TW494111B - High activity catalysts for the preparation of polyethylene with an intermediate molecular weight distribution - Google Patents

Abstract

A supported alpha-olefin polymerization catalyst composition of this invention of improved activity as measured by productivity is prepared in a multi-step process. An ethylene homopolymerization or ethylene copolymerization catalyst is formed by: (i) providing a slurry of a solid porous inorganic support having reactive hydroxyl (-OH) groups and a non-polar solvent; (ii) impregnating said support having -OH groups, with RMgR' compound, to form an intermediate, which intermediate has an -OH group: Mg ratio of less than 1, wherein each of said R and R' is alkyl of 1 to12 carbon atoms and is the same or different; (iii) treating the intermediate with TiCl4 to form a titanium containing intermediate which has an -OH group: Ti ratio of less than 1; (iv) reacting the titanium containing intermediate with an amount of oxygen containing electron donor containing 1 to 15 carbon atoms, combining the electron donor treated titanium containing intermediate with triethylaluminum to form the catalyst. The catalyst also produces polymers having relatively intermediate molecular weight distribution.

Description

Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 494111 No. 80109623 Patent Application 1 Correction Sheet of Chinese Manual (August 89) 5. Description of the Invention (1) The present invention relates to a method for polymerizing α-olefins. Catalyst used, and method for producing the catalyst. In particular, the present invention relates to a catalyst, and a method for producing the same, which produces high-density polyethylene or linear low-density polyethylene (LLDPE) with intermediate molecular weight distribution suitable for membrane applications, such as a melt flow ratio equivalent to an intermediate value ( MFR). The present invention also relates to a high productivity polymerization process using a catalyst of the present invention. In commercial applications, it is important that ethylene homopolymers and acetamidine copolymers have very narrow molecular weight distributions (MWDs) or very wide MWDs. However, 'polymers with moderate MWDs have recently been found to be important for blending two or more polymer samples into commercially important products, such as film or blow molding applications. Each of the two or more polymer samples blended into the final product may have very different molecular weights. One polymer sample typically has a relatively high molecular weight, as shown by a high load melting index (HLMI) of 0.4-5, while another polymer sample has a relatively low molecular weight, as shown by a melt index (MI) of 20-1 000 . These polymer samples can be prepared in individual polymerization reactors or in tandem polymerization reactors, where relatively high and low molecular weight fractions are prepared sequentially in the polymerization process. One measure of the molecular weight distribution of a resin is the melt flow ratio (MFR), which is the ratio of the high load melt index (HLMI or 121) to the melt index (l2) for a given resin. The melt flow ratio is believed to be an indication of the molecular weight distribution of the polymer, the higher this value, the wider the molecular weight distribution. A resin having a value equivalent to the mMFR value, for example, 15 to 30, has a relatively narrow molecular weight distribution. In addition, resins with a considerable M F R value (ie, 80-1 50) are said to be quite wide (please read the notes on the back before filling this page), 1T -4-

