JPH07108924B2 - Manufacturing method of olefin polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer. More particularly, the present invention relates to a process for making olefin polymers by using a titanium trichloride catalyst component preactivated with an α-olefin in combination with a specific organoaluminum compound component and an organic peroxide.

[Prior Art] It is well known that α-olefins undergo stereoregular polymerization with a Ziegler-Natta catalyst. Specifically, α
-By using a catalyst in which a titanium trichloride catalyst component preactivated by an olefin, an organoaluminum compound component, and an electron donor compound component as the third component are used, it is often the case that the α-olefin undergoes highly stereoregular polymerization. Are known.

Although many kinds of compounds have been proposed as the electron donor compound to be combined with the titanium trichloride catalyst component, there is no description that an organic peroxide is effective in place of the electron donor compound.

On the other hand, in JP-A-61-9408, the combined use of an organic peroxide as a third component is limited to a supported catalyst component defined by a solid catalyst containing magnesium halide and titanium halide as essential components. ing. However, usually, unlike the electron donor compound component which is combined with the supported catalyst component and the titanium trichloride catalyst component, the organic peroxide used for the supported catalyst component is different from the titanium trichloride catalyst component. It is not easy to accurately infer the organic peroxide used for the. Also known is the technique of using aromatic carboxylic acid esters as electron donor compounds in combination with titanium trichloride catalyst components preactivated with α-olefins.

However, in principle, when an olefin polymer is produced in a solvent-free gas phase polymerization process, the aromatic carboxylic acid ester used as one component of the catalyst is all contained in the olefin polymer particles. Esters have a strong odor even if they are present in trace amounts,
An olefin polymer produced by a gas phase polymerization process using an aromatic carboxylic acid ester contains an aromatic carboxylic acid ester and generates a strong malodor during storage of the olefin polymer, during a granulation process or during molding. . Such a bad odor is a problem because it causes environmental pollution during production or processing of an olefin polymer on an industrial scale.

[Object of the Invention] As a result of intensive studies for solving environmental pollution and poor workability due to such malodor, the present inventors have found that instead of the electron donor compound conventionally used as the third component, organic peroxide is used. By combining the product with a titanium trichloride catalyst component pre-activated with α-olefin and an organoaluminum compound, a catalyst system having extremely high polymerization activity is obtained, and this catalyst system provides a highly stereoregular and odorless olefin. The present invention has been completed by finding that a polymer can be obtained.

As is clear from the above description, an object of the present invention is to provide a method for producing an odorless olefin polymer having extremely high stereoregularity.

[Configuration of Invention] The present invention has the following configurations.

preactivated titanium trichloride catalyst component (A) by α- olefin of the general formula A1R ⁶ _m X _3-m compound represented by (wherein R ⁶ is an alkyl group, an aryl group, a cycloalkyl group or an alkoxy group And m is a number 0 <m3,
(Wherein X is C1) (B) and an organic peroxide component (C) represented by the following formula are used to polymerize an α-olefin, and a process for producing an olefin polymer.

R ¹ —O—O—R ² (wherein R ¹ and R ² are hydrocarbon groups with or without oxygen atoms).

The present invention is described in detail below.

The titanium trichloride catalyst component (A) pre-activated with α-olefin is obtained by treating titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound with an electron donor and titanium tetrachloride. Compounds (eg Tokuhiro Akira
53-3356), a compound obtained by treating titanium tetrachloride with an electron donor and titanium tetrachloride, which is obtained by reducing titanium tetrachloride with a reaction product of an organoaluminum compound and an electron donor (for example, Japanese Patent Publication No. 59-28573), and compounds containing titanium trichloride as a main component, such as compounds activated by pulverization after reduction of titanium tetrachloride with metallic aluminum (so-called titanium trichloride (AA)) ( It is obtained by contacting D) with an α-olefin in the presence of the organoaluminum compound component (E) and in the presence or absence of the organic peroxide component (F).

The component (D) is a compound containing titanium trichloride as a main component, which is produced by a known technique. Component (E) has the general formula A1R ⁵
It is a compound represented by _n X _3-n . Here, R ⁵ is an alkyl group, an aryl group, a cycloalkyl group or an alkoxy group, n is a number 0 <n3, and X is C1. Specifically, triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl aluminum, tricyclohexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-butyl aluminum, dicyclopentyl aluminum, ethyl aluminum sesquichloride, Examples include ethylaluminum dichloride, diethylethoxyaluminum, di-i-butylmethoxyaluminum, methylethoxyaluminum chloride and ethylpropoxyaluminum chloride.

The component (F) is a compound represented by the general formula R ³ —O—O—R ⁴ . Here, R ³ and R ⁴ are groups consisting of an aliphatic, alicyclic or aromatic hydrocarbon having or not containing an oxygen atom and having about 1 to 20 carbon atoms. Specifically, dicumyl peroxide, di-i-butyl peroxide, t-butyl cumyl peroxide, bis (1,1-diphenylethyl) peroxide, cumyl-1,1-diphenylethyl peroxide, t-peroxide Butyl-1,1
-Diphenylethyl, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di-t-butylperoxybutane, benzoyl peroxide, p- peroxide
Examples include chlorobenzoyl, o-methylbenzoyl peroxide, lauroyl peroxide, cumyl perbenzoate, t-butyl perbenzoate and cumyl peracetate. Among these, dicumyl peroxide and benzoyl peroxide are preferable.

The α-olefin to be contacted with the component (D) includes ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1, 4-methylpentene-1 and 3-methylpentene-1. And so on.

Component (A) is obtained by contacting component (D) with an α-olefin in the presence of component (E) and in the presence or absence of component (F), so-called pre-activation. The preactivation is carried out in an inert hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-heptane, n-decane, n-undecane and kerosene,
In liquefied olefins such as liquefied propylene and liquefied butene-1, or in gaseous ethylene and propylene,
Alternatively, it can be performed in the absence of them. Hydrogen may be allowed to coexist during the preliminary activation. In addition, the component (D),
The component (E) and the component (F) can also be used after being dissolved or suspended in the inert hydrocarbon solvent or the liquefied olefin.

The pre-activation is performed by mixing the component (D) and the component (E),
Component (D), component (E) and component (F) are brought into contact with α-olefin, and then mixed with α-olefin, component (E) and component (F) are mixed or a reaction product is provided with component (D). And then contacting with α-olefin,
Component (D) and component (E) are mixed in the presence of α-olefin, and component (D), component (E) and component (F) are mixed in the presence of α-olefin. be able to.

The amount of component (E) used is the titanium atom contained in component (D).
It is 0.01 to 1000 mol, preferably 0.1 to 500 mol per 1 mol, and the amount of the component (F) used is 0 per 1 mol of the component (E).
It is ˜2 mol, preferably 0-1 mol. The amount of the α-olefin used is 0.01 to 5000 g, preferably 0.05 to 3000 g, relative to 1 g of the component (D). Pre-activation is temperature -20 ~ +100
C., preferably 0 to 70.degree. C., time 10 seconds to 20 hours, preferably 1 minute to 10 hours to polymerize 0.01 to 2000 g, preferably 0.05 to 500 g of .alpha.-olefin per 1 g of component (D). preferable. At the time of pre-activation, other polymer particles may be allowed to coexist in advance. The polymer may be the same as or different from the desired olefin polymer. Other polymer particles that can coexist are 0 to 10 kg per 1 g of component (D).
Is the range.

Component (B) is a compound represented by the general formula A1R ⁶ _m X _3-m. Here, R ⁶ is an alkyl group, an aryl group, a cycloalkyl group or an alkoxy group, m is a number of 0 <m 3, and X is C 1. Specifically, the same compound as the component (E) can be used.

The component (C) is a compound represented by the general formula R ¹ —O—O—R ² . Here, R ¹ and R ² are groups containing an oxygen atom or not, and having 1 to 20 carbon atoms and consisting of an aliphatic, alicyclic, or aromatic hydrocarbon. Specifically, the same compound as the component (F) can be mentioned. The component (B) and the component (E) and the component (C) and the component (F) may be the same compound or different.

A catalyst for producing an olefin polymer can be obtained by combining the component (A), the component (B) and the component (C). As a combination method, component (A) and component (B)
And component (C) independently supplied to the polymerization vessel, mixture of component (B) and component (C) and component (A) independently supplied to the polymerization vessel, component (A), component (B) and component The component (D) and the component (E) are mixed in the presence of a small amount of α-olefin, and the mixture is polymerized with a part or all of the component (B) and the component (C). There is a mode in which the component (D), the component (B) and the component (C) are mixed in the presence of a small amount of α-olefin, and any method can be adopted. When the three components are combined, each component or any one of the components is butane, pentane, hexane, heptane,
It can also be used by dissolving or suspending it in an inert hydrocarbon such as nonane, decane and kerosene. The temperature in the case of mixing before feeding to the polymerization vessel as described above is -50 to + 50 ° C, preferably -30 to + 30 ° C, and the time is 10 seconds to
It is 50 hours, preferably 1 minute to 30 hours.

The amount of component (B) used is the titanium atom contained in component (A).
It is 0.5 to 1000 mol, preferably 1 to 500 mol per 1 mol. The amount of component (C) used is 0.00 per 1 mol of component (B)
It is 5 to 2 mol, preferably 0.01 to 1 mol.

Component (A), component (B) and component (C) according to the present invention
The olefin polymer can be produced using the catalyst obtained by the combination of The olefin polymer is
In addition to homo- and copolymers of α-olefins having 3 or more carbon atoms, α-olefins having 3 or more carbon atoms and α-olefins having 2 carbon atoms
Also meant are copolymers with olefins. As the α-olefin having 3 or more carbon atoms, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-
1,4-methylpentene-1 and 3-methylpentene-1 can be used. Not only homopolymerization of these α-olefins, but also copolymerization with one or more other α-olefins having 2 or more carbon atoms can be performed. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-butadiene and methyl-, in addition to the α-olefin having 3 or more carbon atoms described above.
1,4-hexadiene and the like can be mentioned. The production of the olefin polymer is carried out in principle by a gas phase process using no inert solvent and a liquid phase process using an inert solvent or the α-olefin itself as a solvent. The production can be carried out by any of a batch system, a semi-continuous system and a continuous system. The polymerization temperature is 40 to 200 ° C., preferably 50 to 150 ° C., and the polymerization pressure is atmospheric pressure to 100 kg / cm ² G, preferably 5 to 50 kg / cm ² .

[Effect of the Invention] The effect obtained by the present invention is that the specific organic peroxide component is combined as the third component combined with the titanium trichloride catalyst component pre-activated by α-olefin and the organoaluminum compound component. Odorless, highly stereoregular olefin polymer can be obtained in high yield by using the catalyst obtained by.

The present invention will be described below with reference to examples and comparative examples. The method for measuring the effects in Examples and Comparative Examples is as follows.

(1) Extraction method Stereoregularity (ESS) means boiling the polymer.
-The ratio of the extraction residue after extraction with heptane (98 ° C) for 6 hours to the total amount before extraction.

(2) Infrared stereoregular product (IR-τ) is the absorbance ratio (A997 / A972) between the crystalline band (997cm ^-1 ) and the amorphous band (972cm ^-1 ) determined by infrared spectroscopy. The larger the value, the higher the stereoregularity.

(3) The presence or absence of odor of the polymer was judged by a odor sensory test after leaving the polymer after polymerization in a nitrogen stream at 50 ° C. for 3 hours. In the odor sensory test, presence / absence of odor sensed by 10 testers was classified into 4 grades A to D and displayed. Rank A is odorless, and if all 10 judges that there is no odor, Rank B
Is a little odor when 1 to 4 out of 10 are odorous, Rank C is odorous when 5 to 9 out of 10 is odorous, and Rank D is a strong odor so
This is the case when all 10 people judge that there is an odor.

Example 1 (1) Preparation of pre-activated titanium trichloride catalyst component n-hexane 60 ml, diethyl aluminum chloride 0.05
mol and diisoamyl ether 0.12 mol were mixed at 25 ° C. for 1 minute and reacted at the same temperature for 5 minutes to give a reaction product (I).
Got Titanium tetrachloride (0.4 mol) was placed in a reactor purged with nitrogen, heated to 35 ° C, and the whole amount of the reaction product (I) was added dropwise to the reactor over 30 minutes. The temperature was raised and the reaction was continued for another 1 hour, the mixture was cooled to room temperature, the supernatant was removed, 400 ml of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain a solid product (II). It was With the total amount of the solid (II) suspended in 300 ml of n-hexane, 16 g of diisoamyl ether and 35 g of titanium tetrachloride were added at 20 ° C. at room temperature for about 1 minute, and the mixture was reacted at 65 ° C. for 1 hour. It was After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 400 ml of n-hexane was added, the mixture was stirred for 10 minutes, and allowed to stand to remove the supernatant.
After repeated times, it was dried under reduced pressure to obtain a titanium trichloride catalyst component. The content of the titanium trichloride catalyst component was 26.4%.

In a reactor purged with nitrogen, 20 ml of n-hexane, 1.38 mmol of diethylaluminum chloride, 50 mg of the titanium trichloride catalyst component and 500 ml of hydrogen were placed and contacted with propylene for 5 minutes at room temperature with a propylene partial pressure of 2 kg / cm ² G. After that, it was filtered and washed with n-hexane to obtain a preactivated titanium trichloride catalyst component as a powder. Titanium trichloride catalyst component 1g
5 g of polypropylene was attached per unit.

(2) Manufacture of olefin polymer Into a reactor equipped with a multi-stage stirrer with an internal volume of 3 l, which had been purged with nitrogen, 1.27 mmol of diethyl aluminum chloride and dicumyl peroxide
After 0.13 mmol, 276 mg of the preactivated titanium trichloride catalyst component and 3 l of hydrogen were added, polymerization was carried out at 70 ° C. for 2 hours while continuously introducing propylene so that the total pressure was 22 kg / cm ² G. Then, unreacted propylene was discharged to obtain 277 g of powdered polypropylene having MFR 5.3. The polymer yield per 1 g of the titanium trichloride catalyst component (component (D)) was 6,020 g, the ESS of the polypropylene was 98.0%, and the IR-π was 0.950. The polypropylene particles were spherical.

