JPH0350208A - Production of propylene/olefin block copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer having both high rigidity and high impact resistance under stable operating conditions by using a catalyst prepared by combining a specified preactivated catalyst component with an organoaluminum compound and an aromatic carboxylic acid ester. CONSTITUTION:A titanium trichloride composition is formed by the reaction of a solid product II, which is obtained by reacting titanium tetrachloride with either an organoaluminum compound A2 or a reaction product I thereof with an electron donor B1 and which is optionally treated by polymerizing an olefin, with an electron donor B2 and an electron acceptor. The obtained composition is combined with an organoaluminum compound A1 and is treated first by polymerizing 0.01-100g of a linear olefin per g of the composition and then by polymerizing 0.001-100g of a nonlinear olefin per g of the composition to prepare a pre-activated catalyst component. This component is optionally combined with an additional organoaluminum compound A1 and an aromatic carboxylic acid ester to constitute a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a propylene-olefin block copolymer. More specifically, we will develop propylene that has both high rigidity and high impact resistance using a specific preactivated catalyst.
This invention relates to a method for producing an olefin block copolymer.

[Conventional technology and its issues] Crystalline polypropylene has high rigidity, hardness, tensile strength,
Although it has heat resistance and the like, impact resistance is insufficient.

In general, rigidity, hardness, etc. and impact resistance of plastic materials are incompatible, and it is often extremely difficult to simultaneously improve the former and the latter.In order to expand the use of crystalline polypropylene, it is necessary to The resistance'ifI! It is desired to further improve not only the resistance but also the rigidity.

As a method to improve the impact resistance of polypropylene,
Following the homopolymerization of propylene, there is a method of block copolymerizing brobylene and an olefin other than propylene. However, while the block copolymer has significantly improved impact resistance compared to crystalline polypropylene,
The problem is that the rigidity decreases.

In order to improve the above-mentioned problems, a propylene-olefin block copolymer is produced using a catalyst that has been preactivated by polymerizing a small amount of a non-straight olefin such as 4,4-dimethylpentene-1 or allyltrimethylsilane. method (Japanese Patent Application Laid-Open No. 63-88.621,
However, when the present inventors produced a block copolymer according to the proposed method, not only did the polymerization activity decrease, but also the formation of lumpy polymers and polymerization This method cannot be used in industrial long-term continuous polymerization methods, especially gas phase polymerization methods, because it poses operational problems such as scale adhesion to vessel walls and poor controllability of the polymerization reaction.

Furthermore, when the obtained block copolymer was processed into a molded article, although a certain improvement was seen in the balance between rigidity and impact resistance, it was still insufficient and further improvement is desired.

On the other hand, the applicant has already produced a propylene-ethylene block copolymer having both high rigidity and impact resistance using a specific titanium trichloride composition, an organoaluminum compound, and a catalyst consisting of an aromatic carboxylic acid ester. (Japanese Patent Publication No. 62-4,402, hereinafter referred to as the "prior invention") has been proposed, but is it even more rigid and durable? rIlI
It is desired to improve the I property.

The present inventors solved the problems faced by the above-mentioned prior art and conducted extensive research into a method for producing a propylene-olefin block copolymer that has both high rigidity and high impact resistance superior to the prior invention. . As a result, when producing a propylene-olefin block copolymer using a combination of catalyst components similar to those used in the prior invention and a catalyst that has undergone a specific preactivation treatment, it is necessary to The inventors have discovered that the manufacturing and quality problems of the prior art can be solved, leading to the present invention.

As is clear from the above description, an object of the present invention is to provide a method for stably producing a propylene-olefin block copolymer having both high rigidity and high impact resistance without causing operational problems. be. Another object is to provide a propylene-olefin block copolymer that has both high rigidity and high impact resistance.

[Means to solve the problem] The present invention has the following configuration.

(1) [1] Copolymerization of propylene and olefins other than propylene using a catalyst consisting of titanium trichloride composition (III), ■organoaluminium compound (A1), and ■aromatic carboxylic acid ester (+:) In the method for producing a propylene-olefin block copolymer, the titanium trichloride composition (III) is an organoaluminum compound (A2) or an organoaluminum compound (
Solid product 1) obtained by reacting titanium tetrachloride with the reaction product (1) of A2) and electron donor (B1) is further subjected to electron polymerization treatment with or without polymerization treatment with olefin. Using a titanium trichloride composition (III) obtained by reacting a donor (B2) with an electron acceptor, the titanium trichloride composition (III) and an organoaluminum compound (A
), and [4] linear olefin is combined with the titanium trichloride composition (+11
) After polymerization reaction of 1 to 100 g of O,O per Ig,
Subsequently, (1) the non-linear olefin is added to the titanium trichloride composition (III);
'O,001g to 100g per Ig, by combining the preactivated catalyst component obtained by polymerization with an additional organoaluminum compound (A1) and an aromatic carboxylic acid ester (E) as necessary, and The molar ratio of the carboxylic acid ester (E) and the titanium trichloride composition (III) (based on the number of TI atoms, the same applies hereinafter) is (E)/(III) snow 0.1 to 10.0, and the organoaluminum compound (A
The molar ratio of 1) and the titanium trichloride composition (III) is (
Using a catalyst with A+)/(Tl!) = 0.1 to 200, 60% to 95% by weight of propylene of the total polymerization amount was polymerized in the first stage, and then total polymerization was performed in the second stage. 40% by weight of the amount ~ 5! ! Production of a propylene-olefin block copolymer characterized by copolymerizing % of propylene and an olefin other than propylene, so that the olefin content in the resulting block copolymer is 3% to 30% by weight. Law.

(2) The manufacturing method according to the above item 1, in which a dialkylaluminum monohalide is used as the organoaluminum compound (A1).

(3) As the organoaluminum compound (A2), the general formula is AIR'J"pjXs-+p*p'+ (in the formula, R1
, R2 represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an alkoxy group, X represents a halogen, and p and p'' represent any number in the range O<p+p'≦3.) The manufacturing method according to item 1 above, using an organoaluminum compound represented by:

(4) As a non-linear olefin, the following formula, CM, -C)I
-R' (wherein R3 represents a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms and optionally containing silicon and having a saturated cyclic structure of a hydrocarbon which may include silicon); The production method described in the above item "it" using the saturated ring-containing hydrocarbon carmer shown below.

(5) As a non-straight chain olefin, the following formula, S C) Iz-CH-R'-R6 7 (wherein, R4 is a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or RB, which represents silicon;
Re, R? represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, but R5, R6, R7
2. The production method according to item 1 above, wherein any one of the branched olefins may be hydrogen.

(In the formula, n is either 0.1, ■ is 1.2, and H
& represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R1+ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or halogen; , when l is 2, each 89 may be the same or different).

The configuration of the present invention will be explained in detail below.

The titanium trichloride composition (III) used in the present invention is produced as follows. First, an organic aluminum (A2) and an electron donor (B+) are reacted to obtain a reaction product (1), A solid product (II) obtained by reacting this (I) with titanium tetrachloride, or a solid product (II) obtained by reacting an organoaluminum compound (A2) with titanium tetrachloride (polymerization of The titanium trichloride composition (III) used in the present invention is obtained as the final solid product (III) obtained by further reacting the electron donor (B2) and the electron acceptor without any treatment or polymerization treatment.
is manufactured.

