JP3885035B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

【０１０６】
表１の結果から、本発明の固体触媒成分および触媒を用いてプロピレンの重合を行うことにより、高活性および高立体規則性を維持し、微粉重合体の発生が極めて少ないことがわかる。
【０１０７】
【発明の効果】
本発明のオレフィン類重合用固体触媒成分による触媒は、ポリマーの立体規則性および収率を高度に維持しながら、極めて微粉の少ない重合体を得ることができる。従って、汎用ポリオレフィンを、低コストで提供し得る。
【図面の簡単な説明】
【図１】本発明の重合触媒を調製する工程を示すフローチャート図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which can maintain a high degree of stereoregularity and yield of a polymer, and can obtain a polymer with less fine powder.
[0002]
[Prior art]
Conventionally, in the polymerization of olefins, many solid catalyst components for olefin polymerization containing magnesium, titanium, an electron donating compound and halogen as essential components have been proposed. In particular, diethoxymagnesium is representative as a magnesium raw material. Solid catalyst components prepared using dialkoxymagnesium compounds have high performance and are widely used industrially.
[0003]
For example, in Patent Document 1 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon compound and a titanium halide is in a powder state. A method for polymerizing olefins and a solid catalyst component prepared by heat treatment with olefin, an olefin polymerization catalyst comprising an organoaluminum compound and an organosilicon compound have been proposed.
[0004]
Moreover, in patent document 2 (Unexamined-Japanese-Patent No. 1-315406), titanium tetrachloride is made to contact the suspension formed with diethoxymagnesium and alkylbenzene, and it is made to react by adding phthalic acid dichloride next. A solid catalyst component prepared by catalytically reacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, and A process for the polymerization of olefins in the presence of a catalyst has been proposed.
[0005]
Each of the above prior arts has a high activity capable of omitting a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also has a high degree of stereoregularity. These efforts are focused on improving the yield of coalescence and increasing the sustainability of the catalytic activity during polymerization, and each has achieved excellent results. This type of highly active catalyst component, organoaluminum compound and silicon Polymerization of olefins using a polymerization catalyst composed of an electron donating compound typified by a compound causes a fine polymer of the solid catalyst component itself and particle breakage due to heat of reaction when polymerized, resulting in a polymer produced There was a tendency to broaden the particle size distribution with a lot of fine powder contained therein. Increasing the amount of finely divided polymer prevents process continuation, causing blockage of piping during polymer transfer, etc., and widening the particle size distribution results in favorable polymer processing. As a result, the amount of fine powder polymer is as small as possible, and a polymer having a uniform particle size and a narrow particle size distribution has been sought.
[0006]
As a method for solving this problem, in Patent Document 3 (Japanese Patent Laid-Open No. 6-157659), a spherical dialkoxymagnesium, an aromatic hydrocarbon compound, and phthalate are added to a mixed solution of an aromatic hydrocarbon compound and titanium tetrachloride. A catalyst for olefin polymerization using a solid catalyst component obtained by adding a suspension of an acid diester, reacting it, and further reacting with titanium tetrachloride has been proposed.
[0007]
In Patent Document 4 (JP-A-6-287225), a suspension of spherical dialkoxymagnesium, an aromatic hydrocarbon compound and a phthalic acid diester is mixed with an aromatic hydrocarbon compound and titanium tetrachloride. Olefin compounds obtained by adding to the solution and reacting, washing the resulting reaction product with an aromatic hydrocarbon compound, drying the solid component obtained by reacting again with titanium tetrachloride, and subjecting to a fine powder removal process Solid catalyst components for polymerization have been proposed.
[0008]
Further, in Patent Document 5 (Japanese Patent Laid-Open No. 6-287217), a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon compound and phthalic acid diester is mixed with an aromatic hydrocarbon compound and titanium tetrachloride. In addition to the above, the reaction product obtained is washed with an aromatic hydrocarbon compound, the solid component obtained by reacting again with titanium tetrachloride is dried, subjected to fine powder removal treatment, and then powdered. A solid catalyst component for polymerizing olefins obtained through a treatment process of adding a nonionic surfactant has been proposed.
[0009]
Although the above-mentioned proposal has the effect of removing the fine powder of the solid catalyst component itself and reducing the amount of fine powder of the resulting polymer to some extent, the generation of ultrafine polymer called microfine is still in particular. The development of a catalyst with little generation of a fine polymer has been desired, but the above-described prior art is not sufficient to solve the problem.
[0010]
On the other hand, as a prior art, there is known a method of preparing a solid catalyst component by dissolving a magnesium compound such as magnesium chloride or diethoxymagnesium with an alkoxytitanium compound to form a uniform solution and then depositing it.
[0011]
For example, in Patent Document 6 (Japanese Patent Laid-Open No. 62-18405), a titanium alkoxy compound, dialkoxy magnesium, a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon compound, and a titanium halide represented by a specific formula are contacted. A catalyst component for polymerization of olefins, which is obtained by the above process and used in combination with a silicon compound and an organoaluminum compound represented by a specific formula, has been proposed.
[0012]
In Patent Document 7 (Japanese Patent Laid-Open No. 3-72503), a magnesium compound represented by a specific formula, a tetraalkyltitanium compound, and a silicon compound represented by a specific formula are subjected to a heat reaction, and then the reaction product. A solid catalyst component for polymerizing olefins obtained by treating with a halogen-containing titanium compound represented by the specific formula and an electron donating compound represented by the specific formula is disclosed.
[0013]
However, any of these conventional methods is a preparation method in which a magnesium compound is dissolved with an alkoxytitanium compound and then a solid catalyst component is precipitated, so that the process of depositing a solid from a solution of the magnesium compound is complicated. In addition, since a large amount of the alkoxytitanium compound is used in the method for preparing the solid catalyst component, there is a problem in that the alkoxytitanium compound remains in the precipitated solid, and the performance such as activity is significantly reduced.
[0014]
[Patent Document 1]
JP 63-3010 A (Claims)
[Patent Document 2]
JP-A-1-315406 (Claims)
[Patent Document 3]
JP-A-6-157659 (Claims)
[Patent Document 4]
JP-A-6-287225 (Claims)
[Patent Document 5]
JP-A-6-287217 (Claims)
[Patent Document 6]
JP-A-62-18405 (Claims)
[Patent Document 7]
Japanese Patent Laid-Open No. 3-72503 (Claims)
[0015]
[Problems to be solved by the invention]
  That is, the object of the present invention is to provide an olefin polymerization catalyst capable of maintaining a high degree of polymer stereoregularity and yield when subjected to olefin polymerization, and obtaining a polymer having a small particle size and a uniform particle size distribution. Solid catalyst component for olefin polymerization as a component ofManufacturing methodIs to provide.
