JP4217272B2 - Propylene-ethylene block copolymer production method - Google Patents

Description

【００８４】
【表２】

【００８５】
［実施例と比較例の結果の考察］
以上の各実施例及び各比較例を対照することにより、本発明では、熱落下秒数の結果が非常に優れ、生成重合体の付着性（べたつき）が極めて少ないことが明示されている。これにより、共重合反応時に生成粒子の相互の付着および反応器壁や撹拌器具への付着が非常に少なく、生産性が高められていることが理解できる。
また、本発明では、衝撃強度やゲルの発生などにおいても良好な結果が示されている。
さらに、比較例１，２および５，６は、第３反応槽での電子供与性化合物（成分（Ｃ）；キラー化合物）を添加せず、比較例２では第２反応槽での電子供与性化合物の添加量が２．０ｍｏｌ／ｍｏｌ−Ａｌを超え、比較例３，４および７，８では第３反応槽での電子供与性化合物の添加量が０．０１ｍｏｌ／ｍｏｌ−Ａｌより少ないので、本発明における電子供与性化合物の添加の有効性、特に、第２反応槽での添加量の規定である０．１〜２．０ｍｏｌ／ｍｏｌ−Ａｌ、第３反応槽での添加量の規定である０．０１〜２．０ｍｏｌ／ｍｏｌ−Ａｌの各数値限定の有効性が実証されている。
【００８６】
【発明の効果】
本発明によると、チーグラー系触媒を使用して、プロピレン重合体をエチレンと共重合してブロック共重合体を製造する方法において、共重合部分のゴム成分によるエラストマー性能を発揮させて、プロピレン重合体における剛性などの本来の優れた性質を損なわずに耐衝撃性を向上させながら、高い重合活性と立体規則性を維持し、生成粒子の相互の付着や器壁などへの粘着を生起せずに、さらにショートパス粒子によるゲルやフィッシュアイなどを削減することが充分に達成される。
【図面の簡単な説明】
【図１】 チーグラー触媒に関する本発明の技術内容の理解を助けるためのフローチャート図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a propylene-ethylene block copolymer. More specifically, the present invention relates to a multistage polymerization method for suppressing the adhesion of produced particles and the generation of gel by adding a specific compound in a method for producing a propylene-ethylene block copolymer by multistage polymerization. Is.
[0002]
[Prior art]
Crystalline polypropylene can be said to be one of the most excellent polymer materials due to its physical properties and economy, but it has the weakness of having insufficient impact resistance, while having excellent properties in rigidity and heat resistance. It was. As a method for improving this point, it is well known to polymerize propylene and other α-olefins such as ethylene to form a block copolymer. The impact resistance can be improved without impairing the original excellent properties such as rigidity in the polymer.
[0003]
However, in this method, the balance between rigidity and impact resistance or the appearance of the molded product is not good, and in order to improve these, the polymerization process of the ethylene-propylene copolymer part (rubber component; EPR) is performed in two or more stages. A method for obtaining a propylene-ethylene block copolymer with an excellent balance between rigidity and impact resistance has been developed by dividing it into multiple stages and producing different structural parts and contributing different properties at each stage. Using a Ziegler catalyst, propylene homopolymerization in the previous stage or copolymerization of other α-olefins such as propylene and ethylene to produce a propylene (co) polymer, and then the presence of the (co) polymer Below, a propylene block copolymer is produced by continuously vapor-phase copolymerizing propylene and other α-olefins such as ethylene in the subsequent stage. (For example, refer to Patent Document 1).
The product obtained here is a polymer or a mixture of copolymers produced at each stage, and is generally called a propylene block copolymer.
[0004]
However, in this copolymerization method, the persistence of the activity of the polymerization catalyst is not sufficient, and in the subsequent gas phase copolymerization, the particles adhere to each other due to the high adhesion of the generated particles, the reactor walls and the stirring of the generated particles. Problems such as adhesion to equipment or productivity reduction due to these adhesions are also derived, and furthermore, in the first stage polymerization, the distribution of the catalyst component polymerization time (residence time in the polymerization tank) is generated, which is relatively short. When particles discharged from the first stage polymerization tank (so-called short pass particles) enter the second stage polymerization tank, particles having a high content of propylene-ethylene copolymer are generated. Such particles do not disperse even when kneaded, but become gels or fish eyes, which causes the appearance of the molded article to be damaged or the mechanical strength to be reduced.
[0005]
Among such problems, as an effective means for solving the problem of high adhesion of the generated particles, a method of adding various compounds to a copolymerization tank is disclosed. For example, organic lithium or organic magnesium is added. Although a method has been proposed (see Patent Documents 2 and 3), the copolymerization activity is significantly reduced.
In addition, a method of adding aluminum alkoxide and hydrocarbon to a subsequent propylene-ethylene copolymerization reaction system (see Patent Document 4), a method of adding an active hydrogen compound such as alcohol (see Patent Document 5), fatty acid Although a method of adding an amide (see Patent Document 6) has been proposed, the problem of adhesion of the generated particles can be solved, but conversely, another problem such as generation of fine powder and its scattering occurs. .
Further, a method of reducing adhesion of generated particles and suppressing scattering of fine powder by supplying saturated hydrocarbons to the reaction system with the superficial velocity in the tank of the copolymerization reaction being equal to or lower than the minimum fluidization rate (Patent Document 7). ), Adding an alkoxy-containing silicon compound and adding hydrocarbons to the copolymerization stage to prevent adhesion of the produced particles and increase the molecular weight of the block copolymer (see Patent Document 8), active hydrogen-containing compound A method of adding a special electron donor such as benzene or a ketone compound to prevent adhesion of the generated particles or improving the moldability of the copolymer (see Patent Documents 9 and 10) has also been proposed. However, it is still not sufficient in catalytic activity, stereoregularity or economic efficiency.
[0006]
On the other hand, in order to reduce gels and fish eyes caused by short path particles, an electron-donating compound such as an active hydrogen compound, an aliphatic ketone compound or an aliphatic ester compound is used for the purpose of deactivating the short path particles. Although a method of adding to the solvent is also proposed (see Patent Documents 11 and 12), it does not lead to a sufficient improvement in polymerization activity and gel reduction.
[0007]
Any of the above methods using a Ziegler-based catalyst is an excellent improvement proposal aimed at solving various problems in producing propylene copolymers by two-stage copolymerization of propylene and other α-olefins such as ethylene. However, it has not been able to sufficiently solve the problems such as the persistence of polymerization activity, adhesion of generated particles and gel and fish eye, and propylene has been attracting attention as a method for improving the impact resistance of polypropylene. By making a block copolymer by copolymerizing with an α-olefin, the elastomer performance due to the rubber component of the copolymerized portion is fully exhibited, and the original excellent properties such as rigidity and stereoregularity in the propylene polymer are obtained. Without damaging it, it suppresses particle adhesion that reduces the productivity by adhering to a reactor, etc. The demand to reduce shy eyes has not been fully met.
[0008]
[Batch display of each patent document in the above prior art]
Patent Document 1: Japanese Patent Laid-Open No. 1-201309 (Claim 1 of Claims)
Patent Document 2: Japanese Patent Laid-Open No. 62-132912 (Claim 1 of Claims)
Patent Document 3: Japanese Patent Application Laid-Open No. 62-135509 (Claim 1 of Claims)
Patent Document 4: Japanese Patent Application Laid-Open No. 58-213012 (Claim 1 of Claims)
Patent Document 5: Japanese Examined Patent Publication No. 63-54294 (Claim 1, Claim 2, Page 2, Column 22, Line 22)
Patent Document 6: Japanese Patent Laid-Open No. 64-45407 (Claim 3 of Claims)
Patent Document 7: Japanese Patent Laid-Open No. 4-331219 (Claim 1 of Claims)
Patent Document 8: Japanese Patent Laid-Open No. 7-90035 (claim 1)
Patent document 9: Japanese Patent Laid-Open No. 61-69821 (claim 1)
Patent Document 10: Japanese Patent Laid-Open No. 63-43915 (claim 1)
Patent Document 11: Japanese Patent Laid-Open No. 7-25960 (Claim 1 of Claims)
Patent Document 12: Japanese Patent Laid-Open No. 2000-63420 (Claim 1 of Claims)
[0009]
[Problems to be solved by the invention]
As described above, by using a Ziegler catalyst and copolymerizing a propylene polymer with another α-olefin such as ethylene to form a block copolymer, the elastomer performance due to the rubber component of the copolymerized portion. While maintaining high polymerization activity and stereoregularity while improving impact resistance without impairing the original excellent properties such as rigidity in the propylene polymer, the adhesion of the generated particles to the vessel wall, etc. Further reduction of gels and fish eyes caused by short-pass particles without occurring has not yet been achieved sufficiently.
