JPS5952166B2 - Method for manufacturing polyolefin - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for highly active polymerization of olefins.

More specifically, the present invention relates to a method for producing a polyolefin that can produce a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms. Among the highly active titanium catalyst components for olefin polymerization supported on magnesium halide, those particularly suitable for the highly stereoregular polymerization of α-olefins having 3 or more carbon atoms are disclosed in, for example, JP-A-48-16986; 1977-108385, JP-A-50-126590, JP-A-51-2029
No. 7 and Japanese Unexamined Patent Publication No. 51-28189.

In each of these proposals, a titanium catalyst is produced using a halogen-containing magnesium compound, preferably magnesium dihalide, particularly preferably magnesium chloride. Conventionally, proposals such as Japanese Patent Publication No. 46-34098 and Japanese Patent Publication No. 47-42137 have been made regarding methods for producing titanium catalysts using rogen-free magnesium compounds as raw materials and polymerizing olefins. As shown in the Comparative Example below, this method was not suitable for highly active and highly stereoregular polymerization of α-olefins having 3 or more carbon atoms.

As a result of intensive studies on the production of supported catalysts using such halogen-free magnesium compounds and their polymerization methods, the present inventors found a method for polymerizing α-olefins with high activity and high stereoregularity, especially for α-olefins having 3 or more carbon atoms. I arrived.

The halogen-free magnesium compound used in the present invention is characterized by the fact that magnesium chloride is extremely hygroscopic.
Although care must be taken in producing the catalyst, these operations are easy, and in particular, it has the advantage of extremely little variation in catalyst performance due to moisture. That is, according to the present invention, a halogen-free magnesium compound A containing an alkoxy group or an allyloxy group, an electron donor B, and a tethane halogen compound C having a halogen/titanium (molar ratio) of 6 or more and an electron donor/tethane. A combination of a solid catalyst component a having a molar ratio of 0.1 or more and a titanium/magnesium weight ratio of 0.05 to 0.5 and an organometallic compound b of a metal from Group 1 to Group 3 of the periodic table. A method for producing a polyolefin is provided, which comprises polymerizing or copolymerizing an olefin using a catalyst.

A representative example of the alkoxy group- or allyloxy group-containing, rogen-free magnesium compound A used in the present invention has the empirical formula Mg(0R)n(0R')2-n (where R and R' are alkyl groups). Or in an aryl group, R and R' may be the same or different.

n is a number representing o≦n≦2. ) can be exemplified.

However, the compound may not be represented by a simple formula such as the above formula, for example, a part of the 0R group and/or 0R' in the above formula may be another organic group, such as an acyloxy group,
It may be substituted with an alkyl group or the like. Furthermore, it may contain other elements such as aluminum, silicon, tin, and germanium. The magnesium compound represented by the above formula is, for example, metal magnesium or alkylmagnesium and a compound having a hydroxyl group in the molecule, such as aliphatic alcohols, aromatic alcohols, phenols, or these compounds combined with aluminum, silicon, tin, or germanium. It is a compound obtained by reaction with other elements such as or a mixture of these compounds.

Furthermore, it can be obtained by an exchange reaction between the magnesium compound of the above formula and the above compound having a hydroxyl group in the molecule. It is particularly preferable to use a compound containing an aralkoxy group or an allyloxy group as the magnesium compound since a high performance catalyst can be obtained.

