JP2957242B2 - Olefin polymerization catalyst, method for producing the same, and method for producing olefin polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization, a method for producing the same, and a method for producing an olefin polymer. More specifically, the present invention provides a polymer for olefin polymerization comprising a specific component and a method for producing an olefin polymer using the catalyst, whereby a polymer having good particle properties can be obtained in high yield. Is what makes it possible.

<Prior Art> A catalyst comprising bis (cyclopentadienyl) zirconium dichloride and methylalumoxane (sometimes called a Kaminski catalyst in the name of the inventor) is extremely high in olefin polymerization or copolymerization. It is well known that it exhibits polymerization activity (JP-A-58-19309).
Nos., 60-35007).

This catalyst system is a homogeneous catalyst which is dissolved in a solution for polymerization, and in which no polymer particles serving as a prototype of polymer particles are present, so that the polymer is obtained in a fine powder form. However, many of the finely divided polymers obtained with such a catalyst system are difficult to handle, and agglomerated polymers are easily generated by aggregation. In order to solve this problem, a method has been proposed in which a catalyst component such as a metallocene compound is supported on an inorganic oxide carrier such as SiO ₂ .
(JP-A-61-108610, JP-A-61-296008, JP-A-63-51407)
Nos. 63-61010 and 63-152608). However, in these proposals, it is essential that the oxide carrier is preliminarily treated with alumoxane or that the oxide carrier is simultaneously treated with a metallocene compound and alumoxane. Without the alumoxane, since the metallocene compound is not supported, it is considered that most of the metallocene compound is substantially supported on the alumoxane rather than the oxide carrier itself, and when used for polymerization, the metallocene compound is not used. Since the supported alumoxane is easily peeled off from the oxide carrier and the polymerization component of fine particles is present, the solution of the above problems is still insufficient.

On the other hand, it has been proposed to directly form particles of alumoxane instead of inorganic oxides and to carry a metallocene compound thereon (JP-A-63-199206, JP-A-63-264606, JP-A-64-51408).
No. and JP-T-63-501962). However, since the catalyst particles are non-uniform and the produced polymer particles contain a large amount of alumoxane, further improvement is desired.

[Summary of the Invention]

<Summary> The present invention has been made as a result of studies to solve the above problems.

That is, the process for producing an olefin polymerization catalyst according to the present invention comprises contacting the following component (i) with the component (ii) and then contacting the contact product with the following component (iii) to obtain a solid catalyst component. (Ie, component (A)), and contacting the solid catalyst component with an alkylalumoxane (ie, component (B)).

Component (i) a catalyst support having a hydroxyl group and containing an element selected from Si, Al and Mg, Component (ii) a halogen compound of a transition metal of Group B of Periodic Table IV, Component (iii) having a conjugated five-membered ring An organometallic compound comprising a compound and a Group IA metal of the periodic table.

The olefin polymerization catalyst according to the present invention is obtained by the above-mentioned method for producing an olefin polymerization catalyst.

Further, the process for producing an olefin polymer according to the present invention comprises contacting the following component (i) with the component (ii), and then contacting the contact product with the following component (iii) to obtain a solid catalyst component ( That is, component (A)) is prepared,
The solid catalyst component and an alkylalumoxane (ie,
Olefin is brought into contact with an olefin polymerization catalyst produced by bringing the component (B)) into contact with the olefin polymerization catalyst.

Component (i) a catalyst support having a hydroxyl group and containing an element selected from Si, Al and Mg, Component (ii) a halogen compound of a transition metal of Group B of Periodic Table IV, Component (iii) having a conjugated five-membered ring An organometallic compound comprising a compound and a Group IA metal of the periodic table.

<Effects> According to the present invention, it is possible to obtain an olefin polymer having good particle properties in high yield. Further, the present invention provides
Since the aggregation of the polymer and the formation of the bulk polymer are small, it can be applied to a gas-phase polymerization method in which the properties of the polymer particles are strictly required.

[Specific description of the invention]

<Olefin polymerization catalyst> The olefin polymerization catalyst according to the present invention comprises the specific component (A) and the specific component (B). here,
“Consisting of” means that other components can be contained in addition to the component (A) and the component (B) as long as the effects of the present invention are not impaired.

Component (A) Component (A) is a solid catalyst component obtained by contacting the following component (i) with the component (ii), and then contacting the contact product with the following component (iii). .

