TWI239265B - A catalyst for the (co)polymerisation of ethylene and a method for the preparation thereof - Google Patents

Abstract

A particulate, modified chromium oxide catalyst for the polymerisation of ethylene or ethylene with olefins, comprising: (a) a chromium-oxide catalyst, (b) a transition metal compound, and (c) a catalyst activator. A method for the preparation of the catalyst comprises the steps of: (a) subjecting a chromium oxide catalyst precursor, which comprises a chromium oxide compound combined with an inorganic support, to a temperature in the range of from 400 to 950 DEG C under oxidising conditions, and (b) impregnating the obtained chromium catalyst with a catalyst activator and with a transition metal compound which comprises at least one cyclopentadienylic ring bonded to said transition metal and at least one ligand selected from the group comprising alkoxy, amido and hydrocarbyl radicals, halogen and hydride bonded to said transition metal, which cyclopentadienylic ring may contain hereto atoms, be unsubstituted or substituted, be bonded to said transition metal through a bridge, and optionally annealed to other substituted or unsubstituted ring structures, and if two cyclopentadienyl rings are present they may be bonded t each other through a bridge, and (c) subjecting the thus obtained particulate catalyst to drying conditions. This catalyst is suitable for producing polyethylenes under conditions of continuous feeding of all reactants.

Description

1239265 —____ Case No. 88107578 _ Year, Month and Five. Description of the Invention (1) Field of the Invention The present invention relates to a catalyst having a dual activation position and a method for preparing the catalyst. The catalyst includes a chromium oxide catalyst A transition metal compound and a catalyst activator. This catalyst is particularly suitable for the manufacture of polyethylene, whether it is a homopolymer or a copolymer. The molecular weight distribution of its product is bimodal or broad. .

Conventional technology Linear polyethylene, like high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE), can be given special properties as chromium oxide and metals by selecting appropriate polymerization conditions and catalysts for the polymerization reaction. Cyclopentadiene complex catalysts are characterized by their ratio to chain transfer. What's more, many comonomers are introduced. Copolymers that may be unevenly interspersed in this way have quite a wide range of properties. The metal cyclopentadiene complexes are all the same. The polymers catalyzed by a single activator have the same common metallocenes that may appear on the polymer backbone, and are the most important metallocenes for general commercial use. The oxidized activated sites can cause different growth. They are prone to produce short-chain polymers, which have been catalyzed by polymers and monomers and branched bonds. Therefore, the resulting molecular weight distribution and good processing catalysts, because of their activated site-site catalysts (SSC), have a narrower molecular weight distribution and are more uniformly distributed in the monomers and branches. This type

5. Description of the invention (2) The polymer has a high degree of collision and good transparency properties. The main disadvantage is that due to the following points: f2 adhesiveness and other excellent engineering pines, the distribution of field knives is relatively narrow, and # 俨 1 rf »borrow ':": °: can combine chromium oxide and metal cyclopentadiene ,people:,:

Si = catalyzed polymer production, the product can be at the same time ::: ,,,, and Zhan 坆 are all for Xu Xi users — Dajinli, # 八 1 The amount can be controlled in Guangxing or '顶 弋 八 田 说, The molecule of the product is very polymer made. = = Extruded? Made. In addition -㈣; = 来 达 剂 'For example, using two different catalysts. == In the case of different catalysts, it is like mixing When using two kinds of these catalysts, they often affect each other and become intricate. (A) The catalyst system where chromium adheres to objects such as stone evening soil. In general, this * 'system contains oxygen gas. After activation, iron is added to the material and / or the above mentioned complexes are first reduced to aromatics at high temperature, where the aromatics are reduced, and the two catalysts ⑻chrome or 鈒 are added separately. Six carbon rings.… 乂 It is better to add the polymerization reactor individually. Chemical agent: The improved polymerization proposed in the patent case can be a transition metal compound of titanium and vanadium. The vanadium or chromium is used. Titanium is preferred, and the ligand is preferably 1239265 Λ η V. Explanation of the invention (3) And carbocyclic group or hetero, 0 ^ & no 'This ring system contains six non-local 7Γ-electrons' like 疋 bad pentamidine ,, from the example you m ^%. This case proposed The catalyst of the Asian and African particles ^ ^ ^ This example is taken as an example, the polyethylene produced has a considerable number of branches, and its molecular | Bali knife cloth has a medium to wide distribution. According to US 5330 950 patent case and us 54 〇 0815 patent: the molecular weight of its ethylene polymer is broad-shaped distribution, this polymer is made using a catalyst containing magnesium oxide Ziegler and chromium oxide mixed. US 539 9622 patent also proposes a polyethylene The method first uses a chromium oxide catalyst to obtain low-density polyethylene particles. Next, a co-catalyst and a catalyst containing yttrium are added. The catalyzed catalyst contains the knife formula (Cp2YXx) yMzLn, where Cp It is a bad pentadiene ring that can be substituted at will, X is a halogen, M is an alkali metal and B is an electron donating ligand, so a catalytic reaction can produce a layer of high-density polyethylene around the aforementioned particles. The catalyst mentioned in this case Non-grainy

The polyethylene manufacturing method mentioned in EP 339571 patent can also obtain polyethylene with a wide molecular weight distribution. The catalyst system used in this method includes: the catalyst (A) is a silica support containing titanium or chromium; the catalyst (B) is A transition metal compound containing a ligand, the ligand containing a total of 7 Γ ~ electrons, like a dichlorozirconium dicyclopentadiene ring (CpgZrCl2); and the catalyst is an oxygen-free type, such as methylaluminum oxy : 1 ^ 1311111 ^ 11〇 & 11,% 80). Because methyl

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The oxygen and the metal cyclopentadiene complex are not impregnated into the catalyst support, so the catalyst does not really have two activation sites. It is conceivable that in this catalyst, the chromium oxide catalyst generates one kind of particle and the metal cyclopentadiene complex generates another two kinds of particles, which are randomly and partially adhered to each other, and can only make a very uneven powder. These two catalytic sites or precursor catalytic sites f are not directly exposed to each other. Not to mention the original effect before the reduction of hexavalent chromium to divalent chromium. Such polymerization results in products containing many undesired low molecular weight polymers.

