JPH04351616A - Production of propylene block copolymer - Google Patents

Abstract

PURPOSE:To stably produce a propylene block copolymer excellent in flexibility and impact resistance in the absence of a solvent. CONSTITUTION:A propylene block copolymer having a specified propylene content, a specified xylene-insol. matter content, a specified ethylene content in the xylene-insol. matter, and a specified MFR is produced by the copolymn. in two steps, the first step comprising propylene homopolymn. or propylene- ethylene copolymn. wherein the propylene content of the resulting polymer amounts to 85wt.% or higher and the conversion of propylene amounts to 30-80wt.% and the second step comprising propylene-ethylene copolymn. wherein the ethylene content of the resulting copolymer amounts to 60wt.% or higher and the conversion of ethylene amounts to 20-70wt.%, both steps being carried out in the absence of a solvent and in the presence of a catalyst comprising a solid catalyst component contg. magnesium, titanium, a halogen, and an electron-donating compd. and at least one electron-donating compd. selected from the group consisting of organometallic compds. of metals of the groups IA, IIA, IIB, IIIB, and IVB of the periodic table.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stably producing a propylene block copolymer having excellent flexibility and impact resistance in a solvent-free system.

0002

BACKGROUND OF THE INVENTION Highly stereoregular polypropylene produced using a stereoregular catalyst has excellent rigidity and heat resistance, but has a problem in that it has low impact strength, particularly at low temperatures. As a method to improve this point, in a method of polymerizing propylene in multiple stages, crystalline polypropylene is polymerized in the previous stage, and propylene and ethylene or other α-olefin are copolymerized in the latter stage to produce propylene. Methods for producing block copolymers have been known for a long time. For example, Japanese Patent Publication No. 43-11230, Japanese Patent Publication No. 49-24593, Japanese Patent Publication No. 48-25781.
No., JP-A No. 53-35789, etc.

0003

[Problem to be solved by the invention] In recent years, soft resins with excellent heat resistance and impact resistance have come to be widely used in automobile products, parts of home appliances, footwear, electric wires and cables, industrial products, etc. . In order to obtain such a soft resin by the above-mentioned method, the polymerization ratio of propylene and ethylene or other α-olefin copolymer in the propylene block copolymer is increased. has caused various problems because it is sticky and soluble in solvents. That is, in the above-mentioned method for producing a propylene block copolymer, in the subsequent step of copolymerizing propylene and ethylene or other α-olefins, if a solvent is used or propylene itself is used as a solvent, the viscosity of the medium will increase. As a result, reaction heat control and slurry transfer become difficult. In addition, in gas phase polymerization where no solvent is present, poor movement of polymer particles within the polymerization vessel,
Particles may adhere to the inner wall of the polymerization vessel, particles may clog the pipes during transport, and long-term stable operation becomes difficult.

On the other hand, JP-A-1-98604 discloses that a thermoplastic elastomer is produced by using a solid catalyst component using an organic porous polymer as a carrier to avoid the stickiness of copolymer particles. is proposed. However, according to studies conducted by the present inventors, when the soft impact-resistant propylene block copolymer intended by the present invention is produced using this catalyst, the polymerization activity per catalyst is low, and the product is There is a problem in that coloring is observed.

[0005]Therefore, it is desired to develop a production method for stably polymerizing a propylene block copolymer having excellent flexibility and impact resistance in a solvent-free system.

[0006]

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors discovered the following manufacturing method and completed the present invention.

That is, the method for producing a propylene block copolymer according to the present invention involves carrying out a polymerization process consisting of the following two steps (I) and (II) with the following components (A) to (2) in the absence of a solvent. Conducted in the presence of a catalyst consisting of a combination of C), the propylene content is 50 wt% or more, the xylene soluble content (25 °C) is 10 to 60 wt%, and the ethylene content in the xylene insoluble content (25 °C) is It is characterized in that it produces a propylene block copolymer having a concentration of 15 to 60 wt% and an MFR of 0.01 to 1000 g/10 minutes. [Polymerization step] (I) A step of homopolymerization of propylene or copolymerization of propylene and ethylene, in which the propylene content in the polymer is 85 wt% or more and the polymerization ratio is 30 to 80%.
The process of wt%. (II) A copolymerization step of propylene and ethylene, the ethylene content in the copolymer being 60 wt% or more,
A step in which the polymerization ratio is 20 to 70 wt%. [Catalyst] Component (A) A solid catalyst containing magnesium, titanium, halogen, and an electron-donating compound. Component (B) Periodic Table IA, IIA, IIB, III
At least one selected from organometallic compounds of Group B and IVB metals. Component (C) Electron-donating compound. The present invention will be explained in detail below.

Solid catalyst component used in the present invention (
Regarding A), for example, the present inventor has disclosed JP-A-63
-3007, JP-A-63-314210, JP-A-6
No. 3-317502, JP-A-64-105, JP-A-1
-165608 and is detailed therein.

For example, a homogeneous solution obtained by reacting metallic magnesium with an electron-donating compound such as an organic compound hydroxide or an organic ester, and an oxygen-containing organic compound of titanium such as a titanium alkoxide is reacted with aluminum halide to form a solid. It can be prepared by obtaining a compound and then reacting it with an electron-donating compound and a halogenated titanium compound. Examples of hydroxylated organic compounds include ethanol, 2-
Examples include alcohols such as ethylhexanol, organic silanols such as trimethylsilanol and triphenylsilanol, and electron-donating compounds include esters, ethers, and ketones such as ethyl acetate and diisobutyl phthalate. , amides, etc.; examples of oxygen-containing organic compounds of titanium include tetraethoxytitanium, tetra-n-butoxytitanium, etc.; examples of aluminum halides include ethylaluminum dichloride, isobutylaluminum dichloride, etc.; Examples of the titanium chloride compound include titanium tetrachloride.

The solid catalyst component (A) thus obtained is filtered or decanted to remove remaining unreacted substances and by-products, and then thoroughly washed with an inert organic solvent. It is preferable to use it by suspending it. It can also be used which is isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent.

Furthermore, prior to the main polymerization, a solid catalyst component (A
) and a small amount of an organometallic compound component or an electron-donating compound component to form the general formula R-CH=CH
2 (wherein R represents a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms) and/or Or after polymerizing a small amount of ethylene to make a prepolymer,
You can also use As the α-olefin, specifically propylene, butene-1, 4-methylpentene-1
, octene-1, etc. Two or more types of these monomers may be used. The amount of α-olefin to be polymerized is 0.1 to 1 g per 1 g of solid catalyst component (A).
100g, more preferably 0.1 to 50g.

The solid catalyst component of component (A) obtained as described above is the component (B) of IA and IIA of the periodic table.
, IIB, IIIB, and IVB group metals, and the electron-donating compound of component (C) for use in olefin polymerization.

[0013] Component (B) in Periodic Table IA, IIA,
Examples of organometallic compounds of group IIB, IIIB, and IVB metals include organometallic compounds consisting of a metal such as lithium, magnesium, zinc, tin, or aluminum and an organic group. As the above organic group, an alkyl group can be exemplified. As this alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is used. Specifically, for example, n-butyllithium, diethylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, tri-i-butylaluminum, tri-n-butylaluminum, tri-n-decylaluminum, tetraethyltin, or tetraethyltin. Examples include butyltin. Above all, it is preferable to use trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms. Further, an alkyl metal halide having an alkyl group having 1 to 20 carbon atoms, such as ethyl aluminum sesquichloride, diethylaluminum chloride, diisobutyl aluminum chloride, or an alkyl metal alkoxide, such as diethylaluminum ethoxide, can also be used. These organometallic compounds may be used alone or as a mixture of two or more.

[0014] As the electron donating compound of component (C),
Organic acid esters, oxygen-containing organic compounds of silicon, nitrogen-containing organic compounds, and the like are suitable. Examples of organic acid esters include mono- or diesters of aromatic carboxylic acids, mono- or diesters of aliphatic carboxylic acids, and the like. Among them, aliphatic carboxylic acid esters and aromatic carboxylic acid esters are preferred. Specifically, examples of the aliphatic carboxylic acid ester include ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, butyl propionate, and ethyl butyrate, each having 2 to 18 carbon atoms. Examples of the aromatic carboxylic acid ester include methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate, each having 1 to 24 carbon atoms. The above organic acid esters may be used alone, or two or more types may be mixed or reacted together. The oxygen-containing organic compound of silicon has the general formula R1sSi
An oxygen-containing organic compound of silicon represented by (OR2)tX4-(s+t) is used. However, in the general formula, R1 and R2 have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
represents a hydrocarbon group or a hydrogen atom such as a straight-chain or branched alkyl group, cycloalkyl group, arylalkyl group, aryl group, and alkylaryl group, and s and t are 0≦s
It represents a number such as ≦3, 1≦t≦4, 1≦s+t≦4, and X represents a halogen atom. Specific examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-propoxysilane.
-butoxysilane, tetra-i-pentoxysilane, tetra-n-hexoxysilane, tetraphenoxysilane, tetrakis(2-ethylhexoxy)silane, tetrakis(2-ethylbutoxy)silane, tetrakis(2-
methoxyethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorophenyltrimethoxysilane Methoxysilane, trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, Ethoxysilane, ethyltri-i-propoxysilane,
Vinyltri-i-propoxysilane, i-pentyltri-n-butoxysilane, methyltri-i-pentoxysilane, ethyltri-i-pentoxysilane, methyltri-n-hexoxysilane, phenyltri-i-pentoxysilane, n-propyl Trimethoxysilane, i-propyltrimethoxysilane, i-butyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, Methyldodecyldiethoxysilane, methyloctadecyldiethoxysilane, methylphenyldiethoxysilane, methyldiethoxysilane, dibenzyldiethoxysilane, diethoxysilane, dimethyldi-n-butoxysilane, dimethyldi-i-pentoxysilane, diethyldiethoxysilane -i-pentoxysilane, di-i-butyldi-i-pentoxysilane, diphenyldi-i-pentoxysilane, diphenyldi-n-octoxysilane, diisobutyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyl Ethoxysilane, trimethyl-i-
Propoxysilane, trimethyl-n-propoxysilane, trimethyl-t-butoxysilane, trimethyl-i-
Alkoxysilane or aryloxysilane such as butoxysilane, trimethyl-n-butoxysilane, trimethyl-n-pentoxysilane, trimethylphenoxysilane, haloalkoxysilane such as dichlorodiethoxysilane, dichlorodiphenoxysilane, tribromoethoxysilane, Alternatively, examples include haloaryloxysilane. The above oxygen-containing organic compounds of silicon may be used alone, or two or more types may be mixed or reacted together. Examples of nitrogen-containing organic compounds include compounds that have a nitrogen atom in the molecule and function as a Lewis base. Specifically, acetic acid N
, N-dimethylamide, benzoic acid N,N-dimethylamide, toluic acid N,N-dimethylamide and other amide compounds, 2,2,6,6-tetramethylpiperidine, 2
, 6-diisopropylpiperidine, 2,6-diisobutylpiperidine, 2,6-diisobutyl-4-methylpiperidine, 2,2,6-trimethylpiperidine, 2,2,
6,6-tetraethylpiperidine, 1,2,2,6,6
-Pentamethylpiperidine, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6
, 6-tetramethyl-4-piperidyl) sebacate, pyridine compounds such as 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 2-isopropyl-6-methylpyridine, 2,2
, 5,5-tetramethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2,2,5-trimethylpyrrolidine, 1,2,2,5,5-pentamethylpyrrolidine, 2,
Pyrrolidine compounds such as 5-diisobutylpyrrolidine, amine compounds such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine, tert-butyldimethylamine, diphenylamine, di-o-tolylamine, N,N Examples include aniline compounds such as -diethylaniline and N,N-diisopropylaniline. The above nitrogen-containing organic compounds are
They may be used alone, or two or more types may be mixed or reacted together. These electron-donating compounds may be used in combination.

The amount of solid catalyst component (A) used is
Preferably, it is used in an amount corresponding to 0.001 to 2.5 mmol titanium atoms per liter. The organometallic compound of component (B) is added in an amount of 0.02 to 50 mm per liter of reactor.
ol, preferably at a concentration of 0.2 to 5 mmol. The electron-donating compound of component (C) is 0.001 to 50 mmol, preferably 0.01 to 50 mmol per liter of reactor.
Use at a concentration of 5 mmol.

[0016] The mode of feeding the three components in the present invention is not particularly limited; for example, component (A), component (B)
), a method in which each component (C) is separately fed into a polymerization vessel, or a method in which component (A) and component (B) are brought into contact with each other, and then component (
A method of polymerizing by contacting component (B) with component (C)
) may be brought into contact with each other and then brought into contact with component (A) for polymerization, or a method in which component (A), component (B), and component (C) are brought into contact with each other in advance for polymerization.

The block copolymer obtained in the present invention has a propylene content of 50 wt% or more and a xylene soluble content (25°C) of 10 to 60 wt%, preferably 20 to 50 wt%.
wt% range, and xylene insoluble content (25°C)
The ethylene content is 15 to 60 wt%, preferably 20
~50 wt%, and the MFR of the polymer is 0.01
~1000g/10min, preferably 0.05-200g
/10 minutes. That is, if the propylene block copolymer obtained in the present invention has a xylene soluble content below the above-mentioned range, it cannot become a resin with the desired flexibility and high impact strength. On the other hand, beyond the above range,
The low crystallinity component in the copolymer increases the stickiness of the copolymer particles, hindering stable operation of the polymerization vessel. Furthermore, if the ethylene content in the xylene-insoluble matter of the copolymer is less than the above range, the copolymer particles will have increased stickiness, making it difficult to stably produce the desired flexible propylene block copolymer. Can not. On the other hand, if it exceeds the above range, the heat resistance of the polymer will decrease.

The present invention uses the above-mentioned catalyst system to produce a propylene block copolymer in two steps, but each step may consist of a plurality of steps.

The polymerization step (I) is a step of homopolymerization of propylene or copolymerization of propylene and ethylene, which is carried out in the presence of the above catalyst system, and the propylene content of the polymer is 85 wt% or more, preferably It is a step in which the polymerization ratio is 90 wt% or more, more preferably 93 wt% or more and 99.5 wt% or less, and the polymerization ratio is 30 to 80 wt%, preferably 45 to 75 wt% of the total polymerization amount. If the propylene content in the copolymer of propylene and ethylene obtained in the polymerization step (I) is less than the above value, the copolymer particles will have increased stickiness due to the low crystallinity component in the copolymer, which will hinder the polymerization. The stable operation of the equipment is hindered. Moreover, if the polymerization ratio is smaller than the above range, the heat resistance of the final copolymer will decrease. Conversely, if the polymerization ratio is greater than the above range, flexibility and impact strength will be impaired.

The polymerization step (II) is a copolymerization step of propylene and ethylene, and the ethylene content in the copolymer is 60 wt% or more, preferably 70 wt% or more, 95 wt.
t% or less, and the polymerization ratio is 20 to 70 of the total polymerization amount.
wt%, preferably 25 to 55 wt%. If the ethylene content in the copolymer obtained in the polymerization step (II) is less than the above-mentioned value, the amount of by-product of low crystalline polymer will increase, which is not preferable. Further, the block copolymer obtained in the present invention has an excellent appearance, but when the appearance is particularly important, it is preferable that the ethylene content in the copolymer is 95 wt% or less. Each polymerization step of the present invention is carried out in the absence of a solvent. Specifically, either a method using propylene itself as a medium or a gas phase polymerization method can be selected;
In the polymerization step (II), it is preferable to select a gas phase polymerization method.

The polymerization conditions are not particularly limited as long as the reaction temperature is below the melting point of the polymer, but the reaction temperature is 20 to 1
00°C, preferably 50-90°C, polymerization pressure 2-50°C
It is selected in the range of kg/cm2G.

[0022] The reactor used in the polymerization step may be any reactor commonly used in the art. For example, using a stirred tank reactor, a fluidized bed reactor, or a circulation reactor, the polymerization operation can be carried out in any one of a continuous system, a semi-batch system, and a batch system.

[0023]

[Examples] The present invention will be illustrated by examples below, but the present invention is not limited to these examples in any way. The properties of the polymers in Examples and Comparative Examples were measured by the following method. Activity: 1g of solid catalyst component (A)
The amount of polymer produced per unit (g) is shown. MFR:ASTM
Melt flow rate according to D-1238 condition E. Flexural modulus: Flexural modulus according to JISK7203. Izod impact strength (-20°C): Izod impact strength according to JISK7110 (notched). Propylene content: Propylene content = 100-ethylene content (wt%) (Ethylene content is measured by infrared absorption spectroscopy.)
Xylene soluble content (Xy): 1g of sample is added to 200ml of xylene
After dissolving the mixture in 1 liter of water, it was left in a constant temperature bath at 25° C. for 1 hour. The precipitated polymer was filtered and the filtrate was collected. After most of the xylene in the filtrate was evaporated, the filtrate was further vacuum dried to recover the xylene soluble content, which was calculated as a percentage of the weight of the original sample. Ethylene content in xylene-insoluble matter (ethylene content XI): After dissolving 1 g of sample in 200 ml of xylene, it was left in a constant temperature bath at 25° C. for 1 hour. The precipitated polymer was filtered, and the residue on the filter paper was washed with xylene, followed by vacuum drying to recover the xylene-insoluble matter. The ethylene content in the xylene-insoluble matter was measured by infrared absorption spectroscopy. Blocking test: width 60mm, length 60mm,
60g of polymer particles was placed in a wooden square container with a height of 60mm, and a 10kg load was applied from above.
The mixture was left to stand for an hour, and then left to stand for 3 hours to cool. Take out the polymer particles blocked in a rectangular parallelepiped shape from the container,
With the surface perpendicular to the surface on which the preparation load is applied facing up, 0.1 to 10
．． A load in the range of 0 kg is applied, and the load required for its destruction is defined as the blocking load. The polymer particles have high stickiness;
The stronger the mutual adhesion, the greater the value of the blocking load measured by this method. In order to stably produce a block copolymer, it is preferable that the blocking load is less than 1.0 kg. Furthermore, if the blocking load exceeds 1.5 kg, stable production of the block copolymer becomes difficult. Measurement of polymer falling speed: The time required for 100 g of polymer particles to fall was measured using a metal funnel with an inner diameter of 9.5 mm and a length of 43 mm.

Reference Example 1 Preparation of Solid Catalyst Component (A) 80 g (3.29 mol) of metallic magnesium powder was placed in a 20 liter reactor equipped with a stirring device, and iodine 4
．． 0g, 2-ethylhexanol 2.06kg (15.
82 mol) and titanium tetrabutoxide 1.12k
g (3.29 mol), diisobutyl phthalate 323 g
After adding (1.16 mol) and further adding 650 ml of decane, the temperature was raised to 90°C, and the mixture was stirred for 1 hour under a nitrogen blanket while removing generated hydrogen gas. Continuing to 140
The temperature was raised to .degree. C. and the reaction was carried out for 1 hour to obtain a homogeneous solution containing magnesium and titanium. After cooling to 0°C, a solution of 2.04 kg (6.58 mol) of i-butylaluminum dichloride diluted to 50% with hexane was added over 2 hours. After everything was added, the temperature was raised to room temperature, and a slurry containing a white solid product was obtained. Then, after settling the solid product in the slurry and removing the supernatant,
Washed with hexane. To the thus obtained slurry containing the white solid, a solution prepared by diluting 11.3 kg of titanium tetrachloride with 7.3 kg of chlorobenzene was added, 394 g (1.4 mol) of diisobutyl phthalate was added, and the mixture was heated at 100°C.
Allowed time to react. The solid part was collected by filtering the product, and a solution prepared by diluting 11.3 kg of titanium tetrachloride with 7.3 kg of chlorobenzene was added again, and the mixture was heated at 100°C.
The mixture was stirred for 1 hour. Hexane was added to the product and the product was thoroughly washed until no titanium compound released was detected. Thus, the solid catalyst component suspended in hexane (
A slurry of A) was obtained. The supernatant was removed and dried under a nitrogen atmosphere, and elemental analysis revealed that Ti was 3.0 wt%.

Reference Example 2 Prepolymerization of solid catalyst component (A) The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 5 liters was sufficiently purged with nitrogen, and a polymer was obtained by the method of Reference Example 1 above. 52 g of solid catalyst component (A), organometallic compound (
37.22g (32g) of triethylaluminum as B)
6 mmol), 19.89 g (81.4 mmol) of diphenyldimethoxysilane as the electron donating compound (C)
were added sequentially, and 3 liters of hexane was added. After adjusting the autoclave internal pressure to 0.1 kg/cm2G and internal temperature to 20℃, stirring was started, and while maintaining the temperature at 20℃, propylene 10
4g was fed in 20 minutes and stirred for 30 minutes. Subsequently, solid components were separated by filtration and thoroughly washed with hexane to obtain a slurry of prepolymerized catalyst components suspended in hexane. After removing the supernatant and drying under a nitrogen atmosphere, the yield was 1.
It was 56g.

Example 1 The inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 30 liters was sufficiently purged with nitrogen and then the temperature was adjusted to 70°C. Then, the internal pressure of the autoclave was adjusted to 1.0 kg/cm2G, and 0.8 kg/cm2 of hydrogen was added. After adding 15.0 liters of liquefied propylene, stirring was started. Catalyst component (
0.900g of triethylaluminum (7.
89 mmol), 0.965 g (3.95 mmol) of diphenyldimethoxysilane as the catalyst component (C), and 0.180 g of the solid catalyst component (A) obtained in Reference Example 1.
(0.11 mmol in terms of Ti) was added sequentially, and ethylene was continuously supplied so that the ethylene partial pressure was 0.6 kg/cm2, and polymerization was carried out at the same temperature for 10 minutes. After a small amount of polymer was removed from the autoclave, stirring was stopped and unreacted gas was purged. (Polymerization step I) Next, after starting stirring and adjusting the internal temperature to 70°C, the internal pressure of the autoclave was adjusted to 1.0 kg/cm2G, and hydrogen was added to 2.3 kg.
g/cm2 was added. Next, the propylene partial pressure is 5.5 kg.
Polymerization was carried out for 280 minutes by continuously supplying each gas so that the partial pressure of ethylene was 7.0 kg/cm2 and 7.0 kg/cm2. (Polymerization Step II) After the polymerization was completed, stirring was stopped and, at the same time, unreacted gas in the system was released to obtain 3.72 kg of polymer. Activity was 20700g/g.

[0027] The MFR of the polymer extracted in the first stage is 15
．． 7g/10min, propylene content was 95.9wt%. On the other hand, the MFR of the final polymer was 6.1 g/10 min.
The propylene content was 68.2 wt%, and the polymerization ratio of the first stage and second stage was 61:39 when calculated from the catalyst residues of the first stage polymer and the final polymer. Moreover, the xylene soluble content (25°C) was 34.8 wt%. Furthermore, the ethylene content in the xylene insoluble matter (25°C) was 28.4 wt%.
Met. Load by blocking test is 0.3kg
, the polymer falling speed was 30.6 seconds. The physical properties of the block copolymer are shown in Table 5.

Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1 to obtain the block copolymers shown in Table 3. The physical properties of the block copolymer are shown in Table 5. Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 1, to obtain the block copolymer shown in Table 4. The physical properties of the block copolymer are shown in Table 6. Since the ethylene content of the copolymer produced in the second stage was lower than in Example 1, the stickiness of the powder increased, the load in the blocking test was 2.0 kg, and the polymer falling speed could not be measured. (No falling) Comparative Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 1, and the block copolymers shown in Table 4 were obtained. The physical properties of the block copolymer are shown in Table 6. however,
Comparative Examples 3 and 4 were not subjected to physical property measurements because the adhesiveness of the polymer particles increased and the particles strongly stuck to each other.

Example 6 Two polymerization vessels each having an internal volume of 3 m3 were connected in series to carry out continuous gas phase polymerization. The propylene partial pressure in the first polymerization reactor is 12.7
kg/cm2, ethylene is 0.015 to propylene
mol/mol, hydrogen was 0.0094 mol/mol relative to propylene, and the prepolymerized solid catalyst obtained in Reference Example 2 was added at 2.4 g/hr.
Each was continuously supplied so that In addition, as component (B), triethylaluminum is added as A to Ti in the catalyst.
Diphenyldimethoxysilane was used as the component (C) so that Si/Al=0 so that l/Ti=70 mol/mol.
．． It was continuously supplied at a concentration of 5 mol/mol. The temperature was adjusted to 70°C. The polymerized polymer particles were discharged into a withdrawal tank and then transferred to a second polymerization vessel. Propylene partial pressure in the second polymerization reactor is 5.4 kg/cm2
, the ethylene partial pressure is 8.6 kg/cm2, and the hydrogen partial pressure is 2.
Each was continuously supplied to the second polymerization vessel at a rate of 1 kg/cm2. The temperature was adjusted to 70°C.

The activity was 37,500 g/g. The MFR of the polymer taken out in the first stage was 13.9 g/10 minutes, and the propylene content was 97.0 wt%. On the other hand, the MFR of the final polymer is 4.2 g/10 min, and the propylene content is 70.1 wt%. The percentage is 66
:34. Also, the xylene soluble content (25°C) is 30.
It was 3wt%. Further, the ethylene content in the xylene insoluble matter (25°C) was 22.3 wt%. Load by blocking test is 0 kg, polymer falling speed is 2
It was 8.2 seconds. The physical properties of the block copolymer are shown in Table 5.

Examples 7 and 8 Polymerization was carried out in the same manner as in Example 6, except that the polymerization conditions were changed as shown in Table 2, to obtain the block copolymers shown in Table 3. The physical properties of the block copolymer are shown in Table 5. Comparative Examples 5 and 6 Example 6 except that the polymerization conditions were changed as shown in Table 2.
The block copolymers shown in Table 4 were obtained by polymerization in the same manner as in Table 4. Operation became impossible as soon as conditions were reached due to increased stickiness of the polymer particles. The physical properties of the block copolymer are shown in Table 6.

Example 9 After the inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 30 liters was sufficiently purged with nitrogen, 600 g of glass beads (1 mm in diameter) were added and the temperature was adjusted to 70°C. Next, adjust the autoclave internal pressure to 1.0 kg/cm2G,
0.09 kg/cm2 of hydrogen was added and stirring was started. 2.70g of triethylaluminum as catalyst component (B)
(23.67 mmol), 2.90 g (11.85 mmol) of diphenyldimethoxysilane as catalyst component (C).
), and the solid catalyst component (A) obtained in Reference Example 1 was added to 0.
540g (0.33mmol in terms of Ti) was added sequentially,
At the same time, the propylene partial pressure was 7.7 kg/cm2, and ethylene was continuously supplied at a ratio of 0.014 mol/mol to propylene, and polymerization was carried out at the same temperature for 120 minutes. After a small amount of polymer was removed from the autoclave, stirring was stopped and unreacted gas was purged. Next, after starting stirring and adjusting the internal temperature to 70°C, the internal pressure of the autoclave was adjusted to 1.0 kg/cm2G, and hydrogen was added at 2.2 kg/cm2G.
cm2 was added. Next, the propylene partial pressure was 5.9 kg/c.
Polymerization was carried out for 200 minutes by continuously supplying each gas so that the partial pressure of ethylene was 8.7 kg/cm2.

After the polymerization was completed, stirring was stopped and at the same time, unreacted monomers in the system were discharged to obtain 4.15 kg of polymer. Activity was 7700g/g. The MFR of the polymer taken out in the first stage was 15.5 g/10 minutes, and the propylene content was 96.7 wt%. On the other hand, the MFR of the final polymer
is 3.4g/10min, propylene content is 64.4wt
%, and when calculated from the catalyst residues of the first stage polymer and the final polymer, the polymerization ratio of the first stage and second stage is 55:45. Moreover, the xylene soluble content (25°C) was 41.0 wt%. Further, the ethylene content in the xylene insoluble matter (25°C) was 33.6 wt%. The load in the blocking test was 0.4 kg, and the polymer falling speed was 33.2 seconds. The physical properties of the block copolymer are shown in Table 5.

Comparative Example 7 (a) Synthesis of organomagnesium compound After purging a flask with an internal volume of 1 liter equipped with a stirrer, reflux condenser, dropping funnel, and thermometer with argon,
Shaved magnesium for metal 32. Og was added. Dripping row
Add 120 g of n-butyl chloride and di-n-butyl ether to
About 30 ml of the solution was added dropwise to the magnesium in the flask to start the reaction. After starting the reaction, 5
The dropwise addition was continued at 0°C over 4 hours, and after the dropwise addition was completed, the reaction was continued at 60°C for an additional 1 hour. Thereafter, the reaction solution was cooled to room temperature and the solid content was filtered off.

n-Butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid, and the concentration was determined by back titration with a 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator). ), the concentration was 2.0 mol/l. (b) Synthesis of solid product After purging a flask with an internal volume of 200 ml equipped with a stirrer and a dropping funnel with argon, Chromosolve 101 manufactured by Johns-Manville was vacuum-dried at 80°C for 0.5 hours5. 0 g and 20 ml of n-butyl ether were added, and while stirring, 14.0 ml of the organomagnesium compound synthesized in (1) was added dropwise from the dropping funnel over 10 minutes while keeping the temperature inside the flask at 80°C. , and further treated at the same temperature for 1 hour. Then n-butyl ether 20
After repeating washing twice with 20 ml of n-heptane and twice with 20 ml of n-heptane, 5.3 g of the organic magnesium treated product was dried under reduced pressure.
I got it. Next, an internal volume of 100 equipped with a stirrer and a dropping funnel.
After purging the flask with argon, 5.0 g of the previously synthesized organomagnesium treated product and 25 m of n-heptane were added.
l, tetrabutoxytitanium 0.44g (1.3mmol
), tetraethoxysilane 4.5g (21.6mmol
) and stirred at 30°C for 30 minutes. Next, 4.6 ml of the organomagnesium compound synthesized in (1) was added dropwise from the dropping funnel over 1 hour while maintaining the temperature inside the flask at 5°C. After the dropwise addition was completed, the mixture was stirred at 5° C. for 1 hour and then at room temperature for 1 hour, washed three times with 25 ml of n-heptane, and dried under reduced pressure to obtain 6.4 g of a brown solid product. (c) Preparation of solid catalyst component After replacing the flask with an internal volume of 100 ml with argon,
6.0 g of the solid product synthesized by the reduction reaction of (1),
Add 30.0 ml of chlorobenzene and 0.41 ml (1.5 mmol) of diisobutyl phthalate, and stir at 80°C.
A time reaction was performed. After the reaction, solid-liquid separation is performed, and n-heptane 3
Washing was performed twice with 0 ml. After washing, add 30.0ml of chlorobenzene and 0.5ml of n-butyl ether to the flask.
3 ml (3.1 mmol) and 9.6 m of titanium tetrachloride
1 (87.3 mmol) was added, and the reaction was carried out at 80° C. for 3 hours. After the reaction was completed, solid-liquid separation was performed at 80° C., followed by washing twice with 30.0 ml of chlorobenzene at the same temperature. The above-mentioned treatment with the mixture of n-butyl ether and titanium tetrachloride was repeated for 1 hour, and then treated with n-heptane 3
Washing was repeated twice with 0 ml and then dried under reduced pressure to obtain 5.1 g of a brown solid catalyst component. Elemental analysis revealed that Ti
was 0.5 wt%.

(d) Production of block copolymer (c) above
3.36 g of the solid catalyst component obtained (0.3 in terms of Ti)
5 mmol), triethylaluminum 3.0 g (26
．． 3 mmol), phenyltrimethoxysilane 0.78
The block copolymer shown in Table 4 was obtained by polymerizing in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1. Activity is 600g/g
When the pellets were visually observed, they were found to be yellowish.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

Effects of the Invention By producing a propylene block copolymer using the production method of the present invention, a propylene block copolymer with excellent flexibility and impact resistance can be produced by polymerization in a polymerization vessel in the absence of a solvent. It can be obtained stably for a long period of time without causing poor movement of the combined particles, adhesion of the particles to the inner wall of the polymerization vessel, clogging of the pipes by the particles during transportation, etc.

[Brief explanation of drawings]

FIG. 1 shows a preparation diagram of the catalyst used in the present invention.

Claims (1)

[Claims] Claim 1: The following two steps (I) are carried out in the absence of a solvent.
) and (II), the following component (A)
It was carried out in the presence of a catalyst consisting of a combination of ~ (C), the propylene content was 50 wt% or more, the xylene soluble content (25 ° C.
) is 10 to 60 wt%, and the xylene insoluble content (25
℃) ethylene content is 15-60 wt%, MF
A method for producing a propylene block copolymer, comprising producing a propylene block copolymer having an R of 0.01 to 1000 g/10 min. [Polymerization step] (I) A step of homopolymerization of propylene or copolymerization of propylene and ethylene, in which the propylene content in the polymer is 85 wt% or more and the polymerization ratio is 30 to 80%.
The process of wt%. (II) A copolymerization step of propylene and ethylene, the ethylene content in the copolymer being 60 wt% or more,
A step in which the polymerization ratio is 20 to 70 wt%. [Catalyst] Component (A) A solid catalyst containing magnesium, titanium, halogen, and an electron-donating compound. Component (B) Periodic Table IA, IIA, IIB, III
At least one selected from organometallic compounds of group B and IVB metals. Component (C) Electron-donating compound.