JPH0562885B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing an α-olefin block copolymer. More specifically, the propylene polymer obtained without deactivating the catalyst can be produced without adhesion between polymer particles or on the inner wall of the reactor, or without clogging pipes or consolidating in silos or hoppers in subsequent steps. , in the gas phase, other α other than propylene
- Polymerization of olefins, or propylene and other α-
By copolymerizing with olefin, propylene-α-
This invention relates to a method for producing olefin block copolymers with high reactor volumetric efficiency. [Prior art] Regarding the polymerization of α-olefins such as ethylene and propylene, the performance of polymerization catalysts has improved significantly in recent years, and the yield of polymer per catalyst component has dramatically increased. The amount of the reduced metal catalyst component to be removed is sufficiently small, making it possible to omit the catalyst removal step. On the other hand, the polymerization methods for these α-olefins include slurry polymerization in an inert hydrocarbon solvent, bulk polymerization in a liquefied monomer such as liquefied propylene, and gas phase polymerization in a gas phase. Although it is legal, it has become popular in recent years because gas phase polymerization does not use a solvent, so there is no need for solvent recovery or purification steps, and it is easy to recover monomers and dry the polymer product. It has started to attract attention. In the field of block copolymers of propylene and other α-olefins, propylene polymers are produced in the first stage, and other α-olefins are produced in the gas phase in the second stage.
Gas phase block copolymerization methods are known in which olefins are polymerized or propylene and other α-olefins are copolymerized. The gas-phase block copolymerization method has economical reasons as mentioned above, as well as product diversification, compared to methods in which the subsequent polymerization is carried out in an inert hydrocarbon solvent or in liquid propylene. There are also some advantages. However, the biggest drawback of the gas phase polymerization method is that the reaction rate is slow because the monomer concentration is relatively low, so the reactor volume must be large. In gas phase polymerization, the energy required to mix the polymer powder, for example, the power of the circulating gas blower in a fluidized bed, and the stirring power in a stirred tank, is determined by the volume of the gas phase reactor. This has a significant impact not only on construction costs but also on variable costs. For this reason, for example, JP-A-56-151713 discloses that when performing gas phase polymerization, the general formula R ³ _n Al (OR ⁴ ) _3-n (where R ³ is selected from an alkyl group, an aryl group, or a halogen atom) is used. At least one group or atom, R ⁴ represents an alkyl group or an aryl group, m is 0, 1 or 2
It is. ) method of adding aluminum alkoxide. Furthermore, Japanese Patent Application Laid-open No. 58-213012 proposes a method of adding a hydrocarbon having no ethylenic double bond in an amount equal to or more than the amount that forms the saturated vapor pressure of the above-mentioned aluminum alkoxide.
Efforts are being made to improve the polymerization rate. However, in this method, although the reaction rate can be improved by adding aluminum alkoxide, the stereoregularity is significantly reduced,
That is, an increase in amorphous polymer is observed. This not only makes it difficult to maintain normal operation due to the formation of lumps due to polymers adhering to each other in the reactor and adhesion to the walls of the polymerization tank, but also causes blockages in piping and the formation of polymers in silos and hoppers. There is a disadvantage that caking occurs and furthermore, the quality of the product is adversely affected. Furthermore, in order to uniformly add a small amount of aluminum alkoxide to the polypropylene polymer powder obtained in the first step, it is necessary to spray it using a large amount of diluent. For this reason, the soluble polymer is eluted into the diluent, resulting in the same adhesion trouble as described above.
Additionally, equipment measures such as a drying process to remove the diluent are required. [Problems to be Solved by the Invention] The present inventors have devised a method to significantly increase the gas phase polymerization rate without causing the above-mentioned sticking phenomenon caused by the increase in amorphous polymer or the introduction of a diluent. As a result of intensive studies, we found that the presence of a specific substance when polymerizing α-olefins other than propylene alone or propylene and other α-olefins in the gas phase greatly increased the reaction rate. The present inventors have discovered that a block copolymer having a significantly improved width and excellent fluidity without adhesion between polymer particles can be obtained, and has completed the present invention. [Means for Solving the Problems] The present invention involves polymerizing propylene alone or propylene and a small amount of other α-olefin in the presence of a catalyst consisting of a titanium-containing solid catalyst component and an organoaluminum compound, and then In a method of polymerizing an α-olefin other than propylene alone or propylene and an α-olefin other than propylene in a gas phase without deactivating the catalyst, the gas phase polymerization is performed in the first step by the weight of the propylene polymer obtained in the first step. This is a method for producing an α-olefin block copolymer, which is characterized in that it is carried out in the presence of siloxanes or polysiloxanes in a weight ratio of 1×10 ⁻⁶ to 0.1. The present invention will be explained in detail below. As the titanium-containing solid catalyst component in the present invention, known carrier-supported catalyst components containing solid magnesium compounds, titanium compounds, and halogens can also be used, but those containing titanium trichloride as the main component are preferably used. Ru. As the material containing titanium trichloride as a main component, conventionally known titanium trichloride can be used. For example, titanium trichloride is activated by ball milling; titanium trichloride is extracted with a solvent; β-type titanium trichloride is treated with a complexing agent such as ether;
Titanium trichloride is further treated with titanium tetrachloride to reduce the aluminum content to 0.15 or less in atomic ratio to titanium: In the presence of ethers, titanium tetrachloride is treated with an organic aluminum compound to form a liquid, which is further heated. titanium trichloride with an aluminum content of 0.15 or less in atomic ratio to titanium as a solid; and the like. Among these titanium trichlorides, particularly preferable ones have an aluminum content in the atomic ratio of aluminum to titanium of 0.15 or less, preferably 0.1 or less,
More preferably, it is 0.02 or less and contains a complexing agent. The organoaluminum compound used as a cocatalyst for the above titanium-containing solid catalyst component has the general formula
It is a compound represented by AlR ⁵ _o X _3-o (wherein R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and n represents a number of 3≧n>1.5). When the titanium-containing solid catalyst component is a carrier-supported catalyst component containing a solid magnesium compound, it is preferable to use AlR ⁵ ₃ or a mixture of AlR ⁵ ₃ and AlR ⁵ ₂ X. In addition, when the titanium-containing solid catalyst component is mainly composed of titanium trichloride, it is preferable to use AlR ⁵ ₂ Chloride is preferred. The titanium trichloride and organoaluminum compounds shown above are generally organoaluminum compounds/
The molar ratio of titanium trichloride is 1 to 30, preferably 2 to 30.
