JP5401282B2 - Propylene-based polymer production method and propylene-based block copolymer - Google Patents

Description

  The present invention relates to a method for producing a propylene polymer and a propylene block copolymer, and more specifically, propylene having excellent flexibility and transparency in gas phase polymerization using a supported catalyst containing a metallocene transition metal compound. The present invention relates to a method for producing a very clean propylene polymer having no odor or stickiness even when it is a polymer, and producing a very clean propylene polymer with little smoke during processing, and a specific propylene block copolymer obtained by the method. is there.

  Propylene polymers are widely used in various applications such as various industrial materials, various containers, daily necessities, films, and fibers because of their excellent heat resistance, moldability, transparency, chemical resistance, and the like. Recently, in addition to conventional Ziegler-Natta catalysts, propylene polymers using metallocene catalysts have been industrialized.

  It is known that a propylene polymer having a sharp molecular weight distribution and composition distribution can be produced by using a metallocene catalyst. By making use of this feature, it is possible to suppress the generation of oligomer components that cause odors and stickiness of the product, or smoke during processing, which is suitable for producing environmentally friendly clean polymers.

However, although the production of such a polymer has been confirmed at a laboratory level with a small production scale, when it comes to production on an industrial scale, due to non-uniformity in the polymerization tank, it is at the laboratory level. Oligomer components may be produced in amounts not found in production.
As a solution for such a situation, for example, for a polymer produced by so-called bulk polymerization using liquid propylene as a polymerization mode, the amount of oligomer component is very high by interposing a washing step with liquefied propylene after the polymerization step. Patent Documents 1 and 2 describe that an extremely small number of polymers can be produced.

On the other hand, in recent years, a more economical and compact gas phase polymerization method tends to be used more frequently as a manufacturing process. Many examples of methods for producing various propylene polymers by combining with the metallocene catalyst have been reported. (For example, see Patent Document 3)
Regarding the removal of the oligomer component when using the gas phase polymerization method, it is very difficult to wash the produced polymer with liquefied propylene or the like in consideration of economy in industrial scale production. In addition, as shown in Patent Document 3, when a so-called block copolymer is produced by multistage polymerization, the rubber component is dissolved during washing, so that the produced polymer itself cannot be washed in the first place. Yes, the means of polymer washing cannot be used in practice.
Moreover, although patent document 4 has description about the method of adjusting the quantity of the scavenger added at the time of superposition | polymerization so that the amount of oligomers of C14-18 may be less than 50 weight ppm, it is object here. C14-18 oligomers are limited to olefinic (unsaturated) oligomers, and according to the examples of the document, the total amount of oligomers including aliphatics is 492 ppm or more. However, since aliphatic oligomers also cause odor, stickiness, or smoke during processing, the method described in Patent Document 4 cannot achieve the object of the present application.
Furthermore, Patent Document 5 describes an example in which isododecane is used as a solvent. However, since hydrocarbons and oligomer components having more than 10 carbon atoms have a high boiling point, it is difficult to remove them even when polymer drying is used.
Therefore, when gas phase polymerization is used, it is essential to suppress the generation of oligomer components during the polymerization, and the development of industrially feasible means that enables this is desired.

  Furthermore, with the supported catalyst containing the metallocene transition metal compound used in the present invention and the commonly used Ziegler-Natta type catalyst, the behavior after being added to the reactor such as initial activity and catalyst dispersion However, the metallocene catalyst tends to make a non-uniform polymerization state. In particular, when a flexible propylene-based copolymer that exhibits the effects of the present invention is produced, this tendency becomes remarkable. Therefore, it has been desired to develop a method for feeding a catalyst different from the Ziegler-Natta type catalyst.

JP 2003-119221 A JP2008-106089 JP2007-297505A Special table flat 10-506418 Special table 2003-533550

  In view of the above-mentioned problems of the prior art, the object of the present invention is to use a supported catalyst containing a metallocene-based transition metal compound, gas phase polymerization, even a propylene-based polymer having excellent flexibility and transparency, An object of the present invention is to provide a very clean propylene-based polymer production method that is free from stickiness and generates less smoke during processing, and a specific propylene-based block copolymer obtained by the method.

  As a result of intensive studies to solve the above problems, the present inventors have used a continuous polymerization method, and a catalyst slurry in which a polymerization catalyst component is suspended in a saturated hydrocarbon having 3 to 8 carbon atoms is either continuous or intermittent. The propylene-based polymer produced is withdrawn from the polymerization reactor continuously or intermittently, and the amount of saturated hydrocarbon added to the polymerization reactor per unit time is fed to the polymerization reactor. By feeding the total to the reactor so that the total amount of propylene polymer produced per unit time is a specific amount, dispersion of the catalyst fed to the reactor in the reactor is improved. It was found that non-uniformity in the reactor was eliminated, and the amount of oligomer components in the produced polymer was suppressed.

That is, according to the first invention of the present invention, in the method for producing a propylene polymer by a gas phase polymerization method in the presence of a polymerization catalyst component containing a metallocene transition metal compound supported on a carrier,
A catalyst slurry in which a polymerization catalyst component is suspended in a saturated hydrocarbon having 3 to 8 carbon atoms using a continuous polymerization method is continuously or intermittently fed to a polymerization reactor, while the produced propylene-based polymer. Is continuously or intermittently withdrawn from the polymerization reactor, in which case the total amount of saturated hydrocarbons added to the polymerization reactor per unit time is the total amount of propylene polymer produced per unit time. A method for producing a propylene polymer, characterized in that the content is adjusted to 0.01 to 1% by weight, is provided.

  According to a second invention of the present invention, in the first invention, the polymerization reactor is a gas phase polymerization reactor provided with a mechanical stirring means. A method is provided.

  According to a third aspect of the present invention, there is provided a method for producing a propylene polymer according to the first or second aspect, wherein the saturated hydrocarbon is normal hexane or normal heptane. .

  According to a fourth aspect of the present invention, there is provided a method for producing a propylene-based polymer according to any one of the first to third aspects, wherein the continuous polymerization method is a multistage polymerization of two or more stages. Provided.

According to a fifth aspect of the present invention, the propylene-based polymer is a propylene homopolymer or a random copolymer of ethylene and / or a C4 to C20 α-olefin and propylene (A 30 to 90% by weight, and a polymer component (B) which is a propylene-based random copolymer containing ethylene and / or a C4 to C20 α-olefin higher than the polymer component (A). A method for producing a propylene-based polymer according to the first invention is provided, which is a propylene-based block copolymer having a content of a hydrocarbon compound having 30 or less carbon atoms of 50 ppm by weight or less .

According to the production method of the present invention, there is no odor or stickiness even with a propylene polymer excellent in flexibility and transparency, and a very clean propylene polymer with little smoke during processing, Since it can be manufactured industrially and stably, it is very useful industrially.
In addition, the propylene block copolymer of the present invention is a very clean propylene block copolymer having no odor or stickiness even with a propylene block copolymer having excellent flexibility and transparency, and having very little smoke during processing. Since it is a propylene polymer, it is very useful industrially.

FIG. 1 is a flow sheet showing an outline of the polymerization apparatus used in Examples 1 to 6 and Comparative Examples 1 and 2. FIG. 2 is a flow sheet showing an outline of the polymerization apparatus used in Examples 7 to 11 and Comparative Example 3.

DESCRIPTION OF SYMBOLS 1 Catalyst component supply piping 2 Liquefied propylene supply piping 3 for catalyst component supply assistance 3 Organaluminum supply piping 4 Raw material mixed gas supply piping 5 Raw material liquefied propylene supply piping 6 Unreacted gas extraction piping 10 Polymerization reactor 11 Polymer extraction piping 101 Catalyst component Supply pipe 102 Liquefied propylene supply pipe 103 for assisting catalyst component supply 103 Organoaluminum supply pipe 104, 107 Raw material mixed gas supply pipe 105, 108 Raw material liquefied propylene supply pipe 106, 109 Unreacted gas extraction pipe 110 Polymerizer (first polymerization step)
111 Polymer Extraction Pipe 112 from the First Polymerization Step 112 Polymer Supply Pipe 113 to the Second Polymerization Step Polymer Extraction Pipe 120 from the Second Polymerization Step Polymerizer (Second Polymerization Step)
130 Degassing tank

The present invention is a production method for producing a propylene polymer by gas phase polymerization using a supported catalyst containing a metallocene transition metal compound, and using a continuous polymerization method, the polymerization catalyst component has 3 to 8 carbon atoms. As the catalyst slurry suspended in the saturated hydrocarbon solvent, the total amount of the saturated hydrocarbon added to the polymerization reactor per unit time is equal to the total amount of the produced propylene polymer per unit time. A method for producing a clean propylene-based polymer in which the amount of oligomer components in the produced polymer is suppressed, and a specific propylene-based polymer obtained by the method, characterized by being fed to a reactor so as to have a specific amount The present invention relates to a block copolymer.
The present invention also relates to a polymer component (A) 30 to 90% by weight and a polymer component (A) which is a propylene homopolymer or a random copolymer of ethylene and / or a C4 to C20 α-olefin and propylene. The content of the hydrocarbon compound having 10 to 70% by weight of the polymer component (B) which is a propylene random copolymer containing higher ethylene and / or C4 to C20 α-olefin, and having 30 or less carbon atoms. The present invention relates to a propylene-based block copolymer that is 50 ppm by weight or less.
Hereinafter, the contents will be described in detail.

