JP3385681B2 - Method for producing propylene block copolymer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high rigidity, high impact strength
A method for producing an excellent propylene block copolymer.
Is what you do. BACKGROUND OF THE INVENTION Propylene is used alone in the first stage
Polymerization or copolymerization of propylene with other α-olefins
To produce a stereoregular (co) polymer of propylene
In the presence of (co) polymer, propylene and other α-
Refin is vapor-phase copolymerized to form a propylene block copolymer.
It is known to produce coalescence. Products obtained here
Is the density of the polymer or copolymer produced in each step.
Propylene block copolymerization
It is called the body. [0003] This method uses a propylene block copolymer.
It is extremely useful for maintaining the balance between rigidity and impact resistance.
However, the first stage polymerization step in liquid propylene and
Because it consists of the second stage copolymerization process,
The most important requirement is the activity persistence of the polymerization catalyst. first
In the stage and the second stage polymerization process, a plurality of polymerization vessels are respectively used.
May be used. [0004] Furthermore, a major problem in the subsequent gas phase polymerization method.
The problem is that the viscosity increases and the fluidity deteriorates,
Cause line blockage or scaling, or
Productivity per unit time is remarkable due to low monomer concentration
These problems may not be improved.
Was desired. [0005] In addition, in the stereoregular polymerization of propylene,
Thus, the polymerization activity of what is usually referred to as a supported catalyst,
Although showing high activity at the beginning, activity persistence is poor,
When producing a propylene block copolymer,
Lowers the copolymerization activity and produces high yield of copolymer
It was difficult. Increased proportion of copolymer in later stage
The following means are conceivable as a method for causing the error to occur. (1) To shorten the polymerization time in the former stage,
At a later stage
To increase the amount of copolymer of However, this one
The method reduces the overall catalyst efficiency and, consequently,
This will increase the catalyst residue in the polymer,
It is problematic in quality. (2) The polymerization temperature in the former stage is lowered, and the polymerization catalyst
By suppressing the deactivation of
How to increase body mass. However, in this method,
Decreased overall catalytic efficiency and steric regularity of the copolymer
Lowers the rigidity of the product,
However, there is a problem that the amount of catalyst residue increases. (3) Increasing the copolymerization temperature in the latter stage
A method of increasing the amount of the copolymer in a later stage. But
However, in this method, the amount of the copolymer in the subsequent stage is increased.
Is possible, but the molecular weight of the produced rubber component is low
Therefore, the rate of improvement in impact strength is small, and
There is a disadvantage that the bodies easily stick to each other. (4) To increase the copolymerization pressure in the subsequent stage
A method of increasing the amount of the copolymer in a later stage. But
However, with this method, there is a restriction on the equipment,
Equipment increases equipment costs and, consequently, product costs.
There is a problem that leads to up. (5) Prolonging the copolymerization time in the latter stage
Law. However, in this method, the polymerization rate
In comparison, the polymerization time in the latter stage is lower, so the copolymerization time
Longer periods will reduce overall productivity, so
Not good. (6) Mixing of ethylene and propylene in the latter stage
Use a greater amount of ethylene than propylene
How to use. However, in this method, random sharing
The production rate of the polymer decreases, and the homopolymer of ethylene becomes
It is easy to form and impact resistance of propylene block copolymer
This is not preferable because the effect of improving the impact is reduced. (7) A specific compound is used at the time of copolymerization in the latter stage.
How to add. However, in this method, for example,
When an organoaluminum compound is added,
The formation of lumps due to the adhesion between the polymers causes a problem in operation.