The catalyst for the polymerization of olefins mentioned in EP A 0 287 666 patent includes: (A) a metal cyclopentadiene complex, such as a dichlorinated di% pentadiene ring (CpjrCl2), randomly attached to On silica, (B) is an aluminoxide and (C) is an organoaluminum compound like triisobutylaluminum. The polymers paid by this method have a narrow molecular weight distribution.

The WO 0 96/1 41 54 patent proposes a catalyst with a dual activation site. The catalyst is made by sintering; the soil support is soaked with dibutyl inlay, monobutanol and titanium tetragas, and it can also be mixed with Methylaluminum oxide and (BuCp) 2ZrCl2 together / fork bubble. Such a catalyst contains a non-metal cyclopentadiene complex and a metal cyclopentadienium complex. The transition metal compound can be used in a single reaction in a single reactor. The molecular weight of the polyethylene product is two. Style distribution. An object of the present invention is to provide a catalyst having a dual activation position. The catalyst can be used in a single polymerization reactor to produce ethylene.

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According to our control, we can find such a multi-function two-V knife polymer in two-top type or widely. The position of the catalyst catalyst polymer particles is now dilute. So the fusion can be very suitable for the sub-quantity distribution. We are surprised that the chemical has its characteristics. Polymer particles made simultaneously on this substrate. The feature of this invention, which is widely used in the thin film blowing of chromium and metal cyclopentadiene, is that the catalyst will be in the same chromium-forming and single-activated-position catalyst. Poly-Polymer = 〒 activated site catalyst polyethylene resin. This tree has a particularly good extrudability and can be blow-molded. SUMMARY OF THE INVENTION The present invention provides a particulate modified rhenium chromium oxide catalyst that can be used to catalyze the polymerization of ethylene or the polymerization of ethylene and olefins. The catalyst comprises: a) a type of chromium oxide catalyst comprising chromium oxide and an inorganic support ^ 丨, b) a transition metal compound containing a cyclopentadiene ring connected to the cyclopentadiene ring, and the cyclopentadiene ring may contain other atoms in an irreplaceable or substitutable manner, via A bridge is connected to the above transition metal, and can be optionally connected to other replaceable or irreplaceable ring structures through the process of slow cooling. If there are two cyclopentadiene rings at the same time, they may pass through The bridges are linked together, and c) a catalyst activator. The invention also provides a catalyst for the polymerization of ethylene or the polymerization of ethylene and olefins.

Ϊ239265 Case No. 88107578 V. Description of the invention (6) The method for preparing the catalyst 5 includes the following steps: a) A chromium oxide catalyst precursor containing a combination of chromium oxide and an inorganic support, under oxidizing conditions Processing to obtain oxidation state chromium, b) immersing the chromium catalyst obtained in the previous step with the catalyst activator and the metal compound, and the transition metal compound mentioned above contains at least two cycloadiene rings bonded to the transition metal, In addition, the transition metal contains two or more ligands selected from the following groups, which include alkoxydifluorene, a group and a hydrocarbon group, a halogen and a hydride, and the aforementioned cyclopentadiene is divided into two others. Atoms, these atoms are an irreplaceable or cocoa :, connected to the above-mentioned transition metal through a bridge, and replaced; 连接 = connected by slow cooling process to other replaceable or undesirable two possible two if you, if you At the same time, two cyclopentadiene rings exist, and they are connected together by bridges,] c) adding the granular catalyst obtained in another step Dry. The most suitable catalyst in the present invention can be the catalyst of the oxidation state of the oxygen obtained in step a) above and then by the method described above. It can be used for homopolymerization reaction or coupling reaction of ethylene. '1239265 _MM 88107578__year 3 a V. Description of the invention (7) " ^ ----— Figure 1 shows a graph of the production of polyethylene with different catalysts. Curve (I) represents the catalyst of the present invention. Line ^ knife 1-metal cyclopentadiene complex catalyst is distributed, and the curve (11 is a thorn. A "two emulsified chromium catalyzed detailed description of the present invention ^ The catalyst precursor of the present invention includes a support on this branch There are oxide complexes and metal ring formations-the wrong person reads a, "The appropriate catalyst support for people is talented ..." The 3 milk compounds of the machine, preferably silica, alumina, and silica and alum = stone The content of the support material of the evening soil must exceed the reset percentage of one hundred hundred swords. When preparing the catalyst precursor, the appropriate amount of chromium compound is first connected to the surface of the support. It can also be added together or separately with the chromium compound. A small amount of titanium is a compound. The aforementioned chromium compound can be any suitable complex, or an inorganic or organic chromium compound that can be oxidized to chromium oxide. The content of the chromium compound mixed with the inorganic support must be sufficient Make the end The content is between 0.001 and 10% per hundred, preferably between 0.1% and 2%. This percentage is based on the weight of metal chromium compared to the weight of inorganic support = juice: chromium compounds. It can be attached to the surface of the support in a variety of different ways. One possible method is to co-precipitate the chromium compound with the inorganic oxygen-containing compound, and then form a precipitate on the catalyst particles to ensure that these two components are included.

