JPH0742327B2 - Method for producing ethylene copolymer - Google Patents

Description

Detailed Description of the Invention

 <Field of Industrial Application> The present invention relates to a method for producing an ethylene copolymer. Further details
New production of granular olefin elastomer
It is about law. Among various elastomers, the olefin-based elastomer is
It has excellent heat resistance, ozone resistance, and color stability
Mainly used in the fields of automobiles, home appliances, and construction
It <Prior Art> In the prior art, olefin elastomers are generally
It is manufactured by the solution polymerization method. This solution polymerization method is
Unreacted monomer recovery process, deashing process, stripping process
It requires many steps such as
Since it is dissolved, the viscosity of the system is high, stirring is difficult,
The heat is difficult and the manufacturing cost is very disadvantageous. As a method to solve this problem, ethylene and propylene
Random copolymerization with propylene in liquefied propylene
A method of combining is proposed in JP-A-59-71306.
ing. No improvement in productivity was observed in this method.
However, it is necessary to carry out the polymerization at an extremely low temperature of 40 ° C or less.
The problem is that the catalyst activity decreases, and it is large due to the removal of polymerization heat.
Incurring economic disadvantages such as requiring refrigeration equipment. Furthermore, the thermoplastic elastomer can be directly applied by the gas phase polymerization method.
A manufacturing method is proposed in JP-A-59-230011.
However, even in such a method, adhesion of polymer particles
To prevent gas and perform stable gas phase polymerization.
And a very large amount of inert gas such as nitrogen as a monomer.
It is necessary to dilute the polymer to carry out the polymerization. like this
The method reduces productivity and causes a disadvantage in industrial production.
Ku. <Problems to be Solved by the Invention> In this situation, the problems to be solved by the present invention, that is,
The object of the present invention is to provide an olefin-based elastomer with a solution weight.
It can be manufactured by a legal method or by a slurry polymerization method at low temperature.
Manufacturing technology, and gas phase at low temperature and low monomer concentration
Improved production technology by polymerization method
Providing a method for efficiently producing granular ethylene copolymer
To do. That is, according to the present invention, ethylene and α-olefin
By performing random copolymerization in the gas phase.
To obtain ethylene copolymers with improved powder properties.
It Contains a lot of low crystalline polymers such as ethylene-propylene rubber
In general, the adhesion of polymer particles is extremely large for
Therefore, it is difficult to carry out stable gas phase polymerization. That is, as the α-olefin gas phase polymerization reactor,
Mixing tank type reactor, fluidized bed type reactor, fluidized bed type with agitator
Although reactors have been proposed, the adhesion of polymer particles has increased.
Larger stirring speed in a reactor that stirs
In order to achieve the
There are enormous difficulties in designing. Also, in such a situation
Since it is difficult to achieve uniform mixing,
It will be localized and a part of the polymer will agglomerate
Due to damage to the agitator and thermometer inside the reactor,
It is difficult to extract polymer particles from the reactor using
Become. On the other hand, there is a reaction that polymerizes in a fluidized state with unreacted monomer.
The slugging phenomenon is likely to occur in the
The amount of polymer particles scattered to the circulation line significantly increases,
Adhesion to the line and blockage occur. Further, under such circumstances, it is difficult to uniformly mix the polymer.
There is a problem that some of the lumps are agglomerated. Furthermore, if the adhesion of polymer particles is high, transfer the particles.
It is easy to cause blockage in the piping. Also the bottom of the cyclone
Stable removal due to bridging in the hopper
There is a problem that is difficult to do. Therefore, the gas phase polymerization method is a liquid form that dissolves a low crystalline polymer.
Despite having the advantage of not using media, in reality
It is extremely important to produce a polymer rich in low crystalline polymer.
Was difficult. In a further improved gas phase polymer process, the catalyst is substantially
Since the residue is not removed, the catalyst system used
It is necessary to use a product with highly improved polymerization activity.
There is. The present inventors have conducted diligent research to solve the above problems.
As a result, combining a specific catalyst system and gas phase polymerization
More efficient granular ethylene copolymer with excellent performance
The inventors have found that they can be obtained and achieved the present invention. <Means for Solving Problems> The present invention comprises (A) at least titanium, magnesium and chlorine.
The catalyst component has an average particle size of 5 to 1,000 μ and a pore radius of 100 to
Organic porous with a pore volume of 5,000 Å of 0.1 cc / g or more
A solid catalyst component impregnated into a high-quality polymer carrier, and (B)
Using a catalyst system containing at least an aluminum compound,
In the gas phase, ethylene and α-olefins and, if necessary,
Random copolymerization with polyene was carried out, and the
Tylene content of 5-95% by weight, tetralin at 135 ℃
Intrinsic viscosity 0.3-10, density 0.86-0.90g / cm³Is me
Ethylene characterized by obtaining fin-based elastomer
It relates to a method for producing a copolymer. The present invention will be specifically described below. (A) Solid catalyst component The solid catalyst component (A) used in the present invention is at least
Average particle size of catalyst component consisting of tan, magnesium and chlorine
Fine diameters of 5 to 1,000μ and pore radii of 100 to 5,000Å
For organic porous polymer carriers with pore volume of 0.1 cc / g or more
It is impregnated. The performance required for the catalyst of the present invention includes ethylene and α
-Sufficiently high activity and good in olefin copolymer
To produce ethylene copolymers with excellent physical properties and particles
For example, forming polymer particles with good child properties.
You can Manufacture ethylene copolymers with good particle properties
In order to achieve this, the average particle size of the solid catalyst component is an important factor.
