JP2834227B2 - Method for producing propylene block copolymer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION <Technical Field> The present invention relates to a propylene block copolymer having high rigidity, high impact strength and good flowability under a condition substantially free of a solvent, and It relates to a method of polymerizing with high activity.

<Prior Art> Crystalline polypropylene has excellent rigidity and heat resistance, but has a problem of low impact strength, particularly low-temperature impact strength.

As a method for improving this point, a method in which propylene and ethylene or other olefins are polymerized stepwise to form a block copolymer is already known (JP-B-43-11230, JP-B-44-16668, Japanese Patent Publication No. 44-20621
No., JP-B-49-24593, JP-B-49-30264, JP-A-48
-25781, JP-A-50-115296, JP-A-53-35789,
JP-A-54-110072, etc.).

However, when propylene and ethylene are polymerized in two or other stages, the impact resistance is improved,
Since the product contains a copolymerized portion, there is a problem that a low-crystalline polymer is by-produced in a large amount. In particular, the general method of increasing the generation rate of the rubbery copolymer to improve the impact strength of the block copolymer involves increasing the adhesiveness of the polymer particles as the rubbery copolymer is generated. Tend to. As a result, adhesion between polymer particles, adhesion to the inner wall of the apparatus, and the like occur, and stable long-term continuous operation is often difficult. In particular, when a solvent is not used, for example, in gas phase polymerization, deterioration of fluidity due to adhesion of polymer particles is a very serious problem in operation. Therefore,
There is a demand for the development of a technology capable of preventing the polymer particles from sticking when the production ratio of the rubbery copolymer is increased and increasing the operation stability.

Therefore, the present inventors have proposed a method of adding a specific compound at the time of polymerization of a rubbery copolymer to prevent the tackiness of the polymer particles and to increase the operation stability (Japanese Patent Application No. Sho 63). −
217299, Japanese Patent Application No. 63-229412, and Japanese Patent Application No. 63-262062).

However, the above-mentioned method also has problems such as a complicated catalyst system at the time of polymerization of the rubbery copolymer. Therefore,
There is a demand for the development of a technology capable of preventing the adhesiveness of the polymer particles without adding any compound during the polymerization of the rubbery copolymer and capable of stable operation.

[Summary of the Invention]

<Summary> As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using a specific catalyst, and have reached the present invention.

That is, the method for producing a propylene block copolymer according to the invention of the present invention uses a catalyst comprising a combination of the following catalyst components (A) and (B), and under the conditions substantially in the absence of a solvent, Carrying out the polymerization steps (1) and (2) to obtain a propylene block copolymer having a propylene rubbery copolymer (20 ° C. xylene solubles) content of 10 to 70% by weight. It is assumed that.

Catalyst Component (A) A catalyst product of the following components (A ₁ ) and (A ₂ ).

Component (A ₁ ) A contact product of the following components (i), (ii) and (iii).

Component (i): a solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components, Component (ii): general formula (However, R ¹ represents a branched hydrocarbon residue, R ² represents a hydrocarbon residue which is the same or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3. Component (iii): organoaluminum compound, component (A ₂ ) A silicon compound represented by the following general formula.

▲ R ⁴ _m ▼ Si (OR ⁵ ) _a X _4-ma (where R ⁴ is a hydrocarbon residue, R ⁵ is the same or different hydrocarbon residue as R ⁴ , X is halogen, m and a
Are 0 ≦ m <4 and 0 ≦ a <4, respectively, and 0 ≦ m + a
<Each number in the range of 4.) Component (B) Organoaluminum compound.

Polymerization Step (1) A step of polymerizing propylene or a propylene / ethylene mixture in one step or multiple steps to form a propylene homopolymer or a propylene / ethylene copolymer having an ethylene content of 7% by weight or less (the polymerization in this step). The amount is an amount corresponding to 10 to 90% by weight of the total polymerization amount).

(2) a step of polymerizing the propylene / ethylene mixture in one or more stages to obtain a propylene / ethylene copolymer having a polymerization ratio (weight ratio) of propylene / ethylene of 90/10 to 10/90 (provided that The polymerization amount in this step is
This is an amount corresponding to 90 to 10% by weight of the total polymerization amount).

<Effect> By producing a propylene block copolymer by a method using substantially no solvent with the catalyst according to the present invention, propylene having high activity, that is, high yield per catalyst, high rigidity and high impact strength can be obtained. The block copolymer can be manufactured stably.

Further, according to the present invention, even when the weight of the rubbery copolymer is increased (for example, 60% by weight), the adhesiveness of the polymer particles is small, and the trouble in the operation operation which has been conventionally regarded as a problem is solved. Can be solved.

Furthermore, when polymerization is carried out with the catalyst of the present invention, the catalyst activity during the polymerization of the rubber component (in the present invention, the polymerization step (2)) is high, and the activity persistence is good.

In many conventionally known catalyst systems, there is often a problem that the catalytic activity is reduced during polymerization of the rubber component, but the catalyst system of the present invention does not have the above-mentioned problems and is extremely industrially suitable. It is advantageous.

Furthermore, as an effect when using the catalyst of the present invention,
The polymer has good properties. For example, considering the polymer bulk specific gravity, in the present invention, 0.45 g / cc
The above is also possible.

[Specific description of the invention]

[I] Catalyst The catalyst according to the present invention comprises the following components (A) and (B)
Combination of Here, "consisting of a combination" means not only a combination of the listed components (ie, (A) and (B)) but also a combination of daily supplementary components. is there.

Component (A) Component (A) of the present invention is a contact product of component (A ₁ ) and component (A ₂ ).

Component (A ₁₎ component of the present invention (A ₁₎ is a catalyst products of component (i) ~ component (iii). Here, the term “contact product” refers to a contact product containing only the listed components (i.e., (i) to (iii)), as well as a contact product containing a suitable auxiliary component. Is what it means. Such auxiliary components include ethylenically unsaturated compounds (details below).

Component (i) Component (i) is a solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that in addition to the three components listed, other purposeful elements may be contained, and each of these elements exists as a purposeful arbitrary compound. And that these elements may be present as bonded to each other.

The Ziegler catalyst component itself containing titanium, magnesium and halogen is known. In the present invention,
Known solid components can be used.
For example, in the present invention, JP-A-53-45688 and JP-A-54-3894.
No. 54-31092, No. 54-39483, No. 54-94591,
No. 54-118484, No. 54-131589, No. 55-75411, No. 5
5-90510, 55-90511, 55-127405, 55-147
No. 507, No. 55-155003, No. 56-18609, No. 56-70005
No. 56-72001, No. 56-86905, No. 56-90807,
Nos. 56-155206, 57-3803, 57-34103, 57
No.-92007, No.57-12003, No.58-5309, No.58-131
Nos. 0, 58-5311, 58-8706, 58-27732,
58-32604, 58-32605, 58-67703, 58-1
No. 17206, No. 58-127708, No. 58-183708, No. 58-183
Nos. 709, 59-149905 and 59-149906 are used.

Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. Among these magnesium compounds, magnesium halide is preferred.

The titanium compound serving as a titanium source is represented by the general formula Ti (OR
⁶ ) _{4-n Xn} (where R ⁶ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms. X represents a halogen,
n shows the number of 0 <= n <= 4. )). Specific _{examples, TiCl 4, TiBr 4, Ti} (OC 2 H 5) C1 3, Ti (OC 2 H 5) 2 C1 2, Ti (OC 2 H 5) 3 C1, Ti (O-iC 3 H 7 _{) C1 3, Ti (O-} nC 4 H 9) C1 3, Ti (O-nC 4 H 9) 2 C1 2, Ti (OC 2 H 5) Br 3, Ti (OC 2 H 5) (OC 4 H _{9) 2 C1, Ti (O} -nC 4 H 9) 3 C1, Ti (OC 6 H 5) C1 3, Ti (O-iC 4 H 9) 2 C1 2, Ti (OC 5 H 11) C1 _{3, Ti (OC 6 H 13} ) C1 3, Ti (OC 2 H 5) 4, Ti (O-nC 3 H 7) 4, Ti (O-nC 4 H 9) 4, 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 ] _{4 and the} like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (where X ′ represents halogen) can also be used. Specific examples of such molecular _{compounds, TiCl 4 · CH 3 COC 2} H 5, TiCl 4 · CH 3 CO 2 C 2 H 5, TiCl 4 · CH 6 H 5 NO 2, TiCl 4 · CH 3 COCl, _{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 · C 4 H 4 O and the like.

Preferred among these titanium compounds are TiCl ₄ , Ti (OEt) ₄ , Ti (OBu) ₄ , Ti (OBu) Cl _{3 and the} like.

In addition, the general formula Ti (OR ⁷ ) _3-n X _n (where R ⁷ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms;
Represents a halogen, and n represents a number satisfying 0 <n ≦ 3). Specific examples include TiCl ₃ , T
iBr ₃ , Ti (OCH ₃ ) Cl ₂ , Ti (OC ₂ H ₅ ) Cl _{2 and the} like.

Furthermore, titanocene compounds such as dicyclopentadienyldichlorotitanium, dicyclopentadienyldimethyltitanium, and bisindenyldichlorotitanium can be used.

The halogen source is usually supplied from the above-mentioned halogen compounds of magnesium and / or titanium, but other halogen sources, for example, known halides such as aluminum halides, silicon halides, and phosphorus halides. It can also be supplied from a halogenating agent.

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

The solid component used in the present invention includes SiCl
₄ , silicon compounds such as CH ₃ SiCl ₃ , polymer silicon compounds such as methyl hydrogen polysiloxane, Al (OiC
_{3 H 7) 3, AlCl 3} , AlBr 3, Al (OC 2 H 5) 3, Al (OCH 3) 2 C
l and other aluminum compounds and B (OCH ₃ ) ₃ , B (CO ₂
Other components such as boron compounds such as H ₅ ) ₃ and B (OC ₆ H ₅ ) ₃ may be used, and these may remain in the solid components as components such as silicon, aluminum and boron.

Furthermore, in producing this solid component, an electron donor can be used as an internal donor.

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

More specifically, (a) a compound having 1 carbon atom such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol;
To 18 alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenol, nonyl phenol, naphthol, (c) acetone C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde Kind, (e)
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, 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, cellosolve benzoate, methyl toluate, Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valero C2-20 organic acid esters such as lactone, coumarin, phthalide and ethylene carbonate; (f) inorganic acid esters such as ethyl silicate, butyl silicate and silicate esters such as phenyltriethoxysilane; G) C2-C2 such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and phthaloyl isooxide;
15 acid halides, (C) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether;
(Ii) acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine,
Tribenzylamine, aniline, pyridine, picoline,
Amines such as tetramethylethylenediamine,
Examples thereof include nitriles such as acetonitrile, benzonitrile, and trinitrile. Two or more of these electron donors can be used. Among these, organic acid esters and acid halides are preferred, and phthalic acid esters, cellosolve acetate and phthalic halides are particularly preferred.

The use amount of each of the above components can be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The amount of the titanium compound used is preferably in the range of 1 × 10 ^{−4 to} 1000, and more preferably in the range of 0.01 to 10, in terms of a molar ratio to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio to the amount of magnesium used, regardless of whether or not the titanium compound and / or the magnesium compound contains halogen. ^It is preferably in the range of ^{-2 to} 1000, and more preferably in the range of 0.1 to 100.

The amount of silicon, aluminum and boron used is 1 × 10
The range is preferably from ^{-3 to} 100, and more preferably from 0.01 to 1.

The amount of the electron donating compound used is 1 × 10 ^-3 to 10
And preferably in the range of 0.01 to 5.

The component (i) is produced using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor, for example, by the following structural method.

(A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound.

(B) A method in which alumina or magnesium is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, and a titanium halide-containing compound are brought into contact therewith.

(C) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, a compound represented by the following formula is suitable.

(Where R represents a hydrocarbon residue having about 1 to 10 carbon atoms, and n represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes). Empolysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7 tetramethylcyclotetrasiloxane, 1,3,5,7,9 pentamethylcyclopentasiloxane, etc. Is preferred.

(D) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the solid component precipitated with a halogenating agent or a titanium halide compound is brought into contact with the titanium compound.

(E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, and the like, and then contacted with an electron donor and a titanium compound as necessary.

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

In this way, a Ziegler catalyst solid component (i) containing titanium, magnesium and halogen as essential components is obtained.

Component (ii) Component (ii) used to produce component (A) is:
General formula (However, R ¹ represents a branched hydrocarbon residue, R ² represents a hydrocarbon residue which is the same or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3. Respectively). It goes without saying that component (ii) may be a mixture of two or more compounds of the formula

Here, R ¹ is preferably branched from a carbon atom adjacent to a silicon atom. In this case, the branching group may be 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 ^one in which the carbon atom adjacent to the silicon atom, ie, the carbon atom at the α-position, is a secondary or tertiary carbon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. The carbon number of R ¹ is usually 3 to 20, preferably 4 to 10.

R ² is usually a branched or straight-chain aliphatic hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms. R ³ is usually an aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms.

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

(CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H _{5) 2, (C 2 H} 5) 3 CSi (CH 3) (OCH 3) 2, (CH 3) (C 2 H 5) CHSi (CH 3) (OCH 3) 2, ((CH 3) 2 CHCH _{2) 2 Si (OCH 3)} 2, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OCH 3) 2, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OC _{2 H 5) 2, (CH} 3) 3 CSi (OCH 3) 3, (CH 3) 3 CSi (OC 2 H 5) 3, (C 2 H 5) 3 CSi (OC 2 H 5) 3, (CH _{3) (C 2 H 5)} CHSi (OCH 3) 3, (C 2 H 5) (CH 3) 2 CSi (OCH 3) 3, (C 2 H 5) (CH 3) 2 CSi (OC 2 H 5 ) ₃ , Of these, preferred are those in which the carbon at the α-position of R ¹ is a secondary or tertiary C 3-20 branched chain hydrocarbon residue, particularly R ¹
Is a silicon compound having a tertiary carbon atom at the α-position and a branched chain hydrocarbon residue having 4 to 10 carbon atoms.

Component (iii) Component (iii) to constitute the solid catalyst component for the Ziegler-type catalyst is an organoaluminum compound.

Since it is an organoaluminum compound, this compound has at least one organic group-aluminum bond. In this case, the organic group may have about 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
About 6 hydrocarbyl groups are typical.

The remaining valence of aluminum (if any) of the organoaluminum compound which is filled with at least one organic group of valence is hydrogen atom, halogen atom, hydrocarbyloxy group (hydrocarbyl group has 1 carbon atom).
To about 10 and preferably about 1 to 6) or the aluminum via an oxygen atom (specifically, in the case of methylalumoxane, Others will be satisfied.

Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride And organoaluminum compounds such as methylaluminoxane. Further specific examples of organoaluminum compounds can be found in the examples of organoaluminum compounds described below as component (B).

Preparation of Solid Catalyst Component (A1) The contacting method and amount of components (i) to (iii) can be arbitrary as long as the effect is recognized, but the following conditions are generally preferred.

The amount ratio of the component (i) to the component (ii) is preferably in the range of 0.01 to 1000 in terms of the atomic ratio of silicon of the component (ii) to the titanium component constituting the component (i) (silicon / titanium), and is preferably It is in the range of 0.1-100. The quantitative ratio of the component (iii) to the component (i) is 0.01 to 100, preferably 0.1 to 30, in terms of the metal atom ratio (metal / titanium) of the organometallic compound.
Range.

The contact order and the number of contacts of the components (i) to (iii) are as follows:
Although there is no particular limitation, for example, the following method can be used.

(B) Component (i) → Component (ii) → Component (iii) (b) Component (i) → Component (iii) → Component (ii) (c) Component (i) → Component (ii) + Component ( iii)｝ → {Component (ii) + Component (iii)} (d) {Component (ii) + Component (iii)} → Component (i) (e) Component (i), (ii) and (iii) Simultaneous contact method (f) In the methods (a) to (d), a washing step is performed between each step. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C.
Degree. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like. At the time of these contacts, other components other than components (i) to (iii), such as methyl hydrogen polysiloxane, ethyl borate, aluminum triisopropoxide, and aluminum trichloride, as long as the effects of the present invention are not impaired. , Silicon tetrachloride, a tetravalent titanium compound, a trivalent titanium compound, and the like.

When preparing the component (A1) of the present invention, an ethylenically unsaturated compound such as an olefin or a diene compound may be used as an optional component. Specific examples of such ethylenically unsaturated compounds include ethylene, propylene,
-Butene, 2-butene, isobutylene, 1-pentene,
2-pentene, 2-methyl-1-butene, 3-methyl-
1-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene, 3- Methyl-2-pentene, 4-methyl-2-
Pentene, 2-ethyl-1-butene, 2,3-dimethyl-
1-butene, 3,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene,
-Decene, 1-undecene, 1-dodecane, 1-tridecane, 1-tetradecane, 1-pentadecane, 1-hexadecane, 1-heptadecane, 1-octadecane, 1-
Nonadecane, styrene, α-methyl-styrenedivinylbenzene, 1,2-butadiene, isoprene, hexadiene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,3- Pentadiene,
2,6-octadiene, cis-2, trans4-hexadiene, tr
ans2, trans4-hexadiene, 1,2-heptadiene, 1,4
-Heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene, 1,3-
Cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 1,3-butadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9 -Decadiene, 1,13-tetradecadineene and the like. These are usually polymerized when they are brought into contact with the component (A ₁ ) together with an organoaluminum compound, if necessary. Therefore, the component (A ₁ ) thus produced is said to have undergone the so-called prepolymerization. Will be.

These ethylenically unsaturated compounds are considered to polymerize during the preparation of the component (A ₁ ), so that the amount of the compound used is 0.01 to 100 times by weight, preferably 0.1 to 100 times the weight of the component (A ₁ ) before the use of the compound. ~ 10 times the weight.

Component (A ₂₎ component used in the present invention (A ₂₎ of the general formula R ▲ ⁴ _m below
▼ Si (OR ⁵ ) _a X _4-ma (where R ⁴ is a hydrocarbon residue and R ⁵
Represents a hydrocarbon residue which is the same as or different from R ⁴ , X represents a halogen, m and a each represent 0 ≦ m <4, 0 ≦ a <4
, Where 0 ≦ m + a <4 each represent a number).

R ⁴ and R ⁵ are each preferably a hydrocarbon residue having about 1 to 20 carbon atoms, and X is preferably chlorine from the viewpoint of economy.

Specific examples of such _{compounds, SiCl 4, SiBr 4, (} CH 3) SiCl 3, (CH 3) 2 SiCl 2, (C 2 H 5) SiCl 3, (n-C 3 H 7) SiCl 3 _{, (iC 3 H 7) 2} SiCl 2, (CH 3) 3 SiCl, (n-C 4 H 9) SiCl 3, (n-C 10 H 21) SiCl 3, Si (OCH 3) Cl 3, Si ( _{OCH 3) 2 Cl 2, Si} (OC 2 H 5) Cl 3, Si (OC 4 H 9) Cl 2, Si (OC 6 H 5) Cl 3, Si (OC 8 H 17) 2 Cl 2, (CH ₃ ) Si (OCH ₃ ) Cl ₂ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₄ H ₉ ) _{4 and the} like. Among them, preferred are SiCl ₄ , SiBr ₄ , (CH ₃ ) SiCl ₃ , (C ₂ H ₅ ) SiCl ₃ , and particularly preferred is SiCl ₄ .

Component (A ₁₎ and the contact of the component contact components (A ₂₎ (A ₁₎ and component (A ₂₎ is at any one as long as the effects of the present invention is observed, in general, the following There are such methods. The contact temperature is -50 to 20
It is about 0 ° C, preferably about 0 to 100 ° C. As a contacting method, it is general that the contact is carried out by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons.

The amount of the component (A ₂ ) used is in the range of 0.01 to 1000, preferably 0.1 to 100 as Si / Ti (molar ratio) with respect to the titanium component present in the component (A ₁ ).

Component (B) Component (B) is an organoaluminum compound.

As a specific example, Or (Where R ⁸ and R ⁹ are the same or different and may be a hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms, R ¹⁰ is a hydrocarbon residue having about 1 to 20 carbon atoms, X is a halogen , N, and m are numbers satisfying 0 ≦ n ≦ 3 and 0 <m <3, respectively). Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethyl Alkyl aluminum halides such as aluminum sesquichloride and ethyl aluminum dichloride; alkyl aluminum hydrides such as (c) diethyl aluminum hydride and diisobutyl aluminum hydride; and (d) aluminum alkoxides such as (a) diethyl aluminum ethoxide and diethyl aluminum phenoxide.

In addition to these organoaluminum compounds (a) to (d), organometallic compounds, for example, (Where 1 ≦ a ≦ 3, R ¹¹ and R ¹² are the same or different and are hydrocarbon residues having about 1 to 20 carbon atoms)
An alkylaluminum alkoxide represented by the formula (1) can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, and a combination of triethylaluminum and diethylaluminum ethoxide and diethylaluminum chloride can give.

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

(II) polymerization step The polymerization step of the present invention performed in the presence of the catalyst component,
It comprises at least two steps, step (1) and step (2). Although any of the steps (1) and (2) may be performed first, it is industrially advantageous to perform the steps in this order ((1) → (2)). Both steps are performed in the substantial absence of a solvent. In any case, in both steps, the subsequent step is carried out in the presence of at least a part of the product of the preceding step according to a conventional method for producing a block copolymer.

Formation of Catalyst The catalyst of the present invention is formed by bringing the catalyst components (A) and (B) into contact with each other, either temporarily or stepwise, inside or outside the polymerization system. A catalyst may be added in each step, and in particular, the latter step can be carried out by adding component (B).

Polymerization Step (1) In the polymerization step (1), propylene alone or a propylene / ethylene mixture is supplied to a polymerization system having the above-mentioned catalyst components (A) and (B), and polymerized in one or more stages to obtain a propylene single-sided polymer. 7% by weight containing coal or ethylene
Or less, preferably 0.5% by weight or less of the propylene / ethylene copolymer, 10 to 90% by weight of the total polymerization amount, preferably
This is a step of forming an amount corresponding to 20 to 80% by weight.

If the ethylene content in the propylene / ethylene copolymer exceeds 7% by weight in the polymerization step (1), the bulk density of the final copolymer decreases, and the amount of low-crystalline polymer by-produced greatly increases. On the other hand, when the polymerization ratio is less than the lower limit of the above range, the amount of by-product of the low crystalline polymer also increases.

The polymerization temperature in the polymerization step (1) is 30 to 95 ° C, preferably
The polymerization pressure is usually 1 to 50 kg / cm ² G.
Range. In the polymerization step (1), it is preferable to control the MFR using a molecular weight modifier such as hydrogen to increase the fluidity of the final copolymer during melting.

Polymerization Step (2) In the polymerization step (2), the propylene / ethylene mixture is polymerized in one or more stages, and the polymerization ratio (weight ratio) of propylene / ethylene is 90/10 to 10/90, preferably 70/30 to 90/90. Three
0/70, a step of obtaining a propylene / ethylene copolymer containing a propylene rubbery copolymer in a ratio of 0/70 (however, the polymerization amount in this step is 90 to 10% by weight of the total polymerization amount, preferably 80% -20% by weight).

In the polymerization step (2), other comonomers may coexist. For example, α-olefins such as 1-butene, 1-pentene, 1-hexene, and 4-methyl-pentene-1 can be used.

The polymerization temperature in the polymerization step (2) is 30 to 90 ° C., preferably
50-80 ° C. The polymerization pressure is usually in the range of 1 to 50 kg / cm ² G.

When the process proceeds from the polymerization step (1) to the polymerization step (2), it is preferable to purge the propylene gas or the propylene / ethylene mixed gas and the hydrogen gas and then proceed to the next step.

In the polymerization step (2), the molecular weight regulator may or may not be used depending on the purpose.

Polymerization Mode The production method of the copolymer according to the present invention is a batch type, a continuous type,
It can be carried out by any of the semi-batch methods. At this time, there are a method of performing polymerization using the monomer itself used as a medium, a method of performing polymerization in a gaseous monomer without using a medium, and a method of performing polymerization by combining these.

A preferred polymerization mode is a method in which polymerization is performed in a gaseous monomer without using a medium, for example, a method in which produced polymer particles are caused to flow by a monomer stream to form a fluidized bed, or the produced polymer particles are reacted with a stirrer in a reaction tank. In which stirring is performed.

[III] Produced propylene block copolymer A propylene copolymer to be produced by performing polymerization in the substantial absence of a solvent according to the present invention has a propylene rubbery copolymer content of 10 to 70% by weight, Preferably 20-70
%, Particularly preferably 35 to 60% by weight.
Here, the “rubber-like polymer of propylene” refers to a xylene-soluble component at 20 ° C.

The present invention is a method for producing a propylene block copolymer. However, the term "block copolymer" as used herein is not necessarily an ideal form, that is, a block in which the block generated in step (1) and the block generated in step (2) exist on one molecular chain. , Does not mean only,
It encompasses the physical mixture of polymers formed in each step as conventionally used and the various forms of polymers between this and the ideal block copolymers described above.

[Production of component (A ₁ )]

200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then MgCl ₂ was added thereto.
0.1 mol, Ti a _{(O-nC 4 H 9)} 4 was 0.2 mol introduced and reacted for 2 hours at 95 ° C.. After completion of the reaction, the temperature was lowered to 40 ° C., and then 12 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then, 0.05 ml of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 90 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane.

Subsequently, 0.003 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into a flask at 90 ° C. for 30 minutes, and reacted at 95 ° C. for 1 hour. After completion of the reaction, n-
Washed with heptane. Then, 0.7 g of WCl ₆ and 80 ml of heptane were introduced and reacted at 90 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane.
The titanium content in the resulting solid was 0.72 weight percent. This is used as a component (i) for producing a solid component (A ₁ ).
And

Next, in a flask sufficiently purged with nitrogen, fully purified n
-80 ml of heptane were introduced, 4 g of component (i) obtained above were added thereto, and then (C) as component (ii)
5.56 mmol of H ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , component (ii)
As i), 1.7 g of triethylaluminum was introduced and contacted at 30 ° C. for 2 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A ₁ ).

[Contact between Component (A ₁ ) and Component (A ₂ )] Into a flask sufficiently purged with nitrogen, 50 ml of sufficiently purified n-heptane was introduced, and 4 g of the component (A ₁ ) prepared above was added to the component (A). 1.98 g of SiCl ₄ was introduced as A ₂ ), and contact was made at Si / Ti (molar ratio) = 20 at 30 ° C. for 2 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Propylene copolymerization)

Propylene was copolymerized by a method disclosed in Japanese Patent Publication No. 61-33721 using a horizontal biaxial gas-phase polymerization tank having an internal volume of 13 liters.

After the inside of the polymerization tank was replaced with sufficiently purified nitrogen, 400 g of a sufficiently dehydrated and deoxygenated polymer carrier was added. Next, the component (B) triethyl aluminum 500
Milligram and 100 mg of the component (A) synthesized above were introduced. In the first polymerization step (1), after introducing 1000 ml of hydrogen, the temperature was raised to 75 ° C., and propylene was introduced at a constant rate of 1.3 g / min. The rotation speed of the polymerization tank was 350 rpm. Polymerization temperature 75
C. and the introduction of propylene was stopped after 2 hours and 56 minutes. The polymerization was continued at 75 ° C., and when the polymerization pressure reached 1 kg / cm ² G, a part of the polymerization sample was collected.

Then, of H ₂ was added 500 ml, was initiated polymerization step (2). The second-stage polymerization was performed at a constant rate of 0.59 g / min for propylene and 0.40 g / min for ethylene at 70 ° C.
For 2 hours and 33 minutes. The introduction of propylene and ethylene was stopped, and residual pressure polymerization was performed until the polymerization pressure reached 1 kg / cm ² G. After the completion of the polymerization, purging was performed to take out the polymer. 383 grams of polymer were obtained. MFR of formed polymer
Is 7.5 g / 10 min and the polymer bulk density (BD) is 0.44 (g
/ cc) and the polymer fall speed was 5.5 seconds. The weight of the rubbery copolymer was 40.5 weight percent.

The polymerization tank had no polymer adhesion, and the MFR of the intermediate sample was 17.3 g / 10 minutes.

The polymer falling speed means the time required for 50 grams of polymer to fall.

Example 2 [Production of Component (A)] The component (A ₁ ) was produced exactly in the same manner as in Example 1, and introduced into a flask in the same manner. Then, as component (A ₂ ), Si
3.85 g of (OC ₂ H ₅ ) ₂ Cl ₂ was added and contacted at 50 ° C. for 2 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Propylene copolymerization)

Under the polymerization conditions of Example 1, the polymerization time of the assembly step (1) was set to 3 hours and 10 minutes, and the polymerization of the polymerization step (2) was performed for 1 hour.
The polymerization was carried out in exactly the same manner, except that the time was changed to 50 minutes. 38
0 g of polymer were obtained, MFR = 7.3 g / 10 min, polymer BD = 0.40 (g / cc), polymer falling speed = 6.4
Seconds. The weight of the rubbery copolymer was 35.0% by weight.

In preparation of Example 3 [Production of Component (A)] [Component (A ₁₎ of Production] ingredients of Example ₁ (A 1), component (i),
Component (A ₁ ) was produced in exactly the same manner except that 4 g of divinylbenzene was added at the time of contact between component (ii) and component (iii).

(Propylene copolymerization)

Under the polymerization conditions of Example 1, the polymerization time of the polymerization step (1) was 2 hours and 42 minutes, and the polymerization time of the polymerization step (2) was 2 hours.
The polymerization was carried out in exactly the same manner, except that the time was changed to 52 minutes. 38
4 grams of polymer were obtained, MFR = 7.0 g / 10 min, polymer BD = 0.45 (g / cc), polymer drop rate = 5.4
Seconds. The weight of the rubbery copolymer was 44.8% by weight.

Example 4 Ingredient (A ₁₎ preparation of] the same manner as in Example 1, MgCl ₂ and _{Ti (O-nC 4 H 9} ) 4 and performs the reaction of methylhydropolysiloxane, the generated solid component n- heptane Washed.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then, 11.6 ml of SiCl ₄ was mixed with 25 ml of n-heptane and introduced into the flask at 30 ° C. for 30 minutes.
For 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Next, as the silicon compound of the component (ii), (C
2.4 ml of H ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was introduced,
Next, 6.0 g of triethylaluminum of the component (iii) was introduced, and the mixture was contacted at 30 ° C. for 2 hours. After contacting finished, thoroughly washed with n- heptane to obtain a component (A _1). The titanium content in the component (A ₁ ) was 3.15% by weight.

[Production of component (A)]

The component (A ₁ ) was introduced in the same manner as in Example 1, and 5.6 g of SiCl ₄ was added as the component (A ₂ ), followed by contact at 50 ° C. for 3 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane to obtain Component (A).

(Propylene copolymerization)

Under the polymerization conditions of Example 1, the polymerization time of the polymerization step (1) was 2 hours and 42 minutes, and the polymerization time of the polymerization step (2) was 2 hours.
The polymerization was carried out in exactly the same manner, except that the time was changed to 52 minutes. 38
4 grams of polymer were obtained, FMR = 7.7 g / 10 min, polymer BD = 0.43 (g / cc), polymer drop rate = 5.9
Seconds. The weight of the rubbery copolymer was 44.9% by weight.

In the production of ingredients of Example 1 [Production of Component (A)] Comparative Example 1 (A), without using the component (A _2), was used component (A ₁₎ as it is as the component (A).

(Propylene copolymerization)

Propylene was copolymerized in exactly the same manner as in Example 1. 383 grams of polymer were obtained, MFR = 7.9 / 10 minutes, polymer BD = 0.26 (g / cc), polymer drop rate = did not drop, and the weight of the rubbery copolymer was 40.3% by weight.

[Brief description of the drawings]

FIG. 1 is for helping to understand the technical contents of the present invention relating to the Ziegler catalyst.

Claims (1)

(57) [Claims] 1. The following polymerization steps (1) and (2) are carried out using a catalyst comprising a combination of the following catalyst components (A) and (B) under conditions substantially in the absence of a solvent: A process for producing a propylene block copolymer, wherein the weight of a rubbery copolymer of propylene (20 ° C. xylene-soluble component) is 10 to 70% by weight. . Catalyst Component (A) A contact product of the following components (A ₁ ) and (A ₂ ). Component (A ₁ ) A contact product of the following components (i), (ii) and (iii). Component (i): a solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components, Component (ii): general formula (However, R ¹ represents a branched hydrocarbon residue, R ² represents a hydrocarbon residue which is the same or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number of 1 ≦ n ≦ 3. Component (iii): organoaluminum compound, Component (A ₂ ) A silicon compound represented by the following general formula. ▲ R ⁴ _m ▼ Si (OR ⁵ ) _a X _4-ma (where R ⁴ is a hydrocarbon residue, R ⁵ is the same or different hydrocarbon residue as R ⁴ , X is halogen, m and a
Are 0 ≦ m <4 and 0 ≦ a <4, respectively, and 0 ≦ m + a
<Each number in the range of 4.) Component (B) Organoaluminum compound. Polymerization Step (1) A step of polymerizing propylene or a propylene / ethylene mixture in one step or multiple steps to form a propylene homopolymer or a propylene / ethylene copolymer having an ethylene content of 7% by weight or less (the polymerization in this step). The amount is an amount corresponding to 10 to 90% by weight of the total polymerization amount). (2) a step of polymerizing the propylene / ethylene mixture in one or more stages to obtain a propylene / ethylene copolymer having a polymerization ratio (weight ratio) of propylene / ethylene of 90/10 to 10/90 (provided that The polymerization amount in this step is
This is an amount corresponding to 90 to 10% by weight of the total polymerization amount).