First, the reaction between the organoaluminum compound (A2) and the electron donor (B, ) to obtain the reaction product (I) is carried out in a solvent (D) at -20°C to 200°C, preferably -lθ°C to
Perform at 100°C for 30 seconds to 5 hours, (82), (B
1), (D) There are no restrictions on the order of addition, and the ratio of amounts used is 0.1 to 8 mol, preferably 1 to 4 mol, of the electron donor and 0.5 to 51 mol, preferably the solvent, per 1 mol of organic aluminum. A suitable value is 0.5 to 2 It. Aliphatic hydrocarbons are preferred as solvents.

In this way, reaction product (I) is obtained. Reaction product (1
) can be used in the next reaction as a liquid R (sometimes referred to as reaction product liquid (1)) without separation.

Next, the reaction between the reaction product (I) or the organoaluminum compound (A2) and titanium tetrachloride (C) is
Conducted at 0°C, preferably 10 to 90°C for 5 minutes to 8 hours.
Although it is preferable not to use a solvent, aliphatic or aromatic hydrocarbons can be used.

(A2) or (1), (C) and the solvent may be mixed in any order, and it is preferable that the mixing of the entire amount be completed within 5 hours.The amount of each used in the reaction is 1 titanium tetrachloride. per mole, the solvent is 0 to 3.000 raft
, the organoaluminum compound (A2) or the reaction product (1) has a ratio (Al/Ti) of the number of ^1 atoms in said (A,) or said (1) to the number of Ti atoms in titanium tetrachloride of 0. .05-10, preferably 0.06-0.3.

After the reaction is completed, the liquid part is separated and removed by filtration or decantation, and after repeated washing with the solvent, the obtained solid product (!■) is left suspended in the solvent for the first step. It may be used for this purpose, or it may be further dried and taken out as a solid substance for use.

It is also possible to polymerize the solid product (I) obtained by reacting this organoaluminum compound (A2) or reaction product (1) with titanium tetrachloride and use it in the next reaction. be.

In the present invention, "to polymerize" means to polymerize the solid product (II) by bringing a small amount of olefin into contact with the solid product (II) under polymerizable conditions. II) is coated with a polymer.

As a method for polymerizing with an olefin, (1) an olefin is added in any step of the reaction of the organoaluminum compound (A) or the reaction product (1) with titanium tetrachloride to form a solid product ( Method of polymerization treatment, (2) Organoaluminum compound (A2): f L/
< is after the reaction between the reaction product (1) and titanium tetrachloride,
A method of polymerizing the solid product (II) by adding an olefin; (3) After the reaction of the organoaluminum compound (A2) or the reaction product (1) with titanium tetrachloride, the liquid is separated by filtration or decantation. After separating and removing the parts, there is a method in which the obtained solid product (!) is suspended in a solvent, an organoaluminum compound and an olefin are further added, and polymerization is carried out.

Organoaluminum compound (A2) or reaction product (
When adding an olefin during any process of the reaction between 1) and titanium tetrachloride, and when adding an olefin after the reaction between the organoaluminum compound (A2) or the reaction product (I) and titanium tetrachloride, Reaction temperature 30-90'
e "q For 5 minutes to 10 hours, pass the olefin through at atmospheric pressure or add it to a pressure below 10 kg/crn"G.

The amount of olefin added is 100 g of solid product (!
For that, using 10 to 5,000 g of olefin, 0.
It is desirable to polymerize 05g to 1,000g.

After the polymerization treatment with olefin is completed, the reaction between the organoaluminum compound (A) or the reaction product (I) and titanium tetrachloride is completed, and the liquid portion is separated and removed by filtration or decantation, and the obtained solid product is If (II) is suspended in a solvent and then carried out, a solid product (u)
Add 100g of solvent to 10hjZ ~ 2000mJZ, organic aluminum compound 0.5g ~ s, 000g, reaction temperature 30 ~ 90 ° C. for 5 minutes ~ 10 hours, add 10 ~ 5,000g of olefin at O ~ 10kg/crrIIG. , it is desirable to combine 0.05 to 1,000 g.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as that used in (A2) or different. After the reaction, the liquid portion was separated and removed by filtration or decantation. After further repeated washing with a solvent, the resulting polymerized solid product (hereinafter sometimes referred to as solid product (II-A))
may be used in the next step while suspended in a solvent, or may be further dried and taken out as a solid for use.

The solid product (II-A) is then reacted with an electron donor (B2) and an electron acceptor (F). This reaction can be carried out without a solvent, but Preferable results are obtained using group hydrocarbons.The amount used is either solid product (!■) or (II-A)
For 100g, (Bz)O-1g to 1,000g,
Preferably 0.5g to 200g, (F)O, 1g to
1,000 g 1 preferably 0.2 g to 500 g, solvent 0 to 3.000 mλ, preferably 100 to 1,000 m
It is J2.

As for the reaction method, ■ solid product (+ or (n −
A method of simultaneously reacting an electron donor (B2) and an electron acceptor (F) with (II) or (II'-A)
) is reacted with (F) and then (B2) is reacted; ■(!ri or (II-A) is reacted with (B,) and then (F) is reacted; ■( B2) and (F)
There is a method of reacting (!ri) or (If -A) after reacting, but any method may be used.

The reaction conditions are 40°C to
It is desirable to react at 200°C, preferably 50°C to 100°C, for 30 seconds to 5 hours, and in method (2) (!
or (II-A) and (B2) at 0°C to 5°C.
After reacting at 0°C for 1 minute to 3 hours, (F) is
React under the same conditions as in ■. In addition, in the method of , The reaction is carried out under the same conditions as in (2) above. Solid product (II) or (II-A
), (Ih), and (F), the liquid portion is separated and removed by filtration or decantation, and washing with a solvent is repeated to obtain the titanium trichloride composition (III) used in the present invention. It will be done.

The organoaluminum compound (A2) used in the production of the titanium trichloride composition (III) used in the present invention includes:
Is the general formula ^lR'J'p? Xs−+p*pj”+ (in the formula 81, R2 represents a hydrocarbon group or alkoxy group represented by an alkyl group, cycloalkyl group, or aryl group, X represents a halogen, and p and p' represent O<p◆ An organoaluminum compound represented by ), representing any number with p°≦3, is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-butylaluminum, tri-n-hexylaluminum, tri-n-decylaluminum, tri-2-methylpentylaluminum, tri-n- Trialkylaluminums such as octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, cytobutylaluminum monochloride,
Dialkyl aluminum monohalides such as diethyl aluminum monofluoride, diethyl aluminum monobromide, and diethyl aluminum monoiodide; dialkyl aluminum halides such as diethyl aluminum hydride; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride and ethyl aluminum sesquichloride; , ethylaluminum dichloride, 1-butylaluminum dichloride, and other alkylaluminum dihalides. In addition, alkoxyalkylaluminums such as sonoethoxydiethylaluminum, jetoxy, and monoethylaluminum can also be used.

Two or more types of these organoaluminum compounds can also be used in combination.

As the electron donor used in the present invention, various ones are shown below, but it is preferable to mainly use ethers as (821) and to use nityls as other electron donors.

Those used as electron donors are organic compounds having any of oxygen, nitrogen, sulfur, and phosphorus atoms, that is,
Ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, sulfides Hydrogen, thioethers, thioalcohols, etc.

Specific examples include diethyl ether, moro-propyl ether, di-n-butyl ether, diisoamyl ether, moro-pentyl ether, moro-hexyl ether,
Diisoamyl ether, moro-octyl ether, diisoamyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, talesol,
Alcohols such as xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate,
Vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, anisic acid Esters such as propyl, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, acetaldehyde,
Aldehydes such as benzaldehyde, fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, Nitrilic acid such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, lysine, quinoline, α-picoline, 2,4.
6-trimethylpyridine, N,N.

Amines such as N',N'-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N,N.

