JPH0733407B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Use of the Invention The present invention relates to a method for producing a polyolefin.

(B) Conventional Technology For example, there is the Natta Method as a conventional technology.

The product produced by this Natta method did not have a round particle shape and had a large variation in particle size.

(C) Problem to be Solved by the Invention The object of the present invention is to polymerize ethylene or copolymerize ethylene and α-olefin using a novel highly active maintained catalyst to give a round and smooth surface. It is an object of the present invention to provide a method for producing a polyolefin having an appearance and having a small variation in particle size.

(D) Means for Solving the Problems The present invention is to solve the above problems, and comprises (a) a step of reacting a hydropolysiloxane with an organomagnesium compound, and (b) a reaction product of the step (a). , The following general structural formula (I): R ¹ (COOH) ₂ (I) wherein R ¹ is a hydrogen atom or a divalent organic group containing 1 to 20 carbon atoms, An acid compound and / or the following structural formula (I
I): R ¹ (CO) ₂ O (II) wherein R ¹ is hydrogen or a divalent organic group containing 1 to 20 carbon atoms, and an organic acid anhydride having and / or Structural formula (II
I): R ¹ (COOR ² ) ₂ (III): Here, R ¹ is a hydrogen atom or a divalent organic group containing 1 to 20 carbon atoms, and R ² is 1 to 12 carbon atoms. And a reaction product of an organic diacid ester having a monovalent organic group, which has the following general structural formula (V
I): TiXn (OR ⁵ ) ₄ -n (VI) wherein R ⁵ is selected from one organic group containing 1 to 8 carbon atoms, X is a halogen atom, and n = 1 to 4 , A solid component (A) is produced by a production method comprising the step of reacting with a titanium halide compound having, and ethylene is polymerized by using the solid component (A) and the organoaluminum compound (B). The present invention provides a method for producing a polyolefin, which comprises copolymerizing with an α-olefin.

The products according to the invention have a round and smooth appearance, have a consistent particle size which makes them easy to handle in the industry and easy to transport.

Since the catalyst has a considerably high activity, it is possible to omit the deashing step from the manufacturing process, has a consistent particle size, and has a very small amount of very fine powder. Therefore, the centrifugation and drying processes can be carried out very smoothly, and the pipeline is not blocked by the powder. Also, due to the round and smooth appearance, there is less resistance during pipeline transportation, and less resistance during transportation makes handling easier.

The features of the present invention are as follows.

1. Since the catalyst has a very high activity, the deactivation and deashing steps in the manufacturing process can be omitted.

2. The molecular weight regulator such as hydrogen (molecular weight
for sensitivity to the regulator),
The molecular weight of the polymer can be easily controlled.

3. Less production of paraffin wax.

4. Suitable for two-step polymerization of α-olefin in cooperation with ethylene or for copolymerization. It regulates the molecular weight distribution and enables the polymer to meet the processing requirements of various products.

5. The powder particles have a consistent particle size, and have a round and smooth appearance, few fine powders, and easy to transport.

DISCLOSURE OF THE INVENTION OF THE INVENTION According to the present invention, an organic diacid compound used as a catalyst component has the following general formula (I): R ¹ (COOH) ₂ (I) (wherein R ₁ is hydrogen, or 1 to divalent organic group containing 20 carbon atoms, such as _{= CHC 4 H 9, = CH} 2, a = C ₆ H _4.) is an organic diacid compound having a. Examples of this compound are: phthalic acid, malonic acid, butylmalonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, bromosuccinic acid, methylsuccinic acid. , Maleic acid (cis-maleic ac
id), fumaric acid (trans-maleic acid), methyl maleic acid, methylene succinic acid, 3-oxyglutaric acid, 2-
Amino-1,4-succinic acid, glutamic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, dichlorophthalic acid,
m-phthalic acid, p-phthalic acid, oxysuccinic acid, dioxysuccinic acid, dioxymalonic acid, and chlorophthalic acid.

