TW585876B - Ziegler-Natta catalyst for tuning MWD of polyolefin, method of making, method of using, and polyolefins made therewith - Google Patents

Abstract

Heat treatment of a preactivated Ziegler-Natta type catalyst provides for control of the MWD of resulting polyolefins made with such catalyst, with such catalyst maintaining high activity and excellent fluff morphology. A polyolefin catalyst produced by a process comprising: (a) contacting a soluble magnesium dialkoxide compound of the general formula Mg(OR'')2 with a halogenating agent capable of exchanging one halogen for one alkoxide to form a reaction product A, where R"" is a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms; (b) contacting reaction product A with a first halogenating/titanating agent to form reaction product B; (c) contacting reaction product B with a second stronger halogenating/titanating agent to form reaction product C; (d) contacting reaction product C with an organoaluminum preactivating agent to form a preactivated catalyst; and (e) heating the preactivated catalyst at a temperature in the range of 90 DEG C to 150 DEG C, for a time in the range of thirty minutes to a twenty-four hours; wherein the first mild chlorinating/titanating agent is a blend of two tetra-substituted titanium compounds with all four substituents being the same and the substituents being a halide or an alkoxide with 2 to 6 carbon atoms, and the second stronger chlorinating/titanating agent is a titanium halide.

Description

585876 A7 B7 Ministry of Economic Affairs, Smart Wealth, 1 Bureau, 8 Workers' Exemption Cooperative Cooperative ¾ V. Description of the Invention (1) Reference to Related Techniques The application for this invention was filed on January 28, 1997, with the term "olefin polymerization" A part of US Patent Application Serial No. 0 8/7 8 '8 2 using the Ziegel-Natta catalyst as the title is a continuation of the application, which is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. The scope of the present invention The present invention relates to catalysts, methods for producing these catalysts, methods for using catalysts, and polymers obtained from these catalysts. In another aspect, the present invention relates to polyolefin catalysts, methods for making these catalysts, polyolefin polymerization, and polyolefins. In another point of view, the present invention relates to Ziegler-Natta catalysts, methods of making these catalysts, methods of using these catalysts, and polyolefin polymerization inverse polyolefins. 2. Description of related techniques Since the early 1950s, Ziegel-type catalysts in polymerization techniques have been well known, their general manufacturing methods and their subsequent use. However, although there is a lot of knowledge about Zigall catalysts, there is still a fixed research in improving the polymer field, catalyst life, catalyst activity, and the ability to produce polyolefins with certain characteristics. U.S. Patent No. 4,255,544, issued to Kimura et al. On March 10, 1981, discloses the use of ethylene poly () Please read the notes on the back #Fill this page first) 0 Pack *

. • I This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 585876 A7 ____B7 _ V. Description of the invention (2) Legal 'wherein the preparation of component A is borrowed. By magnesium dialkoxide It reacts with a halogen-containing silicon compound and an alcohol to provide a solid material, and then the solid material is reacted with a titanium halide in the presence of an alkoxy-containing silicon compound. U.S. Patent No. 4,914,609, issued to Job et al. On April 3, 990, discloses the preparation of olefin polymerization catalysts with improved activity and selectivity. (A) halogenating a magnesium compound including at least one aryloxy, alkyl, or carbonate or alkoxy group with a first tetravalent titanium halide and a first electron donor; (b) subjecting the resulting product to the first Two tetravalent titanium halides are contacted; and (c) the resulting halogenated product is washed with an inert hydrocarbon liquid. In this method, a second electron donor is used in step (a) or (b), and the product of step (b 2) is combined with a third tetravalent titanium halide in step (b 2) at 4 The product is contacted at a temperature of 0 ° C to 14 and then rinsed in step (c). U.S. Patent No. 4,155,187 issued to Shelly on October 13, 1992 discloses a polymerization method for a Ryzen catalyst, which is usually a silicon-containing compound, a dialkyl magnesium, an alcohol The reaction product of a halide-containing metal compound, an aluminum alkoxide, and a second halide-containing metal compound 0 U.S. Patent No. 5,6 1 0,246 issued to Buehler et al. On March 11, 1997 Reveals a method for synthesizing acrylic acid using a catalyst supported by silicon dioxide. The catalyst includes silicon dioxide and (1) at least one hydrocarbon-soluble magnesium-containing compound and (2) a first modified compound selected from the group consisting of silicon halide, boron halide, aluminum halide, and mixtures thereof (please Please read the notes on the back ^ Fill this page first) 0 Equipment · Industrial and Intellectual Property Office of the Ministry of Economy Α7 Β7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumers' Cooperatives, Innu V. Invention Description (3) and the product obtained by contacting it with a second designated modified compound in a random order. U.S. Patent No. 5,6 31, 3 34 issued to Zandona on May 20, 1997 discloses a method for manufacturing at least one catalyst solid for olefin (co) polymerization, the catalyst comprising Co-precipitated magnesium and at least one transition metal. However, despite these advances in prior art, none of these prior art documents disclose or suggest heat treatment of pre-activated polyolefin catalysts. • Furthermore, none of these prior art documents disclose or suggest that heat treatment with pre-activated polyolefin catalysts will provide any effect on polymer molecular weight distribution ("MWD"). Therefore, polyolefin catalysts are required in this technical field. There is also a need in the art for a method for producing a polyolefin catalyst. There is also a need in the art for a method for polymerizing olefins. There is also a need in the art for various MWD polyolefins. There is also another need in this technical field to allow the production of various polyolefin catalysts of M W D type with catalysts that also have high activity and excellent loose morphology. There is also a need in the art for a method for achieving polyolefin M W D using a hydrocarbon heat-treated pre-activated polyolefin catalyst. Those who are familiar with this technology will understand these and other requirements in this technology field when reviewing this specification (including its graphics and patent application scope). This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please First read the notes on the back and fill in this page) 