JP2002121205A - Method for producing propylene-ethylene block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a propylene-ethylene block copolymer while reducing gels and fisheyes, without forming a polymer lamp and attached polymer, in a good state of fluidity. SOLUTION: This method for producing the propylene-ethylene block copolymer comprises continuously carrying out the first-stage and the second-stage polymerizations in the presence of a catalyst comprising the following components (A) and (B), and adding the following component (C) to the position higher than 50% of a fluidized bed for the second-stage polymerization, and a vapor phase-circulating system of the polymerization vessel so that the activity may become 0.3-0.95 time as much as that at the time when the component (C) is not added: (A) a solid catalyst component consisting essentially of Ti, Mg, a halogen and an electron donor; (B) an organoaluminum compound; (C) an electron donative compound; (1) the first-stage polymerization: a step for polymerizing propylene in liquid propylene or in a vapor phase state to provide a crystalline propylene polymer; and (2) the second stage polymerization: a step for polymerizing a mixture of the propylene and ethylene in a vapor phase state to provide a gummy copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a propylene-ethylene block copolymer.
More specifically, the present invention provides a continuous propylene-ethylene block copolymer by producing a crystalline polymer of propylene in the first stage polymerization and a rubbery copolymer of propylene and ethylene in the second stage polymerization. In the production, by adding an electron-donating compound at a specific ratio to the polymerization tank of the second tank first tank and the gas circulation line of the polymerization tank, with high rigidity and high impact resistance, A method for producing a propylene-ethylene block polymer capable of producing a propylene-ethylene block polymer in a state in which gels and fish eyes are reduced, the generation of a bulk polymer and an attached polymer is reduced, and there is no stickiness and good fluidity. It is about.

[0002]

2. Description of the Related Art Crystalline polypropylene has excellent rigidity and heat resistance, but has the problem of low impact strength, particularly at low temperatures. As a method for improving this point, a method for producing a block copolymer by stepwise polymerizing propylene with ethylene or another olefin is already known (for example, Japanese Patent Publication No.
No. 11230).

In the continuous polymerization method, the polymerization time (residence time in the polymerization tank) of the catalyst component is distributed in the first-stage polymerization tank, and the particles (short-path) discharged from the first-stage polymerization tank in a relatively short time. When the particles enter the second stage polymerization tank, particles having a high content of the propylene-ethylene copolymer are generated. Such particles do not disperse even by kneading,
It becomes a gel or fisheye, which causes the appearance of the product to deteriorate or the mechanical strength to decrease.

In order to increase the impact strength, it is effective to increase the proportion of the copolymer in the second stage. However, when the proportion of the copolymer is increased, ordinary particles which are not short-passed are not effective. However, it is easy to adhere to the polymerization tank wall, etc., and once deposited, the heat removal is insufficient, so that a lump polymer is generated, which may hinder the operation. In addition, the stickiness of the particles increases, and the fluidity of the generated powder deteriorates, which hinders extraction and transfer from the polymerization tank.

As a method for reducing the formation of gel / fish eyes due to such short-path particles and reducing the adhesion of particles having a high copolymer content, an electron-donating compound is added to the polymerization system of the second stage polymerization. There are known ways to do this.

[0006] The effect of the electron donating compound is estimated as follows. That is, the electron-donating compound selectively acts on the polymerization active sites relatively near the surface of the polymer particles to deactivate these active sites, but the short-pass particles have a small particle size and are easily deactivated completely. Therefore, the particles are usually selectively deactivated even in an added amount that does not completely deactivate the particles. In addition, since the active points on the surface of the ordinary particles are selectively deactivated, the copolymer is formed inside the particles, and even if the copolymer content is high, the increase in the adhesion of the surface is relatively suppressed.

The method of adding the electron-donating compound to the second-stage polymerization system may be roughly divided into a method in which the polymer formed in the first-stage polymerization tank is added during the transfer to the second-stage polymerization tank, There are two methods of adding to the polymerization tank itself.

[0008] In the former method, an electron-donating compound is added to a polymer transfer pipe from the first-stage polymerization tank to the second-stage polymerization tank. There is a method in which a separate reaction tank is provided and added to the reaction tank. In these methods, all particles come into contact with the electron-donating compound before being subjected to copolymerization in the second-stage polymerization tank, so the adhesion and gel reduction effects are large, but the deactivation effect is exhibited even in a relatively small amount. Therefore, there is a problem that it is difficult to control an appropriate addition amount without excessively reducing the activity in the second-stage polymerization tank.

For the purpose of adding the electron donating compound little by little, there is a method of adding the compound after diluting it with a solvent or the like which does not affect the catalytic activity. The diluent introduced into the second-stage polymerization tank together with the acidic compound accompanies the monomer recovery system and the product powder, and increases the load on the equipment, which is not preferable.

In the latter method, besides adding an electron-donating compound by providing a dedicated supply port in the second-stage polymerization tank, a method involving entrainment with a reagent such as hydrogen, a method involving entrainment with a circulating monomer, etc. is there. In these methods, it is relatively easy to control the amount of the electron-donating compound added in view of the activity in the second-stage polymerization tank, but the position at which the polymer is introduced from the first-stage polymerization tank and the electron-donating property Depending on the positional relationship with the supply point of the compound, particles that are insufficiently in contact with the electron-donating compound may be generated, and these may grow and generate adhesion or a bulk polymer. Increasing the amount of the electron-donating compound can suppress the adhesion and the formation of the bulk polymer, but at this time, the polymerization activity is sacrificed, and the required copolymer content cannot be obtained.

[0011]

SUMMARY OF THE INVENTION The present invention provides a propylene-ethylene block by producing a crystalline polymer of propylene in a first stage polymerization and a rubbery copolymer of propylene and ethylene in a second stage polymerization. When the copolymer is continuously manufactured, it has high rigidity and high impact strength, reduces gels and fish eyes, reduces the formation of bulk polymers and adherent polymers, and has good non-sticky fluidity. And a method for producing a propylene-ethylene block polymer.

[0012]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, when adding an electron-donating compound to the second-stage polymerization system, a second-stage first tank was added. The present inventors have found that the above problem can be solved by adding an electron-donating compound to both the polymerization vessel main body and the gas circulation line of the polymerization vessel, and have completed the present invention.

That is, in the present invention, the following first-stage polymerization and second-stage polymerization are continuously carried out in the presence of a catalyst comprising the following components (A) and (B) to form a propylene-ethylene block copolymer. In the method for producing a coalescence, the following component (C) is placed in both the position above 50% of the fluidized bed of the main body of the first polymerization tank in the second stage polymerization and the gas phase circulation system of the polymerization tank.
Wherein the amount of propylene is adjusted so that the activity of the second stage polymerization is 0.3 to 0.95 times that of the case where the component (C) is not added.
An object of the present invention is to provide a method for producing an ethylene block copolymer.

(A) Solid catalyst component containing titanium, magnesium, halogen and an electron donor as essential components (B) Organoaluminum compound (C) Electron-donating compound (1) First stage polymerization Propylene alone or propylene and ethylene A step of producing a crystalline propylene polymer by polymerizing the mixture in one or more polymerization tanks in liquid propylene or in a gaseous phase, (2) second-stage polymerization. A step of producing a rubbery copolymer by polymerizing in one or more polymerization tanks in the state.

The present invention also relates to a second stage, wherein the component (C) is placed in a position above 50% of the fluidized bed of the first polymerization vessel main body.
Where C _{1 is} the addition amount of C and C ₂ is the addition amount of component (C) to the gas circulation line of the second stage first polymerization tank, C ₁ and C ₂ satisfy the following formula (1). -To provide a method for producing an ethylene block copolymer.

0.05 ≦ C ₁ / (C ₁ + C ₂ ) ≦ 0.8 (1)

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a propylene-ethylene block copolymer in which a first stage polymerization and a second stage polymerization are continuously carried out in the presence of a catalyst comprising components (A) and (B). Is manufactured.

<Catalyst> Component (A) The component (A) used in the present invention is a solid catalyst component for stereoregular polymerization of α-olefin, which contains titanium, magnesium, halogen and an electron donor as essential components. It is.

Here, "containing as an essential component" means that besides the above-mentioned four components, other suitable elements may be contained, and each of these elements may be any compound suitable for the purpose. And that these elements may be present as being bonded to each other.

The solid components containing titanium, magnesium and halogen are known per se. For example, JP-A-53-45688, JP-A-54-3894, and JP-A-54-3894.
Nos. 31092, 54-39483, 54-945
No. 91, No. 54-118484, No. 54-13158
No. 9, No. 55-75411, No. 55-90510,
No. 55-90511, No. 55-127405, No. 5
5-147507, 55-155003, 56
-18609, 56-70005, 56-72
No. 001, No. 56-86905, No. 56-90807
Nos. 56-155206, 57-3803, 57-34103, 57-92007, 57-
No. 121003, No. 58-5309, No. 58-531
No. 0, No. 58-5311, No. 58-8706, No. 5
8-27732, 58-32604, 58-3
No. 2605, No. 58-67703, No. 58-1172
No. 06, No. 58-127708, No. 58-18370
No. 8, No. 58-183709, No. 59-149905
Nos. 59-149906 and 63-108008
Nos. 63-264607 and 63-264608
JP-A-1-79203, JP-A-1-98603, JP-A-7-258328, JP-A-8-269125, and JP-A-11-21
309 are used.

The magnesium compound used as a magnesium source in the present invention includes metal magnesium, magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, magnesium oxide, magnesium hydroxide. And magnesium carboxylate. Among these, Mg (OR ¹ ) _{2 -m} X _m such as magnesium dihalide and dialkoxy magnesium (where R ¹ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, and X is And m is 0 ≦ m ≦ 2).

Further, as a titanium compound serving as a titanium source,
Is represented by the general formula Ti (OR^Two)_4-nX_n(Where R^TwoIs hydrocarbon
A basic group, preferably having about 1 to 10 carbon atoms;
Represents a halogen, and p is 0 ≦ n ≦ 4. )
Compounds. As a specific example, TiCl_Four,
TiBr_Four, TiI_Four, Ti (OC_TwoH_Five) Cl_Three, Ti
(OC_TwoH_Five)_TwoCl_Two , Ti (OC_TwoH_Five)_ThreeCl, Ti
(OiC_ThreeH₇) Cl_Three, Ti (On-C_FourH₉) C
l_Three, Ti (On-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH _Five
 ) Br_Three, Ti (OC_TwoH_Five) (On-C)_FourH₉)_TwoC
1, Ti (On-C_FourH ₉ )_ThreeCl, Ti (OC
₆H_Five) Cl_Three , Ti (OiC_FourH₉)_TwoCl_Two, Ti
(OC_FiveH₁₁) Cl_Three, Ti (OC₆H₁₃) Cl_Three, Ti
(OC_TwoH_Five)_Four , Ti (On-C_ThreeH₇)_Four, Ti (O
-N-C_FourH₉)_Four , Ti (OiC_FourH₉)_Four, Ti
(On-C₆H₁₃)_Four, Ti (On-C₈H₁₇)_Four ,
Ti (OCH_TwoCH (C_TwoH_Five ) C_FourH₉)_FourEtc.
You.

