JPS6339604B2 - - Google Patents

Description

[Detailed description of the invention]

[] Object of the Invention The present invention relates to a solid catalyst component for olefin polymerization. More specifically, (2) (a) at least one halogen atom is added to a solid obtained by co-pulverizing (A) (1) (a) an acyl halide compound and (b) a magnesium dihalide. contains a tetravalent titanium compound and (b) a phosphorus-halogen bond, and P=
(B) (1) A tetravalent titanium compound containing at least one halogen atom and (2) a solid component obtained by contacting the mixture or addition reaction product with an organic phosphorus compound containing an O bond. ) Regarding a solid catalyst component for olefin polymerization obtained by contacting an addition product with an organic carboxylic acid ester in a liquid or solution state, the purpose is to have extremely high polymerization activity and excellent stereospecificity. However, another object of the present invention is to provide a novel solid catalyst component for olefin polymerization for producing an olefin polymer having an extremely high bulk density. [] Background of the Invention Recently, many catalyst systems (hereinafter referred to as "catalyst system A") obtained from a solid component in which a titanium compound is supported on magnesium halide and an organoaluminum compound have been proposed. It is said that these catalyst systems have higher polymerization activity than conventional catalyst systems and have the potential to eliminate the need to remove catalyst residue from the polymer. Some of the inventors also
In order to obtain propylene-based polymers that already have a practical "melt flow index" (hereinafter referred to as "MFI"), various catalysts that are highly crystalline in this MFI region and have high polymerization activity have been developed. proposed a system (for example, JP-A No. 53-277,
53-1276, 53-2583, 53-5287, 53-5287, 53-2583, 53-5287,
53-19395). When these catalyst systems are used to polymerize olefins (e.g. propylene),
When the concentration of the organoaluminum compound used as a cocatalyst is quite high, not only is the polymerization activity high, but the resulting polymer is also highly crystalline in the practical MFI range. However, since the amount of catalyst system (including cocatalyst) used is significant compared to the resulting polymer, the catalyst residue (ash) remaining in the resulting polymer must be removed, otherwise the A relatively large amount of catalyst residue remains during coalescence. On the other hand, when olefin is polymerized using a catalyst system in which the amount of organoaluminum compound used is extremely low, not only the polymerization activity is low but also the crystallinity of the resulting polymer is decreased. From the above, it is difficult to reduce the total solid catalyst residue of the produced polymer to a certain value or less. In addition, since an organic carboxylic acid ester is used as the third component to obtain a highly crystalline polymer, the polymer tends to have an odor unless the ester is removed by washing with an organic solvent. . [] Structure of the Invention Based on the above, the present inventors conducted various searches to obtain an olefin polymer that solved these problems. (hereinafter referred to as "acyl halide") and (b) magnesium dihalide (hereinafter referred to as "co-pulverized solid material"). (b) A tetravalent titanium compound containing a halogen atom (hereinafter referred to as a titanium compound) and (b) a phosphorus-halogen bond containing a
(B) (1) A titanium compound and (2) A solid catalyst component for olefin polymerization obtained by contacting an addition product with an organic carboxylic acid ester under conditions where the addition product is in a liquid or solution state is used as a main catalyst, and as a co-catalyst. It has been shown that when an olefin is polymerized using a catalyst system obtained from an organoaluminum compound or an organoaluminum compound and an electron-donating organic compound (as a third component), a polymer can be obtained by solving all of the above-mentioned problems. Heading, we arrived at the present invention. [] Effects of the invention When olefin is polymerized using the above catalyst system, the following effects (characteristics) are exhibited. (1) Even when olefin is polymerized using a catalyst system in which the amount of organoaluminum compound used is extremely low, the polymerization activity is extremely high, so even if all the solid catalyst residue remaining in the polymer is not removed, the catalyst residue remains. Not only can a very low amount of polymer be obtained, but also the resulting polymer has good crystallinity. (2) In order to obtain a polymer with particularly high crystallinity, it is possible to obtain a polymer with high crystallinity even if another electron-donating organic compound is used as a third component instead of the organic carboxylic acid ester mentioned above. Therefore, the odor of the polymer can be suppressed without removing the electron-donating organic compound after polymerization by washing with an organic solvent or the like. (3) The obtained polymer has an appearance in which each powder particle is packed to the inside, and has a transparent appearance. And for this reason, the bulk density is extremely high,
Highly liquid. Therefore, the productivity in the step of drying and transferring the polymer after completion of polymerization is excellent. [] Detailed Description of the Invention (A) Production of co-pulverized solid material The co-pulverized solid material is obtained by co-pulverizing an acyl halide and a magnesium dihalide. (1) Acyl halide The acyl halide used in the present invention is