0 Packing and ordering 585876 ^ I: A7 B7 V. Description of the invention (4) ○ Description of the invention One object of the present invention is to provide polyolefin catalysts. Another object of the present invention is to provide a method for producing a polyolefin catalyst. Another object of the present invention is to provide a polyolefin-based polymerization method. Still another object of the present invention is to provide various M W D polyolefins. Still another object of the present invention is to provide polyolefin catalysts of polyolefin type which allow production of various M W D with catalysts also having high activity and excellent loose morphology. It is even an object of the present invention to provide a method for performing polyolefin M W D using a heat-treated, pre-activated polyolefin catalyst. According to a specific embodiment of the present invention, a polyolefin catalyst is provided. The catalyst is produced by a method comprising the following steps: a) Synthesis of a soluble magnesium dialkoxide of the general formula Mg (〇R ") 2, which comprises a dialkyl magnesium of the general formula Mg RR 'and a general formula R" 〇Η Reaction products of alcohols, where R, R 'and R "are each a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, and any two or more of R, R' and R" may The same or different; b) contacting a magnesium dialkoxide compound with a mild halogenating agent capable of being exchanged with a halogen to alkoxide to form a reaction product "A"; c) bringing the reaction product "A" to the first Contacting two halogenated / titanating reagents to form a reaction product "B"; and d) contacting the reaction product "B" with a second stronger halogenating / titanating reagent to form a reaction product "C"; e) to The reaction product "C" is contacted with an organoaluminum pre-activator to form the paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Intellectual Property Agency Consumers Cooperatives Innu 585876 Α7 Β7 Five 'invention theory (6) (Read Notes on the back page write) to further embodiment of the present invention set based another embodiment provides that the α - olefin polymerization method of. Generally the method comprises the steps of: a) contacting one or more alpha-olefin monomers together in the presence of a catalyst under polymerization conditions; and b) extracting the poly-hydrocarbon polymer. Monomers are preferably ethylene monomers and polymers are polyethylene polymers. The catalyst used in this method is composed of steps: (i) synthesizing a magnesium dialkoxide of the general formula Mg (〇R ") 2 from a dialkyl magnesium of the general formula MgRR 'and an alcohol of the general formula R" 〇Η. , Which are the reaction products contained herein, where R, R 'and R "are each a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms, and any two or more of R, R' and R" May be the same or different; ii) contact a magnesium dialkoxide compound with a mild halogenating agent capable of exchanging a alkoxide with a halogen to form a reaction product "A"; iii) contact the reaction product "A" with the first Contacting a halogenation / titanating reagent to form a reaction product "B"; and iv) contacting a reaction product 'B "with a second stronger halogenating / titanating reagent to form a reaction product" C "; v) to The reaction product "C" is contacted with an organoaluminum pre-activator to form a pre-activated catalyst; and vi) the pre-activated catalyst is heated. The employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumers Cooperative, print those familiar The skilled person is reviewing this manual (including its graphics and patent applications) These and other purposes of this technique will be understood when the technique is described. A brief description of the figure. Figure 1 is a bar graph showing the effect of heat treatment on the MWD of the catalyst. The paper dimensions are applicable to China National Standard (CNS) A4 (210 × 297 (Mm) -9- 585876 t A7 B7 Printed by the Anti-Poverty Cooperative of the 1st Bureau of Wisdom and Finance of the Ministry of Economic Affairs Ⅴ. Description of Invention (9) Examples include diethylmagnesium, dipropylmagnesium, dibutylmagnesium, butylethylmagnesium, etc. . Butyl magnesium (B EM) is the preferred dialkyl magnesium. In the field application of the present invention, the metal dialkanol is preferably a magnesium compound with the general formula M g (〇 R ”) 2 'here R , Is a hydrocarbon group of 1 to 20 carbon atoms or a substituted hydrocarbon group. Magnesium dialkanol compounds are magnesium compounds of the general formula MgRR '(wherein R and R are alkyl groups of 1 to 10 carbon atoms and may be the same or different) and alcohols of the general formula R "〇Η Alcohols are the reaction products of straight-chain or branched-chain alcohols and R "-based alkyl groups of 4-20 carbon atoms). • The metal dialkanol is preferably soluble and unreduced. Unreduced compounds have the advantage of forming M g C 1 2. Instead of the insoluble T i + 3 species formed by the reduction of the compounds, such as M g RR ′, they tend to form catalysts with a wide particle size distribution. . In addition, M g (〇R ”) 2 has a lower reactivity than M g RR ', and is chlorinated by a mild chlorinating agent, followed by simultaneous chlorination / titanation with a mild reagent and a second The chlorination / titanation reaction with a stronger reagent gradually and successively reacts more strongly, which can generate a more uniform product, that is, a larger catalyst particle size and a more uniform catalyst particle size distribution. Useful Non-limiting examples of preferred species of metal dialkanols include magnesium butoxide, magnesium pentoxide, magnesium hexanolate, magnesium di (2-ethylhexanol) and any alkanolate suitable for making the system soluble. Most The best metal alkanol species is bis (2-ethylhexanol) magnesium. Alkyl magnesium compounds (MgRR ') (such as butyl ethyl (3 £ ")) and alcohols (1101 ·!) (Such as 2-ethylhexyl) Alcohol) reaction can be generated (please read the precautions on the back first ^ Fill this page)

I Packing ·, 11 丨% This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 585876 A7 ____B7____ 5. Description of the invention (1) Production of magnesium dialkoxide as a non-limiting example For example, di (2-ethylhexanol) magnesium is exemplified by the following chemical formula:

MgRR, + 2R "〇H-Mg (〇R") 2 + RH + R, H In the case of BEM, RH and R 'Η are butane and ethyl, respectively. The reaction occurs at room temperature and forms a solution with the reactants. Any two or more R groups may be the same, or R groups may be all different from each other. In the field application of the present invention, any alcohol which gives the desired metal dialkanol can be utilized. The alcohol can be any non-limiting example of any alcohol of the general formula R "〇Η, where R" is an alkyl group of 4 to 20 carbon atoms. The alcohol may be a linear or branched alcohol. Non-limiting examples of alcohols include butanol, isobutanol, 2-ethylhexanol, and the like. The preferred alcohol is 2-ethylhexanol. The amount of alcohol usually added ranges from about 0.5 equivalents to about 4 equivalents (the equivalent is relative to the entire magnesium or metal compound), and preferably from about 1 to about 3 equivalents. Although Xianxin can utilize almost any alcohol ', it is best to utilize high carbon branched alcohols, for example, 2-ethyl-1-hexanol. Usually the alcohol used will have at least 3 carbon atoms ', at least 4 preferably', at least 5 more preferably and at least 6 carbon atoms. Alkyl metal compounds have a high degree of association 'due to the lack of electron bonding, so that they generate high molecular weight species that are very viscous in solution. Adding an aluminum alkyl (such as triethylaluminum) can reduce this high viscosity and disintegrate the association between various metal molecules. The preferred ratio of aluminum alkyl to metal is from 0.0001 to 1: 1, more preferably from 0.01: 1 to 0.001, and from 0.03 to 1 to 0.05: 1 is the best. In addition, the electron donor can be used to further reduce the viscosity of metal alkyls, such as ether. This paper size applies Chinese National Standard (CNS) A4 specifications (2 丨 〇 > < 297 mm) = 13- (Please read the back first Note: Please fill in this page again.) Install (refill this book, 1T, Intellectual Property Bureau, Ministry of Economic Affairs, S Industrial Consumption Cooperative, India 585876 9 'A7 B.7 V. Description of Invention (13) In another option, the first The chloride / titanate reagent can be a single compound. An example of the first chloride / titanate reagent is T (〇C 2 H 5) 3 C 1, T i (〇C 2 H 5) 3 Cl, T i (〇C 3 H 7) 2 C 1 2, T i (〇c 3 H 7) Cl, T 1 (〇c 4 H 9) C 1 3, T i (〇c 6 H 1 3) 2 C 1 2. T i (〇c 2 H 5) 2 B r 2 and butyl i (〇c 1 2 H 5) C 1 3 are single compounds. The first halogenation / titanation step is performed in a hydrocarbon solvent. Suitable Non-limiting examples of hydrocarbon solvents include heptane, hexane, toluene, octane, and the like. The preferred solvent is hexane. The solid product "B" is precipitated at room temperature, followed by the addition of a halogenation / titanium reagent Soluble "A". The amount of halogenation / titanium reagent used must be sufficient to precipitate the solid product from the solution. The amount of halogenation / titanium reagent used is usually based on the titanium to metal ratio, usually from about 0.5 to about 5 as The range is preferably from about 1 to about 4, and most preferably from about 1.5 to about 2.5. The solid product precipitated in this first titanation step is then recovered by any recovery technique "B "And then washed with a hydrocarbon solvent. Compounds suitable for use as the second halogenation / titanation reagent include those compounds suitable for use as the first halogenation / titanation reagent, except that the second reagent is a stronger reagent Outer (preferred). The second stronger halogenation / titanation reagent is preferably titanium halide, and more preferably titanium tetrachloride [T i C 1 4]. Usually the first solid product "B" is in a hydrocarbon solvent. Slurry for the first paper size to apply Chinese National Standards (CNS) 8-4 specifications (210 > < 297mm) (Please read the notes on the back first and fill in this page first) Packing. 11 Intellectual Property Bureau, Ministry of Economic Affairs Employee Consumer Cooperative Seal ¾ 585876 A7 _ _B7__ _ V. Description of the invention (14) Two halogenation / titanation steps to produce the reaction product or catalyst component "C". The hydrocarbon solvents suitable for the first halogenation / titanation step can be used. The amount of titanium tetrachloride used is usually in the range of about ο · 1 to about 5 equivalents, and preferably in the range of about 0. 15 to about 4 equivalents. The range is about 0.175 to about 2.5 good. The catalyst component "C" can be combined with an organoaluminum co-catalyst component ("pre-activator") to form a pre-activated catalyst suitable for olefin polymerization. The co-catalyst used with the transition metal containing the catalyst component "C" is typically an organometallic compound of metals 1a, IIa, and IIIa, such as alkyl aluminum ·, alkyl aluminum hydride, alkyl lithium aluminum, Alkyl zinc, alkyl magnesium and the like. The preactivator is preferably an organoaluminum compound. The organoaluminum preactivator is preferably an aluminum alkyl of formula A 1 Ra3, where Ra is an alkyl or halide having 1 to 8 carbon atoms, R ′ is the same or different, and at least one R Is an alkyl group. Organoaluminum preactivators are more preferably trialkylaluminum 'such as trimethylaluminum (TMA), triethylaluminum (TEA 1), and triisobutylaluminum (T i B A 1). The best pre-activator is T E A 1. The ratio of A 1 to titanium ranges from 0 · 1: 1 to 2: 1, and preferably 0 · 2 5: 1 to 1.2: 1. The pre-activated catalyst is then heat-treated at a temperature ranging from about 90 ° C to about 150 ° C, and preferably at a temperature ranging from about 100t to about 125 ° t. It is preferred to maintain the mud at the elevated temperature for a period ranging from about 0.5 hours to about 24 hours, and preferably for a period ranging from about 1 hour to about 4 hours. The final solid catalyst is then recovered and washed with a hydrocarbon solvent. (Please read the precautions on the back ^ Fill this page first) Pack. Write. Tai Tai Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumers' Cooperatives. This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -17- 585876 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Disclosure of Inventions (15) Electron donors and disintegrating agents, the first mild halogenation / titanation reagent or the second stronger halogenation / The titanating reagent is added together. The use of an electron donor is optimal in the second halogenation / titanation step. Electron donors are well known for use in the preparation of olefins, and any suitable electron donor that will provide a suitable catalyst can be utilized in the present invention. Also known as Lewis bases are electron donating systems to organic compounds of oxygen, nitrogen, phosphorus or sulfur, which can donate catalyst electron pairs. The electron donor can be favorably selected from aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyl esters, propenyl derivatives (especially alkyl acrylates or alkyl methacrylates) Mono- or polyfunctional compounds between silyl esters) and silane. A preferred example of a suitable electron donor is di-n-butyl phthalate. A more preferred example of a suitable electron donor is an alkylsilyl alkoxide of the general formula RS i (〇R ') 3. For example, methylsilyl triethyl J salt [MeSi (〇Et3)] Here, R and R 'are alkyl groups having 1 to 5 carbon atoms, and may be the same or different. The catalyst system of the present invention should be supported by any well-known Ziegel-Natta catalyst The components are inert solids without chemical reaction. The supporting system is preferably a magnesium compound. Examples of magnesium compounds that can be used to provide a support for the catalyst component are magnesium halides, dialkoxymagnesium, alkoxymagnesium halides and residual salts of magnesium. The preferred magnesium compound is magnesium chloride (M g C 1 2). If necessary, the Ziegel-Natta type catalyst is pre-polymerized. The pre-polymerization process is usually accomplished by contacting a small amount of monomer with the catalyst after it has been contacted with the co-catalyst. In U.S. Patent No. 5,106,804, No. (Please read the precautions on the back first