494111 No. 86109623 Patent Application Chinese Specification Revised Page (August 89) 5. Description of the invention (of MWD. Resins with intermediate MWD have a value of 30-70iMFR. Many catalyst systems present production of very low MFR values Resin trends. For example, U.S. Patent No. 4,732,8,82 to Allen et al. Discloses a triethylaluminum activated alpha-olefin polymerization catalyst composition that produces a polymer with a relatively low MFR value and a low sintered extract. It It is possible to produce an ethylene homopolymer having an intermediate molecular weight distribution or a catalyst composition containing ethyl hydrocarbon / i_dilute hydrocarbon copolymer up to 10 mol%, that is, MF R of 30-70, which Has a fairly good I > Watt Index response [Flow index response refers to the ability of a catalyst to produce a polymer with a relatively low molecular weight compared to a polymer made with another catalyst under the same polymerization conditions.] The measurement productivity in a multi-step process is improved The active α-olefin polymerization catalyst composition of the present invention is formed by the following: formation of an ethylene homopolymerization catalyst or an ethylene copolymerization catalyst: (i) providing a solid solid with reactive hydroxyl groups; Slurry of non-polar inorganic carrier in non-polar solvent; (ii) impregnate the carrier with hydroxyl group with RMgR, compound to form an intermediate 'this intermediate has a Mg / basic ratio greater than 1, Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative, please read the notes on the back before filling out this page} where each of R and R 'is an alkyl group of 1 to 12 carbon atoms and is the same or different; (iii) TiC U is used to process the intermediate To form a titanium-containing intermediate having a Ti / Mg ratio greater than 0.5; (iv) reacting the titanium-containing intermediate with an oxygen-containing electron donor containing 1 to 15 carbon atoms; combining a titanium-containing intermediate treated with an electron donor And triethylaluminum to form a catalyst. This catalyst also produces a highly active -5- table paper wave scale applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm). Polymer. Poly = poly-linear polyethene prepared in the presence of the catalyst composition of the present invention, which is a homopolymer or a vinyl of ethylene: high: 込 (copolymer. Compare catalyst combinations previously known Inventory of Things * = Similar Poly Polymer, this polymer exhibits a relatively intermediate flow: FR). Therefore, the polymerization prepared by the catalyst composition of the present invention is particularly cooperative as a component for resin manufacturing for film and blow molding applications. The catalyst produced by the present invention is described below in terms of its manufacturing method. The carrier materials printed by the catalyst synthesis, the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economics are solid, granular, porous, and preferably inorganic materials. Some of these carrier materials include inorganic materials. , Such as silicon and, or aluminum oxide. The intercept material is used in the form of a dry powder having an average particle size of i to 250 microns, preferably 10 to 150 microns, and the carrier material is also porous and Have a surface area of at least 3 square meters per square gram (square meter per gram), and preferably at least 50 square meters per gram. This carrier material should be dried, i.e. no absorbed water. Drying of this carrier material can be performed at a temperature of ≈ 00. Heating is performed to i 〇 〇 t, preferably 600 ° C. When the support is silica, it is at least 200 °, preferably 200 ° to 850 ° C, and most preferably 600. 〇Heating. The support material must have at least some active hydroxyl (OH) groups to produce the catalyst composition of the present invention. In a preferred embodiment, the carrier is silica, which has been dehydrated by fluidizing with nitrogen and heating at 600 ° C. for 16 hours before use in the first catalyst synthesis step to reduce the amount to 0.7 g. ¾ Moore (Emol / g) Surface Concentration. The second concrete of the best embodiment is a high surface area, amorphous stone (surface area = 300 square meters / gram; pore volume of 1.65 cubic centimeters / gram), and it is a 6-paper scale applicable to Chinese national standards ( CNS) A4 size (210X297 mm) A7

494111 No. 86109623 Patent Application Chinese Specification Revised Page (June 1989) V. Description of the Invention (4) Davison Chemical Division of WR · Grace Company under the brand name ~ 〇11 ... or avis on 9): > Substances for sale. Hard rock is in the form of spherical particles, for example, obtained by spray drying. The two-drug carrier material was slurried in a non-polar solvent, and the resulting slurry was contacted with y kinds of organomagnesium compositions having a test formula of RmMgR'n. The carrier material in solution is prepared by introducing the carrier into the solvent, preferably while stirring, and heating to 25HG (rC, preferably 4G. To 6 (rc). The slurry is then contacted with the above-mentioned organic magnesium The composition is continuously heated at the above temperature. The organomagnesium composition has an experimental formula RmMgR, n, wherein 11 and 11 • are the same or different C4-Cl2 alkyl groups, preferably C4_C1G alkyl groups, and more preferably c4-c8 It is n-alkyl, and is preferably butyl and ^^ are both butyl, and 111 and 11 are 0, 丨, or 2 as long as m + n is equal to the valence of Mg. All reactants used, that is, the organomagnesium composition (RmMgR'n) transition metal compound, and the oxygen-containing electron donor compound are at least partially soluble and are liquid at the reaction temperature. Preferably. The non-polar falling agent is alkane Hydrocarbons, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although many other materials can also be used, including cycloparaffins, such as cyclohexane, aromatics, such as benzene and Ethylbenzene. The best non-polar solvent is hexane. Before use, the non-polar solvent should be purified. Impregnated by silica gel and / or molecular sieve to remove residual water, oxygen, polar compounds, and other substances that can negatively affect the activity of the catalyst. In the best embodiment of the synthesis of this catalyst, only physical or chemical is added The amount of organic magnesium composition deposited on the support is important because any excess organic rhenium composition in the solution can react with other synthetic chemicals and (please read the precautions on the back before filling this page)