[(A) Production of co-pulverized solids]

Anhydrous magnesium chloride (commercially available anhydrous magnesium chloride at approximately 500℃ in a dry nitrogen stream)
(obtained by heating and drying for 15 hours)
20 g (0.21 mol) and 6.0 g of benzoyl chloride (0.043 mol) in a container for a vibrating ball mill (cylindrical stainless steel, internal volume 1, porcelain balls with a diameter of 10 mm filled to about 50% by apparent volume). I put it in.
This was attached to a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 Hz and co-pulverized for 15 hours to obtain a co-pulverized solid. [(B) Production of addition reaction product (1)] Separately, put 120 ml of toluene (as a solvent) in a 500 ml flask, and add 82.8 g (0.44 mol) of titanium tetrachloride (as a titanium-based compound) and
61.0 g (0.23 mol) of diphenyl phosphorochloridate (as a phosphorus-containing organic compound) was added and reacted, and by heating to 60°C, a brown homogeneous solution containing the addition reaction product (1) was obtained. Obtained. [(C) Production of solid component (a)] Add 15.0 g of the above co-pulverized solid to this liquid,
Stirring was performed for 30 minutes at a temperature of 60°C (preparation of carrier-supported material). After separating the obtained solids,
Wash the solution with toluene until the addition reaction product of titanium tetrachloride and diphenyl phosphorochloridate is no longer observed in the solution to remove a mud-like solid [hereinafter referred to as "solid component (a)"]. Obtained. [(D) Production of addition product () and solid catalyst component (A)] Separately, put 120 ml of toluene (as a solvent) in a 500 ml flask, and add 82.8 g (0.44 mol) of titanium tetrachloride (titanium-based as a compound) and
Add 39.6 g (0.22 mol) of p-ethyl anisate (as an organic carboxylic acid ester) and react.
By heating to 60°C, a dark red homogeneous liquid was obtained (creation of a liquid containing the addition reaction product ()). Add the solid component (a) matsudo to this liquid and heat at 60°C.
Stirring was carried out for 60 minutes at a temperature of . (Creation of supported support). After separating the solids obtained, approx.
The solution was washed with toluene at 60° C. until no addition product of titanium tetrachloride and p-ethyl anisate was observed in the solution. By drying this solid at a temperature of 40°C, a powdery solid catalyst component (A) was obtained. Obtained solid catalyst component (A)
Chemical analysis of this solid catalyst component revealed that
The content of titanium atoms in (A) was 4.6% by weight. [(E) Polymerization and physical properties of the produced polymer] 36 mg of the solid catalyst component (A) produced by the above method was placed in a 3.0 stainless steel autoclave at a molar ratio of 1/4 with triethylaluminum in advance.
of tetraethoxysilane at a temperature of 80°C.
80mg of substance obtained by time reaction
(0.48 mol as aluminum), followed immediately by 760 g of propylene and 0.10 g of hydrogen. Raise the temperature of the autoclave to internal temperature (polymerization system)
was kept at 80℃. After 1 hour, the content gas was released to terminate the polymerization. As a result, 198 g of powdered polypropylene was obtained. That is, the polymerization activity is
5500g/g-Solid catalyst component (A)/time, 120Kg/g
-Ti is time. This polypropylene powder
HR was 97.1%. The bulk density of the polypropylene powder was 0.42 g/cc, and the shape of the powder was transparent, hard, and coarse particles with good fluidity. The ash content in this powder was determined by the following method. Place about 15 g of the powder in a constant weight porcelain crucible,
It was dried for about 4 hours in a vacuum dryer set at a temperature of 60°C to a constant weight (accurate weighing result: 14.87 g). Next, the mixture was burned in a combustion furnace at a temperature of 500°C for 30 minutes, and then ashed in an electric furnace at a temperature of 700°C for 10 minutes, and the amount of ash remaining in the crucible was precisely weighed. The amount of ash was 3.1 mg. i.e. ash content (ash content divided by original polypropylene powder content)
was determined to be 0.021%. The above polypropylene powder was used as 100 parts by weight of powder and a stabilizer without any particular purification.
0.15 parts by weight of tetrakis [methylene-3-
(3′5′-di-tertiary-butyl-4′-hydroxyphenyl)propionate] methane (manufactured by Ciba Geigy, trade name Irganox 1010), 0.20 parts by weight of distearylthiodipropionate and 0.10 parts by weight The inner diameter of the calcium stearate is 20mm,
210 under nitrogen atmosphere using an extruder with L/D of 40
