JPH09216916A - Production of ethylene/alpha-olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene/α-olefin copolymer having a narrow compsn. distribution by copolymerizing ethylene and an α-olefin in the persence of a metallocene catalyst at a specified pressure and temp. while supplying a monomer mixture in a specified way. SOLUTION: A monomer mixture comprising ethylene and a 3C or higher α-olefin is supplied from a supply line 1 to a tube reactor and simultaneously a metallocene catalyst is supplied to the reactor from a supply line 4; the monomer mixture is also supplied to the reactor from supply lines 2 and 3 installed at the side of the reactor in parallel to the flow direction of the monomer mixture and the catalyst, from supply lines 5 and 6; and the monomer mixture is polymerized under a reaction pressure of 300-4,000kgf/cm<2> at a temp. in the range from the m.p. of the resultant copolymer to 300 deg.C, thus giving an ethylene/α-olefin copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION Ethylene and α-olefins having 3 or more carbon atoms are used as a reactor in the presence of an olefin polymerization catalyst at a reaction pressure of 300 to 4000 kgf / cm ² and a reaction temperature of the melting point of the copolymer to 300 ° C. The reaction mixture obtained by the copolymerization is depressurized to 40 to 300 kgf / cm ² , the unreacted monomer mixture is separated from the copolymer by a density difference in a separator, and the unreacted monomer mixture is cooled. By doing so, the copolymer entrained in it is precipitated, and the unreacted monomer is recovered by separating the precipitated copolymer in a new separator, and the resulting unreacted monomer is used as a raw material. A method for producing an ethylene / α-olefin copolymer, which comprises supplying ethylene and an α-olefin having 3 or more carbon atoms to a reactor (hereinafter, referred to as “high temperature / high pressure method ethylene / α-olefin copolymer production method”). That.) Has been known.

The present invention relates to a method for producing a high temperature / high pressure ethylene / α-olefin copolymer using a metallocene catalyst as a catalyst and a tubular reactor as a reactor.

(The term "melting point" in the present specification means that after melting a sample at 200 ° C. for 5 minutes in a differential scanning calorimeter,
The temperature is lowered to 30 ° C. at a rate of 10 ° C./min to solidify,
The maximum peak temperature of the endothermic curve obtained by raising the temperature at a rate of 10 ° C./min. )

[0004]

2. Description of the Related Art By the way, in a method for producing an ethylene / α-olefin copolymer by a high temperature and high pressure method, the heat of reaction generated with the progress of the copolymerization reaction is closely related to the reaction yield, and the heat of reaction is removed. The higher the yield, the higher the reaction yield.
When a tank-type reactor with a stirrer is used, it is difficult to forcibly remove the heat of reaction from the outside due to the restriction of heat transfer due to the mode of the reactor. And the total amount of heat released to the outside can be generated, and the reaction yield is relatively low (the reaction yield on a weight basis is about 10 to 15).
%). On the other hand, when using a tubular reactor as the reactor, the heat transfer is less restricted as in the case of a tank reactor with a stirrer, so the reaction heat can be forcibly removed from the outside. A higher reaction yield (reaction yield on a weight basis is about 15 to 25%) can be obtained as compared with the case of using a tank reactor with a machine.

On the other hand, in the copolymerization reaction of ethylene and α-olefin, the reaction rate of ethylene is much higher than the reaction rate of α-olefin, that is, ethylene is preferentially consumed during the production of the copolymer. Therefore, the α-olefin concentration in the monomer mixture of ethylene and α-olefin increases as the reaction progresses. This differs depending on the type of reactor.For example, in a tank reactor with a stirrer, the stirring is close to perfect mixing, so the α-olefin concentration in the reactor is uniform, whereas In a reactor of the type, there is no stirrer, and since the tube length with respect to the inner diameter of the tube is very large, the flow in the reactor is an extruding flow, and the α-olefin concentration varies from the reactor inlet to the outlet (monomer mixture It has a concentration gradient that increases from the upstream side to the downstream side). Therefore, a high-density copolymer is produced near the inlet of the tubular reactor, a low-density copolymer is produced near the outlet of the reactor, and as a result, the copolymer obtained from the reactor is Become a blend of these,
Its composition distribution tends to be broader than in a tank reactor with a stirrer. Further, as is well known, the molecular weight of the copolymer decreases as the α-olefin concentration increases,
The molecular weight distribution of the copolymer tends to be broader than that of a tank reactor with a stirrer. Such a tendency is remarkable in a general Ziegler-based catalyst which is said to have several kinds of active sites that form copolymers having different properties.