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Case No. 8810757R V. Description of the invention (8) ± _η Revision 2. Convenient methods have been widely known and published in many publications, as well as in the aforementioned patents. ^ ^ ,, " " § Any remaining solution after the secondary bubble reaction is completed will be removed to obtain a dry solid. The catalyst precursor of the described solid L chromium oxide / support can be purchased directly from the manufacturer. Therefore, its detailed preparation instructions are redundant. Useful catalyst precursors have an average particle size ranging from 10 micrometers to more than 150 micrometers, preferably between 2 micrometers and 20 micrometers, and the particle size distribution is narrow to broad. Such particles may be in the form of spheres' produced by spray drying of suspensions or irregular geometries resulting from the comminution of solid materials. The surface area of the final catalyst particles should be between 150 and 600 square meters per gram, preferably between 400 and 550 square meters per gram, and their pore volume is 1 to 3 cubic meters. Cm / g. The catalyst precursor thus obtained must be activated before use. The activation step is sintered in dry air or other oxygen-containing body to 400 to 950 ° C. 'Best achieved at 5500 to 90 (rc, the burn time is 10 minutes to 72 hours') It is 2 to 20 hours. The oxidized catalyst precursor can be further reduced with carbon monoxide or carbon monoxide with inactive components such as nitrogen or argon. The reduction is usually performed at 300 to 50 ° C for 5 minutes to 48 hours' is preferably 1 to 10 hours. When the reduction reaction is over, most of the chromium should be in the divalent oxidation state. Such a reduction step is not absolutely necessary. Unreduced chromium oxide will still be in the end. During the polymerization reaction, olefin monomer was 1239265, i.e. 88107578. V. Description of the invention (9) Suppressor. The only disadvantage is the activation site of the chromium oxide catalyst, there will be a period of induction before. It must be stored in a non-activated hydrocarbon solvent, He TeΪ, whether it is in dry powder or suspended in a clam. Steps and benefits of the process For the preparation of chromium, it is catalyzed that the premetallic compound cyclopentadiene ring is irreplaceable or bridged with the process to connect the two metal transition metals. Different metal transition metals are selected to contain at least oxy groups. The final ammonium catalyst system will be immersed in the catalyst in one step and then connected to the substitutable ferrous metal. Other compounds are preferable. Their compounds are usually cyclopentadiene from titanium, and the following groups are formed and broken. The obtained chromium oxide / support catalyst and transition, the above-mentioned transition metal compound has at least one transition metal. As for the cyclopentadiene ring atom, the difluorene ring can be bound together: Randomly through the cyclic structure of the slow cooling generation. If two rings may be linked together via a bridge at the same time, this is called a metal cyclopentadiene complex. There are many complexes that can be applied to this Invented, but among them the compounds of rhenium are preferred, and this transition metal group is selected from the group consisting of an alkyl group, a hydrogen atom and a hydride. This invention most generally believed ligands, part or all of the action and / or the monomer and the catalyst heteroaryl opening.

Page 17 1239265 Correction

Case No. 88107578 V. Description of the invention (10) The applicable metal cyclopentadiene compounds containing the above-mentioned components are known and mentioned in the aforementioned patent cases (for example, the former widely known as 41 Γ. The preferred metal cyclopentadiene The fluorene compound is bis-base polepentadiene) -transition metal function, and is preferably dichlorobis ((pentadiene)) or dichlorobis (n-butylcyclopentadiene) fluorene. Gold complex catalysts are often referred to as " single activated site catalysts, and SSC ° has been used to prepare supportive metal cyclopentadienyl complex catalysts. The applicant has previously claimed the Norwegian patent No. 960898. Medium = Out, and its detailed description is listed in the reference materials of this article. Mingzhi particles can produce polymer particles with good appearance. The catalyst of this catalyst must then contain an active agent such as aluminum oxide or ion active agent, such as aluminum oxide or ion active agent. It is aluminoxyl, methylaluminum oxy (Me thy 1 a 1 um i noxan, Μ Α. 1 l ·, put in 4 彳 狄 / * i master and slave from the k. Ming oxygen can be attached first On an emulsified chromium / support catalyst, — At the same time or afterwards. The most convenient s ”: is a diisocyanate complex of epithelium and is dissolved in a solvent at the same time: a solution of metal-like cyclopentadiene benzene and Chromium oxide / support H't is like toluene, and then immerse the mixed nail in an inactivated environment by radicals and soak it together. Finally, the solvent can be wrapped in the final catalyst; the catalyst can be used. The catalyst contains: 铪 and Shao. In this catalyst-0.4 to 100% to 5%, preferably 0.6%, and most preferably .2; =:% & quot 5 to 2 per cent., Preferably about a percentage: 522 wrong; and 5 to 100 per cent replacement of aluminum; this percentage is

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_88107578_ £ V. Description of the invention (11) The catalyst of the present invention has high activity in the polymerization reaction when the weight of the metal itself is compared with the total weight of the catalyst. ★ Every ^ is unexpected, because the different catalytic positions are close Contact, ^ consistently in ^ will cause each other to be inactive, especially the activation position of chromium oxide = usually covered by the methyl layer oxygen of layer j, so it should become inactive. However, every 2 catalysts can simultaneously produce chromium oxide and metal cyclopentadiene 226. Ping complex catalyst polyethylene can be used for the polymerization of ethylene or ethylene with a single comonomer up to 20% by weight and a different comonomer. The two olefin comonomers have a molecular formula like CH strict CHR, where two bins have no carbon atoms, and preferably 1 to 10 carbon atoms. The special 3 to 8 olefins include propylene, butylene, butylhexene, and 4-methylpentene. In addition, styrene and norborene can also be used as comonomers. The polymerization can be carried out in a conventional reactor like a single reactor or preferably in a continuous reactor. This catalyst is suitable for the polymerization of various types of dilute hydrocarbons, especially for gaseous and suspended polymerizations. The word "polyethylene," as used herein, includes ethylene homopolymers and ethylene copolymers. The polyethylene produced by the present invention has a broad or double top molecular weight distribution (MWD), which is the MWD pattern. The low and / or high molecular weight part has more or less obvious tail lines. Figure 1 shows the use of the catalyst of the present invention

Page 19 Case No. 88107578 1239265

5. Description of the invention The typical molecular weight distribution of the polyethylene obtained in (12). The catalyst is characterized in that a catalyst particle contains an activated complex and an activation site of a metal cyclopentadiene complex. The complex activation site in the catalyst behaves like a general chromium / di " oxidation catalyst, and the polyethylene obtained has High average molecular weight and wide envy 'MWD. Figure 1 shows a typical chromium-catalyzed polyethylene MWD curve (curve. Similarly, the activation position of the metal cyclopentadiene complex in the catalyst is different from the chromium activation position and the polyethylene produced has a low average fraction. And narrow MWD (Figure II curve II). The catalyst of the present invention combines the characteristics of the first two chemical agents into the same catalyst particle. Therefore, each polymer contains chromium and metal cyclopentadiene. Complex-catalyzed polymer: Therefore, the final polymer resin has a better shape than the polymer resin generally made from a single activated site catalyst solution, so the final polymer can be processed to obtain a homogeneous melt.

