JPH09176227A - Production of propylene/olefin block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a propylene/olefin copolymer continuously and stably for a long time by copolymerizing propylene with an olefin other than propylene in the presence of an olefin polymerization catalyst comprising a specified solid catalyst component (component A), an organoaluminum compound and optionally an electron donor in two stages in which the weight ratio between the reactants are different from each other. SOLUTION: Component A is prepared by spraying a melt of a mixture represented by formula I (wherein R is a 1-10C alkyl; and (m) is 3-6), cooling the sprayed melt and partially removing the alcohol from the cooled product to obtain a solid component represented by formula II (wherein R is defined as in formula I; and (n) is 0.4-2.8) and having an X-ray diffraction spectrum which, as compared with an X-ray diffraction spectrum of formula I, has no new peak at a diffraction angle 2θ of 7-8 or has a peak having an intensity at most 2.0 times as high as that of the maximum peak appearing at a diffraction angle 2θ of 8.5-9 deg., and a titanium halide compound (e.g. titanium tetrachloride) and an electron donor are brought into contact with the solid component at 110-135 deg.C in an aliphatic hydrocarbon solvent having a boiling point of 90-180 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a propylene-olefin block copolymer. More specifically, a novel solid catalyst component suitable for gas phase polymerization, having a relatively large particle size and a spherical shape, and having excellent crush resistance during polymerization,
Propylene-using an olefin polymerization catalyst comprising an organoaluminum compound and, if necessary, an electron donor
The present invention relates to a method for producing an olefin block copolymer.

[0002]

2. Description of the Related Art A so-called propylene-olefin block copolymer, which is composed of a propylene-based polymer portion and a propylene-olefin copolymer portion, is a propylene-based copolymer having both rigidity and impact resistance, It is used for various molded products mainly in the field, home appliances field and large sundries field. In recent years, in order to further improve its impact resistance, ethylene-propylene rubber (EPR) is added to a propylene-olefin block copolymer, or a propylene-olefin copolymer moiety is added during the production of a propylene-olefin block copolymer. Increasing the amount (Japanese Patent Laid-Open No. 55-80418) has been practiced. Further, for the purpose of further improving the quality of conventional propylene-olefin block copolymers, in the propylene-olefin block copolymer, the intrinsic viscosity difference between the polymer portion mainly composed of propylene and the propylene-olefin copolymer portion is By relatively reducing the amount, attempts have been made to reduce fish eyes (FE), improve surface impact resistance, improve impact whitening properties, etc. (JP-A-49-61278, JP-A-63-112612). Japanese Patent Laid-Open No. 5-3
31327 gazette).

On the other hand, as a process for producing a propylene-olefin polymer, in recent years, compared with the conventional slurry polymerization process using a polymerization solvent and the bulk polymerization process using propylene itself as a polymerization solvent, the safety is high, Gas phase polymerization processes, which are resource saving and energy saving processes, have been adopted. Even in the gas phase polymerization process having such characteristics, when the amount of the above-mentioned propylene-olefin copolymer part is increased, or when the intrinsic viscosity difference between the propylene-based polymer part and the propylene-olefin copolymer part is increased. Is relatively small,
Since the resulting propylene-olefin block copolymer becomes sticky and deteriorates in fluidity, its production is difficult, even if it is not as in the conventional process, and it is impossible to carry out continuous production particularly for a long period of time. It was

As a method for solving the above problems, a solid catalyst component suitable for gas phase polymerization of olefins, having a large particle size, a spherical shape, and excellent crush resistance during polymerization,
Attempts have been made to develop a solid catalyst component capable of obtaining a propylene-olefin block copolymer having low viscosity and good fluidity. For example, as one of the prior arts, it was obtained by emulsifying a melt of a carrier component in a suitable oil to form spherical molten particles, which was then added to a cooled hydrocarbon medium and rapidly solidified. Method using carrier (JP-A-55-135102, JP-A-55-13510)
3 and JP-A-56-67311).

Another method is disclosed in JP-A-49-65999.
JP-A-52-38590, JP-A-58-58
45206, JP-A-57-198709,
JP-A-59-131606, JP-A-63-289
Japanese Patent Publication No. 005 discloses a method of using a carrier obtained by spraying a water or alcohol solution of a magnesium compound in a heated nitrogen stream and evaporating water or alcohol from the generated droplets by heated nitrogen. Further, in Japanese Patent Publication No. 63-503550, a mixture of magnesium chloride, alcohol and an electron donor is sprayed in a molten state into a chamber cooled with an inert liquid fluid, and the carrier obtained without evaporation of the solvent is used. The method used is shown.

Further, JP-A-4-296305 discloses that MgCl ₂ .3EtO obtained by a spray method.
A method for obtaining a solid catalyst component for olefin polymerization by reacting titanium tetrachloride at a relatively low temperature using an H carrier, then adding diisobutyl phthalate, and subsequently reacting in a nonane solvent under high temperature conditions. Is disclosed.

On the other hand, the applicant of the present invention previously disclosed in Japanese Patent Laid-Open No. 3-1190
No. 03 (hereinafter sometimes referred to as the previous invention), a mixture of a magnesium compound and an alcohol is sprayed in a molten state to obtain a spherical solid component without substantial evaporation of the alcohol, and then the alcohol is removed from the solid component. Is partially removed to obtain a spherical carrier, and then the carrier is contacted with a halogen-containing titanium compound and an electron donor to obtain a final solid catalyst component for olefin polymerization. According to this method, a solid catalyst component for olefin polymerization having a spherical shape and a large particle size can be obtained. However, when it is used for gas phase polymerization of an olefin, it is crush resistant during polymerization and the fluidity of the resulting polymer. Further improvements were desired.

[0008]

As described above, the solid catalyst component for olefin polymerization obtained by the method of the prior art is combined with an organoaluminum compound and, if necessary, an electron donor to obtain a propylene-olefin block copolymer. When used as a catalyst for coalescence production, there is a problem in shape and particle size and crush resistance during polymerization, so a propylene-olefin block copolymer having low viscosity and good fluidity, particularly propylene-olefin, is used. A propylene-olefin block copolymer having a relatively large amount of the copolymer portion, or a propylene-based polymer portion and propylene-
There was a problem that it was impossible to obtain a propylene-olefin block copolymer having a relatively small difference in intrinsic viscosity of the olefin copolymer portion with high polymerization activity and continuously for a long period of time. .

The present inventors have earnestly studied a method for producing a propylene-olefin block copolymer which solves the above problems of the prior art. As a result, the above invention was improved, and a molten mixture of a magnesium compound represented by a specific compositional formula and an alcohol was sprayed in a cooled spray tower to obtain a solid component without substantial evaporation of the alcohol, In a carrier having a specific X-ray diffraction spectrum obtained by removing a specific amount of alcohol from the solid component under the conditions of, a halogen-containing titanium compound and an electron in the presence of a solvent having a specific boiling point under specific temperature conditions. A final solid obtained by contacting a donor with a titanium halide compound is used as a solid catalyst component for olefin polymerization, and a catalyst obtained by combining this with an organoaluminum compound and, if necessary, an electron donor. When producing a propylene-olefin block copolymer by using It found, leading to the present invention based on this finding.

As is apparent from the above description, the object of the present invention is a novel solid catalyst suitable for gas phase polymerization, having a good shape, a large particle size, and excellent crush resistance during polymerization. Another object of the present invention is to provide a method for continuously and stably producing a propylene-olefin block copolymer by using a catalyst in which a component, an organoaluminum compound, and optionally an electron donor are combined.

