Solid catalyst component for olefin polymerization and method for manufacturing the same, catalyst for olefin polymerization and method for manufacturing the same, and method for manufacturing an olefin polymer

Abstract

The present invention provides a solid catalyst component for polymerizing olefins that, when provided for the polymerization of olefins, can easily prepare an olefin polymer in which the content of residual volatile organic compounds is significantly reduced in a short period of time, while appropriately suppressing the decrease in polymerization activity per unit time and improving drying efficiency, even without using phthalic acid esters. The solid catalyst component for polymerizing olefins contains magnesium, titanium, a halogen, and a 1,3-diether compound, wherein the ratio of the 1,3-diether compound included in the solid catalyst component for polymerizing olefins is 2.50 to 15.00 mass%, and the specific surface area of ​​the solid catalyst component for polymerizing olefins is 250 m2 / g or more.

Description

Technology Field

[0001] The present invention relates to a solid catalyst component for olefin polymerization and a method for manufacturing the same, a catalyst for olefin polymerization and a method for manufacturing the same, and a method for manufacturing an olefin polymer. Background Technology

[0002] Recently, polyolefins such as polypropylene (PP) are being used in various applications, including containers and films, in addition to molded products such as automotive parts and home appliances.

[0003] Conventionally, as a method for polymerizing olefins, many methods for polymerizing propylene alone or with other α-olefins have been proposed, using a catalyst for polymerizing olefins comprising a solid catalyst component containing magnesium, titanium, a halogen, and an internal electron-donating compound as essential components, an organoaluminum compound, and an external electron-donating compound (see, for example, Patent Documents 1 to 3). Prior art literature

[0004] Japanese Patent Publication No. 57-63310, U.S. Patent No. 4399054, Japanese Patent Publication No. 2016-532738 The problem to be solved

[0005] As described in Patent Document 1, catalysts for the polymerization of olefins using phthalic acid esters as electron-donating compounds have been widely used in the past. However, di-n-butyl phthalate and benzylbutyl phthalate, which are types of phthalic acid esters, are designated as Substances of Very High Concern (SVHC) under the European Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) regulations. Furthermore, from the perspective of reducing environmental burden, there is a growing demand to switch to catalyst systems that do not use SVHC substances.

[0006] Meanwhile, catalyst systems using electron-donating compounds that are not subject to SVHC regulation, such as those using succinic acid esters, maleic acid esters, and malonic acid esters, as well as the catalyst systems described in Reference 2 and Reference 3, are known. However, even with these catalyst systems, it was difficult to achieve performance equivalent to that of using phthalic acid esters. In particular, in polymerization facilities where a process exists in which a solid catalyst component, an organoaluminum compound, and an external electron-donating compound are brought into contact under an inert gas atmosphere such as a nitrogen atmosphere, there is a tendency to significantly reduce polymerization activity when electron-donating compounds that are not subject to SVHC regulation are used. Under these circumstances, further improvements were required for olefin polymerization catalysts using electron-donating compounds that are not subject to SVHC regulation.

[0007] Furthermore, when using such conventional polymerization catalysts, unreacted monomers or oligomers, or organic solvents used during polymerization, may remain as volatile organic compounds in the resulting olefin polymer. Consequently, after the polymerization reaction, the olefin polymer is transferred to a subsequent process after the volatile organic compounds are degassed from the reactor. However, even if the olefin polymer has a low amount of residual gas, if degassing takes a long time, there is a concern that the pressure within the system may rise in the subsequent process or the rate of impurity incorporation into the recycling system may increase, making it prone to process troubles or degradation of the quality of the obtained polymer. In this regard, it has been desired not only to have a low amount of residual volatile organic compounds in the polymer but also to have the volatile organic compounds remaining in the polymer removed in a short period of time; however, conventionally, a polymerization catalyst capable of significantly reducing the content of volatile organic compounds in the polymer in a short period of time has not been proposed.

[0008] Under these circumstances, the present invention aims to provide a solid catalyst component for polymerizing olefins and a method for manufacturing the same, a catalyst for polymerizing olefins and a method for manufacturing the same, and a method for manufacturing an olefin polymer, which, even without using phthalate esters, can easily prepare an olefin polymer in which the decrease in polymerization activity per unit time is appropriately suppressed and drying efficiency is improved, and the content ratio of residual volatile organic compounds is significantly reduced in a short period of time when provided for the polymerization of olefins. means of solving the problem

[0009] In order to solve the above technical problem, the inventors have carefully examined and found a compound containing magnesium, titanium, and a halogen, as well as containing 2.50 to 15.00 mass% of a 1,3-diether compound, and having a specific surface area of ​​250 m² 2 It was discovered that the above technical problem can be solved by a solid catalyst component for polymerizing olefins with a value of 1 / g or more, and based on this finding, the present invention was completed.

[0010] That is, the present invention is,

[0011] (1) A solid catalyst component for polymerizing olefins containing magnesium, titanium, halogen and 1,3-diether compounds,

[0012] The proportion of the above 1,3-diether compound included in the solid catalyst component for the polymerization of olefins is 2.50 to 15.00 mass%, and

[0013] The specific surface area of ​​the above-mentioned solid catalyst component for olefin polymerization is 250 m² 2 Solid catalyst component for olefin polymerization characterized by having a content of / g or more,

[0014] (2) The work volume is 0.250~1.000cm 3 A solid catalyst component for polymerizing olefins described in (1) above, which is / g

[0015] (3) The above 1,3-diether compound is of the following general formula (I);

[0016] R 1 OCH2CR 2 R 3 CH2OR 4 (I)

[0017] (during food, R 2 and R 3 It represents silver, a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl or cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, an alkylamino group having 1 to 12 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. R 2 and R 3 They may be identical or different. R 2 and R 3 Silver may combine with each other to form rings. R 1 and R 4 represents an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent. 1 and R 4 A solid catalyst component for polymerizing olefins described in (1) or (2), which is one or more selected from compounds represented as (which may be identical or different from each other),

[0018] (4) A method for manufacturing a solid catalyst component for polymerizing olefins as described in any one of (1) to (3), wherein the specific surface area is 5 m² 2 A method for preparing a solid catalyst component for polymerizing olefins described in any one of (1) to (3), characterized by contacting a magnesium compound with a g or more, a tetravalent titanium halogen compound, and a 1,3-diether compound with each other.

[0019] (5) A solid catalyst component for polymerizing olefins described in any one of (1) to (3) above, and the following general formula (II)

[0020] R 5 p AlQ3 - p (II)

[0021] (during food, R 5 A catalyst for polymerizing olefins characterized by comprising one or more organoaluminum compounds selected from compounds represented by , wherein is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number such that 0 < p ≤ 3.

[0022] (6) A solid catalyst component for polymerizing olefins obtained by the method of producing the solid catalyst component for polymerizing olefins described in any one of (1) to (3) above or the solid catalyst component for polymerizing olefins described in claim 4, and the following general formula (II)

[0023] R 5 p AlQ3 - p (II)

[0024] (during food, R 5 One or more organoaluminum compounds selected from compounds represented by , wherein is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number such that 0 < p ≤ 3,

[0025] A method for manufacturing a catalyst for polymerizing olefins characterized by bringing them into contact with each other,

[0026] (7) A method for producing an olefin polymer, characterized by polymerizing olefins using the olefin polymerization catalyst described in (5) above or the olefin polymerization catalyst obtained by the method described in (6).

[0027] (8) A method for producing an olefin polymer described in (7), wherein the polymerization of the olefins is a propylene homopolymer or a copolymer of propylene and an α-olefin other than propylene.

[0028] It is to provide. Effects of the invention

[0029] According to the present invention, by containing a predetermined amount of a 1,3-diether compound instead of a phthalic acid ester and controlling the specific surface area to a predetermined range, when applied to the polymerization of olefins, the decrease in polymerization activity per unit time is appropriately suppressed and drying efficiency is improved, thereby enabling the easy preparation of an olefin polymer in which the content ratio of residual volatile organic compounds is significantly reduced in a short period of time. Furthermore, according to the present invention, a catalyst for the polymerization of olefins comprising the above-mentioned solid catalyst component, a method for preparing the same, and a method for preparing an olefin polymer can be provided.

[0030] That is, according to the present invention, when provided for the polymerization reaction of olefins, the decrease in polymerization activity per unit time is appropriately suppressed, and since degassing occurs quickly after the reaction, the risk of pressure rise within the system and the rate of impurity incorporation into the recycling system in subsequent processes can be reduced, thereby reducing process troubles and the degradation of the quality of the obtained polymer. Furthermore, drying efficiency is improved, and residual volatile organic compound components can be significantly reduced in a short time. Thus, a solid catalyst component for polymerizing olefins and a method for manufacturing the same can be provided. In addition, according to the present invention, a catalyst for polymerizing olefins comprising said solid catalyst component, a method for manufacturing the same, and a method for manufacturing an olefin polymer can be provided. Specific details for implementing the invention

[0031] <Solid catalyst component for olefin polymerization and method for manufacturing the same>

[0032] First, the solid catalyst component for olefin polymerization according to the present invention will be described.

[0033] The solid catalyst component for olefin polymerization according to the present invention is a solid catalyst component for olefin polymerization containing magnesium, titanium, a halogen, and a 1,3-diether compound, wherein

[0034] The proportion of the above 1,3-diether compound included in the solid catalyst component for the polymerization of olefins is 2.50 to 15.00 mass%, and

[0035] The specific surface area of ​​the above-mentioned solid catalyst component for olefin polymerization is 250 m² 2 It is characterized by being greater than / g.

[0036] The solid catalyst component for olefin polymerization according to the present invention contains a specific amount of magnesium, titanium, halogen, and a specific internal electron-donating compound.

[0037] As a solid catalyst component for olefin polymerization according to the present invention, a contact reaction product formed by contacting a raw material component that serves as a source of magnesium, titanium, and halogen with a specific internal electron-donating compound in an organic solvent and reacting them can be cited. Specifically, as a raw material component that serves as a source of magnesium, titanium, and halogen, a magnesium compound and a tetravalent titanium halogen compound can be used, and a contact reaction product formed by contacting these raw materials with a specific internal electron-donating compound comprising one or more 1,3-diether compounds can be cited.

[0038] Examples of the above magnesium compounds include one or more selected from dialkoxymagnesium, magnesium dihalide, and alkoxymagnesium halide.

[0039] Among the magnesium compounds mentioned above, dialkoxymagnesium or magnesium dihalide is preferred, specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride, magnesium dibromide, magnesium diiodide, etc., and diethoxymagnesium and magnesium dichloride are particularly preferred.

[0040] Among the magnesium compounds mentioned above, dialkoxymagnesium may be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

[0041] The above dialkoxymagnesium is preferably in granular or powder form, and may be used in an irregular or spherical shape.

[0042] When spherical dialkoxymagnesium is used, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution is obtained, and the handling characteristics of the polymer powder produced during polymerization are improved, thereby suppressing the occurrence of clogging caused by fine particles contained in the produced polymer powder.

[0043] The dialkoxymagnesium of the above-mentioned structure does not necessarily have to be spherical; elliptical or potato-shaped forms may also be used.

[0044] In addition, the average particle size (average particle size D50) of the above dialkoxymagnesium is preferably 1.0 to 200.0 μm, and more preferably 5.0 to 150.0 μm. Here, the average particle size D50 refers to the particle size of 50% of the cumulative particle size in the volumetric cumulative particle size distribution when measured using a laser light scattering diffraction particle size meter.

[0045] When the dialkoxymagnesium is spherical, the average particle size D50 is preferably 1.0 to 100.0 μm, more preferably 5.0 to 80.0 μm, and even more preferably 10.0 to 70.0 μm.

[0046] In addition, regarding the particle size distribution of dialkoxymagnesium, it is desirable that the fine and coarse particles are small and the particle size distribution is narrow.

[0047] Specifically, when measured using a laser light scattering diffraction particle size analyzer, it is preferable that the proportion of particles with a particle size of 5.0 μm or less in dialkoxymagnesium be 20% or less, and more preferable that it be 10% or less. Meanwhile, when measured using a laser light scattering diffraction particle size analyzer, it is preferable that the proportion of particles with a particle size of 100.0 μm or more be 20% or less, and more preferable that it be 10% or less.

[0048] In addition, when the particle size distribution is expressed as ln(D90 / D10), it is preferable that it be 3 or less, and more preferable that it be 2 or less. Here, D90 refers to the particle size of 90% in the volumetric integrated particle size distribution when measured using a laser light scattering diffraction particle size analyzer. Also, D10 refers to the particle size of 10% in the volumetric integrated particle size distribution when measured using a laser light scattering diffraction particle size analyzer.

[0049] The method for manufacturing dialkoxymagnesium of the above concept is exemplified in, for example, Japanese Patent Publication No. 58-41832, Japanese Patent Publication No. 62-51633, Japanese Patent Publication No. Hei 3-74341, Japanese Patent Publication No. Hei 4-368391, Japanese Patent Publication No. Hei 8-73388, etc.

[0050] In the solid catalyst component for olefin polymerization according to the present invention, the magnesium compound serving as the raw material component for the magnesium source has a specific surface area of ​​5 m² 2It is desirable that it be greater than / g, and 5~50m 2 It is more desirable that it is / g, and 10~40m 2 It is more desirable to have / g.

[0051] As described below, by using a magnesium compound having a specific surface area within the above range in addition to containing a predetermined amount of a 1,3-diether compound, it becomes easier to prepare a solid catalyst component having a desired specific surface area.

[0052] In addition, in the present application, the specific surface area of ​​a magnesium compound refers to a value measured by the BET method. For example, the specific surface area of ​​a magnesium compound can be measured by the BET method (automatic measurement) in the presence of a mixed gas of nitrogen and helium using an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech Co., Ltd. after vacuum drying the sample at 50°C for 2 hours.

[0053] The magnesium compound above is preferably in a solution or suspension state during the reaction, and by being in a solution or suspension state, the reaction can be appropriately carried out.

[0054] If the above magnesium compound is a solid, it can be made into a magnesium compound in solution by dissolving it in a solvent having the ability to solubilize the magnesium compound, or into a magnesium compound suspension by suspending it in a solvent that does not have the ability to solubilize the magnesium compound.

[0055] In addition, if the magnesium compound is a liquid, it may be used as is as a magnesium compound in solution, or it may be used as a magnesium compound in solution by further dissolving it in a solvent that has the ability to solubilize the magnesium compound.

[0056] As a compound capable of solubilizing a solid magnesium compound, at least one compound selected from the group consisting of alcohols, ethers, and esters may be cited, and alcohols such as ethanol, propanol, butanol, and 2-ethylhexanol are preferred, and 2-ethylhexanol is particularly preferred.

[0057] Meanwhile, as media that do not have the ability to solubilize solid magnesium compounds, one or more selected from saturated hydrocarbon solvents or unsaturated hydrocarbon solvents that do not dissolve magnesium compounds may be cited.

[0058] In the solid catalyst component for olefin polymerization according to the present invention, the tetravalent titanium halogen compound, which is a raw material component serving as a source of titanium and halogen, is not particularly limited but is the following general formula (III)

[0059] Ti(OR 6 ) r X4 - r (III)

[0060] (during food, R 6 It is suitable to be one or more compounds selected from the group of titanium halides or alkoxytitanides represented by , where represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and r is an integer such that 0≤r≤3.

[0061] Examples of titanium halides represented by the above general formula (III) include one or more titanium tetrahalides selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc.

[0062] In addition, as an alkoxytitan halide represented by the above general formula (III), one or more selected from methoxytitan trichloride, ethoxytitan trichloride, propoxytitan trichloride, n-butoxytitan trichloride, dimethoxytitan dichloride, diethoxytitan dichloride, dipropoxytitan dichloride, di-n-butoxytitan dichloride, trimethoxytitan chloride, triethoxytitan chloride, tripropoxytitan chloride, tri-n-butoxytitan chloride, etc.

[0063] As a tetravalent titanium halogen compound, titanium tetrahalide is preferred, and titanium tetrachloride is more preferred.

[0064] These titanium compounds may be used alone or in combination of two or more.

[0065] The solid catalyst component for olefin polymerization according to the present invention contains a 1,3-diether compound. The 1,3-diether compound is thought to act as a compound having an electron-donating group (an internal electron-donating compound) among the solid catalyst components for olefin polymerization.

[0066] In the present application, the term 1,3-diether compound refers to a group of compounds having a structure in which an ether group is bonded to the 1,3 position of propane as a basic framework (1,3-dialkoxypropane structure), and may also include a desired substituent.

[0067] As a 1,3-diether compound, the following general formula (I);

[0068] R 1 OCH2CR 2 R 3 CH2OR 4 (I)

[0069] (during food, R 2 and R 3It represents silver, a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl or cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, an alkylamino group having 1 to 12 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. R 2 and R 3 They may be identical or different. R 2 and R 3 Silver may combine with each other to form rings. R 1 and R 4 represents an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent. 1 and R 4 One or more types selected from compounds represented by (which may be identical or different) can be cited.

[0070] Specifically, one or more selected from 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene may be cited, and among these, one or more selected from 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene are preferred.

[0071] The solid catalyst component for polymerizing olefins according to the present invention has a content of a 1,3-diether compound of 2.50 to 15.00 mass%, preferably 4.50 to 15.00 mass%, and more preferably 4.50 to 12.00 mass%.

[0072] By limiting the content ratio of the 1,3-diether compound in the solid catalyst component for olefin polymerization according to the present invention to within the above range, the specific surface area of ​​the solid catalyst component can be easily controlled to a desired range.

[0073] The solid catalyst component for olefin polymerization according to the present invention may be formed using an internal electron-donating compound other than a phthalic acid ester (hereinafter referred to as "another internal electron-donating compound") together with a 1,3-diether compound as an internal electron-donating compound.

[0074] Accordingly, in the present application documents, the term "internal electron-donating compound" refers to either the case of a 1,3-diether compound alone or the case including a 1,3-diether compound and other internal electron-donating compounds.

[0075] Other internal electron-donating compounds are not particularly limited but are organic compounds other than 1,3-diether compounds, and are preferably organic compounds containing oxygen or nitrogen atoms, and examples include one or more selected from alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing Si-OC bonds or Si-NC bonds.

[0076] As other internal electron-donating compounds, one or more selected from ether compounds such as monoethers, diethers, and ether carbonates, or esters such as monocarboxylic acid esters and polycarboxylic acid esters, are more preferable, and one or more selected from aromatic polycarboxylic acid esters such as aromatic dicarboxylic acid diesters, aliphatic polycarboxylic acid esters, alicyclic polycarboxylic acid esters, diethers, and ether carbonates are even more preferable.

[0077] Other internal electron-donating compounds include, in particular, aliphatic polycarboxylic acid esters such as diethyl maleate, dibutyl maleate, dimethyl dibutyl maleate, diethyl dibutyl maleate, diisobutyl maleate, diethyl succinate, dimethyl diethyl succinate, 2,3-diisopropyl diethyl succinate, di-n-butyl malonicate, diethyl malonicate, diisobutyl malonicate, diisobutyl malonicate, dimethyl benzylidene malonicate, diethyl benzylidene malonicate, and dibutyl benzylidene malonicate; diethyl cyclohexanedicarboxylate, di-n-propyl cyclohexanedicarboxylate, dibutyl cyclohexanedicarboxylate, diisobutyl cyclohexanedicarboxylate, and 1-cyclohexene-1,2-dicarboxylic acid diethyl, One or more selected from alicyclic polycarboxylic acid esters such as 1-cyclohexene-1,2-dicarboxylic acid di-n-propyl, 1-cyclohexene-1,2-dicarboxylic acid dibutyl, 1-cyclohexene-1,2-dicarboxylic acid diisobutyl, 4-cyclohexene-1,2-dicarboxylic acid diethyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-propyl, 4-cyclohexene-1,2-dicarboxylic acid dibutyl, and 4-cyclohexene-1,2-dicarboxylic acid diisobutyl are preferred; and ether carbonates such as (2-ethoxyethyl)ethyl carbonate and (2-ethoxyethyl)phenyl carbonate are preferred.

[0078] When the solid catalyst component for polymerizing olefins according to the present invention includes another internal electron-donating compound, the content ratio of the other internal electron-donating compound in the solid catalyst component for polymerizing olefins according to the present invention may be 0.0 to 17.5 mass%.

[0079] When the solid catalyst component for polymerizing olefins according to the present invention includes other internal electron-donating compounds, the total content ratio of the 1,3-diether compound and other internal electron-donating compounds included in the solid catalyst component for polymerizing olefins is preferably 2.50 to 20.00 mass%, more preferably 4.50 to 20.00 mass%, and even more preferably 4.50 to 15.00 mass%.

[0080] Even if the total content ratio of 1,3-diether compounds and other internal electron-donating compounds is within the above range, a solid catalyst component for olefin polymerization with a large specific surface area can be easily prepared.

[0081] In the present application, the respective contents of 1,3-diether compounds and other internal electron-donating compounds among the solid catalyst components for olefin polymerization refer to values ​​measured by a calibration curve prepared in advance using a standard solution by gas chromatography. For example, the respective contents of 1,3-diether compounds and other internal electron-donating compounds can be obtained using a calibration curve based on a standard solution of the compound being measured when measured under the following conditions using gas chromatography (manufactured by Shimadzu Corporation, GC-14B).

[0082] <Measurement Conditions>

[0083] Column: Packed column (φ2.6×2.1m, Silicone SE-30 10%, Chromosorb WAWDMCS 80 / 100, Manufactured by GL Sciences Inc.)

[0084] Detector: FID (Flame Ionization Detector)

[0085] Carrier gas: Helium, flow rate 40 ml / min

[0086] Measurement temperature: Vaporization chamber 280°C, column 225°C, detector 280°C, or vaporization chamber 265°C, column 180°C, detector 265°C

[0087] The content of magnesium atoms in the solid catalyst component for olefin polymerization according to the present invention is preferably 10.0 to 70.0 mass%, more preferably 10.0 to 50.0 mass%, even more preferably 15.0 to 40.0 mass%, and particularly preferably 15.0 to 25.0 mass%.

[0088] In addition, the content of titanium atoms in the solid catalyst component for olefin polymerization according to the present invention is preferably 0.5 to 8.0 mass%, preferably 0.5 to 5.0 mass%, and more preferably 0.5 to 3.5 mass%.

[0089] In addition, the content of halogen atoms in the solid catalyst component for olefin polymerization according to the present invention is preferably 20.0 to 88.0 mass%, more preferably 30.0 to 85.0 mass%, even more preferably 40.0 to 80.0 mass%, and even more preferably 45.0 to 75.0 mass%.

[0090] In the present application documents, the content of magnesium atoms in the solid catalyst component for olefin polymerization refers to the value measured by the EDTA titration method, in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

[0091] In the present application documents, the content of titanium atoms in the solid catalyst component for olefin polymerization refers to a value measured in accordance with the method (redox titration) described in JIS 8311-1997 “Method for quantifying titanium in titanium ore”.