It That is, the average particle size of the solid catalyst component is 5 to 1,000 μ,
Preferably 10-600μ, particularly preferably 15-500μ
It When the average particle size is smaller than 5μ, the polymer particles are attached.
The adhesion force increases, and in the fluidized bed gas phase reactor, the contact force is increased.
Problems such as scattering of the medium and polymer particles occur. on the other hand,
If the average particle size is larger than 1,000μ, fluidized bed
The minimum fluidization rate was significantly increased in a phase reactor
It becomes difficult to obtain a stable fluidized state because
The problem that the child agglomerates occurs. The fixed catalyst component will be described more specifically. Organic porous polymer used as component (A) of the present invention
Examples of the carrier include polystyrene type and polyacrylic acid ester.
Tell, polymethacrylate ester, polyacryloni
Trill-based, polyvinyl chloride-based, polyolefin-based porous
Quality polymer beads and the like. Specifically, police
Ren, styrene-divinylbenzene copolymer, styrene
-N, N'-alkylenedimethacrylamide copolymer, su
Tylene-ethylene glycol dimethacrylate copolymer
Coalesced, polymethyl acrylate, polyethyl acrylate,
Methyl acrylate-divinylbenzene copolymer, acrylic
Ethyl acetate-divinylbenzene copolymer, polymethacrylate
Methyl methacrylate, methyl methacrylate-divinylbenzene
Polymer, polyethylene glycol dimethacrylate
, Polyacrylotolyl, acrylonitrile-divinyl
Benzene copolymer, polyvinyl chloride, polyvinylpyrroli
Gin, polyvinyl pyridine, ethyl vinyl benzene-di
Vinylbenzene copolymer, polyethylene, ethylene-a
Methyl acrylate copolymer, polypropylene, etc.
You can Of these organic porous polymer carriers, the carrier is preferably
Styrene, polyvinyl chloride, polyolefin,
Polyacrylonitrile-based porous polymer beads are used
And more preferably polystyrene, styrene-divinyl
Benzene copolymer and polyvinyl chloride are used. The average particle size of the organic porous polymer carrier is 5 to 1,000μ,
It is preferably 10 to 600 μ, and particularly preferably 15 to 500 μ.
And the pore volume at a pore radius of 100 to 5,000Å is 0.1cc /
g or more, preferably 0.2 cc / g or more, particularly preferably 0.25 cc
/ g or more. Pore volume of organic porous polymer carrier is small
In other words, the catalyst component cannot be effectively impregnated.
Moreover, the pore volume of the organic porous polymer carrier is 0.1 cc / g or more.
However, even if it exists in the pore radius of 100 to 5000 Å
If not, the catalyst component cannot be effectively impregnated.
Yes. Next, at least the amount of the organic porous polymer carrier contained in the carrier is
About catalyst component consisting of tan, magnesium and chlorine
This will be specifically described. In the catalyst component of the present invention, the titanium / magnesium source is used.
The child ratio is 0.01 to 0.8, preferably 0.02 to 0.2. Also, salt
The atomic ratio of elemental / magnesium is 1.8 to 10, preferably 2.0.
~ 5.0. As a method for producing such a catalyst component, for example, Japanese Patent Publication Sho
35-495, JP-A-46-4393, JP-B-46-31330,
KAISHO 47-42283, JP-A-49-86483, JP-B-57-2436
No. 1, Japanese Patent Application No. 60-139951, Japanese Patent Publication No. 39-12105, Japanese Patent Publication No.
43-13050, JP-B-46-34092, JP-B-46-34098
No. 47, Japanese Patent Publication No. 41676, Japanese Patent Publication No. 55-23561, etc.
Mention may be made of the method shown. Next, the catalyst component is impregnated into the organic porous polymer carrier.
As a method, a mechanical method such as grinding or a slurry state
However, the latter method is used in terms of particle properties.
Is preferred. Specific examples of such a method include, for example, JP-A-52-42585.
JP-A-54-148093, JP-A-56-47407, JP-A-5
9-230006, Japanese Patent Laid-Open No. 61-37803, Japanese Patent Application No. 61-228963
Do not touch the porous carrier such as silica gel disclosed in the publication.
A method of impregnating a medium component can be applied. Examples of these methods include (1) using a porous carrier as an organic magnesia such as Grignard reagent.
TiCl after treatment with um compounds_Four(2) Porous carrier is treated with organic magnesia such as Grignard reagent
Halogenating agent and / or alcohol after treatment with um compounds
And react with TiCl_FourTreated with titanium compounds such as
Method, (3) magnesium halide compound and / or alcohol
Xymagnesium compounds as alcohols, ethers, etc.
After dissolving with various donors of TiCl_FourAnd so on, and this
(4) magnesium halide compound and / or alcohol
Xymagnesium compounds as alcohols, ethers, etc.
After being dissolved with various donors of, the porous carrier is impregnated,
Further TiCl_Four(5) Alkoxy titanium compound in the presence of a porous carrier.
Reduced with organomagnesium compounds such as Grühl reagent
Then treated with a mixture of thethetel compound and titanium tetrachloride.
The method such as the method described above can be exemplified. These ways
Among them, the method exemplified in (5) is preferably used.