Amides such as N', N', N-pentamethyl-No-β-dimethylaminomethylphosphate triamide and octamethylpyrophosphoramide, ureas such as N, N, N', N'-tetramethylurea, Isocyanates such as phenyl isocyanate and toluyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphine, etc. phosphites such as phite, monocutylphosphite, triethylphosphite, tri-n-butylphosphite, triphenylphosphite, ethyldiethylphosphinite, ethylditylphosphinite, phenyldiphenylphosphinite, etc. Other examples include phosphinites, thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used in combination1
The electron donor (B1) for obtaining the reaction product (I) and the (B1) with which the solid product (II-A) is reacted may be the same or different.

The electron acceptor (F) used in the present invention is I11 of the periodic table.
It is represented by halides of elements in group ~■.

Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, panazicum tetrachloride, and antimony pentachloride. Although these may be used as a mixture, titanium tetrachloride is most preferred.

Haggi is used as a solvent. Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, l-octane, etc. Carbon tetrachloride, chloroform Hydrogen halides such as , dichloroethane, trichloroethylene, and tetrachloroethylene can also be used.

As aromatic compounds, aromatic hydrocarbons such as naphthalene,
and its derivatives such as alkyl substituted products such as mesitylene, aniline, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and 1-phenylnaphthalene, and halogens such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene. Chemical substances, etc. are shown.

Olefins used in polymerization include ethylene,
Propylene, butene-1, pentene-1, hexene-1
, straight chain monoolefins such as heptene-1, and branched chain monoolefins such as 4-methyl-pentene-112-methyl-pentene-1. They can also be used in combination.

The titanium trichloride composition (ITI
) and an organoaluminum compound (A, ),
To this, a direct olefin is added to the titanium trichloride composition (
III) 0.01g to 100g per Ig of the titanium trichloride composition (III) After the polymerization reaction, a non-straight olefin is subsequently added to O.001g to 100g per Ig of the titanium trichloride composition (III).
The preactivated catalyst component subjected to the polymerization reaction is combined with an additional organoaluminium compound (A1) and an aromatic carboxylic acid ester as necessary to prepare a catalyst for use in the present invention.

In the first stage activation with a linear olefin, titanium trichloride composition (III) Ig, organoaluminum compound (AI) 0.005 g to 500 g, solvent 0 to 50 g
1. Hydrogen 0-1. OOOmj2, and linear olefin 0.01g~s, 000g, 0℃~100
At a temperature of ℃ and a pressure of atmospheric pressure to 50 kg/cm'G,
Titanium trichloride composition (III) I over a period of 1 minute to 10 hours
0.01 to 100 g of straight olefin per g is polymerized.

Titanium trichloride composition (III) Polymerization reaction amount per Ig is 0
．． If the amount is less than 100 g, the improvement in drivability and the rigidity and impact resistance of the resulting propylene-olefin block copolymer will be insufficient. It will be disadvantageous.

After the first stage preliminary activation is completed, the reaction mixture can be used as it is for the next second stage preactivation reaction. In addition, coexisting solvents, unreacted linear olefins, organoaluminum compounds (A, An additional organoaluminum compound (AI) may be added to this product for use in the second stage preactivation with a non-linear olefin.

In the second stage activation with a non-straight chain olefin, O per Ig of titanium trichloride composition (II) was used instead of the straight chain olefin under the same reaction conditions as the first stage activation.
001g~5. From 0.001g per Ig of titanium trichloride composition (III) using QOOg of non-direct olefin
It is desirable to polymerize 100 g, preferably 1 g to long O, O. If the polymerization reaction amount is less than 0.001 g, the rigidity and impact resistance of the resulting block copolymer will be insufficiently improved, and if it exceeds 100 g, there will be no effect. The improvement in performance becomes less noticeable and becomes economically disadvantageous.

For the first and second stage preactivation treatments, it is essential to first perform the preactivation treatment using the direct-quenching olefin and then perform the preactivation treatment using the non-directly-quenching olefin in accordance with the above-mentioned method. However, if the order of the pre-activation process is reversed, the effects of the present invention cannot be obtained.

In addition, after the completion of the second-stage preactivation treatment, a third-stage preactivation treatment using a linear olefin may be additionally performed in a reaction amount of 100 g or less per Ig of the titanium trichloride composition (Hl). It is possible.

Preactivation can also be performed in a hydrocarbon solvent such as n-pentane, n-hexane, n-hebutane, toluene, etc., and hydrogen may be present in the preactivation.

After the preactivation reaction is completed, the catalyst obtained by adding a predetermined amount of aromatic carboxylic acid ester (E) to the preactivated catalyst component slurry can be used as it is for the propylene-olefin block copolymer, or , removing the coexisting solvent, unreacted olefin, and organoaluminum compound (A) by filtration or decantation,
A solvent is added to the dried powder or the powder to create a suspended state, and this is combined with an additional organic aluminum compound (AI) and an aromatic carboxylic acid ester (E) to form a catalyst, and propylene - A method for subjecting to olefin block copolymerization, coexisting solvents, and unreacted olefins are evaporated by vacuum distillation or an inert gas stream, and the stems are removed, or a granular material is added to the granular material, or a solvent is added to the granular material. It can also be used in propylene-olefin block copolymerization by creating a suspended state, adding an organoaluminum compound (AI) to this as necessary, and further combining it with an aromatic carboxylic acid ester (E) to form a catalyst. It is.

During propylene-olefin block copolymerization,
The total amount of the above titanium trichloride composition (In), the organoaluminum compound (AI) including the additional organoaluminum compound (Al), and the aromatic carboxylic acid ester (E
), the aromatic carboxylic acid ester (
E) and the titanium trichloride composition (III) molar ratio (E
)/(III) is 0.1 to 10.0, and the organoaluminum compound (AI) and the titanium trichloride composition (III
) is used in a range where the molar ratio (A+)/H■) is 0.1 to 200.

If the amount of the aromatic carboxylic acid ester (E) is less than the above range, the isotuffity is insufficiently improved and high rigidity cannot be obtained, and if it is too much, the polymerization activity decreases and is not practical. The number of moles of the titanium trichloride composition (rn) refers to the number of Ti gram atoms actually contained in (III).

As the straight-set olefin used in the first stage preactivation treatment of the present invention, straight-set olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1, etc. are used, especially ethylene, Propylene is preferably used. These direct olefins are used in amounts of 1 fi or more.

The non-linear olefin used in the second stage preactivation treatment of the present invention has the following formula: CH2 snow CH-R' (wherein R3 has a saturated cyclic structure of a hydrocarbon that may contain silicon, (Representing a saturated ring hydrocarbon having 3 to 18 carbon atoms which may contain silicon,) represented by the following formula, (wherein R4 is the number of carbon atoms which may contain silicon) Represents a rectified hydrocarbon group of 1 to 3 carbon atoms or silicon, R1, 16 and R7 represent a rectified hydrocarbon group of 1 to 6 carbon atoms which may contain silicon, but R5, R11, R Any one of ? may be hydrogen.) Branched olefins represented by ■
The following formula, (wherein n is either 0.1 and m is 1.2, R6 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R9 is Represents a hydrocarbon group having 1 to 12 carbon atoms that may contain silicon, hydrogen, or halogen, and when ■ is 2, each Rg may be the same or different, an aromatic monomer represented by It is the body.