The above organic diacid compound (I) has the following general formula (II): R ¹ (CO) ₂ O (II) (wherein R ¹ is hydrogen or a divalent group containing 1 to 20 carbon atoms). The organic acid anhydride of the above diacid compound (I) having an organic group of, for example, ═CHC ₄ H ₉ , ═CH ₂ , ═C ₆ H ₄ .
Examples of this compound are: phthalic anhydride, malonic anhydride, butylmalonic anhydride, oxalic anhydride, succinic anhydride, adipic anhydride, glutaric anhydride, dodecenesuccinic acid ( dodecenesuccinic anhydrid
e), maleic anhydride, 2-chloromaleic anhydride, propylene succinic anhydride, methyl succinic anhydride, and methylene succinic anhydride.

The organic diacid compound used in the catalyst compound of the present invention has the following general formula (III): R ¹ (COOR ² ) ₂ (III) (wherein R ¹ is hydrogen or 1 to 20 carbon atoms). divalent organic radical containing, for example, _{= CHC 4 H 9, = CH} 2, a = C ₆ H _4, organic with R ² is a monovalent organic group containing 1 to 12 carbon atoms.) It is a diacid ester compound. Examples of this compound are: dimethyl phthalate, diethyl phthalate, di-n-propylphthalat.
e), diisopropyl phthalate, dibutyl phthalate (di
-N-butylphthalate), diisobutyl phthalate, divaleryl phthalate, di-n-caproyl phthalate, dicapyrlyl phthalate, dimethyl malonate, diethyl malonate, malon. Acid diisopropyl, di-n-butyl malonate, dicaproyl malonate, dcaproyl malonate, dicaprylyl malonate, dimethyl butylmalonate, dimethyl butylmalonate, diethyl butylmalonate, butyl Dipropyl butylmalonate, dibutyl butylmalonate, dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dimethyl succinate, diethyl succinate,
Dipropyl succinate, dibutyl succinate, dicaproyl succinate, dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dicaproyl glutarate
l glutarate), dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dicaproyl adipate, dicaproyl adipate, dimethyl suberate, dipropyl suberate, diethyl suberate, dibutyl suberate, dimethyl methylsuccinate. ), Diethyl methylsuccinate, dipropyl methylsuccinate, dibutyl methylsuccinate, dicaproyl methylsuccinate, dicaprylyl methylsuccinat
e), m-dimethyl phthalate, m-diethyl phthalate,
m-dibutyl phthalate, p-dimethyl phthalate, and
p-Diethyl phthalate.

The hydropolysiloxane used in the catalyst component of the present invention has the following structural unit (IV): R ³ aHbSiO _{(4-ab) / 2} (IV) (wherein R ³ is an alkyl group, an aryl group or an aralkyl group). Groups (aralkyl), alkoxyl groups, and allyloxy groups (a
selected from monovalent organic groups including ryloxy) and a is 1, 2
Or equal to 3 and a + b ≦ 3. ) Is an organosilicon compound having a polymerization degree of any degree, or a mixture thereof, at 100 ° C. at 25 ° C.
It has a viscosity below Stokes and the structure of the end groups is probably capped with any inert groups such as trialkylsilyl groups. Examples of this compound are: tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane. Siloxane,
And chlorophenylhydropolysiloxane.

The organomagnesium used in the catalyst component of the present invention has the following structural formula (V): (MgR ⁴ ₂ ) m (R ⁴ MgX) n (V) (wherein R ⁴ is an alkyl group and X is a halogen). Atoms, m and n are values between 0 and 1, and m + n =
It is 1. ) Is an organomagnesium compound having m = 0, n = 1
Is a Grignard reagent (R ⁴ MgX) in a narrow sense, and when m = 1, n = 0, alkylmagnesium (Mg
R ⁴ ₂ ). Further, examples of the organomagnesium compound include organohalides of magnesium represented by the formula (V) and complex compounds thereof with ethers. An example of this compound is as follows. Methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride (n-proyl magnesium chloride), ethyl magnesium bromide, butyl magnesium chloride (n-butyl magnesium chloride),
Tert.-butyl magne chloride
sium chloride), diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diphenyl magnesium, dioctyl magnesium, phenyl magnesium chloride, and ethyl n-butyl magnesiu
m).

The method for producing the liquid (a) by reacting the hydropolysiloxane (IV) with the organomagnesium compound (V) is as follows: Hydropolysiloxane is used as a suitable solvent under an inert gas atmosphere. Add little by little into the organomagnesium compound synthesized in. After the addition is complete, continue stirring until the reaction is complete.

Generally, the reaction proceeds at a temperature of −50 ° C. to 100 ° C., preferably room temperature to 80 ° C., and a reaction time is 30 minutes to 300 minutes.

Inert hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene, and dimethylbenzene can be selected for use as the solvent in the reaction. Further, ether type solvents such as diethyl ether, dibutyl ether, and tetrahydrofuran can be used for the organomagnesium compound.

Addition ratio of hydropolysiloxane and an organic magnesium compound in the material is generally ^{SiO: Mg-R 4 = 1} : 0.05 to 1 are preferred.

When ether is used as a solvent for the organomagnesium compound, the final solid component (A) tends to have poor quality. Therefore, it is generally necessary to add instead an inert organic solvent having a higher boiling point than the ether. Further, a distillation technique can be used as a method for removing ether.

The reaction between the diacid compound (I), the acid anhydride compound (II), the diacid ester compound (III) and the reaction product (a) of the hydropolysiloxane and the organomagnesium compound is: The reaction proceeds from 50 ° C to 100 ° C, and the reaction time is several minutes to 100 minutes. The addition ratio is R ¹ (COOH) ₂ or R ¹ (CO) ₂ O, or R ¹ (COOR) ₂ : MgR ⁴ = 1: 1 to 50
Is. When said organic diacid compounds and their ester compounds (I), (II) and (III) are solid compounds, these compounds are liquid (a) before the mixture is stirred and several hours have passed. Must be completely dissolved in.

The addition of the organic diacid compound helps to increase the activity of the reaction product, and the powder of the polymerization product tends to have a smooth, rounded appearance. When such an organic diacid compound is not added, the reaction product still has the property of high activity, nevertheless the product morphology is poor and there is an excess of fine powder, which means that It is disadvantageous for the process of centrifugation and drying during the polymerization process. But,
The addition of an excessive amount of the organic diacid compound causes a decrease in activity, and the addition amount which is too low does not promote the improvement of the morphology.

However, by adding the organic diacid compound, the particle size can be increased, and the appearance of the powder of the polymerization product becomes round and smooth.

In addition, it is possible to obtain the advantages of both compounds when the mixed organic diacid compound and its ester compound are used simultaneously. That is, the activity can be increased, the polymerization product can be formed into a round and smooth appearance, the bulk density can be increased, the particle size can be increased, and the fine powder can be extremely reduced.

The titanium halide compound used in the catalyst of the present invention is
The following general structural formula (VI): TiXn (OR ⁵ ) ₄ -n (VI) (wherein R ⁵ is a monovalent organic group containing 1 to 20 carbon atoms, X is a halogen atom, n = 1 to 4). This compound is as follows: titanium tetrachloride, titanium tetrabromide, ethoxy titanium trichloride, butoxy titanium trichrolide, diethoxy titanium dichloride, dipropoxy dichloride. Dipropoxy titanium dichlorid
e) and dibutthoxy titanium dichloride (dibuthoxy titaniu)
m dichloride).

The alcohol component used in the catalyst component of the present invention has the following general structural formula (VII): R ⁶ OH (VII) (wherein R ⁶ is a monovalent organic group containing 1 to 20 carbons, The carbon atom may be either a straight chain or a branched chain). The alcohol compound may be a mixture of two or more alcohols that participate in the reaction. Examples of this alcohol compound are: ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, n.
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, isobutyl alcohol, n-pentyl alcohol, isopentyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethyl 1-
Hexyl alcohol and n-dodecyl alcohol.

The organoaluminum compound mixed with the alcohol and used as the catalyst component of the present invention has the following general structural formula (VI
II): AlR ⁷ nX ₃ -n (VIII) (wherein R ⁷ is obtained from a monovalent organic group containing 1 to 8 carbon atoms, and X is a halogen atom, a hydrogen atom, or an alkoxyl group. Yes, 3>n> 0. Examples of this compound are as follows: aluminum chloride (diethyl aluminum chrolide), aluminum dibutyl chloride (dibutyl aluminium chloride), aluminum diethyl hydride (diethyl aluminium hydride), hydrogen. Dibutyl aluminium hydrid
e), ethoxy aluminum diethyl (diethyl ethoxy)
aluminum) and aluminum trichloride (ethyl)
aluminum sesquichloride).