Organosilicon having a bond of Si--O
In the presence of compound and organic porous polymer carrier,
Organic titanium such as Grignard reagent
Etherification of the solid product obtained by reduction with
Using the method of treating with a mixture of compound and titanium tetrachloride
be able to. Also, the amount of catalyst component impregnated in the organic porous polymer carrier
Is 1 to 70% by weight as the content in the solid catalyst component, preferably
3 to 60% by weight, particularly preferably 5 to 55% by weight
It Amount of catalyst component impregnated into organic porous polymer support
If it is too large, the particle properties of the polymer deteriorate. On the contrary, there are few
If it is too low, the activity per solid catalyst decreases. Used in the synthesis of catalyst components used in the present invention
Titanium compounds have the general formula Ti (OR¹)_aX_b(R¹Has 1 to 1 carbon atoms
20 hydrocarbon groups, X is a halogen atom, and a and b are 0 ≦ a
Represented by ≦ 4, 0 ≦ b ≦ 4 and a + b = 3 or 4
It is a number. ) Is represented. Specifically, titanium trichloride, ethoxytita
Dichloride, butoxy titanium dichloride, tetrachloride
Titanium, ethoxytitanium trichloride, butoxytita
Trichloride, phenoxytitanium trichloride,
Dibutoxy titanium dichloride, diphenoxy titanium di
Chloride, tributoxytitanium chloride, tetrae
Toxytitanium, tetrabutoxytitanium, tetraphenoki
Cytitanium and the like can be preferably used. Next, the following are used as magnesium compounds
It Has a magnesium-carbon bond or a magnesium-hydrogen bond
Examples of the compound having the reducing ability include diethyl
Gnesium, dibutyl magnesium, dihexyl magne
Sium, ethyl magnesium chloride, butyl magne
Sium chloride, hexyl magnesium chloride,
Butyl ethoxy magnesium, butyl magnesium high
Dride or the like is preferably used. These magnesiumation
The compound is in the form of a complex compound with an organoaluminum compound.
You may use. On the other hand, magnesiumation without reducing ability
As a mixture, magnesium dichloride, magnesium
Dihalogenated magnesium such as muzibromide, methoki
Simmagnesium chloride, ethoxymagnesium chloride
Ride, butoxy magnesium chloride, phenoxy
Magnesium chloride, diethoxy magnesium, di
Butoxy magnesium, diphenoxy magnesium, etc.
Alkoxy magnesium compound, magnesium lauric acid
Calcium, magnesium stearate, etc.
Bonates and the like are preferably used. These magnesium compounds having no reducing ability have been previously
Or Magnesium with reducing ability when preparing solid catalyst
It may be one synthesized from the compound by a known method. In addition, by adding a known ester compound to the solid catalyst component
Good. Such ester compounds are mono- and poly-carbohydrates.
Acid ester, specifically, aliphatic carboxylic acid ester
Tell, olefin carboxylic acid ester, alicyclic carvone
Examples thereof include acid esters and aromatic carboxylic acid esters. Specific examples include methyl methacrylate and ethyl benzoate.
, Butyl benzoate, methyl toluate, and toluic acid
Chill, ethyl anisate, diethyl succinate, di succinate
Butyl, diethyl malonate, dibutyl malonate, male
Dimethyl acid salt, dibutyl maleate, diethyl itaconate
, Dibutyl itaconate, monoethyl phthalate, phthalate
Dimethyl acid, methyl ethyl phthalate, diethyl phthalate
, Di-n-propyl phthalate, diisopropyl phthalate
, Di-n-butyl phthalate, diisobutyl phthalate,
Di-n-heptyl phthalate, di-n-octyl phthalate,
Examples thereof include diphenyl phthalate. (B) Organoaluminum compound In the present invention, in combination with the above-mentioned solid catalyst component A).
The organoaluminum compound B) used as
It has one Al-carbon bond in the molecule. representative
The general formula is shown below. ▲ R² _c▼ AlY_3-c R³R^FourAl-O-AlR^FiveR⁶ Where R², R³, R^Four, R^FiveAnd R⁶Is carbonized with 1 to 8 carbon atoms
A hydrogen group and Y represent halogen, hydrogen or an alkoxy group.
C is a number represented by 2 ≦ C ≦ 3. Specific examples of the organic aluminum compound include triethyl
Aluminum, triisobutylaluminum, trihex
Trialkyl aluminum such as silaluminum, die
Chill aluminum hydride, diisobutyl aluminum
Dialkyl aluminum hydra such as um hydride
Id, trialkyl aluminum and dialkyl aluminum
A mixture of um hydride, tetraethyl dialumoxa
And alkyl alumokis such as tetrabutyl dialumoxane
Sun can be illustrated. These organoaluminum compounds
C, trialkyl aluminum, trialkyl aluminum
A mixture of um and dialkylaluminum halide, al
Cylalumoxane is preferred, especially triethyl
Luminium, triisobutylaluminum, triethyl
Mixture of aluminum and diethylaluminum chloride
And tetraethyl dialumoxane are preferred. The amount of organoaluminum compound used depends on the amount of titanium in the solid catalyst.
Choose from a wide range of 1 to 1,000 moles per mole of atom
However, the range of 5 to 600 mol is particularly preferable. In addition, during the polymerization, it is necessary to control the molecular weight of the polymer.
A known electron donating compound may be allowed to coexist. Scarecrow
Of the electron-donating compounds, preferably Si-OR⁷Bond (R⁷
Represents a hydrocarbon group having 1 to 20 carbon atoms. ) Having organic
Silicon compounds can be used. Among such organosilicon compounds, more preferably general
Formula ▲ R⁸ _d▼ Si (OR⁷)_4-d(R⁷And R⁸Has 1 to 20 carbon atoms
Hydrocarbon group, d represents a number of 0 ≦ d ≦ 3. )
Alkoxysilane compounds can be used. Specific examples of such an alkoxysilane compound include tet
Lamethoxysilane, methyltrimethoxysilane, dimethy
Ludimethoxysilane, ethyltrimethoxysilane,
Nyltrimethoxysilane, phenylmethyldimethoxysilane
Orchid, tetraethoxysilane, methyltriethoxysila
Amine, ethyltriethoxysilane, vinyltriethoxysilane
Orchid, phenyltriethoxysilane, diphenyldimetho
Xysilane, diphenyldiethoxysilane, butyltri
Ethoxysilane, tetrabutoxysilane, vinyltrib
Examples include toxysilane and diethyldiethoxysilane.
be able to. (C) Polymerization method The present invention uses the above catalyst system to produce ethylene α-
Of ethylene copolymers for random copolymerization of olefins
It proposes a manufacturing method. More specific modes of polymerization are shown below. Polymerization involves the randomization of ethylene and α-olefins in the gas phase.