(3) Odor sensory test Since polypropylene immediately after polymerization had an unreacted propylene odor, it was left in a nitrogen stream at 50 ° C for 3 hours and then subjected to an odor sensory test. There was no propylene odor, and when 10 testers smelled directly, all 10 judged that there was no odor (odor rank A). After the sensory test, 0.1% by weight of an antioxidant and 0.1% by weight of a lubricant were added to polypropylene and mixed well in a Henschel mixer (trade name), and a uniaxial structure having a vent part at the center of 20 mm in diameter was prepared. When granulated at 220 ° C using a granulator, three testers judged that the vent gas discharged had an odor (odor rank B), and all of the molten polymer at the outlet of the granulator had no odor. It was judged (odor rank A).

Comparative Example 1 The production of an olefin polymer and the odor sensory test were performed in the same manner as in Example 1 except that dicumyl peroxide was not used in (2) of Example 1.

Comparative Example 2 An olefin polymer was prepared and an odor sensory test was conducted in the same manner as in Example 1 except that methyl toluate was used in place of dicumyl peroxide in (2) of Example 1.

Example 2 The production of an olefin polymer and the odor sensory test were conducted in the same manner as in Example 1 except that benzoyl peroxide was used instead of dicumyl peroxide in (2) of Example 1.

Comparative Example 3 The production of an olefin polymer and the odor sensory test were performed in the same manner as in Example 2 except that ethyl anisate was used instead of benzoyl peroxide.

Example 3 TiCl ₃ (AA) manufactured by Toho Titanium Co., Ltd. in 30 ml of n-hexane
(Ti content 22.5%) 200 mg and diethylaluminum chloride 4.7 mmol were mixed, and contacted with propylene at room temperature for 5 minutes at a propylene partial pressure of 5 kg / cm ² G, then filtered, washed with n-hexane, and prepared. An activated titanium trichloride catalyst component was obtained. 20 g of propylene reacted with 1 g of the TiCl ₃ (AA).

In place of the preactivated titanium trichloride catalyst component obtained in (1) of Example 1 in (2) of Example 1, 4.2 g of preactivated titanium trichloride, diethylaluminum 4.
An olefin polymer was prepared and an odor sensory test was conducted in the same manner as in Example 1 except that 7 mmol, cumyl peroxide-1,1-diphenylethyl 0.46 mmol instead of dicumyl peroxide and 2.5 l of hydrogen were used.

Example 4 Purified hexane 1, diethylaluminum chloride 3.4 mol, dicumyl peroxide 0.3 mmol, and the titanium trichloride catalyst component (component (D )) 50 mg was charged and reacted at 20 ° C. at a propylene partial pressure of 1 kg / cm ² G for 10 minutes. 10 g of propylene reacted with 1 g of the component (D). After the reaction was completed, unreacted propylene was removed and 100 ml of hydrogen was introduced. Next, polymerization was carried out at 70 ° C. for 2 hours while continuously introducing propylene so that the total pressure was 7 kg / cm ² G. Then, unreacted propylene was discharged and methanol 20
ml was added, the mixture was stirred at 70 ° C. for 10 minutes, filtered and dried to obtain 172 g of polypropylene powder (MFR2.2). A hexane-soluble polymer 0.50 was obtained from the filtrate.

Comparative Examples 4 and 5 Olefin polymer was prepared in the same manner as in Example 4, except that dicumyl peroxide was not used (Comparative Example 4) and methyl toluate was used instead of dicumyl peroxide (Comparative Example 5). The smell sensory test was performed.

The results of each of the above-described Examples and Comparative Examples are shown in the table below.

[Brief description of drawings]

The figure is a flow sheet showing the manufacturing steps of the method of the present invention.

Claims (2)

[Claims] 1. A titanium trichloride catalyst component (A) pre-activated by an α-olefin, a compound represented by the general formula A1R ⁶ _m X _3-m (wherein R ⁶ is an alkyl group, an aryl group, a cyclo group). It is an alkyl group or an alkoxy group, and m is 0 <m3
And X is C1) (B) and an organic peroxide component (C) represented by the following formula: Manufacturing method of olefin polymer. R ¹ —O—O—R ² (wherein R ¹ and R ² are hydrocarbon groups with or without oxygen atoms). 2. The method for producing an olefin polymer according to claim 1, wherein the polymerization of α-olefin is carried out in a gas phase.