Used in a range of 15. In the present invention, the above catalyst may be used as it is, but as a pretreatment, a small amount of α is added to the catalyst consisting of titanium trichloride and an organoaluminum compound.
- Preferably the olefin is prepolymerized. The above method involves adding titanium trichloride and an organoaluminum compound to an inert solvent such as hexane, heptane, etc.
It is sufficient to supply an α-olefin such as putene-1 or a mixture thereof for polymerization. This pretreatment is generally referred to as prepolymerization, and known polymerization conditions can be used as they are. The polymerization temperature is preferably 30 to 70°C. The higher the polymerization rate per unit weight of titanium trichloride, the better;
It is generally in the range of TiCl ₃ . Furthermore, a molecular weight regulator such as hydrogen may be added during prepolymerization. Furthermore, it is preferable that the prepolymerization is carried out uniformly in a batch manner. This prepolymerization is effective in improving polymer properties such as bulk density. Furthermore, an additive for improving stereoregularity may be used as a third component in the catalyst made of titanium trichloride and an organoaluminum compound described above. For this purpose, various compounds including NOP or si, and hydrocarbon compounds are used. The amount of the third component added is generally per mole of titanium trichloride.
The amount ranges from 0.0001 to 5 mol, preferably from 0.001 to 1 mol. The main polymerization of propylene carried out in the first stage can be carried out by known slurry polymerization, gas phase polymerization, or the like. These polymerization methods may be either batchwise or continuous, and the reaction conditions are 1 to 100 atmospheres, preferably 5 to 40 atmospheres, and 50 to 90°C, preferably 60 to 80°C. In slurry polymerization, inert hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons used in normal olefin polymerization are used as polymerization catalysts, including normal hexane, normal heptane, cyclohexane, benzene, and toluene. is preferably used. Moreover, propylene itself can also be used as a solvent. Further, as a method for controlling the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen or diethylzinc can be appropriately added to the polymerization reaction. Although propylene alone may be polymerized in the first stage of the present invention, propylene and other α-olefins may be used in combination. Other α-olefins include α-olefins such as ethylene, butene-1, 4-methylpentene-1, etc.
- Olefin, etc., and the amount thereof is preferably small enough that the product does not lose its properties as a propylene polymer, for example, 10% by weight or less based on propylene. The propylene polymer obtained in this way is
Without deactivating the catalyst contained therein, a portion of the reaction medium is removed or transferred to a gas phase polymerizer without removal. That is, when the polymer is obtained by a solvent polymerization method, inert hydrocarbons and unreacted monomers are removed by evaporation using a centrifugal separator, hydrocyclone, or flash device. Furthermore, when liquid propylene itself is used as the medium, it can be sent as it is to a gas phase polymerization vessel without performing solid-liquid separation, in addition to similar known solid-liquid separation means. The most important features of the invention were obtained by the method described above. α-olefin other than propylene alone in propylene polymer, or propylene and other α-olefin
- By polymerizing olefin in the gas phase in the presence of siloxanes or polysiloxanes in the propylene polymer, extremely high polymerization activity can be obtained, and the powder properties of the polymer can be improved, especially in powder form. The purpose of this invention is to obtain a block polymer with improved bulk density and excellent fluidity without polymer stickiness. The polysiloxanes used in the present invention are polysiloxanes having a chain, cyclic or spiro structure, that is, the general formula: (In the formula, R ¹ and R ² are hydrogen atoms, carbon numbers 1 to 20
represents an alkyl group, aryl group, alkoxy group, aryloxy group or halogen. ) is a silicon compound having a repeating unit represented by the following formula, and those having a degree of polymerization of 2 to 3000 are selected. Specifically, for example, octamethyltrisiloxane, octaethylcyclotetrasiloxane [Si
(C ₂ H ₅ ) ₂ O] ₄ , dimethylpolysiloxane [Si
(CH ₃ ) ₂ O) _n , methylethylpolysiloxane [Si
Alkylsiloxane polymers such as (CH ₃ )(C ₂ H ₅ )O) _n ; hexaphenylcyclotrisiloxane [Si(C ₆ H ₅ ) ₂ O] ₃ , diphenylpolysiloxane [Si
Arylsiloxane polymers such as (C ₆ H ₅ ) ₂ O] _n , diphenylhexamethyltetrasiloxane (CH ₃ ) ₃
Alkylarylsiloxane polymers such as SiO [Si(C ₆ H ₅ ) ₂ O] ₂ Si(CH ₃ ) ₃ , methylphenylpolysiloxane [Si(CH ₃ )(C ₆ H ₅ )O] _n ; 1, Haloalkylsiloxanes such as 7-dichlorooctamethyltetrasiloxane (CH ₃ ) ₂ ClSiO [Si(CH ₃ ) ₂ O] ₂ Si(CH ₂ ) ₂ Cl; dimethoxypolysiloxane [Si(OCH ₃ ) ₂ ] _n , Examples include alkoxysiloxane polymers such as ethoxypolysiloxane [Si(CO ₂ H ₅ ) ₂ ] _n ; organic polysiloxanes such as diphenoxypolysiloxane polymers. Here, m represents a number from 2 to 3000. Furthermore, as the polysiloxane of the present invention, compounds generally called silicone oils can also be used, and commercially available silicone oils with a viscosity of 0.5 to 2 x 10 ⁶ centistokes and mixtures thereof are preferably used. Specifically, Shin-Etsu Silicone KF50, KF54, KF69, KF96, KF99 (product name) from Shin-Etsu Chemical Co., Ltd.