The polyethylene produced by the catalyst of the present invention may have part of the same average molecular weight as that of polyethylene catalyzed by a metal cyclopentadiene complex, and its MWD may be the same as that of chromium catalyzed polyethylene. Before proceeding to the polymerization reactor to carry out the polymerization reaction, the catalyst may optionally use a well-known method to introduce a small amount of ethylene for pre-polymerization. Generally speaking, the polymerization is performed under the conditions of ^ 0 and C, and the total pressure reaches 70 bar (bar). Oxygen is added to control the molecular weight and melting coefficient of the polymer, = the degree of divergence of the polyethylene backbone and the polymer The density number is widely known and need not be repeated. The typical polymerization conditions fascinate sweat in the examples below.

Page 20 1239265 Case number 88107578 V. Description of the invention (13)

* The density of polyethylene obtained under the above-mentioned uncoupled reaction conditions is between 910 and 960 kg / m3, and the melting coefficient (MFR 2) is between, • οι and more than 100 g / min. Fortunately, it is between 0 and 60 g / gram (measured according to the method of ASTM 1 238). For a description of the polyethylene produced, reference is made to the following examples. In the present invention, the following examples will be used for further detailed description. The examples will explain the borrowing of iLi dagger △ two gas fossil catalyst catalyst precursor Xi Yu. In the following description of the examples, three named A, B And C different chrome / silicon oxide catalyst precursor products. Another soil support was added for comparison. Table 1 lists the relevant physical and chemical catalyst precursors that can be purchased from different companies, such as Grace, Bayskos, and PQ, which can also indicate that these chromium / silicon dioxide e-catalysts are widely used. Degree. month! The sintering / activation reaction of the catalyst precursor is performed at the warm temperature as listed in Table 1: it is carried out in a fluidized bed, and all the steps are based on Changzhi. 10 grams of various catalyst precursors activated in dry air / 1239265 Amendment No. 88107578 V. Description of the invention (14) Sintering for 5 hours to activate chromium to hexavalent chromium (chromium trioxide) and reduce the surface warfare. Chando 'can also be reduced with carbon monoxide in nitrogen after the oxidation step. ’Table 1 Chromium / Silica dioxide catalyst BC〇 1 · 〇 1 · 0 〇 〇 < 0.3 〇 2.6 2 · 5 〇 1 · 〇 2 · 5 490 450 580 /-815 /-600 /-815/380

A Chromium (wt%) 0.5 Iv (wt%) 0.8 Titanium (wt%) 0 Pore volume (ml / g) 2.5 Surface area (square meter / g) 400 in air / carbon monoxide 580 / 380 activation temperature (° C) 680/380 620/380 ———:: — = — ----------------- ------------ = = = = = = = = = = = = Soaked with the metal cyclopentadiene complex and methyl sodium oxygen All the burned components listed in Table 1 are transferred to the glove box and then dried In the absence of oxygen and nitrogen, according to the following with dichlorobis- (n-butylcyclopentadiene) hydrazone and methyl ^ 1239265 Case No. 88107578 V. Description of the invention (15) 1) Weigh a quantitative stir bar 2 ) Will be 30% of the metal salt; dichlorobis- (Zhengshi triangle flask; the weight of the methyl aluminum oxide dissolved in toluene and then added to the base% pentyl ^ Mu) by mistake into the containing magnet 3) more Add one Jiamo bran face, one a, two man and stir the contents of the two-corner bottle for 30 minutes; g & $ eight catalyst ingredients are placed in a tommax triangle bottle with a lid and a magnetic stirrer; Stir 3 〇minutes, then the lid is perforated, insert two small tubes and then introduce nitrogen into the catalyst component 30 minutes. When the solution of step _ is added to the: Intermediate: syringe-dropwise added, ... to get no agglomeration, the flow of ' Saturated powder 0 Soaked powder 7) Store the bell in the flask, and then store the catalyst in Table 2. Under nitrogen, see Table 2 until use. Various catalysts chromium catalyst zirconium compound methylaluminum oxide (g) (g) (ml) (ml) 3. 00 0. 033 3. 57 3. 63 2. 00 0. 022 2. 38 0 2. 00 0 033 3. 57 3. 93 catalyst