I. About the catalyst used 1. Catalyst In the method for producing a propylene polymer of the present invention, it is necessary to use a supported catalyst containing a metallocene transition metal compound. Since the catalyst containing a metallocene-based transition metal compound has a feature of narrow molecular weight distribution and composition distribution, the conditions in the polymerization reactor are uniform, and unless there are places where the polymerization conditions are locally different, Because there is almost no generation of low molecular weight polymerization components that cause sticky components that hinder stable operation or polymerization components that are extremely biased in composition, there is no odor or stickiness, and there is very little smoke during processing. It is very suitable for producing a very clean propylene polymer. In order to provide an industrial and stable production method of a propylene polymer by a gas phase polymerization method, which is an object of the present invention, it is essential to use a supported catalyst supported on a carrier. The catalyst system required for the present invention is not particularly limited as long as it is a supported catalyst containing a metallocene-based transition metal compound, but among them, as a supported catalyst system containing a metallocene-based transition metal compound that is suitably used, (A) a metallocene complex comprising a transition metal compound of Group 4 of the periodic table having a conjugated five-membered ring ligand, (b) a carrier supporting it, (c) a cocatalyst for activating it, and as required There may be mentioned those composed of (d) organoaluminum compounds used accordingly. Hereinafter, (a) to (d) will be described.
In the description of the present specification, a long period type is used as the periodic table of elements.

(1) Metallocene transition metal compound (a)
Examples of the metallocene transition metal compound used in the present invention include metallocene complexes of Group 4-6 transition metal compounds in the periodic table having a conjugated five-membered ring ligand as representative examples. Those represented by either general formula are preferred.

  (In the formula, A and A ′ are cyclopentadienyl groups which may have a substituent, Q is a binding group that bridges between two conjugated five-membered ring ligands at an arbitrary position, and M is a period. (Transition metals selected from groups 4 to 6 in the table, X and Y are auxiliary ligands)

In the above general formula, when the cyclopentadienyl group has a substituent, examples of the substituent include hydrocarbon groups having 1 to 30 carbon atoms (including heteroatoms such as halogen, silicon, oxygen, and sulfur). This hydrocarbon group may be bonded to the cyclopentadienyl group as a monovalent group, or when there are a plurality of these groups, two of them are each at the other end (ω-end). ) May form a ring together with a part of cyclopentadienyl. Other examples of this substituent include an indenyl group, a fluorenyl group, or an azulenyl group, and these groups may further have a substituent on the side ring, and among them, an indenyl group or an azulenyl group. Is preferred.
Q is preferably an alkylene group, a silylene group, a silafluorene group, or a germylene group.
M is preferably titanium, zirconium, hafnium or the like. In particular, zirconium and hafnium are mentioned.
The auxiliary ligands X and Y react with the component (c) to produce an active metallocene having an olefin polymerization ability. Therefore, as long as this purpose is achieved, X and Y are The type is not limited, and examples thereof include a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon group that may have a hetero atom. Among these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable.

  The propylene block copolymer preferably produced in the present invention is characterized by being free from odor and stickiness. This feature is particularly effective when the propylene block copolymer is highly flexible. In order to produce such a preferable propylene-based block copolymer, JP-A-10-226712, JP-A-2000-95791, JP-T2003-522259, JP-T2003-533550, JP-A-2003-533550, It is preferable to use a metallocene compound described in Kaikai 2005-68261.

(2) Carrier (b)
As the catalyst carrier used in the present invention, known ones can be used. Preferred carriers include inorganic compound carriers such as silica, titania, alumina, silica-alumina, silica-magnesia, ion-exchange layered silicate, and polypropylene. Examples thereof include polymer carriers such as powder and polyethylene powder.
Among these, in order to adjust the shape of the polymer particles and increase the particle size, it is particularly preferable to use a supported catalyst having a controlled particle shape and particle size. As a method for producing such a supported catalyst having a controlled particle shape and particle size, for example, when an inorganic compound carrier is used, the following examples can be given.

  The particle diameter of the raw material inorganic compound carrier is usually 0.01 to 5 μm in average particle diameter, and the particle fraction of less than 1 μm is 10% or more, preferably the average particle diameter is 0.1 to 3 μm, The particle fraction of less than 1 μm is preferably 40% or more. As a method of obtaining inorganic compound carrier particles having such a particle size, a dry fine particle formation method, for example, a fine particle formation by a jet mill, a ball mill, a vibration mill or the like, or a pulverization method in a wet state, polytron, etc. is used. There are methods such as pulverization by forced stirring, dyno mill, pearl mill and the like.

Further, the carrier may be granulated to a preferred particle size, and the granulation method includes, for example, stirring granulation method, spray granulation method, rolling granulation method, briquetting, fluidized bed granulation Method and submerged granulation method. A preferable granulation method is a stirring granulation method, a spray granulation method, a rolling granulation method or a fluidized granulation method, and more preferably a spray granulation method. The particle strength will be described later, but it can also be controlled in this granulation step. In order to obtain a preferred range of crushing strength, it is preferable to use an inorganic compound carrier having a particle size distribution as described above.
Further, the granulation methods in the case of granulating in multiple stages may be combined, and the combination is not limited, but preferably, the spray granulation method and the spray granulation method, the spray granulation method and the rolling method. A combination of a granulation method, a spray granulation method and a fluidized granulation method may be mentioned.

The shape of the granulated particles obtained by the granulation method as described above is preferably spherical, and specifically, M / L (where L is the value of the maximum particle diameter in the projected view and M is L The values of the diameters orthogonal to each other are shown.) For the particles having a value of 0.8 to 1.0, the number is 50% to 100% of all particles, preferably 85% to 100% of all particles. % Or less.
M / L is obtained by observing 100 or more of arbitrary particles with an optical microscope and image-processing them.

  The concentration of the silicate in the raw slurry in the spray granulation in which spherical inorganic compound carrier particles are obtained is usually 0.1 to 50% by mass, preferably 0.5 to 30% by mass, although it depends on the slurry viscosity. Preferably it is 5.0-20 mass%. The temperature at the inlet of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but when water is taken as an example, it is usually selected in the range of 80 to 260 ° C, preferably 100 to 220 ° C. Any desired dispersion medium can be used. As the dispersion medium, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, or the like may be used alone, or two or more kinds may be used in combination. However, water is preferred.

  The inorganic compound carrier particles thus obtained may be used as a catalyst carrier as it is, and in that case, the particle size is preferably selected in the range of 1 to 200 μm, more preferably 10 to 150 μm.

Further, in order to obtain particles having a desired shape with a desired particle diameter, the particle diameter of the raw material may be prepared by at least two stages of granulation processes. For example, it is possible to control the particle shape and particle size by granulating to a particle size that can be granulated to some extent in the first-stage granulation step, and granulating again using the granulated particle size.
Specifically, as such a stepwise granulation method, first, the inorganic compound carrier fine particles of the raw material having an average particle diameter of 0.01 to 5 μm are first granulated in the first stage granulation step to perform primary granulation. Granule particles are produced. The particle diameter of the primary granulated particles is preferably 1 to 25 μm, more preferably 1 to 15 μm.
Next, the primary granulated particles thus granulated are further slurried and granulated. At that time, since the slurry viscosity is relatively low, the slurry concentration can be increased, and by adopting appropriate spray granulation conditions, the particle size and particle shape suitable for the polymerization catalyst component should be obtained. Can do. The final particle size is usually 25 to 200 μm, preferably 25 to 150 μm, although it depends on the type of raw inorganic compound carrier.

  The granulation conditions can be selected appropriately so that particles having good properties can be obtained by the granulation method. For example, in the spray granulation method, the inlet temperature of hot air during spraying can be set in a wide temperature range of about 90 ° C to 300 ° C. The outlet temperature is defined by the flow rate of spray from the nozzle or disk, the flow rate of hot air, and the like, and is 80 ° C. to 150 ° C. As the spray format, a general spray drying method such as a disk type, a pressurized nozzle type, or a two-fluid nozzle type can be applied. The particle size can be controlled by setting the flow rate of the spray liquid, the rotational speed or disc size of the disc, the pressure of the pressure nozzle, the flow rate of the carrier gas, and the like.