In such a situation, the present invention, in such a situation, after propylene homopolymerization or copolymerization of propylene and another α-olefin such as ethylene to produce a propylene (co) polymer, in the presence of the (co) polymer, When producing a propylene block copolymer by continuously vapor-phase copolymerizing propylene and other α-olefin such as ethylene in the subsequent stage, among propylene-α-olefin block copolymers, it is particularly versatile. In the highly important propylene-ethylene block copolymer, the elastomer performance of the rubber component of the copolymerized part is demonstrated, and the impact resistance is improved without impairing the original excellent properties such as rigidity in the propylene polymer. However, it maintains high polymerization activity and stereoregularity, and does not cause sticking of the generated particles to the vessel wall, etc. That to reduce such as a gel or fish eye, it is an object to be solved by invention.
[0010]
[Means for solving the problems]
In order to solve the above problems, the present inventors use a Ziegler-based catalyst, and propylene (co) polymer by homopolymerizing propylene or copolymerizing propylene and other α-olefins such as ethylene in the previous stage. In the process for producing a propylene block copolymer by continuously gas phase copolymerizing propylene and other α-olefin such as ethylene in the subsequent stage in the presence of the (co) polymer, -Among the α-olefin block copolymers, especially for propylene-ethylene block copolymers that are highly versatile and important, the impact resistance is sufficiently improved, and the impact resistance and high rigidity are exceptionally excellent. Maintain a high level of polymerization activity and stereoregularity while maintaining a good balance, without causing the particles to stick to the walls of the vessel, etc. It aims to reduce eye and, for such a Ziegler catalyst and additives or raw material monomer ratio and polymerization conditions in a multistage polymerization meditating general thinking and retrieval, extensive investigations and experiments on them.
[0011]
When the copolymerization stage is set to two stages or more (the total polymerization process is three stages or more), the ratio of the rubber component in the whole polymer or the ethylene ratio in the rubber component can be easily controlled. As a gel killer, the generation of gels and fish eyes due to short path particles can be reduced, so that the present inventors use a plurality of electron donors (electron-donating compounds) at a specific quantitative ratio. In combination with multiple stages, the copolymerization process was set to two-stage polymerization, and various experimental studies were conducted by adding an electron donating compound to investigate the influence of the electron donor under various conditions.
As a result, even if the copolymerization stage is changed from one stage to two stages or more, if the copolymerization stage is two stages or more, the electron-donating compound is lost due to reaction or dissipation in the first-stage copolymerization tank, In some cases, the effect in the second-stage copolymerization tank may be insufficient. On the other hand, if the amount of the electron-donating compound added to the first-stage copolymerization tank is simply increased, the catalytic activity is seriously reduced. Turned out to be.
[0012]
Therefore, based on this important recognition, further investigation is continued, and in the method for producing a propylene-ethylene block copolymer, the use of an electron donating compound (gel killer) when the copolymerization step is two or more steps. In the process of seeking a reasonable embodiment of the present invention, it was possible to obtain groundbreaking new knowledge about the use manner of the electron donating compound.
That is, using a Ziegler catalyst, propylene is homopolymerized in the former stage or propylene and ethylene are copolymerized to produce a propylene (co) polymer, and then in the presence of the (co) polymer, propylene is continuously produced in the latter stage. In the gas phase copolymerization of ethylene and ethylene, an electron donor is selected as an additive, in particular, a special electron donor combination is adopted, and the polymerization reaction is made into a three-stage polymerization to form an electron donor (electron-donating compound). When used multiple times and combined in multiple stages at a specific quantitative ratio, the concentration of the electron-donating compound lost due to reaction or dissipation in the first-stage copolymerization tank (second-stage polymerization tank) Compared with the case where a large amount of electron donor is put in the first-stage copolymerization tank and is increased again in the first-stage copolymerization tank, the decrease in the catalytic activity is suppressed, and the generated particles adhere to the wall of the vessel. Promising to suppress sex The lead, even such further gel and fish eyes due to the short-path particles led to the perception that we do not generate.
[0013]
Specifically, in the course of transferring the polymer (powder) from the first-stage polymerization tank (reaction tank) to the second-stage polymerization tank (reaction tank) or the electron donor compound in the second-stage polymerization tank, organoaluminum as a catalyst component. The gel is reduced by adding it in the range of 0.1 to 2.0 mol per 1 mol of the compound, and the polymer (powder) is transferred from the second stage polymerization tank to the third stage polymerization tank (reaction tank) or in the second stage. By adding an electron donating compound to the three-stage polymerization tank in the range of 0.01 to 2.0 mol with respect to 1 mol of the organoaluminum compound, the inside of the third-stage polymerization tank is lowered due to the reaction and dissipation in the second-stage polymerization tank. Increases the electron-donating compound concentration of the catalyst, suppresses excessive decrease in catalytic activity and maintains high stereoregularity, while improving impact resistance, and adheres particles to each other and to the inner wall of the polymerization tank in the third stage polymerization tank Can improve, we found that it is also reducing the occurrence of gel or fish eye in the same time the molded article, thereby completing the present invention.
In addition, in the conventional method for producing a propylene-ethylene block copolymer, the stickiness of the produced polymer and the generation of a gel (also referred to as a bright spot because the surface of the molded body appears to partially shine). Although it is already known to use a so-called killer of an electron donor to suppress these occurrences, a killer is added to each step of multi-stage copolymerization, and a specific addition method or killer material is added. Employment is the first realization of the present invention.
[0014]
The feature of the present invention is that the electron-donating compound as an additive in the propylene block two-stage polymerization, which is well known as a so-called gel killer, is not used in the propylene block three-stage polymerization, but is studied closely. Based on the experiments, in order to simultaneously suppress the adhesion of particles and reduce the generation of gels while suppressing the decrease in catalytic activity, the polymerization reaction is made into a three-stage polymerization, and an electron donor (electron-donating compound) is added. It was used multiple times and combined with them in a specific quantitative ratio to form a new and unique configuration, and the overall action of each of these configurations resulted in the contents of the examples described later. As can be seen, the multi-stage copolymerization of the highly versatile and highly important propylene-ethylene block copolymer provides an exceptional balance of impact resistance and high rigidity. While maintaining high polymerization activity and stereoregularity, the impact resistance is improved and adhesion of the generated particles to each other and the vessel wall does not occur. It has been achieved to reduce.
[0015]
The present invention, which has been created as described above in detail and has special characteristics in configuration and function, is generally described as follows. (Inclusive of all invention groups, collectively referred to as “present invention”)
The invention in the following [1] is a basic invention, and [2] the following inventions are a group of inventions as embodiments in the basic invention.
[0016]
[1] Propylene-ethylene block copolymerization is carried out by successively conducting the following first-stage polymerization, second-stage polymerization and third-stage polymerization in the presence of a catalyst comprising the following components (A) and (B). In the method for producing a coalescence, the following component (C) is added in the middle of the transfer of the polymer from the first stage polymerization tank to the second stage polymerization tank, or 0.1 mol to 1 mol of the following component (B) in the second stage polymerization tank. 2.0 mol is added, and the following component (C) is added in the middle of the transfer of the polymer from the second-stage polymerization tank to the third-stage polymerization tank, or 0.01-3 to 1 mol of the following component (B) in the third-stage polymerization tank. The manufacturing method of the propylene-ethylene block copolymer characterized by adding 2.0 mol.
(A) Solid catalyst component containing titanium, magnesium and halogen as essential components and an electron donor as an optional component
(B) Organoaluminum compound
(C) electron donating compound
(1) First stage polymerization
A process for producing a crystalline propylene polymer by polymerizing propylene alone or a mixture of propylene and ethylene in one or more polymerization vessels in liquid propylene, in an inert solvent or in a gas phase.
(2) Second stage polymerization
A process for producing a rubbery copolymer by polymerizing a mixture of propylene and ethylene in a gas phase.
(3) Third stage polymerization
A process for producing a rubbery copolymer by polymerizing a mixture of propylene and ethylene in a gas phase.