A

B

C

Page 23 1239265 Case No. 88107R7 ^ V. Description of the invention (16) D 3. 40 = 0 1. 20 Polymerization reaction ^^ The laboratory is equipped with a plate stirrer and heated to 80 to 100 t. Luo ^ Early Han should suppress Λ, then put Yu Ding, θ into the amount of catalyst, add anti i cry (Yuan Ke \ Khan began to stir. After adjusting the temperature to the required value, vinyl will be jealous: two Λ Or without adding hydrogen) until a predetermined pressure is reached. Ethylene =. During the polymerization, ethylene was continuously added to maintain it. -The consumption of ethylene is also monitored at any time during the dimerization reaction; the olefin is a comonomer, and it is put into reaction with isobutyrene: ancient: outside can also be added at the same time, all the reagents used are continuously " Polymerization grade ". Lice: When using dihexene, use a tube to add the reactor in stages with ethylene. The constant temperature of the reactor uses the method of automatic heating and / or cooling == to the exact range of positive / negative 0.2 t. The polymerization reaction is terminated when a predetermined polymerization reaction time is reached. The obtained compound was weighed, and samples were collected for further processing and testing. One of the samples of main f is mixed with additives to stabilize the polymer for the next reaction. 0 / The reactor conditions for polymerization are listed in Tables 3 to 7 on page 24 1239265 1 88107578 V. Description of the invention (17 ) The properties of the polymer prepared by the anamorphic method are determined by the following method: The rabbit solution blanket 'MFR' is in accordance with the method of ASTM D 1 238 in an amount of 2.16 kg and 21.6 kg in 19. Determined. The ratio of the melting coefficient measured at 21.6 kg and 2.16 kg is called the F R ruler. The relationship between the molecular weight (mw, ㈣ 1 ecu 1 ar weight) measured by GPC and gel permeation chromatography (GPC) and the zero viscosity (~) measured by kinetics are as follows: The known equation expresses: ^ ο'K · (Mw) α where K is a proportionality constant and α > 丨. Because zero viscosity is not easy to calculate, it is often replaced by τ? (0 · 05). Therefore, a large " (005) value indicates a high molecular weight. A polymer with a broad molecular weight distribution (MWD) has a significant thinning shearing force than a polymer with a narrow MWD. Therefore, even if a polymer with a broad MWD has a large β (0. 05) value, its value of 7 (300) is very small. The polydispersity index, PI, is expressed by the following formula: PI = 105 / X, where X is G, and G, is the horizontal coordinate of the intersection. The stiffness coefficient G * is defined as: G * = G '+ iG'f, where the real part, the storage factor G, represents the elasticity of the polymer, and the imaginary part, the loss factor G ,, represents the viscosity of the polymer Stagnation. More elastic polymers have larger G values. Therefore, the G / frequency vs. G " / frequency plot can be used to know the elasticity of the polymer. When G, with

Page 25 1239265 _ Case No. 88107578__Year Month Day ____ V. Description of the invention (18) When the slope is steep, the X value at the intersection will be smaller and the PI value will increase, that is, a more flexible polymer ( Polymers with broad MWD) have larger PI values. Diafiltration chromatography 'GPC' uses molecular size to separate and calculate Mw, Mn and MWD. It can also be used to estimate polymer fractions made from different activation sites. Multiplex analysis uses infrared rays in the range of 1 250 to 8 9 0 1 / cm to detect polymer end groups and comonomer content. Unsaturated end groups of polyethylene made from chromium catalysts are mainly ethylenic groups, while those made from metal cyclopentadiene complex catalysts are mainly composed of trans-vinyl groups. The fractions of polyethylene obtained from different catalysts can be calculated quantitatively. Example 1 is 9 In an 8-liter large stainless steel reactor, ethylene and hexene in weight percent are added, and then in the presence of the above-mentioned catalyst A, according to the former = two ordinary polymerization steps at 80 (Example丨) and "It (Example 2) carried out = mouth reaction. Experimental parameters and polymerization results are listed in Table 3. They show that the polymerization temperature has little effect on the activity of the catalyst.

Make steps. Low activity = oxidized chromium (not reduced). Repeat the polymerization of Example 丨. Experimental parameters and polymerization results are shown in Table 3. Polymerization reaction

Page 26 1239265 __Case No. 88107578 Year, Month, Day and Date_ V. Description of the Invention (19) Example 4 (for comparison) Use a chromium oxide catalyst that has not been soaked with metal cyclopentadiene complex and aluminum oxide The polymerization step of Example 2 was repeated. The experimental parameters and polymerization results are listed in Table III. The activity of this catalyst is low. Example 5 (for comparison) A conventional metal cyclopentadiene complex catalyst (SSC) was used to repeat the polymerization step of Example 1. The experimental parameters and polymerization results are listed in Table III. The activity of this catalyst is low. Example 6 (for comparison) The polymerization step of Example 2 was repeated with a catalyst containing no metal cyclopentadiene complex. The catalyst has the same properties as those of Examples 1 and 2 except that the chromium oxide / stone oxidite catalyst is not immersed with the metal cyclopentadiene complex 'and is only soaked with fluorenyloxymethane (M A 0). The activity of this catalyst is very low. The catalysts of the present invention used in Examples 1 and 2 have significantly higher activity than the general metal cyclopentadiene complex (single activation site) catalyst of Example 5 and the general chromium catalyst of Example 4. The catalyst of Example 6 was not soaked with the metal cyclopentadiene complex, and its activity was very low. The double-activated site catalysts of the present invention seem to contain more activated polymerization sites than other catalysts. The catalysts of the present invention appear to have higher activity values than the sum of the catalyst activities of Examples 5 and 6. From the point of view of t and good management, it seems that the dual activation site f of the present invention seems to have a synergistic effect. 1239265

From Tables 3 and 2), its characteristics are not as good as those between metals. This has the amount of metal rings. It is also possible that the compound has a specific MWD (comparative and MWD (comparable to the car). The present invention is between the general olefin complex and the result to support the idea of pentadiene complex determination. Cyclopentene Example 5) A polymer prepared by using the catalyst described in Example 4) (Example 1), a chromium catalyst (Comparative Example 4), and a generalizing agent (Comparative Example 5). The idea of catalysts in the polymerization reaction with contemporaneous and chromium activation sites. At the same time, the polymer catalyzed by a polydiene complex made from a dual activated site catalyst has a higher Mw and a lower Mw When using a polymer film to perform infrared analysis, the polymer composition catalyzed by the catalytic, intermediate metal cyclopentadiene complex activation site can be measured. From the results in Table 3, it is confirmed that the metal cyclopentane is in the polymerization reaction. The two complexes and chromium activation sites are both activated. It is apparent that the catalysts of the present invention can simultaneously produce different polyethylenes. Table III Polymerization