etc. Examples of siloxanes include hexamethyldisiloxane. Siloxanes or polysiloxanes (hereinafter referred to as polysiloxanes) are added after the first step of propylene polymerization is completed, but these polysiloxanes do not have any adverse effect on the first step of propylene polymerization. Therefore, there is no problem in adding it to the polymerization vessel in the previous stage from the beginning. When adding to the first-stage polymerization vessel, for example, in the middle of polymerization in case of batch polymerization, or in the middle of polymerization in case of batch-type polymerization, or in the first-stage propylene polymerization vessel if the first-stage propylene polymerization is carried out in multiple tanks. It does not matter whether it is supplied to either tank. When adding after the completion of the propylene polymerization in the first stage, it may be added before or after separating the solvent or propylene monomer from the propylene polymer. Any method can be used for adding the polysiloxanes. For example, when adding to the first-stage polymerization vessel, the polysiloxane can be added alone, but it can also be supplied together with a solvent, propylene, or other α-olefin. Moreover, it can also be supplied mixed with the catalyst and the third component in advance. In addition, when adding polysiloxanes to a subsequent polymerization reactor, the polysiloxanes can be directly supplied to the reactor in liquid form, or the polysiloxanes can be dissolved and diluted in an inert hydrocarbon solvent or liquid propylene. can do. Alternatively, polysiloxanes may be directly dissolved in an α-olefin gas other than propylene, or a mixed gas of propylene and other α-olefins, or dissolved in an inert hydrocarbon solvent, liquid propylene, etc., to be supplied to a gas phase polymerization reactor. A method of diluting and supplying may also be used. The above addition method may be any method, but a method in which the polysiloxane to be added is effectively added to the propylene polymer in the first stage is preferred. The amount of polysiloxanes present is 1 x 10 ^-6 to 0.1 weight ratio, preferably 5 x 10 ^-6 to 0.01 weight ratio, more preferably 1 x 10 ^-5 to 0.005 weight ratio with respect to the propylene polymer obtained in the first stage. , most preferably 2×
The weight ratio ranges from 10 ^-5 to 0.001. In addition, the proportion of the above-mentioned polysiloxanes based on the weight of the solid catalyst is 1 to 1 x 10 ⁵ weight %, preferably 5 to 1 x 10 ⁴ weight %, more preferably 10 to 5 x 10 ² weight %, most preferably 20 ~1000% by weight. If the amount of polysiloxanes added is too large, the viscosity of the polysiloxanes themselves tends to cause the polymer particles to adhere, which is not preferable. If it is too small, the effects of the present invention will not be fully exhibited. Polysiloxanes are added to the first-stage polymerization vessel from the beginning, or polysiloxanes are added after the first-stage propylene polymerization is completed, and polymer separation (solid-liquid) is performed before supplying the propylene polymer to the second-stage gas phase polymerization vessel. separation), add in advance an amount such that the polysiloxanes in the propylene polymer supplied to the gas phase polymerization vessel have the above concentration, or add the polysiloxanes to the gas phase polymerization vessel. It is preferable. Conventionally, in a method for preventing crust formation in a reactor for alpha-olefin polymerization in the presence of solid catalyst particles comprising titanium and chlorine in a combined state, less than 1% by weight, preferably from about 50 to
A method of carrying out polymerization in the presence of silicone oil in an amount of about 5000 ppm is proposed in JP-A-59-86608. This method is an effective method for preventing the formation of a shell in a polymerization reactor, but it also improves the polymerization activity of the catalyst in gas phase polymerization and improves the powder properties of the polymer, especially the bulk density of the powder, which is a feature of the present invention. This method does not improve the effect of . In the present invention, α-olefins other than propylene that are polymerized or copolymerized in a gas phase include α-olefins having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, and mixtures thereof, and more preferably ethylene or ethylene. and propylene are used. The conditions for gas phase polymerization are usually 30 to 100℃, 1
Polymerization or copolymerization is carried out so that the polymerization rate is 50 Kg/cm ² and the polymerization ratio is 3 to 50% by weight, preferably 10 to 30% by weight. When using an ethylene-propylene mixed gas, which is a more preferred embodiment, the composition of the gas (propylene/(ethylene + propylene)) is 10 to 90 mol%, preferably
It is 20 to 80 mol%. The production method of the present invention basically consists of a first stage of polymerizing propylene alone or propylene and a small amount of other α-olefins to obtain a propylene polymer, and a first step of polymerizing propylene alone or propylene with a small amount of other α-olefins, and a first step of polymerizing propylene alone or with a small amount of other α-olefins. and a second stage for gas phase polymerization of α-olefin. However, in the present invention, the subsequent gas phase polymerization can be carried out in multiple stages, and in each reactor, the polymerization temperature, hydrogen concentration, monomer composition,
It is also possible to change the reaction amount ratio. When gas phase polymerization is carried out in multiple stages, polysiloxanes may be added to any stage. In the present invention, the equipment used for the latter stage gas phase polymerization is not particularly limited, and any known fluidized bed, stirring tank,
Equipment such as a fluidized bed with a stirrer or a moving bed is preferably used, and the polymerization can be carried out continuously or batchwise. After the completion of gas phase polymerization, the polymer taken out continuously or batchwise is subjected to inactivation treatment or deashing treatment with alkylene oxide, alcohol, or hydrogen, and removal of amorphous polymer with a solvent, etc., as necessary. It's okay. The first feature of the method of the present invention is that it has the most favorable feature for gas phase polymerization, which is that the polymerization activity in gas phase polymerization can be greatly improved. Secondly, the properties of the powder are greatly improved, the bulk density of the powder is improved, and the polymer is prevented from adhering to the inner wall of the reactor and stirring blades, contributing to stable operation. Thirdly, regardless of the amount of polysiloxanes added, the amount of amorphous polymer produced in the first stage or gas phase polymerization does not change, that is, the production of soluble polymer by boiling n-hexane extraction method. The amount does not change at all regardless of the presence or absence of polysiloxanes, and a block copolymer that maintains good powder properties can be obtained. Fourthly, the molecular weight of the polymer polymerized in the previous stage or gas phase polymerization vessel does not change. Fifth, the composition of the resulting polymer remains unchanged. For example, in the case of propylene-ethylene copolymer, the chain length distribution of ethylene-propylene evaluated by 13C-NMR is:
There is no difference at all whether polysiloxanes are added or not. As described above, according to the method of the present invention, the subsequent gas phase polymerization can be carried out with extremely high activity without phenomena such as viscosity, while maintaining fluidity, and the impact-resistant polymer with good powder properties can be produced. Excellent block copolymers can be obtained. Particularly in a continuous process, the block copolymer can be extracted smoothly and products with stable quality can be obtained. [Example] The present invention will be described below with reference to Examples, but the present invention is not limited thereto unless it departs from the gist thereof. Further, FIGS. 1 and 2 are flowcharts to help understand the technical content included in the present invention, and the present invention is not limited by the flowcharts unless it departs from the gist thereof. do not have. In the following Examples and Comparative Examples, bulk density, angle of repose, n-hexane extraction residue, and activity were measured by the following methods. (1) Measurement of bulk density According to JIS-K-6721. (2) Angle of Repose The angle of repose during rotation was measured using a three-wheel cylinder rotation method and an angle of repose measuring device manufactured by Tsutsui Rikagaku Kikai Co., Ltd. (3) n-hexane extraction residue In the improved Soxhlet extractor, boiling n-hexane
Remaining amount (wt%) after extraction with hexane for 3 hours (4) Activity Catalyst efficiency: CE Total amount of propylene polymer produced per 1 g of titanium trichloride catalyst component (g-polymer/g-
TiCl ₃ ) Activity Represents catalytic efficiency per unit time. Example 1 A Preparation of solid titanium trichloride At room temperature, 500 ml of purified toluene was placed in a 1 volume flask that had been sufficiently purged with nitrogen, and while stirring,
65.1 g (0.5 mol) of n-butyl ether, 94.9 g (0.5 mol) of titanium tetrachloride, and 28.6 g (0.25 mol) of diethylaluminium chloride were added to obtain a brown homogeneous solution. The temperature was then raised to 40°C, and after 30 minutes, precipitation of purple fine particles was observed, but the temperature was maintained at 40°C for 2 hours. After further holding at 96° C. for about 1 hour, a granular purple solid was separated and washed with n-hexane to obtain about 80 g of solid titanium trichloride. B Production of titanium trichloride containing propylene polymer Purification n in a 500 ml flask that was sufficiently purged with nitrogen
- Pour 250 ml of hexane, add 1.9 g of diethylaluminum chloride and 2.5 g (0.016 mol) of solid titanium trichloride obtained in A above as TiCl ₃ , then maintain the temperature at 40°C and, while stirring, propylene gas.
Contact treatment was carried out by blowing 12.5 g into the gas phase for about 10 minutes. The solid components were then allowed to settle and the supernatant liquid was removed by decantation and washed several times with n-hexane to obtain solid titanium trichloride containing a propylene polymer. C Production of propylene block copolymer In an induction stirring autoclave with a capacity of 2 and purged with dry nitrogen, 1.3 mmol of diethyl aluminum monochloride as a cocatalyst, 0.2 mmol of methyl methacrylate as a third component, and Shin-Etsu Silicone KF96 manufactured by Shin-Etsu Chemical Co., Ltd. , 0.35g, hydrogen gas 1.2Kg/cm ² ,
700g of liquefied propylene was charged. When the temperature of the autoclave reached 70°C, the propylene polymer-containing solid titanium trichloride obtained in step B above was added.
25 mg of TiCl ₃ was injected under pressure with nitrogen to start the polymerization reaction. After 3 hours, unreacted propylene was immediately purged, and 50 g of purified polymer powder was sampled under a nitrogen atmosphere. Subsequently, 0.08 kg/cm ² of hydrogen gas was blown into this reactor, and when the temperature reached 80°C, a propylene-ethylene mixed gas was supplied, and the gas composition of the gas phase was changed to propylene/(propylene + ethylene) = 65 mol%. The gas phase polymerization reaction was continued at 80° C. for 35 minutes while maintaining the pressure at 15 Kg/cm ² G. After the reaction is complete, purge unreacted monomer gas,
348 g of powdered polypropylene block copolymer was obtained. The polymer obtained in the first stage polymerization has a bulk density of 0.46
(g/cc), n-hexane extraction residue 99.3 (wt%), and angle of repose 34°. When silicon atoms contained in the block copolymer were analyzed using the molybdenum blue method, they were detected at a concentration of 305 ppm. In addition, the bulk density of the obtained block copolymer is
0.45 (g/cc), n-hexane extraction residue, 97.8 (wt%), angle of repose 40°. The catalyst efficiency from the Ti content analysis in the polymer using fluorescent X-rays was 13900 (g-
PP/g-TiCl ₃ ), the final polymer product was 16300 (g
-polymer/g- _TiCl3 ), the catalyst efficiency of the copolymerization part by gas phase polymerization is 2400 (g-polymer/g- _TiCl3 ), and the activity is 4110 (g-polymer/g-TiCl3).
g-TiCl ₃ hr). Examples 2 and 3 In C) of Example 1, Shin-Etsu Silicone
A propylene block copolymer was produced in the same manner as in Example 1, except that the polysiloxanes listed in Table 1 were added in place of KF96. The results are shown in Table 1. Comparative Example 1 In C) of Example 1, Shin-Etsu Silicone
A propylene block copolymer was produced in the same manner as in C) of Example 1, except that KF96 was not used. The results are shown in Table 1. As is clear from the results in Table 1, when polysiloxanes are added in the first stage, the activity in the first stage polymerization, molecular weight control, stereoregularity, powder properties, and stereoregularity in gas phase polymerization are affected. The activity in gas phase polymerization is greatly improved without any influence. Example 4 In C) of Example 1, the supplied ethylene-
A propylene-block copolymer was produced in the same manner as in Example 1, except that only ethylene was supplied instead of the propylene mixed gas, the pressure was 10 Kg/cm ² G, and the amount of Shin-Etsu Silicone KF96 added was 0.07 g. I did this. The results are shown in Table 1. Comparative Example 2 A propylene-block copolymer was produced in the same manner as in Example 4, except that no polysiloxanes were added, and only ethylene was supplied. The results are also listed in Table 1. Example 5 A In C) of Example 1, the polysiloxane to be added was changed to Shin-Etsu Silicone KF54, and the mixture was heated to 80°C and purified nitrogen was heated to 3 kg/cm2 while maintaining the internal pressure at 5 kg/ ^cm2 . An autoclave flowing at a speed of 1/min was prepared, and the propylene slurry after the previous stage polymerization was fed little by little in batches, and the propylene was flush-purged. After the supply was completed, 35 g of the flashed polymer was sampled under a purified nitrogen atmosphere. The amount of polymer remaining in the polymerization tank at the front stage was 84 g. B Next, 0.08Kg/ ^cm2 of hydrogen gas was blown into the autoclave into which the polymer had been transferred, and a propylene-ethylene mixed gas was supplied to change the gas composition to propylene/ethylene.