Therefore, when a tubular reactor is used as the reactor in the method for producing an ethylene / α-olefin copolymer by the high temperature and high pressure method, a higher reaction yield can be obtained as compared with a tank reactor with a stirrer. On the other hand, the composition distribution and molecular weight distribution of the copolymer tend to be broad. Further, when a metallocene catalyst is used as a catalyst, the composition distribution and molecular weight distribution of the copolymer are broadened. Among them, the broadened composition distribution is a characteristic of the copolymer obtained by the metallocene catalyst, that is, transparency and impact resistance. Properties and blocking properties are deteriorated, which is not preferable.

Japanese Unexamined Patent Publication (Kokai) No. 5-202131 discloses an ethylene homopolymer and an ethylene copolymer obtained by radical polymerization reaction under the conditions of a pressure of 500 to 5000 bar and a reaction temperature of 40 to 320 ° C. using a tubular reactor as a reactor. However, the above problems in the case of using an ionic copolymerization reaction, particularly a metallocene catalyst, have not been solved. In addition, JP-A-5-
In Japanese Patent No. 310831, by supplying two or more different metallocene catalysts each having a different reactivity ratio in a single reactor to simultaneously produce polyethylene and an ethylene / α-olefin copolymer, the molecular weight, Although it discloses that the desired polymer can be easily and easily obtained with respect to the weight fraction and the like, the above problems when using the tubular reactor have not been solved.

[0008]

SUMMARY OF THE INVENTION The present invention provides a solution to the above problems, that is, a method for producing a high temperature / high pressure ethylene / α-olefin copolymer using a metallocene catalyst as a catalyst in a tubular reactor. It is an object of the present invention to provide a method in which a copolymer having a narrow composition distribution is obtained by devising a method for supplying ethylene and an α-olefin having 3 or more carbon atoms.

[0009]

According to the present invention, in the presence of a metallocene catalyst, a reaction pressure of 300 to 4000 kgf / cm ² , a melting point of the copolymer to a reaction temperature of 300 ° C., ethylene and α having 3 or more carbon atoms are used. -In the method for producing an ethylene / α-olefin copolymer in which an olefin is copolymerized in a tubular reactor, ethylene or ethylene and a carbon number of 3
The present invention relates to a method for producing an ethylene / α-olefin copolymer, characterized in that the above-mentioned α-olefin monomer mixture is fed from the side of the reactor in the flow direction of the monomer mixture.

Hereinafter, the present invention will be described in detail.

An example of the tubular reactor used in the present invention will be described with reference to FIG. The tubular reactor may have a general shape, the tube length is 50 to 1000 m, and the ratio of the tube length to the tube diameter is 1000 to 50000, preferably 2000 to 40.
000. The average residence time of the reaction mixture in the reactor is 30 to 300 seconds, preferably 30 to 120 seconds.
Although the tubular reactor has a continuous structure, it can be divided into three parts, a preheating part, a reaction part, and a cooling part, depending on the function. In the preheating part, a monomer mixture of ethylene and α-olefin is preheated by a heating medium. Then, in the reaction part, while removing the reaction heat with a cooling medium, a copolymer is obtained by a copolymerization reaction by supplying a catalyst,
In the cooling section, the reaction mixture consisting of the unreacted monomer mixture and the copolymer is forcibly cooled by the cooling medium.

The supply of ethylene or a monomer mixture of ethylene and an α-olefin having 3 or more carbon atoms is a method of supplying from the side of the monomer mixture in the reactor in the flow direction. It is preferable to supply while distributing to 1 to 5 points of the reactor. In FIG.
Are supplied to two locations. The larger the number of these feeding points, the more uniform the α-olefin concentration in the reactor, that is, the smaller the compositional distribution of the copolymer obtained, but if the number of feeding points exceeds 5, the above-mentioned It becomes difficult to control the balance of the supply amount of the monomer mixture. Further, the supply amount at each supply location is preferably 1/80 to 1 times the amount supplied from the tip of the reactor upstream of the flow of the monomer mixture via the preheating section, and particularly 1 / 50-2 /
A three-fold amount is preferred. When each supply amount is smaller than 1/80 times the amount supplied via the preheating part, the effect of reducing the composition distribution of the obtained copolymer is small, and each supply amount is supplied via the preheating part. If the amount is larger than the amount of 1 times, it becomes difficult to control the reaction temperature in each reaction part. The interval between the supply points is the amount of the monomer mixture supplied to each supply point,
The length is preferably 1/15 to 1/2 times the tube length of the reactor, particularly 1
A length of / 10 to 1/3 times is preferable. If the interval between the supply points is smaller than 1/15 times the tube length of the reactor, it will be difficult to remove the heat of reaction in each reaction part, while the interval between the supply points will be greater than 1/2 the tube length of the reactor. And the composition distribution of the copolymer obtained in each reaction part is likely to spread.

The monomer mixture other than that supplied through the preheating section can be supplied to the reaction section without preheating, and the sensible heat can remove the reaction heat. The supply temperature at that time is 30 to 1 when the reaction heat is efficiently removed, that is, the reaction yield is improved to obtain a high production rate.
00 ° C is preferable, and 30 to 70 ° C is particularly preferable.

The heating medium of the preheating section and the cooling medium of the cooling section are not particularly limited, but for example, hot water or steam can be used, and the temperature thereof is the fluidity of the obtained copolymer and the temperature at the time of heat transfer. Considering heat loss, the melting point of the copolymer is preferably +10 to 60 ° C, and more preferably the melting point of the copolymer is +10 to 40 ° C.

The reaction section can be further divided and referred to for each catalyst supply point. In FIG. 1, the reaction section having three reaction regions, that is, the catalyst supply lines 4 to 5 is referred to as the first reaction section and the catalyst. The supply lines 5 to 6 will be hereinafter referred to as a second reaction section, and the catalyst supply line 6 to a cooling section will be hereinafter referred to as a third reaction section.

In order to make the composition distribution of the resulting copolymer smaller, the practical catalyst type is also taken into consideration.
A method of individually supplying 2 to 4 kinds of metallocene catalysts satisfying the relationship of the following formula (1) from the upstream side of the flow of the monomer mixture in the tubular reactor in the order of smaller k in the following formula (1). You may use together. Here, a preferable catalyst is one having a low density of the copolymer obtained by using each catalyst under the same reaction conditions except that the same reactor is used and the kind of the catalyst is different. The density of the k-th thing (represented by D ^k g / cm ³ ) and the density of the k−1-th thing (represented by D ^k-1 g / cm ³ ) counting from 0 are 0 when k is 2 or more. ^{.003 ≦ D k -D k-1} ≦ 0.02 (1) is preferably a "density of the copolymer" in ^{0.003 ≦ D k -D k-1} ≦ 0.01 ( present invention, JIS K
Measured according to 6760. ) Each catalyst satisfies the relationship of. The method of supplying such a catalyst is such that the upstream of the monomer mixture flow is considered in consideration of the α-olefinic concentration gradient increasing from the upstream side to the downstream side of the monomer mixture flow in the tubular reactor. It is possible to obtain a catalyst from the reactor by selecting a catalyst which gives a low density copolymer on the side and a catalyst which gives a high density copolymer on the downstream side of the flow of the monomer mixture. It means that the spread of the composition distribution of the copolymer can be made smaller. Therefore, if the density of the copolymer obtained by each catalyst does not satisfy the above relationship, the effect as an auxiliary method for obtaining a copolymer having a narrow composition distribution is small. Further, when the catalysts are individually supplied, the supply ratio of each catalyst due to the grade transition can be easily changed without temporarily destabilizing the temperature control, and further, the reaction different for each catalyst supply location. It is possible to take the temperature. The catalyst may be supplied independently from the catalyst supply line, but in order to improve the catalyst activity, the catalyst supply line is joined with the supply line of ethylene or a monomer mixture of ethylene and α-olefin. Alternatively, a method of supplying the catalyst to the reactor while sufficiently dispersing the catalyst in the monomer mixture may be used. In FIG. 1, there are three catalyst supply lines 4 to 6, of which supply lines 5 and 6 are provided.
Are joined to supply lines 2 and 3 of ethylene or a monomer mixture of ethylene and α-olefin, respectively. Further, the supply ratio of each catalyst is not particularly limited, but when two kinds of catalysts are used, for example, 10: 1 to 1:10 is preferable, and 5: 1 to 1: 5 is particularly preferable.