Pellets were prepared while kneading at .degree. The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products. MFI was 3.2 g/10 min. Comparative Example 1 20.0 g of anhydrous magnesium chloride used in Example 1 (A) was used instead of the co-pulverized solid material used in producing the solid component (a) in Example 1 (C). Otherwise, a solid material [hereinafter referred to as "solid component (b)"] was prepared in the same manner as in Example 1 (C). (D) of Example 1 except that the same amount of solid component (b) was used in place of the solid component (a) used in producing the solid catalyst component (A) in (D) of Example 1. ) An addition product was produced in the same manner as in ) to create a solid catalyst component [hereinafter referred to as "solid catalyst component (B)"]. Chemical analysis revealed that the content of titanium atoms in this solid catalyst component (B) was 1.7% by weight. Polymerization of propylene was carried out under exactly the same conditions as in (E) of Example 1, except that 39 mg of solid catalyst component (B) was used in place of the solid catalyst component (A) used in (E) of Example 1. I did it. As a result, 67 g of powdered polypropylene was obtained. That is, the polymerization activity is
1720g/g-solid catalyst component (B)・hour, and
101Kg/g-Ti・hour. The HR of this polypropylene powder was 87.7%. The bulk density of the polypropylene powder was 0.31 g/cc, and its shape was powdery without transparency. Example 2 6.0 g of benzoyl bromide (0.032 mol) was used in place of the benzoyl chloride used in Example 1 (A).
Co-pulverization was carried out in the same manner as in Example 1 (A) except that a co-pulverized solid was prepared. In place of the co-pulverized solid used in producing the solid component (a) in (C) of Example 1, an equivalent amount (15.0 g) of the co-pulverized solid obtained as described above was used. Stirring was performed in the same manner as in Example 1 (C). As a result, a mat-like solid was obtained.
Furthermore, instead of the solid component (a) used in producing the solid catalyst component (A) in Example 1 (D),
Example 1 except that 15.0 g of this solid was used.
A powder [hereinafter referred to as "solid catalyst component (C)"] was obtained by stirring, washing and drying in the same manner as in (D). The content of titanium atoms in this solid catalyst component (C) was 4.8% by weight. Polymerization of propylene was carried out under the same conditions as in (E) of Example 1, except that 38 mg of solid catalyst component (C) was used instead of the solid catalyst component (A) used in (E) of Example 1. Summer. As a result, 245 g of powdered polypropylene was obtained. That is, the polymerization activity is 6450
g/g - solid catalyst component (C)/hour, 134Kg/
g-Ti・time. Further, the HR of this polypropylene powder was 95.9%. Furthermore, the bulk density of this polypropylene powder is 0.39 g/cc,
The shape of the powder was similar to that of Example 1, and had a transparent appearance, and was a hard coarse particle with good fluidity. Further, pellets were prepared from this polypropylene powder in the same manner as in Example 1. of the obtained pellets
MFI was 3.5 g/10 minutes. Examples 3 to 6, Comparative Example 2 Diphenyl phosphorobromidate [hereinafter referred to as "compound (2)"] was used instead of diphenyl phosphorochloridate used as the phosphorus-containing organic compound in (B) of Example 1. ], dicresyl phosphorochloridate [hereinafter referred to as “compound (3)”], di-n-butyl phosphorochloridate [hereinafter referred to as “compound (4)”], or phenyl phenyl phosphorochloridate [ Hereinafter referred to as "compound (5)"]
-1 (B) in Example 1, except that the amounts shown in Table 1 were used.
A liquid containing the addition reaction product was prepared by reacting in the same manner as above. Addition reaction product (1) used in (C) of Example 1
(In Comparative Example 2, except that the solution containing the addition reaction product was used as described above instead of the solution containing
(82.8 g of titanium tetrachloride was used instead of the addition reaction product). After stirring in the same manner as in Example 1 (e), washing was performed to prepare each solid component. After stirring, washing and I did drying. The content of titanium atoms in each solid catalyst component obtained is shown in Table 1-1. Instead of the solid catalyst component (A) used in Example 1 (E), each solid catalyst component obtained as above was used (the amounts used are shown in Table 1-2). Polymerization of propylene was carried out in the same manner as in Example 1 (E). The yield of each polypropylene obtained, the polymerization activity calculated from them, and the HR bulk density of each polypropylene powder,
The ash content and the presence or absence of transparency are shown in Table 1-2.
In addition, each obtained polypropylene powder was used in Example 1.
Pellets were made in the same way. The MFI of each pellet obtained is shown in Table 1-2.