[2] The component (C) added during the transfer of the polymer from the first stage polymerization tank to the second stage polymerization tank or the component (C) added to the second stage polymerization tank is an electron donating compound containing an oxygen atom. The propylene according to [1], wherein the component (C) added during the transfer of the polymer from the polymerization tank to the third stage polymerization tank or the component (C) added to the third stage polymerization tank is an electron donating compound having active hydrogen -Manufacturing method of ethylene block copolymer.
[3] To the second stage polymerization tank, component (C) is added during the transfer of the polymer from the first stage polymerization tank to the second stage polymerization tank, and to the third stage polymerization tank, the second stage polymerization tank is added. The production of the propylene-ethylene block copolymer in [1] or [2], wherein the component (C) is added to the third stage polymerization tank during the transfer of the polymer to the third stage polymerization tank Method.
[4] In the first-stage polymerization, a propylene homopolymer or a propylene-ethylene copolymer having an ethylene content of 7% by weight or less is formed in an amount corresponding to 5 to 90% by weight of the total polymerization amount. The method for producing a propylene-ethylene block copolymer in [1] to [3].
[5] The polymerization amount in the second stage polymerization is formed in an amount corresponding to 1 to 90% by weight of the total polymerization amount, and the polymerization amount in the third stage polymerization corresponds to 1 to 50% by weight of the total polymerization amount. The method for producing a propylene-ethylene block copolymer according to [1] to [4], wherein the propylene-ethylene block copolymer is formed in an amount of
[6] The propylene-ethylene block copolymer weight in [1] to [5], wherein the total polymerization amount in the second stage polymerization and the third stage polymerization is an amount exceeding 30% by weight of the total polymerization amount Manufacturing method of coalescence.
[7] In the second stage polymerization, the polymerization ratio (weight ratio) of propylene and ethylene is 70/30 to 30/70, and in the third stage polymerization, the polymerization ratio (weight ratio) of propylene and ethylene is 70/30. It is -0/100, The manufacturing method of the propylene-ethylene block copolymer in [1]-[6] characterized by the above-mentioned.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
In the following, in the method for producing a propylene-ethylene block copolymer by continuously performing the first stage polymerization, the second stage polymerization and the third stage polymerization, respectively, the embodiment in the present invention, the catalyst component and the electron donation The type of the organic compound (gel killer), the addition mode of the electron donating compound (gel killer), and the polymerization mode will be specifically described in detail.
[0018]
(1) About catalyst components
1. Ingredient (A)
The component (A) used in the present invention is a solid catalyst component for stereoregular polymerization of α-olefin, which contains titanium, magnesium and halogen as essential components and an electron donating compound as an optional component. “Contained as an essential component” means that it may contain other purposeful elements in addition to the listed three components, and each of these elements exists as an arbitrary purposeful compound. As well as the fact that these elements may exist as bonded to each other. In addition, component (A) may be preliminarily polymerized before being subjected to polymerization as required.
Solid components themselves containing titanium, magnesium and halogen are well known. For example, they are typically described in JP-A-53-45688, 54-3894, etc., or in each of the aforementioned patent documents. in use. In the present invention, known solid catalyst components described in these are used, but each compound constituting the solid catalyst component will be briefly described.
[0019]
a. Magnesium compound
Examples of the magnesium compound used as a magnesium source in the present invention include metal magnesium, magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, magnesium oxide, magnesium hydroxide, and magnesium. Examples thereof include carboxylates.
Among these, Mg (OR such as magnesium dihalide and dialkoxymagnesium¹)_2-mX_m(Where R¹ Is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X is halogen, and m is 0 ≦ m ≦ 2. ) Is preferred.
[0020]
b. Titanium compound
As a titanium compound used as a titanium source, general formula Ti (OR²)_4-nX_n(Where R² Is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X is halogen, and n is 0 ≦ n ≦ 4. ) Is exemplified. As a specific example, TiCl₄, Ti (OC₂H₅)₂Cl₂, Ti (OC₂H₅)₃Cl, Ti (O-iC₃H₇) Cl₃, Ti (O-nC₄H₉) Cl₃, Ti (O-nC₄H₉)₂Cl₂, Ti (O-nC₄H₉)₃Cl, Ti (O—C₆H₅) Cl₃, Ti (O-iC₄H₉)₂Cl₂, Ti (OC₅H₁₁) Cl₃, Ti (OC₆H₁₃) Cl₃, Ti (OC₂H₅)₄, Ti (O-nC₃H₇)₄, Ti (O-nC₄H₉)₄, Ti (O-iC₄H₉)₄, Ti (O-nC₆H₁₃)₄ Etc.
[0021]
TiX '₄A molecular compound obtained by reacting an electron donor described later in (X ′ represents halogen) can also be used as a titanium source. Specific examples of such molecular compounds include TiCl.₄・ CH₃COC₂H₅TiCl₄・ CH₃CO₂C₂H₅TiCl₄・ C₆H₅NO₂TiCl₄・ CH₃COCl, TiCl₄・ C₆H₅COCl, TiCl₄・ C₆H₅CO₂C₂H₅TiCl₄・ ClCOC₂H₅TiCl₄・ C₄H₄O etc. are mentioned.
[0022]
In addition, TiCl₃(TiCl₄Including those reduced with hydrogen, those reduced with aluminum metal, or those reduced with an organometallic compound), TiBr₃, Ti (OC₂H₅) Cl₂TiCl₂It is also possible to use titanium compounds such as dicyclopentadienyl titanium dichloride and dicyclopentadienyl titanium trichloride.
[0023]
Among these titanium compounds, TiCl₄, Ti (OC₄H₉)₄, Ti (OC₂H₅) Cl₃Is more preferred, TiCl₄, Ti (OC₄H₉)₄Is more preferable.
[0024]
c. halogen
The halogen is usually supplied from the aforementioned magnesium and / or titanium halogen compounds, but other halogen sources such as Br₂, I₂, ICl₃Halogen such as, interhalogen compounds, AlCl₃, AlBr₃, AlI₃  Aluminum halide such as BCl₃, BBr₃, BI₃ Boron halides such as SiCl₄ Silicon halides such as PCl₃, PCl_Five Phosphorus halides such as WCl₆ Tungsten halides such as MoCl_FiveIt is also possible to supply from a known halogenating agent such as a molybdenum halide. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.
[0025]
d. Arbitrary compound (electron donor)
In the component (A) of the present invention, an electron donor (electron-donating compound) can be used as an optional component (internal donor) as necessary.
Optional electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and acid halides. Examples thereof include oxygen-containing electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonate esters.
[0026]
Specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, hexanol, octanol, phenylethyl alcohol and isopropylbenzyl alcohol, and (b) alkyl groups such as phenol, xylenol and naphthol. Phenols having 6 to 25 carbon atoms, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, (d) carbon such as acetaldehyde, propionaldehyde, octyl aldehyde, etc. 2 to 15 aldehydes, (fo) methyl formate, ethyl acetate, cellosolve acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, cyclohexyl benzoate , Phenyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, monoester of organic acid, or diethyl phthalate Dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl diisopropyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, dibutyl diisopropyl tartrate, dimethyl norbornanedienyl-1,2-dicarboxylate, 1,1 -Organic polyvalent carboxylic acid esters such as diethyl cyclobutanedicarboxylate, organic acid esters having 2 to 20 carbon atoms, (f) Silicate esters such as ethyl silicate and butyl silicate, or inorganic acid esters such as ethylene carbonate (To) acetyl chloride, benzoyl chloride, toluic acid chloride, phthaloyl chloride and other acid halides having 2 to 15 carbon atoms, (thi) methyl ether, ethyl ether, butyl ether, amyl ether, tetrahydrofuran, diphenyl ether, 2,2 -Dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl -1,3-dimethoxypropane, 2,2-dimethyl C2-C20 ethers such as ru-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane, acids such as (li) acetamide, benzoic acid amide, toluic acid amide Amides, amines such as (nu) methylamine, ethylamine, triethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, tetramethylethylenediamine, nitriles such as (l) acetonitrile, benzonitrile, ) Alkoxy ester compounds such as ethyl 2- (ethoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, (wa) ethyl 2-benzoylbenzoate, 2- (4 '-Methylbenzoyl) ethyl benzoate, 2- Ketoester compounds such as ethyl benzoyl-4,5-dimethylbenzoate, (f) sulfonic acid esters such as methyl benzenesulfonate, ethyl benzenesulfonate, ethyl p-toluenesulfonate, and p-toluenesulfonate-n-butyl Kind, (yo) R³ _pR⁴ _q Si (OR⁵)_r (OR⁶)_4-pqr  (Where R³ And R⁴ Are each a branched, cyclic or straight chain hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, and R⁵ Is a hydrocarbon group having 1 to 10 carbon atoms and R⁶ Is a hydrocarbon group having 1 to 4 carbon atoms, p, q, and r are 1 ≦ p ≦ 2, 0 ≦ q ≦ 1, 0 ≦ r ≦ 2, and p + q + r ≦ 3, respectively. And the like, and the like.