As described above, the reaction conditions may be those usually adopted. That is, the reaction temperature of the first, second and third reaction parts is from the melting point of the copolymer to 300 ° C, and when the activity of the catalyst to be supplied is emphasized, the melting point to 250 ° C is preferable. The reaction pressure is 300 to 4000 kgf / cm.
² , but 500-3000 considering the production cost
kgf / cm ² is preferred.

The metallocene catalyst used in the present invention is, for example, a) a transition metal compound containing a transition metal of Group 4 of the periodic table, and b).
A protic acid, a Lewis acid, an ionizable ionic compound or a Lewis acidic compound, and c) Periodic group 1, 2 or 13
The catalyst is composed of an organometallic compound containing any one of the group Sn, Zn or Zn, but is not limited thereto.

The transition metal compound containing a transition metal of Group 4 of the periodic table used in the present invention is represented by the following general formula (2):
(3)

[0020]

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[0021]

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[In the formula, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, wherein R1 and R2 are each independently the following general formula (4), (5), (6) or (7).

[0023]

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(In the formula, each R6 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an amino group or an oxygen-containing hydrocarbon group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. Or halogen)), which forms a sandwich structure together with M1, and R4 and R5 are each independently the following general formulas (8), (9), (10) or (1
1)

[0025]

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(In the formula, each R7 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an amino group or an oxygen-containing hydrocarbon group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. Or halogen), which forms a sandwich structure with M1 and R3 is represented by the following general formula (1)
2)

[0027]

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(In the formula, R8 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms, M2 is a carbon atom, A silicon atom, a germanium atom or a tin atom), and R4 and R5
, And p is an integer of 1 to 5. ].

Examples of the compound represented by the general formula (2) or (3) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl). Hafnium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butyl) Cyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethyl Cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, methylenebis (cyclopentadienyl)
Titanium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) hafnium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopenta) Dienyl) hafnium dichloride, methylenebis (butylcyclopentadienyl) titanium dichloride, methylenebis (butylcyclopentadienyl) zirconium dichloride, methylenebis (butylcyclopentadienyl) hafnium dichloride, methylenebis (tetramethylcyclopentadienyl) titanium dichloride , Methylenebis (tetramethylcyclopentadienyl) Ruconium dichloride, methylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, Ethylenebis (tetrahydroindenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) hafnium dichloride, ethylenebis (2-methyl-1-indenyl) titanium dichloride, ethylenebis (2-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-9-)
Fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,
7-dimethyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,
7-di-t-butyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2, 7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentane) Dienyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadiene) 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl -9
-Fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9) -Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-
2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, dimethylsilanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopentane Dienyl) hafnium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilane Diylbis (butylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) zirconiumdichloride Chloride, dimethylsilanediylbis (butylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) ) Titanium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (indenyl) titanium dichloride, dimethylsilanediylbis (2
-Methyl-indenyl) titanium dichloride, dimethylsilanediylbis (tetrahydroindenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-)
2,7-dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (2,7
4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-
Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl Bis (tetramethylcyclopentadienyl)
Zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-9- Fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) Zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis 2,4-Dimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride Dimethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-indenyl) hafnium dichloride, dimethylsilanediylbis (tetrahydroindenyl) hafnium Dichloride, dimethylsilanediyl (cyclopentadienyl-9
-Fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-
t-butyl-9-fluorenyl) hafnium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethyl Silanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride,
Diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methyl-
Indenyl) titanium dichloride, diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9- Fluorenyl) titanium dichloride,
Diethylsilanediyl (cyclopentadienyl-2,7
-Di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium Dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (tetramethylcyclopentadiene (Enyl) zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, diethylsilane Landiylbis (tetrahydroindenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (Cyclopentadienyl-2,7-di-t-butyl-9
-Fluorenyl) zirconium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride,
Diethylsilanediylbis (indenyl) hafnium dichloride, diethylsilanediylbis (2-methyl-
Indenyl) hafnium dichloride, diethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9- Fluorenyl) hafnium dichloride,
Diethylsilanediyl (cyclopentadienyl-2,7
-Di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylsilanediylbis (2,4,5-
Trimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (4- t-Butyl-2-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2-methyl-indenyl) ) Titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl) titanium dichloride, diphenylsilanediyl (cyclopen Dienyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-) 9
-Fluorenyl) titanium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (3 -Methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-indenyl) Zirconium dichloride, diphenylsilanediyl bis (tetrahydroindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-
9-fluorenyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl)
Hafnium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Hafnium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (indenyl)
Hafnium dichloride, diphenylsilanediylbis (2-methyl-indenyl) hafnium dichloride,
Diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, Diphenyl silanes such as diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride and the above-mentioned Group 4 transition metal compound dimethyls, diethyls,
A dihydro body, a diphenyl body, a dibenzyl body, etc. can be illustrated.