【table】

[Table] Examples 7 and 8, Comparative Examples 3 and 4 Benzoic acid was used instead of p-anisate, which was used as the organic carboxylic acid ester when preparing the addition product () in (D) of Example 1. Ethyl [hereinafter referred to as "compound (6)"] or methyl toluate [hereinafter referred to as "compound (7)]" was used, and 120
ml of xylene (the amount used is 2-1)
(shown in the table), a liquid containing the addition product was prepared in the same manner as in Example 1. Each of the obtained liquids (Comparative Example 3
In this case, add the solid component (a) in the same manner as in (C) of Example 1 to a solution of 82.8 g of titanium tetrachloride in 120 ml of toluene), and stir under the same conditions as in (D) of Example 1. , washed and dried. The titanium atom content of each solid catalyst component obtained is shown in Table 2-1. In place of the solid catalyst component (A) used in Example 1 (E), the solid catalyst component or solid component (a) titanium atom content 1.8% by weight) obtained as above was used. (The amounts used are shown in Table 2-2), and propylene polymerization was carried out in the same manner as in Example 1 (E). The yield of each polypropylene obtained, the polymerization activity calculated from them, and the powder of each polypropylene.
HR, bulk density, ash content, and presence or absence of transparency are shown in Table 2-2. Furthermore, pellets were prepared from each of the obtained polypropylene powders in the same manner as in Example 1.
The MFI of each pellet obtained in 2-2
Shown in the table.

【table】

[Table] Examples 9 to 11, Comparative Examples 5 and 6 Solid catalyst component (A) used in (E) of Example 1
The amount of triethylaluminum (hereinafter referred to as "TEA") used was changed as shown in Table 3-1, and instead of the reaction product of triethylaluminum and tetraxysilane used as the organic aluminum compound, triethylaluminum (hereinafter referred to as "TEA") was used.
(hereinafter referred to as "Compound (8)") or tetraethyl dialmoxane (hereinafter referred to as "TEDAO"), and tetraethoxysilane (hereinafter referred to as "Compound (8)") or Compound (6) as an electron donating compound. Except for using the amounts shown in Table 1 (however, in Example 10, no electron-donating compound was used),
Polymerization of propylene was carried out under the same conditions as in (E) of Example 1 (Examples 9 to 11).The amount of solid component (a) used in Comparative Example 4 was changed as shown in Table 3-1. In place of TEA, compound (8), and the reaction product used as the organoaluminum compound, TEA was used, and compound (6) was used as the electron donating compound in the amounts shown in Table 3-1. Other than that, propylene polymerization was carried out under exactly the same conditions as in Comparative Example 4. Comparative example 5,
6). Table 3-2 shows the yield of polypropylene obtained as described above and the polymerization activity calculated from the yield. Further, the HR, bulk density, presence or absence of transparency, and ash content of each of the obtained polypropylene powders are shown in Table 3-2. Furthermore, pellets were prepared from each of the obtained polypropylene powders in the same manner as in Example 1. The MFI of each pellet obtained is
- Shown in Table 2. In comparative examples using conventional catalysts, it is clear that the ash content in the resulting polymer increases as a highly stereoregular polymer is sought. Furthermore, in all of the comparative examples, the shape of the polymer is powdery (no transparency), and it is also clear that the fluidity is poor.