In some cases, this may cause obstacles (JP-A-53-30686). Ma
Also proposed a method of adding aluminum alkoxide
However, a significant decrease in stereoregularity occurs,
There is a problem that the mer sticks. [0013] When trying to prevent adhesion between polymers
Use alkyl lithium or alkyl magnesium
Technology is disclosed, but copolymerization activity is significantly reduced
(JP-A-62-132912, JP-A-62-135509,
JP-A-2-117905). Prevents adhesion between polymers and copolymerizes
Using titanium trichloride catalyst system as a method to improve the activity
Both aluminum alkoxide and hydrocarbons
Japanese Patent Application Laid-Open No. 58-213012 discloses a method of adding
Gazette), these effects would not be exhibited
Not specified. Method for improving flowability of block copolymer
As a method of adding a metal alkoxide (JP-A-61
-69823) and a compound having a Si-OC bond.
(Japanese Patent Laid-Open No. 61-215613), siloxanes
(JP-A-63-146914), siliconization
A method of adding a compound (Japanese Patent Application Laid-Open No.
136010), but there is a decrease in activity
Or any problem such as a decrease in stereoregularity. On the other hand, the generation of by-products is reduced,
To improve the processability of copolymers, special electronic
A technique for adding a donor has also been proposed (JP-A-56-151).
No. 713, JP-A-60-59139, JP-A-61-69821
JP, JP-A-61-69822, JP-A-61-69823,
JP-A-63-43915). However, the polymerization activity is low.
Costs and high costs due to the large amount of additives
Disadvantage. An object of the present invention is to improve the above-mentioned drawbacks,
Significant improvement in copolymerization activity in gas phase copolymerization reaction
Easily produce block copolymers with extremely good fluidity.
It is to provide a technology that can be manufactured. [Technical Means for Solving the Problems] The present invention relates to (A)
Tan-containing solid catalyst component, (B) organoaluminum compound
In the presence of a catalyst containing the component and (C) an electron donating compound,
In the first stage, propylene or propylene and another α-olefin
Polymerization, followed by deactivation of the above catalyst system.
Without adding halogenated malonic ester in the second step.
Of propylene and α-olefins other than propylene
Propylene block characterized by performing gas phase copolymerization
The present invention relates to a method for producing a copolymer. The catalyst (A) according to the present invention contains titanium.
Examples of the solid catalyst include a supported high activity catalyst.
Here, magnesium, titanium, halogen elements and
It is possible to use catalytic solid components that require child donation.
Wear. The method for producing the catalyst solid component is not particularly limited,
For example, JP-A-54-94590, JP-A-56-55405,
Nos. 56-45909, 56-163102, 57-63310
No. 57-115408, No. 58-83006, No. 58-830
No. 16, No. 58-138707, No. 59-149905,
JP 60-23404, JP 60-32805, JP 61-18330
No. 61-55104, JP-A-2-77413, 2-11
The method proposed in Japanese Patent Publication No. 7905 can be adopted. Teens
Typical production methods include (1) magnesium chloride and other
Gnesium compound, electron donor, and TiCl _Four Such as halo
Method of co-grinding titanium genide compound, (2) Mag
Dissolve the cesium compound and the electron donor, and add
Precipitating a catalyst solid by adding a titanium logenide compound
And the like. In the present invention, Japanese Patent Application Laid-Open No. 60-152511
, The catalyst described in JP-A-61-31402 and JP-A-62-81405
Solid components are particularly preferred for achieving the effects of the present invention.
No. According to the production method described in these, aluminum halide
Reaction of the silicon with the organosilicon compound,
The solids are precipitated by reacting the solid compound. In the above reaction
Aluminum halide that can be used is anhydrous
Of aluminum halide is preferred, but due to hygroscopicity
It is difficult to use completely anhydrous one,
Aluminum halide containing
Wear. Specific examples of aluminum halide include trisalt
Aluminum iodide, aluminum tribromide, aluminum triiodide
Aluminum trichloride is particularly preferred.
Good. The organosilicon compound used in the above reaction
Specific examples include tetramethoxysilane, tetraethoxy
Sisilane, tetrabutoxysilane, methyltriethoxy
Silane, ethyltributoxysilane, phenyltrimeth
Xysilane, phenyltributoxysilane, dimethyldi
Ethoxysilane, diphenyldimethoxysilane, dife
Nildiethoxysilane, trimethylmonoethoxysila
Methoxysila such as trimethylmonobutoxysilane
And dimethoxysilane compounds.
