JPH0346481B2 - - 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 not significantly reduced. Regarding the possible methods. 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. An object of the present invention is to provide a method for polymerizing olefins which has excellent sustainability of catalytic activity, and even better polymerization activity per unit catalyst and stereoregular polymerization ability. Another object of the present invention is to provide a polymerization method in which the stereoregularity index does not tend to decrease even in the production of high melt index polymers.
Other objects and effects of the present invention will become more apparent from the following description. According to the present invention, [A] titanium and magnesium obtained by the mutual reaction of at least three components: (a) a magnesium compound having substantially no reducing ability, (b) a titanium compound, and (c) an electron donor; , a titanium catalyst component containing a halogen and an electron donor as essential components,
A titanium catalyst component in which the electron donor is an ester of an unsaturated carboxylic acid selected from the group consisting of maleic acid and substituted maleic acid and a linear aliphatic alcohol, or an ester of a saturated linear dicarboxylic acid having 2 to 5 carbon atoms. , characterized in that the olefin is polymerized or copolymerized in the presence of a catalyst formed from [B] an organoaluminum compound catalyst component and [C] an organosilicon compound catalyst component having a Si-O-C bond. A method for polymerizing olefins is provided. The titanium catalyst component (A) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen, and a specific electron donor described below as essential components.
This titanium catalyst component (A) contains magnesium halide with lower crystallinity than commercially available magnesium halides, and its specific surface area is usually about 50 m ² /
It is preferably about 60 to about 800 m ² /g, more preferably about 100 to about 400 m ² /g, and its composition is not substantially changed by washing with hexane at room temperature. The titanium catalyst component
In (A), halogen/titanium (atomic ratio) is approximately 5
from about 200, particularly from about 5 to about 100, with an electron donor/titanium (molar ratio) of from about 0.1 to about 10,
In particular, those having a magnesium/titanium (atomic ratio) of about 0.2 to about 6, about 2 to about 100, particularly about 4 to about 50 are preferred. The component (A) also includes:
It may also contain other electron donors, metals, elements, functional groups, etc. Such a titanium catalyst component (A) can be obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), an electron donor and a titanium compound, but optionally with other reactants, such as silicon, Compounds such as phosphorus and aluminum can be used. As a method for producing such a titanium catalyst component (A), for example, JP-A-50-108385 and JP-A-50-126590 are used.
No. 51-20297, No. 51-28189, No. 51-
No. 64586, No. 51-92885, No. 51-136625, No. 52
-87489, 52-100596, 52-147688,
No. 52-104593, No. 53-2580, No. 53-40093,
No. 53-43094, No. 55-135102, No. 55-135103
No. 56-811, No. 56-11908, No. 56-18606
It can be manufactured according to the method disclosed in No. Some examples of methods for producing these titanium catalyst components (A) will be briefly described below. (1) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding or not grinding, with or without grinding aids, pretreated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds, or without pretreatment. The solid obtained is reacted with a titanium compound that forms a liquid phase under reaction conditions. However, the above electron donor is used at least once. (2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex. (3) React the material obtained in (2) with a titanium compound. (4) React the material obtained in (1) or (2) with an electron donor and a titanium compound. (5) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding in the presence or absence of grinding aids etc. and in the presence of titanium compounds, pre-treated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds, or without pre-treatment. The solid obtained is treated with a halogen or a halogen compound or an aromatic hydrocarbon. However, the above electron donor is used at least once. (6) Treating the compound with a halogen or a halogen compound. Among these catalyst components, those using liquid titanium halides or those using halogenated hydrocarbons during or after the action of the titanium compound in catalyst preparation are particularly preferred. The electron donor to be contained in the titanium catalyst component [A] of the present invention is an unsaturated dicarboxylic acid selected from maleic acid and substituted maleic acid, that is, an unsaturated dicarboxylic acid of the formula
HOOCR ₁ = CR ₂ COOH (R ₁ and R ₂ are hydrogen or any hydrocarbon group with or without a substituent) and any linear aliphatic alcohol with or without a substituent It is an ester of More specifically, monoethyl maleate, diethyl maleate, di-n-propyl maleate, mono-n-butyl maleate, di-n-butyl maleate, di-n-hexyl maleate, di-n-octyl maleate, maleic acid. acid di-n-decyl,
Di-n-chlorobutyl maleate, dimethyl citraconate, diethyl citraconate, di-n-propyl citraconate, di-n-butyl citraconate, mono-n-butyl citraconate, di-n-hexyl citraconate, di-n-octyl citraconate, di-n-decyl citraconate, diethyl ethyl maleate,
Di-n-propyl ethyl maleate, di-n-butyl ethyl maleate, di-n-octyl ethyl maleate, butyl diethyl maleate, diethyl propyl maleate, di-n-propyl propyl maleate, di-n-butyl propyl maleate, Di-n-hexyl propyl maleate, di-n-octyl propyl maleate, diethyl butyl maleate,