  When primary granulated particles are granulated again to produce secondary particles, the secondary granulated particles have a larger size. The particle size increase rate of the primary particles relative to the raw material particles is preferably 3 to 500%, more preferably 5 to 300%. Further, the particle size increase rate of the secondary particles relative to the primary particles is preferably 3 to 200%, more preferably 3 to 100%. Therefore, it is possible to obtain particles with better powder properties when the primary granulation condition and the secondary granulation condition are different. For example, it is possible to obtain particles in which secondary granulation is preferable to lower the rotational speed of the disk than primary granulation. The secondary granulation disk rotation speed is preferably 1000 to 30000 rpm lower than the primary granulation disk rotation speed, and more preferably 5000 to 20000 rpm. The drying temperature is preferably lower in the secondary granulation than in the primary granulation. The hot air inlet temperature for secondary granulation is preferably 10 to 80 ° C. lower than the hot air inlet temperature for primary granulation, and more preferably 20 to 50 ° C. lower. Specifically, depending on the disk size, in the primary granulation, the hot air inlet temperature is preferably 130 to 250 ° C, more preferably 150 to 200 ° C. The disk rotation speed is preferably 10,000 to 30,000 rpm. In secondary granulation, the hot air inlet temperature is preferably 90 ° C to 180 ° C, more preferably 100 to 150 ° C. The disk rotation speed is preferably 5000 to 20000 rpm.

During granulation, organic substances, inorganic solvents, inorganic salts, and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, Examples thereof include latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate.
In this manner, a supported catalyst having a maintained particle shape and particle size can be produced by supporting a metallocene complex on a granulated inorganic compound carrier.

(3) Cocatalyst (activator component) (c)
The cocatalyst is a component that activates the metallocene complex, and is a compound that can react with the auxiliary ligand of the metallocene complex to convert the complex into an active species having an olefin polymerization ability. Specifically, (c- 1) an aluminum oxy compound, (c-2) an ionic compound or Lewis acid capable of reacting with component (a) to convert component (a) into a cation, (c-3) a solid acid, (c- 4) Ion exchange layered silicate and the like. Hereinafter, (c-1) to (c-4) will be described.

(C-1): Aluminum Oxy Compound It is well known that an aluminum oxy compound can activate a metallocene complex. Specifically, examples of the compound include aluminoxane, one type of trialkylaluminum, or two or more types of trialkyl. It is a compound that can be obtained by the reaction of aluminum and alkylboronic acid in a ratio of 10: 1 to 1: 1 (molar ratio). When aluminoxane is used, methylaluminoxane or methylisobutylaluminoxane is preferred. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.

(C-2): An ionic compound or Lewis acid (c-2) compound capable of reacting with component (a) to convert component (a) into a cation reacts with component (a) An ionic compound or Lewis acid capable of converting the component (a) into a cation. Examples of such an ionic compound include cations such as a carbonium cation and an ammonium cation, triphenyl boron, and tris (3 , 5-difluorophenyl) boron, and complexed compounds with organic boron compounds such as tris (pentafluorophenyl) boron.
Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (a) and can convert a component (a) into a cation. Examples of the metallocene catalyst using the non-coordinating boron compound described above are disclosed in JP-A-3-234709 and JP-A-5-247128.

(C-3): Solid acid Examples of the solid acid include alumina, silica-alumina, silica-magnesia and the like.

(C-4): Ion exchange layered compound The ion exchange layer compound occupies most of the clay mineral, and is preferably an ion exchange layered silicate.
An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. You may go out. Various known silicates can be used. Specific examples include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).

(I) 2: 1 type minerals Smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc .; vermiculite group such as vermiculite; mica such as mica, illite, sericite, sea chlorite Pylophilite-talc group such as pyrophyllite and talc; Chlorite group such as Mg chlorite.
(Ii) 2: 1 ribbon type minerals Sepiolite, palygorskite and the like.

The silicate used as a raw material in the present invention may be a layered silicate in which the above mixed layer is formed. In the present invention, the main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. As the silicate used in the present invention, those obtained as natural products or industrial raw materials can be used as they are without any particular treatment, but chemical treatment is preferred. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.
Moreover, since these ion-exchange layered silicates usually contain adsorbed water and interlayer water, it is preferable to use them after removing moisture by heat dehydration under an inert gas flow.

  Those having the functions of both the support (b) and the cocatalyst (c), specifically, the ion-exchangeable layered compound of the above (c-4) can be used as the support and cocatalyst.

(4) Organoaluminum compound (d)
As the organoaluminum compound used in the metallocene catalyst system as necessary, those containing no halogen are used in the present invention. Specifically, the organoaluminum compound is represented by the general formula AlR _3-i X _i
(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen or an alkoxy group, and i is a number of 0 <i ≦ 3. However, when X is hydrogen, i is 0 <i <. 3)
The compound shown by is used.

  Specific compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trioctylaluminum, or diethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, diisobutylaluminum ethoxide, etc. A halide-containing alkylaluminum such as an alkoxy-containing alkylaluminum or diethylaluminum halide. Of these, trialkylaluminum is particularly preferred. More preferred are triisobutylaluminum and trioctylaluminum.

2. Use amount of catalyst component In the above catalyst component, the use amounts of the component (a) and the component (c) are used in an optimum amount ratio in each combination.
When component (c) is an aluminum oxy compound, the molar ratio of Al / transition metal is usually 10 or more and 100,000 or less, more preferably 100 or more and 20,000 or less, and particularly preferably 100 or more and 10,000 or less. On the other hand, when an ionic compound or Lewis acid is used as the component (c), the molar ratio of the transition metal to the transition metal is usually 0.1 to 1000, preferably 0.5 to 100, and more preferably 1 to 50. It is.
When a solid acid or an ion-exchange layered silicate is used as component (c), the transition metal complex dose is usually 0.001 to 10 mmol, preferably 0.001 to 1 mmol, per 1 g of component (c). Range.
These use ratios are examples of general ratios, and are not limited to the above-described use ratio ranges as long as the catalyst is suitable.

  The catalyst used in the present invention is made by supporting a polyolefin production catalyst comprising a transition metal complex and a co-catalyst as a catalyst for olefin polymerization (main polymerization), if necessary, after being supported on a carrier, ethylene, propylene, Even if a prepolymerization treatment for preliminarily polymerizing a small amount of olefins such as 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene is performed. Good. A known method can be used as the prepolymerization method.

II. About polymerization As a method for producing the propylene-based polymer of the present invention, it is essential to polymerize by using a gas phase polymerization method. When the production of the propylene-based polymer of the present invention is carried out by multistage polymerization, at least the first stage (hereinafter also referred to as “first process” or “first polymerization process”) uses a gas phase polymerization method. It is essential.
When this polymerization is carried out by so-called slurry polymerization in which polymerization is carried out in an inert solvent or so-called bulk polymerization in which polymerization is carried out in liquid propylene, a recovery operation of the polymerization solvent is required, which increases the burden on the economy and the environment. In particular, in the case where the propylene polymer to be polymerized is a polymer having a relatively low melting point, there is a concern that the amount of the eluted component in the solvent may increase or the polymer may be dissolved. The problem arises that it is not possible to increase For this reason, the present invention is carried out by gas phase polymerization.

  On the other hand, when the production of the propylene-based polymer of the present invention is carried out by multistage polymerization, generally the propylene-based block is generally used after the second stage (hereinafter also referred to as “second process” or “second polymerization process”). When producing a copolymer, the propylene-ethylene random copolymer component produced in the second and subsequent steps is often a rubber component, and it is eluted in the presence of a liquid such as a solvent. A polymerization method is used, and in particular, a gas phase polymerization method is recommended for producing a polymer having a large proportion of components produced in the second and subsequent steps.

  Moreover, the polymerization method adopts a continuous method in which a catalyst is continuously or intermittently introduced into a reactor and a polymer is continuously or intermittently extracted from the viewpoint of industrial production in consideration of manufacturing costs. It is essential. In the present invention, when a multistage polymerization method is used, depending on the case, each step can be further divided. In particular, a method of making various types of rubber components by dividing the second and subsequent steps into two or more stages is one of the physical property improving methods.

The polymerization temperature T1 in the first step is preferably 35 to 80 ° C., the difference (Tm−T1) from the melting point Tm in the propylene homopolymer or propylene-α-olefin random copolymer component produced in the step, More preferably, the temperature is set to 40 to 75 ° C. When (Tm-T1) is smaller than 40 ° C., the properties of the propylene homopolymer or propylene-α-olefin random copolymer component to be polymerized deteriorate, and stable operation cannot be performed. On the other hand, when the temperature is higher than 80 ° C., the polymerization temperature becomes too low, and it becomes difficult to secure the cooling water temperature for heat removal, and the temperature falls below the temperature range where industrial production is allowed. From such a viewpoint, the absolute value of the polymerization temperature in the first step is desirably higher than 50 ° C.
Further, it is preferable to design a desired Tm in advance and to set the polymerization temperature T1 for the Tm.