The bound paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -18-585876 Α7 Β7 V. Description of the invention (16) 5 '153,158 and No. 5,594,071 Pre-polymerization Method, which is incorporated herein for reference. The catalyst can be used in any method known for the homopolymerization or copolymerization of alpha-olefins of any type. For example, the catalysts of the present invention help to catalyze ethylene, propylene, butene, pentene, hexene, 4-methylpentene, and other α-olefins having at least 2 carbon atoms, and also help catalyze Its mixture. The catalyst of the present invention is used to polymerize ethylene to produce polyethylene. The catalyst obtained according to the present invention has very high activity, which depends at least in part on the olefin polymerization conditions. The catalyst usually has an activity of at least 6,000 grams of PE / g catalyst, and can also be greater than 100,000 grams of PE / g catalyst. In addition, a polymer having an excellent bulk morphology is provided with the obtained catalyst of the present invention. Therefore, the catalyst of the present invention is used to supply large polymer particles with a uniform size distribution, of which small and very fine particles (less than about 125 microns) appear only in low concentrations. The catalyst of the present invention including a large and easily transferable powder having a high powder bulkiness easily conforms to the polymerization production method. Indun, a consumer co-operative of the Intellectual Property 1 Bureau of the Ministry of Economic Affairs, can be monolithic, muddy or gaseous. The catalyst of the present invention is preferably used in the mud phase polymerization. The polymerization conditions (for example, temperature and pressure) depend on the type of equipment used and the type of polymerization method used, and are conditions known in the art. For example, the temperature may be in the range of about 50-200 C and the pressure may be in the range of about 10-800 bpm. The olefin monomer can be introduced into the non-reactive heat that is liquid under the reaction conditions. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) 585876 A7,. — — B7 V. Description of the invention (17) Transfer Polymerization in the dilution zone of the reagent. Examples of such dilutions are hexane and isobutane. The second α-olefin may be present in the copolymerization of ethylene with another α-olefin (eg, butene or hexene) at a ratio of 0.02 to 10 mol%. good. Regarding the polymerization method, it may preferably include an internal electron donor and an external electron donor or a stereoselective control agent (S C A) in the catalyst synthesis to activate the catalyst during polymerization. An internal electron donor can be used in the catalyst formation during the chlorination or chlorination / titanation step. Compounds suitable as internal electron donors for the preparation of well-known supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, having N, P and / or S atoms Electron donors and special ether types. To the esters of phthalic acid (such as diisobutyl phthalate, dioctyl ester, diphenyl ester and phenyl butyl ester), esters of glutaric acid (such as diisobutyl glutarate and diethyl ester), Pivalic acid alkyl and aryl esters, maleic acid alkyl, cycloalkyl and aryl esters, alkyl carbonate and aryl esters (such as diisobutyl carbonate, ethylphenyl ester, and diphenyl ester) and succinic acid Acid esters (such as succinic acid mono and diethyl esters). External donors that can be used in the catalyst preparation according to the present invention include a silyl compound, such as a siloxysilane of the general formula Si Rm (OR ') 4-m, where R is selected from the group consisting of alkyl , Cycloalkyl, aryl, and ethenyl, wherein R may be the same as R ′; when m is 0, 1, or 2, the R ′ groups may be the same or different, and m is 2 Or 3, the R groups may be the same or different. The internal administration system of the present invention is selected from the silane compounds of the following formula: (Please read the precautions on the reverse side and fill in this page) Binding and ordering the printing of papers to employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies Chinese national standards (CNS ) A4 specification (210 X 297 mm> _ 2〇- 585876 A7 B7 V. Description of the invention (is)

R —Si--R

OR where R 1 and R 4 both include a tertiary alkyl or cycloalkyl group, and R 1 and R 4 are R 2 and R 3 system or aryl groups. r; [may be pentyl, cyclohexyl or tert-butyl; R 2 and R 3 are propyl or butyl, and need not be the same; and isopropyl, cyclopentyl, cyclohexyl or tert-butyl. Hexylmethyldimethoxysilane (CMD S-based silane (D IDS), cyclohexyl isopropyl CIDS), dicyclopentyldimethoxysilyl tert-butyldimethoxysilane (DTDS). Polyethylene MWD (MW / MD) produced using the above catalysts, with a MWD of at least 5. at least 6.0 · and at least 7. The employees' cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs printed the disaster to the first grade of silicon , Two or the same or different; is methyl, isopropyl, ring can be methyl, ethyl, R 4 can also be methyl, special external donor is ring), diisopropyl di Methoxydimethoxysilane (c PDS) or di will have a MWD of at least 4.0 and 0, preferably 0 or even better. Please read back & precautions before filling this page The examples only provide the following examples of the present invention, which are illustrated below, to illustrate specific specific embodiments of the present invention. Of course, the examples are provided by way of illustration, and are not intended to limit the scope of the specification or patent application in any way. The example is to provide an example of a morphologically-controlled polyethylene catalyst 'its -21-the paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) 585876 A7 B7 V. Description of the invention ( 19) Allow fines to be obtained with catalysts Adjusted polymer characteristic molecular weight distribution (MWD). Controlling MWD allows a single catalyst system to be used for various polymer grades ranging from injection molding (narrow MWD) to blown film (wide MWD). The catalyst is prepared as follows: step 1 .

