JPH0367083B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the production of olefin polymers (hereinafter, the use may include olefin copolymers) by polymerization of olefins (hereinafter, the use may include olefin copolymerization). Regarding the method. In particular, the present invention relates to a method for producing an olefin polymer that can yield a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms. Furthermore, in the polymerization of α-olefins having 3 or more carbon atoms, even if the melt index of the polymer is changed using a molecular weight regulator such as hydrogen during polymerization, the stereoregularity of the polymer is less likely to deteriorate. Regarding possible methods.
It also has the advantage that there is very little decrease in activity with the passage of polymerization time. Furthermore, the polymerization of ethylene has the characteristic that a polymer with a narrow molecular weight distribution can be obtained. The present invention also relates to a method for polymerizing olefins, which enables production of granular or spherical polymers with good fluidity and excellent particle size distribution when slurry polymerization or gas phase polymerization is employed, and which also has excellent bulk specific gravity. . More specifically, the present invention provides: [A] At least one phosphorus compound () and a magnesium compound () selected from phosphoric acid esters, phosphorous acid esters, and phosphoric acid amides
Liquid magnesium compound [D] obtained from
A solid Ti-containing product obtained by precipitation from a mixed solution of and a liquid titanium compound () or a solid Ti-containing product obtained by contacting the liquid magnesium compound [D] with a precipitant other than a titanium compound (). A solid Ti-containing product obtained by contacting and supporting a liquid titanium compound () on the resulting solid product, wherein a polycarboxylic acid ester is added before, during, or after the formation of the solid titanium-containing product. () Solid titanium catalyst component obtained by supporting magnesium, titanium, halogen, and polycarboxylic acid ester as essential components [B] Organoaluminum compound and [C] Organosilicon compound having Si-O-C bond The present invention relates to a method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst system formed from catalyst components. There have already been many proposals regarding methods for producing solid catalyst components containing magnesium, titanium, halogen, and electron donors as essential components. It is also known that highly stereoregular polymers can be obtained with high catalytic activity. However, many of them require further improvement in terms of activity, stereoregularity, etc. of the polymer. For example, in order to obtain high-quality olefin polymers without post-polymerization post-treatment operations, the formation ratio of stereoregular polymers must be extremely high, and the polymer yield per transition metal must be sufficiently high. must not. Depending on the type of target polymer, some of the conventionally proposed technologies can be said to be at an acceptable level from the above viewpoint, but the residual halogen content in the polymer, which is related to rusting in molding machines, is From the point of view of
There are only a few that can be said to have sufficient performance. Moreover, most of them have the disadvantage that when producing a polymer with a large melt index, the yield and stereoregularity are considerably reduced. The same applicant has published JP-A-56-811 and JP-A-Sho.
In Publication No. 56-11908, α- having 3 or more carbon atoms
We proposed a method for producing olefin polymers or copolymers that are particularly suitable for olefin polymerization, have uniform particle size and particle size distribution, and have good fluidity. In this proposal, there is no mention at all of the use of a polycarboxylic acid ester as an electron donor in forming the fixed titanium catalyst component. Further, there is no mention of the combined use of these esters and the organosilicon compound catalyst component specified in [C] above. Furthermore, there is no mention of a method for obtaining a liquid magnesium compound from a magnesium compound and at least one phosphorus compound selected from phosphoric acid esters, phosphorous acid esters, phosphoric acid amides, and phosphorous acid amides. On the other hand, JP-A-58-19307 also proposes a method of preparing a catalyst similar to the above proposal using a phosphorus compound, but this proposal also uses a polyhydric carboxylic acid ester and There is no mention of the combined use of the specified organosilicon compound catalyst components. The present inventors have conducted research to provide a further improved method for polymerizing olefins. As a result, by using a new type of catalyst formed from the titanium catalyst component [A] containing a polyhydric carboxylic acid ester and the above [B] and [C], the particle size, particle size distribution, Polymers with excellent shape and bulk specific gravity can be formed, and these excellent polymers also have high catalytic performance.