Wear. In particular, tetraethoxysilane, methyltriethoxy
Sisilane, phenyltrimethoxysilane, dimethyldie
Toxisilane is preferred. Aluminum halide and organosilicon compound
The amount of compound used in the reaction of the product is the element ratio (Al / Si)
In the range of 0.4 to 1.5, preferably 0.7 to 1.3
When reacting, inert solvents such as hexane and toluene
It is preferred to use a medium. Reaction temperature is usually 10-100
° C, preferably 20 to 80 ° C, and the reaction time is usually 0.2 to
5 hours, preferably 0.5 to 3 hours. Grignard compound used in the above reaction
Specific examples of ethyl magnesium chloride,
Ropyl magnesium chloride, butyl magnesium chloride
Loride, hexylmagnesium chloride, octyl
Magnesium chloride, ethyl magnesium bromide
, Propyl magnesium bromide, butyl magnesium
Umbromide, ethylmagnesium iodide, etc.
Organic magnesium halide. Grignard
As a solvent for the toluene compound, for example, diethyl ether,
Dibutyl ether, diisopropyl ether, diisoa
Aliphatic ethers such as mill ether, tetrahydrofuran
Aliphatic cyclic ethers such as can be used. The amount of the Grignard compound used is
Of the reaction product of aluminum genoide and organosilicon compounds
Element ratio to aluminum halide used for preparation
(Mg / Al) in the range of usually 0.5 to 3, preferably 1.5 to 2.3.
It is an enclosure. The reaction temperature is usually -50 to 100 ° C, preferably-
20 ~ 50 ° C, reaction time is usually 0.2 ~ 5 hours, preferably 0.
5 to 3 hours. Aluminum halide and organosilicon compound
Reaction with substances, followed by reaction with Grignard compounds
The obtained white solid is converted into an electron donor and halogenated
Contact treatment with titanium compound. Or electron donating solid
After contact treatment with the body, contact treatment with the titanium halide compound
Manage. For the contact treatment, a conventionally well-known method can be adopted.
You. For example, the above solid is dispersed in an inert solvent, and
Dissolves electron donor and / or titanium halide compound
Or use an electron donor or
// Disperse solid in liquid titanium halide compound
Let it. In this case, the solid and the electron donor or / and halo
The temperature is usually under stirring while the contact treatment with the titanium
50-150 ° C, contact time is not particularly limited, but usually 0.2
Can be done in ~ 5 hours. Also, this contact processing is
It can be done several times. Titanium halides usable for contact treatment
Compounds include tetrachlorotitanium, tetrabromotitanium
, Trichloromonobutoxytitanium, tribromomonoe
Toxy titanium, trichloromonoisopropoxy titanium,
Dichlorodiethoxytitanium, dichlorodibutoxytita
Monochlorotriethoxytitanium, monochlorotrib
Toxic titanium etc. can be mentioned. In particular, tetra
Chloro-titanium and trichloromonobutoxytitanium are preferred
No. The electron donor used in the above contact treatment is
Preferably, aromatic esters, of which,
Luic acid diesters are particularly preferred. Specific examples of diesters
Are diethyl orthophthalate and diorthophthalate.