BuEtMg / DIAE / TEAI (1: 0 · 6 · · 0.03) + 2-ethylhexanol (2.09) to provide soluble intermediate A. Step 2 · Intermediate + 1 · 0 C I T 1 (〇P! ·) 3 to provide soluble intermediate B. Step 3. Intermediate B + Ti (〇Bu) 4 / Ti C 14 (2.0 · 1.0) to provide a solid pre-catalyst. Step 4. Pre-catalyst + Ding Yi (: 14 (0.25) + Ding £ 1, 1 to provide the final catalyst. Step 5. This paper size is in accordance with China National Standard (CNS) A4 size (210X297 mm) _ 22 _ (Please read the precautions on the back before filling out this page) One pack. Im Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585876 A7 B7 V. Description of the invention (20) Then the final catalyst will be at 90 ° C, heated for the time shown in Table 1 below: Polymerization The reactor used for the polymerization of ethylene (pressurized tank project) has a capacity of 4 liters and is equipped with four Mixing baffle. Bing Chan and hydrogen are introduced into the reaction vessel through the Teledyne-Hastings Raydist mass flow controller, while maintaining a fixed reaction internal pressure with a back pressure regulator mounted on the vault. Use a connection to the Barber-Coleman controller Kammer valve maintains the reaction temperature (in the reactor jacket) with steam and cold water. Hexane is used as the diluent. Experimental variables:

Temperature 8 CTC reaction time. 60 minutes pressure 125 lbs / sq. Inch catalyst 0 · 2 ml mud (about 10 mg catalyst) total catalyst TEAL@〇.25mmol/L please read the back t & Note: Please fill in this page again, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs «. Fast Stream 2 C \ 2 Η 5 -23- This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm) 585876 Α7 Β7 5 Description of the invention (21) Table 1: Time (time, 90 ° C) co-catalyst SR5 M w / M η 〇 (control) TEA1 10.4 5.4 2 TEA1 11.1 6.7 4 TEA1 11.7 6.8 6 TEA1 12.5 6.4 24 TEA1 12.8 6.8 ( (Please read the notes on the back before filling out this page) Sample the catalyst solution at 2, 4, 6, and 24 hours. The SR 5 and GPC data (TEA 1) presented in Table 1 and Fig. 1 show that the heat treatment at this stage significantly widens the characteristic M W D. It can be found here that the M W D increases steadily over the first 6 hours of heating. After this point, it no longer widens. However, the data show that it is possible to fine-tune the molecular weight distribution of the catalyst to the expected level based on polymer applications. Eventually, it was found that the catalyst with heat treatment im provides high activity without any loss and excellent loose morphology. Printed by the Consumers' Cooperative of the 1st Bureau of Wisdom and Finance of the Ministry of Economic Affairs. Although the specific embodiments of the present invention have been described in detail, it should It is understood that those skilled in the art will understand and easily perform various other improvements without departing from the spirit and scope of the present invention. Therefore, I do not want to limit the scope of the patent application attached to the examples and descriptions stated here, but rather to interpret the scope of the patent application to include all the characteristics of the patented innovations belonging to the present invention, including all those that may be familiar with the technology. The property of being treated by an equivalent belonging to the present invention. This paper size applies to China National Standard (CNS > Α4 size (210X297 mm) · 24-

Claims (1)

585876 A8 B8 C8 ____ D8 VI. Scope of Patent Application Annex 2A: (Please read the note on the back of # before filling out this page) No. 90 1 2665 Patent Application No. 3 Chinese Application for Patent Scope Replacement. February 1993 6th Amendment 1. A polyolefin catalyst produced by the following steps, a) halogenation of a soluble magnesium dialkoxide compound of the general formula M g (〇R ”) 2 with the ability to exchange one alkoxide with one halogen Agent to form reaction product A, where R "is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms; b) contacting reaction product A with the first halogenating / titanating reagent to form Reaction product B; and c) contacting reaction product B with a second stronger halogenating / titanating reagent to form reaction product C; d) contacting reaction product C with an organoaluminum preactivator to form a preactivated Catalysts; and printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs e) heating the pre-activated catalysts at a temperature ranging from 90 t to 150 t for a time ranging from 30 minutes to 24 hours ; The first mild chlorination / titanation The agent is a blend of two tetra-substituted titanium compounds in which all four substituents are the same and are halide or alkanolate having 2 to 6 carbon atoms, and The stronger chlorinating / titanating agent is titanium halide. 2. The catalyst according to item 1 of the scope of the patent application, wherein the soluble magnesium dialkoxide compound is an alkyl magnesium compound of the general formula M g RR '(wherein this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 585876 A8 B8 C8 D8 々, the scope of patent application R and R 'is an alkyl group of 1 to 10 carbon atoms, and may be the same or different) and the alcohol of the general formula R "0H (wherein the alcohol is straight The reaction product of a chain or branched chain alcohol and R "(alkyl group of 4-20 carbon atoms). 3. The catalyst according to item 2 of the patent application scope, wherein the soluble magnesium compound is bis (2-ethylhexanol) magnesium. 4. The catalyst according to item 2 of the patent application, wherein the alkylmagnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium. 5. The catalyst according to item 2 of the patent application scope, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol. 6. The catalyst according to item 2 of the scope of patent application, wherein the reaction frame includes the hospital base. 7. The catalyst according to item 6 of the application, wherein the aluminum alkyl is triethylaluminum. 8. The catalyst according to item 7 of the scope of patent application, wherein the ratio of alkyl aluminum to magnesium is from 0 · 0 0 1: 1 to 1: 1. 9. The catalyst according to item 1 of the scope of patent application, wherein the catalyst has a loose morphology conforming to the polymerization production method and will provide a uniform particle size distribution with a small number of particles smaller than 125 microns. 10. The catalyst according to item 2 of the scope of patent application, wherein the reaction 尙 includes an electron donor. 1 1. The catalyst according to item 10 of the patent application range, wherein the ratio of the electron donor to the magnesium ranges from 0: 1 to 10: 1. 12. The catalyst according to item 11 of the scope of patent application, wherein the electron donor is an ether. (Please read the precautions on the back before filling this page) Order the paper printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -2-585876 A8 B8 C8 D8 VI. Application scope of patent 1 3 · If the catalyst in the scope of patent application No. 1 is used, the halogenating agent has the general formula C 1 AR ”X, where A is the unreduced oxyphilic compound (please read the back Note that if you fill out this page again, R ”x has a hydrocarbyl moiety from 2 to 6 carbon atoms and X is the valence of A minus 1. 1 4 _ As the catalyst in the scope of patent application, the first mild chlorination / titanation reagent is a blend of titanium halide and organic titanate. 15. The catalyst according to item 14 of the scope of patent application, wherein the first mild chlorinating / titanating reagent is T i C 1 4 and T (0 B u) 4 from 0 · 5: 1 to 6: 1 TiCl4 / Ti (〇Bu) 4 is a blend in the range. 16. The catalyst according to item 1 in the scope of patent application, wherein step b) 尙 comprises an electron donor of the general formula RSi (〇R,) 3, wherein R and R ′ are alkyl groups having 1-5 carbon atoms It can be the same or different. The catalyst according to item 16 of the scope of patent application, wherein the electron donor is methylsilyl triethanolate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18 · If the catalyst in the first scope of the patent application, the second stronger halogenation / titanation reagent is titanium tetrachloride, and the range of titanium to magnesium is 0: 1 to 2: 1. 19 · As the catalyst in item 1 of the scope of patent application, the organoaluminum preactivator is an aluminum alkyl of the general formula A 1 R a 3, where r-is a radical or halogenated having 1 to 8 carbon atoms In fact, Ra is the same or different, and at least one R ^ is the base. 2. If the catalyst for item 19 of the scope of patent application, the organic aluminum paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~-585876 A8 B8 C8 D8 The activator is trialkylaluminum. 2 1. The catalyst according to item 20 of the scope of patent application, wherein the ratio of aluminum to Chin ranges from 0 · 1: 1 to 2: 1. 2 2. A polymer produced by a method comprising the following steps: a) contacting one or more α-olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst is composed of: i) a A magnesium alkoxide compound of the general formula Mg (OR ") 2 is contacted with a dentin capable of exchanging a halogenate with a halogenate to form a reaction product A, where R" has from 1 to 20 carbon atoms Hydrocarbyl or substituted hydrocarbyl; ii) contacting reaction product A with the first halogenation / titanation reagent to form reaction product B; iii) contacting reaction product B with the second stronger halogenation / titanation reagent To form a reaction product C; 1 v) contact the reaction product C with an organoaluminum pre-activator to form a pre-activated catalyst; and v) place the pre-activated catalyst in a range of 90 to 150 t Produced by heating at a temperature ranging from 30 minutes to 24 hours; where the first mild chlorination / titanation reagent is a blend of two tetra-substituted titanium compounds, the All 4 substituents in iso-titanium compounds are the same and are halide or Alkoxides of 2 to 6 carbon atoms, and the second stronger chlorinating / titanating agent is a titanium halide. 2 3 · If you apply for the polymer in item 22 of the patent scope, including monomers. &Quot; ------ (Please read the precautions on the back before filling out this page), 1T Consumer Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs The size of the printed paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -4- 585876 A8 B8 C8 D8 6. The scope of patent application is ethylene monomer and the polymer in it is polyethylene. 24. The polymer according to item 23 of the scope of patent application, wherein polyethylene has a molecular weight distribution greater than 4.0. (Please read the «Notes on the back side before filling out this page} 2 5 · If the polymer in the scope of patent application No. 22, the polymerization has a monolithic phase, mud phase or gas phase. 2 6 · If the scope of patent application The polymer according to item 22, wherein the soluble magnesium dialkanol compound is an alkyl magnesium compound of the general formula MgRR '(wherein R and R' are alkyl groups of 1 to 10 carbon atoms, and may be the same or different ) Reaction product of the reaction with an alcohol of the general formula R "ΟΗ (wherein the alcohol is a linear or branched chain alcohol and R" is an alkyl group of 4 to 20 carbon atoms). 2 7 A polymer according to item 2, wherein the soluble magnesium compound is bis (2-ethylhexanol) magnesium, and the alkyl magnesium compound is selected from the group consisting of diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and butyl ethyl magnesium. The group and its alcohols are groups composed of ethanol, propanol, isopropanol, butanol, isobutanol, and 2-ethylhexanol. Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 8 · If applied The polymer of the scope of the patent No. 23, wherein the reaction 尙 includes an aluminum alkyl, and The ratio of base aluminum to magnesium is 0 · 0 0 1: 1 to 1: 1. 2 9. If the polymer of the scope of the patent application No. 23, any one of steps i)-ν) 尙 contains an electron donor, And the ratio of the electron donor to magnesium is in the range of 0: 1 to 10: 1. 30. The polymer according to item 29 of the patent application, wherein the electron donor is an ether. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm): 5_ ~ 585876 Printed by A8, B8, C8, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, A8 B8 C8 ___ D8 VI. Application scope of patents The polymer according to item 22, wherein the halogenating agent has the general formula C 1 AR ”x, where A is an unreduced oxyphilic compound 'R” X is a hydrocarbon group having 2 to 6 carbon atoms and X It is the price of A minus 1. 3 2 · The polymer according to item 22 of the patent application range, in which the first mild chlorination / titanation reagents are Ti C 1 4 and Ti (〇Bu) 4 from 0.5: 1 to 6: TiCl4 / T i (〇BU) 4 is a blend in the range. 3 3 · If the polymer in the scope of the patent application No. 22, the second stronger halogenation / titanation reagent is titanium tetrachloride, and the range of titanium to magnesium is ◦: 1 to 2: 1. 3 4 · The polymer according to item 22 of the patent application range, wherein the organoaluminum preactivator is an aluminum alkyl of the general formula A 1 R a 3, where R-is an alkyl group having 1 to 8 carbon atoms or The halides, R- are the same or different, and at least one R- is an alkyl group, and the ratio of AI to titanium ranges from 0.1: 1 to 2: 1. 3 5 · —A method for preparing a catalyst, the method comprising: a) contacting a soluble magnesium dialkoxide compound of the general formula M g (〇R ”) 2 with a halogenating agent capable of exchanging an alkoxide with a halogen To form a reaction product A, where R "is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms; b) contacting the reaction product A with the first halogenation / titanation reagent to form a reaction product B; and c) the reaction product B and the second stronger halogenation / titanation reagent. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -6- ----- ^ --- --- (Please read the precautions on the back before filling in this page), 1T 585876 A8 B8 C8 D8 VI. Contact for patent application to form reaction product C; d) Contact the reaction product C with organoaluminum preactivator, To form a pre-activated catalyst; and e) heating the pre-activated catalyst at a temperature ranging from 90 ° C to 150 ° C over a time ranging from 30 minutes to 24 hours; A mild chlorination / titanation reagent is a blend of two tetra-substituted titanium compounds. All four substituents in isotitanium compounds are the same and are halide or alkoxides having 2 to 6 carbon atoms, and the second stronger chlorinating / titanating agent is halo titanium. 36. The method according to item 35 of the scope of patent application, wherein the soluble magnesium dialkanol compound is an alkyl magnesium compound containing the general formula Mg RR '(wherein R and R' are alkyl groups of 1 to 10 carbon atoms, And may be the same or different) and the reaction product of the reaction of the general formula R ″ Η alcohol (wherein the alcohol is a linear or branched alcohol and R ”is an alkyl group of 4 to 20 carbon atoms) 3 7 The method as claimed in claim 35, wherein the soluble magnesium compound is bis (2-ethylhexanol) magnesium. 38. The method according to item 36 of the application, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium, or butyl ethyl magnesium. 39. The method of claim 36, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol. 40. The method of claim 36, wherein the reaction 尙 comprises an aluminum alkyl. 4 1 · If you apply for the method of item 40 in the scope of patent application, the paper size of aluminum alkyl is applicable to China National Standard (CNS) A4 specification (210X297 mm) · (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T. 585876 A8 B8 C8 D8 6. The scope of patent application is diethyl bromide. 4 2 · As for the method in the scope of patent application No. 41, where the ratio of the courtyard base to magnesium is 0 · 0 0 1: 1 to 1: 1 ° 4 3 · In the method of the scope of patent application No. 35, where The catalyst has a loose morphology that conforms to the polymerization production method and will provide a uniform particle size distribution with a small number of particles smaller than 125 microns. 4 4 · The method according to item 36 of the patent application scope, wherein the reaction 尙 includes an electron donor. 4 5 · The method according to item 44 of the patent application range, wherein the ratio of the electron donor to magnesium is in the range of 0: 1 to 10: 1. 4 6 · The method according to item 35 of the scope of patent application, wherein the halogenating agent has the general formula C 1 AR ”X ·, where A is an unreduced oxyphilic compound, and R” m X has from 2 to 6 carbons The hydrocarbyl portion of the atom and X are the valences of A minus one. 47. The method of claim 46, wherein the halogenating agent is C 1 T i (〇 1 Pr) 3. 48. The method according to item 47 of the scope of patent application, wherein the ratio of titanium to magnesium is between 0.5 to 5. 4 9 · Method as claimed in item 35 of the scope of patent application, in which the first mild chlorination / titanation reagent is a blend of titanium halide and organic titanate 0 50 · As item 35 in the scope of patent application Method, in which the first mild chlorination / titanation reagents are Ti C 1 4 and Ti (〇B u) 4 to TiCl4 / Ti (〇Bu) 4 from 0.5: 1 to 6: 1 This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297). ^ (Please read the precautions on the back before filling out this page), 1T. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -8- 585876 A8 B8 C8 D8 Six, the patent application scope of the blend. (Please read the precautions on the reverse side before filling out this page) 5 1 · If you apply for the method in item 35 of the patent scope, the reaction 尙 includes the electron donor. 5 2 · The method according to item 35 of the scope of patent application, wherein the second stronger halogenation / titanation reagent is titanium tetrachloride, and the range of titanium to magnesium is 0: 1 to 2: 1. 53. The method according to item 52 of the patent application range, wherein the titanium tetrachloride is present in a range of 0.1 to 5.0 equivalents. 5 4 · The method according to item 35 of the scope of patent application, wherein the organoaluminum preactivator is an aluminum alkyl of the general formula A 1 R a 3, where R ~ is an alkyl or halogenated group having 1 to 8 carbon atoms The substances are the same or different, and at least one R ~ is an alkyl group. 5 5 · The method according to item 54 of the application, wherein the organoaluminum preactivator is trialkylaluminum. 56. The method of claim 55, wherein the ratio of aluminum to titanium ranges from 0. 1: 1 to 2: 1. 57. The method according to item 56 of the patent application scope, wherein the organoaluminum preactivator is T E A 1. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 58. For example, the method of claim 35 in the scope of patent application, in which the electron donor exists in any one of steps a), b), c) or d), and the electronics in it The donor-to-metal ratio ranges from 0: 1 to 10: 1. 59. The method according to item 35 of the scope of patent application, in which the catalyst helps to produce polyethylene with the expected molecular weight distribution. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -g- 585876 A8 B8 C8 D8 VI. Application for patent scope 60. A method for polymerizing α-olefins, comprising: a) contacting one or more α-olefin monomers together in the presence of a catalyst under polymerization conditions, wherein The catalyst system consists of: i) contacting a magnesium alkoxide compound of the general formula M g (〇R ”) 2 with a halogenating agent capable of exchanging an alkoxide with a halogen to form a reaction product A, where the R” system A hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms; ii) contacting the reaction product A with a first halogenation / titanating reagent to form a reaction product B; iii) contacting the reaction product B with a second Contacting a stronger halogenation / titanating reagent to form a reaction product C; iv) contacting the reaction product C with an organoaluminum pre-activator to form a pre-activated catalyst; and v) contacting the pre-activated catalyst with 90 ° C to 150 ° C 30 minutes to 24 hours are produced by the method of heating in a range of time; the first mild chlorination / titanation reagent is a blend of two tetra-substituted titanium compounds, the All four substituents are the same and are halides or alkoxides with 2 to 6 carbon atoms, and the second stronger chlorination / titanation reagent is titanium halide. 61. The method of claim 60, which includes: b) extracting a polyolefin polymer. 62. The method of claim 60 in which the monomer is an ethylene monomer and the polymer therein is polyethylene. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) —- — J ^ ------ (Please read the precautions on the back before filling this page), 1T Ministry of Economic Affairs wisdom Printed by the Consumer Cooperative of the Property Bureau 585876 A8 B8 C8 D8 VI. Application for Patent Scope 63 3. The method for applying for Patent Scope Item No. 62, wherein polyethylene combustion has a molecular weight distribution of at least .4.0. 64. The method according to item 60 of the patent application scope, wherein the polymerization has a monolithic phase, a slurry phase, or a gas phase. 65. The method according to item 60 of the scope of patent application, wherein the halogenating agent has the general formula C1AR ", " 'x., Wherein A is an unreduced oxyphilic compound, and R" x is from 2 to Hydrocarbyl moiety of 6 carbon atoms. 6 6 · The method according to item 65 of the patent application scope, wherein the halogenating agent is C 1 T i (〇 1 pr) 3. 67. The method according to item 60 of the scope of patent application, wherein the first chlorination / titanation reagent is two tetra-substituted titaniums having the general formula T i C 1 4 / T 1 (〇R ”) 4 Blends of compounds, where R "" "" 4 is a hydrocarbon-based moiety having 2 to 6 carbon atoms. 6 8 · The method according to item 67 of the patent application, wherein the first chlorination / titanation reagent Is a blend of T i C 1 4 / T i (〇B u) 4 ', wherein the ratio of T i C 1 4 to T i (〇B u) 4 is 0.5 ·· 1 to 6 ·· 1 6 9. The method according to item 68 of the scope of patent application, wherein the ratio of titanium to magnesium present in step (i 1) is in the range of 0.5 to 5.0. The method of item 60, wherein the second stronger halogenation / titanation reagent is T i C 1 4. 7 1 · The method of item 70 of the scope of patent application, wherein Ti C 14 is from 0.1 to 1 5 · 0 equivalents are in range. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) f. ------ (Please read the precautions on the back before filling this page) Order the Ministry of Economic Affairs Intellectual Property Bureau employees Printed by Fei Cooperative -11-585876 A8 B8 C8 D8 ^ Application for patent scope 7 2. For the method of applying for the scope of patent No. 60, the organic activation agent is TEA 1. 7 3. For the scope of patent application No. 6 The method of item 0, in which the electron donor is present in any one of steps i-iv, and the ratio of the electron donor to the metal is in the range of 0: 1 to 10: 1. (Please read the precautions on the back first Refill this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -12- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)