JPH0358368B2 - - Google Patents

Description

[Detailed description of the invention]

[] Background of the Invention (1) Technical Field The present invention relates to a catalyst component that provides a highly active polymer with good polymer properties. Conventionally, magnesium compounds such as magnesium halides, magnesium oxyhalides, dialkylmagnesiums, alkylmagnesium halides, magnesium alkoxides, or complexes of dialkylmagnesium and organic aluminum have been used as carriers for transition metal compounds such as titanium compounds to achieve high activity. It is known to be a catalyst, and many inventions have been proposed. However, according to the present inventor's knowledge, although these prior art techniques have a certain degree of catalytic activity, the properties of the produced polymer are not sufficient, and improvements are desired. Polymer properties are extremely important in slurry polymerization, gas phase polymerization, and the like. Poor polymer properties may cause polymer adhesion within the polymerization tank and failure to extract the polymer from the polymerization tank. Further, the polymer concentration in the polymerization tank is closely related to the polymer properties, and if the polymer properties are not good, the polymer concentration in the polymerization tank cannot be increased. What is not possible is a high polymer concentration.
This is extremely disadvantageous in terms of industrial production. (2) Prior Art According to Japanese Patent Publication No. 51-37195, a method has been proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide and further reacted with organoaluminum. According to JP-A-54-16393, a method is proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide or the like, and then a halogen-containing compound and a reducing compound are reacted. [] SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above-mentioned problems, and attempts to achieve this object by means of a supported transition metal catalyst component prepared in a specific manner. Therefore, the catalyst component for olefin polymerization according to the present invention is characterized by being a contact product of the following component (A ₁ ) and component (A ₂ ). Component (A ₁ ) Magnesium dihalide, general formula below

[Formula] (R ₁ to _{R 4} are hydrocarbon residues, n is a number of 2 or more) and the following general formula:

A contact product of a polymeric silicon compound having a structure represented by the formula: (R ₅ is a hydrocarbon residue). Component (A ₂ ) At least one of the following components (a) and (b), or this and component (c). (a) Liquid titanium compound (However, when used alone or in combination with component (c), this titanium compound must contain a halogen.) (b) Silicon halogen Compound. (c)

A polymer silicon compound having a structure represented by the formula: (R ₆ is a hydrocarbon residue). Effects When olefins are polymerized using the solid catalyst component according to the present invention as the transition metal component of a Ziegler catalyst, a polymer with high activity and excellent polymer properties can be obtained. The reason why a polymer with high activity and good polymer properties can be obtained is not necessarily clear, but it is due to the chemical interaction of the components used in the present invention and the special physical properties of the solid component (A ₁ ) used and the catalyst component produced. This seems to be due to the characteristics. [] Detailed Description of the Invention 1 Component (A ₁ ) (1) Composition Component (A ₁ ) is a solid composition composed of magnesium dihalide, polytitanate, and a specific polymeric silicon compound. This solid composition (A ₁ ) is neither magnesium dihalide nor a complex of magnesium dihalide and polytitanate, but is another solid. At present, its contents have not been fully analyzed, but according to the results of compositional analysis, this solid composition contains titanium, magnesium, halogen, and silicon. The specific surface area of this component (A ₁ ) is often small, usually less than 10 m ² /g, and
According to the results of line diffraction, no peaks characterizing magnesium dihalide were observed, and from an X-ray perspective, it seems to be a different compound from magnesium dihalide. (2) Production Component (A ₁ ) is produced by mutual contact of magnesium dihalide, polytitanate and certain polymeric silicon compounds. (1) Magnesium dihalide Examples include MgF ₂ , MgCl ₂ , MgBr ₂ , etc. (2) Polytitanate ester This is the general formula