Sobutyl, dipentyl orthophthalate, orthophthalic acid
Dihexyl, di-2-ethylhexyl orthophthalate,
And di-n-heptyl orthophthalate. After the above contact treatment, the treated solid is generally
From the treatment mixture and washed thoroughly with an inert solvent to obtain
Used as the catalyst solid component (A) of the present invention
can do. The organic alcohol of the catalyst (B) component in the present invention
As a minium compound, halogenoalkylaluminium
And trialkyl aluminum. Specific examples of the halogenoalkylaluminum
Is diethyl aluminum monochloride, dibutyl
Aluminum monochloride, di-normal propyl aluminum
Nium monochloride, methyl aluminum sesquichlora
, Ethyl aluminum sesquichloride, butyl alcohol
Luminium sesquichloride, butyl aluminum ces
Kibromide and the like. Specific examples of trialkyl aluminum
Is trimethyl aluminum, triethyl aluminum
Aluminum, triisobutyl aluminum, trihexyl aluminum
And trioctyl aluminum. The above-mentioned organoaluminum compounds are all
It can also be used as a mixture. Also, alkyl
Polyaluminum obtained by the reaction between aluminum and water
Noxane can be used as well. As the catalyst (A) component, magnesium, titanium
Catalyst solids that require essential elements, halogen elements and electron donors
When using a catalyst, the catalyst (B) is converted to an organoaluminum
It is preferable to use trialkyl aluminum as the compound.
Good. The amount of trialkyl aluminum used is
Indispensable for calcium, titanium, halogen element and electron donor
Elemental ratio of aluminum to titanium (A
l / Ti), preferably from 20 to 1000, particularly preferably from 150 to
500. As the electron donating compound of the catalyst (C) component
Is an alkoxy group-containing silicon such as alkoxysilane
Compound, organic acid ester, inorganic acid ester, acid halide,
Ether, acid amide, N, N-dialkyl amide,
Min, nitrile, acid anhydride, ketone, alcohol, al
Use of aldehyde, carboxylic acid, isocyanate, etc.
Can be. Of these, alkoxy group-containing silicon compounds are preferred.
It can be used appropriately. Alkoxy-containing silicon compounds
As a specific example of the product, t-butylmethyldimethoxysila
T-butylethyldimethoxysilane, t-butylpropyl
Rudimethoxysilane, di-t-butyldimethoxysilane,
Diisopropyldimethoxysilane, cyclohexylmethyl
Ludimethoxysilane, cyclohexylethyldimethoxy
Silane, dicyclohexyldimethoxysilane, dicyclo
Pentyl dimethoxysilane, tetramethoxysilane,
Traethoxysilane, tetra-n-propoxysilane,
Tora-n-butoxysilane, tetra-isopentoxysila
, Tetra-n-hexoxysilane, methyltrimethoxy
Silane, methyltriethoxysilane, methyltri-n-butyl
Toxysilane, methyltriisopentoxysilane, methyl
Rutri-n-hexoxysilane, ethyltriethoxysila
, Ethyltriisopropoxysilane, ethyltriiso
Pentoxysilane, n-butyltriethoxysilane, iso
Butyltriethoxysilane, isopentyltriethoxy
Silane, isopentyltri-n-butoxysilane, dimethyl
Rudiethoxysilane, dimethyldi-n-butoxysilane,
Dimethyldiisopentoxysilane, diethyldiethoxy
Silane, diethyldiisopentoxysilane, diisobuty
Rudiisopentoxysilane, di-n-butyldiethoxy
Orchid, diisobutyl diisopentoxy silane, trimethyl
Lumethoxysilane, trimethylethoxysilane, trime
Tyl isobutoxy silane, triethyl isopropoxy
Orchid, tri-n-propylethoxysilane, tri-n-butyl
Ruethoxysilane, triisopentylethoxysilane,
Phenyltriethoxysilane, phenyltriisobutoki
Sisilane, phenyltriisopentoxysilane, diphe
Nildiethoxysilane, diphenyldiisopentoxy
Orchid, diphenyldioctoxysilane, triphenylmeth
Toxisilane, phenylmethyldimethoxysilane, tri
Phenylethoxysilane, triphenylisopentoxy
Silane, benzyltriethoxysilane, benzyltrib
Toxysilane, dibenzyldiethoxysilane, cyclope
Methyltrimethoxysilane, cyclohexylmethyldim
Toxysilane, 2-methylcyclopentyl trimethoxy
Run, 2,3-dimethylcyclopentyltrimethoxysila
, Cyclopentyltriethoxysilane, tricyclope
Alkoxysilane compounds such as ethyl ethoxysilane
Or dialkoxysilane compounds. these
Alkoxysilane compounds or dialkoxysilanes
There are two types of alkoxy group-containing silicon compounds such as compounds
These may be used in combination. The amount of the electron donating compound used is determined based on the amount of the component (B)
0.01 to 5 moles, especially 0.1 to 1 mole per mole
Is preferred. The first stage polymerization is a homopolymerization of propylene.