To be specific, examples of the saturated ring-containing hydrocarbon carmer (2) include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3- In addition to vinylcycloalkanes such as methylvinylcyclohexane, 4-methylvinylcyclohexane, and vinylcyclohebutane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane, cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, and cyclotetramethylene Vinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, Saturated ring hydrocarbon polymers having a silicon atom in the saturated ring structure such as cyclotetramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, cyclobutyldimethylvinylsilane, cyclopentyldimethyl Vinyl Cylil, Cyclopenyl Ethyl Ethyl Vinyl Cylil, Cyclopenyl Julbinyl Silan, Cyclohexylvinyl Silan, Cyljemethyl Vinyl Silan, Cyclohexyl Eettlumethyl Vinyl Silan, Cyclobicyl Jemethyl Lyluslan, Cyclopentiljiruslan, Cyclo Pennil Jillyl. Rohexylmethylluslan, to Cyclro, Kisirujemethylal Lylan, Cyclohexyleett Lemethylluslan,
Examples include saturated ring-containing hydrocarbon polymers containing silicon in addition to the saturated ring structure, such as cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, and 4-trimethylsilylallylcyclohexane.

Examples of the branched olefins (3) include 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
1st class 3-position branched olefin, 4-ethylhexene-1,
4-position branched chain olefin such as 4,4-dimethylpentene-1,4,4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethyl silane, alkenylsilanes such as allyltriethylsilane, allyltri-n-propylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane, dimethyldiallylsilane,
Examples include diallysilanes such as ethylmethyldiallylsilane and diethyldiallylsilane.

In addition, as the aromatic monomer (2), styrene, its flexible conductors O-methylstyrene, alkylstyrenes such as pt-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethyl Styrene, dialkylstyrenes such as 3,4-dimethylstyrene and 3,5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p
-Halogen-substituted styrenes such as fluorostyrene, p-
Trialkylsilylstyrenes such as trimethylsilylstyrene, m-triethylsilylstyrene, p-ethyldimethylsilylstyrene, allyltoluenes such as 0-allyltoluene and p-allyltoluene, 2-allyl-p-xylene, 4-allyl- 0-xylene, 5-allyl-1-
Allylxylenes such as xylene, alkenylphenylsilanes such as vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane, allylethylmethylphenylsilane, and 4-(o-tolyl)- Examples include butene-1 and l-vinylnaphthalene, and these non-straight olefins are 1fI or higher.

The organoaluminum compound (A1) combined with the titanium trichloride composition (II+') and the organoaluminum compound (A,) used as necessary have the general formula ^
A dialkylaluminum monohalide represented by IRIOnllx is preferred; in the formula, RIQ and R11 represent a hydrocarbon group or an alkoxy group such as an alkyl group, an aryl group, an alkaryl group, or a cycloalkyl group, and X represents a halogen; Examples include diethylaluminum monochloride, di-n-propylaluminum monochloride, dialkylaluminum monohalide, molo-
Examples include butylaluminum monochloride, diethylaluminum monoiodide, diethylaluminum monobromide, and the like.

Specific examples that can be used as the aromatic carboxylic acid ester (E), which is another component constituting the catalyst, include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate,
Methyl toluate, ethyl toluate, 2-toluate
Ethylhexyl, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate,
Methyl naphthoate, propyl naphthoate, naphthoic acid 2
-ethylhexyl, ethyl phenylacetate, etc.

The propylene-olefin block copolymerization of the present invention is carried out using a catalyst consisting of a combination of the thus obtained preactivated catalyst component and optionally an additional organoaluminum compound (A) and aromatic carboxylic acid ester (E). , polymerization of propylene is carried out as the first stage.

Usually, the polymerization temperature is 20-100°C, preferably 40-90°C.
It is 0°C. If the temperature is too low, the polymerization activity will be low and it is not practical, and if the temperature is too high, it will be difficult to increase isotafticity! i Polymerization is usually carried out at a pressure of normal pressure to 50 kg/cm2G for about 30 minutes to 15 hours. During the first polymerization, steps such as adding an appropriate amount of hydrogen to adjust the molecular weight are the same as in conventional polymerization methods.

The block copolymerization of propylene and olefin of the present invention can be carried out, for example, by slurry polymerization carried out in an inert solvent such as n-hexane or n-hebutane, bulk polymerization carried out in liquefied propylene, or gas phase polymerization carried out in gaseous propylene. It is possible to carry out the polymerization by any type of polymerization, and it is also possible to carry out a combination of these types.

In the first stage propylene polymerization, as long as the final propylene-olefin block copolymer can maintain high rigidity, for example, 5% by weight or less of ethylene,
Olefins such as butene-1 or 4-methylpentene-1 can be used in combination with propylene.

However, in order to maintain high rigidity of the propylene-olefin block copolymer obtained by the method of the present invention, homopolymerization of propylene is desirable and easy to carry out.

In addition, due to the balance between rigidity and impact resistance of the obtained block copolymer, in the first stage polymerization, the total polymer amount (note, excluding the soluble polymer extracted in the solvent) is 60 to 90% by weight.
Polymerize 5% by weight of propylene. This first stage polymerization can also be carried out in multiple stages.

Following the first stage polymerization, the first stage polymerization mixture is used to copolymerize propylene and an olefin other than propylene in the second stage under polymerization conditions within the same range as the first stage. The ranges of 0 mm humidity temperature, polymerization pressure and polymerization time in 1 stage or multiple stages are the same as in the case of the first stage described above.

Note that one stage of polymerization means one break in the continuous or temporary supply of monomers. In this second stage copolymerization, propylene and an olefin other than propylene are copolymerized in an amount of 403 to 5% by weight based on the total polymer amount.

However, the olefin content in the finally obtained block copolymer (note, excluding the soluble polymer eluted in the solvent) must be within the range of 3% to 30% by weight. When only 60% by weight of propylene is polymerized visually, the amount of olefin copolymerized in the second stage is 3.
Since it is limited to 0% by weight or less, in that case, the remaining 1%
For amounts above 0% by weight, propylene must be copolymerized.

Specific examples of olefins other than propylene used in combination with propylene in the second stage described above include straight-chain monoolefins such as ethylene, butene-11pentene-11hexene-1, and heptene-11octene-1. Class, 4
-methyl-pentene-1,2-methyl-pentene-1,
Examples include branched monoolefins such as 3-methylbutene-1 and styrene, and one or more of these may be used.

Thus, the propylene-olefin block copolymer dipolymer obtained by the method of the present invention is a propylene-olefin block copolymer having high rigidity and high impact resistance, and can be processed by known injection molding, vacuum forming, or extrusion. It is provided as various molded products using techniques such as molding and blow molding.

[Function] In the conventional method using a catalyst that has been preactivated only with a non-straight olefin, the catalyst component during preactivation is ultra-finely pulverized or swollen during the reaction of the non-straight olefin. The shape will deteriorate significantly. Therefore, when the preactivated catalyst component is dried before being used in block copolymerization, it solidifies into lumps during drying.
If a lumpy polymer is produced, or if the preactivated catalyst component is used in a slurry state for block copolymerization, it may cause operational problems such as runaway polymerization and scale adhesion to the reactor wall. As a result, the obtained block copolymer also had insufficient improvement in the balance of rigidity and impact resistance.

In contrast to the above conventional techniques, the two-stage preactivation treatment according to the present invention provides a firm preactivated catalyst that has a good shape and is less likely to be crushed by the first stage preactivation treatment using a directly-quenched olefin. By forming these components, it maintains its good shape even during the second stage pre-activation treatment with a non-straight olefin. Therefore, when the preactivated catalyst component is used in block copolymerization, stable and continuous polymerization operation is possible regardless of drying conditions.

In addition, as a result of stable polymerization operation, the propylene obtained
The quality of the olefin block copolymer is also stable, and the straight chain olefin polymer block of the straight chain olefin-non-linear olefin block copolymer produced by the two-stage preactivation treatment is a propylene-olefin block copolymer. As a result, the dispersibility of the non-linear olefin polymer block in the propylene-olefin block copolymer is highly improved, so the nucleation effect of the non-linear olefin polymer block is significantly exhibited. It is presumed that the rigidity and fim resistance are improved.