Component (i) a catalyst support having a hydroxyl group and containing an element selected from Si, Al and Mg, Component (ii) a halogen compound of a transition metal of Group B of Periodic Table IV, Component (iii) having a conjugated five-membered ring An organometallic compound comprising a compound and a Group IA metal of the periodic table.

Component (i) The component (i) is a catalyst carrier having a hydroxyl group and containing an element selected from Si, Al and Mg. Specifically, porous inorganic oxide carriers such as silica, alumina, and magnesia, Al (OH) ₃ , Mg (OH) ₂ , and Mg (OH) Cl are exemplified. Component (i) has a surface area of 1 to 500 m ² / g (BET
Method), particles having an average particle size of 1 to 100 μm are preferred. Since these generally adsorb surface water, they are generally used after dehydration and drying to remove surface water in a nitrogen or air atmosphere or at 100 to 900 ° C. under reduced pressure.

Component (ii) Component (ii) is a halogen compound of a transition metal of Group IVB of the Periodic Table.

As the halogen constituting such a compound, chlorine, bromine, iodine, particularly chlorine is preferable. The transition metal of Group IVB of the periodic table is specifically titanium, zirconium and hafnium, and among these, zirconium is particularly preferred.

Component (ii), which is a compound of the above halogen and a transition metal belonging to Group IVB of the Periodic Table IV, has all the valences of the transition metal constituting the above halogen (the halogen may be plural kinds). It does not need to be satisfied, and some of the halogens may be substituted with, for example, an alkoxy group or an amino group having about 1 to 12 carbon atoms.

Specific examples of preferred compounds as component (ii) include:
(A) Titanium halide compounds such as TiCl ₄ , TiCl ₃ (OC
_{2 H 5), TiCl 3 (} OC 4 H 9), TiCl 2 (OC 4 H 9) 2, TiCl 3, Ti
(B) zirconium halogen compounds such as Br ₄ and TiI ₄ ,
For example _{ZrCl 4, ZrBr 4, ZrCl 3} (OC 2 H 5) etc., (c) hafnium halides, for example HfCl _4, HfBr _4, and the like. Of these, particularly preferred are tetrachlorides, specifically, titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.

Component (iii) Component (iii) is an organometallic compound composed of a compound having a conjugated five-membered ring and a Group IA metal of the periodic table. Typical examples of the compound having a conjugated five-membered ring include cyclopentadiene, indene and fluorene, and examples of the Group IA metal of the periodic table include lithium, sodium and potassium. Specific examples include cyclopentadiethyl lithium, cyclopentadienyl sodium, cyclopentadienyl potassium, indenyl lithium, fluorenyl lithium, ethylenebisindenyl lithium,
Lithium dimethylsilyl (biscyclopentadienyl), lithium dimethylsilyl (bisindenyl), sodium dimethylsilyl (bisindenyl), potassium dimethylsilyl (bisindenyl), lithium isopropylcyclopentadienylfluorenyl, and the like.

<Preparation of Component (A)> Component (A) is obtained by contacting the above-mentioned components (i) and (ii), and then contacting the contact product with component (iii). is there.

The contact between the component (i) and the component (ii) is usually carried out by (a) a hydrocarbon solvent such as hexane, heptane, toluene or the like.
(B) halogenated hydrocarbon solvents such as methylene dichloride, 1,2-dichloroethane, dichlorobenzene, chloroform, trichloroethane, trifluoroethylene,
In a solvent selected from (c) ether solvents such as tetrafluoroethane and the like, for example, diethyl ether, dibutyl ether, tetrahydrofuran and the like, the components (i) and (i)
i) are added sequentially or simultaneously. An appropriate contact temperature is -78 ° C to 100 ° C, and a suitable contact time is 30 minutes to 20 hours. The amount of component (i) and component (ii) used is
0.001 to 100, preferably a molar ratio of i) / component (i)
0.01 to 50. After the contact product obtained after the contact (i.e., the carrier supporting the transition metal halide), the carrier is washed with the solvent, and then, as a transition metal atom in the carrier, 0.01 to 10% by weight, preferably 0.05 to 5% by weight. You can do it.

The contact of the component (iii) can be carried out in the same solvent as used when the component (i) and the component (ii) are brought into contact. The contact temperature at this time is -78 ° C to 100 ° C, and the contact time is 3
0 minutes to 48 hours is appropriate. The amount of the component (iii) used is 0.5 to 100, preferably 1 to 100, in terms of a metal atom mole ratio with respect to the transition metal supported by the contact of the component (i) and the component (ii).
Ten.

Component (B) Component (B) is an alkylalumoxane. Such an alkylalumoxane has the general formula [I] and the general formula [II] Can be represented by In the alkylalumoxane, R is a lower hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and is preferably a methyl group, an ethyl group, or an isobutyl group. And particularly preferably a methyl group. n is an integer of 2 or more, preferably 4 or more. Further, the alkylalumoxane may be a halogenated alkylalumoxane in which a part of R is substituted with a halogen atom such as chlorine or bromine. Further, a plurality of the alkyl groups [I] and [II] may be mixed in one molecule. As the method for producing the alkylalumoxane, for example, a method obtained by reacting a trialkylaluminum with water, and in the present invention, a method obtained by preparing under various known conditions can be used. . For example, benzene, toluene or other aromatic hydrocarbon solvent into a salt having water of crystallization, such as copper sulfate pentahydrate, and reacted with a trialkyl aluminum under a temperature condition of about -40 to 40 ° C. Alumoxane can be obtained. In this case, the amount of water used is usually from 0.5 to
1.5.

<Formation of Catalyst> The catalyst for olefin polymerization according to the present invention is obtained by polymerizing the above components (A) and (B) (and, if necessary, the third component) in the presence or absence of the olefin to be polymerized. It can be formed by contacting a plurality of times in a tank or outside the polymerization tank at a time, stepwise or dividedly. The amount of the component (B) used is 1 to 100,000, preferably 10 to 30,000 in terms of the molar ratio of Al / transition metal to the transition metal in the component (A).

<Olefin Polymerization> The olefin polymerization catalyst according to the present invention is applied not only to ordinary slurry polymerization but also to a liquid phase solventless polymerization, a solution polymerization, or a gas phase polymerization method using substantially no solvent. Also applies. Further, the present invention is also applicable to a system in which continuous polymerization, batch polymerization or preliminary polymerization is performed. Therefore, the method for producing an olefin polymer according to the present invention, which comprises contacting an olefin with the catalyst and polymerizing the catalyst, employs each of the above-mentioned polymerization methods or polymerization modes.

Hexane, as a polymerization solvent in the case of slurry polymerization,
Saturated aliphatic or aromatic hydrocarbons, such as heptane, pentane, cyclohexane, benzene, and toluene, alone or in a mixture are used. The polymerization temperature is about −78 ° C. to about 200 ° C., preferably 0 ° C. to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator as an auxiliary. In the case of slurry polymerization, the amount of the component (A) used is 0.0001 to 1.0.
It is preferably within the range of gram component (A) / liter solvent.

Olefins to be polymerized with the catalyst system according to the present invention, in other words, the olefins to be contacted with the catalyst according to the invention has the general formula R-CH = CH ₂ (wherein R represents a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms And may have a branched group). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Preferred are ethylene and propylene. In these polymerizations, up to 50% by weight, preferably up to 20% by weight, of the above-mentioned olefins can be copolymerized with ethylene, and up to 30% by weight of the olefins, especially ethylene, with respect to propylene. , Can be copolymerized. Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefin, etc.) can also be performed.

[Experimental example]

Example 1 (Preparation of Component (A)) 6.0 g of MgCl ₂ .6H ₂ O was heat-treated under reduced pressure at 100 ° C. for 1 hour, then heated to 200 ° C. for 4 hours, and further heated to 285 ° C. for 2 hours. , By heat treatment under reduced pressure, Mg (O
H) Cl was obtained.

Next, 1.7 g of Mg (OH) Cl obtained by the above method and 10.3 ml of TiCl ₄ were reacted at 80 ° C. for 2 hours. After the completion of the reaction, the supernatant was removed, washed sufficiently with n-heptane, and dried under reduced pressure at 40 ° C. to obtain a solid component (a). This solid contained 0.53% by weight of titanium.
The solid component (a) was diluted with 10 ml of toluene, and 0.19 ml (0.38 mmol) of a previously synthesized tetrahydrofuran dilute solution of sodium cyclopentadienide (0.38 mmol) (NaCp / Ti = 2 (molar ratio)) was added. )) And reacted at room temperature for 1 hour. After the completion of the reaction, the supernatant was removed, followed by drying under reduced pressure to obtain the component (A). Component (A) contained 0.52 weight percent titanium. The tetrahydrofuran dilute solution of sodium cyclopentadienide was synthesized according to the synthetic method described in Experimental Chemistry Course (Vol. 13), page 45, Organometallic Compounds.

(Production of component (B)) Toluene solution 565 containing 48.2 g of trimethylaluminum
Under stirring, 50 g of copper sulfate pentahydrate was added to the ml at 5 ° C. at 5 ° intervals at 0 ° C. After completion, the temperature of the solution is slowly raised to 25 ° C., and the reaction is carried out at 25 ° C. for 2 hours and further at 35 ° C. for 2 days. The remaining copper sulfate solid is separated to obtain a toluene solution of alumoxane. The concentration of methylalumoxane is 27.3
mg / ml (2.7 w / v%).

(Polymerization of ethylene) In a 100 ml glass container, 20 ml of toluene, 11.0 mmol of methylalumoxane of component (B) and a solid component of component (A) were added in an amount of 0.11 in terms of titanium atom.
After the addition of mmol, ethylene was polymerized at 40 ° C. under atmospheric pressure for 1 hour. The obtained polymerization reaction solution was mixed into 1 liter of a methanol solution of hydrochloric acid to terminate the polymerization. The solvent was separated by filtration and dried, yielding 1.21 grams of polyethylene. This is 230g-polyethylene in titanium yield
/g-titanium.atm.Hr.

Example 2 (Preparation of Component (A)) The amount of the tetrahydrofuran dilute solution of sodium cyclopentadienide used in preparing Component (A) of Example 1 was 0.1 ml (0.19 mmol (NaCp / Ti = 1
(Molar ratio))) Component (A) was prepared under the same conditions as in Example 1 except that it was added.

(Polymerization of Ethylene) Polymerization was carried out under the same conditions as in Example 1 except that the above component (A) was used. The result was 1.16 grams of polymer. Titanium yield is 220 g-polyethylene / g-
It was titanium, atm, and Hr.

Comparative Example-1 A solid component (A) which is an intermediate in the preparation of the component (A) of Example-1 was polymerized under the same conditions as in Example-1 except that the solid component (A) was used instead of the component (A). Was carried out. As a result, 0.04 g of a polymer was obtained. 8g titanium yield
-Polyethylene / g-titanium-atm-Hr.

Example 3 (Preparation of Component (A)) A 300 ml round bottom flask in which 4 g of "952" silica manufactured by Devison and 40 ml of n-heptane, which had been dried in a nitrogen stream at 600 ° C. for 4 hours, was replaced with 40 ml of nitrogen. Was introduced. Then, add 10 ml of titanium tetrachloride,
The reaction was performed at 80 ° C. for 2 hours. After completion of the reaction, the resultant was sufficiently washed with n-heptane and dried under a nitrogen stream to obtain a solid component (b). The solid component (b) contained 3.12% by weight of titanium. Next, 2 g of the solid component (b) and 40 ml of toluene were introduced, and the mixture was cooled to -40 ° C or lower. Then, 1.99 mmol of toluene-diluted indene lithium obtained by the method described below was added.
Introduced over 15 minutes. After the introduction, the temperature was returned to room temperature over 1 hour, followed by a reaction at room temperature for 4 hours. After the completion of the reaction, the resultant was sufficiently washed with toluene. This component (A) contained 2.36 weight percent titanium. For the synthesis of lithium indene, 8 ml of indene was added to 50 ml of toluene.
After adding milliliters and cooling to −40 ° C. or lower, 0.069 mol of butyllithium (diluted solution in hexane) was added dropwise over 15 minutes, and the temperature was maintained at −40 ° C. or lower for 1 hour. Performed by stirring for hours.

(Polymerization of Ethylene) After sufficiently replacing the inside of a stirring type autoclave having an internal volume of 1.5 liters with ethylene, the dehydration and deoxygenation of n was sufficiently performed.
-After introducing 500 ml of heptane, 10.0 mmol of the component (B) methylalumoxane and 0.02 mmol of the component (A) synthesized above in terms of titanium atom, hydrogen was pressurized to 1 K / gauge pressure, Then, ethylene was introduced and polymerization was carried out at 75 ° C. for 2 hours at a total pressure of 7 K / gauge. The results are shown in Table 1.

Comparative Example-2 Polymerization was carried out under the same conditions as in Example-3, except that the solid component (b), which is an intermediate product when preparing the component (A) of Example-3, was used instead of the component (A). Was carried out. The results are shown in Table 1.

Example-4 (Preparation of component (A)) 50 ml of tetrahydrofuran was cooled to -40 ° C or lower, and 0.6 g of zirconium tetrachloride was dissolved therein. Next, 3 g of “952” silica treated in the same manner as in Example 3 was introduced, and the temperature was slowly raised to room temperature over 1 hour, followed by a reaction at room temperature for 2 hours. After the completion of the reaction, the solid was sufficiently washed with toluene and dried under a nitrogen stream to obtain a solid component (c). The solid component (c) contained 2.79% by weight of zirconium. The results of the determination of zirconium were obtained by dissolving the sample in 1N nitric acid, adding excess EDTA, and performing back titration with bismuth nitrate. Next, 2.5 g of the above solid component was introduced into 50 ml of tetrahydrofuran and cooled to -40 ° C or lower. Next, 3.4 mmol of the indenyl lithium obtained in Example 3 was added dropwise over 15 minutes, the reaction was allowed to proceed at -40 ° C for 1 hour, and then the temperature was raised to room temperature over 1 hour, and then reacted at room temperature for 2 hours. Was. After completion of the reaction, the reaction product was sufficiently washed with toluene. Next, 100 mmol of methylalumoxane was added and reacted at room temperature for 1 hour. After the completion of the reaction, the resultant was sufficiently washed with toluene to obtain a component (A). This component (A)
It contained 2.28 weight percent zirconium.

(Polymerization of ethylene) Ethylene was polymerized under the same conditions as in Example-3. The results are shown in Table 1.

Comparative Example-3 Ethylene was prepared under the same conditions as in Example-4 except that a solid component (c), which is an intermediate product when preparing component (A) of Example-4, was used instead of component (A). Polymerization was performed. The results are shown in Table 1.

Example-5 (Preparation of component (A)) Except for using 1.7 mmol of a compound obtained by reacting ethylenebisindene with 2 times mol of butyllithium in place of indenyllithium of Example-4, all of Example-4 was used. Component (A) was prepared under the same conditions as described above. This component (A) contained 1.69 weight percent zirconium.

(Polymerization of ethylene) Ethylene was polymerized under the same conditions as in Example-3. The results are shown in Table 1.

Examples-6, 7 and Comparative Example-4 Polymerization of propylene was carried out using the solid components of Examples 4,5 and Comparative Example-3. The polymerization was carried out under the conditions of 500 ml of n-heptane, 100 mmol of methylalumoxane and 0.01 mmol of the component (A) in terms of zirconium atom, and a propylene pressure of 7 K / gauge pressure at 50 ° C. for 2 hours. After completion of the polymerization, the polymerization slurry was introduced into 2 liters of methanol-hydrochloric acid, detouched, and the filtrate was evaporated to obtain polypropylene. Table 2 shows the results.

[Brief description of the drawings]

FIG. 1 is to assist in understanding the technical contents of the present invention relating to the Ziegler catalyst.

Continuation of the front page (56) References JP-A-61-296008 (JP, A) JP-A-61-108610 (JP, A) JP-A-63-66206 (JP, A) JP-A-3-74412 (JP) JP-A-3-263410 (JP, A) JP-A-3-709 (JP, A) JP-A-2-501227 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C08F 4/60-4/70

Claims (3)

(57) [Claims] 1. The solid catalyst component (ie, component (A)) is contacted with the following component (i) and component (ii), and then by contacting the contact product with the following component (iii). A method for producing a catalyst for olefin polymerization, which comprises preparing and contacting the solid catalyst component with an alkylalumoxane (ie, component (B)). Component (i) a catalyst support having a hydroxyl group and containing an element selected from Si, Al and Mg, Component (ii) a halogen compound of a transition metal of Group B of Periodic Table IV, Component (iii) having a conjugated five-membered ring An organometallic compound comprising a compound and a Group IA metal of the periodic table. 2. A solid catalyst for olefin polymerization obtained by the production method according to claim 1. 3. The solid catalyst component (ie, component (A)) is brought into contact with the following components (i) and (ii) and then contacting the contact product with the following component (iii). An olefin polymer, which is prepared by contacting the solid catalyst component with an alkylalumoxane (i.e., component (B)) to produce an olefin polymerization catalyst and contacting the olefin with the olefin polymerization catalyst. Manufacturing method. Component (i) a catalyst support having a hydroxyl group and containing an element selected from Si, Al and Mg, Component (ii) a halogen compound of a transition metal of Group B of Periodic Table IV, Component (iii) having a conjugated five-membered ring An organometallic compound comprising a compound and a Group IA metal of the periodic table.