Also, TiX '_Four(Where X 'is a halogen
It is. ) By reacting with an electron donor described later
The compound can also be used as a titanium source. like that
Specific examples of the molecular compound include TiCl_Four・ CH_ThreeCOC
_TwoH_Five, TiCl_Four・ CH_ThreeCO _Two C_TwoH_Five, TiCl_Four・ C
₆H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl, TiCl_Four・ C
₆H_FiveCOCl, TiCl_Four・ C₆H_FiveCO_TwoC_TwoH_Five, TiC
l_Four・ ClCOC_TwoH_Five, TiCl_Four・ C_FourH_FourO etc.
It is.

Also, TiCl ₃ (including TiCl ₄ reduced with hydrogen, reduced with aluminum metal, reduced with an organometallic compound, etc.), TiB
It is also possible to use titanium compounds such as r ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , dicyclopentadienyltitanium dichloride, and cyclopentadienyltitanium trichloride. Among these titanium compounds, TiC
_{l 4, Ti (OC 4 H} 9) 4, Ti (OC 2 H 5) Cl 3 are preferred.

The halogen is usually supplied from the above-mentioned magnesium and / or titanium halides, but other halogen sources such as AlCl ₃ , A
aluminum halides such as lBr ₃ and AlI ₃ , B
Halides of boron such as Cl ₃ , BBr ₃ , BI ₃ , S
silicon halides such as iCl _4, PCl ₃ , PCl ₅
, A tungsten halide such as WCl ₆ , and a molybdenum halide such as MoCl ₅ . Halogen contained in the catalyst component is fluorine, chlorine,
It may be bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

Examples of the electron donor include oxygen-containing electrons such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, and acid anhydrides. Examples include donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonic acid esters.

More specifically, (a) a compound having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol and isopropylbenzyl alcohol; Alcohols, (b) phenol, cresol, xylenol, ethyl phenol, propyl phenol, isopropyl phenol, nonyl phenol, naphthol, etc., which may have an alkyl group having 6 carbon atoms.
(C) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; (d) acetaldehyde, propionaldehyde;
C2 to C15 aldehydes such as octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl (fo) formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, propionic acid ethyl,
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,
γ-butyrolactone, α-valerolactone, coumarin,
Organic acid monoesters such as phthalide, or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2- Dimethyl carboxylate, cyclopropane-1,2-dicarboxylic acid-n-hexyl,
Organic acid esters having 2 to 20 carbon atoms of organic acid polyvalent esters such as diethyl 1,1-cyclobutanedicarboxylate; inorganic acid esters such as silicate esters such as (f) ethyl silicate and butyl silicate; (G) C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl isochloride; (T) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl Ether, tetrahydrofuran,
Anisole, diphenyl ether, 2,2-dimethyl-
1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2
-Isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl- 2-isopropyl-1,3
-Dimethoxypropane, 2,2-dicyclopentyl-
1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-
C2-C2 such as 1,3-diethoxypropane and 2,2-diisopropyl-1,3-diethoxypropane
0 ethers, (li) acetic acid amide, benzoic acid amide,
Acid amides such as toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, amines such as aniline, pyridine, picoline, tetramethylethylenediamine, (l) acetonitrile, benzonitrile, Nitriles such as tolunitrile, (ヲ) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl)
-Ethyl benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, 3-
Alkoxy ester compounds such as ethyl ethoxy-2-s-butylpropionate and ethyl 3-ethoxy-2-t-butylpropionate, (v) ethyl 2-benzoylbenzoate, 2- (4'-methylbenzoyl) benzoate Ketoester compounds such as ethyl acrylate, ethyl 2-benzoyl-4,5-dimethylbenzoate, (f) methyl benzenesulfonate, ethyl benzenesulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, p- -n- butyl toluenesulfonate, sulfonic acid esters such as p- toluenesulfonic acid -s- butyl, ^{_{(yo) R 3 p R 4 q Si}} (OR 5) r (OR 6) 4-pqr
(Where R ³ and R ⁴ are each a branched, cyclic or linear hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, and R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms. , R ⁶ is a hydrocarbon group having 1 to 4 carbon atoms, p,
q and r are respectively 1 ≦ p ≦ 2, 0 ≦ q ≦ 1, 0 ≦ r ≦ 2
And p + q + r ≦ 3. And the like.

As the solid catalyst component (A), the above-mentioned solid components may be used as they are, or solid catalyst components obtained by contacting with another electron donor may be used.