Furthermore, although the detailed mechanism is unknown, the propylene-olefin block copolymer obtained by the method of the present invention is due to the high rigidity polymer production ability possessed by the catalyst combined with a predetermined amount of aromatic carboxylic acid ester. Combined with the effect of the two-stage pre-activation process described above, this results in a product that has both high rigidity and high impact resistance.

[Example] The present invention will be explained below with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.

(1) MFR: Melt flow rate JIS 721O
According to condition 14 in Table 1. (j# position: glxo minute) (2)
Olefin content: Based on infrared absorption spectroscopy.

(3) Tetrakis[methylene-3-(3°, 5°-di-t-
Butyl-4°-hydroxyphenyl)propionate cometa 20.1 parts by weight, and calcium stearate 0
．． 1 part by weight, and the mixture was passed through a screw with a diameter of 40@
It was granulated using an extrusion granulator. Then, the granules were molded using an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C.
An IS-type test piece was prepared, and the test piece was left in a room with a humidity of 50% and a room temperature of 23° C. for 88 hours, and then its flexural modulus was measured in accordance with JIS 7203.

(II: kgf/crn'') (4) Impact resistance: ■Izot impact strength: A test piece was prepared in the same manner as in (3), and the izod impact strength was measured in accordance with JIS 7110.

(Unit: kgf·cm/cm) ■ DuPont impact strength: A test piece was prepared in the same manner as in (3), and the DuPont impact strength was measured by the following method.

Pen lead with tip roundness (R) of 0.25 inches, inner diameter of the lead holder 1.5 inches, load drop height 1 m, load 1100
Using a DuPont impact tester consisting of ~5,000 g, a load was dropped from a height of 1 m at a temperature of -20°C,
The load at which 50% of the test piece cracked was determined, and the load was multiplied by the falling height (100 cm) to determine the 'fI impact strength. (Unit: kgf-c■
) Example 1 (1) Preparation of titanium trichloride composition (III) n-hexane 6J2, diethylaluminium monochloride (D
EAC) 5.0 mol and diisoamyl ether 12 mol were mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (■) (diisoamyl ether/DEAC molar ratio 2.4). Ta. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35°C, and the entire amount of the reaction product solution (I) was added dropwise over 30 minutes, kept at the same temperature for 30 minutes, and heated to 75°C. Raise the temperature and react for an additional hour.
The operation of cooling to room temperature, removing the supernatant, adding 201 g of n-hexane, and removing the supernatant by decantation was repeated four times to obtain 1.9 g of solid product (II).

The entire amount of this (!■) was suspended in n-hexane 30J2, 200 g of diethylaluminium monochloride was added, and the mixture was heated at 30°C with 1.5 g of propylene. OKg was added and reacted for 1 hour to obtain a polymerized solid product (II-A) (propylene reaction amount: 0.6g).

After the reaction, after removing the supernatant liquid, adding 30 IL of n-hexane and removing by decantation was repeated twice to obtain a solid product (II-A) subjected to the above polymerization treatment.
Kg was suspended in 62 n-hexane, 8 was added to 3.5 titanium tetrachloride at room temperature for about 1 minute, and the mixture was heated to 80°C for 30
After reacting for a minute, 1.6 g of diisoamyl ether was further added and reacted at 80° C. for 1 hour.

After the reaction was completed, the supernatant was removed by decantation, and then
N-hexane No. 01 was added thereto, stirred for 10 minutes, allowed to stand, and the supernatant liquid removed. The procedure was repeated five times, followed by drying under reduced pressure to obtain a titanium trichloride composition (III). The titanium content in 1 g of titanium trichloride composition (III) was 192 mg.

(2) Preparation of preactivated catalyst components After purging a stainless steel reactor with an internal volume of 1 sojt equipped with an inclined impeller stirrer with nitrogen gas, 1
00ft, diethyl aluminum monochloride 260
g, and the titanium trichloride composition (II
I) 1.8 g was added at room temperature. Next, the temperature inside the reactor was raised to 40°C, 2.4 g of propylene was added, and the temperature was raised to 40°C.
The first preactivation treatment was carried out for 1 hour at (1.0 g of proprene reacted per Ig of titanium trichloride composition (III)).

After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 801 n-hexane. Subsequently, after adding 100 JZ of n-hexane and 260 g of diethylaluminium monochloride, the temperature inside the reactor was raised to 40°C, and 2.8 g of vinylcyclohexane was added.
A second stage preactivation treatment was performed at 40° C. for 2 hours. (
1.0 g of vinylcyclohexane per tg of titanium trichloride composition (III) (reaction) After completion of the reaction, the mixture was washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Production of block copolymer
After charging 30 kg of polypropylene powder with an MFR of 30 to a D@4 horizontal first-stage polymerization vessel, n-hexane was added to the preactivated catalyst component obtained in (2) above to give a concentration of 4.0 @% by volume.
The suspension was made into an n-hexane suspension, and then the suspension was mixed with 10.4 milligram atoms (Har) of diethylaluminium, monochloride, and methyl P-toluate, each in a molar ratio of 7 to titanium atoms. .0 and 1.
It was supplied as a catalyst from the same pipe so that the concentration was 0.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 18.5% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cm'G. Polymerization was carried out at 70°C.

During the polymerization, the polymer was extracted at a rate of 13.5 kg/hr so that the polymer retention level in the polymerization vessel was 45% by volume. When a part of the extracted polymer was collected and analyzed, the MFR was 70.0. After the first stage polymerization was completed, the polymerization mixture consisting of the extracted catalyst and polymer was continuously introduced into a horizontal second stage polymerization vessel having an internal volume of 150ρ similar to the first stage polymerization vessel. .

While introducing the polymerization mixture into the second stage polymerization vessel as described above, hydrogen was added to the gas phase of ethylene and propylene so that the concentration in the gas phase in the polymerization vessel was maintained at 8.5% by volume. The molar ratio is maintained at 0.38, and the total pressure is 5.5 kg/cm"G.
Ethylene and propylene were each continuously supplied to the second-stage polymerization vessel so as to maintain the temperature, and copolymerization of ethylene and propylene was carried out at 60°C. During the copolymerization, 15.7 kg of block copolymer was continuously fed from the polymerization vessel so that the retention level of the block copolymer in the polymerization vessel was 44% by volume.
g/hr.

The extracted block copolymer was then contacted with nitrogen gas containing 0.2% by volume of propylene oxide at 95°C for 30 minutes, and then with steam at 100°C for 30 minutes. It was further dried with nitrogen gas at 100°C to obtain a propylene-ethylene block copolymer.

Propylene-ethylene block copolymerization was carried out continuously for 168 hours as described above, but no operational problems occurred and a propylene-ethylene block copolymer was stably produced. In addition, the MFR of the obtained copolymer is 2
5.0, the ethylene content was 8, and the Sli amount was %.

Comparative Example 1 In (2) of Example 1, the second preactivation treatment with vinylcyclohexane was omitted, and only propylene was reacted to obtain a preactivated catalyst component. A propylene-ethylene block was co-produced in the same manner as in (3) of Example 1, except that the pre-activated component was supplied so that the total pressure in the first stage polymerization vessel was 23 g/cm"G. A polymer was obtained.