Copolymerization. The α-olefin copolymerized with ethylene is propylene.
Len, butene-1, pentene-1, hexene-1, 4-
Examples include methylpentene-1,3-methylbutene-1 and the like.
be able to. Especially propylene and butene-1 are preferred
Yes. The copolymerization of the present invention facilitates vulcanization of the copolymer.
Ethylene, α-olefin and polyene
It can be polymerized. As a specific example of such polyene
Butadiene, dicyclopentadiene, 1,3,7-o
Kutatriene, vinylcyclohexane, 5-ethylidene
-2-norbornene, 5-isopropenyl-2-norbo
Lunene, 1,4-hexadiene, 1,5-hexadiene, 1,9
-Decadien, etc. are mentioned. Of these, the non-conjugated di
Enes are preferred, and straight chain, non-conjugated dienes are particularly preferred. Ethylene content in copolymer of ethylene and α-olefin
Is 5 to 95% by weight, preferably 15 to 90% by weight. Generate
When the ethylene content of the copolymer exceeds the above range,
It is not preferable because rubber properties are impaired. Also few
In this case, low temperature properties and rubber properties are impaired, which is preferable.
Not good. When polyene coexists in the case of copolymerization, the copolymerization
The iodine value in the coalescence will be 2-50, preferably 3-40
I will Further, in the present invention, the polymerization is carried out in two or more steps by changing the ethylene concentration.
Can be implemented in. At that time, a small amount of
Homopolymerization of ethylene or α-olefin (eg total weight
3% by weight or less based on the combined amount) may be performed. Polymerization conditions are below the melting temperature of the polymer, preferably 20
~ 85 ℃, particularly preferably 40 ~ 75 ℃ temperature range, normal pressure ~ 40
kg / cm²Monomer does not liquefy in the polymerization tank within the pressure range of
It is preferable to carry out under conditions. Furthermore, the copolymer is the final product
Hydrogen is a molecular weight regulator for the purpose of controlling the melt flowability of the product.
It is preferable to add and polymerize. Also during polymerization
Inert gas may coexist in the mixed gas.
If the ratio is too large, the productivity will be significantly reduced. (For example
(Amount exceeding 25 mol%), so that
Coexistence is not preferable. Randomization of ethylene and α-olefin produced by polymerization
The molecular weight of the copolymer is the same as that of tetralin at 135 ° C.
Degree [η] is 0.3 to 10, preferably 0.5 to 8, particularly preferably
Is 1 to 5. If [η] is too small, sufficient tensile strength
No strength can be obtained. On the contrary, if [η] is too large, it will be molded.
Sex significantly deteriorates. The gas phase polymerization reactor for carrying out the present invention is not particularly limited.
Well known stirred mixing tank type reactor, fluidized bed type reactor
Reactor, fluidized bed reactor with stirrer
Wear. <Example> The method of the present invention will be described in more detail with reference to the following examples.
However, the present invention is limited only by these examples.
Not a thing. The physical properties in the examples were measured by the following methods.
Of. Intrinsic viscosity (hereinafter abbreviated as [η]): 13 in tetralin solvent
It was measured at 5 ° C. Ethylene and 1,9-decadiene content measurement: infrared absorption
722, 733, 736c for ethylene using spectra
m^-1, 1,640 cm for 1,9-decadiene^-1Absorption band of
Was used to quantify. The calculated ethylene content was in good agreement with the value obtained from the mass balance.
It was Pore volume: As a measurement model, Micromeritics
Mercury injection method using Asizer 9310 (Porosimeter)
Measure the pore volume in the range of 40 to 75,000Å with the
It was Average particle size of solid catalyst: determined by optical microscope observation. Adhesion of polymer particles: width 30mm, length 53mm, height 12mm
Adhere two shear test cells made of minium plates and stack them on top of each other.
Put polymer particles to measure inside under a load of 1,000 g
After preloading for 30 seconds, vertical load 50g, 100g, 200g, 3
Applying 00g and 400g, the take-up speed is 100mm / min at room temperature.
Shear stress for each vertical load
To measure. Measures vertical load and shear stress using least squares method
Approximate a straight line, and add the shear stress when extrapolating to a vertical load of 0 g.
It was taken as the adhesive force. Density: according to the method specified in JIS K6760. However, 100 ° C
After the annealing treatment was performed for 1 hour in water, the measurement was performed. Example 1 (A) Synthesis of organomagnesium compound Contents equipped with stirrer, reflux condenser, dropping funnel, and thermometer
After replacing the flask of product 1 with argon,
32.0 g of scraped magnesium for a roll was added. Add 120 g of butyl chloride and 50 of dibutyl ether to the dropping funnel.
Charge 0 ml and add about 30 ml to the magnesium in the flask.
Then, the reaction was started. 4 hours at 50 ℃ after starting the reaction
To continue the dropping, and after the dropping, continue the reaction at 60 ° C for another hour.