[0011]

The present invention provides the following (1).
To (7). (1) a) A mixture (A) of a magnesium compound represented by the following compositional formula I and an alcohol is sprayed in a molten state into a spray tower, and the compositional formula below is substantially evaporated in the spray tower without substantial evaporation of alcohol. Solid component represented by I (B)
After obtaining a solid component (B) by cooling to a temperature at which the alcohol is obtained, alcohol is partially removed from the solid component (B), the solid component is represented by the following composition formula II, and the solid component is represented by X-ray diffraction. Compared with (B), no new peak is generated at the diffraction angle 2θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is the same as that of the X-ray diffraction spectrum of the solid component (C). A solid component (C) having 2.0 times or less the intensity of the maximum peak existing at a diffraction angle 2θ of 8.5 to 9 degrees is obtained, and then the solid component (C) has a boiling point of 90 to 180 ° C. Using an aliphatic hydrocarbon solvent (S) at a temperature of 110 to 135 ° C., a halogen-containing titanium compound and an electron donor (E
1) is contacted to obtain a solid component (D), and the solid component (D) is further contacted with a halogen-containing titanium compound to obtain a solid catalyst component (F) and MgCl ₂ · mROH compositional formula I (where R is Represents an alkyl group having 1 to 10 carbon atoms, m =
It is 3.0 to 6.0. ), MgCl ₂ · nROH composition formula II (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ), B) an organoaluminum compound (AL), and optionally c) an olefin polymerization catalyst comprising an electron donor (E2), as a first stage reaction of an olefin other than propylene with propylene A polymer portion mainly composed of propylene having a weight ratio of 10/90 or less is polymerized in an amount of 20 to 95% by weight based on the total polymerization amount, and then, as a second stage, a reaction weight ratio of olefin other than propylene and propylene is 10/90. To 90/10 of the propylene-olefin copolymer part in the total polymerization amount of 80 to
A method for producing a propylene-olefin block copolymer, which comprises copolymerizing 5% by weight. (2) The production method according to the above item 1, wherein the aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. is an isoparaffin mixture. (3) The average particle size of the solid catalyst component (F) is 50 to 300 μ.
The manufacturing method according to the first or second aspect, wherein m is m. (4) The polymerization amount of the polymer portion mainly composed of propylene is 30 to 80% by weight of the total polymerization amount, and the polymerization amount of the propylene-olefin copolymer portion is 70 to 20% by weight of the total polymerization amount. To the manufacturing method according to any one of 3 to 3. (5) Intrinsic viscosity [η] _{PP of} the polymer portion mainly composed of propylene and intrinsic viscosity [η] _{EP of the} propylene-olefin copolymer portion ([η] _PP / [η] _EP ) is 0.5 to 2. The manufacturing method according to any one of items 1 to 4, which is 2. (6) Any one of the above items 1 to 5 wherein the polymerization of the polymer portion mainly composed of propylene is carried out by bulk polymerization or gas phase polymerization, and the polymerization of the propylene-olefin copolymer portion is carried out by gas phase polymerization. The manufacturing method described in. (7) The production method according to any one of the above items 1 to 6, wherein the polymerization of the polymer portion mainly containing propylene and the polymerization of the propylene-olefin copolymer portion are both continuously carried out.

The structure and effects of the present invention will be described in detail below. The magnesium compound used in the production of the solid catalyst component (F) in the present invention is anhydrous magnesium chloride and may contain a trace amount of water such that it is contained in a commercial product. The alcohol used has the general formula RO
It is an alcohol that can be represented by H (R represents an alkyl group having 1 to 10 carbon atoms). Specifically, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3 -Methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-
Examples thereof include ethylhexanol, 1-octanol, 2-octanol, 1-nonanol, 1-decanol and the like. Of these, ethanol is the most preferable. It is also possible to use a mixture of two or more of these alcohols.

In the production of the solid catalyst component (F) according to the present invention, first, the mixture (A) of magnesium chloride and alcohol is brought into a molten state. The mixing ratio of magnesium chloride and alcohol is the composition formula MgCl ₂ · mROH (however,
R represents an alkyl group having 1 to 10 carbon atoms. ) In m
Is mixed so as to be 3.0 to 6.0. A more preferable range of m is 3.0 to 5.8, and a particularly preferable range of m is 3.0 to 5.5. If m is less than 3.0, the resulting solid catalyst component for olefin polymerization will have problems such as deterioration in shape and olefin polymerization activity. Further, when m exceeds 6.0, the crush resistance of the obtained solid catalyst component for olefin polymerization deteriorates.

The mixture (A) of magnesium chloride and alcohol having the above composition is brought into a molten state by heating it. The heating temperature is not particularly limited as long as it is equal to or higher than the temperature at which the mixture becomes a molten state, but is preferably 80 to 200 ° C, more preferably 100 to 180 ° C, and particularly preferably 110.
160 ° C. If the heating temperature is too low, problems such as deterioration of the shape of the obtained solid catalyst component for olefin polymerization and reduction of olefin polymerization activity occur. Further, if the heating temperature is too high, the crush resistance of the obtained solid catalyst component for olefin polymerization deteriorates.

The thus obtained mixture of magnesium compound and alcohol in a molten state is fed into a spray nozzle attached to the spray tower by using a pump or a heated pressurized inert gas, and the spray tower cooled from the nozzle. Is sprayed inside. As the inert gas, an inert gas such as nitrogen, helium or argon is used, but nitrogen is most preferably used. Further, the spray nozzle has a function of dispersing a mixture of a magnesium compound and an alcohol in a molten state in the spray tower, but a two-fluid nozzle of a type for feeding an inert gas into the spray tower is preferably used. In the spray, the size of the solid component (B) to be produced or the particle size distribution is adjusted by selecting the nozzle size, the flow rate of the inert gas, or the spray flow rate of the mixture of the molten magnesium compound and alcohol. It is possible to

The spray for producing the solid catalyst component (F) used in the present invention is carried out in a cooled spray tower, and the cooling is usually a cooled inert gas or a cooled inert gas. It is carried out by introducing a liquid fluid such as liquid nitrogen into the spray tower. Further, during the spraying, a cooled inert hydrocarbon solvent (S1) such as hexane can be sprayed from another nozzle to accelerate the cooling. The cooling must be performed to a temperature at which the solid component (B) can be obtained without substantial evaporation of the alcohol, that is, a temperature at which the composition formula of the mixture (A) of magnesium chloride and alcohol and the solid component (B) does not change. There is. Therefore, the inside of the spray tower is usually -70 to 10 ° C, preferably -50 to
The temperature is 0 ° C, particularly preferably -40 to -5 ° C. If the cooling temperature is too high, evaporation of alcohol will occur,
The particle shape of the obtained solid component (B) is poor, and moreover, it becomes inhomogeneous, so that the object of the present invention cannot be achieved. Moreover, it is not practical that the cooling temperature is too low.

After spraying by the above method, the obtained solid component (B) is collected in the inert hydrocarbon solvent (S1) introduced at the bottom of the spray tower or at the bottom of the spray tower. Examples of the inert hydrocarbon solvent (S1) used as needed during spraying include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, 1,2
-Used are halogenated aliphatic hydrocarbons such as dichloroethane and 1,1,2-trichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene. Is
Aliphatic hydrocarbons are preferable, and hexane is particularly preferable. The composition of the solid component (B) has the same composition as the mixture (A) of magnesium chloride and alcohol and the mixture (A) in a molten state before spraying, and its average particle size is about 50 to 300 μm. , A spherical shape is obtained.