(ethylene + propylene) = 65 mol%, pressure 15
A propylene-block copolymer was produced by carrying out gas phase polymerization while maintaining the temperature at Kg/cm ² . The results are also listed in Table 1. Comparative Example 3 A propylene-block copolymer was produced in the same manner as in Example 5 except that Shin-Etsu Silicone KF54 was not added. The results are shown in Table 1. Example 6 A Preparation of solid titanium trichloride 500 ml of purified toluene was placed in a flask with a volume of 1 which was sufficiently purged with nitrogen at room temperature, and under stirring, n
-65.1 g (0.5 mol) of butyl ether, 94.9 g (0.5 mol) of titanium tetrachloride, and 28.6 g (0.25 mol) of diethylaluminium chloride were added to obtain a brown homogeneous solution. Next, the temperature was raised to 40°C, and after 30 minutes, a purple solid was observed to precipitate, but the temperature remained unchanged for 2 hours.
The temperature was maintained at ℃. Further, after holding at 96°C for about 1 hour, granular purple solids were separated and washed with n-hexane to obtain about 80g of solid titanium trichloride. B Production of titanium trichloride containing propylene polymer Purification n in a 500 ml flask that was sufficiently purged with nitrogen
- Pour 250 ml of hexane, add 1.9 g of diethylaluminum chloride and 2.5 g (0.016 mol) of solid titanium trichloride obtained in A above as TiCl ₃ , then maintain the temperature at 40°C and, while stirring, propylene gas.
Contact treatment was carried out by blowing 12.5 g into the gas phase for about 10 minutes. Next, the solid component was allowed to settle and the supernatant liquid was removed by decantation, and washed several times with n-hexane to obtain a propylene polymer-containing solid titanium trichloride. C Production of propylene block copolymer 1.3 mmol of diethylaluminium monochloride as a cocatalyst and 1.2 Kg/cm ² of hydrogen gas were placed in an induction stirring autoclave with a capacity of 2 and purged with dry nitrogen.
700g of liquefied propylene was charged. When the temperature of the autoclave reaches 70℃,
25 mg of the propylene polymer-containing titanium trichloride obtained in the above B as TiCl ₃ was injected under pressure with nitrogen to start a polymerization reaction. After 3 hours, unreacted propylene was quickly purged and 20 g of polymer powder was sampled under a purified nitrogen atmosphere. Subsequently, 0.08 kg/cm ² of hydrogen gas was blown into the reactor, and when the temperature reached 80°C, 0.35 g of Shin-Etsu Silicone KF96 manufactured by Shin-Etsu Chemical Co., Ltd. and a propylene-ethylene mixed gas were supplied to determine the gas composition of the gas phase. Propylene/(propylene + ethylene) = 65 mol%, pressure 15Kg/
The gas phase polymerization reaction was continued at 80° C. for 36 minutes while maintaining the temperature at cm ² G. After the reaction was completed, unreacted monomer gas was purged to obtain 388 g of powdered polypropylene block copolymer. Catalytic efficiency (CE) from analysis of Ti content in the polymer using fluorescent X-rays was 14,000 (g-PP/g-TiCl ₃ ) for the sample at the end of homopolymerization and 16,470 (g-polymer/g-TiCl 3 ) for the final polymerized product. g-TiCl ₃ ), and the catalytic efficiency of the copolymerization part by gas phase polymerization is
2470 (g-polymer/g-TiCl ₃ ), activity is 4140
(g-polymer/g-TiCl ₃ ·hr). Various measurement results are shown in Table 2. Examples 7-8 In C) of Example 6, Shin-Etsu silicone
Using propylene polymer-containing solid titanium trichloride obtained by polymerizing in the same manner as in step B) of Example 6, except that various polysiloxanes shown in Table 2 were added in place of KF96, C of Example 6 was prepared. ) A propylene block copolymer was produced in the same manner. Various measurement results are shown in Table 2. Comparative Example 4 In C) of Example 6, Shin-Etsu Silicone
C) of Example 6, except that KF96 was not used.
A propylene-block copolymer was produced in the same manner as above for 72 minutes. The catalyst efficiency was 13600 (g-
PP/g-TiCl ₃ ), the final polymerization product was 16000 (g
-polymer/g- _TiCl3 ), and the catalytic efficiency of the copolymerized part by gas phase polymerization was 2400 (g-polymer/g- _TiCl3 ), but the activity was 2000 (g-TiCl3).
Polymer/g-TiCl ₃ hr). Various measurement results are shown in Table 2. Comparative Example 5 In C) of Example 6, Shin-Etsu Silicone
Except that 0.2 mmol of diethylaluminum monoethoxide/n-hexane solution was added in place of KF96 at a molar ratio of 1.5 per 1 g of titanium trichloride contained in the propylene polymer used in the subsequent polymerization. Gas phase polymerization was carried out in the same manner as in Example 6 at 80°C for 35 minutes. The catalyst efficiency was 13900 (g) at the end of the first stage polymerization.
-PP/g- _TiCl3 ), 16450 in the final polymerization product
(g-PP/g-TiCl ₃ ), the catalytic efficiency of the copolymerization part by gas phase polymerization is 2550 (g-polymer/g-
TiCl ₃ ) and has an activity of 4370 (g-polymer/g
−TiCl ₃・hr). The bulk density of the obtained block copolymer was 0.39 g/
cc, n-hexane extraction residue is 94.0% by weight Angle of repose is
It was 50°. The results are shown in Table 2. Example 9 In C of Example 6, the composition of the mixed gas to be supplied is propylene/(propylene + ethylene) = 40
mol%, and the amount of Shin-Etsu Silicone KF96 to be added was 0.07 g, and the other conditions were the same as in Example 6.
Gas phase polymerization was carried out at ℃ for 30 minutes. The catalyst efficiency is 14000 (g-PP/g-TiCl ₃ ) at the end of homopolymerization,
The final polymerization product was 17000 (g-polymer/g-
TiCl ₃ ), and the catalytic efficiency of the copolymerized portion by gas phase polymerization was 2600 (g-polymer/g-TiCl ₃ ), and the activity was 5200 (g-polymer/g-TiCl ₃ ·hr). Various measurement results are shown in Table 2. Comparative Example 6 In the same manner as in Example 9, except that Shin-Etsu Silicone KF96 was not added, the temperature was 57°C at 80°C.