I got it. Then, the reaction solution was cooled to room temperature, and the solid content was filtered off.
did. 1 butylmagnesium chloride in dibutyl ether
Hydrolyze with normal sulfuric acid to prepare 1N sodium hydroxide solution
When the concentration was determined by back titration with a
(Uses Nolphthalein), the concentration is 2.0 mol /
It was (B) Synthesis of solid product Flask with internal volume of 1,000 ml equipped with stirrer and dropping funnel
Was replaced with argon, and then styrene-divinylbenzene
Copolymer (average particle size 50μ, porosimeter measurement
Result Pore radius (cc / g) between 100 and 5,000Å
(Hereinafter abbreviated as dVp) was dVp = 1.05cc / g. ) 80
74.0 g dried under reduced pressure at ℃ for 30 minutes and 370 ml heptane,
6.69 g (19.7 mmol) of trabutoxytitanium, tetrae
Add 70.9 g (340 mmol) of toxysilane and 45 minutes at 30 ℃
It was stirred for a while. Next, 180 ml of the organomagnesium compound synthesized in (A)
While maintaining the temperature in the flask at 5 ° C, 45 from the dropping funnel.
It dripped over minutes. After the dropping is completed, the temperature is 5 ° C for 45 minutes, then 30 ° C.
After stirring for 45 minutes at 30 minutes, wash twice with 300 ml of hexane.
The product was returned and dried under reduced pressure to obtain 126.3 g of a brown solid product. (C) Synthesis of solid catalyst component After replacing a flask with an internal volume of 1,000 ml with argon,
114.6 g of a solid product synthesized by the reduction reaction of (B),
382 ml of toluene and 32.1 ml of diisobutyl phthalate (120 ml
Limol) was added and the reaction was carried out at 95 ° C. for 1 hour. After the reaction, solid-liquid separation is performed and washed with 300 ml of toluene twice.
It was After washing, put 382 ml of toluene and butyl ether into the flask.
25.3 ml (149 mmol) and titanium tetrachloride 447 ml (4,07
0 mmol) was added and the reaction was carried out at 95 ° C. for 3 hours. reaction
After completion, after solid-liquid separation at 95 ℃, at the same temperature toluene 300m
It was washed twice with l. Butyl ether and tetra salt mentioned above
The treatment with the mixture with titanium oxide is carried out again for 1 hour,
After repeated washing twice with 300 ml of hexane, dry under reduced pressure.
After drying, 93.9 g of a brown solid catalyst component was obtained. Titanium atom is 0.51% by weight in the solid catalyst component.
Contains 7.2% by weight of Mu atom and 2.5% by weight of Phthalates
It was The average particle size of this solid catalyst component was 50 μm. (D) Polymerization Using an autoclave with a stirrer and an internal volume of 5,
A random copolymerization of len and propylene was carried out. Dispersant of polypropylene powder 50g in autoclave
Was charged, the pressure was reduced, and the temperature was raised to 60 ° C. Then water
0.61 kg / cm²Supply G, ethylene / propylene = 50 /
10kg / cm with 50vol% mixed gas²Heat up to G, then triethyl
Aluminum 0.5g and phenyltrimethoxysilane 0.13g
And a small amount of 418.2 mg of the solid catalyst component prepared in (C) above.
Of heptane and argon into the autoclave.
I entered. And the total pressure is 10kg / cm²Ethylene to keep in G
/ Propylene mixed gas is fed and ethylene /
Propylene copolymerization was carried out in the gas phase. After the polymerization was completed, unreacted monomers were purged and polypropylene
The powder dispersant is screened to remove fine powder and coarse particles.
151 g of granular elastomer having a good Uder property was obtained. or,
No polymer adhered to the inner wall of the autoclave and the stirrer
I didn't. Amount of total polymer produced per gram of solid catalyst (g) (hereinafter P / cat
Abbreviated. ) Was P / cat = 360. Polymerization conditions and polymerization
The fruits are shown in Table 1 and Table 2, respectively. Comparative Example 1 (A) Synthesis of Solid Product A flask with an internal volume of 1 equipped with a stirrer and a dropping funnel was used.
After replacing with Lgon, 600 ml of heptane, tetrabutoxy
Titanium 7.6g (22.2mmol) and tetraethoxysilane
Add 78.1 g (375 mmol) to make a homogeneous solution and
Stir for minutes. Next, the composition synthesized in (A) of Example 1
Machine magnesium compound 200ml, the temperature in the flask 5
Gradually drop from the dropping funnel over 3 hours while maintaining at ℃
did. After completion of dropping, stir at room temperature for another hour and then at room temperature
After solid-liquid separation and repeated washing with 600 ml of heptane three times
After drying under reduced pressure, 64.5 g of a dark brown solid product was obtained. (B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 200 ml with argon,
13.8 g of a solid product synthesized by the reduction reaction of (A),
69 ml of ruene and 10.1 ml of diisobutyl phthalate (37.7 mm
Mol) was added and the reaction was carried out at 95 ° C. for 1 hour. After the reaction, solid-liquid separation was carried out, and the mixture was washed twice with 69 ml of toluene. After washing, add 69 ml of toluene and butyl ether to the flask.
5.0 ml (30 mmol) and titanium tetrachloride 88.5 ml (805 mm
Mol) was added and the reaction was carried out at 95 ° C. for 3 hours. End of reaction
Then, after solid-liquid separation at 95 ° C, 2 ml of toluene (69 ml) was added at the same temperature.
Washed twice. By the above-mentioned mixture of butyl ether and titanium tetrachloride,
Again for 1 hour and then with 69 ml of n-heptane
After washing twice, it was dried under reduced pressure to give a brown solid catalyst.
10.4 g of ingredient was obtained. Titanium atom is 1.8% by weight in the solid catalyst component.
21 wt% Mu atom and 6.5 wt% phthalate ester
It was (C) Polymerization In the same manner as in (D) of Example 1, using the above solid catalyst.
Ethylene / propylene copolymerization was performed. Polymerization conditions and weight
The results are shown in Tables 1 and 2, respectively. In this case, the solid catalyst component is impregnated into the porous polymer carrier.
Since it has not been done, the particle properties were extremely bad. That is, oh
As a result of open inspection of the clave, polymer particles were
It was attached to the pyrene powder dispersant and agglomerated. Polymerization conditions
And the results of polymerization are shown in Tables 1 and 2, respectively. Comparative Example 2 (A) Synthesis of Solid Product A flask having an inner volume of 300 ml equipped with a stirrer and a dropping funnel was used.
After replacing with argon, silica gel (average particle size 60μ,
d) Vp = 0.69 cc / g. ) At 700 ° C under nitrogen atmosphere
Calcinated for 8 hours 10.0g, heptane 50.0ml, tetrabu
Toxytitanium 1.31 g (3.86 mmol), tetraethoxy
Add 13.8 g (66.1 mmol) of silane and stir at 30 ° C for 45 minutes.
I stirred. Next, the organomagnesium compound synthesized in (A) of Example 1
35.5 ml of the product was added dropwise while maintaining the temperature in the flask at 5 ° C.
The solution was added dropwise from the outlet over 45 minutes. 45 minutes at 5 ° C after completion of dropping
For another 45 minutes at 30 ° C, then twice with 50 ml heptane
Repeated washing to dry under reduced pressure to obtain 21.0 g of a brown solid product.
Obtained. (B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 200 ml with argon,
(A) 9.34 g of solid product synthesized by reduction reaction
31.1 ml of ene and 3.53 ml of diisobutyl phthalate (13.2 mm
Mol) was added and the reaction was carried out at 95 ° C. for 1 hour. After the reaction, solid-liquid separation was performed, and washing with 31 ml of toluene was performed twice.
After washing, add 31.1 ml of toluene and butyl ether to the flask.
2.06 ml (12.2 mmol) and titanium tetrachloride 36.4 ml (33
1 mmol) was added and the reaction was carried out at 95 ° C. for 3 hours. reaction
After the completion, after solid-liquid separation at 95 ℃, toluene 31 ml at the same temperature
It was washed twice with. Butyl ether and tetrachloride mentioned above
The treatment with the mixture with titanium is carried out again for 1 hour and then
Was washed twice with 31 ml of heptane, repeated, and dried under reduced pressure.
To obtain 8.23 g of a brown solid catalyst component. The solid catalyst component contains 2.4% by weight of titanium atoms and magnesium.
5.0% by weight of Mu atom and 2.5% by weight of phthalate ester
It was The average particle size of this solid catalyst component was 60μ.
It was (C) Polymerization In the same manner as in (D) of Example 1, using the above solid catalyst.
Ethylene / propylene copolymerization was performed. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively. In this case, the solid catalyst component is an organic porous polymer carrier.
Since it is impregnated with silica gel, the particle properties are
It was bad. That is, as a result of open inspection of the autoclave,
Polymer particles adhere to polypropylene powder dispersant and agglomerate
Had changed. The polymerization conditions and results are shown in Table 1 and Table 2, respectively.
The results are shown in Table 2. Comparative Example 3 (A) Synthesis of solid product A flask having an internal volume of 200 ml equipped with a stirrer and a dropping funnel was used.
After replacing with argon, styrene-divinylbenzene
Polymer (dVp = 0.08cc / g (pore radius less than 100Å and 5,000
The pore volume including the above was 0.93 cc / g). ) 80
5.0g and heptane 25.0ml, which was vacuum dried at ℃ for 1 hour,
Tetrabutoxy titanium 0.28 g (0.67 mmol), tetra
Add 2.42 g (11.6 mmol) of ethoxysilane, and add 4 at 30 ℃.
Stir for 5 minutes. Next, the organomagnesium compound synthesized in (A) of Example 1
Add 6.1 ml of the product dropwise while keeping the temperature in the flask at 5 ° C.
The solution was added dropwise from the container over 1 hour. 45 minutes at 5 ° C after completion of dropping
After stirring for 45 minutes at 30 ℃, wash 3 times with 30 ml of heptane.
Repeated purification and dried under reduced pressure to obtain 5.7 g of a brown solid product.
It was (B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
5.6 g of a solid product synthesized by the reduction reaction of (A), torr
18.7 ml of ene and 0.50 ml of diisobutyl phthalate (1.9 mm
Mol) was added and the reaction was carried out at 95 ° C. for 1 hour. After the reaction, solid-liquid separation is performed and washed twice with 18.7 ml of toluene.
It was After washing, add 18.7 ml of toluene and butyl ether to the flask.
1.24 ml (7.3 mmol) and titanium tetrachloride 21.9 ml (199
Was added and the reaction was carried out at 95 ° C. for 3 hours. End of reaction
After the completion of solid-liquid separation at 95 ℃, use 18.7 ml of toluene at the same temperature.
It was washed twice. The above-mentioned butyl ether and tetrachloride
Treat with a mixture of tongue for another hour and
After washing twice with 18.7 ml of butane, dry under reduced pressure.
