JPH0575763B2 - - 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 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) a halogenated hydrocarbon compound and/or an aromatic in contact with group hydrocarbon compounds or in the interaction of the above three components.
A titanium catalyst component containing titanium, magnesium, a halogen, and an electron donor as essential components obtained by carrying out the reaction of component (b) in the coexistence of a halogenated hydrocarbon, wherein the electron donor is maleic. ester of an unsaturated carboxylic acid selected from the group consisting of acid, fumaric acid, substituted maleic acid, and substituted fumaric acid and a straight-chain aliphatic alcohol, or an ester of a saturated straight-chain dicarboxylic acid having 2 to 5 carbon atoms, (B) organic Aluminum compound catalyst component and (C) in the formula, RnSi(OR ¹ ) _4-o (in the formula, n<4, R is a hydrocarbon group, provided that n R, (4-n)
A method for polymerizing olefins is provided, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst formed from a silicon compound catalyst component represented by OR ( ^one group may be the same or different). Ru. The titanium catalyst component (A) obtained by the above method used in the present invention has magnesium, titanium, halogen, and a specific electron donor described below as essential components, and has a halogen with lower crystallinity than commercially available magnesium halides. The specific surface area is usually 3 m ² /g or more, preferably about 60 to about 800 m 2 /g.
m ² /g, more preferably about 100 to about 400 m ² /g
The composition is not substantially changed by washing with hexane at room temperature. In the titanium catalyst component (A), the halogen/titanium (atomic ratio) is about 5 to about 200, particularly about 5 to about 100, and the electron donor/titanium (molar ratio) is about
0.1 to about 10, especially about 0.2 to about 6, magnesium/titanium (atomic ratio) about 2 to about 100,
Particularly preferred is about 4 to about 50.
Component (A) may also include other electron donors, metals, elements,
It may also contain a functional group. In the mutual reaction of (a) a magnesium compound with reducing ability, (b) a titanium compound, and (c) an electron donor, other reaction reagents, such as compounds such as silicon, phosphorus, and aluminum, may be used. When producing component (A), (1) a method in which the interaction of (a), (b), and (c) is brought into contact with a halogenated hydrocarbon and/or an aromatic hydrocarbon; (2) (a)(b); ) In the mutual reaction of (c), a method such as a method of carrying out the reaction of (b) in the coexistence of a halogenated hydrocarbon can be adopted. The mutual reaction of (a), (b), and (c) can be done by reacting (a), (b), and (c) simultaneously, by reacting (c) after reacting (a) and (b), or by reacting (c) after reacting (a) and (b). A method of reacting a) and (c) and then reacting (b), a method of reacting (b) and (c) and then reacting (a), or a method of reacting any component more than once. Therefore, a method that combines these methods can be adopted. Further, any of the above-mentioned reaction reagents are
It can be used at any stage of the above method. In the mutual reaction, aliphatic hydrocarbons such as hexane, heptane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, chlorotoluene, 1,2-
It can be carried out in a solvent such as a halogenated hydrocarbon such as dichloroethane, trichloromethane, carbon tetrachloride, chlorobutane, or chlorhexane.
In this case, when a halogenated hydrocarbon is used in the reaction of component (b), the interaction product does not need to be brought into contact with the aromatic hydrocarbon and/or the halogenated hydrocarbon, but of course it is not necessary to bring it into contact with the aromatic hydrocarbon and/or the halogenated hydrocarbon. Good too. The interaction can also be carried out in the absence of a solvent as described above.
This may be carried out by means such as mechanical crushing. The temperature of the interaction is usually around -50 to 400℃,
In particular, it is preferable to set the temperature in the range of about 0 to 150°C. When the mutual contact is carried out in a halogenated hydrocarbon, it is effective to use the halogenated hydrocarbon in a ratio of 10 to 1000 mol per mol of the titanium compound. Further, when the interaction product is brought into contact with a halogenated hydrocarbon and/or an aromatic hydrocarbon, it is preferable to use about 10 to 1000 parts by weight of the contacting agent per 1 part by weight of the interaction product.
The temperature of the contact is suitably in the range of 0 to 150°C. 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, fumaric acid, substituted maleic acid, and substituted fumaric acid, that is, the formula HOOCR ₁ = CR ₂ COOH (R ₁ , _R2
is an ester of an unsaturated dicarboxylic acid represented by (hydrogen or any hydrocarbon group with or without a substituent) and any linear aliphatic alcohol with or without a substituent. More specifically, monoethyl maleate, diethyl maleate, di-n-propyl maleate, mono-n-butyl maleate, di-n-butyl maleate, di-n-maleate.