Furthermore, it has been discovered that this can be achieved with the benefit of extremely little activity loss with the passage of polymerization time. Furthermore, when trying to obtain a polymer with a large melt index by coexisting a molecular weight regulator, such as hydrogen, in the polymerization system during polymerization, the defect in the conventional method that the stereoregularity is considerably reduced is also reduced. In addition to the advantage of being able to adjust the melt index with the use of small amounts of hydrogen, it was found that the use of molecular weight modifiers such as hydrogen also had the unexpected benefit of improving catalyst activity. . In addition, it was found that a polymer with a narrow molecular weight distribution can be obtained in the polymerization of ethylene. Accordingly, it is an object of the present invention to provide an improved method for polymerizing olefins. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. In the present invention, the magnesium compound () used for preparing the solid titanium catalyst component [A] is
Magnesium compounds that do not have reducing ability, ie, magnesium compounds that do not have magnesium-carbon bonds or magnesium-hydrogen bonds, are preferred, and these may be derived from magnesium compounds that have reducing ability. Magnesium compounds without such reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium,
Alkoxymagnesiums such as butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium, dimethylphenoxymagnesium; magnesium laurate, magnesium stearate; Examples include carboxylic acid salts. Moreover, the magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds. Furthermore, it may be a mixture of two or more of these compounds. Among these, particularly preferred magnesium compounds are halogen-containing magnesium compounds, particularly magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride. The liquid magnesium compound [D] may be a mixed solution of a magnesium compound and a phosphorus compound, but
It may also be diluted with an inert solvent such as an inert hydrocarbon. Inert solvents that may be used to prepare liquid magnesium compounds include pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene; benzene, toluene, xylene , ethylbenzene, cumene, and cymene; and halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, and chlorobenzene. The amount of phosphorus compound () such as phosphate ester, phosphite ester or phosphoric acid amide used when obtaining liquid magnesium compound [D] varies depending on the type thereof or the type of magnesium compound. , usually 0.05 to 20 mol, preferably 0.1 mol to 10 mol, more preferably 0.5 mol to 6 mol, per mol of the magnesium compound, and the temperature during the catalytic reaction is -50°C to 300°C.
℃, preferably 10℃ to 150℃. The phosphorus compound () used when obtaining liquid magnesium compound [D] is (R′O) _k (R ² ₂ N) _l R ³ _n P(OH) _o or (R ⁴ O) _a (R ⁵ ₂ N) _b R ⁶ _c P(O)(OH) _d Cl _e It is a phosphorus compound represented by the formula. (k here
+l+m+n=3, 0<k+l3, 0k,
l, m, n3, a+b+c+d+e=3, 0<
a+b3, 0a, b, c, d, e3, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be different or the same, and usually have 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms.
12, more preferably 1 to 6 substituted or unsubstituted hydrocarbon groups. Examples of the substituent include halogen, alkoxy group, and aryloxy group. ) Specific examples of these phosphorus compounds include trimethyl-, triethyl-, tributyl-, trihexyl-, trioctyl-, trioleyl-, triphenyl-, tris(2-chloroethyl)-, diethyl-, dibutyl-, dioctyl-phosphite; Dimethyl methyl, diethyl ethyl,
dibutyl butyl, diphenyl phenyl,
Phosphite esters such as ethyl ethyl, phenyl phenyl phosphonite; ethyl diethyl, phenyl diethyl phosphinite; diphthyl fluorochloridite; butyl fluoro dichloridite, trimethyl, triethyl, tributyl -, trihexyl-, trioctyl-, trioleyl-, triphenyl-, tris(2-chloroethyl)-, diethyl-, dibutyl-, dioctyl-phosphate; dimethyl methyl-, diethyl ethyl-, dibutyl-
Butyl, diphenyl phenyl, ethyl ethyl, phenyl phenyl phosphonate; methyl dimethyl, butyl dibutyl,
Phosphate esters such as phenyl/diphenyl-phosphinate. phosphoric acid amides such as hexamethyl-, hexaethyl-, hexabutyl-, hexaphenyl-phosphoric triamides; Among these phosphorus compounds, preferred are phosphorous esters represented by the formula (RO)- ₃ P, phosphoric esters represented by the formula (RO)- ₃ PO, and phosphoric esters represented by the formula (R ₂ N)- ₃ PO. It is a phosphoric acid amide. Particularly preferred are (RO)-
It is a phosphoric acid ester represented by _{the 3PO} formula. The magnesium compound () used in the present invention may contain other magnesium compounds or magnesium metal that can be converted into the magnesium compound.