One embodiment of a production apparatus used for producing the solid component (B) according to the present invention is shown in FIG. 1 for explaining the present invention. In FIG. 1, a magnesium compound and alcohol are introduced into a melting tank 4 equipped with a heating jacket 5 from pipes 1 and 2, and a mixture (A) of a magnesium compound and alcohol is heated by the heating jacket 5 to be in a molten state. The molten mixture (A) is introduced from the pipe 7 into the spray tower 9 cooled by the cooling jacket 10 from the two-fluid nozzle 8 by the pressurized nitrogen introduced from the pipe 3 through the heat retaining pipe 6. It is sprayed with heated nitrogen. Further, an inert hydrocarbon solvent (S1) 11 is previously introduced into the lower part of the spray tower and cooled. The solid component (B) produced by cooling and solidifying the molten mixture (A) in the spray tower 9 is collected in the inert hydrocarbon solvent (S1) 11 at the lower part of the spray tower. The solid component (B) thus obtained is an inert hydrocarbon solvent (S1).
Along with this, it is taken out from the pipe 12 and, if necessary, the inert hydrocarbon solvent (S1) is separated, and then sent to the next step.
On the other hand, a gas component and a solid component (B) entrained in the gas
Is introduced into the cyclone 14 via the pipe 13. The entrained solid component (B) is discharged from the pipe 15, and the gas component is discharged from the pipe 16.

In the present invention, following the above steps, alcohol is partially removed from the obtained solid component (B) to obtain the solid component (C). As a method for partially removing alcohol, various known methods can be used. For example, a method of heating the solid component (B), a method of placing the solid component (B) under reduced pressure, and a method of ventilating the solid component (B) with an inert gas heated at atmospheric temperature or heated are mentioned. Furthermore, it is also possible to use these partial removal methods of alcohol in combination. Among these methods, as a method that can easily achieve the object of the present invention, a method in which and are combined is preferably cited.

Alcohol is partially removed from the solid component (B) by the above process. The composition of the solid component (C) after the alcohol partial removal process is represented by the formula MgCl ₂ · n.
In ROH (provided that R represents an alkyl group having 1 to 10 carbon atoms), it is necessary to select conditions for the step of removing the alcohol portion so that n falls within the range of 0.4 to 2.8. A more preferable range of n is 0.8 to 2.5, and a particularly preferable range of n is 1.0 to 2.2. n
Is less than 0.4, the olefin polymerization activity of the obtained solid catalyst component for olefin polymerization is lowered. Further, when n exceeds 2.8, the solid component (C) is destroyed in the next contact step with titanium halide, and the obtained solid catalyst component for olefin polymerization contains amorphous fine powder particles. The crush resistance deteriorates.

The solid component (C) according to the method of the present invention is required to satisfy the following conditions in addition to the above conditions. That is, in the X-ray diffraction spectrum of the solid component (C), as compared with the X-ray diffraction spectrum of the solid component (B),
No new peak is generated at the diffraction angle 2θ = 7 to 8 °, or even if the new peak is generated, the intensity of the new peak is the diffraction angle 2θ = 8.5 of the X-ray diffraction spectrum of the solid component (C).
The condition is that the intensity is 2.0 times or less, more preferably 1.5 times or less, and particularly preferably 1.0 times or less than the intensity of the maximum peak existing at 9 degrees. By satisfying the conditions, the crush resistance of the obtained solid catalyst component for olefin polymerization is further improved.

In addition to the above-mentioned conditions, the conditions for the above-mentioned alcohol partial removal step satisfying the above-mentioned X-ray diffraction spectrum conditions are: It should be noted that it is preferable to carry out the above step, and the alcohol removing step also takes a relatively long time. As specific conditions, for example, a container equipped with a vibrating device in which the solid components (B) to (C) flow is used, and the heating temperature is 0 under reduced pressure.
The partial removal step of alcohol is carried out under conditions of -100 ° C, preferably 10-80 ° C, most preferably 20-60 ° C for 2 to 1000 hours, preferably 3 to 500 hours.

In the method of the present invention, a halogen-containing titanium compound and an electron donor are added to the solid component (C) obtained by the above method in the presence of an aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. The body is contacted at a temperature of 110 to 135 ° C. to obtain a solid component (D).

The halogen-containing titanium compound to be brought into contact with the solid component (C) has a general formula of Ti (OR ¹ ) _4-u X _u
(In the formula, R ¹ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u is 0 <u ≦.
It is an arbitrary number of 4. ) A halogen-containing titanium compound represented by Specifically, titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride,
Phenoxy titanium trichloride, ethoxy titanium tribromide, butoxy titanium tribromide, diethoxy titanium dichloride, dibutoxy titanium dichloride, diethoxy titanium dibromide, dibutoxy titanium dibromide, triethoxy titanium chloride and the like. To be One or more kinds of these halogen-containing titanium compounds are used. Most preferred is titanium tetrachloride.

The electron donor (E1) brought into contact with the solid component (C) is any one of oxygen, nitrogen, sulfur and phosphorus.
An organic compound having the above atoms is used. Among them, ether, alcohol, ester, aldehyde, fatty acid, ketone, nitrile, amine, amide, isocyanate, phosphine, phosphite, acid anhydride, Si-O
An electron donor such as an organosilicon compound having a -C bond is used. Of these electron donors, esters are preferably used. Specifically, aliphatic monocarboxylic acid esters such as ethyl acetate, vinyl acetate, isobutyl acetate, octyl acetate, cyclohexyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid. Aromatic monocarboxylic acid esters such as cyclohexyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl methyl malonate, ethyl malonate Diethyl acid butyl, diethyl butyl malonate, dibutyl maleate, dioctyl maleate, diethyl butyl maleate, diethyl itaconate, etc., aliphatic polycarboxylic acid esters, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-phthalate n- Propyl, diisopropyl phthalate, di -n- butyl, diisobutyl phthalate, di -n- heptyl phthalate, di-2
Examples thereof include aromatic polycarboxylic acid esters such as ethylhexyl, di-n-octyl phthalate, diethyl isophthalate, diethyl terephthalate, and dibutyl naphthalene dicarboxylate. One or more of these electron donors are used. Most preferred are aromatic polycarboxylic acid esters.

When the solid halogen component titanium compound and the electron donor (E1) are brought into contact with the solid component (C), an aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. is used. Here, the solvent having a boiling point of 90 to 180 ° C. means that the vapor pressure of the solvent is the standard atmospheric pressure (1.01325).
X10 ⁵ Pa) means a solvent having a temperature of 90 to 180 ° C. Specific examples of such an aliphatic hydrocarbon solvent include saturated, unsaturated or halide compounds as long as the aliphatic hydrocarbon has a boiling point of 90 to 180 ° C., but n-heptane, n-octane, n-paraffins such as n-nonane and n-decane, 2,2,3,3-
Tetramethylbutane, 2-ethylpentane, 2,2,3
-Trimethylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, 2,
2-dimethylhexane, 2,3-dimethylhexane,
2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 2-methylheptane, 3-methylheptane, 4-
Isoparaffin such as methylheptane, or a mixture thereof is preferably used, and a mixture of isoparaffin is particularly preferable. The isoparaffin mixture is, for example, Isopar C (boiling range: 97 to 104 ° C.)
They are commercially available from Exxon Chemical Co., Ltd. under the trade names of Isopar E (boiling point range: 116 to 142 ° C.) and Isopar G (boiling point range: 160 to 174 ° C.), and are easily available.