Esters such as di-n-propyl butyl maleate and di-n-butyl butyl maleate can be mentioned. Among these, diesters of maleic acid and substituted maleic acid with linear alcohols having about 2 to 10 carbon atoms are preferred, and in particular maleic acid and diesters of substituted maleic acid and substituted maleic acids with alkyl groups having 1 to 4 carbon atoms and linear alcohols having about 2 to 8 carbon atoms are preferable. Particular preference is given to diesters with straight-chain alcohols. The electron donor to be contained in the titanium catalyst component (A) can also be selected from esters of saturated linear dicarboxylic acids having 2 to 5 carbon atoms.
Such compounds are esters of oxalic acid, malonic acid, succinic acid or glutaric acid, e.g.
Dimethyl oxalate, dimethyl oxalate, di-n-propyl oxalate, diiso-propyl oxalate, di-n-butyl oxalate, monoiso-butyl oxalate,
Diiso-butyl oxalate, di-n-hexyl oxalate, di-n-octyl oxalate, diiso- oxalate
Octyl, diiso-decyl oxalate, di-n-propyl malonate, diiso-propyl malonate, di-n-butyl malonate, diiso-butyl malonate, di-tert-butyl malonate, di-n-hexyl malonate , di-n-octyl malonate, di-iso- malonate
Octyl, diisodecyl malonate, dimethyl glutarate, diethyl glutarate, di-glutarate
-propyl, diiso-propyl glutarate, di-n-butyl glutarate, diiso-butyl glutarate,
Di-n-octyl glutarate, di-iso- glutarate
Octyl, didecyl glutarate, diethyl succinate, diethyl succinate, di-n-propyl succinate, diiso-propyl succinate, di-n-succinate
Butyl, diisobutyl succinate, monosuccinate
iso-butyl, di-n-octyl succinate, diiso-octyl succinate, di-n-hexyl succinate,
Examples include esters such as di-n-decyl succinate. Among these, it is preferable to use an ester of the saturated linear dicarboxylic acid and an alcohol having 3 or more carbon atoms, especially a diester of a saturated linear dicarboxylic acid having 3 to 5 carbon atoms and an alcohol having 3 to 10 carbon atoms. One or more types of the above esters can be contained. Furthermore, when incorporating the above-mentioned esters into the titanium catalyst component (A), it is not necessary to use them as starting materials, and compounds that can be converted into these compounds during the preparation process of the titanium catalyst component (A) are not necessarily used as starting materials. may be used to convert these compounds during the preparation step. The above compounds can also be used in the form of addition compounds with other compounds such as aluminum compounds, phosphorus compounds, and amine compounds. In the present invention, the magnesium compound used in the preparation of the solid titanium catalyst component [A] is preferably a magnesium compound that does not have reducing ability, that is, a magnesium compound that does not have a magnesium-carbon bond or a magnesium-hydrogen bond. It may be derived from a magnesium compound having the 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; such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium Examples include alkoxymagnesium such as phenoxymagnesium, allyloxymagnesium such as dimethylphenoxymagnesium, and magnesium carboxylate such as magnesium laurate and magnesium stearate. Further, 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. In the present invention, there are various titanium compounds (ii) 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≦ A tetravalent titanium compound represented by g≦4) is suitable. More specifically, _TiCl4 ,
Titanium tetrahalides such as _TiBr4 , _TiI4 ; Ti
( _OCH3 ) _Cl3 , Ti _{( OC2H5} ) _Cl3 , Ti(On− _{C4H9 )}
Trihalogenated alkoxytitanium such _{as Cl3} , Ti( _{OC2H5 ) Br3} , Ti( _OisoC4H9 ) _Br3 ; 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; Ti(OCH ₃ ) ₄ , Ti(OC ₂ H ₅ ) ₄ , T(On−
Examples include tetraalkoxytitanium such as C ₄ H ₉ ) ₄ . Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon. In preparing the titanium catalyst component (A), a titanium compound, a magnesium compound, an electron donor to be supported, and other electron donors that may be used as necessary, such as alcohol, phenol,
The amount of monocarboxylic acid ester, silicon compound, aluminum compound, etc. to be used varies depending on the preparation method and cannot be unconditionally specified, but for example, the amount of the electron donor to be supported per 1 mole of magnesium compound
0.05 to 5 mol, titanium compound 0.05 to 1000
The proportion can be on the order of moles. 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 catalyst component [B], and a silicon compound [C]. As the above [B] component, (i) an organoaluminum 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 to 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); (ii) 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); Examples include complex alkylated products of aluminum and aluminum. Examples of the organoaluminum compounds that belong to (i) above 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 where and R ¹ is the same as above. X is halogen, and m is preferably 0<m<3. ), general formula R ¹ mAlH _3-n (where R ¹ is the same as above, m is preferably 2
≦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,
Examples include those represented by m+n+q=. Among the aluminum compounds belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum,
Besides trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxide, alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R ¹ ₂ . ₅ Al( ^OR2 _{) 0.5}
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc., with an average composition of alkyl aluminum sesquihalides, such as
Partially halogenated alkylaluminiums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide etc., dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as propyl aluminum dihydride, partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide It is. Compounds belonging to (ii) above include LiAl
Examples include (C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Further, as a compound similar to (i), it may be an organic aluminum 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 ,

[Propylene polymerization]

Purified hexane in an autoclave with an internal volume of 2
750 ml of hydrogen was charged, 0.75 mmol of triethylaluminum, 0.075 mmol of diphenyldimethoxysilane, and 0.015 mmol of the catalyst component [A] in terms of titanium atoms were charged under a propylene atmosphere at room temperature.
ml was introduced, the temperature was raised to 70°C, and polymerization was carried out for 2 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 powdered polymer after drying was 190 g, and the yield was 190 g.
The extraction residue rate with heptane was 96.7%, the MI was 11, and the apparent density was 0.36 g/ml. On the other hand, 3.3 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 12900 g-PP/mmol-Ti and the total II was 95.1%. Example 2, 3, 4, 5, 6, 7, 8, 9 [Preparation of catalyst component [A]] In Example 1, di-n-butyl maleate 6.9
Catalyst component [A] was prepared according to the method shown in Example 1, except that ml was changed to the compound and amount shown in Table 1. The composition and specific surface area of the catalyst components are shown in Table 1. [Propylene polymerization] In Example 1, triethylaluminum
0.75mmol and diphenyldimethoxysilane
0.075mmol each of triethylaluminum
2.5mmol and diphenyldimethoxysilane
Change the amount to 0.25 mmol and further increase the polymerization time from 2 hours to 4 hours.
Polymerization of propylene was carried out according to the method shown in Example 1, except that the time was changed. The results are shown in Table 1. Example 10 [Preparation of catalyst component [A]] 20 g of anhydrous magnesium chloride, di-maleic acid
Add 6.9 ml of butyl and silicone oil (TSS-451, 20 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid to a stainless steel (SUS-32) ball with a diameter of 15 mm in a nitrogen atmosphere.
The product was placed in a stainless steel (SUS-32) ball mill container with an internal volume of 800 ml and an internal diameter of 100 mm containing 2.8 kg, and was left in contact for 24 hours with an impact acceleration of 7 G. 15 g of the obtained co-pulverized material was suspended in 150 ml of titanium tetrachloride, and after contacting with stirring at 110°C for 2 hours, the solid part was collected by filtration, and free titanium tetrachloride was found in the washing liquid. The catalyst component [A] is obtained by thoroughly washing with purified hexane until it is no longer detected and then drying. The components were 2.4% by weight of titanium, 62.0% by weight of chlorine, and 20.0% by weight of magnesium in terms of atoms, and the specific surface area was 192 m ² /g. [Propylene Polymerization] Propylene polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1. Example 11 [Purification of catalyst component [A]] High-speed stirring device with internal volume 2 (manufactured by Tokushu Kika Kogyo)
After sufficiently replacing with N ₂ , 700ml of refined kerosene, commercially available.
10 g of MgCl ₂ , 24.2 g of ethanol, and 3 g of Emazol 20 (trade name, manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 120° C. and 800 rpm for 30 minutes. Under high speed stirring,
Using a Teflon tube with an inner diameter of 5 mm, refined kerosene 1 previously cooled to -10°C was charged and transferred to a 2-glass flask (equipped with a stirrer).
The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, the temperature was raised to 120° C. with stirring. During temperature rise
At 80° C. 1.5 ml of di-n-butyl succinate was added. 120
After stirring and mixing for 2 hours at 120°C, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and stirring and mixing was performed again at 120°C for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. The component is titanium in terms of atoms.
2.0% by weight, 66.0% by weight of chlorine, and 21.0% by weight of magnesium, and its specific surface area was 240m ² /g. [Propylene Polymerization] Propylene polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1. Example 12 [Preparation of catalyst component [A]] Catalyst component [A] was prepared in the same manner as in Example 11 except that di-n-butyl succinate was changed to diiso-butyl succinate. did. The composition and specific surface area of the catalyst components are shown in Table 1. [Propylene Polymerization] Propylene polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1.