It is also possible to form the magnesium compound by dissolving it while converting it into the magnesium compound. For example, a magnesium compound having an alkyl group, an alkoxyl group, an allyloxyl group, an acyl group, an amino group, a hydroxyl group, etc., magnesium oxide, magnesium metal, etc. are dissolved in the phosphorus compound () or in an inert solvent in which the phosphorus compound is dissolved. Or, by suspending the compound, it is halogenated with a halogenating agent such as hydrogen halide, a halogen-containing silicon compound, a halogen, a halogen-containing aluminum compound, a halogen-containing lithium compound, or a halogen-containing sulfur compound to produce a halogen-containing magnesium compound that does not have reducing ability. Examples include a method of dissolving the substance by causing the substance to dissolve. Also, Grignard reagents, dialkylmagnesiums, magnesium hydrides, or complex compounds of these with other organometallic compounds, such as M〓Mg〓R ¹ _p R ² _q X _r Y _{s [} wherein M is aluminum, zinc, boron or Beryllium atom, R ¹ and R ² are hydrocarbon groups, X and Y are OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a group, R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are hydrogen atoms or hydrocarbon groups, R ⁹ is a hydrocarbon group, α, β>0, p,
q, r, s≧0, m is the valence of M, β/α≧0.5,
p+q+r+s=m〓+2β, 0≦(r+s)/(α
+β)<1.0], alcohol, ketone,
Esters, ethers, acid halides, silanols,
It is also possible to solubilize a magnesium compound that does not have reducing ability in a hydrocarbon solvent by treating it with a compound that can eliminate its reducing ability, such as siloxane, oxygen, water, acetal, or an alkoxy or allyloxy compound such as silicon or aluminum. In the present invention, there are various titanium compounds () used for preparing the solid titanium catalyst component [A], but usually Ti(OR) _g X _4-g (R is a hydrocarbon group, X is a halogen, 0≦g4 ) A tetravalent halogen-containing titanium compound is preferred. More specifically, titanium tetrahalides such as _TiCl4 , _TiBr4 , _TiI4 ; Ti _{( OCH3} ) _Cl3 , Ti( _OC2H5 )
_Cl3 , Ti(On- _C4H9 ) _Cl3 , Ti _{( OC2H5} ) _{Br3 ,} Ti
( _OisoC4H9 ) _{Br3 ,}

Trihalogenated alkoxytitanium such as [Formula]; Ti
(OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On−
_{Dihalogenated alkoxy} titanium such as _{C4H9 ) 2Cl2} , Ti( _OC2H5 ) _2Br2 ; Ti( _OCH3 ) _3Cl , _Ti
(OC ₂ H ₅ ) ₃ Cl, Ti (On−C ₄ H ₉ ) ₃ Cl, Ti
Monohalogenated trialkoxytitanium such as (OC ₂ H ₅ ) ₃ Br; tetraalkoxy titanium such as Ti(OC ₂ H ₅ ) ₄ , mixtures thereof, or combinations of these with other metals such as aluminum compounds, silicon compounds, sulfur compounds, etc. Examples include mixtures with compounds, hydrogen halides, halogens, and the like. Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. The liquid titanium compound (2) may be a single liquid titanium compound or a mixture thereof, or may be in the form of a titanium compound dissolved in the inert solvent. In the present invention, solid titanium catalyst component [A]
(a) forming a solid product from a mixture of a liquid magnesium compound [D] and a liquid halogen-containing titanium compound (); or (b) forming a solid product from a mixture of a liquid magnesium compound [D] and a precipitating agent other than a titanium compound. () to form a solid product, which is then catalytically supported with a titanium compound (), preferably a halogen-containing titanium compound. In both methods, it is necessary to catalytically support the polycarboxylic acid ester before, during or after the formation of the solid product. Precipitating agents other than titanium compounds used in the above method (b) include, for example, organometallic compounds of metals from Groups 1 to 3 of the periodic table, halogens directly bonded to silicon atoms, hydrocarbon groups, hydrogen, etc. Examples include silicon compounds, halides such as tin, phosphorus, and sulfur. Among these, silicon compounds are particularly preferred. The first part of the periodic table can be used for this purpose.
