JPS63277204A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer having excellent polymerization activity, stereoregularity and particle shape, by (co)polymerizing an olefin in the presence of a catalyst composed of a solid catalyst component derived from Mg compound, boron compound, etc., and an organometallic compound of a group I-III metal of the periodic table. CONSTITUTION:An olefin is (co)polymerized in the presence of a catalyst composed of (A) a solid catalyst component obtained by thermally reacting an Mg compound of formula I (R<1> and R<2> are alkyl, aryl or aralkyl; 0<=n<=2) [e.g. Mg(OCH3)2] with a boron compound of formula II (R<3> is alkyl, aryl or aralkyl) [e.g. B(OCH3)3] and Al(OCH2C6H5)3] and an Si compound of formula III (R<4> is alkyl, aryl or aralkyl) (e.g. tetramethoxysilane) and treating the reaction product with a halogen-containing Ti compound and an electron donative compound (e.g. diethyl ether) and (B) an organometallic compound of a group I-III metal of the periodic table (e.g. triethylaluminum).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an α-olefin polymer using a novel solid catalyst component. More specifically, polymerization activity,
Using a catalyst consisting of a new supported catalyst component that provides a polymer with excellent stereoregularity and particle properties, an organometallic compound of a group I to II metal, and an electron-donating compound if necessary, ethylene, propylene , butene-/, 1-methylpentene-/, 3-methylbutene-/, and other α-olefin polymers.

In particular, the present invention relates to a method for producing a polymer having high activity toward α-olefins having 3 or more carbon atoms, high stereoregularity, and good particle properties.

[Conventional technology]

Conventionally, there have been many proposals for producing catalysts that produce highly active and highly stereoregular polymers for α-olefins having 3 or more carbon atoms using supported catalysts, but most of them have been It is not fully satisfactory in terms of activity and stereoregularity, and further improvements are desired. Furthermore, the particle properties of the obtained polymer are also insufficient, and improvements are desired. Particle properties are an extremely important factor in slurry polymerization, gas phase polymerization, etc. If the particle properties are poor, it may cause problems such as adhesion in the polymerization tank, failure to extract the polymer, or blockage of pipes. Become.

For example, Tokukai Akira! λ-ta 07t, JP-A-33-2310
discloses a method using a three-component catalytic reaction product of M2 alkoxide, T1 halide, and electron donor as catalyst components, but the polymerization activity, stereoregularity, and particle properties of the resulting polymer are insufficient. Met.

JP-A-6-/λo'yii discloses a method using T1 tetraalkoxide in addition to the above three components. That is, a MW alkoxide is treated with a T1 tetraalkoxide in heptane, and the resulting treated solid is treated with an organic acid ester and a T1 halide. In this method as well, the polymerization activity (polymer yield per Ti/P, per 7 hours, per propylene pressure/A?/crd) is
At most io, oo.

y -pp/7- Ti -Aii'/ffl ppy
It has a strong writing hour, the highest tactical index, and a bulk density of 0.30 P/.
It did not show sufficiently high performance near CC.

Furthermore, in JP-A-20603, a liquid is formed by contacting an M1 alkoxide and/or a Mn alkoxide with a T1 tetraalkoxide, and the liquid is reacted with a fluid comprising a halogenating agent.
and an electron donor to form a treated solid; and post-treating the solid with a transition metal halide.

An important objective of the process is to produce a catalyst component that provides a polyolefin containing a narrow and high particle diameter distribution and a minimal particulate content in the polymer. Regarding the particle size distribution, there are many large particles and it cannot be said that the distribution is necessarily narrow, but it is recognized that the size of fine particles has decreased considerably. However, especially regarding stereoregularity, the improvement effect cannot be said to be sufficiently high, and the tactical index is 70% or less.

The present inventors previously disclosed in Japanese Patent Application Sho TL-//1732 that magnesium dialkoxide is an electron-donating compound.
We have proposed a method for producing catalyst components with excellent polymerization activity, stereoregularity, and particle properties by treating them with silicon tetraalkoxide and titanium compounds such as titanium tetrachloride, but further improvements in particle properties are needed. was desired.

[Purpose of the invention]

In order to obtain a solid catalyst component that provides a polymer with even better particle properties while maintaining the high activity and stereoregularity of the above-mentioned catalyst system, the present inventors have conducted intensive studies on the production method, and have developed the present invention. invention has been achieved. That is, the gist of the present invention is
General formula Mr(oR')n(OR")z-n (wherein, R
1. R2 represents an alkyl group, an aryl group, or an aralkyl group, and R1 and R2 may be the same or different. nIf
Indicates i≧n≧Of. ), a boron compound represented by the general formula B(OR3)3 (in the formula, R3Fi represents an alkyl group, an aryl group, or an aralkyl group), and a general formula 81 (OR').

