contracting states (corrected)RBV | RBV | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0832905
- Publication, DOCDB
- 0832905
- Publication, EPODOC
- EP0832905
- Application
- 97115713
- Application, DOCDB
- 97115713
- Application, EPODOC
- EP19970115713
Titles3
- German
- Verfahren zur Herstellung von Polyethylen mit breiter Molekulargewichtsverteilung
- English
- Process for the preparation of polyethylene having a broad molecular weight distribution
- French
- Procédé de préparation de polyéthylène ayant une distribution large de poids moléculaire
Classification
- CPC, 3
- C08F297/08
- C08F10/02
- C08F210/16
- IPC, 4
- C08F4 69
- C08F10 02
- C08F210 16
- C08F297 08
Designated states16
- Contracting states, 16
- Austria
- Belgium
- Switzerland
- Germany
- Denmark
- Spain
- Finland
- France
- United Kingdom
- Greece
- Ireland
- Italy
- Liechtenstein
- Netherlands (Kingdom of the)
- Portugal
- Sweden