1. 1T printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China, No. 86109623 Patent Application Specification Revised Page (89 ^ y), Invention Description (5) Precipitation outside the carrier. The drying temperature of the carrier affects the organic magnesium composition The number of positions on the available carrier-the higher the drying temperature, the lower the number of positions. Therefore, the exact molar ratio of the organomagnesium composition to the hydroxyl group changes and must be determined on a per unit basis to determine only the exact organomagnesium The composition is added to the solution and deposited on the carrier without leaving any excess organomagnesium composition in the solution. In addition, it is believed that the molar amount of the organomagnesium composition deposited on the carrier is greater than the molar amount of the hydroxyl on the carrier Therefore, the molar ratios given are intended only as a guideline, and the exact amount of the organomagnesium composition in this specific embodiment must be controlled by the functional limitations of the above discussion, that is, it must be less effective on the carrier material. Adding more than this amount of solvent, the excess can react with other compounds used in the preparation, thus forming a precipitate other than the carrier ', which is harmful to the synthesis of this catalyst And must be avoided. The amount of organomagnesium composition that is not greater than the amount deposited on the carrier can be determined by any conventional method, for example, by adding an organic compound to a slurry of the carrier in a solvent, and at the same time, until detection The organic magnesium composition is a solution in a solvent. For example, for a silica carrier heated at 600 t, the amount of the organic magnesium composition added to the slurry is such that the molar ratio of Mg to ⑽⑴H) on the solid carrier is ^ to 3: 1, preferably u ·] to 2: 1, more preferably 41 to magic 8 ", and most preferably 1.4: 1. The organomagnesium composition is dissolved in a non-polar solvent to form a solution from which the organomagnesium composition is deposited on a support. It is also possible to add an excess of the organomagnesium composition deposited on the carrier, and then remove any excess organomagnesium composition, e.g. borrowing or washing. However, this alternative is less desirable than the preferred embodiment described above. After the addition of organomagnesium compounds, 'slurry contacts at least one kind of soluble in non-polar solvent -8-This paper is suitable for the national standard of the country (TTNS) A4 specifications. Revised Page of Chinese Specification for Patent Application No. (August 89) V. Description of the Invention (6 doses of transition metal compounds. This synthesis step is between 2 5. to 7. 2 / j L, preferably 30. to 65 t, And the best is to be carried out at 40%. In the preferred embodiment, the amount of the transition metal core compound added is not greater than that which can be deposited on the support. The Mg of the support is related to the transition metal and the transition metal recording. The exact mole ratio is therefore different (for example, depending on the drying temperature of the carrier), and must be determined on a piece-by-piece basis. For example, for heating a stone-cutting carrier at 200 ° to 8 °, the amount of transition hydrazone compound is such that the carrier is derived from The molar ratio of the transition metal compound to the base of the transition metal compound is 1 to 2.G 'is preferably 丨 2. The amount of the transition metal compound is also such that the molar ratio of Mg to the transition metal is 0.05 to 3 , Preferably 1 to 2. These mole ratios have been found to produce catalyst compositions that can produce resins having a ratio of 30 to 60 when the flow ratio of intermediate melts. Suitable transition metal compounds for use herein are compounds of metals from groups 4 and 5 of the periodic table. As announced by Chemical and Engineering News 63 (5), 27, MM, as long as this compound is soluble in non-polar solvents. Non-limiting examples of this compound are titanium and vanadium halides, such as titanium tetrachloride Ticl4, tetrachloride Vanadium Yd, trichloride VOC13, and vanadium alkoxides, in which the alkoxide moiety has 1 to 20 carbon atoms, preferably! Branched or undivided alkyl groups of 6 to 6 carbon atoms. The best transition metal compound is a compound, preferably a tetravalent: compound. The best compound is a tetrachloride. A mixture of this transition metal compound can also be used and there is usually no limitation on the transition metal compound that can be included. It can be alone Any transition metal compound used can also be used in combination with other transition metal compounds. The oxygen-containing electron donors used in catalyst synthesis each have the formula 1 ^ (:: 〇〇112 and 1 ^ _ 0-R4, or 114-0 11. Anti 1 and 112 can be the same or different and each contains 1 (please read the notes on the back before filling this page) Order -9- A7 ___ B7 5. Description of the invention (7) to 15 carbon atoms. Each heart And! ^ May be alkyl, aryl, alkyl-substituted aryl groups' R3 and R4 may be the same or different and each contain 1 to 凌 ling atoms, and may be alkyl, aryl, alkyl substituted Aryl group or aryl substituted alkyl group, or alkylene group; this definition includes forming an alkylene group with I, so R3R4 is defined as a cyclic ether. Preferred oxygen-containing electron donors include p-cresol, Methanol, ethyl benzoate, tetrahydrofuran, and n-butyl ether. Most preferably, the oxygen-containing electron donor is ethyl benzoate, tetrahydrofuran, or n-butyl ether. Preferably, the electron donor is an ester or an ether, which is synthesized by adding a catalyst after the addition of a transition metal to the synthetic slurry. The electrical preform (gD) is added in an effective amount to increase the productivity of the catalytic sword, and its selectivity to the polymer produced is in the range of 0.1 to 40,000 HLMI ranging from 30 to 60 MFR. In practice, this amount ranges from a Ti / ED mole ratio of 0.5 to 2.0. Non-polar solvents are slowly removed after the precursor is formed, for example, by distillation or eruption. The temperature at which the non-polar solvent is removed from the synthesis mixture affects the productivity of the resulting catalyst composition. A lower solvent removal temperature results in a catalyst composition that is substantially more active than a producer at Chevron Solvent removal temperature. Therefore, ′ is preferably at 40β to 65 ° C, more preferably at 45 · to 55 ° C, and most preferably at 5 ° C to remove the non-polar solvent by drying, distillation or evaporation or any other conventional method. The resulting free mud moving powder is referred to herein as a catalyst precursor and combines an organic chain activator. The combination of the precursor of the present invention and triethylaluminum as an activator produces an α-olefin polymerization catalyst composition having very high activity. This activator is used in an amount effective to at least promote the polymerization activity of the solid catalyst component of the present invention. The amount of activator is sufficient to give 丨 5: 丨 to 1000: 1, preferably 20.0: 1 to this paper size. Applicable to the Chinese National Standard (CNS) Ba Shi ^ (21〇 > < 297 Gongling) ) (Please read the precautions on the back first v equipment-Zhima page)

、 1T Chinese Ministry of Economic Affairs Central Standard Bureau Staff Consumer Cooperative Printed Out of 4111 No. 86109623 Patent Application Chinese Manual Correction Page (August 89)---... ..... V. Description of the invention (8) 300.1 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Wood Economy, and the best is 25: 1 to 100: 1 of the eighth: Ding 丨 Moore ratio. Without wishing to be bound by any theory of operation, it is believed that the catalyst composition 2 of the present invention is produced by chemically impregnating the carrier with the catalyst ingredients of the carrier slurry sequentially added in a non-polar solvent. Therefore, all catalyst synthesis chemical components must be soluble in the non-polar solvents used in the synthesis. The order of addition of the reagents is also important because the chemical reaction between the non-polar solvent (liquid) and the solid carrier material or the chemical components of the catalyst intermediate (solid) supported by this material sequentially predicts the catalyst synthesis step. Therefore, the reaction is a solid-liquid reaction. For example, the catalyst synthesis step must be performed in a manner that avoids the reaction of two or more reagents in a non-polar solvent to form a reaction product of a non-polar solvent that is insoluble outside the pores of the solid catalyst support. This insoluble reaction product cannot react with the support or catalyst intermediate, and therefore cannot be added to the solid support of the catalyst composition. The catalyst precursor of the present invention is prepared under substantially anhydrous, oxygen, and other catalyst poisons. This catalyst toxin can be eliminated during the catalyst preparation step by any known method, for example, by preparation under an atmosphere of nitrogen, argon or other inert gas. Inert gas flushing can serve the dual purposes of excluding external contaminants during preparation and removing unwanted reaction by-products from the preparation of net and liquid reaction products. Purification of non-polar solvents for catalysts is also useful in this regard. The catalyst can be activated in situ by separately adding an activator and a catalyst to the polymerization medium. It can also be before the introduction of the polymerization medium, for example, up to 2 hours before it is introduced into the polymerization medium ', at -40, to 100 ° (: temperature combination catalyst and agent 0 -11-This paper size applies to Chinese national standards (CNS) A4 specification (210X297mm) '-------- (Please read the precautions on the back before filling this page)

、 1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 494111 Patent Application No. 86109623 Revised Chinese Manual (August 89)

'Explanation of the invention (9) By any suitable method, the ethylene homopolymer or ethene / 1-ethene copolymer is polymerized with the catalyst prepared in accordance with the present invention. This method includes the following steps: in suspension, in solution, or in the gas phase. Polymerization. Gas-phase polymerization is preferred, for example, in stirred-bed reactors, and especially fluidized-bed reactors. The molecular weight of the polymer can be controlled by known methods, for example, by using hydrogen. Use Made in accordance with the invention When the polymerization is carried out at a relatively low temperature, for example, 30. to 105 ° C, the molecular weight can be appropriately controlled by hydrogen. This molecular weight control can be proved by a measurable positive change in the melting index (h) of the polymer produced The molecular weight distribution of the polymer prepared in the presence of the catalyst of the present invention, as expressed by the MFR value, changes from 30 to 60, preferably 32 to 50. As known to those skilled in the art, this MFR value The equivalent molecular weight distribution of a polymer means no. Also as known to those skilled in the art, this MFR value is an indication of a polymer suitable as an ingredient for polymers used in film or blow molding applications. MFr The meaning here is the ratio of the high-load melting index (HLMI or 121) divided by the melting index, that is, a lower MFR value of MFR = ih represents a relatively narrow molecular weight distribution polymer. The catalyst prepared according to the present invention is highly active and May have an activity of at least 1 to 5 kg of polymer per gram of ethylene per 100 psia of ethylene per hour. The polyethylene polymer prepared according to the present invention is a homopolymer of ethyl acetate or one or more ethyl acetate C3_C10a-copolymer of olefin. Therefore, there are two kinds of monomers-12-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