Comparative Example 2 In Example 1 (2), the first preactivation treatment with propylene was omitted and only vinylcyclohexane was reacted to obtain a preactivated catalyst component. The preactivated catalyst component was heated at a total pressure of 23 kg/cm in the first stage polymerization vessel.
(3) of Example 1 except for supplying so that 'G'
When propylene-ethylene block copolymerization was carried out in the same manner as above, the produced bulk polymer blocked the polymer extraction pipe from the polymerization vessel, so the propylene-ethylene block copolymerization was completed within 4 hours after the start of polymerization. Polymerization had to be stopped.

Comparative Example 3 In (2) of Example 1, the first and second stage preactivation treatments were performed in the reverse order, and propylene was reacted after the reaction of vinylcyclohexane to obtain a preactivated catalyst component.
Example 1 ((
When block copolymerization was carried out in the same manner as in 3), the produced bulk polymer blocked the polymer extraction pipe from the polymerization vessel, so block copolymerization was stopped 6 hours after the start of polymerization. I had to.

Comparative Example 4 In (3) of Example 1, the catalyst consisting of diethylaluminum monochloride and the preactivated catalyst component used in Comparative Example 1 was used as the preactivated catalyst component without supplying methyl p-toluate. Supply to the first stage polymerization vessel so that the total pressure inside the first stage polymerization vessel is maintained at 23 g/cm'G, and the hydrogen concentration in the gas phase within the first stage polymerization vessel. Propylene-ethylene block copolymerization was carried out in the same manner except that the hydrogen concentration in the gas phase in the second stage polymerization vessel was set to 9.5% by volume and 4.0% by volume.

Comparative Example 5 Polypropylene was obtained in the same manner as in Example 1 (3) except that the second stage copolymerization of propylene and ethylene was omitted.

Comparative Example 6 and Examples 2 and 3 In Example 1 (2), the amounts of propylene and vinylcyclohexane used were varied to obtain preactivated catalyst components whose reaction amounts were as shown in the table. The preactivated catalyst component was heated to a total pressure of 23 g/cm2G in the first stage polymerization vessel.
A propylene-ethylene block copolymer was obtained in the same manner as in (3) of Example 1, except that it was supplied so as to be as follows.

Example 4 (1) A titanium trichloride composition (III') was obtained in the same manner as in Example 1 (1).

(2) A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that 980 g of propylene was used and 6.2 kg of allyltrimethylsilane was used in place of vinylcyclohexane.

(3) Add 30 kg of polypropylene powder with an MFR of 10 to the horizontal first stage polymerization vessel used in (3) of Example 1, add n-hexane to the preactivated catalyst component obtained in (2) above, and After forming a suspension in n-hexane of .0% by weight, the suspension was mixed with diethylaluminum monochloride and p
-)-Methyl toluate was continuously supplied as a catalyst from the same pipe so that the molar ratio to titanium atoms was 7.0 and 1.0, respectively.

In addition, hydrogen was supplied to the gas phase of the polymerization vessel so that the concentration remained at 8.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cla'lE, and the polymerization of propylene was carried out in the first stage. was carried out at 70°C.

During the polymerization, the polymer was continuously extracted at a rate of 13.5 kg/hr so that the polymer retention level in the polymerization vessel was 45% by volume. When a part of the extracted polymer was collected and analyzed, the VFR was 15.0. After the N1-stage polymerization was completed, the polymerization reaction mixture consisting of the catalyst and polymer that was taken out was continuously introduced into the horizontal second-stage polymerization vessel used in Example 1 (3).

While introducing the polymerization reaction mixture from the first stage polymerization vessel into the second stage polymerization vessel as described above, hydrogen and ethylene were introduced so that the concentration in the gas phase in the polymerization vessel was maintained at 22% by volume. Ethylene and propylene are each continuously supplied to the second stage polymerization vessel so that the molar ratio in the gas phase of propylene is maintained at 0.29 and the total pressure within the polymerization vessel is maintained at 5.0 kg/cm2G, Copolymerization of ethylene and propylene was carried out at 60°C.

During the copolymerization, the block copolymer was continuously extracted from the second stage polymerization vessel at a rate of 5.5 kg/hr so that the retention level of the block copolymer in the second stage polymerization vessel was 44% by volume. did. The extracted block copolymer was subjected to the same post-treatment as in Example 1, and a propylene-ethylene block copolymer was continuously produced for 168 hours. During this period, operation was stable and no manufacturing problems occurred. The VFR of the obtained block copolymer was 10.0. The ethylene content was 6.0% by weight.

Comparative Example F In (2) of Example 4, the second-stage preactivation treatment with allyltrimethylsilane was omitted, only propylene was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was Block copolymerization was carried out in the same manner as in Example 4 (3) except for using the following.

Comparative Example 8 In (2) of Example 4, the first stage preactivation treatment with propylene was omitted, only allyltrimethylsilane was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was When propylene-ethylene block copolymerization was carried out in the same manner as in (3) of Example 4, except for using The block copolymerization had to be stopped 12 hours after starting.

Comparative Example 9 Preactivation was carried out in the same manner as in (2) of Example 4, except that the order of the first and second preactivation treatments was reversed and propylene was reacted after the reaction of allyltrimethylsilane. A catalyst component was obtained.

Example 4 ((
When propylene-ethylene block copolymerization was carried out in the same manner as in 3), the produced bulk polymer blocked the polymer extraction pipe from the polymerization vessel, so after the start of polymerization,
The block copolymerization had to be stopped after 15 hours.

Example 5 (1) A titanium trichloride composition (III) was obtained in the same manner as in Example 1 (+1).

(2) In (2) of Example 1, the amount of propylene used was changed to 1.2 g, and 3-g was replaced with vinylcyclohexane.
A preactivated catalyst component was obtained in the same manner except that 2.6 g of methylbutene-1 was used.

(3) After charging 30 kg of polypropylene powder with an MFR of 10 into the horizontal first-stage polymerization vessel used in (3) of Example 1, n-hexane was added to the preactivated catalyst component obtained in (2) above, and 4 After forming a suspension in n-hexane of .0% by weight, the suspension has a concentration of 6.7 milligram atoms per titanium atom.
hr, diethylaluminium monochloride and p
- Methyl toluate was continuously supplied as a catalyst from the same pipe so that the molar ratio to titanium atoms was 7.0 and 0.5, respectively.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 4.5% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cm'G, and the polymerization of propylene was carried out in the first stage. It was carried out at 70°C.

During the polymerization, the polymer was continuously withdrawn at a rate of 13.5 g/hr so that the retention level in the polymerization vessel was 45% by volume. When a part of the extracted polymer was collected and analyzed, the VFR was 10.0. After the first stage polymerization was completed, the extracted polymerization reaction mixture consisting of the catalyst and polymer was continuously introduced into the horizontal second stage polymerization vessel used in Example 1 (3).

While introducing the polymerization reaction mixture from the first stage polymerization vessel into the second stage polymerization vessel as described above, hydrogen was also introduced so that the concentration in the gas phase in the polymerization vessel was maintained at 12.5% by volume. Ethylene and propylene are continuously added to the second stage polymerization vessel so that the molar ratio of ethylene and propylene in the gas phase is maintained at 0.45 and the total pressure within the polymerization vessel is maintained at 3.0 Kg/cm”G. Copolymerization of ethylene and propylene was carried out at 60°C.

During the copolymerization, the block copolymer was continuously extracted from the second stage polymerization vessel at a rate of 14.5 kg/hr so that the retention level of the block copolymer in the second stage polymerization vessel was 44% by volume. did. Example 1 about the extracted block copolymer
The same post-treatment as above was carried out, and the production of a propylene-ethylene block copolymer was carried out continuously for 1611 hours.

During this period, operation was stable and no manufacturing problems occurred. The VFR of the obtained block copolymer was 8.
0, the ethylene content was 4.3% by weight.