【table】

[Table] Examples 13, 14, 15, 16, 17, 18, 19 Using the solid catalyst component [A] described in Example 1,
Triethylaluminum added during polymerization
0.75mmol to 2.51mmol, and 0.075mmol of diphenyldimethoxysilane to 0.25mmol of phenyltriethoxysilane, vinyltrimethoxysilane
0.30mmol methyltrimethoxysilane 0.45mmol,
Propylene polymerization was carried out in the same manner as in Example 1, except that 0.30 mmol of tetraethoxysilane, 0.25 mmol of ethyltriethoxysilane, 0.25 mmol of vinyltriethoxysilane, and 0.25 mmol of methylphenyldimethoxysilane were added, and the polymerization time was changed from 2 hours to 4 hours. I did this. The polymerization results are shown in Table 2.

【table】

[Table] Examples 20, 21, 22 Using the solid catalyst component [A] described in Example 1,
Propylene polymerization was carried out in the same manner as in Example 13, except that the amount of hydrogen added during polymerization was changed to 400 ml, 800 ml, and 1600 ml. The polymerization results are shown in Table 3.

[Table] Comparative Example A titanium catalyst component was prepared according to Example 1 described in JP-A-55-36203. Using this titanium catalyst component, propylene was polymerized according to the method shown in Example 1, except that diphenyldimethoxysilane was replaced with methyltriethoxysilane. The polymerization results are shown in Table 4.

【table】 [Brief explanation of drawings]

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

Claims (1)

[Scope of Claims] 1 [A] At least (a) a magnesium compound having substantially no reducing ability, (b) a titanium compound, and
(c) A titanium catalyst component containing titanium, magnesium, halogen, and an electron donor as essential components obtained by mutual reaction of three components of an electron donor, wherein the electron donor is maleic acid and substituted maleic acid. a titanium catalyst component which is an ester of an unsaturated carboxylic acid and a linear aliphatic alcohol selected from the group consisting of, or an ester of a saturated linear dicarboxylic acid having 2 to 5 carbon atoms; [B] an organoaluminum compound catalyst component; C] An olefin-based polymer characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organosilicon compound catalyst component having a Si-O-C bond (however, the propylene content
(excluding random copolymers of propylene with a crystallinity of 40 to 90 mol% and a crystallinity of 40% by weight or less and an α-olefin having 4 or more carbon atoms).