【table】

[Table] Comparative Examples 7 to 9 Instead of the solid component (a) used in Example 1 (D), 15.0 g of co-pulverized solid material produced in the same manner as Example 1 (A) was used. A powder [hereinafter referred to as "solid catalyst component (M)"] was obtained by stirring, washing and drying in the same manner as in Example 1 (D). The content of titanium atoms in this solid catalyst component (M) was 2.2% by weight (Comparative Example 7). 15.0 g (0.16 mol) and 4.5 g (0.032 mol) of anhydrous magnesium chloride used in (A) of Example 1
flask with benzoyl chloride (inner volume 500 c.c.)
I put it in. 100 ml of toluene (as a solvent) was added and stirred well at 60° C. for 15 hours. Then, it was thoroughly washed with hexane and dried under reduced pressure at a temperature of 40° C. for 2 hours. Instead of the co-pulverized solid material used in (C) of Example 1, the solid material obtained as above was used at 15.0%
A solid substance [hereinafter referred to as "solid component (C)"] was obtained by stirring under the same conditions as in Example 1 (C) except that g was used. Stirring, washing, and drying were performed in the same manner as in Example 1 (D), except that 15.0 g of solid component (C) was used instead of solid component (a) used in Example 1 (D). Summer. As a result, a powdery solid [hereinafter referred to as "solid catalyst component (N)"] was obtained. The content of titanium atoms in this solid catalyst component (N) was 1.2% by weight (Comparative Example 8). 6.7 g of titanium tetrachloride (0.035 mol) and 2.4 g of diphenylphosphorochloridate (9 mmol) were added to the co-pulverized solid prepared in the same manner as in Example 1 (A).
and 1.6 g of p-ethyl anisate (9 mmol)
was added, and co-pulverization was further carried out for 1 hour under the same conditions as in Example 1 (A) to produce a co-pulverized solid [hereinafter referred to as "solid catalyst component (P)"]. The content of titanium atoms in this solid catalyst component was 4.6% by weight. In place of the solid catalyst component (A) used in (E) of Example 1, the solid catalyst component (M) or solid catalyst component (P) obtained as described above was used, respectively. (shown in Table 4-1), propylene polymerization was carried out under the same conditions as in Example 1 (E). The yield of each polypropylene obtained and the polymerization activity calculated from them were determined in Section 4-1.
Shown in the table. Further, the HR, bulk density, presence or absence of transparency, and ash content of each of the obtained polypropylene powders are shown in Table 4-2. Furthermore, pellets were prepared from each of the obtained polypropylene powders in the same manner as in Example 1. of each pellet obtained
MFI is shown in Table 4-2.

【table】

[Table] From the above Examples and Comparative Examples, it is clear that the polymerization activity is only high when propylene is polymerized using a catalyst system that combines the solid catalyst component of the present invention and an organoaluminum compound (or these and an electron-donating organic compound). However, the bulk density and crystallinity of the obtained polymer are high, the polymer is packed to the inside and the particles have a transparent appearance, and the ash content based on the catalyst residue is small. It is clear that the catalyst component has excellent performance as a solid catalyst component for olefin polymerization. The preparation process of the solid catalyst component for olefin polymerization of the present invention is shown in FIG.

[Brief explanation of the drawing]

FIG. 1 is a flowchart of the process of preparing a solid catalyst component for olefin polymerization according to the present invention.

Claims (1)

[Claims] 1 (A) (1) A solid product obtained by co-pulverizing (a) an acyl halide compound and (b) a magnesium dihalide, (2) (a) () formula TiX ¹ _o (OR ¹ ) _4-o () [In the formula (), X ¹ is a chlorine atom, a bromine atom, or an iodine atom, and R ¹ is a fatty acid having at most 12 carbon atoms. is a group, alicyclic or aromatic hydrocarbon group, and n is 1 to 4.
is the number of ] (b) Organophosphorus compound represented by the formula () R ² _q (OR ³ ) _r X ² _s P(O) () [In the formula (), X ² is a halogen atom, and R ² and R ³ are Even if the number of carbons is large
A hydrocarbon group selected from the group consisting of 20 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, or halogen-substituted or alkoxy-substituted products thereof, and q is 0 or 1, , q+r+s is 3. ] The solid component obtained by catalyzing the mixture or addition reaction product with (B) (1) the titanium compound represented by the above formula () and (2) the organic carboxylic acid ester A solid catalyst component for olefin polymerization obtained by catalyzing the addition product under conditions where the addition product is in a liquid state or in a liquid state.