(In the formula, R4 represents an alkyl group, an aryl group, or an aralkyl group.) A solid obtained by heating a silicon compound and then treating the reaction product with a halogen-containing titanium compound and an electron-donating compound. Polymerizing or copolymerizing an olefin in the presence of a catalyst consisting of a catalyst component (A), an organometallic compound of a metal from groups I to III of the periodic table (B), and optionally an electron-donating compound (C). A method for producing a first/fin polymer is characterized in that:

C Structure of the Invention] The present invention will be described in detail (A) (a) General formula Mt (OR' )H(OR
2) Magnesium compound represented by 2-n and general formula B
(OR3), and a boron compound represented by the general formula 5
t(oR').

A solid catalyst component obtained by treating a heated reaction product of a silicon compound represented by (b) with a halogen-containing titanium compound and (C) an electron-donating compound; This is a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin using a catalyst containing a metal organometallic compound as an essential component and optionally (C) an electron-donating compound.

General formula up(on')n(ou2)2 used in the present invention
Specifically, the magnesium compound (aI) represented by -n is My (QC!H3)2, MW (QC!2H5
)2, Mr (OC3H7)z, MY(oc4Hs)
z, MV (OCgHs)z, MP (OCHzCa
Hs)z, Mp (QC!.

Hs ) (OC4H9), H7(OC2H5) (O
C6H5), y, y (OC6H4CHs)2, and other dialkoxymagnesiums, diaryloxymagnesiums, dialkyloxymagnesiums, and alkyloxyaryloxymagnesiums. These can also be used in combination.

Boron compound (R2) represented by general formula B(OR3)3
As, B (OCH3)3, B (OCzHs)
3, B (QC! 3H7) 3, B (QC! 4H9) 3,
B (QC!6H5)3, B (OCR2C,H5)a
etc. These can also be used in combination.

Silicon compound (R3
) Examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetra(2-ethylhexoxy)silane, tetraphenoxysilane, and tetra(P-methylphenoxy)silane. These can also be used in combination.

Among these, those in which at least one of the magnesium compound, boron compound, and silicon compound contains an aryloxy group as an alkoxy group are preferred.

A reaction product from three types of compounds: a magnesium compound (al), a boron compound (R2), and a silicon compound (R3) (
As a method to obtain a), (=1), (R2), (
A method of simultaneously contacting and reacting R3), a method of reacting (R3) after reacting (at) and (R2),
A method of reacting (R2) after reacting al) and (R3), or a method of reacting (R2) and (R3) and then reacting (a
Examples include a method of reacting with Furthermore, an inert hydrocarbon solvent may be present during the reaction. The reaction temperature is Otsu 0℃
~-00°C, preferably io.

The temperature is 0.degree. C. to 0.degree. C., and the reaction time is about 3 to 3 hours. The amounts of each component used, expressed in molar ratios, are usually as follows.

Mf(oR')n (oRr)2-n'B(OR3)3
θ, Oj ~ Hiro, preferably O02 ~ lsi
(OR4)4o,/~j1 Preferably 0.2-2 The magnesium compound (al) of the present invention and the boron compound (R2
) and the silicon compound (R3) can be obtained as a liquid by changing the composition ratio of (al), (R2), and (R3), but it is possible to obtain a liquid product by changing the composition ratio of (al), (R2), and (R3), but it is also possible to obtain a liquid product in the form of a slurry containing solid components. Good results are often obtained when using

If it is in liquid form, it will pass through a homogeneous liquid state during the reaction with titanium halide, which will be described later, but there is a tendency for solid components to be difficult to form thereafter.

In addition, when obtaining the heating reaction product (a) of the magnesium compound (a) of the present invention, the boron compound (a), and the silicon compound (R3), the general formula R50H (wherein R6 is an alkyl group, an aryl group, or an aralkyl group) may be reacted to exchange the alcohol.

Specifically, R50H used here is ethanol,
butanol, hexanol, coethylhexanol,
Alcohols such as benzyl alcohol; phenols such as phenol, cresol, xylenol, and butylphenol.

In the present invention, the heated reaction product (a) obtained as described above is treated with a halogen-containing titanium compound (1)) and an electron-donating compound (C) in the presence or absence of an inert hydrocarbon solvent. A solid catalyst component (A) f is obtained by the treatment.