The reaction of the mixture (b) of the alcohol and the organoaluminum compound of the present invention proceeds at 0 ° C to 150 ° C, and the reaction time is 30 minutes to 300 minutes. Further, R ⁶ OH: Al-R ⁷ = 01 to 10: 1, and the selected alcohol and organoaluminum compound are not limited to one kind, but each is selected from one or more kinds so as to be mixed together when used. It The reaction is carried out in an inert aromatic hydrocarbon solvent such as benzene, toluene,
Or it must be done in phenyl chloride.

When the organic diacid compound that has been catalytically reacted with the reaction product (a) of the hydropolysiloxane and the organomagnesium compound is then contacted with the mixture of the alcohol and the organoaluminum compound (b), the reaction is from 0 ° C to 150 ° C. , The reaction time is 30 to 300 minutes, and Al: Mg = 0.1 to 20: 1.

The reaction of the titanium halide compound with the reaction product of the liquid (a) and the organic diacid compound, or with the reaction product of the liquid (a) and the mixture (b) of the organic diacid compound and the organic aluminum compound. The reaction of the titanium halide compound must be carried out at -30 ° C to 150 ° C, preferably 0 ° C to 100 ° C, the reaction time is 30 minutes to 300 minutes, and Ti: Mg
= 1 to 20: 1. Preferably, the reaction should be carried out in an inert aromatic hydrocarbon solvent such as benzene, toluene, or phenyl chloride. When paraffinic solvents such as hexane or heptane are used, the product still has highly active properties, but the particle size distribution is poor and the bulk density is low, which is a disadvantage for handling.

At the end of the reaction, the upper liquid part is removed and the solid part is then washed with an inert organic solvent, leaving behind the free titanium halide compound to obtain the solid component (A). Effective paraffin cleaning solvents include hexane, heptane, and kerosene. Paraffin washing is performed at room temperature to 70 ° C. until the solvent layer becomes colorless. When the free titanium halide is properly cleaned, the activity of the product decreases and the low molecular weight paraffin wax increases.

In the solid component (A) prepared by the above method, each gram of the solid is 1 to 10% by weight of titanium atom.
Is.

The organoaluminum compound (B) used in the second composition of the catalyst of the present invention has the following general structural formula (IX): AlR ⁸ nX ₃ -n (IX) (wherein R ⁸ is a carbon of 1 to 8). Which is obtained from a monovalent organic group containing atoms, X is a halogen atom, a hydrogen atom or an alkoxyl group, and n = 1 to 3).

Examples of this compound are: aluminum trimethyl, aluminum triethyl, aluminum tributyl, aluminum diethyl chloride, aluminum dibutyl chloride, aluminum diethyl hydride, aluminum dibutyl hydride, ethoxy aluminum diethyl (diethyl).
ethoxy aluminium), and aluminum ethyl trichloride.

The catalyst component of the present invention requires that the solid component (A) is formed during and after contact with the organoaluminum compound (B), and the composition is stirred in a container under an atmosphere of inert gas. The composition ratio is Ti: Al = 1: 1 to 1000
Gram atomic ratio.

The polymerization of ethylene and the copolymerization of ethylene with α-olefins according to the invention can be carried out in the liquid phase and in the gas phase, under the same conditions as for most Ziegler-Natta type catalysts, and
In the case of a liquid phase, which can also use a continuous multi-stage polymerization method,
The catalyst component is dispersed in an inert organic solvent, for example, hexane, heptane, or kerosene, and the α-olefin polymerization step is preferably 30 ° C to 200 ° C, more preferably 6 ° C.
It is carried out in a reactor at a temperature of 0 ° C to 100 ° C. The pressure required for the reaction is usually 50 kg / cm ² , and a molecular weight regulator such as hydrogen can be used at 1-80% of the total reaction pressure. The amount of organoaluminum compound (B) added to the polymerization is 0.1 to 50 ml of aluminum per liter of solvent, more preferably 0.3 to 10 ml.

In order to control the molecular weight, hydrogen, or a method such as changing the temperature or the amount of the catalyst used can be used, but the hydrogen method is most effective.

In the present invention, the α-olefin copolymerizable with ethylene is propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. In the case of copolymerization, the α-olefin added is 0 to 10%.

FIG. 1 shows a flow chart of the production process of the polyolefin of the present invention described above.

(E) Examples The present invention will be described by the following examples, but these examples are given only for illustrating the present invention and do not limit the present invention.

Analytical technique: Mi ₂ : Melting index, ASTM D1238, 190 ° C., 2.16 kg, unit g / 10 min Example 1 1. Preparation of reaction product (a) n-butylmagnesium (corresponding to 90 mmol of magnesium) Of a solution of tetrahydrofuran containing chloride
50 ml and 34 ml of toluene are placed in a glass reaction vessel whose inside is thoroughly dried and which is purged with nitrogen. While stirring, add trimethylsilyl group (viscosity at 25 ° C
Capped with 30 cm Stokes) (ca
pped) 5.9 ml of methylhydropolysiloxane (corresponding to 99 mmol of silicon) are slowly added dropwise. Since the reaction is exothermic, it must be cooled by a cooling medium. After dropping, let the solution react at 70 ℃ for 1 hour,
Then it is cooled to room temperature. 50 ml of orene is added thereto, and the solution is distilled under reduced pressure at 160 mmHg and 50 ° C. to remove 90 ml of a mixed solvent of tetrahydrofuran and toluene. Then 90 ml of toluene are added to it and the solution is distilled again under the same conditions. The liquid thus obtained is diluted with toluene to obtain a liquid (a) having a magnesium concentration of 1.33 mol /.

2. Preparation of solid component (A): 50 ml of the reaction product (a) and 83 ml of toluene are put into a glass reaction vessel whose inside is sufficiently dried and whose atmosphere is replaced with nitrogen. Then on a precision balance 1.254 g phthalic acid and 1.29 g
Take g diethyl phthalate, add to the solution, then stir the solution and heat to 50 ° C. until the phthalic acid is completely dissolved and evenly dispersed. Into the dropping funnel, 40 ml of titanium tetrachloride is placed, and the titanium tetrachloride is dropped into the liquid of the above mixture with gradual stirring. The liquid of the mixture is maintained at 50 ° C until the addition is complete and the reaction is continued for more than 2 hours. The free component is then washed off several times with n-heptane solvent at room temperature until the solvent above is clear, thus giving the solid component (A).
Each gram of this catalyst component contains 85 mg of titanium atom.

3. Polymerization of ethylene: 800 ml of n-heptane are thoroughly dried on the inside: and placed in a 2 l stainless steel autoclave equipped with stirring, heating and cooling, completely nitrogen-substituted. After it was heated to 60 ° C in an autoclave, 1.0 mmol of aluminum triethyl and 4 parts of the solid component (A) were added.
mg is added one after another, followed by 2.5 kg / cm ² of hydrogen.
The autoclave is then heated to 85 ° C., into which is continuously fed ethylene so as to maintain a total pressure of 8.0 kg / cm ² G. After the reaction is allowed to continue for more than 1 hour, the autoclave is cooled, the pressure is reduced and the solid is filtered and dried to obtain 180 g of white polyethylene (PE) powder. The catalyst efficiency is 45 kg / g catalyst (cata), Mi ₂ is 3.3, the bulk density is 0.275 g / ml, the average particle size is 280μ, the product (<74μ) The amount of fine powder was 0.42%.

Comparative Example 1 2. Preparation of solid component (A): According to the production method of the solid component (A) of Example 1, except that phthalic acid and diethyl phthalate were not used in the reaction, titanium tetrachloride was directly added to the liquid component (a). The solid component (A) is obtained by dropwise addition. It contains 70 mg of titanium atom per 1 g of the obtained component.

3. Polymerization of ethylene This is the same as the polymerization condition 3 of Example 1. 125 g of white polyethylene powder are obtained. In the obtained powder,
The catalyst efficiency is 31 kg / g, Mi ₂ is 2.9, and the bulk density is
0.231 g / ml, average particle size 150μ, product (<
The amount of fine powder in 74μ) was 5.5%.

Comparative Example 2 2. Preparation of solid component (A): According to the method for producing the solid component (A) of Example 1, except that
Only 1.254 g of phthalic acid is used in the reaction to obtain the solid component (A). The resulting component contains 85 mg titanium atom per gram.

3. Production of ethylene This is the same as the polymerization condition 3 of Example 1, and 175 g of white polyethylene powder is obtained. In this obtained powder,
The catalyst efficiency is 44 kg / g of catalyst, Mi ₂ is 2.7, bulk density is 0.265 g / ml, average particle size is 170μ, and the amount of fine powder in the product (<74μ) is 0.6. %Met.

Example 2-8 2. Production of solid component (A): According to the production method of the solid component (A) of Example 1, except that the ratio of the organic diacid compound and its ester used is shown in Table 1.
It was manufactured as shown in.

3. Production of ethylene: The solid component (A) is as shown in Table 1, and the polymerization conditions are the same as in Example 1. The properties of the polymerization products are shown in Table 1.

Comparative Example 3-5 2. Solid Component (A): According to the method for producing the solid component (A) of Example 1, except that
The proportions of the organic diacid compound and its ester used are shown in Table 1.

3. Polymerization of ethylene: The solid component (A) is as shown in Table 1, and the polymerization conditions are the same as in Example 1. The properties of the polymerization products are detailed in Table 1. Although the invention has been described with respect to a few particular embodiments, it will be appreciated by those skilled in the art that many variations are possible without departing from the spirit and scope of the invention.

(F) Effects of the Invention As described in detail above, according to the method of the present invention, it is possible to produce a polyolefin having a smooth appearance, a narrow particle size variation range, and an extremely small amount of fine powder. .

[Brief description of drawings]

 FIG. 1 shows a flow chart illustrating the method of the present invention.

Claims (24)

[Claims] 1. The reaction product of (a) reacting a hydropolysiloxane with an organomagnesium compound and (b) the reaction product of step (a) are represented by the following general structural formula (I): R ¹ (COOH) ₂ ( I) wherein R ¹ is a hydrogen atom, or a divalent organic group containing 1 to 20 carbon atoms, and / or an organic diacid compound having the following structural formula (I
I): R ¹ (CO) ₂ O (II) wherein R ¹ is hydrogen or a divalent organic group containing 1 to 20 carbon atoms, and an organic acid anhydride having and / or Structural formula (II
I): R ¹ (COOR ² ) ₂ (III): Here, R ¹ is a hydrogen atom or a divalent organic group containing 1 to 20 carbon atoms, and R ² is 1 to 12 carbon atoms. And a reaction product of an organic diacid ester having a monovalent organic group, which has the following general structural formula (V
I): TiXn (OR ⁵ ) ₄ -n (VI) wherein R ⁵ is selected from one organic group containing 1 to 8 carbon atoms, X is a halogen atom, and n = 1 to 4 A solid component (A) is produced by a production method comprising the step of reacting with a titanium halide compound having, and ethylene is polymerized or ethylene is produced by using the solid component (A) and the organoaluminum compound (B). A method for producing a polyolefin, which comprises polymerizing with an α-olefin. 2. An optional pretreatment of the reaction product of step (b) with a mixture of at least one alcohol and at least one organoaluminum compound prior to step (c), said alcohol compound being General structural formula (VI
I): R ⁶ OH (VII) wherein R ⁶ is a monovalent organic group containing 1 to 20 carbon atoms. 3. The organoaluminum compound mixed with the at least one alcohol has the following general structural formula (VII
I): AlR ⁷ nX ₃ -n (VIII) wherein R ⁷ is selected from monovalent organic groups containing 1 to 8 carbon atoms, X is a halogen atom, a hydrogen atom or an alkoxyl group, and n is The method of claim 2, wherein 0 <n <3. 4. A pretreatment mixture comprising the alcohol and the organoaluminum is reacted at 0 ° C. to 150 ° C., the reaction time is 30 minutes to 300 minutes, and R ⁶ OH: Mg—R ⁴ = 0.
Method according to claim 2, characterized in that it is between 1 and 10: 1. 5. The hydropolysiloxane has the following structural unit (IV): R ³ aHbSiO _{(4-ab) / 2} (IV) wherein R ³ is an alkyl group, an aryl group, an aryl-alkyl group, It is selected from the group of monovalent organic groups consisting of an alkoxyl group and an alkoxyl group and an aryloxyl group, a is 0, 1, or 2, and b is 1, 2
Or 3, and a + b ≦ 3, the hydropolysiloxane is a mixture having a single structure or a random degree of polymerization, and the viscosity of the hydropolysiloxane is
The method of claim 1, wherein the stroke is 1000 strokes or less at 25 ° C. 6. The organomagnesium compound has the following structural formula (V): (MgR ⁴ ₂ ) m (R ⁴ MgX) n (V) wherein R ⁴ is an alkyl group and X is a halogen atom. Yes, m and n are values between 0 and 1, and m + n = 1
The method of claim 1, comprising: 7. The reaction between the hydropolysiloxane (IV) and the organomagnesium compound (V) is -50 ° C. to 100 ° C.
In after 30 minutes to 300 minutes, hydropolysiloxane ratio of polysiloxane to organic magnesium compound is ^{Si-O: Mg-R 4} = 1: 0.05 to 1
The method according to claim 1, wherein the method is a molar ratio. 8. The reaction of the reaction product of step (a) according to claim 1 with the organic diacid compound (I) or organic acid anhydride (II) or ester of organic diacid (III), The process is carried out at 50 ° C. to 100 ° C., the reaction time is several minutes to 100 minutes, and the organic diacid compound (I) or organic acid anhydride (II) or organic diacid ester to the process according to claim 1 ( The reaction product of a) has an addition ratio of R ¹ (COOH) ₂ or R ¹ (CO) ₂ O or
The method according to claim 1, wherein R ¹ (COOR ² ) ₂ : MgR ⁴ = 1: 1 to 50. 9. The process (a) according to claim 1, wherein the organic diacid compound (I), the organic acid anhydride (II) or the organic diacid ester (III) is a solid and before the reaction proceeds. 9. It is completely dissolved in the reaction product of
The method described in. 10. The organic diacid compound (I) or organic acid anhydride (II) or ester (III) of organic diacid is contacted with the reaction product of step (a) of claim 1 to carry out the reaction. The method of claim 1, wherein the reaction proceeds from 0 ° C to 150 ° C, the reaction time is from 30 minutes to 300 minutes, and Al: Mg = 0.1 to 20: 1. 11. The solid component (A) is the step (c) of claim 1.