4.7 g of a reddish solid was obtained. When the solid catalyst component was analyzed, the titanium atoms were
Trace amount was detected, but magnesium atom and phthalic acid ester
Ter was not detected. (C) Polymerization Using the solid catalyst component synthesized in (B) above,
Conduct ethylene / propylene copolymerization under the same conditions as (D)
However, no polymer was obtained. Compared to Example 1, the organic porous polymer carrier was
Also the pore volume in the pore radius range of 100 to 5,000 Å i.e.
When dVp is extremely small, a catalyst component with polymerization activity should be used.
It cannot be retained inside the porous polymer, and effective ethylene / prepolymer
It does not act as a propylene catalyst. Examples 2 and 3 Using the solid catalyst component prepared in (C) of Example 1, solid
Catalyst input, polymerization temperature, hydrogen partial pressure, feed ethylene /
The propylene mixed gas composition and polymerization time are shown in Table 1.
In the same manner as in (D) of Example 1 except that the conditions are changed to
Random copolymerization of ethylene and propylene was carried out. Heavy
The conditions and the polymerization results are shown in Tables 1 and 2, respectively. Example 4 (A) Synthesis of solid catalyst component Performed after replacing a flask having an internal volume of 100 ml with argon.
2.74 solid product synthesized by reduction reaction of (B) of Example 1.
g, toluene 9.1 ml, butyl ether 0.60 ml (3.5 mm
1) and titanium tetrachloride 10.6 ml (96.4 mmol)
Then, the reaction was carried out at 95 ° C for 3 hours. After reaction, solid-liquid at 95 ° C
After separation, wash twice with 10 ml of toluene at the same temperature
It was A mixture of the above-mentioned butyl ether and titanium tetrachloride
Repeat the treatment with and wash twice with 10 ml of heptane.
After repeated purification, it was dried under reduced pressure to give a brown solid catalyst component 2.47.
got g. The solid catalyst component contains 2.0% by weight of titanium atom,
It contained 6.9% by weight of gnesium atoms. This solid touch
The average particle size of the medium component was 50μ. (B) Polymerization Using 378.5 mg of the solid catalyst component prepared in (A) above,
In the same manner as in (D) of Example 1, ethylene and propylene
We conducted random copolymerization. Different polymerization conditions and results
These are shown in Tables 1 and 2. Example 5 Using the solid catalyst component prepared in (A) of Example 4, solid
Conditions of catalyst loading, hydrogen partial pressure and polymerization time shown in Table 1
Except that the electron-donating compound did not coexist.
Of ethylene and propylene in the same manner as in (D) of Example 1.
Random copolymerization was carried out. Polymerization conditions and results
They are shown in Table 1 and Table 2, respectively. Example 6 Using the solid catalyst component prepared in (C) of Example 1,
Using an autoclave with a stirrer of product 5,
Copolymerization of benzene, propylene and 1,9-decadiene
Was carried out. Dispersant of polypropylene powder 50g in autoclave
Was added, the pressure was reduced, and the temperature was raised to 60 ° C. Then hydrogen
0.14 kg / cm²G supply, ethylene / propylene = 50 / 50Vo
l% mixed gas 10kg / cm²Pressurize to G, then triethylal
Add 0.5 g of minium and 0.13 g of phenyltrimethoxysilane.
Argon with a quantity of heptane into the autoclave
Pressed in. Then, add 15 ml of 1,9-decadiene to argon.
After press-fitting into the autoclave, (C) of Example 1
331.0 mg of the solid catalyst component prepared in Step 1 was mixed with a small amount of heptane.
Argon into the autoclave with a total pressure of 10
kg / cm²Keep the ethylene / propylene mixed gas at G
Feed for 60 minutes ethylene, propylene and 1,9-deca
Random copolymerization of dienes was performed. After the polymerization was completed, unreacted monomers were purged to obtain fine powder and coarse particles.
140g of granular elastomer with good powder properties
Obtained. In addition, the inner wall of the autoclave and the stirrer are polymer
Was not attached at all. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively. Example 7 Using the solid catalyst component prepared in Example 1 (C),
Using an autoclave with a stirrer of 5
Random copolymerization of butene-1 was carried out. Dispersant of polypropylene powder 50g in autoclave
Was charged, the pressure was reduced, and the temperature was raised to 60 ° C. Then water
0.34 kg / cm²G supply, ethylene / butene-1 = 80/20
Vol% mixed gas 5kg / cm²Pressurize to G, then triethyl
Aluminum 0.5g and phenyltrimethoxysilane 0.13g
And 408.3 mg of the solid catalyst component prepared in (C) of Example 1.
Autoclave with argon with a small amount of heptane
Pressed in. And the total pressure is 5kg / cm²Echi to keep G
Feed the ren / butene-1 mixed gas and leave it for 60 minutes.
N-butene-1 copolymerization was carried out in the gas phase. After the polymerization was completed, unreacted monomers were purged to obtain fine powder and coarse particles.
93g of granular elastomer with good powder properties
Obtained. In addition, the inner wall of the autoclave and the stirrer are polymer
Was not attached at all. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively. Example 8 Using the solid catalyst component prepared in (C) of Example 1,
A 26 fluidized bed gas phase polymerizer was used to
Random copolymerization of N-1 was carried out. After raising the temperature of the polymerization tank to 70 ° C, the polypropylene was previously dried under reduced pressure.
300g powder as a dispersant, and then
4.26 g of chill aluminum and phenyltrimethoxysilane
1.11 g and 1.2 of solid catalyst component prepared in (C) of Example 1
0 g was pressed into the tank with a small amount of hexane. And ethylene
So that the molar ratio of / butene-1 / hydrogen is 53 / 26.5 / 20.5
Prepared mixed gas 7-7.5kg / cm²In the polymerization tank under the pressure of G
At a flow rate of 0.3 m / sec. In addition,
When the molar ratio of hydrogen / butene-1 / hydrogen deviates from the set value
Occupy the polymerization tank by adjusting the molar ratio by adding
Polymer height / polymerization tank diameter (l / d) = 2-4
Ethylene / butene-1 fluidized bed gas phase copolymerization
I went on time. After the polymerization is completed, the amount of
The polymer was discharged from the polymerization tank and remained in the tank.