[0027]
Two or more kinds of these electron donors can be used. Among these, organic acid ester compounds, acid halide compounds and ether compounds, and organic alkoxysilicon compounds are preferable, and phthalic acid diester compounds, acetic acid cellosolve ester compounds, phthalic acid dihalide compounds, diether compounds, and alkoxy are particularly preferable. It is an alkoxy silicon compound having 2 to 3 groups.
[0028]
2. Ingredient (B)
Component (B) used in the present invention is an organoaluminum compound, and R⁷ _3-s AlX_s Or R⁸ _3-t Al (OR⁹ )_t(Where R⁷ And R⁸Is a C1-C20 hydrocarbon group or hydrogen atom, R⁹ Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and s and t are 0 ≦ s <3 and 0 <t <3, respectively. ) Or alumoxanes.
[0029]
Specifically, (I) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride, Alkylaluminum halides such as ethylaluminum sesquichloride and ethylaluminum dichloride, (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, (d) alkylaluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide, (e) Methylalumoxane, butylalumoxane, methylisobutylalmo Alumoxanes, such as acid, and the like.
[0030]
These organoaluminum compounds (a) to (e) can be used in plural kinds. For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum monochloride And a combination of triisobutylaluminum and methylalumoxane.
[0031]
The ratio of the organoaluminum compound component of component (B) to the titanium component in the solid catalyst component of component (A) is generally Al / Ti = 1 to 1000 mol / mol, preferably Al / Ti = It is used at a rate of 10 to 500 mol / mol.
[0032]
3. Optional component (electron donor)
In the polymerization catalyst of the present invention, in addition to the components (A) and (B), an electron donor (electron donating compound) can be used as an optional component (external donor) as required.
Examples of such an electron donating compound include those equivalent to the electron donor described in detail in paragraphs 0025 to 0027, which can be used as an optional component in component (A). When such an electron donating compound is used, it may be the same as or different from the compound in component (A).
[0033]
Preferred electron donating compounds are diethers, inorganic acid esters, organic acid esters, organic acid halides and organic silicon compounds, and particularly preferred are inorganic and organic silicate esters and diethers.
Preferred inorganic and organic silicate esters are R¹⁰ _u R^{1 1} _vSi (OR^{1 2} )_{Four- u - v}(However, R^{1 0} Is a branched C3-C20, preferably C4-10 aliphatic hydrocarbon group, or C5-C20, preferably C6-10 cyclic aliphatic hydrocarbon group, R¹¹ Is a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, R¹² Represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, u represents 0 ≦ u ≦ 3, v represents 0 ≦ v ≦ 3, and u + v ≦ 3. Inorganic and organic silicon compounds. In the general formula R¹⁰ Is preferably branched from a carbon atom adjacent to the silicon atom. The diethers are preferably 2,2-disubstituted 1,3-diethers.
[0034]
4). Ingredient (C)
The electron donating compound (killer compound) added to the copolymerization stage, that is, the second stage polymerization and the third stage polymerization, which is characterized in the present invention, is usually an organic compound containing oxygen, nitrogen, phosphorus or sulfur. A compound is used. This electron donating compound is used as a killer compound in order to suppress the stickiness of the produced polymer and the generation of gels and fish eyes in the molded product.
[0035]
Specifically, alcohols, phenols, ketones, aldehydes, acetals, organic acids, acid anhydrides, acid halides, esters, ethers, amines, amides, nitriles, phosphines, Examples thereof include phosphyllamides, thioethers, thioesters, and organosilicon compounds containing a Si—O—C bond.
[0036]
More specifically, the following can be mentioned.
a. Alcohol
Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, dodecanol, octadecyl Alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, 2,2-dimethyl-1,3-propanediol, 2,2-diisopropyl-1,3-propane Diol, 2,2-diisobutyl-1,3-propanediol, 2-isopropyl-2-isobutyl-1,3-propa Diol, 2-isopropyl-2-s-butyl-1,3-propanediol, 2-t-butyl-2-methyl-1,3-propanediol, 2-t-butyl-2-isopropyl-1,3- 1 to 20 carbon atoms such as propanediol, 2,2-dicyclopentyl-1,3-propanediol, 2,2-dicyclohexyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol Alcohol etc. can be illustrated.
[0037]
b. Phenols
Examples thereof include phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol.
[0038]
c. Ketones
Examples thereof include ketones having 1 to 20 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone.
[0039]
d. Aldehydes
Examples thereof include aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.
[0040]
e. Acetals
Examples include acetals having 3 to 24 carbon atoms such as dimethyldimethoxymethane, 1,1-dimethoxycyclohexane, and 1,1-dimethoxycyclopentane.
[0041]
f. Organic acids
1 to 20 carbon atoms which may have two or more carboxyl groups such as formic acid, acetic acid, propionic acid, valeric acid, caprylic acid, pivalic acid, acrylic acid, methacrylic acid, monochloroacetic acid, benzoic acid, maleic acid and phthalic acid Examples of the carboxylic acid are:
[0042]
g. Acid anhydrides
Examples thereof include acid anhydrides derived from the above organic acids, including intramolecular condensates and heteromolecular condensates.
[0043]
h. Acid halides
Examples thereof include acid halides in which the hydroxyl group of the organic acid is substituted with a chlorine atom, a bromine atom, or an iodine atom.
[0044]
i. Esters
Methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, methyl methacrylate, dimethyl maleate, Esters derived from the above alcohols and acids such as methyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, methyl carbonate, ethyl carbonate, etc. Can be illustrated.
[0045]
j. Ethers
Dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl-t-butyl ether, tetrahydrofuran, anisole, vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, 1,1-dimethoxyethane, o-dimethoxybenzene, 2, 2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxy Propane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3- Dimethoxypropane, 2,2-dicyclopen 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, , 2-diisopropyl-1,3-diethoxypropane and the like ethers derived from the alcohol or phenol.
[0046]
k. Amines
Examples thereof include amines having 1 to 21 carbon atoms such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine.
[0047]
l. Amides
Examples thereof include amides derived from the organic acids and amines such as acetic acid amide, benzoic acid amide, and toluic acid amide.
[0048]
m. Nitriles
Examples thereof include nitriles having 2 to 10 carbon atoms such as acetonitrile, benzonitrile and tolunitrile.
[0049]
n. Phosphines
Examples include phosphines such as trimethylphosphine, triethylphosphine, and triphenylphosphine.
[0050]
o. Phosphyllamides
Illustrative are phosphyllamides such as hexamethylphosphyltriamide.
[0051]
p. Thioethers
Examples thereof include thioethers in which the oxygen atom of the ether is substituted with a sulfur atom.
[0052]
q. Thioesters
Examples thereof include thioesters in which the oxygen atom of the ester is substituted with a sulfur atom.
[0053]
r. Organosilicon compound containing Si-O-C bond
Tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxylane, trimethylethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, phenyltri Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chloro Triethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltria Examples thereof include organosilicon compounds such as riloxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, and dimethyltetraethoxydisiloxane.
[0054]
Of these, alcohols, ketones, and amines are preferable, and methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methylamine, and ethylamine are particularly preferable.
[0055]
These electron donating compounds may be used in combination of two or more as required. Moreover, you may add another compound to each polymerization tank, respectively. In particular, oxygen-containing electron-donating compounds having a large gel-reducing effect, such as alcohols, phenols, ketones, organic acid esters, and organic alkoxysilicones, are transferred from the first stage polymerization tank to the second stage polymerization tank. A compound having active hydrogen, for example, alcohol, which is supplied during the transfer of the polymer or into the second stage polymerization tank, has a lower rate of activity reduction than the added amount, and has an effect in suppressing powder stickiness accompanying the increase in rubber It is preferable to supply amines and amines having active hydrogen to the third stage polymerization tank during the transfer of the polymer from the second stage polymerization tank to the third stage polymerization tank.
Here, an electron-donating compound containing oxygen, which has a large gel reduction effect, is supplied during the transfer of the polymer from the first-stage polymerization tank to the second-stage polymerization tank or to the second-stage polymerization tank. A compound having active hydrogen that has a low rate and has an effect in suppressing the stickiness of the powder accompanying the increase in rubber is being transferred to the second stage polymerization tank in the middle of transferring the polymer from the second stage polymerization tank to the second stage polymerization tank. It is one of the characteristics of the present invention that the supply is preferable.
When such a specific electron donating compound is combined, the generation of gel and stickiness of the generated particles (powder) can be efficiently suppressed in combination with the setting of multistage copolymerization.
[0056]
(2) About polymerization process
1. Basic features of the polymerization process of the present invention
The polymerization process of the present invention forms a composite structure with a killer compound addition method, a specific combination of killer compounds, or the like as a constituent element. As described above, when the copolymerization stage is set to two stages or more (the total polymerization process is three stages or more), it is easy to control the ratio of the rubber component in the whole polymer or the ethylene ratio in the rubber component, and thereby the optimum elastomer. In the present invention, the electron donor suppresses the stickiness of the particles at each stage, and further, as a so-called gel killer, can reduce the generation of gels and fish eyes due to short pass particles. Has set the copolymerization process to two-stage polymerization.
That is, using a Ziegler catalyst, propylene is homopolymerized in the former stage or propylene and ethylene are copolymerized to produce a propylene (co) polymer, and then in the presence of the (co) polymer, propylene is continuously produced in the latter stage. When ethylene and ethylene are vapor-phase copolymerized, the polymerization reaction is a three-stage polymerization, and an electron donor (electron-donating compound; killer compound) is used multiple times, and they are combined in multiple stages at a specific quantitative ratio. The concentration of the electron-donating compound lost due to reaction or dissipation in the first-stage copolymerization tank (second-stage polymerization tank) is increased again in the second-stage copolymerization tank, and the decrease in catalyst activity is suppressed. Therefore, it has a positive effect on the suppression of the adhesion of the produced particles to the vessel wall, and further, gels and fish eyes due to short path particles are not produced.
[0057]
2. First stage polymerization
In the first stage polymerization, propylene alone or a mixture of propylene and ethylene is used in the presence of the catalyst component (A), component (B) and, if necessary, an electron donating compound as an internal or external donor. This is a step of producing a crystalline propylene polymer by polymerization in the above polymerization tank.
In this first stage polymerization, a propylene homopolymer or a propylene-ethylene copolymer having an ethylene content of 7% by weight or less is formed in an amount corresponding to 5 to 90% by weight of the total polymerization amount. When the ethylene content in the propylene-ethylene polymer exceeds 7% by weight in the first stage polymerization, the bulk density of the final copolymer is lowered, the amount of by-product of the low crystalline polymer is greatly increased, and the rigidity is increased. descend. Moreover, if the polymerization ratio is less than the lower limit of the above range, the amount of by-product of the low crystalline polymer is also increased.
The polymerization temperature in the first stage polymerization is 30 to 130 ° C, preferably about 50 to 100 ° C, and the polymerization pressure is usually in the range of 0.1 to 5 MPaG. In the first stage polymerization, it is preferable to control the MFR using a molecular weight regulator such as hydrogen to enhance the fluidity at the time of melting of the final copolymer.
[0058]
3. Second stage polymerization
The second stage polymerization is a process for producing a rubber-like polymer by polymerizing a mixture of propylene and ethylene in a gas phase in the presence of a catalyst equivalent to the catalyst used in the first stage polymerization. In this second stage polymerization, a rubber having a propylene / ethylene polymerization ratio (weight ratio) of 90/10 to 10/90, preferably 80/20 to 20/80, more preferably 70/30 to 30/70. -Like polymer (rubber-like component; EPR) is produced. The polymerization amount in this step is 90 to 1% by weight of the total polymerization amount, preferably 50 to 2% by weight, more preferably 35 to 2% by weight.
In the second stage polymerization, another comonomer may coexist. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene can be used.
The polymerization temperature of the second stage polymerization is 30 to 110 ° C, preferably about 50 to 90 ° C. The polymerization pressure is usually in the range of 0.1 to 5 MPaG. When moving from the first stage polymerization to the second stage polymerization, it is preferable to purge the propylene gas or propylene-ethylene mixed gas and hydrogen gas and move to the next step. In the second stage polymerization, a molecular weight regulator such as hydrogen gas may or may not be used depending on the purpose.
[0059]
4). Third stage polymerization
In the third-stage polymerization, as in the second-stage polymerization, a mixture of propylene and ethylene is polymerized in a gas phase in the presence of a catalyst equivalent to the catalyst used in the first-stage polymerization, and a rubbery heavy polymer is obtained. This is a process for producing a coalescence (rubber-like component; EPR). In this third-stage polymerization, propylene / ethylene having a polymerization ratio (weight ratio) of 90/10 to 0/100, preferably 80/20 to 0/100, more preferably 70/30 to 0/100. A rubbery polymer is produced. The polymerization amount in this step is 50 to 1% by weight of the total polymerization amount, preferably 35 to 2% by weight, and more preferably 20 to 3% by weight.
In the third stage polymerization, another comonomer may coexist. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene can be used.
The polymerization temperature of the third stage polymerization is 30 to 110 ° C, preferably about 50 to 90 ° C. The polymerization pressure is usually in the range of 0.1 to 5 MPaG. Even in the third stage polymerization, a molecular weight modifier such as hydrogen gas may or may not be used depending on the purpose.
In the present invention, if polymerization is carried out such that the total amount of polymerization in the second and third stages exceeds 30% by weight, it is particularly advantageous in achieving improvement in impact strength.
The polymer thus obtained by multistage polymerization becomes a uniform mixture of the polymer or copolymer produced in each stage, but is generally referred to as a propylene-ethylene block copolymer.
[0060]
5). Polymerization mode
The process for producing a copolymer according to the present invention is carried out in a continuous manner. The first-stage polymerization is a bulk polymerization method in which polymerization is performed using the monomer propylene itself as a medium, a slurry polymerization method in which polymerization is performed using an inert solvent as a medium, or polymerization in a gaseous monomer without using a medium. It is carried out by any of the gas phase polymerization methods.
The second stage polymerization and the third stage polymerization are carried out by a gas phase polymerization method. In the case of slurry polymerization or solution polymerization, a rubbery component is eluted, and costs such as recovery of a solvent and drying of a produced polymer are required. Therefore, a gas phase polymerization method is preferable.
A preferable polymerization mode of the gas phase polymerization method is, for example, a method in which the produced polymer particles are fluidized with a monomer stream to form a fluidized bed, or a method in which the produced polymer particles are agitated in a reaction vessel with an agitator.
[0061]
(3) About addition method of component (C)
1. Basic features
In the present invention, the specific use mode of the electron donating compound (killer compound) of the component (C) is the basis of the invention, and among the use modes, the addition method is most characteristic.
Specifically, first, component (C) is added during the transfer of the polymer from the first stage polymerization to the second stage polymerization or into the second stage polymerization tank, and the polymer from the second stage polymerization to the third stage polymerization is added. It is characterized in that it is added in the middle of the transfer or to the third stage polymerization tank.
[0062]
2. Addition mode
As a method of adding the component (C) during the transfer of the polymer from the first stage polymerization to the second stage polymerization, it is added to the polymer transfer pipe from the first stage polymerization tank to the second stage polymerization tank, or the first There is a method in which a separate reaction tank is provided between the stage polymerization tank and the second stage polymerization tank and added thereto. In this case, in addition to newly providing the reaction tank, it is also possible to use an existing tank in the middle of the transfer flow path such as a degassing drum for purging the monomer and hydrogen in the first stage polymerization.
As a method of adding the component (C) to the second-stage polymerization tank, the second-stage polymerization tank is provided with a dedicated supply port, or is added to the circulating monomer, or a raw material such as hydrogen as a molecular weight regulator. There are methods such as allowing them to accompany gas.
[0063]
As a method of adding the component (C) during the transfer of the polymer from the second-stage polymerization to the third-stage polymerization, it is added to the polymer transfer pipe from the second-stage polymerization tank to the third-stage polymerization tank, or the second There is a method in which a separate reaction tank is provided between the stage polymerization tank and the third stage polymerization tank and added thereto. In this case, in addition to newly providing the reaction tank, it is also possible to use an existing tank in the middle of the transfer flow path such as a degassing drum for purging the second-stage polymerization monomer or hydrogen.
As a method of adding the component (C) to the third-stage polymerization tank, the third-stage polymerization tank is added by providing a dedicated supply port, or is accompanied by a circulating monomer, or is accompanied by a raw material gas such as hydrogen. There are methods.
[0064]
The component (C) may be added from only one of the above polymerization tank addition positions at the time of addition to each polymerization tank, or may be divided and supplied to two or more addition positions. Moreover, you may add a different kind of electron-donating compound about the addition to each polymerization tank.
Component (C) may be added as it is, or may be added after being diluted with an inert hydrocarbon solvent such as hexane or heptane, an inert gas such as nitrogen, or a monomer.
In order to reduce the gel, it is preferable to deactivate the short-pass particles efficiently. Therefore, it is more preferable to add during the transfer of the polymer from the first stage polymerization to the second stage polymerization, which has good contact efficiency with the polymer. It is preferable to add to the stage polymerization tank.
[0065]
3. Addition amount
The amount of the component (C) added during the transfer of the polymer from the first stage polymerization to the second stage polymerization or in the second stage polymerization tank is 0.1 to 1 mol of the component (B) supplied to the polymerization system. The range is 2.0 mol, and preferably 0.2 to 1.7 mol.
The amount of the component (C) added during the transfer of the polymer from the second stage polymerization to the third stage polymerization or into the third stage polymerization tank is 0.01 to 1 mol of the component (B) supplied to the polymerization system. The range is 2.0 mol, preferably 0.02 to 0.5 mol, and more preferably 0.05 to 0.3 mol.
When the component (C) is less than these ranges, there is no effect of improving particle adhesion, and when the component (C) is more, the activity of the catalyst is significantly reduced.
[0066]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0067]
The measuring method and measuring apparatus for each physical property value in the present invention are shown below.
1. Rubbery component content (EPR content)
The rubber-like component content (EPR content) was obtained by subjecting a sample collected from each polymerization tank to the following conditions by the temperature rising elution fractionation method using “CFC-T-102L” temperature rise elution fractionation apparatus manufactured by Mitsubishi Chemical. It was measured. In addition, EPR was made into the elution component below 40 degreeC. [CFC measurement conditions]
Sample concentration 2.0 mg / mL
Solvent (flow rate) Orthodichlorobenzene (1.0 mL / min)
Column size 0.46mmφ × 15cm
Filler glass (0.1mmφ)
Temperature drop rate 1.0 ° C / min
Temperature increase rate 1.0 ℃ / min
Injection volume 0.5mL
GPC column TSK GMHXL-HT (8mmφ x 30cm) x 3
GPC measurement temperature 135 ℃
Detector IR (MIRAN 1A)
Measurement wavelength 3.42 μm
Molecular weight conversion PP conversion
2. MFR
MFR is a value measured at a temperature of 230 ° C. under a load of 21.18 N in accordance with JIS-K-7210-1995.
3. Heat fall seconds
Heat drop seconds is 100cm³After heating the powder sample in an oven at 110 ° C. for 1 hour, a metal funnel (diameter 1 cm, angle 45 °) was placed on a powder tester (model number PT-E) manufactured by Hosokawa Micron Co., Ltd. and dropped while vibrating the metal funnel. The time (seconds) required for the measurement was measured.
The heat drop seconds represent a measure of powder fluidity, and the larger the value, the worse the fluidity and the greater the adhesion of the produced polymer particles.
4). DuPont impact strength
To 100 parts by weight of propylene / ethylene block copolymer powder, 0.03 parts by weight of calcium stearate and 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) were added, mixed with a Henschel mixer, and then melt-kneaded at 250 ° C. Branulated particles were obtained.
Next, with an injection molding machine, the resin temperature is 210 ° C. and the injection pressure is 400 kg / cm.²Then, a test piece of 80 mm × 80 mm × 2 mm was prepared at a mold temperature of 60 ° C., and this test piece was measured at −20 ° C. according to JIS K7211, using an impact tester manufactured by Toyo Seiki Co., Ltd. .
5). Gel amount
Using a heat press molding machine, pellets granulated by the method described in the method for measuring DuPont impact strength were used to obtain a film sample cut into 40 mm × 40 mm from an 80-100 μm thick film using an image analyzer device. Image processing, gel number measurement, film 100cm²The number of gels per hit was determined.
6). Ethylene content in polymer
It calculated | required from the infrared absorption spectrum of the film obtained by press-molding a polymer.
[0068]
Example-1
1. Production of solid catalyst component (A)
Mg (OEt) is added to a 100L autoclave equipped with a jacket for heating and cooling, a stirrer, and a baffle.₂Charge 20 mol, then Ti (OBu)₄Mg (OEt)₂ Ti (OBu) against magnesium in₄/Mg=0.45 (molar ratio) was charged, and the temperature was increased while stirring at 165 rpm. After reacting at 135 ° C. for 2.0 hours, the temperature was lowered to 125 ° C., and MeSi (OPh)₃ A toluene solution of Mg (OEt)₂ MeSi (OPh) for magnesium₃/Mg=0.67 (molar ratio). After completion of the addition, the reaction was carried out at the same temperature for 4 hours. After completion of the reaction, the temperature was lowered to 25 ° C., and Ti (OBu)₄ And Si (OEt)₄ Mg (OEt)₂ Ti (OBu) against magnesium in₄/Mg=0.15 (molar ratio), Si (OEt)₄/Mg=0.05 (molar ratio) was added to obtain a slurry of the contact product (a *).
Next, after being diluted with toluene so that [Mg] = 0.53 mol / L · toluene, the mixture was cooled to −10 ° C. while stirring at 165 rpm, and diethyl phthalate was converted into Mg (OEt).₂ It added so that it might become diethyl phthalate / Mg = 0.10 (molar ratio) with respect to magnesium in. Subsequently, TiCl₄ Mg (OEt)₂TiCl for magnesium in_Four/Mg=4.0 (molar ratio) was added dropwise over 6.0 hours to obtain a uniform solution. At this time, the phenomenon that the viscosity of the liquid increased to become a gel did not occur.
The obtained uniform solution was heated to 15 ° C. at 20 ° C./Hr and held at that temperature for 1 hour. Next, the temperature was raised again to 50 ° C. at 20 ° C./Hr and held at 50 ° C. for 1 hour. Furthermore, the temperature was raised to 117 ° C. at 120 ° C./Hr, and the treatment was performed at the same temperature for 1 hour.
After completion of the treatment, heating / stirring was stopped, and the supernatant liquid was removed, followed by washing with toluene so that the residual liquid ratio = 1/55 to obtain a solid slurry.
Next, the amount of toluene in the obtained solid slurry was changed to TiCl.₄ Concentration = 1.5 mol / L · Toluene, adjusted to TiCl at 25 ° C.₄First prepared Mg (OEt)₂ TiCl_Four/Mg=5.0 (molar ratio) was added. The slurry was heated with stirring at 165 rpm and reacted at 117 ° C. for 1 hour.
After completion of the reaction, heating / stirring was stopped, the supernatant was removed, and the residue was washed with toluene to a residual liquid ratio = 1/150 to obtain (A *) toluene slurry.
A part of the solid slurry obtained here was transferred to a reaction tank having a three-way receding blade having an inner diameter of 660 mm and a straight body part of 770 mm, diluted with n-hexane, and the concentration of (A *) was 3 g / L. It was made to become. While stirring this slurry at 300 rpm, at 25 ° C., triethylaluminum was added so that triethylaluminum / (A *) = 3.44 mmol / g, and t-butylethyldimethoxysilane was further added to t-butyl. Ethyldimethoxysilane / (A *) = 1.44 mmol / g was added. After completion of the addition, the mixture was kept at 25 ° C. for 30 minutes with continuous stirring.
Next, propylene gas was fed to the liquid phase at a constant rate for 72 minutes for prepolymerization of the catalyst. After stopping the propylene gas feed, the slurry was washed with n-hexane by a sedimentation washing method to obtain a slurry of the solid catalyst component (A) with a residual liquid ratio = 1/12. The obtained solid catalyst component (A) contained 2.9 g of a propylene polymer per 1 g of the (A *) component.
[0069]
2. Propylene-ethylene block copolymer production
Two reactors of a gas phase fluidized bed type having a capacity of 1000 L are connected in series via a solid-liquid separator to one 200 L reactor with a stirrer, and propylene homopolymerization is carried out in the first reactor. In the following two reactors, propylene and ethylene were copolymerized by gas phase polymerization. In the first reaction tank, liquefied propylene, the above 1. 0.4 g / hr of the prepolymerized catalyst component obtained in (hereinafter referred to as catalyst solid amount excluding prepolymerized polymer), 7.3 g / hr of triethylaluminum, 2.2 g / hr of cyclohexylmethyldimethoxysilane and molecular weight Hydrogen was continuously supplied as a regulator so that the concentration in the propylene liquid was 0.4 mol%. The polymerization temperature was 70 ° C., the polymer slurry concentration in the reaction vessel was 20% by weight, and the average residence time was kept at 1 hour.
Unreacted propylene and hydrogen were removed from the slurry continuously extracted from the first tank, and the obtained polymer powder was continuously supplied to the second tank, and gas phase polymerization was performed while maintaining the temperature at 70 ° C. . The gas phase ethylene / monomer (ethylene + propylene) ratio = 0.33 weight ratio was maintained. The hydrogen concentration / monomer ratio in the gas phase was 0.7 mol%. Acetone as an electron donating compound was supplied to the circulating gas line of the second tank so as to be 0.096 mol / hr. The average residence time of this gas phase reactor was 2 hours.
The polymer powder continuously extracted from the second tank was supplied to the third tank, and gas phase polymerization was performed while maintaining the temperature at 70 ° C. The gas phase ethylene / monomer (ethylene + propylene) ratio = 0.33 weight ratio was maintained. The hydrogen concentration / monomer ratio in the gas phase was 0.7 mol%. Ethanol was supplied to the circulating gas line as an electron donating compound so as to be 0.019 mol / hr. The average residence time of this gas phase reactor was 1 hour.
The polymer powder continuously withdrawn from the third tank is separated from unreacted gas and then treated with water vapor-containing nitrogen gas to obtain a propylene-ethylene block copolymer at a production rate of 15.0 kg / hr. It was.
A small amount of polymer discharged from each polymerization tank was extracted and MFR was measured. Further, for the polymers in the second polymerization tank and the third polymerization tank, the EPR content measurement and the ethylene content in the polymer were measured. The EPR content of the polymer in the second polymerization tank was 31.0 wt%, and the ethylene content in the polymer was 16 The EPR content of the polymer in the third polymerization tank was 35.1 wt%, and the ethylene content in the polymer was 18.4 wt%. Moreover, since the polymerization ratio of each polymerization tank is 64.9 wt%, 29.1 wt%, and 6.0 wt%, respectively, the ethylene content in the components produced in the second and third polymerization tanks is respectively 53 wt% and 49 wt%. Table 1 shows the MFR and polymerization ratio of the polymer in each polymerization tank, the ethylene content in the components produced in the second and third polymerization tanks, the number of seconds of heat drop of the final sample, the DuPont impact strength, and the number of gels.
[0070]
Example-2
In the polymerization of Example 1, the polymerization conditions were adjusted so that a propylene-ethylene block copolymer having a copolymer resin structure shown in Table 1 was obtained. The results are shown in Table 1.
[0071]
  Comparative Example-A
  In the polymerization of Example 1, the electron donating compound added to the third tank is acetone, and the polymerization conditions are such that the addition amount of acetone and the copolymer resin structure of the propylene-ethylene block copolymer are as shown in Table 1. Adjusted. The results are shown in Table 1.
[0072]
Example-4
In the polymerization of Example 1, the active hydrogen-containing compound of the electron donating compound added to the third tank is ethylamine, and the addition amount of ethylamine and the copolymer resin structure of the propylene-ethylene block copolymer are as shown in Table 1. The polymerization conditions were adjusted so that The results are shown in Table 1.
[0073]
Comparative Examples-1 and 2
In the polymerization of Example 1, the polymerization conditions were adjusted so that the propylene-ethylene block copolymer having the copolymer structure shown in Table 1 was obtained under the condition that the electron donating compound was not supplied to the third tank. The results are shown in Table 1.
[0074]
Comparative Example-3
In the polymerization of Example 1, the electron donating compound added to the third tank is acetone, and the polymerization conditions are such that the addition amount of acetone and the copolymer resin structure of the propylene-ethylene block copolymer are as shown in Table 1. Adjusted. The results are shown in Table 1.
[0075]
Comparative Example-4
In the polymerization of Example 1, the electron donating compound added to the third tank is ethanol, and the polymerization conditions are such that the added amount of ethanol and the copolymer resin structure of the propylene-ethylene block copolymer are as shown in Table 1. Adjusted. The results are shown in Table 1.
[0076]
  Comparative Example-B
    1. Production of solid catalyst component (A)
  In a 5 liter reaction vessel equipped with a reflux condenser, 40 g of chip-shaped metal magnesium (purity 99.5%, average particle size 1.6 mm) and 1250 ml of n-hexane were placed in a nitrogen gas atmosphere at 68 ° C. After stirring for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65 ° C. to obtain preactivated metallic magnesium.
  To this metallic magnesium, 700 ml of n-butyl ether and 2.5 ml of n-butyl magnesium chloride in n-butyl ether (1.75 mol / L) were added, and the resulting suspension was kept at 55 ° C., and further to 250 ml of n-butyl ether. A solution in which 192.5 ml of n-butyl chloride was dissolved was added dropwise over 50 minutes. After reacting for 4 hours at 70 ° C. with stirring, the reaction solution was kept at 25 ° C.
  HC (OC₂ H₅ )₃ 278.5 ml was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, the reaction product solid was washed 6 times with 1500 ml each of n-hexane, dried under reduced pressure at room temperature for 1 hour, 19.0% magnesium and 28.9% chlorine. 158 g of magnesium-containing solid was collected.
  In a 1500 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 31.5 g of a magnesium-containing solid and 250 ml of n-heptane were placed in a nitrogen gas atmosphere to form a suspension, and 2,2 while stirring at room temperature. , 2-Trichloroethanol (100 ml, 0.02 mmol) and n-heptane (55 ml) were added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, washed 4 times with 500 ml each of n-hexane at room temperature, and further washed twice with 500 ml each of toluene to obtain a solid component.
  200 ml of toluene is added to the above solid components, and TiCl is further added.₄TiCl so that the volume ratio of / toluene is 3/2₄Was added and the temperature was raised to 90 ° C. While stirring, a mixed solution of 10 ml of di-n-butyl phthalate and 25 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance was filtered off at 90 ° C. and washed twice with 500 ml each of toluene at 90 ° C. In addition, new TiCl₄TiCl so that the volume ratio of / toluene is 3/2₄And stirred at 120 ° C. for 2 hours.
  The resulting solid material was filtered off at 110 ° C. and washed 7 times with 500 ml of n-hexane at room temperature. Thus, a solid catalyst component in which a titanium compound was supported on a magnesium compound was obtained. A part of the solid catalyst component was dried under a nitrogen atmosphere and subjected to elemental analysis. As a result, titanium was 1.6% by weight.
  After replacing the nitrogen container with an internal volume of 10 L with a stirrer, 6000 ml of n-hexane and an n-hexane solution containing 200 g of the solid catalyst component were added, and the contents were kept at 20 ° C. Subsequently, 70 g of triethylaluminum was added, and 400 g of propylene was supplied over 120 minutes while maintaining the system at 20 ° C. with stirring. After the supply of propylene was stopped, stirring was continued for another 20 minutes to complete the reaction. After allowing to stand for 20 minutes, the supernatant liquid is removed by a decantation method, 6000 ml of n-hexane is further added, the mixture is stirred at 25 ° C., and then it is allowed to settle and the supernatant liquid is removed by repeating the operation 5 times. A polymerization catalyst was obtained.
[0077]
2. Propylene-ethylene block copolymer production
Two reactors of a gas phase fluidized bed type having a capacity of 1000 L are connected in series via a solid-liquid separator to one 200 L reactor with a stirrer, and propylene homopolymerization is carried out in the first reactor. In the following two reactors, propylene and ethylene were copolymerized by gas phase polymerization. In the first reaction tank, liquefied propylene, the above 1. So that the concentration of the prepolymerized catalyst component 0.4 g / hr obtained in 1), triethylaluminum 7.3 g / hr, cyclohexylmethyldimethoxysilane 2.2 g / hr, and hydrogen as a molecular weight regulator is 0.8 mol% in the propylene liquid. Continuously fed. The polymerization temperature was 70 ° C., the polymer slurry concentration in the reaction vessel was 20% by weight, and the average residence time was kept at 1 hour.
Unreacted propylene and hydrogen were removed from the slurry continuously extracted from the first tank, and the obtained polymer powder was continuously supplied to the second tank, and gas phase polymerization was performed while maintaining the temperature at 70 ° C. . The gas phase ethylene / monomer (ethylene + propylene) ratio was kept at 0.15 weight ratio. The hydrogen concentration / monomer ratio in the gas phase was 0.7 mol%. Acetone as an electron donating compound was supplied during the transfer of powder from the first tank to the second tank so that the concentration became 0.032 mol / hr. The average residence time of this gas phase reactor was 2 hours.
The polymer powder continuously extracted from the second tank was supplied to the third tank, and gas phase polymerization was performed while maintaining the temperature at 70 ° C. The gas phase ethylene / monomer (ethylene + propylene) ratio = 0.33 weight ratio was maintained. The hydrogen concentration / monomer ratio in the gas phase was 0.7 mol%. Acetone as an electron donating compound was supplied to the circulation gas line so as to be 0.032 mol / hr. The average residence time of this gas phase reactor was 1 hour.
The polymer powder continuously withdrawn from the third tank is separated from unreacted gas and then treated with water vapor-containing nitrogen gas to obtain a propylene-ethylene block copolymer at a production rate of 15.0 kg / hr. It was.
A small amount of polymer discharged from each polymerization tank was extracted and MFR was measured. Furthermore, the EPR content measurement and the ethylene content measurement of the polymer in the second polymerization tank and the third polymerization tank were performed. The EPR content of the polymer in the second polymerization tank was 18.1 wt%, and the ethylene content in the polymer was 5 The EPR content of the polymer in the third polymerization tank was 30.4 wt%, and the ethylene content in the polymer was 12.1 wt%. Moreover, since the polymerization ratio of each polymerization tank is 69.6 wt%, 15.4 wt%, and 15.0 wt%, respectively, the ethylene content in the components produced in the second and third polymerization tanks is respectively 31 wt% and 49 wt%. Table 2 shows the MFR and the polymerization ratio of the polymer in each polymerization tank, the ethylene content in the components produced in the second and third polymerization tanks, the number of seconds of heat drop of the final sample, the DuPont impact strength, and the number of gels.
[0078]
  Comparative Example-C
  In the polymerization of Comparative Example B, the polymerization conditions were adjusted so that the amount of acetone added to the third tank and the resin structure of the propylene-ethylene block copolymer were as shown in Table 2. The results are shown in Table 2.
[0079]
  Examples-7-8
  In the polymerization of Comparative Example-B, the electron donating compound added to the third tank is ethanol, and the polymerization conditions are adjusted so that the amount of ethanol added and the resin structure of the propylene-ethylene copolymer are as shown in Table 2. did. The results are shown in Table 2.
[0080]
  Comparative Examples-5-6
  In the polymerization of Comparative Example-B, the polymerization conditions were adjusted so that a propylene-ethylene block copolymer having a copolymer structure shown in Table 2 was obtained under the condition that the electron donating compound was not supplied to the third tank. The results are shown in Table 2.
[0081]
  Comparative Example-7
  In the polymerization of Comparative Example-B, the electron donating compound added to the third tank is acetone, and the polymerization conditions are adjusted so that the addition amount of acetone and the resin structure of the propylene-ethylene copolymer are as shown in Table 2. did. The results are shown in Table 2.
[0082]
  Comparative Example-8
  In the polymerization of Comparative Example-B, the electron donating compound added to the third tank is ethanol, and the polymerization conditions are adjusted so that the amount of ethanol added and the resin structure of the propylene-ethylene copolymer are as shown in Table 2. did. The results are shown in Table 2.
[0083]
[Table 1]

[0084]
[Table 2]

[0085]
[Consideration of results of Examples and Comparative Examples]
By contrasting each of the above Examples and Comparative Examples, it is clearly shown in the present invention that the result of the heat drop seconds is very excellent and the adhesion (stickiness) of the produced polymer is extremely small. Thereby, it can be understood that the produced particles are hardly adhered to each other during the copolymerization reaction and to the reactor wall and the stirring device, and the productivity is improved.
In the present invention, good results are also shown in impact strength and gel generation.
Further, Comparative Examples 1, 2 and 5, 6 do not add the electron donating compound (component (C); killer compound) in the third reaction tank, and Comparative Example 2 does not add the electron donating compound in the second reaction tank. The addition amount of the compound exceeds 2.0 mol / mol-Al, and in Comparative Examples 3, 4 and 7, 8, the addition amount of the electron donating compound in the third reaction tank is less than 0.01 mol / mol-Al. Effectiveness of addition of electron donating compound in the present invention, in particular, 0.1 to 2.0 mol / mol-Al, which is the amount of addition in the second reaction tank, and the amount of addition in the third reaction tank. The effectiveness of each numerical limitation of 0.01 to 2.0 mol / mol-Al has been demonstrated.
[0086]
【The invention's effect】
According to the present invention, in a method for producing a block copolymer by copolymerizing a propylene polymer with ethylene using a Ziegler-based catalyst, the propylene polymer exhibits the elastomer performance due to the rubber component of the copolymer part. While maintaining high polymerization activity and stereoregularity while improving impact resistance without impairing the original excellent properties such as rigidity in the product, it does not cause mutual adhesion of generated particles and adhesion to the vessel wall Further, it is possible to sufficiently reduce gels and fish eyes caused by short path particles.
[Brief description of the drawings]
FIG. 1 is a flowchart for helping understanding of the technical contents of the present invention relating to a Ziegler catalyst.

Claims (5)

Propylene-ethylene block copolymer is produced by successively conducting the following first-stage polymerization, second-stage polymerization and third-stage polymerization in the presence of a catalyst comprising the following components (A) and (B). In the method of the above, the following component (C), which is an electron donating compound containing an oxygen atom, is transferred to the second stage polymerization tank in the course of transferring the polymer from the first stage polymerization tank to the second stage polymerization tank. B) An electron donating compound which is added in an amount of 0.1 to 2.0 mol per 1 mol and has active hydrogen in the middle of the transfer of the polymer from the second stage polymerization tank to the third stage polymerization tank or in the third stage polymerization tank The following component (C) is 0.05 to 2 with respect to 1 mol of the following component (B).
0 mol addition, The manufacturing method of the propylene-ethylene block copolymer characterized by the above-mentioned.
(A) Solid catalyst component containing titanium, magnesium and halogen as essential components and an electron donor as an optional component (B) Organoaluminum compound (C) Electron donating compound (1) First stage polymerization Propylene alone or propylene and ethylene Is polymerized in one or more polymerization tanks in liquid propylene, in an inert solvent or in a gas phase, and a propylene homopolymer or a propylene-ethylene copolymer having an ethylene content of 7% by weight or less is totally polymerized. (2) Second-stage polymerization in which the amount is equivalent to 5 to 90% by weight of the amount. A mixture of propylene and ethylene is polymerized in a gas phase to produce a rubbery copolymer having a total polymerization amount of 1 Step of producing in an amount corresponding to ˜90% by weight (3) Third-stage polymerization A mixture of propylene and ethylene is polymerized in a gas phase to form a rubbery copolymer Process of manufacturing in an amount corresponding to body 1 to 50% by weight of the total polymerization amount   The method for producing a propylene-ethylene block copolymer according to claim 1, wherein the component (C) is selected from alcohols, ketones and amines.   The component (C) is added to the second-stage polymerization tank during the transfer of the polymer from the first-stage polymerization tank to the second-stage polymerization tank, and the third-stage polymerization tank is transferred from the second-stage polymerization tank to the third-stage polymerization tank. The production of the propylene-ethylene block copolymer according to claim 1 or 2, wherein the component (C) is added during the transfer of the polymer to the stage polymerization tank or in the third stage polymerization tank. Method.   4. The propylene-ethylene according to claim 1, wherein the total polymerization amount in the second stage polymerization and the third stage polymerization is an amount exceeding 30% by weight of the total polymerization amount. 5. A method for producing a block copolymer.   In the second stage polymerization, the polymerization ratio (weight ratio) of propylene and ethylene is 70/30 to 30/70, and in the third stage polymerization, the polymerization ratio (weight ratio) of propylene and ethylene is 70/30 to 0 / The method for producing a propylene-ethylene block copolymer according to any one of claims 1 to 4, which is 100.

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