As organometallic compounds of Group 3 or Group 3 metals,
Those listed below that can be used as component (B) of the present invention can be mentioned. In addition, as a silicon compound, general formula R ¹ R ² R ³ R ⁴ Si (R ¹ , R ² , R ³ ,
R ⁴ represents hydrogen, a hydrocarbon group, an alkoxyl group, an allyloxyl group, or a halogen, and these may be the same or different), such as silicon tetrahalide, silicon tetraalkyl, and alkyl halide. Silicon, alkyl silicon hydride, alkoxy silicon halide, allyloxy silicon halide, alkyl alkoxy silicon, etc. can be mentioned. More specifically, _SiCl4 , _{CH3SiCl3 ,} ( _CH3 ) _{2SiCl2 ,
( CH3} ) _3SiCl , ( _CH3O ) _SiCl3 , ( _C2H5O ) _SiCl3 ,
(C ₂ H ₅ O) ₂ SiCl ₂ , (C ₂ H ₅ O) ₃ SiCl, (C ₆ H ₅ O)
Examples include SiCl ₃ and (CH ₃ ) ₃ (C ₂ H ₅ O)Si. Other examples of silicon compounds include polysiloxanes having halogens, hydrocarbon groups, hydrogen, etc. directly bonded to silicon. Two or more kinds of these compounds can be used. Further, these can be used after being diluted with the above-mentioned inert solvent. Suitable polyhydric carboxylic acid esters () to be supported in the titanium catalyst component [A] are:

[Formula] or

[Formula] or

[Formula] (where R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or substituted or unsubstituted hydrocarbon groups,
R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Also R ³ and R ⁴
may be connected to each other. The hydrocarbon group substituted here includes those containing different atoms such as N, O, and S, such as C-O-C, COOR, COOH,
It has groups such as OH, _SO3H , -C-N-C-, and _NH2 . ) can be exemplified. Specific examples of preferable polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, and butylmalonate. Diethyl acid, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate , aliphatic polycarboxylic acid esters such as di-2-ethylhexyl fumarate, diethyl itaconate, and dioctyl citraconate, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, and nadzic acid. Alicyclic polycarboxylic acid esters such as diethyl, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, Di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, Examples include aromatic polycarboxylic acid esters such as diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, and dibutyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid. Other examples of polyvalent carboxylic acid esters supported in the titanium catalyst component include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2 sebacate. - Esters of long-chain dicarboxylic acids such as ethylhexyl can be mentioned. When supporting these polyvalent carboxylic acid esters, it is not necessarily necessary to use them as starting materials, but instead use compounds that can be converted into these compounds during the preparation process of the titanium catalyst component, and convert them into these compounds at the stage of preparation. It's okay. The polyhydric carboxylic acid ester is used in an amount of, for example, about 0.01 to about 1 mole of the magnesium compound ().
It is preferably used in a proportion of 1.0 mol, particularly about 0.10 to about 0.50 mol. In the method (a) of forming a solid product containing magnesium and titanium from a mixture of a liquid magnesium compound [D] and a liquid titanium compound (), a method of directly reacting the two or another precipitating agent () There is a method using In the direct reaction method, it is preferred to use a liquid halogen-containing titanium compound, preferably in an amount sufficient to form a solid product. The amount of titanium compound () used varies depending on its type, contact conditions, and other usage amounts, but it is approximately 0.1 mol or more per 1 mol of magnesium compound ().
Usually about 1 to about 1000 mol, preferably about 2 to about 200 mol. Further, in the method (b) of forming a magnesium-containing solid product through a contact reaction between the liquid magnesium compound [D] and the precipitant (), and supporting the titanium compound on this solid product, or the above-mentioned ( When a precipitant () is used in the process a), the amount of precipitant () used is preferably sufficient to form a solid product, and the amount of precipitant () used depends on the type of precipitant () used. , about 0.1 mol or more, usually about 1 to about
Preferably it is 1000 mol, especially about 2 to about 200 mol. Further, the amount of the titanium compound () used when supporting the titanium compound on the magnesium-containing solid product is the same as in the method (a) described above,
Also, the temperature during the contact reaction is -70℃ to about +200℃
More preferably, the temperature ranges from about 10°C to about 150°C. The solid product obtained by the above method (a) or method (b) differs in shape and size depending on the formation conditions. In order to obtain a solid product with uniform shape, particle size, etc., it is preferable to avoid rapid formation; for example, [D] and () or [D] and ()
are mixed in contact with each other in the liquid state to form a solid product by mutual reaction, the two are mixed at a temperature sufficiently low that their contact does not rapidly form a solid product. Afterwards, the temperature is preferably increased to gradually form a solid product. According to this method, it is easy to obtain a granular or spherical solid product having a relatively large particle size and a narrow particle size distribution. The polymer obtained by slurry polymerization or gas phase polymerization using the granular or spherical solid catalyst component with a good particle size distribution obtained as described above is granular or spherical and has a large particle size distribution and bulk density. Good fluidity. Note that when we say granules here, even when looking at an enlarged photograph, they look like fine powders have aggregated to form granules, so it can be said that the granules have many irregularities due to the manufacturing method of the solid catalyst component. It is possible to obtain something close to a true sphere. In addition, the contact temperature in the above contact is, for example,
An example is a range of about -70°C to about +200°C. The temperatures of the two liquids to be brought into contact may be different. Generally, in order to obtain a high-performance solid catalyst component in the preferred granular or spherical form as described above, it is sometimes preferable to adopt a method that does not use very high temperatures when mixing the two, as described above. Temperature conditions of high temperature, for example about -70°C to about +50°C, are preferred. In this case, if the contact temperature is low, precipitation of solids may not be observed.