May be used, but the copolymerization of propylene with another α-olefin
It may be. As α-olefins, ethylene, butene
1,3-methylbutene-1,3-methylpentene-1,4-methyl
Lupentene-1, hexene-1, 4-methylhexene-1, octane
Ten-1, styrene, 2-methylstyrene, 3-methylstyrene
, 4-methylstyrene, vinylcyclohexane, vinyl
Cyclopentane, 2-vinylnaphthalene, 9-vinylant
Acyclic monoolefins such as helix, cyclopentene,
Cyclic monoolefins such as cyclohexene and norbornene
, Dicyclopentadiene, 5-ethylidene norbornene
-2,4-vinylcyclohexene or 1,5-hexadiene
And the like. In the crystalline polymer obtained in the first step,
The proportion of α-olefins other than pyrene is polypropylene
Less than 10% by weight.
Preferably. Other than propylene in the crystalline polymer
Low crystallinity when the ratio of α-olefin exceeds 10% by weight
Polymer by-products increase. Necessary for adjusting the molecular weight of the produced polymer
Accordingly, hydrogen may be added as a chain transfer agent. In the first step, propylene homopolymerization or
Crystalline weight due to copolymerization of pyrene and other α-olefin
After the coalescence is produced, the above catalyst system is not deactivated,
Subsequently, the halogenated malonic ester is added in the second step.
Of propylene and α-olefins other than propylene
Produce propylene block copolymer by gas phase copolymerization
You. As a specific example of the halogenated malonic ester,
Malonic acid monochlorodiethyl ester, malonic acid
Dichlorodiethyl ester, malonic acid monochloride
Ester, malonic acid dichlorodimethyl ester, malo
Monochlorodipropyl ester, dichloromalonate
Dipropyl ester, monochlorodibutyl malonate
Chlor such as ter, malonic acid dichlorodibutyl ester
Malonate, malonic acid monobromodiethyles
Bromination of ter, malonic acid dibromodiethyl ester, etc.
And malonic esters. Among these, Malo
Acid monochlorodiethyl ester and malonic acid dichloride
Rhodiethyl ester can be suitably used. the above
May be used as a mixture of two or more. The halo
There is no particular limitation on the amount of the genated malonic ester
With respect to the organoaluminum compound of component (B)
The ratio is usually 0.001 to 1.0, more preferably 0.
01 to 0.6. In the above range, the gas phase copolymerization
The polymerization activity of the reaction is further improved. The halogenated malonic ester is
Of hydrocarbon compounds having no ethylenically unsaturated double bond
It may be added to the polymerization system as a solution. Ethylenically unsaturated
Specific examples of hydrocarbon compounds having no double bond
Means butane, pentane, hexane, heptane, octa
Aliphatic hydrocarbon compounds such as
Alicyclic carbonization such as chlorohexane and methylcyclohexane
Hydrogen compounds and their halides.
Among them, hexane and heptane are preferably used.
it can. Do not have these ethylenically unsaturated double bonds
The amount of hydrocarbon compound used should be
There is no particular limitation as long as it forms an atmospheric pressure.
0.1 to 50 per kg of crystalline polypropylene obtained on the floor
It is preferably 0 g, especially 1 to 200 g. The halogenated malonic ester or
Is the ethylenically unsaturated halogenated malonic ester
Method of adding a solution of a hydrocarbon compound having no double bond and
There is no particular limitation on the method of batch addition, continuous
Use a method of intermittent addition, a method of intermittent addition, etc.
be able to. Among them, the method of continuous addition is preferred.