It is a polytitanate ester represented by the formula: Here, R ₁ ~
R ₄ is the same or different hydrocarbon residue, preferably an aliphatic or aromatic hydrocarbon having 1 to 10 carbon atoms, especially an aliphatic hydrocarbon having 2 to 6 carbon atoms. n is a number greater than or equal to 2, especially
Shows numbers up to 20. The value of n is desirably selected so that the polytitanate itself or in liquid form as a solution can be subjected to the contact step with other components. A suitable n for handling is about 2 to 14, preferably about 2 to 10. Specific examples of such polytitanate esters include tetraisopropyl polytitanate (n = 2-10), tetra-n-butyl polytitanate (n = 2-10), and tetra-n-hexyl polytitanate (n =
2 to 10), and tetranormal octyl polytitanate (n=2 to 10). Among these, isopropyl polytitanate and tetra-n-butyl polytitanate are preferred. (3) Polymeric silicon compound This is the formula

It is a compound having the structure shown by the formula: R is a hydrocarbon residue having about 1 to 10 carbon atoms, particularly about 1 to 6 carbon atoms. Specific examples of polymeric silicon compounds having such structural units include methylhydropolysiloxane, ethyl-hydroxypolysiloxane, phenylhydropolysiloxane, and cyclohexylhydropolysiloxane. The degree of polymerization is not particularly limited, but considering the handling, the viscosity is from 10 centistokes to
It is preferable to have a diameter of about 100 centistokes. Furthermore, although the terminal structure of the hydropolysiloxane does not have a significant effect on the present invention, it is desirable that it be capped with an inert group, such as a trialkylsilyl group. (4) Contact (amount ratio) of each component The amount of each component used may be arbitrary as long as the effect of the present invention is recognized, but it is generally preferable to fall within the following range. The amount of polytitanate used is the molar ratio to magnesium dihalide.
It may be within the range of 0.1 to 10, preferably 1 to
It is within the range of 4. The amount of polymer silicon compound used is 1 molar ratio to magnesium dihalide.
It may be within the range of ×10 ^-2 to 100, preferably
It is within the range of 0.1 to 10. (Contact method) The solid component (A ₁ ) of the present invention is obtained by contacting the three components described above. Contacting the three components can be carried out by any generally known method. Generally, −100
The contact may be made at a temperature range of ℃ to 200℃.
Contact time is usually about 10 minutes to 20 hours. It is preferable that the three components are brought into contact with each other under stirring, and they can also be brought into contact by mechanical grinding using a ball mill, vibration mill, or the like. The order of contacting the three components can be arbitrary as long as the effects of the present invention are observed, but by bringing magnesium dihalide and titanium tetraalkoxide into contact with each other,
It is common to then contact the polymeric silicon compound. Contacting the three components can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium in this case include hydrocarbons, halogenated hydrocarbons, dialkylpolysiloxanes, and the like. Specific examples of hydrocarbons include hexane, heptane, toluene, cyclohexane, etc. Specific examples of halogenated hydrocarbons include n-butyl chloride, 1,
Examples of dialkyl polysiloxanes include dichloroethylene, carbon tetrachloride, and chlorobenzene. Specific examples of dialkyl polysiloxanes include dimethyl polysiloxane and methyl-phenyl polysiloxane. 2 Component (A ₂ ) Component (A ₂ ), at least one of the following components (a) to (b), or this and component (c), i.e. (a), (b),
(a)+(b), (a)+(e), (b)+(c), or (a)+(b)+(c)
,
It is. (a) Liquid titanium compound Here, “liquid” refers to not only those that are liquid themselves (including those that are complexed and become liquid), but also those that are liquid as a solution. include. Typical compounds have the general formula Ti(OR)
_4-n X _n (where R is a hydrocarbon residue,
Preferably it has about 1 to 10 carbon atoms,
X represents halogen, m represents the number of 0m4). Specific examples include TiCl ₄ , TiBr ₄ , Ti(OC ₂ H ₅ )
Cl ₃ , Ti(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti
(O-iC ₃ H ₇ )Cl ₃ , Ti (O-nC ₄ H ₉ )Cl ₃ , Ti
(O−nC ₄ H ₉ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ )Br ₃ , Ti
(OC ₂ H ₅ ) (OC ₄ H ₉ ) ₂ Cl, Ti(O−nC ₄ H ₉ ) ₃ Cl,
Ti(O- _C6H5 ) _Cl3 , _{Ti (} O- _iC4H9 ) _{2Cl2 ,}
Ti(OC ₅ H ₁₁ )Cl ₃ , Ti(OC ₆ H ₁₃ )Cl ₃ , Ti
(OC ₂ H ₅ ) ₄ , Ti(C-iC ₄ H ₉ ) ₄ , Ti(O-
nC ₄ H ₉ ) ₄ , Ti(O-nC ₃ H ₇ ) ₄ , Ti(O-
iC ₃ H ₇ ) ₄ Ti[O-CH ₂ CH(CH ₃ ) ₂ ] ₄ , Ti[O-
C(CH ₃ ) ₃ ] ₄ , Ti(OC ₅ H ₁₁ ) ₄ , Ti(O-
C ₆ H ₁₃ ) ₄ , Ti (O-nC ₇ H ₁₅ ) ₄ , Ti [OCH
(C ₃ H ₇ ) ₂ ] ₄ , Ti [OCH(CH ₃ )C ₄ H ₉ ] ₄ , Ti
(OC ₈ H ₁₇ ) ₄ , Ti (OC ₁₀ H ₂₁ ) ₄ , Ti [OCH ₂ CH
(C ₂ H ₅ ) C ₄ H ₉ ] ₄ , etc. Further, this titanium compound (a) may be a molecular compound obtained by reacting TiX' ₄ (herein, X' represents a halogen) with an electron donor. A specific example is _TiCl4・
CH ₃ COC ₂ H ₅ , TiCl ₄・CH ₃ CO ₂ C ₂ H ₅ ,
_{TiCl4 ・ C6H5NO2} , _{TiCl4 ・ CH3COCl} ,
TiCl ₄・C ₆ H ₅ COCl, TiCl ₄・C ₆ H ₅ CO ₂ C ₂ H ₅ ,
Examples include TiCl ₄ .ClCO ₂ C ₂ H ₅ , TiCl ₄ .C ₄ H ₄ O, and the like. (b) Silicon halogen compound A compound represented by the general formula R′ _4-1 SiX ₁ can be used. (Here, R' is hydrogen or a hydrocarbon residue (preferably up to about 4 carbon atoms), X is a halogen, and 1 is a number of 114.) Specific examples of this compound include SiCl ₄ ,
_{HSiCl3 , CH3SiCl3 , SiBr4} , ( _C2H5 ) _{2SiCl2 ,}
(CH ₃ ) ₃ SiCl, etc. (c) The definitions of the polymeric silicon compound R ⁶ and the degree of polymerization are the same as those described for those used when producing the solid component (A ₁ ) above. Component (A ₁ )
You can use the same one used for. 3. Contact between component (A ₁ ) and component (A ₂ ) (1) Amount ratio The amount of each component to be used is arbitrary as long as the effect of the present invention is recognized, but generally it is within the following range. preferable. The amount of liquid titanium compound used is based on the solid component.
The molar ratio to the magnesium dihalide constituting (S) may be within the range of 1×10 ⁻² to 100, preferably within the range of 0.1 to 10. The amount of the silicon halogen compound to be used may be within a molar ratio of 1 x 10 ^-2 to 100, preferably within a range of 0.1 to 10, relative to the magnesium dihalide constituting the solid component (A ₁ ). be. The amount of the polymer silicon compound to be used may be in a molar ratio of 1×10 ⁻³ to 10, preferably 0.05 to 5.0, relative to the magnesium dihalide constituting the solid component (A ₁ ). (2) Contact method The solid couplant component of the present invention comprises the aforementioned solid component (A ₁ ) and component (A ₂ ), that is, components (a), (b),
(a)+(b), (a)+(c), (b)+(c), or (a)+(b)+(c)
It is obtained by contacting in general,
-100℃~200℃, preferably 0℃~100℃,
The contact may be made within a temperature range of Contact time is usually about 10 minutes to 20 hours. The solid component (A ₁ ) and components (a) to (c) are preferably brought into contact with each other under stirring, and may also be brought into contact by mechanical pulverization using a ball mill, vibration mill, or the like. The order of contact may be arbitrary as long as the effects of the present invention are observed. For the solid component (A ₁ ), the component
Any of the components (a), (b), and (c) may be contacted first. Further, the contact in the present invention can also be carried out in the presence of a dispersion medium. As the dispersion medium at this time, the same one used when producing the solid component (A ₁ ) can be used. 4 Polymerization of α-olefin (1) Formation of catalyst The catalyst component of the present invention can be used in the polymerization of α-olefin in combination with an organometallic compound as a cocatalyst. Any of the organometallic compounds of metals from groups 1 to 10 of the periodic table known as cocatalysts can be used. Particularly preferred are organic aluminum compounds. Specific examples of organoaluminum compounds include the general formula R ³ _3-p AlX _p or R ⁴ _3-q Al
(OR ⁵ ) _q (where R ³ , R ⁴ and R ⁵ are hydrogen or hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different; X is a halogen atom; p and q are each 0p< 2, gq1). Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride,
Alkylaluminum halides such as ethylaluminum dichloride, (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, (d) alkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxy, diethylaluminum phenoxide, etc. can give. In addition to these organoaluminum compounds (a) to (c), other organometallic compounds, such as R ⁷ _3-a Al(OR) ⁸ _a
An alkyl aluminum alkoxide represented by (1a3, R ⁷ and R ⁸ are hydrocarbon residues having about 1 to 20 carbon atoms which may be the same or different) can also be used in combination.
For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, a combination of triethylaluminum, diethylaluminium chloride and diethylaluminium ethoxide. Can be used in combination with The amount of these organometallic compounds to be used is not particularly limited, but it is preferably within the range of 0.5 to 1000 in weight ratio to the solid catalyst component of the present invention. (2) α-Olefin The α-olefin polymerized using the catalyst system of the present invention has the general formula R-CH=CH ₂ (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and may have a branched group). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Particularly preferred are ethylene and propylene. In these polymerizations, up to 50% by weight, preferably 20% by weight, of the α-
Copolymerization with olefins can be carried out. Further, copolymerization with copolymerizable monomers other than the above α-olefin (eg, vinyl acetate, diolefin) can also be carried out. (3) Polymerization The catalyst system of the present invention is of course applicable to ordinary slurry polymerization, but can also be continuously applied to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. It is applicable to both polymerization, batch polymerization, and prepolymerization. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, hebutane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. The polymerization temperature is
Room temperature to about 200℃, preferably 50℃ to 150℃
In this case, hydrogen can be used as an auxiliary molecular weight regulator. In addition, a small amount of Ti(OR) _4-b X _b (where R is a hydrocarbon residue having about 1 to 10 carbon atoms, X is a halogen,
b is the number of 0b4),
It is possible to control the density of the polymer that is polymerized. Specifically 0.890 to 0.965
It can be controlled within certain limits. 5 Experimental Examples Example 1 (1) Synthesis of solid component (A ₁ ) 50 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and then 0.1 mol of MgCl ₂ was introduced into the flask.

68 milliliters of [Formula] (R=n-C ₄ H ₉ ) (hereinafter abbreviated as TBT-2) was introduced,
The reaction was carried out at 90°C for 2 hours. After the reaction is completed, 40℃
lower the temperature to , then add methylhydrodiene polysiloxane (20 centistokes)
18 milliliter was introduced and allowed to react for 2 hours. When the generated solid component was washed with n-heptane and a portion was taken out for compositional analysis, it was found that Ti=
13.5 weight percent, Cl=12.5 weight percent, Mg=4.8 weight percent, and Si=1.3 weight percent. (2) Production of catalyst component 50 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and the entire amount of the solid component (A ₁ ) synthesized above was introduced. Then 0.06 mol of TiCl ₄ and n-heptane
50 ml was introduced and the reaction was carried out at 70°C for 2 hours. After the reaction is completed, wash with n-heptane,
It was used as a catalyst component. When a portion was taken out and analyzed for composition, Ti = 9.5% by weight, Cl =
37.2% by weight, Mg=11.9% by weight. (3) Polymerization of ethylene Internal volume 1.5 with stirring and temperature control equipment
In a little stainless steel autoclave,
After repeating vacuum-ethylene displacement several times, thoroughly dehydrated and deoxygenated n-heptane was
milliliter was introduced, followed by 200 milligrams of triethylaluminum and 10 milligrams of the catalyst component synthesized above. Next, hydrogen was introduced until the pressure reached 4.5Kg/ ^cm2 , and further,
Ethylene was introduced to give a total pressure of 9 Kg/cm ² .
Polymerization was carried out for 3 hours. These reaction conditions were kept the same during the polymerization. However, the pressure, which decreases as the polymerization progresses, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were purged, the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer overnight. 115 grams of polymer (PE) were obtained (yield based on catalyst (g PE/g solid catalyst component) = 11500).
When the melt flow rate (MSR) of this polymer was measured at 190℃ and a load of 2.16Kg, the MFR
= 4.5. The bulk specific gravity of the polymer was 0.45 (g/cc). Example 2 The catalyst component was produced in exactly the same manner as in Example 1 except that 0.075 mol of TiCl ₄ and 0.025 mol of SiCl ₄ were used instead of TiCl ₄ and the reaction temperature was changed to 50°C. Polymerization of ethylene was carried out in exactly the same manner. 251 grams of polymer was obtained [yield based on catalyst=25100 (g·PE/g solid catalyst component)]. MFR=8.7, polymer bulk specific gravity=0.41 (g/cc). Example 3 The catalyst component of Example 1 was prepared in exactly the same manner as in Example 1, except that 0.04 mol of TiCl ₄ and 12 ml of methyl-hydrodiene polysiloxane were used instead of TiCl ₄ . Polymerization of ethylene was carried out in exactly the same manner. 106 grams of polymer was obtained [yield based on catalyst=10600 (g·PE/g solid catalyst component)]. MFR=4.3, polymer bulk specific gravity=0.46 (g/cc). Example 4 In the production of component (A ₁ ) of Example 1, TBT
-instead of 2

[Formula] (R=n-C ₄ H ₉ ) (hereinafter abbreviated as TBT-4) was used, but the production was carried out in exactly the same manner. Further, the catalyst component was produced in exactly the same manner as in Example 1 except that 0.05 mol of SiCl ₄ was used instead of TiCl ₄ . The Ti content in the catalyst component was 3.5 weight percent.
Polymerization of ethylene was also carried out under exactly the same conditions as in Example 1. 118 grams of polymer was obtained (yield based on catalyst = 11800 (g.PE/g solid catalyst component)). MFR=4.9, polymer bulk specific gravity=0.44 (g/cc). Example 5 In the production of component (A ₁ ) of Example 1, instead of TBT-2,

[Formula] (R=n-C ₄ H ₉ ) (hereinafter abbreviated as TBT-7) was used, but the production was carried out in exactly the same manner. Further, the catalyst component was produced in exactly the same manner as in Example 1 except that 0.04 mol of SiCl ₄ and 12 ml of methyl-hydrodiene polysiloxane were used instead of TiCl ₄ . The Ti content in the catalyst component was 14.6 weight percent. Polymerization of ethylene was carried out in exactly the same manner as in Example 1, except that triisobutylaluminum was used instead of triethylaluminum as the organoaluminum component. 96 grams of polymer was obtained [yield based on catalyst=9600 (g·PE/g solid catalyst component)]. MFR＝
3.8, polymer bulk specific gravity = 0.41 (g/cc). Example 6 The catalyst component of Example 1 was produced in exactly the same manner as in Example 1 except that 0.03 mol of _{TiCl 4 ,} 0.01 mol of SiCl ₄ and 15 ml of methylhydrodiene polysiloxane were used instead of TiCl 4 .
The Ti content in the catalyst component was 14.0 weight percent. Polymerization of ethylene was carried out in exactly the same manner as in Example 1. 109 grams of polymer was obtained [yield based on catalyst=10900 (g·PE/g solid catalyst component)].
The MFR was 5.0 and the bulk specific gravity of the polymer was 0.42 (g/cc). Examples 7 to 10 Using the catalyst components produced in Example 1, Table-
Polymerization was carried out in exactly the same manner except that the organoaluminium shown in Example 1 was used. The results are shown in Table-1. Example 11 This example concerns the polymerization of an ethylene-butene-1 gas mixture. Using the solid component prepared in Example 1, butene-1 was added instead of ethylene.
Polymerization was carried out under exactly the same conditions except that an ethylene-butene-1 mixed gas containing 7.5 mol percent was used and the _H2 concentration in the polymerization tank was 2.5 mol percent. 243 grams of polymer were obtained.
MFR=2.2, polymer bulk specific gravity=0.44 (g/cc), and polymer density=0.934 (g/cc). Example 12 This example concerns the polymerization of propylene. Into the autoclave used in Example 1, 800 milliliters of sufficiently dehydrated and deoxygenated n-heptane was introduced, followed by triethylaluminum.
385 mg, 123 mg of ethyl para-toluate, and 26 mg of the catalyst component synthesized in Example 4.
Introduced milligrams. 2 at 65℃ and 9Kg/ ^cm2
Time polymerization was carried out. 27 grams of poimer were obtained. T-II = 71 weight percent, Product II = 85 weight percent. In addition, T-II is II for all polymers including polymers soluble in the polymerization medium.
(i.e., the content of boiling n-heptane insolubles) Product II means II for the solid product excluding the soluble polymer described above.

[Table] Example 13 In the production of _the catalyst component in Example 6, except that 0.025 mol of Ti(OC ₂ C ₅ )Cl was used instead of TiCl ₄ and 0.02 mol of (CH ₃ )SiCl ₃ was used instead of SiCl 4. A catalyst component was produced in the same manner as in Example 6. The Ti content in the catalyst component was 15.1 weight percent. Polymerization of ethylene was carried out in exactly the same manner as in Example 6 except that this catalyst component was used. 88 grams of polymer was obtained (catalyst yield = 8800 (g PE/
g solid catalyst component)]. MFR=6.33 Polymer bulk specific gravity=0.44 (g/cc).

[Brief explanation of drawings]

FIG. 1 is a flowchart to help understand the technical content of the present invention regarding a Ziegler type catalyst.

Claims (1)

[Scope of Claims] 1. A catalyst component for olefin polymerization, which is a contact product of the following component (A ₁ ) and component (A ₂ ). Component (A ₁ ) Magnesium dihalide, polytitanate ester represented by the following general formula [Formula] (R ₁ to _{R 4} are hydrocarbon residues, n is a number of 2 or more) and the following general formula [Formula] ( R ₅ is a contact product of a polymeric silicon compound with a structure represented by (hydrocarbon residue). Component (A ₂ ) At least one of the following components (a) and (b), or this and component (c). (a) A liquid titanium compound (provided that when used alone or in combination with component (c), this titanium compound must contain a halogen). (b) Halogen compounds of silicon. (c) A polymer silicon compound having a structure represented by the formula (R ₆ is a hydrocarbon residue).