In this case, the reaction may be carried out at elevated temperatures, preferably from about 50 to about 150° C., or a solid product may be precipitated by prolonged contact.
The solid product is further heated with a liquid halogen-containing titanium compound or a liquid halogenated hydrocarbon, preferably titanium tetrachloride, 1,2-dichloroethane, chlorobenzene, methyl chloride, hexachloroethane, etc., for example, at about 20 to about 150°C. It may be washed at a temperature of In the present invention, when forming the solid product as described above, a method is adopted in which porous inorganic and/or organic compounds can coexist and the solid product is deposited on the surface of these compounds. It's okay. At this time, the porous compound is brought into preliminary contact with a magnesium compound in a liquid state,
It is also possible to contact a liquid titanium compound while containing a liquid magnesium compound. Examples of these porous compounds include silica, alumina, polyolefin, and products treated with halogen-containing compounds. Solid titanium catalyst component [A] thus obtained
The composition of magnesium/titanium (atomic ratio) is, for example, about 2 to about 100, preferably about 4 to about 100.
50, more preferably about 5 to about 30, halogen/titanium (atomic ratio), for example about 4 to about 100,
Preferably from about 5 to about 90, more preferably from about 8 to about 50, and the polyhydric carboxylic acid ester/titanium (molar ratio) is, for example, from about 0.01 to about 100, preferably from about 0.2 to about 10, more preferably from about 0.4 to about 100. A value of approximately 6 is preferred. Further, as already mentioned, in many cases, the shape is granular or approximately spherical. Further, the specific surface area thereof is, for example, about 10 m ² /g or more, preferably about 100 m 2 /g or more.
The value is 1000m ² /g. The halogen in the solid titanium catalyst component [A] is chlorine, bromine, iodine, fluorine, or two or more thereof, and chlorine is particularly preferred. In the present invention, olefin polymerization or copolymerization is carried out using a combination catalyst of the solid catalyst component [A] obtained as described above, an organoaluminum compound [B], and a silicon compound catalyst component [C]. As the organoaluminum compound [B], (1) a compound having at least one Al-carbon bond in the molecule, for example, a compound having the general formula R ¹ mAl(OR ² )nHpXq (where R ¹ and R ² are carbon atoms, Usually 1 or
15 hydrocarbon groups, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is 0<m≦3, 0≦n<3, p is 0≦p<
3. q is a number of 0≦q<3, and m+n
+p+q=3); (2) Group metals represented by the general formula M ¹ AlR ¹ ₄ (where M ¹ is Li, Na, K, and R ¹ is the same as above); Complex alkylated product of and aluminum. Examples of organoaluminum compounds belonging to the above (1) include the following. General formula R ¹ mAl(OR ² ) _3-n (where R ¹ and R ² are the same as above. m is preferably a number of 1.5≦m≦3), general formula R ¹ mAlX _3-n ( Here ^{, R 1 is} the _same as above. ≦
m<3. ), general formula R ¹ mAl(OR ² )nXq (where R ¹ and R ² are the same as above, X is halogen, 0<m≦3, 0≦n<3, 0≦q<3,
+n+q=3). Among the aluminum compounds belonging to (1), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum,
In addition to trialkenylaluminums such as triisoprenylaluminum, dialkylaluminum alkoxides such as diethylaluminum ethoxide, dibutylaluminum butoxide, alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R ¹ _2.5 Al ( OR ² ) Partially alkoxylated alkyl aluminum halogenides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, with an average composition expressed as _0.5 , etc. , partially halogenated alkyl aluminum, diethylaluminium hydride, alkyl aluminum sesquihalogenides such as ethyl aluminum sesquibromide, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. ,
Dialkyl aluminum hydrides such as dibutyl aluminum hydride, partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy Partially alkoxylated and halogenated alkyl aluminums such as bromide. Compounds belonging to (2) above include LiAl
Examples include (C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Also
A compound similar to (1) may be an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl(C ₄ H ₉ ) ₂ ,

Examples include [Formula]. Among these, it is particularly preferable to use trialkylaluminum and the above-mentioned alkyl aluminum in which two or more aluminums are combined. The organosilicon compound catalyst component [C] having a Si-O-C bond used in the present invention is, for example, an alkoxysilane, an aryloxysilane, or the like. An example of such is the formula RnSi(OR ¹ ) _4-o , where 0≦n≦3, R is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group. groups, etc., or halogen, R ¹
is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyalkyl group, provided that n R, (4-n)
The ^OR groups may be the same or different. ) can be mentioned. or,
Other examples include siloxanes having ^one OR group, silyl esters of carboxylic acids, and the like. In addition, as another example, a compound that does not have a Si-O-C bond and a compound that has an O-C bond may be reacted in advance or reacted at the reaction site to form a Si-O-C bond.