Example 6 and Comparative Examples 10 to 12 (3) In (3) of Example 5, the molar ratio of methyl p-toluate to titanium atoms was changed as shown in the table, and each catalyst component was added to the first stage. Propylene-ethylene block copolymerization was carried out in the same manner as in Example 5, except that the total pressure in the polymerization vessel was 23g/crs'G.

Example 7 (1) Preparation of titanium trichloride composition (III) n-hebutane ελ, di-n-butylaluminum 1,000 chloride
6 mol, 10 mol of moro-butyl ether at 30°C.
The mixture was mixed for 20 minutes and reacted for 20 minutes to obtain a reaction product liquid (1). The entire amount of this reaction product liquid (1) was added dropwise over 60 minutes to a solution consisting of toluene at 5°C and 64 moles of titanium tetrachloride kept at 45°C, and then the temperature was raised to 85°C and the reaction was further carried out for 2 hours. Thereafter, the process of cooling to room temperature, removing the supernatant, adding 30 Il of n-hebutane, and removing the supernatant by decantation was repeated twice to obtain a solid product (II) 4.9
I got g.

The entire amount of this (1■) was suspended in n-hebutane at 30°C, and 2.0 kg of moro-butyl butyl ether and 15 g of titanium tetrachloride were added at room temperature for about 20 minutes, and the mixture was reacted at 90°C for 2 hours. After cooling, decantation, washing with n-hebutane and drying were performed to obtain a titanium trichloride composition (III). The content of titanium atoms in 1 g of titanium trichloride composition (III) was 255 mg.

(2) Preparation of preactivated catalyst components In the reactor used in Example 1 (2), n-hexane 1001, diethylaluminum monochloride 1.
73 kg and 0.9 kg of the titanium trichloride composition (Hl) obtained in (1) above were added at room temperature. The temperature inside the reactor was set to 35°C, and 45ONl of ethylene was supplied over 1 hour at the same temperature to perform the first preactivation treatment (0.5 g of ethylene per Ig of titanium trichloride composition (III)). reaction).

Next, unreacted ethylene was removed, and 4,4-dimethylpentene-1 was added to 3.6 g without washing the reaction mixture, and a second preactivation treatment was performed at 40°C for 2 hours (trichloride 1.0 g of 4,4-dimethylpentene-1 was reacted per 1 g of titanium composition (III), and a preactivated catalyst component was obtained in a slurry state.

(3) Production of block copolymer The preactivated catalyst component slurry obtained in (2) above (diethylaluminum monochloride also methyl 11-toluate was added to the titanium atoms at a molar ratio of 1.0 at a rate of 19.6 milligram atoms/hr in terms of titanium atoms, and n-hexane was added from a separate tube. It was continuously supplied at 24Kg/hr.

Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 18.5% by volume, and propylene was supplied so that the total pressure was maintained at 8 kg/cs+'G. Polymerization of propylene was carried out at 70°C.

During the polymerization, the polymer slurry was continuously extracted so that the polymer slurry retention level in the polymerization vessel was 80% by volume. Subsequently, the extracted polymer slurry is
It was continuously introduced into a first stage second stage polymerization vessel with an internal volume of 150 Jil similar to that used in the stage. Hydrogen was further supplied to the polymerization reactor so that the concentration in the gas phase of the polymerization reactor was maintained at 16% by volume, and propylene was supplied so that the total pressure was maintained at 10 kg/cm'G. The stepwise propylene polymerization was carried out at 70°C.

During the polymerization, the polymer slurry was continuously extracted as a polymer at a rate of 13.8 kg/hr so that the retention level of the polymer slurry in the polymerization vessel was 68% by volume.

When a part of the extracted polymer slurry was collected, dried, and analyzed, the MFR was 50.0. After the first stage polymerization, which consists of two stages, has been completed, the extracted polymerization mixture consisting of the catalyst, n-hexane, and polymer is subsequently subjected to the first stage polymerization.
The mixture was continuously introduced into a second stage polymerization vessel having an internal volume of 1001, which was of the same type as the first stage polymerization vessel.

While introducing the polymerization mixture into the second stage polymerization vessel as described above, hydrogen was added to the gas phase of ethylene and propylene so that the concentration in the gas phase in the polymerization vessel was maintained at 15.5% by volume. The molar ratio is maintained at 0.45, and the total pressure is 5.4 kg/cm2.
Ethylene and propylene were each continuously supplied to the second stage polymerization vessel so as to maintain G, and copolymerization of ethylene and propylene was carried out at 50°C. During the copolymerization, the block copolymer slurry was continuously drawn out from the polymerization vessel into a flash tank having an internal volume of 40 IL so that the retention level of the block copolymer slurry in the polymerization vessel was 62% by volume.

While reducing the pressure in a flash tank and removing unreacted hydrogen, ethylene, and propylene, 1 kg of methanol was
/hr and contact treatment was carried out at 70°C.

Subsequently, after neutralization with an aqueous sodium hydroxide solution, the polymer is subjected to known steps of water washing, separation, and drying, and propylene-
Ethylene block copolymer at 15kg/hr 1611
Obtained continuously for hours. During the production of the block copolymer,
No operational problems occurred and production was extremely stable. The obtained copolymer had an MFR of 30.0 and an ethylene content of 4.6% by weight.

Comparative Example 13 In (3) of Example 7, 0.9 kg of the titanium trichloride composition (In) obtained in (1) of Example 7 and 1.9 kg of diethylaluminum monochloride were used instead of the preactivated catalyst component slurry. 73 kg, and n-hexane 4
Using a catalyst component slurry mixed with 0j2, each catalyst component was heated at a total pressure of 8 kg/c in the first stage polymerization vessel.
Block copolymerization was carried out in the same manner except that I112 was supplied to the polymerization vessel so as to maintain it.

Comparative Example 14 In (1) of Example 7, during the reaction to obtain the solid product (II), 16 mol of diethylaluminium monochloride was used instead of the reaction product solution (1), and the temperature was 0.
After the dropwise addition, the mixture was heated to 75°C in the same manner as in Example 7 (1), stirred and reacted for 1 hour, and then refluxed for 4 hours at the boiling temperature of titanium tetrachloride (approximately 136°C) to turn purple and cooled. After that, it was filtered and dried to obtain titanium trichloride (RA). Block copolymerization was carried out in the same manner as in Example 7, except that titanium trichloride (RA) was replaced with titanium trichloride composition (III) of Example 7.

Example 8 (1) Preparation of titanium trichloride composition (III) 27.0 mol of titanium tetrachloride was added to 121 n-hexane, and after cooling to 1°C, a mixture of n-hexane containing 27.0 mol of diethylaluminium monochloride was added. - 12.52 kg of hexane was added dropwise at 1°C over 4 hours.

After the dropwise addition was completed, the temperature was kept at the same temperature for 15 minutes to react, then the temperature was raised to 65°C over 1 hour, and the reaction was further continued at the same temperature for 1 hour.The supernatant liquid was removed and n-hexane 1041 was added. ,
The operation of removing by decantation was repeated 5 times, and of the 5.7 kg of solid product (II) obtained, 1.8 g was suspended in 111 L of n-hexane, and 1.21 g of diisoamyl ether and Ethyl benzoate at 0.4°C was added.

After stirring this suspension at 35°C for 1 hour, 3J of n-hexane was added.
A treated solid was obtained by washing with 5 times of water. The resulting treated solid was dissolved in 6J! of a raw hexane solution containing 40% by volume of titanium tetrachloride and 10% by volume of silicon tetrachloride. suspended in it.