494111 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. The description of the invention (i〇) The copolymer of the unit can also be three kinds of monomers: ethylene / 2/1 Greek copolymer, ethylamidine / 4 • methyl n • pentane. Copolymer, / Butadiene A-hexamethylene terpolymer, Acetyl / propanetrimethylene terpolymer propylene / 1-butene terpolymer. It is preferred that the polyethylene polymer produced according to the present invention contains at least a proportion of ethylene units. A particularly desirable method for producing a polyethylene polymer according to the present invention is a bed reactor. Reactors and methods of operation are described in Levlne et al., US Patent No. 4,013 82, U.S. Patent No. 4,302,566, and WwHn et al. US Patent No. 4,4813 () 1, all of which are incorporated herein by reference. For reference. The polymer produced in this reactor contains catalyst particles because the catalyst is not separated from the polymer. Preferably, in accordance with the present invention, a dual type ethylene polymer blend having the required assembly portability and mechanical properties is obtained by including a fluidized bed reactor operating in a tandem mode under the following conditions, at least Two gas phase polymerizations result from a step comprising the gaseous monomer component of the major part of acetamidine. In the first reaction, at a ratio of not less than 0.3 foot hydrogen / acetamole and an ethyl acetate partial pressure of not higher than 0.3, a monomer composition and a small amount of hydrogen-containing gas are brought into contact with the present invention under polymerization conditions. A catalyst is used to produce a relatively high molecular weight (ΗMW) polymer powder, where the polymer is deposited on catalyst particles. The catalyst-containing HM w polymer powder is then used with additional activators (or catalysts) as appropriate, which may be the same as or different from the co-catalyst used in the first reaction preparation but without additional transition metal components' and with hydrogen and The gaseous mixture of the monomer composition is transferred together (please read 1 on the back, y Caution page) f

、 1T 13-This paper is suitable for financial specifications. TT7 ^^ 7mm 494111 A7 B7 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (11) to the second reactor, where the other polymerization is at least 0.9 Hydrogen / ethylene mole ratio, which is high enough that it is at least 8.0 times the first reactor and at least 1.7 times the ethylene partial pressure of the first reactor to produce a relatively low molecular weight (LMW) polymer, It is mostly deposited on and within the HMW polymer / catalyst particles from the first reactor such that the HMW polymer portion of the bi-polymer leaving the second reactor is at least 0.35. The above conditions provide a method in which the generation of fine particles that tend to contaminate the compressor and other devices is kept to a relatively low degree. In addition, this condition provides a degree of productivity in the first reactor and an increased degree of productivity in the second reactor, resulting in a favorable melt flow ratio (MFR, indicator of molecular weight distribution) and a high degree of homogeneity (to a low degree Gel and low-density index) double polymer blends resulting from a high degree of blending of HMW and LMW polymers of each final polymer particle inherently generated by the processing operation. Bi-type blends can be processed into films and containers for household industrial chemicals with an excellent combination of mechanical properties without undue difficulty. The gaseous monomer entering the two reactors may consist entirely of ethylene or may contain minor ethylene and a small amount of co-monomers such as alpha-fluorene hydrocarbons containing 3 to 10 carbon atoms. Co-monomers can be present in the monomer composition entering either or both reactors. In many cases, the monomer composition is not the same in the two reactors. For example, in the manufacture of resins intended for high-density films, it is preferred that the monomer entering the first reactor contains a small amount of comonomer such as 1-hexene, so that the HMW component of the bi-type product is a copolymer, and is fed to The monomers of the second reactor essentially comprise ethylene, so that the LMW component of the product is essentially an ethylene homopolymer. When using comonomers to obtain the desired copolymer in either or two reactors, the comonomers are paired with B (please read the precautions on the back page first). Installation · 1T This paper size applies to Chinese national standards (CNS ) A4 size (210X 297 mm) A7 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12 The mole ratio can be, for example, 0 005 to 〇7, preferably 004 to 〇 Range of 6. Hydrogen may or may not be used to adjust the molecular weight of the HMW polymer produced in the first reactor. Therefore, hydrogen may be fed to the first reactor so that the molar ratio of chlorine to ethylene (H2 / c2 ratio) is The ratio is, for example, up to 0, preferably from 0.05 to 0.2. In the second reactor, it is necessary to produce a compound having a sufficiently low molecular weight and a sufficient amount of = MW? ≪ Difficulty of processing produces bi-type resins that can form end-use products, such as films and containers for household industrial chemicals, which have an excellent combination of mechanical properties. Therefore, hydrogen and ethylene-containing monomers are fed to the second reactor, making gas Phase hydrogen to ethylene mole ratio is 0.9, preferably 0.9. A range of 9, 5.0 is optimally in a range of 10 to 35. In addition, in order to provide a sufficient molecular weight difference between the polymers in the first and second reactors to obtain the required processing and mechanical properties For a bi-type resin product with a sufficiently wide molecular weight distribution, the hydrogen to ethylene mole ratio in the two reactors should be such that the ratio in the second reactor is at least 80 times the ratio in the first reactor, for example, In the range of 80 to 10,000 times the ratio of the first reactor, and preferably 10 to 2000 times this ratio. The aforementioned hydrogen to ethylene ratios are used to obtain The required molecular weights of the HMW and LMW polymers produced in the second reactor tend to produce relatively high polymer productivity in the first reactor and relatively low productivity in the second reactor. They tend to sequentially generate too little LMW. Polymer bi-polymer product to maintain satisfactory rationality. An important part of the present invention is that by using ethylene partial pressure in two reactors, the polymer productivity of the first reactor can be reduced and improved This production of the second reactor To greatly overcome this 15-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (please read the precautions on the back of the threat first \ ^ | ^ this page)-Pack-494111 A7 V. Invention Explanation (I3 discovery of effects. Therefore, use