It may be used after being converted into a compound having an -OC bond. As an example of this, for example, Si-O-C
Examples include the combined use of a halogen-containing silane compound or silicon hydride that does not have a bond, and an alkoxy group-containing aluminum compound, an alkoxy group-containing magnesium compound, other metal alcoholates, alcohols, formic acid esters, ethylene oxides, and the like. It may also contain an organosilicon compound or other metals (eg, aluminum, tin, etc.). More specifically, trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, metritrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane , γ-chloropropyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriethoxysilane Isopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxysilane Examples include siloxane and phenyldiethoxydiethylaminosilane. Among these, particularly preferred are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, ethyl silicate, These are those represented by the formula RnSi(OR ¹ ) _4-o such as diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenylmethoxysilane. Component [C] can also be used in the form of an adduct with other compounds. Olefins used for polymerization include ethylene,
These include propylene, 1-butene, 4-methyl-1-pentene, 1-octene, etc., and these can be used not only for homopolymerization but also for random copolymerization and block copolymerization. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as copolymerization components. Polymerization can be carried out in either liquid phase or gas phase. When carrying out liquid phase polymerization, 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. The amount of catalyst to be used is, per reaction volume, component [A] is about 0.0001 to about 1.0 mmol in terms of titanium atoms, component [B] is about 1 mole of titanium atom in component [A], and component [B] is Component [C] is added to component [C] per mole of metal atom in component [B] such that the amount of metal atoms in component is about 1 to about 2000 mol, preferably about 5 to about 500 mol. The amount of Si atoms is preferably about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, particularly preferably about 0.05 to about 1 mole. These catalyst components [A], [B], and [C] may be brought into contact with each other during polymerization, or may be brought into contact with each other before polymerization. In contacting before polymerization, only two arbitrary components may be freely selected and brought into contact, or two or three components may be brought into contact with a part of each component. Furthermore, each component may be brought into contact with each other before polymerization under an inert gas atmosphere or under an olefin atmosphere. When the three components are brought into contact with each other before polymerization, the liquid layer may or may not be removed after contact, and component [C] may or may not be newly added during polymerization. The polymerization temperature of the olefin is preferably about 20 to about 200°C, more preferably about 50 to about 180°C, and the pressure is about atmospheric pressure to about 100 Kg/cm ² , preferably about 2 to about 50 Kg/cm ² . Preferably it is carried out under pressure conditions. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. In the present invention, especially α-
When applied to the stereoregular polymerization of olefins,
Polymers with a high stereoregularity index can be produced with high catalytic efficiency. In addition, in olefin polymerization using the same solid catalyst component as previously proposed, in many cases, when trying to obtain a polymer with a large melt index by using hydrogen, the stereoregularity tends to decrease to a considerable extent. However, by adopting the present invention, it is possible to reduce this tendency. Furthermore, in relation to high activity, the polymer yield per unit solid catalyst component is superior to conventional proposals at the level of obtaining polymers with the same stereoregularity index. The residue, especially the halogen content, can be reduced, and the catalyst removal operation can of course be omitted, and the tendency of molds to rust during molding can be significantly suppressed. In addition, in slurry polymerization and gas phase polymerization, it is possible to produce granular polymers or almost spherical polymers, which are produced by agglomeration of fine powders, and such granular or spherical polymers have low fluidity. Depending on the application, it may be possible to use it without pelletizing it. In addition, it is not only possible to change the melt index of the polymer with less molecular weight regulator such as hydrogen than in conventional catalyst systems, but surprisingly, by increasing the amount of molecular weight regulator such as hydrogen, , it has the characteristic that the activity of the catalyst system tends to improve. This is something that did not exist in conventional catalyst systems, and when trying to obtain a high melt index polymer with conventional catalyst systems, increasing the amount of molecular weight regulator such as hydrogen reduces the partial pressure of the olefin monomer. As a result, the activity of the polymerization system inevitably decreased, but the catalyst system according to the present invention does not cause these problems at all.
In fact, the activity tends to improve. In addition, with conventional catalyst systems, activity decreases with the passage of polymerization time, but with this catalyst system, this is almost not observed, so for example, when used in multi-stage continuous polymerization, the amount of polymer produced can be significantly increased. Connect. Furthermore, since this catalyst system is very stable even at high temperatures, for example, even when propylene is polymerized at 90°C, no significant decrease in stereoregularity is observed. Furthermore, when this catalyst system is applied to the polymerization of ethylene, a polymer with a narrow molecular weight distribution can be obtained. Next, the present invention will be explained in more detail with reference to examples. Example 1 [Preparation of solid titanium catalyst component [A]] 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and tri-n-butyl phosphate
40.8 ml (150 mmol) was heated at 100°C for 2 hours to form a homogeneous solution, and then cooled to room temperature. The total amount of the homogeneous solution obtained in this way was heated to −20°C.
The mixture was added dropwise over 1 hour to 200 ml of titanium tetrachloride maintained at . After the charging was completed, the mixture was heated to 110° C. over 4 hours, and when it reached 110° C., 2.7 ml (12.5 mmol) of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring.
After 2 hours of reaction, collect the solid part by heating,
This solid portion was resuspended in 200 ml of titanium tetrachloride, and then heated and reacted again at 110° C. for 2 hours.
After the reaction is complete, collect the solid part by heating again.
It was thoroughly washed with decane and hexane at 110°C.
Solid titanium catalyst component [A] was prepared by the above operation. The composition of the solid titanium catalyst component [A] was 2.4% by weight of titanium, 58% by weight of chlorine, 18% by weight of magnesium, and 13.3% by weight of diisobutyl phthalate. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
750 ml was charged, and 2.5 mmol of triethylaluminum, 0.25 mmol of diphenyldimethoxysilane, and 0.015 mmol of the titanium catalyst component [A] in terms of titanium atoms were charged in a propylene atmosphere at room temperature. After introducing 200ml of hydrogen, the temperature was raised to 70℃, and
Propylene polymerization was carried out for hours. The pressure during polymerization was maintained at 7 kg/cm ² G. After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. The yield of white powdery polymer after drying was 398.3g,
The extraction residue rate with boiling n-heptane was 99.0%.
MFR is 3.1dg/min, and its apparent bulk specific gravity is 0.40g/min.
It was hot in ml. The particle size distribution of the white powdery polymer was as shown in Table 1. On the other hand, 2.9 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 26.700 g-PP/mmol-Ti, and II (t-II) in the total polymer was 98.3%. Examples 2, 3, 4, 5, 6, 7 Same as Example 1 except that diisobutyl phthalate was changed to the compound shown in Table 2 in preparing the solid titanium catalyst component [A] of Example 1. A solid titanium catalyst component [A] was prepared by the following procedure, and propylene polymerization was also carried out. The catalyst composition and polymerization results are shown in Table-2. Examples 8 and 9 In preparing the solid titanium catalyst component [A] in Example 1, the same operation as in Example 1 was performed except that tri-n-butyl phosphate was changed to the compound shown in Table 3. A solid titanium catalyst component [A] was prepared according to the method, and propylene polymerization was also carried out. The catalyst composition and polymerization results are shown in Table-2. Examples 10, 11, 12, 13, 14, 15, 16 Using the solid titanium catalyst component [A] of Example 1, the diphenyldimethoxysilane described in [Polymerization] of Example 1 was converted into the compound shown in Table 4. Instead, propylene polymerization was carried out. The polymerization results are shown in Table 4. Example 17 In Example 1, propylene polymerization was carried out by changing the polymerization temperature from 70°C to 90°C. The polymerization results are shown in Table-5. Examples 18, 19, 20 In Example 1, propylene polymerization was carried out by changing the amount of hydrogen added during polymerization to the amount shown in Table 5. The polymerization results are shown in Table-5. Example 21 1 part purified hexane in an autoclave with an internal volume of 2
1.0 mmol of triethylaluminum, 0.1 mmol of phenyltriethoxysilane, and solid titanium catalyst component [A] under a nitrogen atmosphere at room temperature.