[0092] In the present application documents, the content of halogen atoms in the solid catalyst component for olefin polymerization refers to the value measured by the silver nitrate titration method, in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to form an aqueous solution, a predetermined amount is taken, and the halogen atoms are titrated with a standard silver nitrate solution.

[0093] The specific surface area of ​​the solid catalyst component for olefin polymerization according to the present invention is 250 m² 2 / g or more, 250~600m 2 It is desirable that it is / g, and 250~500m 2 It is more desirable that it is / g, and 250~450m 2 It is more desirable to have / g.

[0094] The solid catalyst component for olefin polymerization according to the present invention has a large specific surface area compared to conventional solid catalyst components for olefin polymerization, and when provided for the polymerization of olefins, the decrease in polymerization activity per unit time is appropriately suppressed, and an olefin polymer with a significantly reduced content of volatile organic compounds can be easily prepared.

[0095] In the present application, the specific surface area of ​​a solid catalyst component for olefin polymerization refers to a value measured by the BET method (automatic measurement) in the presence of a mixed gas of nitrogen and helium using an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech Co., Ltd., after vacuum drying a sample at 50°C for 2 hours.

[0096] The average particle size (average particle size D50) of the solid catalyst component for olefin polymerization according to the present invention is not particularly limited, but is preferably 5.0 to 100.0 μm, more preferably 10.0 to 80.0 μm, and even more preferably 15.0 to 70.0 μm.

[0097] Here, the average particle size D50 refers to the particle size of 50% of the cumulative particle size distribution in the volumetric cumulative particle size distribution when measured using a laser light scattering diffraction particle size analyzer.

[0098] The solid catalyst component for olefin polymerization according to the present invention has a large specific surface area compared to conventional solid catalyst components, even though the average particle size D50 is within the above range.

[0099] The solid catalyst component for olefin polymerization according to the present invention has a pore volume of 0.250 to 1.000 cm³ 3 It is desirable that it is / g, and 0.300~0.900cm 3 It is more desirable that it is / g, and 0.350~0.800cm 3 It is more desirable to have / g.

[0100] In the present application, the pore volume of the solid catalyst component for olefin polymerization according to the present invention refers to a value measured (automatically measured) under the following conditions using a BELSORP-miniII manufactured by MicrotracBEL in accordance with JIS Z 8831-2 (method for measuring mesopores and macropores by gas adsorption).

[0101] <Measurement Conditions>

[0102] Sample amount: 0.15g

[0103] Average adsorption time: 300 seconds

[0104] Adsorption temperature: 77K

[0105] Pretreatment conditions: Vacuum exhaust

[0106] Measurement Mode: High-precision mode (simultaneous measurement of dead volume and saturated vapor pressure)

[0107] Measurement range: Pore diameter 1.1–355.0 nm (BJH method)

[0108] The solid catalyst component for olefin polymerization according to the present invention can easily provide a high specific surface area by having a pore volume within the above range.

[0109] According to the present invention, by containing a predetermined amount of a 1,3-diether compound and controlling the specific surface area to a predetermined range, a solid catalyst component for polymerizing olefins can be provided, which allows for the easy preparation of an olefin polymer with a significantly reduced content of volatile organic compounds and a decrease in polymerization activity per unit time when provided for the polymerization of olefins.

[0110] That is, according to the present invention, even without using phthalic acid ester, when provided to the polymerization reaction of olefins, the decrease in polymerization activity per unit time is appropriately suppressed, and since degassing is easy in a short time after the reaction, the risk of pressure increase in the system and the rate of impurity incorporation into the recycling system in subsequent processes can be reduced, thereby reducing process troubles and the deterioration of the quality of the obtained polymer, and furthermore, drying efficiency is improved, so that the residual volatile organic compound component can be significantly reduced in a short time, and a solid catalyst component for polymerizing olefins can be provided.

[0111] Next, a method for manufacturing a solid catalyst component for olefin polymerization according to the present invention will be described.

[0112] The method for manufacturing a solid catalyst component for olefin polymerization according to the present invention is a method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, wherein the specific surface area is 5m² 2 It is characterized by bringing a magnesium compound with a g or more, a tetravalent titanium halogen compound, and a 1,3-diether compound into contact with each other.

[0113] The details of the magnesium compound, the tetravalent titanium halogen compound, and the 1,3-diether compound are as described above. In addition, it is desirable to appropriately mix the amounts of the magnesium compound, the tetravalent titanium halogen compound, and the 1,3-diether compound to satisfy the respective contents of the magnesium compound, the tetravalent titanium halogen compound, and the 1,3-diether compound.

[0114] In the method for preparing a solid catalyst component for olefin polymerization according to the present invention, the solid catalyst component for olefin polymerization according to the present invention may use other internal electron-donating compounds described above, excluding phthalic acid esters, together with a 1,3-diether compound.

[0115] The details of the above 1,3-diether compound are as described above. In addition, it is desirable to appropriately formulate the amount of another internal electron-donating compound to satisfy the content of the other internal electron-donating compound.

[0116] When bringing the internal electron-donating compounds, including the magnesium compound, the tetravalent titanium halogen compound, and the 1,3-diether compound, into contact with each other, the process may be carried out in the presence of the third component, polysiloxane.

[0117] Polysiloxane is a polymer having siloxane bonds (-Si-O- bonds) in its main chain; it is also collectively referred to as silicone oil, and has a viscosity of 0.02 to 100.00 cm at 25°C. 2 / s (2~10,000 centistoks), more preferably 0.03~5.00cm 2 It refers to a chain-like, partially hydrogenated, cyclic, or modified polysiloxane that is liquid or viscous at room temperature and has / s (3~500 centistokes).

[0118] Examples of chain polysiloxanes include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-dibromotetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane, etc. as disiloxanes, examples of polysiloxanes other than disiloxanes include dimethylpolysiloxane, methylphenylpolysiloxane, etc., examples of partially hydrogenated polysiloxanes include methylhydrogenpolysiloxane with a hydrogenation rate of 10 to 80%, and examples of cyclic polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Examples include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, etc., and examples of modified polysiloxanes include dimethylsiloxanes substituted with higher fatty acid groups, dimethylsiloxanes substituted with epoxy groups, and dimethylsiloxanes substituted with polyoxyalkylene groups. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferred, and decamethylcyclopentasiloxane is particularly preferred.

[0119] It is preferable that the treatment (contact treatment) in which raw material components serving as sources of magnesium, titanium, and halogens are brought into contact with an internal electron-donating compound including a 1,3-diether compound be carried out in an organic solvent. Furthermore, an inert organic solvent is preferred as the organic solvent.

[0120] As the above inert organic solvent, it is preferable that it is liquid at room temperature (20°C) and has a boiling point of 50 to 150°C, and more preferable that it is an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is liquid at room temperature and has a boiling point of 50 to 150°C.

[0121] Specifically, as the above-mentioned inert organic solvent, one or more selected from straight-chain aliphatic hydrocarbon compounds such as hexane, heptane, and decane; branched aliphatic hydrocarbon compounds such as methylheptane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene may be used.

[0122] Among the above inert organic solvents, an aromatic hydrocarbon compound that is liquid at room temperature and has a boiling point of 50 to 150°C is suitable because it can improve the activity of the solid catalyst component obtained and improve the stereoregularity of the polymer obtained.

[0123] Raw material components that serve as sources of magnesium, titanium, and halogens, and internal electron-donating compounds including 1,3-diether compounds, can be brought into contact with each other by mixing them using a suitable inert organic solvent.

[0124] The temperature during the above reaction is preferably 0 to 130°C, more preferably 40 to 130°C, even more preferably 30 to 120°C, and even more preferably 80 to 120°C. In addition, the reaction time is preferably 1 minute or more, more preferably 10 minutes or more, more preferably 30 minutes to 6 hours, even more preferably 30 minutes to 5 hours, and even more preferably 1 to 4 hours.