The protonic acid used in the present invention is represented by the following general formula (13) [HL1 _l ] [M2R5 ₄ ] (13) (wherein, H is a proton and L1 is independently a Lewis base, l is 0 <l ≦ 2, M2 is a boron atom, an aluminum atom or a gallium atom, and R5
Are each independently a halogen-substituted aryl group having 6 to 20 carbon atoms. ).

The Lewis acid is represented by the following general formula (14) [C] [M2R5 ₄ ] (14) (wherein C is a carbonium cation or tropylium cation, and M2 is a boron atom, an aluminum atom or a gallium atom). And R5 each independently represents a halogen-substituted aryl group having 6 to 20 carbon atoms.).

The ionized ionic compound is represented by the following general formula (15) [M3L2 _m ] [M2R5 ₄ ] (15) (wherein M3 is a group 2, 8, 9 or 10 of the periodic table, 1
A cation of a metal selected from Group 1 or Group 12,
L2 is a Lewis base or a cyclopentadienyl group, m is 0 ≦ m ≦ 2, M2 is a boron atom, an aluminum atom or a gallium atom, and R5 are independently halogen-substituted with 6 to 20 carbon atoms. It is an aryl group. ).

The Lewis acidic compound is represented by the following general formula (16) [M2R5 ₃ ] (16) (wherein, M2 is a boron atom, an aluminum atom or a gallium atom, and each R5 independently has 6 to 20 carbon atoms.
Is a halogen-substituted aryl group. ).

The protonic acid represented by the general formula (13) used as a constituent component of the catalyst of the present invention, the general formula (14)
The Lewis acid represented by, the ionized ionic compound represented by the general formula (15) or the Lewis acidic compound represented by the general formula (16) is a compound capable of converting the above transition metal compound into a cationic compound, It is a compound that provides a counter anion that weakly coordinates and / or interacts with the produced cationic compound but does not react.

Specific examples of the protonic acid represented by the general formula (13) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl). ) Borate, hydronium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) Aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) Nyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri-n-butylammonium tetrakis (pentafluorophenyl) aluminate, etc. However, the present invention is not limited to these.

Specific examples of the Lewis acid represented by the general formula (14) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, Examples include, but are not limited to, tropylium tetrakis (pentafluorophenyl) aluminate.

The ionized ionic compound represented by the general formula (15) is specifically a lithium salt such as lithium tetrakis (pentafluorophenyl) borate or lithium tetrakis (pentafluorophenyl) aluminate, or a salt thereof. Ether complexes, ferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) aluminate, silver tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) aluminate, etc. Examples thereof include, but are not limited to, silver salts.

Specific examples of the Lewis acidic compound represented by the general formula (16) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane and tris (2,2). 3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum, etc. However, the present invention is not limited to these.

Periodic table groups 1 and 2 used in the present invention
The organometallic compound containing Group 13, Group 13, Sn or Zn is
The following general formula (17) M5R16 _n (17) [In the formula, M5 is an element of Group 1, Group 2 or Group 13 of the periodic table, Sn or Zn. R16 is independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy having 6 to 20 carbon atoms. At least one R16 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms. n is equal to the oxidation number of M5. ] It is a compound represented by these.

Examples of the compound represented by the general formula (17) include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n.
-Propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triamyl aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-
n-butylaluminum ethoxide, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di-n
-Propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride and the like.

The above a) a transition metal compound containing a transition metal of Group 4 of the periodic table, b) a protonic acid, a Lewis acid, an ionizable ionic compound or a Lewis acidic compound, and c) a group 1, 2 or 13 of the periodic table. Examples of the method for preparing the catalyst from the organometallic compound containing any of Sn, Zn, and Zn include, but are not limited to, a method of mixing these compounds in an inert solvent. Further, the amount of the protonic acid, the Lewis acid, the ionized ionic compound or the Lewis acidic compound in the catalyst is preferably 0.1 to 100 times mol, particularly 0.5 to 30 times mol with respect to the transition metal compound. Preferably.
Furthermore, the amount of the organometallic compound is not particularly limited, but is preferably 1 to 10000 times mo of the transition metal compound.
l.

The α-olefin having 3 or more carbon atoms to be copolymerized in the present invention is propylene, 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene,
Examples thereof include styrene, and these may be used alone or in combination of two or more. Further, the α-olefin is not limited to the above.

[0043]

EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Ethylene / α described in Examples and Comparative Examples
-Physical properties of the olefin copolymer were measured by the following methods.

(A) The melt flow rate (MFR) is
According to JIS K7210, 190 ℃, load 2.16k
It was measured under the condition of g.

(B) The composition distribution index R, which is an index of the composition distribution of the copolymer, was calculated by the following formula.

R = Qm / Vm Qm in the above formula is DS using a differential scanning calorimeter (DSC) [DSC-7 manufactured by Perkin Elmer Co., Ltd.].
After the sample was melted in C at 200 ° C for 5 minutes, 10 ° C /
Decrease the temperature to 30 ℃ at the speed of minute to solidify,
The amount of heat of fusion per unit mass of the sample obtained from the endothermic curve obtained by raising the temperature at a rate of minutes, and Vm in the formula
Is the peak potential difference per unit mass of the sample obtained from the endothermic curve.

Example 1 In a process for producing an ethylene / α-olefin copolymer by a high temperature / high pressure method, a pipe length was 800 m, a ratio of the pipe length to the pipe inner diameter was 27,000, three catalyst supply lines were used, and ethylene and α-olefin were used. A tubular reactor having three supply lines for the monomer mixture of was used. Of the three catalyst supply lines, as shown in FIG. 1, only one catalyst is supplied to the reactor from a position 120 m downstream from the tip of the reactor upstream of the flow of the monomer mixture, and the remaining The two are joined to the feed line of the monomer mixture and then fed to the reactor. Further, among the three supply lines of the monomer mixture, one is the tip (main stream) of the reactor upstream of the flow of the monomer mixture, and the other two are the tips of the reactors respectively. 270m and 400m downstream.
The temperature of supplying the monomer mixture to the reactor was 40 ° C., and the temperature of the heating medium in the preheating section and the cooling medium in the reaction section and the cooling section were 120 ° C.
The monomer mixture was heated to 80 in the preheating section using steam at ℃.
Heated up to ℃, continuously supply metallocene catalyst to each reaction part, reaction pressure 900 kgf / cm ² , reaction temperature of each reaction part 220 ℃, the average residence time of the reaction mixture in the reactor is 100 seconds continuously After the polymerization, the reaction mixture in the cooling section was cooled to 210 ° C., and the obtained copolymer was separated from the unreacted monomer mixture in a separator and passed through an extruder under the separator to obtain pellets. Discharged. The production rate of the obtained copolymer was 4.3 t / h. Metallocene catalysts include diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, N, N-dimethylanilinium tetrakis (pentafluorophenyl)
The borate and triisobutylaluminum have a boron / zirconium molar ratio of 1.2, an aluminum / zirconium molar ratio of 250, and a zirconium concentration of 650 μmo.
A toluene solution adjusted to 1 / l was used.

Example 2 The amount of the monomer mixture supplied to the first reaction section was 16.2 t /
h, the supply amount of the monomer mixture to the second reaction part is 3.0 t /
The procedure was performed in the same manner as in Example 1 except that the reaction temperature in the first reaction section was 180 ° C and the reaction temperature in the second reaction section was 200 ° C. The production rate of the obtained copolymer is 4.2 t / h.
Met.

Example 3 The amount of the monomer mixture supplied to the first reaction section was 19.7 t /
h, the amount of the monomer mixture supplied to the second reaction section is 1.0 t /
h, the supply amount of the monomer mixture to the third reaction part is 3.0 t /
The same procedure as in Example 1 was repeated except that the metallocene catalyst was used for the second and third reaction sections and the metallocene catalyst / metallocene catalyst supply ratio was 1/1. The production rate of the obtained copolymer was 4.3 t / h. The metallocene catalyst includes diphenyl (cyclopentadienyl) [(2-dimethylamino) fluorenyl] zirconium dichloride, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and triisobutylaluminum in a boron / zirconium molar ratio. 1.2, aluminum / zirconium molar ratio of 250, zirconium concentration of 650 μmol / l
The toluene solution prepared in 1. was used. Further, when D ¹ is the density of the copolymer obtained when only the metallocene catalyst is used and D ² is the density when only the metallocene catalyst is used, D ¹ is 0.9071 g / cm ³
And D ² is 0.9119 g / cm ³ and D ² −D ¹ is 0.0
It was 048 g / cm ³ .

Example 4 The amount of the monomer mixture supplied to the first reaction section was 14.0 t /
h, the supply amount of the monomer mixture to the second reaction section is 4.6 t /
h, the reaction pressure is 500 kgf / cm ² , the reaction temperature of each reaction part is 230 ° C., 1-butene is used as the α-olefin, and the α-olefin concentration at the reactor inlet is 50
The same procedure as in Example 1 was carried out except that the content was changed to mol%. The production rate of the obtained copolymer was 4.3 t / h.

Comparative Example 1 The amount of the monomer mixture supplied to the first reaction section was 23.7 t / h.
And was performed in the same manner as in Example 1 except that the monomer mixture was not supplied to the second and third reaction sections. The production rate of the obtained copolymer was 4.4 t / h.

The results of each example are shown in Table 1.

[0054]

[Table 1]

[0055]

As described above, the high temperature / high pressure process ethylene / α using a metallocene catalyst as a catalyst in a tubular reactor
In the method for producing an olefin copolymer, a copolymer having a narrow composition distribution can be obtained by devising a method of supplying ethylene and an α-olefin having 3 or more carbon atoms to the reactor.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a tubular reactor of the present invention.

[Explanation of symbols]

1,2,3: Supply line of ethylene and α-olefin monomer mixture 4,5,6: Supply line of catalyst 7: Supply line of heating medium 8: Supply line of cooling medium

Claims (1)

[Claims] 1. 300 to 400 in the presence of a metallocene catalyst.
Reaction pressure of 0 kgf / cm ² , melting point of copolymer ~ 300
In the method for producing an ethylene / α-olefin copolymer in which ethylene and α-olefin having 3 or more carbon atoms are copolymerized in a tubular reactor at a reaction temperature of ℃, ethylene or ethylene and α-olefin having 3 or more carbon atoms are further used. Ethylene / α-characterized in that the monomer mixture of olefin is fed from the side in the reactor with respect to the flow direction of the monomer mixture.
Process for producing olefin copolymer.