Specifically, a suitable magnesium compound is Mg(0
CH3)(0C6H,), Mg(0CH,)(0C6H
, CH3), Mg(0CH3)( 0C6H,C21-
Ll), Mg(0CH3)(0C6H,C3H7),
Mg(0CH3) [0C6H3(CH3),], Mg(
0CH3) (0C6H4C4H,), Mg(0C2H,
)( 0C.H,), Mg(0C,H,)(0C.H4
CH3), Mg(0C2H,)(0C6H4C2H5)
, Mg(0C2H,)(0C.H.C3H,), Mg(
0C, H5) [0C. H3(CH3), ], Mg(0C
,H,) (0C.H4C.H9), Mg(0C3H,
)(0C.H4CH3), Mg(0CH,)(0C6H
4C1), Mg(0C,H,)(0C6H4C1), M
g(0C4H,)(0C6H4C1), Mg(0CH,
)(0C6H40CH,), Mg(0C2H,)(0C
6H40CH,), Mg(0C8H,,)(0C6H4
0CH,), Mg(0CH,)(0C,0H,), Mg
(0C,H,) (0C,0H,), Mg(0C,H,)
(0C,0H7), Mg(0C6H,0)(0C,H,
), Mg(0C6H10)(0C6H4CH,), Mg
(0C6H10) (0C6114Cノ), Mg (0C6
H5),, Mg(0C6H4CH3), Mg(0C6H
,C,H5),,Mg(0C6H4C,H,),,Mg
(0C6H4C4H,), Mg(0C6H4C8H1
,),,Mg(0C6H4C,H1,),,Mg[0C
6H4C(CH,)C6H5]2, Mg[0C6H, (
CH3), ], MgC. OC6H, (CH,), (C
4H,)]2,Mg(0C6H40CH,),,Mg(
0C6H4C1),, Mg(0C10H,),, Mg(
0C,0H6CH, ), Mg(0C,0H6C,H,
),, Mg[0C10H,CH,)2],, Mg(0C10H60CH,)2. Mg(0C10H4
Allyloxy group-containing magnesium compounds such as C0, M
g(0CH,)(0CH,C6H5), Mg(0CH,
)(0C2H4C6H,), Mg(0CH,)[0CH
(CH,)C6H,LMg(0CH,)[0C(CH,
), C6H5], Mg(0CH,)(0CH,C6H4
C,H,), Mg(0CH,)[0C(CH,),C6
H4C,H? ], Mg(0C,H,)(0CH2C6H
,), Mg(0C2H,)(0C2H4C6H5), M
g(0C,H5) [0CH(CH,)C6H,], Mg
(0C2H,)[0C(CH,),C6H,LMg(0
C,H,)(0CH,C6H4C,H,), Mg(0C
,H,)(0CH,C6H,), Mg(0CH,C6H
,),,Mg(0C,H4C6H5),,Mg[0CH
(CH,)C,H,],,Mg[0C(CH,)2C6
Examples include aralkoxy group-containing magnesium compounds such as Mg(0CH,C,H4C,H,)2, MgI, OC(CH,), C6H4C3H, ], or mixtures thereof.

Electron donor B is an ester, an amine, an amide, a ketone,
Ethers, lactams, etc., preferably esters,
More preferred are aromatic carboxylic acid esters. Specific examples of esters are given below.

Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, butyl acetate, amyl acetate, octyl acetate,
Cyclohexyl acetate, methyl propionate, 2-ethylhexyl propionate, ethyl butyrate, ethyl valerate,
Aliphatic esters such as methyl chloroacetate, methyl dichloroacetate, methyl crotonate, propiolactone, γ-butyrolactone, 8-valerolactone, ethylene carbonate;
Alicyclic esters such as methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate ,
Benzyl benzoate, chlorphenyl benzoate, methyl toluate, ethyl toluate, propyl toluate, butyl toluate, amyl toluate, allyl toluate, methyl ethyl benzoate, ethyl ethyl benzoate, ethyl xylene carboxylate, methyl anisate, Ethyl anisate, propyl anisate, butyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, methyl oxybenzoate, ethyl oxybenzoate, methyl aminobenzoate, ethyl aminobenzoate, methyl chlorbenzoate, chlorbenzoic acid Examples of other electron donors are N, N, N
', ~-Tetramethylethylenediamine, amines such as isoquinoline, acetone, 2,5-hexanedione,
Examples include ketones such as acetophenone, veratrol, ethers such as tetrahydrofurfuryl methyl ether, nitro compounds such as nitrobenzene, and lactams such as ε-caprolactam. On the other hand, as the titanium compound C, it is preferable to use a halide, such as TiCl4, TiCl, TiBr4, T
il4,Ti(0CH3)C2,,Ti(0C,H5)
C2,,Ti(0C4H,)Cl,,Ti(0C,H,
)Cl, , Ti(0C,H5)2C1, or other titanium halides or alkoxy halides, or complex compounds of these with electron donors can be used.

A particularly preferred titanium compound is TiCl4. Solid catalyst component a is produced using the above-mentioned magnesium compound A, electron donor B, and titanium compound C as essential components, but in addition to the above, other additional components [however, with respect to magnesium compound A] Excluding halogenating agents] may also be used as raw materials.

Such additional components may be, for example, organic or inorganic inert diluents. Such additional components include, for example, B2O3, NaCl, Na2SO4, AIl2O3,
Examples include SiO, CaCl2, aluminum alkoxide, phenoxide, polysiloxane, alkoxysilane, polyethylene, polypropylene, and polystyrene. Solid catalyst component a can be obtained by contacting components A, B, and C in any order, but preferably components Al. It is preferable to adopt a method of contacting component B and then contacting component C.

Although any contacting method can be used, a preferred method is to co-pulverize components A and B and then bring them into contact with component C in a liquid phase. The co-pulverization treatment is generally carried out in the substantial absence of oxygen, water, etc. using, for example, a pole mill, vibration mill, impact mill, or the like.

It is desirable to select the grinding conditions appropriately depending on the type of raw material and the grinding equipment, but in general, the grinding time is between 1 hour and 1 hour.
The grinding time is about 0 days, and the grinding temperature can be selected around room temperature, and there is no need for cooling or heating. This operation widens the half-width of the strongest diffraction line of the raw material magnesium compound. The extent of the spread is, for example, 1.05 times or more. Although the structure of the product obtained by this method is unknown, its composition does not change after washing with an inert diluent or the like. The amount of component B used is preferably 0.01 to 2 mol per 1 atom of magnesium in component A,
More preferably, it is 0.05 to 1 mol.

To contact component C in a liquid phase, a liquid titanium compound such as tethane tetrachloride may be used alone, or the tethane compound may be dissolved in an inert solvent such as hexane, heptane, or kerosene. It is better to adopt this method.

There is no particular limit to the degree of contact, but it is preferably between o and 20.
It is preferable to contact at 0° C. for about 0.5 hours or more. After contact,
Component a is preferably isolated by filtration, thoroughly washed with an inert solvent, and then subjected to polymerization. In the present invention, the halogen/titanium (molar ratio) is 6 or more, preferably 6 to 50, the electron donor/tetane (molar ratio) is 0.1 or more, preferably 0.1 to 1, and the titanium/magnesium (by weight) A solid catalyst component a having a ratio of 0.05 to 0.5 is used as a component of the catalyst.

The halogen content in the solid catalyst component a usually originates from the halogen content of the tethane compound C. Although it varies depending on the type of halogen and electron donor, a typical weight ratio of magnesium, tethane, halogen, and electron donor in solid catalyst component a is 1:(0.05 to 0.5):(
1 to 5) (0.1 to 1.5), and its composition is not substantially changed by washing with hexane at room temperature. These usually exhibit a surface area of 10 d/g or more, preferably 20 d/g or more. Organometallic compounds b of Group 1 to Group 3 metals in the periodic table are those having a hydrocarbon group directly bonded to the metal, such as alkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum hydrides, alkylaluminum halides, alkylaluminum alkoxides, dialkyl Examples include zinc, dialkylmagnesium, and alkylaluminum halides.

Among these, preferred compounds are Al (C,H,),
Al(CH,),,Al(C3H,)3,Al(C4
H,)3, trialkyl or trialkenyl aluminum such as Al(Cl2H2,)3, (C2H5)2A
I0AI(C2H,)2, (C4H9)2AI0AI(
C,H,)2,(C,H,),AIN(C6H,)A
Al via oxygen or nitrogen atoms such as l(C2H,)2
Alkylaluminum compounds with a structure in which many atoms are linked together, dialkylaluminum hydrides such as (C2H,)2AIH) (C4H,)2AIH, (C2H,)2
AICI, (C2H,)2A11, (C4H,)2AI
Dialkyl aluminum halides such as CI, (C,H
, ), Al(0C.H,), (C2H,)2A1(0C
6H,) or phenoxides, the most preferred being trialkylaluminum.

Olefins used in the polymerization include ethylene, propylene, 1-butene, 4-methyl-1-benzene, etc., and these can be used not only for homopolymerization but also for random copolymerization and block copolymerization.

Further, during copolymerization, a polyunsaturated compound such as a conjugated diene or a non-conjugated diene can be selected as a copolymerization component. These may be aimed at crystalline polymers or amorphous polymers, but when used in the polymerization of α-olefins having 3 or more carbon atoms, polymers with high stereoregularity can be produced in high yields. can get. Polymerization can be carried out in either liquid phase or gas phase.

When carried out in a liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium. In the case of liquid phase polymerization, the solid catalyst component a is 0.001 to 0.5 mmol in terms of titanium atoms per liquid phase 11, and the organometallic compound b of a metal of Groups 1 to 3 of the periodic table is added. is preferably maintained at 0.1 to 50 mmol in terms of metal atoms. A molecular weight regulator such as hydrogen may be used during the polymerization. Furthermore, in order to control the stereoregularity of α-olefins having 3 or more carbon atoms, oxygen-containing electron donors such as ethers, ethylene glycol derivatives, and ester organic acids, as well as amines, sulfur-containing compounds, nitriles, etc. may be coexisting, and especially Aromatic oxygen-containing compounds, especially aromatic carboxylic acid esters, are preferred. The type of aromatic carboxylic acid ester is selected from those mentioned above for use in preparing the solid catalyst component a, and particularly preferred are benzoic acid ester and nuclear-substituted benzoic acid ester, and benzoic acid ester, These include toluic acid ester, anisic acid ester, phthalic acid diester, terephthalic acid diester, hydroxybenzoic acid ester, and aminobenzoic acid ester, and the most preferred ones are methyl p-toluate and ethyl p-toluate. These may be used in the form of addition reaction products with the organometallic compounds. The effective amount of the compound to be used is usually 0.0% per mole of the organometallic compound.
The amount is preferably 0.01 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.1 to 1 mol. The polymerization temperature of the olefin is preferably 20 to 200°C,
More preferably, the temperature is about 50 to 180°C, and the pressure is normal pressure to 50! It is preferable to carry out under pressurized conditions, preferably about 2 to 20 Kf/CrA.

Polymerization can be carried out in any of the batch, semi-continuous and continuous modes. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. According to the present invention, it is possible to obtain a highly stereoregular polymer in high yield, particularly from an α-olefin having 3 or more carbon atoms.

Next, the present invention will be explained in more detail with reference to examples.

Example 1 20.3 moles of commercially available Mg(0CH,) were charged into a round bottom flask under a nitrogen atmosphere, and further 0.6 moles of phenol was diluted in 200% hexane.

The temperature is raised while stirring, and the distillate is removed by distillation to remove Mg.
(0C6H5)2 was obtained. The half width of the diffraction line showing the maximum intensity of the X-ray spectrum of this product was 0.49. Next, 0.2 mol of the above Mg (0C6H5) and 0.033 mol of ethyl benzoate were added in a nitrogen atmosphere with a diameter of 157 mm. Internal volume 800T that accommodates 100 stainless steel (SUS32) balls! ! It was charged into a stainless steel ball mill cylinder with a t1 inner diameter of 100 u, and was brought into contact with 125 rTn for 100 hours.

The half width of the diffraction line showing the maximum intensity of the X-ray spectrum of the obtained solid treated product was 5.83t. The above solid treated product was suspended in 200 ml of titanium tetrachloride and stirred at 80° C. for 2 hours to react.

After the reaction was completed, the solid portion was collected by filtration and thoroughly washed with hexane to obtain a titanium-containing solid catalyst component. The ingredient is
Titanium 3.5% by weight, chlorine 54% by weight, magnesium 1%
8.0% by weight, and 11.1% by weight of ethyl benzoate. An autoclave with an internal volume of 22 cm was charged with 750 ml of hexane from which oxygen and moisture had been sufficiently removed, and triethylaluminum 5.0 mm
1 and 1.59 mm01 of methyl p-toluate were charged, and after 5 minutes, 0.03 mm01 of the titanium-containing solid catalyst component was charged in terms of titanium atoms. The system was heated to 60°C,
Total pressure 7.0Kf/Cf with propylene! The pressure was increased to i, and then 350 me of hydrogen was introduced, and polymerization was carried out for 4 hours. After the polymerization was completed, the solid component was filtered through phosphorus to obtain 244 g of white powdery polypropylene. The extraction residue with boiling n-heptane was 96.2%, the bulk specific gravity was 0.36, and the melt index was 4.9. On the other hand, 12.1 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Example 2 or
8 20.3 mol of commercially available Mg (0CH,) was charged into a round bottom flask under a nitrogen atmosphere, and the alcohols and phenols shown in Table 1 were diluted with 200% hexane and charged.