[0125] Low-temperature aging may be performed prior to the above reaction. Here, low-temperature aging refers to a preliminary reaction in which each component is brought into contact with each other at a temperature lower than the temperature during the above reaction.

[0126] The temperature during low-temperature aging is preferably -20 to 70℃, more preferably -10 to 60℃, and even more preferably -10 to 30℃. In addition, the low-temperature aging time is preferably 1 minute to 6 hours, more preferably 5 minutes to 4 hours, and even more preferably 30 minutes to 3 hours.

[0127] When magnesium compounds and tetravalent titanium halogen compounds are used as raw material components that serve as sources for magnesium, titanium, and halogens, and these are brought into contact with internal electron-donating compounds including 1,3-diether compounds using an inert organic solvent, the amount of tetravalent titanium halogen compound used per mole of magnesium compound is preferably 0.5 to 100.0 moles, more preferably 1.0 to 50.0 moles, and even more preferably 1.0 to 10.0 moles.

[0128] In addition, the amount of internal electron-donating compound containing 1,3-diether used per 1 mole of magnesium compound is preferably 0.03 to 0.3 moles, more preferably 0.06 to 0.3 moles, and even more preferably 0.03 to 0.2 moles.

[0129] In addition, the amount of inert organic solvent used is preferably 0.001 to 500 moles per mole of magnesium compound, more preferably 0.5 to 100 moles, and even more preferably 1.0 to 20 moles.

[0130] In the contact treatment of each of the above components, it is preferable to carry out the reaction while stirring in a container equipped with a stirrer under an inert gas atmosphere and conditions where moisture, etc., have been removed.

[0131] After the reaction is completed in the above contact treatment, the obtained reaction solution can be left to stand and the supernatant liquid appropriately removed to form a wet phase (slurry phase) to obtain a solid catalyst component. In addition, it is also possible to obtain a solid catalyst component by drying the wet phase reaction solution by hot air drying, etc.

[0132] The above reaction solution may be subjected to a cleaning treatment, and the cleaning treatment is typically performed using a cleaning solution.

[0133] As for the cleaning solution, the same as the above-mentioned inert organic solvent may be used, and one or more selected from straight-chain aliphatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C, such as hexane, heptane, and decane; cyclic aliphatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C, such as methylcyclohexane and ethylcyclohexane; aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C, such as toluene, xylene, ethylbenzene, and orthodichlorobenzene; and aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C are preferred.

[0134] By using the above washing solution, by-products or impurities can be easily dissolved and removed from the reaction solution to obtain a reaction solution after washing. In addition, it is also possible to obtain a solid catalyst component by drying the reaction solution after washing using methods such as hot air drying.

[0135] The above cleaning treatment is preferably performed at a temperature of 0 to 120°C, more preferably at a temperature of 0 to 110°C, even more preferably at a temperature of 30 to 110°C, even more preferably at a temperature of 50 to 110°C, and even more preferably at a temperature of 50 to 100°C.

[0136] It is preferable to perform the washing treatment by adding a desired amount of washing solution to the reaction solution and stirring, and then removing the liquid phase by filtration or decanting.

[0137] In addition, the number of washes may be multiple (2 or more times).

[0138] After bringing each of the above components into contact with one another, by performing a washing treatment, impurities such as unreacted raw material components or reaction by-products (alkoxytitan halide or titanium tetrachloride carboxylic acid complex, etc.) remaining in the reaction solution after washing can be removed.

[0139] Appropriate post-treatment may be performed after the above contact treatment or cleaning treatment.

[0140] When performing the above post-treatment, for example, a form in which a tetravalent titanium halogen compound is additionally contacted with the reaction solution obtained after the end of the above reaction or the reaction solution obtained after the above cleaning treatment, or a form in which cleaning is performed after additionally contacting with a tetravalent titanium halogen compound. The cleaning after the above post-treatment can be performed in the same way as the cleaning of the reaction solution described above.

[0141] The reaction product obtained after the above post-treatment or the reaction product obtained by washing after said post-treatment is typically in a suspension state, and each reaction product in said suspension state can be left to stand and the supernatant liquid removed to form a wet state (slurry state) to obtain a solid catalyst component. In addition, the solid catalyst component in said wet state can be obtained by drying it by hot air drying or the like.

[0142] According to the present invention, a method for easily manufacturing a solid catalyst component for olefin polymerization according to the present invention can be provided.

[0143] <Catalyst for Olefin Polymerization and Method for Manufacturing the Same>

[0144] Next, a catalyst for polymerizing olefins according to the present invention will be described.

[0145] The olefin polymerization catalyst according to the present invention comprises a solid catalyst component for olefin polymerization according to the present invention and the following general formula (II)

[0146] R 5 p AlQ3 - p (II)

[0147] (during food, R 5 It is characterized by comprising one or more organoaluminum compounds selected from compounds represented by (where is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number of 0 < p ≤ 3).

[0148] The details of the solid catalyst component for olefin polymerization included in the catalyst for olefin polymerization according to the present invention are as described in the description of the solid catalyst component for olefin polymerization according to the present invention.

[0149] The olefin polymerization catalyst according to the present invention comprises one or more organic aluminum compounds selected from the specific olefin polymerization solid catalyst component and a compound represented by general formula (II).

[0150] The olefin polymerization catalyst according to the present invention is an organic aluminum compound, with the following general formula (II)

[0151] R 5 p AlQ3 - p (II)

[0152] (during food, R 5 It includes one or more compounds selected from those represented by , where is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number of 0 < p ≤ 3.

[0153] In an organoaluminum compound represented by general formula (II), R 5 ... is an alkyl group having 1 to 6 carbon atoms, and specifically, examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, etc.

[0154] In the organoaluminum compound represented by the above general formula (II), Q represents a hydrogen atom or a halogen atom, and when Q is a halogen atom, examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0155] As for the organoaluminum compound represented by the above general formula (II), specifically, one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride can be cited, and triethylaluminum and triisobutylaluminum are suitable.

[0156] The olefin polymerization catalyst according to the present invention preferably contains 1 to 2000 moles of an organic aluminum compound per mole of titanium atom constituting the solid catalyst component for olefin polymerization, and more preferably contains 50 to 1000 moles.

[0157] The olefin polymerization catalyst according to the present invention can be suitably manufactured according to the method for manufacturing the olefin polymerization catalyst according to the present invention described below.

[0158] The inventors have discovered that the olefin polymerization catalyst according to the present invention can appropriately suppress the decrease in polymerization activity for olefins by employing a 1,3-diether compound instead of a phthalic acid ester, and can appropriately suppress the decrease in polymerization activity by limiting the amount of the 1,3-diether compound constituting the solid catalyst component to a certain range and maintaining the specific surface area and pore volume of the solid catalyst component to a certain range, and can also significantly reduce the amount of volatile organic compounds remaining in the obtained olefin polymer in a short period of time, thereby completing the present invention.

[0159] That is, according to the present invention, in a series of processes in which unreacted monomers and volatile substances are purged to discharge polymer particles present in the final reactor when provided for a polymerization reaction of olefins, and then reactive monomers and volatile substances are removed by additional steam treatment, and then dried, the time required until the end of the drying process can be significantly reduced and the drying efficiency can be significantly improved, thereby providing a catalyst for polymerizing olefins that can be easily prepared.

[0160] Next, a method for manufacturing a catalyst for polymerizing olefins according to the present invention will be described.

[0161] A method for preparing an olefin polymerization catalyst according to the present invention comprises a solid catalyst component for olefin polymerization according to the present invention or a solid catalyst component for olefin polymerization obtained by the method for preparing a solid catalyst component for olefin polymerization according to the present invention, and the following general formula (II)

[0162] R 5 p AlQ3 - p (II)

[0163] (during food, R 5 The invention is characterized by contacting one or more organoaluminum compounds selected from compounds represented by (where Q is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number of 0 < p ≤ 3) with each other.