The method according to claim 1, wherein the reaction proceeds at -30 to 150 ° C, the reaction time is 30 to 300 minutes, and Ti: Mg = 1 to 20: 1. 12. The organoaluminum compound (B) has the following general structural formula (IX) AlR ⁸ nX ₃ -n (IX) wherein R ⁸ is a monovalent organic group containing 1 to 8 carbon atoms. The method according to claim 1, wherein X is a halogen atom, a hydrogen atom or an alkoxyl group, and n = 1 to 3, wherein X is selected. 13. The organic diacid compound is phthalic acid, malonic acid, butylmalonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, bromosuccinic acid, succinic acid. Methyl acid, maleic acid, fumaric acid, methyl maleate, methylenesuccinic acid, 3-oxyglutaric acid, aspartic acid, glutamic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, diclophthalic acid, m-phthalic acid, p-phthalic acid, Oxysuccinic acid, dioxysuccinic acid, dioxymalonic acid,
The method of claim 1, wherein the method is selected from the group consisting of chlorophthalic acid, and mixtures thereof. 14. The acid anhydride is phthalic anhydride, malonic anhydride, butylmalonic anhydride, oxalic anhydride,
Succinic anhydride, adipic anhydride, glutaric anhydride, dodecenesuccinic anhydride, maleic anhydride, 2-
Chloromaleic anhydride, propylene succinic anhydride,
The method of claim 1, wherein the method is selected from the group consisting of methyl succinic anhydride, methylene succinic anhydride, and mixtures thereof. 15. The organic diacid ester is dimethyl phthalate, diethyl phthalate, n-dipropyl phthalate,
N-dibutyl phthalate, isodibutyl phthalate, n-dipentyl phthalate, n-dihexyl phthalate, dioctyl phthalate, dimethyl dipropionate, diethyl dipropionate, isodipropyl dipropionate, n-dibutyl dipropionate, dipropionate Dihexyl, dioctyl dipropionate, dimethylbutyldipropionate, diethylbutyldipropionate, dipropylbutyldipropionate, dibutylbutylpropionate,
Dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl glutarate, diethyl glutarate, dipropyl glutarate, glutaric acid Dibutyl,
Dihexyl glutarate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dihexyl adipate, dimethyl suberate, dipropyl suberate, diethyl suberate, dibutyl suberate, dimethyl methyl succinate, diethyl methyl succinate , Dipropylmethylsuccinate, dibutylmethylsuccinate, dihexylmethylsuccinate, dioctylmethylsuccinate, dimethyl m-phthalate, diethyl m-phthalate, dibutyl m-phthalate,
The method of claim 1, wherein the method is selected from the group consisting of p-dimethyl phthalate, diethyl p-phthalate and mixtures thereof. 16. The hydropolysiloxane is tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane. 6. The method of claim 5, wherein the method is selected from the group consisting of :, chlorophenylhydropolysiloxane, and mixtures thereof. 17. The organomagnesium compound is magnesium chloride, magnesium chloride, magnesium chloride, magnesium chloride n-propyl, magnesium chloride n-butyl, magnesium ethyl bromide, magnesium tert-butyl chloride, magnesium diethyl, magnesium dipropyl, magnesium dibutyl. 7. The method of claim 6, wherein the method is selected from the group consisting of :, magnesium dioctyl, magnesium diphenyl, magnesium phenyl chloride, magnesium n-butylethyl, and mixtures thereof. 18. The titanium halide compound is titanium tetrachloride, titanium tetrabromide, ethoxytitanium trichloride, butoxytitanium dichloride, diethoxytitanium dichloride,
The method of claim 1, wherein the method is selected from the group consisting of dipropoxytitanium dichloride, dibutoxytitanium dichloride, and other related titanium halide compounds and mixtures thereof. 19. The alcohol compound in the pretreatment process is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol,
Isopentyl alcohol, n-hexyl alcohol, n
A method according to claim 2, characterized in that it is selected from the group consisting of: octyl alcohol, 2-ethyl 1-hexyl alcohol, n-dodecyl alcohol, and other alcohol compounds and mixtures thereof. 20. The organoaluminum in the pretreatment process is aluminum chloride diethyl chloride, aluminum chloride dibutyl,
A process according to claim 2 characterized in that it is selected from aluminum diethyl hydride, aluminum dibutyl hydride, diethyl ethoxyaluminum, ethyl aluminum tridichloride, and mixtures thereof. 21. The organoaluminum compound (B) is aluminum trimethyl, aluminum triethyl, aluminum tributyl, aluminum diethyl chloride, aluminum dibutyl chloride, aluminum diethyl hydride, aluminum dibutyl hydride, ethoxy aluminum diethyl, aluminum trichloride aluminum ethyl, And selected from the group consisting of mixtures thereof.
The method described in. 22. Ethylene polymerization or copolymerization is Ti: Al = 1: 1.
Process according to claim 1, characterized in that it is carried out by contacting the solid component (A) with the organoaluminum compound (B) in a ratio of from 1000 to 1000. 23. Ethylene polymerization or copolymerization of 30 to 200 ° C. in an inert organic a solvent temperature, carried out under atmospheric pressure to a pressure of 50 kg / cm ^2, 1 to the gas molecular weight modifier of the reaction pressure Process according to claim 1, characterized in that 80% is given and the organoaluminum compound being polymerized is present in an amount of 0.1 to 50 mmol per liter of solvent. 24. The α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, or 4-methyl-1-pentene α-olefins. The method according to 1.