The amounts of the solid component (C), the halogen-containing titanium compound, the electron donor (E1) and the solvent (S) used are shown below. MgCl ₂ 1 in solid component (C)
The halogen-containing titanium compound is used in an amount of 1 to 100 mol, preferably 3 to 50 mol, per mol. Electron donor (E
1) is used in an amount of 0.01 to 1.0 mol, preferably 0.01 to 0.8 mol, based on 1 mol of MgCl ₂ in the solid component (C). Further, the solvent (S) is 1 kg of the solid component (C).
To 5 to 100 dm ³ , preferably 5 to 70 dm ³ .

The order of contacting the halogen-containing titanium compound and the electron donor (E1) to the solid component (C) is not particularly limited, but after the solid component (C) is suspended in the solvent (S), first, After contacting the halogen-containing titanium compound,
A method of contacting with an electron donor (E1) is preferable.

As the conditions for contacting the halogen-containing titanium compound and the electron donor (E1) with the solid component (C), the contact temperature is 110 to 135 ° C., preferably 115.
-135 degreeC, Most preferably, it is 120-135 degreeC.
If the contact temperature is too high or too low, the olefin polymerization activity of the obtained olefin polymerization catalyst component will decrease. The contact time is 5 minutes to 20 hours, preferably 10 minutes to 15 hours, most preferably 10 minutes to 10 hours.

In the above step, the solid component (D) obtained by contacting the halogen-containing titanium compound and the electron donor (E1) with the solid component (C) is separated by a method such as filtration or decantation. , Followed by contact with a halogen-containing titanium compound.

The halogen-containing titanium compound to be contacted with the solid component (D) has the same general formula as that used for contacting the solid component (C) described above with Ti (OR ¹ ).
_4-u X _u (wherein R ¹ is an alkyl group, a cycloalkyl group,
Alternatively, an aryl group and X represents halogen. U is 0
It is an arbitrary number of <u ≦ 4. ) A halogen-containing titanium compound represented by the formula (4) is used, and titanium tetrachloride is most preferably used.

In contacting the solid component (D) with the above halogen-containing titanium compound, it is a more preferred embodiment to use the solvent (S2) in order to more effectively achieve the object of the present invention. As the solvent (S2), those mentioned above as the inert hydrocarbon solvent (S1) which is optionally used in the spraying step, and the aliphatic carbonization used in obtaining the solid component (D) are used. Hydrogen solvent (S)
Although the same hydrocarbon solvents as those mentioned above can be used, aromatic hydrocarbons such as benzene, toluene and xylene are preferably used, and toluene is particularly preferably used. Use of the solvent, in particular, aromatic hydrocarbon leads to the effect of further improving the olefin polymerization activity of the obtained olefin polymerization catalyst.

The amounts of the solid component (D), the halogen-containing titanium compound and the solvent (S2) used are shown below. The halogen-containing titanium compound is 1 to 100 mol, preferably 3 to 1 mol of MgCl ₂ in the solid component (D).
Use ~ 50 moles. The solvent (S) is 0 to 100 dm ³ , preferably 5 to 1 kg of the solid component (D).
Use ~ 70 dm ³ .

As the conditions for contacting the halogen-containing titanium compound with the solid component (D), the contact temperature is 110-110.
135 ° C., preferably 115-135 ° C., most preferably 120-135 ° C., contact time 5 minutes to 20 hours, preferably 10 minutes to 15 hours, most preferably 1
0 minutes to 10 hours.

After the completion of contact of the halogen-containing titanium compound with the solid component (D), the solid obtained is separated by a method such as filtration or decantation, and the separated solid is washed with an inert hydrocarbon solvent (S3). Then, unreacted substances, by-products, etc. are removed to obtain the final solid catalyst component (F) for olefin polymerization. As the inert hydrocarbon solvent (S3) used for washing, the same inert hydrocarbon solvent as the above-mentioned inert hydrocarbon solvent (S1) can be used.

Thus, the average particle size of the obtained solid catalyst component (F) depends on the average particle size of the solid component (C),
In the subsequent process, the particle size will be reduced to some extent, but normally,
The average particle diameter of 90 to 100% of the average particle diameter of the solid component (C) is shown. Here, the average particle size of the solid catalyst component (F) preferable for achieving the object of the present invention is 30 to 300 μm.
m, more preferably 50 to 200 μm, and particularly preferably 60 to 150 μm.

The solid catalyst component (F) obtained by the above-described method of the present invention is an organometallic compound catalyst component, preferably an organoaluminum compound (AL), and, if necessary, the same as the known solid catalyst component for olefin polymerization. Accordingly, it is used as a catalyst for olefin polymerization in combination with an electron donor (E2) for the production of the propylene-olefin block copolymer of the present invention, or more preferably a catalyst pre-activated by reacting a small amount of olefin with the catalyst. Used for the polymerization of olefins.

The organoaluminum compound (AL), which is the organometallic compound catalyst component used in the olefin polymerization catalyst according to the present invention, has a general formula of AlR ² _p R ³ _q X
_{3- (p + q)} (In the formula, R ² and R ³ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group and an aryl group or an alkoxy group, X represents a halogen, and p and q are 0. <P + q ≦
Represents any number of 3. An organoaluminum compound represented by the formula (1) is preferably used.

Specific examples thereof include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, tri-n-octylaluminum and the like. Alkyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisobutyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide and other dialkyl aluminum monohalides, diethyl aluminum hydride and other dialkyl aluminum hydrides, ethyl aluminum sesquichloride and other aluminum alkyls. Sesquihalide, ethyl aluminum dichlorate Examples thereof include monoalkylaluminum dihalides such as Cd and the like, and alkoxyalkylaluminums such as diethoxymonoethylaluminum can also be used. Of these, preferred are trialkylaluminums and dialkylaluminum monohalides, and most preferred are trialkylaluminums. Further, these organoaluminum compounds can be used not only as one type but also as a mixture of two or more types.

The electron donor (E2) optionally used as the olefin polymerization catalyst of the present invention is used for the purpose of controlling the stereoregularity of the olefin polymer obtained in the ordinary olefin polymerization. Known electron donors that are used as necessary are used, specifically, the same electron donors as those mentioned as the above-mentioned electron donor (E1) are used, and Si-is particularly preferable. O-
It is a compound having a C bond. Specifically, methyltrimethoxysilane, methyltriethoxysilane, t-butyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyl Examples thereof include ethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane and trimethyltriethoxysilane. These electron donors may be used alone or in combination of two or more.

The amount of each catalyst component constituting the olefin polymerization catalyst according to the present invention is the same as that used in olefin polymerization as a catalyst for olefin polymerization by combining generally known catalyst components. Specifically, with respect to 1 mol of Ti atom in the solid catalyst component obtained by the method of the present invention,
1 to 2 Al atoms in the organoaluminum compound (AL)
The organoaluminum compound (AL1) is 000 mol, preferably 5 to 1000 mol, and the electron donor (E2) is 0 to 10 mol, preferably 1 mol of Al atom in the organoaluminum compound (AL). Is 0.01-
Use 5 moles.

As the olefin used for pre-activation, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and 4-methylpentene are used. -1, 2
And branched-chain monoolefins such as methylpentene-1. These olefins may be the same as or different from the olefin to be polymerized, and two or more kinds of olefins may be mixed and used.