  The polymerization pressure needs to be set in consideration of the polymerization activity from the catalyst performance in the gas phase polymerization. On the other hand, it must be set within a range where propylene is not liquefied within the above polymerization temperature range. In consideration of the above, the sum of partial pressures of monomers related to polymerization, specifically, propylene and α-olefin is usually 0.1 to 4.5 MPa, preferably 0.5 to 4 MPa, more preferably Is preferably selected in the range of 1 to 3.5 MPa.

In the reactor, in addition to the above-mentioned monomers, so-called inert gas such as nitrogen, propane, n-butane and isobutane which are not directly related to the reaction may be present.
Moreover, it is preferable to use a molecular weight regulator so that the fluidity of the polymer is appropriate, and hydrogen is preferred as the regulator. The MFR is selected in the range of usually 0.1 to 3000 g / 10 minutes, preferably 0.5 to 2000 g / 10 minutes, more preferably 0.5 to 1000 g / 10 minutes, depending on the application of the polymer. The total pressure in the polymerization reactor is the sum of the partial pressures of hydrogen and the like when using monomers (propylene, α-olefin), inert gas (nitrogen, propane, etc.), and molecular weight regulator as listed above. Therefore, although the value varies depending on the situation, it is preferably 0.5 to 6 MPa, more preferably 0.5 to 5 MPa in consideration of the pressure resistance design of the reactor from the viewpoint of industrial production.

  When the present invention is carried out using a multistage polymerization method, the polymerization temperature in the second and subsequent steps is usually 30 to 100 ° C, preferably about 50 to 80 ° C. Since the propylene-α-olefin copolymer component produced in the second and subsequent steps is a rubber component or a component close thereto, if the polymerization temperature is too high, stable production cannot be achieved due to deterioration of powder properties. End up. The polymerization pressure after the second step is usually 0.1 to 5 MPa, preferably 0.5 to 3 MPa.

  The mass average molecular weight of the propylene-based polymer component in the second and subsequent steps is usually from 50,000 to 2,000,000, preferably from 70,000 to 1,500,000, and more preferably from 70,000 to 1,200,000. In order to adjust the molecular weight of the polymer to the above preferred range, it is preferable to use a molecular weight regulator, and hydrogen is preferred as the regulator.

The gas phase polymerization process is broadly divided into a process with mechanical stirring and a process without mechanical stirring, with the polymer phase forming a fluidized bed by blowing up gas from the bottom of the reactor. Can be divided into the process of proceeding. However, in the latter case, when the particle size of the polymerized polymer to be produced becomes large, it is necessary to increase the flow rate of the gas to be blown up, and the blower becomes large, which is economically disadvantageous. Furthermore, it is known that when the powder particle size is increased, a normal flow state cannot be formed no matter how much the gas flow rate is increased, which is not preferable from the viewpoint of stable operation. For these reasons, it is preferable to use a gas phase polymerization process with mechanical stirring in order to produce the propylene polymer component that is the object of the present invention.
If it is a gas phase polymerization process with mechanical stirring, there is no restriction | limiting in the form of a reactor, A vertical type, a horizontal type, or another form can be used.
The gas phase polymerization process with mechanical stirring can be achieved by using a gas phase polymerization reactor equipped with mechanical stirring means.
Furthermore, since the object of the present invention is stable production of a propylene polymer on an industrial scale, it can be applied to a reactor of a size used on an industrial scale. Specifically, the reactor volume is preferably 50 liters or more.

  In the present invention, a supported catalyst used for polymerization is suspended in a saturated hydrocarbon solvent having 3 to 8 carbon atoms, preferably in a saturated hydrocarbon solvent having 4 to 7 carbon atoms, and more preferably in normal hexane or normal heptane. And the catalyst slurry is fed to a polymerization reactor. If the number of carbon atoms of the saturated hydrocarbon used in the solvent is greater than 9, the boiling point of the solvent becomes high, which may result in incomplete evaporation of the solvent in the drying process, resulting in a high oligomer concentration in the product. This is not preferable.

  In the present invention, it is essential to control the ratio of the total amount of the saturated hydrocarbon solvent having 3 to 8 carbon atoms to the production amount of the propylene-based polymer within a certain range. The hydrocarbon solvent evaporates after a certain time after being fed to the reactor. If there is too much hydrocarbon solvent, it takes a long time to evaporate, so the polymerization proceeds without the catalyst being dispersed in the part wetted by the solvent, causing local temperature rise, etc. Is more likely to do. On the other hand, when the amount of the hydrocarbon solvent is too small, this means that the catalyst slurry concentration is in a high state, and the catalyst dispersion after feeding is also deteriorated, and a local temperature rise may occur as well. Becomes higher. In other words, in order to achieve good dispersion of the catalyst, various studies were carried out in view of the need for a certain balance in the amount of hydrocarbon solvent fed, and as a result, the propylene heavy polymer produced in the reactor was By controlling the total amount of the saturated hydrocarbon solvent having 3 to 8 carbon atoms added to the reactor with respect to the combined production amount within a certain range, the catalyst dispersion after feeding is maintained in a good state, and the local amount It has been found that the polymerization reaction proceeds under uniform conditions without causing a typical temperature rise.

  Specifically, the total amount of the saturated hydrocarbon solvent having 3 to 8 carbon atoms added to the reactor is 0.01 to 1% by weight, preferably 0.05, based on the production amount of the propylene-based polymer. It is controlled to be ˜1% by weight, more preferably 0.1% to 1% by weight. In addition, when manufacture of a propylene polymer is performed by a multistage polymerization method, the ratio of the saturated hydrocarbon solvent is calculated with respect to the final production amount. Moreover, since the continuous method is adopted, the above ratio can be calculated per unit time. The case where the above ratio is less than 0.01% by weight indicates that only a small amount of saturated hydrocarbon solvent is added into the reactor, which means that the catalyst slurry concentration is high. The catalyst dispersion after feeding becomes poor, the polymerization conditions in the reactor become uneven, and the amount of oligomer components that cause odor and stickiness may increase as a result. This is not preferable. In the case where the ratio is greater than 1% by weight, the amount of solvent brought into the reactor is too large, and the polymerization conditions in the reactor are still non-uniform, resulting in the formation of oligomer components. This is not preferable because the amount may increase or the solvent itself may not evaporate and remain in the product polymer.

  When the catalyst slurry is fed to the reactor under the above conditions, if the flow rate of the catalyst slurry is low, the catalyst slurry adheres to the vicinity of the feed pipe outlet, polymerization proceeds there, and the resulting polymer is fed to the feed pipe. May be blocked. In order to prevent this, it is necessary to increase the catalyst slurry flow rate. Examples of a method preferably used for increasing the flow rate of the catalyst slurry include appropriately reducing the pipe diameter, and assisting with liquefied propylene. In the case of assisting with liquefied propylene, the flow rate in the feed pipe is set to be 1 to 200 cm / sec, preferably 5 to 100 cm / sec in order to achieve the above-mentioned purpose and to prevent polymerization in the pipe. Is done. Moreover, in order to prevent superposition | polymerization in piping, the temperature of the liquefied propylene used is set to -40-40 degreeC, Preferably it is -30-30 degreeC.

  In addition, when producing a flexible propylene copolymer that exhibits the effects of the present invention, if the temperature of the drying process after polymerization is increased, the flexible component of the polymer dissolves and the fluidity of the powder May deteriorate and industrially stable continuous production may not be achieved. Therefore, since the temperature of the drying process cannot be set high, it is difficult to remove the oligomer component and the solvent in the drying process. For this reason, it is necessary to reduce the amount of oligomer produced during polymerization and the amount of solvent used. Specifically, assuming that the temperature of the dryer is Td (° C.), the temperature is set to 60 ≦ Td ≦ Tm−20, preferably 60 ≦ Td ≦ Tm−25 (Tm represents the melting point of the polymer). When the dryer temperature is lower than 60 ° C., the monomer is not sufficiently dried, which is not preferable in terms of quality as well as safety.

III. Propylene Polymer and Propylene Block Copolymer Produced The propylene polymer produced according to the present invention is polymerized by a gas phase polymerization method using a supported catalyst containing a metallocene transition metal compound. If there is, there is no particular limitation.

  The polymer to be produced is selected from a propylene homopolymer, a propylene-α-olefin random copolymer, and a propylene-based block copolymer depending on the intended use of the polymer to be produced. The α-olefin used in the case of the propylene-α-olefin random copolymer or the propylene block copolymer is an α-olefin having 2 to 20 carbon atoms excluding propylene, preferably ethylene, 1-butene, 1-hexene, 1-octene, particularly preferably ethylene is used.

The melting peak temperature (Tm) (hereinafter also referred to as melting point) of the propylene-based polymer or propylene-based block copolymer produced in the present invention is preferably 105 ° C. or higher. If the melting point is significantly lower than the above range, the polymer itself may partially melt at an industrially possible polymerization temperature, making it difficult to maintain stable operation. The upper limit is not particularly limited, but is preferably 160 ° C., more preferably 155 ° C. in the case of a flexible propylene-based block copolymer in which the effects of the present invention are particularly exerted.
When the produced polymer is a propylene-α-olefin random copolymer, the α-olefin content in the component is controlled and used so that the melting point of the copolymer is preferably 105 ° C. or more. Depending on the metallocene catalyst, it is generally in the range of 10% by mass or less. The α-olefin content is controlled by the amount of α-olefin added during polymerization.

  In the present invention, a remarkable effect is exhibited particularly in a propylene-based block copolymer produced by using a multistage polymerization method. Details will be described below.

A preferred propylene-based block copolymer produced by the present invention is a propylene homopolymer or propylene-α-olefin having a melting peak temperature Tm by a differential scanning calorimeter (DSC) of preferably 105 ° C. or higher in the first step. 30-90% by weight of random copolymer component (A) (hereinafter referred to as component (A)), propylene-α-olefin containing α-olefin higher than the content contained in component (A) in the second step It is characterized by containing 70 to 10% by weight of copolymer component (B) (hereinafter referred to as component (B)).
The melting peak temperature Tm of the component (A) is measured as a melting peak temperature by a differential scanning calorimeter (DSC) by a conventional method with respect to the component (A) sampled in a small amount after the first step. If sampling is difficult, the component (A) separated by the method described later may be used.

  The proportion of the component (A) polymerized in the first step and the component (B) polymerized in the second step is 30 to 90/70 to 10% by weight, preferably 40 to 90/60 to 10% by weight, more preferably Is 40-80 / 60-20% by weight. When the proportion of the component (A) is larger than 90% by weight, the effect of the component (B) is small, and the meaning of producing by multistage polymerization is reduced. Moreover, when the ratio of a component (B) becomes larger than 70 weight%, the powder property of a polymerization polymer will deteriorate and it will interfere with industrial stable operation.

  The α-olefin content in the component (B) polymerized in the second step is set higher than the α-olefin content in the component (A) polymerized in the first step. In the block copolymer of the present invention, the lower the crystallinity of the component (B) with respect to the component (A), the greater the flexibility improvement effect, and the crystallinity is in the propylene-α-olefin random copolymer. The α-olefin content is controlled.

  Furthermore, the preferable propylene-based block copolymer produced according to the present invention preferably has a hydrocarbon compound content of 30 or less carbon atoms of 50 ppm or less. If it exceeds 50 ppm, odor, stickiness, and fuming during processing become conspicuous, which is not preferable. The lower limit is preferably as small as possible from the viewpoint of cleanliness, but is preferably 10 ppm or more, and more preferably 15 ppm or more, considering the balance with industrial feasibility such as the load of the drying process.

Hereinafter, the ratio of the component (A) and the component (B) when the α-olefin is ethylene, and the method for measuring the ethylene content thereof will be described.
The ratio of component (A) to component (B) and their ethylene content are measured using TREF (temperature-temperature elution fractionation method) as follows.
First, using the difference in crystallinity between the component (A) and the component (B), a temperature T (C) for dividing the components (A) and (B) is determined from the elution curve obtained by TREF measurement, and T The proportion of the component eluted until (C) is regarded as the proportion of component (B), and the proportion of the component eluted at T (C) or higher is regarded as the proportion of component (A).
The technique for evaluating the crystallinity distribution of the propylene-ethylene random copolymer by TREF measurement is well known to those skilled in the art. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L .; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J .; B. P. Soares, A .; E. A detailed measurement method is shown in Hamielec, Polymer; 36, 8, 1639-1654 (1995) and the like.

In the present invention, the measurement is specifically performed as follows. A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, o-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is flowed through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.
A component having a low elution temperature has low crystallinity and is highly flexible, while a component having a high elution temperature has high crystallinity, thereby increasing rigidity and improving heat resistance. In the elution curve (dwt% / dT curve with respect to temperature) of the propylene-ethylene random block copolymer in the present invention, the crystalline propylene-ethylene random copolymer component (A), The amorphous propylene-ethylene random copolymer component (B) is observed as a component eluting at different temperatures due to the difference in crystallinity. That is, component (A) is observed on the high temperature side because of high crystallinity, and component (B) is observed on the low temperature side because it is low crystalline or amorphous, or does not show a peak within the TREF measurement temperature. When each peak temperature is T (A) and T (B) (when the peak is not shown, the lower limit of the measurement temperature is −15 ° C.), the temperature T (C) between the two peaks ({T (A) In + T (B)} / 2), both components are almost separable.

  At this time, in TREF, the integrated amount of the components eluted up to T (C) is defined as W (B) wt%, and the integrated amount of the portion eluted at T (C) or higher is defined as W (A) wt%. W (B) substantially corresponds to the amount of the low crystallinity or amorphous component (B), and W (A) substantially corresponds to the amount of the high crystallinity component (A).

Next, the T (C) soluble component = component (B) and the T (C) insoluble component = component (A) are separated by a temperature rising column separation method using a preparative separation apparatus. The specific method of separation is
Based on T (C) determined by TREF measurement, T (C) soluble component = component (B) and T (C) insoluble component = component (A And determine the ethylene content of each component by NMR. The temperature rising column fractionation method refers to a measurement method disclosed in, for example, Macromolecules, 21, 314-319 (1988).

As the separation conditions, a glass bead carrier (80 to 100 mesh) is packed in a cylindrical column having a diameter of 50 mm and a height of 500 mm, and maintained at 140 ° C. Next, 200 mL of the o-dichlorobenzene solution (10 mg / mL) of the sample dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (C) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (C), 800 mL of o (dichlorobenzene) of T (C) is allowed to flow at a flow rate of 20 mL / min, whereby components soluble in T (C) existing in the column are obtained. Elute and collect.
Next, the column temperature is increased to 140 ° C. at a rate of temperature increase of 10 ° C./min, left at 140 ° C. for 1 hour, and then 800 mL of 140 ° C. solvent o-dichlorobenzene is flowed at a flow rate of 20 mL / min. , And eluting and recovering insoluble components at T (C).
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is collected by filtration and dried overnight in a vacuum dryer.
Then, the ethylene content of each fractionated component is determined by NMR. A specific method is shown below.

Measurement of ethylene content by NMR The ethylene content of the obtained polymer is determined by analyzing a ¹³ C-NMR spectrum measured under the following conditions by a proton complete decoupling method.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent equipment (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene: heavy benzene = 4: 1 (volume ratio)
Concentration: 100 mg / ml
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more The attribution of the spectrum may be performed with reference to Macromolecules, 17, 1950 (1984), for example. The spectral assignments measured under the above conditions are as shown in Table 1 below. In the table S is the symbol such as _{alpha alpha} Carman et al (Macromolecules, 10,536 (1977)) in accordance with notation, P is represented each methyl carbon, S is methylene carbon, T is a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six kinds of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules, 15, 1150 (1982), the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .
By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
In addition, the [propylene random copolymer component] of the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby producing the following minute peak.

In order to obtain an accurate ethylene content, it is necessary to include the peaks derived from these heterogeneous bonds in the calculation.However, it is difficult to completely separate and identify the peaks derived from the heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is determined using the relational expressions (1) to (7) as in the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. And
Conversion from mol% to mass% of ethylene content is carried out using the following formula: ethylene content (mass%) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
Here, X is the ethylene content in mol%.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by these examples, unless it deviates from the summary.
The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated with molecular sieve MS-4A.
First, a measurement method, an evaluation method, and a device for each physical property value are shown.

I. Physical property measurement method, evaluation method and apparatus (1) MFR
A polypropylene-type polymer shows the melt index value measured by JIS-K-6758.

(2) Ethylene content in polymer Measured according to the method described above.

(3) Polymer melting point (Tm)
Using a DSC7 differential scanning calorimeter manufactured by Perkin Elmer, Inc., the sample was heated from room temperature to 230 ° C. under the condition of 80 ° C./minute, held at that temperature for 10 minutes, and then at −10 ° C./minute. The temperature was lowered to 50 ° C., held at the same temperature for 3 minutes, and then the peak temperature when melted under a temperature rising condition of 10 ° C./min was defined as the melting point (Tm).

(4) Measurement of the amount of oligomer component having 1 to 30 carbon atoms The injection-molded molded product was cut out at 2 mm × 50 mm, 200 mg of the sample was filled in a TGS tube manufactured by GERSTEL, and the TDS tube was inserted into a TDS-A device manufactured by GERSTEL. During the heating period, gas was introduced into GERSTEL CIS4 filled with TENAX, and CIS4 was cooled to -150 ° C to collect volatile components generated from the sample.
The collected components were introduced into the gas chromatogram by rapid vaporization to 320 ° C. The introduced gas was measured by gas chromatogram / mass spectrometry under the following conditions.
Device: HP6890
Column: DB-5ms 0.25mm x 30m
Temperature: 40 ° C. × 5 min → 10 ° C./min to 300 ° C. × 15 min
Detector: HP5973N
The amount of hydrocarbon is determined by gas chromatogram / mass spectrometry using normal heptane as a solvent and measuring aliphatic straight-chain saturated hydrocarbons with a concentration of 1, 5, and 10 μg / ml under the same conditions as the sample. A calibration curve was prepared by measurement, and quantification was performed in terms of aliphatic straight-chain saturated hydrocarbon having 20 carbon atoms.

(5) Measurement of the amount of smoke emitted After adding 0.05 parts by weight of IRGANOX1010 (manufactured by Ciba Japan) and IRGAFOS168 (manufactured by Ciba Japan) as antioxidants to the sample and blending them using a supermixer, a uniaxial 30 mm The mixture was melt-kneaded with an extruder at an extrusion temperature of 200 ° C. and a screw rotation speed of 100 rpm to obtain pellets. The pellet obtained by the above method is placed on the hopper of a multifilament spinning machine with a gear pump (die: Φ1.3 mm x 15 holes) equipped with a die pack having a discharge port for discharging vaporized substances generated in the die from one place. Then, melt extrusion was performed under the conditions of an extrusion temperature of 280 ° C., a gear pump rotation speed of 30 rpm, and a discharge rate of 1 kg / h, and the presence or absence of fuming was determined by visually observing the discharge port of the die pack. When the periphery of the discharge port looks white, it was judged that there was smoke, and when the periphery of the discharge port did not look white, it was marked as ○.

II. Examples and Comparative Examples (Example 1)
1. Preparation of prepolymerization catalyst Chemical treatment of silicate: 2.25 liters of distilled water and then 665 g of sulfuric acid (96%) were slowly added dropwise to a 3 liter glass separable flask equipped with a stirring blade. At 50 ° C., 400 g of montmorillonite (manufactured by Mizusawa Chemical Co., Ltd., Benclay SL; average particle size: 50 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 3.5 hours. The reaction was stopped by adding this reaction solution to 2 L of pure water, and the slurry was filtered under reduced pressure to collect the cake. Four liters of distilled water was added to the cake to reslurry and then filtered. This operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried at 120 ° C. overnight. After drying, 173.4 g was weighed and used in the next step.
The acid-treated clay was added to an aqueous solution in which 195.8 g of lithium sulfate hydrate was dissolved in 868 mL of pure water in a 3 liter plastic beaker and reacted at room temperature for 2 hours. The slurry was filtered and washed 5 times with 3 liters of distilled water.
The collected cake was dried at 120 ° C. overnight. The chemically treated silicate was dried in a kiln dryer.

Preparation of catalyst: 100 g of the dry silicate obtained above was introduced into a glass reactor equipped with a stirring blade having an internal volume of 3 liters, mixed with 580 ml of mixed heptane, and a normal heptane solution of trinormal octyl aluminum (concentration: 142.9 mg / concentration). l) 642.5 ml was added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to adjust the amount of silicate slurry to 2.0 liters. Next, 30.75 ml of a normal heptane solution of trinormal octylaluminum was added to the prepared silicate slurry and reacted for 1 hour. In another flask, (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium (synthesis is disclosed in Japanese Patent Laid-Open No. Hei 10- This was carried out in accordance with an example of Japanese Patent No. 110136.) A slurry obtained by adding mixed heptane (300 mL) to 2440 mg (3.0 mmol) was added and reacted at 60 ° C. for 1 hour.

Preliminary polymerization: Subsequently, 2.1 liters of normal heptane was introduced into a stirring autoclave having an internal volume of 10 liters which had been sufficiently substituted with nitrogen, and kept at 40 ° C. The previously prepared silicate / metallocene complex slurry was introduced therein. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 2 hours, the supply of propylene was stopped and maintained for an additional hour. After completion of the prepolymerization, the remaining monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then about 3 liters of the supernatant was decanted. Subsequently, 4.7 ml of a normal heptane solution of triisobutylaluminum (0.71 M / L) and 2.8 liters of heptane were added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then supernatant 2.8. Removed liters. This operation was further repeated 3 times. Subsequently, 8.5 ml of a normal heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.2 g of polypropylene per 1 g of catalyst was obtained.
Further, normal hexane was added to the obtained prepolymerized catalyst to prepare a 1.5 % by weight catalyst slurry as a catalyst component containing no prepolymerized polymer.

2. Polymerization FIG. 1 is a flow sheet of the polymerization apparatus used in the examples.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 10 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was raised while introducing propylene and hydrogen, and when the polymerization conditions were completed, the normal hexane slurry of the prepolymerized catalyst prepared above from the pipe 1 was added as 0.78 g / in as a catalyst component not containing the prepolymerized polymer. It was supplied so as to be constant for hr. At that time, liquefied propylene for assisting (temperature: 10 ° C.) was supplied from the pipe 2 so that the flow rate was 20 cm / second. Further, triisobutylaluminum was supplied as an organoaluminum compound from the pipe 3 at a constant 15 mmol / hr. While maintaining the conditions of a reaction temperature of 60 ° C., a reaction pressure of 2.0 MPaG, and a stirring speed of 35 rpm, hydrogen gas was continuously supplied from the circulation pipe 4 so as to maintain the hydrogen / propylene molar ratio in the gas phase of the reactor at 0.0005. To produce a propylene homopolymer.

  The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 5. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 6 and refluxed to the polymerization reactor 10. The propylene homopolymer obtained by the main polymerization was intermittently withdrawn from the polymerization vessel 10 through the pipe 11 so that the retained level of the polymer was 65% by volume of the reaction volume, and was dried at a temperature of 80 ° C. for 1 hour. . At this time, the production amount of the propylene homopolymer was 7 kg / hr. At this time, the addition amount of normal hexane with respect to the polymer production amount was 0.73 wt%. Table 3 summarizes the measurement results of MFR, Tm, oligomer amount and smoke generation of the resulting propylene homopolymer.

(Comparative Example 1)
In Example 1, a propylene homopolymer was produced in the same manner as in Example 1 except that the normal hexane slurry concentration of the prepolymerization catalyst was changed to 0.5 % by weight . At this time, the addition amount of normal hexane with respect to the polymer production amount was 2.21 wt%. Table 3 summarizes the measurement results of MFR, Tm, oligomer amount and smoke generation of the resulting propylene homopolymer.

(Example 2)
1. Production of prepolymerized catalyst In Example 1, a catalyst was produced in the same manner as in Example 1 except that the final catalyst slurry concentration was 0.8 wt% as a catalyst component not containing a prepolymerized polymer. .

2. Polymerization Polymerization was performed using the same polymerization apparatus as in Example 1 under the following conditions.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 10 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was raised while introducing propylene, ethylene, and hydrogen, and when the polymerization conditions were completed, the normal hexane slurry of the prepolymerized catalyst prepared above from the pipe 1 was added as a catalyst component containing no prepolymerized polymer to a concentration of 0. It was supplied so as to be constant at 35 g / hr. At that time, assisting liquefied propylene (temperature 20 ° C.) was supplied from the pipe 2 so that the flow rate was 20 cm / second. Further, triisobutylaluminum was supplied as an organoaluminum compound from the pipe 3 at a constant 15 mmol / hr. While maintaining the conditions of a reaction temperature of 60 ° C., a reaction pressure of 2.0 MPaG, and a stirring speed of 35 rpm, the mixed gas molar ratio of ethylene / propylene in the gas phase of the reactor was 0.11, and the hydrogen / propylene molar ratio was 0.001. Ethylene gas and hydrogen gas were continuously supplied from the circulation pipe 4 so as to be maintained, and a propylene-ethylene random copolymer was produced.

  The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 5. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 6 and refluxed to the polymerization reactor 10. The propylene-ethylene random copolymer obtained by the main polymerization is intermittently withdrawn from the polymerization vessel 10 through the pipe 11 so that the retained level of the polymer is 65% by volume of the reaction volume, and dried at a temperature of 80 ° C. for 1 hour. Carried out. At this time, the production amount of the propylene-ethylene random copolymer was 7 kg / hr. At this time, the amount of normal hexane added relative to the amount of polymer produced was 0.62 wt%. Table 3 shows the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-ethylene random copolymer.

(Example 3)
1. Preparation of prepolymerization catalyst Silicate chemical treatment: To a glass separable flask equipped with a 10 liter stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Mizusawa Chemical Co., Ltd. Benclay SL; average particle size = 50 μm) was further dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The mass after drying was 710 g. The chemically treated silicate was dried in a kiln dryer.

Preparation of catalyst: 100 g of the dried silicate obtained above was introduced into a glass reactor with a stirring blade having an internal volume of 3 liters, 580 ml of mixed heptane, and 420 ml of heptane solution of triethylaluminum (0.60 M) were added. Stir at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry at 2.0 liters. Next, 4.8 ml of a triisobutylaluminum normal heptane solution (0.71 M / L) was added to the prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] (synthesized in JP-A-10-226712) A mixture obtained by adding 16.5 ml of a triisobutylaluminum normal heptane solution (0.71 M) to 1090 mg (1.5 mmol) and 870 ml of mixed heptane and carrying out the reaction at room temperature for 1 hour is obtained as a silicate slurry. And stirred for 1 hour.

Preliminary polymerization: Subsequently, 2.1 liters of normal heptane was introduced into a stirring autoclave having an internal volume of 10 liters that had been sufficiently substituted with nitrogen, and maintained at 40 ° C. The previously prepared silicate / metallocene complex slurry was introduced therein. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 2 hours, the supply of propylene was stopped and maintained for another 2 hours. After completion of the prepolymerization, the remaining monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then about 3 liters of supernatant was decanted. Subsequently, 4.7 ml of a normal heptane solution of triisobutylaluminum (0.71 M / L) and 2.8 liters of normal heptane were added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then the supernatant was treated with 2. Removed 8 liters. This operation was further repeated 3 times. Subsequently, 8.5 ml of a normal heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.1 g of polypropylene per 1 g of catalyst was obtained.
Further, normal hexane was added to the obtained prepolymerized catalyst to prepare 0.8 % by weight of a catalyst slurry as a catalyst component containing no prepolymerized polymer.

2. Polymerization Polymerization was performed using the same polymerization apparatus as in Example 1 under the following conditions.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 10 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was increased while introducing propylene, ethylene and hydrogen, and when the polymerization conditions were completed, 0.47 g of the normal hexane slurry of the prepolymerized catalyst prepared above from the pipe 1 was used as a catalyst component not containing the prepolymerized polymer. / Hr was supplied so as to be constant. At that time, liquefied propylene for assisting (temperature −20 ° C.) was supplied from the pipe 2 so that the flow rate became 10 cm / sec. Further, triisobutylaluminum was supplied as an organoaluminum compound from the pipe 3 at a constant 15 mmol / hr. While maintaining the conditions of a reaction temperature of 60 ° C., a reaction pressure of 2.0 MPaG, and a stirring speed of 35 rpm, the mixed gas molar ratio of ethylene / propylene in the gas phase of the reactor was set to 0.06, and the hydrogen / propylene molar ratio was set to 0.00015. Ethylene gas and hydrogen gas were continuously supplied from the circulation pipe 4 so as to be maintained, and a propylene-ethylene random copolymer was produced.

  The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 5. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 6 and refluxed to the polymerization reactor 10. The propylene-ethylene random copolymer obtained by the main polymerization is intermittently withdrawn from the polymerization vessel 10 through the pipe 11 so that the retained level of the polymer is 65% by volume of the reaction volume, and dried at a temperature of 80 ° C. for 1 hour. Carried out. At this time, the production amount of the propylene-ethylene random copolymer was 7 kg / hr. At this time, the amount of normal hexane added relative to the amount of polymer produced was 0.83 wt%. Table 4 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-ethylene random copolymer.

(Comparative Example 2)
1. Production of Preliminary Polymerization Catalyst Preliminary polymerization catalyst was produced in the same manner as in Example 3 except that slurrying into normal hexane, which was the final step of Example 3, was not carried out.

2. Polymerization A propylene-ethylene random copolymer was produced in the same manner as in Example 3 except that the prepolymerized catalyst produced above was fed to the reactor in a dry state and assisted propylene was not used.
Table 4 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-ethylene random copolymer.

Example 4
1. Production of Prepolymerized Catalyst Normal heptane was added to the prepolymerized catalyst obtained in Example 3 to prepare a 3.0 wt% catalyst slurry as a catalyst component containing no prepolymerized polymer.

2. Polymerization Using the same apparatus as in Example 1, the normal heptane slurry of the prepolymerized catalyst produced above was fed as a catalyst component containing no prepolymerized polymer at a constant 0.32 g / hr, and the gas phase of the reactor was supplied. Example 3 except that ethylene gas and hydrogen gas were continuously supplied from the circulation pipe 4 so as to maintain a mixed gas molar ratio of ethylene / propylene in 0.06 and a hydrogen / propylene molar ratio of 0.0006. Similarly, a propylene-ethylene random copolymer was produced.
At this time, the addition amount of normal heptane with respect to the polymer production amount was 0.15 wt%. Table 4 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-ethylene random copolymer.

(Example 5)
1. Production of prepolymerized catalyst In Example 4, a catalyst was produced in the same manner as in Example 4 except that the final catalyst slurry concentration was 0.8 wt% as a catalyst component not containing a prepolymerized polymer. .

2. Polymerization Using the same apparatus as in Example 1, the normal heptane slurry of the prepolymerized catalyst produced above was fed as a catalyst component containing no prepolymerized polymer so that the constant was 0.28 g / hr, and the gas phase of the reactor was Example 3 except that ethylene gas and hydrogen gas were continuously supplied from the circulation pipe 4 so as to maintain the mixed gas molar ratio of ethylene / propylene at 0.11 and the hydrogen / propylene molar ratio at 0.00025. Similarly, a propylene-ethylene random copolymer was produced.
At this time, the addition amount of normal heptane with respect to the polymer production amount was 0.50 wt%. Table 4 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-ethylene random copolymer.

(Example 6)
In Example 3, normal hexane slurry of a prepolymerized catalyst was supplied as a catalyst component not containing a prepolymerized polymer so as to be constant at 0.17 g / hr, the reaction temperature was 55 ° C., the ethylene / Except that ethylene gas and hydrogen gas were continuously supplied from the circulation pipe 4 so as to maintain the mixed gas molar ratio of propylene at 0.24 and the hydrogen / propylene molar ratio at 0.00085, the same as in Example 3, A propylene-ethylene random copolymer was produced.
At this time, the addition amount of normal hexane with respect to the polymer production amount was 0.30 wt%. Table 4 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-ethylene random copolymer.

(Example 7)
1. Preparation of prepolymerized catalyst The same procedure as in Example 1 was performed.

2. Polymerization (1) First Polymerization Step FIG. 2 is a flow sheet of the polymerization apparatus used in the examples.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 110 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was raised while introducing propylene and hydrogen, and when the polymerization conditions were satisfied, the hexane slurry of the prepolymerized catalyst produced above from the pipe 101 was converted to 1.06 g / hr as a catalyst component not containing the prepolymerized polymer. Supply was made constant. At that time, assisting liquefied propylene (temperature 20 ° C.) was supplied from the pipe 102 so that the flow rate was 30 cm / second. Further, triisobutylaluminum was supplied as an organoaluminum compound from the pipe 103 so as to be constant at 15 mmol / hr. While maintaining the conditions of a reaction temperature of 60 ° C., a reaction pressure of 2.0 MPaG, and a stirring speed of 35 rpm, hydrogen gas was continuously supplied from the circulation pipe 104 so as to maintain the hydrogen / propylene molar ratio in the gas phase of the reactor at 0.00075. Propylene homopolymer (A) was produced.
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 105. The unreacted gas discharged from the polymerization vessel was cooled and condensed outside the reactor system through the pipe 106 and refluxed to the polymerization vessel 110. The propylene homopolymer (A) obtained by the main polymerization is intermittently withdrawn from the polymerization vessel 110 through the pipe 111 so that the polymer retention level becomes 65% by volume of the reaction volume, and the polymerization vessel 120 in the second polymerization step. Supplied to. At this time, a part of the propylene homopolymer (A) was extracted from the degassing tank 130 to obtain MFR and Tm.

(2) Second polymerization step Propylene homopolymer (A) from the first polymerization step and a mixed gas of propylene and ethylene are fed to a horizontal polymerization vessel 120 (L / D = 3.7, internal volume 100 L) having a stirring blade. It was supplied intermittently to carry out copolymerization of propylene and ethylene. The reaction conditions were a stirring speed of 18 rpm, a reaction temperature of 65 ° C., a reaction pressure of 1.9 MPaG, and an ethylene / propylene molar ratio in the gas phase was adjusted to 1.50. No hydrogen feed was performed in the second polymerization step. Oxygen gas was supplied from the pipe 107 as a polymerization activity inhibitor for adjusting the polymerization amount of the propylene-ethylene random copolymer (B).
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 108. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 109 and then refluxed to the polymerization reactor 120. The propylene-based block copolymer produced in the second polymerization step is intermittently withdrawn from the polymerization vessel 120 through the pipe 113 so that the polymer retention level is 50% by volume of the reaction volume, and the temperature is 80 ° C. for 1 hour. Drying was performed. At this time, the production amount of the propylene-based block copolymer was 9.5 kg / hr.
At this time, the addition amount of normal hexane with respect to the polymer production amount was 0.73 wt%. Table 5 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-based block copolymer.

(Example 8)
1. Preparation of prepolymerized catalyst The same procedure as in Example 3 was performed.

2. Polymerization (1) First Polymerization Step Using the same polymerization apparatus as in Example 7, polymerization was performed under the following conditions.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 110 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was increased while introducing propylene, ethylene and hydrogen, and when the polymerization conditions were completed, the hexane slurry of the prepolymerized catalyst produced above from the pipe 101 was treated as 0.48 g as a catalyst component not containing the prepolymerized polymer. / Hr was supplied so as to be constant. At that time, assisting liquefied propylene (temperature: 10 ° C.) was supplied from the pipe 102 so that the flow rate was 20 cm / sec. Further, triisobutylaluminum was supplied as an organoaluminum compound from the pipe 102 so as to be constant at 15 mmol / hr. While maintaining the conditions of a reaction temperature of 60 ° C., a reaction pressure of 2.0 MPaG, and a stirring speed of 35 rpm, the mixed gas molar ratio of ethylene / propylene in the gas phase of the reactor was set to 0.06, and the hydrogen / propylene molar ratio was set to 0.0005. The propylene-ethylene random copolymer (A) was produced by continuously supplying ethylene gas and hydrogen gas from the circulation pipe 104 so as to maintain the same.
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 105. The unreacted gas discharged from the polymerization vessel was cooled and condensed outside the reactor system through the pipe 106 and refluxed to the polymerization vessel 110. The propylene-ethylene random copolymer (A) obtained by the main polymerization is intermittently withdrawn from the polymerization vessel 110 through the pipe 111 so that the retained level of the polymer is 65% by volume of the reaction volume. The polymerization vessel 120 was supplied. At this time, a part of the propylene-ethylene random copolymer (A) was extracted from the degassing tank 130 to obtain MFR and Tm.

(2) Second polymerization step Propylene-ethylene random copolymer (A) and propylene, ethylene from the first polymerization step in a horizontal polymerization vessel 120 (L / D = 3.7, internal volume 100 L) having a stirring blade, A mixed gas of hydrogen was intermittently supplied to carry out copolymerization of propylene and ethylene. The reaction conditions were a stirring speed of 18 rpm, a reaction temperature of 65 ° C., a reaction pressure of 1.9 MPaG, and an ethylene / propylene molar ratio in the gas phase was adjusted to 1.2 and a hydrogen / propylene molar ratio was adjusted to 0.0012. Oxygen gas was supplied from the pipe 107 as a polymerization activity inhibitor for adjusting the polymerization amount of the propylene-ethylene random copolymer (B).
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 108. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 109 and then refluxed to the polymerization reactor 120. The propylene-based block copolymer produced in the second polymerization step is intermittently withdrawn from the polymerization vessel 120 through the pipe 113 so that the polymer retention level is 50% by volume of the reaction volume, and the temperature is 80 ° C. for 1 hour. Drying was performed. At this time, the production amount of the propylene-based block copolymer was 9.5 kg / hr.
At this time, the amount of normal hexane added relative to the amount of polymer produced was 0.62 wt%. Table 5 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-based block copolymer.

(Comparative Example 3)
In Example 8, the prepolymerized catalyst produced in Comparative Example 2 was fed to the reactor in a dry state, and the propylene-based block copolymer was prepared in the same manner as in Example 8 except that propylene for assist was not used. Production was carried out.
Table 5 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-based block copolymer.

(Examples 9 to 11)
In Example 8, the polymerization conditions were changed as shown in Table 6 to produce a propylene-based block copolymer.
Table 7 summarizes the measurement results of MFR, ethylene content, Tm, oligomer amount, and smoke generation of the resulting propylene-based block copolymer.

III. Evaluation As is apparent from the above, the specific item of the production method of the present invention is “the total amount of saturated hydrocarbon added to the polymerization reactor per unit time is the unit of the amount of the produced propylene polymer per unit time. The content of the hydrocarbon compound having 30 or less carbon atoms is 103 wt.% Obtained in Comparative Example 1 by a method not satisfying the requirement of “adjust to 0.01 to 1 wt% with respect to the total of Compared with the amount as high as ppm, all of the production methods according to the present invention were 50 ppm by weight or less and the content of hydrocarbon compounds having 30 or less carbon atoms was low.
In addition, “a catalyst slurry in which a polymerization catalyst component is suspended in a saturated hydrocarbon having 3 to 8 carbon atoms is fed continuously or intermittently to the polymerization reactor” is a specific matter of the production method of the present invention. What was obtained by the comparative example 2 or the comparative example 3 by the method which does not satisfy | fill requirements has many hydrocarbon compound content of 30 or less carbon atoms with 198 weight ppm and 183 weight ppm, respectively, and also at the time of processing of the manufactured polymer As compared with the case where smoke generation was observed, it was revealed that all the processes according to the production method of the present invention did not generate smoke.
In addition, “a propylene homopolymer or a polymer component (A) 30 to 90% by weight, which is a random copolymer of propylene homopolymer or ethylene and / or a C4 to C20 α-olefin and propylene”, which is a specific matter of the present invention, and a polymer component A hydrocarbon compound comprising 10 to 70% by weight of a polymer component (B) which is a propylene-based random copolymer containing ethylene and / or a C4 to C20 α-olefin higher than (A), and having 30 or less carbon atoms In Comparative Example 3, which does not satisfy the requirement of “propylene-based block copolymer having a content of 50 ppm by weight or less”, all of the present invention emits smoke compared to the case where smoke was observed during polymer processing. It became clear that was not seen.
Therefore, the production method of the present invention industrially and stably produces a clean propylene-based polymer in which the content of hydrocarbon compounds having 30 or less carbon atoms is as low as 50 ppm by weight and no fuming is observed during polymer processing. It is clear that it has great technical significance in that it is a production method that can be performed. In addition, the propylene polymer of the present invention is a clean propylene polymer having a hydrocarbon compound content of 30 or less carbon atoms of as low as 50 ppm by weight and showing no fuming during polymer processing. It is clear that it has special significance.

The method for producing a propylene polymer of the present invention is a very clean propylene polymer that has no odor or stickiness even when it is a propylene polymer having excellent flexibility and transparency, and has little smoke during processing. Since the coalescence can be produced industrially and stably, it is very useful industrially.
In addition, the propylene block copolymer of the present invention is a very clean propylene block copolymer having no odor or stickiness even with a propylene block copolymer having excellent flexibility and transparency, and having very little smoke during processing. Since it is a propylene-based block copolymer, it is very useful industrially.

Claims (5)

In the method of producing a propylene polymer by a gas phase polymerization method in the presence of a polymerization catalyst component containing a metallocene transition metal compound supported on a carrier,
A catalyst slurry in which a polymerization catalyst component is suspended in a saturated hydrocarbon having 3 to 8 carbon atoms using a continuous polymerization method is continuously or intermittently fed to a polymerization reactor, while the produced propylene-based polymer. Is continuously or intermittently withdrawn from the polymerization reactor, in which case the total amount of saturated hydrocarbons added to the polymerization reactor per unit time is the total amount of propylene polymer produced per unit time. A method for producing a propylene polymer, characterized in that the content is adjusted to 0.01 to 1% by weight based on the weight.   The method for producing a propylene-based polymer according to claim 1, wherein the polymerization reactor is a gas phase polymerization reactor equipped with a mechanical stirring means.   The method for producing a propylene-based polymer according to claim 1 or 2, wherein the saturated hydrocarbon is normal hexane or normal heptane.   The method for producing a propylene-based polymer according to any one of claims 1 to 3, wherein the continuous polymerization method is a multistage polymerization of two or more stages. The propylene polymer is a propylene homopolymer or a random copolymer of ethylene and / or a C4 to C20 α-olefin and propylene, 30 to 90% by weight, and a polymer component (A) Content of hydrocarbon compound consisting of 10 to 70% by weight of polymer component (B) which is propylene-based random copolymer containing higher ethylene and / or C4 to C20 α-olefin method for producing a propylene polymer according to claim 1, but characterized in that it is a propylene block copolymer is 50 wt ppm or less.

Images