[0164] In the method for manufacturing a catalyst for polymerizing olefins according to the present invention, the details of the solid catalyst component for polymerizing olefins are as described in the description of the solid catalyst component for polymerizing olefins according to the present invention.

[0165] In addition, regarding the method for manufacturing an olefin polymerization catalyst according to the present invention, the details of the organoaluminum compound represented by general formula (II) are as described in the description of the olefin polymerization catalyst according to the present invention.

[0166] As described above, in the method for manufacturing a catalyst for polymerizing olefins according to the present invention, by employing a 1,3-diether compound instead of a phthalic acid ester, the decrease in polymerization activity for olefins can be appropriately suppressed, and by limiting the amount of the 1,3-diether compound constituting the solid catalyst component to a certain range and maintaining the specific surface area and pore volume of the solid catalyst component to a certain range, the decrease in polymerization activity can be appropriately suppressed, and the amount of volatile organic compounds remaining in the obtained olefin polymer can be significantly reduced in a short period of time, thereby completing the present invention.

[0167] In the method for preparing a catalyst for polymerizing olefins according to the present invention, the solid catalyst component for polymerizing olefins and the organic aluminum compound may be contacted in the absence of olefins, or may be contacted in the presence of olefins (within the polymerization system).

[0168] In order to prevent deterioration of the solid catalyst component for olefin polymerization or the obtained olefin polymerization catalyst, it is preferable to carry out the contact between the above-mentioned solid catalyst component for olefin polymerization and the organoaluminum compound under an inert gas atmosphere such as argon or nitrogen, or under a monomer atmosphere such as propylene.

[0169] In addition, considering ease of operation, it is also desirable to perform the process in the presence of a dispersion medium such as an inert solvent, and as an inert solvent, aliphatic hydrocarbon compounds such as hexane, heptane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene are used, and aliphatic hydrocarbons are more preferred, and among them, hexane, heptane, and cyclohexane are more preferred.

[0170] The temperature at which the solid catalyst component for polymerizing olefins and the organic aluminum compound are contacted is preferably less than 15℃, more preferably -15℃ to 10℃, and even more preferably 0℃ to 10℃.

[0171] The contact time when contacting the solid catalyst component for polymerizing olefins and the organoaluminum compound is preferably 30 minutes or less, more preferably 5 seconds to 20 minutes, even more preferably 30 seconds to 15 minutes, and even more preferably 1 minute to 10 minutes.

[0172] Typically, when an organoaluminum compound acting as a co-catalyst is brought into contact with a solid catalyst component for olefin polymerization, the reaction proceeds rapidly, causing the 1,3-diether compound constituting the solid catalyst component to detach or the solid catalyst component to be activated by the organoaluminum compound acting as a co-catalyst. In particular, under an inert gas atmosphere, the loss of activity of the catalyst active sites (titanium active sites) is likely to occur due to excessive reaction.

[0173] Meanwhile, by performing contact treatment at the above contact temperature and contact time, the excessive reaction of the titanium active site in the solid catalyst component by the organoaluminum compound can be suppressed, thereby effectively suppressing the loss of activity of the catalyst active site.

[0174] In the manufacturing method according to the present invention, the content ratio of the solid catalyst component and the organic aluminum compound constituting the olefin polymerization catalyst obtained can be arbitrarily selected within the range in which the effects of the present invention are obtained and are not particularly limited.

[0175] According to the present invention, when applied to the polymerization of olefins, it is possible to provide a catalyst for polymerizing olefins that can easily prepare an olefin polymer with excellent polymerization activity per unit time and a significantly reduced content of volatile organic compounds, and also provide a method for easily manufacturing the olefin polymerization catalyst accordingly.

[0176] That is, according to the present invention, when provided for the polymerization reaction of olefins, the decrease in polymerization activity per unit time is appropriately suppressed, and since degassing is easy in a short time after the reaction, the risk of pressure rise in the system in subsequent processes and the rate of incorporation of impurities into the recycling system are reduced, thereby reducing process troubles and the deterioration of the quality of the obtained polymer, as well as improving drying efficiency and significantly reducing residual volatile organic compound components in a short time, can be provided for a method to easily prepare an olefin polymer.

[0177] <Method for Manufacturing Olefin Polymers>

[0178] Next, a method for manufacturing an olefin polymer according to the present invention will be described.

[0179] The method for manufacturing an olefin polymer according to the present invention is characterized by polymerizing olefins using an olefin polymerization catalyst according to the present invention or an olefin polymerization catalyst obtained by the manufacturing method according to the present invention.

[0180] In the method for manufacturing an olefin polymer according to the present invention, it is preferable that the polymerization of the olefin is a propylene homopolymerization or a copolymerization of propylene and an α-olefin other than propylene.

[0181] As α-olefins other than propylene, one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., are suitable, and ethylene or 1-butene is suitable.

[0182] In the method for manufacturing an olefin polymer according to the present invention, homopolymerization of propylene may be performed, or copolymerization of propylene and other α-olefins may be performed. When copolymerizing propylene and other olefins, a random copolymerization in which propylene and a small amount of α-olefin monomer other than propylene (such as ethylene) are used as comonomers and polymerized in a single step is representative, and a block copolymerization in which homopolymerization of propylene is performed in a first step (first polymerization tank), and copolymerization of propylene and other α-olefins such as ethylene is performed in a second step (second polymerization tank) or in multiple steps (multi-stage polymerization tank), is preferred.

[0183] In the method for manufacturing an olefin polymer according to the present invention, the polymerization of the olefin can be carried out in the presence or absence of an organic solvent.

[0184] In addition, the olefins to be polymerized can be used in either a gaseous or liquid state.

[0185] Polymerization of olefins can be carried out, for example, in a reactor such as an autoclave, by introducing olefins in the presence of a catalyst for polymerizing olefins according to the present invention, under heating and pressurization conditions.

[0186] In the method for manufacturing an olefin polymer according to the present invention, when polymerizing an olefin (hereinafter appropriately referred to as the polymerization), a preliminary polymerization (hereinafter appropriately referred to as the preliminary polymerization) may be performed by contacting a part or all of the components of the olefin polymerization catalyst obtained in the method according to the present invention with the olefin to be polymerized.

[0187] In carrying out prepolymerization, the order of contact between the components of the olefin polymerization catalyst obtained in the manufacturing method according to the present invention and the olefins is optional, but it is preferable to first introduce an organoaluminum compound into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, then contact a solid catalyst component for olefin polymerization, and then contact one or more olefins such as propylene.

[0188] During the pre-polymerization, monomers such as olefins or styrene, identical to those used in the main polymerization, may be used, and the pre-polymerization conditions are also identical to the polymerization conditions.

[0189] By performing the above prepolymerization, catalytic activity is enhanced, making it easier to further improve the stereoregularity and particle properties of the obtained polymer.

[0190] In the manufacturing method according to the present invention, the specific surface area of ​​the olefin polymer obtained is 250 to 600 m² 2 It is desirable that it is / g, and 250~500m 2 It is more desirable that it is / g, and 250~450m 2 It is more desirable to have / g.

[0191] The olefin polymer obtained by the manufacturing method according to the present invention is formed using the olefin polymerization catalyst according to the present invention or the olefin polymerization catalyst obtained by the manufacturing method according to the present invention, and thus has a larger specific surface area compared to conventional olefin polymers, which allows for a significant reduction in the content of volatile organic compounds.

[0192] In the present application, the specific surface area of ​​the olefin polymer refers to a value measured by the BET method (automatic measurement) in the presence of a mixed gas of nitrogen and helium using an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech Co., Ltd., after vacuum drying the sample at 50°C for 2 hours.

[0193] According to the present invention, a method for preparing an olefin polymer can be provided, which allows for easy preparation of an olefin polymer in which the content of residual volatile organic compounds is significantly reduced in a short period of time by improving drying efficiency under excellent polymerization activity.

[0194] That is, according to the present invention, in a series of processes in which unreacted monomers and volatile substances are purged to discharge polymer particles present in the final reactor when provided for a polymerization reaction of olefins, and then reactive monomers and volatile substances are removed by additional steam treatment, and then dried, the time required until the end of the drying process can be significantly reduced and the drying efficiency can be significantly improved, thereby providing a catalyst for polymerizing olefins that can be easily prepared.

[0195] Examples

[0196] Next, the present invention will be described in more detail with reference to examples, which are merely illustrative and do not limit the invention.

[0197] (Example 1)

[0198] <Preparation of Solid Catalyst Components>

[0199] The interior of a 500 ml round-bottom flask equipped with a stirrer was sufficiently purged with nitrogen gas (inert gas), and diethoxymagnesium (magnesium compound) (average particle size D50 is 20.0 μm, specific surface area 20.4 m² 2 20g of (g) and 60ml of toluene (inert organic solvent) were added, and a suspension containing diethoxymagnesium was obtained.

[0200] Next, the above-mentioned diethoxymagnesium-containing solution was added to a mixed solution of 50 ml of toluene and 40 ml of titanium tetrachloride (a tetravalent titanium halogen compound) that was pre-filled in a 500 ml round-bottom flask equipped with a stirrer and sufficiently replaced with nitrogen gas, to form a suspension.

[0201] Next, the obtained suspension was reacted at -6°C for 1 hour, then 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (1,3-diether compound) and 14.0 mmol of (2-ethoxyethyl)ethyl carbonate (another internal electron-donating compound) were added, and after further raising the temperature to 100°C, the reaction treatment was carried out for 2 hours while stirring.

[0202] After the reaction was completed, the supernatant was drained and washed four times with 150 ml of toluene at 90°C. 20 ml of titanium tetrachloride and 100 ml of toluene were added to the obtained reaction product, and the temperature was raised to 100°C and reacted for 15 minutes, repeating this process four times. Then, the solid catalyst component was obtained by washing six times with 150 ml of n-heptane (inert organic solvent) at 40°C.

[0203] After solid-liquid separation, the content of titanium atoms in the obtained solid catalyst component was measured by the method described above and was 2.3 mass%. Also, the content of magnesium atoms in the obtained solid catalyst component was measured by the method described above and was 19.9 mass%. Also, the content of halogen atoms in the obtained solid catalyst component was measured by the method described above and was 65.0 mass%.

[0204] In addition, the average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the method described above. The results are shown in Table 1.

[0205] <Formation of Polymerization Catalyst (Preliminary Contact)>

[0206] 7 ml of n-heptane (inert solvent), 1.32 millimoles of triethylaluminum (organic aluminum compound), and 0.00165 millimoles of the solid catalyst component (equivalent to a titanium atom) were loaded into an autoclave equipped with a stirrer and having a volume of 2.0 liters, which was completely replaced with nitrogen gas, and under a nitrogen atmosphere, the internal temperature of the autoclave was maintained at 10°C for 3 minutes to form a polymerization catalyst.

[0207] <Olefin Polymerization>

[0208] Next, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged into the autoclave having the polymerization catalyst formed as described above, and the autoclave was heated to 20°C, and a preliminary polymerization was carried out for 5 minutes at the internal temperature of the autoclave at 20°C, after which the autoclave was heated to 70°C, and a polymerization reaction was carried out for 1 hour at the internal temperature of the autoclave at 70°C.

[0209] In addition, the polymerization activity during the above polymerization reaction was determined by the following method, and for the obtained polymer, the amount of volatile organic compounds recovered and the emission rate of volatile organic compounds were calculated by the following method. The results are shown in Table 1.

[0210] <Polymerization Activity>

[0211] The polymerization activity (kg-PP / g-cat), which represents the amount of polymer produced (F) kg per 1 g of solid catalyst component and per 1 hour of polymerization time, was calculated by the following formula.

[0212] Polymerization activity (kg-PP / g-cat) = Produced polymer (F) kg / Solid catalyst component g / 1 hour

[0213] <Recovery Amount of Volatile Organic Compounds>

[0214] 200g of the polymer obtained by the above reaction was taken and air-dried at room temperature for 12 hours, then placed in an autoclave with a capacity of 2 liters, and a vacuum pump (manufactured by Ulvac Inc., model number G-100D, achievable vacuum level 10-3 Pressure drying was performed at 70°C for 2 hours by Torr.

[0215] Next, the operation of pressurizing the inside of the autoclave with propylene gas to 0.5 MPa and then depressurizing it to 0.1 MPa was repeated a total of three times. After that, the inside of the autoclave was pressurized with propylene gas to 0.8 MPa, and the temperature was raised to 70°C and maintained for 1 hour. After that, the gas components inside the autoclave were released out of the system, and the pressure was reduced to atmospheric pressure for 3 minutes. Then, the entire amount of polymer was recovered into a flask within 5 minutes, and the mass P(g) of the flask containing the polymer with residual volatile organic compound components was measured.

[0216] While heating the above flask to 70°C, drying was performed using a rotary evaporator, and the flask mass S(g) was measured every 3 hours. After confirming that the flask mass had reached a constant weight (after 12 hours), drying was stopped.

[0217] In addition, the above constant weight refers to the completion of the recovery of volatile organic compounds (recovery amount R in n hours). n It means a state where =0[mass ppm])

[0218] At this time, the amount of volatile organic compounds recovered (volatile organic compound content per 1g of polymer) was calculated for each using the following formula.

[0219] Amount of volatile organic compounds recovered (mass ppm) = [{P(g) - S(g)} / 200(g)] × 1,000,000

[0220] <Emission Rate of Volatile Organic Compounds>

[0221] The amount of volatile organic compounds recovered R 3 hours after the start of drying, when drying by the above rotary evaporator is performed every 3 hours until constant weight is reached. 1 (mass ppm), amount of volatile organic compound recovered R when drying by the above rotary evaporator is performed for 12 hours 2(mass ppm) and the amount of volatile organic compounds recovered R when drying by the rotary evaporator is performed until constant weight is reached 3 (Mass ppm) was measured. The results are shown in Table 1.

[0222] In addition, the time required to reach constant weight at this time (time), the ratio of volatile organic compound recovery amount (mass%) calculated by the following formulas, and the amount of volatile organic compound recovered to reach constant weight after 3 hours from the start of drying are shown in Table 1.