This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After the reaction was completed, the resulting solid was washed three times using 20 IL of n-hexane each time, and then dried under reduced pressure. A titanium trichloride composition (III) was thus obtained.

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (II
As I), 1.8 kg of the titanium trichloride composition (III) obtained in the above (1) was used, the amount of propylene used was 2.5 kg, and p was used instead of vinylcyclohexane.
A preactivated catalyst component was obtained in the same manner except that 9.6 g of -trimethylsilylstyrene was used.

(3) Production of block copolymer A VFR was installed in the horizontal first stage polymerization vessel used in (3) of Example 1.
After adding 30 kg of Is polypropylene powder, n-hexane was added to the preactivated catalyst component obtained in (2) above to make a 4.0°C mass % n-hexane suspension. 20.5 milligram atoms/hr in terms of titanium atoms
Then, as a breeding aluminum compound (AI), an equimolar mixture of diethylaluminum monoiodide and di-n-propylaluminium monochloride was added so that the molar ratio was 6.0 to titanium atoms, and further as an aromatic carboxylic acid ester. Ethyl p-anisate was continuously supplied as a catalyst from the same pipe so that the molar ratio to titanium atoms was 1.0.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 9.5% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cm2G, and the first stage propylene polymerization was carried out at 70°C. It was carried out in

During the polymerization, the polymer was continuously added at 1.5 kg/hr so that the polymer retention level in the polymerization vessel was 45% by volume.
I pulled it out. When a part of the extracted polymer was collected and analyzed, the MFR was 20.0. After the first stage polymerization was completed, the extracted polymerization reaction mixture consisting of the catalyst and polymer was continuously introduced into the horizontal N2-stage polymerization vessel used in Example 1 (3).

While introducing the polymerization reaction mixture from the first stage polymerization vessel into the second stage polymerization vessel as described above, hydrogen and ethylene were added so that the concentration in the gas phase in the polymerization vessel was maintained at 31% by volume. The molar ratio of propylene in the gas phase is 0.34. The molar ratio of butene-1 and propylene in the gas phase is maintained at 0 and 0, and the total pressure inside the polymerization vessel is 4. Copolymerization of ethylene, butene-1 and propylene was carried out so as to maintain g/ca+''G at θ.

During the copolymerization, the block copolymer was continuously extracted from the second stage polymerization vessel at a rate of 15.3 kg/hr so that the retention level of the block copolymer in the second stage polymerization vessel was 44% by volume. did. Example 1 about the extracted block copolymer
The same post-treatment as above was carried out, and the block copolymer was produced continuously for 168 hours.

During this period, operation was stable and no manufacturing problems occurred. The MFR of the obtained block copolymer is 15
．． The total content of 0 ethylene and butene-1 was 5.3% by weight.

Comparative Example 15 In (2) of Example 8, the second stage preactivation treatment with p-trimethylsilylstyrene was omitted, and only propylene was reacted to obtain a preactivated catalyst component. Example 8 (3) except that the preactivated catalyst component was used and each catalyst component was further supplied to the polymerization vessel so that the total pressure in the first stage polymerization vessel was maintained at 23 g/cI112G. Block copolymerization was carried out in the same manner.

The preactivation treatment conditions and results of the above Examples and Comparative Examples are shown in the table.

[Effects of the Invention] The main effect of the present invention is that a propylene-olefin block copolymer having both high rigidity and high impact resistance can be stably obtained without any production problems.

As is clear from the above examples, the propylene-olefin block copolymer obtained by the method of the present invention has the following properties:
Compared to known block copolymers obtained by conventional methods and block copolymers obtained by the method of the prior invention, it has good stiffness and impact resistance, and in particular, the stiffness is significantly improved. (Examples 1 to 8, Comparative Examples 1.4.7.
(see 13.15).

Therefore, it can be widely applied to the fields of various molding methods, especially the field of injection molding, and exhibit its characteristics.

On the other hand, even if a catalyst that has been preactivated with a non-directly quenched olefin is used, if the preactivation treatment is not performed according to the method of the present invention, operational problems will occur, and long-term continuous operation will not be possible. It's impossible. Furthermore, the obtained block copolymer also had insufficient improvement in the balance between rigidity and 'fI impact resistance (see Comparative Example 2.3.8).

[Brief explanation of drawings]

Figure 1 shows Manufacturing process for detailed explanation of the present invention Process diagram (flow sheet) It is. that's all Special permission Out wish Man Chisso Corporation

Claims (1)

[Claims] (1) Using a catalyst consisting of [1] titanium trichloride composition (III), [2] organoaluminum compound (A_1), and [3] aromatic carboxylic acid ester (E) In a method for producing a propylene-olefin block copolymer by copolymerizing propylene and an olefin other than propylene, the titanium trichloride composition (III) is an organoaluminum compound (A_2) or an organoaluminum compound (A
Reaction product (I) between _2) and electron donor (B_1)
Solid product (II) obtained by reacting titanium tetrachloride with
using a titanium trichloride composition (III) obtained by polymerizing with an olefin or reacting an electron donor (B_2) with an electron acceptor without polymerizing the titanium trichloride composition. compound (III) and organoaluminum compound (A
_1), and [4] straight chain olefin is added to the titanium trichloride composition (III).
After polymerizing 0.01 g to 100 g per 1 g, [5] non-linear olefin is added to the titanium trichloride composition (III
) 0.001g to 100g per 1g of the preactivated catalyst component obtained by polymerization reaction, optionally an additional organoaluminum compound (A_1), and an aromatic carboxylic acid ester (E) are combined, and the aromatic The molar ratio of the carboxylic acid ester (E) and the titanium trichloride composition (III) (based on the number of Ti atoms, the same applies hereinafter) is (E)/(III) = 0.1.
~10.0, and the organoaluminum compound (A_1)
The molar ratio of the titanium trichloride composition (III) is (A_1)
/(III)=0.1 to 200, propylene is polymerized in the first stage in an amount of 60% to 95% by weight of the total polymerization amount, and then in the second stage, 40% by weight of the total polymerization amount is polymerized. A propylene-olefin block copolymer characterized by copolymerizing propylene in an amount of 5% to 5% by weight and an olefin other than propylene so that the olefin content in the resulting block copolymer is 3% to 30% by weight. Polymer manufacturing method. (2) The production method according to claim 1, in which a dialkylaluminum monohalide is used as the organoaluminum compound (A_1). (3) As the organoaluminum compound (A_2), the general formula is AlR^1_pR^2_p_'X_3_-_(_p
___+_p_'_) (wherein, R^1 and R^2 represent a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group, or an alkoxy group, X represents a halogen, and p, p'
represents an arbitrary number satisfying 0<p+p'≦3. ) Claim 1 using an organoaluminum compound represented by
Manufacturing method described in Section. (4) The non-linear olefin has the following formula, CH_2=CH-R^3 (wherein, R^3 has a saturated cyclic structure of a hydrocarbon that may contain silicon, and may contain silicon. The manufacturing method according to claim 1, which uses a saturated ring-containing hydrocarbon monomer represented by (representing a saturated ring-containing hydrocarbon group having 3 to 18 carbon atoms). (5) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4 is a chain hydrocarbon group with 1 to 3 carbon atoms that may contain silicon, Or represents silicon, R^
5, R^6, R^7 represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, but R^5, R^
Any one of 6 and R^7 may be hydrogen. ) Claim 1 using branched olefins represented by
Manufacturing method described in Section. (8) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is either 0 or 1, m is either 1 or 2, and R
^5 represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R^9 represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or It represents halogen, and when m is 2, each R^9 may be the same or different. ) The manufacturing method according to claim 1, using an aromatic monomer represented by: