TWI388578B - A catalyst component for olefin(co)polymerization, preparation thereof, a catalyst comprising the same and use thereof - Google Patents

Description

Catalyst component for olefin polymerization or copolymerization, preparation method thereof, catalyst containing the catalyst component and application thereof Field of invention

The present invention relates to a catalyst component for the polymerization or copolymerization of olefins, a process for the preparation thereof, a catalyst comprising the catalyst component and its use in the polymerization or copolymerization of olefins.

Background of the invention

Supported high activity Zieglcr-Natta catalysts are widely used in the polymerization of olefins. One conventional method for preparing such a highly active supported catalyst is a coprecipitation process in which a magnesium halide is dissolved in a solvent system to form a homogeneous solution, and then the active magnesium halide is precipitated by treatment with a titanium halide, and simultaneously and/or subsequently activated titanium. The components are loaded up. No. 4,784,983 discloses a catalyst system for the polymerization and copolymerization of olefins comprising: (a) a solid catalyst component comprising Ti, (b) an alkyl aluminum compound, and (c) an organic rhodium, wherein The component (a) is a homogeneous solution formed by dissolving magnesium halide in a solvent mixture composed of an organic epoxy compound and an organophosphorus compound, and the solution is mixed with titanium tetrahalide or a derivative thereof, and is selected from the group consisting of a carboxylic anhydride, a carboxylic acid, and an ether. In the presence of a ketone-producing precipitating agent, a solid is precipitated; the solid is treated with a polycarboxylate to be supported on a solid, and the separated solid is treated with a titanium tetrahalide or a mixture thereof with an inert diluent. And get it. When the catalyst system is used for the polymerization of propylene, the catalyst activity is high, and the obtained polymer has a high degree of isotacticity and a large apparent density.

Patent application CN1229092 discloses a reminder similar to USP 4,784,983 The preparation method of the chemical agent, wherein in the step of dissolving the magnesium halide to form a homogeneous solution, the magnesium halide is modified by adding ethanol, so that the activity of the prepared catalyst is greatly improved in catalyzing the polymerization of ethylene. However, this catalyst is not suitable for the production of polypropylene and ethylene-propylene copolymer.

Summary of invention

It is an object of the present invention to provide a catalyst component for the polymerization or copolymerization of olefins.

Another object of the present invention is to provide a catalyst for the polymerization or copolymerization of olefins.

Another object of the present invention is to provide a process for the preparation of the olefin polymerization or copolymerization catalyst component of the present invention.

It is still another object of the present invention to provide a process for the polymerization or copolymerization of olefins.

Still another object of the invention is to provide the use of the olefin polymerization or copolymerization catalyst of the invention.

The catalyst of the invention has high catalytic activity and anti-impurity property when used for propylene polymerization and ethylene-propylene copolymerization; the catalyst particles have good morphology, the particle distribution is narrow, and the average particle diameter can be adjusted in the range of 5 μm to 25 μm; Various polymerization processes such as bulk method and gas phase method; the molecular weight distribution Mw/Mn of the polymer is large, and the shape of the polymer particles is good and the fine powder is small. The excellent anti-impurity performance of the catalyst of the present invention can effectively reduce the resin production cost. The catalyst of the invention is particularly suitable for the production of impact propylene copolymers and BOPP film resins.

Detailed description of a preferred embodiment

In a first aspect, the present invention relates to a catalyst component for olefin polymerization or copolymerization comprising magnesium, titanium, a halogen, an internal electron donor compound and an alkoxy group derived from a surface modifier, wherein the surface is derived from The modifier has an alkoxy group content of greater than 0 but less than 5% by weight, based on the weight of the catalyst component.

In the present invention, the term "catalyst component" means a main catalyst component or a procatalyst which, together with a cocatalyst component and an optional external electron donor, constitute a catalyst for olefin polymerization or copolymerization of the present invention.

The catalyst component of the present invention can be obtained by a process comprising the steps of: i) dissolving a magnesium compound in a solvent mixture of an organic epoxy compound, an organophosphorus compound, and optionally an inert diluent to form a homogeneous solution, ii Treating the above solution with a titanium compound, precipitating a solid precipitate comprising magnesium and titanium, in the presence of a co-precipitating agent, optionally in the presence of at least one internal electron donor compound, iii) treating the solid precipitate with at least one surface modifying agent And simultaneously or subsequently further loading at least one titanium compound and at least one internal electron donor to obtain a treated solid precipitate, and iv) washing the treated solid precipitate with an inert diluent, wherein The surface modifier is selected from the group consisting of alcohols, and the helper is at least one selected from the group consisting of carboxylic anhydrides, carboxylic acids, ethers, and ketones.

According to a preferred embodiment, the catalyst component of the present invention can be prepared as follows: (1) dissolving the magnesium compound in a solvent mixture composed of an organic epoxy compound, an organophosphorus compound and an inert diluent under stirring to form a homogeneous solution; In the presence of a co-precipitating agent, at a temperature of -30 to 60 ° C, preferably -30 to 5 ° C, a titanium compound is dropped into a uniform solution of the above magnesium compound or a homogeneous solution of the magnesium compound is dropped into the titanium compound, and then The reaction mixture is heated to 60-110 ° C and stirred at this temperature for 0.5-8 hours; the mother liquor is filtered off, the remaining solid is washed with an inert diluent to obtain a solid containing magnesium and titanium; (2) the solid is suspended In an inert diluent, a surface modifier and a titanium compound are added at a temperature of -30 to 50 ° C, and the temperature is raised to 10 to 80 ° C under stirring, and an internal electron donor is added, and the internal electron donor can be added at a time. It can be added several times at different temperatures; continue to react at 100~130 °C for 0.5-8 hours, filter out the liquid, and then treat the mixture with titanium compound and inert diluent for 1~2 times, filter out the liquid, use Inert diluent The release agent washes the solid to prepare a titanium-containing solid catalyst component.

The magnesium compound used in the present invention is selected from the group consisting of magnesium dihalide, a complex of water and an alcohol of a magnesium dihalide, a derivative in which one of the halogen atoms is replaced by a hydrocarbon group or a hydrocarbyloxy group, and a mixture of them. Examples of the above magnesium compound include, but are not limited to, magnesium dichloride, magnesium dibromide, magnesium diiodide, preferably magnesium dichloride.

The organic epoxy compound used in the present invention is selected from the group consisting of aliphatic olefins having 2 to 8 carbon atoms, diolefins or halogenated aliphatic olefins or oxides of diolefins, glycidyl ethers and internal ethers. At least one. Examples thereof include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether.

The organophosphorus compound used in the present invention is selected from a hydrocarbyl ester or a halogenated hydrocarbyl ester of orthophosphoric acid or phosphorous acid such as, but not limited to, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, Triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite.

The prodrug for use in the present invention is selected from one of a carboxylic acid, a carboxylic anhydride, an ether, a ketone, or a mixture thereof. For example, but not limited to: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, two Benzophenone, methyl ether, ether, propyl ether, dibutyl ether, pentyl ether.

The surface modifying agent used in the present invention is selected from the group consisting of alcohols, preferably linear or isomeric alcohols of 1 to 8 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, octanol , isooctanol or a mixture thereof.

The titanium compound used in the present invention has a general formula of Ti(OR) _4-n X _n wherein R is the same or different C ₁ -C ₁₄ aliphatic hydrocarbon group or aromatic hydrocarbon group, and X is a halogen. n is an integer from 0 to 4. Examples include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxy, titanium dichlorodiethoxylate, trichloro-ethoxy Base titanium and mixtures thereof, preferably titanium tetrachloride. The titanium compounds used in the steps ii) and iii) of the above production method may be the same or different.

At least one internal electron donor compound must also be added to the preparation of the catalyst component of the invention. The use of internal electron donor compounds in, for example, propylene polymerization catalysts is well known in the art, and these commonly used internal electron donor compounds, such as polycarboxylic acids, monocarboxylic or polycarboxylates, anhydrides, ketones, singles Ether or polyethers and amines can be used in the present invention. Examples of internal electron donor compounds useful in the present invention include, but are not limited to: (i) aliphatic or aromatic polycarboxylate compounds such as phthalates, malonates, succinates, pentane Diester, adipate, maleate, naphthalene dicarboxylate, trimellitate, trimellitate, pyromellitate, pivalate or carbonate. Specifically, for example, diethyl malonate, dibutyl malonate, dibutyl adipate, diethyl adipate, diethyl phthalate, diisobutyl phthalate Ester, di-n-butyl phthalate, diisooctyl phthalate, diethyl 2,3-diisopropylsuccinate, 2,3-diisopropylsuccinic acid Butyl ester, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate, 2-B Diisobutyl butyl 2-methyl succinate, diethyl 2-ethyl-2-methyl succinate, diethyl maleate, di-n-butyl maleate, naphthalene dicarboxylate Diethyl acid, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, triethyl trimellitate, tributyl trimellitate, pyromellitic acid Ethyl ester, tetrabutyl pyromelliate, and the like.

(ii) a polyol ester compound, for example, a polyol ester compound represented by the formula (I):

Wherein ^{_{R 1 -R 6, R 1 -R}} 2 n groups are the same or different hydrogen, halogen or substituted or unsubstituted straight or branched chain C ₁ -C _{2 0} alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C _{2 0} monocyclic or polycyclic aryl radical, C ₇ -C _{2 0} alkylaryl, C ₇ -C _{2 0} arylalkyl, C ₂ -C _{1 0} alkenyl group or a C ₂ -C _{1 0} ester group; but R ₁ and R ₂ are not hydrogen, and R ₃ -R ₆ and R ¹ -R ^{2 n} groups optionally contain one or several hetero atoms as carbon or hydrogen atoms or a combination of both Said hetero atom is selected from nitrogen, oxygen, sulfur, hydrazine, phosphorus or a halogen atom, and one or more of R ₃ -R ₆ and R ¹ -R ^{2 n} groups may be joined to form a ring; An integer of from 0 to 10; such a polyol ester compound is disclosed in detail in WO 03/068828 and WO 03/068723, the disclosure of which is incorporated herein by reference. Among the above polyol ester compounds, a compound represented by the formula (II) is preferred:

Wherein the R ₁ -R ₆ , R ¹ -R ² group is as defined in the formula (I).

In the polyol ester compound represented by the formula (I) or the formula (II), it is preferred that R ₃ , R ₄ , R ₅ and R _{6 are} not hydrogen at the same time, and R ₃ , R ₄ , R ₅ and R At least one group of ₆ is selected from the group consisting of halogen, C ₁ -C _{1 0} linear or branched alkyl, C ₃ -C _{10 0} cycloalkyl, C ₆ -C _{1 0} aryl, C ₇ -C _{1 0} alkaryl or aralkyl.

Further, the compound of the formula (I) further includes a compound of the formula (III):

Wherein the R ₁ -R ₆ group is as defined in the formula (I); R' is the same or different hydrogen, halogen atom, linear or branched C ₁ -C ₂₀ alkyl group, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl or C ₇ -C ₂₀ aralkyl.

In the above polyol ester compound represented by the general formulae (I), (II) and (III), it is preferred that at least one of R ₁ and R ₂ is selected from a phenyl group, a halogenated phenyl group, and an alkylphenyl group. Or a halogenated alkylphenyl group.

Examples of the polyol ester electron donor compound include 1,3-pentanediol dibenzoate.

(iii) a diether compound such as a 1,3-diether compound represented by the formula (IV):

Wherein R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI are the same or different from each other, and are selected from the group consisting of hydrogen, a halogen atom, a linear or branched C ₁ -C ₂₀ alkyl group, and C ₃ -C ₂₀ a cycloalkyl group, a C ₆ -C ₂₀ aryl group, a C ₇ -C ₂₀ alkaryl group, and a C ₇ -C ₂₀ aralkyl group, and R ^VII and R ^VIII may be the same or different from each other, and are selected from a straight chain or a branch. C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl and C ₇ -C ₂₀ aralkyl; R ^I -R ^VI The groups can be bonded to form a ring. Preference is given to 1,3-diethers in which R ^VII and R ^{VIII are} selected from C ₁ -C ₄ alkyl groups. These 1,3-diether compounds are disclosed in Chinese Patent No. ZL89108368.5 and Chinese Patent No. CN11411285A, the disclosure of which is hereby incorporated by reference.

The term "internal electron donor compound" as used in the present invention is not included in the present invention. An alcohol used as a surface modifier in the invention.

The inert diluent used in the present invention is not limited in principle as long as it does not interfere with the progress of the method. However, an alkane solvent such as hexane, heptane, octane, decane or the like, or an aromatic hydrocarbon solvent such as benzene, toluene, xylene or the like is preferably used. The inert diluents used in the various steps of the preparation process may be the same or different.

In the preparation of the catalyst component of the present invention, the amount of each raw material used is 0.2 to 10 moles per mole of the magnesium compound, preferably 0.5 to 4 moles; and the organic phosphorus compound is 0.1 to 3 moles. , preferably 0.3 to 1 mole; the helper is 0.03 to 1 mole, preferably 0.05 to 0.4 mole; the surface modifier is 0.005 to 15 moles, preferably 0.06 to 10 moles, more preferably 0.1 to 3 moles, most preferably 0.2 to 1.5 moles; the titanium compound is 0.5 to 20 moles, preferably 1 to 15 moles; the electron donor compound is 0.005 to 10 moles, preferably 0.01 to 2 moles.

The catalyst component of the present invention has substantially the following composition: titanium 1 to 10 wt%, magnesium 10 to 20 wt%, halogen 40 to 70 wt%, electron donor compound 5 to 25 wt%, and alkoxy group derived from a surface modifier greater than 0. However, it is less than 5 wt%, and the inert diluent is 0 to 10 wt%, based on the total weight of the catalyst component.

In the catalyst component of the present invention, the content of the alkoxy group derived from the surface modifier is more than 0 but less than 5%, preferably 0.01 to 3%, more preferably 0.02 to 2%, still more preferably 0.05 to 1.5%, most preferably 0.1 to 1%. The alkoxy content is determined by the method described below. The term "alkoxy group derived from a surface modifier" as used in the present invention does not include an alkoxy moiety of an ester contained in the catalyst component as an internal electron donor.

In a second aspect, the invention relates to a catalyst for the polymerization or copolymerization of olefins comprising the following components: A) a catalyst component of the invention; B) an organoaluminum compound; and C) optionally an external electron donor Compound.

The organoaluminum compound used as component B of the catalyst of the present invention has the general formula AlR _n X _3-n , wherein R may be hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, particularly an alkyl group or an aralkyl group. Base, aryl; X is halogen, especially chlorine or bromine; n is a number satisfying 0 < n ≦ 3. Specific compounds such as: trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, monohydrogen diethyl aluminum, monohydrogen diisobutyl aluminum, monochlorodiethyl aluminum, monochloroethylene An alkyl aluminum halide such as isobutyl aluminum, sesquiethyl aluminum chloride or diethyl aluminum chloride, wherein triethyl aluminum or triisobutyl aluminum is preferred.

In the catalyst system of the present invention, the molar ratio of aluminum in component B to titanium in component A is from 5 to 5,000, preferably from 20 to 500.

Optional component C in the catalyst system of the invention may be a conventional external electron donor compound, such as an organic rhodium compound. The organogermanium compound has the formula R _n Si(OR ¹ ) _4-n , wherein n is an integer from 0 to 3, and R and R ¹ are the same or different alkyl groups, cycloalkyl groups, aryl groups, A halogenated alkyl group or the like, and R may be a halogen or a hydrogen atom. Examples include, but are not limited to, trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl phenoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl Cyclohexyldiethoxydecane, methylcyclohexyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane,phenyltriethoxydecane,phenyltrimethoxydecane , vinyl trimethoxy decane. Depending on the type of olefin and/or the type of internal electron donor, the C component may or may not be added during polymerization.

The catalyst of the present invention can be used for the polymerization of ethylene, and ethylene with other α-olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-pentene, 1-octene Co-polymerization. The catalyst of the present invention can also be used for the polymerization of propylene, as well as propylene and other α-olefins such as ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-pentene, 1-octyl Copolymerization of an ene or the like. The catalyst of the present invention is particularly suitable for the homopolymerization of propylene and the copolymerization of propylene and ethylene.

Accordingly, in a third aspect, the invention relates to a process for the polymerization or copolymerization of olefins comprising contacting ethylene or propylene and optionally an alpha-olefin comonomer with a catalyst of the invention under polymerization conditions.

The catalyst of the present invention is suitable for use in slurry polymerization, bulk polymerization, and gas phase polymerization processes. These processes and polymerization conditions are well known in the art.

In a fourth aspect, the invention relates to the use of a catalyst of the invention in the polymerization or copolymerization of olefins.

In the present invention, since the use and control of the at least one surface modifying agent is derived from the content of the alkoxy group of the surface modifying agent, the catalyst performance is greatly improved. The catalyst has high catalytic activity and anti-impurity performance when used in propylene polymerization or ethylene-propylene copolymerization, and has good particle morphology and narrow particle distribution, and is suitable for various polymerization processes such as slurry method, bulk method and gas phase method, and molecular weight distribution of polymer. Mw/Mn is large, and the polymer particles are in good shape and less fine powder; its excellent anti-impurity performance can effectively reduce the production cost of the resin; and the copolymerization performance of the catalyst is excellent in ethylene-propylene copolymerization, ethylene in the copolymer The content is higher. The catalyst is particularly suitable for the production of impact propylene copolymers and BOPP film resins.

Detailed description of the preferred embodiment

The examples are given below to illustrate the invention and not to limit the invention.

Test Method for Alkoxy Group Content from Surface Modifier: The catalyst component powder sample is decomposed in a deionized aqueous solution such that the OR in the sample forms ROH. The ROH in the aqueous phase was then determined by gas chromatography, thereby obtaining an OR content.

Specific operation method: After replacing the dry sample bottle with nitrogen, weigh about 0.2g (accurate to 0.0001g), add 0.003g (about 6ul, accurate to 0.0001g), and slowly inject 4ml of deionized water. To decompose the catalyst (there will be exothermic pressure when adding the water-decomposing catalyst, so be sure to press the cap by hand and place the sample vial in a container filled with water to allow rapid cooling), and squeeze the cap to oscillate for 2-3 minutes. After standing for 5 min or more, the aqueous phase was taken to 0.5 ul and measured by a chromatograph.

Example 1

1. Preparation of Magnesium/Titanium Solids In a reaction vessel which was repeatedly substituted with high purity nitrogen, 6.5 kg of anhydrous magnesium chloride, 132.7 liters of toluene, 5.4 liters of epichlorohydrin, and 16.9 liters of tributyl phosphate were successively added. The reaction mixture was stirred at a stirring speed of 130 rpm and a temperature of 60 ° C for 2.5 hours, and then 1.89 kg of phthalic anhydride was added, and the reaction was continued for one hour. The temperature was lowered to -28 ° C, 56 liters of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 85 ° C, and the temperature was maintained for one hour. The mother liquor was filtered off, and the residual solid was washed with toluene and then with hexane several times and dried to give a solid material A containing magnesium/titanium.

2. Preparation of solid titanium catalyst component The solid A prepared above was suspended in 93 liters of toluene, and 1.4 liters of ethanol and 48 liters of titanium tetrachloride were added at -10 ° C, and the temperature was gradually raised to 110 ° C under stirring, and the temperature was raised. During the process, 0.5 liter of diisobutyl phthalate (DIBP) was added at 20 ° C, and 2.0 liters of di-n-butyl phthalate (DNBP) was added at 80 ° C, and then kept at 110 ° C for 1 hour. After filtering off the liquid, 48 liters of titanium tetrachloride and 72 liters of a toluene solution were added, and the temperature was kept at 110 ° C for 2 hours, and the treatment was repeated once more. The liquid was then filtered off, and the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.58% (wt), the DNBP content is 7.63% (wt), the DIBP content is 2.49% (wt), the DEP content is 1.5% (wt), and the ethoxy group content is 0.17% (wt). The specific surface area was 348 m ² /g, the pore volume was 0.32 cm ³ /g, and the average pore diameter was 3.78 nm.

3. Polymerization reaction After a 5 liter stainless steel reaction vessel was sufficiently replaced with nitrogen, 5 ml of a 0.5 mol/L triethylaluminum hexane solution and 1 ml of a 0.1 mol/L methylcyclohexyldimethoxy group were added. The decane (CHMMS) hexane solution and the catalyst component prepared above were 10 mg, then 10 ml of hexane was added to rinse the feed line, and then 1 liter (standard state) of hydrogen, and 2 liters of purified propylene were added, and the temperature was raised to 70 ° C. The polymerization was carried out at this temperature for 2 hours. After completion of the reaction, the reaction vessel was cooled and stirred to remove the reaction product, which was dried to give 790 g of a white polymer. The catalyst activity was 79,000 g of polypropylene per gram of catalyst component, the polymer bulk density was 0.46 g/cm ³ , the fine powder content of less than 80 mesh was 0.5 wt%, the molecular weight distribution of the polymer was Mw/Mn of 6.0, and the MI was 6.7 g. /10min.

4. Polymerization reaction After the 5 liter stainless steel reaction vessel was sufficiently replaced by nitrogen, 10 ml of a 0.3 mol/L triethylaluminum hexane solution and 5 ml of a 0.1 mol/L methylcyclohexyldimethoxy group were added. Base decane (CHMMS) hexane solution and 10 mg of the catalyst component prepared above, then add 10 ml of hexane to rinse the feed line, then add 5 liters (standard state) of hydrogen and 2 liters of refined propylene, and warm to 70 ° C. The polymerization was carried out at this temperature for 1 hour. Then, the pressure in the autoclave (gauge pressure) was lowered to 0, the temperature was raised to 80 ° C, and the mixture was passed through a constant pressure of 1.0 Mpa, and polymerization was carried out for 45 minutes under the conditions. The gas molar ratio in the mixed gas was hydrogen/ethylene/propylene = 0.005: 1.0: 1.25. The polymer product is then recovered. The catalyst activity was 83,500 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.38 g/cm ³ , the ethylene content of the polymer was 14.7 wt%, and the xylene solubles were 21.1 wt%.

Example 2

1. Preparation of Magnesium/Titanium Solids In a reaction vessel which was repeatedly subjected to high-purity nitrogen gas replacement, 4.8 g of anhydrous magnesium chloride, 93 ml of toluene, 4.0 ml of epichlorohydrin, and 12.5 ml of tributyl phosphate were successively added. The mixture was stirred for 2 hours under stirring at a speed of 450 rpm and a temperature of 60 °C. 1.4 g of phthalic anhydride was added and the reaction was continued for one hour. The reaction mixture was cooled to -28 °C. 56 ml of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 85 ° C, and the temperature was maintained for one hour. The mother liquor was filtered off, and the residual solid was washed with toluene and then with hexane several times and dried to obtain a solid A containing magnesium/titanium.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 72 ml of toluene, and 1.7 ml of n-butanol and 48 ml of titanium tetrachloride were added at -10 °C. The reaction mixture was gradually warmed to 110 ° C with stirring. During the temperature rise, 1.5 ml of DNBP was added at 80 ° C, and the temperature was maintained at 110 ° C for 1 hour after the temperature. After filtering off the liquid, the remaining solid was treated with 48 ml of titanium tetrachloride and 72 ml of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, after filtering off the liquid, the remaining solid was washed 5 times with hexane, and dried under vacuum to give a solid titanium catalyst component. The titanium content is 2.13% (wt), the DNBP content is 12.8% (wt), the butoxy group content is 0.1% (wt), the specific surface area of the catalyst is 282.1 m ² /g, and the pore volume is 0.27 cm ³ /g. The average pore diameter was 3.79 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 68000 g of polypropylene/g catalyst component, the polymer bulk density was 0.42 g/cm ³ , and the fine powder content of less than 80 mesh was 1.0 wt%, the polymer had a molecular weight distribution Mw/Mn of 5.2 and an MI of 7.2 g/10 min.

4. Polymerization 2 The polymerization conditions were the same as those in the polymerization reaction 2 of Example 1. The catalyst activity was 73,600 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.37 g/cm ³ , and the ethylene content of the polymer was 13.3 wt. %, xylene solubles was 17.0% by weight.

Example 3

1. Preparation of magnesium/titanium solids is the same as in Example 2.

2. Preparation of solid titanium catalyst component The solid A prepared above was suspended in 72 ml of toluene, 3.0 ml of isooctanol was added at 10 ° C, the temperature was lowered to -10 ° C, and 48 ml of titanium tetrachloride was added. The reaction mixture was gradually warmed to 110 ° C, and 1.0 ml of DIBP was added at 80 ° C, and the temperature was maintained at 110 ° C for 1 hour. After filtering off the liquid, the remaining solid was treated with 48 ml of titanium tetrachloride and 72 ml of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, after the liquid was filtered off, the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.34% (wt), the DIBP content is 10.57% (wt), the DIOP content is 0.8% (wt), the octyloxy group content is 0.1% (wt), and the specific surface area of the catalyst is 273.6 m ² /g. The pore volume was 0.26 cm ³ /g, and the average pore diameter was 3.78 nm.

3. Polymerization 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 62,300 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.46 g/cm ³ , and the fine powder content of less than 80 mesh was The molecular weight distribution Mw/Mn of the polymer was 5.4 g and the MI was 5.8 g/10 min.

4. Polymerization 2 The polymerization conditions were the same as those in the polymerization reaction 2 of Example 1. The catalyst activity was 55,900 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.35 g/cm ³ , and the ethylene content of the polymer was 16.4 wt. %, xylene solubles was 21.2% by weight.