Hexyl, di-n-octyl maleate, di-n-decyl maleate, di-n-chlorobutyl maleate, dimethyl citraconate, diethyl citraconate, di-n-propyl citraconate, di-n-butyl citraconate, mono-n- citraconate Butyl, di-n-hexyl citraconate, di-n-citraconate
Octyl, di-n-decyl citraconate, dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, di-n-butyl fumarate, n-hexyl fumarate, n-octyl fumarate, diethyl ethyl maleate, ethyl maleic acid. di-n-propyl acid,
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, di-n-propyl butyl maleate,
Mention may be made of esters such as di-n-butyl butyl maleate. 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, such as dimethyl oxalate, diethyl oxalate, di-n-propyl oxalate, diiso-propyl oxalate, di-n-oxalate. -butyl, monoisobutyl 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, dimethyl 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 for preparing the solid titanium catalyst component (A) is a magnesium compound having reducing ability. That is, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, and butylmagnesium. Examples include magnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, and butylmagnesium hydride. These may be complex compounds formed with other metal compounds such as organoaluminum compounds. Furthermore, it may be a magnesium compound having reducing ability obtained by reacting with a silicon compound such as a hydrosilane compound. Also ether, thioether, ketone,
It may be a magnesium compound that is reacted with an electron donor such as an aldehyde, carboxylic acid, or alcohol and still retains reducing ability. These magnesium compounds may be in liquid form or may be in solid form. These can be used alone,
Alternatively, it may be used after being diluted with a hydrocarbon, ether, or the like. In the present invention, there are various titanium compounds used for preparing the solid titanium catalyst component (A).
Usually, a tetravalent titanium compound represented by Ti(OR) _g X _4-g (R is a hydrocarbon group, X is a halogen, 0≦g≦4) is suitable. More specifically, _TiCl4 , _TiBr4 ,
Titanium tetrahalides such as _TiI4 ; Ti( _OCH3 ) _Cl3 , _Ti ( _OC2H5 ) _Cl3 , Ti(On _{- C4H9 ) Cl3} , Ti( _OC2H5 ) _Br3 , Ti Trihalogenated alkoxytitanium _such as ( _{OisoC4H9 ) Br3} ; Ti _{( OCH3} ) _2Cl2 , Ti( _OC2H5 ) _{2Cl2 ,} Ti(On- _{C4H9 ) 2Cl2 ,} Ti Dihalogenated alkoxytitanium such as (OC ₂ H ₅ ) ₂ Br ₂ ; Ti(OCH ₃ ) ₃ Cl, Ti(OC ₂ H ₅ ) ₃ Cl, Ti
Monohalogenated trialkoxytitanium such as (On _{− C4H9 ) 3Cl} , Ti( _OC2H5 ) _3Br ; Ti( _OCH3 ) ₄ , Ti
Examples include tetraalkoxytitanium such as ( _OC2H5 ) _{4 and} Ti ₍ On- _C4H9 ) 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,
It may also be used 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 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 is polymerized or copolymerized 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 component (B), (i) an organoaluminum compound having at least one Al-carbon bond in the molecule, for example, a compound with the general formula R ¹ mAl(OR ² ) _o H _p X _q (where R ¹ and R ² is a hydrocarbon group containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and 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) a general formula M ¹ AlR ¹ ₄ (where M ¹ is Li, Examples include complex alkylated products of aluminum and group metals represented by Na, K, and R ¹ is the same as above. 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 (here and ^{R 1} is the _same as above ^.
m < 3), general formula R ¹ mAl (OR ² ) _o X _q (where R ¹ and R ² are the same as above, X is halogen, 0 < m < 3, 0 < n < 3, 0 < If q<3, m
+n+q=3). Among the aluminum compounds belonging to (i), 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 ( ^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 alkylaluminums such as alkylaluminum dihydrides such as propylaluminum dihydride, partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide It is aluminum. 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 ,

[Preparation of solid catalyst component (A)]

MAGALA 7.5E (7.5
(n-C ₄ H ₉ ) ₂ Mg・(C ₂ H ₅ ) ₃ Al in heptane solution)
A solution equivalent to 50 mmol in terms of magnesium atoms was added dropwise over 30 minutes to 100 ml of a heptane solution of trichlorosilane (1 mmol-Si/l) cooled to 0°C. The stirring speed at this time is
It was set to 400 rpm. After dropping, heat to 20℃ for 1 hour.
The temperature was further increased to 60° C. over 1 hour, and the reaction was carried out at this temperature for 2 hours, and the solid material produced in this reaction was collected by filtration. At room temperature
After adding the solid in 150 ml of TiCl ₄ at 120 °C
When the temperature reached 120°C, 2.9 ml of di-n-butyl maleate was added, and the mixture was reacted at the same temperature for 2 hours with stirring. After the reaction was completed, the solid portion was collected by filtration, washed four times with 300 ml of hexane, and resuspended in 200 ml of 1,2-dichloroethane, followed by a reaction at 80° C. for 2 hours. After the reaction was completed, the solid portion was collected by filtration and washed four times with 300 ml of hexane to obtain a solid catalyst component (A).
The components are titanium 1.9% by weight and chlorine 62.0% in terms of atoms.
% by weight, and magnesium was 21.0% by weight. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
750 ml of the reactor was charged, and 2.51 mmol of triethylaluminum, 0.50 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. After introducing 200 ml of hydrogen, the temperature was raised to 70°C and polymerization was carried out for 4 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 248.5g,
−Extraction residual rate with heptane is 96.7%, MI is 4.7,
Its apparent density was 0.35 g/ml. On the other hand, 3.2 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 16800 g-PP/mmol-Ti, and the total was 95.5%. Example 1a [Preparation of solid catalyst component (A)] In Example 1, 1,2-dichloroethane
A solid catalyst component (A) was prepared in the same manner as in Example 1 except that 200 ml of xylene was replaced with 200 ml of xylene. [Polymerization] Propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1. Examples 2, 3, 4 [Preparation of solid catalyst component (A)] In Example 1, di-n-butyl maleate
The solid catalyst component was prepared in the same manner as in Example 1, except that 2.9 ml was replaced with 2.6 ml of di-n-butyl malonate, 2.8 ml of di-n-butyl succinate, and 2.3 ml of diethyl succinate.
(A) was prepared. [Polymerization] Propylene polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1. Example 5 [Preparation of solid catalyst component (A)] 64 ml of a decane solution of diethyl aluminum chloride (converted to aluminum atoms) was added to 125 ml of a commercially available diethyl ether solution (converted to magnesium atoms, 250 mmol) with stirring. (converted to 125 mmol) when the temperature in the system is
The mixture was gradually added dropwise while maintaining the temperature below 30°C. After the completion of the dropwise addition, the temperature of the system was raised to 35° C. and the reaction was carried out under reflux for 4 hours, after which the solid product was separated by filtration and thoroughly washed with hexane. 20 g of the solid material thus obtained was resuspended in 50 ml of hexane in the reactor, 6.8 ml of di-n-butyl maleate was added to this suspension, and the reaction was carried out at 65°C for 2 hours. After that, hexane was removed using an evaporator and a solid substance was collected. The total amount of the solid material, 3.3 ml of titanium tetrachloride, and 3.0 ml of silicone oil (TSS-451, 20 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid were added to a 2.8 kg ball made of stainless steel (SUS-32) with a diameter of 15 mm in a nitrogen atmosphere. Contained internal volume 800ml, internal diameter 100
The sample was placed in a ball mill container made of stainless steel (SUS-32) and left in contact for 24 hours with an impact acceleration of 7G. 15 g of the obtained co-pulverized product was suspended in 150 ml of 1,2-dichloroethane, and after contacting at 80°C with stirring for 2 hours, the solid portion was collected by filtration and thoroughly washed with purified hexane 1. The catalyst component (A) was obtained by further drying. [Polymerization] Propylene polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Table] Examples 6, 7, 8, 9, 10, 11, 12 Using the solid catalyst component (A) described in Example 1, 0.50 m of diphenyldimethoxysilane added during polymerization.
mol, phenyltrimethoxysilane 0.50 mmol,
Vinyltrimethoxysilane 0.84mmol, methyltrimethoxysilane 0.84mmol, tetraethoxysilane 0.84mmol, ethyltriethoxysilane 0.50
mmol, vinyltriethoxysilane 0.50 mmol,
The same procedure as in Example 1 was carried out except that methylphenyldimethoxysilane was changed to 0.50 mmol. The polymerization results are shown in Table 2. Comparative Example 1 [Preparation of Solid Catalyst Component (A)] A solid catalyst component (A) was prepared in the same manner as in Example 1 except that 1,2-dichloroethane was not used. [Polymerization] Propylene polymerization was carried out in the same manner as in Example 1. The yield of white powdery polymer after drying is
The weight is 187.7g, the extraction residue rate with boiling n-heptane is 95.9%, the MI is 5.3, and the apparent density is 0.34.
g/ml. On the other hand, 2.8 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore the activity is 12700
g-pp/mmol-Ti, total 94.5%
It was hot.

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Claims (1)

[Scope of Claims] 1. (A) At least a three-component interaction product of (a) a magnesium compound having reducing ability, (b) a titanium compound, and (c) an electron donor is combined with a halogenated hydrocarbon compound and/or Titanium, magnesium, halogen, and electron donor obtained by contacting with an aromatic hydrocarbon compound or by performing the reaction of component (b) in the interaction of the above three components in the presence of a halogenated hydrocarbon compound A titanium catalyst component having as an essential component, the electron donor being an ester of an unsaturated carboxylic acid selected from the group consisting of maleic acid, fumaric acid, substituted maleic acid, and substituted fumaric acid and a linear aliphatic alcohol. or an ester of a saturated linear dicarboxylic acid having 2 to 5 carbon atoms, (B) an organoaluminum compound catalyst component, and (C) a formula RnSi(OR ¹ ) _4-o (wherein n<4, R is a hydrocarbon group, However, in the presence of a catalyst formed from a silicon compound catalyst component represented by n R and (4-n) OR ⁽¹ group may be the same or different), olefin is polymerized or copolymerized. A method for polymerizing olefin, characterized by: