JPH0714991B2 - Method for producing propylene copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a propylene copolymer. More specifically, the present invention provides the presence of a particular catalyst,
The present invention relates to a method for producing a propylene copolymer, particularly a propylene block copolymer, by polymerizing propylene or a propylene / ethylene mixture in at least two steps.

According to the method of the present invention, it is possible to produce a propylene copolymer having high rigidity, high impact strength and good fluidity while suppressing the by-product of high activity and low crystalline component.

Prior art As a method for improving the impact strength of crystalline polypropylene having excellent rigidity and heat resistance, particularly impact resistance at low temperature, propylene and ethylene or other olefins are gradually polymerized to form a block. The method of forming a copolymer is already known (Japanese Patent Publication No. 43-11230).
No. 44-16668, No. 44-20621, No. 49-24593,
49-30264, JP-A-48-25781, 50-115296,
53-35789, 54-110072, etc.).

However, when propylene and ethylene are polymerized in two stages or in multiple stages, impact resistance is improved, but on the other hand, there is an industrial problem that a large amount of low crystalline polymer is by-produced due to the inclusion of a copolymerized portion. ing. Therefore, many attempts have been made to reduce the low crystalline component produced as a by-product.

On the other hand, a titanium trichloride-type catalyst is well known as an olefin stereoregular catalyst, but it requires a detouching step because of its low activity.

A method of introducing a magnesium compound into a solid catalyst component in order to improve activity until detouching is well known. Furthermore, in order to suppress these by-produced low-crystal components, a method of using an electron donor as a solid catalyst component or a polymerization additive is also well known (JP-A-47-9842, 50-1265).
No. 90, No. 51-57789, etc.).

Then, a method for producing a propylene block copolymer by using these catalyst systems has been proposed (JP-A-52-98045, JP-A-53-88049, etc.). However, in these methods, a large amount of low crystalline components are first produced as a by-product, which is not practically satisfactory.

Furthermore, in order to improve this, as a polymerization additive, Si-
It has been proposed to use an organosilicon compound having an O—C or Si—O—N bond (Japanese Patent Laid-Open No. 58-83016). However, this method has the following problems because the molecular weight of the rubber portion or polyethylene portion which is an ethylene / propylene copolymer is small.

(1) The produced rubber is easily extracted from the polymer, and this becomes a by-product low crystalline component, and the produced polymer is sticky, and the polymer causes aggregation, sticking and the like, which causes an operating trouble.

(2) Low temperature impact resistance is not improved.

(3) In order to maintain the MFR of the entire polymer, the molecular weight of the crystalline polypropylene portion must be necessarily increased, which deteriorates the spiral flow, that is, the fluidity of the polymer in the mold.

SUMMARY OF THE INVENTION The present invention provides a method for producing a propylene copolymer, which comprises carrying out the following steps in the presence of the following catalyst.

Catalyst A catalyst comprising the following components (A) and (B), component (A) component (i): solid component containing titanium, magnesium and halogen as essential components, and component (ii): general formula R ¹ R ² _3- nSi (OR ³ ) n (where R ¹ is a carbon atom branched from the carbon atom adjacent to the silicon atom is 4
~ 10 branched chain hydrocarbon group, R ² is a branched or linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ³ is 1 to 10 carbon atoms.
A solid compound obtained by washing a product obtained by contacting a chain-like aliphatic hydrocarbon group of 4 with a silicon compound represented by (n is a number of 1 ≦ n ≦ 3) with an inert solvent. Component, component (B) Organoaluminum compound, process Process comprising the following process (1) and process (2) to produce a propylene copolymer having a total ethylene content of 3 to 40% by weight, process (1) propylene alone Or a step of polymerizing a propylene / ethylene mixture having an ethylene content of 5% by weight or less in a single step or in multiple steps to form a polymer in an amount corresponding to 60 to 95% by weight of the total polymerization amount, step (2) ethylene content of 20 to A step of polymerizing a propylene / ethylene mixture corresponding to 100% by weight in a single stage or multiple stages.

The present invention also provides a method for producing a propylene copolymer, which comprises carrying out the following steps in the presence of the following catalyst.

Catalyst A catalyst comprising the following (A) and component (B): Component (A) Component (i): A solid component containing titanium, magnesium and halogen as essential components was contacted with olefins in the presence of an organoaluminum compound. Prepolymerized component, and component (ii): general formula R ¹ R ² _3- nSi (OR ³ ) n (where R ¹ is 4 carbon atoms branched from the carbon atom adjacent to the silicon atom)
To 10 branched chain hydrocarbon groups, R ² is a branched or straight chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n is 1 ≦ n.
A solid compound component obtained by washing the product obtained by contacting the product obtained by contacting the silicon compound represented by ≤3) with an inert solvent, and the component obtained by washing the product obtained by washing the product with an inert solvent. (B) Organoaluminum compound, step A step of producing a propylene copolymer having the following steps (1) and (2) and having a total ethylene content of 3 to 40% by weight: step (1) propylene homopolymer or ethylene content A step of polymerizing a propylene / ethylene mixture of 5% by weight or less in a single stage or in multiple stages to form a polymer in an amount corresponding to 60 to 95% by weight of the total polymerization amount, step (2) ethylene content 20 to 100% by weight The step of polymerizing a propylene / ethylene mixture corresponding to 1-stage or multi-stage polymerization.

EFFECTS OF THE INVENTION According to the method of the present invention, by-production of a highly active and low crystalline component is suppressed, and the molecular weight of the propylene / ethylene copolymerized portion and / or the polyethylene portion is increased, that is, high rigidity and high Impact strength propylene copolymers, especially propylene / ethylene block copolymers, can be prepared.

In addition, since the obtained copolymer powder has no stickiness, the operation troubles due to the aggregation and sticking of the copolymer powder are eliminated.

In addition, since the catalyst used in the method of the present invention has excellent activity sustainability, it is easy to operate for a long time without any deterioration in catalyst activity in the latter half of the multistage polymerization.

Furthermore, since the molecular weight of the crystalline polypropylene portion in the obtained copolymer can be reduced, the fluidity (for example, spiral flow) of the product polymer is improved. Further, in the present invention, since the catalyst system is simple, it becomes easy to control the desired product performance.

Detailed Description of the Invention (Catalyst) The catalyst used in the method of the present invention comprises the specific components (A) and (B).

Component (A) The component (A) of the catalyst used in the present invention is a solid catalyst component obtained by bringing the following component (i) and component (ii) into contact with each other.

The solid component containing titanium, magnesium and halogen used as the component (i) as essential components is a known solid component. For example, JP-A-53-45688 and JP-A-54-3894.
No. 54-31092, No. 54-39483, No. 54-94591,
54-118484, 54-13589, 55-75411, 55
-90510, 55-90511, 55-127405, 55-14
No. 7507, No. 55-155003, No. 56-18609, No. 56-70005
No. 56, No. 56-72001, No. 56-86905, No. 56-90807,
56-155206, 57-3803, 57-34103, 57
-92007, 57-121003, 58-5309, 58-531
0, 58-5311, 58-8706, 58-27732,
58-32604, 58-32605, 58-67703, 58-1
17206, 58-127708, 58-183708, 58-183
Those described in each of the publications such as 709, 59-149905, and 59-149906 are used.

The magnesium compound serving as the magnesium source of the catalyst used in the present invention is magnesium halide,
Examples thereof include dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide and magnesium carboxylate.

Further, the titanium compound serving as the titanium source has a general formula of Ti (O
R ⁴ ) _4- nXn (wherein R ⁴ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents halogen, and n represents a number of 0 ≦ n ≦ 4). ). Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC
₂ H ₅ ) Cl, Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-
_{nC 3 H 7) Cl 3,} Ti (O-nC 4 H 9) Cl 3, Ti (O-nC 4 H 9) 2 Cl
₂ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC ₄ H ₉ ) ₂ Cl, Ti (O
_{-NC 4 H 9) Cl, Ti} (O-C 6 H 5) Cl, Ti (O-iC 4 H 9) 2 C
l ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC ₂ H ₅ ).
_{4, Ti (O-nC 3} H 7) 4, Ti (O-nC 4 H 9), Ti (O-iC
₄ H ₉ ) ₄ , Ti (O-nC ₆ H ₁₃ ) ₄ , Ti (O-nC
₈ H _{17) 4,} Ti _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] is _4, and the like. Of these, TiCl ₄ is particularly preferable.

It is also possible to use a molecular compound obtained by reacting TiX ' ₄ (where X'represents halogen) with an electron donor described later. Specific examples include TiCl ₄・ CH ₃ COC ₂ H ₅ , TiCl ₄・ CH ₃
CO ₂ H ₅ , TiCl ₄ / C ₆ H ₅ NO ₂ , TiCl ₄ / CH ₃ COOl, TiCl ₄ / C ₆ H ₅
COCl, TiCL ₄・ C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄・ ClCOC ₂ H ₅ , TiCl ₄・
Examples include C ₄ H ₄ O.

The halogen source is usually supplied from the above-mentioned magnesium and / or titanium halogen compounds, but is supplied from known halogenating agents such as aluminum halides, silicon halides and phosphorus halides. You can also do it.

Halogen contained in the catalyst component is fluorine, chlorine, bromine,
It may be iodine or a mixture thereof, with chlorine being particularly preferred.

Solid components used in the present invention include SiC in addition to the above essential components.
l ₄ , CH ₃ SiCl ₃ , silicon compounds such as methylhydrogenpolysiloxane, Al (OisoC ₃ H ₈ ) ₃ , AlCl ₃ , AlBr ₃ , Al
Aluminum compounds such as (OC ₂ H ₅ ) ₃ and Al (OCH ₃ ) ₂ Cl, and boron compounds such as B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ Other components may be used, and these may remain in the solid component as components such as silicon, aluminum and boron.

Further, when the solid component is produced, the electron donor can be used as an internal donor.

Examples of electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acids. Examples thereof include oxygen-containing electron donors such as anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, it has 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octal, dodecanol, octatedyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropylbenzyl alcohol.
Alcohols of 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol; acetone, methylethylketone, methylisobutylketone,
C3 to C3 such as acetophenone and benzophenone
15 ketones; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other carbons 2 to 15 aldehydes; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, acetic acid Cyclohexyl, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl Ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-ptyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate and the like having 2 or more carbon atoms. 20 organic acid esters; inorganic acid esters such as silicic acid esters such as ethyl silicate, butyl silicate, and phenyltriethoxysilane; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid cloyd, phthaloyl chloride, y Acid halides having 2 to 15 carbon atoms such as phthaloyl chloride; 20 ethers having 2 carbon atoms such as methyl ether, ethyl ether, isopropyl nitrate, butyl ether aluminum ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid amide; Acetamides such as benzoic acid amide and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine; acetonitrile, benzonitrile, trinitrile, etc. And the like. Two or more kinds of these electron donors can be used.

The Ti / Mg atomic ratio is 1 × 1
It is in the range of 0 ^-2 to 1, and the halogen / Mg atomic ratio is 0.5 to 4
Of electron donors / M
The g molar ratio is preferably in the range of 1 or less.

When silicon, aluminum and boron compounds are contained, these compounds are in a molar ratio of 1 × 10 ^{−3 to} 100, preferably 1 × 10 ⁻² to the amount of the magnesium compound used. It is within the range of 1.

The solid component used in the method of the present invention can be produced by a known method, but the following production method is preferable.

(B) A method of producing activated magnesium halide by simultaneously or gradually bringing them into contact with each other in a co-grinding state or in a liquid state. to this,
Further, a halogenating agent may be contacted.

(B) If necessary, an electron donor may be added to the protrusion obtained by reacting a magnesium compound in a uniform state with or without an electron donor with a halogenating agent, a reducing agent, or the like. A method for producing a catalyst by contacting a body with a titanium compound.

(C) A method of producing a catalyst by allowing an organomagnesium compound such as a Grignard reagent to act with a halogenating agent, a reducing agent, etc., and then contacting this with an electron donor and a titanium compound.

(D) A method for producing a catalyst by contacting a halogenating agent and / or a titanium compound with an alkoxymagnesium compound in the presence or absence of an electron donor.

As the catalyst component (i) used in the present invention, the solid component obtained as described above may be used as it is, or the solid component may be prepolymerized by contacting it with olefins in the presence of an organoaluminum compound. It can also be used as a component. When the component (i) is prepolymerized, the component (ii) is preferably contacted after prepolymerization.

When the component (i) is prepolymerized, the prepolymerization conditions of the olefins for producing the component (i) are not particularly limited, but the following conditions are generally preferable. The polymerization temperature is 0 to 80 ° C, preferably 10 to 60
℃. The amount of polymerization is 0.00 per gram of solid component
It is preferred to polymerize 1 to 50 grams of olefins, more preferably 0.1 to 10 grams of olefins.

As the organoaluminum component at the time of prepolymerization, those generally known can be used.

As a specific example, Al (C ₂ H ₅ ) ₃ , Al (isoC ₄ H ₉ ) ₃ , Al
_{(C 5 H 13) 3,} Al (C 8 H 17) 3, Al (C 10 H 21) 3, Al (C 2
H ₅ ) ₂ Cl, Al (isoC ₄ H ₉ ) ₂ Cl, Al (C ₂ H ₅ ) ₂ , H, Al (isoC ₄ H ₉ ) ₂ H, Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ) Etc.

Of these, Al (C ₂ H ₅ ) ₃ and Al (isoC are preferable.
₄ H ₉ ) ₃ . It is also effective to use a combination of trialkylaluminum and alkylaluminum halide, a combination of trialkylaluminum, alkylaluminum halide and alkylamminium ethoxide.

Specific examples are: Al (C ₂ H ₅ ) ₃ Al (C ₂ H ₅ ) ₂ Cl
Combined use of (isoC ₄ H ₉ ) ₃ and Al (isoC ₄ H ₉ ) ₂ Cl, Al (C ₂ H ₅ ).
₃ and Al (C ₂ H ₅ ) _1.5 Cl _1.5 used together, Al (C ₂ H ₅ ) ₃ and Al (C ₂
A combination of H ₅ ) ₂ Cl and Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ) can be mentioned.

The amount of the organoaluminum component used during the prepolymerization is 1 to 2 in terms of Al / Ti (molar ratio) with respect to the Ti component in the solid component (A).
It is 0, preferably 2-10. In addition to these, known electron donors such as alcohols, esters and ketones can be added during the prepolymerization.

As olefins used during prepolymerization, ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
Penten-1 etc. are mentioned. It is also possible to make hydrogen coexist during the prepolymerization.

Thus, a prepolymerized component (i) is obtained by contacting a solid component containing titanium, magnesium and halogen as essential components with olefins in the presence of an organoaluminum compound.

The component (ii) to be contacted with the above component (i) for producing the component (A) of the sensuala used in the method of the present invention is represented by the general formula R ¹ R ² _3- nSi (OR ³ ) n (however, , R ¹ is a branched chain hydrocarbon group having 4 to 10 carbon atoms branched from a carbon atom adjacent to a silicon atom, and R ² is a branched or straight chain aliphatic hydrocarbon group having 1 to 10 carbon atoms. To
R ³ is a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms, and n is 1 ≦
a silicon compound represented by each of n ≦ 3).

Here, R ¹ is a branched chain hydrocarbon group having 4 to 10 carbon atoms, which is branched from the carbon atom adjacent to the silicon atom. In that case, the branching group is preferably an alkyl group, a cycloalkyl group or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group). More preferred R
¹ is a carbon atom adjacent to a silicon atom, that is, an α-position carbon atom is a secondary or tertiary carbon atom.

In particular, those having a tertiary carbon atom bonded to a silicon atom are preferable.

Specific examples of the silicon compound as the component (ii) are shown below.

_{(CH 3) 3 C-Si} (OCH 3) 3, (CH 3) 3 C-Si (OC 2 H 5) 3 etc.

The contact conditions of the above-mentioned component (i) (either prepolymerized or non-prepolymerized) and component (ii) may be arbitrary as long as the effect of the present invention is recognized,
Generally, the following conditions are preferred. The contact temperature is
It is about -50 to 200 ° C, preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring and crushing machine, a method of contacting by stirring in the presence of an inert diluent, and the like. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes. Whether the component (i) and the component (ii) are prepolymerized or not, the ratio of the amounts of the component (i) and the component (ii) is as follows.
The atomic ratio (silicon / titanium) of silicon of the component (ii) to the titanium component constituting the may be in the range of 0.01 to 1000,
It is preferably within the range of 0.1 to 100. The product obtained by contacting the components (i) and (ii) is washed with an inert solvent such as n-heptane and used as the catalyst component (A).

Component (B) Component (B) is an organoaluminum compound. Specific examples include R ⁵ _3- nAlXn or R ⁶ _3- mAl (OR) ⁷ m (wherein R ⁵ and R ⁶ may be the same or different and are a hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms). , R ⁷ is a hydrocarbon residue, X is halogen, and n and m are numbers 0 ≦ n <3 and 0 <m <3, respectively.). In particular,
(A) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethyl Alkyl aluminum halides such as aluminum dichloride, (ha) diethyl aluminum halide, diisobutyl aluminum halide, (d) diethyl aluminum ethoxide, and aluminum alkoxide such as diethyl aluminum phenoxide.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds such as R ⁸ _3- aAl (OR) ⁹ a (here, 1
≦ a ≦ 3, R ⁸ and R ⁹ are the same or different hydrocarbon residues having about 1 to 20 carbon atoms. It is also possible to use an alkylaluminium alkoxide represented by the formula (1) together. For example, combined use of triethylaluminum diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diexide, combined use of triethylaluminum, diethylaluminum ethoxide and diethylaluminum chloride. Can be given.

The amount of component (B) used is in the range of 0.1 to 1000, preferably 1 to 100, by weight ratio of component (B) / component (A).

(Polymerization) The polymerization step in the method of the present invention performed in the presence of the catalyst comprises at least two steps, step (1) and step (2), and step (1) and step (2) are carried out in this order. Is industrially advantageous.

Step (1): In the step (1), propylene alone or a propylene / ethylene mixture having an ethylene content of 5% by weight or less, preferably 0.5% by weight or less is fed to the polymerization system in which the catalyst is present, and the propylene / ethylene mixture is fed in one or more stages. This is a step of forming a polymer in an amount corresponding to 60 to 95% by weight of the polymerization amount.

When the ethylene content in the propylene / ethylene mixture exceeds the above-mentioned value in the step (1), the bulk density of the final copolymer is lowered and the amount of the low crystalline biopolymer by-product is greatly increased. Further, when the polymerization ratio is less than the above range, the same phenomenon occurs.

On the other hand, when the polymerization ratio exceeds the above range, the amount of by-products of the low crystalline polymer decreases, but the impact resistance, which is the object of the block copolymer, decreases, which is not preferable.

The polymerization temperature in step (1) is 30 to 90 ° C., preferably 50 to
80 ° C. The polymerization pressure is about 1 to 40 kg / cm ² .

It is preferred to use a molecular weight regulator in step (1) so that the flowability of the final polymer gives favorable results. Hydrogen can be mentioned as a preferable molecular weight regulator.

Step (2): In the step (2), after the step (1), a propylene / ethylene mixture having an ethylene content of 20 to 100% by weight is further introduced to make the total amount of the polymer 5 in one stage or in multiple stages.
Is a step of forming an amount of polymer corresponding to ˜40% by weight.

If the polymerization ratio in the step (2) is less than the above range, the impact resistance is poor, and if it exceeds the above range, the amount of the low crystalline polymer by-product is significantly increased, and the viscosity of the polymerization solvent is increased to improve the operation. Problems also arise.

In the step (2), another comonomer may coexist.
Specifically, α-olefins such as 1-butene, 1-pentene and 1-hexene can be exemplified.

In the step (2), the polymerization temperature is 30 to 90 ° C, preferably 50 to 80
℃. The polymerization pressure is about 1 to 40 kg / cm ² .

At the time of shifting from the step (1) to the step (2), it is preferable to purge the propylene gas or the propylene / ethylene mixed gas and the hydrogen gas and move to the next step.

The molecular weight modifier may be used in the step (2) depending on the purpose. That is, when the impact resistance of the final polymer is important, it is preferable to carry out in the substantial absence of a molecular weight modifier, while on the other hand, when importance is attached to transparency, gloss, whitening, etc. Is preferably carried out in the presence of

Polymerization method: The copolymer according to the present invention can be produced by a batch method, a continuous method, or a semi-batch method. At this time, a method of polymerizing in an inert hydrocarbon solvent such as heptane, a method of polymerizing the monomer itself used as a medium, a method of polymerizing with a gaseous monomer without using a medium, and further It is possible to employ a method in which the above are combined and polymerized.

Experimental Example Example A-1 [Production of Component (A)] 200 mL of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly replaced with nitrogen, and then MgC was added.
l ₂ of 0.4 cell and Ti (O-nC ₄ H ₉ ) ₄ of 0.8 mol were introduced, and 95
After reacting at ℃ for 2 hours, after the reaction is completed, cool to 40 ℃,
Then, 48 milliliters of methylhydropolysiloxane (20 centistokes) was introduced and the reaction was carried out at that temperature for 3 hours. After completion of the reaction, the reaction product was washed with n-heptane.

Next, 50 milliliters of n-heptane purified in the same manner as above was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.24 mol of the above product in terms of Mg atom was introduced. Next, 0.4 mol of SiCl ₄ was added to the flask at 30 ° C. for 30 minutes and reacted at 70 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane.

Furthermore, 0.02 mol of triethyl borate diluted with 25 milliliters of n-heptane was added to the flask at 70 ° C. for 30 minutes, and the reaction was further performed for 1 hour. After completion of the reaction, n-
Wash with heptane.

Furthermore, 0.016 mol of phthaloyl chloride was added to n-heptane 2
The product diluted with 5 milliliters was added to Fusco at 70 ° C. for 30 minutes, and the reaction was continued for 1 hour. After the reaction is completed, n
-Washed with heptane.

Finally, 0.5 gram of phosphorus pentachloride was added and reacted at 95 ° C for 6 hours.

The solid component (component (i)) thus obtained had a Ti-support rate of 1.80 weight percent.

N was dewatered and deoxygenated in a flask that had been thoroughly purged with nitrogen.
-Heptane (50 milliliters) was introduced, and 5 g of the component (i) obtained above and t-butylmethyldimethoxysilane were introduced as the component (ii) so that the atomic ratio Si / Ti = 6. Then, this was contacted at 30 ° C. for 2 hours.
After completion of contact, the catalyst component (A) was obtained by sufficiently washing with n-heptane.

[Copolymerization of propylene]

After fully replacing the inside of the stirring autoclave with an internal volume of 1.5 liters with propylene, 500 milliliters of sufficiently dehydrated and deoxygenated n-heptane was introduced, and further 30 milligrams of the above catalyst component (A), triethylaluminum (catalyst component (B)) 125 mg was introduced under a propylene atmosphere.

In the first stage polymerization, after introducing 220 milliliters of hydrogen, the temperature was raised to 75 ° C. and propylene was introduced at a constant rate of 0.932 g / min.

After 3 hours, the introduction of propylene was stopped and the polymerization was continued at 75 ° C. When the pressure reached 2 kg / cm ² gauge, 1/10 of the sample was taken and the gas phase was purged to 0.2 kg / cm ² gauge.

In the second stage polymerization, propylene was introduced at a constant rate of 0.0546 g / min and ethylene was introduced at a constant rate of 0.218 g / min at 60 ° C. for 1.5 hours.

After completion of the polymerization, the gas phase was purged, and the slurry was dried and dried to obtain 182.9 g of a polymer. On the other hand, the liquid was dried to obtain 2.79 g of a by-product low crystalline polymer. The MFR of the produced polymer was 2.19 g / 10 minutes, and the bulk density (BD) was 0.451 g / cc.

The MFR of the polymer obtained by drying the intermediate sample was 4.55 g / 10 minutes.

The polymer MFR (see JP-A-61-215613) produced in the second step estimated from the produced polymer and the intermediate sample was 8.7 × 10 ⁻³ g / 10 min.

Examples A-2, 3 and Comparative Examples A-1, 2 Example A- except that the silicon compound shown in Table A-1 was used as the component (ii) in the contact between the component (i) and the component (ii). In the same manner as in 1, the production of the catalyst component and the copolymerization of propylene were carried out.

The results are shown in Table A-1.

Example A-4 [Preparation of catalyst component (A)] 200 mL of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly replaced with nitrogen, and then MgC.
l ₂ of 0.1 mol and Ti (O-n-C ₄ H ₉ ) ₄ of 0.2 mol were introduced,
The reaction was carried out at 95 ° C for 2 hours. After the reaction was completed, the temperature was lowered to 40 ° C,
Then, 12 milliliters of methylhydropolysiloxane (20 centistokes) was introduced and the reaction was carried out for 3 hours.

Next, 25 milliliters of n-heptane purified in the same manner as above was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.03 mol of the above product was introduced in terms of Mg atom. Then, a mixture of 25 milliliters of n-heptane and 0.05 mol of SiCl ₄ was added to 3
The mixture was added to the flask at 0 ° C for 30 minutes and reacted at 70 ° C for 3 hours. After completion of the reaction, it was washed with n-heptane.

Further, a mixture of 25 milliliters of n-heptane and 0.003 mol of phthalic acid chloride was added to the flask at 30 ° C. for 30 minutes and reacted for 1 hour. After completion of the reaction, it was washed with n-heptane.

Finally, 25 ml of TiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After the reaction was completed, it was thoroughly washed with n-heptane.

The solid component (component (i)) thus obtained had a Ti-support ratio of 2.50 weight percent.

The catalyst component (A) was obtained by contacting the component (i) with the component (ii) in the same manner as in Example A-1 except that this component (i) was used.

[Copolymerization of propylene]

Copolymerization of propylene was carried out in the same manner as in Example A-1 except that the catalyst component (A) was changed to 24.4 mg.

The results are shown in Table A-2.

Example A-5 A catalyst component was produced in the same manner as in Example A-4 except that heptyl phthalate was used in place of phthaloyl chloride in the production of the catalyst component (i) of Example A-4, and propylene was further added. The copolymerization of

The results are shown in Table A-2.

Example A-6 [Manufacture of catalyst component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly replaced with nitrogen, and then MgC.
l ₂ of 0.4 mol and Ti (O-n-C ₄ H ₉ ) ₄ of 0.8 mol were introduced,
The reaction was carried out at 95 ° C for 2 hours. After the reaction was completed, the temperature was lowered to 35 ° C and 1,3,5,7-tetramethylcyclotetrasiloxane 60 was added.
Milliliter was introduced and reacted for 5 hours. After completion of the reaction, the reaction product was washed with n-heptane.

Next, 100 milliliters of n-heptane purified in the same manner as above was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.12 mol of the above product in terms of Mg atom was introduced. Next, 0.24 mol of SiCl was introduced into the flask at 20 ° C for 30 minutes and reacted at 50 ° C for 3 hours. After completion of the reaction, it was washed with n-heptane.

The solid component (component (i)) thus obtained had a Ti-support rate of 4.48% by weight.

The catalyst component (A) was obtained by contacting the component (i) with the component (ii) in the same manner as in Example A-1 except that this component (i) was used.

[Copolymerization of propylene]

In the copolymerization conditions of Example A-1, the first stage polymerization temperature
The procedure of Example A-1 was repeated except that the temperature was changed to 70 ° C., and the feed monomer alone was introduced at a constant rate of 0.273 g / min in the second stage polymerization.

The results are shown in Table A-2.

Example B-1 [Production of Component (A)] 200 mL of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly replaced with nitrogen, and then MgC was added.
l ₂ 0.4 _{moles, Ti (O-nC 4 H} 9) 4 was 0.8 mol introduction, 95
The reaction was carried out at 0 ° C for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced, and the reaction was carried out for 3 hours.
After completion of the reaction, the reaction product was washed with n-heptane.

Next, 50 milliliters of n-heptane purified in the same manner as above was introduced into a flask which had been sufficiently replaced with nitrogen, and 0.24 mol of the above product in terms of Mg atom was introduced. Then n-heptane
25 mol of LiCl was mixed with 0.4 mol of SiCl ₄ and the mixture was introduced into the flask at 30 ° C. for 30 minutes and reacted at 70 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane.

Further, 25 milliliters of n-heptane was mixed with 0.016 mol of phthalic acid chloride, and the mixture was introduced into the flask at 70 ° C for 30 minutes and reacted at 70 ° C for 1 hour. After completion of the reaction, it was washed with n-heptane.

Finally, 25 ml of TiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After the reaction was completed, it was thoroughly washed with n-heptane.

The Ti content of the solid component thus obtained was 2.58 weight percent.

To a stainless steel stirring tank having an internal volume of 1.5 liter and equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, 4.2 g of triethylaluminum, and 20 g of the solid component obtained above were introduced. The temperature in the stirring tank was adjusted to 20 ° C., propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes. After the completion of the polymerization, it was thoroughly washed with n-heptane [component (i)]. A portion was taken out and the amount of propylene polymerized was examined.
It was in grams.

50 milliliters of sufficiently dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly replaced with nitrogen, and then 5 g of the component (i) obtained above and t-butyltrimethoxysilane [component (ii)] were added. 0.82 milliliter (Si / t
i = 3 (atomic ratio)] and contacted at 30 ° C. for 30 minutes. After completion of the reaction, it was thoroughly washed with n-heptane to obtain a component (A).

(Propylene Copolymerization) After thoroughly replacing the inside of the stirring autoclave with an internal volume of 1.5 liters with propylene, it was thoroughly dehydrated and deoxygenated.
-Heptane (500 milliliters) was introduced, and further, 15 milligrams of the above component (A) and 125 milligrams of triethylaluminum [component (B)] were introduced at 75 ° C in a propylene atmosphere.

In the first stage polymerization, after adding 220 milliliters of hydrogen, propylene was introduced at a constant rate of 0.932 g / min at 75 ° C.

After 3 hours, the introduction of propylene was stopped and the polymerization was continued at 75 ° C. When the pressure reaches 2 kg / cm ² gauge, sample 1
/ 10 was collected and the gas phase was purged to 0.2 kg / cm ² gauge.

In the second-stage polymerization, propylene was introduced at a constant rate of 0.0546 g / min and ethylene was introduced at a constant rate of 0.218 g / min at 75 ° C. for 1.5 hours.

After completion of the polymerization, the gas phase was purged, and the slurry was dried and dried to obtain 164.7 g of a polymer. On the other hand, the filtrate was dried to obtain 1.61 g of a by-product low crystalline polymer (PAP). The MFR of the produced polymer was 2.32 g / 10 minutes, and the bulk density (BD) was 0.47 g / cc.

Also, by drying the intermediate sample, MFR8.72g / 10
Minutes of polymer was obtained.

The results are shown in B-1.

Examples B-2, 3 In the production of the component (A) of Example B-1, the component (ii)
Except that the silicon compound in Example 1 was changed as shown in Table B-1.
A catalyst component was produced in the same manner as in Example B-1, and each component thus obtained was subjected to copolymerization of propylene in the same manner as in Example B-1.

The results are shown in Table B-1.

Comparative Example B-1, 2 In the production of the component (A) of Example B-1, the component (ii)
A catalyst component was produced in the same manner as in Example B-1 except that the silicon compound shown in Table B-1 was used instead of the silicon compound of
Next, propylene was copolymerized in the same manner as in Example B-1 except that the first stage continuous polymerization was carried out for 90 minutes and the residual pressure was purged to 0.2 kg / cm ² gauge. The results are shown in Table B-1.

Example B-4 Same as Example B-1 except that 0.016 mol of diheptyl phthalate was used instead of phthalic acid chloride in the production of the solid catalyst component in the production of component (A) of Example B-1. Copolymerization of propylene was carried out in the same manner as in Example B-1 except that the catalyst component was produced and the catalyst component was used.

The results are shown in Table B-2.

Example B-5 In the production of the component (A) of Example B-1, 0.027 mol of cellocerve acetate was used in the production of the solid catalyst component, and in the polymerization of propylene, one-step continuous polymerization was carried out for 90 minutes, and the residual pressure was An experiment was conducted in the same manner as in Example B-1 except that the pressure was purged to 0.2 kg / cm ² gauge.

The results are shown in Table B-2.

Example B-6 [Production of Component (A)] n was dewatered and deoxygenated in a flask that had been sufficiently replaced with nitrogen.
-Introduce 200 milliliters of heptane, then add MgCl ₂ to 0.
4 mol, 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ was introduced, and 2 at 95 ℃
Reacted for hours. After the reaction was completed, the temperature was lowered to 35 ° C and 1,3,
60 milliliters of 5,7-tetramethylcyclotetrasiloxane was introduced and reacted for 5 hours. After completion of the reaction, the reaction product was washed with n-heptane.

Next, 100 milliliters of n-heptane purified in the same manner as above was introduced into a flask that had been sufficiently replaced with nitrogen, and 0.12 mol of the above product in terms of Mg atom was introduced. Then SiCl ₄ 0.24
Mols were introduced into the flask at 20 ° C. for 30 minutes and reacted at 50 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane.

The Ti content of the solid component thus obtained was 4.48% by weight.

In the apparatus for producing the catalyst component (i) used in Example B-1, 500 ml of fully dehydrated and deoxygenated n-heptane, 217 g of triisobutylaluminum,
20 grams of solid component were introduced. The temperature in the stirring tank was set to 15 ° C., propylene was introduced at a constant rate, and propylene was polymerized for 30 minutes. After the completion of the polymerization, it was thoroughly washed with n-heptane. A portion was taken out and the amount of propylene polymerized was examined.
It was in grams [component (i)].

A component (A) was produced in the same manner as in Example B-1 except that this component (i) was used and t-butylmethyldimethoxysilane was used as the component (ii) in a proportion of 0.75 ml / 5 g-component (i). did.

[Copolymerization of propylene]

Using the catalyst component (A) obtained above, the first stage polymerization temperature is 70
Copolymerization of propylene was carried out in the same manner as in Example B-1 except that the temperature was changed to ° C and that only the feed monomer was introduced at a constant rate of 0.273 g / min in the second stage polymerization.

The results are shown in Table B-2.

Examples B-7 to B-8 In the production of the component (A) of Example B-1, the component (ii)
The component (A) was produced in the same manner as in Example B-1, except that the silicon compound in Example 1 was used instead of the compound shown in Table B-3, and the catalyst component was used in Example B-1. Similarly, propylene was copolymerized.

The results are shown in Table B-3.

[Brief description of drawings]

FIG. 1 is intended to help the understanding of the technical content of the present invention regarding the Ziegler catalyst.

Claims (1)

[Claims] 1. A method for producing a propylene copolymer, which comprises carrying out the following steps in the presence of the following catalyst: Catalyst A catalyst comprising the following (A) and component (B), component (A) component (i): solid component containing titanium, magnesium and halogen as essential components, and component (ii): general formula R ¹ R ² _3- nSi (OR ³ ) n (However, R ¹ is a carbon atom branched from a carbon atom adjacent to a silicon atom and has 4 carbon atoms.
~ 10 branched chain hydrocarbon group, R ² is a branched or linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ³ is 1 to 10 carbon atoms.
A solid catalyst obtained by washing a product obtained by contacting a chain aliphatic hydrocarbon group of 4 with a silicon compound represented by the formula (n is a number of 1 ≦ n ≦ 3) with an inert solvent. Component, component (B) Organoaluminum compound, process Process comprising the following process (1) and process (2) to produce a propylene copolymer having a total ethylene content of 3 to 40% by weight, process (1) propylene alone Or a step of polymerizing a propylene / ethylene mixture having an ethylene content of 5% by weight or less in a single step or in multiple steps to form a polymer in an amount corresponding to 60 to 95% by weight of the total polymerization amount, step (2) ethylene content of 20 to A step of polymerizing a propylene / ethylene mixture corresponding to 100% by weight in a single stage or multiple stages.