[0016]
[Means for Solving the Problems]
Under such circumstances, the present inventors have conducted intensive studies, and as a result, the fine powder polymer obtained by polymerizing olefins is caused by dialkoxymagnesium as a raw material and is generated when a solid catalyst component is formed. And a reaction step of reacting magnesium metal with alcohol in the presence of a catalyst to obtain a solid, and then contacting the solid with a surfactant in an inert organic solvent to form a suspension. The tetravalent titanium halogen compound (b) and the electron donating property were obtained by sequentially carrying out the surfactant contact step and then the first removal step of removing the solvent in the suspension. A solid product forming step in which compound (c) is contacted to form a solid product, and then a surfactant is contacted with the solid product in an inert organic solvent to form a suspension. The catalyst by the solid catalyst component for olefin polymerization prepared by sequentially performing the agent contact step and then the second removal step of removing the solvent in the suspension maintains the polymer activity and stereoregularity at a high level, And it discovered that a polymer with very few fine powders was obtained, and came to complete this invention.
[0017]
  That is, the solid catalyst component for olefin polymerization of the present invention for achieving the above objectManufacturing methodWith magnesium metal and alcoholSelected from alkyl halides, metal halides, dialkoxymagnesium, iodine and acetatesA reaction step of reacting in the presence of a catalyst to obtain a solid, and then the solidOne or more compounds selected from polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid esterSurfactant obtained by sequentially performing a first surfactant contact step in which a suspension is formed by contacting with each other in an inert organic solvent, followed by a first removal step in which the solvent in the suspension is removed (A),Contacting the tetravalent titanium halogen compound (b) and the electron donating compound (c)The resulting solid material is washed with a liquid hydrocarbon compound at room temperature.A solid product forming step to form a solid product, then the solid product in an inert organic solventOne or more compounds selected from polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid esterA second surfactant contacting step for bringing the suspension into contact with each other, and then a second removing step for removing the solvent in the suspension.The electron donating compound (c) is methyl benzoate, ethyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, diethyl maleate, dibutyl maleate, dimethyl adipate, One or more selected from diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, phthalic dichloride, and aromatic dicarboxylic acid diester.
[0018]
  In addition, the present inventionUsing the solid catalyst component obtained by the production methodThe catalyst for olefin polymerization is the above-mentioned(A)Solid catalyst component,(B) the following general formula (1);
R¹ _pAlQ_3-p                      (1)
(Wherein R¹Represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3. ) And an (C) external electron donating compound..
[0019]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, first, a reaction step in which magnesium metal and alcohol are reacted in the presence of a catalyst to obtain a solid, and then the solid and a surfactant are contacted in an inert organic solvent to form a suspension. Dialkoxymagnesium is prepared by sequentially performing a first surfactant contact step and then a first removal step of removing the solvent in the suspension.
[0020]
In this case, the metal magnesium used is preferably, for example, a powdery material with good reactivity of several tens to several hundreds of mesh, more specifically about 100 mesh. The alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, etc., preferably ethanol. It is desirable to sufficiently remove the water in the alcohol before reacting with metal magnesium.
[0021]
Examples of the catalyst include alkyl halides such as methyl bromide, methyl chloride, ethyl bromide and ethyl chloride, metal halides such as magnesium chloride and aluminum chloride, dialkoxymagnesium such as diethoxymagnesium, iodine and acetic acid. Esters are used. Of these, iodine and diethoxymagnesium are particularly preferred.
[0022]
Metal magnesium and alcohol can be reacted by a known method, but as a preferred catalytic reaction method, the final addition ratio of metal magnesium and alcohol to the reaction system is metal magnesium / alcohol (weight ratio) = 1/2 ~ The final addition ratio of magnesium metal and alcohol was continuously or intermittently added to the reaction system under reflux of the alcohol and containing the catalyst, and allowed to react for 5 to 80 minutes. Is kept under reflux for 1 to 30 hours, and an aging reaction is performed to obtain a solid. The catalyst is preferably added at the beginning of the reaction step.
[0023]
The solid material obtained as described above may be a suspension using the alcohol used in the above reaction as a solvent, or may be dried after removing the alcohol. Thereafter, a first surfactant contacting step in which the solid and the surfactant are contacted in an inert organic solvent to form a suspension, and then a first removing step in which the solvent in the suspension is removed. Do it sequentially.
[0029]
  As the surfactant to be brought into contact with the solid material,Polyoxyethylene alkyl phenyl ethers such as nonylphenol ether, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyglycerol fatty acid esters such as polyglycerol monostearate, sorbitan monostearate, sorbitan distearate, etc. One or more selected from sorbitan fatty acid estersOnThe
[0030]
The solid and the surfactant are brought into contact with each other in an inert organic solvent to form a suspension. The inert organic solvent dissolves the surfactant and does not dissolve the magnesium compound. Are saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, and halogenated compounds such as methylene chloride and 1,2-dichlorobenzene. Examples thereof include hydrocarbon compounds, alcohols such as methanol, ethanol and isooctyl alcohol, and ethers such as diethyl ether. Among these, aromatic hydrocarbon compounds such as toluene and xylene are preferably used.
[0031]
The conditions for contacting the solid and the surfactant in an inert organic solvent are as follows: the contact temperature is -20 to 150 ° C., preferably 10 to 130 ° C., particularly preferably 50 to 110 ° C., and the contact time is 1 minute. -50 hours, preferably 10 minutes to 30 hours, particularly preferably 30 minutes to 10 hours.
[0032]
In the method of the present invention, the amount of the solid and the surfactant used when the solid and the surfactant are brought into contact with each other in the inert organic solvent are as follows. Is 0.01 to 3 g, preferably 0.05 to 1.5 g, particularly preferably 0.10 to 1.0 g, and most preferably 0.05 to 0.7 g. The amount of the inert organic solvent is 0.5 to 100 ml, preferably 1 to 50 ml, particularly preferably 3 to 30 ml, with respect to 1 g of the solid.