Gas phase polymerization was carried out for minutes. The catalyst efficiency was 13800 (g-PP/g-TiCl ₃ ) at the end of homopolymerization, and 16250 (g-polymer/g-TiCl ₃ ) for the final polymerization product.
The catalyst efficiency of the copolymerization part by gas phase polymerization is 2450 (g-polymer/g-TiCl ₃ ), and the activity is
It was 2580 (g-polymer/g-TiCl ₃ ·hr). Various measurement results are shown in Table 2. Example 10 In C) of Example 6, only ethylene was supplied instead of the mixed gas, and the pressure was set to 10 kg/
cm ² G, the amount of Shin-Etsu Silicone KF96 to be added is 0.07
30 g at 80°C in the same manner as in Example 6, except that the
Gas phase polymerization was carried out for minutes. The catalyst efficiency is 13900 (g-PP/g-TiCl ₃ ) at the end of the single process, 16450 (g-polymer/g-TiCl ₃ ) for the final polymerized product, and 2450 (g-TiCl 3 ) for the ethylene polymer portion. Polymer/g-TiCl ₃ ) and activity was 5100 (g-polymer/g-TiCl ₃ ·hr). Various measurement results are shown in Table 2. Comparative Example 7 In the same manner as in Example 10 except that Shin-Etsu Silicone KF96 was not added, only ethylene was supplied and gas phase polymerization was carried out at 80° C. for 60 minutes. The catalyst efficiency is 14,000 (g-PP/g-TiCl ₃ ) at the end of propylene homopolymerization, 16,300 (g-polymer/g-TiCl ₃ ) for the final polymerization product, and 2,300 (g-TiCl 3 ) for the ethylene polymer portion. -Polymer/
g- _TiCl3 ), and the activity was 2510 (g-polymer/g- _TiCl3 ·hr). Various measurement results are shown in Table 2. Example 11 A In C) of Example 6, heat separately to 80°C and increase internal pressure to 5Kg/cm ² with purified nitrogen.
The propylene slurry after the first stage polymerization was fed in small batches into an autoclave through which purified nitrogen was flowing at a rate of 3/min while maintaining the autoclave at a constant temperature, and the propylene was flush-purged. After the supply was completed, 20 g of the flashed polymer was sampled under a purified nitrogen atmosphere. The amount of polymer remaining in the first stage polymerization tank was 105 g. B Next, 0.08Kg/ ^cm2 of hydrogen gas was injected into the autoclave into which the polymer was transferred, and Shin-Etsu Silicone
0.175 g of KF96 and a propylene-ethylene mixed gas were supplied, the gas composition of the gas phase was propylene/(ethylene + propylene) = 65 mol%, and the pressure was 15 Kg/cm ²
The gas phase polymerization reaction was continued at 80°C for 35 minutes while maintaining the temperature. The catalyst efficiency was 13,700 (g) at the end of homopolymerization.
-PP/g- _TiCl3 ), the final polymerization product is 16100
(g-polymer/g-TiCl ₃ ), and the catalyst efficiency of the copolymerized portion by gas phase polymerization was 2390 (g-polymer/g-TiCl ₃ ). The activity was 4100 (g-polymer/g-TiCl ₃ ·hr). Various measurement results are shown in Table 2. Example 12 In the same manner as in A) of Example 11, the first-stage propylene polymer slurry was fed into the second-stage polymerization tank in a batch manner, and after the propylene was flash-separated, propylene was added under a purified nitrogen atmosphere. A sample of 28 g of polymer was taken. The amount of polymer remaining in the first stage polymerization tank was 107 g. Then, in B) of Example 9, Shin-Etsu silicone
80 in the same manner as in B) of Example 9, except that the addition of KF96 was changed to the addition of 0.01 g of Shin-Etsu Silicone KF54.
The gas phase polymerization reaction was continued for 35 minutes at °C. The results are shown in Table 2. Comparative Example 8 Propylene block copolymerization was carried out for 75 minutes in the same manner as in Example 11, except that Shin-Etsu Silicone KF96 was not added. The catalyst efficiency was 13900 (g-
PP/g-TiCl ₃ ), the final polymerization product was 16100 (g
-polymer/g- _TiCl3 ), and the catalytic efficiency of the copolymerization part by gas phase polymerization is 2200 (g-polymer/g-TiCl3).
g-TiCl ₃ ), and the activity of gas phase polymerization is 1760
(g-polymer/g-TiCl ₃ ·hr). Various measurement results are shown in Table 2. Example 13 A Production of solid titanium trichloride catalyst component 50 toluene, 50 moles of titanium tetrachloride and di-
50 moles of n-butyl ether were added. While stirring and maintaining the temperature at 25°C, 25 mol of diethylaluminum chloride was added to obtain a brown homogeneous solution. Next, the temperature was raised to 40℃, and after 30 minutes, a purple fine-grained solid was observed to precipitate, but it remained as it was.
It was held at 40°C for 2 hours. Next, the temperature was raised to 96°C and held for about 1 hour, and then the granular purple solid was separated and washed with n-hexane to give a temperature of about 8000°C.
g of solid titanium trichloride was obtained. Next, 125 mol of n-hexane was charged into a 200 capacity autoclave which was sufficiently purged with nitrogen, and 16 mol of di-n-propylaluminum chloride and the solid titanium trichloride catalyst complex were added under stirring.
Prepare _TiCl3 so that the amount is 2500g. Next, the internal temperature was adjusted to 30° C., and while stirring, propylene gas was started to be blown into the reactor, and the blowing of propylene gas was continued at the same temperature until the amount of polymerized propylene reached 12,500 g. Thereafter, the solid was separated and washed repeatedly with n-hexane to obtain polypropylene-containing titanium trichloride (titanium-containing solid catalyst component). B. Production of propylene-ethylene block copolymer An apparatus consisting of a 1,500 capacity reaction tank with a stirrer and a 700 capacity gas phase reactor with a helical type stirrer connected in series was used. In the first polymerization tank, polypropylene was produced by liquid phase bulk polymerization of propylene. The polymerization tank was operated at a liquid level of 800,
Propylene, hydrogen, catalyst, cocatalyst, and third product were each continuously supplied to the polymerization tank at predetermined ratios. As the catalyst, the titanium trichloride catalyst obtained in A) above was used.
2.5 g/hr, diethylaluminum chloride as a cocatalyst at 9.8 g/hr, hydrogen as a molecular weight regulator at 20 g/hr, and methyl methacrylate as a third component at 0.33 g/hr in a propylene solution.
Polypropylene was continuously produced under the conditions that the polymerization temperature was 70°C, the residence time was 3 hours, and the gas phase gas composition (hydrogen/propylene) was 5 mol%. The polypropylene slurry obtained in the first polymerization tank is continuously fed to the second gas phase polymerization tank, and the composition of propylene/(propylene + ethylene) is 65 mol% and the composition of hydrogen/(propylene + ethylene) is 1 mol. %, hydrogen while adjusting the internal pressure of the reactor to 10Kg/cm ² G.
Ethylene and propylene mixed gas was circulated. The temperature was adjusted by the temperature of the circulating mixed gas so that the temperature inside the gas phase polymerization vessel was 70°C. In this gas phase polymerization vessel, the retention amount of the polymer was adjusted so that the residence time of the polymer was 1.2 hours, and the polymer was continuously extracted to obtain a copolymer in the form of a powder. A diluted solution of Shin-Etsu Silicone KF96 in n-hexane is added to the mixed gas fed to the gas phase polymerization vessel, and the amount of Shin-Etsu Silicone KF96 relative to the propylene polymer is
It was supplied at a concentration of 100ppm. Continuous operation was carried out in this manner for 60 days, during which time there were no problems with adhesion and safe operation was possible. After the operation was completed, the gas phase reactor was opened and inspected, but there was no adhesion to the vessel walls. Typical values such as activity during continuous operation are shown below and Table 3.
Shown below. The catalyst efficiency of the first stage polymer is
13500 (g-PP/g-TiCl ₃ ), and the catalyst efficiency of the block polymer after gas phase polymerization was 15880 (g-polymer/g-TiCl ₃ ). The catalyst efficiency for gas phase polymerization alone is 2380 (g-polymer/g-TiCl ₃ ), and the activity is 1980 (g-polymer/g-TiCl ₃ hr).
It was hot. The properties of the obtained block copolymer were good, with a bulk density of 0.48 g/cc, an angle of repose of 40°, and n-
The hexane extraction residue was 97.6% by weight. The results are shown in Table 3. Comparative Example 9 A solid titanium trichloride catalyst component obtained in the same manner as in Example 13 A) was used, except that Shin-Etsu Silicone KF96 used in Example 13 B) was not added.
Continuous polymerization was carried out in the same manner as in Example 13 B). In this case, the catalytic efficiency of the polymer in the first stage is 13600 (g-PP/g-TiCl ₃ ), and the catalytic efficiency of the polymer after gas phase polymerization is 1462 (g-polymer/g-TiCl 3 ).
g- _TiCl3 ). The catalyst efficiency for gas phase polymerization alone was 1020 (g-polymer/g-TiCl ₃ ) and the activity was 850 (g-polymer/g-TiCl ₃ ·hr). That is, the amount of polymerization in the gas phase polymerizer did not increase, and the desired ethylene-propylene copolymer content could not be obtained. The results are shown in Table 3. Comparative Example 10 Instead of the Shin-Etsu Silicone KF96 used in Example 13, diethyl aluminum monoethoxide was used at the same molar ratio per 1 g of titanium trichloride, and silicone oil was supplied in B) of Example 13. Similarly, as n-hexane diluted solution, 1/hr
Continuous polymerization was carried out in the same manner as in Example 13 by supplying a mixed gas with . As a result, on the third day after starting continuous polymerization, the stirring power of the stirrer in the gas phase polymerization reactor suddenly increased, and continuous operation became impossible. When the inside of the gas phase reactor was inspected after the operation was completed, bulk polymer was found to be attached to the stirring blades and the vessel wall. Typical results obtained up to the time of shutdown were as follows. Catalytic efficiency of first stage polymerization 13600 (g
-PP/g- _TiCl3 ), and the catalyst efficiency of the polymer after gas phase polymerization was 16050 (g-polymer/g- _TiCl3 ). The catalyst efficiency for gas phase polymerization alone was 2450 (g-polymer/g-TiCl ₃ ) and the activity was 2040 (g-polymer/g-TiCl ₃ ·hr). The bulk density of the obtained block copolymer was 0.40 g/
cc, the angle of repose was 49°, and the residue after n-hexane extraction was 93.5% by weight. The results are shown in Table 3. Example 14 Continuous polymerization of propylene-ethylene block copolymer Two reactors equipped with agitators with a capacity of 1000 and 400 were connected in series, and one stirred fluidized tank type gas phase polymerization tank with a capacity of 1500 was connected in series. In the first and second reaction vessels, propylene homopolymerization was continuously performed in liquefied propylene, and in the third reaction tank, propylene and ethylene were continuously copolymerized by gas phase polymerization. The first reaction tank contained liquefied propylene, Example 1
4.0g/hr of the catalyst component obtained in the same manner as above, and 10g/hr of the cocatalyst diethylaluminum chloride.
hr, 0.52 g/hr of methyl methacrylate, and 15 g/hr of hydrogen as a molecular weight regulator were continuously supplied. Polymerization temperature is 70℃ in the first tank and 67℃ in the second tank.