Was used as the dispersant for the next polymerization, and the same
By repeating the combination 6 times, the
The amount of polypropylene powder used for the first time is negligible
It was reduced to a degree. The polymer obtained is a powder free of fines and coarse particles.
It has good properties and contains 82.8% by weight of ethylene.
, [Η] = 1.4 Adhesive force = 4.6g / cm²Met. Also, 6
The amount of total polymer produced per gram of solid catalyst in one polymerization is
It was P / cat = 540. Comparative Example 4 (A) Synthesis of Solid Product A flask having an internal volume of 100 ml equipped with a stirrer and a dropping funnel was used.
After replacing with argon, styrene-divinylbenzene
Polymer (dVp = 0.75cc / g, average particle size 1,300μ) at 80 ℃
What was dried under reduced pressure for 30 minutes 6.00 g and heptane 30.0 ml, Tet
Labtoxititanium 0.27 g (0.79 mmol), tetraeth
Add 2.88 g (13.8 mmol) of xysilane and 45 minutes at 30 ℃
It was stirred. Next, the organomagnesium compound synthesized in (A) of Example 1
Add 7.3 ml of the product dropwise while maintaining the temperature in the flask at 5 ° C.
The solution was added dropwise from the outlet over 45 minutes. 45 minutes at 5 ℃ after the dropping
For another 45 minutes at 30 ° C, then twice with 30.0 ml heptane
Repeated washing and vacuum drying to obtain 7.45 g of a brown solid product.
Obtained. (B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
6.71 g of a solid product synthesized by the reduction reaction of (A),
Ruene 22.4 ml and diisobutyl phthalate 0.92 ml (3.44 ml
Limol) was added and the reaction was carried out at 95 ° C. for 1 hour. After the reaction, solid-liquid separation is performed and washed twice with 22.4 ml of toluene.
It was After washing, add 22.4 ml of toluene to the flask and put it into the flask.
Ether 1.48 ml (8.74 mmol) and titanium tetrachloride 26.2 ml
(238 mmol) was added and the reaction was carried out at 95 ° C for 3 hours.
After completion of the reaction, solid-liquid separation was performed at 95 ° C, and then toluene 2 was added at the same temperature.
It was washed twice with 2.4 ml. With the above-mentioned butyl ether
The treatment with the mixture with titanium tetrachloride was repeated for 1 hour.
After further washing twice with 22.4 ml of heptane, depressurization
After drying, 5.73 g of a brown solid catalyst component was obtained. The solid catalyst component contains 0.14% by weight of titanium atoms, and magnesium
2.5% by weight of Mu atom and 0.9% by weight of Phthalates
It was (C) Polymerization Ethylene was produced in the same manner as in Example 8 using the above solid catalyst.
/ Butene-1 copolymerization was performed, but the catalyst was not sufficiently dispersed.
As the polymerization progresses, the fluidized state becomes unstable and the fluidized bed
It became difficult to continue the gas phase copolymerization. Also, the generated polymer
Apparently it contains a lot of bulk polymer and hollow polymer
I was there. Compared to Example 8, an organic porous polymer carrier was used.
If the average particle size of the solid catalyst component is extremely large,
Stable in ethylene / butene-1 fluidized bed gas phase polymerization
It was difficult to obtain a stable flow state. <Effects of the Invention> As described above, the specific catalyst system of the present invention and the gas phase polymerization method are combined.
By combining them, the following effects can be obtained. (1) Efficient and stable granular ethylene copolymer
Can be manufactured at a higher cost than the conventional method.
It can be lowered. (2) Since the catalytic activity per titanium atom is very high,
Even if no special catalyst residue removal operation is performed,
Halogen source closely related to color, stability and corrosivity
Very low content of titanium and titanium atoms. That is, catalyst residue
No need for equipment for removing residue, reducing production costs
It becomes possible. (3) Since the ethylene copolymer is obtained in granular form, handling
It is easy to mold and process.

[Detailed Description of Drawings]

FIG. 1 is a flow chart for facilitating the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shozo Kawamata 5-1 Anezaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Hirosei Takara 1-5 5 Anesaki Kaigan, Ichihara, Chiba Sumitomo Chemical Kogyo Co., Ltd. (72) Inventor Kiyoji Kawai 1-5 Anezaki Kaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd. (56) Reference JP-A-2-97508 (JP, A)

Claims (2)

[Claims] 1. A catalyst component comprising at least (A) titanium, magnesium and chlorine and having an average particle size of 5 to 1,000 μm.
And the pore volume at a pore radius of 100 to 5,000Å is 0.1cc / g
A solid catalyst component impregnated in the organic porous polymer carrier as described above and (B) a catalyst system containing at least an organoaluminum compound are used, and random ethylene and α-olefins and, if necessary, polyene are used in a gas phase. Copolymerization is carried out, the ethylene content in the copolymer is 5 to 95% by weight, tetralin 135 ° C.
A method for producing an ethylene copolymer, which comprises obtaining an olefin elastomer having an intrinsic viscosity of 0.3 to 10 and a density of 0.86 to 0.90 g / cm ³ . 2. The method according to claim 1, wherein the ethylene copolymer is a random copolymer composed of ethylene, an α-olefin and a polyene.