Table 1
The compound was obtained. The compound obtained as described above was used in place of Mg(0C6H,)2 in Example 1, and Example 1
Catalyst synthesis was carried out in the same manner as described above, and propylene polymerization was carried out.

The results are shown in Table 1. Comparative Example Mg (0-g=>-CH3) synthesized in Example 2, 20
g was suspended in TiCl42OOmt and reacted at 80° C. for 2 hours with stirring.

After the reaction was completed, the solid portion was taken out by filtration, washed with hexane, and then dried. The titanium-containing solid catalyst component includes titanium 4.
0% by weight, 59% by weight of chlorine, and 18.0% by weight of magnesium. When the titanium catalyst obtained above was subjected to propylene polymerization under the same conditions as in Example 1, only 15.8 g of white powdery polypropylene and 1.7 g of a solvent-soluble polymer were obtained.

The residue of the powder extracted with boiling n-heptane was 90.8%. Examples 9 to 12 Using the titanium catalyst synthesized in Example 2, under the polymerization conditions of Example 1, and using the compounds shown in Table 2 as organic acid esters to be combined with organoaluminum, the same procedure as in Example 1 was carried out. Polymerization of propylene was carried out.

The results are shown in Table 2. Examples 13 to 16 Same as Example 1 except that 0.2 mol of the magnesium compound Mg(0CH,)(0-<=>) synthesized in Example 3 and the organic acid ester shown in Table 3 were used. A titanium-containing catalyst component was synthesized, and propylene polymerization was carried out under the same conditions as in Example 1.

Claims (1)

[Scope of Claims] 1. Halogen/titanium (molar ratio) derived from a halogen-free magnesium compound A containing an alkoxy group or an allyloxy group, an electron donor B, and a halogen compound C of titanium.
is 6 or more, electron donor/titanium (molar ratio) is 0.1 or more, titanium/magnesium (weight ratio) is 0.05 to 0.
．． A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin using a combination catalyst of the solid catalyst component a of No. 5 and an organometallic compound b of a metal from Group 1 to Group 3 of the periodic table. 2. The method according to claim 1, wherein the solid catalyst component a has a halogen/titanium (molar ratio) of 6 to 50 and an electron donor/titanium (molar ratio) of 0.1 to 1. 3 Magnesium compound A has the general formula Mg(OR)_n(OR')_2_-_n (however, R,
R' is an alkyl group or an aryl group, and R and R' may be the same or different. n is a number representing 0≦n≦2. ) The method according to claim 1 or 2, using a compound represented by: 4. The method according to claim 3, wherein a magnesium compound in which R and/or R' are an aralkyl group is used. 5. The method according to claim 4, wherein the aralkyl group is selected from the group consisting of a phenylalkyl group, a lower alkyl-substituted phenylalkyl group, a lower alkoxy-substituted phenylalkyl group, and a halogen-substituted phenylalkyl group. 6 In the formula, R and or R' are a phenyl group, a naphthyl group, a lower alkyl-substituted phenyl group, a lower alkyl-substituted naphthyl group, a lower alkoxy-substituted phenyl group, a lower alkoxy-substituted naphthyl group, a halogen-substituted phenyl group, and a halogen-substituted naphthyl group. 4. The method according to claim 3, wherein the aryl group is an aryl group selected from the group consisting of: 7. The method according to any one of claims 1 to 6, wherein electron donor B is an organic acid ester. 8. The method according to claim 7, wherein the organic acid ester is an aromatic carboxylic acid ester. 9. The method according to any one of claims 1 to 8, wherein the titanium halogen compound C is titanium tetrachloride. 10
10. The method according to claim 1, wherein the solid catalyst component a is obtained by causing titanium tetrachloride to act on a co-pulverized product of magnesium compound A and electron donor B in a liquid phase. Method. 11. The method according to any one of claims 1 to 10, wherein the organometallic compound b is an organoaluminum compound. 12. The method according to any one of claims 1 to 11, in which an electron donor C is coexisting during olefin polymerization. 13. The method according to any one of claims 1 to 12, wherein the electron donor C is an organic acid ester.