Two or more of these electron donors can be used. Of these, preferred are organic acid ester compounds, acid halide compounds, organic silicon compounds and ether compounds, and particularly preferred are phthalic acid diester compounds, acetic acid cellosolve ester compounds, phthalic acid dihalide compounds and diether compounds. The component (A) may be preliminarily polymerized before being subjected to polymerization, if necessary.

Component (B) Component (B) which can be used in the present invention is an organoaluminum compound. Specific examples, R ⁷ _3-s AlX s
Or R ⁸ _3-t Al (OR ⁹ ) t (where R ⁷ and R ⁸
Is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom,
R ⁹ is a hydrocarbon group, X is halogen, and s and t are 0 ≦ s <3 and 0 <t <3, respectively. ).

Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum; Alkyl aluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride; (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; (d) diethylaluminum ethoxide and diethylaluminum Examples thereof include alkylaluminum alkoxides such as phenoxide.

These organoaluminum compounds (a) to (d) may be replaced with another organometallic compound, for example, R ¹⁰ _3-u Al (O
R ¹¹ ) _u (where R ¹⁰ and R ¹¹ are the same or different and are a hydrocarbon group having 1 to 20 carbon atoms, and u is 0 <
u ≦ 3. ) May 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, triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride And the like.

The ratio of the organoaluminum compound component (B) to the titanium component in the solid catalyst component (A) is generally Al / Ti = 1 to 1000 mol / mol. / Ti = 10 to 500 mol / mol is used.

In addition to the components (A) and (B), an electron-donating compound can be used, if necessary, as a catalyst component.

Examples of such an electron donating compound include those which can be used as the electron donor in the component (A). When such an electron donating compound is used, it may be the same as or different from the compound in the component (A).

Preferred electron-donating compounds are ethers, inorganic acid esters, organic acid esters and organic acid halides, and organosilicon compounds, and particularly preferred are inorganic and organic silicate esters, phthalic acid esters, and cellosolo acetate. Butter and phthalic halides.

Preferred silicate esters are those represented by the general formula: R ¹² _v R ¹³ _w Si (OR ¹⁴ ) _4-vw (where R ¹² is a branched aliphatic carbon having 3 to 20, preferably 4 to 10 carbon atoms) Hydrogen residue, or 5 carbon atoms
20, preferably a cycloaliphatic hydrocarbon residue of 6 to 10, R ¹³ having 1 to 20 carbon atoms, preferably branched or linear aliphatic hydrocarbon residue 1 to 10, R ¹⁴ is a carbon Number 1
10 to 10, preferably 1 to 4 aliphatic hydrocarbon residues
Is an organic silicon compound represented by 0 ≦ v ≦ 3, and w is a number satisfying 0 ≦ w ≦ 3 and v + w ≦ 3). Preferably, R ^{12 in the} above general formula is branched from a carbon atom adjacent to a silicon atom.

Component (C) The electron donating compound to be added to the second stage polymerization is usually an organic compound containing oxygen, nitrogen, phosphorus or sulfur.

Specifically, alcohols, phenols, ketones, aldehydes, acetals, organic acids, acid anhydrides, acid halides, esters, ethers, amines, amides, nitriles, Phosphines,
Examples include phosphylamides, thioethers, thioesters, and organosilicon compounds containing a Si—O—C bond. More specifically, the following can be mentioned.

Alcohols: methanol, ethanol,
n-propyl alcohol, isopropyl alcohol, n
-Butyl alcohol, sec-butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, Isopropylbenzyl alcohol, ethylene glycol, diethylene glycol, 2,2-dimethyl-
1,3-propanediol, 2,2-diisopropyl-
1,3-propanediol, 2,2-diisobutyl-
1,3-propanediol, 2-isopropyl-2-isobutyl-1,3-propanediol, 2-isopropyl-2-s-butyl-1,3-propanediol, 2-
t-butyl-2-methyl-1,3-propanediol,
2-t-butyl-2-isopropyl-1,3-propanediol, 2,2-dicyclopentyl-1,3-propanediol, 2,2-dicyclohexyl-1,3-propanediol, 2,2-diphenyl- C1-C20 alcohols such as 1,3-propanediol, 2,2-dimethyl-1,3-propanediol and 2,2-diisopropyl-1,3-propanediol.

Phenols: phenol, cresol,
C6 to C25 phenols which may have an alkyl group, such as xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol.

Ketones: C1-C20 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone.

Aldehydes: C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.

Acetals: Acetals having 3 to 24 carbon atoms such as dimethyldimethoxymethane, 1,1-dimethoxycyclohexane, and 1,1-dimethoxycyclopentane.

Organic acids: having two or more carboxyl groups such as formic acid, acetic acid, propionic acid, valeric acid, caprylic acid, pivalic acid, acrylic acid, methacrylic acid, monochloroacetic acid, benzoic acid, maleic acid and phthalic acid Good carboxylic acids having 1 to 20 carbon atoms.

Acid anhydrides: Acid anhydrides derived from the above organic acids, including intramolecular condensates and heterogeneous condensates.

Acid halides: Acid halides in which the hydroxyl groups of the above organic acids have been substituted with chlorine, bromine and iodine atoms.

Esters: methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, methacrylic acid Methyl, dimethyl maleate,
Esters derived from the above alcohols and acids, such as methyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, methyl carbonate, and ethyl carbonate.

Ethers: dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl-t-butyl ether, anisole, vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, 1,1-dimethoxyethane, o-dimethoxy Benzene, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1 , 3-
Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2
-Methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3- Ethers derived from said alcohols or phenols, such as diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane.

Amines: C1 to C21 amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine.

Amides: Acetamide, Benzoamide,
Amides derived from the organic acids and the amines, such as toluic acid amide.

Nitriles: Nitriles having 2 to 10 carbon atoms, such as acetonitrile, benzonitrile and tolunitrile.

Phosphines: phosphines such as trimethylphosphine, triethylphosphine and triphenylphosphine.

Phosphylamides: phosphylamides such as hexamethylphosphyltriamide.

Thioethers: thioethers in which the oxygen atoms of the above ethers have been replaced by sulfur atoms.

Thioesters: Thioesters obtained by substituting an oxygen atom of the above esters with a sulfur atom.

Organosilicon compounds containing Si--O--C bonds: tetramethoxysilane, tetraethoxysilane,
Tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxylan, trimethylethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, γ-chloropropyltri Methoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxy Silane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxy ) Silane, vinyl triacetoxy silane, organic silicon compounds such as dimethyl tetraethoxy disiloxane. Of these, alcohols, ketones and esters are preferred, and particularly preferred are methanol, ethanol, isopropyl alcohol, acetone and methyl acetate.

These electron donating compounds may be used in combination of two or more as necessary. Further, different compounds may be added to the two addition positions.

Polymerization Step The polymerization step of the present invention comprises two stages, a first stage polymerization and a second stage polymerization. It is industrially advantageous to carry out the first stage polymerization and the second stage polymerization in this order (first stage → second stage).

First-stage polymerization In the first-stage polymerization, propylene alone or a mixture of propylene and ethylene is mixed with at least one component in the presence of component (A), component (B) and, if necessary, an electron-donating compound. In the polymerization tank to produce a crystalline propylene polymer. In the first stage polymerization, a propylene homopolymer or a propylene / ethylene copolymer having an ethylene content of 7% by weight or less is formed in an amount corresponding to 10 to 90% by weight of the total polymerization amount. When the ethylene content in the propylene / ethylene polymer exceeds 7% by weight in the first stage polymerization,
The bulk density of the final copolymer decreases, and the amount of by-products of the low crystalline polymer 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 first stage polymerization is 30 to 130 ° C., preferably 50 to 130 ° C.
重合 100 ° C., and the polymerization pressure is usually 0.1-5 MP
aG range. In the first stage polymerization, 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.

Second Stage Polymerization The second stage polymerization is a process for producing a rubbery polymer by polymerizing a mixture of propylene and ethylene in one or more polymerization tanks. In the second stage polymerization, the polymerization ratio (weight ratio) of propylene / ethylene is 90/10 to 10/90, preferably 80/20 to 20/80, and particularly preferably 70/10.
Produce a rubbery polymer of propylene in a ratio of 30-30 / 70. However, the polymerization amount in this step is 90 to 10% by weight of the total polymerization amount. In the second stage polymerization, other comonomers may coexist. For example, 1-butene,
Α-olefins such as 1-pentene, 1-hexene and 4-methyl-1-pentene can be used.

The polymerization temperature of the second stage polymerization is 30 to 110
° C, preferably about 50 to 90 ° C. The polymerization pressure is usually in the range of 0.1 to 5 MPaG. When moving from the first-stage polymerization to the second-stage polymerization, it is preferable to purge with propylene gas or a propylene / ethylene mixed gas and hydrogen gas before moving to the next step. In the second stage polymerization, a molecular weight regulator may or may not be used depending on the purpose.

Polymerization Mode The process for producing the copolymer according to the invention is carried out by a continuous process. That is, a part of the polymer generated in the first-stage polymerization is continuously extracted, added to the second-stage polymerization, and then the second-stage polymerization is performed.

The first-stage polymerization is carried out by a bulk polymerization method in which polymerization is carried out using propylene itself as a medium, or a gas phase polymerization method in which polymerization is carried out in a gaseous monomer without using a medium. carry out. The second stage polymerization is carried out by a gas phase polymerization method. A preferred polymerization mode of the gas phase polymerization method is, for example, a method of forming a fluidized bed by flowing the produced polymer particles with a monomer stream, or forming a fluidized bed by mechanically stirring the produced polymer particles in a polymerization tank with a stirrer. And so on.

The present invention relates to a method for adding the electron-donating compound of the component (C) to a position above 50% of the fluidized bed of the first polymerization tank main body in the second stage polymerization and to the polymerization tank. Characterized in that it is added to both of the gas circulation systems. The height of the fluidized bed is the height of the polymer particle phase flowing in the polymerization tank.

In one of the inventions of this patent, the addition amount of the component (C) to a position above 50% of the fluidized bed of the main body of the second stage first polymerization tank is C ₁ , and When the amount of component (C) to the gas circulation line of the polymerization vessel and C _2, C ₁ and C ₂ is characterized by satisfying the following formula (1).

0.05 ≦ C ₁ / (C ₁ + C ₂ ) ≦ 0.8 (1) If the value of the formula (1) is less than 0.05, the particles that the electron-donating compound cannot fully act on may be present. It does not provide a sufficient gel reduction effect or adhesion prevention effect. When the value of the formula (1) exceeds 0.8, the change in the activity with respect to the change in the added amount becomes large,
Operation control becomes difficult.

The amount of component (C) added is such that the activity of the second stage polymerization is 0.3 to 0.95 times, preferably 0.5 to 0.9 times, that of the case where no component is added. Adjust C ₁ + C ₂ .

Usually, the polymer transferred from the first stage polymerization is introduced into the polymerization tank from the upper part of the gas phase polymerization tank. For this reason, particles having high activity increase in the upper part. Also, as the flow in the polymerization tank progresses, the probability that large-diameter particles are present in the lower part of the polymerization tank and small-particle diameter particles are present in the upper part is increased. Since the particle size increases as the polymer grows, relatively ungrown particles, that is, particles having high activity, increase in the small particle size particles. For this reason, particles with high activity increase in the upper part of the gas phase polymerization tank, and if an electron-donating compound is added to this portion, it is possible to selectively inactivate small particles having high activity. It becomes possible.

[0070]

The following examples are provided to further illustrate the present invention. The present invention is not limited thereby without departing from the gist thereof.

Measurement of Physical Properties a. EPR content: Mitsubishi Chemical "CFC-T-102L"
Table 1 shows the results of the temperature-elution fractionation method using the temperature-elution fractionation apparatus.
The measurement was carried out under the conditions described in The EPR was an eluted component at 40 ° C. or lower.

[0072]

[Table 1]

B. Bulk density (ρB): JIS-K-67
21. c. Particle size distribution of polymer: Measured using a standard sieve of Mitamura Riken Co., Ltd., and the slope of the Rosin-Rammler plot was defined as the n-term, which was used as a measure of the particle size distribution. Fractions below 75μ were expressed as fines in% by weight. c. MFR: Measured according to JIS-K-6758. d. Ti content in polypropylene polymer: A pressed sheet having a thickness of 100 μm of the polypropylene was prepared, and a fluorescent X
It was quantified by linear analysis.

In the following examples, Me represents a methyl group, Et represents an ethyl group, Bu represents an n-butyl group, and P represents
h represents a phenyl group.

Example 1 (1) Production of solid catalyst component (A) In a 100 L autoclave equipped with a heating / cooling jacket, a stirrer, and a baffle, Mg (OEt) ₂ : 2
0 mol, and then Ti (OBu) ₄ was added to magnesium in the charged Mg (OEt) _2.
It was charged so that (OBu) ₄ /Mg=0.45 (molar ratio), and the temperature was increased while stirring at 165 rpm.

After reacting at 135 ° C. for 2.0 hours,
The temperature was lowered to 5 ° C., and a toluene solution of MeSi (OPh) ₃ was added to magnesium in Mg (OEt) ₂ , MeSi (OPh) ₃ /Mg=0.67 (molar ratio).
Was added so that After completion of the addition, the reaction was carried out at the same temperature for 4 hours. After the completion of the reaction, the temperature was lowered to 25 ° C. and Ti (OB
u) ₄ and Si (OEt) ₄ , and charged Mg (OEt) ₂
Ti (OBu) ₄ / Mg =
0.15 (molar ratio), Si (OEt) ₄ /Mg=0.0
5 (molar ratio) to obtain a slurry of the contact product (a ^* ).

Then, after diluting with toluene so that [Mg] = 0.53 mol / L · toluene, 165 r
While stirring at pm, the mixture was cooled to −10 ° C., and diethyl phthalate was added to magnesium in Mg (OEt) ₂ charged with diethyl phthalate / Mg = 0.10 (molar ratio).
Was added so that Subsequently, TiCl ₄ was added to magnesium in the charged Mg (OEt) ₂ ,
6.0 such that Cl ₄ /Mg=4.0 (molar ratio).
The solution was dropped over time to obtain a homogeneous solution. At this time, the phenomenon that the viscosity of the liquid increased and the liquid became gel-like did not occur.

The obtained homogeneous solution was heated at 20 ° C./Hr at 15 ° C.
And kept at the same temperature for 1 hour. Then again 2
The temperature was raised to 50 ° C. at 0 ° C./Hr and kept at 50 ° C. for 1 hour. Further, the temperature was raised to 117 ° C. at 120 ° C./Hr, and the treatment was performed at the same temperature for 1 hour. After the treatment, the heating / stirring was stopped, and the supernatant was removed.
The slurry was washed to 1/55 to obtain a solid slurry.

Next, the amount of toluene in the obtained solid slurry was adjusted so that the TiCl ₄ concentration was 1.5 mol / L · toluene, and TiCl ₄ was added at 25 ° C. in Mg (OEt) ₂ initially charged. Of magnesium, Ti
It was added so that Cl ₄ /Mg=5.0 (molar ratio). The temperature of the slurry was increased while stirring at 165 rpm, and the reaction was performed at 117 ° C. for 1 hour.

After the completion of the reaction, the heating and stirring were stopped, the supernatant was removed, and the residue was washed with toluene to a residual liquid ratio of 1/150 to obtain a toluene slurry (A ^* ). .

A part of the solid slurry obtained here was transferred to a reaction tank having an inner diameter of 660 mm and a straight body portion of 770 mm and having a three-way swept wing, diluted with n-hexane and adjusted to a concentration of 3 g (A ^* ). / L. While stirring this slurry at 300 rpm, triethylaluminum is converted into triethylaluminum / (A ^* ) = at 25 ° C.
3.44 mmol / g.
-Butylethyldimethoxysilane was added so that t-butylethyldimethoxysilane / (A ^* ) = 1.44 mmol / g. After completion of the addition, the mixture was kept at 25 ° C. for 30 minutes while continuously stirring.

Next, propylene gas was fed to the liquid phase at a constant speed over 72 minutes. After stopping the supply of the propylene gas, washing with n-hexane was performed by a sedimentation washing method to obtain a slurry of the solid catalyst component (A) at a residual liquid ratio of 1/12. The obtained solid catalyst component (A) is (A ^* )
Each gram of the component contained 2.9 g of a propylene polymer. (2) a propylene - ethylene as the block copolymer process illustrated in manufacturing drawing 2, stirred gas-phase polymerization vessel having an internal volume of 0.9m stirrer with liquid phase polymerization vessel 1 of ³ and 1.9m ³ 8 In the meantime, a propylene-based process is performed by a process incorporating a classification system consisting of a concentrator 3 (liquid cyclone) and a settling hydraulic classifier 4 and a degassing system consisting of a double-pipe heat exchanger 5 and a fluidized flash tank 6. Continuous production of an ethylene block copolymer was performed.

To the propylene polymerization tank 1, liquefied propylene was fed at 115 kg / Hr, and hydrogen was fed so that the hydrogen composition in the gas phase was 0.4 mol%. Also, triethylaluminum at 30.6 g / Hr, t
-Butyl-ethyldimethoxysilane was fed at 1.3 g / Hr. Further, the solid catalyst component obtained in Example 1 (1) was fed at 0.85 g / Hr as the (A ^* ) component.

The polymerization temperature was 70 ° C. and the pressure was 3.24M.
PaG and propylene partial pressure were adjusted to 2.76 MPaG, and the liquid volume in the polymerization tank was adjusted to 0.47 m ³ .

The slurry polymerized in the polymerization tank 1 had a slurry concentration of about 25% by weight, and was fed to the concentrator 3 using the slurry pump 2 at a volume flow rate of about 12 m ³ / Hr. From the upper part of the concentrator 3, a supernatant liquid containing almost no solid particles was taken out, and fed from the lower part of the hydrodynamic classifier 4 at a linear velocity of 4.1 cm / sec. On the other hand, the high-concentration slurry extracted from the lower part of the concentrator 3 was directly fed to the upper part of the hydraulic classifier 4 and brought into countercurrent contact with the supernatant.

Since the slurry extracted from the upper part of the liquid classifier 4 contains fine particles, the slurry is circulated to the original propylene polymerization tank 1, and from the lower part of the classifier 4, the slurry containing a large amount of large particles is discharged. Was extracted. The slurry concentration of the slurry was about 30% by weight. Further, the extraction rate of the slurry was adjusted to be 35 kg / Hr as the polypropylene particles contained in the slurry.

The average residence time of the polypropylene catalyst extracted from the lower part of the liquid classifier 4 in the propylene polymerization tank 1 and the circulation line is 1.8 hours, and the average particle diameter D
p50 was 620 μm and average catalyst efficiency was 41200 g / g. In addition, the value of this catalyst efficiency showed good agreement with the value of the catalyst efficiency obtained by measuring the Ti content of the polypropylene particles.

The slurry extracted from the lower part of the hydraulic classifier 4 was fed to the fluidized flash tank 6 through the countercurrent double tube heat exchanger 5. In the fluidized flash tank 6, the temperature inside the tank was maintained at 70 ° C. while feeding heated propylene gas from below. The solid polypropylene particles obtained here were sent to a gas-phase polymerization tank 8, where propylene and ethylene were copolymerized.

In order to enhance the mixing effect, a gas mixture of ethylene, propylene, hydrogen and nitrogen was circulated by a gas blower 10 in a gas phase polymerization tank 8 provided with an auxiliary stirring blade. Further, 14.6 g / Hr of ethanol as the component (C) was fed by using the pump 7, of which 4.6 g / Hr was placed at 70% of the height of the bed tank, and the remaining 10 g / Hr was supplied to the gas circulation system. Adjusted to feed to. Ethylene and propylene were fed so that the sum of the partial pressures of ethylene and propylene was 1.37 MPaG and the mole fraction of propylene was constant at 55 mol%. Hydrogen was fed so that the hydrogen concentration was 1.8 mol%. The polymerization temperature was 70 ° C., and the average residence time in the gas phase polymerization tank 8 was adjusted to 2.0 hours.

The polymer particles extracted from the gas-phase polymerization tank 8 were analyzed at several points to find that MFR = 22 ± 1.5 g / 10
min, bulk density = 0.45-0.46 g / cc, EP
The R content was 24 ± 1% by weight.

Under these conditions, the polymerization operation was continued for 10 days, but no fouling was observed in the upper part of the gas phase polymerization tank or the gas circulation line.

Example 2 (1) Production of Propylene-Ethylene Block Copolymer In the process shown in FIG. 2, 26 g / Hr of isopropyl alcohol was fed as the component (C) from the pump 7, and 6 g / Hr of the bed The remaining 20 g / Hr was adjusted so as to be fed to the gas circulation system at a position 80% of the height of the tank, and the average residence time in the gas phase polymerization tank 8 was adjusted to be 2.2 hours. Example 1
In the same manner as in (2), continuous production of a propylene-ethylene block copolymer was performed.

The polymer particles extracted from the gas-phase polymerization tank 8 were analyzed at several points to find that MFR = 20 ± 2 g / 10 mi
n, bulk density = 0.46-0.47 g / cc, EPR content = 25 ± 1% by weight.

After continuous operation for 10 days under these conditions, each part was opened, but no fouling was observed in the upper part of the gas phase polymerization tank and the circulation line.

Comparative Example 1 (1) Production of Propylene-Ethylene Block Copolymer In Example 1 (2), except that the ethanol feed from pump 7 was fed to the gas circulation system in the process shown in FIG. Similarly, continuous production of a propylene-ethylene block copolymer was carried out.

The polymer particles extracted from the gas-phase polymerization tank 8 were analyzed at several points to find that MFR = 20 ± 2 g / 10 mi
n, bulk density = 0.45 to 0.47 g / cc, EPR content = 25 ± 1% by weight.

After continuous operation for 10 days under these conditions, when each part was opened, fouling was observed in the upper part of the gas phase polymerization tank and the circulation line.

Comparative Example 2 (1) Production of Propylene-Ethylene Block Copolymer In the process shown in FIG. 2, the ethanol was not fed from pump 7, and the average residence time in gas phase polymerization tank 8 was 1.6 hours. A continuous production of a propylene-ethylene block copolymer was carried out in the same manner as in Example 1 (2), except that the above was used.

The polymer particles extracted from the gas-phase polymerization tank 8 were analyzed at several points to find that MFR = 20 ± 2 g / 10 mi
n, bulk density = 0.32 to 0.35 g / cc, EPR content = 25 ± 1% by weight.

After continuous operation for 10 days under these conditions, when each part was opened, fouling was observed in the vapor phase polymerization vessel main body, the upper part of the vapor phase polymerization vessel, and the circulation line.

[0101]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting understanding of the invention.

FIG. 2 is a flowchart showing a polymerization apparatus used in Examples.

[Explanation of symbols]

 1, liquid phase polymerization tank 3, concentrator 4, sedimentation liquid classifier 5, double tube heat exchanger 6, fluid flash tank 7, pump 8, stirred gas phase polymerization tank 10, 12 blower 14, fine cyclone

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Fumihisa Watanabe F-term (reference) 4J011 MA02 MA03 MA11 MA19 MB01 4J026 HA03 HA04 HA20 HA27 HA35 HA39 HB02 HB03 HB04 HB20 HB27 HB35 HB39 HB48 HE01 4J028 AA01A AB01A AC04A AC05A AC06A AC07A AC10A AC14A AC15A AC17A BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC24B BC27B CA08C CA14C CA15C CA17C CA18C CA19C CA20C CA22C CA25C CA52C CB23C CB24C CB25C CB27C CB29C CB35C CB36C CB43C CB44C CB45C CB49C CB52C CB53C CB54C CB57C CB58C CB59C CB63C CB64C CB66C CB68C CB81C CB83C CB87C CB90C CB91C CB92C EA02 EB02 EB04 EC01 EC02 ED01 ED02 ED03 ED04 ED05 ED09 EF02 FA04 4J128 AA01 AB01 AC04 AC05 AC06 AC07 AC10 AC14 AC15 AC17 AD00 BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC24B BC27B CA08C CA14C CA15C CA17C CA18C CA19C CA20C CA22C CA25C CA52C CB23C CB24C CB25C CB27C CB29C CB35C CB36C CB43C CB44C CB45C CB49C CB52C CB53C CB54C CB57C CB58C CB59C CB63C CB64C CB66C CB68C CB81C CB83C CB87C CB90C CB91C CB92C EA02 EB02 EB04 EC01 EC02 ED01 ED02 ED03 ED04 ED05 ED09 EF02 FA04

Claims (2)

[Claims] 1. A propylene-ethylene block copolymer is produced by continuously performing the following first stage polymerization and second stage polymerization in the presence of a catalyst comprising the following components (A) and (B): In the method, the following component (C) is added to both the position above 50% of the fluidized bed of the first polymerization vessel main body of the second stage polymerization and the gas phase circulation system of the polymerization vessel to carry out polymerization, A method for producing a propylene-ethylene block copolymer, characterized in that the addition amount is adjusted so that the activity of the second-stage polymerization is 0.3 to 0.95 times that when the component (C) is not added. (A) Solid catalyst component containing titanium, magnesium, halogen and an electron donor as essential components (B) Organoaluminum compound (C) Electron-donating compound (1) First-stage polymerization Propylene alone or a mixture of propylene and ethylene, A step of polymerizing in one or more polymerization tanks in liquid propylene or in a gaseous phase to produce a crystalline propylene polymer; (2) second-stage polymerization a mixture of propylene and ethylene A step of producing a rubbery copolymer by polymerizing in one or more polymerization tanks. 2. The addition amount of the component (C) to a position above 50% of the fluidized bed of the main body of the second stage first polymerization tank is C ₁ ,
When the amount of component (C) to the gas circulation line of the second stage the first polymerization vessel and C _2, propylene according to claim 1, C ₁ and C ₂ is to satisfy the following formula (1) - A method for producing an ethylene block copolymer. 0.05 ≦ C ₁ / (C ₁ + C
₂ ) ≦ 0.8 (1)