Example 4

1. Preparation of magnesium/titanium solids is the same as in Example 2.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 72 ml of toluene, and 2.5 ml of isooctanol and 48 liters of titanium tetrachloride were added at 0 °C. The reaction mixture was gradually warmed to 110 ° C, and 1.0 ml of di-n-butyl phthalate (DNBP) was added at 80 ° C, and the temperature was maintained at 110 ° C for 1 hour after warming. After filtering off the liquid, the remaining solid was treated with 48 ml of titanium tetrachloride and 72 ml of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, after the liquid was filtered off, the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.36% (wt), the DNBP content is 9.75% (wt), the DIOP content is 0.65% (wt), the octyloxy group content is 0.12% (wt), and the specific surface area of the catalyst is 245.3 m ² /g. The pore volume was 0.25 cm ³ /g, and the average pore diameter was 3.90 nm.

3. Polymerization 1

The polymerization conditions of propylene were the same as those of the polymerization reaction 1 in Example 1. The catalyst activity was 77600 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.46 g/cm ³ , and the fine powder content of less than 80 mesh was 0.3 wt%. The molecular weight distribution Mw/Mn of the material was 5.1 and the MI was 6.3 g/10 min.

4, polymerization 2

The polymerization conditions were the same as those in the polymerization reaction 2 in Example 1. The catalyst activity was 81,400 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.38 g/cm ³ , and the ethylene content of the polymer was 13.0 wt%. The solution was 16.4% by weight.

Example 5

1. The preparation of the magnesium/titanium solid was the same as in Example 1.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 93 liters of toluene, and 1.4 liters of ethanol was added at -10 °C. The reaction mixture was gradually warmed to 30 ° C, maintained for 30 minutes, then cooled to -10 ° C, and 48 liters of titanium tetrachloride was added. The reaction mixture was then gradually warmed to 110 ° C, and 2.0 liters of di-n-butyl phthalate (DNBP) was added at 80 ° C, and the temperature was maintained at 110 ° C for 1 hour after warming. After the liquid was filtered off, the remaining solid was treated with 48 liters of titanium tetrachloride and 72 liters of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, the liquid was filtered off, and the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.56% (wt), the DNBP content is 8.64% (wt), the DEP content is 0.7% (wt), the ethoxy group content is 0.24% (wt), and the specific surface area of the catalyst is 284.7 m ² /g. The pore volume was 0.27 cm ³ /g, and the average pore diameter was 3.53 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 78,000 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.47 g/cm ³ , and the fine powder content of less than 80 mesh was The molecular weight distribution of the polymer was 0.5% by weight, Mw/Mn was 5.3, and MI was 5.6 g/10 min.

4. Polymerization 2 The polymerization conditions were the same as those in the polymerization reaction 2 of Example 1. The catalyst activity was 81,600 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.38 g/cm ³ , and the ethylene content of the polymer was 14.5 wt. %, xylene solubles was 19.3 wt%.

Example 6

1. The preparation of the magnesium/titanium solid was the same as in Example 1.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 93 liters of toluene, and 1.4 liters of ethanol was added at -10 °C. . The reaction mixture was gradually warmed to 30 ° C, maintained for 30 minutes, then cooled to -10 ° C, and 48 liters of titanium tetrachloride was added. Then, the reaction mixture was gradually warmed to 110 ° C, and 1.7 liters of diisobutyl phthalate (DIBP) was added at 80 ° C, and the temperature was maintained at 110 ° C for 1 hour after the temperature. After the liquid was filtered off, the remaining solid was treated with 48 liters of titanium tetrachloride and 72 liters of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, after the liquid was filtered off, the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.56% (wt), the DIBP content is 7.83% (wt), the DEP content is 3.2% (wt), the ethoxy group content is 0.15% (wt), and the specific surface area of the catalyst is 297.6 m ² /g. The pore volume was 0.29 cm ³ /g, and the average pore diameter was 3.49 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 74,000 g of polypropylene per gram of the catalyst component, and the polymer bulk density was 0.47 g/cm ³ , and the fine powder content of less than 80 mesh was 0.4 wt%, the molecular weight distribution of the polymer Mw/Mn was 5.8, and the MI was 5.8 g/10 min.

4. Polymerization reaction 2 The polymerization conditions were the same as those in the polymerization reaction 2 in Example 1. The catalyst activity was 63,200 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.38 g/cm ³ , and the ethylene content of the polymer was 15.8 wt. %, xylene solubles was 22.32% by weight.

Example 7

1. The preparation of the magnesium/titanium solid was the same as in Example 1.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 93 liters of toluene, and 1.4 liters of ethanol was added at -25 °C. The reaction mixture was gradually warmed to 30 ° C, maintained for 30 minutes, then cooled to -10 ° C, and 48 liters of titanium tetrachloride was added. The reaction mixture was then gradually warmed to 110 ° C, and 4.5 liters of 1,3-pentanediol dibenzoate was added at 40 ° C, and the temperature was maintained at 110 ° C for 1 hour after warming. After the liquid was filtered off, it was kept at a constant temperature of 110 ° C for 2 hours with 48 liters of titanium tetrachloride and 72 liters of toluene, and the treatment was repeated once more. Then, after the liquid was filtered off, the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 3.19% (wt), the 1,3-pentanediol dibenzoate content is 10.3 wt%, the ethoxy group content is 0.15% (wt), and the specific surface area of the catalyst is 283.5 m ² /g. The volume was 0.27 cm ³ /g, and the average pore diameter was 3.65 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 61,500 g of polypropylene per gram of the catalyst component, and the polymer bulk density was 0.44 g/cm ³ , and the fine powder content of less than 80 mesh was 0.4 wt%, the molecular weight distribution of the polymer Mw/Mn was 8.5, and the MI was 3.8 g/10 min.

4. Polymerization 2 The polymerization conditions were as described in Polymerization 2 of Example 1. The catalyst activity was 64,800 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.37 g/cm ³ , and the ethylene content of the polymer was 14.9 wt. %, xylene solubles was 18.62% by weight.

Example 8

1. The preparation of the magnesium/titanium solid was the same as in Example 1.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 93 liters of toluene, and 1.4 liters of ethanol was added at 35 °C. After the reaction mixture was maintained at this temperature for 30 minutes, 48 liters of titanium tetrachloride was added, and then the temperature was gradually raised to 110 ° C, and 2.0 liters of diisobutyl phthalate (DIBP) was added at 40 ° C, and after 110 ° C to temperature. Constant temperature for 1 hour. After the liquid was filtered off, the remaining solid was treated with 48 liters of titanium tetrachloride and 72 liters of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, the liquid was filtered off, and the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 3.27% (wt), the DIBP content is 6.80% (wt), the DEP content is 2.1% (wt), the ethoxy group content is 0.14% (wt), and the specific surface area of the catalyst is 307.4 m ² /g. The pore volume was 0.29 cm ³ /g, and the average pore diameter was 4.09 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene are the same as those in the polymerization reaction 1 of Example 1. The catalyst activity is 58,000 g of polypropylene per gram of the catalyst component, the polymer bulk density is 0.45 g/cm ³ , and the fine powder content of less than 80 mesh is 0.4 wt%, the molecular weight distribution of the polymer Mw/Mn was 5.6, and MI was 5.4 g/10 min.

4. Polymerization 2 The polymerization conditions were the same as those in the polymerization reaction 2 of Example 1. The catalyst activity was 62,100 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.39 g/cm ³ , and the ethylene content of the polymer was 13.7 wt. %, xylene solubles was 16.86 wt%.

Example 9

1. Preparation of magnesium/titanium solids is the same as in Example 2.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 72 ml of toluene, and 3.0 ml of ethanol and 48 ml of titanium tetrachloride were added at -10 °C. The reaction mixture was gradually warmed to 110 ° C, and 1.0 ml of DIBP was added at 80 ° C during the temperature rise, and the temperature was maintained at 110 ° C for 1 hour after the temperature. After filtering off the liquid, the remaining solid was treated with 48 ml of titanium tetrachloride and 72 ml of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. Then, after the liquid was filtered off, the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.85% (wt), the DIBP content is 11.5% (wt), the ethoxy group content is 1.3% (wt), the specific surface area of the catalyst is 321.5 m ² /g, and the pore volume is 0.30 cm ³ /g. The average pore diameter was 3.62 nm.

3. Polymerization 1 The polymerization conditions of propylene were the same as those of the polymerization reaction 1 in Example 1. The catalyst activity was 59,400 g of polypropylene per gram of the catalyst component, and the polymer bulk density was 0.43 g/cm ³ , which was less than 80 mesh (0.18 mm). The fine powder content was 2.4% by weight, the molecular weight distribution of the polymer was Mw/Mn of 5.6, and the MI was 5.7 g/10 min.

Example 10

1. Preparation of Magnesium/Titanium Solids In a reaction vessel which was repeatedly subjected to high-purity nitrogen gas replacement, 4.8 g of anhydrous magnesium chloride, 93 ml of toluene, 4.0 ml of epichlorohydrin, and 12.5 ml of tributyl phosphate were successively added. The mixture was stirred for 2 hours under stirring at a speed of 450 rpm and a temperature of 60 °C. Then 1.4 g of phthalic anhydride was added and the reaction was continued for one hour. The reaction mixture was cooled to -28 ° C, 56 ml of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 85 ° C, and 0.5 ml of DNBP was added at 80 ° C, and the temperature was kept at 85 ° C for one hour. The mother liquor was filtered off, and the remaining solid was washed with toluene and then with hexane several times, and then dried to obtain a solid material A containing magnesium/titanium.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 72 ml of toluene, and 1.0 ml of ethanol and 48 ml of titanium tetrachloride were added at -10 °C. The reaction mixture was gradually warmed to 110 ° C, and 1.0 ml of DIBP was added at 80 ° C during the temperature rise, and the temperature was maintained at 110 ° C for 1 hour after the temperature. After filtering off the liquid, the remaining solid was treated with 48 ml of titanium tetrachloride and 72 ml of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. After filtering off the liquid, the remaining solid product was washed 5 times with hexane and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.54% (wt), the DNBP content is 4.8% (wt), the DIBP content is 6.9% (wt), the DEP content is 1.3% (wt), and the ethoxy group content is 0.20% (wt). The specific surface area was 305.4 m ² /g, the pore volume was 0.28 cm ³ /g, and the average pore diameter was 3.64 nm.

3. Polymerization 1

The polymerization conditions of propylene were the same as those of the polymerization reaction 1 in Example 1, and the catalyst activity was 65000 g of polypropylene/g catalyst component, the polymer bulk density was 0.47 g/cm ³ , and the fine powder content of less than 80 mesh was 0.6 wt%. The molecular weight distribution Mw/Mn of the material was 5.4, and the MI was 6.9 g/10 min.

4. Polymerization reaction 2 The copolymerization conditions were the same as those in the polymerization reaction 2 of Example 1. The catalyst activity was 71,500 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.39 g/cm ³ , and the ethylene content of the polymer was 13.9. The wt%, xylene solubles were 16.8% by weight.

Example 11

1. Preparation of Solids Containing Magnesium and Titanium In a reaction vessel which was repeatedly substituted with high purity nitrogen, 4.8 g of anhydrous magnesium chloride, 93 ml of toluene, 8.0 ml of epichlorohydrin, and 10.0 ml of tributyl phosphate were successively added. The mixture was stirred for 2 hours under stirring at a speed of 450 rpm and a temperature of 60 °C. Then, 1.4 g of phthalic anhydride was added, and the reaction was continued for one hour, and the temperature was lowered to -28 °C. 56 ml of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 85 ° C, and the temperature was maintained for one hour. The mother liquid was filtered off, washed with toluene and then washed with hexane several times, and dried to obtain a solid A containing magnesium and titanium.

2. Preparation of solid titanium catalyst component The solid A prepared above was suspended in 72 ml of toluene, 1.0 ml of ethanol and 48 ml of titanium tetrachloride were added at -10 ° C, and the reaction mixture was gradually heated to 110 ° C with stirring. . During the warming up, 1.5 ml of DIBP was added at 80 °C. The temperature was maintained at 110 ° C for 1 hour after the temperature. After filtering off the liquid, the remaining solid was treated with 48 ml of titanium tetrachloride and 72 ml of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. The liquid was then filtered off and the remaining solid product was washed 5 times with hexanes and dried in vacuo to give a solid titanium catalyst component. The titanium content is 3.12% (wt), the DIBP content is 15.7% (wt), the DEP content is 0.4% (wt), the ethoxy group content is 0.18% (wt), and the specific surface area of the catalyst is 295.4 m ² /g. The pore volume was 0.28 cm ³ /g, and the average pore diameter was 3.70 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene are the same as those in the polymerization reaction 1 of Example 1. The catalyst activity is 64000 g of polypropylene/g catalyst component, and the polymer bulk density is 0.47 g/cm ³ , which is less than 80 mesh fine powder content. The molecular weight distribution Mw/Mn was 5.8 and the MI was 6.4 g/10 min.

Example 12

1. Preparation of a solid containing magnesium and titanium is the same as in Example 1.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 93 liters of toluene, and 1.4 liters of ethanol was added at -25 °C. The reaction mixture was then gradually warmed to 30 ° C, maintained for 30 minutes, then cooled to -10 ° C, and 48 liters of titanium tetrachloride was added. The reaction mixture was gradually warmed to 110 ° C, and 1.5 liters of diisobutyl phthalate (DIBP) and 1.8 liters of ethyl benzoate (EB) were added at 40 ° C, and the temperature was maintained at 110 ° C for 1 hour after warming. After the liquid was filtered off, the remaining solid was treated with 48 liters of titanium tetrachloride and 72 liters of toluene at 110 ° C for 2 hours, and the treatment was repeated once more. The liquid was then filtered off and the remaining solid product was washed 5 times with hexanes and dried in vacuo to give a solid titanium catalyst component. The titanium content is 2.1% (wt), the DIBP content is 4.2% (wt), the EB content is 2.0% (wt), the DEP content is 0.8% (wt), and the ethoxy group content is 0.13% (wt). The specific surface area was 304.3 m ² /g, the pore volume was 0.29 cm ³ /g, and the average pore diameter was 3.42 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 64,300 g of polypropylene per gram of the catalyst component, and the polymer bulk density was 0.44 g/cm ³ , and the fine powder content of less than 80 mesh was 0.4 wt%, the molecular weight distribution of the polymer Mw/Mn was 6.3, and the MI was 9.8 g/10 min.

4. Polymerization 2 The polymerization conditions were the same as those in the polymerization reaction 2 of Example 1. The catalyst activity was 73,200 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.36 g/cm ³ , and the ethylene content of the polymer was 14.5 wt. %, xylene solubles was 18.5 wt%.

Comparative example 1

1. Preparation of Solid Titanium Catalyst Component 4.8 g of anhydrous magnesium chloride, 93 ml of toluene, 4.0 ml of epichlorohydrin, and 12.5 ml of tributyl phosphate were placed in a reaction vessel which had been completely replaced with high-purity nitrogen. The mixture was stirred at a stirring speed of 450 rpm and a temperature of 60 ° C for 2 hours, and 1.4 g of phthalic anhydride was added to continue the reaction for one hour. The mixture was cooled to -28 ° C, 56 ml of titanium tetrachloride was added dropwise, and the temperature was gradually raised to 85 ° C, and 2.0 ml of DNBP was added at 80 ° C, and the temperature was maintained at 85 ° C for one hour. The mother liquor was filtered off, and the remaining solid was treated with toluene 60 ml and 40 ml of titanium tetrachloride at 110 ° C for 2 hours, and the treatment was repeated once more. The solid after filtration was washed with hexane 5 times and dried to give a solid titanium catalyst component. The titanium content is 1.9% (wt), the DNBP content is 12.50% (wt), the specific surface area of the catalyst is 180.5 m ² /g, the pore volume is 0.22 cm ³ /g, the average pore diameter is 4.12 nm, and the ethoxy group content is 0.

2. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 55,000 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.47 g/cm ³ , and the fine powder content of less than 80 mesh was 1.5 wt%, the molecular weight distribution of the polymer Mw/Mn was 4.3, and the MI was 4.5 g/10 min.

3. Polymerization reaction 2 The polymerization conditions were the same as those in the polymerization reaction 2 in Example 1. The catalyst activity was 46,200 g of polypropylene per gram of the catalyst component, the polymer bulk density was 0.35 g/cm ³ , and the ethylene content of the polymer was 9.5 wt. %, xylene solubles was 13.8% by weight.

Comparative example 2

1. Preparation of magnesium/titanium solids is the same as in Example 2.

2. Preparation of Solid Titanium Catalyst Component The solid A prepared above was suspended in 72 ml of toluene, and 8.0 ml of ethanol and 48 ml of titanium tetrachloride were added at -10 °C. The mixture was gradually warmed to 85 ° C, and 1.0 ml of DIBP was added at 80 ° C during the temperature rise, and the temperature was maintained at 85 ° C for 1 hour after the temperature. Then, the liquid was filtered off, and the remaining solid product was washed 5 times with hexane, and dried under vacuum to obtain a solid titanium catalyst component. The titanium content is 4.32% (wt), the DIBP content is 13.5% (wt), the ethoxy group content is 5.5% (wt), the specific surface area of the catalyst is 170.6 m ² /g, and the pore volume is 0.22 cm ³ /g. The average pore diameter was 4.65 nm.

3. Polymerization reaction 1 The polymerization conditions of propylene were the same as those in the polymerization reaction 1 of Example 1. The catalyst activity was 36,400 g of polypropylene per gram of the catalyst component, and the polymer bulk density was 0.43 g/cm ³ , which was less than 80 mesh (0.18 mm). The fine powder content was 5.6 wt%, the molecular weight distribution of the polymer was Mw/Mn of 5.3, and the MI was 6.2 g/10 min.

Comparative example 3

1. Preparation of titanium-containing solid catalyst component 4.8 g of anhydrous magnesium chloride, 93 ml of toluene, 4.0 ml of epichlorohydrin, 12.5 ml of tributyl phosphate, and 1 ml of ethanol were added to a reaction vessel which had been completely replaced with high-purity nitrogen. . The mixture was stirred at a stirring speed of 450 rpm and a temperature of 60 ° C for 2 hours. 1.4 g of phthalic anhydride was added and the reaction was continued for one hour. The temperature was lowered to -28 ° C, and 56 ml of titanium tetrachloride was added dropwise. The reaction mixture was gradually warmed to 85 ° C, and 2.0 ml of DNBP was added at 80 ° C, and the temperature was maintained at 85 ° C for one hour. The mother liquor was filtered off, and 60 ml of toluene and 40 ml of titanium tetrachloride were added, and the mixture was treated at 110 ° C for 2 hours, and the treatment was repeated once more. The liquid was filtered off, and the remaining solid product was washed 5 times with hexane and dried to give a solid titanium catalyst component. The titanium content is 3.56% (wt), the DNBP content is 12.20% (wt), the ethoxy group is 0.30% (wt), the specific surface area of the catalyst is 150.4 m ² /g, the pore volume is 0.21 cm ³ /g, and the average pore diameter is 0.21 cm ³ /g. It is 4.23 nm.

2. Polymerization 1 The polymerization conditions of propylene were the same as in Example 1. The catalyst activity was 25,300 g of polypropylene/g of catalyst component, the polymer bulk density was 0.43 g/cm ³ , and the fine powder content of less than 80 mesh (0.18 mm) was 10.2 wt. %, the polymer had a molecular weight distribution Mw/Mn of 4.8 and an MI of 4.9 g/10 min.

Claims (19)

A catalyst component for olefin polymerization or copolymerization comprising magnesium, titanium, a halogen, an internal electron donor compound, and an alkoxy group derived from a surface modifier selected from the group consisting of alcohols, Wherein the internal electron donor compound is selected from the group consisting of a polycarboxylic acid, a monocarboxylic acid ester or a polycarboxylic acid ester, an acid anhydride, a ketone, a monoether, a polyether, and an amine, wherein the surface is derived from The modifier has an alkoxy group content of from 0.01 to 3% by weight, based on the weight of the catalyst component. A process for preparing a catalyst component for olefin polymerization or copolymerization as described in claim 1, comprising the steps of: i) dissolving a magnesium compound in an organic epoxy compound, an organophosphorus compound, and optionally inertia Forming a homogeneous solution in a solvent mixture consisting of a diluent, ii) treating the solution with a titanium compound in the presence of a co-precipitating agent, optionally in the presence of at least one internal electron donor compound, to precipitate a solid containing magnesium and titanium a precipitate, iii) treating the solid precipitate with at least one surface modifying agent, and simultaneously or subsequently further loading at least one titanium compound and at least one internal electron donor compound to form a treated solid precipitate, and Iv) washing the treated solid precipitate with an inert diluent, wherein the surface modifier is selected from the group consisting of alcohols, and the helper is selected from the group consisting of carboxylic anhydrides, carboxylic acids, ethers and ketones. At least one of the groups. A catalyst for olefin polymerization or copolymerization comprising: A) a catalyst component as described in claim 1; B) an organoaluminum compound; and C) optionally an external electron donor compound. A process for the polymerization or copolymerization of olefins comprising contacting ethylene or propylene and optionally an alpha-olefin comonomer with a catalyst as described in claim 3 under polymerization conditions. The process of claim 4, which is carried out in a slurry, bulk or gas phase. A catalyst component for olefin polymerization or copolymerization obtained by a process comprising the steps of: i) dissolving a magnesium compound in a solvent mixture of an organic epoxy compound, an organophosphorus compound, and optionally an inert diluent. Forming a homogeneous solution, ii) treating the solution with a titanium compound in the presence of a co-precipitating agent, optionally in the presence of at least one internal electron donor compound, to precipitate a solid precipitate comprising magnesium and titanium, iii) Treating the solid precipitate with at least one surface modifying agent and simultaneously or subsequently further loading at least one titanium compound and at least one internal electron donor compound to form a treated solid precipitate, and iv) by inert dilution The treated solid precipitate is washed, wherein the surface modifier is selected from the group consisting of alcohols, and the helper is selected from the group consisting of carboxylic anhydrides, carboxylic acids, ethers and ketones. At least one of the group, wherein the catalyst component contains 0.01 to 3% by weight, based on the weight of the catalyst component, of an alkoxy group derived from the surface modifier. The catalyst component according to claim 6, wherein the surface modifier is selected from the group consisting of a linear alcohol or an isomeric alcohol having 1 to 8 carbon atoms. The catalyst component of claim 6, wherein the surface modifier is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, octanol, isooctanol or a mixture thereof. The catalyst component according to claim 6, wherein the magnesium compound is selected from the group consisting of a complex of water and an alcohol of magnesium dihalide, magnesium dihalide, and a halogen atom of the magnesium dihalide is hydrolyzed. Or a group consisting of a magnesium dihalide derivative substituted with a hydrocarbyloxy group, and a mixture thereof; wherein the titanium compound has the general formula Ti(OR) _4-n X _n , wherein R is the same or different An aliphatic hydrocarbon group or an aromatic hydrocarbon group of C ₁ to C ₁₄ , X is a halogen, and n is an integer of 0 to 4. The catalyst component of claim 9, wherein the magnesium compound is magnesium dichloride, and wherein the titanium compound is titanium tetrachloride. The catalyst component according to claim 6, wherein the internal electron donor compound is selected from the group consisting of diethyl phthalate, diisobutyl phthalate, and phthalic acid. N-butyl ester, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropylsuccinate, 2,3-diisopropyl Diisobutyl succinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate , 2-isobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, sebacic acid Ethyl ester, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalate, dibutyl naphthalate, trimellitic acid Ethyl ester, tributyl trimellitate, triethyl trimellitate, tributyl trimellitate, tetraethyl pyromelliate, tetrabutyl pyromelliate, 1,3-dibenzoate A group consisting of pentanyl ester, ethyl benzoate, and mixtures thereof. The catalyst component of claim 6, wherein the inert diluent is hexane, heptane, octane, decane, benzene, toluene, or xylene. The catalyst component according to claim 6, wherein the surface modifier is used in an amount of from 0.06 to 10 moles per mole of the magnesium compound. The catalyst component according to claim 6, wherein the internal electron donor compound is used in an amount of from 0.01 to 2 moles per mole of the magnesium compound. The catalyst component according to claim 6, wherein the surface modifying agent-derived alkoxy group is contained in an amount of from 0.02 to 2% by weight based on the weight of the catalyst component. A catalyst for olefin polymerization or copolymerization comprising: A) a catalyst component as described in claim 6; B) an organoaluminum compound; and C) optionally, an external electron donor compound. A process for the polymerization or copolymerization of an olefin comprising contacting ethylene or propylene and optionally an alpha-olefin comonomer with a catalyst as described in claim 16 under polymerization conditions. The method of claim 17, which is carried out in a slurry, bulk or gas phase. A catalyst component for olefin polymerization or copolymerization comprising magnesium, titanium, chlorine, an internal electron donor compound and a surface modifier derived from the group consisting of C ₁ -C ₈ alcohols a C ₁ -C ₈ alkoxy group, wherein the internal electron donor compound is selected from the group consisting of polycarboxylic acids, monocarboxylic or polycarboxylic acid esters, acid anhydrides, ketones, monoethers and polyethers and amines. a group, wherein the content of the C ₁ -C ₈ alkoxy group derived from the surface modifier is 0.01 to 3% by weight, and the catalyst component is obtained by a method comprising the following steps, based on the weight of the catalyst component; : i) dissolving magnesium dichloride in a solvent mixture of an organic epoxy compound, an organophosphorus compound and optionally an inert diluent to form a homogeneous solution, ii) selected from the group consisting of carboxylic anhydrides, carboxylic acids, ethers and ketones. The solution is treated with titanium tetrachloride in the presence of at least one co-precipitating agent in the group, optionally in the presence of at least one internal electron donor compound, to precipitate a solid precipitate comprising magnesium and titanium, iii Treating the solid with at least one of the surface modifying agents Precipitate, and simultaneously or subsequently further supporting the titanium tetrachloride and at least one internal electron donor compound, to form a treated solid precipitate, and iv) an inert diluent washed with the treated solid precipitate.