Example 1 Catalyst A

Comparison for comparison Comparison for comparison A2 X Chromium oxide 3 SSC Chromium / methylaluminum oxide 4 Chromium / silicon dioxide activation

1239265 — —_ Case No. 88107578_Year Month Day_ 5. Description of the invention (21) Oxidation temperature 680 680 680 680 600 (1) 680 (° 〇 Reduction temperature 380 380 No reduction, no reduction, no reduction 380 (t :) Polymerization reaction Reactor temperature 80 94 80 94 8〇94 (° 〇Total pressure 26.0 30. 5 26. 0 30. 5 26 · 〇30 · (pressure)

Cat · weight 0 · 649 0.653 0.888 0.41 2 0 · 708 〇, 892 (g) Induction time 0 0 1 5 0 1.5 (minutes) Reaction time 72 78 96 173 78 173 (minutes) Polymer yield 1 8 2 0 1850 980 1265 163〇1010 (g) Productivity 2810 2830 1000 30 70 2〇4〇1130 (g / g) Active 2370 2280 680 1200 154〇400 (g / g · hour) (1) = Shi Xitu support Okonomiyaki

Page 29___ 一 1239265 _Case No. 88107578_Year Month Day Amendment V. Description of the Invention (22) (2) = Unreduced chromium oxide (3) = Only X chromium oxide (4) = Without metal Cyclopentadiene complex immersion Table III (continued) Properties of polyethylene Example 1 2 3 4 5 6 For comparison For comparison For comparison MFR2 0. 43 0. 60 0. 12 0. 03 0. 96 < 0 01 MFR21 10. 2 15 5. 5 2. 8 16. 5 1. 4 FRR 17. 2 25 46 90 17. 2 > 140 Density 947 948 947 953 946 947 G, (〇 · 05) 404 305 2140 582 9 11 11320 77 (0. 05) 1 7563 13801 66701 182780 7696 323525 η (300) 1353 1168 1431 1323 1412 1533 PI 0. 5 0.6 0. 8 4. 5 0. 4 7. 7

Mw 1 60, 0 0 0 140,000 20 0, 0 0 0 nd 135,000 5 60, 0 00 Μη 45,000 44, 000 41,000 nd 53, 000 12,500 MWD 3. 6 3. 2 4 · 9 nd 2. 5 42 ° / 〇ssc 82 90 70 0 100 0

Page 30 1239265 Case number 88107578 V. Description of the invention (23)

-3-_LQ In a 2 liter stainless steel reactor, use 1 liter of isobutane as the reaction medium and add 0.16 to 2.92 weight percent of hexene as a co-monomer and then polymerize ethylene in the presence of catalyst A effect. At the same time as ethylene was added 0, 1 270 or 70,000 moles of hydrogen. The polymerization reaction was terminated after 60 minutes. The experimental parameters and polymerization results are listed in Table IV.

iJfe Examples 11 and 1 2 (for comparison) The polymerization reaction steps of Examples 7 to 10 were followed. The catalyst used is a common metal cyclopentadiene complex. The experimental parameters and polymerization results are listed in Table IV. Table 5 shows that when the polymerization temperature is 94 ° C instead of 85 ° C, the polyethylene has a higher molecular weight, a broader molecular weight distribution (MWD), and a clear tail of the MWD curve. The reason is that as the temperature increases, the activity of the chromium activation site also increases. Table 4 Polymerization Example 7 8 9 10 11 12 (for comparison) (for comparison)

Page 31 1239265 Case No. 88107578 Amendment V. Description of the invention (24) Catalyst reference number AAAA SSC SSC Oxidation temperature 680 680 680 680 600 600 (° 〇 Reduction temperature 380 380 380 380 NA NA (° 〇C6 in iC4 0. 16 2.92 2 · 92 2. 92 0. 16 2.92 Weight percentage H2 in C2 0 1270 70 0 0 0 1270 7000 «Molar part reactor temperature 94 85 94 94 94 94 (t :)- Total pressure 30.5 22. 0 25 · 0 25. 0 30. 5 25. 0-(Air pressure) Cat. Weight 0.094 0. 130 0.142 0.104 0. 093 0. 099 (g) Productivity (g / g) 1800 1540 1100 1590 30 60 2830 Active 200 0 1670 1270 1850 3220 3110 • (g / g · hour) NA = Not applicable Table 4 (Continued)

Page 32 1239265 _Case No. 88107578_Revision V. Description of the invention (25) Properties of polyethylene Example 7 8 9 10 11 12 (for comparison) (for comparison MFR2 1. 3 25 > 80 1. 8 16. 8 > 100 (g / 10 minutes) MFR21 24 35 (g / 10 minutes) Density 946 930 930 956 932 (g / cubic inch) FRR 21/2 18.5 19. 4 G, 0. 05 30 0. 5 570 4 57 0. 0 5 6080 330 25500 500 7/300 1250 210 1140 270 PI 0. 41 nd 0. 72 nd Mw 135000 550 0 0 30 0 0 0 115000 60 00 0 1 0 0 0 0 Μη 38000 1 9 0 0 0 40 0 0 2 6 0 0 0 1 5 00 0 300 0 Mw / Mn 3. 6 2. 9 7.5 4.4 4 3. 3 Cr / SSC 5/95 10/90 nd 10/90 nd MFR powder measurement examples 1 3 and 1 4

Page 33 1239265 _Case No. 88107578 __ Year Month _ Amendment ___ V. Description of the invention (26) The catalyst B mentioned in Table 1 and Table 2 was burned to 5 8 5 ° C and then reduced to 3 8 0 ° C, and then soaked with the metal cyclopentadiene complex catalyst and aluminoxide as described above, put it into a 2 liter stainless steel high-pressure steam cooker to perform the polymerization reaction of acetamidine according to the above general polymerization reaction steps. 1 liter of isobutyl sinter was used as the reaction medium, and 0.16 or 2.92 weight percent of hexamethylene co-monomer was added. At the same time, ethylene was added with 270 parts per million moles of hydrogen. The polymerization reaction was terminated after 60 minutes. The experimental parameters and polymerization results are shown in Table 5.