After charging 0.02 mmol in terms of titanium atoms to create a closed system, the temperature was raised. After introducing 4.0Kg/ ^cm2 of hydrogen at 60℃,
Ethylene is introduced and the system is kept at a constant temperature of 70°C and the total pressure is maintained at 8.0Kg/cm ² G. Two hours after the introduction of ethylene, the system is cooled to terminate the reaction. After the polymerization is completed, the slurry containing the produced polymer is filtered to collect a white powdery polymer. The yield of white powdery polymer after drying was 274.5g, its apparent density was 0.38g/ml, MI was 3.9dg/min, and the particle size distribution was very good, with a fine powder size of 105μ or less being 0.1
Powder having a particle size of 105μ to 840μ accounted for 99.4% by weight of the total. In addition, it was measured by GPC (gel permeation chromatography).
Mw/Mn was 4.9. Example 22 [Preparation of solid titanium catalyst component [A]] 5.3 g of ethoxymagnesium chloride, 25 ml of decane, and 40.8 g of tri-n-butyl phosphate
ml was subjected to heating reaction at 100°C for 3 hours to form a homogeneous solution, and then cooled to room temperature. The entire amount of the homogeneous solution thus obtained was added dropwise to 200 ml of silicon tetrachloride maintained at 0°C.
After the charging is completed, the temperature of this mixture is raised to 50°C, and a reaction is carried out at 50°C for 4 hours. After the reaction, collect the solid part by heating, resuspend this solid part in 200 ml of titanium tetrachloride, and then add diisobutyl phthalate.
2.7 ml was added and a heating reaction was carried out at 120°C for 2 hours. After the reaction is completed, collect the solid part by heating,
It was thoroughly washed with decane and hexane at 110°C.
The composition of the obtained solid titanium catalyst component [A] was 1.9% by weight of titanium, 61% by weight of chlorine, and 21% by weight of magnesium.
wt% and diisobutyl phthalate 9.8 wt%
It was hot. [Polymerization] Propylene polymerization was carried out in the same manner as in Example 1. As a result, the activity is 23.300g-PP/mmol
-Ti, MFR is 3.6dg/min, apparent bulk specific gravity is 0.38
g/ml, t-II was 97.2%. Example 23 The solid titanium catalyst component described in Example 1 was used to carry out propylene-ethylene copolymerization. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
750 ml was charged, and 2.5 mmol of triethylaluminum and 0.25 mmol of diphenyldimethoxysilane were charged under a propylene atmosphere at 40°C, and further, 0.015 mmol of the solid titanium catalyst component [A] described in Example 1 was charged in terms of titanium atoms. did. Next, after introducing 100ml of hydrogen, propylene-ethylene mixed gas (ethylene
7.7mol%) was introduced, the temperature was raised to 60℃,
Polymerization was carried out for 2 hours. The pressure during polymerization is 2.0Kg/
It was kept at cm ² G. After the polymerization was completed, the slurry containing the produced copolymer was separated into a white powdery copolymer and a liquid phase. The yield of the white powdery copolymer was 193.4 g, the apparent bulk specific gravity was 0.37 g/ml, the MFR was 5.4 dg/min, the ethylene content was 4.5 mol%, and the melting point was 136°C. Further, the yield of the solvent-soluble copolymer was 10.2 g. Therefore, the activity is 13600g-PP/mmol-Ti, and the yield is
It was 95.0% by weight.

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【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart schematically showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Scope of Claims] 1 [A] A liquid magnesium compound [D] obtained from at least one phosphorus compound () selected from phosphoric acid esters, phosphite esters, and phosphoric acid amides and a magnesium compound (); A solid Ti-containing product obtained by precipitation from a mixed solution of a titanium compound (), or a solid Ti-containing product obtained by precipitation by contacting the liquid magnesium compound [D] with a precipitant () other than a titanium compound A solid Ti-containing product obtained by contacting and supporting a liquid titanium compound () on a solid product, which is a polyhydric carboxylic acid ester () before, during, or after the formation of these solid titanium-containing products. A solid titanium catalyst component containing as essential components magnesium, titanium, halogen, and polycarboxylic acid ester obtained by supporting [B] an organoaluminum compound and [C] an organosilicon compound catalyst having a Si-O-C bond. 1. A method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst system formed from the components.