JP5527852B2 - Propylene polymerization method - Google Patents

Description

  The present invention relates to a method for polymerizing propylene using a metallocene catalyst. More specifically, the present invention relates to a propylene polymerization method for obtaining a polymer in a high yield when a part of the raw material is FCC propylene in the polymerization of propylene using a supported metallocene catalyst.

  When propylene polymerization or propylene-ethylene copolymerization is performed using a Ziegler-Natta catalyst, a polymer having a wide molecular weight distribution and composition distribution is obtained. In the case of propylene homopolymerization, a polymer having a wide molecular weight distribution with a large amount of low regularity and low molecular weight components can be obtained, and in the case of propylene-ethylene copolymer, a polymer having a large composition distribution with a large amount of low crystallinity components. Is obtained. The component causes deterioration in physical properties and production problems. When the amount of the component is high, problems such as odor and appearance (stickiness, etc.) occur, and the quality is adversely affected. Also, unlike the metallocene catalyst described later, the Ziegler-Natta catalyst has low reactivity with hydrogen, which is a chain transfer agent, so it is necessary to supply a large amount of hydrogen in the polymerization process of low molecular weight components, and the polymerization activity is also low. descend.

  In recent years, metallocene catalysts having few of these drawbacks have been developed. The metallocene catalyst has good reactivity with hydrogen, which is a chain transfer agent, and can polymerize a low molecular weight component without reducing the activity. Further, since the active sites are uniform as compared with conventional Ziegler-Natta catalysts, there is an advantage that a uniform polymer can be produced, and it is known to give a good propylene polymer with few sticky components.

  On the other hand, the metallocene catalyst is extremely reactive with impurities in the raw material propylene. As a result, the catalytic activity and quality are greatly influenced by the purity of the raw material, and the productivity is lowered, so that there are many difficulties in industrially producing the product. Further, in recent years, the demand for propylene as a monomer for producing polypropylene has rapidly increased, and industrial propylene has been secured by loading up an ethylene plant, fluid catalytic cracking process of heavy oil, and the like. The industrial propylene (hereinafter referred to as FCC propylene) obtained by the latter contains a large amount of impurities, particularly carbonyl sulfide (COS, boiling point-50.2 ° C.) and carbon monoxide (CO, boiling point— Impurities such as 191.5 ° C. are becoming close up as poisonous substances for highly active metallocene catalysts, and the need to reduce them as much as possible is increasing.

Several methods for reducing impurities are known. For example, purification by distillation is generally performed before contact with the catalyst. Distillation can efficiently separate impurities that differ greatly from the boiling point of propylene (−47.70 ° C.), but among the aforementioned impurities, COS is particularly close to the boiling point of propylene. Since it was difficult to separate to a low concentration, it was not appropriate. Further, adding a distillation facility to increase the removal efficiency has a drawback of requiring a high capital investment and increasing the operating cost.

Other purification methods include purification methods using a purification catalyst. As a purification catalyst, there are those in which metal atoms having a large surface area are supported on an inorganic carrier, and those purified by physical adsorption or chemical reaction by contacting with a composite oxide composed of metal oxides.
As for the contact method, if the propylene is brought into contact in the gas state, the purification tower packed with the purification catalyst becomes enormous, and the operation cost is increased, which is disadvantageous economically. Generally, the raw material propylene is used for the purpose of increasing the removal efficiency. Numerous purification methods have been proposed in which they are contacted with an appropriate purification catalyst in the liquid phase.
For example, for the purpose of removing CO and COS in propylene, raw material propylene is made of a composite oxide of copper oxide and zinc oxide or a composite oxide of copper oxide, aluminum oxide and silicon oxide (for example, Patent Document 1 and 2)) in a liquid phase, and then contacted with a Ziegler-Natta catalyst. However, since CO and COS removal efficiency was still insufficient, in the polymerization of propylene using a highly active supported metallocene catalyst, sufficient catalytic activity could not be obtained by the contact method, and physical properties were also unstable. There was a problem to become.

On the other hand, as a propylene polymerization method using a metallocene catalyst, an adsorbent containing nickel deposited on a carrier has been proposed (see, for example, Patent Document 3). According to this document, in order to stabilize the catalytic activity of the metallocene catalyst, an adsorbent in which the total weight of nickel oxide and metallic nickel is supported on 10 to 80% by weight (support 20 to 90% by weight) of the sorbent. It is necessary to use it. However, it has been economically problematic to use an adsorbent containing a large amount of a noble metal such as nickel on an industrial scale in an olefin polymerization process.

  Under these circumstances, CO and COS can be efficiently removed, and a highly active metallocene catalyst is used, and a highly stable and highly polymerized polymer is obtained without using a purification catalyst containing a large amount of noble metals. Research and development of a propylene polymerization method capable of obtaining

  In view of the problems of the prior art described above, the object of the present invention is to use not only co-produced propylene from an ethylene plant using naphtha as a raw material but also FCC propylene obtained by fluid catalytic cracking of heavy oil, An object of the present invention is to provide a propylene polymerization method capable of stably obtaining a polymer with high productivity without using a purification catalyst containing a large amount of.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors contacted a raw material propylene containing 5% by weight or more of FCC propylene with a composite composed of palladium and aluminum oxide, and then brought into contact with a metallocene catalyst. As a result, the propylene polymerization activity was dramatically increased, and the present invention was completed.

That is, according to the first aspect of the present invention, the raw material propylene containing FCC propylene obtained by the fluid catalytic cracking of heavy oil 5 wt% or more, Ri Do palladium and aluminum oxide, the total weight of the palladium is palladium There is provided a process for polymerizing propylene, characterized in that it is contacted with a composite comprising 0.01 to 5% by weight of a composite comprising aluminum oxide and then contacted with a metallocene catalyst.

  According to a second aspect of the present invention, in the first aspect, a mixture comprising about 5 to 60% by weight of FCC propylene obtained by fluid catalytic cracking of heavy oil is used as a raw material propylene. A method for polymerizing propylene is provided.

According to a third aspect of the present invention, in the first or second aspect, the propylene is brought into contact with at least one of the following (1) to (3) before contacting with the metallocene catalyst. A polymerization process is provided.
(1) Molecular sieve (2) Metal oxide or composite oxide of metal oxide (3) Alumina

According to a fourth aspect of the present invention, there is provided a propylene polymerization method according to any one of the first to third aspects, wherein the metallocene catalyst is supported on an ion-exchange layered silicate.

  According to the present invention, in the polymerization using raw material propylene containing FCC propylene, the activity of the metallocene catalyst is remarkably increased, so that the catalyst cost can be greatly reduced.

  The present invention is characterized in that a raw material propylene containing 5% by weight or more of FCC propylene obtained by fluid catalytic cracking of heavy oil is brought into contact with a composite composed of palladium and aluminum oxide and then brought into contact with a metallocene catalyst. This is a propylene polymerization method. Below, the polymerization method of propylene of this invention is demonstrated in detail.

  The preparation of the raw material propylene used in the polymerization of the present invention is, for the time being, a propylene for polymerization including propylene, industrial propylene, etc. that are conventionally obtained by various general means such as naphtha decomposition (hereinafter simply referred to as “polymerization”). It is characterized by containing an appropriate amount of FCC propylene mixed with FCC propylene and containing at least 5% by weight of FCC propylene, but usually 1 to 99% by weight of conventional propylene for polymerization, 99% to FCC propylene. It can be prepared with the specification of a mixture containing 1% by weight. Actually, in order to remarkably improve the effectiveness of the composite of palladium and aluminum oxide when the activity of the catalyst, the quality of polypropylene, and the effective use of FCC propylene, FCC propylene is 5 technically and economically. It is recommended that the weight percent or more be the propylene for polymerization.

  Considering the promotion of the use of FCC propylene, the content of so-called FCC propylene in which part of the raw material propylene is replaced with FCC propylene is 5 wt% or more, for example, 7 wt%, 10 wt%, 15 wt%, 20 wt% %, 35% by weight, 40% by weight, and in some cases, 100% by weight are optionally included. On the other hand, if the FCC propylene content is 2 wt% or 3 wt%, so-called 5 wt% or less, not only the composite of palladium and aluminum oxide cannot be demonstrated, but also the effective use of FCC propylene is hindered. Usually, in view of meeting the appropriate and effective demand for FCC propylene, even if the content of FCC propylene is in the range of about 5 to 100% by weight, the efficacy of the composite consisting of palladium and aluminum oxide is enhanced. In addition, it is useful in the polymerization technique that the catalytic activity of the metallocene catalyst can be maintained relatively stably. In terms of promoting effective use and consumption of FCC propylene as a raw material propylene, in order to increase the efficiency most efficiently and productivity, about 95 to 40% by weight of conventional propylene for polymerization and about 5% of FCC propylene are used. It is recommended to use a mixture of ~ 60 as raw material propylene. Within such a range, polymerization can be achieved while maintaining the metallocene catalyst activity, and it is possible to use a material having an FCC propylene content of 100% by weight as the raw material propylene.

  The propylene content of what is obtained as a conventional propylene for polymerization by naphtha cracking, etc. is a purity that does not contain a relatively large amount of impurities by arbitrarily adjusting the propylene content usually in the range of 1 to 99.99 wt% by distillation purification or the like. Often used are those with high values. On the other hand, in the case of FCC propylene, the propylene content can be arbitrarily adjusted in the range of usually 1 to 99.99% by weight by distillation purification or the like. Conventional propylene for polymerization such as so-called naphtha cracking, which contains a small amount of olefinic compound and also contains a relatively large amount of a catalyst deactivating material such as tar, carbonyl sulfide, carbon monoxide caused by heavy oil as a raw material. In many cases, impurities are contained.

  Propylene as raw material can be produced by various methods and contains propylene containing some CO and COS that are not detrimental to the catalyst, especially from ethylene plant load-up and heavy oil catalytic cracking products. It is also possible to use conventional propylene for polymerization obtained by separating the C3 fraction obtained. In particular, in the case of FCC propylene, the content of CO and COS is relatively high due to the fact that it is obtained by catalytic cracking of heavy oil as compared with the conventional propylene for polymerization obtained by naphtha cracking or the like. The content of CO and COS contained in the raw material propylene obtained by mixing them can be assumed to be within a wide range of usually 0.1 to 300 ppm by weight, but if possible, about 100 ppm or less, more preferably 50 ppm or less, preferably Is most preferably 10 ppm or less, most preferably 1 ppm or less. If CO and COS are contained in the raw material propylene at a concentration exceeding 100 ppm, as a pretreatment, the concentration of CO and COS is set to 100 ppm by other means such as copper oxide / zinc oxide treatment or distillation in advance. Decreasing below is significant not only in reducing the concentration of CO and COS, but also in removing other impurities, and thus achieving the effect of the present invention.

  As a homopolymer composed of propylene of the present invention or a copolymer component composed of propylene and other olefins, the melt flow rate (MFR) (g / 10 min), which is useful as a guide when processing instead of molecular weight, is shown. , MFR of about 0.1 to 1000 can be arbitrarily polymerized. For example, when polymerizing raw material propylene composed of a mixture containing 95% by weight of conventional propylene for polymerization by naphtha cracking of the present invention and 5% by weight of FCC propylene, assuming that the MFR of polypropylene is about 2.0, it contains FCC propylene. When the amount is increased, for example, when the FCC propylene contains 10% by weight, the MFR is about 2.5, and when the amount is 20% by weight, the MFR is about 4.0. If the content of propylene is increased, it is predicted that the quality will be hindered and the polymerization controllability of polypropylene will be slightly worse. This was obtained by fluid catalytic cracking of heavy oil, and carbon monoxide (CO) and / or carbonyl sulfide (COS), which affect the catalytic activity in the polymerization, was relatively used as a catalyst poison. It can be inferred that it is caused by slightly increasing the amount. Therefore, considering the circumstances of promoting the effective use of FCC propylene and obtaining good quality propylene, it is important in achieving the present invention that the raw material propylene contains 5% by weight or more of FCC propylene. It is.

Considering the quality of polypropylene, the efficiency of polymerization, the quality of conventional propylene for polymerization (NCP) by naphtha decomposition, and the use of FCC propylene (FCCP), and also the amount of CO and COS contained in the raw material propylene Then, the most appropriate embodiment is illustrated as follows.

Embodiment 1 2 3 4 5 6 7 8
(weight%)
FCCP 5 10 16 24 36 42 65 100
NCP 95 90 84 76 64 64 58 35 0

Even if a part of the raw material propylene is replaced with FCC propylene, if it is subjected to contact treatment with a composite of palladium and aluminum oxide, the catalytic activity is maintained, and a polypropylene (co) polymer based on a metallocene catalyst is produced. The achievement of being able to develop a polymerization method that can be achieved with a high yield is due to the findings of the present inventors.

The catalyst used in the present invention is a metallocene catalyst in which a metallocene complex as an active site precursor is supported on a support. If it is not supported, particle properties deteriorate and adhesion and blockage in the polymerization system occur, which is not preferable.

Hereinafter, the metallocene catalyst used in the polymerization of the present invention will be described in detail.
(1-1) Catalyst component The supported metallocene catalyst generally includes (W) a metallocene complex composed of a transition metal compound of Group 4-6 of the periodic table (short-period type) having a conjugated five-membered ring ligand, and (X) a co-catalyst that activates, (Y) an organoaluminum compound used as necessary, and (Z) a support.

(W) Metallocene Complex As a typical metallocene complex used in the present invention, a metallocene complex of a transition metal compound in Groups 4 to 6 of the periodic table having a conjugated five-membered ring ligand can be given. Among these, a bridged metallocene complex represented by the following general formula (1) is preferable.

In formula (1), M is Zr or Hf. F and G are auxiliary ligands, and the component (
It reacts with the cocatalyst of X) to produce an active metallocene having olefin polymerization ability. E and E ′ are an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group. Q is a group that crosslinks E and E ′. E
And E ′ may further have a substituent on the side ring.

E and E ′ are preferably an indenyl group or an azulenyl group, particularly an azulenyl group.
Q represents a binding group that crosslinks between ligands such as two conjugated five-membered rings at an arbitrary position, and is specifically preferably an alkylene group, a silylene group, or a germylene group.
M is a metal atom of a transition metal selected from Groups 4 to 6 of the periodic table, preferably titanium, zirconium, hafnium or the like. Zirconium or hafnium is particularly preferable.
F and G are auxiliary ligands and react with the cocatalyst of component (X) to produce an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, F and G are not limited in the type of ligand, and each may have a hydrogen atom, a halogen atom, a hydrocarbon group, or a hetero atom. Examples include groups. Among these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable.
The following can be illustrated as a specific compound of a metallocene complex.

In a metallocene complex having a structure in which a substituent has two cyclopentadienyl ligands constituting a ring and they are bridged, as an azulene-based one, dimethylsilylene bis {1- (2- Methyl-4-isopropyl-4H-azurenyl)} hafnium dichloride, dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} hafnium dichloride, dimethylsilylenebis [1- {2-methyl-4- (4-Chlorophenyl) -4H-azulenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-
Methyl-4- (4-fluorophenyl) -4H-azulenyl}] hafnium dichloride,
Dimethylsilylenebis [1- {2-methyl-4- (3-chlorophenyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-methyl-4- (2,
6-dimethylphenyl) -4H-azulenyl}] hafnium dichloride, dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} hafnium dichloride, diphenylsilylenebis {1- (2-methyl-) 4-phenyl-4H-azurenyl)} hafnium dichloride, methylphenylsilylenebis {1- (2-methyl-4-)
Phenyl-4H-azulenyl)} hafnium dichloride, methylphenylsilylenebis [
1- {2-Methyl-4- (1-naphthyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} hafnium dichloride, dimethylsilylenebis [ 1- {2-ethyl-4- (1-anthracenyl) -4H-azulenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-
Ethyl-4- (2-anthracenyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-ethyl-4- (9-phenanthryl) -4H-azulenyl}] hafnium dichloride, dimethylmethylenebis [1 -{2-methyl-4- (4-biphenylyl) -4H-azurenyl}] hafnium dichloride, dimethylgermylenebis [
1- {2-Methyl-4- (4-biphenylyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis {1- (2-ethyl-4- (3,5-dimethyl-4-trimethylsilylphenyl-4H-) Azulenyl)} hafnium dichloride, and the like.

Azulene-based compounds with different conjugated multi-membered ring ligands include dimethylsilylene [
1- {2-methyl-4- (4-biphenylyl) -4H-azurenyl}] [1- {2-methyl-4- (4-biphenylyl) indenyl}] hafnium dichloride, dimethylsilylene {1- (2-ethyl -4-phenyl-4H-azurenyl)} {1- (2-methyl-4,5
-Benzoindenyl)} hafnium dichloride and the like.

Examples of the metallocene complex having a structure in which two indenyl ligands are bridged include dimethylsilylene bis {1- (2-methyl-4-phenylindenyl)} hafnium dichloride, dimethylsilylene bis {1- (2-Methyl-4,5-benzoindenyl)} hafnium dichloride, dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl)]
Indenyl}] hafnium dichloride, and the like.

Compounds in which the silylene group of the compounds of these specific examples is replaced with a germylene group or vice versa are also exemplified as preferred examples. Compounds with hafnium replaced by zirconium
Can be used.

(X) Cocatalyst (activator component)
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. X-1) to (X-4) are mentioned.
(X-1) Aluminum Oxy Compound (X-2) An ionic compound or Lewis acid (X-3) solid acid (X that can react with the component (W) to convert the component (W) into a cation -4) Ion exchange layered silicate

Component (X) has an acid point of pKa of -8.2 or less, and the amount thereof requires 0.001 mmol or more of 2,6-dimethylpyridine per 1 g of component (X) to neutralize it. And more preferably 0.01 mmol or more.
The amount of acid sites having a pKa of −8.2 or less may be measured by the method described in JP-A-2002-53609. However, in the case of precise measurement, the examples in Japanese Patent Application No. 2007-325541 are used. As described, it is preferable to quantitatively determine the color of the indicator by an instrument while quantitatively determining it with a visible ultraviolet spectrum.
Here, acid is one of the categories of substances, and is defined to refer to substances that are Bronsted acids or Lewis acids. In addition, the acid point is defined as a constituent unit in which the substance exhibits the properties as an acid, and the amount is determined by the amount of 2,6-dimethylpyridine required for neutralization per unit weight by an analytical means such as a titration method. Is grasped by the molar amount. An acid point having a pKa of −8.2 or less is referred to as a “strong acid point”.
Component (X) used in the present invention has a marked improvement in polymerization activity when it contains a specific amount or more of strong acid sites.

It is well-known that the aluminum oxy compound of (X-1) can activate a metallocene complex, and as such a compound, specifically, compounds represented by the following general formulas (2) to (4) are included. Can be mentioned.

In each of the general formulas (2) to (4), R ¹ represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly a hydrocarbon group having 1 to 6 carbon atoms. Moreover, several R < ¹ > may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.
Among the above general formulas, the compounds represented by (2) and (3) are also called aluminoxanes, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. 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.
The compound represented by the general formula (4) is 10 kinds of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula: R ² B (OH) ₂ : It can be obtained by a reaction of 1: 1 to 1: 1 (molar ratio).
In the general formula, R ¹ and R ² represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (X-2) is an ionic compound or a Lewis acid capable of reacting with the component (W) to convert the component (W) to a cation. Examples thereof include complexes of cations such as a nium cation and an ammonium cation with organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron. Examples of the Lewis acid as described above include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halides 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 (W) and can convert a component (W) into a cation.

Examples of the solid acid (X-3) include alumina, silica-alumina, silica-magnesia, molybdic acid, niobic acid, titanic acid, tungstic acid, complex acids thereof, and heteropolyacid.

The ion-exchange layered compound (X-4) occupies most of the clay mineral, and is preferably an ion-exchange layered silicate.
An ion-exchange layered silicate (hereinafter, sometimes simply abbreviated as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other by a binding force, and contains Refers to a silicate compound in which the ions to be exchanged are exchangeable. Most silicates are naturally produced mainly as the main component of clay minerals, so impurities other than ion-exchange layered silicates (
Quartz, cristobalite, etc.) are often included, but they may be included.
Various known silicates can be used. Specific examples include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
Smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and stevensite; vermiculites such as vermiculite; mica such as mica, illite, sericite and sea chlorite; Pyrophyllite-talc group: Chlorite group such as Mg chlorite, sepiolite, palygorskite, etc.

The layered silicate which formed said mixed layer may be sufficient as a silicate. Main component silicate is 2:
A silicate having a type 1 structure is preferable, a smectite group is more preferable, and montmorillonite is particularly preferable. As for silicates, those obtained as natural products or industrial raw materials can be used as they are without any particular treatment, but it is preferable to carry out chemical treatment. Specific examples include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like. Acid treatment is preferable. These processes may be used in combination with each other. These processing conditions are not particularly limited, and known conditions can be used.

In addition, 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. Depending on the degree of these chemical treatments, the ion exchange property may be small, but there is no particular problem if the raw material before the chemical treatment is an ion exchangeable layered silicate.

(Y) Organoaluminum compound As the organoaluminum compound used as needed for the metallocene catalyst system, one containing no halogen is used. Specifically, the following general formula (5)
AlR _3-i X _i (5)
(In Formula (5), R is a C1-C20 hydrocarbon group, X is hydrogen, an alkoxy group, i is 0 <= i.
≤3 indicates a number. However, when X is hydrogen, i is 0 ≦ i <3. )
The compound shown by is used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trioctylaluminum, or dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, diisobutylaluminum ethoxide, etc. Alkyl-containing alkylaluminums, and further halide-containing alkylaluminums such as diethylaluminum halides are mentioned.
Of these, trialkylaluminum, especially triisobutylaluminum,
Trioctyl aluminum is preferred.

(Z) Carrier Examples of the carrier used in the metallocene catalyst system include various known inorganic or organic fine particle solids.
Examples of inorganic solids include porous oxides, and 100 to 1,000 as necessary.
Baked at a temperature of 150 ° C, preferably 150 to 700 ° C.
_{Specifically, SiO 2, Al 2 O 3} , MgO, ZrO 2, TiO 2, B 2 O 3, CaO
, ZnO, BaO, etc. ThO _2, or mixtures thereof, for example, _SiO 2 -MgO,
SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O
₃ and SiO ₂ —TiO ₂ —MgO. Of these, SiO ₂ or Al
Which the ₂ O ₃ as a main component is preferable.

Moreover, if it is a solid thing among the said (X) promoters, it can be used as a support | carrier and promoter, and it is preferable. Specific examples of the support / co-catalyst include (X-3) solid acid and (X
-4) Ion exchange layered silicate and the like. In order to improve the particle properties of the copolymer, various known granulations are preferably performed.

Organic fine particulate solids include ethylene, propylene, 1-butene, 4-methyl-1-
Produced mainly from α-olefin having 2 to 14 carbon atoms such as pentene
Examples thereof include a polymer or a solid of a polymer or a copolymer formed mainly of vinylcyclohexane or styrene.

The average particle diameter of the carrier is usually 5 to 300 μm, preferably 10 to 200 μm, more preferably 30 to 100 μm.
The specific surface area of the carrier is usually 50 to 1,000 m ² / g, preferably 100 to 500.
m ² / g, and the pore volume of the carrier is usually 0.1 to 2.5 cm ³ / g, preferably 0.2.
˜0.5 cm ³ / g.
Further, the cocatalyst (X) used as the carrier and cocatalyst is preferably one having an average particle diameter and a specific surface area in the same range as described above.

(1-2) Contact of catalyst component In the contact of component [W], component [X] (promoter) and component [Z] (support), the order of contact is not limited. is there.
(I) After contacting the component [W] and the component [X], the component [Z] is contacted.
(Ii) After contacting the component [W] with the component [Z], the component [X] is contacted.
(Iii) The component [Z] and the component [X] are contacted, and then the component [W] is contacted (note that
When a solid promoter such as an ion-exchange layered silicate is used as a support and promoter, the component [Z
] And component [X] are originally carried in contact with each other, and this is the order of contact)
.
(Iv) Component [W], component [X], and component [Z] are contacted simultaneously.
Among these, the order of (iii) is preferable.

Moreover, also when using component [Y] (organoaluminum compound) as needed, you may make component [Y] contact in any said step. Preferably, the component [Z] and the component [X] are contacted, the component [Y] is contacted, and then the component [W] is contacted.

The temperature at which the component (W) and the component (Y) are brought into contact (in which case the component (X) may be present) is preferably 0 to 100 ° C., more preferably 20 to 80 ° C., and particularly preferably 30 to 30 ° C. 6
0 ° C. When it is lower than this temperature range, the reaction slows down, and when it is higher, the decomposition reaction of component (W) proceeds.
Moreover, when making a component (W) and a component (Y) contact (in that case component (X) may exist), it is preferable to make an organic solvent exist as a solvent. In this case, the concentration of the component (W) in the organic solvent is preferably high, and is preferably 3 mM or more, more preferably 4 mM or more, and particularly preferably 6 mM or more.

Among the catalyst components described above, the amounts used of the component (W) and the component (X) are used in an optimum amount ratio in each combination.
When component (X) is an aluminum oxy compound, the molar ratio of Al / transition metal is usually 1
0 or more and 100,000 or less, further 100 or more and 20,000 or less, especially 100 or more and 10,
A range of 000 or less is suitable. On the other hand, when an ionic compound or a Lewis acid is used as component (X), the molar ratio of the transition metal to the transition metal is in the range of 0.1 to 1,000, preferably 1 to 100, more preferably 2 to 10. is there.

(1-3) Prepolymerization The catalyst used in the present invention is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance to improve particle properties.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-
It is possible to use hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like, and it is particularly preferable to use propylene.
The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. Moreover, the amount of prepolymerization is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 1 part by weight of the co-catalyst component (X). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.

The prepolymerization temperature is not particularly limited, but is usually 0 ° C to 100 ° C, preferably 10 to 70 ° C.
More preferably, it is 20-60 degreeC. Below this range, the reaction rate may decrease or the activation reaction may not proceed, and if it exceeds this range, the prepolymerized polymer may be dissolved, or the prepolymerization rate may be too high and the particle properties may deteriorate. There is a possibility that the active point may be deactivated due to a side reaction.
During the prepolymerization, the prepolymerization can be carried out in a liquid such as an organic solvent, and it is preferable to do so. The concentration of the solid catalyst during the prepolymerization is not particularly limited, but preferably 50
g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

The propylene to be polymerized by the metallocene catalyst as described above first comprises 5% by weight or more of propylene obtained by fluid catalytic cracking of heavy oil, that is, FCC method, that is, FCC propylene. The remaining raw material propylene other than FCC propylene is usually conventional propylene for polymerization, such as recycled by-product propylene which produces ethylene by naphtha cracking. The FCC method is a well-known technique, and the contents thereof can be known from, for example, “Chemical Dictionary”, Vol. 9, paragraphs 746-747 (published by Kyoritsu Shuppan, 1989).

The raw material propylene in the present invention is FCC propylene itself or in the form of raw material propylene containing 5% by weight or more thereof, which is “detoxified” by contacting with a specific composite. In addition, when many components which become catalyst poisons, such as a sulfur compound and an oxygen-containing compound, exist in FCC propylene, it is preferable to provide a step for removing these impurities in advance when polymerizing with a highly active metallocene catalyst. . Given that FCC propylene could not be used as propylene for polymerization due to its toxicity to the metallocene catalyst, the greater the proportion of FCC propylene in the raw material propylene, the more prominent the treatment effect of the composite of the present invention.

[Propylene compound treatment]
The main feature of the present invention is that a raw material propylene containing a specific amount of FCC propylene is brought into contact with a specific composite before polymerization with a highly active metallocene catalyst. The composite used in the present invention is a composite of palladium and aluminum oxide.
In the treatment with the composite of raw material propylene containing FCC propylene, the content of CO and COS contained in the raw material propylene is usually 0.1 to 300 ppm, and a wide range of parts by weight can be assumed. 30 ppm or 5 ppm, the specification of the correspondence of the contact treatment is determined according to the quality of what the nature of FCC propylene contained in the raw material propylene to be treated and what amount it contains. Furthermore, the embodiment of the contact treatment between the raw material propylene and the composite is determined according to the processing capacity, the amount of the composite present, the form of the contact, and the contact area of the liquid phase or gas. Optimal conditions such as size, contact time, temperature, pressure, and supply amount are set. In order to increase the efficiency of the contact treatment, it is also possible to use a so-called molded body having a physically increased contact area in which the composite is supported over a wide range on the surface of the porous body.
Furthermore, as described later, in some cases, the opportunity for contact between the raw material propylene and the composite is arbitrarily arranged as one place, two places, and three places in series as needed, as well as the composite contact portion. In addition, the so-called multistage contact allows the content of CO and COS to be decreased sequentially, and is within the design specifications. In order to promote contact efficiency, conditions such as contact area, temperature, pressure, liquid phase / gas phase, propylene flow rate, contact time, etc. are arbitrarily adjusted according to the situation.

[Compound of palladium and aluminum oxide]
The palladium / aluminum oxide composite used in the present invention has various complicated actions such as adsorption, decomposition, oxidation, reduction, or deactivation of a small amount of catalyst poison, particularly COS and CO, contained in raw material propylene. Although it is presumed to be, it can be inferred that it is generally an adsorption action. It has been found that the composite of palladium and aluminum oxide acts equally effectively on both COS and CO. Of course, it is possible to use the composite alone as the adsorbing material, but it is possible to contact with the raw material propylene by forming a so-called three-dimensional structure in a state of being supported on a porous body such as zeolite. It also increases the efficiency and may increase the adsorption action.
If the function of the composite consisting of palladium and aluminum oxide deteriorates after the contact treatment, it is possible to restore the function to some extent by known treatment means such as heat treatment, chemical treatment, and cleaning with inert gas. It is.
This composite of palladium and aluminum oxide, if available, can be obtained and used, and can be easily produced by combining palladium and aluminum oxide.

The composition of the composite of palladium and aluminum oxide is preferably 0.01 to 5% by weight of palladium and 99.99 to 95% by weight of aluminum oxide, more preferably 0.01 to 1% by weight of palladium. Aluminum oxide is 99.99 to 99% by weight. If it exceeds 5% by weight, the cost becomes very high, and if it is less than 0.01%, sufficient removal activity cannot be obtained. In the composite, water, other metal oxides, and a binder component may be mixed within a range that does not impair the object of the present invention. There is no restriction | limiting in particular in the shape of the composite of palladium and aluminum oxide, What was shape | molded in the shape of a cylinder, a disk, etc. besides powder form and a granular form may be sufficient. In general, a spherical or cylindrical shaped body of about 1 to 30 mm is used.

[Contact processing]
The temperature at which the raw material propylene and the composite are brought into contact with each other is usually 0 to 80 ° C, preferably 10 to 60 ° C, and particularly preferably 20 to 50 ° C. If the treatment temperature is too low, the activity of the solid catalyst in the polymerization of propylene decreases. On the other hand, if the pressure is too high, the processing pressure becomes high, and the processing operation becomes difficult. The contact time is generally in the range of 1 minute to 100 hours, and the treatment pressure is generally 0.2 to 5 MPa, preferably 0.5 to 4 MPa. As a contact method between propylene and the composite, any contact method or means can be adopted, but it is desirable that the propylene is contacted in a liquid phase. This is because if the propylene is brought into contact in a gas state, the packed tower of the composite becomes huge, which is economically disadvantageous.

Also, so-called other impurity purification catalysts such as various organic or inorganic sulfur compounds as impurities can be used together with the composite. That is, propylene is passed through one or more additional purification catalysts prior to contacting the composite. As a result, the composite is guarded and has a long life. It is also possible to pass one or more additional purification catalysts after contacting the composite. If necessary, a contact method using a combination with another purification catalyst can be employed for impurities that cannot be purified by the composite.
That is, in order to promote the contact efficiency, the contact opportunity between the raw material propylene and the composite can be implemented by providing two sets of the purified catalyst contact portion and the composite contact portion as a set. Of course, the content of CO and COS can be reduced sequentially by setting the refined catalyst part and the composite part as a set, and if necessary, arranging them in series in one, two, or three places in multiple stages. Are possible, and composite aspects are within the design specifications.

Examples of purification catalysts that can be added include synthetic zeolites such as molecular sieves (MS) 3A, 4A, 5A, and 13X, and activated alumina, or metal oxides such as copper oxide, zinc oxide, palladium, and nickel.
Specifically, the raw material propylene before contact with the metallocene catalyst is a so-called contact of a composite part composed of palladium and aluminum oxide (hereinafter also simply referred to as “composite”) and contact with an additional purification catalyst part. An example of an embodiment by combined contact is as follows.
(1) Combined contact with composite after contact with molecular sieve (2) Combined contact with composite after contact with metal oxide or metal oxide (3) Combined contact with composite after contact with alumina (4) Combined contact with metal oxide or composite oxide of metal oxide after composite treatment (5) After contact with composite oxide of metal oxide or metal oxide, composite, then composite oxidation of metal oxide or metal oxide In the contact treatment with the composite such as multi-stage contact with the product and the refinable catalyst that can be added, various combinations of changes and the number of times can be arbitrarily set in multiple stages in consideration of the properties of the raw material propylene.

This is because contact with a composite of palladium and aluminum oxide exclusively reduces the content of CO and COS sequentially, whereas this additional purifying catalyst can be used in various other organic or inorganic catalysts. It is also beneficial to sequentially reduce catalyst poisons such as sulfur compounds, and is useful for maintaining the overall activity of the metallocene catalyst by detoxifying any overall catalyst poison.
That is, it is also useful to use a combined contact in which the raw material propylene is contacted with a molecular sieve, a metal oxide or a metal oxide composite oxide, or alumina after contact with the composite in advance. In addition, any aspect in which purification catalyst portions that can be added are arbitrarily provided in multiple stages, and before and after the contact is arbitrarily changed, are included in the technical scope of the present invention.

<Polypropylene polymerization>
For the polymerization of propylene of the present invention, any method can be adopted as long as the catalyst component and the monomer come into efficient contact. Specific polymerization forms are applied to slurry polymerization using a hydrocarbon solvent, bulk polymerization in a liquefied monomer, or gas phase polymerization substantially using no solvent.

  In the case of slurry polymerization, a hydrocarbon solvent such as hexane, heptane, pentane, or cyclohexane is used as the polymerization solvent.

  The polymerization reaction is applied to continuous polymerization, semi-continuous polymerization, and batch polymerization. Furthermore, a multistage polymerization method in which the polymerization reaction is performed in two or more stages having different reaction conditions is also possible.

As conditions at the time of superposition | polymerization, superposition | polymerization temperature is 30-150 degreeC normally, Preferably it is 50-100 degreeC. The polymerization pressure is normal pressure to 5 MPa, preferably normal pressure to 4 MPa.

  In the polymerization of the present invention, hydrogen can be used for the purpose of adjusting the molecular weight of the polymer. Moreover, as a monomer to be used, not only propylene alone but also a monomer copolymerizable with propylene, such as ethylene, 1-butene, 1-hexene and the like can be used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The physical properties of the polymer obtained by the present invention were measured by the following method.
(1) Ethylene content by ¹³ C-NMR: The ethylene content described below is a value determined by analyzing a ¹³ C-NMR spectrum according to the following conditions by a proton complete decoupling method.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (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 number: 5,000 times or more The attribution of the spectrum may be performed with reference to, for example, Macromolecules 17, 1950 (1984). The attribution of spectra measured under the above conditions is as shown in Table 1. Table 1 Symbols such as S _{alpha alpha} in accordance with notation Carman et al (Macromolecules 10,536 (1977)), P represents respectively the 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 of the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby generating a minute peak.

  In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is obtained by 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. We will ask for it.

Conversion from mol% to wt% of ethylene content is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
Here, X is the ethylene content in mol%.
(2) Melt flow rate (MFR): determined in accordance with JIS K7210 (230 ° C., 2.16 kg load).
In addition, the catalyst manufacturing method and the polymerization method of propylene which were used in the Example and the comparative example are as follows.

[Example 1]
[Production of solid catalyst]
(I) Chemical treatment of silicate Using a glass separable flask with a 3 liter stirring blade, 1130 ml of distilled water was added slowly, followed by 750 g of concentrated sulfuric acid (96%), and montmorillonite (Mizusawa Chemical) Benclay SL manufactured by company; average particle size 25 μm, particle size distribution 10-60 μm, composition (weight%): Al 8.45, Mg 2.14, Fe 2.34, Si 32.8, Na 2.62) are dispersed in 300 g, up to 90 ° C. The temperature was raised over 1 hour, maintained at that temperature for 5.5 hours, and then cooled to 50 ° C. over 1 hour. This slurry was filtered under reduced pressure to recover the cake. Further, this cake was washed with distilled water until the pH of the final washing solution exceeded 3.5, and dried overnight at 110 ° C. in a nitrogen atmosphere.

(Ii) Preparation of solid catalyst The following operations were carried out under inert gas using deoxygenated and dehydrated solvents and monomers. The previously chemically treated montmorillonite was dried at 200 ° C. under reduced pressure for 2 hours. 20 g of the dried montmorillonite obtained above was introduced into a glass reactor equipped with a stirring blade with an internal volume of 1 liter, heptane containing 3% toluene (hereinafter abbreviated as mixed heptane), and a heptane solution of triethylaluminum (0 .596M) 84 ml was added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane (washing rate <1/100) to prepare 200 ml of silicate slurry.
Next, rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl] synthesized according to the same synthesis method as in Example 1 of JP-A-11-240909. }] 87 ml of mixed heptane was added to 218 mg (0.3 mmol) of zirconium, and after sufficient stirring, 4.25 ml of a heptane solution of triisobutylaluminum (0.706 M) was added and reacted at room temperature for 1 hour. Then, in addition to the previously prepared silicate slurry, after stirring for 1 hour, mixed heptane was added to prepare 500 ml.
Subsequently, the previously prepared silicate / metallocene complex slurry was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped, the temperature was raised to 50 ° C., and then maintained for another 2 hours. The prepolymerized catalyst slurry was recovered with a siphon, and about 300 ml of the supernatant was removed, followed by drying at 45 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 1.9 g of polypropylene per 1 g of catalyst was obtained.

[Propylene compound treatment]
A packed tower having an inner diameter of 78 mm and a height of 1300 mm was packed with 6.5 kg of “0.5% Pd alumina pellets” (a cylindrical molded product having an average diameter of about 3 mm and an average length of about 4 mm) manufactured by N.E. Then, a mixed liquefied propylene of 90% by weight of propylene by naphtha decomposition and 10% by weight of FCC propylene was passed through this packed tower at a flow rate of 20 kg / hour at a temperature of 30 ° C. and used for the polymerization of propylene.

[Polypropylene polymerization]
After fully replacing the inside of the stirred autoclave with an internal volume of 3 L with propylene, add 2.81 ml of triisobutylaluminum heptane solution (2.02 M) at room temperature, 25 ml of hydrogen, 15 g of ethylene, and then liquid propylene 750 g was introduced, and the temperature in the tank was raised to 70 ° C. While maintaining the internal temperature at 70 ° C., 1 ml of the prepolymerized catalyst normal heptane slurry (10 mg-catalyst / ml) obtained above and 10 mg (excluding the weight of the prepolymerized polymer) as a catalyst were added with argon. Press fit,
Polymerization was carried out at 70 ° C. for 1 hour. After polymerization for a specified time, 10 ml of ethanol was injected into the autoclave with argon and the remaining gas was purged. The obtained polymer was dried at 110 ° C. for 1 hour. As a result, 288 g of polymer was obtained. The catalyst activity was 28,800 g-PP / g-catalyst.hour, MFR = 2.6 (g / 10 min), ethylene content = 1.8 (
% By weight). The polymerization results are shown in Table 2.

[Example 2]
Before contacting propylene with the composite of palladium and aluminum oxide, “MS-4A 1.6” (average diameter: about 1.5 mm, average length: about 10 mm) made by Union Showa Co., Ltd. as a molecular sieve The experiment was conducted in the same manner as in Example 1 except that the contact was made.

[Example 3]
Propylene to be treated was made 40% by weight of propylene by naphtha decomposition and 60% by weight of FCC propylene, and after contacting with MS-4A 1.6 of propylene, JGC Catalysts & Chemicals Co., Ltd. as a metal oxide composite oxide An experiment was conducted in the same manner as in Example 2 except that the contact was made with “copper oxide / zinc oxide N-211” (a cylindrical molded product having an average diameter of about 6 mm and an average length of about 6 mm).

[Comparative Example 1]
The experiment was performed in the same manner as in Example 1 except that no purification catalyst treatment was performed on propylene.

[Comparative Example 2]
The experiment was performed in the same manner as in Example 2 except that propylene was not treated with the composite of palladium and aluminum oxide.

[Comparative Example 3]
The experiment was performed in the same manner as in Example 2 except that propylene was replaced with a composite treatment of palladium and aluminum oxide and a composite oxide treatment of copper oxide and zinc oxide was performed.

[Reference Examples 1 to 3]
The combined contact treatment with a refined catalyst capable of adding propylene to a composite of palladium and aluminum oxide (composite) can be carried out according to the specifications of Example 1.

Raw material propylene
Naphtha decomposition / FCC raw material propylene contact treatment (weight ratio)
1 After 80/20 molecular sieve contact, composite 2 60/40 After metal oxide or metal oxide composite contact, composite 3 20/80 After alumina contact, composite

Regarding the raw material propylene after contact in the embodiments of the above Reference Examples 1 to 3, in accordance with Example 1, the catalyst activity (g-PP / g-catalyst · hour), the ethylene content, and the MFR of polymerized polypropylene (g / 10 min) can be used to confirm the specifications of the raw material propylene and the significance of the combined contact treatment.

As a result, as is apparent from Table 2 above, in Example 1 using the propylene polymerization method of the present invention, the propylene contact conditions of the present application were satisfied, so the catalytic activity of the metallocene catalyst was dramatically increased. The catalyst cost can be greatly reduced. In Example 2, high catalytic activity and physical property stability were maintained over a long period of time by contacting with MS-4A before contacting the composite of palladium and aluminum oxide. In Example 3 as well, even when FCC propylene has a high content and a substantial amount of impurities, high catalytic activity and physical property stability are maintained over a long period of time by removing impurities in the previous stage in advance. .
On the other hand, in Comparative Examples 1 to 3 that did not satisfy the requirements of the present application, the catalytic activity was low due to the influence of CO, COS, etc. in FCC propylene, and the physical properties were unstable. In Comparative Example 3, although CO and COS can be removed to a certain level, the case of using a metallocene catalyst was inferior to the Example of the present application.

As described above, the propylene polymerization method of the present invention has excellent catalytic activity in propylene polymerization using a highly active supported metallocene catalyst, even when containing 5% by weight or more of FCC propylene. It is suitable for the polymerization method. Moreover, since a refining catalyst containing a large amount of noble metal is not used, its industrial applicability is very large.
In addition, since it is possible to achieve the production of high-quality polypropylene (co) polymers composed of FCC propylene, by promoting and expanding the demand for FCC propylene, fluid catalytic cracking of heavy oil as a raw material for propylene can be achieved. Not only will it contribute to the expansion, demand and progress of the technical field, it will also contribute significantly to the development of the technical field of polymerization of propylene.

Patent No. 3017856 JP-A-6-1805 Special table 2010-525134 gazette

Claims (4)

The raw material propylene containing FCC propylene obtained by the fluid catalytic cracking of heavy oil 5 wt% or more, Ri Do palladium and aluminum oxide, the total weight of the palladium complex composed of palladium and aluminum oxide 0.01-5 A method for polymerizing propylene, comprising contacting with a metallocene catalyst after contacting with a composite having a weight percentage .   2. The propylene polymerization method according to claim 1, wherein a mixture comprising 5 to 60% by weight of FCC propylene obtained by fluid catalytic cracking of heavy oil is used as raw material propylene. The method for polymerizing propylene according to claim 1 or 2 , wherein the polymer is contacted with at least one of the following (1) to (3) before contacting with the metallocene catalyst.
(1) Molecular sieve (2) Metal oxide or composite oxide of metal oxide (3) Alumina The method for polymerizing propylene according to any one of claims 1 to 3 , wherein the metallocene catalyst is supported on an ion-exchange layered silicate.