Example 15 (for comparison) The catalyst on the support of Shi Xitu was changed to a metal cyclopentadiene complex catalyst with a single activation site, and then the polymerization reaction procedure of Example 13 was followed. The experimental parameters and polymerization results are listed in Table 5. "

Catalyst B is a chromium / silicon dioxide catalyst with a low porosity. It is commonly used to make high molecular weight polyethylene. Examples 13 and 14 show that the low-porosity catalysts can be driven by the catalysed substance and can also be used as catalysts with dual activation sites, and the activity is to the extent of accessible. The melting coefficient of the final polyethylene product is controlled by hydrogen, while the density is controlled by dihexene. Even if the obtained MWD is narrow, it can be seen from the OD curve that the MWD is a double top. In this example, the effect of the chromium activation site is not as significant as that of the aforementioned catalyst A.

1239265 Case No. 88107578_Year Month Day Amendment V. Description of Invention (27) Table V Example 13 14 15 (for comparison) Catalyst BB SSC Reference number Oxidation temperature 585 585 600 (° 〇 Reduction temperature 380 380 — (° 〇C6 在iC4 0.16 2. 92 0. 16 weight percent H2 in C2 0 1270 1270 1270 parts per million mole reactor temperature 85 94 94 (° 〇 total pressure 27 · 5 25. 0 30 · 5 (pressure ) Cat. Weight 0.139 0.094 0.093 (g) Productivity (g / g) 1550 1810 30 60 Activity to P4000 1530 2 0 0 0 3220

Page 35 1239265 ». 88ΐ〇7578 Che Yueyue __correction

V. Description of the invention (28) (g / g · hour) MFR2 22 (g / 10 minutes) MFR21 nd (g / 10 minutes) Density 953 (g / cubic inch) Rheology: G, (0.05) 2. 9 η (0.05) 570 η (300) 240 The two-phase structure has Mw 70000 Μη 1 5000 Mw / Mn 4. 7 Cr / SSC 5/95 10/90 22. 8 16 · 8 nd nd 933 956 4 · 1 4.0 660 500 250 270 Yes No 60 00 0 One 1 500 0 10/90 4. 0

nd = Undetermined f Grade—jfi to 19 The catalyst C mentioned in Tables 1 and 2 was burned to 0 ° C after heating to 815 ° C (Examples 16 to 1 s), or without reduction (Example 丨 9), and then soaked with the metal cyclopentadiene complex catalyst and aluminoxide as described above, 1239265

Polymerization of ethylene was performed according to the above-mentioned polymerization reaction steps. The polymerization conditions and results are shown in Table 6. / Example 20 and lower the activation temperature of catalyst C to 62 ° C, and then repeat the polymerization reaction steps of Examples 16 to 18. Experimental parameters and polymerization results are listed in the table

fExample 2 2 (for comparison) The polymerization reaction steps of Example 19 were repeated using a metal cyclopentadiene complex catalyst with a normal single activation site. The experimental parameters and polymerization results are listed in Table 6.

All of the polyethylenes obtained from the catalysts of Examples 16 to 21 had high molecular weight, broad molecular weight distribution, and two-phase structure. The GPC curve has tails at both low and high molecular weights. The molecular weight of polyethylene obtained from catalyst C is higher than that obtained from catalyst A. If the common metal cyclopentadiene complex catalyst obtained with the catalyst precursor c (Comparative Example 2 2) is used, the polyethylene obtained has a narrow MWD and the MWD curve has no tail. The catalysts of Examples 16 to 21 all have dual activation sites and have acceptable activity. From these examples, it can be seen that a catalyst having a double activation site can be obtained even if chromium is not reduced.

Page 37 1239265 Case No. 88107578 Amendment V. Description of Invention (30) Table 6 Polymerization Example 16 17 18 19 20 21 22 Catalyst CCCCC (for C comparison) SSC Reference Number Oxidation Temperature 8 15 815 815 815 620 620 600 ( ° 〇 Reduction temperature 3 8 0 380 380 without 380 380 (t) C6 in iC4 0 · 16 2. 92 2. 92 reduction 5.96 2. 92 2. 92 5. 96 weight percentage H2 in C2 0 0 1270 0 1270 0 0 Molar reactor temperature 94 85 94 85 85 94 85 (° 〇Total pressure 30.5 22.0 25. 0 19. 5 22 · 0 25. 0 19. 5 (atmospheric pressure) Cat. T * 0. 796 0. 146 0. 139 0. 609 0. 135 0.119 0. 567 (g) Induction time 1 0 1 1 0 0 0 (minutes) ❿

Page 38, 1239265, Case No. 88107578, Rev. V. Description of the invention (31) Reaction time 56 60 60 56 60 60 42 (minutes) Polymer yield 111 〇178 176 610 224 205 1420 (g) Productivity 1400 (g / g ) 1220 1270 1000 1620 1720 2600 Activity against P4000 1280 1300 1370 1100 1800 1780 3160 (g / g · h) NA = Not applicable Table 6 (continued) Properties of polyethylene Example 16 17 18 19 20 21 22 (for comparison ） MFR2 〇.77 1. 3 16.4 1.10 21. 4 1. 50 1.10 (g / 10 minutes) MFR21 16 30 nd 22 nd 30 17. 5 (g / 10 minutes) FRR21 / 2 20.8 23 20 20 15 · 9 Density 942 926 933 915 934 925 912 (g / m3) G, 0.05 290 31 8 139 5. 5 14 16 ?? 〇. 0 5 1 670 0 5580 790 11090 530 5260 6720