The halogen-containing titanium compound (b) used here includes titanium tetrachloride, titanium tetrabromide, titanium titanium and
710 gene-alcoholate compounds and the like.

Examples of the electron donating compound (C) generally include phosphorus-containing compounds, oxygen-containing compounds, sulfur-containing compounds, and nitrogen-containing compounds. Among these, oxygen-containing compounds are preferably used.

As the oxygen-containing compound, for example, the following general formula (in the formula R6,
R7 represents a hydrocarbon group which may be substituted with an alkoxy group, and may be bonded to each other to form a cyclic group.

Further, k represents a number from 1 to 3. ) can be mentioned.

Specifically, ethers such as diethyl ether, dipropyl ether, diethylene glycol, polypropylene glycol, ethylene oxide, propylene oxide, and furan; ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and phenylpropyl ketone; ethyl acetate , methyl propionate, ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, furovir toluate,
Esters of carboxylic acids such as butyl toluate, methyl ethylbenzoate, ethyl ethylbenzoate, ethyl xylenecarboxylate, methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate; Examples include cyclic esters such as γ-butyllactone, and silicon-containing carboxylic esters such as β-trimethoxysilylethyl benzoate, but carboxylic esters are preferably used, and particularly preferred are carboxylic esters. Aromatic carboxylic acid esters are used.

In the method of the present invention, the component (a) is replaced with (b) and (C).
As a method of processing with components, (a) is treated with (b) + (C)
A method in which (a) is treated with (b) and then treated with (C), a method in which (a) and (C) are brought into contact in advance, and then (b) is treated with (b).
), but it is also possible to use a method in which reactant (a) is prepared in the presence of (C) and reacted, and then treated with (b). Also (b) and (C)
A method of repeating the treatment step at least once or more may also be preferably adopted.

After the treatment, the solid catalyst component (A) is obtained by washing with an inert hydrocarbon solvent and appropriately removing components soluble in the solvent. The amounts of each of the components (b) and (C) used in the catalyst production process in the seven steps are usually expressed in molar ratios as follows with respect to 1 mole of the magnesium compound in the component (a).

Halogen-containing titanium compound (b) 0. /~ioo
Preferably /~≠0, electron donating compound (C) θ, θ
/~/Q preferably θ, /~/, and the titanium content in the obtained solid catalyst component (A) is 0. /~IO weight section,
Preferably from 0.2! The amount of each of the above components used is adjusted so that the weight % is achieved.

Processing temperature is usually -70°C to 00°C, preferably -70°C
°C~/j′θ°C. Specifically, for example, when bringing component (a) into contact with component (b) and then component (C),
(,) component and (b) component at -70℃! 0°C, preferably -30°C to 30°C, and then add component (c) to 50°C.
0° C. to 200° C., preferably 70° C.
) -70°C to 50°C when the components are brought into contact at the same time,
Preferably, the contact is carried out at -30°C to 30°C, and then! θ℃
Good results can be obtained by heating to .lamda..theta.O.degree. C., preferably 70.degree. C. to tO.degree.

When the contact temperature is lowered, when component (a), component (b), and optionally component (C) are brought into contact at the same time, the whole becomes more likely to become a uniform liquid, and this uniform liquid is heated to an elevated temperature to precipitate a solid. As a result, a solid catalyst component with good particle properties can be obtained.

The treatment can be carried out in the presence or absence of an inert solvent, and the reaction time is 0. ! It is about 6 hours.

The thus obtained solid catalyst component (A) and periodic table No.
Polyolefins are produced by polymerizing or copolymerizing olefins using a catalyst system comprising an organometallic compound (B) of a group metal and, if necessary, an electron-donating compound (C).

Next, the organometallic compound (B) of a metal of Groups 1 to m of the periodic table used in this catalyst system is preferably of the general formula A
tRnx3. Examples include compounds represented by -n. In the above formula, R is a hydrocarbon group having 7 to 20 carbon atoms, particularly an aliphatic hydrocarbon group, X is a halogen, and n is a number of 2 to 3. Specific examples of the organoaluminum compound include triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, monovinyldiethylaluminum, diethylaluminium monochloride, etc., but trialkylaluminum is preferably used. It will be done.

Further, as the electron donating compound (C), the component (C) used in the production of the solid catalyst component (A) is used, preferably a carboxylic acid ester, and particularly preferably an aromatic carboxylic acid ester.

The ratio of the catalyst components to be used is such that the molar ratio of titanium in the catalyst component (A) to the aluminum compound in the component (B) to the electron donating compound in the component (C) is l:3~zoo'', o~ioo, preferably , l:2
0S-200: selected to be 3-50.

The olefins to be subjected to polymerization or copolymerization are Teha, ethylene, Furopylene, Phthene-/, 3-Mef-Fruftene-7
1≠-methylpentene/etc., and preferred α-olefins having 3 or more carbon atoms, especially propylene. Further, the polymerization can be applied not only to homopolymerization but also to random or block copolymerization.

The polymerization reaction is carried out using an inert hydrocarbon, such as hexa/, heptane, toluene, pentane, butane or mixtures thereof,
Alternatively, the polymerization can be carried out by a slurry polymerization method in which a liquefied α-olefin to be polymerized is used as a solvent, or a gas phase polymerization method in which the polymerization is carried out in a gas phase.

The temperature is 50 to 100°C, preferably 60 to 100°C, and the pressure is not particularly limited, but is usually selected from the range of atmospheric pressure to 100 atm.

Hydrogen can also be present in the polymerization system as a molecular weight regulator, thereby making it possible to easily change the melt 70-index.

Other means commonly used for polymerization and copolymerization of α-olefins can also be applied to the method of the present invention. For example, there is a method in which the three catalyst components (A), (B), and (C) or the co-components (A) and (B) are used for pretreatment with an α-olefin.

〔Example〕

The present invention will be explained in more detail with reference to Examples,
The present invention is not limited in any way by these Examples unless it departs from the gist thereof.

Further, FIG. 7 is a 70-chart diagram for helping understanding the technical contents included in the present invention, and the present invention is not limited in any way by the flowchart diagram as long as it does not deviate from the gist thereof.

In the examples, polymerization activity (shown as K-t:l:
α-olefin pressure/Isl/crA per /R,
Solid catalyst component (A) / Polymer production amount per r (?
), and the catalyst efficiency (denoted as OK) is the amount of polymer produced (2) per solid catalyst component (A) / .

Isotactic index (denoted as AE) is the residual amount (% by weight) after 6 hours of extraction with boiling n-hebutane in a modified Soxhlet extractor.

Bulk density (expressed as ρB, unit y/ac') was measured according to J.Eng.S-1,72/. Melt flow index (shown as MIP) is ASTM-D-/
Measured according to 231r.

The particle size distribution of the polymer was measured using a standard sieve manufactured by Mitamura Riken.

Example 1 (1) Production of solid catalyst component Purified N2 was added to a 300g flask equipped with a stirrer and a thermometer.
Commercially available MP(OCzHs)zsrr was collected under the seal, and B(OC4Hs)3! A toluene solution of tr and tetraphenoxysila; y Ir, t tr was added. After the addition, the temperature was raised and the reaction was carried out at 130° C. for 2 hours to obtain a reaction product in the form of a white solid slurry.

A purified toluene solution was added to this reaction product, and −λO′
It was cooled to C. T i Ct4 kota after cooling? When r was added, the whole became a homogeneous solution. Thereafter, the formation of solid particles was observed by gradually increasing the temperature. 10
After raising the temperature to "C", ethyl benzoate/jtr was added and the mixture was kept at the same temperature for 7 hours, followed by washing with purified toluene to obtain a solid product.

The resulting solid product was then treated with TiCl41r J? r
and ethyl benzoate/, 39r and at 7° C.
Time processed. Thereafter, it was washed with purified toluene at room temperature to obtain a solid catalyst component. What is the T1 content of this thing? % by weight.

(2) Polymerization and purification of propylene Place triethylaluminum/, 0 mmol, methyl halamethylbenzoate, 0,
Add 3 mmol of liquid propylene, and add H2 so that /, Ok'i/cd, liquid propylene 700 Ir'fc
I prepared it.

Next, after adding the above solid catalyst component /J'~, the temperature was increased to 70°C.
The temperature was raised to 1, and polymerization was carried out for 7 hours. Thereafter, excess propylene was purged to obtain powdered polypropylene powder JYr. Catalyst efficiency Cffj is /ri, j 00 f-PP/
t-cat, tzo for polymerization activity, and ρB of the obtained polymer is 0. ψ/? /cc, AE 4.7%,
My engineer was Hiroshi, 3rd year. In addition, the particle size distribution of the polymer is 6
76% of the total polymer particles have a particle size of 00 μm to 0 μm.
The amount of fine powder of less than ioo μm was θ,/chi.

Example λ In Example 1 (1), M as the magnesium compound
y(OC4Hs)z7. Example 1 (1
) A solid catalyst component was obtained. The T1 content of this product was 0.5% by weight.

Using the obtained solid catalyst component, the polymerization of probile/ was carried out in the same manner as in Example (2), and the catalyst efficiency CV
= , 2 u, 000 V-PP/? -eat, polymerization activity was -400, ρB = o, ukot/ec, II = 6.6chi, M FI = l, 3. In addition, the particle size distribution of the obtained polymer was ≠00μ771-200μm
The polymer with particle size is the total octopus%, iooμm
The following amounts of fine powder were θ and flathead.

Example 3 Commercially available MP (002H
5) B(OC4Hg)33 rr in zz tr, tetraethoxysilane≠, g tr and phenol 1,
2 fr toluene solution was added. After addition, the temperature was raised, i
The reaction was carried out at oo°C for 1 hour and then at 130°C for 7 hours. Distillation of ethanol was observed during the reaction. The obtained reaction product was in the form of a white solid slurry.

A solid catalyst component was obtained in the same manner as in Example (1) except that this reaction product was used. The T1 content was expressed as % by weight.

If propylene was polymerized in the same manner as in Example/(2), the catalyst efficiency would be C'E2=,2/,000? -PP
/? -cat, for polymerization activity; 70θ, ρ, = o, t
x, z v/ce.

Any def, 0%, MFI=7°3. Furthermore, the particle size distribution of the obtained polymer was almost the same as in Example 1.

Example ≠ A solid catalyst component was prepared in the same manner as in Example 3, except that tetraethoxysilane was replaced with a toluene solution of tetraphenoxysilane 1.1 fr, and phenol was replaced with n-butanol A, t fr. I got it. This thing T
1 content was 289% by weight.

When propylene was polymerized in the same manner as in Example/(2), the catalyst efficiency GK-λλ,,t00f-PP/? −
cat, polymerization activity; 7! θ, 4m = 0. u 3
r/ee, XX = 7.7%, MF engineering = V6. Moreover, the particle size distribution of the obtained polymer was almost the same as that of Example λ.

〔Effect of the invention〕

As described above, according to the present invention, a polymer having excellent polymerization activity, stereoregularity, and particle properties can be obtained.

[Brief explanation of drawings]

FIG. 1 is a flow chart diagram illustrating one aspect of the present invention. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent attorney: Yo Hase - and others/names

Claims (7)

[Claims] (1) (A) (a) General formula Mg(OR^1)_n(OR
^2)_2_-_n (In the formula, R^1 and R^2 represent an alkyl group, an aryl group, or an aralkyl group, and R^1 and R^2 may be the same or different. n is 2≧n≧ 0), a boron compound represented by the general formula B(OR^3)_3 (wherein R^3 represents an alkyl group, an aryl group, or an aralkyl group), and a boron compound represented by the general formula Si A silicon compound represented by (OR^4)_4 (wherein R^4 represents an alkyl group, an aryl group, or an aralkyl group) is heated and reacted, and then (b) a halogen-containing titanium compound, and (c) an electron It is characterized by polymerizing or copolymerizing an olefin in the presence of a solid catalyst component obtained by treatment with a donor compound and (B) an organometallic compound of a metal of Groups I to III of the Periodic Table. A method for producing an olefin polymer. (2) When a heating reaction product of the three components of a magnesium compound, a boron compound, and a silicon compound is treated with a halogen-containing titanium compound, a solid is formed after it has passed through a homogeneous system. The method described in section 1). (3) When treating a three-component thermal reaction product (a) of a magnesium compound, a boron compound, and a silicon compound with a halogen-containing titanium compound (b) and an electron-donating compound (c), the components (a) and (b) The components are contacted at -70°C to 50°C and then component (c) is contacted at 50°C to 200°C, or components (a), (b) and (c) are simultaneously contacted at -70°C to
The method according to claim 1 or 2, characterized in that the contact is carried out at 50°C and then at 50°C to 200°C. (4) The heating reaction product (a) of a magnesium compound, a boron compound, and a silicon compound includes a solid product consisting of magnesium, boron, silicon, and an alkoxy group. 1)～(3
) The method described in any of the above. (5) Claims (1) to (5) characterized in that any one of the magnesium compound, boron compound, and silicon compound contains an aryloxy group as an alkoxy group.
4) The method described in any of the above. (6) Claim No. (1) characterized in that the treatment of a three-component heating reaction product of a magnesium compound, a boron compound, and a silicon compound with a halogen-containing titanium compound and an electron-donating compound is repeated two or more times. ~(5)
The method described in any of the paragraphs. (7) The method according to claim (1), characterized in that the olefin is polymerized or copolymerized in the presence of the electron-donating compound (C).