No. In the case of a continuous addition method, the addition rate is
Crystalline polypropylene obtained at the stage 0.01 ~ per kg
3 g is preferred. The propylene and propylene obtained in the second step
The proportion of the rubbery copolymer with α-olefins other than
Usually 3 to 40% by weight of the total block copolymer amount, more preferred
Or 5 to 30% by weight. Propylene in the rubbery copolymer
The proportion of α-olefin other than len is preferably 10 to 40% by weight.
Good. In the polymerization mode of the present invention, the liquid
Lumped form in which the monomer in the solid state is polymerized as a solvent
In the second stage, the monomer is brought into contact with the catalyst in a gaseous state.
It can be carried out by gas phase polymerization with contact. In the bulk polymerization, propylene or propylene
Keeps the monomer mixture of styrene and other α-olefins in a liquid state
It is preferable to carry out under a certain temperature and pressure condition. Polymerization temperature
The temperature is usually 30 to 90 ° C, preferably 50 to 80 ° C. polymerization
The time is usually between 5 minutes and 5 hours. In the gas phase polymerization, propylene or propylene
And a mixed monomer with α-olefin
It is performed under a temperature and pressure condition that can maintain a phase state. α-
As olefins, ethylene, butene-1, 3-methylbut
Ten-1, 3-methylpentene-1, 4-methylpentene-1, f
Xen-1, 4-methylhexene-1, octene-1, styrene
2-methylstyrene, 3-methylstyrene, 4-methyls
Tylene, vinylcyclohexane, vinylcyclopenta
, 2-vinylnaphthalene, 9-vinylanthracene, etc.
Acyclic monoolefin, cyclopentene, cyclohexene
Cyclic olefins such as norbornene and dicyclo
Pentadiene, 5-ethylidene norbornene-2,4-vinyl
Dioles such as cyclohexene or 1,5-hexadiene
Fins can be mentioned. The copolymerization pressure is usually from atmospheric pressure to 20 kg / cm ^Two ,
Preferably atmospheric pressure to 10 kg / cm ^Two , The polymerization temperature is usually from 30 to
The temperature is 95 ° C, preferably 40 to 70 ° C. The polymerization time is usually 30
Minutes to 10 hours, preferably 1 to 5 hours. As the solid catalyst component (A), magnesium
System, titanium, halogen element and electron donor
When using a catalyst solid, before performing the first stage polymerization,
Using the solid catalyst component (A) in advance,
(B) and the presence of the silicate compound component (C)
It is also possible to prepolymerize a defined amount of propylene.
Prepolymerized solid, or washed solid after prepolymerization
By using these in the main polymerization,
Improve polymerization activity and stereoregularity of polymer
it can. In the present invention, the prepolymerized solid is
When used as a solid catalyst component in
The silicate compound component (C) can be omitted
You. The prepolymerization in the present invention is performed by a gas phase method,
It can be performed by a Lee method, a lump method, or the like. Pre-polymerization
The solid obtained in this step is separated before use in the main polymerization, or
Alternatively, the main polymerization can be carried out continuously without separation. The prepolymerization time is usually 0.1 to 10 hours,
0.1 to 100 g of prepolymer is formed per 1 g of the solid catalyst component.
It is preferable to continue the pre-polymerization until the temperature is lower. Solid catalyst component
If the amount is less than 0.1 g / g, the polymerization activity is not sufficient and the catalyst
Residue increases and the stereoregularity of polypropylene is sufficient
Absent. If it exceeds 100 g, the crystallinity of polypropylene
Tends to decrease. The pre-polymerization temperature is 0-100 ° C,
It is preferably carried out at 5 to 60 ° C. in the presence of each catalyst component. 50 ℃
When performing prepolymerization at a high temperature exceeding
Lowering the pyrene concentration or shortening the polymerization time
preferable. Otherwise 0.1 to 10 per gram of solid catalyst component
It is difficult to control the production of 0 g of prepolymer,
Also, the crystallinity of the polypropylene obtained by the main polymerization decreases.
You. Use of Organoaluminum Component in Prepolymerization
The amount is usually Al / Ti base relative to titanium atom of the solid catalyst component.
The prime ratio is 0.5 to 1000, preferably 1 to 500. Shirike
The amount of the salt compound used is usually
Element ratio of Si / Al to aluminum
1, preferably 0.1 to 0.5. Prepolymerization is also necessary.
Hydrogen can be allowed to coexist if necessary. According to the present invention, propylene and α-olefin
High molecular weight and flowability of rubber-like copolymer component
Propylene block copolymer with good copolymerization activity
It can be manufactured stably and efficiently with good performance. Embodiments of the present invention will be described below. In the embodiment
In the above, the copolymer ratio is the second stage in the total polymer.
Polymer weight ratio (polymer yield in the second stage / total polymer yield
Amount x 100%). Example 1 (1) Preparation of catalyst solid component (A) 15 mmol of anhydrous aluminum chloride was added to 50 ml of toluene.
And at 25 ° C. add another 15 mmol of methyltriethoxysilane.
Add dropwise while stirring, and after reacting for 1 hour at the same temperature.
Was. The reaction product is cooled to -5 ° C and butyl
Diisoamylue containing 30 mmole of gnesium chloride
20 ml of the solution was dropped into the reaction product over 30 minutes,
After the temperature was maintained for 30 minutes, the temperature was raised to 25 ° C. in 30 minutes. Same temperature
After reacting for 1 hour, the precipitated solid was filtered off, toluene and
After washing with toluene, the precipitated solid was separated into 30 ml of toluene.
Sprinkle with 150 ml of titanium tetrachloride and di-n-heptyl phthalate
4.0 mmol was added and reacted at 90 ° C. for 1 hour. Same temperature
The solid is separated at room temperature, washed with toluene and heptane,
Each time, the solid was dispersed in 30 ml of toluene and titanium tetrachloride 15
Add 0 ml and contact at 90 ° C for 1 hour to separate the solid catalyst
Then, it was sufficiently washed with toluene and heptane. 30 catalyst solids
After drying in a nitrogen atmosphere at ℃, the titanium content was measured and 2.
A value of 7 wt% was obtained. (2) Prepolymerization A 2 L stainless steel autoclave with a stirrer was weighed,
Triethylaluminum n-hexane solution 2ml
(1.8 mmol) and diisopropane diluted with n-heptane
3.3 ml (0.3 mmol) of rudimethoxysilane solution, hydrogen
Is 7.0kg / cm ^Two And 900ml of liquid propylene
Fill the autoclave and reach 10 ° C for 10 minutes with stirring
Set. Next, the prepared catalyst solid 8.0 mg (titanium content
2.7wt%) Press-in and reserve propylene at the same temperature for 10 minutes
Polymerized. (3) First stage liquid propylene
Immediately after the completion of the prepolymerization, place the autoclave in a separate bath for 60 minutes.
Heat to 15 ° C and stir for 15 minutes at the same temperature with stirring.
Bulk polymerization was performed. Next, unreacted gas is discharged out of the system
Autoclave after thoroughly replacing the inside with nitrogen.
0.25kg / cm gauge pressure ^Two And then weigh it.
From the weight difference of the autoclave,
The calculated amount was 110 g. (4) The inside of the second-stage gas phase copolymerization reaction system is 0.25 kg / cm in gauge pressure. ^Two End of bulk polymerization held at
After that, set the autoclave temperature to 40 ° C,
And propylene mixed gas at a volume ratio of 1: 1 (each
To the autoclave at 150 Ncc / min.
2.0kg / cm gauge pressure ^Two Was adjusted to Same temperature, same pressure
N-heptane 15m
Malonic acid monochlorodiethyl ester diluted with l 0.0
Continuous injection of the entire volume of the solution containing 90 mmol into the system
did. Copolymerization pressure is 2.0kg / cm in gauge pressure ^Two I'll keep it
Unreacted gas is discharged out of the system and copolymerized at 40 ° C for 3 hours
The reaction was performed. Next, open the lid and open the inside of the autoclave.
Observation showed that all of the polymer adhered to the walls and stirring blades.
And the fluidity of the polymer particles was extremely good.
Was. The obtained copolymer is dried under reduced pressure at 60 ° C for 20 hours.
Then, the weight was measured, and the yield was 153 g. I
Therefore, the polymer obtained during the second stage gas phase copolymerization reaction
The weight was 43 g and the copolymer ratio was 28.10 wt%.
Was. Example 2 In the second-stage gas phase copolymerization reaction, malonic acid monochloride
Instead of ethyl ester, dichlorodiethyl malonate
Propylene was used in the same manner as in Example 1 except that a stell was used.
A ren block copolymer was produced. First stage bulk polymerization
The yield of polypropylene after the reaction was 111 g,
The total yield after the step gas phase copolymerization reaction was 155 g. Auto
Inside the clave, no polymer adheres to the walls or stirring blades
Not observed, and the fluidity of the polymer particles was extremely good.
The polymer yield obtained during the gas phase copolymerization reaction was 44 g.
And the copolymer ratio was 28.39 wt%. Example 3 In the second stage gas phase copolymerization reaction, malonic acid
0.040 mmol of ethyl ester and n-hepta
As in Example 1 except that the amount of
Thus, a propylene block copolymer was produced. First stage
The yield of polypropylene after the end of the bulk polymerization reaction is 112 g.
The total yield after the second-stage gas phase copolymerization reaction was 150 g.
Was. The inside of the autoclave is polymer on the wall and on the stirring blade
No adhesion of polymer particles at all
And the polymer yield obtained during the gas phase copolymerization reaction is good.
The amount was 38 g, and the copolymer ratio was 25.33 wt%. Comparative Example 1 In the second-stage gas phase copolymerization reaction, halogenated malonic acid
Without the addition of any stells and hydrocarbons
Propylene block copolymerization was performed in the same manner as in Example 1.
Body manufactured. Polypropylene after completion of the first stage bulk polymerization reaction
The yield of pyrene was 111 g, after the second stage gas phase copolymerization reaction.
Total yield was 123 g. The inside of the autoclave is a wall
White powder adheres to the agitator and stirring blades, and the copolymer at the bottom
I was gathering. Polymer yield obtained during gas phase copolymerization reaction
Was 12 g, and the copolymer ratio was 9.76% by weight.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a preparation process and a polymerization process of a catalyst of the present invention.

Continuation of the front page (56) References JP-A-55-115417 (JP, A) JP-A-7-145220 (JP, A) JP-A-6-100639 (JP, A) JP-A-7-41529 (JP) JP-A-7-90035 (JP, A) JP-A-7-41530 (JP, A) JP-A-6-136073 (JP, A) JP-A-63-284211 (JP, A) 63-225613 (JP, A) JP-A-63-225611 (JP, A) JP-A-63-46211 (JP, A) JP-A-63-33407 (JP, A) JP-A-61-69822 (JP, A) A) JP-A-5-262826 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 297/08 C08F 4/64

Claims (1)

(57) [Claims] (1) Titanium-containing solid catalyst component, (B)
In the presence of a catalyst containing an organoaluminum compound component and (C) an electron donating compound, polymerization of propylene or propylene and another α-olefin is carried out in the first step, and subsequently, the above catalyst system is deactivated. A method for producing a propylene block copolymer, characterized in that a halogenated malonic ester is added in the second step to carry out a gas phase copolymerization of propylene with an α-olefin other than propylene.