The slurry was continuously extracted from the first tank and supplied to the second tank. The average residence time is 1st tank,
The total time for the second tank was 4.0 hours. The polymer slurry from the second tank was continuously supplied to the third tank, and gas phase polymerization was carried out while maintaining the temperature at 60° C. and the pressure at 9.0 Kg/cm ² G. The compositions of ethylene and propylene in the gas phase were adjusted to propylene/(ethylene + propylene) = 65 mol% and hydrogen/(ethylene + propylene) = 15 mol%. Further, silicone oil KF96 (CS20: viscosity (25°C) 20 centistokes) manufactured by Shin-Etsu Chemical Co., Ltd. was supplied at 4.5 g/hr to the circulating gas of this gas phase polymerization system. The average residence time in this gas phase reactor was 2.0 hours, and the polymerized powder continuously extracted from the third tank was separated from unreacted gas and then treated with propylene oxide vapor to form a powdered polymer. was obtained at a rate of 45Kg/hr. A propylene homopolymerized portion of the obtained polymer,
The ratio of propylene-ethylene copolymer part is 86/14
It was hot. In addition, the bulk density of the powder is 0.46g/cc,
The residual amount after n-hexane extraction was 97.5% by weight. This operation was continued for 14 days, and stable operation of the entire system was achieved.After the operation was completed, the reactor was opened, and no deposits or lumps were observed inside the reactor. The results showed that the activity of gas phase polymerization was significantly improved to approximately twice that of the comparative example in which no silicone oil was supplied, and the powder properties were also good. Comparative Example 11 A propylene-ethylene block copolymer was continuously produced in the same manner as in Example 14, except that silicone oil was not supplied to the gas phase polymerization system. However, in this case, the activity of the gas phase polymerization part is low, and in order to obtain the same (propylene homopolymerization part)/(propylene/ethylene copolymerization part) composition (=86/14) as in Example 14, it is necessary to Polymerization pressure 15
It was necessary to raise the temperature to Kg/ ^cm2・G and further increase the residence time to 2.5 hours. The bulk density of the obtained polymer powder was 0.42g/
The residual amount after extraction with cc, n-hexane was 97.4% by weight. Furthermore, after 14 days of continuous operation, the reactor was opened and inspected, and adhesion was found on the inner wall of the reactor and part of the stirring blade. Example 15 A Preparation of supported catalyst Mg was added to a 300 ml flask that had been sufficiently purged with dry nitrogen.
(OC ₂ H ₅ ) ₂ 5.0g, Ti (OC ₄ H ₉ ) ₄ 7.4g, Si (OC ₂ H ₅ )
_4.4.6g was collected and reacted at 130°C for 1 hour. Thereafter, 8.2 g of phenol (C ₆ H ₅ OH) was diluted in 8 ml of toluene and added thereto, and the reaction was further continued at 130° C. for 1 hour, and the formation of a solid was observed. Then add 80 ml of toluene to this system and 25 g of
TiCl ₄ and 1.3 g of ethyl benzoate were added and treated at 80° C. for 1 hour, followed by washing three times with toluene.
Furthermore, 83 g of TiCl ₄ and 1.3 g of ethyl benzoate were added again, and the mixture was treated at 80° C. for 1 hour, and finally washed thoroughly with toluene to obtain a supported solid catalyst.
The amount of Ti supported was 2.5% by weight. B. Production of propylene-ethylene block copolymer Triethylaluminum was added as a cocatalyst to an induction stirring autoclave purged with dry nitrogen.
0.78 mmol, 0.24 mmol of methyl p-methylbenzoate as the third component, 0.6 Kg/cm ² of hydrogen gas, and 700 g of liquefied propylene were charged. The temperature of the autoclave was raised to 70°C, and 15 mg of the supported solid catalyst obtained in A above was pressurized to start the polymerization reaction. This polymerization reaction was carried out for 1 time while maintaining the temperature at 70℃.
After this period, unreacted propylene was immediately purged, and 40 g of the polymer was sampled under a purified nitrogen atmosphere. Subsequently, 0.070 g of silicone oil KF96 (20・CS) manufactured by Shin-Etsu Chemical Co., Ltd. was added to this reactor.
After raising the temperature to 60°C, hydrogen gas and propylene-ethylene mixed gas were introduced, and propylene-ethylene copolymerization was continued for 40 minutes in the gas phase. During this time, the gas phase gas composition was propylene/(propylene + ethylene) = 65 mol%, H ₂ /(propylene + ethylene)
(ethylene) = 0.7 mol%, and the pressure was controlled at 10 Kg/cm ² ·G. After the reaction is complete, purge unreacted monomer gas,
210 g of powdered polypropylene block copolymer was obtained. The weight ratio of the propylene homopolymerized portion and the propylene-ethylene copolymerized portion in the obtained copolymer was 85/15. Comparative Example 12 Propylene-ethylene block copolymerization was carried out in the same manner as in Example 15, except that silicone oil was not added to the propylene-ethylene gas phase copolymerization system, and 200 g of powder polymer was produced. Obtained union. However, the activity of the propylene-ethylene gas phase copolymerization part in the latter stage is low, and the propylene homopolymerization part and propylene-ethylene copolymerization part of the obtained block copolymer are
The weight ratio to the ethylene copolymerized portion was 91/9. Comparing the polymerization activity of the copolymerization part in the gas phase with Example 15, in Example 15 it was 2600g・polymer/g・catalyst, whereas in this comparative example
It was 1500g polymer/g catalyst.

【table】

【table】

【table】

【table】

〔Effect of the invention〕

According to the method of the present invention, the subsequent gas phase polymerization can be carried out with extremely high activity without phenomena such as sticking, while maintaining fluidity, and has excellent impact resistance with good powder properties. Particularly in the continuous method, the block copolymer can be smoothly extracted and a product with stable quality can be obtained.

[Brief explanation of the drawing]

1 and 2 are flowcharts showing one embodiment of the present invention.

Claims (1)

[Scope of Claims] 1. Polymerizing propylene alone or propylene and other α-olefins in the presence of a catalyst, and then producing siloxanes or polysiloxanes per gram of the propylene polymer produced without deactivating the catalyst. α other than propylene by adding 1×10 ^-6 ~0.1g of
- A method for producing a propylene-α-olefin block copolymer, which comprises polymerizing an olefin alone or propylene and an α-olefin other than propylene in a gas phase. 2 As polysiloxanes, the general formula (In the formula, R ¹ and R ² are hydrogen atoms, carbon numbers 1 to 20
represents an alkyl group, aryl group, alkoxy group, aryloxy group or halogen. ), and has a degree of polymerization of 2 to 2.
3000. The manufacturing method according to claim 1, characterized in that a silicon compound having a molecular weight of 3000 is used. 3. The manufacturing method according to claim 1, characterized in that silicone oil is used as the polysiloxane. 4. The production method according to claim 1 or 3, wherein the catalyst comprises titanium trichloride and dialkyl aluminum chloride.