[0223] Drying efficiency of volatile organic compounds (mass%) = (Amount of volatile organic compounds recovered R after 3 hours from the start of drying) 1 / Amount of volatile organic compounds recovered R when dried until constant weight is reached 3 )×100

[0224] Amount of volatile organic compounds recovered (mass ppm) until constant weight is reached 3 hours after the start of drying = (Amount of volatile organic compounds recovered when drying treatment is performed until constant weight is reached R) 3 )-(Amount of volatile organic compounds recovered R 3 hours after the start of drying 1 )

[0225] (Example 2)

[0226] In the preparation of the solid catalyst component of Example 1, 8.5 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 12.5 millimoles of (2-ethoxyethyl)ethyl carbonate were added instead of 10.0 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 millimoles of (2-ethoxyethyl)ethyl carbonate; otherwise, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0227] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0228] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0229] (Example 3)

[0230] In the preparation of the solid catalyst component of Example 1, the solid catalyst component was prepared in the same manner as in Example 1, except that 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 mmol of (2-ethoxyethyl)ethyl carbonate were added, and only 15.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added. Then, the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0231] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0232] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0233] (Example 4)

[0234] In the preparation of the solid catalyst component of Example 1, 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 mmol of (2-ethoxyethyl)ethyl carbonate were added instead of 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 10.0 mmol of diethyl benzylidenemalonicate; except for these additions, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0235] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0236] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the drying efficiency of volatile organic compounds, the time required to reach a constant weight, the ratio of volatile organic compounds recovered, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0237] (Example 5)

[0238] In the preparation of the solid catalyst component of Example 1, 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 mmol of (2-ethoxyethyl)ethyl carbonate were added instead of 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 10.0 mmol of dimethyl diisobutylmalonicate; except for these additions, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0239] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0240] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0241] (Example 6)

[0242] In the preparation of the solid catalyst component of Example 1, 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 mmol of (2-ethoxyethyl)ethyl carbonate were added instead of 10.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 10.0 mmol of 2,3-diisopropylsuccinate diethyl were added; otherwise, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0243] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0244] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0245] (Comparative Example 1)

[0246] In the preparation of the solid catalyst component of Example 1, 22.4 millimoles of only 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added instead of 10.0 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 millimoles of (2-ethoxyethyl)ethyl carbonate; otherwise, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0247] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0248] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0249] (Comparative Example 2)

[0250] In <Preparation of Solid Catalyst Component> of Example 1, the average particle size D50 (the particle size at 50% of the cumulative particle size distribution in the volumetric cumulative particle size distribution) is 20.0 μm, and the specific surface area is 20.4 m² 2 Instead of 20g of diethoxymagnesium / g, the average particle size D50 (the particle size at 50% of the cumulative particle size in the volumetric cumulative particle size distribution) is 38.9μm, and the specific surface area is 18.8m² 2A solid catalyst component was prepared in the same manner as in Example 1, except that 20 g of diethoxymagnesium / g was charged, and 24.0 millimoles of only 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added instead of 10.0 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 millimoles of (2-ethoxyethyl)ethyl carbonate were added, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0251] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0252] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0253] (Comparative Example 3)

[0254] In the preparation of the solid catalyst component of Example 1, 7.2 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 12.5 millimoles of (2-ethoxyethyl)ethyl carbonate were added instead of 10.0 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 millimoles of (2-ethoxyethyl)ethyl carbonate; otherwise, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0255] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0256] In addition, the polymerization activity during the above polymerization reaction was determined by the same method as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were determined by the same method as in Example 1. The results are shown in Table 1.

[0257] (Comparative Example 4)

[0258] In the preparation of the solid catalyst component of Example 1, 3.6 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 15.0 millimoles of (2-ethoxyethyl)ethyl carbonate were added instead of 10.0 millimoles of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 14.0 millimoles of (2-ethoxyethyl)ethyl carbonate; except for these additions, the solid catalyst component was prepared in the same manner as in Example 1, and the formation of a polymerization catalyst (preliminary contact) and olefin polymerization were carried out.

[0259] The average particle size, specific surface area, and pore volume of the obtained solid catalyst component were measured by the same method as in Example 1.

[0260] In addition, the polymerization activity during the above polymerization reaction was determined in the same manner as in Example 1, and for the obtained polymer, the amount of volatile organic compounds recovered, the time required to reach a constant weight, the drying efficiency of volatile organic compounds, and the amount of volatile organic compounds recovered until a constant weight was reached 3 hours after the start of drying were calculated by the same method as in Example 1. The results are shown in Table 1.

[0261]

[0262] From Table 1, it can be seen that in Examples 1 to 6, the polymerization activity per unit time is excellent because a specific solid catalyst component containing a specific proportion of a 1,3-diether compound is used instead of phthalic acid ester. Furthermore, in Examples 1 to 6, regarding the olefin polymers obtained, the drying efficiency of volatile organic compounds {(R 1 / R 3 )×100} is high, and the amount of volatile organic compounds recovered (R) until constant weight is reached 3 hours after the start of drying. 3 -R 1 It can be seen that, in terms of the low amount of ) drying efficiency, it is possible to easily provide an olefin polymer in which volatile organic compounds are easily released in a short time and their content ratio is significantly reduced. That is, in Examples 1 to 6, it can be seen that an olefin polymer capable of releasing volatile organic compounds in a short time can be prepared while appropriately suppressing the decrease in polymerization activity per unit time.

[0263] Meanwhile, from Table 1, the specific solid catalyst component mentioned above was not used in Comparative Examples 1 to 4. For this reason, it can be seen that the polymerization activity is inferior compared to the above examples (Comparative Examples 3 and 4). In addition, regarding the olefin polymers obtained, the drying efficiency of volatile organic compounds {(R 1 / R 3 {100} is low, and the amount of volatile organic compounds recovered (R) until constant weight is reached 3 hours after the start of drying. 3 -R 1 In many respects, it can be seen that volatile organic compounds are difficult to release in a short period of time and their content ratio is difficult to reduce (Comparative Examples 1 to 4). That is, in Comparative Examples 1 to 4, it can be seen that suppression of the decrease in polymerization activity per unit time and the release of volatile organic compounds in a short period of time in the obtained olefin polymer cannot be achieved at the same time.

[0264] Generally, process problems are likely to arise not only when the amount of volatile organic compounds remaining in the olefin polymer is large, but also when the volatile organic compounds remaining in the olefin polymer are difficult to degas and require a long time for their release. For example, as is evident from the comparison between Example 4 and Comparative Example 4 shown in Table 1, the amount of volatile organic compounds contained in the obtained olefin polymer (the amount of volatile organic compounds recovered up to a constant weight R) 3 Even if the ) is the same, in Example 4, since a specific solid catalyst component according to the present invention is used, it can be seen that drying efficiency is improved, volatile organic compounds are easily released in a short time, and an olefin polymer with a significantly reduced content ratio can be easily provided. Industrial applicability

[0265] According to the present invention, even without using phthalate esters, when provided for the polymerization of olefins, the decrease in polymerization activity per unit time can be appropriately suppressed, and drying efficiency is improved, thereby enabling the easy preparation of an olefin polymer in which the content ratio of residual volatile organic compounds is significantly reduced in a short period of time. In addition, a solid catalyst component for polymerizing olefins and a method for preparing the same can be provided, a catalyst for polymerizing olefins comprising the solid catalyst component according to the invention and a method for preparing the same, and a method for preparing an olefin polymer.

Claims

Claim 1 A method for manufacturing a solid catalyst component for olefin polymerization, wherein the specific surface area is 10 to 40 m² 2 A solid catalyst component for polymerizing olefins containing magnesium, titanium, a halogen, and a 1,3-diether compound, by contacting dialkoxymagnesium / g, a tetravalent titanium halogen compound, and a 1,3-diether compound with each other, wherein the ratio of the 1,3-diether compound included in the solid catalyst component for polymerizing olefins is 2.50 to 15.00 mass%, and the specific surface area of ​​the solid catalyst component for polymerizing olefins is 250 m² 2 A method for manufacturing a solid catalyst component for olefin polymerization, characterized by manufacturing a solid catalyst component for olefin polymerization having a content of 1g or more. Claim 2 In claim 1, the pore volume of the solid catalyst component for olefin polymerization obtained is 0.250 to 1.000 cm³ 3 Method for preparing a solid catalyst component for olefin polymerization, with a content of / g. Claim 3 In claim 1, the 1,3-diether compound is of the following general formula (I); R 1 OCH2CR 2 R 3 CH2OR 4 (I)(In the food, R 2 and R 3 It represents silver, a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl or cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, an alkylamino group having 1 to 12 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. R 2 and R 3 They may be identical or different. R 2 and R 3 Silver may combine with each other to form rings. R 1 and R 4 represents an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent. 1 and R 4 A method for preparing a solid catalyst component for olefin polymerization, comprising one or more selected from compounds represented as (which may be identical or different). Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete

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