Page 39, 1239265, Case No. 88107578, Amendment V. Description of the Invention (32) 7/30 0 1 200 1150 210 1030 200 1260 1390 pI 0.59 0.44 0. 64 0. 42 Two-phase structure with or without Mw 190000 145000 80 0 0 0 168000 78000 120000 120000 Μη 20000 20000 1 0 0 0 1 2000 1 6 000 27000 40000 Mw / Μη 9.5 7. 3 8. 0 14 4. 9 4. 4 3 Cr / SSC 20/80 1 / 9 1/9 30/70 1/9 1/9 nd = Not determined Example 2 3 In a stainless steel reactor, 1.8 litres of isobutane and 20 ml of 1-hexane were added. The reactor was heated to 90 °. (: Then add ethylene to 5 atmospheres. Catalyst A of Table 1 was activated at 680-380 ° C, then added to the reactor and immediately started the polymerization reaction. After 60 minutes, the polymerization reaction was terminated and the polyethylene product was removed. Experimental parameters and polymerization The reaction results are shown in Table 7. The zirconium was replaced with hafnium in the catalyst, and the polymerization step of Example 2 3 was repeated. So the metal cyclopentadiene a substance soaked with the chromium oxide / silica catalyst was dichlorobis. (N-butylcyclopentadiene) 铪. This catalyst is the same as the catalyst of Example 23. The experimental parameters and polymerization results are listed in the table.

Page 40 1239265 Case No. 88107578 _η Revision V. Description of the invention (33) 70 Example 25 (comparative use case) The polymerization step of Example 23 was repeated but the catalyst used was not the same as the metal cyclopentadiene The mixture was soaked together. Therefore, the catalyst is a chromium oxide / silica catalyst. The experimental parameters and polymerization results are listed in Table 7. Table seven

Example 23 24 25 (comparative) Catalyst A, File A, 铪 X Oxidation and oxidation temperature 680 680 680 (° 〇 Reduction temperature 380 380 380 (° 〇C6 in iC4 of 1. 1 1. 1 1. 1 weight percent Cat · Weight (g) 0.110 0.202 0. 144 Activity 1180 250 310 (g / g · h) MFR2 3. 6 nd 0. 21 Page 41 1239265

(G / 10 minutes) MFR21 60 (g / 10 minutes) G, 5KPa (Pa) 575 V (300) (Pa. S) 2465 Mw 92, 300 Mw / Mn 2. 5 0-78 7.9 1410 3380 400, 00 0 2 1 8, 0 00 381,500 203,500 3.4 12. 0 nd = AA Example 2 6 (for comparison) A polymerization reaction step similar to that used in the patent EP 339,5 7 1 (Showa Denk) was performed. Two different catalysts are used: (a) a granular complex / silica catalyst, and (b) a metal cyclopentadiene complex compound and methylammonium oxide as described on page n of this patent. Simultaneously immerse the catalyst solution prepared in steps (1) to (3). Polymerization was carried out according to the polymerization reaction steps described on page 12, except that in this example hydrogen gas and chromium / silica catalyst, catalytic solution and isobutane at a pressure of .5 were added to the reactor at 30 t. The internal temperature of the reactor was increased to 80 ° C and then ethylene was added. The polymerization reaction continued for 44 minutes. A layer of low molecular weight polymer is formed on the reactor wall and agitator. The resulting polymer had a density of 956 grams per cubic inch, an MFR2 of 1.5 and an MFR21 of 38 grams / 10 minutes. Molecular weight of polyethylene (Mw)

Is ΗΟ, ΟΟΟ, Mn is 1 900 and Mw / Mn is 70. GPC

Page 42 1239265 Case No. 88107578 Revised

Page 43 1239265 Case No. 88107578 Revised

Page 44

Claims (1)

1239265 __ charm 88107578_ 年月 日 _ Amendment VI. The scope of patent application is that the catalyst contains 0.4% to 1% by weight of chromium; approximately 0.2% by weight of zirconium; and About 5% by weight; this percentage is calculated by comparing the weight of the metal itself with the total weight of the catalyst. 5. According to any of claims 1 to 4 of the scope of the patent application, a granular modified chrome oxide catalyst that can be used to catalyze the polymerization of ethylene or the polymerization of ethylene and α-olefins is characterized in that the catalyst is a sphere or similar spheroid Of particles. 6. A method for preparing a catalyst that catalyzes the polymerization of ethylene or the polymerization of ethylene and olefins. It is characterized by including the following steps: a) a precursor; b) a cyclopentyl group comprising a metal; The random structure is bridged by c) The species include, the compound diene ring in the previous step, and the carbonization of other compounds are obtained by slowing down, such as the step of emulsifying chromium and gasification in the previous step, and soaking. Oxygen and halogen atoms are selected by linking to the radicals. The cold process of this bridge will be together at the same time. The complex catalysis of heating under the inorganic support obtained in the above step, the ligands on the above-mentioned metal and hydrogen atoms At least 400 ° C to 95 ° C and at least one active transition metal compound connected to the combination of its two cyclopentanes by a bond and the transition contains the group, and one of the foregoing is irreplaceable As for the transition metal, it can replace or not exist in a dilute ring, and the granular catalyst is dried. Chromium oxide catalysis Metal up to alkoxy cyclopentadiene or substitutable, and substitutable they may 1239265 _Case No. 88107578_ Modification of Year of the Month_ 6. Application for Patent Scope 7. A method for preparing a catalyst for the polymerization of ethylene or the polymerization of ethylene with α-fluorene according to item 6 of the scope of application for patent, characterized in step a) The obtained precursor of the oxidation state catalyst may first undergo a reduction reaction to reduce most of the chromium to a divalent oxidation state, and then perform the reaction in step b). 8. A granular modified thallium chromium oxide catalyst that can be used to catalyze the polymerization of ethylene or the polymerization of ethylene with an α-olefin according to item 1 of the scope of the patent application, wherein the transition metal compound is a bis- (alkylcyclopentadiene) -transition Metal halide Page 47