[0033]
Next, a first removal step of removing the solvent in the suspension obtained in the first surfactant contact step is performed. That is, after treating the surface of the solid with a surfactant, the solvent in the suspension is removed by decantation, filtration, or the like to obtain the dialkoxymagnesium of the present invention. By treating the solid with the surfactant in this way, the surfactant is adsorbed and coated on the surface of the solid particles. Further, fine powder adhering to the surface of the solid particles relatively weakly is peeled off from the surface of the solid particles and dispersed in a solvent. After the first removal step, by performing a washing step of washing the residue obtained in the first removal step with the inert solvent or the like, it is dissolved in the solvent contained in the residue obtained after the first removal step. It is preferred to remove excess surfactant. When removing the solvent in the suspension, it is desirable to remove fine dialkoxymagnesium particles dispersed in the solvent of several μm or less, specifically, 1 μm or less by decantation or the like.
[0034]
The dialkoxymagnesium thus obtained is obtained by coating the surface of the particles with a surfactant, and the content of the surfactant in the dialkoxymagnesium is 0.001 to 1% by weight, preferably 0. 0.01 to 0.5% by weight, particularly preferably 0.01 to 0.1% by weight.
[0035]
In this invention, when performing the said 1st surfactant contact process, it can be set as the manufacturing method of dialkoxymagnesium which also uses an alkoxytitanium compound together. Specifically, when the solid and the surfactant are brought into contact with each other in an inert solvent, the surfactant contacting step is performed by bringing the alkoxytitanium compound into coexistence with the solid, and then the first removal step is performed. Do. Also in this case, the above-described cleaning process can be performed after the first removal process. Moreover, in this invention, after performing the said 1st surfactant contact process and also performing the above-mentioned 1st removal process, the alkoxy titanium compound contact process which makes an alkoxy titanium compound contact is performed, The manufacturing method of dialkoxymagnesium can do. After the alkoxy titanium compound contact step, the alkoxy titanium compound is removed by decantation or filtration. Also in this case, the washing step can be performed after the first removal step and the alkoxy titanium compound contact step.
[0036]
As the alkoxytitanium compound used at this time, the general formula Ti (OR⁴)_rX_4-r(Where R⁴Represents 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 of 1 to 4. And a compound selected from the group consisting of trialkoxytitanium halides, dialkoxytitanium dihalides, and alkoxytitanium trihalides.
[0037]
Specifically, tetraalkoxy titanium such as tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetraisobutoxy titanium, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride , Trialkoxy halides such as tributoxy titanium chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, dialkoxy dihalides such as dibutoxy titanium dichloride, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride Examples thereof include alkoxy titanium trihalides such as butoxy titanium trichloride. Of these, tetraalkoxytitanium is preferable, and tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, and most preferably tetraethoxytitanium.
[0038]
The above-described alkoxytitanium compound, for example, tetraalkoxytitanium such as tetrabutoxytitanium, has a property of dissolving a solid substance that is dialkoxymagnesium. In the present invention, the method for producing dialkoxymagnesium using an alkoxytitanium compound is made by utilizing the properties of the above-described alkoxytitanium compound, that is, by reacting magnesium metal and an alcohol in the presence of a catalyst. The alkoxytitanium compound is brought into contact with the obtained powdery dialkoxymagnesium (solid), or the residue or residue obtained in the first removal step, which has been washed in the washing step. Fine powder existing on the surface of dialkoxymagnesium and unevenness of the surface are considered to be the main cause of the fine powder polymer produced in the olefin polymerization. When the solvent is removed after the contact, dialkoxymagnesium is used. It is considered that a part of the surface of magnesium is dissolved with an alkoxytitanium compound to remove fine powder on the surface and irregularities that cause fine powder.
[0039]
In the first surfactant contact step, the solid and the alkoxytitanium compound are brought into contact with each other in an inert organic solvent to form a suspension, or the residue or residue after the first removal step is washed away. When the alkoxytitanium compound is brought into contact with the washed one, depending on the amount of the alkoxytitanium compound relative to the solid or the residue after the first removal step or the residue washed by the washing step, All the residues are dissolved to form a uniform solution, and the intended dialkoxymagnesium cannot be obtained. Therefore, in the method of the present invention, the solid matter or the residue after the first removal step or the residue is not dissolved in the solid residue in the washing step, and the solid matter (solid magnesium compound) is left undissolved. To obtain a solid. Therefore, in the method of the present invention, the amount of the solid material and the alkoxytitanium compound used when contacting the above solid material and the above alkoxytitanium compound is 0.0001-1 ml per 1 g of the solid material. , Preferably 0.001 to 0.5 ml, particularly preferably 0.005 to 0.1 ml, most preferably 0.005 to 0.05 ml. The amount of the inert organic solvent is 0.5 to 100 ml, preferably 1 to 50 ml, particularly preferably 3 to 30 ml, with respect to 1 g of the solid.
[0040]
The dialkoxymagnesium of the present invention can also be obtained by the method for producing dialkoxymagnesium using the alkoxytitanium compound. Here, as described above, the solid material which is dialkoxymagnesium reacts with the alkoxytitanium compound to form a magnesium and titanium compound, and a part thereof is dissolved in the solvent, but the solvent in the suspension is removed. Therefore, it is preferable not to leave the dialkoxymagnesium as much as possible in order to obtain a polymer with less fine powder. However, it is inevitable that the dialkoxymagnesium of the present invention is mixed with impurities such as a trace amount of an alkoxytitanium compound. Therefore, the titanium content in dialkoxymagnesium when treated with an alkoxytitanium compound is 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, particularly preferably 0.1 to 0.5%. % By weight.
[0041]
The dialkoxymagnesium (a) obtained as described above is contacted with the titanium compound (b) and the electron donating compound (c) to prepare a solid catalyst component. At this time, when this dialkoxymagnesium is subjected to a washing step at the time of its preparation, it remains as a suspension with the inert organic solvent used in the washing step, or is separated or dried as necessary. To serve. Considering the simplification of the manufacturing process, it is desirable to use the suspension as it is without separation and drying. However, when an inert organic solvent such as alcohol or ether that reacts with the titanium compound (b) is used, it is desirable to sufficiently remove dialkoxymagnesium by drying under vacuum or heating.
[0042]
The dialkoxymagnesium obtained as described above is in the form of granules or powder, and its shape is indefinite or spherical. Among these, spherical dialkoxymagnesium, when used as a raw material for the solid catalyst component, gives a polymer powder having a better particle shape and narrow particle size distribution, and the handling operability of the resulting polymer powder during the polymerization operation is improved. And the problems such as clogging caused by the fine powder contained in the produced polymer powder are solved.
[0043]
Spherical dialkoxymagnesium does not necessarily have to be a spherical shape, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .
[0044]
Further, the dialkoxymagnesium of the present invention having an average particle size of 1 to 200 μm can be used. Preferably it is 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.
[0045]
The specific surface area of the dialkoxymagnesium of the present invention is 10 to 100 m.²/ G, preferably 20-80m²/ G, particularly preferably 25-50 m²/ G. Furthermore, the specific surface area of dialkoxymagnesium of the present invention is characterized by being larger than the specific surface area of the solid before treatment with the alkoxytitanium compound obtained by reacting metal magnesium and alcohol. Increase by 5 to 50%, preferably 10 to 30% of the specific surface area.
[0046]
The tetravalent titanium halogen compound (b) used in the solid product formation step in the preparation of the solid catalyst component (A) of the present invention has the general formula Ti (OR⁵)_nY_4-n(Wherein R⁵Represents an alkyl group having 1 to 4 carbon atoms, Y represents a halogen atom such as a chlorine atom, bromine atom or iodine atom, and n is an integer of 0 or 1 to 3. Or a compound selected from the group consisting of titanium halides and alkoxytitanium halides.
[0047]
Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride. The Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These tetravalent titanium halogen compounds can be used alone or in combination of two or more.
[0048]
  The electron donating compound used in the solid product production step in the preparation of the solid catalyst component (A) of the present invention (hereinafter sometimes simply referred to as component (c)) is used., Methyl benzoate, ethyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, adipine Examples thereof include dicarboxylic acid diesters such as diisodecyl acid, dioctyl adipate, and phthalic acid diester, and phthalic acid dichloride.
[0050]
Among the above electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and derivatives thereof are particularly preferable in terms of improving hydrogen activity during polymerization. Among these, specific examples of phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-phthalate. Butyl, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate Di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, phthalate Bis (2-ethylhexyl) acid, di-n-nonyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl phthalate) ), N-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate (heptyl) ), N-pentyl (2-ethylhexyl) phthalate, n-pentyl phthalate (iso-nonyl), iso-pentyl phthalate (n-decyl), n-pentylundecyl phthalate, iso-pentyl phthalate (iso) -Hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl) N-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (iso-nonyl), n-phthalate Heptyl (neo-decyl) are exemplified phthalate 2-ethylhexyl (an iso-nonyl) is, these one or more kinds are used.
[0051]
Moreover, as a phthalic-acid diester derivative, following General formula (3);
(R⁶)_lC₆H₄(COOR⁷) (COOR⁸(3)
(Wherein R⁶Represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and R⁷And R⁸Represents an alkyl group having 1 to 12 carbon atoms, and R⁷And R⁸May be the same or different and the substituent R⁶The number l of 1 is 1 or 2, and when l is 2, R⁶May be the same or different. ) Is preferred.
[0052]
In the general formula (3), R⁶Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, A neopentyl group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group, R⁶The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. R⁶Is preferably a methyl group, a bromine atom or a fluorine atom, more preferably a methyl group or a bromine atom.
[0053]
In the general formula (3), R⁷And R⁸Are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 2,2 A dimethylbutyl group, a 2,2-dimethylpentyl group, or an isooctyl group, a 2,2-dimethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, an isodecyl group, and an n-dodecyl group; Among these, an ethyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, an isohexyl group, and an isooctyl group are preferable, and an ethyl group, an n-butyl group, and a neopentyl group are particularly preferable. In addition, the substituent R⁶The number l of 1 is 1 or 2, and when l is 2, R⁶May be the same or different. When l is 1, R⁶Is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the phthalate derivative of the above general formula (3), and when l is 2,⁶Is preferably substituted with hydrogen atoms at positions 4 and 5.
[0054]
Examples of the phthalic acid diester derivative represented by the general formula (3) include diethyl 4-methylphthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, dineopentyl 4-bromophthalate, and diethyl 4-bromophthalate. Di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, dineopentyl 4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4-methylphthalate-t -Butyl neopentyl, 4-ethyl phthalate-t-butyl neopentyl, 4,5-dimethylphthalate dineopentyl, 4,5-diethyl phthalate dineopentyl, 4,5-dimethyl phthalate-t-butyl neopentyl, 4, 5-diethylphthalic acid t- butyl neopentyl, 3-fluoro-phthalic acid dineopentyl, 3-chlorophthalic acid dineopentyl, 4-chlorophthalic acid dineopentyl, include 4-bromophthalic acid dineopentyl.
[0055]
The above esters are preferably used in combination of two or more, and the esters are used so that the total carbon number of the alkyl group of the ester used is 4 or more compared to that of other esters. It is desirable to combine.
[0056]
In the present invention, the components (a), (b), and (c) are contacted in the presence of an aromatic hydrocarbon (d) (hereinafter sometimes referred to simply as “component (d)”). The method of preparing the component (A) by the above is a preferred embodiment of the preparation method, and specifically, the component (d) is preferably an aromatic hydrocarbon having a boiling point of 50 to 150 ° C. such as toluene, xylene, ethylbenzene, etc. Used. Moreover, these may be used independently or may be used in mixture of 2 or more types.
[0057]
In the preparation of the solid product in the preparation of the solid catalyst component (A) of the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. By using polysiloxane, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O— bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm.²/ s (2 to 10000 centistokes), more preferably 0.03 to 5 cm²It is a linear, partially hydrogenated, cyclic or modified polysiloxane that is liquid or viscous at room temperature and has / s (3 to 500 centistokes).
[0058]
As the chain polysiloxane, dimethyl polysiloxane and methylphenyl polysiloxane are used. As the partially hydrogenated polysiloxane, methyl hydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid groups. Examples thereof include substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.
[0059]
In the present invention, the above components (a), (b) and (c) and, if necessary, the component (d) or the component (e) are contacted to form a solid product. A method for preparing the product will be described. Specifically, the magnesium compound (a) is suspended in an alcohol, a halogenated hydrocarbon solvent, a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and electron donation such as phthalic acid diester is performed. A method of obtaining a solid component by contacting the functional compound (c) and / or the tetravalent titanium halogen compound (b). In the method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming the particles by a so-called spray drying method in which the liquid is sprayed and dried, a solid product having a spherical shape and a sharp particle size distribution can be obtained.
[0060]
The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature is a temperature at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. , It becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
[0061]
A preferred method for preparing a solid product of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d), A method of preparing a solid product by reacting, or by suspending component (a) in component (d) and then contacting component (c), then contacting component (b) and reacting Mention may be made of the method of preparing the solid product. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (b) or the component (b) and the component (c) into contact with the solid product thus prepared again or multiple times. At this time, it is desirable to carry out in the presence of the aromatic hydrocarbon (d).
[0062]
As a particularly preferred method for preparing the solid product in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the component (b And a mixed solution formed from the component (d) is brought into contact with the suspension and then reacted.
[0063]
The most preferable method for preparing the solid product in the present invention includes the following methods. A suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (b) and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction process (first reaction process). After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the solid substance after washing is used as a solid product. Thereafter, the washed solid material is further brought into contact with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C., and the temperature is raised. A solid product can also be obtained by repeating the reaction treatment (secondary reaction treatment) and washing with a hydrocarbon compound that is liquid at room temperature after completion of the reaction 1 to 10 times.
[0064]
The solid product obtained as described above is subjected to a second surfactant contacting step in which a surfactant is brought into contact with the solid product in an inert organic solvent to form a suspension, and then the suspension is suspended. The solid catalyst component (A) of the present invention is prepared by performing a second removal step of removing the solvent in the liquid.
[0065]
As the surfactant, the same ones as described above are used, and among them, the preferred surfactant used in the present invention is a nonionic surfactant, particularly a slightly lipophilic surfactant having an HLB value of 3 to 15. Nonionic surfactants are preferred. Specifically, polyoxyethylene alkyl phenyl ethers such as nonylphenol ether, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyglycerin fatty acid esters such as polyglycerol monostearate, sorbitan monostearate, sorbitan One or more selected from sorbitan fatty acid esters such as distearate are particularly preferably used.
[0066]
The solid product and the surfactant are brought into contact with each other in an inert organic solvent. The inert organic solvent dissolves the surfactant and does not dissolve the solid product. Specifically, pentane, hexane Saturated hydrocarbon compounds such as heptane, octane, nonane, decane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, and halogenated hydrocarbon compounds such as methylene chloride and 1,2-dichlorobenzene. Can be mentioned. Among these, aromatic hydrocarbon compounds such as toluene and xylene, and saturated hydrocarbon compounds such as hexane and heptane are preferably used. Among these, aromatic hydrocarbon compounds such as toluene and xylene are preferably used.
[0067]
The conditions for contacting the solid product and the surfactant in an inert organic solvent are as follows: the contact temperature is -20 to 150 ° C, preferably 10 to 130 ° C, particularly preferably 50 to 110 ° C, and the contact time is 1. Minutes to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 3 hours.
[0068]
In the method of the present invention, the amount of the solid product and the surfactant used when contacting the solid product and the surfactant in the inert organic solvent is as follows: The surfactant is 0.01 to 3 g, preferably 0.05 to 1.5 g, particularly preferably 0.10 to 1.0 g, most preferably 0.05 to 0.7 g based on 1 g of the product. . The amount of the inert organic solvent is 0.5 to 100 ml, preferably 1 to 50 ml, particularly preferably 3 to 30 ml, with respect to 1 g of the solid product.
[0069]
After forming the suspension as described above and treating the surface of the solid product, the solvent in the suspension is removed by decantation or filtration, and if necessary, washing with an inert organic solvent is performed 1 to 10 times. To obtain the solid catalyst component (A) of the present invention. By treating the solid product with the surfactant in this way, the surfactant is adsorbed and coated on the surface of the solid product particles. Further, fine powder adhering to the surface of the solid product particles relatively weakly is peeled off from the surface of the solid product particles and dispersed in a solvent. Subsequent washing removes excess surfactant dissolved in the solvent and, when removing the solvent in the suspension, fine powder dispersed in the solvent of several μm or less, specifically 1 μm or less. It is desirable to remove the solid product particles by decantation or the like.
[0070]
The solid catalyst component (A) prepared as described above can be brought into contact with the component (b) or the component (b) and the component (c) again. At this time, it is desirable to carry out the suspension in the aromatic hydrocarbon compound (d) as in the preparation of the solid product. Thus, by contacting again, the performance of the solid catalyst component such as activity can be improved.
[0071]
Further, when the component (b) or the component (b) and the component (c) are contacted again as described above, the solid catalyst component is again contacted with a surfactant in an inert solvent to form a suspension. Thereafter, the solvent in the suspension can be removed. By repeating the treatment with the surfactant a plurality of times in this manner, the fine powder polymer when the fine powder and the olefin in the solid catalyst component are polymerized can be further reduced.
[0072]
Based on the above, as a particularly preferable method for preparing the solid catalyst component (A) in the present invention, a solid material is obtained by reacting metal magnesium and an alcohol such as ethanol in the presence of a catalyst under reflux of the alcohol. The solid and surfactant are then contacted in an inert organic solvent such as toluene to form a suspension, and then the solvent in the suspension is removed to obtain dialkoxymagnesium (a). The dialkoxymagnesium (a) thus obtained is suspended in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and then the tetravalent titanium halogen compound (b) is contacted with the suspension. Then, reaction treatment is performed. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more electron donating compounds (c) such as phthalic acid diesters are added at −20 to 20 A contact treatment is performed at 130 ° C. to carry out a reaction treatment to obtain a solid product (1). In this case, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more electron donating compounds. After washing this solid product (1) with a hydrocarbon compound that is liquid at room temperature (intermediate washing), the tetravalent titanium halogen compound (b) is again added in the presence of the aromatic hydrocarbon compound in the range of -20 to 100. The mixture is contacted at 0 ° C. and subjected to a reaction treatment to obtain a solid reaction product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed with a hydrocarbon compound that is liquid at room temperature (final washing), a nonionic surfactant is added to the suspension, and the mixture is treated at room temperature to 100 ° C. The solid catalyst component (A) is obtained by washing with a hydrocarbon compound that is liquid at room temperature by decantation.
[0073]
As a particularly preferred method for preparing the solid catalyst component (A) in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., A solid product is prepared by bringing the mixed solution formed from component (b) and component (d) into contact with the suspension, followed by reaction, and then to the solid product in an inert organic solvent. A preparation method can be mentioned by performing a second surfactant contact step in which a surfactant is contacted to form a suspension, followed by a second removal step in which the solvent in the suspension is removed. In addition, a suspension is formed from component (a), component (c), and aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and a mixed solution formed from component (b) and component (d) A surfactant contacting step in which a solid substance is prepared by contacting the suspension with the suspension, followed by reaction, and the surfactant is contacted with the solid product in an inert organic solvent to form a suspension. Then, the mixed solution formed from component (b) and component (d) is added to and contacted with the solid material, and then the surfactant is contacted with the solid product in an inert organic solvent. A preparation method can be mentioned by performing a surfactant contact step for forming a turbid liquid and then performing a removal step for removing the solvent in the suspension. Furthermore, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and a mixed solution formed from the component (b) and the component (d) Is contacted with the suspension and then reacted to prepare a solid material, and then the mixed solution formed from the component (b) and the component (d) is added to the solid material and brought into contact, and then Performing a second surfactant contact step in which a surfactant is brought into contact with the solid product in an inert organic solvent to form a suspension, followed by a second removal step of removing the solvent in the suspension. A preparation method can be mentioned by performing.
[0074]
As the most preferable preparation method (i) of the solid catalyst component (A) in the present invention, the following methods can be mentioned. A suspension is formed from the dialkoxymagnesium (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (b) and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction process (first reaction process). After completion of the reaction, the obtained solid substance is washed with a hydrocarbon compound that is liquid at room temperature such as benzene, toluene, xylene, and ethylbenzene, and the solid product obtained after washing or a suspension containing the solid product is washed. After adding a nonionic surfactant and an inert organic solvent, the treatment is performed at room temperature to 100 ° C., and then the inert organic solvent is removed at room temperature by decantation to obtain the solid catalyst component (A) as a solid substance. . Further, the solid substance is newly contacted with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C. The solid catalyst component (A1) can also be obtained by repeating the operation of washing with a liquid hydrocarbon compound at room temperature after the completion of the reaction 1 to 10 times.
[0075]
Moreover, as the most preferable preparation method (ii) of the solid catalyst component (A) in the present invention, the following methods can be exemplified. That is, a nonionic surfactant and an inert organic solvent are added to a suspension containing the solid catalyst component (A1) or the solid catalyst component (A1) obtained by the above preparation method (i), and the temperature is changed from room temperature to 100 ° C. Then, the inert organic solvent is removed at room temperature by decantation to obtain the solid catalyst component (A) as a solid substance. Furthermore, the solid substance is newly contacted with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C. The solid catalyst component (A2) can also be obtained by repeating the operation of washing with a hydrocarbon compound that is liquid at room temperature after the completion of the reaction.
[0076]
Furthermore, examples of the most preferable preparation method (iii) of the solid catalyst component (A) in the present invention include the following methods. That is, after completion of the first reaction treatment of the preparation method (i), the obtained solid substance is newly replaced with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. to −20. Contacting at ~ 100 ° C, heating up, reaction treatment (secondary reaction treatment), and after completion of the reaction, washing with liquid hydrocarbon compound at room temperature is repeated 1 to 10 times to obtain after washing A nonionic surfactant and an inert organic solvent are added to the obtained solid product or suspension containing the solid product, treated at room temperature to 100 ° C., and then treated with decantation at room temperature. The solvent is removed to obtain the solid catalyst component (A) as a solid substance. Furthermore, the solid substance is newly contacted with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C. The solid catalyst component (A3) can also be obtained by repeating the operation of washing with a hydrocarbon compound that is liquid at room temperature after the reaction is completed.
[0077]
The amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, a tetravalent titanium halogen compound (b) per mole of the magnesium compound (a) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol. More preferably, it is 0.02 to 0.6 mol, and the aromatic hydrocarbon compound (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol. is there.
[0078]
Further, the content of titanium, magnesium, halogen atom, electron donating compound, and surfactant in the solid catalyst component (A) in the present invention is not particularly defined, but preferably 0.5 to 8.0 weight of titanium. %, Preferably 1.0-6.0% by weight, more preferably 1.5-4.0% by weight, magnesium 10-70% by weight, more preferably 10-50% by weight, particularly preferably 15-40%. % By weight, more preferably 15-25% by weight, 20-85% by weight of halogen atoms, more preferably 30-85% by weight, particularly preferably 40-80% by weight, still more preferably 45-75% by weight, and electrons The total amount of donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight, particularly preferably 2 to 20% by weight, and the surfactant is 0.01 to 10% by weight, preferably 0.0%. 5 wt%, more preferably from 0.1 to 1 wt%.
[0079]
As the organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention, a compound represented by the above general formula (1) can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide and diethylaluminum hydride, and one or more can be used. Triethylaluminum and tri-iso-butylaluminum are preferable.
[0080]
The external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is used for the preparation of the solid catalyst component described above. The same electron donating compounds that can be used are used, among which ethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl benzoate and Esters such as ethyl benzoate and organosilicon compounds.
[0081]
As said organosilicon compound, the compound represented by the said General formula (2) is used. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.
[0082]
Specific examples of the organosilicon compound include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxy. Silane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxy Orchid, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane Bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane Bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopenty Dipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5- Dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxy Silane, cyclohexyl Tildimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, cyclohexyl (n -Butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane , Phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Rutriethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltri Methoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, te A tributoxysilane etc. can be mentioned. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldi Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxy Silane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylsilane Lopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) is 1 It can be used in combination of two or more species.
[0083]
Next, the olefin polymerization catalyst of the present invention is formed from the above-mentioned solid catalyst component (A), component (B), and component (C) for olefin polymerization, and the polymerization of olefins in the presence of the catalyst. Copolymerization is performed. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.
[0084]
The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is titanium in the solid catalyst component (A). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The organosilicon compound (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the component (B).
[0085]
The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) for olefin polymerization is further added. It is desirable to contact.
[0086]
The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.
[0087]
Furthermore, in the present invention, when the olefin is polymerized using the catalyst formed from the solid catalyst component for olefin polymerization (A), the component (B), and the component (C) (also referred to as main polymerization), the catalytic activity, In order to further improve the stereoregularity and the particle properties of the resulting polymer, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.
[0088]
In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefin. After contacting the solid catalyst component (A) for homopolymerization, an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.
[0089]
When olefins are polymerized in the presence of an olefin polymerization catalyst formed according to the present invention, the resulting polymer has very little fines and a uniform particle size distribution compared to the case where a conventional catalyst is used. And high degree of stereoregularity and yield of the polymer can be maintained. The catalyst for olefin polymerization of the present invention is very advantageous particularly for a polyolefin production process by a gas phase method.
[0090]
【Example】
Hereinafter, examples of the present invention will be described in detail while comparing with comparative examples.
Example 1
(Preparation of diethoxymagnesium)
Suspension in which 5 g of metal magnesium fine powder with a particle size of 100 mesh or less, 130 ml of ethanol at room temperature and 3 g of iodine were charged into a 2-liter round bottom flask equipped with a stirrer and a reflux condenser and sufficiently substituted with nitrogen gas. Formed. The suspension was then warmed with stirring to initiate the reaction under ethanol reflux. After starting the reaction, 5 g of metal magnesium powder having a particle size of 100 mesh or less and 60 ml of ethanol were simultaneously added to the flask four times over 30 minutes. After completion of the addition, the mixture was kept for 10 hours with stirring under reflux of ethanol. (The final added magnesium is 25 g, and ethanol is 370 ml (about 292 g), final added magnesium metal / ethanol = 1/12). Then, after cooling to room temperature, the supernatant was decanted and vacuum dried to obtain about 100 g of a spherical solid (reaction process).
[0091]
Next, 10 g of the solid substance obtained above and 100 ml of normal temperature toluene were put into a 500 ml round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer, and stirred, and then sorbitan which is a nonionic surfactant. 1.1 g of distearate (Emazole S-20; manufactured by Kao Corporation) was added and stirred to form a suspension. Then, it contacted for 6 hours at 100 degreeC, stirring, and obtained suspension (1st surfactant contact process). Next, the supernatant of the suspension obtained by standing was removed by decantation (first removal step), and a washing step of adding 100 ml of 90 ° C. toluene and stirring, this operation was repeated five times. A suspension of diethoxymagnesium and toluene was prepared.
[0092]
[Preparation of solid catalyst component (A)]
The supernatant of the diethoxymagnesium suspension was removed, and 50 ml of toluene and 2.4 ml of di-n-butyl phthalate were added to form a suspension. On the other hand, 30 ml of titanium tetrachloride and 20 ml of toluene are charged into a 500 ml round bottom flask which is sufficiently replaced with nitrogen gas and equipped with a stirrer to form a mixed solution, and the above suspension is suspended in this mixed solution. The liquid was added. Thereafter, the temperature of the mixed solution was raised, and the mixture was reacted at 90 ° C. with stirring for 2 hours (solid product forming step; first reaction treatment). After completion of the reaction, the obtained solid product was washed with 100 ml of 90 ° C. toluene three times, and then 1.1 g of sorbitan distearate (Emazole S-20; manufactured by Kao Corporation) and 100 ml of 90 ° C. toluene were added. A suspension was formed by contact with stirring at 90 ° C. for 5 minutes (second surfactant contact step). Thereafter, the supernatant was removed from the suspension by decantation (second removal step). To this, 30 ml of titanium tetrachloride and 70 ml of toluene were newly added. After completion of the reaction, the solid catalyst component was obtained by washing 10 times with 100 ml of n-heptane at 40 ° C. The titanium content in the solid catalyst component was measured and found to be 3.2% by weight.
[0093]
[Formation and polymerization of polymerization catalyst]
700 ml of n-heptane was charged into a stainless steel autoclave with a stirrer having an internal volume of 1800 ml that had been sufficiently dried with nitrogen gas and then replaced with propylene gas, and maintained in a propylene gas atmosphere. A polymerization catalyst was formed by charging 0.21 mmol of cyclohexylmethyldimethoxysilane and 0.0053 mmol of Ti as the solid catalyst component. Next, a preliminary polymerization was carried out at 20 ° C. for 30 minutes while applying propylene pressure of 0.2 MPa and keeping stirring. Thereafter, 150 ml of hydrogen was charged, and the polymerization was continued for 2 hours at 70 ° C. with a propylene pressure in the system of 0.7 MPa. In addition, the pressure which falls as superposition | polymerization advances was supplemented by supplying only propylene continuously, and was kept at the constant pressure during superposition | polymerization. According to the above polymerization method, propylene was polymerized, and the produced polymer was filtered and dried under reduced pressure to obtain a solid polymer. On the other hand, the filtrate is condensed to obtain a polymer dissolved in the polymerization solvent, the amount of which is (M), and the amount of the solid polymer is (N). The obtained solid polymer is extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount is defined as (P). The polymerization activity (Y) per solid catalyst component is represented by the following formula.
(Y) = [(M) + (N)] (g) / solid catalyst component amount (g)
The total polymer (HI) insoluble in n-heptane is represented by the following formula.
(HI) = {(P) (g) / [(M) + (N)] (g)} × 100
Further, the melt flow rate (MFR), bulk specific gravity (BD) of the produced solid polymer, fine powder of the produced solid polymer (44 μm or less, 105 μm or less), average particle size (μm) and particle size distribution [(D90-D10) / D50] was measured, and the results shown in Table 1 were obtained.
[0094]
The melt flow rate value (MFR) of the produced solid polymer (N) was measured in accordance with ASTM D 1238 and JIS K 7210.
[0095]
Example 2
10 g of diethoxymagnesium prepared in Example 1, 50 ml of toluene, and 2.4 ml of di-n-butyl phthalate were placed in a 500-milliliter round bottom flask that was sufficiently replaced with nitrogen gas and equipped with a stirrer and a reflux condenser. A suspension was formed upon injection. On the other hand, 30 ml of titanium tetrachloride and 20 ml of toluene are charged into a 500 ml round bottom flask which is sufficiently replaced with nitrogen gas and equipped with a stirrer to form a mixed solution, and the above suspension is suspended in this mixed solution. The liquid was added. Thereafter, the temperature of the mixed solution was raised, and the mixture was reacted at 90 ° C. with stirring for 2 hours (solid product forming step; first reaction treatment). After completion of the reaction, the obtained solid product was washed with 100 ml of 90 ° C. toluene three times, and then 1.1 g of sorbitan distearate (Emazole S-20; manufactured by Kao Corporation) and 100 ml of 90 ° C. toluene were added. A suspension was formed by contact with stirring at 90 ° C. for 5 minutes (second surfactant contact step). Thereafter, the supernatant was removed from the suspension by decantation (second removal step). To this, 30 ml of titanium tetrachloride and 70 ml of toluene were newly added. After completion of the reaction, the mixture was washed 5 times with 100 ml of n-heptane at 40 ° C. Next, 1.1 g of sorbitan distearate (Emazole S-20; manufactured by Kao Co., Ltd.) and 100 ml of n-heptane at 40 ° C. were added and contacted with stirring at 40 ° C. for 5 minutes to form a suspension. Thereafter, the supernatant was removed from the suspension by decantation. Further, it was washed 5 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 2.7% by weight.
[0096]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component prepared as described above was used. The polymerization results are shown in Table 1.
[0097]
Example 3
10 g of diethoxymagnesium prepared in Example 1, 50 ml of toluene, and 2.4 ml of di-n-butyl phthalate were placed in a 500-milliliter round-bottom flask fully substituted with nitrogen gas and equipped with a stirrer and a reflux condenser. Input to form a suspension. On the other hand, 30 ml of titanium tetrachloride and 20 ml of toluene are charged into a 500 ml round bottom flask which is sufficiently replaced with nitrogen gas and equipped with a stirrer to form a mixed solution, and the above suspension is suspended in this mixed solution. The liquid was added. Thereafter, the temperature of the mixed solution was raised, and the mixture was reacted at 90 ° C. with stirring for 2 hours (solid product forming step; first reaction treatment). After completion of the reaction, the obtained solid product was washed 4 times with 100 ml of toluene at 90 ° C., 30 ml of titanium tetrachloride and 70 ml of toluene were newly added to this, and the temperature was raised to 110 ° C. and reacted with stirring for 2 hours. (Secondary reaction treatment). After completion of the reaction, the mixture was washed 5 times with 100 ml of n-heptane at 40 ° C. Next, 1.1 g of sorbitan distearate (Emazole S-20; manufactured by Kao Corporation) and 100 ml of n-heptane at 40 ° C. were added and contacted with stirring at 40 ° C. for 5 minutes to form a suspension (second) Surfactant contact step). Thereafter, the supernatant was removed from the suspension by decantation (second removal step). Further, it was washed 5 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 2.6% by weight.
[0098]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component prepared as described above was used. The polymerization results are shown in Table 1.
[0099]
Example 4
The solid catalyst component was changed in the same manner as in Example 2 except that a special polycarboxylic acid type polymer surfactant (Poise 520; manufactured by Kao Corporation) was used instead of sorbitan distearate (Emazole S-20; manufactured by Kao Corporation). The polymerization catalyst was formed and polymerized. The polymerization results are shown in Table 1.
[0100]
Example 5
A solid catalyst component was prepared in the same manner as in Example 2 except that sorbitan laurate (Leodol SP L10; manufactured by Kao) was used instead of sorbitan distearate (Emazole S-20; manufactured by Kao). Formation and polymerization were performed. The polymerization results are shown in Table 1.
[0101]
Comparative Example 1
(Preparation of diethoxymagnesium)
The reaction process similar to Example 1 was performed and the spherical solid substance was obtained. This was used for preparation of the solid catalyst component (A) without being treated with the first surfactant.
[0102]
[Preparation of solid catalyst component (A)]
In a 500 milliliter round bottom flask fully substituted with nitrogen gas and equipped with a stirrer and reflux condenser, 10 g of the surfactant-untreated diethoxymagnesium obtained above, 50 ml of toluene and di-n-phthalate 2.4 ml of butyl was added to form a suspension. On the other hand, 30 ml of titanium tetrachloride and 20 ml of toluene are charged into a 500 ml round bottom flask which is sufficiently replaced with nitrogen gas and equipped with a stirrer to form a mixed solution, and the above suspension is suspended in this mixed solution. The liquid was added. Thereafter, the mixed solution was heated and reacted at 90 ° C. with stirring for 2 hours. After completion of the reaction, the obtained solid product was washed with 100 ml of toluene at 90 ° C. four times, and then 30 ml of titanium tetrachloride and 70 ml of toluene were newly added thereto, and the temperature was raised to 110 ° C. I let you. After completion of the reaction, the solid catalyst component was obtained by washing 10 times with 100 ml of n-heptane at 40 ° C. The titanium content in the solid catalyst component was measured and found to be 2.9% by weight.
[0103]
Comparative Example 2
The solid catalyst component (A) obtained in Comparative Example 1 was dried, and 1.1 g of sorbitan distearate (Emazole S-20; manufactured by Kao Corporation) was mixed with 10 g of the dried solid catalyst component.
[0104]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component prepared as described above was used. The polymerization results are shown in Table 1.
[0105]
[Table 1]

[0106]
From the results in Table 1, it can be seen that propylene polymerization is carried out using the solid catalyst component and catalyst of the present invention, so that high activity and high stereoregularity are maintained, and generation of a fine powder polymer is extremely small.
[0107]
【The invention's effect】
The catalyst based on the solid catalyst component for olefin polymerization of the present invention can obtain a polymer with very little fine powder while maintaining a high degree of polymer stereoregularity and yield. Therefore, general-purpose polyolefin can be provided at low cost.
[Brief description of the drawings]
FIG. 1 is a flowchart showing steps for preparing a polymerization catalyst of the present invention.

Claims (4)

A reaction step in which metal magnesium and alcohol are reacted in the presence of a catalyst selected from alkyl halides, metal halides, dialkoxymagnesium, iodine and acetate esters to obtain solids;
Next, the solid is contacted with one or more compounds selected from polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester in an inert organic solvent and suspended. A first surfactant contact step for forming a liquid;
Thereafter dialkoxy magnesium obtained by sequentially performing a first removing step of removing the solvent of the suspension (a), contacting the tetravalent titanium halide (b) and the electron donating compound (c) A solid product forming step in which the solid material obtained is washed with a liquid hydrocarbon compound at room temperature to form a solid product,
Then, the solid product is suspended in contact with one or more compounds selected from polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester and sorbitan fatty acid ester in an inert organic solvent. A second surfactant contacting step for forming a liquid, and then a second removing step for removing the solvent in the suspension, wherein the electron-donating compound (c) is methyl benzoate, benzoic acid Ethyl, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, Phthalic acid dichloride and fragrance Method for producing olefin polymerization solid catalyst component, wherein the at least one selected from a dicarboxylic acid diester. Method for producing olefin polymerization solid catalyst component according to claim 1, wherein the alcohol is ethanol. Production of olefin polymerization solid catalyst component of claim 1, said inert organic solvent used in the first surfactant contacting step and the second surfactant contacting step is characterized in that the aromatic hydrocarbon compound Way . Method for producing olefin polymerization solid catalyst component according to claim 1, wherein the tetravalent titanium halide (b) is titanium tetrachloride.

Images