Dsia, such as "Reaction" <ethylene partial pressure is not higher than 100 P. For example, in the range of 15 to 100, preferably rotten, and the ethylene partial pressure in the second reactor is, for example, at 26 to 2 p. Dry fence, preferably 45 to 12 () release, in any designated party: Cantonese partial pressure so that the second ethylene partial pressure to the first-reactor ratio of 1.7, preferably 1. 7 to 7.0, and more preferably 20 to 40. If required for any purpose, for example, controlling the velocity of a surface gas or absorbing the heat of reaction, &amp; monomers and hydrogen, such as nitrogen, can be present in one or two reactors. Therefore, the total pressure in the two reactors can be, for example, 100 to 600 psig, preferably in the range of 200 to 35 psig. The polymerization temperature in the first reaction may be, for example, 60. To 130 ° C, preferably 60 ° to 90 ° C, and the temperature in the second reactor may be, for example, 80 ° to 1301 :, preferably 90. To 12 o. (Range of range. For the purpose of controlling molecular weight and productivity in the two reactors, it is preferred that the temperature in the second reactor be at least 10%, and preferably 30% to 60% higher than the temperature in the first reactor. The residence time of the catalyst in each reactor is controlled so that productivity is suppressed in the first reactor and enhanced in the second reactor, which is consistent with the nature of the bi-polymer product. Therefore, the residence time can be, for example, between The first reactor is from 0.5 to 6 hours, preferably from 1 to 3 hours, and, for example, from 1 to 12 hours, preferably from 2.5 to 5 hours, in the second reactor. The residence time ratio of the first reactor is in the range of 5 to 0.7, preferably 2 to 1. The surface gas velocity through the two reactors is high enough to effectively disperse the reaction heat to prevent the temperature from rising to partially melted polymer and The degree of shutdown of the reactor is high enough to maintain the integrity of the fluidized bed. The gas velocity is between -16-this paper size applies to China National Standard (CNS) A4 specifications (2! 0X297 mm) I t etc. ( (Please read the "Precautions Benwa" on the back of the threat) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 494111 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (14) For example, 40 to 120, preferably 50 to 90 cm / s The treatment in the first reactor is related to the productivity of the polymer per gram atom of the transition metal in the catalyst multiplied by 106. For example, it can range from 6 to 1 6.0, preferably 3.2 to 9.6. Fan Ye, · In the second reactor, the productivity is, for example, 0.6 to 9.6 'preferably in the range of 1.6 to 3.5, and in all processes, the productivity is in' for example, 2 · 2 to 2 5 · 6, A range of 4 · 8 to 16 · 0 is preferred. The above range is based on the analysis of the residual catalyst metal in the resin product. The polymer produced in the first reactor has, for example, 0.05 to 5, and more preferably A flow index ⑺ or ^ of 0.1 to 3 g / 10 minutes, at i9 (rc measured in accordance with ASTM D-1 23 8, Condition F), and, for example, from 0890 to 0960, preferably from 0.900 to Density in the range of 0.940 g / cc. The polymer produced in the first reactor has, for example, between 10 and 400. Fortunately, the melting index is in the range of 15 to 2000 g / 10 minutes (^ or 込, measured at 190Ό according to ASTM D-1 23 8, Condition E), and, for example, 0.890 to 0.976, preferably 0.930 Densities in the range of 0.976 g / cc. These are calculated based on a single-reactor processing model that uses full-state processing data. The final granular bipolymer obtained from the second reaction kit has at least 0,35. A weight fraction of HMW polymer in the range of 0.35 to 0.75, more preferably 045 to 065, for example, a flow in the range of 3 to 200, preferably 6 to 1000 g / 10 minutes Index, for example, a melt flow ratio (MFR, calculated as the ratio of the flow index to the melt index) in the range of 60 to 250, preferably 80 to 150, for example, in the range of 089 to 0965 , Preferably a density in the range of 0091 to 0 · 960m, for example, in the range of 127 to 1270, preferably 380 (please read the note on the back page first)

、 1T -17 ~ 494111 A7 B7 5. Description of the invention The average particle size (APS) in the range of (15) to 1100 microns, and less than 10% by weight. Fortunately, it is less than J weight! . /. Fine particle content (defined as particles passing through a 20 mesh screen). Regarding the fine particle content, it has been found that a very low amount of fine particles' is produced in the first (HMW) reactor and the percentage of fine particles is changed very little in the second reactor. It is surprising because in the first or gas phase sole reactor, the fluidized bed system effluent produces a relatively low molecular weight (LMW) polymer as defined herein, with a considerable amount of fine particles. The possible explanation is that in the method of the present invention, the LMW polymer formed in the second reactor is mainly deposited in the pore structure of the HMW polymer particles generated in the first reactor, reducing the formation of LMW fine particles . This is shown by the increase in the sedimentary body density (SBD) in the second reactor while the APS remains fairly constant. When a pellet is formed from a granular resin that is stabilized and compounded by a Brabender extruder twice to determine uniform blending, the pellet has, for example, 3 to 2000 ', preferably 6 to 100 g / 10 A flow index in the range of minutes, for example, a melt flow ratio in the range of 60 to 250, preferably 80 to 150, and a heterogeneous index in the range of 1.0 to 1.5, preferably ι · 〇 to ι · 3 (HI, the ratio of the FI of the particles to the spherical resin). HI indicates the relative degree of heterogeneity between particles of the spherical resin. The following examples further describe important features of the present invention. However, the specified reactants and reaction conditions used in the examples are not to be construed as limiting the scope of the invention to those skilled in the art. Example 1 Preparation of catalyst: All operations were performed under nitrogen atmosphere using standard Schenk technology (please read the notes on the back first. • Installation-Ready for this page). system

494111 Patent Application No. 86109623

Chinese Manual Correction Page (February 91)-沴 7 _ Team 厶 · Β7

V. Description of the invention (16 Place 7 • ~ grade 955 silica in a 200 ml Schenk flask, first dry at 600 ° C under nitrogen flush for 16 hours. Hexane (90 ml) is added to silica. Dibutyl Magnesium (7.0 mmol) was added to the stirred slurry at 5 (Γ to 55 t, and stirring was continued for 1 hour. Ticu (70 mmol) was added to the reaction flask (50 to 55 C) and stirred continuously; 1 hour. The electron donor (70 millimolar) was then added to the flask (50. to 55.0) and stirring was continued for another i hours. Then the nitrogen was flushed through a steaming chamber at 50 ° C to remove the burnt. The rate of change was $ 4.3g, depending on the electron donor used. These catalysts were used to prepare ethylene / hexanene copolymers under the same polymerization conditions. Typical examples are shown below. Slow nitrogen purge at 50 ° C The next i. 6-liter stainless steel autoclave was filled with 750 ml of anhydrous hexane, 30 ml of anhydrous 丨 hexadecane, and 3.0 ethyl ethoxide. The reactor was closed, and the stirring was increased to 900 rpm. , And the internal temperature increased to 85. (: The internal pressure was increased by 12 psi with hydrogen. Ethylene was introduced to maintain the pressure at 120 psig. Reduced to 80. (:, 20.0 mg of catalyst was introduced into the reactor with ethylene overpressure, and the internal temperature increased and maintained at 85.0. Polymerization continued for 60 minutes, then the ethylene supply was stopped and the reactor could be cooled to room temperature Double polyethylene and air-dried. The following are the productivity, flow index, and melt flow ratio of the catalyst prepared according to the sequence. -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 494111 No. 86109623 Patent Application Specification Revised Page (October 88) A7 B7 Supplement

V. Description of the invention (17

DBM

TiCL

SiO 2 '&gt;

Ex. JXX 2 3 4 5 6 Electron donor without (control) p-cresol methanol ethyl benzoate tetrahydro-n-butyl ether productivity '590 1120 1150 2250 2720 2780 _ &gt; Electron donor- &gt; Melt index flow Index MFR ⑹ (Ϊ21) 0.03 2.4 70.1 0.13 5.1 39.8 0.08 3.5 43.4 0.19 5.7 30.5 0.16 6.0 36.4 0.22 6.9 31.3 (Please read the notes on the back before filling out this page) * Productivity is based on gram catalyst · hour-lOOpsi Polyethylene units are given. X X Comparative data show that the addition of an electron donor substantially increases the producer of the catalyst. The use of ether as an electron donor (Examples 5 and 6) produces a catalyst with the highest productivity. Therefore, tetrahydrofuran and n-butyl ether are comparable electron donors. Ester (ethyl benzoate) electron donors produce catalysts with slightly lower productivity, while alcohols and substituted phenol electron donor catalysts are less active than ether electron donor catalysts. The polymer produced by the catalyst of the present invention exhibits an intermediate molecular weight distribution, as shown by an MFR value of 30-45, and a low molecular weight, as shown by a higher melting index (12) value. Therefore, this catalyst has a better melt index response than the comparative catalyst. -20 This paper size applies to China National Standard (CNS) A4 (210X297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs.

Claims (1)

494111 8 8 8 8 ABCD Cantonese Patent Application No. 86109623 (Amended in February 91) 6. Scope of patent application 1. An ethylene homopolymerization or ethylene copolymerization catalyst, which controls the molecular weight distribution of the polymerization product when measured by the melt flow ratio (MFR), wherein the catalyst is formed by the following steps: (i) providing a reaction (-〇Η) -based solid porous inorganic carrier and a non-polar solvent slurry; (ii) RMgR, the compound impregnates the carrier with the -0Η group to form an intermediate, the intermediate has less than 1- OH group ·· Mg ratio, wherein each R and the alkyl group having 1 to 12 carbon atoms are the same or different, and RMgR1 is soluble in the non-polar solvent; wherein RMgR used in step (i) The amount is such that the molar ratio Mg: OH is from 1: 1 to 3: 1, (iii) the intermediate is treated with T i C 14 to form an intermediate containing — which has a -0 group of less than 1: T i Ratio; where the amount of T i C 14 present in step (iii) is such that the molar ratio of M g to T i is 0.5 to 2, the improvements include: (iv) titanium-containing intermediates and 2 to 15 carbon atom oxygen-containing electron donor reactions; titanium-containing intermediates that have been electron-donor treated In combination with triethylaluminum; where the electron donor system is present in an amount effective to provide titanium (metal) of 0.5 to 2: the molar ratio of the electron donor, and among them melts at a high load of 0.1 to 40,000 Under the index (HLMI), the MFR range of the measurement is 30 to 60, wherein the solid porous inorganic carrier is at a temperature of from 100 ° C to 100 ° C before being contacted with the solvent in step (i). Heating at temperature. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm). Fan Li Special request Medium A B c D 2 · According to the catalyst in item i of the scope of patent application, 11 and 11 are finished. 3. The catalyst according to item 2 of the scope of patent application, wherein the amount of TiCl4 present in this step (m) is such that the molar ratio of Mg: Ti is 1 to 1.5. 4. The catalyst according to item 3 of the scope of patent application, wherein the amount of RMgR used in this step (〇 is such that the molar ratio Mg: 0H is 1.1: 1 to 2: 1. 5. According to the scope of patent application The catalyst of item 4, wherein the solid, porous inorganic support is silica, and it is heated at a temperature of at least 200 C before being contacted with the solvent in step (i). 6. According to item 5 of the scope of patent application Catalyst, wherein the silica has a surface hydroxyl concentration of 0.7 millimolars / gram, a surface area of 300 square meters / gram, and a pore volume of 1.65 cubic meters / gram after heating. 7 · A method of homopolymerization or copolymerization of acetamidine, which This includes contacting a feed containing ethylene with a catalyst according to item 1 of the patent application under ethylene homopolymerization or copolymerization conditions to obtain the molecular weight distribution of the polymer product as measured by MFR.