For the olefin polymerization according to the present invention, in which the solid catalyst component (F) for olefin polymerization according to the above-mentioned method of the present invention, the organoaluminum compound (AL) and, if necessary, the electron donor (E2) are combined. The production process of the propylene-olefin block copolymer using the catalyst or the catalyst pre-activated by reacting a small amount of olefin with the catalyst is not limited, and liquid phase polymerization such as suspension polymerization or bulk polymerization carried out in a solvent is not limited. It is also suitable for the case where the propylene-based polymer portion is polymerized by bulk polymerization or gas phase polymerization, and the propylene-olefin copolymer portion is polymerized by gas phase polymerization. The advantages of the olefin polymerization catalyst according to the method are particularly exerted. In addition, in the production of the propylene-olefin block copolymer, it is a preferable use form to use a pre-activated catalyst.

Pre-activation is carried out by adding 1 g of the solid catalyst component (F) in the presence of a catalyst obtained by combining the above-mentioned catalyst components.
In contrast, 0.05 g to 5,000 g, preferably 0.05 g to 3,000 g of olefin is used, and 0 ° C to 10 ° C.
It is desirable to react olefin at 0 ° C. for 1 minute to 20 hours to produce 0.01 g to 2,000 g, preferably 0.05 g to 500 g of olefin polymer per 1 g of the solid catalyst component (F).

The catalyst thus obtained or the preactivated catalyst is used for producing the propylene-olefin block copolymer of the present invention. The polymerization of the polymer portion mainly composed of propylene in the first stage may be slurry polymerization, bulk polymerization or gas phase polymerization, but bulk polymerization or gas phase polymerization is preferable from the viewpoint of obtaining high polymerization activity. Second
The polymerization of the propylene-olefin copolymer portion at the stage is preferably gas phase polymerization. In slurry polymerization or bulk polymerization, the propylene-olefin copolymer part is eluted in the solvent, which makes it difficult to produce a propylene-olefin block copolymer having a relatively high content of the propylene-olefin copolymer part. , It is difficult to continue continuous stable operation.

The polymerization conditions of the polymer portion mainly composed of propylene in the first stage are different depending on the polymerization mode, but in the case of the gas phase polymerization method, it was obtained by the above method while mixing and stirring a certain amount of powder. The polymerization temperature of the olefin polymerization catalyst or the pre-activated catalyst is 20 to 120 ° C., preferably 40 to
Reaction of olefins other than propylene with propylene by supplying propylene or propylene and olefins other than propylene under conditions of a polymerization pressure of atmospheric pressure to 9.9 MPa, preferably 0.59 MPa to 5.0 MPa under conditions of 100 ° C. Polymerization is carried out so that the polymer portion mainly composed of propylene whose weight ratio is usually 10/90 or less becomes 20 to 95% by weight of the total polymerization amount.

When it is desired to maintain the high rigidity of the propylene-olefin block copolymer finally obtained, the reaction weight ratio of olefin other than propylene and propylene in the polymer portion mainly composed of propylene is preferably 5%. / 95 or less, particularly preferably 3/97 or less, and when the impact resistance of the propylene-olefin block copolymer finally obtained is desired to be improved,
The polymer portion mainly composed of propylene is preferably 20 to
Polymerization is carried out at 80% by weight, particularly preferably 20 to 70% by weight. The molecular weight of the PP component is adjusted by using a molecular weight regulator such as hydrogen during the polymerization so that the intrinsic viscosity of the PP component becomes a desired value ([η] _PP ).

Subsequent to the first stage polymerization, in the second stage, the polymerization temperature is usually 20 to 120 ° C., preferably 40 to 120 ° C.
Propylene-olefin copolymerization is carried out by copolymerizing a mixed monomer of propylene and an olefin other than propylene under the conditions of 100 ° C. and a polymerization pressure of atmospheric pressure to 9.9 MPa, preferably 0.59 MPa to 5.0 MPa. The coalesced part is generated. In the method of the present invention, propylene-
The olefin content other than propylene in the olefin copolymer portion is controlled by controlling the molar ratio of the olefin other than propylene and the propylene in the mixed monomer to obtain an olefin content other than propylene in the propylene-olefin copolymer portion. Reaction weight ratio of propylene is 10/90 ~
It is adjusted to 90/10 and the copolymerization amount of the propylene-olefin copolymer portion is 5 to 80% by weight based on the total polymerization amount.

When it is desired to improve the impact resistance of the finally obtained propylene-olefin block copolymer, the reaction weight ratio of olefin other than propylene and propylene in the propylene-olefin copolymer part is preferable. Is 20/80 to 75/25, particularly preferably 25/7
It is adjusted to be 5 to 65/35, and the weight ratio of the propylene-olefin copolymer part to the total polymerization amount is 20 to 80% by weight, particularly preferably 30 to 80% by weight.
Adjust so that Here, the polymerization ratio of the polymer portion mainly composed of propylene and the propylene-olefin copolymer portion is controlled by adjusting the polymerization time of each of the first stage and the second stage, and during the second stage copolymerization. It is adjusted by a known method using a catalyst polymerization activity modifier such as carbon oxide or hydrogen sulfide.

Furthermore, in order to control the molecular weight of the propylene-olefin copolymer part, a molecular weight regulator such as hydrogen is used during the polymerization, and the intrinsic viscosity of the EP component is a desired value ([η]).
It is similar to the first stage that it is implemented as _EP ). In addition, when it is desired to reduce the fish eye (FE) of the finally obtained propylene-olefin block copolymer, improve impact whitening properties, improve bending whitening properties, reduce molding shrinkage, and the like, Intrinsic viscosity [η] _{PP of} polymer part mainly composed of propylene and intrinsic viscosity [η] _EP ratio of propylene-olefin copolymer part ([η] _PP / [η]
_EP ) is adjusted to 0.5 to 2, preferably 0.6 to 1.8, and particularly preferably 0.6 to 1.6T6.

The intrinsic viscosity [η] _EP of the propylene-olefin copolymer portion cannot be directly measured. Therefore, the intrinsic viscosity [η] _EP of the propylene-olefin copolymer portion was calculated based on the following formula (1). Note [eta] _W is the intrinsic viscosity [eta] _W of the entire block copolymer, relative to [eta] _PP is the intrinsic viscosity [eta] _PP of the polymer portion composed mainly of propylene, and W _PP is the total polymerization amount It represents the polymerization ratio (% by weight) of the polymer portion mainly composed of propylene. [Η] _EP = (100 x [η] _W- W _PP x [η] _PP ) /
(100-W _PP )

The olefins to be copolymerized with propylene in the method of the present invention are ethylene, butene-1,
Linear monoolefins such as hexene-1 and octene-1,
3-methylbutene-1,4-methylpentene-1,2-
Not only branched chain monoolefins such as methylpentene-1 but also butadiene, isoprene, chloroprene, 1,4-
Diolefins such as hexadiene, 1,7-octadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, allyltrimethyl Silane,
And styrene. Of these, linear monoolefins and diolefins are preferably used, and ethylene and butene-1 are particularly preferably used. Further, these olefins to be copolymerized with propylene are not limited to one kind, and can be used in combination with each other.

In the method of the present invention, the above-mentioned first and second
For the second-stage polymerization, it is possible to use one or more polymerization vessels. Although it may be a batch system, an anti-continuous system or a continuous system, it is industrially preferable that both the first and second stages are carried out continuously from the viewpoint of productivity.

After completion of the block copolymerization, in the case of gas phase polymerization, unreacted monomers and hydrogen can be separated from the polymerization system to obtain a particulate block polymer. Thus, the propylene-olefin block copolymer obtained by the method of the present invention is an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a colorant, if necessary. After blending various additives such as inorganic or organic fillers, and further various synthetic resins, they are usually heated and melted and kneaded for about 20 seconds to 30 minutes at 190 to 350 ° C. using a melt kneader, and if necessary, After being extruded into a strand shape, it is further chopped and provided as a molding material in the form of granules, that is, pellets.

[0056]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The definitions of terms used in Examples and Comparative Examples and measurement methods are as follows. X-ray diffraction spectrum: X-ray diffractometer JDX8200T manufactured by JEOL Ltd. whose X-ray source is Cu-Kα ray,
It was measured at a tube voltage of 50 KV and a tube current of 150 mA. Particle size distribution of the solid component: The particle size distribution of the solid component was measured by dispersing the solid component in mineral oil using a particle size distribution measuring device (Mastersizer MS20) manufactured by Malvern Instruments Ltd. by a laser light diffraction method. Average particle size: The particle size distribution is measured according to the above (2), and the volume of the solid component for each particle size is integrated, and the integrated volume is 5
The particle size at 0% is shown. (Unit: μm) Span: 90% of the total volume as in (3) above
When the particle size is D _0.9 , the particle size when the cumulative volume is 10% of the total is D _0.1 , and the average particle size of (3) above is D _0.5 , the following formula span = (D _0.9 -D _0.1 ) / D _0.5 . It is an index showing the degree of particle size distribution. A large span indicates a wide particle size distribution, and a small span indicates a narrow particle size distribution. Polymerization activity: The amount of polymerized olefin (kg) per 1 kg of the solid catalyst component for olefin polymerization is shown and is a measure of olefin polymerization activity. (Unit: kg / polymer / kg / solid catalyst component) BD: Indicates bulk density. (Unit: kg / m ³ ) Intrinsic viscosity: Determined using an automatic viscosity measuring device AVS2 manufactured by Mitsui Toatsu Co., Ltd. using tetralin (tetrachloronaphthalene) as a solvent under a temperature condition of 135 ° C. (Unit: dl / g)

Folding whitening resistance: A high-speed stirring mixer (Note, Henschel mixer) was prepared by adding 0.1 part by weight of a phenolic heat stabilizer and 0.1 part by weight of calcium stearate to 100 parts by weight of block copolymer particles. , Trade name) at room temperature (23 ° C.) for 10 minutes, and the mixture was granulated using an extruder with a screw diameter of 40 mm. Then, a JIS type test piece was prepared from the granulated product with an injection molding machine at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C., and the test piece was placed in a room at a humidity of 50% and a temperature of 23 ° C. Time adjusted. Molding shrinkage ratio: The ratio of the length obtained by subtracting the length of the total length of the tensile test piece (JIS K7113 tensile test piece) adjusted under the same conditions as above (7) from the total length of the mold of the molding machine to the length of the mold. It was calculated from the following formula multiplied by 100. (Unit:%) Molding shrinkage rate (%) = 100 × (total length of mold−total length of test piece) / total length of mold

Example 1 (1) Production of solid component (c) First, the solid component (b) was produced using the apparatus shown in FIG. 8 kg of anhydrous MgCl ₂ was introduced from the pipe 1 and 15.5 kg of dry ethanol was introduced from the pipe 2 into the stainless steel melting tank 4 having an internal volume of 60 dm ³ which was replaced with nitrogen. The mixture (A) was heated to 130 ° C. by passing heated steam through the jacket 5 with stirring, and the composition was M.
A molten mixture (A) having a gCl ₂ · 4.0 EtOH was obtained. After stirring for another 2 hours, pipe 3 to 130 ° C
Nitrogen heated to 1 was introduced into the melting tank 4, and the pressure of the gas phase portion of the melting tank 4 was increased to 0.5 MPa. Subsequently, the uniform molten mixture (A) is sprayed at a rate of 15 kg / h through the pipe 6 into the cooled spray tower 9 by the two-fluid nozzle 8 together with the heated nitrogen at 130 ° C. introduced from the pipe 7. did. 250 dm ^{3 of} n-hexane cooled to −15 ° C. was previously introduced into the spray tower 9, and a refrigerant of −30 ° C. was used for maintaining this temperature during spraying and for cooling the inside of the spray tower 9. Was poured into a jacket 10 attached to the spray tower 9. The nozzle 8 is a small precision two-fluid nozzle (BN-90, manufactured by Shizuto Kyoritsu Shokai), and the flow rate of heated nitrogen introduced from the pipe 7 is 40 dm ³ / m.
It was in. The solid component (b) produced by cooling and solidifying the molten mixture (A) was collected in the cooled n-hexane 11 introduced at the bottom of the spray tower 9. Solid component (b)
And n-hexane were taken out of the system from the pipe 12, and then n-
Hexane was separated to obtain 18.8 kg of a solid component (b). From the obtained analysis result of the solid component (b), the composition of the solid component (b) is the same as that of the molten mixture (A) MgCl ₂
-It was 4.0 EtOH. The shape was spherical, the average particle size was 130 μm, and the span was 1.5.

An internal volume of 450 dm in order to partially remove ethanol in 18.8 kg of the obtained solid component (b).
^It was transferred to a vacuum dryer of ³ and under a reduced pressure of 267 Pa,
20 hours at 35 ° C, 4 hours at 45 ° C, followed by 5
11.5 kg of solid component (c) after drying at 0 ° C. for 24 hours
Obtained. From the analysis result, the composition of this solid component (c) is MgC.
It was l ₂ · 1.7 EtOH. For the solid component (c), using a sieve, small particles of less than 65 μm and 180 μm
The larger particles were removed to obtain 8.6 kg of a solid component (c) having an average particle size of 120 μm and a span of 0.9.

Solid component (b) (M
The X-ray diffraction spectrum of (gCl ₂ · 4.0 EtOH) is shown in FIG. 2. The X-ray diffraction spectrum of the solid component (c) (MgCl ₂ · 1.7 EtOH) from which ethanol was partially removed is shown in FIG. 3. No new peak appeared at the diffraction angle 2θ = 7 to 8 degrees.

(2) Production of solid catalyst component for olefin polymerization Inner volume 110d with condenser and filter attached
Solid component (c) 8.6k in m ³ stainless steel reactor
g, Isopar E isoparaffins mixture (Exxon Chemical Co., Ltd.) 37dm ^3, was placed titanium tetrachloride 74kg halogen-containing titanium compound. When the mixture in the reactor was heated with stirring and reached 100 ° C., diisobutyl phthalate as an electron donor (E1) 1.8 k
g was added. Further, the inside of the reactor was heated to 127 ° C., and contact treatment was carried out at the same temperature for 1.5 hours. After the lapse of processing time, the liquid phase part was removed by filtration. Then, 37 dm ^{3 of} toluene and 74 kg of titanium tetrachloride were added and heated at 120 ° C. for 1 hour, and then the liquid phase part was removed by filtration. After that, toluene 70 dm
After adding ³ and heating at 115 ° C. for 0.5 hours, the liquid phase part was removed, and n-hexane was used at 50 dm ³ per time, and 3
It was washed twice to obtain 6.0 kg of the final solid catalyst component (f) for olefin polymerization. The solid catalyst component (f) thus obtained was spherical and had an average particle size of 115 μm.
And the span was 1.0. In addition, solid catalyst component (f)
The titanium content was 2.0% by weight and the magnesium content was 19.1% by weight.

(3) Production of Propylene-Olefin Block Copolymer A stainless reactor having an internal volume of 20 dm ³ equipped with a stirrer with a tilted blade was replaced with nitrogen, and then 18 dm ³ of tri-heptane and triethyl were added to the reactor. Aluminum 150 mm
ol, diisopropyldimethoxysilane 22 mmol,
Then, 180 g of the solid catalyst component (E) obtained in (2) above was added at room temperature, heated to 40 ° C., and then reacted at a propylene partial pressure of 0.03 MPa for 3 hours to obtain a preactivated catalyst. (Propylene 3.0 g per 1 g of the solid catalyst component (f)
reaction)

A polypropylene powder (average particle size 1500 μm) in which polymer particles of 500 μm or less were removed only at the start of polymerization was placed in a first-stage horizontal type polymerization vessel (L / D = 6, internal volume 100 dm ³ ) having a stirring blade. Of 0.5 g / h as the solid catalyst component (f), and a 15 wt% n-hexane solution of triethylaluminum and diisopropyldimethoxysilane in the solid catalyst component (f). For 1 mol of Ti atom,
It was continuously supplied from the pipe 1 so that the molar ratio was 90 and 15, respectively. In addition, hydrogen is circulated from the circulation pipe 2 so that the ratio of hydrogen concentration in the polymerization vessel to propylene concentration is 0.0046, and propylene is fed from the pipe 3 so that the total pressure in the polymerization vessel is kept at 2.5 MPa. Supplied within. Other reaction conditions are a temperature of 70 ° C. and a stirring speed of 40 r.
It was done in pm. The heat of polymerization reaction was removed by the heat of vaporization of the raw material propylene supplied from the pipe 3. The unreacted gas discharged from the polymerizer was cooled and condensed outside the reactor system through the pipe 4 and was returned to the main polymerization step. The polymer portion mainly composed of propylene (hereinafter sometimes abbreviated as PP component) obtained in the present polymerization vessel is passed through the pipe 6 so that the retained level of the polymer is 50% by volume of the reaction volume. It was taken out from the polymerization vessel at the stage. At this time, PP from the pipe 5
By intermittently extracting a part of the components, the polymer particle size, the intrinsic viscosity of the polymer, and the Mg content in the polymer were subjected to inductively coupled plasma emission spectroscopy (ICP method) to determine the polymer yield per unit weight of the catalyst. Served to ask.

A second-stage horizontal polymerization vessel (L / D =) having a stirring blade, which is connected in series to the first-stage polymerization vessel described above.
6, the inner volume was 100 dm ³ ) and ethylene and propylene were copolymerized in the presence of a PP component containing a catalyst continuously supplied from a pipe 6. Reaction conditions are stirring speed 4
0 rpm, temperature 65 ° C., pressure 2.1 MPa, gas composition of gas phase in polymerization vessel is ethylene / propylene molar ratio = 0.3
The hydrogen / ethylene molar ratio was 0 and 0.01. Carbon monoxide as a polymerization activity inhibitor for controlling the polymerization amount of the propylene-olefin copolymer portion (hereinafter sometimes abbreviated as EP component), and hydrogen gas for controlling the molecular weight of the EP component are provided as pipes 8. Supplied respectively. The reaction heat was removed by the heat of vaporization of the raw material liquid propylene supplied from the pipe 7. The unreacted gas discharged from the polymerizer is pipe 10
Was cooled and condensed outside the reactor system through the circulation pipe 9 in the main copolymerization step. The propylene-based block copolymer produced in the copolymerization step was withdrawn from the polymerizer at 11 kg / h through the pipe 11 so that the retained level of the polymer was 50% by volume of the reaction volume. The extracted propylene-ethylene block copolymer is separated from unreacted monomers and hydrogen, and subsequently subjected to contact treatment with nitrogen gas containing 5% by volume of steam at 100 ° C. for 30 minutes, followed by the method of the present invention. Obtained as propylene-ethylene block copolymer particles.

The above-mentioned propylene-ethylene block copolymerization was continuously carried out for 170 hours, during which no troubles in production occurred, and the inside of the polymerization system was inspected after the completion of the polymerization. No adhesion of the polymer to the wall of the polymerization vessel or accumulation of the lumpy polymer in the polymerization vessel was observed, and it was found that the operation could be continued for a longer period of time.

Comparative Example 1 (1) Production of solid component (c) Solid component (b) 18.8 in the same manner as in Example 1 (1).
kg. The conditions for partially removing ethanol in 18.8 kg of the obtained solid component (b) are as follows: under reduced pressure of 267 Pa, 60 ° C. for 2 hours, 70 ° C. for 3 hours, 8
The same procedure as in (1) of Example 1 was carried out except that the procedure was carried out at 0 ° C. for 3.5 hours to obtain 11.5 kg of a solid component. For the solid component, using a sieve, small particles of less than 65 μm and 180 μm
The larger particles were removed to obtain 6.9 kg of a solid component having an average particle size of 115 μm and a span of 1.2. Subsequently, the operation of obtaining the solid component (b), drying under reduced pressure, and sieving were separately repeated in the same manner to obtain 13.8 kg of the solid components.

The composition of the above solid component, from which ethanol was partially removed, was MgCl ₂ .1.7 EtOH. The X-ray diffraction spectrum of the solid component is shown in FIG. A new peak appeared at the diffraction angle 2θ = 7.6 degrees, and the intensity of the new peak was 3.0 times the intensity of the peak at the diffraction angle 2θ = 8.8 degrees.

(2) Production of Solid Catalyst Component for Olefin Polymerization In (2) of Example 1, 8.6 kg of the sieved solid component obtained by the above method is used in place of the solid component (c). Except that the final solid catalyst component was 6.0
kg. The average particle size of the final solid catalyst component obtained was 8
The span was 1.5 at 0 μm.

(3) Production of propylene-olefin block copolymer The same as in Example 1 (3) except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (f). To obtain a preactivated catalyst. Using the obtained pre-activated catalyst, propylene was prepared in the same manner as in (3) of Example 1.
When ethylene block copolymerization was carried out, the fluidity of the copolymer particles deteriorated and it became sticky, so at 74 hours after the start of polymerization, the copolymer could not be extracted from the second-stage polymerization vessel, The production of the block copolymer was discontinued. When the inside of the polymerization system was inspected after the production was stopped, the pipes 4 and 8 were clogged with the polymer, adhesion of the polymer to the stirrer or the wall of the polymerization vessel was observed, and accumulation of the bulk polymer in the polymerization vessel was observed.

Comparative Example 2 (1) Production of Solid Catalyst Component for Olefin Polymerization Decane 3 was added in a stainless reactor equipped with a stirrer.
7.5 liters, anhydrous magnesium chloride 7.14 kg,
And 35.1 liters of 2-ethyl-1-hexanol were mixed, and heated and reacted at 140 ° C. for 4 hours with stirring to obtain a uniform solution. 1.67 kg of phthalic anhydride was added to the homogeneous solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the uniform solution.
The obtained homogeneous solution was cooled to room temperature (23 ° C.), and then the entire amount of this homogeneous solution was added dropwise to 200 liters of titanium tetrachloride kept at −20 ° C. over 3 hours. After the dropping, the temperature was raised to 110 ° C over 4 hours, and when the temperature reached 110 ° C, 5.03 liter of diisobutyl phthalate was added, and 2 hours 1
The reaction was carried out at 10 ° C. with stirring.

After the completion of the reaction for 2 hours, the solid part was collected by hot filtration, resuspended in 275 liters of titanium tetrachloride, and then the reaction was continued again at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was collected by hot filtration again,
-Washing was sufficiently performed with hexane until no free titanium was detected in the washing liquid. Subsequently, the solvent was separated by filtration, and the solid portion was dried under reduced pressure to obtain a solid catalyst component for olefin polymerization containing 2.4% by weight of titanium and 17.1% by weight of magnesium. The average particle size of the solid catalyst component is 22μ
m, span was 1.0.

(2) Production of propylene-olefin block copolymer The same as in Example 1 (3) except that the final solid catalyst component obtained in (1) above was used in place of the solid catalyst component (f). To obtain a preactivated catalyst. Using the obtained pre-activated catalyst, propylene was prepared in the same manner as in (3) of Example 1.
When ethylene block copolymerization was carried out, the fluidity of the copolymer particles deteriorated and it became sticky, so at 8 hours after the start of polymerization, the copolymer could not be extracted from the second-stage polymerization vessel, The production of the block copolymer was discontinued. When the inside of the polymerization system was inspected after the production was stopped, the pipes 4 and 8 were clogged with the polymer, adhesion of the polymer to the stirrer or the wall of the polymerization vessel was observed, and accumulation of the bulk polymer in the polymerization vessel was observed.

Examples 2 and 3 and Reference Example 1 Same as Example 1 except that the polymerization conditions in the first and second stages were changed as shown in Table 1 in (3) of Example 1. Then, a propylene-ethylene block copolymer was produced.

Table 1 shows the production conditions, the polymerization results, and the quality evaluation results for the above Examples 1 to 3, Comparative Examples 1 and 2, and Reference Example 1.

[0075]

[Table 1]

[0076]

As is apparent from the above-mentioned Examples, the main effect of the present invention is that the solid catalyst component obtained by the method of the present invention is used as a catalyst component for olefin polymerization in propylene-olefin block copolymerization. When applied, a propylene-olefin block copolymer having a relatively large amount of a propylene-olefin copolymer part, which has been difficult to continuously produce in the past, or a polymer part mainly containing propylene and a propylene-olefin copolymer part. That is, it is possible to obtain a propylene-olefin block copolymer having a relatively small difference in intrinsic viscosity of the polymer portion with high polymerization activity and continuously and stably.

On the other hand, when a solid catalyst component obtained by a method other than the method of the present invention is applied to propylene olefin polymerization as a catalyst component for olefin polymerization, the generation of finely divided polymer or the formation of an adhesive polymer results in operation. In order to cause the above problem, the propylene-olefin block copolymer having a relatively large amount of the propylene-olefin copolymer portion, and the propylene-based polymer portion and propylene-
In the propylene-olefin block copolymer in which the difference in intrinsic viscosity of the olefin copolymer portion is relatively small, continuous production itself becomes difficult (Comparative Examples 1 to 3).

[Brief description of the drawings]

1 is a solid component (B) for illustrating the method of the present invention.
3 is a process diagram of the manufacturing apparatus of FIG.

[Explanation of symbols]

 1: Raw material supply pipe 2: Raw material supply pipe 3: Pressurized nitrogen supply pipe 4: Melting tank 5: Heating jacket 6: Molten mixture (A) transport pipe 7: Heating nitrogen supply pipe 8: Two-fluid nozzle 9: Spray tower 10 : Cooling jacket 11: Inert hydrocarbon solvent (S1) 12: Solid component (B) collection pipe 13: Gas discharge pipe 14: Cyclone 15: Gas-entrained solid component (B) discharge pipe 16: Gas discharge pipe

FIG. 2 shows an X-ray diffraction spectrum of the solid component (b) obtained in Example 1.

FIG. 3 shows an X-ray diffraction spectrum of the solid component (c) obtained in Example 1.

FIG. 4 shows the solid component (MgCl ₂ .1.
7EtOH) X-ray diffraction spectrum.

FIG. 5 is a process diagram of a propylene-olefin block copolymer continuous production apparatus for explaining the method of the present invention.

[Explanation of symbols]

 17: Catalyst supply pipe 18: Circulation pipe 19: Raw material supply pipe 20: Unreacted gas discharge pipe 21: First stage polymerizer 22: PP component extraction transfer pipe 23: Raw material supply pipe 24: Hydrogen, activity inhibitor supply pipe 25: Circulation pipe 26: Unreacted gas discharge pipe 27: Copolymer withdrawal pipe 28: Second stage polymerization vessel

FIG. 6 is a flow chart of an olefin polymerization catalyst for explaining the method of the present invention.

Claims (7)

[Claims] 1. A) A mixture (A) of a magnesium compound represented by the following composition formula I and an alcohol is sprayed in a molten state into a spray tower, wherein the inside of the spray tower is treated without substantial evaporation of alcohol. After obtaining the solid component (B) by cooling to a temperature at which the solid component (B) represented by the composition formula I is obtained, alcohol is partially removed from the solid component (B), and the following composition formula II, and compared with the solid component (B) in X-ray diffraction, the diffraction angle 2θ = 7 to
There is no occurrence of a new peak at 8 degrees, or even if it occurs, the intensity of the new peak exists at the diffraction angle 2θ = 8.5 to 9 degrees of the X-ray diffraction spectrum of the solid component (C). A solid component (C) having a peak intensity of 2.0 times or less is obtained, and thereafter, an aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. is used as the solid component (C). Thirteen
A solid catalyst component (which is obtained by contacting a halogen-containing titanium compound and an electron donor (E1) with each other at a temperature of 5 ° C. to obtain a solid component (D), and further bringing the halogen-containing titanium compound into contact with the solid component (D) ( F) and MgCl ₂ · mROH composition formula I (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. ), MgCl ₂ · nROH composition formula II (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ), B) an organoaluminum compound (AL), and optionally c) an olefin polymerization catalyst comprising an electron donor (E2), as a first stage reaction of an olefin other than propylene with propylene A polymer portion mainly composed of propylene having a weight ratio of 10/90 or less is polymerized in an amount of 20 to 95% by weight based on the total polymerization amount, and then, as a second stage, a reaction weight ratio of olefin other than propylene and propylene is 10/90. To 90/10 of the propylene-olefin copolymer part in the total polymerization amount of 80 to
A method for producing a propylene-olefin block copolymer, which comprises copolymerizing 5% by weight. 2. The aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. is an isoparaffin mixture.
The production method described in 1. 3. The average particle size of the solid catalyst component (F) is 50 to 50.
It is 300 micrometers, The manufacturing method of Claim 1 or 2. 4. The polymerization amount of the polymer portion mainly composed of propylene is 30 to 80% by weight of the total polymerization amount, and the polymerization amount of the propylene-olefin copolymer portion is 70 to 20% by weight of the total polymerization amount. 4. The manufacturing method according to any one of 1 to 3. 5. The intrinsic viscosity [η] _{PP of} the polymer portion mainly composed of propylene and the intrinsic viscosity [η] _EP ratio ([η] _PP / [η] _EP ) of the propylene-olefin copolymer portion are 0. 5
The manufacturing method according to any one of claims 1 to 4, wherein 6. The method according to claim 1, wherein the polymerization of the polymer portion mainly containing propylene is carried out by bulk polymerization or gas phase polymerization, and the polymerization of the propylene-olefin copolymer portion is carried out by gas phase polymerization. The manufacturing method described. 7. The production method according to claim 1, wherein the polymerization of the polymer portion mainly containing propylene and the polymerization of the propylene-olefin copolymer portion are both continuously carried out.